EP1123333A1 - Agent de revetement, procede permettant de le preparer et son utilisation comme vernis clair, notamment pour recouvrir des matieres plastiques - Google Patents

Agent de revetement, procede permettant de le preparer et son utilisation comme vernis clair, notamment pour recouvrir des matieres plastiques

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Publication number
EP1123333A1
EP1123333A1 EP99947425A EP99947425A EP1123333A1 EP 1123333 A1 EP1123333 A1 EP 1123333A1 EP 99947425 A EP99947425 A EP 99947425A EP 99947425 A EP99947425 A EP 99947425A EP 1123333 A1 EP1123333 A1 EP 1123333A1
Authority
EP
European Patent Office
Prior art keywords
coating
acid
mgkoh
weight
coating composition
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Withdrawn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
EP99947425A
Other languages
German (de)
English (en)
Inventor
Guido Wilke
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 Coatings GmbH
Original Assignee
BASF Coatings GmbH
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Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1123333A1 publication Critical patent/EP1123333A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • Coating agent process for its production and its use as an effect clear lacquer, in particular for coating plastics
  • the present invention relates to a polyurethane coating composition containing
  • the present invention also relates to methods for producing the
  • plastic-based molded parts are used increasingly, which are used together with metal parts and which one Need painting. This applies in particular to motor vehicle parts which are increasingly being manufactured from plastic parts, such as, for example, bumper cladding, spoilers, sills, wheel arch linings and side cladding or protective strips.
  • plastics made from polycarbonate and polycarbonate blends, preferably with a polycarbonate content of more than 5% by weight, based on the proportion of plastic, are increasingly being used for such molded parts.
  • plastics are generally sensitive to the effects of weather, such as UN radiation and moisture, and show a corresponding effect
  • Burden of many problems e.g. Yellowing, embrittlement or cracking, if appropriate preventive measures are not taken.
  • plastics which, due to their use, for example, as exterior automotive parts, are exposed to clearcoats or topcoats.
  • Light protection agents are usually added to the paints used for this purpose in order to avoid or at least reduce the problems caused by UV radiation.
  • benzophenone derivatives for example, various benzophenone derivatives, benzotriazole derivatives, triazines, acrylates, salicylates, oxazolines, organic Nickel compounds, ferrocene derivatives, sterically hindered amines, among others, are used individually or in combination as light stabilizers.
  • DE-A-43 26 670 discloses a polyurethane coating composition based on a polybutyl resin containing hydroxybutyl (meth) acrylate and, if appropriate, further polyacrylate and / or polycondensation resins and polyisocyanates as crosslinking agents and its use as a clearcoat in the field of automotive refinishing and for Coating of plastics known.
  • the clear lacquer contains a mixture of benzotriazine as UV absorber and a light stabilizer based on sterically hindered amines (Tinuvin® 292 from Ciba Geigy, light stabilizers based on bis (1,2,6,6-pentamethyl-4-piperidyl ) sebacat).
  • EP-B-0455 211 discloses an effect basecoat for the direct coating of non-primed plastic substrates consisting of polypropylene or containing polypropylene. This effect described there In addition to physically drying binders, basecoat contains cellulose acetobutyrate and 0.5 to 15% by weight of one or more chlorinated polyolefms. Clearcoats and topcoats are not described in EP-B-0455 211, however.
  • US Pat. No. 5,145,839 discloses coating compositions which contain mixtures of the light stabilizers (L1) and (L2). It is not specified which special binder combinations are to be used.
  • the coating compositions can serve to coat plastics and can contain pigments in opaque concentration.
  • Coating agents can be used to coat plastics.
  • EP-A-0 518 779 discloses a coating agent for the coating of plastics which contains a polyester polyol (A) and / or a polyether polyol as a binder, triisocyanates as a crosslinking agent and
  • HALS sterically hindered amines
  • Ll light stabilizers
  • the present invention is therefore based on the object of providing coating compositions which, in addition to good weather resistance of the resulting coatings, also have good adhesion to the plastic substrates and which form a hydrolysis-resistant composite (ie good adhesion after exposure to moisture) with good chemical resistance and good strength at room temperature, whereby the composite shows a ductile fracture behavior even at low temperatures of -20 to -30 ° C.
  • the new coating agents as a clear coat, are said to bring about significantly higher color stability after exposure to radiation in the colored plastic parts or the basecoats, and in themselves are less susceptible to cracking than the conventional coating agents.
  • the new coating compositions are intended to deliver coatings which are based on colored or uncolored, in particular colored substrates give the visual impression of an effect and / or metallic finish.
  • the polyester (A) has an OH number of 80 to 200 mg KOH / g and an acid number ⁇ 10 mgKOH / g,
  • the polyacrylate resin (B) has an OH number of 80 to 200 mgKOH / g and an acid number ⁇ 20 mgKOH / g,
  • the light stabilizer (L2) is a ⁇ -inoether-functionalized on the basis of sterically hindered amines and
  • the present invention also relates to processes for the preparation of this coating composition and the use of this coating composition as an effect clearcoat, in particular for coating plastics.
  • coating compositions according to the invention provide coatings which give the visual impression of an effect and / or metallic coating in the color of the colored or uncolored substrate.
  • the coatings according to the invention are not opaque, but rather transparent. Consequently, they are called effect clearcoats in the context of the present invention
  • the coating agent as a binder is a mixture of
  • At least one polyester (A) with an OH number of 80 to 200 mg KOH / g, preferably 130 to 180 mgKOH / g, and with an acid number ⁇ 10 mgKOH / g, preferably ⁇ 5 mgKOH / g, and
  • the coating composition preferably contains the polyester (component (A)) and the polyacrylate resin (component (B)) in amounts such that the mixture consists of
  • component (A) 40 to 80% by weight, preferably 55 to 70% by weight, of component (A) and
  • component (B) 60 to 20% by weight, preferably 45 to 30% by weight, of component (B),
  • the binders are also preferably used in the coating composition according to the invention in amounts such that the sum of the amount of polyesters (A) used and the amount of polyacrylate resins (B) used is 30 to 70% by weight, particularly preferably 40 to 60 % By weight, based in each case on the solids content of the binders and on the total weight of the base lacquer (ie coating agent without crosslinker component (C)).
  • polyesters with the OH numbers and acid numbers mentioned above are suitable for use in the coating compositions according to the invention.
  • the polyesters (A) preferably have a number average molecular weight of 700 to 1,500.
  • Polyesters which have been produced without the use of monools and monocarboxylic acids are particularly preferably used.
  • the polyesters are also particularly preferably free of unsaturated fatty acids.
  • Aromatic, aliphatic and cycloaliphatic di- and polycarboxylic acids may be mentioned as examples of di- and polycarboxylic acids which can be used as component (p1). Aromatic, optionally together with aliphatic, di- and polycarboxylic acids are preferably used as component (pl).
  • polycarboxylic acids examples include phthalic acid, isophthalic acid, terephthalic acid, halogenophthalic acids, such as tetrachloro- or tetrabromophthalic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3- Cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 4-
  • the cycloeopathic polycarboxylic acids can be used both in their ice and in their trans form and as a mixture of both forms.
  • esterifiable derivatives of the abovementioned polycarboxylic acids such as, for example, their mono- or polyvalent esters with aromatic alcohols with 1 to 4 C atoms or hydroxy alcohols with 1 to 4 C atoms.
  • anhydrides of the above acids can also be used if they exist.
  • monocarboxylic acids which can optionally be used together with the polycarboxylic acids are benzoic acid, tert-butylbenzoic acid, lauric acid, isononanoic acid and hydrogenated fatty acids of naturally occurring oils, preferably isononanoic acid.
  • Suitable diols (p2) for the preparation of the polyester (A) are, for example
  • Hydroxypivalic acid neopentyl glycol ester, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanedimethanol, trimethylpentanediol and
  • Ethyl butyl propanediol Ethyl butyl propanediol.
  • aliphatic polyether diols such as linear or branched poly (oxyethylene) glycols, poly (oxy propylene) glycols and / or
  • Poly (oxybutylene) glycols and mixed polyether diols such as
  • the polyether diols usually have a molecular weight Mn of 400 to 3000.
  • aromatic or alkylaromatic diols such as, for. B. 2-alkyl-2-phenyl-propane-l, 3-diol, bisphenol derivatives with ether functionality, etc.
  • Esters of hydroxycarboxylic acids with diols are also suitable as further diols, it being possible to use the diols mentioned above as the diol.
  • Examples of hydroxycarboxylic acids are hydroxypivaic acid or dimethylolpropanoic acid.
  • polyols suitable as component (p3) are ditrimethylolpropane, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, homopentaerythritol, dipentaerythritol, trishydroxy thiocyanate, 1,2,4 butanetriol, propane and hexane triols, trihydroxycarboxylic acids such as trishydroxyacid acids such as trishydroxyacid acids such as trishydroxy acids.
  • the polyols with at least 3 OH groups can be used alone or as a mixture become.
  • triols can be used together with monohydric alcohols, such as, for example, butanol, octanol, lauryl alcohol, cyclohexanol, tert-butylcyclohexanol, ethoxylated or propoxylated phenols.
  • monohydric alcohols such as, for example, butanol, octanol, lauryl alcohol, cyclohexanol, tert-butylcyclohexanol, ethoxylated or propoxylated phenols.
  • component (p4) Compounds which have a group which is reactive toward the functional groups of the polyester are particularly suitable as component (p4) for the preparation of the polyesters (Al). Diepoxide compounds, optionally also monoepoxide compounds, can be used as modifying component (p4). Suitable components (p4) are described, for example, in DE-A-40 24 204 on page 4, lines 4 to 9.
  • component (p4) for the preparation of the polyesters (A) are compounds which, in addition to a group which is reactive toward the functional groups of the polyester (A), also have a tertiary amino group, for example monoisocyanates with at least one tertiary amino group or mercapto compounds with at least one tertiary Amino group.
  • a tertiary amino group for example monoisocyanates with at least one tertiary amino group or mercapto compounds with at least one tertiary Amino group.
  • the polyester (A) is prepared by the known methods of esterification, as described, for example, in DE-A-40 24 204, page 4, lines 50 to 65.
  • the reaction is usually carried out at temperatures between 180 and 280 degrees C, optionally in the presence of a suitable esterification catalyst, such as e.g. Lithium octoate, dibutyltin oxide,
  • the polyesters (A) are usually prepared in the presence of small amounts of a suitable solvent as an entrainer.
  • a suitable solvent as an entrainer z.
  • cyclo alpha hydrocarbons e.g. B. cyclohexane used.
  • polyacrylate resins (B) with the abovementioned OH numbers and acid numbers are also suitable for use in the coating compositions according to the invention.
  • the polyacrylate resins preferably have a number average molecular weight of 2,500 to 5,000.
  • Polyacrylate resins in which glycidyl esters of carboxylic acids branched at the ⁇ -C atom are polymerized in are also preferably used.
  • Polyacrylate resins (B) which are obtainable by polymerization in an organic solvent or a solvent mixture and in the presence of at least one polymerization initiator and, if appropriate, in the presence of regulators are particularly preferably used
  • a6) optionally an ethylenically copolymerizable with (al), (a2), (a3), (a4), and (a5), which is different from (al), (a2), (a4) and (a5) and is essentially acid group-free unsaturated monomer or a mixture of such monomers,
  • component (a1) can be copolymerized with (a2), (a3), (a4), (a5) and (a6), essentially acid group-free esters of (meth) acrylic acid or a mixture of such ( Meth) acrylic acid esters are used.
  • alkyl acrylates and alkyl methacrylates with up to 20 carbon atoms in the alkyl radical such as, for example, methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate and cycloaophatic (meth) acrylic acid esters, such as eg cyclohexyl (meth) acrylate, Isobornyl (meth) acrylate, dicyclopentaen (meth) acrylate and tert-butylcyclohexyl (meth) acrylate.
  • alkyl acrylates and alkyl methacrylates with up to 20 carbon atoms in the alkyl radical such as, for example, methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate and
  • Ethyltriglycol (meth) acrylate and methoxyougoglycol (meth) acrylate with a number average molecular weight Mn of preferably 550 or other ethoxylated and / or propoxylated hydroxyl group-free (meth) acrylic acid derivatives can also be used as component (a1).
  • Component (a2) which can be copolymerized with (al), (a2), (a3), (a4), (a5) and (a6) and is different from (a5) is ethylenically unsaturated
  • Monomers which carry at least one hydroxyl group per molecule and are essentially free of acid groups or a mixture of such monomers is used.
  • Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-ethylenically unsaturated carboxylic acid are mentioned as examples. These esters can be derived from an alkylene glycol esterified with the acid, or they can be obtained by reacting the acid with an alkylene oxide.
  • component (a2) preference is given to hydroxyalkyl esters of acrylic acid or methacrylic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, reaction products of cycües esters, such as e.g. epsilon-caprolactone and this
  • Hydroxyalkyl esters or mixtures of these hydroxyalkyl esters or epsilon-caprolactone-modified hydroxyalkyl esters.
  • hydroxyalkyl esters examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
  • esters of other unsaturated acids such as ethacrylic acid, crotonic acid and similar acids with up to about 6 carbon atoms per molecule, can also be used.
  • olefinically unsaturated polyols can also be used as component (a2).
  • Preferred polyacrylate resins (B) are obtained when trimethylolpropane monoallyl ether is at least partially used as component (a2).
  • the proportion of trimethylolpropane monoallyl ether is usually 2 to 10% by weight, based on the total weight of the monomers (a1) to (a6) used to prepare the polyacrylate resin. In addition, however, it is also possible to add 2 to 10% by weight, based on the total weight of the monomers used to prepare the polyacrylate resin, of trimethylolpropane monoallyl ether to the finished polyacrylate resin.
  • the olefinically unsaturated polyols such as in particular
  • TrimethylolpropanmonoaUylether can be used as the sole hydroxyl-containing monomers, but especially in proportion in combination with other of the hydroxyl-containing monomers mentioned.
  • each can contain at least one acid group, preferably one carboxyl group, per molecule, with (al), (a2), (a4), (a5) and (a6), ethylenically unsaturated monomer or a mixture of such monomers be used.
  • Acrylic acid and / or methacrylic acid are particularly preferably used as component (a3).
  • other ethylenically unsaturated carboxylic acids with up to 6 carbon atoms in the molecule can also be used.
  • Efhacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid are mentioned as examples of such acids.
  • ethylenically unsaturated sulfonic or phosphonic acids or their partial esters can be used as component (a3).
  • Mono (meth) acryloyloxyethyl maleate, mono (meth) acryloyloxyethyl maleate and mono (meth) acryloyloxyethyl phthalate can also be used as component (a3).
  • Vinylaromatic hydrocarbons, such as styrene, alpha-alkylstyrenes and vinyltoluene, are used as component (a4).
  • component (a5) the reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule is used.
  • Glycidyl esters of strongly branched monocarboxylic acids are available under the trade name "Cardura”.
  • the reaction of acrylic or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha carbon atom can be done beforehand. take place during or after the polymerization reaction.
  • the reaction product of acrylic and / or methacrylic acid with the glycidyl ester of versatic acid is preferably used as component (a5). This glycidyl ester is commercially available under the name "Cardura E10".
  • component (a6) all of which can be copolymerized with (al), (a2), (a3), (a4) and (a5), differ from (al), (a2), (a3) and (a4) and are essentially free of acid groups ethylenically unsaturated monomers or mixtures of such monomers can be used.
  • Component (a6) can be one or more vinyl esters of monocarboxylic acids having 5 to 18 carbon atoms in the molecule and 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 crack products from paraffinic hydrocarbons, such as
  • Mineral oil fractions can contain both branched and straight-chain Aeyeüsche and / or cycloaüphatic olefins.
  • olefins When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed 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 can 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 aphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used.
  • Polysiloxane macromonomers can also be used as component (a6) in combination with other monomers suitable as component (a6).
  • Polysiloxane macromonomers are suitable which have a number average molecular weight Mn of 1,000 to 40,000 daltons, preferably 2,000 to 10,000 daltons, and an average of 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule. Suitable are, for example, those in DE-A 38 07 571 on pages 5 to 7, that in DE-A 37 06 095 in columns 3 to 7, that in EP-B 358 153 on pages 3 to 6 and the polysiloxane macromonomers described in columns 5 to 9 of US Pat. No. 4,754,014.
  • acryloxysilane-containing vinyl monomers with the above-mentioned molecular weights and contents of ethylenically unsaturated double bonds are also suitable, for example compounds which can be prepared by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with methacrylic acid and / or hydroxyalkyl esters of (meth) acrylic acid.
  • polysiloxane macromonomers listed in DE-A 4421 823 are preferably used as component (a6).
  • polysiloxane macromonomers suitable as component (a6) are also those in the international patent application with the publication number WO 92/22615 on page 12, line 18, to page 18, line 10, compounds mentioned.
  • the amount of the polysiloxane macromonomer (a6) used to modify the acrylate copolymers is less than 5% by weight, preferably 0.05 to 2.5% by weight, particularly preferably 0.05 to 0.8% by weight, in each case based on the total weight of the monomers used to prepare the copolymer (B).
  • component (al) 5 to 50% by weight, preferably 10 to 40% by weight, of component (al),
  • component (a2) 3 to 45% by weight, preferably 15 to 35% by weight, of component (a2),
  • component (a3) 1 to 15% by weight, preferably 5 to 10% by weight, of component (a3),
  • component (a5) 3 to 50% by weight, preferably 15 to 35% by weight, of component (a5) and
  • component (a6) 0 to 30% by weight, preferably 0 to 25% by weight, of component (a6),
  • the polyacrylate resins (B) used according to the invention are prepared in an organic solvent or solvent mixture and in the presence of at least one polymerization initiator and, if appropriate, a regulator.
  • organic Solvents polymerization initiators and regulators are used in the solvents, regulators and polymerization initiators customary for the production of polyacrylate resins.
  • the solvents can participate in the reaction with the crosslinking component (C) and thus act as a reactive diluent.
  • Examples of usable solvents are butyl glycol, 2-methoxypropanol, n-butanol, methoxybutanol, n-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl 2-ethylenedioethylene glycol, trimethyl ethylene glycol diethyl ether, diethylene glycol ether, diethyl ethylene glycol diethyl ether, 3-methoxybutanol and derivatives based on propylene glycol, e.g. Ethyl ethoxypropionate, isopropoxypropanol, methoxypropylacetate and others.
  • propylene glycol e.g. Ethyl ethoxypropionate, isopropoxypropanol, methoxypropylacetate and others.
  • Free-radical initiators such as e.g. tert-butyl peroxyethyl hexanoate, benzoyl peroxide, azobisisobutyronitrile and tert-butyl perbenzoate.
  • the initiators are preferably used in an amount of 2 to 25% by weight, particularly preferably 4 to 10% by weight, based on the total weight of the monomers.
  • Suitable regulators are mercaptans, e.g. Mercaptethanol, thiol glycolic acid esters and hydrogen chloride etc. called.
  • the regulators are preferably used in an amount of 0.1 to 15% by weight, particularly preferably 0.5 to 5% by weight, based on the total weight of the monomers.
  • the polymerization is advantageously carried out at a temperature of 80 to 160 degrees C, preferably 110 to 160 degrees C.
  • the coating agent can still 0 to 25 wt .-%, based on the weight of the base coat without crosslinking component and based on the Solids content, one or more, from the components (A) and (B), containing hydroxyl group-containing binders, such as hydroxyl group-containing polyurethane resins, other polyesters or other acrylate resins.
  • hydroxyl group-containing binders such as hydroxyl group-containing polyurethane resins, other polyesters or other acrylate resins.
  • the crosslinking agents (C) in the coating compositions of the invention comprise one or more di- and / or polyisocyanates with free or blocked isocyanate groups.
  • any organic polyisocyanates with aliphatic, cycloaliphatic, aromatic and / or aromatically bound isocyanate groups can be used.
  • Polyisocyanates with 2 to 5 isocyanate groups per molecule are preferably used.
  • small amounts of organic solvent, preferably 1 to 25% by weight, based on pure polyisocyanate can be added to the polyisocyanates in order to improve the incorporation of the isocyanate.
  • isocyanates are, for example, in "Methods of Organic Chemistry", Houben-Weyl, Volume 14/2, 4th Edition, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70, and by W. Siefken, Liebigs Ann. Chem. 562, 75 to 136.
  • 2,4,4'-triisocyanatodiphenyl ether, 4,4 ', 4 "triisocyanatotriphenylmethane Preferred, optionally in combination with the above-mentioned polyisocyanates, isocyanurate groups and / or biuret groups and / or AUophanatg ppen and or urethane groups and / or urea polyisocyanates containing groups, polyisocyanates containing urethane groups are obtained, for example, by reacting some of the isocyanate groups with polyols, such as, for example, trimethylolpropane and glycerol.
  • polyols such as, for example, trimethylolpropane and glycerol.
  • Aliphatic and / or cycloaliphatic polyisocyanates are preferably dimerized and trimerized
  • the polyisocyanate component (C) can also consist of any mixtures of the polyisocyanates mentioned.
  • the polyisocyanate component (C) is preferably used in the form of the compounds containing free isocyanate groups and the
  • Coating agent formulated accordingly as two-component paints In this case, part of the total solvent used can also be added to the crosslinking component.
  • one-component lacquers based on blocked isocyanates can also be shaped if blocking agents with a sufficiently low deblocking temperature are used to block the polyisocyanates.
  • blocking agents are well known to the person skilled in the art and need not be explained in more detail here.
  • the isocyanate component (C) is usually used in such an amount that the equivalent ratio of OH groups of the binders and, if appropriate, of OH groups of the light stabilizers to the isocyanate groups of the crosslinker is between 1.2: 1 and 0.7: 1.
  • the coating composition according to the invention can optionally contain further crosslinking agents, in particular components based on the triazine which crosslink with the hydroxyl groups of the binders and optionally the light stabilizers with the formation of ether and / or ester.
  • the crosslinkers reacting with the hydroxyl groups of the binders to form ether are
  • Aminoplast resins are well known to those skilled in the art and are offered as sales products by many companies. These are condensation products from aldehydes, in particular formaldehyde, and for example urea, melamine, guanamine and benzoguanamine.
  • the aminoplast resins contain alcohol, preferably methylol, which in the Are usually partially or preferably completely etherified with alcohols. Melamine-formaldehyde resins etherified with lower alcohols, in particular with methanol or butanol, are used in particular.
  • the triazine-based crosslinkers which react with the hydroxyl groups of the binder to form ester groups are
  • Umestemngsvemetzer such as preferably tris (alkoxycarbonylamino) triazine or the like, as described for example in EP-A-604 922.
  • This further crosslinking agent is usually used in an amount of 0 to 30% by weight, based on the weight of the isocyanate component. If the coating agent is also thermally sensitive to coating
  • substrates preferably contains no further crosslinking agents or only those other crosslinking agents which are curable even at low temperatures.
  • the coating compositions are a combination of light stabilizers
  • the light stabilizers (L1) are present in the coating composition according to the invention in an amount of at least 3% by weight.
  • the quantitative upper limit varies depending on the coating agent and is reached in all cases when an increase in the amount of light stabilizer (LI) no longer has a further positive effect, but there is a risk that other valuable technological properties of the coating agent will be affected due to the high level of additives to be pulled.
  • Amounts of 3 to 10% by weight are particularly advantageous because this enables the desired effects to be achieved with a comparatively small amount in all variants of the coating compositions according to the invention. Within this range, the 3 to 7% by weight should be emphasized. It represents the optimum in terms of the amount used and the effects achieved.
  • the quantity ratio of the light stabilizers (L1): (L2) can vary widely and can be adapted in an outstanding manner to the respective coating agents. According to the invention, quantitative ratios of (L1): (L2) of 0.1 to 10 are advantageous and are therefore used with preference. Within this range, quantitative ratios of 0.5 to 8 are particularly preferred and those of 1 to 7 are particularly preferred.
  • Light stabilizers of the benzotriazole type and / or triazine type are preferably used as light stabilizers (L1) based on a UV absorber.
  • Suitable light protection agents (Ll) are therefore, for example the products available commercially under the following names:
  • CYAGARD® UV-1164L from Dyna Cytec, light stabilizer based on 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -l, 3,5-triazine, average molecular weight 510, 65% in xylene
  • Particularly preferred light stabilizers (L1) are immobilizable light stabilizers based on benzotriazole and / or triazine, i.e. Light stabilizers which contain at least 1 group reactive towards the crosslinking agent, in particular at least one aliphatic OH group, per molecule.
  • immobilizable light stabilizers used particularly preferably as component (L1) are the products obtainable commercially under the following names:
  • CYAGARD® UV-3925 from Dyno Cytec, immobilizable light stabilizer based on triazine, average molecular weight 541
  • Suitable light stabilizers (L2) are all light stabilizers based on sterically hindered amines (HALS) in which the amino function is ether-substituted (referred to in the present application as aminoether function). Suitable light stabilizers (L2) are therefore, in particular, amino ether-functional substituted piperidine derivatives, such as Amino ether functionalized 2,2,6,6, tetramethylpiperidine derivatives.
  • HALS sterically hindered amines
  • the light stabilizer (L2) Due to the amino ether function, the light stabilizer (L2) is only weakly basic in character. It is therefore preferred that light stabilizers based on sterically hindered amines are used as light stabilizers (L2), which have a pK ⁇ value of at least 9.0, preferably of at least 9.5. In this case, sterically hindered amines are preferably used as light stabilizers (L2) which cannot be hydrolyzed both under the storage and application conditions and in particular under the conditions of use of the coated substrates (especially when exposed to moisture).
  • Suitable as component (L2) are, for example, the products commercially available under the following names:
  • Tinuvin® 123 from Ciba Geigy, light stabilizer based on bis (l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, average molecular weight 737, pKg value 9.6 and the corresponding light stabilizers available under the name Sanol® from Sankyo.
  • Particularly preferred light stabilizers (L2) are immobilizable, amino ether-functionalized light stabilizers based on sterically hindered amines, i.e. Light stabilizers which contain at least 1 molecule reactive to the crosslinking agent, in particular at least 1 OH group, per molecule.
  • Particularly preferred light stabilizers (L2) are therefore substituted piperidine derivatives, such as e.g. Amino ether functionalized 2,2,6,6, tetramethylpiperidine derivatives which contain at least 1 molecule, in particular at least 1 OH group, which is reactive towards the crosslinking agent per molecule.
  • immobilizable light stabilizers used particularly preferably as component (L2) are also the corresponding commercially available products.
  • Another essential component of the coating agent according to the invention is at least one effect pigment (EP).
  • EP effect pigment
  • EP effect pigments
  • suitable effect pigments are metal effect pigments, pearlescent pigments or other effect pigments.
  • suitable metal effect pigments to be used according to the invention are aluminum pigments, gold bronzes based on copper or copper-zinc alloys or mixtures, fire-colored bronzes or iron oxide-aluminum pigments.
  • suitable pearlescent pigments to be used according to the invention are fish silver, basic lead carbonate, bismuth oxychloride or metal oxide gum pigments.
  • suitable other effect pigments to be used according to the invention are micronized titanium dioxide, platelet-shaped graphite, platelet-shaped iron oxide, multilayer effect pigments from PVD films or liquid crystal pigments (cholesterols).
  • the concentration of the effect pigments (EP) to be used according to the invention in the coating compositions according to the invention varies very widely. It is important here that the concentration is so high that the desired optical effect is achieved by the effect clearcoat, on the one hand, but is so low that the intrinsic color of the substrate is not covered, but can make its contribution to the overall optical effect.
  • the effect pigments (EP) are present in an amount of 0.01 to 10, preferably 0.05 to 7 and in particular 0.5 to 5% by weight, based on the total amount of the coating composition according to the invention are.
  • the coating composition according to the invention also contains, as component (D), customary organic solvents used for the production of lacquers, preferably in an amount of 0 to 69% by weight, based on the weight of the coating composition.
  • component (D) customary organic solvents used for the production of lacquers, preferably in an amount of 0 to 69% by weight, based on the weight of the coating composition.
  • solvents are used in books Use of the binder in the form of solutions or dispersions introduced into the coating compositions.
  • other solvents can also be added to the coating compositions in order to specifically control the properties of the coating composition in a manner known to those skilled in the art.
  • the coating composition according to the invention preferably also contains 0 to 5% by weight, particularly preferably 0 to 2% by weight, of one or more cellulose esters, in each case based on the solids content of the starch lacquer and based on the solids content of the CeUulose ester.
  • suitable CeUuloseester are cellulose nitrate, cellulose propionate, cellulose butyrate, CeUuloseacetobutyrat, cellulose acetopropionate. Mixtures of the same and the like. Mixtures of different CeUulose esters can of course also be used.
  • CeUulose acetobutyrate is preferably used.
  • the coating agent according to the invention can also contain other additives customary for the particular formulation, such as e.g. Stabilizers such as antioxidants and radical scavengers, flow control agents, rheology additives, etc., preferably in an amount of 0 to 1 wt .-%, based on the total weight of the coating agent or base paint.
  • the coating composition according to the invention is generally prepared from the individual constituents by means of mixing and optionally dispersing.
  • the effect pigments (EP) in a mixed lacquer.
  • This mixed lacquer can be mixed in the desired ratio with the pigment-free coating agent or its pigment- and polyisocyanate-free precursor before application.
  • the mixed lacquer itself can also be applied to the colored substrates and then overpainted with the pigment-free coating agent.
  • the mixed paints also contain other components.
  • constituents which are also present in the pigment-free coating agent.
  • suitable constituents are the polyester resins (A) described above, CeUulosacetobutyrat (CAB), aminoplast resins, light stabilizers (L1) and / or (L2), silicone additives or solvents (D). Waxes can also be used.
  • the effect clear coats produced using the coating compositions according to the invention are notable for excellent optical quality with strong optical effects such as metallic, pearlescent or color change effects (flip-flop) and, moreover, also for good adhesion to plastics even after exposure to moisture as well as good resistance to weathering and chemicals and good low-temperature impact.
  • the invention therefore also relates to the use of the coating compositions for the production of coatings with these properties.
  • the coating composition according to the invention is preferably used for coating plastics, in particular colored, thermoplastic plastics or plastic blends, such as are used in particular for large-area exterior automotive parts. It is also preferred for the coating of polycarbonate-containing plastics, such as polycarbonate or polycarbonate / polybutylene terephthalate blends.
  • the coating composition according to the invention can of course also be used for other coatings. It can therefore also be applied to other substrates, such as metal, wood or paper.
  • the application is carried out using conventional methods, for example spraying, knife coating, dipping or brushing.
  • Polymer blends modified plastics or fiber-reinforced plastics. It can also be used for the coating of plastics used in books, in particular in motor vehicle construction.
  • non-functional and / or non-polar substrate surfaces these must be subjected to a pretreatment, such as plasma or flame treatment, in a known manner before coating.
  • the polymerization was continued at 142 ° C. for 180 min.
  • the mixture is then cooled to a temperature below 100 ° C. and dissolved in 338.2 parts of xylene, 93.1 parts of SheUsol® A, 344.8 parts of butyl acetate and 79.6 parts of butyl glycol acetate.
  • the result was a solution of the polyacrylate resin with 54% non-volatile content (60 min 130 ° C.
  • the plastic sheets to be painted made of black-colored PC / PBT blend, were produced in a customary and known manner by extrusion from the corresponding raw materials using conventional stabilizers and, if appropriate, pigments and then using the so-called "injection molding" process.
  • the light stabilizer (L2) Tinuvin R 123 from Ciba Geigy (Bis (l-
  • the mixed lacquers 1 to 5 were mixed with the pigment-free precursor described above, 7.5% by weight of the mixed lacquer and 92.5% by weight of the precursor always being used, and the percentages given the resulting base coat are covered.
  • the above-described plastic sheets of preparation example 3 were wiped with a cloth soaked in i-propanol before coating.
  • the coating agents la, lb and lc and 2 to 5 according to the invention described above were applied within 2 hours after the addition of isocyanate using a pneumatic spray gun with air atomization in such a way that a dry film layer thickness of 32 + 2 ⁇ m resulted.
  • the liquid films were flashed off at room temperature for 10 minutes and then cured in a forced air oven at 90 ° C. for 45 minutes.
  • the test panels were then 8 days at 23 ° C and 50% rel. Moist stored.
  • Adhesion was then determined using the cross hatch / tape tear test, the steam jet test (100 bar, 80 ° C, beam angle / plane 90 °, 10 cm) and the manual peel test.
  • the steam jet test a St. Andrew's cross is cut through the paint film with a knife to the substrate and a steam jet is aimed at the intersection. Liability is then assessed.
  • the manual peeling test is cut into the paint film with a knife and an attempt is made to peel or scratch the paint film from the substrate.
  • Examples la, lb and lc resulted in colorless effect clear coats with an excellent metallic effect.
  • Example 2 resulted in a colorless effect clearcoat with a pronounced, very appealing pearlescent effect.
  • Example 4 resulted in a colored effect clearcoat with a pronounced, very appealing blue-green pearlescent effect.
  • Example 5 a colored effect clear coat also resulted, which had a pronounced, very appealing red-green pearlescent effect.
  • Example 6 For the production of the two-layer effect clearcoat 6 of example 6, the mixed lacquer 5 was first applied using a pneumatic spray gun in such a way that a dry film layer thickness of ⁇ “micrometers resulted. The liquid film was vented at room temperature for 10 minutes, after which the pigment-free base coating was applied in the same way so that a dry film thickness of 32 ⁇ 2 micrometers resulted. The two-layer system was then cured in a forced-air oven at 90 ° C. for 45 minutes. The test panels were then stored as described in Examples 1 to 5, after which the adhesion of the two-layer effect clearcoat obtained was tested as described in Examples 1 to 5. The liability was fine. The two-layer effect clearcoat 6 had an outstanding red-green pearlescent effect, which proved to be extremely stable in the UV weathering for 3000 hours. There were also no cracks in the two-layer effect clearcoat.
  • Example 6 For UV weathering, the test panels of Example 6 were weathered in a XENOTEST 1200 device from Heraeus (3 air-cooled xenon high-pressure burners, each with 4500 W; quartz internal and external filters; 3 third-shell UV special glass; synchronization, 17 min dry phase and 3 min spraying with deionized water).
  • the irradiation intensity was 70 W / m 2 at 300 - 400 nm, the black panel temperature approx. 38 ° C.
  • the air humidity was> 60% during the dry phase and> 95% during the irrigation phase.
  • Example 6 was repeated, except that instead of mixed lacquer 5, mixed lacquer 4 was used.
  • the result was a two-layer effect clearcoat with a blue-green pearlescent effect, which otherwise had the same advantageous properties as that of Example 6.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Window Of Vehicle (AREA)

Abstract

L'invention concerne un agent de revêtement contenant: a) une ou plusieurs résines polyester (A); b) une ou plusieurs résines polyacrylate (B); c) un ou plusieurs di- et/ou polyisocyanates (C) ayant des groupes isocyanate libres ou bloqués; d) un ou plusieurs agents photoprotecteurs (L1) à base d'un absorbeur d'U.V.; e) un ou plusieurs agents photoprotecteurs (L2) à base d'amines à encombrement stérique; f) un ou plusieurs pigments (P) et g) un ou plusieurs solvants (D) organiques. 1.) le polyester (A) présent un indice hydroxyle compris entre 80 et 200 mg KOH/g et un indice d'acidité < 10 mg KOH/g; 2.) la résine polyacrylate (B) présente un indice hydroxyle compris entre 80 et 200 mg KOH/g et un indice d'acidité < 20 mg KOH/g; 3.) l'agent photoprotecteur (L2) à base d'amines à encombrement stérique est fonctionnalisé par amino-éthers et 4.) les pigments à effet spécial contenus dans l'agent de revêtement se trouvent dans une concentration non couvrante.
EP99947425A 1998-10-05 1999-09-27 Agent de revetement, procede permettant de le preparer et son utilisation comme vernis clair, notamment pour recouvrir des matieres plastiques Withdrawn EP1123333A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19845740A DE19845740A1 (de) 1998-10-05 1998-10-05 Beschichtungsmittel, Verfahren zu seiner Herstellung und seine Verwendung als Effekt-Klarlack, insbesondere zur Beschichtung von Kunststoffen
DE19845740 1998-10-05
PCT/EP1999/007160 WO2000020480A1 (fr) 1998-10-05 1999-09-27 Agent de revetement, procede permettant de le preparer et son utilisation comme vernis clair, notamment pour recouvrir des matieres plastiques

Publications (1)

Publication Number Publication Date
EP1123333A1 true EP1123333A1 (fr) 2001-08-16

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EP99947425A Withdrawn EP1123333A1 (fr) 1998-10-05 1999-09-27 Agent de revetement, procede permettant de le preparer et son utilisation comme vernis clair, notamment pour recouvrir des matieres plastiques

Country Status (5)

Country Link
US (1) US6620868B1 (fr)
EP (1) EP1123333A1 (fr)
JP (1) JP2002526616A (fr)
DE (1) DE19845740A1 (fr)
WO (1) WO2000020480A1 (fr)

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JP4268347B2 (ja) * 2001-05-30 2009-05-27 富士フイルム株式会社 乾式分析素子用の管理血清
EP1285608A1 (fr) 2001-08-09 2003-02-26 Emilia GmbH &amp; Co.KG Vitrine réfrigérée
DE10335491A1 (de) * 2003-08-02 2005-02-24 Basf Coatings Ag Thermisch härtender, transparenter Beschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung
DE10345043A1 (de) * 2003-09-27 2005-04-21 Rhein Chemie Rheinau Gmbh Mikrogel-enthaltende Zusammensetzung
DE102005054867A1 (de) * 2005-11-17 2007-05-24 Basf Coatings Ag Physikalisch, thermisch und physikalisch und thermisch härtbare, Metalleffektpigmente enthaltende, wässrige Gemische, Verfahren zu ihrer Herstellung und ihre Verwendung
US9045643B2 (en) * 2006-04-21 2015-06-02 Nippon Sheet Glass Company Limited Bright pigment, method for producing the pigment, and waterborne resin composition containing the pigment
KR20090064381A (ko) * 2006-08-29 2009-06-18 니혼 이타가라스 가부시키가이샤 진주 광택 안료
EP2147954B1 (fr) * 2007-04-18 2017-12-13 Nippon Sheet Glass Company, Limited Pigment photoluminescent et composition cosmétique utilisant celui-ci
JP4615612B2 (ja) * 2007-04-27 2011-01-19 日本板硝子株式会社 光輝性顔料と、それを含有する光輝性塗料組成物および自動車外板コート物
DE102007023539A1 (de) 2007-05-18 2008-11-20 Basf Coatings Ag Wässrige, pigmentierte Beschichtungsmittel, Verfahren zu deren Herstellung und deren Verwendung zur Herstellung von Mehrschichtlackierungen
WO2009051243A1 (fr) * 2007-10-18 2009-04-23 Nippon Sheet Glass Company, Limited Pigment photoluminescent
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DE19845740A1 (de) 2000-04-13
JP2002526616A (ja) 2002-08-20
US6620868B1 (en) 2003-09-16

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