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WO2001064803A1 - Materiau de recouvrement acrylique durcissable, avec agent de protection solaire incorpore par polymerisation, et son utilisation - Google Patents

Materiau de recouvrement acrylique durcissable, avec agent de protection solaire incorpore par polymerisation, et son utilisation Download PDF

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Publication number
WO2001064803A1
WO2001064803A1 PCT/EP2001/002285 EP0102285W WO0164803A1 WO 2001064803 A1 WO2001064803 A1 WO 2001064803A1 EP 0102285 W EP0102285 W EP 0102285W WO 0164803 A1 WO0164803 A1 WO 0164803A1
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WIPO (PCT)
Prior art keywords
coating material
meth
material according
groups
actinic radiation
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PCT/EP2001/002285
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German (de)
English (en)
Inventor
Ekkehard Sapper
Hubert Baumgart
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BASF Coatings GmbH
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BASF Coatings GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F290/02—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 end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • 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
    • C08F290/02—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 end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06

Definitions

  • the present invention relates to a new coating material curable physically or thermally and or with actinic radiation.
  • the present invention also relates to a method for producing the new coating material.
  • the new invention relates to the use of the new coating material for the production of single- or multi-layer clear coats or multi-layer coats which give color and / or effects.
  • Coating materials curable physically or thermally and / or with actinic radiation based on (meth) acrylate copolymers are known.
  • Thermally curable one-component (1K), two-component (2K) or multi-component (3K, 4K) clearcoats are known from German patent application DE 42 04 518 A1, European patent applications EP 0 594 068 A1, 0 594 20 071 A1 , 0 594 142 A 1. 0 604 992 A 1 or 0 596 460 A 1 the national patent applications WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615 or the American patents US 5,474,811 A 1, 5,356,669 A 1 or 5,605,965 A 1 known.
  • one-component (LC) clearcoats are known to contain binders containing hydroxyl groups and crosslinking agents such as blocked polyisocyanates, tris (alkoxycarbonylamino) triazines and / or aminoplast resins. In a further variant, they contain, as binders, polymers with pendant carbamate and / or allophanate groups and carbamate and / or
  • two-component (2K) or multicomponent (3K, 4K) clearcoats contain, as essential components, binders containing hydroxyl groups and polyisocyanates as crosslinking agents, which are stored separately until they are used.
  • Thermally curable clear powder coatings are known, for example, from German patent application DE 42 22 194 A1 or the product information from BASF Lacke + Weg AG, "Powder coatings", 1990.
  • Powder clear lacquers are known to contain epoxy group-containing binders and polycarboxylic acids as crosslinking agents.
  • Thermally curable powder slurry clearcoats are known, for example, from US Pat. No. 4,268,542 A1 and German patent applications DE 195 18 392 A1 and 196 13 547 A1 or are described in the unpublished German patent application DE 198 14 471.7.
  • Powder slurry clearcoats are known to contain powder clearcoats dispersed in an aqueous medium.
  • UV-curable clearcoats and powder clearcoats are known, for example, from European patent applications EP 0 928 800 A1, 0 636 669 A1, 0 410 242 A.
  • the known coating materials generally have very good optical and mechanical properties and very good scratch and acid resistance. However, their weather stability and etch resistance, particularly under extreme climatic conditions, often leave something to be desired. This then conflicts with the use of the known coating materials for the production of clearcoats in particularly demanding fields of application, such as, for example, automotive painting.
  • sealers which protect against coloring and / or effects Serve multi-layer paintwork on car bodies before scratching.
  • sealers are very thin, particularly scratch-resistant clearcoats that are applied in layer thicknesses of less than 5.0 to a maximum of 20 ⁇ m.
  • the weather stability and etch resistance of clearcoats can be improved to a certain extent by using conventional and known light stabilizers. In many cases, however, the clearcoats become cloudy due to the incompatibility of the light stabilizer and matrix. This incompatibility can also lead to increased migration of the light stabilizers into the underlying paintwork, which greatly reduces the light protection effect. Migration can also create liability problems.
  • weather stability and etch resistance can be improved by using special binders and / or a special cross-linking chemistry.
  • this requires a considerable amount of synthesis and development, because in many cases suitable suitable components are not commercially available.
  • the object of the present invention is to find a new coating material which is curable physically or thermally and / or with actinic radiation and which no longer has the disadvantages of the prior art, but instead provides clearcoats which have an excellent optical and mechanical property profile, are scratch-resistant and are acid-resistant and have particularly high weather stability and etch resistance.
  • the new physically or thermally and / or actinic radiation-curable coating material which contains at least one (meth) acrylate copolymer with copolymerized light stabilizers.
  • the new coating material curable physically or thermally and / or with actinic radiation is referred to as “coating material according to the invention”.
  • the coating materials of the invention can be in the form of anhydrous and solvent-free liquids and melts (so-called 100% systems), powders, dispersions of powders in water (so-called powder slurries) or in the form of dispersions or solutions in at least one organic solvent or water , They can be one-component (IC), two-component (2K) or multi-component (3K, 4K) systems.
  • IC one-component
  • 2K two-component
  • 3K, 4K multi-component
  • the coating materials of the invention are physically curing.
  • Physical hardening requires i. a. no crosslinking agents, but is done by releasing solvents from the applied layer.
  • the connection takes place via loop formation between the polymer molecules, the molecular weight of which does not change.
  • the physical hardening can also take place through the coalescence of binder particles, as is often the case with dispersions (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 274 and 275: »hardening «).
  • the coating materials of the invention are thermosetting. Here, they can be self-cross-linking or cross-linking.
  • self-crosslinking denotes the property of a binder to undergo crosslinking reactions with itself.
  • a prerequisite for this is that the binders already contain both types of complementary reactive functional groups which are necessary for crosslinking on the other hand, those coating materials are referred to in which one type of complementary reactive functional groups in the binder and the other type in a hardener or crosslinking agents - if used in the present case.
  • actinic radiation means electromagnetic radiation, such as visible light, UV radiation or X-rays, in particular UV radiation, and corpuscular radiation such as electron beams.
  • the coating materials of the invention are furthermore curable thermally and with actinic radiation, which experts also refer to as “dual cure”.
  • the essential component of the coating material of the invention is at least one (meth) acrylate copolymer (A) which contains at least one light stabilizer (a) in copolymerized form.
  • Suitable light stabilizers (a) are all light stabilizers which can be copolymerized with ethylenically unsaturated monomers to form (meth) acrylate copolymers.
  • the light stabilizers (a) contain at least one, in particular one, group with at least one, in particular one, ethylenically unsaturated bond.
  • Suitable groups of this type are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl, vinyl ether, vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbomenyl, isoprenyl, Isopropenyl, allyl or butenyl ester groups, in particular
  • Light stabilizers (a) which are suitable according to the invention and are polymerized into the (meth) acrylate copolymer (A) come from the classes of the triazoles. Triazine, Benzophenone, Oxalanilide and or Sterically Hindered Airline (HALS).
  • Examples of particularly suitable light stabilizers (a) are the monomers (al) to (a4) listed below. They can be produced by customary and known methods of low molecular weight organic chemistry.
  • the light stabilizers (a) are copolymerized in the preparation of the (meth) acrylate copolymer (A). Or they become only when the coating material of the invention is crosslinked by copolymerization with ethylenically unsaturated precursors of the (meth) acrylate copolymer (A), such as reactive thinners (cf.Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 491: »reactive thinner «), installed. According to the invention, it is advantageous to introduce them into the (meth) acrylate copolymers (A) to be used according to the invention, because the corresponding (meth) acrylate copolymers (A) are more widely applicable.
  • the content of polymerized light stabilizers (a) in the (meth) acrylate copolymers (A) to be used according to the invention can vary widely and depends on the requirements of the individual case.
  • the content is preferably selected so that there is as much polymerized light stabilizer (a) in the coating material according to the invention as there is as free, i.e. H. non-chemically bound, light stabilizer is present in the usual and known coating materials. Due to the special advantages of the (meth) acrylate copolymers (A), in the vast majority of cases even comparatively less light stabilizer (a) can be used.
  • the (meth) acrylate copolymers (A) preferably contain the copolymerized light stabilizers (a) in an amount of 0.1 to 5.0, particularly preferably 0.3 to 4.5, very particularly preferably based on (A) 0.5 to 4.0 and in particular 0.7 to 3.5% by weight.
  • (Meth) acrylate copolymers (A) preferably also at least one, in particular at least two, reactive functional group (s) (c) which react with reactive functional groups (c) of their own type or with others, complementary, functional groups (d) can initiate thermally initiated crosslinking reactions.
  • the complementary functional groups (c) and (d) can be present in one and the same basic structure, which is the case with so-called self-crosslinking systems.
  • the functional groups (d) can, however, also be present in a further additive (B), for example a crosslinking agent (B), which is different from the (meth) acrylate copolymer (A) to be used according to the invention, which is the case with so-called externally crosslinking systems.
  • B further additive
  • B for example a crosslinking agent (B)
  • Reactive functional groups (c) and (d) are also used when component (A) is to be curable thermally and with actinic radiation (dual cure). They are then selected so that they do not interfere with, or even completely prevent, the polymerization or crosslinking reaction of the groups (e) described below, which is triggered by the actinic radiation.
  • reactive functional groups (d) and (e) which add to olefinically unsaturated double bonds can be subordinate, i.e. H. to be used in non-distracting quantities.
  • variable R stands for an aromatic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic
  • the selection of the respective complementary groups (c) and (d) is further based on the fact that they must not undergo any undesirable reactions during storage and application of the coating material and on the temperature range in which the crosslinking is to take place.
  • Crosslinking temperatures of 90 to 200 ° C. can be used for the thermally curable coating materials according to the invention.
  • crosslinking agents (B) anhydride, carboxy, epoxy, blocked isocyanate, urethane, methylol, methylol ether, N-methylol, N-alkoxymethylamino, siloxane, amino, hydroxy and / or beta-hydroxyalkylamide groups, in particular blocked isocyanate groups or epoxy groups, on the other hand.
  • methylol, methylol ether, N-methylol or N-alkoxymemylamino groups are preferably used.
  • crosslinking agents (B) are aminoplast resins, such as those found in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, page 29, “Aminoharze”, the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff., The book “Paints, Coatings and Solvents", second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP 0 245 700 A1 as well as in the article by B.
  • crosslinking temperatures from room temperature to 90 ° C can also be used.
  • the (meth) acrylate copolymers (A) preferably contain hydroxyl groups and the crosslinking agents (B) contain unblocked isocyanate groups.
  • suitable crosslinking agents (B) are therefore polyisocyanates, such as isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea and / or uretdione groups containing polyisocyanates.
  • Polyisocyanates containing urethane groups are obtained, for example, by reacting some of the isocyanate groups with polyols, such as, for example, trimethylolpropane and glycerol.
  • the (meth) acrylate copolymers (A) to be used according to the invention contain at least one, preferably at least two, groups (s) which have at least one bond which can be activated with actinic radiation. This becomes reactive when irradiated with actinic radiation and enters into other activated bonds of its kind, polymerization reactions and / or crosslinking reactions, which take place according to radical and / or ionic mechanisms.
  • suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds. Of these, the carbon-carbon double bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention. For brevity, they are referred to as "double bonds".
  • Particularly suitable double bonds are, for example, in (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl.
  • the acrylate groups offer very special advantages, which is why they are used with particular preference.
  • the (meth) acrylate copolymers (A) to be used according to the invention can contain hydrophilic functional groups which make them water-soluble or -dispersible and by the monomers described below (b) are introduced.
  • the content of hydrophilic functional groups can vary very widely and depends on the requirements of the individual case. It is only limited at the bottom by the fact that so many hydrophilic functional groups have to be used that the (meth) acrylate copolymers (A) to be used according to the invention are water-soluble or water-dispersible.
  • the upper limit is that the hydrophilic functional groups present must not reduce the water resistance of the coatings produced from the coating materials of the invention.
  • the hydrophilic functional groups are used in an amount of 9 to 200 meq.
  • acid groups or amino groups are used as hydrophilic functional groups, this corresponds to acid numbers or amine numbers of 5 to 112 mg KOH / g.
  • Acid numbers or amine numbers of 10 to 100, particularly preferably 12 to 80, particularly preferably 15 to 70, very particularly preferably 18 to 60 and in particular 20 to 50 mg KOH / g are used.
  • the glass transition temperature of the (meth) acrylate copolymers (A) to be used according to the invention can vary very widely and depends primarily on the intended use of the coating materials according to the invention.
  • the person skilled in the art can determine the optimum glass transition temperatures for the respective intended use via the material composition, i.e. H. adjust the type and amount of the monomers (b) described in detail below, whereby he can calculate the glass transition temperatures using Fox's formula:
  • W n weight fraction of the nth monomer
  • the glass transition temperatures are preferably between -30 and 180, preferably -20 and 160, particularly preferably -10 and 140, very particularly preferably 0 and 120 and in particular 10 and 100 ° C.
  • the number average molecular weights of the (meth) acrylate copolymers (A) to be used according to the invention can likewise vary very widely.
  • Number average molecular weights of 1,000 to 150,000, preferably 1,500 to 120,000, particularly preferably 2,000 to 1,000,000, very particularly preferably 2,500 to 80,000 and in particular 3,000 to 60,000 daltons are preferably set. They preferably have a non-uniformity in the molecular weight of 1.1 to 15, in particular 1.5 to 12.
  • the preparation of the (meth) acrylate copolymers (A) to be used according to the invention offers no special features, but in addition to the light stabilizers (a) to be used according to the invention, ethylenically unsaturated monomers (b) are used, as is customary for the preparation of (meth) Acrylate copolymers are used.
  • Suitable monomers (b) to be used according to the invention are:
  • (b 1) "hydrophilic monomers” such as (bla) acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid and its half esters, fumaric acid and its half esters or itaconic acid and its half esters; olefinically unsaturated sulfonic acids such as vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers), or p-vinylbenzenesulfonic acid or phosphonic acids or their partial esters or maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalate acrylate mono (meth) methyloxy (methoxy) mono (methyl).
  • monomers containing acid groups (bla) can be found in published patent application DE 196 25 773 A1, column 2, line 58, to column 3, line 8, or from the international
  • Patent application WO 98/49205 page 3, lines 23 to 34, known;
  • suitable monomers (a) of this type are from the DE 196 25 773 A1, column 3, line 65 to column 4, line 20, known;
  • the monomers (bla) or (blb) can be used together with the monomers (blc).
  • the common use of the monomers can be used together with the monomers (blc).
  • (bla) and (blb) are only recommended in exceptional cases because there is a risk of the formation of insoluble polyelectrolyte complexes.
  • the carboxyl group-containing monomers (bla) in particular acrylic acid and methacrylic acid, are particularly advantageously used with particular preference.
  • substantially acid-free (meth) acrylic esters such as (meth) acrylic or alkyl cycloalkyl esters having up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert. -Butyl-, Hexyl-, Ethylhexyk, Stearyl- and
  • Propylene glycol diethylene glycol, dipropylene glycol, butylene glycol, pentane-l, 5-diol, hexane-1,6-diol, octahydro-4,7-methano-lH-indenedimethanol- or cyclohexane-1,2 -, -1,3- or -l, 4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol di-, tri- or tetra (meth) acrylate.
  • minor amounts of higher-functional monomers are understood to mean amounts which do not lead to crosslinking or gelling of the copolymers: (b3) substantially acid-free hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid which are derived from an alkylene glycol which has been esterified with the acid.
  • alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl -, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol- or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomaleinate, monofum
  • (b4) Vinyl esters of monocarboxylic acids with 5 to 18 carbon atoms in the molecule which are branched in the alpha position.
  • the branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins.
  • olefins When such olefins are reacted with formic acid or with carbon monoxide and water, a Mixture of carboxylic acids in which the carboxyl groups are predominantly located on a quaternary carbon atom.
  • Other olefinic starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene.
  • the vinyl esters (b4) can, however, also be prepared from the acids in a manner known per se, for example by letting the acid react with acetylene.
  • vinyl esters of saturated aliphatic monocarboxylic acids with 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferred, but in particular Versatic® acids (cf.Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag , Stuttgart, New York, 1998, "Versatic® Acids", pages
  • reaction products of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position in particular one Versatic® acid, or an equivalent amount of acrylic and / or methacrylic acid instead of the reaction product which is then reacted during or after the polymerization reaction with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, which is branched in the alpha position;
  • Cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbones, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene.
  • amido-containing monomers such as (meth) acrylic acid amides such as
  • (b8) monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid;
  • vinylaromatic hydrocarbons such as styrene, vinyltoluene, diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene;
  • nitriles such as acrylonitrile and / or methacrylonitrile
  • vinyl compounds in particular vinyl and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or
  • N-vinylamides such as vinyl-N-methylformamide, N-ninylcaprolactam or ⁇ -ninylpyrrolidone; 1-Ninylimidazol; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-
  • allyl compounds in particular AU ether and esters such as allyl methyl. - ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.
  • Mn have from 1,000 to 40,000 and on average 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; in particular Polysiloxane macromonomers which have a number average molecular weight Mn of 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, as described in DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in columns 3 to 7, EP 0 358 153 B1 on pages 3 to 6, and US Pat. No. 4,754,014 A1 in Columns 5 to 9, described in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18 to page 18, line 10;
  • the (meth) acrylate copolymers (A) to be used according to the invention also have no special procedural features, but are carried out using the methods known and known in the plastics field of continuous or discontinuous radical-initiated copolymerization under atmospheric pressure or overpressure in stirred tanks, autoclaves, tubular reactors, Loop reactors or Taylor reactors at temperatures from 50 to 200 ° C in bulk, in solution or in emulsion, especially in a mini emulsion.
  • Suitable free-radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; peroxodicarbonates; Potassium, sodium or
  • ammonium peroxodisulfate ammonium peroxodisulfate
  • Azo initiators for example azo dinitriles such as azobisisobutyronitrile
  • C-C-cleaving initiators such as benzpinakolsil ether
  • a combination of a non-oxidizing initiator with hydrogen peroxide Combinations of the initiators described above can also be used.
  • Comparatively large amounts of free-radical initiator are preferably added, the proportion of the initiator in the reaction mixture, based in each case on the total amount of the monomers (a) and (b) and of the initiator, particularly preferably 0.2 to 20% by weight, being very particular is preferably 0.5 to 15% by weight and in particular 1.0 to 10% by weight.
  • thiocarbonylthio compounds or mercaptans such as dodecyl mercaptan can be used as chain transfer agents or molecular weight regulators.
  • the content of the coating materials of the invention in the (meth) acrylate copolymers (A) to be used according to the invention can be extremely broad vary.
  • coating materials according to the invention which are physically curable, self-crosslinking, thermally curable, curable with actinic radiation or self-crosslinking, thermal and curable with actinic radiation, they can, based in each case on the coating material of the invention, up to 100% by weight, preferably up to 95% by weight .-% and in particular up to 90 wt .-%.
  • the coating materials of the invention essentially consist of the (meth) acrylate copolymers (A).
  • the content is preferably 5.0 to 80, preferably 6.0 to 75, particularly preferably 7.0 to 70, very particularly preferably 8.0 to 65 and in particular 9.0 to 60% by weight.
  • the coating materials of the invention may also contain at least one customary and known additive (B).
  • suitable additives (B) are the crosslinking agents (B) already described above. If they are used, their amount depends on the number of complementary reactive functional groups present (c). The person skilled in the art can therefore easily determine the optimum amount of crosslinking agent (B) for the individual case on the basis of his general specialist knowledge, possibly with the aid of preliminary preliminary tests.
  • suitable additives (B) are color and / or effect pigments, organic and inorganic, transparent or opaque fillers, nanoparticles, thermally and / or reactive diluents curable with actinic radiation, low-boiling organic solvents and high-boiling organic solvents ("long solvents" ), Water, UV absorber, Light stabilizers, radical scavengers, thermolabile free radical initiators. Photoinitiators and coinitiators, catalysts for thermal crosslinking.
  • Venting agents slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting and diperging agents, adhesion promoters, flow control agents, film-forming aids, sag control agents (SCA), rheology control additives (thickeners), flame retardants, siccatives, drying agents.
  • SCA sag control agents
  • thickeners rheology control additives (thickeners)
  • flame retardants siccatives, drying agents.
  • Anti-skinning agents corrosion inhibitors, waxes, matting agents.
  • the type and amount of additives (B) depend on the intended use of the coatings produced using the coating materials of the invention.
  • a coating material according to the invention is used to produce primers, filler coatings, stone chip protection primers.
  • Solid-color topcoats or basecoats it usually contains color and / or effect pigments (B) and optionally opaque fillers. If a coating material according to the invention is used, for example, to produce clearcoats or sealants - which is the preferred use - these additives (B) are naturally not present in the coating material in question.
  • suitable effect pigments (B) are metal plate pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes and non-metallic effect pigments, such as, for example, pearlescent or interference pigments.
  • metal plate pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1
  • non-metallic effect pigments such as, for example, pearlescent or interference pigments.
  • suitable inorganic color pigments (B) are titanium dioxide, iron oxides, Sicotrans yellow and carbon black.
  • suitable organic coloring pigments (B) are thioindigo pigments indanthrene blue, cromophthal red, irgazine orange and heliogen green.
  • thioindigo pigments indanthrene blue cromophthal red
  • irgazine orange irgazine orange
  • heliogen green thioindigo pigments indanthrene blue
  • Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998 pages 180 and 181, "iron blue pigments” to "iron oxide black”, pages 451 to 453 “pigments” to “pigment volume concentration”, page 563 "thioindigo pigments” and See page 567 “Titanium dioxide pigments”.
  • Suitable organic and inorganic fillers (B) are chalk, calcium sulfates, barium sulfate, silicates such as talc or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour.
  • silicas oxides such as aluminum hydroxide or magnesium hydroxide
  • organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour.
  • thermally curable reactive diluents (B) are positionally isomeric diethyloctanediols or hydroxyl group-containing hyperbranched compounds or dendrimers.
  • Suitable reactive thinners (B) curable with actinic radiation are those described in Römpp Lexikon Lacke und Drackmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword “reactive thinners”.
  • Suitable low-boiling organic solvents (B) and high-boiling organic solvents (B) (“long solvents”) are ketones such as
  • Methyl ethyl ketone or methyl isobutyl ketone esters such as ethyl acetate or butyl acetate, ethers such as dibutyl ether or ethylene glycol, diethylene glycol, Propylene glycol, dipropylene glycol, butylene glycol or
  • thermolabile radical initiators (B) are organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.
  • Suitable catalysts (B) for crosslinking are dibutyltin dilaurate, lithium decanoate or zinc octoate.
  • An example of a suitable deaerating agent (B) is diazadicycloundecane.
  • emulsifiers (B) are nonionic emulsifiers, such as alkoxylated alkanols and polyols, phenols and alkylphenols or anionic emulsifiers such as alkali salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols.
  • nonionic emulsifiers such as alkoxylated alkanols and polyols, phenols and alkylphenols
  • anionic emulsifiers such as alkali salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols.
  • Suitable wetting agents (B) are siloxanes, fluorine-containing compounds, carboxylic acid half-esters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes.
  • Suitable adhesion promoter (B) is tricyclodecanedimethanol.
  • suitable film-forming aids (B) are cellulose derivatives such as cellulose acetobutyrate (CAB).
  • Suitable transparent fillers (B) are those based on silicon dioxide, aluminum oxide or zirconium oxide; In addition, reference is made to the Römpp Lexicon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252.
  • Sag control agents (B) are ureas, modified ureas and / or silicas, as described, for example, in references EP 0 192 304 A1, DE 23 59 923 A1, DE 18 05 693 A1, WO 94/22968, DE 27 51 761 C 1, WO 97/12945 or "färbe + lack", 11/1992, pages 829 ff.
  • rheology-controlling additives are those known from the patent specifications WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97/12945; crosslinked polymeric microparticles, as disclosed, for example, in EP 0 008 127 A1; inorganic layered silicates such as aluminum-magnesium silicates, sodium-magnesium and
  • Montmorillonite type sodium magnesium fluorine lithium layered silicates Silicas such as aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;
  • a suitable matting agent (B) is magnesium stearate.
  • suitable precursors (B) for organically modified ceramic materials are hydrolyzable organometallic compounds, in particular of silicon and aluminum.
  • Suitable additional binders are oligomeric and polymeric, linear and / or branched and / or block-like, comb-like and / or random (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins, curable thermally and / or with actinic radiation, as in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457: “Polyaddition” and “Polyadditionharze (polyadducts)", pages 463 and 464: "Polycondensates”, “Polycondensation” and “Polycondensation Resins” , as well as pages 73 and 74: "Binder”.
  • suitable additional binders are the poly (mefh) acrylates or acrylate copolymers described in the patent DE 197 36 535 A1, polyesters, in particular the alkyds, acrylates described in the patents DE 40 09 858 A1 or DE 44 37 535 A1 Polyesters, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters, polyurethanes and acrylated polyurethanes, such as those in the patents EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A 1, EP 0 730 613 A 1 or DE 44 37 535 A 1, or polyureas.
  • additives (B) listed above as well as examples of suitable UV absorbers, radical scavengers, leveling agents, flame retardants, siccatives, drying agents, skin inhibitors, corrosion inhibitors and waxes (B) are described in the textbook “Varnish Additives” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, described in detail.
  • the additives (B) are used in customary and known, effective amounts.
  • the production of the coating materials has no special features, but is carried out in a customary and known manner by mixing the above-described components (A) and, if appropriate, (B) in suitable mixing units such as stirred kettles, dissolvers, stirrer mills or extruders according to those suitable for the production of the respective coating materials Method.
  • suitable mixing units such as stirred kettles, dissolvers, stirrer mills or extruders according to those suitable for the production of the respective coating materials Method.
  • the application of the coating materials according to the invention on primed and unprimed substrates can be carried out by all customary application methods, e.g. Spraying, knife coating, brushing, pouring, dipping, watering, trickling or rolling.
  • the substrate to be coated can rest as such, with the application device or system being moved.
  • the substrate to be coated in particular a coil, can also be moved, the application system being stationary relative to the substrate or being moved in a suitable manner.
  • Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as, for example, hot air - hot spraying.
  • the application can be carried out at temperatures of max. 70 to 80.degree. C. are carried out so that suitable application viscosities are achieved without there being any change or damage to the waterborne basecoat and its overspray, which may need to be reprocessed, in the event of brief thermal exposure.
  • hot spraying can be designed in such a way that the coating material is heated only very briefly in or shortly before the spray nozzle.
  • the spray booth used for the application can be operated, for example, with a circulation that can be tempered, if necessary, which is equipped with a suitable absorption medium for the overspray, e.g. B. the
  • Coating material itself is operated.
  • application is preferably carried out under illumination with visible light of a wavelength of over 550 ⁇ m or with exclusion of light. This avoids material changes or damage to the coating materials and the overspray.
  • the coating materials according to the invention are applied in a wet layer thickness such that, after they have hardened, layers result in the layer thicknesses necessary and advantageous for their functions.
  • it is preferably 10 to 150 ⁇ m
  • in the case of basecoat it is preferably 5 to 50, preferably 5 to 40, particularly preferably 5 to 30 and in particular 10 to 25 ⁇ m
  • in the case of clearcoats it is preferably 10 to 100, preferably 15 to 80, particularly preferably 20 to 75 and in particular 25 to 70 ⁇ m.
  • Highly scratch-resistant coatings generally have smaller layer thicknesses, for example less than 5.0 ⁇ m.
  • All of these painting rods can be produced from a coating material according to the invention. According to the invention, however, it is advantageous if the clearcoats and / or the highly scratch-resistant coatings (sealers) are produced from a coating material according to the invention.
  • Fillers in particular aqueous fillers, are used, such as those from US Pat. Nos. 4,537,926 A1, EP 0 529 335 A1, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89/10387, US 4,450,200 A1, US 4,614,683 A1 or WO 490/26827.
  • Water-based lacquers in particular water-based lacquers based on polyurethane, such as those from the patents EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96 / 12747, EP 0 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1 , EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A 1, EP 0 543 817 A 1, WO 95/14721, EP 0 521 928 A 1, EP 0 522 420 A 1, EP 0 522 419 A 1, EP 0 649 8
  • coating materials according to the invention are used only for the production of the sealers, customary and known clearcoats, as are known from the patent applications and patents cited at the beginning, can be used.
  • the resulting layers are preferably cured together (wet-on-wet method).
  • the hardening can take place after a certain rest period. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min.
  • the rest period is used, for example, for the course and degassing of the layers and for the evaporation of volatile components such as water and or organic solvents.
  • the rest period can be increased by the application Temperatures up to 90 ° C and or by a reduced air humidity ⁇ 10g water / kg air, especially ⁇ 5g / kg air, are supported and shortened, as long as no damage or changes of the lacquer layers occur, such as a premature complete crosslinking of the thermal and or coating materials curable according to the invention with actinic radiation.
  • the physical hardening has no special features in terms of method, but takes place when organic solvents and / or water are evaporated by entanglement and or coalescence.
  • the physical hardening can be supported by heat treatment and / or radiation with actinic radiation.
  • the thermal hardening has no special features in terms of method, but is carried out according to the customary and known methods such as heating in a forced air oven or irradiation with near infrared (NIR) or infrared. As with the actinic radiation curing described below, the thermal curing can also be carried out in stages.
  • the thermal curing advantageously takes place at temperatures above 100.degree. In general, it is advisable not to exceed temperatures of 200 ° C., preferably 190 ° C. and in particular 185 ° C.
  • the curing with actinic radiation is preferably carried out with UV radiation and / or electron beams.
  • a dose of 1,000 to 2,000, preferably 1,100 to 1,900, particularly preferably 1,200 to 1,800, very particularly preferably 1,300 to 1,700 and in particular 1,400 to 1,600 mJ / cm 2 is preferably used here. If necessary, this hardening can be supplemented with actinic radiation from other radiation sources.
  • electron beams work is preferably carried out under an inert gas atmosphere. This can be done, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the top layer of paint. In the case of curing with UV radiation, it is also possible to work under inert gas in order to avoid the formation of ozone.
  • the usual and known radiation sources and optical auxiliary measures are used for curing with actinic radiation.
  • suitable radiation sources are flash lamps from VISIT, high-pressure or low-pressure mercury vapor lamps, which may be doped with lead to open a radiation window up to 405 nm, or electron beam sources.
  • Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters.
  • shadow areas such as cavities, folds and other undercuts due to construction, can be combined with point, small area or all-round emitters with an automatic movement device for irradiating cavities or edges to be (partially) cured.
  • the curing can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, curing alternately with UV radiation and electron radiation.
  • thermal curing and curing with actinic radiation are used together (dual cure), these methods can be used simultaneously or alternately be used. If the two curing methods are used alternately, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, it may prove advantageous to start with actinic radiation and end with it.
  • Suitable substrates are all surfaces to be painted which are not damaged by curing the paintwork thereon under heat or combined use of heat and actinic radiation; these are e.g. B. metals, plastics, foils, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, as well as composites of these materials.
  • primers can be used which are produced in a customary and known manner from electrocoat materials (ETL). Both anodic (ATL) and cathodic (KTL) electrodeposition coatings, but especially KTL, come into consideration for this.
  • ETL electrocoat materials
  • ATL anodic
  • KTL cathodic
  • the substrate can also have been subjected to a surface treatment, for example galvanizing or phosphating or anodizing.
  • primed or non-primed plastics such as B. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DIN 7728T1) can be painted.
  • the plastics to be painted can of course also be polymer blends, modified plastics or fiber-reinforced plastics. It can also Plastics usually used in vehicle construction, in particular motor vehicle construction.
  • non-functionalized and / or non-polar substrate surfaces these can be subjected to a pretreatment, such as with a plasma or with flame treatment, or provided with a hydro primer in a known manner before the coating.
  • the coating materials according to the invention are therefore suitable for the painting of buildings and the painting of motor vehicle bodies, windows or doors, industrial painting, including coil coating, container coating and the impregnation or coating of electrical components.
  • industrial painting they are suitable for painting practically all parts for private or industrial use such as radiators, household appliances, small parts made of metal such as screws and nuts, hubcaps, rims, packaging or electrical components such as motor windings or transformer windings.
  • the coating materials of the invention provide clear coats and color and or effect multi-coat coatings which have a very good surface smoothness, corrosion protection, adhesion to the substrate and interlayer adhesion, high stone chip resistance, hardness, scratch resistance, weather resistance, etch resistance and
  • the paint finishes are therefore of a particularly high quality and have a long service life, even under extreme climatic conditions, which makes them economically and technically particularly attractive to the user.
  • the (meth) acrylate copolymers (AI) to (A5) were prepared by radical copolymerization in solution of the monomers listed in Table 1. The concentration of the solutions was adjusted so that a solids content of 65% by weight resulted. Tert-butyl peroxy-2-ethylhexanoate (TBPEH) was used as the initiator in an amount of 10 parts by weight per 100 parts by weight of monomers. Table 1 also gives an overview of important properties of the resulting (meth) acrylate copolymers (AI) to (A5).
  • the (meth) acrylate copolymers (AI) to (A5) of Preparation Examples 1 to 5 were used to produce the clearcoats 1 to 5 and the clearcoats 1 to 5 of the invention.
  • the constituents specified in Table 2 were mixed with one another in the stated amounts and homogenized.
  • Table 2 The material composition of the clearcoats 1 to 5 according to the invention
  • test panels of Examples 1-4 were exposed to Jacksonville weathering for 8, 10 and 14 weeks. After these periods, the weather resistance and etch resistance of the test panels were assessed and graded as follows:
  • the clear coat 5 was subjected to the CAM 180 test (short weathering, xenon test).
  • the gloss was measured reflectometrically at an angle of 20 ° using a BYK reflectometer according to DIN 67530: 1982-01 or ISO 2813: 1994 after the periods indicated in Table 4.

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  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne un matériau de recouvrement pouvant être durci physiquement ou thermiquement et/ou à l'aide d'un rayonnement actinique, qui contient au moins un copolymérisat (méth)acrylique (A), ce dernier contenant au moins un agent de protection solaire (a) incorporé par polymérisation.
PCT/EP2001/002285 2000-03-03 2001-03-01 Materiau de recouvrement acrylique durcissable, avec agent de protection solaire incorpore par polymerisation, et son utilisation Ceased WO2001064803A1 (fr)

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DE10010416.9 2000-03-03
DE10010416A DE10010416A1 (de) 2000-03-03 2000-03-03 Pysikalisch oder thermisch und/oder mit aktinischer Strahlung härtbarer Beschichtungsstoff und seine Verwendung

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WO2011006552A1 (fr) 2009-07-14 2011-01-20 Basf Coatings Gmbh Polycarbonates haute transparence munis d’un revêtement résistant à l’abrasion, procédé de fabrication et utilisation associés
DE102009032921A1 (de) 2009-07-14 2011-01-27 Basf Coatings Gmbh Kratzfestbeschichtete Polycarbonate mit hoher Transparenz, Verfahren zu deren Herstellung und deren Verwendung
US9266998B2 (en) 2009-07-14 2016-02-23 Basf Coatings Gmbh Scratch-resistant-coated polycarbonates with high transparency, process for their production, and their use

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