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    • 专利摘要:
    (A) applying an inorganic or organic substrate to a low temperature plasma discharge, a corona discharge, a high energy ultraviolet radiation or an electron beam emission, and then blocking radiation or discharge, At least one photoinitiator containing at least one ethylenically unsaturated group is applied to an inorganic or organic substrate under reduced pressure or standard pressure and then reacted with the radical moiety resulting therefrom, (C1) a step of coating a composition containing at least one ethylenically unsaturated monomer or oligomer onto the precoated substrate with the photoinitiator and then curing the coating with UV / VIS radiation, or (C2) depositing a metal, metalloid or metal oxide from a gaseous phase onto a precoated substrate with a photoinitiator in the presence of UV light, characterized in that the process comprises the steps of . The invention also relates to the use of photoinitiators having one or more ethylenically unsaturated groups for making such layers and to such an adhesive film.
    公开号:KR20010080920A
    申请号:KR1020017005352
    申请日:1999-10-20
    公开日:2001-08-25
    发明作者:바우어미카엘；쾰러만프레트；쿤츠마르틴；미제프류보미르
    申请人:에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러；시바 스페셜티 케미칼스 홀딩 인크.；
    IPC主号:
    专利说明:

    TECHNICAL FIELD The present invention relates to a method for producing an adhesive surface coating,
    [1] The present invention relates to a method for forming a layer that is preferably deposited on an inorganic or organic material. A further object of the present invention is the use of the photoinitiator having at least one ethylenically unsaturated group in the manufacture of said layer and the strongly deposited layer itself.
    [2] The deposition power of inorganic or organic materials such as polyethylene, polypropylene or fluorine-containing polyolefins known as Teflon R films, especially lacquers (coatings), coating layers or metal layers on non-polar materials is often insufficient, Additional coating measures must be applied in order to obtain. One method is to apply a special primer, a so-called primer, and then form the desired layer thereon.
    [3] Another method is to coat the material to be coated after the plasma treatment or the corona treatment, and again between the two steps, for example, a graft process with an acrylic monomer can be interposed (J. Polym. Sci., Part A: Polym. Chem. 31, 1307-1314 (1993)).
    [4] The generation of cold plasma and the deposition of plasma-applied organic or inorganic thin layers have long been known and are described, for example, by AT Bell (JR Holahan, New York, Quot; Fundamentals of Plasma Chemistry " in " Technology and Application of Plasma Chemistry ") or H. Suhr (Plasma Chem. Plasma Process 3 (1), 1, (1983).
    [5] It is also known, for example, that after the plastic surface is exposed to plasma processing, the next coating has better deposition potential for the plastic substrate. HJ Jacobasch et al. Describe this in a reference to low temperature plasma under vacuum (Farbe + Lack 99 (7), 602-607 (1993)) and also by J. Friedrich et al. Refers to plasma under reduced pressure or standard pressure conditions (here, the low temperature plasma discharges the corona) (Surf. Coat. Technol. 59, 371-6 (1993).
    [6] A photoinitiator having at least one ethylenically unsaturated group is then grounded (grafted) onto the substrate to be coated, and the photo-curable type of locker layer is placed on the grounded substrate thus grounded to obtain a particularly well-deposited layer . The resulting layer is surprisingly good in depositing power, which does not show any deterioration after storage for several days or even after daylighting.
    [7] The process can be carried out simply and has a high throughput per unit time since a long drying process or slow network formation reaction is not necessary. The method is particularly suitable for materials which are composed of various synthetic resins and / or metals or glasses and thus will have different deposition forces for various members without pretreatment and which also exhibit different affinities for substrate means in conventional primer treatments It is very suitable.
    [8] The object of the present invention,
    [9] (A) applying an inorganic or organic substrate to a low temperature plasma discharge, a corona discharge, a high energy ultraviolet radiation or an electron beam emission and then blocking radiation or discharge,
    [10] Add to
    [11] (B) applying at least one photoinitiator containing at least one ethylenically unsaturated group onto an inorganic or organic substrate under vacuum or standard pressure and then reacting with the resulting radical moiety, and
    [12] (C1) or (c2) of coating the thus coated substrate with a photoinitiator using a composition comprising at least one ethylenically unsaturated monomer or oligomer, followed by curing the coating with UV / VIS radiation, or
    [13] (C2) depositing a metal, metalloid or metal oxide from a gaseous phase onto a precoated substrate with a photoinitiator in the presence of UV light to form an adhesive surface tack on the inorganic or organic substrate .
    [14] A variety of methods for obtaining a plasma under vacuum are described in the literature. At that time, electrical energy can be applied in an inductive or capacitive manner. It may be a direct current or an alternating current, the frequency of which may vary in the range of several kHz to MHZ. Microwave (GHz) range.
    [15] The principles of plasma generation and maintenance are described, for example, in the overview articles of Bell &
    [16] As the primary plasma gas, for example, He, argon, xenon, N 2 , O 2 , steam or air may be used.
    [17] The method according to the invention is not itself sensitive to the absorption of electrical energy to itself as well.
    [18] The process can be operated batchwise, for example, in a rotary drum, or in the case of foil, fiber or fabric, continuously. These methods are well known and are described in the state of the art.
    [19] The method may also be carried out under corona discharge conditions. Corona discharge occurs under standard pressure, and air is the most commonly used ionized gas. In principle, however, other gases may be used, in which case the work must be done in a closed system in order to keep the atmospheric air isolated. Another method is to use air as an ionized gas in a corona discharge and thus work in an outwardly open device, for example, continuously passing the foil between discharge electrodes. Such process batches are known and described, for example, in J. Adhesion Sci. Technol. Vol 7, No 10, 1105 (1993). When the corona discharge is used in an open device, it is preferably operated under oxygen exclusion, which can be achieved by a sufficient number of inert gas flows.
    [20] The method can be carried out using high energy electromagnetic radiation to treat the substrate in vacuum or under oxygen exclusion. As high-energy electromagnetic radiation, it is contemplated that radicals can be generated at the surface. Examples are short-wave ultraviolet or x-ray. In this regard, we should mention special electron beams already used to cure lacquers and pigments and also to adhere foils. However, it is also possible to use short-wave ultraviolet rays (particularly vacuum ultraviolet rays) such as those generated by ordinary ultraviolet lamps or excimer lamps. However, radiation having a wavelength of 300 nm or less, particularly preferably 260 nm or less, is preferred.
    [21] In addition to conventional lamps for broadly flattening illumination, lasers that operate in the corresponding wavelength range can also be used for point light illumination or to " depict " If a mask or a descriptive laser is used, the photoinitiator may be added only in a certain range, alternatively, so that the network formation (cross-linking) is different and the deposition power is different in subsequent layers.
    [22] The substrate having the grafted photoinitiator may be irradiated in the form of an image by irradiation through a mask or using a laser beam moving on the surface, so that the surface may be newly modified in the irradiated range. Thus, for example, a pattern with different hydrophobic / hydrophilic and / or metallic coatings can be made. Pattern-wise irradiation in the presence of a radiation-curable combination may result in the formation of patterns having, for example, different deposition and / or adhesion and / or other properties determined by color and / or other combinations.
    [23] The inorganic or organic substrate to be treated may be present in any solid form. Preferably, the substrate is present in the form of a powder, fiber, foil or three-dimensional workpiece.
    [24] Preferably, the inorganic or organic substrate is a thermoplastic, elastomeric, reticular, or network-bonded polymer, metal oxide, glass or metal.
    [25] Examples of thermoplastic, elastomeric, reticular, or network-linked polymers are described below.
    [26] 1. Polymers of mono and diolefins, such as polymers of polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene and cycloolefins, Polymers of cyclopentene or norbornene; High density polyethylene (HDPE), high density polyethylene (HDPE-HMW), high density ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE) , Low density polyethylene (LDPE), low density linear polyethylene (LLDPE), (VLDPE) and (ULDPE).
    [27] Polyolefins, i.e. polymers of monoolefins as mentioned, for example, in this paragraph, especially polyethylene and polypropylene, can be prepared by several methods, in particular by the following method:
    [28] a) Radically (usually at high pressure and high temperature)
    [29] b) by a catalyst comprising at least one metal of the group IVb, Vb, VIb or VIII. These metals usually can have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls which can be π-coordinated or σ-coordinated. These metal complexes may be free-form or may be immobilized on a carrier, for example, on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst may itself be active in the polymerization or may be added in an additional step such as a metal alkyl, a metal hydride, a metal alkyl halide, a metal alkyl oxide or a metal alkyloxane, wherein the metal is a Group Ia, IIa and / May be used. The activator can be modified, for example, with further ester-, ether-, amine- or silyl ether groups. These catalysts are commonly referred to as Ziegler (Natta), TNZ (DuPont), Metallocene or Single Site Catalyst (SSC) from Philips, Standard Oil Indiana.
    [30] 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, mixtures of polypropylene with polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of several polyethylene species Example: LDPE / HDPE).
    [31] 3. Copolymers of mono- and diolefins with one another or with other vinyl monomers such as ethylene-propylene copolymers, mixtures of linear low density polyethylene (LLDPE) and low density polyethylene (LDPE), propylene-butene- Copolymers, ethylene-butene copolymers, ethylene-butene-1 copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers , Copolymers of propylene-butadiene-copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their carbon monoxide , Or an ethylene-acrylic acid-copolymer and salts thereof (isomers) and a diene such as ethylene and a diene such as propylene and hexadiene, dicyclopentadiene or ethylidene norbornene; Also suitable are mixtures of the copolymers and mixtures with the polymers mentioned under 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene- Mixtures with other polymers such as LLDPE / ethylene-vinyl acetate-copolymers, LLDPE / ethylene-acrylic acid copolymers and modified or statistically constructed polyalkylene / carbon monoxide-copolymers and polyamides thereof.
    [32] 4. Mixtures of hydrocarbon resins (eg C 5-9 ) and hydrogenated versions thereof (eg tackifying resins) and polyalkylene and starch.
    [33] 5. Polystyrol, poly- (p-methylstyrol), poly- (a-methylstyrol).
    [34] 6. Copolymers of styrol or alpha -methylstyrene with diene or acrylic derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene- Butadiene-alkyl-methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methacrylate; High impact resistant mixtures of a styrol-copolymer and other polymers, such as polyacrylates, diene-polymers or ethylene-propylene-diene-terpolymers; And block copolymers of styrene, for example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
    [35] 7. Graft copolymers of styrene or alpha -methylstyrene, for example, styrene on polybutadiene, polybutadiene-styrene copolymer, styrene on polybutadiene-acrylonitrile copolymer, styrene on polybutadiene and acrylonitrile Methacrylonitrile); Styrol, acrylonitrile and methyl methacrylate on polybutadiene; Styrene rolls on polybutadiene and maleic anhydride; Styrene on polybutadiene, acrylonitrile and maleic anhydride or maleic acid imide; Styrene and maleimide imide on polybutadiene, styrene on polybutadiene and alkyl acrylate or alkyl methacrylate, styrene on ethylene-propylene-diene-terpolymer and acrylonitrile, polyalkyl acrylate or polyalkyl methacrylate phase Styrene and acrylonitrile on acrylate-butadiene-copolymer, and copolymers mentioned in 6) thereof, for example, so-called ABS-, MBS-, ASA- or AES-polymers Mixtures with such copolymers as are present.
    [36] 8. Chlorinated and brominated copolymers from halogen-containing polymers such as, for example, polychloroprene, chlor rubber, isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, Chlorohydrin homopolymers and copolymers, in particular polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; And copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
    [37] 9. Polymers derived from alpha, beta -unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polymethylmethacrylates impact-modified by butyl acrylate, polyacrylamides and polyacrylics Ronitril.
    [38] 10. Monomers mentioned in 9), copolymers with each other or with other unsaturated monomers, such as acyl nitrile-butadiene-copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate- Acrylonitrile-vinyl halide-co-polymer, or acrylonitrile-alkyl methacrylate-butadiene-terpolymer.
    [39] 11. Polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate , Polyallyl melamine; And their copolymers with the olefins mentioned in item 1.
    [40] 12. Copolymers of homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxides, polypropylene oxides or bisglycidyl ethers thereof.
    [41] 13. polyoxymethylene, including polyacetates such as polyoxymethylene, and comonomers such as ethylene oxide; Polyacetates modified with thermoplastic polyurethanes, acrylates or MBS.
    [42] 14. Polyphenylene oxide, polyphenylene sulfide and mixtures thereof with styrene polymers or polyamides.
    [43] 15. Polyurethanes derived from polyethers, polyesters and polybutadienes having hydroxy groups on one side of the terminal position and aliphatic or aromatic polyisocyanates on the other, and their preliminary products.
    [44] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactam, for example polyamides 4, polyamides 6, polyamides 6/6, 6/10, 6/9 , 6/12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylene, diamines and adipic acid; Hexamethylenediamine and iso- and / or terephthalic acid and, optionally, elastomers as modifiers, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene-isophthalamide. Block copolymers, olefin copolymers, ionomers or chemically bonded or grafted elastomers of polyamides and polyolefins as described above; Or a copolymer or elastomer of polyether and, for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Polyamides or copolyamides modified with EPDM or ABS; And condensed polyamides during processing (" RIM-polyamide ").
    [45] 17. Polyurea, polyamide, polyamide-imide, polyetherimide, polyesterimide, polyhydantoin and polybenzimidazole.
    [46] 18. Polyesters derived from dicarboxylic acids and dialcohols and / or hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol cyclohexane terephthalate, Polyhydroxybenzoates, and block-polyether-esters derived from polyethers having hydroxyl end groups; Also a polyester modified with polycarbonate or MBS.
    [47] 19. Polycarbonates and polyester carbonates.
    [48] 20. Polysulfone, polyether sulfone and polyether ketone.
    [49] 21. On the one hand, aldehydes, on the other hand, are derived from phenols, ureas or melamines, for example phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.
    [50] 22. Anhydrous and anhydrous alkyl resins.
    [51] 23. Copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and unsaturated ester resins derived from vinyl compounds as netting agents, for example their halogen containing flame retardant modifications.
    [52] 24. A network-forming acrylic resin derived from substituted acrylic acid esters, for example, epoxy acrylates, urethane-acrylates or polyester-acrylates.
    [53] 25. Alkyd resins, polyester resins and acrylate resins which are formed with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
    [54] 26. A reticulated epoxide resin derived from an aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compound, for example, a conventional resin such as an anhydride or amine in the presence or absence of an accelerator, Glycidyl-ether, bisphenol-F-diglycidyl ether.
    [55] 27. Natural resins such as cellulose, natural rubber, gelatin, and derivatives thereof chemically modified in their polymeric group, such as cellulose acetate, cellulose propionate, cellulose butyrate, and cellulose ethers such as methylcellulose ; And derivatives thereof.
    [56] 28. A mixture of the above polymers (polyblend), for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, 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.
    [57] It should be understood within the scope of the present invention that paper, which is in particular in the form of a cardboard and which may additionally be additionally coated with Teflon R, also comprises a tissue network polymer. Such a description is, for example, commercially available.
    [58] Preferably, thermoplastic, reticulated or textured plastic is understood as polyolefin, polyamide, polyacrylate, polycarbonate, polystyrol, or acrylic / melamine-, alkyd- or polyurethane locker.
    [59] Particularly preferred are polycarbonate, polyethylene, polypropylene, polyamide and polyimide.
    [60] Synthetic resins may be present in the form of foils, injection molded articles, extruded workpieces, fibers, felt or textiles.
    [61] As the inorganic substrate, particularly glass, metal oxide and metal may be considered. The inorganic substrate may preferably be a silicate and metalloid- and metallic glass present as a powder having an average particle size of 10 nm to 2000 μm. The inorganic substrate may be dense or porous particles. Examples of oxides and silicates are SiO 2, TiO 2, ZrO 2 , MgO, NiO, WO 3, Al 2 O 3, La 2 O 3, silica gels, clays and zeolites. Preferred inorganic substrates are, in addition to metals, silica gel, aluminum oxide, titanium oxide, glass, and mixtures thereof.
    [62] To use the process according to the invention, all photoinitiators having at least one ethylenically unsaturated group are in principle suitable.
    [63] As the metal base material, Fe, Al, Ti, Ni, Mo, Cr or a steel alloy may be considered.
    [64] Preferably the photoinitiator is a compound of formula I or formula Ia.
    [65] (RG) -A- (IN)
    [66] (IN) -A- (RG ') - A- (IN)
    [67] In this formula,
    [68] (IN) is a unit structure of a photoinitiator,
    [69] A represents a space group or a simple bond,
    [70] (RG) means one or more functional ethylenically unsaturated groups,
    [71] (RG ') represents a divalent moiety comprising at least one functional ethylenically unsaturated group.
    [72] (IN) (II) or formula (III), < / RTI >
    [73] Wherein R < 1 & (A), -CR 6 R 7 R 8 (B) or a group of the formula (III);
    [74] R 2 represents hydrogen, C 1 -C 12 -alcohol, halogen, group (RG) -A-,
    [75] When R < 1 > represents a group (A), two residues R < 2 > in the ortho position relative to the carbonyl group are taken together with -S- or Lt; / RTI >
    [76] R 3 and R 4 independently of one another are C 1 -C 6 -alkyl, C 1 -C 6 -alkanoyl, phenyl or benzoyl, wherein the residue phenyl or benzoyl is optionally substituted with halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio or C 1 -C 6 -alkoxy,
    [77] R 5 represents hydrogen, halogen, C 1 -C 12 -alkyl or C 1 -C 12 -alkoxy or group (RG) -A-,
    [78] R 6 is OR 9 or N (R 9) 2, or, , , , Or SO 2 R 9 ,
    [79] R 7 and R 8 independently of one another are H, C 1 -C 12 -alkyl, C 1 -C 12 -alkenyl, C 1 -C 12 -alkoxy, phenyl or benzyl, or C 2 -C 6 -alkylene, Forming,
    [80] R 9 is hydrogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkanoyl,
    [81] R 10 is hydrogen, C 1 -C 12 -alkyl or phenyl,
    [82] Compounds of formula (I) or (Ia) in which X 1 represents oxygen or sulfur are preferred.
    [83] Preferably the (IN) in the compounds of formula (I) or (Ia) means the following group:
    [84] , , , , or .
    [85] A represents a spacer group -Z- [(A 1 ) a -Y] c - [(A 2 ) b -X] d ,
    [86] X, Y and Z independently of one another is a simple bond, -O-, -S-, -N (R 10) -, - (CO) -, - (CO) O-, - (CO) N (R 10) -, -O- (CO) -, -N (R 10 ) - (CO) - or -N (R 10 )
    [87] A 1 and A 2 independently of one another are C 1 -C 4 -alkylene, C 3 -C 12 -cycloalkylene, phenylene, phenylene-C 1 -C 4 -alkylene or C 1 -C 4 -alkylene, Alkylene-phenylene-C 1 -C 4 -alkylene,
    [88] a, b, c and d independently of one another represent a number of 0 to 4,
    [89] R 10 is preferably a compound of formula (I) or (la) as defined above.
    [90] Wherein A is a spacer group -Z- [(CH 2 ) a -Y] c - [(CH 2 ) b -X] d and X, Y, Z, Compounds of formula (I) or (Ia) are particularly preferred.
    [91] (RG) represents R c R b C = CR a -, (RG ') represents Represents a, R a, R b, R c are each H or C 1 -C 6 - alkyl is, in particular, represent H or CH 3, are particularly preferred compounds of formula Ⅰ or Ⅰa.
    [92] The preparation of such photoinitiator compounds is well known to the expert and is already described in many publications.
    [93] Thus, for example, compounds containing unsaturated groups can be prepared by reacting 4- [2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methyl-ethane [Irgacure R 2959, Ciba Specialty Chemicals (Ciba Specialty Chemicals) with an acryloyl group or a methacryloyl group-containing isocyanate or other acryloyl group or a compound containing a methacryloyl group 4 922 004).
    [94] The following publications show specific examples of suitable photoinitiator compounds comprising ethylenically unsaturated groups and their preparation:
    [95] Unsaturated aceto derivatives and benzophenone derivatives are described, for example, in US 3 214 492, US 3 429 852, US 3 622 848 and US 4 304 895, ),
    [96] Copolymerizable ethylenically unsaturated acetophenone compounds can be derived, for example, from US 4,922 004 (for example, or ).
    [97] 2-Acrylyl-thioxanthone is described in Eur. Polym. J. 23 , 985 (1987).
    [98] The ≪ / RTI > are described in DE 2 818 763.
    [99] Further unsaturated carbonate group containing photoinitiator compounds can be derived from EP 377 191.
    [100] Uvecryl R 36 from UCB is a benzophenone linked to an acrylic group through an ethylene oxide unit (see Technical Bulletin 2480/885 (1985) or New Polym. Mat. 1 , 63 (1987)]: .
    [101] Chem. Abstr. 128: 283649) Are disclosed.
    [102] Further suitable ethylenically unsaturated photoinitiator bonded compounds can be derived from DE 19501025. For example, there can be mentioned 4-vinyloxycarbonyloxybenzophenone, 4-vinyloxycarbonyloxy-4-chlorobenzophenone, 4-vinyloxycarbonyloxy-4'-methoxybenzophenone, N-vinyloxycarbonyl 4-aminobenzophenone, vinyloxycarbonyloxy-4'-fluorobenzophenone, 2-vinyloxycarbonyloxy-4'-methoxybenzophenone, 2-vinyloxycarbonyloxy- Vinyloxycarbonyloxyacetophenone, 4-vinyloxycarbonyloxyacetophenone, 4-vinyloxycarbonyloxyacetophenone, 4-vinyloxycarbonyloxyacetophenone, 4-vinyloxycarbonyloxybenzyl, 4-vinyl (2-vinyloxycarbonyloxy-2-propyl) -ketone, ((4-methoxycarbonyloxy-2-propyl) -methoxybenzoyloxy) benzyloxycarbonyloxy-4-methoxybenzyl, vinyloxycarbonylbenzoin ether, (2-vinyloxycarbonyloxy-2-propyl) -ketone, phenyl- (1-vinyloxycarbonyloxy) -cyclohexyl ketone, 2- vinyloxycarbonyloxy- Lenone, 2- (N-vinyloxycarbo 2-vinyloxycarbonyloxyoctanoic acid, 2-vinylcarbamoyloxymethylanthraquinone, 2- (N-vinyloxycarbonyl) -aminoanthraquinone, 2- Oxantone or to be.
    [103] US 4 672 079 discloses, in particular, 2-hydroxy-2-methyl (4-vinylpropiophenone), 2-hydroxy- Benzoyl cyclohexanol, p- (1-methylvinyl) benzoyl-cyclohexanol.
    [104] (2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methyl-ethane (Irgacure R 2959, Ciba Specialty Chemicals) described in JP 2-292307, And isocyanates containing an acryloyl or methacryloyl group are also suitable, for example, or (Wherein R is H or CH 3 ).
    [105] Additional examples of suitable photoinitiators include, or to be.
    [106] The following examples are described in W. Baumer et al., Radcure '86, Conference Proceedings, 4-43 to 4-54:
    [107] , , , or .
    [108] G. Wehner et al. Reported in Radtech '90 North America that:
    [109] .
    [110] The meanings of the substituents in the various moieties are described below.
    [111] C 1 -C 12 -alkyl is linear or branched and is, for example, C 1 -C 8 -, C 1 -C 6 - or C 1 -C 4 -alkyl.
    [112] Examples thereof are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, t-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl- , Nonyl, decyl, undecyl or dodecyl, such as in particular methyl or butyl.
    [113] C 1 -C 6 -alkyl and C 1 -C 4 -alkyl are also straight-chain or branched, for example up to the corresponding carbon number only. The C 1 -C 6 -alkyl substituent for benzoyl or phenyl is in particular C 1 -C 4 -alkyl, for example methyl or butyl.
    [114] Halogen is fluorine, chlorine, bromine or iodine, in particular chlorine or bromine, preferably chlorine.
    [115] R < 1 > represents a group (A), together with two residues R < 2 > in the ortho position relative to the carbonyl group, , There arises a structure having, for example, the following thioxanthone bases or anthraquinone units:
    [116] , .
    [117] C 1 -C 6 -alkanoyl is straight-chain or branched, for example C 1 -C 4 -alkanoyl. Examples thereof are formyl, acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl or hexanoyl, preferably acetyl.
    [118] C 1 -C 4 -alkanoyl has the above meaning only up to the corresponding carbon number.
    [119] C 1 -C 12 -alkoxy represents a straight-chain or branched residue and is, for example, C 1 -C 8 -alkoxy, C 1 -C 6 -alkoxy or C 1 -C 4 -alkoxy. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, t-butyloxy, pentyloxy, hexyloxy, heptyloxy, Butyloxy, sec-butyloxy, sec-butyloxy, sec-butyloxy, sec-butyloxy, isohexyloxy, Iso-butyloxy, t-butyloxy, preferably methoxy.
    [120] C 1 -C 8 -alkoxy, C 1 -C 6 -alkoxy and C 1 -C 4 -alkoxy are also straight-chain or branched and, for example, have only the abovementioned meaning up to the corresponding number of carbon atoms.
    [121] C 1 -C 6 -alkylthio is a straight-chain or branched residue and is, for example, C 1 -C 4 -alkylthio. Examples thereof include methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, iso-butylthio, t-butylthio, pentylthio or hexylthio, Isopropylthio, n-butylthio, sec-butylthio, iso-butylthio, t-butylthio, preferably methylthio.
    [122] C 1 -C 4 -alkylthio is also straight-chain or branched and has, for example, only the abovementioned meaning up to the number of carbon atoms in question.
    [123] The phenyl or benzoyl group substituted by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio or C 1 -C 6 -alkoxy can for example be a single to five double, Or triple, in particular double or triple, phenyl ring. Preferred are, for example, 2,4,6-trimethylbenzoyl, 2,6-dichlorobenzoyl, 2,6-dimethylbenzoyl or 2,6-dimethoxybenzoyl.
    [124] C 1 -C 4 -alkylene and C 2 -C 6 -alkylene are linear or branched alkylene, for example C 2 -C 4 -alkylene, for example methylene, ethylene, propylene, isopropylene n-butylene, sec-butylene, iso-butylene, t-butylene, pentylene or hexylene. Preferred are C 1 -C 4 -alkylene, for example ethylene or butylene, , , Or -C (CH 3) 2 -CH 2 -, and a methylene and ethylene.
    [125] Phenylene-C 1 -C 4 -alkylene represents phenylene substituted at one position of the aromatic ring by C 1 -C 4 -alkylene, while C 1 -C 4 -alkylene-phenylene-C 1 -alkylene- -C 4 -alkylene represents phenylene which is substituted with C 1 -C 4 -alkylene at two positions of the phenylene ring. And the alkylene moieties are each linear or branched and have the same meanings as given above, for example up to the corresponding number of carbon atoms. An example of this is , , , .
    [126] However, the alkylene group may be located at another position of the phenylene ring, for example, at the 1,3-position.
    [127] Cycloalkylene is, for example, C 3 -C 12 -, C 3 -C 8 -cycloalkylene, such as cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene, especially Cyclopentylene and cyclohexylene, preferably cyclohexylene. However, C 3 -C 12 -cycloalkylene is (Wherein x and y are independently of each other 0 to 6, and the sum is x + y 6) or (Wherein x and y are each independently 0 to 7, and the sum is x + y 7).
    [128] Phenylene means 1,4-phenylene, 1,2-phenylene or 1,3-phenylene, especially 1,4-phenylene.
    [129] The C 2 -C 12 -alkenyl moiety may be singly or multiply unsaturated and may be straight-chain or branched and is, for example, C 2 -C 8 -alkenyl, C 2 -C 6 -alkenyl or C 2 -C 4 -Alkenyl. Examples are allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, 1-octenyl, decenyl or dodecenyl, to be.
    [130] When R 7 and R 8 together form C 2 -C 6 -alkylene, they together with the carbon atoms to which they are attached represent a C 3 -C 7 -cycloalkyl ring. C 3 -C 7 -cycloalkyl is, for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, in particular cyclopentyl and cyclohexyl, preferably cyclohexyl.
    [131] R c R b C = CR a - is, for example, -CH = CH 2 or -C (CH 3 ) = CH 2 , preferably -CH = CH 2 .
    [132] The photoinitiator is precipitated onto the treated workpiece, where the photoinitiator can be evaporated, for example, in a high temperature apparatus under vacuum, after interruption of the discharge or exposure (process step (a)) to form radicals to react with the radical sites. Evaporation is done with solid or molten or with a suitable solvent, and the vapor pressure of the solvent is preferably set to a vapor pressure similar to the vapor pressure of the photoinitiator.
    [133] In the case of corona discharge under atmospheric conditions, the photoinitiator may be applied by spraying from solution. Preferably, the process is preferably corona discharge followed by a continuous process, for example, through a nozzle behind the discharge zone.
    [134] Following application of the photoinitiator, the workpiece may be stored or immediately subjected to further processing, i. E. Radiation curable lacquers having ethylenically unsaturated bonds may be applied by known techniques. This step can be done by injection, dipping, spraying, rubbing, scratching, rolling or throwing.
    [135] The unsaturated compounds of the radiation curable locker composition may have one or more ethylenically unsaturated double bonds. The compound may be a low molecular weight (monomer) or a high molecular weight (oligomer). Examples of monomers having a double bond include alkyl-acrylates, hydroxyalkyl-acrylates or hydroxyalkyl-methacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate , 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate or ethyl methacrylate. What is also interesting is silicon-acrylate. Further examples are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrol, alkyl-styrene, halo-styrene , N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.
    [136] Examples of monomers having several double bonds are ethylene glycol-, propylene glycol-, neopentyl glycol-, hexamethylene glycol- or bisphenol-A-diacrylate, 4,4'-bis (2- acryloyloxy- Trimethylolpropane triacrylate, pentaerythritol triacrylate or -tetraacrylate, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, tri Tris (hydroxyethyl) isocyanurate-triacrylate or tris- (2-acryloylethyl) isocyanurate.
    [137] Examples of high molecular weight (oligomer) polyunsaturated compounds are acrylated epoxide resins, acrylated or vinyl ether groups, epoxy group containing polyesters, polyurethanes and polyethers. Further examples of unsaturated oligomers are unsaturated polyester resins prepared from maleic acid, phthalic acid, and one or more diols and having a molecular weight of about 500 to 3000. In addition, oligomers of vinyl ether-monomers and vinyl ether-oligomers and maleate-terminated oligomers having a polyester backbone, a polyurethane backbone, a polyether backbone, a polyvinyl ether backbone and an epoxide backbone can also be used. As described in WO 90/01512, particular combinations of oligomers and polymers having vinyl ether groups are very suitable. However, copolymers of monomers of vinyl ether and maleic acid action may also be considered. Such an unsaturated oligomer may also be referred to as a prepolymer.
    [138] Particularly suitable are, for example, esters of ethylenically unsaturated carboxylic acids with polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the chain or side chain groups, such as unsaturated polyesters, polyamides and polyurethanes And copolymers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth) acrylic groups in the side chain, and mixtures of one or more of the foregoing polymers.
    [139] Examples of unsaturated hydrocarbons are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids such as linolenic acid or oleic acid. Preferred are acrylic acid and methacrylic acid.
    [140] As the polyol, aromatic and especially aliphatic and alicyclic polyols are suitable. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) -propane, and novolak and resole. Examples of polyepoxides are based on the above polyols, especially aromatic polyols and epichlorohydrin. Polymers and copolymers containing hydroxyl groups in polymer chains or in side groups, such as polyvinyl alcohols and copolymers thereof or polymethacrylic acid hydroxyalkyl esters or copolymers thereof, It is suitable.
    [141] Examples of the aliphatic and alicyclic polyols are preferably alkylene diols having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, Butanediol or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, preferably polyethylene glycol having a molecular weight of 200 to 1,500, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerin, tris- (beta -hydroxyethyl) amine, trimethylol Ethane, trimethylol propane, pentaerythritol, dipentaerythritol and sorbitol.
    [142] The polyol can be partially or wholly bound to one or more unsaturated carboxylic acids, wherein the free hydroxy group in the ester moiety can be modified, for example, etherified or esterified with other carboxylic acids.
    [143] Examples of esters:
    [144] Trimethylol propane triacrylate, trimethylol ethane triacrylate, trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, terrmethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Acrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol triacrylate, dipentaerythritol triacrylate, dipentaerythritol triacrylate, dipentaerythritol triacrylate, dipentaerythritol triacrylate, dipentaerythritol triacrylate, But are not limited to, polytetrafluoroethylene, polytetrafluoroethylene, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, Erythritol octamethacrylate, pent Dipentaerythritol hexa taconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol diacrylate, dipentaerythritol pentaisocyanate, dipentaerythritol triisostearate, Butanediol dimethacrylate, 1,4-butanediol diacetonate, sorbit triacrylate, sorbit tetraacrylate, pentaerythritol modified triacrylate, sorbit tetramethacrylate, sorbitol pentaacrylate, sor Acrylate, 1,4-cyclohexane diacrylate, bisacrylates of polyethylene glycol having a molecular weight of 200 to 1,500 and bis (meth) acrylates having a molecular weight of 200 to 1,500, Methacrylate, or a mixture thereof. Also suitable as the components are amides of the same or different unsaturated carboxylic acids of aromatic, alicyclic and aliphatic polyamines having preferably 2 to 6, in particular 2 to 4, amino groups. Examples of the polyamines are ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, 1,2-butylene diamine, 1,3- Butylene diamine, di-beta-aminoethyl ether, di-beta-aminoethyl ether, diethylenediamine, diethylenediamine, diethylenediamine, Diethylenetriamine, triethylenetetramine, di ( - aminoethoxy) ethane or di ( - aminopropoxy) ethane. Additional suitable polyamines are oligomers, optionally with polymers and copolymers having additional amino groups in the side chain and with an amonomer group. Examples of such unsaturated amides are methylene-bis-acrylamide, 1,6-hexamethylene-bis-acrylamide, diethylenetriamine-tris-methacrylamide, bis (methacrylamidopropoxy) - methacrylamidoethyl methacrylate, N [( - hydroxyethoxy) ethyl] -acrylamide.
    [145] Suitable unsaturated polyesters and polyamides can be derived, for example, from maleic acid and diols or diamines. The maleic acid may be partially substituted by another dicarboxylic acid. They may be used in combination with ethylenically unsaturated comonomers such as styrene. The polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from long chains of, for example, from 6 to 20 carbon atoms.
    [146] Polybutadiene, polyisoprene, and copolymers thereof are also known. Suitable copolymers are, for example, olefins such as ethylene, propene, butene, hexene, (meth) acrylate, acrylonitrile, styrene or vinyl chloride. This may be, for example, a reaction product in which a novolac-based epoxide resin is reacted with (meth) -acrylic acid, or a homopolymer or copolymer of vinyl alcohol or hydroxyalkyl derivative thereof substituted with (meth) (Meth) acrylate, or a homopolymer or copolymer of (meth) acrylate substituted with hydroxyalkyl (meth) acrylate.
    [147] Particularly preferably, an acrylate compound or a methacrylate compound is used as the compound of single or multiple ethylenically unsaturated compounds.
    [148] Particularly highly preferred are polyunsaturated acrylate compounds such as those already mentioned above.
    [149] Particularly preferred is a process wherein at least one of the ethylenically unsaturated monomers or oligomers of the radiation curable composition is a mono-, di-, tri- or tetra-functional (1-4 functional) acrylate or methacrylate .
    [150] Preferably the composition comprises at least one additional photoinitiator or co-initiator for curing by UV / VIS radiation in addition to one or more ethylenically unsaturated monomers or oligomers.
    [151] Within the scope of the present invention, UV / VIS radiation will be understood as electron radiation having a wavelength of from 250 to 450 nm. A range of 305 to 450 nm is preferable. Suitable lamps are known to experts and are on the market.
    [152] As the photoinitiator in the radiation-curable lacquer, the compounds of the formula (I) or (Ia) may also be used with all other initiators known from the state of the art.
    [153] Typical examples are described below, which may be used alone or as a mixture of each other. For example, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives such as -Hydroxycycloalkylphenylketone or 2-hydroxy-2-methyl-1-phenylpropanone, dialkoxyacetophenone, (4-methylthiobenzoyl) -1-methyl-1-morpholino-ethane, (4-morpholino-benzoyl) - 1-benzyl- 1 -dimethyl Aminopropane, 4-aroyl-1,3-dioxolane, benzoin alkyl ethers and benzyl ketals such as benzyl dimethyl ketal, phenyl glyoxalate and its derivatives, dimeric phenyl glyoxalate, monoacyl phosphine oxide, (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, a bisacylphosphine oxide such as bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethyl- (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide or bis (2,4,6-trimethylbenzoyl) - (2,4-dipentoxyphenyl ) Phosphine oxide, trisacylphosphine oxide, ferrocenium compounds or titanocenes, such as dicyclopentadienyl-bis (2,6-difluoro-3-pyrrolophenyl) -titanium. An additional class of photoinitiators is oxime esters. The following compounds can be exemplified: 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- -1-one oxime-O-acetate, 1- (4-phenylsulfanyl-phenyl) - l, 2- 1-one oxime-O-acetate or 1- (4-phenylsulfanyl-phenyl) -octane-l, 2-dione 2-oxime-O-benzoate.
    [154] As an auxiliary initiator, for example, a sensitivity modifier that accelerates photopolymerization by moving or broadening the spectral sensitivity can be considered. This is especially true for aromatic carbonyl compounds such as benzophenone, thioxanthone, especially isopropylthioxanthone, anthraquinone derivatives, 3-acylcoumarin derivatives, terphenyl, styrylketone, and 3- Methylene) -thiazoline, camphorquinone, also eosin pigments, rhodamine pigments and erythrosine pigments. When the grafted photoinitiator layer according to the present invention is composed of a benzophenone or a benzophenone derivative, for example, an amine may be considered as a photosensitizer.
    [155] A further example of a photoinitiator is as follows.
    [156] 1. Thioxanthone
    [157] 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbo (2-methoxyethoxycarbonyl) -thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthio 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl- 3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanone, 3,4-di- [2- (2-methoxyethoxy) ethoxycarbonyl] Methyl-6-dimethoxymethyl-thioxanthone, 2-methyl-6- (1,1- Dimethoxybenzyl) -thioxanthone, 2-morpholinomethylmethylthioxanthone, 2-methyl-6-morpholinomethylmethylthioxanthone, N-allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N- (1,1, 3-tetramethylbutyl) -thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxyoctanoate, 6-ethoxycarbonyl- 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N, N-trimethyl-1-propane ammonium chloride;
    [158] 2. Benzophenone
    [159] Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethyl Aminobenzophenone, 4,4'-diethylaminobenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4- (4-methylthiophenyl) Benzoyl benzoate, 4- (2-hydroxyethylthio) -benzophenone, 4- (4-tolylthio) benzophenone, 4-benzoyl-N, N, N N, N, N-trimethyl-1-propanammonium chloride monohydrate, 4- (13-acryloyl-l, 4-benzoylphenoxy) , 7,10,13-pentaooxatridecyl) -benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) oxy] ethyl-benzoimethanemonium chloride;
    [160] 3 . 3-acyl coumarin
    [161] Benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di (propoxy) -cumarin, 3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl- Carbonyl-bis [5,7-di (propoxy) -cumarin], 3,3'-carbonyl- bis (7-methoxy coumarin), 3,3'- Benzoyl-5,7-dimethoxy-coumarin, 3-benzoyl-5,7-diethoxy-coumarin, 3-benzoyl- Benzoyl-5,7-di (methoxyethoxy) -cumarin, 3-benzoyl-5,7-di (allyloxy) -cumarin, 3-benzoyl- Coumarin, 3-benzoyl-7-diethylamino-coumarin, 3-isobutyloyl-7-dimethylamino- coumarin, 5,7-dimethoxy-3- (1-naphthoyl) Dimethoxy-3- (1-naphthoyl) -cumarin, 3-benzoylbenzo [f] coumarin, 7-diethylamino-3-thienoylcoumarin, 3- (4-cyanobenzoyl) Toxicomarin.
    [162] 4 . 3- (aroylmethylene) -thiazoline
    [163] 3-methyl-2-benzoylmethylene- beta -naphthothiazoline, 3-methyl-2-benzoylmethylene- beta -benzothiazoline, 3-ethyl-2-propionylmethylene- beta -naphthothiazoline;
    [164] 5. Other Carbonyl Compounds
    [165] 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2- (4-dimethylamino-benzylidene) -indan-1-one, such as 2,5- bis (4-diethylaminobenzylidene) cyclopentanone, 3- (4-dimethylaminophenyl) -1-indan-5-yl-propenone, 3-phenylthioetherimide and N-methyl-3,5-di (ethylthio) phthalimide;
    [166] In addition to these additives which are important for curing, further additives, in particular light protective agents, may be contained in the radiation curable composition.
    [167] When a suitable photoinitiator is selected, the lacquer can be a pigment type, in which case either a color pigment or a white pigment can be used.
    [168] The lacquer may be applied with a layer thickness of from about 1 to about 100 microns, preferably from about 1 to about 40 microns. In the range where the layer thickness is less than 5 占 퐉, the pigmented lacquer is also referred to as a printing pigment.
    [169] As the photoprotective agent, an ultraviolet absorbent such as hydroxyphenyl-benztriazole-, hydroxyphenyl-benzophenone absorbent, oxalic acid amide absorbent or hydroxyphenyl-s-triazine absorbent may be added. These compounds may be used alone or as a mixture with or without the use of sterically hindered amines (HALS).
    [170] Examples of ultraviolet absorbers and light-blocking agents are as follows.
    [171] 1. Synthesis of 2- (2'-hydroxyphenyl) -benzotriazole
    [172] For example, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5'-di- (5'-t-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) (3'-t-butyl-2'-hydroxy-5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-t-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'- 2-hydroxyphenyl) -benzotriazole, 2- (3 ', 5'-bis (4'- alpha, alpha -dimethylbenzyl) -2 ' -hydroxyphenyl) -benzotriazole; 2- (3'-t-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) -5- chloro-benzotriazole, 2- 2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-t-butyl-2'-hydroxy -5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'- Ethyl) phenyl) -benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'- ) - benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) - (2-isooctyloxycarbonylethyl) phenyl-benzotriazole, a mixture of 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) Hydroxy-5'- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -benzotriazole with polyethylene glycol (2-hydroxyphenyl) Reaction with 300 Water; [R-CH 2 CH 2 -COO (CH 2) 3] 2 - ( wherein, R represents 3'-t- butyl-4'-hydroxy -5'-2H- benzotriazol-2-yl- Phenol).
    [173] 2. 2-Hydroxybenzophenone ,
    [174] For example, 4-hydroxy-derivatives, 4-methoxy derivatives, 4-octoxy derivatives, 4-decyloxy derivatives, 4-dodecyloxy derivatives, 4-benzyloxy derivatives, 4'-trihydroxy derivatives, 2'-hydroxy-4,4'-dimethoxy-derivatives.
    [175] 3. Optionally an ester of substituted benzoic acid
    [176] For example, 4-t-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcin, bis- (4-t- butylbenzoyl) -resorcin, benzoyl resorcin, Butyl-4-hydroxybenzoic acid-2,4-di-t-butylphenyl ester, 3,5-di-t-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5 Di-t-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-t-butyl-4-hydroxybenzoic acid-2-methyl-4,6-di-t-butylphenyl ester.
    [177] 4. Acrylate
    [178] Examples include, but are not limited to, α-cyan-β, β-diphenylacrylic acid-ethyl ester and -isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano- -Butyl ester, -Carbomethoxy-p-methoxy-cinnamic acid methyl ester, N- ( -Carbomethoxy- - cyanovinyl) -2-methyl-indoline.
    [179] 5 . Sterically hindered amine ,
    [180] (2,2,6,6-tetramethyl-piperidyl) succinate, bis- (2,2,6,6-tetramethyl-piperidyl) 2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-t-butyl-4-hydroxybenzyl-malonic acid- , 6-pentamethylpiperidyl) ester, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine with cortic acid, N ', N'- Condensation products of bis- (2,2,6,6-tetramethyl-piperidyl) -hexamethylenediamine with 4-t-octylamino-2,6-dichloro-1,3,5-s- Tris- (2,2,6,6-tetramethyl-4-piperidyl) -nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) , 3,4-butanetetraoate, 1,1 '- (1,2-ethanediyl) -bis- (3,3,5,5-tetramethyl-4-piperazinone), 4-benzoyl- , 2,6,6-tetramethyl-4-piperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis- (1,2,2,6,6-penta Methylpyridine (2-hydroxy-3,5-di-t-butylbenzyl) -malonate, 3-n-octyl-7,7,9,9-tetramethyl- , 3,8-triazaspiro [4.5] decane-2,4-dione, bis- (1-octyloxy-2,2,6,6- tetramethylpiperidyl) succinate, N ', N' Condensation product from bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine , 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2- 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3, Condensation product of 5-triazine and 1,2-bis- (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-tri (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl- Dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrole Di-2, 5-dione.
    [181] 6. Oxalic acid diamide
    [182] For example, 4,4'-dioctyloxy-oxanilide, 2,2'-diethoxy-oxanilide, 2,2'-dioctyloxy-5,5'-di- Di-dodecyloxy-5,5'-di-t-butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-t-butyl-2'-ethyloxanilide and its 2-ethoxy- -Butyl-oxanilide, mixtures of o-methoxy-, p-methoxy-, o-ethoxy and p-ethoxy-disubstituted oxanilides.
    [183] 7. 2- (2-Hydroxyphenyl) -1,3,5-triazine
    [184] For example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy- Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-4-octyloxyphenyl) -Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis- (4-methylphenyl) (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy- 2- (2-hydroxy-4- (2-hydroxy-3-octyl) (2-hydroxyphenyl) oxy] phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyl / tridecyl- Propyl) oxy-2-hydroxy-phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine.
    [185] In addition to the above-described light-blocking agents, further stabilization schemes such as phosphites or phosphonites are suitable.
    [186] 8. Phosphite and phosphonite
    [187] Triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris- (nonylphenyl) -phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) -phosphite, diisodecyl pentaerythritol diphosphite, bis- (2,4- Di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis- (2,4- ) -Pentaerythritol diphosphite, bis- (2,4,6-tri-t-butylphenyl) -pentaerythritol diphosphite, tristearyl-sorbit-triphosphite, tetrakis- (2,4- Di-t-butylphenyl) -4,4'-biphenylene-diphosphonite, 6-isooctyloxy-2,4,8,10-t- butyl- , 3,2-dioxaphosphosine, 6-fluoro-2,4,8,10- Di-t-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphosine, bis- (2,4- , Bis- (2,4-di-t-butyl-6-methylphenyl) -ethylphosphite.
    [188] In addition, conventional additives in the field, such as, for example, antistatic agents, running aids and build-up improvers can be used.
    [189] When the metal, metal oxide or metal oxide layer is coated as the strong build deposit, it preferably relates to the following metals: gold, silver, chromium, molybdenum, aluminum, or copper, particularly preferably aluminum and copper. The following further metalloids and metal oxides are preferred: aluminum oxide, chromium oxide, iron oxide, copper oxide and silicon oxide.
    [190] And metaloid or metal oxide is evaporated under vacuum conditions and the photoinitiator is deposited on the precoated substrate in the presence of ultraviolet light. The crucible temperature for the evaporation process varies depending on the metal used, preferably 300 to 2000 占 폚, particularly preferably 800 to 1800 占 폚.
    [191] The ultraviolet light during deposition can be generated, for example, by a bipolar arc.
    [192] The metal-coated substrate is suitable for the diffusion barrier layer, the electromagnetic shielding part, or it constitutes a decorative element.
    [193] Preferably, process step (a) is performed by a low temperature plasma discharge.
    [194] The process is carried out over a wide pressure range, with the discharge characteristic moving from the pure cold plasma to the corona discharge direction with increasing pressure and eventually discharging the pure corona at a standard pressure of about 1000 to 1100 mb.
    [195] Preferably, the process is performed at a process pressure of 10 -6 to atmospheric pressure (1013 mbar), the plasma process is particularly preferred in the range of 10 -4 to 10 -2 mb, and the corona process is particularly preferred at atmospheric pressure.
    [196] Preferably, the process is performed such that an inert gas or a mixture of an inert gas and a reactive gas is used as the plasma gas.
    [197] Particularly preferably, He, Ar, Kr, Xe, N 2 , O 2 or H 2 O are used alone or as a mixture as a plasma gas.
    [198] Preferably, the temperature at which the photoinitiator is evaporated in vacuum is 20 to 250 ° C, particularly preferably 40 to 150 ° C.
    [199] Preferably the deposited photoinitiator layer has a monomolecular layer thickness of from 100 nm, in particular from 10 to 60 nm.
    [200] Preferably, the plasma treatment of the inorganic or organic substrate in step (a) is from 1 to 300 seconds, particularly preferably from 10 to 200 seconds.
    [201] The deposition of the photoinitiator in process step (b) is preferably carried out in vacuum for 1 to 10 minutes.
    [202] When carrying out corona discharge, preferably the solution or melt of the photoinitiator is sprayed immediately following the discharge zone. Corona discharge can also be performed in a protective gas atmosphere.
    [203] When the substrate is pretreated by plasma discharge, corona discharge or high energy radiation, the further processing time depends on the lifetime of the radicals formed on the surface. In principle, it is advantageous to apply the photoinitiator as soon as possible, since there are initially many reactive radicals on the surface for the graft reaction. However, for many purposes, it may be feasible to delay reaction step (b) in time. However, the reaction step (b) is preferably carried out immediately after the reaction step (a) or within 10 hours.
    [204] A further object of the present invention is to provide a method of manufacturing a semiconductor device comprising the steps of (a) applying an inorganic or organic substrate to a low temperature plasma discharge, corona discharge, high energy ultraviolet radiation or electron beam emission,
    [205] (B) applying at least one photoinitiator containing at least one ethylenically unsaturated group onto an inorganic or organic substrate under vacuum or standard pressure and then reacting with the resulting radical moiety, and
    [206] (C1) of coating a composition comprising at least one ethylenically unsaturated monomer or oligomer onto the precoated substrate with the photoinitiator, and then curing the coating with UV / VIS radiation, or
    [207] (C2) depositing a metal, metalloid or metal oxide from a gas phase onto a precoated substrate with a photoinitiator in the presence of UV light, wherein the further object of the present invention is to provide a process for the preparation of a composition comprising one or more ethylenically unsaturated groups Is used to form an adhesive surface coating on an inorganic or organic substrate.
    [208] The object of the present invention is also an adhesive surface coating obtained by the above method.
    [209] Such an adhesive surface coating is important as a protective layer or sheath means, which layer can additionally be pigmented again and is also important, for example, for coating in resist techniques.
    [210] The following examples illustrate the invention in detail.
    [211] Example 1
    [212] Plasma is treated at 40 kHz in a commercially available parallel plate reactor. As a substrate, a 3 mm thick continuous-plastic component made of PP / EPDM is used, one half of which is rigid and the other half is ductile. This substrate (substrate) was 3 × 10 -2 exposed to argon plasma for 20 seconds at mb, also to expose more of the substrate to an argon / O 2 plasma (75/25), only their base so as to be exposed on only one side of the plasma Are placed in the respective holders. The plasma is deposited and the pressure drops to 2 x 10-4 mb. In the plasma chamber, in the heated plasma, Of the photoinitiator is vaporized at 50 to 52 캜 within 180 seconds, resulting in a layer thickness of about 30 nm. Thickness measurement is performed by a commercially available crystal oscillator.
    [213] Thus 89% of the pretreated substrate Avenue methacrylate (Ebecryl) R 604 (UCB) , 10% SR R 344 [ Sartomer (Sartomer)], 1% Avenue methacrylic R 350 (UCB) and 2% different Cure 1173 (CIBA Specialty Chemicals) in a radiation curable epoxy acrylate composition.
    [214] The immersed specimens were cured on both sides in turn at a belt speed of 3 m / min with two mercury intermediate pressure lamps of 80 W / cm < 2 > in a processor of AETEK.
    [215] Deposition strength is obtained by mesh method and adhesive tape.
    [216] In both specimens, there is complete tearing of the lacquer on the bottom without the photoinitiator layer.
    [217] In the pretreatment with the photoinitiator, only the minimum number of incisions in the cross cuts were relaxed and the consistency in both the flexible and hard sections of the specimens was equally good. The argon / O 2 plasma treated specimen shows slightly better consistency.
    [218] Even after 10 days of sunshine, the excellent deposition power values did not change.
    [219] Example 2
    [220] Teflon R foil with a thickness of 1 mm is used as a substrate. The plasma condition and the photoinitiator correspond to Example 1. The lacquer composition in Example 1 is applied to a thickness of 30 mu m.
    [221] In both specimens, the lacquer tears completely on the underside without the photoinitiator layer.
    [222] In the face pretreated with a photoinitiator, only the minimum number of incisions in the cross-cut section is relaxed and the deposition power is excellent. Specimens treated with argon / O 2 plasma show slightly better deposition.
    [223] Example 3. Copper layer on PTFE
    [224] Teflon R foil with a thickness of 5 mm is used as a base material. The plasma condition and the photoinitiator correspond to Example 1.
    [225] After the photoinitiator layer is formed, the copper layer is deposited by the positive arc method (VALICO method) at a pressure of 2 × 10 -4 mb in the same reactor. The crucible temperature is 1500 to 1600 占 폚. At this time, a layer thickness of 1 mu m is deposited within one minute.
    [226] The copper layer is not loosened from the substrate in the tear test by the adhesive tape.
    [227] Example 4. Pretreatment with vacuum ultraviolet light
    [228] In the vacuum chamber, several polymer foils are irradiated with short wavelength ultraviolet light of 172 nm for 2 minutes. An excimer lamp (Excivac R, Heraeus Nobelite, Kleinostheim, Germany) was used for the investigation, and the chamber pressure was 3 × 10 -2 mb. When irradiated with an excimer wire, half of the specimen foil is covered with aluminum foil on both sides to prevent radicals from forming. After the irradiation is finished, the pressure is lowered to 8 × 10 -4 mb, and the photoinitiator in Example 1 is evaporated at 120 ° C. for 2 minutes in the heating crucible. Initiator coated substrates are applied with the radiation curable combination in Example 1 as a coated sol. These specimens were cured at a belt speed of 10 m / min with two mercury intermediate-pressure lamps of 80 W / cm 2 in a treatment machine of Atech. The deposition intensity is obtained by the mesh thickness. In the case of using a polypropylene foil as a substrate, a slightly elevated deposition force of the lacquer film is achieved in the irradiated and deposited areas, but no deposition power is achieved on the irradiated, non-deposited side. No resilience is achieved in foil that has just been investigated. When using a polyester (Mylar R , DuPont, 100 탆) as the substrate, a very good deposition force of the lacquer film is achieved in the irradiated and deposited areas (the layer is not stripped anymore) The locker can be easily peeled off. The deposition power is only slightly increased even in the case of the film which is only irradiated.
    权利要求:
    Claims (21)
    [1" claim-type="Currently amended] (A) applying an inorganic or organic substrate to a low temperature plasma discharge, a corona discharge, a high energy ultraviolet radiation or an electron beam emission, and then blocking radiation or discharge,
    (B) placing at least one photoinitiator containing at least one ethylenically unsaturated group on an inorganic or organic substrate under reduced pressure or standardized pressure and reacting with one or more radical sites therefrom; and
    (C1) a step of coating a composition comprising at least one ethylenically unsaturated monomer or oligomer onto the precoated substrate with the photoinitiator, followed by curing the coating with UV / VIS radiation, or
    (C2) depositing a metal, metalloid or metal oxide from a gaseous phase onto a precoated substrate with a photoinitiator in the presence of UV light, to form an adhesive surface coating on the inorganic or organic substrate.
    [2" claim-type="Currently amended] The method of claim 1 wherein the inorganic or organic substrate is present in the form of a powder, fiber, foil or as a three-dimensional workpiece.
    [3" claim-type="Currently amended] The method of claim 1 wherein the inorganic or organic substrate is a thermoplastic, elastomeric, textured, networked polymer, metal oxide, glass or metal.
    [4" claim-type="Currently amended] The method of claim 1, wherein the photoinitiator is a compound of Formula I or Formula IA.
    Formula I
    (RG) -A- (IN)
    Ia
    (IN) -A- (RG ') - A- (IN)
    In this formula,
    (IN) is a unit structure of a photoinitiator,
    A represents a space group or a simple bond,
    (RG) means one or more functional ethylenically unsaturated groups,
    (RG ') represents a divalent moiety comprising at least one functional ethylenically unsaturated group.
    [5" claim-type="Currently amended] 5. The compound according to claim 4, wherein in the compound of formula (I) or formula (Ia)
    (IN) (II) or formula (III), < / RTI >
    Wherein R < 1 & (A), -CR 6 R 7 R 8 (B) or a group of the formula (III)
    R 2 represents hydrogen, C 1 -C 12 -alcohol, halogen, group (RG) -A-,
    When R < 1 > represents a group (A), two residues R < 2 > in the ortho position relative to the carbonyl group are taken together with -S- or Lt; / RTI >
    R 3 and R 4 are independently from each other C 1 -C 6 -alkyl, C 1 -C 6 - alkanoyl, phenyl or benzoyl, wherein the phenyl or benzoyl are each halogen, in some cases, C 1 -C 6 - Alkyl, C 1 -C 6 -alkylthio or C 1 -C 6 -alkoxy,
    R 5 represents hydrogen, halogen, C 1 -C 12 -alkyl or C 1 -C 12 -alkoxy or group (RG) -A-,
    R 6 is OR 9 or N (R 9) 2, or , , , Or SO 2 R 9 ,
    R 7 and R 8 independently of one another are H, C 1 -C 12 -alkyl, C 1 -C 12 -alkenyl, C 1 -C 12 -alkoxy, phenyl or benzyl, or C 2 -C 6 -alkylene, Forming,
    R 9 is hydrogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkanoyl,
    Alkyl or phenyl, - R 10 is hydrogen, C 1 -C 12
    Wherein X < 1 > is oxygen or sulfur.
    [6" claim-type="Currently amended] 5. The compound according to claim 4, wherein in the compound of formula (I) or (Ia)
    (IN) , , , , or / RTI >
    [7" claim-type="Currently amended] 5. The compound according to claim 4, wherein in the compound of formula (I) or formula (Ia)
    A represents a spacer group -Z- [(A 1 ) a -Y] c - [(A 2 ) b -X] d ,
    X, Y and Z independently of one another is a simple bond, -O-, -S-, -N (R 10) -, - (CO) -, - (CO) O-, - (CO) N (R 10) -, -O- (CO) -, -N (R 10) - (CO) - or -N (R 10) - (CO ) denotes a O-;
    A 1 and A 2 independently of one another are C 1 -C 4 -alkylene, C 3 -C 12 -cycloalkylene, phenylene, phenylene-C 1 -C 4 -alkylene or C 1 -C 4 -alkylene, Alkylene-phenylene-C 1 -C 4 -alkylene;
    a, b, c and d independently of one another represent a number from 0 to 4;
    Wherein R < 10 > is as defined in claim 5.
    [8" claim-type="Currently amended] A compound according to claim 7, wherein A is a spacer group -Z - [(CH 2 ) a -Y] c - [(CH 2 ) b -X] d - and X, Y, Z , a, b, c and d are as defined in claim 7.
    [9" claim-type="Currently amended] 5. The compound according to claim 4, wherein in the compound of formula (I) or formula (Ia)
    (RG) is R c R b C = CR a - represents,
    (RG ') Lt; / RTI >
    R a , R b and R c are each H or C 1 -C 6 -alkyl, in particular H or CH 3 -.
    [10" claim-type="Currently amended] 3. The composition of claim 1 wherein at least one of the ethylenically unsaturated monomers or oligomers of the composition is a mono-, di-, tri- or tetra-functional (1, 2, 3 or 4 functional) acrylate or monoacrylate Characterized in that.
    [11" claim-type="Currently amended] The method of claim 1, further comprising one or more photoinitiators or co-initiators to cure the composition containing one or more ethylenically unsaturated monomers or oligomers with UV / VIS.
    [12" claim-type="Currently amended] The method of claim 1, wherein the process pressure is between 10 -6 mb and atmospheric pressure.
    [13" claim-type="Currently amended] The method according to claim 1, wherein an inert gas or a mixture of an inert gas and a reactive gas is used as the plasma gas.
    [14" claim-type="Currently amended] The method according to claim 13, wherein N 2 , He, Ar, Kr, Xe, O 2 or H 2 O are used alone or as a mixture.
    [15" claim-type="Currently amended] The process according to claim 1, wherein the photoinitiator has a vaporization temperature of 20 to 250 ° C.
    [16" claim-type="Currently amended] The method of claim 1, wherein the deposited photoinitiator layer or metal layer has a monomolecular layer thickness of about 100 nm.
    [17" claim-type="Currently amended] The method of claim 1, wherein the plasma treatment step (a) is performed within 1 to 300 seconds.
    [18" claim-type="Currently amended] The method of claim 1, wherein the step (b) of depositing the photoinitiator is performed within 1 to 10 minutes.
    [19" claim-type="Currently amended] 2. Process according to claim 1, characterized in that process step (b) is carried out immediately after process step (a) or within 10 hours.
    [20" claim-type="Currently amended] (A) applying an inorganic or organic substrate to a low temperature plasma discharge, a corona discharge, a high energy ultraviolet radiation or an electron beam emission, and then blocking radiation or discharge,
    (B) placing at least one photoinitiator containing at least one ethylenically unsaturated group on an inorganic or organic substrate under reduced pressure or standardized pressure and reacting with one or more radical sites therefrom; and
    (C1) a step of coating a composition comprising at least one ethylenically unsaturated monomer or oligomer onto the precoated substrate with the photoinitiator, followed by curing the coating with UV / VIS radiation, or
    (C2) depositing a metal, metalloid or metal oxide from a gas phase onto a precoated substrate with a photoinitiator in the presence of UV light, wherein the photoinitiator comprises at least one ethylenically unsaturated group, Use of a photoinitiator for forming an adhesive surface coating for use in forming an adhesive surface coating on a substrate.
    [21" claim-type="Currently amended] An adhesive film obtained according to the method of claim 1.
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    同族专利:
    公开号 | 公开日
    KR100602905B1|2006-07-24|
    AU756047B2|2003-01-02|
    JP2002528568A|2002-09-03|
    AU1041000A|2000-05-15|
    DE59908436D1|2004-03-04|
    DK1135219T3|2004-05-10|
    AT258467T|2004-02-15|
    US6548121B1|2003-04-15|
    CA2348378A1|2000-05-04|
    SK5642001A3|2001-09-11|
    WO2000024527A1|2000-05-04|
    CZ20011444A3|2001-09-12|
    BR9914847A|2001-07-10|
    EP1135219B1|2004-01-28|
    ES2213394T3|2004-08-16|
    CN1325327A|2001-12-05|
    EP1135219A1|2001-09-26|
    JP4755758B2|2011-08-24|
    CN1146476C|2004-04-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-10-28|Priority to CH2178/98
    1998-10-28|Priority to CH217898
    1998-12-14|Priority to CH247398
    1998-12-14|Priority to CH2473/98
    1999-10-20|Application filed by 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러, 시바 스페셜티 케미칼스 홀딩 인크.
    2001-08-25|Publication of KR20010080920A
    2006-07-24|Application granted
    2006-07-24|Publication of KR100602905B1
    优先权:
    申请号 | 申请日 | 专利标题
    CH2178/98|1998-10-28|
    CH217898|1998-10-28|
    CH247398|1998-12-14|
    CH2473/98|1998-12-14|
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