EP1468059A2 - Revetements durcissables par radiation a adherence amelioree - Google Patents

Revetements durcissables par radiation a adherence amelioree

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Publication number
EP1468059A2
EP1468059A2 EP03704346A EP03704346A EP1468059A2 EP 1468059 A2 EP1468059 A2 EP 1468059A2 EP 03704346 A EP03704346 A EP 03704346A EP 03704346 A EP03704346 A EP 03704346A EP 1468059 A2 EP1468059 A2 EP 1468059A2
Authority
EP
European Patent Office
Prior art keywords
meth
weight
acid
radiation
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03704346A
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German (de)
English (en)
Inventor
Ralf Fink
Wolfgang Paulus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1468059A2 publication Critical patent/EP1468059A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/40—Compositions for pressure-sensitive adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to radiation-curable coatings, the adhesion of which is improved by mixing in adhesives.
  • Radiation-curable lacquers based on acrylate resins are known and are often used for coatings on substrates such as metals or plastic moldings.
  • the adhesion of the paint to the substrate is adversely affected by the polymerisation loss of the paint layer applied to the substrate during radiation curing.
  • the object of the present invention was to develop radiation-curable coatings with higher adhesion.
  • the object was achieved by mixtures comprising at least one radiation-curable composition (I) and at least one pressure-sensitive adhesive (II).
  • the radiation-curable compositions (I) which can be used according to the invention are known per se and are not restricted. They usually contain at least one radical and / or cationically polymerizable group. Polymerizable groups can be those which have unsaturated bonds, preferably carbon-carbon double bonds.
  • Radically polymerizable groups are, for example, isolated ethylenically unsaturated groups, conjugated unsaturated groups, vinylaromatic groups, vinyl and vinylidene chloride groups, N-vinylamides, vinylpyrrolidones, vinyl lactams, vinyl esters, (meth) acrylic esters or acrylonitriles.
  • Cationically polymerizable groups are, for example, isobutylene units or vinyl ethers.
  • the preferred radiation-curable compositions (I) preferably contain acrylate, methacrylate or vinyl ether functions as polymerizable groups.
  • a radiation-curable composition (I) which can be used according to the invention usually contains
  • compounds (A) there are radiation-curable, free-radically polymerizable compounds with several, i.e. at least two, copolymerizable, ethylenically unsaturated groups.
  • Compounds (A) are preferably vinyl ether or (meth) acrylate compounds, particularly preferred are the acrylate compounds, i.e. the derivatives of acrylic acid.
  • Preferred vinyl ether and (meth) acrylate compounds (A) contain 2 to 20, preferably 2 to 10 and very particularly preferably 2 to 6 copolymerizable, ethylenically unsaturated double bonds.
  • Such compounds (A) are particularly preferred with a content of ethylenically unsaturated double bonds of 0.1-0.7 mol / 100 g, very particularly preferably 0.2-0.6 mol / 100 g.
  • the number-average molecular weight M n of the compounds (A) is preferably below 15000, particularly preferably from 300 to 12000, very particularly preferably from 400 to 5000 and especially at 500 - 3000 g / mol (determined by gel permeation chromatography with polystyrene as standard and tetrahydrofuran as eluent).
  • (Meth) acrylate compounds which may be mentioned are (meth) acrylic esters and in particular acrylic esters and vinyl ethers of highly functional alcohols, in particular those which contain no further functional groups or at most ether groups in addition to the hydroxyl groups.
  • examples of such alcohols are e.g. bifunctional alcohols such as ethylene glycol, propylene glycol and their higher condensed representatives e.g.
  • trifunctional and higher-functional alcohols such as glycerol, trimethylolpropane, butanetriol, tri ethylolethane, pentaerythritol, ditrimethylolol propane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, especially ethoxylated and / or propoxylated alcohols.
  • the alkoxylation products can be obtained in a known manner by reacting the above alcohols with alkylene oxides, in particular ethylene or propylene oxide.
  • alkylene oxides in particular ethylene or propylene oxide.
  • the degree of alkoxylation per hydroxyl group is 0 to 10, i.e. 1 mol of hydroxyl group can be alkoxylated with up to 10 mol of alkylene oxides.
  • polyester (meth) acrylates which are the (meth) acrylic acid esters or vinyl ethers of polyesterols.
  • polyesterols examples are those which can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols.
  • the starting materials for such hydroxyl-containing polyesters are known to the person skilled in the art.
  • Preferred dicarboxylic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid, tetrahydrophthalic acid, terephthalic acid, their isomers and hydrogenation products, and esterifiable derivatives, such as anhydrides or dialkyl esters of the acids mentioned.
  • Suitable polyols are the abovementioned alcohols, preferably ethylene glycol, 1,2-and 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol and polyglycols of the ethylene glycol and propylene glycol types .
  • suitable radiation-curable compounds (A) are also unsaturated polyester resins which essentially consist of polyols, in particular diols, and polycarboxylic acids, in particular dicarboxylic acids, one of the esterification components containing a copolymerizable, ethylenically unsaturated group.
  • it is maleic acid, fumaric acid or maleic anhydride.
  • Polyester (meth) acrylates can be used in several stages or in one stage, e.g. described in EP-A 279 303, can be prepared from (meth) acrylic acid, polycarboxylic acid and polyol.
  • compounds (A) can e.g. are urethane or epoxy (meth) acrylates or vinyl ethers.
  • Urethane (meth) acrylates are e.g. obtainable by reacting polyisocyanates with hydroxyalkyl (meth) acrylates or vinyl ethers and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols.
  • Urethane (meth) acrylates which are dispersible in water without the addition of emulsifiers additionally contain ionic and / or nonionic hydrophilic groups, which e.g. can be introduced into the urethane by structural components such as hydroxycarboxylic acids.
  • polyurethanes which can be used according to the invention as (A) essentially contain:
  • Component a) includes, for example, aliphatic, aromatic and cycloaliphatic di- and polyisocyanates with an NCO functionality of at least 1.8, preferably 1.8 to 5 and particularly ders preferably 2 to 4 in question, and their isocyanurates, biurets, allophanates and uretdiones.
  • the diisocyanates are preferably isocyanates with 5 4 to 20 carbon atoms.
  • Examples of common diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate,
  • cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, l-isocyanato-3 , 3,5-terimethyl-5- (isocyanato-methyl) cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis (iso-
  • Mixtures of the diisocyanates mentioned can also be present.
  • Hexamethylene diisocyanate, 1,3-bis (isocyanato-methyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclo-30 hexyl) methane are preferred.
  • Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing urethane or allophanate groups.
  • cyanates polyisocyanates containing oxadiazinetrione groups, uretaminimine-modified polyisocyanates of linear or branched C 4 -C 2 o -alkylene diisocyanates, cycloaliphatic diisocyanates with a total of 6 to 20 C atoms or aromatic diisocyanates with a total of 8 to 20 C atoms or mixtures thereof into consideration.
  • aliphatic or cycloaliphatic di- and polyisocyanates for example the above-mentioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.
  • Isocyanurate group-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates are particularly preferred.
  • the isocyanurates present here are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologues which have more than one isocyanurate ring.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO functionality of 3 to 4.5.
  • Uretdione diisocyanates with aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups preferably aliphatic and / or cycloaliphatic bound and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the uretdione diisocyanates can be used in the preparations according to the invention as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).
  • These polyisocyanates containing biuret groups generally have an NCO content of 18 to 22% by weight and an average NCO functionality of 3 to 4.5.
  • These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 3.
  • Polyisocyanates containing oxadiazinetrione groups preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Such polyisocyanates containing oxadiazinetrione groups can be prepared from diisocyanate and carbon dioxide.
  • the polyisocyanates 1) to 6) can be used in a mixture, if appropriate also in a mixture with diisocyanates.
  • Component b) is a compound which carries at least one group which is reactive toward isocyanate and at least one group which can be polymerized by free radicals or cationically.
  • Groups which are reactive toward isocyanate can be, for example, -OH, -SH, -NH 2 and -NHR 4 , where R 4 is hydrogen or an alkyl group containing 1 to 4 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, seJ-butyl or tert-butyl means.
  • Polymerizable groups can be those which have unsaturated bonds, preferably carbon-carbon double bonds.
  • Radically polymerizable groups are, for example, isolated ethylenically unsaturated groups, conjugated unsaturated groups, vinylaromatic groups, vinyl and vinylidene chloride groups, N-vinylamides, vinylpyrrolidones, vinyl lactams, vinyl esters, (meth) acrylic esters or acrylonitriles.
  • Cationically polymerizable groups are, for example, isobutylene units or vinyl ethers.
  • Components b) can, for example, monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (hereinafter referred to briefly as "(meth) acrylic acid”), crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylic acid idolglycolic acid or vinyl ether with di - Or be polyols, preferably 2 to 20 carbon atoms and at least two hydroxyl groups have, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1, 3-propylene glycol, 1, 1-dimethyl-1,2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1, 4-butanediol , 1, 5-pentanediol, neopentyl glycol, hydroxypivalic acid
  • esters or A ide of (meth) acrylic acid with amino alcohols such.
  • B. 2-aminoethanol, 2- (methylamino) ethanol, 3-amino-l-propanol, l-amino-2-propanol or 2- (2-aminoethoxy) ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine , or vinyl acetic acid can be used.
  • Unsaturated polyether or polyesterols or polyacrylate polyols with an average OH functionality of 2 to 10 are also suitable.
  • amides of ethylenically unsaturated carboxylic acids with amino alcohols are hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide, N Hydroxyalkylcrotonamides such as N-hydroxymethylcrotonamide or N-hydroxyalkylmaleinimides such as N-hydroxyethylmaleinimide.
  • hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide
  • N Hydroxyalkylcrotonamides such as N-hydroxymethylcrotonamide
  • N-hydroxyalkylmaleinimides such
  • 2-Hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropy1 (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate are preferably used, 1, 6-hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate as well as 4-hydroxybutyl vinyl ether, 2- Aminoethyl (meth) acrylate, 2-amino-propyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-amino-butyl (meth) acrylate, 6-aminohexyl
  • RG denotes at least one group that is reactive toward isocyanate
  • R 2 is an aliphatic, cycloaliphatic or aromatic radical containing 1 to 20 carbon atoms.
  • RG examples include -OH, -SH, -NH 2 or -NHR 4 , in which R 4 has the meaning given above, but may differ from the radical used there.
  • Examples of DG are -COOH, -SO 3 H or -PO 3 H and their anionic forms, which can be associated with any counterion, for example Li + , Na + , K + , Cs + , Mg 2+ , Ca + , Ba 2+ , ammonium, methylammonium, diethylammonium, trimethylammonium, ethylammonium, diethylammonium, triethylammonium, tributylammonium, di-iso-propyl-ethyl-ammonium, benzyldiethylammonium, monoethanolammonium, diethanolammonium, hydroxymethylammonium, triethanolammonium, Hydroxyethyl-diethylammonium, monopropanolammonium, dipropanolammonium, tripropanolammonium, piperidinium, piperazinium, N, N'-dimethylpiperazinium, morpholinium
  • R 2 can, for example, methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, 1,3-butylene, 1,6-hexylene, 1, 8-octylene, 1,12-dodecylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthylene, 1,3-naphylene, 1,4-naphylene, 1,6- Naphthy1en, 1, 2-cyclopentylene, 1, 3-cyclopentylene, 1, 2-cyclohexylene, 1, 3-cyclohexylene or 1, 4-cyclohexylene.
  • Component c) is preferably, for example, mercaptoacetic acid, mercaptopropionic acid, thiolic acid, mercaptosuccinic acid, glycine, iminodiacetic acid, sarcosine, alanine, ⁇ -alanine, leucine, isoleucine, aminobutyric acid, hydroxyacetic acid, hydroxypivalic acid, lactic acid, lactic acid, lactic acid, lactic acid, lactic acid, lactic acid, Hydroxy decanoic acid, dimethylol propionic acid, dimethylol butyric acid, ethylenediamine triacetic acid, hydroxydodecanoic acid, hydroxyhexadecane Acid, 12-hydroxystearic acid, aminonaphthalenecarboxylic acid, hydroxypropanesulfonic acid, hydroxypropanesulfonic acid, mercaptoethanesulfonic acid, mercaptopropanesulfonic acid, aminomethanes
  • the abovementioned acids if they are not already salts, are partially or completely neutralized, preferably with alkali salts or amines, preferably tertiary amines.
  • Component d) may be a compound which carries at least two groups which are reactive toward isocyanate, for example -OH, -SH, -NH 2 or -NHR 5 , in which R 5 is hydrogen or an alkyl group containing 1 to 4 carbon atoms, such as methyl, Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, seJc-butyl or tert-butyl means.
  • diols or polyols such as hydrocarbon diols having 2 to 20 carbon atoms, e.g. Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,1-dimethylethane-1,2-diol, 1,6-hexanedio1, 1,10-decanedio1, bis (4-hydroxycyc1ohexane) isopropylidene, tetramethylcyclobutanediol , 1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol, decalinediol, etc., their esters with short-chain dicarboxylic acids, such as adipic acid, cyclohexanedicarboxylic acid, and their carbonates, prepared by reaction of the diols with pho
  • Diethylene glycol triethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, pentaerythritol, 1,2- and 1,4-butanediol, 1,5-pentanediol are also conceivable.
  • unsaturated polyether or polyesterols or polyacrylate polyols with an average OH functionality of 2 to 10 are also suitable, as are polyamines, such as, for example, polyethyleneimine or polymers containing free amine groups, for example poly-N-vinylformamide.
  • cycloaliphatic diols such as e.g. Bis (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutane diol, 1,2-, 1,3- or 1,4-cyclohexane diol, cyclooctane diol or norbornane diol.
  • Compounds with at least one isocyanate-reactive group are suitable as component e). These can be, for example, 1 to 20 carbon atoms-containing monoalcohols, mercaptans or monoamines, e.g. Methanol, ethanol, iso-propanol, n-propanol, n-butanol, iso-butanol, se ⁇ r-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 1, 3-propanediol monomethyl ether, 1, 2-propanediol monoethyl ether, 1,2-propanediol monomethyl ether, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol, 2-ethy
  • the polyurethanes which can be used according to the invention as (A) are obtained by reacting components a) and b) with one another.
  • the molar composition a): b) per 3 mol reactive isocyanate groups in a) is generally as follows: b) 0.1-3.0, preferably 0.5-2.8, particularly preferably 1.0-2.5 and in particular 1.5-2.5 mol isocyanate-reactive groups,
  • the polyurethane (A) can still contain free isocyanate groups, but more than 70% of the isocyanate groups present in a) before 20 of the reaction are preferably reacted, particularly preferably more than 80%, very particularly preferably more than 90% and in particular more than 95%.
  • the formation of the adduct from the compound containing isocyanate groups and the compound which contains groups reactive toward isocyanate groups is generally carried out by mixing the components in any order, if appropriate at elevated temperature.
  • the compound which contains groups reactive toward isocyanate groups is preferably added to the compound containing isocyanate groups, preferably in several steps.
  • the compound containing isocyanate groups is particularly preferably introduced and the compounds which contain groups reactive toward isocyanate are added.
  • the isocyanate-containing compound a) is initially introduced and then b) is added. If desired, further desired components can subsequently be added.
  • the reaction is carried out at temperatures between 5 and 100 ° C., preferably between 20 to 90 ° C. and particularly preferably between 40 and 80 ° C. and in particular between 60 and 80 ° C.
  • Anhydrous means that the water content in the reaction system is not more than 5% by weight, preferably not more than 3% by weight and particularly preferably not more than 1% by weight.
  • the reaction is carried out in the presence of at least one suitable inert gas, e.g. Nitrogen, argon, helium, carbon dioxide or the like.
  • suitable inert gas e.g. Nitrogen, argon, helium, carbon dioxide or the like.
  • the reaction can also be carried out in the presence of an inert solvent, e.g. Acetone, so-butyl methyl ketone, toluene, xylene, butyl acetate or ethoxyethyl acetate.
  • an inert solvent e.g. Acetone, so-butyl methyl ketone, toluene, xylene, butyl acetate or ethoxyethyl acetate.
  • the reaction is preferably carried out in the absence of a solvent.
  • the urethane (meth) acrylates preferably have a number-average molecular weight M n of 500 to 20,000, in particular from 750 to 10,000, particularly preferably 750 to 3000 g / mol (determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standard).
  • the urethane (meth) acrylates preferably have a content of 1 to 5> particularly preferably 2 to 4 mol (meth) acrylic groups per 1000 g urethane (meth) acrylate.
  • the urethane vinyl ethers preferably have a content of 1 to 5, particularly preferably 2 to 4, mol of vinyl ether groups per 1000 g of urethane vinyl ether.
  • Epoxy (meth) acrylates can be obtained by reacting epoxides with (meth) acrylic acid.
  • Vinyl ether epoxides are obtainable by reacting epoxides with hydroxyalkyl vinyl ethers.
  • suitable epoxides are epoxidized olefins or glycidyl ethers, e.g. Bisphenol A diglycidyl ether or aliphatic glycidyl ether such as butanediol diglycidyl ether.
  • the epoxy (meth) acrylates and vinyl ethers preferably have a number average molecular weight M n of 500 to 20,000, particularly preferably from 750 to 10,000 g / mol and very particularly preferably from 750 to 3000 g / mol; the content of (meth) acrylic or vinyl ether groups is preferably 1 to 5, particularly preferably 2 to 4 per 1000 g of epoxy (meth) acrylate or vinyl ether epoxide (determined by Gel permeation chromatography with polystyrene as standard and tetrahydrofuran as eluent).
  • Suitable radiation-curable compounds (A) are carbonate (meth) acrylates which on average preferably contain 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) acrylic groups and very particularly preferably 2 (meth) acrylic groups.
  • the number average molecular weight M n of the carbonate (meth) acrylates is preferably less than 3000 g / mol, particularly preferably less than 1500 g / mol, particularly preferably less than 800 g / mol (determined by gel permeation chromatography with polystyrene as standard, solvent tetrahydrofuran).
  • the carbonate (meth) acrylates can be obtained in a simple manner by transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, for example hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or transesterification with (meth) acrylic acid esters, such as it eg is described in EP-A 92 269. They are also available by converting phosgene, urea derivatives with polyvalent, e.g. dihydric alcohols.
  • vinyl ether carbonates can also be obtained by reacting a hydroxyalkyl vinyl ether with carbonic acid esters and optionally dihydric alcohols.
  • (meth) acrylates or vinyl ethers of polycarbonate polyols such as the reaction product of one of the di- or polyols mentioned and a carbonic acid ester and a (meth) acrylate or vinyl ether containing hydroxyl groups.
  • Suitable carbonic acid esters are e.g. Ethylene, 1,2- or 1,3-propylene carbonate, dimethyl, diethyl or dibutyl carbonic acid.
  • Suitable hydroxyl-containing (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1, -butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate and pentaerythritol mono-, di- and tri (meth) acrylate.
  • Suitable hydroxyl group-containing vinyl ethers are, for example, 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.
  • Particularly preferred carbonate (meth) acrylates are those of the formula:
  • R is H or CH 3
  • X is a C-C ⁇ s alkylene group and n is an integer from 1 to 5, preferably 1 to 3.
  • R preferably represents H and X preferably represents C- to Cio-alkylene, for example 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene or 1,6-hexylene, particularly preferably for C 4 - to Cs-alkylene.
  • X very particularly preferably represents C 6 ⁇ alkylene.
  • They are preferably aliphatic carbonate (meth) acrylates.
  • (meth) acrylates or vinyl ethers of polyether polyols can also be used as radiation-curable compounds (A).
  • These can be polyether alcohols, or preferably polyvalent polyether alcohols having a statistical average of 2 to 70, preferably 2 to 60, of polyalkylene oxide units, as are obtainable in a manner known per se by alkoxylation of suitable starter molecules. Any monohydric or polyhydric alcohols can be used as starter molecules to produce these polyether alcohols.
  • Alkylene oxides suitable for the alkoxylation are ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and vinyloxirane, which can be used in the alkoxylation reaction in any order or as a mixture.
  • Suitable starter molecules are, for example, trimethylol propane, trimethylol ethane, neopentyl glycol, hydroxypivalic acid neopentyl glycol esters, pentaerythritol, glycerol, ditrimethylol propane, dipentaerythritol, sorbitol, mannitol, diglycerol, 1,2-propanediol, ethylene glycol, 2,2-dimethyl , 2-ethanediol, neopentyl glycol, 1,3-propanediol, 1, 2-butanediol or 1,4-butanediol.
  • Polyether alcohols containing vinyl ether groups are obtained, for example, by reacting hydroxyalkyl vinyl ethers with alkylene oxides.
  • Polyether alcohols containing (meth) acrylic acid groups can be obtained, for example, by transesterification of (meth) acrylic acid esters with the polyether alcohols, by esterification of the polyether alcohols with (meth) acrylic acid or by using hydroxyl-containing (meth) acrylates as described above under b).
  • Preferred polether alcohols are polyethylene glycols with a molecular weight between 106 and 2000, preferably between 106 and 898, particularly preferably between 238 and 678.
  • Poly-THF with a molecular weight between 162 and 2000 and poly-1,3-propanediol with a molecular weight between 134 and 1178 can also be used as polyether alcohols. 15
  • Radically crosslinkable copolymers which have been modified by a polymer-analogous reaction can also be used according to the invention as compounds (A).
  • Copolymers and processes for their preparation are described, for example, in DE-A 43 37 480, DE-A 43 37 481, DE-A 43 37 482 and WO 97/46594 as well as DE-A 100 166 52 and DE-A 100 166 53.
  • Polymer-analog modified copolymers which can be used according to the invention can be produced, for example, in two steps as follows.
  • a copolymer (F) is produced in a copolymerization from the monomers (fl) 30 to (f3), which carries reactive groups, via which it can be converted into the modified copolymer in a subsequent polymer-analogous reaction.
  • monomers (f3) are used as monomers (fl) and (f2) which, in addition to the olefinic double bond, carry an additional 35 reactive groups which are inert under the conditions of the copolymerization.
  • the copolymers (F) thus obtained are reacted in a second step with those vinyl compounds (G) which additionally have functionalities which react with the reactive groups of the copolymer (F) to form chemical bonds.
  • the number average molecular weight M n of the polymers according to the invention is, for example, between 1500 and 10000, preferably between 1500 and 6000 and particularly preferably between 2000 and 45 4000.
  • the polydispersity M w / M n is a measure of the molecular weight distribution of the copolymers and ideally has the value 1, but values below 4.0, in particular, are also sufficient in practice under 3.5.
  • the information on the polydispersity and the number-average and weight-average molecular weights M n and M w relate here to gel permeation chromatography measurements, polystyrene being used as the standard and tetrahydrofuran as the eluent.
  • the method is described in the analyst paperback vol. 4, pages 433 to 442, Berlin 1984.
  • the molecular weight and the molecular weight distribution of the copolymers according to the invention are determined by the polymerization conditions in the preparation of the copolymers (F).
  • copolymers (F) with low polydispersity and low molecular weight is particularly favored when reaction temperatures from 140 to 210, preferably from 150 to 180 and particularly preferably from 150 to 170 ° C. and reaction times from 2 to 90, preferably from 5 to 25 and particularly preferably from 10 to 15 minutes.
  • reaction is advantageously carried out under pressure, preferably under the autogenous pressure of the system.
  • pressures higher than 30 bar are generally not required.
  • Such polymerization conditions can be achieved in particular in an annular gap thin-film reactor with a recirculation device, since the exothermic polymerization can be carried out here under largely isothermal conditions because of the favorable ratio of heat exchange surface to reaction volume.
  • Copolymerizations in annular gap thin-film reactors are described, for example, in DE-A 4 203 277 and DE-A 4 203 278. They are generally known and can be designed, for example, in the manner of a tubular reactor equipped with a rotor, and are available, for example, from Buss SMS GmbH Maschinenstechnik. They are preferably equipped with a device with which part of the product can be returned to the reactor inlet. Other polymerizers, such as stirred kettles, are also suitable, provided that sufficient heat dissipation is ensured.
  • the polymerization can be carried out in bulk, but solution polymerization is generally preferred because of the low viscosity of the resulting polymer solutions.
  • the amount of solvent is generally 0 to 30, preferably 10 to 25 wt .-%, based on the total amount of the monomers used.
  • Suitable solvents are all liquids which are inert towards the reactants, for example ethers such as ethylene glycol ether and ethylene diglycol ether, esters such as butyl acetate and ketones such as methyl amyl ketone.
  • ethers such as ethylene glycol ether and ethylene diglycol ether
  • esters such as butyl acetate
  • ketones such as methyl amyl ketone.
  • Regulatory solvents such as alkyl aromatics, e.g. Toluene, xylenes and especially cumene and m-xylene and aliphatic alcohols, e.g. Isopropanol.
  • Suitable radical initiators are, in particular, those radical-forming compounds whose decomposition temperature is 140 to 200 ° C., for example di-tert-butyl peroxide and dibenzoyl peroxide.
  • the amount of initiators is preferably 0.5 to 10, particularly preferably 1 to 5 mol% of the total amount of the monomers used.
  • the monomer type (fl) thus includes monomers with non-reactive radicals and those of the type (f3). In the following, the first mentioned monomers and then the monomers (f3) with the functional groups are explained in more detail.
  • the C 1 -C 1 -alkyl esters of methacrylic acid are to be mentioned primarily, for example ethyl methacrylate, 2-ethylhexyl methacrylate and n-butyl methacrylate and especially methyl ethacrylate.
  • Methoxyethyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate are also suitable.
  • alkyl esters of acrylic acid are of particular importance.
  • examples of other well-suited monomers of this type are iso-, n- and tert-butyl acrylate.
  • styrene and 1-methylstyrene for example 4-tert-butylstyrene and 2-chlorostyrene are particularly suitable.
  • Further free-radically polymerizable monomers (f2) are vinyl ethers of C 2 - to co-fatty acids, such as especially vinyl acetate and vinyl propionate, vinyl halides such as vinyl chloride and vinylidene chloride, conjugated dienes such as butadiene and isoprene, vinyl ethers of C 1 -C 6 to ⁇ alkanols, for example Vinyl iso-butyl ether, acrylonitrile, methacrylonitrile and the C ⁇ ⁇ to Cio-alkyl esters of crotonic acid and maleic acid.
  • Heterocyclic vinyl compounds such as 2-vinylpyridine and N-vinylpyrrolidone are also suitable.
  • the monomers (f3) which can belong to each of the classes (fl) and (f2), carry functional groups which, in a condensation or addition reaction with a vinyl compound (G) carrying a complementary group, achieve the desired functionalization of the copolymers ( F) can be carried out to the copolymer according to the invention.
  • Such functional groups are e.g. the hydroxyl group, the carbonamide group, the amino group, the carbonyl group in aldehyde or ketone function, the isocyanate group and especially the carboxyl group and the epoxy group.
  • Corresponding monomers (f3) are primarily the relatively inexpensive compounds 2-hydroxyethyl acrylate and methacrylate, allyl alcohol, 2-aminoethyl acrylate and methacrylate, acrolein, methacrolein and vinyl ethyl ketone, acrylamide and methacrylamide, vinyl isocyanate, methacryloyl isocyanate, dimethyl-3-isopropenyl-benzyl (TMI) and 4-isocyanatostyrene and especially acrylic acid, methacrylic acid, crotonic acid, maleic acid and their anhydrides as well as glycidyl acrylate and glycidyl methacrylate.
  • the polymers (F) are 50 to 85 mol%, preferably 60 to 85 mol% of one or more of the monomers (fl) and 15 to 50 mol%, preferably 15 to 40 mol% of one or more of the monomers (f2). 5
  • the proportion of one or more of the monomers (f3) in the total amount of the monomers (fl) and (f2) is 5 to 50 mol%, preferably 15 to 40 mol%, particularly preferably 20 to 35 mol%.
  • the monomer mixtures usually contain 60 to 25 95 mol%, preferably 65 to 90 mol% of one or more of the monomers (fl) and 5 to 40 mol%, preferably 10 to 35 mol% of one or more of the monomers (f2 ).
  • the proportion of one or more of the monomers (f3) in the total amount of the monomers (fl) and (f2) used is 5 to 50 mol%, preferably 15 to 40 mol%, particularly preferably 20 to 35 mol% ,
  • the copolymers (F) are preferably liberated after their preparation, e.g. by distillation from the solvent and excess monomers and removes the remaining small amounts of residual monomers and volatile oligomers at reduced pressure or by passing nitrogen through the melt.
  • a continuously operated thin-film evaporator for example, in which the copolymer is preferably at temperatures of 180 to 220 ° C. above the polymer, is particularly suitable for this purpose.
  • the polymers (F) are derivatized in a polymer-analogous reaction. To this end, they are reacted with functional olefinically unsaturated monomers (G), hereinafter referred to as vinyl monomers (G), whose functional groups are complementary to those in the polymer.
  • G functional olefinically unsaturated monomers
  • Pairs such as (meth) acryloyl isocyanate / hydroxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate / (meth) acrylic anhydride and hydroxyalkyl (meth) acrylate / (meth) acryloyl chloride are particularly suitable here.
  • the combination of glycidyl methacrylate or glycidyl acrylate with methacrylic acid or acrylic acid is particularly preferred.
  • Another way of obtaining the free-radically crosslinkable polymers is to partially hydrolyze the ester groups which may be present in the copolymer (F) and then to react the carboxyl groups formed with glycidyl methacrylic acid esters or glycidyl acrylic acid esters.
  • the polymer-analogous conversion of the polymers (F) with the complementary monomeric functional vinyl compounds (G) to the free-radically crosslinkable vinyl group-carrying polymers takes place at reaction temperatures of 70 to 150 ° C, preferably 80 to 150 ° C, particularly preferably 90-140 ° C and in particular 100-130 ° C and residence times of 3 to 20 minutes and a conversion of 50 to 100%.
  • the reaction is particularly preferably carried out in a reaction extruder.
  • Suitable catalysts are all those which are usually used to accelerate the reaction between the complementary groups.
  • phosphines such as triphenylphosphine and amines such as dirnethylbenzylamine, dimethylethanolamine and tributylamine and tetraalkylammonium halides
  • Isocyanate / alcohol pair of reactants for example, organotin compounds.
  • the ratio of functional groups of the polymer (F) to the functional vinyl monomers (G) is preferably 0.7: 1 to 1.3: 1, preferably 0.8: 1 to 1.2: 1 and very particularly preferably 1: 1 ,
  • An excess of functional groups on the polymer (F) can serve to modify the properties of the crosslinked polymer, for example to make it less electrostatically chargeable.
  • Such free groups are in particular the carboxyl group, the hydroxyl group and the carbonamide group.
  • the monomers (G) used in excess or unreacted are usually, e.g. in the extruder, removed again by degassing.
  • inhibitors in amounts of from 1 to 5000 ppm, preferably from 1 to 1000, to the polymers (F) before the polymer-analogous reaction.
  • Suitable inhibitors are e.g. Phenylthiazines, sterically hindered o-phenols or shark ethers of hydroquinone.
  • the copolymer (F) is used in solution or dispersion with a solids content of at least 60, preferably 80 to 90% by weight, particularly preferably free of volatile constituents.
  • the polymer-analogous reactions can be carried out particularly cheaply in an extruder, in particular in a self-cleaning multi-screw extruder.
  • polymer-analog modified copolymers are those which are obtainable by polymer-analogous reaction of epoxy group-containing (meth) acrylic polymers (H) with at least one olefinically unsaturated, aliphatic C 3 to Cg monocarboxylic acid (J).
  • Suitable epoxy group-containing (meth) acrylate copolymers (H) for the preparation of the polymer-analogous reaction products according to the invention are, in particular, copolymers of acrylic acid esters and / or methacrylic acid esters which contain 40 to 95% by weight
  • Acrylic ester and / or methacrylic ester and 5 to 60 and in particular 10 to 35 wt .-% of a copolymerizable olefinic contain unsaturated monomer copolymerized with an epoxy group.
  • Suitable esters of acrylic and / or methacrylic acid are, in particular, alkyl esters with 1 to 10 carbon atoms in the alkyl radical, such as
  • the copolymers can also other copolymerizable olefinically unsaturated monomers e.g. Polymerized styrene, OC-methylstyrene, acrylonitrile or methacrylonitrile, vinyl ether or vinyl esters such as vinyl acetate, provided that the other monomers do not contain any functional groups which significantly impair the polymer-analogous reaction between the epoxy and carboxyl groups.
  • Suitable copolymers of olefinically unsaturated monomers with an epoxy group are, in particular, olefinically unsaturated glycidyl esters and ethers such as allyl glycidyl ether, glycidylerotonate, and preferably glycidyl methacrylate and glycidyl acrylate.
  • Suitable hard and soft homopolymers forming monomers are e.g. in Ulimann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol.A21, p.169 (1992).
  • the copolymers (H) preferably have an average molecular weight M n of approximately 1500 to 10,000 and in particular approximately 1500 to 6000 and a polydispersity M w / M n of less than 4 and in particular less than 3.
  • copolymers (H) The preparation of such copolymers (H) is known per se (cf. for example EP-B 156 170 or DE-A 43 37 481) and is preferably carried out by radical copolymerization in bulk or solution at temperatures above 150 ° C. in a short polymerization time ( ⁇ 90, preferably ⁇ 25 minutes) up to a conversion of about 80 to 90% and subsequent degassing of the copolymer (H).
  • Monomers (J) containing carboxylic acid groups for the polymer-analogous reaction are olefinically unsaturated aliphatic Cs-C ß- monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid and / or alkyl onoesters of olefinically unsaturated aliphatic C 4 -Cs-dicarboxylic acids such as -CC-alkyl monoesters maleic or fumaric acid.
  • the reaction of the copolymers (H) with acrylic acid and / or methacrylic acid is preferred.
  • the copolymer (H) In order to avoid the formation of crosslinks and to achieve a high degree of conversion of the epoxy groups of the copolymer (H) in the polymer-analogous reaction, it has proven to be essential to use the copolymer (H) with a clear molar excess of the carboxyl groups of the monomer (J) in relation to implement the amount of the epoxy groups of the copolymer (H).
  • the copolymer is reacted with 1.5 to 3 and preferably with 2 to 3 equivalents, based on the amount of the epoxy groups of the copolymer (H), of the unsaturated carboxylic acid (J).
  • a tetraalkylammonium halide in particular a bromide or a chloride, can be used as reaction accelerator for the epoxy-carboxylic acid reaction in the polymer-analogous reaction.
  • the alkyl group in the ammonium salt generally contains 1 to 10 carbon atoms.
  • Tetraalkylammonium halides, the alkyl groups of which each contain 4 to 8 carbon atoms, are preferred. Tetra-n-butylammonium bromide has proven to be very suitable as a reaction accelerator.
  • the amount of the tetraalkylammonium halide admixed can generally be 0.1 to 3 and in particular 0.5 to 3% by weight, based on the copolymer (H).
  • the polymer-analogous reaction is usually carried out in a highly concentrated solution with a solids content of copolymer (H) of at least 60% and in particular at least 70%, but preferably essentially solvent-free or in bulk at a temperature of 100 to 150 ° C. and preferably at 120 to 150 ° C with effective mixing of the reactants.
  • the reaction is generally ended when a degree of conversion of the epoxy groups of the copolymer (H) of at least 80%, preferably of at least 90 to 98%, has been reached.
  • the reaction time is preferably less than 30 minutes.
  • the polymer-analogous reaction can take place in known reactors such as stirred tanks. Mixers can also advantageously be connected downstream of the reactors, as a result of which a further increase in the conversion degrees of settlement of the epoxy groups of the copolymer can be achieved.
  • the polymer-analogous reaction is preferably carried out in a continuous
  • an extruder temperature of 100 to 150 and preferably 120 to 150 ° C has proven to be advantageous.
  • Multi-screw extruders and in particular twin-screw extruders with co-rotating screw shafts such as the twin-screw ZSK screw extruders from Werner & Pfleiderer are very suitable for the polymer-analogous implementation of the copolymers (H) in bulk with the reactive monomers. So can be in
  • the converted mass is advantageously degassed, i.e. largely exempted from volatile constituents by applying a vacuum, the depending on the vacuum applied
  • temperature in the degassing zone can be the same or different from the reaction temperature.
  • the generally melted mass is then discharged. It can then e.g. subsequent processing into powders of suitable particle diameters.
  • reaction products have, in particular, glass transition temperatures in the range from -20 to + 70 ° C. and are easy to filter.
  • Particularly preferred compounds (A) are urethane or carbonate (meth) acrylates or vinyl ethers or polymer-analog modified, free-radically cross-linkable copolymers, in particular urethane (meth) acrylates or polymer-analog modified, free-radical cross-linkable copolymers.
  • Compounds (A) are often used in a mixture with compounds (B) which serve as reactive diluents.
  • Suitable reactive diluents are radiation-hardenable, free-radically or cationically polymerizable compounds with only one ethylenically unsaturated, copolymerizable group.
  • C ⁇ Co-alkyl (meth) acrylates vinyl aromatics with up to 20 carbon atoms, vinyl esters of up to 20 carbon atoms containing carboxylic acids, ethylenically unsaturated nitriles, vinyl ethers of alcohols containing 1 to 10 carbon atoms and aliphatic hydrocarbons 2 to 8 carbon atoms and 1 or 2 double bonds.
  • (meth) acrylic acid is used in the context of this document for acrylic acid and methacrylic acid.
  • Preferred (meth) acrylic acid alkyl esters are those with a C 1 -C 8 -alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
  • vinyl aromatic compounds e.g. Vinyl toluene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene are considered.
  • nitriles are acrylonitrile and methacrylonitrile.
  • Suitable vinyl ethers are, for example, vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.
  • Butadiene, isoprene, as well as ethylene, propylene and isobutylene may be mentioned as non-aromatic hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds.
  • N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam can also be used.
  • Photoinitiators known to those skilled in the art can be used as photoinitiators (C), e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K.K. Dietiker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P.K.T. Oldring (Eds), SITA Technology Ltd, London.
  • Mono- or bisacylphosphine oxides such as Irgacure 819 (bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide), as described e.g. are described in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide (lucirin TPO),
  • Ethyl-2, 4, 6-trimethylbenzoylphenylphosphina benzophenones, hydroxyacetophenones, phenylglyoxylic acid and their derivatives or mixtures of these photoinitiators.
  • examples are benzophenone, acetophenone, Acetonaphthochinon, methyl ethyl ketone, valerophenone, hexanophenone, ⁇ -phenyl-butyrophenone, p-morpholino propiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholine linodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-Metho - xyacetophenone, ß-methylanthraquinone, tert-butylanthraquinone, anthraquinone carbonate, benzaldehyde, ⁇ -tetralone
  • Non-yellowing or little yellowing photoinitiators of the phenylglyoxalic acid ester type are also suitable, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
  • phosphine oxides cc-hydroxyketones and benzophenones are preferred.
  • mixtures of different photoinitiators can also be used.
  • the photoinitiators can be used alone or in combination with a photopolymerization promoter, e.g. of the benzoic acid, amine or similar type can be used.
  • typical coatings additives include, for example, antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, brighteners, antistatic agents, flame retardants, thickeners, thixotropic agents, flow control agents, binders, antifoams, fragrances, surface-active agents, viscosity modifiers, plasticizers, plasticizers, tackifying resins (tackifiers), chelating agents or compatibilizers (compatibilizer, see below) can be used.
  • antioxidants for example, antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, brighteners, antistatic agents, flame retardants, thickeners, thixotropic agents, flow control agents, binders, antifoams, fragrances, surface-active agents, viscosity modifiers, plasticizers, plasticizers, tackifying resins (tackifiers),
  • accelerators for thermal post-curing e.g. Tin octoate, zinc octoate, dibutyltin laurate or diaza [2.2.2] bicycloctane can be used.
  • one or more photochemically and / or thermally activatable initiators can be added, for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobis-iso-butyronitrile, cyclohexylsulfonylacetyl peroxide, di-iso-propyl percarbonate -Butyl peroctoate or benzopinacol, as well as, for example, those thermally activatable initiators which have a half-life at 80 ° C.
  • photochemically and / or thermally activatable initiators can be added, for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobis-iso-butyronitrile, cyclohexylsulfonylacetyl peroxide, di-iso
  • di-t-butyl peroxide cumene hydroperoxide
  • dicumyl peroxide t-butyl perbenzoate
  • silylated pinacoles which, for , B. are commercially available under the trade name ADDID 600 from Wacker or hydroxyl-containing amine N-oxides, such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2, 2.6, 6-tetramethylpiperidine-N-oxyl etc.
  • suitable initiators are described in "Polymer Handbook", 2nd edition, Wiley & Sons, New York.
  • chelating agents e.g. Ethylenediamine acetic acid and its salts and ⁇ -diketones are used.
  • Suitable fillers include silicates, e.g. B. by hydrolysis of silicon tetrachloride available silicates such as Aerosil from Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates etc.
  • silicates e.g. B. by hydrolysis of silicon tetrachloride available silicates such as Aerosil from Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates etc.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin brands from Ciba specialty chemistry) and benzophenones. These can be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2, 2, 6, 6-tetramethylpiperidine, 2, 6-di-tert. -butylpiperidine or its derivatives, e.g. B. bis- (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate. Stabilizers are usually used in amounts of 0.1 to 5.0% by weight, based on the solid components contained in the preparation.
  • suitable radical scavengers for example sterically hindered amines such as 2, 2, 6, 6-tetramethylpiperidine, 2, 6-di-tert. -butylpiperidine or its derivatives, e.g. B. bis- (2,2,6,6-tetra-methyl-4-
  • Suitable stabilizers are, for example, N-oxyls, such as e.g. 4-hydroxy-2, 2,6, 6-tetramethyl-piperidine-N-oxyl,
  • compositions for (I) are, for example
  • compound (A) consists of 10 to 100% by weight, based on the total amount of compound (A), of urethane (meth) acrylate (s), polymer-analogously modified copolymers, epoxy acrylates, polyether acrylates or polyester acrylates.
  • Suitable pressure sensitive adhesives (II) are those which are miscible with the radiation-curable compositions (I). Miscible here means completely miscible with one another at the curing temperature in the range of the composition of (I) and (II) (see below). This includes both complete solubility of the pressure-sensitive adhesive (II) in the radiation-curable composition (I) and systems in which there is a miscibility gap; the pressure-sensitive adhesives (II) are preferably soluble in (I).
  • Adhesives which require an additional connection as hardener component are preferably not used. These can be, for example, polyepoxide compounds, e.g. Polyepoxide compounds with a molecular weight below 2000 g / mol, in particular polyepoxide compounds with an epoxy value of 1 to 15.
  • the curing temperature of the pressure-sensitive adhesives (II) is above the glass transition temperature T g of the binder (A) and of the (B) optionally used as recti-thinner, for example it is at least 20 ° C higher, preferably at least 30 ° C and particularly preferably at least 50 ° C higher ,
  • the upper limit of the curing temperature is given by the thermal stability of the substrate of the coating.
  • Typical curing temperatures are 40-120 ° C, preferably 50-110 ° C and particularly preferably 60-100 ° C.
  • the temperature can remain the same or be raised.
  • the curing time is generally between a few minutes and several hours, for example from 1 minute to 5 hours, i o preferably 2 minutes to 3 hours, particularly preferably 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
  • Particularly suitable as pressure-sensitive adhesives (II) are those which contain at least one adhesive IS composition which can be crosslinked by active energy radiation.
  • pressure sensitive adhesives are viscoelastic adhesives which, in solvent-free form, remain permanently sticky and tacky at room temperature and, with low substrate specificity, immediately apply to light pressure adhere to all substrates.
  • Typical substrates for adhesion adhesives 25 are glass, plastics or metals.
  • the pressure sensitive adhesives are particularly suitable are those adhesives that have a permanent tack at room temperature, for example a glass transition temperature T g above -60 ° C, 30 Trains t forthcoming from -60 ° C to -10 ° C.
  • the glass transition temperature can be determined by conventional methods such as differential thermal analysis or differential scanning calorimetry (DSC method, see e.g. ASTM 3418/82, so-called “midpoint temperature”).
  • DSC method differential thermal analysis or differential scanning calorimetry
  • the acrylate adhesives are preferred among the pressure sensitive adhesives. These are adhesives based on acrylic monomers, especially acrylic and methacrylic acid esters. These are solutions or dispersions of polyacrylates or 45 methacrylates. In many cases, it is a question of (co) polymers based on ethyl and / or butyl acrylate, the properties of which, eg hardness and elasticity, can be achieved by using suitable comonomers. eren, for example methacrylates, can be specifically set during the polymerization and may contain additional functional groups (carboxy, hydroxyl groups) to improve the adhesive properties.
  • (Meth) acrylate adhesives are e.g. in G. Auchter, 0. Aydin, A.
  • Main monomers therein are, for example, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-propyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid iso-butyl ester, (meth) acrylic acid-seJc-butyl ester, (meth) acrylic acid-n-pentyl ester, (meth) acrylic acid-isopentyl ester, (meth) acrylic acid-2-methyl-butyl ester, (meth) acrylic acid amyl ester, (meth) acrylic acid-n - Hexyl ester, (meth) acrylic acid-2-ethyl butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid n-heptyl ester, (meth) acrylic acid n-octyl ester, (meth) acrylic acid 2-ethyl hexyl
  • Methyl vinyl ketone vinyl toluene, vinyl naphthalene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, rt-butyl vinyl ether, seJc-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, n-octyl vinyl ether, ethylene, prop , 1-butene, 2-butene, isobutene, cyclopentene,
  • Suitable secondary monomers are e.g.
  • Functionalized monomers are, for example, those which carry carboxyl, hydroxyl, epoxy, allyl, carboxamide, A in, isocyanate, hydroxymethyl, methoxymethyl or silyloxy groups.
  • These can be, for example, (meth) acrylic acid, (meth) acrylic acid formal, (meth) acrylic acid hydroxymethyl ester,
  • the weight-average molecular weight of the acrylic PSAs is, for example, between 200,000 and 1,500,000 g / mol, preferably between 250,000 and 1200,000, particularly preferably between 300,000 and 900,000.
  • the gel content i.e. the portion of an adhesive film which is soluble under THF when stored at room temperature for 24 hours is between 30 and 70, preferably between 30 and 60 and particularly preferably between 40 and 60% by weight.
  • the glass transition temperature of the acrylate adhesive measured by the DSC method, is between -60 and -10 ° C, preferably between -55 and -20 ° C and particularly preferably between -55 and -30 ° C.
  • Radiation-crosslinkable adhesives are particularly suitable according to the invention as pressure-sensitive adhesives (II).
  • adhesives that can be cross-linked by active energy radiation.
  • These adhesives generally contain poly (meth) acrylate, preferably polyacrylate, optionally in combination with aliphatic or aromatic epoxy resins, urethanes, polyesters or polyethers. Epoxy resins, aliphatic, aromatic or mixed aliphatic-aromatic urethanes are preferably used.
  • the crosslinking takes place through active energy radiation, but it can also be crosslinked via a second curing mechanism or other curing mechanisms (dual cure), e.g. by moisture, oxidation or exposure to heat, preferably by heat, e.g. at the specified curing temperature.
  • a second curing mechanism or other curing mechanisms e.g. by moisture, oxidation or exposure to heat, preferably by heat, e.g. at the specified curing temperature.
  • crosslinking monomers can also be added, for example 1,3-butylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate.
  • a photoinitiator can be added for crosslinking by UV light, e.g. the compounds described under (C).
  • the photoinitiator can also be bound to the poly (meth) acrylate.
  • the photoinitiator can then e.g. cyclic imide structures, e.g. Maleimide or maleimide derivatives, benzo or acetophenone groups act.
  • the latter are e.g. in EP-Bl 377 199, page 3, line 14 to page 13, line 45, and in EP-A 395 987, page 3, line 24 to page 5, line 42 and are hereby incorporated by reference.
  • UV acrylates acResin ® A 203 UV and acResin ® A 258 UV from BASF AG are particularly suitable.
  • the photoinitiator crosslinks the
  • Poly (meth) acrylate preferably by a chemical grafting reaction of the photoinitiator with a spatially adjacent polymer chain.
  • the crosslinking can take place by inserting a carbonyl group of the photoinitiator into an adjacent C-H bond to form a -C-C-O-H group.
  • 0.0001 to 1 mol, particularly preferably 0.0002 to 0.1, very particularly preferably 0.0003 to 0.01 mol of at least one photoinitiator (C) can be added to the poly (meth) acrylate, or the poly ( Meth) acrylate contains these amounts in the form of a molecular group which is effective as a photoinitiator and is bound to the poly (meth) acrylate.
  • the data are based on 100 g of poly (meth) acrylate.
  • the photoinitiator is preferably acetophenone, benzophenone, benzoin ether, benzil dialkyl ketals or their derivatives.
  • the photoinitiator is preferably bound to the poly (meth) acrylate.
  • the photoinitiator preferably contains an acrylic, methacrylic or vinyl ether group.
  • Suitable copolymerizable photoinitiators are acetophenone or benzophenone derivatives which contain at least one, preferably an ethylenically unsaturated group.
  • the ethylenically unsaturated group is preferably an acrylic or methacrylic group.
  • the ethylenically unsaturated group can be bonded directly to the phenyl ring of the acetophenone or benzophenone derivative. Generally there is a spacer group between the phenyl ring and the ethylenically unsaturated group.
  • the spacer group can e.g. contain up to 100 carbon atoms.
  • Suitable acetophenone or benzophenone derivatives are e.g. in EP-A-346 734, page 3, line 8 to page 6, line 50, DE-A-4 037 079, page 3, line 46 to page 6, line 45 and DE-A-3 844 444 page 5, Line 52 to page 16, line 56 are described and are also disclosed by this reference in the present application.
  • acetophenone and benzophenone derivatives are those of the formula
  • R 1 particularly preferably represents an alkylene group, in particular a C-Cs-alkylene group.
  • the glass transition temperature (T g ) according to the DSC method of the radiation-crosslinkable polyacrylate or the radiation-crosslinkable adhesive composition is preferably -60 to + 10 ° C, particularly preferably -55 to 0 ° C, very particularly preferably -55 to -10 ° C.
  • the radiation-crosslinkable or radiation-curable polyacrylates which can be used according to the invention can typically be processed at a temperature of 20 to 130 ° C.
  • the dynamic viscosity at this temperature is generally from 1 to 100 Pas, preferably from 5 to 80, particularly preferably from 10 to 60 and in particular from 20 to 60 Pas.
  • the weight-average molecular weight of the radiation-crosslinkable acrylic PSAs is, for example, between 200000 and 1500000 g / mol, preferably between 250000 and 1200000, particularly preferably between 300000 and 900000 ,
  • the gel content i.e. the portion of an adhesive film which is soluble under THF when stored at room temperature for 24 hours is between 30 and 70, preferably between 30 and 60 and particularly preferably between 40 and 60% by weight.
  • the radiation-crosslinkable adhesives generally have a wavelength range with at least one absorption maximum, in which radiation in this wavelength range leads to an increased proportion of crosslinked product.
  • This absorption maximum can be easily determined in the course of tests customary in the art by irradiation in the individual absorption maxima with different radiation doses and measurement of the product properties. Such a procedure is described for example in K.-H. Schumacher, U. Düsterwald, B. Meyer-Roscher, "UV-crosslinkable acrylate adhesives", lecture at the VIIIth Adhesive Tape Forum, Kunststoff, 1998.
  • the radiation-crosslinkable polyacrylates which can be used according to the invention crosslink when irradiated with radiation having a wavelength of up to 300 nm, preferably in the UV-C range at wavelengths between 150 and 260 nm, particularly preferably in the range from 200 to 260 nm and in particular from 250 to 260 nm.
  • the radiation dose in this area should be at least 1 mJ / cm 2 , preferably at least 5, particularly preferably at least 10 and in particular at least 20 mJ / cm 2 .
  • the radiation-crosslinkable adhesives can be mixed with other resins that increase the stickiness (tackifier). These can be, for example, the above-mentioned pressure sensitive adhesives, provided they do not absorb in the same UV range that is necessary for crosslinking the radiation-crosslinkable adhesive, for example resin acid, hydrated, esterified or partially esterified rosins, such as rosic acid, polymeric rosinic acid or Rosinic acid esters, such as partially or fully hydrogenated abietic acid esters, Foral ® 85 E or Foral 105 (from Hercules), terpene resins, terpene phenolic resins, aromatic hydrocarbon resins, aliphatic, saturated hydrocarbon resins and petroleum resins.
  • resin acid for example, the above-mentioned pressure sensitive adhesives, provided they do not absorb in the same UV range that is necessary for crosslinking the radiation-crosslinkable adhesive
  • resin acid hydrated, esterified or partially esterified rosins, such as rosic acid, polymeric
  • Dispersion is used in this document as a generic term according to Römpp Chemie Lexikon - CD Version 1.0, Stuttgart / New York: Georg Thieme Verlag, 1995, and includes emulsions, suspensions and solutions.
  • Suitable solvents (III) are, for example, water, methanol, ethanol, isopropanol, n-propanol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol, triethylene glycol Butyl methyl ketone, diethyl ketone, dimethyl formamide, dirnethyl sulfoxide, dioxane, tetrahydrofuran, tert-butyl methyl ether, tert-butyl ethyl ether, toluene, xylene, pentane, hexane, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, but
  • the mixtures according to the invention contain at least one radiation-curable composition (I) and at least one pressure-sensitive adhesive (II).
  • Exemplary mixtures contain e.g.
  • (I) and / or (II), and optionally components (A), (B), (C) and / or (D) can be dispersed in the solvent (III).
  • the proportion of (III) in the respective solution is determined by its solution properties. It can be between 10 and 99% by weight, preferably between 20 and 98% by weight and particularly preferably between 30 and 95% by weight.
  • the mixtures according to the invention are prepared by intimately mixing components (I), or their individual components (A) to (D), and (II), and, if appropriate, the solvent (III) in any order. If necessary, this can be done under protective gas.
  • the temperature during production is not restricted and is generally limited by the freezing or glass transition temperature and by the boiling point or the curing temperature of the respective components or mixtures.
  • the temperature is from 0 ° C to 80 ° C, preferably from 10 ° C to 70 ° C and particularly preferably from 20 ° C to 60 ° C.
  • Mixtures are carried out by customary processes known to those skilled in the art, at least one mixture according to the invention, for example in the form of a dispersion or without solvent (III), being applied to the substrate to be coated in the desired thickness and the volatile constituents of the dispersion, if appropriate with heating, removed. If desired, this process can be repeated one or more times.
  • the application to the substrate can in a known manner, for. B. by spraying, spraying, dipping, filling, knife coating, airblade, brushing, rolling, rolling or pouring.
  • the coating thickness is generally in a range from about 3 to 1000 g / m 2 and preferably 10 to 200 g / m 2 .
  • a method for coating substrates in which a coating composition (lacquer) containing a mixture according to the invention, optionally mixed as a lacquer formulation with further lacquer-typical additives and / or thermally curable resins, is applied to the substrate, optionally dried the above-mentioned curing temperature is thermally treated and then cured, optionally at temperatures up to the curing temperature, with electron beams or UV exposure under an oxygen-containing atmosphere or preferably under an inert gas.
  • a coating composition lacquer
  • a mixture according to the invention optionally mixed as a lacquer formulation with further lacquer-typical additives and / or thermally curable resins
  • the process for coating substrates can also be carried out in such a way that, after the mixture or coating formulation according to the invention has been applied, it is first cured with electron beams or UV exposure under oxygen or, preferably, under inert gas and then thermally treated at the curing temperature. Thermal and radiation curing can of course also take place in parallel.
  • the films formed on the substrate can only be cured thermally. In general, however, the coatings are cured both by irradiation with high-energy radiation and thermally.
  • the finished coating has a glass transition temperature above the usage temperature, usually above room temperature.
  • active energy rays are ultraviolet, X-ray and electron beams; ultraviolet and electron beams are preferred.
  • coating of substrates can also be carried out as follows, where:
  • step iii) optionally irradiating the film formed in step ii) with high-energy radiation, the film being prehardened, and then optionally machining the object coated with the prehardened film or bringing the surface of the prehardened film into contact with another substrate,
  • Steps iv) and iii) can also be carried out in the reverse order.
  • H. the film can first be cured thermally and then with high-energy radiation.
  • Typical curing temperatures are 40-120 ° C, preferably 50-110 ° C and particularly preferably 60-100 ° C. The temperature can remain the same or be raised during the course of the hardening process.
  • the curing time is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably 2 minutes to 3 hours, particularly preferably 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
  • Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulse lamps, metal halide drains, xenon lamps, electrodeless discharge lamps, carbon arc lamps, electron flash devices, which enables radiation curing without a photo initiator or exciter.
  • High-pressure mercury vapor lamps, lasers, pulsed lamps (flashing light), halogen lamps or pail emitters serve as radiation sources.
  • the radiation dose usually sufficient for crosslinking in UV curing is in the range from 80 to 3000 mJ / cm 2 .
  • radiation sources can also be used for curing, e.g. two to four.
  • the radiation can optionally also be in the absence of oxygen, for. B. are carried out under an inert gas atmosphere. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases. Irradiation can also be carried out by covering the coating material with transparent media. Transparent media are e.g. B. plastic films, glass or liquids, e.g. B. water. Irradiation in the manner as described in DE-A 199 57 900 is particularly preferred.
  • the mixtures according to the invention are particularly suitable for coating substrates such as wood, paper, textile, leather, Fleece, plastic surfaces, glass, ceramics, mineral building materials, such as shaped cement blocks and fiber cement boards, or metals or coated metals, preferably of glass, plastics or metals.
  • substrates such as wood, paper, textile, leather, Fleece, plastic surfaces, glass, ceramics, mineral building materials, such as shaped cement blocks and fiber cement boards, or metals or coated metals, preferably of glass, plastics or metals.
  • the mixtures according to the invention are particularly suitable for coating metal and / or plastic films, if appropriate in a composite, in particular for coating metal and / or plastic films which are used as materials in the food sector, for example for packaging.
  • plastics are understood to be the technical plastics known per se to the person skilled in the art, e.g. Polymers and copolymers containing (meth) acrylic acid esters, vinyl aromatic compounds, e.g. Styrene, divinylbenzene, vinyl esters, e.g. Vinyl acetate, halogenated ethylenically unsaturated compounds e.g. Vinyl chloride,
  • vinylidene chloride conjugated unsaturated compounds, e.g. Butadiene, isoprene, chloroprene, ⁇ , ⁇ -unsaturated nitriles, e.g. Acrylonitrile, monounsaturated compounds, e.g. Ethylene, propylene, 1-butene, 2-butene, isobutene, cyclic monounsaturated compounds, e.g. Cyclopentene, cyclohexene, N-vinylpyr-
  • N-vinyl lactams e.g. N-vinyl caprolactam
  • vinyl ether e.g. Contain methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether in copolymerized form.
  • Polyethylene, polypropylene, polystyrene, polyester, polyamides, polyesters, polyvinyl chloride, polycarbonate, polyvinyl acetal, polyacrylonitrile, polyacetal, polyvinyl alcohol, polyvinyl acetate, phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins or polyurethanes may be mentioned by name.
  • ABS AMMA, EP, EPS, EVA, EVAL, HDPE, LDPE, MBS, MF, PA, PA6, PA66, PAN, PB, PBTP, PC, PE, PEC, PEP, PETP, PF, PI, PIB may be mentioned in particular , PMMA, POM, PP, PS, PUR, PVAC, PVAL, PVC, PVDC, PVP, SAN, SB, SMS, UF and UP plastics (abbreviations according to DIN
  • UV lamp output 80 W / cm
  • Basonat® HI 100 50 mol NCO 20
  • Basonat® HB 100 50 mol NCO
  • Kerobit® TBK di-tert-butyl cresol 0.1% with respect to total solid
  • Basonat® HI 100 polyfunctional isocyanate based on hexamethylene diamine with a high proportion of isocyanurate
  • Basonat® HB 100 polyfunctional isocyanate based on hexamethylene diamine with a high proportion of biuret
  • Kerobit® TBK were purchased from BASF AG, Ludwigshafen.
  • composition 1 35 30 parts of composition 1 above, dissolved with a solids content of 65.4% in ethyl acetate (19.62% by weight)
  • the formulation batch is applied to a glass plate (Laro quality, 148 mm 5 x 90 mm x 2 mm) with a coating knife wet with a layer thickness of 150 ⁇ m, annealed for 15 minutes at 60 ° C., after 15 minutes with a second uncoated glass plate likewise at 60 ° C covered and immediately exposed warm twice at lOm / min.
  • the dry layer was 43 ⁇ m, a very good intermediate adhesion was shown.
  • the glass plates could no longer be separated by hand.
  • the glass plates slid apart without effort.
  • composition 1 from example 1 dissolved with a solids content of 65.4% in ethyl acetate (19.62% by weight)
  • composition 1 from Example 1 The ingredients were mixed with a laboratory stirrer at room temperature at about 2000 rpm, first AC Resin® A 203 UV and then Irgacure® 2959 of composition 1 from Example 1 being added.
  • the formulation batch is wet with a layer thickness of 150 ⁇ m with a box doctor on a glass plate (Laro quality, 148 mm x
  • the dry layer was 39 ⁇ m, a very good intermediate adhesion was shown.
  • the glass plates could no longer be separated by hand.
  • the formulation batch is coated with a layer thickness of 30 ⁇ m with 10 of a wire doctor blade wet on a 12 ⁇ m thick polyester film, corona, annealed for 15 minutes at 60 ° C., after the 15th
  • the dry layer was 76 ⁇ m. It turned out to be a very good one
  • the two films could not be pulled apart with hands 20 without injury.
  • the glass plates slid slightly apart.
  • the films showed no adhesion.
  • composition 1 36.6 parts of composition 1 dissolved in a solids content of 35 65.4% in ethyl acetate (23.9364% by weight)
  • Viscosity 170 mPa.s
  • the constituents of the formulation were mixed together at room temperature at about 2000 rpm using a laboratory stirrer, the 11.3 parts of ethyl acetate then the AC Resin® 203 and finally Irgacure® 2959 being metered in.
  • the formulation batch is treated with a layer of 30 ⁇ m wet with a wire squeegee onto a 12 ⁇ m polyester film, corona treated, applied, annealed at 60 ° C for 15 minutes, covered with a second polyester film after 15 minutes and pressed on with a rubber roller, after pressing on with the rubber roller immediately exposed twice lOm / min.
  • the dry layer was 34 ⁇ m. Good adhesion was found.
  • the two films could not be pulled apart with the hands without injury.
  • the formulation batch from Example 3 is coated with a wire doctor blade wet with a wire doctor blade onto a 12 ⁇ m thick polyester film, corona treated, annealed for 5 minutes at 60 ° C., after which the formulation batch with a layer thickness of 15 ⁇ m was wet again with a wire doctor blade mounted on the previously coated polyester film, tempered again at 60 ° C. for 5 minutes, covered with a second polyester film after the 5 minutes and pressed on with a rubber roller, then exposed twice at 10 lm / min at room temperature.
  • the dry layer was approx. 39 ⁇ .
  • the rigidity was good.
  • composition 1 from example 1 dissolved with a solids content of 50% in ethyl acetate (40% by weight)
  • the formulation batch is corona treated with a wire squeegee with a wire squeegee, coated with a wire squeegee, applied, annealed for 15 minutes at 60 ° C, covered with a second polyester film after 15 minutes and pressed on with a rubber roller, immediately afterwards twice 10 mm / min exposed.
  • the dry layer was approx. 30 ⁇ m.
  • composition 2 dissolved in 50% solids in ethyl acetate (15% by weight).
  • the formulation batch is applied to a glass plate (Laro quality, 148 mm x 90 mm x 2 mm) wet with a box squeegee with a layer thickness of 50 ⁇ m, annealed for 15 minutes at 60 ° C., after 15 minutes with a second uncoated glass plate also at 60 ° C. covered and immediately exposed warm twice at lOm / min.
  • a glass plate Lisco quality, 148 mm x 90 mm x 2 mm
  • the glass plates slid slightly apart.
  • composition 2 from Example 5 dissolved with a solids content of 50% in ethyl acetate (15% by weight).
  • the formulation batch was applied to a glass plate (Laro quality, 148 mm x 90 mm x 2 mm) wet with a box doctor blade with a layer thickness of 50 ⁇ m, annealed for 15 minutes at 60 ° C., after 15 minutes with a second uncoated glass plate also at 60 ° C. covered and immediately exposed warm twice at lOm / min.
  • the glass plates could no longer be separated by hand.
  • the glass plates slid slightly apart.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des mélanges qui contiennent au moins une matière (I) durcissable par radiation et au moins un adhésif de contact (II).
EP03704346A 2002-01-15 2003-01-03 Revetements durcissables par radiation a adherence amelioree Withdrawn EP1468059A2 (fr)

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DE10201420A DE10201420A1 (de) 2002-01-15 2002-01-15 Strahlungshärtbare Beschichtungen mit verbesserter Haftung
DE10201420 2002-01-15
PCT/EP2003/000011 WO2003060029A2 (fr) 2002-01-15 2003-01-03 Revetements durcissables par radiation a adherence amelioree

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WO2003060029A2 (fr) 2003-07-24
AU2003206689A1 (en) 2003-07-30
WO2003060029A3 (fr) 2004-03-25
US20090018231A1 (en) 2009-01-15
US20050025903A1 (en) 2005-02-03
DE10201420A1 (de) 2003-07-24
AU2003206689A8 (en) 2003-07-30

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