MXPA01004213A - Method for producing adhesive surface coatings - Google Patents

Abstract

The invention relates to a method for producing adhesive surface coatings on an inorganic or organic substrate, characterized by the following steps:a) subjecting the inorganic or organic substrate to low-temperature plasma discharge, corona discharge, high-energy UV radiation or electron emission, then disrupting the radiation or discharge, in a further step b) applying one or several photoinitiators, containing at least one ethylenically unsaturated group, under reduced or normal pressure on the inorganic or organic substrate and allowing it to react with the radical sites meanwhile formed, and c1) coating the substrate thus pre-coated with the photoinitiator with a composition containing at least one ethylenically unsaturated monomer or oligomer, and curing the coating by UV/VIS radiation or c2) depositing on the substrate thus pre-coated with the photoinitiator a metal, metalloid or metal oxide from the gaseous phase in the presence of UV light. The invention also relates to the use of photoinitiators having at least one ethylenically unsaturated group for producing such layers and the adhesive coatings as such.

Description

A Process for the Preparation of Adherent Coatings of the Surface The present invention relates to a process for the preparation of coatings with high adhesion strength on inorganic or organic substrates. Other objects of the present invention are the use of photoinitiators with at least one ethylenically unsaturated group for the preparation of these layers, as well as the adherent coatings themselves. The adhesion of lacquer layers, coatings or metallic layers on inorganic or organic substrates, in particular on non-polar substrates such as polyethylene, polypropylene or polyolefins containing fluorine, as they are known under the trade name Teflon®, is often not enough , so additional coating measures must be performed to obtain satisfactory results. One option is that, in a first step, special background lacquers are applied, called primers, and in a second step the desired coating is applied over them. One more possibility is to subject the coated substrates to a plasma or corona treatment and then apply the coating. Between these two steps a grafting process can be inserted with, for example, acrylate monomers (J. Polym, Sci., Part A: Polym, Chem. 31, 1307-1314 (1993) .The preparation of low temperature plasmas and the plasma-supported separation of thin organic or inorganic layers has been known for a long time and is described, for example, by AT Bell, "Fundametals of Plasma Chemistry" in "Technology and Application of Plasma Chemistry", published by JR Holahan and AT Bell, Wiley, New York (1974) or by H. Sur, Plasma Chem. Plasma Process 3 (1), 1, (1983) It is also known that, for example, plastic surfaces can be subjected to a plasma treatment and , therefore, the application of later lacquer presents a better adhesion, HJ Jacobasch et al., describe the above in Farbe + Lack 99 (7), 602-607 (1993) for low temperature plasmas under vacuum conditions and J Friedrich et al., In Surf, Coat, Technol. 59, 371-6 (1993) for plas lower vacuum to atmospheric pressure conditions, while the low temperature plasma becomes a corona discharge. Now, it has been found that coatings with particularly good adhesion are obtained by grafting a photoinitiator containing at least one ethylenically unsaturated group onto the substrate to be coated. On the substrate grafted in this way a layer of photocurable lacquer is applied and cured. The coatings obtained have a surprisingly good adhesion force which does not show considerable deterioration after storage for several days and also after illumination in sunlight. This procedure allows a simple realization and a high performance for each unit of time, since long drying steps or slow crosslinking reactions are not required. The procedure is particularly suitable for work pieces that are made up of different plastics and / or metals, that is, glasses and that, therefore, would present different adhesion in the different pieces if a pre-treatment is not carried out, that is, that with a conventional primer treatment have different affinities with respect to the background substance. An object of the present invention is a process for the preparation of adhesive coatings on an inorganic or organic substrate, characterized in that in a first step a) on the inorganic or organic substrate a low temperature plasma discharge, corona discharge or ultraviolet radiation with high energy content or electronic radiation is applied, then radiation or discharge is removed, in a further step b) apply on the organic or inorganic substrate one or more photoinitiators containing at least one ethylenically unsaturated group under vacuum or under normal pressure and react with the radical points generated therein, and cl) the substrate previously coated with photoinitiator is coated with a composition containing at least one ethylenically unsaturated monomer or oligomer and the coating is cured by UV / VIS or c2) a photoinitiator coated on the substrate is thus coated with a photoinitiator. metal, semimetallic or metallic oxide from the gas phase in the presence of ultraviolet light.

The possibilities for obtaining plasmas under vacuum conditions have already been described multiple times in the literature. Electric power can be introduced inductively or capacitively. It can be direct current or alternating current, where the frequency of alternating current can vary from few kHz to the area of the MHz. Also allow a power in the area of microwaves (Ghz). The principles of plasma preparation and preservation are described, for example, in the aforementioned articles by A. T. Bell and H. Suhr.

As primary plasma gases, for example, He, argon, xenon, N2, 02, water vapor or air can be used. Essentially, the method, according to the present invention, is not sensitive to the incorporation of electrical energy. The process can be carried out discontinuously, for example, in a rotating drum or, in the case of sheets, fibers or fabrics in a continuous manner. These procedures are known and described according to the state of the art. The procedure can also be performed under corona discharge conditions. Corona discharges are generated under normal pressure conditions, using air as ionized gas in most cases. However, other gases can also be used initially, working in these cases in closed systems in order to avoid contact with atmospheric air. Another possibility is to use air as ionisation gas in corona discharges, working in this way with a set of apparatuses open towards the outside and passing, for example, a sheet continuously between the discharge electrodes. These process arrangements are known and described, for example, in J. Adhesion Sci. Technol. Vol. 7, No. 10, 1105, (1993). If a corona discharge is used in an open set of apparatuses, it is preferred to work under the exclusion of oxygen, which is achieved by a sufficiently large flow of inert gas. The procedure can also be carried out using electromagnetic radiation with a high energy content for the treatment of substrates under vacuum or with the exclusion of oxygen. As electromagnetic radiation with high energy content are considered those that are capable of generating radicals on the surface. Examples are the ultraviolet radiation of short wave or X-radiation. In this context, mention should be made, in particular, of electronic rays such as are already used for the curing of lacquers and paints and bonds by adhesion of sheets. But shortwave ultraviolet radiation (in particular, UV radiation under vacuum) can also be applied, as generated by UV lamps or excimer lamps. Preferably, it is radiation with a wavelength less than 300 nm, particularly preferably less than 260 nm. Apart from conventional lamps for the exposure of large surfaces, lasers can also be used which operate within the corresponding range of wavelengths for the exposure of points or for the illustrative "description" of the surface. If masks or laser writers are used, only certain areas with photoinitiators can be selectively charged, which leads to different wetting and, with respect to the coating that follows, to different adhesions. Substrates with grafted photoinitiator can also be exposed in the form of images by irradiation by a mask or by using laser beams carried across the surface. In this way, a modification of the surface is again obtained, however only in the exposed areas. In this way, for example, drawings with different hydrophobicity / hydrophilicity and / or metallization can be generated. If the exposure in images is performed in the presence of a light curing formulation, these drawings are obtained with, for example, a different adhesion and / or tackiness and / or different color and / or other properties depending on the formulation. The inorganic or organic substrate to be treated can be in any solid form. Preference is given to substrates in the form of a powder, of a fiber, of a sheet or in the form of a three-dimensional work piece. Preference is given to an inorganic or organic substrate which is a thermoplastic polymer, elastomer, crosslinked or crosslinked structure, metal oxide, glass or metal. Examples for these thermoplastic polymers, elastomers, crosslinked structure or crosslinked are mentioned below: 1. Polymers of mono- and diolefins, for example, polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, as well as cycloolefin polymerization products such as, for example, cyclopentene or norbornene; in addition polyethylene (in any case, crosslinked), for example, high density polyethylene (HDPE), high density polyethylene and high molar mass (HDPE-HMW), high density polyethylene and ultra-high molar mass (HDPE- UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) und (ULDPE).

Polyolefins, ie polymers of monoolefins as mentioned, for example, in the preceding paragraph, in particular, polyethylene and polypropylene can be prepared according to different procedures, in particular, according to the following methods: a) in radical form (usually , under high pressure and high temperature). b) by means of a catalyst, the catalyst usually containing one or more metals from group Ivb, Vb, Vib or VIII. Usually, these metals possess one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls, and / or aryls that can be coordinated in their p or s position.

These metal complexes can be free or fixed on a carrier such as, for example, on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts per se can be active in the polymerization or other activators can be used, such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyloxides or metal alkyloxanes, where the metals are elements of the groups , lía and / or Illa. The activators may be modified, for example, with other ester, ether, amino or silyl ether groups. These catalytic systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), Metallocen or Single catalysts Site (SSC). 2. Mixtures of the polymers indicated under 1), for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example, PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example, LDPE / HDPE) . 3. Copolymers of mono- and diolefins with one another or with other vinyl monomers such as, for example, ethylene-propylene-copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene- buten-1-copolymers, propylene-isobutylene-copolymers, ethylene-buten-1-copolymers, ethylene-hexen-copolymers, ethylene-methylpentene-copolymers, ethylene-hepten-copolymers, ethylene-octen-copolymers, propylene-butadiene-copolymers, isobutylene-isoprene-copolymers, ethylene-alkyl acrylate-copolymer, ethylene-alkyl-methacrylate-copolymers, ethylene-vinylacetate-copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid-copolymers and their salts (ionomers), as well as ethylene terpolymers with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; in addition, mixtures of these copolymers with each other and with the polymers described under 1), for example, polypropylene / ethylene-propylene-copolymers, LDPE / ethylene-vinylacetate-copolymers, LDPE / ethylene-acrylic acid-copolymers, LLDPE / ethylene-vinylacetate -polymers, LLDPE / ethylene-acrylic acid-copolymers and in alternating form or statically prepared polyalkylene / carbon monoxide copolymers and their mixtures with other polymers such as, for example, polyamides. 4. Hydrocarbon resins (eg C5-C9), including hydrogenated modifications thereof (eg, tackifying resins) and mixtures of polyalkylenes and starch. 5. Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene). 6. Copolymers of styrene or of α-methylstyrene with dienes or with acrylic derivatives such as, for example, styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butyldien-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene acrylonitrile-methylacrylate; high-resilience blends of styrene-copolymers and another polymer, such as, for example, a polyacrylate, a diene-polymer or an ethylene-propylene-diene-terpolymer; as well as styrene block copolymers such as, for example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene. 7. Styrene and a-methylstyrene graft copolymers, such as, for example, styrene on polybutadiene, ethylene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (ie, methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic acid anhydride on polybutadiene; styrene, acrylonitrile and maleic acid anhydride or maleic acid imide on polybutadiene; styrene and maleic acid imide on polybutadiene, styrene and alkyl acrylates, that is, alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene-terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, as well as their mixtures with the copolymers indicated under figure 6) as are known, for example, as ABS, MBS, ASA or AES polymers. 8. Halogen-containing polymers such as, for example, polychloroprene, chlorine rubber, chlorinated and brominated isobutylene-isoprene copolymer (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, ethylene-chlorinated ethylene copolymers, epichlorohydrin-homopolymers and -copolymers, in particular polymers from halogen-containing vinyl compounds such as, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; as well as its copolymers such as vinyl chloride-vinylidene chloride, vinyl chloride-vinylacetate or vinylidene-vinyl acetate chloride. 9. Polymers derived from α, β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates, polymethylmethacrylates, polyacrylamides and modified polyacrylonitriles at high impact strength by butylacrylate. 10. Copolymers of the monomers indicated under 9) with each other or with other unsaturated monomers such as, for example, copolymers of acrylonitrile-butadiene, copolymers of acrylonitrile-alkyl acrylate, copolymers of acrylonitrile-alkoxyalkylacrylate, copolymers of acrylonitrile-vinylhalogenide or terpolymers of acrylonitrile alkyl methacrylate butadiene. 11. Polymers derived from unsaturated alcohols and amines, that is, their acyl derivatives or acetals such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate or polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine; as well as its copolymers with the olefins mentioned under point 1. 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisclicidyl ethers. 13. Polyacetals such as polyoxymethylene, as well as those polyoxymethylenes containing comonomers such as, for example, ethylene oxide; polyacetals modified with polyurethanes, acrylates or thermoplastic MBS. 14. Polyphenylene oxides and sulphides and their mixtures with polymers of styrene or polyamides. 15. Polyurethanes derived, on the one hand, from polyethers, polyesters and polybutadienes with hydroxyl groups in the final position and, on the other hand, from aliphatic or aromatic polyisocyanates, as well as their previous products. 16. Polyamides and copolyamides which are derived from diamines and dicarbonyl acids and / or aminocarbonyl 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 from m-xylene, diamine and adipin acid; polyamides, prepared from hexamethylenediamine and iso- and / or terephthalic acid and, optionally, an elastomer as a modifier, for example, poly-2,4,4-trimethylhexamethyleneterephthalamide or poly-m-phenylene isophthalamide. Block copolymers of the aforementioned polyamides, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers as, for example, with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. In addition, polyamides modified with EPDM or ABS or copolyamides; as well as condensed polyamides during processing ("RIM polyamide systems"). 17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles. 18. Polyesters which are derived from dicarbonyl acids and dialcohols and / or from hydroxycarbonyl acids or the corresponding lactones such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylene cyclohexanterephthalate, polyhydroxybenzoates, as well as block polyether esters derived from polyethers with hydroxylene groups; also with polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates. 20. Polysulfones, polyethersulfones and polyether ketones. 21. Crosslinked polymers derived, on the one hand, from the aldehydes and, on the other hand, from phenyl-formaldehyde, urea-formaldehyde and melamin-formaldehyde resins. 22. Alkyd resins with and without ability to dry. 23. Unsaturated polyester resins which are derived from the copolyesters of saturated and unsaturated dicarbonyl acids with polyhydric alcohols, as well as vinyl compounds as crosslinking agents, as well as their halogen-containing modifications and which are not very combustible. 24. Crosslinkable acrylic resins which are derived from substituted acrylic acid esters such as, for example, epoxyacrylates, retanacrylates or polyesteracrylates. 25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, uric resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins. 26. Epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example, products of bisphenol-A-diglycidyl ethers, bisphenol-F-diglycidyl ethers, which are crosslinked by common hardeners such as, for example, anhydrides or amines with or without accelerators. 27. Natural polymers such as celluloses, natural rubber, gelatin, as well as chemically chemically transformed derivatives thereof such as cellulose acetate, cellulose propionates and cellulose butyrates, that is, cellulose ethers such as methyl cellulose, as well as resins of rosin and its derivatives. 28. Mixtures ('polyblends') of the aforementioned polymers such as, for example, FF / EPDM, polyamide / -EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / PUR thermoplastic, PC / PUR thermoplastic, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6 6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

Within the framework of the present invention, paper is also understood as a polymer with a crosslinked structure, in particular in the form of cardboard, which can also be coated with Teflon®. Substrates of this type can be obtained, for example, in commerce.

Preferably, with reference to the thermoplastic, crosslinked or crosslinked plastic, it is a polyolefin, polyamide, a polyacrylate, polycarbonate, polystyrene or an acrylic / melamine, alkyd or polyurethane lacquer. In particular, preference is given to polycarbonate, polyethylene, polypropylene, polyamide and polyimide. Plastics may be in the form of sheets, injection molded parts, extruded workpieces, fibers, felts or fabrics. As inorganic substrates are considered, above all, glasses, metal oxides and metals. They may be silicates and semimetallic or metallic oxide glasses, which are preferably in powder form with a mean particle diameter of 10 nm to 2000 nm. It can also be both compact particles and porous particles. Examples for oxides and silicates are Si02, Ti02, Zr02, MgO, NiO, W03, Al203, La203, silica gels, muds and zeolites. Apart from metals, preference is given to inorganic substrates which are silica gels, aluminum oxide, titanium oxide or glass and their mixtures. In principle, all photoinitiators having at least one ethylenically unsaturated group are suitable for the process according to the present invention.

Metal substrates are considered, in particular, Fe, Al, Ti, Ni, Mo, Cr or steel alloys. Preferably, the photoinitiator is a compound of formula I or (RG) -A- (IN) (I), (IN) -A- (RG ') -A- (IN) (la), wherein ( IN) is a basic photoinitiator structure, A is a spacer group or a single bond, (RG) means at least one ethylenically unsaturated functional group, and (RG ') represents a bivalent residue containing at least one ethylenically unsaturated functional group. Preference is given to the compounds of the formula I or the formula, wherein (IN) is a basic photoinitiator structure of the formula (II) or (III) II1 -P-R3 (III) R_ wherein R- represents a group (A), (B) or (III) R2 represents hydrogen, alkyl of 1 to 12 carbon atoms, halogen, the group (RG) -A- or, if R? represents a group (A), two R2 residues in ortho position with respect to the carbonyl group, together they can also represent -S- or wherein R3 and R4 are, independently of each other, alkyl of 1 to 6 carbon atoms, alkanoyl of 1 to 6 carbon atoms, phenyl and benzoyl, wherein the phenyl or benzoyl radicals are substituted, respectively, by halogen, alkyl of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms; R_ means hydrogen, halogen, alkyl of 1 to 12 carbon atoms or alkoxy of 1 to 12 carbon atoms or the group (RG) -A-; R7 and R8 are, respectively and independently of one another, H, alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, phenyl, benzyl or together alkylene of 2 to 6 carbon atoms; R9 is hydrogen, alkyl of 1 to 6 carbon atoms or alkanoyl of 1 to 6 carbon atoms; R is hydrogen, alkyl of 1 to 12 carbon atoms or phenyl; and X, is oxygen or sulfur.

Preferably, in the compounds of the formula I or the Preference is given to the compounds of formula I or A, wherein A represents a spacer group -Z- [. { A1) a-Y] c [(A2) b-X] d; X, Y and Z are, independently of each other and respectively, a single bond, -0-, -S-, -N (R10) -, - (CO) -, - (C0) 0-, - (CO) N (R10) -, -0- (C0) -, -N (R10) - (CO) - O -N (R10) - (CO) O-; Aj_ and A2 represent independently from each other alkylene of 1 to 4 carbon atoms, cycloalkylene of 3 to 12 carbon atoms, phenylene, phenylene alkylene of 1 to 4 carbon atoms or alkylene of 1 to 4 carbon atoms-phenylene -alkylene of 1 to 4 carbon atoms; a, b, c and d mean, independently of each other, a number from 0 to 4; and R, is defined as previously mentioned. Particular preference is given to the compounds of the formula I or the formula, wherein A means a spacer group -Z - [(CH2) aY] c - [(CH2) bX] d- and X, Y, Z, a, b , c and d have the meanings indicated above. Of particular preference, in the compounds of the formula I or represent (RG) RcRbC = CRa-, Ra, Rb, Rc signify H or alkyl of 1 to 6 carbon atoms, respectively, in particular means H or CH3. The preparation of photoinitiator compounds of this type is known and common to the expert and has already been described in several publications. Thus, for example, compounds containing unsaturated groups can be prepared by the reaction with 4- [2-Hydroxyethoxy) -benzoyl] -! - hydroxy-1-methyl-ethane (Irgacure® 2959, Ciba Spezialitátenchemie) with isocyanates which they contain acryloyl or methacryloyl groups or other compounds containing acryloyl or methacryloyl groups; compare, for example, with the patent US 4922004. From the publications that will be indicated below, specific examples can be extracted for suitable photoinitiators compounds with an ethylenically unsaturated function, as well as for their preparation: Unsaturated derivatives of aceto and benzophenone are decribed, example, in US Pat. No. 3214492, US Pat. No. 3,429,852, US Pat. No. 3,622,848 and US Pat. No. 4,30,495, for example, copolymerisable and ethylenically unsaturated acetophenone compounds are deduced, for example, from US Pat. No. 4,922,004, for example, 2-Acryloyl-thioxanthone is published in Eur. Polym. J. 23, 985 (1987).

Examples like They are shown in DE 2818763. Other compounds containing photoinitiators unsaturated carbonate groups can be deduced from EP 377191. Uvecryl® P36, from UCB, is a benzophenone bonded with an acrylic function by ethylene oxide units (compare Technical Bulletin 2480/885 (1985) from UCB or New. Polym, Mat. 1, 63 (1987)) In Chem. Abstr. 128: 283649r is published From DE 19501025 other suitable ethylenically unsaturated photoinitiator compounds can be deduced. Examples are 4-viniloxicarboniloxibenzofenona, 4-vinyloxycarbonyloxy-4'-clorbenzofenon, 4-vinyloxycarbonyloxy-4'-metoxibenzofenona, N-vinyloxycarbonyl-4-aminobenzophenone, vinyloxycarbonyloxy-4'-flúorbenzofenona, 2-vinyloxycarbonyloxy-4'-metoxibenzofenona, 2-vinyloxycarbonyloxy-5-fluoro-4'-chlorobenzophenone, 4-vinyloxycarbonyl acetophenone, 2-vinyloxycarbonyloxyacetophenone, N-vinyloxycarbonyl-4-aminoacetophenone, 4-vinyloxycarbonyloxybenzyl, 4-vinyloxycarbonyloxy-4'-methoxybenzyl, vinyloxycarbonylbenzoin ether, 4-methoxibenzoinviniloxicarbonio, phenyl (2 -viniloxicarboniloxi-2 -propyl) ketone, (4-isopropylphenyl) - (2 -viniloxicarboniloxi-2 -propyl) ketone, fen-yl- (1-vinyloxycarbonyloxy) -ciclohexilcetona, 2-vinyloxycarbonyloxy -9-fluorenone, 2- (N-vinyloxycarbonyl) -9-aminoflúorenona, 2-vinilcarboniloximetilantiraquinona, 2- (N-vinyloxycarbonyl) -aminoantraquinona, 2-viniloxicarboniloxitioxantona, 3-vinilcarboniloxitioxantona or US 4672079 discloses, entr others, the preparation of 2-hydroxy-2-methyl (4-vinilpropiofenona), 2-hydroxy-2-methyl-p- (1-methylvinyl) propiophenone, p-vinilbenzoilciclohexanol, p- (1 -methylvinyl) benzoyl-cyclohexanol. Also suitable are the reaction products described in JP Kokai Hei 2-292307 which are derived from 4 [2-hydroxyethyoxy) -benzoyl] -1-hydroxy-1-methyl-ethane (Irgacure® 2959, Ciba Spezialitátenchemie) and isocyanates containing acrylole or metactillium groups, for example, (where R = H or CH3 Other examples for suitable photoinitiators are The following examples are described in the publication Radcure '86, Conference Proceedings, 4-43 bis 4-54 by W. B umer et al.

G. Wehner et al. exposes in the publication Radtech '90 North America about Next, the meaning of the substituents in the different residues will be explained. Alkyl of 1 to 12 carbon atoms is linear or branched and is, for example, alkyl of 1 to 8, 1 to 6 or 1 to 4 carbon atoms. Examples are methyl, ethyl, propyl, isopopilo, n-butyl, sec-butyl, iso-butyl, tert-butyl, fentilo, hexyl, heptyl, 2, 4, 4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decile, undecyl or dodecyl, in particular, by example, methyl or butyl. Alkyl of 1 to 6 carbon atoms and alkyl of 1 to 4 carbon atoms are, at the same time, linear or branched and have, for example, the meanings indicated above up to the corresponding numbers of carbon atoms, for example, substituents of alkyl of 1 to 6 carbon atoms for benzoyl or phenyl are, in particular, alkyl of 1 to 4 carbon atoms, for example methyl or butyl. Halogen means fluorine, chlorine, bromine and iodine, in particular chlorine and bromine, preferably chlorine. In case one group (A) is R1 # and two R2 residues in ortho position with respect to the carbonyl group O mean together -S- or -c- then they result, for example, structures with basic bodies of thioxanthone or anthraquinone basic bodies Alkanoyl of 1 to 6 carbon atoms is linear or branched and is, for example, alkanoyl of 1 to 4 carbon atoms. Examples are formyl, acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl or hexanoyl, preferably acetyl. Alkanoyl of 1 to 4 carbon atoms have the meanings indicated above up to the corresponding number of carbon atoms. Alkoxy of 1 to 12 carbon atoms represents linear or branched residues and is, for example, alkoxy of 1 to 8, 1 to 6 or 1 to 4 carbon atoms. Examples include methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy or dodecyloxy, in particular, methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, preferably methoxy. Alkoxy of 1 to 8 carbon atoms, alkoxy of 1 to 6 carbon atoms and alkoxy of 1 to 4 carbon atoms are also linear or branched and have, for example, the meanings indicated above up to the corresponding number of carbon atoms. Alkylthio having 1 to 6 carbon atoms represents linear or branched radicals and is, for example, alkylthio having 1 to 4 carbon atoms. Examples are methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, iso-butylthio, tert-butylthio, pentthylthio or hexylthio, in particular, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, tert. -butylthio, preferably, methylthio. Alkylthio of 1 to 4 carbon atoms is also linear or branched and has, for example, the meanings indicated above up to the indicated number of carbon atoms. Halogen-substituted phenyl or benzoyl radicals, alkyl of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms are substituted, for example, in the phenyl ring in simple form up to five times, for example double or triple, in particular , double or triple. Preference is given to, for example, 2, 4, 6-trimethylbenzoyl, 2,6-dichlorobenzoyl, 2,6-dimethylbenzoyl or 2,6-dimethoxybenzoyl. Alkylene of 1 to 4 carbon atoms and alkylene of 2 to 6 carbon atoms are linear or branched, for example, alkylene of 2 to 4 carbon atoms, such as, for example, methylene, ethylene, propylene, n-butylene, sec- butylene, iso-butylene, tert-butylene, pentylene or hexylene. Preference is given to alkylene of 1 to 4 carbon atoms, for example, ethylene or butylene -CH-CH, -CH- (CH2) 2- "CH- (CH2) 3- I2 CH- CH, CH, -C (CH3) 2-CH2-, as well as methylene and ethylene, Phenylene-alkylene of 1 to 4 carbon atoms represents phenylene which is substituted by alkylene of 1 to 4 carbon atoms at an aromatic ring position, while alkylene of 1 to 4 carbon atoms-phenylene-alkylene of 1 to 4 carbon atoms carbon represents phenylene which is substituted by alkylene of 1 to 4 carbon atoms at two positions of the phenylene ring. Meanwhile, the alkylene moieties are linear or branched and have, for example, the meanings indicated above up to the corresponding number of carbon atoms.

However, the alkylene groups can also be positioned in other positions of the phenylene ring, for example, also in the 1,3-position. Cycloalkylene is, for example, cycloalkylene of 3 to 12 or 3 to 8 carbon atoms, for example, cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene, in particular, cyclopentylene and cyclohexylene, preferably cyclohexylene. However, cycloalkylene of 3 to 12 carbon atoms also represents structural units such as: where x and y mean independently of each other 0-6 and the sum of x + y is < 6, or - (C H ^) - V- - (C H2) / where x and y mean in form independent of each other 0-7 and the sum of x + y is < 7. Phenylene means 1,4-, 1,2- or 1,3-phenylene, in particular 1,4-phenylene. Alkenyl residues of 1 to 12 carbon atoms can be single or multiple unsaturated and can be linear or branched and are, for example, alkenyl of 2 to 8 carbon atoms, 2 to 6 carbon atoms or 2 to 4 carbon atoms. carbon atoms. Examples are allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, 1-octenyl, decenyl or dodecenyl, in particular allyl. If R7 and R8 together form alkylene of 2 to 6 carbon atoms, then together with the carbon atom, to which they are bonded, they represent a cycloalkyl ring of 3 to 7 carbon atoms. Cycloalkyl of 3 to 7 carbon atoms is, for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, in particular cyclopentyl and cyclohexyl, preferably cyclohexyl. RcRbC = CRa- means, for example, -CH = CH2 oder -C (CH3) = CH2, preferably, -CH = CH2. After suspending the radical-forming discharge or exposure (process step a)), the photoinitiators can evaporate on a heatable device under vacuum in such a way that they precede the previously treated workpiece, where they react with the radicals. The evaporation can be carried out as a solid substance, a melt or with a suitable solvent, while the vapor pressure of the solvent is preferably close to the vapor pressure of the photoinitiators. In the case of a corona discharge under atmospheric conditions, the photoinitiator can also be applied by spraying in the form of a solution. Preferably, this is done immediately and directly after the corona discharge, for example, in the case of a continuous process by means of nozzles as a continuation of the discharge zone. After application of the photoinitiator, the workpiece can be stored or followed by processing directly, while a layer of radiation curable lacquer containing ethylenically unsaturated bonds can > 'i apply through known technologies. This can be done by • casting, dipping, spraying, - _ - + I gluing, raching, lamination or casting. i% The unsaturated compounds of the coating composition curable by radiation can contain one or more ethylenically unsaturated double bonds. They may be of low molecular weight (monomer) or of a higher molecular weight (oligomer). Examples for monomers with a double bond are alkyl acrylate or methacrylate or hydroxyalkyl acrylate or methacrylate such as, for example, methylacrylate, ethylacrylate, butylacrylate, 2-ethylhexyl- or 2-hydroxyethyl acrylate, isobornylacrylate, methyl ethyl methacrylate. Interesting are also the acrylates of *} I silícona. Other examples are acrylonitrile, actylamide,? - I metacplamide, N-substituted (meth) acryl-amide, vinylester as vi * n "* ylacetate, vinyl ethyle as isobutylvinyl ether, olyloxyethoxy) -diphenylpropane trimethylolpropane-triacplate, J f I peñtaeritrit-triacrilats o -tetraacrilato, vinilacrilato, diviniIbenzene, divinilsuccinato, diallyphthalate, trialilfosfato,? triallylisocyanurate, tris (hydroxy-ethyl) isocyanurate-triacrylate or tris- (2-acryloylethyl) -isocyanurate. Examples for higher molecular weight (oligomers) and multiple unsaturated compounds are acrylated epoxy resins, polyesters containing acrylic vinyl or epoxy ether groups, polyurethanes and polyethers. Other examples for unsaturated oligomers are unsaturated polyester I resins which are often prepared from acid 1 i maleic, phthalic acid and one or several diols and having a molecular weight of about 500 to 3000. Apart i i can also be used monomers and oligomers of vinyl ether, as well as oligomers that end in maleate with! main chains of polyester, polyurethane, polyether, polyvinyl ether and epoxide. In particular, combinations of oligomers and polymers having vinyl ether groups, such as are described in WO I 90/01512, are particularly suitable. But also! Consider the copolymers from monomers functionalized by vinyl ether and maleic acid. These unsaturated oligomers can also be referred to as prepolymers. In particular, esters of carboxylic acids and ethylenically unsaturated polyols or polyepoxides, polymers with ethylenically unsaturated groups in the chain or in side groups such as, for example, unsaturated polyesters, polyamides and polyurethanes and their copolymers are suitable, for example. , alkyd resins, polybutadiene and copolymers of butadiene, polyisoprene and copolymers of isoprene, polymers and copolymers with (meth) acrylic groups in side chains, as well as mixtures of one or more of these polymers. Examples for unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids such as linolenic acid or oleic acid. Preference is given to acrylic and methacrylic acid. Suitable aromatic polyols are aromatic polyols and, in particular, aliphatic and cycloaliphatic polyols. Examples for aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) -propane, as well as novolaks and resols. Examples for polyepoxides are those based on the aforementioned polyols, in particular, the aromatic polyols and epichlorohydrin. Further, polyols and copolymers containing hydroxyl groups in the polymer chain or in side groups such as, for example, polyvinyl alcohol and copolymers thereof or hydroxyalkyl ester of polymethacrylic acid or copolymers thereof are also suitable as polyols. Other suitable polyols are oligoesters with hydroxyl end groups.

Examples for aliphatic and cycloaliphatic polyols are alkylene diols with preferably 2 to 12 carbon atoms such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexandiol, octandiol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols with molecular weights of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerin, tris- (β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. The polyols can be partially or completely esterified with one or more carboxylic acids, while in partial esters the free hydroxyl groups can be, for example, etherified or esterified with other carboxylic acids. Examples for esters are: trimethylolpropanetriacrylate, trimethyloletantriacrilate, Trimethylolpropane trimethacrylate, trimetiloletantrimetacrilato, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraetilenglicoldiacrilato, pentaeritritdiacrilato, pentaeritrittriacrilato, pentaeritrittetraacrilato, dipentaeritritdiacrilato, dipentaeritrittriacrilato, dipentaeritrittetraacrilato, dipentaeritritpentaacrilato, dipentaeritrithexaacrilato, tripentaeritritoctaacrilato, pentaeritritdimetacrilato, pentaeritrittrimetacrilato, dipentaeritritdimetacrilato, dipentaeritrittetrametacrilato, tripentaeritritoctametacrilato, pentaeritritdiitaconato, dipentaeritrittrisitaconato, dipentaeritritpentaitaconato, dipentaeritrithexaitaconato, ethylene glycol diacrylate , 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanedioldiitaconate, sorbittriacrylate, sorbittetraacrylate, pentaerythritol-triacrylate, sorbittetramethacrylate, sorbitpentaacrylate, sorbithexaacrylate, oligoesteracrylates and -methacrylates, glycerindi- and -triacrulate, 1,4- cyclohexandiacrilate, b polyethylene glycol isaacrylates and bismethacrylates with a molecular weight of 200 to 1500, or mixtures thereof.

Also suitable as components are amides of unsaturated carboxylic acids identical or different from aromatic, cycloaliphatic or aliphatic polyamines with preferably from 2 to 6, particularly preferably from 2 to 4, amino groups. Examples for these polyamines are ethylene diamine, 1,2- or 1,3-propylene diamine, 1,2-, 1,3- or 1,4-butylene diamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diamino-cyclohexane, isophorone diamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine, di (β-aminoethoxy) - or di (β-aminopropoxy) ethane. Other suitable polyamines are polymers and copolymers with optionally additional amino groups in the side chain and oligoamides with amino end groups. Examples for these unsaturated amides are: methylene-bis-acrylamide, 1,6-hexamethylene-bis-acrylamide, diethylene triamine-tris-methacrylamide, bis (methacrylamidopropoxy) -ethane, β-methacryl-amido-ethyl methacrylate, N [ß- hydroxyethoxy) ethyl] -acrylamide. Suitable and unsaturated polyesters and polyamides are derived, for example, from maleic acid and dies or diamines. The maleic acid can be replaced in part by other dicarboxylic acids. They can be used together with ethylenically unsaturated comonomers, for example styrene. The polyesters and the polyamides can also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, in particular long chain ones of, for example, 6 to 20 carbon atoms. Examples for polyurethanes are those consisting of saturated or unsaturated diisocyanates and unsaturated, ie saturated, diols. Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers are, for example, olefins such as erthin, propene, butene, hexene, (meth) acrylates, acrylonitrile, styrene or vinyl chloride.

Polymers with (meth) -acrylate groups in the side chain are also known. It can be, for example, reaction products of epoxy resins based on novolac with (meth) acrylic acid, homopolymers or copolymers of vinyl alcohol or its hydroxyalkyl derivatives, esterified with (meth) acrylic acid, or homopolymers or copolymers of (meth) acrylates esterified with hydroxyalkyl (meth) acrylates. Of particular preference, an acrylate or methacrylate compound is used as the ethylenically unsaturated compound in single or multiple form. Of very particular preference are unsaturated acrylate compounds in multiple form as indicated above. Particular preference is given to a process, wherein at least one ethylenically unsaturated monomer or oligomer of the composition curable by radiation is a monofunctional, difunctional, trifunctional or tetrafunctional acrylate or methacrylate. Preferably, the composition contains, apart from at least one ethylenically unsaturated monomer or oligomer, at least one other photoinitiator or coinitiator for curing by UV / VIS radiation. Within the framework of the present invention, UV / VIS radiation should be understood as an electromagnetic radiation within a wavelength range of 250 nm to 450 nm. It is preferably in the range of 305 nm to 450 nm. Suitable lamps are known to the expert and are commercially available. As photoinitiators in the radiation-curable lacquers, both the compounds of the formula I or lac and any other initiator known according to the state of the art can be used.

Next, typical examples that can be used both individually and together as a mixture will be mentioned. For example, benzophenones, benzophenone derivatives, acetophenone, acetophenone derivatives such as, for example, α-hydroxycycloalkylphenyl ketone or 2-hydroxy-2-methyl-1-phenyl-propanonasdialcoxyacetophenones, -hydroxy- or α-aminoacetophenones as, for example, ( 4-methylthiobenzoyl) -1-methyl-1-morpholino-ethane, (4-morpholino-benzoyl) -1-benzyl-1-dimethylamino-propane, 4-aroyl-1, 3-dioxolanes, benzoalkyl ether and benzyl ketals, for example, benzyldimethyl ketal, phenylglyoxalates and the derivatives thereof, dimeric phenylglyoxalates, monoacylphosphinoxides, such as, for example, (2,4-, 6-trimethylbonzoyl) -phenyl-phosphinoxide, bis (2,4,6-trimethylbenzoyl) phosphonoxide, trisacylphosphoxides, ferrocenium compounds or titanocenes such as, for example, dicyclopentadienyl-bis (2,6-difluoro-3-pyrolophenyl) -titanium.

Another category of suitable photoinitiators is that of oxime esters. As examples, the following will be mentioned: 1- (4-phenylsulfanyl-phenyl) -butan-1,2-dion-2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octan-1,2-dion 2 -Oxim-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octan-1,2-dion 2-oxy-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octan-1-on oxim-O -acetate, 1- (4-phenylsulfanyl-phenyl) -butan-1-on. Oxim-O-acetate or 1- (4-phenylsulfanyl-phenyl) -octan-1,2-dion 2-oxy-0-benzoate. As coinitiators, for example, sensitizers that modify are considered, that is, they increase the spectral sensitivity and, therefore, cause an acceleration of the photopolymerization. These are, in particular, carbonyl compounds, for example benzophenone, thioxanthone, especially isopropylthioxanthone also, anthraquinone and 3-acylcoumarin of, terphenyls, estirilcetonas and 3- (aroylmethylene) -thiazolines, quinone of camphor, but also colorants of eosin, rhodamine and erythrosine. As photosensitizers, for example, amines can be considered if the grafted photoinitiator layer, according to the present invention, consists of a benzophenone or a benzophenone derivative.

Further examples of photosensitisers are 1. Thioxantona thioxanthones, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodeciltioxantona, 2, 4-diethylthioxanthone, 2, 4-dimethylthioxanthone, 1-metoxicarboniltioxantona, 2-etoxicarboniltioxantona, 3- (2-methoxyethoxycarbonyl ) -tioxantona, 4-butoxicarboniltioxantona, 3-butoxycarbonyl-7-methylthioxanthone, l-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, l-ethoxycarbonyl-3-etoxitioxantona, 1-ethoxycarbonyl-3-aminotioxantona, l- ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-di- [2- (2-methoxyethoxy) ethoxycarbonyl] -thioxanthone, l-ethoxycarbonyl-3- (1-methyl-1-morpholinoethyl) -thioxanthone, 2-methyl-6- ( 1,1-dimethoxybenzyl) -tioxantona, 2-morfolinometiltioxantona, 2-methyl-6-morfolinometiltioxantona, N-aliltioxantona-3, 4-dicarboximide, N-octiltioxantona-3, 4-dicarboximide, N- (1,1,3, 3-tetramethylbutyl) -thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthon-2-polyethylene glycololyester, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N, N-trimethyl-1-propananium chloride; 2. Benzophenones Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4, 4 '-dimetoxibenzofenona, 4,4'-dimethylbenzophenone, 4, 4' -diclorobenzofenona, 4,4'-dimethylaminobenzophenone, 4, 4 '-dietilaminobenzofenona, 4- methylbenzophenone, 2, 4, 6-trimethylbenzophenone, 4- (4-methylthiophenyl) benzophenone, 3,3 '-dimethyl -4 -metoxibenzofenona, methyl-2-benzoylbenzoate, 4- (2-hydroxyethylthio) benzophenone, 4- ( 4-tolylthio) benzophenone, 4-benzoyl chloride-N, N, N-trimetilbenzolmetanaminio, 2-hydroxy-3- (4-benzoylphenoxy) -N chloride, N, N-trimethyl-l-propanaminium monohydrate, 4- ( 13-acryloyl-l, 4,7,10,13-pentaoxatridecyl) -benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (l-oxo-2-propenyl) oxy] ethyl-benzolemethane amino; 3. 3-acilkumarinas 3-benzoilcumarina, 3 -benzoyl-7-methoxycoumarin, 3-benzoyl-5, 7-di (propoxy) coumarin, 3-benzoyl-6, 8-diclorocumarina, 3-benzoyl-6-chloro-coumarin, 3,3 '-carbonyl-bis [5,7-di (propoxy) -coumarin], 3,3' -carbonyl-bis (7-methoxycoumarin), 3,3'-carbonyl-bis (7-diethylamino-coumarin) , 3-isobutiroilcumarina, 3-benzoyl-5, 7-dimethoxy-coumarin, 3-benzoyl-5, 7-diethoxy-coumarin, 3-benzoyl-5, 7-dibutoxy-coumarin, 3-benzoyl-5, 7-di (methoxyethoxy) coumarin, 3-benzoyl-5, 7-di (allyloxy) coumarin, 3-benzoyl-7-dimetilaminocumarina, 3 -benzoyl-7-diethylaminocoumarin, 3-dimetilaminocumarina -isobutiroi1-7, 5, 7-diemetoxi -3- (1-naphthoyl) coumarin, 5, 7-dimethyloxy-3- (1-naphthoyl) coumarin, 3-benzoylbenzo [f] coumarin, 7-diethylamino-3-tienoilcumarina, 3- (4-cyanobenzoyl ) -5,7-dimethoxycoumarin; 4. 3- (aroylmethylene) -thiazolines 3-methyl-2-benzoilmetilene-beta-naphthothiazoline, 3-methyl-2-benzoilmetilene-benzothiazolium, 3-ethyl-2-ß • propionilmetilen-naphthothiazoline; . Other carbonyl compounds Acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10 -anthraquinone, 9-flurorenone, dibenzosuberone, xanthone, 2,5-bis (4-diethylaminobenzylidene) cyclopentanone, - (para-dimethylaminobenzylidene) ketone such as 2- (4-dimethylamino-benzylidene) -indan-1-one or 3- (4-dimethylamino-phenyl) -l-indan-5-yl-propenyone, 3-phenylthiophthalimide, N methyl-3, 5-di (ethylthio) -phthalimide, N-methyl-3,5-di (ethylthio) -phthalimide.

Apart from these important additives for lacquer hardening, the radiation curable composition may contain other additives, in particular, light-protecting agents. The lacquers can be pigmented, selecting the photoinitiators in an appropriate way. Both color pigments and white pigments can be used. The lacquers can be applied with a layer thickness of about 1 μm to about 100 μm, preferably of approx. 1 μm to 40 μm. Within the range of lower layer thicknesses < 5 μm, the pigmented lacquers are also named multicolored ink. Light-absorbing ultraviolet light absorbers, such as those of the hydroxyphenyl-benztriazole, hydroxyphenyl-benzophenone, oxalic acid amide or hydroxyphenyl-z-triazine type, may be added as a light-protective agent. These compounds can be used individually or as mixtures with or without the use of sterically hindered amines (HALS).

Examples for these absorbers of ultraviolet rays and light-protecting agents are: 1. 2- (2'-Hydroxyphenyl) -benzotriazoles such as, for example, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-butyl-2' - hydroxyphenyl) -benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) -benzo-triazole, 2- (2'-hydroxy-5 '- (1,1,3, 3-tetramethylbutyl) phenyl) - benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) - 5-chloro-benzotriazole, 2- (3 '-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) -benzotriazole, 2- ( 3 ', 5' -i-ter-amyl-2 '-hydroxyphenyl) -benzotriazole, 2- (3', 5'-bis- (a, a-dimethylbenzyl) -2'-hydroxyphenyl) -benzotriazole, mixture of 2 - (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5' - [2- (2- ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro- benzotriazole, 2- (3 '-ter-b util-2 '-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) -benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -benzotriazole, 2- (3 '-ter-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) -benzotriazole , and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenyl-benzotriazole, 2,2'- and ilen-bis [4- (1,1,3, 3- tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; reesterification products of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO (CH2) 3] 2- with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl. 2. 2-Hydroxybenzophenones such as, for example, the derivative of 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4, 2 ', 4' - trihydroxy- and 2'-hydroxy-4,4'-dimethoxy. 3. Esters of benzoic acids, optionally substituted, such as, for example, 4-tert-butyl-phenylsalicylate, phenylsalicylate, octylphenyl salicylate, dibenzoylresorcin, bis- (4-tert-butylbenzoyl) -resorcin, benzoylresorcin, ester 3, 5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-hexadecyl ester, 3,5-di-tert-butyl ester di-tert-butyl-4-hydroxybenzoic acid-octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2-methyl-4,6-di-tert-butylphenyl ester. 4. Acrylates, such as, for example, α-Cyano-β, β-diphenylacrylic acid-ethyl ester, ie, -isooctylester, α-carbo-methoxy cinnamic acid methyl ester, methyl ester, ie, α-cyano-β butylester -methyl-p-methoxy-cinnamic acid, methyl-ester of a-carbomethoxy-p-methoxy-cinnamic acid, N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indoline.

. Sterically hindered amines such as, for example, bis- (2, 2, 6, 6-tetramethyl-piperidyl) -sebacate, bis- (2,2,6,6-tetramethyl-piperidyl) -succinate, bis- (1, 2,2,6,6-pentamethylpiperidyl) -sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonic acid-bis (1, 2, 2,6,6-pentamethyl-piperidyl) - ester, condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product from N, N'-bis- (2, 2, 6, 6-Tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2,6-dichlor-1,3,5-s-triazine, tris- (2, 2, 6, 6-tetramethyl-4-piperidyl) -nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3, 4-butantetratoate, 1,1 '- (1,2-ethanediyl) -bis- (3,3 , 5, 5-tetramethyl-piperazinone), 4-benzoyl-2, 2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis- (1, 2, 2, 6, 6 -pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) -malonate, 3-n-octyl-7, 7,9,9-tetramethyl-l, 3,8-triazaspiro- [4.5] decan-2,4-dione, bis- (1-octyloxy-2,6,6,6-tetramethylpiperidyl) -sebacate, bis- ( l-octyloxy-2,6,6,6-tetramethylpiperidyl) -succinate, condensation product from N, N'-bis- (2, 2, 6,6-tetra-methyl-4-piperidyl) -hexamethylenediamine and 4-morpholino-2,6-dichlor-1,3,5-triazine, condensation product from 2-chlor-4,6-di- (4-n-butylamino-2, 2,6,6-tetramethylpiperidyl) ) -1, 3, 5-triazine and 1,2-bis- (3-aminopropylamino) ethane, condensation product from 2-chlor-4,6-di- (4-n-butylamino-1, 2, 2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) -ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1 , 3, 8-triazaspiro [4.5] decan-2, 4-dione, 3-do-decyl -1- (2, 2, 6, 6-tetramethyl-4-piperidyl) pyrrolidin-2, 5-dione, 3- dodecyl-1- (1,2,2,6,6-penta-methyl-4-piperidyl) -pyrrolidine-2,5-dione. 6. Diamides of oxalic acid such as, for example, 4,4'-di-octyloxy-oxanilide, 2,2 '-diethoxy-oxanilide, 2,2'-di-octyloxy-5, 5'-di-tert-butyl- oxanilide, 2, 2'-di-dodecyloxy-5, 5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N '-bis- (3-dimethylaminopropyl) -oxalamide, -ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixtures with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy-, as well as o- and p-ethoxy-di-substituted oxanilidenes. 7. 2- (2-Hydroxyphenyl) -1,3,5-triazines such as, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2 -hydroxy-4-octyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2, 4- dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxy-phenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2 -hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) ) -1,3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethyl-phenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyl / tridecyl-oxy- (2-hydroxypropyl) oxy-2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

Apart from the above-mentioned light-protecting agents, other stabilizers such as phosphites or phosphonites are also suitable. 8. Phosphites or Phosphonites such as, for example, triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris- (nonylphenyl) -phosphite, trilaurylphosphite, trioctadecylphosphite, distearyl-pentanethritiphosphite, tris- (2, 4-di-tert-butylphenyl) -phosphite, diisodecylpenta-erythritol -diphosphite, bis- (2,4-di-tert-butylphenyl) -pentaerythrithyphosphite, bis- (2,6-di-tert-butyl-4-methylphenyl) -pentaerythrityl diphosphite, bis-isodecyloxy-pentaerythritiphosphite, bis- (2, 4-di-tert-butyl-6-methylphenyl) -pentaerythritiphosphite, bis- (2,4,6-tri-tert-butylphenyl) -penta-erythritipiphosphite, tristearyl-sorbit-triphosphite, tetrakis- (2, 4-di- tert-butylphenyl) -4,4'-biphen-ilen-diphosphonite, 6-isooctyloxy-2,4,8,8-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocline , 6-fluoro-2, 4,8, 10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3, 2-dioxaphosphocin, bis- (2,4-di-tert-butyl) -6-methylphenyl) -methylphosphite, bis- (2, 4-di-tert-butyl-6-methylphenyl) -ethylphosphite.

In addition, conventional additives such as, for example, antistatics, leveling agents and substances that improve adhesion can be used in the art.

If a metal, semi-metal oxide or metal oxide layer is applied as a fixed adhesive layer, it is preferably the following metals: gold, silver, chromium, molybdenum, aluminum or copper, particularly preferably aluminum and copper . In addition, the following semimetallic and metallic oxides are present: aluminum oxide, chromium oxide, iron oxide, copper oxide and silicon oxide. The metals, semi-metallic or metallic oxides are evaporated under vacuum conditions and extracted on the substrate previously coated with photoinitiator in the presence of ultraviolet light. The cup temperatures for the evaporation process depend on the metal used and are preferably 300 to 2000 ° C ', particularly preferably 800 to 1800 ° C. UV radiation during extraction can be generated, for example, by an anodic light arc. Metallically coated substrates are suitable for diffusion barrier layers, protections against electromagnetic influences or form decorative elements. The process can be carried out within a wide range of pressures, the discharge characteristic moving in proportion to the pressure increase of the pure plasma of low temperature in the direction of the corona discharge and, finally, at an atmospheric pressure of approximately 1000 to 1100 mbar it becomes a pure discharge of the crown.

Preferably, the process is carried out under a process pressure of 10"6 mbar up to atmospheric pressure (1013 mbar), of particular preference, within the range of "4 to 10" 2 mbar as a plasma procedure and under atmospheric pressure as a corona process.

Preferably, the process is carried out in such a way that an inert gas is used as a plasma gas or a mixture of an inert gas with a reactive gas. Of particular preference, He, Ar, Kr, Xe, N2, 02 or H20 are used individually or as a mixture as plasma gases. Preferably, the temperature under which the photoinitiator evaporates under vacuum is between 20 ° C and 250 ° C, particularly preferably between 40 ° C and 150 ° C. Preferably, the extracted photoinitiator layer has the thickness of a monomolecular layer up to 100 nm, particularly preferably from 10 nm to 60 nm. Preferably, the plasma treatment of the organic or inorganic substrate a) is carried out from 1 second to 300 seconds, particularly preferably from 10 seconds to 200 seconds.

The extraction of the photoinitiator in step b) of the process is carried out under vacuum, preferably from 1 second to 10 minutes. If a corona discharge is performed, then, preferably, a solution or a melt of the photoinitiator is directly sprayed directly into the discharge zone. The corona discharge can also be carried out under a protective gas atmosphere. If the substrate was previously treated with a plasma or corona discharge or by radiation with high energy content, then the subsequent processing time depends on the lifetime of the radicals generated on the surface. In principle it is valid that advantageously the photoinitiator is applied as quickly as possible, since initially a high number of reactive radicals is on the surface for the graft reaction. However, for many purposes it may also be acceptable for reaction step b) to be carried out with a time delay. However, preferably, the b) of the processing is performed immediately or within 10 hours after step a) of the procedure. A further object of the present invention is the use of photoinitiators containing one or more ethylenically unsaturated groups for the preparation of coatings with high adhesion capacity on inorganic or organic substrates, characterized in that in a first step a) the effect of a low temperature plasma discharge, a corona discharge, an ultraviolet radiation or an electronic radiation on the inorganic or organic substrate is allowed, then the radiation is suspended, in a later step b) apply under vacuum or under atmospheric pressure one or more photoinitiators containing at least one ethylenically unsaturated group on the inorganic or organic substrate and reacted with the radicals generated therein and cl) the substrate in this way previously coated with photoinitiator is coated with a composition containing at least one ethylenically unsaturated monomer or oligomer and the coating is cured by UV / VIS or c2) radiation is extracted onto the substrate in this way previously coated with photoinitiator a metal, a semimetallic or metallic oxide from the gas phase in the presence of ultraviolet light.

In addition, the coatings with high adhesion capacity obtained according to the procedure described above are subject of the present invention. Coatings of this type are important both as protective layers or coating means, these being additionally pigmented, as well as representative coatings as, for example, in the technology of protective paints. The examples that follow will explain the present invention in more detail.

Example 1 The plasma treatment is carried out in a common parallel plate reactor with 40 kHz. As a substrate, a plastic series element with a thickness of 3 mm of PP / EPDM is used, of which one half is hard and the other half is softly modified. A substrate of this type is subjected under 3"10" 2 mbar for 20 seconds to an argon plasma, another substrate is subjected to an argon / 02 plasma (75/25), while the substrates are arranged on a support in such a way , that only one side is exposed to the plasma, respectively.The plasma is suspended and the pressure is reduced to 2 »10" 4 mbar. In the plasma chamber the photoinitiator of the following structural formula it is evaporated in a pan at a temperature of 50 to 52 ° C in 180 seconds, while a layer thickness of about 30 nm is obtained. The thickness is measured using a conventional oscillating quartz. The substrate previously coated in such a way is immersed in a radiation-curable epoxy acrylate composition with 89% Ebecryl® 604 (UCB), 10% SR® 344 (Sartomer), 1% Ebecryl® 350 (UCB) and 2% of Darocur® 1173 (Ciba Spezialitátenchemie). The submerged samples are cured on both sides successively in a processor of the company AETEK with two mercury lamps of medium pressure of 80W / cm2 with a band speed of 3m / min. Adhesion capacity is determined by a net cut and a strip of adhesive tape. In both tests, an adhesion test, that is, an adhesion test of the lacquer layer, is carried out on the underside which does not have a photoinitiator layer. On the side previously treated with photoinitiator only minimal stitches are cut in the cross cuts; the adhesion on the soft segment and the hard segment is equally good. The test that was submitted to the argon / 02 plasma presents a slightly better adhesion result. After 10 days of exposure under sunlight, the extraordinary adhesion values are still preserved.

Example 2 A Teflon® sheet with a thickness of 1 mm is used as the substrate. The plasma and photoinitiator conditions correspond to example 1. The lacquer composition of example 1 is cored, giving a thickness of 30 μm. In both tests, an adhesion test, that is, an adhesion test of the lacquer layer, is carried out on the underside which does not have a photoinitiator layer. On the side previously treated with photoinitiator, only minimal stitches are cut in the cross cuts; the adhesion is excellent. The test that was submitted to the argon / 02 plasma presents a slightly better adhesion result.

Example 3. Copper coating on PTFE A Teflon® sheet with a thickness of 5 mm is used as the substrate. The plasma and photoinitiator conditions correspond to example 1.

After applying the photoinitiator layer, a layer of Cu is extracted in the same reactor by means of an anodic arc-light method ("VALICO 'procedure) under a pressure of 2" 10"4 mbar.The bowl temperature is 1500 up to 1600 ° C. Within one minute, the layer with a thickness of 1 μm is removed.

The copper layer no longer allows a detachment of the substrate by an adhesion test, using an adhesive tape.

Example 4. Pre-treatment with UV vacuum. In a vacuum chamber, different polymer sheets are exposed to short-wave ultraviolet light, that is, with a wavelength of 172 nm for 2 minutes. For radiation, an excimer lamp (Excivac® from the company Heraeus Nobellight, Kleinostheim) is used and the pressure inside the chamber is 3 »10" 2 mbar, during exposure by eximer radiation, one half of the sheet is It covers on both sides with an aluminum foil, so that no radicals are generated there After finishing the exposure, the pressure is reduced to 8 »10" 4 mbar and the photoinitiator of example 1 is evaporated in a pan at a temperature up to 120 ° C for 2 minutes. The coated substrates are coated with a curved radiation formulation of Example 1 by means of a brush application. These tests are cured in a processor of the company AETEK with two mercury lamps of medium pressure of 80W / cm2 at a band speed of 10 m / min. The adhesion capacity is determined by a reticular cut. In the case of a polypropylene sheet as a substrate, a slightly higher adhesion of the lacquer film is obtained on the exposed and vaporized area, while on the non exposed side and where the steam was not applied, no adhesion is obtained. Neither is adhesion achieved on leaves that were only exposed. In the case of polyester sheet (Mylar® DuPont, 100 μm) as a substrate, a very good adhesion of the lacquer film on the exposed and vaporized area is obtained (the layer no longer allows a peeling), while in the area Without treatment, the lacquer is easily removed. Only slightly better adhesion is obtained on exposed films.

Claims (21)

R E I V I N D I C A C I O N S

1. A process for the preparation of adhesive coatings on an inorganic or organic substrate, characterized in that in a first step a) on the inorganic or organic substrate a low temperature plasma discharge, a corona discharge or ultraviolet radiation with high energy content is applied or electronic radiation, then the radiation or discharge is removed, in a further step b) one or more photoinitiators containing at least one ethylenically unsaturated group are applied to the organic or inorganic substrate under vacuum or under normal pressure and reacted with the radical points therein generated, and cl) the substrate previously coated with photoinitiator is coated with a composition containing at least one ethylenically unsaturated monomer or oligomer and the coating cured by UV / VIS or c2) is extracted on the coated substrate in this way with photoinitiator a metal, semimetallic oxide om etálico from the gas phase in the presence of ultraviolet light.

2. A method according to claim 1, characterized in that the inorganic or organic substrate is in the form of a powder, a fiber, a sheet or as a three-dimensional workpiece.

3. A method, according to claim 1, characterized in that the inorganic or organic substrate is a thermoplastic polymer, elastomer, crosslinked or crosslinked structure, a metal oxide, a glass or a metal.

4. A method, according to claim 1, characterized in that the photoinitiator is a compound of formula I or (RG) -A- (IN) (I), (IN) -A- (RG ') -A - (IN) (la), where (IN) is a basic photoinitiator structure, A is a spacer group or a single link, (RG) means at least one ethylenically unsaturated functional group, and (RG ') represents a bivalent residue containing at least one ethylenically unsaturated functional group.

5. A process, according to claim 4, wherein in the compounds of the formula I or the (IN) means a basic structure of formula (II) or (III) fr - P- R, (III) I 3 R_ Ri is a group (A), (B) or (III) Ro represents hydrogen, alkyl of 1 to 12 carbon atoms, halogen, the group (RG) -A- or, if Rj represents a group (A), two radicals R2 in ortho position with respect to the carbonyl group, together can also represent -S- or O _ll_ wherein R3 and R4 are, independently of each other, alkyl of 1 to 6 carbon atoms, alkanoyl of 1 to 6 carbon atoms, phenyl and benzoyl, wherein the phenyl or benzoyl radicals are substituted, respectively, by halogen, alkyl of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms; Rc means hydrogen, halogen, alkyl of 1 to 12 carbon atoms or alkoxy of 1 to 12 carbon atoms or group (RG) -A-, R7 and R8 are, respectively and independently of one another, H, alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, phenyl, benzyl or together alkylene of 2 to 6 carbon atoms; R9 is hydrogen, alkyl of 1 to 6 carbon atoms or alkanoyl of 1 to 6 carbon atoms; R is hydrogen, alkyl of 1 to 12 carbon atoms or phenyl; and Xx is oxygen or sulfur.

6. A process, according to claim 4, wherein in the compounds of the formula I or the (IN) is a group ist

7. A process, according to claim 4, wherein in the compounds of the formula I or the A represents a spacer group -Z- [(Ax) a-Y] c- [(A2) b-X] d; X, Y and Z are, independently of each other and respectively, a single bond, -0-, -S-, -N (R10) -, - (CO) -, - (C0) 0-, - (CO) N (R10) -, -0- (C0) -, -N (R10) - (CO) - or -N (R10) - (CO) O-; Aj and Aj represent, independently of each other, alkylene of 1 to 4 carbon atoms, cycloalkylene of 3 to 12 carbon atoms, phenylene, phenylene alkylene of 1 to 4 carbons or alkylene of 1 to 4 carbon atoms-phenylene. -alkylene of 1 to 4 carbon atoms; a, b, c and d mean, independently of each other, a number from 0 to 4; and R, is defined as previously mentioned.

8. A process, according to claim 7, wherein in the compounds of the formula I or the, A is a spacer group -Z- [(CH2) aY] c- [(CH2) bX] d-, where X, Y, Z, a, b, c and d have the meanings indicated above.

9. A process, according to claim 4, wherein in the compounds of the formula I or the (RG) represents RcRbC = CRa- (RG ') represents Ra, Rb, Rc mean, respectively, H or alkyl of 1 to 5 carbon atoms, in particular, H or CH3.

10. A process according to claim 1, characterized in that at least one of the ethylenically unsaturated monomers or oligomers of the composition is a monofuneional, difunctional, trifunctional or tetrafunctional acrylate or methacrylate.

11. A process according to claim 1, characterized in that the composition containing at least one ethylenically unsaturated monomer or oligomer contains at least one additional photoinitiator or coinitiator for curing by UV / VIS radiation.

12. A method, according to claim 1, characterized in that the process pressure is 10"6 mbar up to atmospheric pressure 13.

A method, according to claim 1, characterized in that an inert gas or an inert gas is used as the plasma gas. a mixture of inert gases with a reactive gas 14.

A process, according to claim 13, characterized in that N2, He, Ar, Kr, Xe, 02 or H20 are used individually or in the form of a mixture.

A method, according to claim 1, characterized in that the temperature, at which the photoinitiator evaporates, is from 20 ° C to 250 ° C.

16. A method, according to claim 1, characterized in that the layer of photoinitiator or the extracted metal layer has the thickness of a monomolecular layer up to a thickness of 100 nm

17. A method, according to claim 1, characterized in that the plasma treatment a) is carried out to within 1 second to within 300 seconds.

18. A method, according to claim 1, characterized in that the extraction of the photoinitiator b) is carried out from 1 second to 10 minutes.

19. A method, according to claim 1, characterized in that step b) of the processing is performed immediately or within 10 hours after step a) of the process.

20. The use of photoinitiators containing one or more ethylenically unsaturated groups for the preparation of coatings capable of adhesion on an organic or inorganic substrate, characterized in that in a first step a) on the inorganic or organic substrate a low temperature plasma discharge, corona discharge or ultraviolet radiation with high energy content or electronic radiation is applied, then radiation or discharge is removed, in a further step b) apply on the organic or inorganic substrate one or more photoinitiators containing at least one ethylenically unsaturated group under vacuum or under normal pressure and react with the radical points generated therein, and cl) coat the substrate previously coated with photoinitiator with a composition containing at least one ethylenically unsaturated monomer or oligomer and the coating is cured by UV / VIS or c2) a metal, semi-metallic or metallic oxide is extracted from the gas phase in the presence of a photoinitiator coated on the substrate in this way with the initiator. ultraviolet light .

21. Coatings with adhesion capacity that are obtained according to the procedure, according to claim 1. Summary The present invention relates to a process for the preparation of adhesive coatings on an inorganic or organic substrate, characterized in that in a first step a) on the inorganic or organic substrate is applied a low temperature plasma discharge, a corona discharge or ultraviolet radiation with high energy content or electronic radiation, then the radiation or discharge is removed, in a further step b) one or more photoinitiators containing at least one ethylenically unsaturated group under vacuum or are applied to the organic or inorganic substrate. under normal pressure and reacted with the radical points generated there, and cl) the substrate previously coated with photoinitiator is coated with a composition containing at least one ethylenically unsaturated monomer or oligomer and the coating cured by UV / VIS or c2) is extracted on the substrate coated in this way with photoinitiator. metal, semimetallic or metallic oxide from the gas phase in the presence of ultraviolet light. Other objects of the present invention are the use of photoinitiators with at least one ethylenically unsaturated group for the preparation of these layers as well as the adhesive coatings themselves.