EP1218462B1 - Procede de realisation de revetements antirayures - Google Patents

Procede de realisation de revetements antirayures Download PDF

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Publication number
EP1218462B1
EP1218462B1 EP00967627A EP00967627A EP1218462B1 EP 1218462 B1 EP1218462 B1 EP 1218462B1 EP 00967627 A EP00967627 A EP 00967627A EP 00967627 A EP00967627 A EP 00967627A EP 1218462 B1 EP1218462 B1 EP 1218462B1
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Prior art keywords
meth
acrylates
process according
coating
acrylate
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EP1218462A1 (fr
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Thomas Jaworek
Reinhold Schwalm
Rainer Königer
Reiner Kranwetvogel
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BASF SE
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BASF SE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S522/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S522/902—Air inhibition

Definitions

  • the present invention relates to a process for producing scratch-resistant coatings based on radiation-curable coating compositions.
  • Radiation-curable coating compositions are generally flowable preparations based on polymers or oligomers having crosslinking groups which, upon exposure to UV radiation, undergo a crosslinking reaction with one another. This leads to the formation of a high molecular weight network and thus to the formation of a solid, polymeric film.
  • radiation-curable coating compositions can be used free of solvents or dispersants. In addition, they are characterized by very short curing times, which is particularly advantageous in continuous processing in painting lines.
  • UV-curable coating compositions generally have a high surface hardness and a good chemical resistance. For some time, there has been a desire for coatings that have a high scratch resistance, so that the coating is not damaged during cleaning, for example, and loses its shine. At the same time, the coatings should retain the properties usually achieved in radiation-cured coatings.
  • the first way is based on increasing the hardness of the coating material.
  • EP-A 544 465 describes coating compositions for scratch-resistant coatings containing colloidal silica and hydrolysis products of alkoxysilyl acrylates.
  • the increase in hardness is based here on the incorporation of the silica in the polymer matrix of the coating.
  • the high hardness is at the expense of other properties, such as the penetration depth or the adhesion, which are essential for coating materials.
  • the second way is based on choosing the coating material so that it is stressed during scratching in the reversible deformation area. These are materials that allow a high reversible deformation. However, there are limits to the use of elastomers as coating material. Such coatings usually show poor chemical stability.
  • a third approach attempts to make coatings with tough, d. H. To produce plastic deformation behavior while keeping the shear stress occurring during scratching within the coating material as small as possible. This is achieved by reducing the friction coefficient, z. B. by using waxes or slip additives. Lacquer additives for UV-curing systems are described, for example, in B.hackl, J. Dauth, M. Dreyer; Paint & Lacquer 1997, 103, 32-36.
  • US Pat. No. 5,700,576 describes a UV-curable, scratch-resistant coating comprising 1-30% by weight of a prepolymeric thickener with thiol groups and 20-80% by weight of one or more polyfunctional acrylates or methacrylates and thinners, in particular reactive diluents, which have a containing free-radically polymerizable group, free-radical initiator and other conventional additives for paint production included.
  • the polymerization and thus curing of the coating is achieved by irradiation with UV light, for. B. under inert gas triggered.
  • JP-A-63214375 describes the preparation of coatings on metallic surfaces wherein the curing of the coating agent takes place under inert gas atmosphere with an oxygen concentration of less than 0.5% by volume.
  • DE-A-29 28 512 describes a method for producing a scratch-resistant coating on a plastic molding, in which applying a coating of at least one free-radically polymerizable monomer and cured by UV radiation, wherein the curing carried out in a low-oxygen or oxygen-free inert gas atmosphere becomes.
  • the present invention has for its object to provide a simple method for the production of scratch-resistant coatings, which overcomes the disadvantages of the prior art.
  • An oxygen partial pressure of 18 kPa corresponds to a volume fraction of the oxygen of about 20% by volume in the case of a protective gas under normal pressure. Under the same conditions, an oxygen partial pressure of 0.2 kPa corresponds to a volume fraction of the oxygen of 2200 ppm oxygen in the protective gas. (See also E.W. Bader / ed.), Handbook of the entire occupational medicine, Vol. 1 Urban and Schwarzenberg, Berlin, Kunststoff, Vienna 1961, p. 665). An oxygen partial pressure of 9 kPa corresponds to 10 vol% oxygen in the protective gas.
  • the coating compositions in the areas where the curing takes place are exposed to an oxygen concentration of less than 18 kPa at the moment of their exposure to UV radiation.
  • the relevant areas are the surface areas of the object to be coated provided with the radiation-curable coating materials at the moment of their exposure to UV radiation.
  • the oxygen partial pressure is preferably not more than 17 kPa ( ⁇ 19 vol%), in particular not more than 15.3 kPa ( ⁇ 17 vol%) and more preferably not more than 13.5 kPa ( ⁇ 15) vol%).
  • Optimum curing results are generally achieved at oxygen partial pressures in the range from 0.5 kPa to 10 kPa ( ⁇ 5,500 ppm-11% by volume), in particular in the range from 0.5 to 6.3 kPa ( ⁇ 5,500 ppm-7% by volume). %).
  • the oxygen partial pressure may not be less than 0.5 kPa, preferably 0.9 kPa ( ⁇ 1 vol%), 1.8 kPa ( ⁇ 2 vol%) or 2.5 kPa ( ⁇ 3 vol%).
  • protective gases are inert gases such as nitrogen, carbon monoxide, carbon dioxide and noble gases, eg. As argon, and mixtures thereof with air or oxygen into consideration, being preferred as inert gases argon and nitrogen and nitrogen in particular.
  • inert gases such as nitrogen, carbon monoxide, carbon dioxide and noble gases, eg. As argon, and mixtures thereof with air or oxygen into consideration, being preferred as inert gases argon and nitrogen and nitrogen in particular.
  • all polymers and / or oligomers which on average have at least one ethylenically unsaturated double bond per polymer or oligomer molecule which are suitable as polymers P1 for the radiation-curable preparations according to the invention are suitable can be radically polymerized under the influence of electromagnetic radiation, such as UV radiation.
  • polymer and oligomer here and below include polymers, polycondensates and polyaddition products, chemically modified polymers and prepolymers.
  • Suitable prepolymers are, for. B. obtainable by reacting polyfunctional compounds having at least two reactive groups, with monofunctional or polyfunctional compounds having at least one ethylenically unsaturated double bond and at least one reactive group which can react with the reactive groups of the aforementioned polyfunctional compounds to form bonds.
  • the polymers or oligomers generally have a number average molecular weight M N of at least 400 g / mol.
  • M N is a maximum of 50,000 and is in particular in the range of 500 to 5,000.
  • Coating agents whose polymers or oligomers P1 per molecule have on average at least 2 and more preferably 3 to 6 double bonds are preferably used in the process according to the invention.
  • the polymers or oligomers P1 preferably have a double bond equivalent weight of from 400 to 2,000, particularly preferably from 500 to 900.
  • the radiation-curable coating compositions preferably have a viscosity of 250 to 11,000 mPas (determined by means of rotary viscometer according to DIN EN ISO 3319).
  • Such radiation-curable polymers and / or oligomers P1 are well known to the person skilled in the art.
  • An overview of such coating compositions can be found for example in P.K.T. Oldring (Editor) Chemistry and Technology of UV- and EB-Formulations for Coatings and Paints, Vol. II, SITA Technology, London 1991.
  • polyether acrylates examples include polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and the corresponding methacrylates.
  • Particularly preferred polymers and / or oligomers P1 are selected from urethane (meth) acrylates, polyester (meth) acrylates, oligoether (meth) acrylates and epoxide (meth) acrylates, wherein, with regard to the weathering stability of the coatings, urethane (meth) acrylates and polyesters (meth) acrylates, especially aliphatic urethane acrylates are particularly preferred.
  • the silicone (meth) acrylates are generally linear or cyclic polydimethylsiloxanes which have acrylic and / or methacrylic groups which are bonded via an oxygen atom or via an alkylene group to the silicon atoms of the polydimethylsiloxane backbone. Silicone acrylates are described, for example, in P.K.T. Oldring (see above), p 135 to p 152 described. The disclosure made there is hereby fully incorporated by reference.
  • Suitable ethylenically unsaturated epoxy acrylates are, in particular, the reaction products of epoxy group-containing compounds or oligomers with acrylic acid or methacrylic acid.
  • Typical epoxy group-containing compounds are the polyglycidyl ethers of polyhydric alcohols. These include the diglycidyl ethers of bisphenol A and its derivatives, furthermore the diglycidyl ethers of oligomers of bisphenol A, as obtainable by reacting bisphenol A with the diglycidyl ether of bisphenol A, furthermore the polyglycidyl ethers of novolaks.
  • the reaction products of acrylic acid or methacrylic acid with the abovementioned epoxides can additionally be modified with primary or secondary amines.
  • Epoxy (meth) acrylates are well known to those skilled in the art and are commercially available. For further details reference is made to PKT Oldring, p. 37 to p. 68 and the literature cited therein.
  • Melamine acrylates are understood to mean the reaction products of melamine / formaldehyde condensation products with hydroxyalkyl esters of acrylic acid or of methacrylic acid, and also with acrylic acid, methacrylic acid or with their ester-forming derivatives.
  • Suitable melamine / formaldehyde condensation products are, for example, hexamethylolmelamine (HMM) and hexamethoxymethylolmelamine (HMMM).
  • HMM and HMMM can be reacted with the amides of ethylenically unsaturated carboxylic acids, e.g. As acrylamide or methacrylamide, are modified to ethylenically unsaturated melamine (meth) acrylates.
  • Polyester (meth) acrylates are also known to the person skilled in the art. They are available by various methods. For example, acrylic acid and / or methacrylic acid can be used directly as an acid component in the construction of the polyesters. In addition, it is possible to use hydroxyalkyl esters of (meth) acrylic acid as alcohol component directly in the construction of the polyester.
  • the polyester (meth) acrylates are preferably prepared by reacting hydroxyl-containing polyesters with acrylic or methacrylic acid or their ester-forming derivatives. It is also possible to start from carboxyl-containing polyesters, which are then reacted with a hydroxyalkyl ester of acrylic or methacrylic acid. Unreacted (meth) acrylic acid may be removed by scrubbing, distillation or, preferably, by reacting with an equivalent amount of a mono- or di-epoxide compound using suitable catalysts, e.g. B. triphenylphosphine, are removed from the reaction mixture. The products of this reaction usually remain in the radiation-curable coating composition and are incorporated into the polymer network during curing. For further details, please refer to P.K.T. Oldring, p. 123 to p. 135, referenced. Their number average molecular weight is usually in the range of 500 to 10,000, and preferably in the range of 800 to 3,000.
  • Suitable hydroxyl-containing polyesters for the preparation of the polyester (meth) acrylates can be prepared in the usual way by polycondensation of di- or polybasic carboxylic acids with diols and or polyols, wherein the OH-bearing component is used in excess. Accordingly, polyesters containing carboxyl groups are prepared by excessively using the carboxyl group-containing component.
  • the carboxylic acid component come in this case aliphatic and / or aromatic C 3 -C 36 carboxylic acids, their esters and anhydrides in question.
  • maleic acid maleic anhydride, succinic acid, succinic anhydride, glutaric, glutaric, adipic, pimelic, succinic, sebacic, phthalic, phthalic, isophthalic, terephthalic, tetrahydrophthalic, tetrahydrophthalic, trimellitic, trimellitic, pyromellitic and pyromellitic anhydrides.
  • diol component comes z.
  • cyclic ethers such as polytetrahydrofuran, polyethylene glycol and polypropylene glycol in question.
  • Particularly suitable alcohols of higher value are trihydric to hexahydric alcohols, such as glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, dipentaerythritol, ditrimethylolpropane, sorbitol, erythritol and 1,3,5-trihydroxybenzene, and also the alkoxylated derivatives of the aforementioned higher-value alcohols.
  • glycerol trimethylolethane
  • trimethylolpropane trimethylolbutane
  • pentaerythritol dipentaerythritol
  • ditrimethylolpropane ditrimethylolpropane
  • sorbitol erythritol and 1,3,5-trihydroxybenzene
  • alkoxylated derivatives of the aforementioned higher-value alcohols such as glycerol, trimethylolethane, trimethyl
  • Polyether (meth) acrylates are also known in principle to the person skilled in the art.
  • Polyether (meth) acrylates are composed of a polyether base body which has acrylate and / or methacrylate groups at its ends.
  • the polyether base body is obtainable for example by specific polymerization of epoxides such as ethylene oxide or propylene oxide or by reacting a polyhydric alcohol, for example an alcohol which has been mentioned above as a polyol component for the production of polyesters, with epoxides such as ethylene oxide and / or propylene oxide.
  • This polyether base body still contains free OH groups, which can be esterified by known processes with acrylic acid and / or methacrylic acid, or ester-forming derivatives such as acid chlorides, C 1 -C 4 -alkyl esters or anhydrides (cf., for example, Houben-Weyl, Vol XIV, 2, Macromolecular Substances II, (1963)). Also suitable as polyethers are polymerization products of tetrahydrofuran and of oxetane.
  • a flexibilization of the polyether (meth) acrylates and the polyester (meth) acrylates is possible, for example, that corresponding OH-functional prepolymers or oligomers (polyether or polyester base) with longer-chain aliphatic dicarboxylic acids, especially aliphatic dicarboxylic acids with at least 6 C. Atoms, such as adipic acid, sebacic acid, dodecanedioic acid and / or dimer fatty acids.
  • This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
  • the preferred urethane (meth) acrylates according to the invention are as a rule oligomeric compounds which have urethane groups and acryloyloxyalkyl or methacryloxyalkyl groups or (meth) acrylamidoalkyl groups.
  • Urethane (meth) acrylates usually have a number average molecular weight M N in the range of 500 to 5,000, preferably in the range of 500 to 2,000 daltons (determined by means of GPC on the basis of authentic comparative samples).
  • Preference according to the invention is given to urethane (meth) acrylates having on average at least two double bonds, in particular having on average three to six double bonds per molecule.
  • the aliphatic urethane (meth) acrylate prepolymers PU which are particularly preferred according to the invention are substantially free of aromatic structural elements, such as phenylene or naphthylene or substituted phenylene or naphthylene groups.
  • the urethane (meth) acrylates used according to the invention or their mixtures with a reactive diluent preferably have a viscosity (determined using a rotational viscometer according to DIN EN ISO 3319) in the range from 250 to 11,000 mPa.s, in particular in the range from 2,000 to 7,000 mPa.s on.
  • aliphatic urethane (meth) acrylates are known in principle to the person skilled in the art and can be prepared, for example, as described in EP-A-203 161. As far as the urethane (meth) acrylates and their preparation are concerned, this document is fully incorporated by reference.
  • Preferred urethane (meth) acrylates according to the invention are obtainable by reacting at least 25% of the isocyanate groups of an isocyanate group-containing compound (component A) with at least one hydroxyalkyl ester of acrylic acid and / or methacrylic acid (component B) optionally with at least one further compound containing at least one isocyanate-reactive functional group (component C), for example chain extender C1.
  • the urethane (meth) acrylate preferably contains no free isocyanate groups.
  • the component B is reacted in stoichiometric ratio with the free isocyanate groups of the reaction product of component A and component C.
  • the urethane (meth) acrylates can also be prepared by first reacting part of the isocyanate groups of a low molecular weight diisocyanate or polyisocyanate as component A with at least one hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid as component B and then reacting the remaining isocyanate groups with the component C, z. B. a chain extender C1, converts. It is also possible to use mixtures of chain extenders.
  • component A, B and C are chosen such that the equivalent ratio of the isocyanate groups to the reactive groups of the chain extender is between 3: 1 and 1: 2, preferably 2: 1 and the equivalent ratio of the remaining isocyanate groups to the hydroxy groups of the hydroxyalkyl ester is 1: 1.
  • Isocyanate group-containing compounds A are understood here and below to mean low molecular weight, aliphatic or aromatic di- or polyisocyanates and aliphatic or aromatic, isocyanate group-containing polymers or oligomers (prepolymers) having at least two and preferably three to six free isocyanate groups per molecule.
  • the boundary between the low molecular weight di- or polyisocyanates or the prepolymers containing isocyanate groups is fluid.
  • Typical prepolymers containing isocyanate groups generally have a number average molecular weight M n in the range from 500 to 5,000 daltons, preferably in the range from 500 to 2,000 daltons.
  • the low molecular weight di- or polyisocyanates preferably have a molecular weight below 500 daltons, in particular below 300 daltons.
  • aromatic di- or polyisocyanates are diisocyanates, such as 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene, 4,4'- and 2,4-diisocyanatodiphenylmethane, p-xylylene diisocyanate, and also isopropenyldiisocyanate.
  • diisocyanates such as 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene, 4,4'- and 2,4-diisocyanatodiphenylmethane, p-xylylene diisocyanate, and also isopropenyldiisocyanate.
  • the polyisocyanates containing isocyanurate groups are, in particular, simple trisisocyanato-isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring.
  • simple trisisocyanato-isocyanurates which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring.
  • the isocyanurate of hexamethylene diisocyanate and the cyanurate of toluene diisocyanate, which are commercially available may be mentioned here.
  • Cyanurates are preferably used in the preparation of urethane (meth) acrylates.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the Uretdiondiisocyanate can z. B. as the sole component or in admixture with other polyisocyanates, in particular the polyisocyanates containing isocyanurate groups for the preparation of urethane (meth) acrylates.
  • Suitable biuret polyisocyanates preferably have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 3 to 4.5.
  • Allophanates of the diisocyanates for example, by reacting excess amounts of diisocyanates with simple, polyhydric alcohols, such as. As trimethylolpropane, glycerol, 1,2-dihydroxypropane or mixtures thereof.
  • suitable allophanate polyisocyanates generally have an NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 3.
  • Suitable hydroxyalkyl esters of acrylic acid and methacrylic acid are the half-esters of acrylic acid or methacrylic acid with C 2 -C 10 -alkanediols, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4- Hydroxybutyl acrylate and 4-hydroxybutyl methacrylate.
  • hydroxyalkyl esters of acrylic acid and / or methacrylic acid may also be used to introduce double bonds into the urethane (meth) acrylate prepolymer hydroxyl-containing esters of acrylic acid or methacrylic acid, such as trimethylolpropane diacrylate or dimethacrylate and hydroxyl-bearing amides of acrylic acid and methacrylic acid, such as 2-hydroxy-ethylacrylamide and 2-hydroxyethylmethacrylamide are used.
  • Suitable chain extenders are aliphatic di- or polyols having up to 20 carbon atoms, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-methyl -1,5-pentanediol, 2-ethyl-1,4-butanediol, 2,2-bis (4'-hydroxycyclohexyl) propane, dimethylolcyclohexane, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, bistrimethylolpropane, erythritol and sorbitol; Di- or polyamines having up to 20 carbon atoms, such as ethylenediamine, 1,3-propanediamine, 1,2-
  • Di- or polymercaptans having up to 20 carbon atoms such as 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1.8 Octanedithiol, 1,9-nonanedithiol, 2,3-dimercapto-1-propanol, dithiothreitol, dithioerythritol, 2-mercaptoethyl ether or 2-mercaptoethyl sulfide.
  • chain extenders are oligomeric compounds having two or more of the abovementioned reactive functional groups, for example hydroxyl-containing oligomers, such as polyethers, polyesters or acrylate / methacrylate copolymers containing hydroxyl groups.
  • Oligomeric chain extenders are extensively described in the literature and typically have molecular weights in the range of 200 to 2,000 daltons.
  • Preferred chain extenders are the di- or polyols having up to 20 carbon atoms, especially the aliphatic diols having 2 to 20 carbon atoms, e.g. For example, ethylene glycol, diethylene glycol, neopentyl glycol and 1,6-hexanediol.
  • Urethane (meth) acrylates which are obtainable by reacting component B with at least one prepolymer containing isocyanate groups with at least two isocyanate groups per molecule as component A are preferably used in the process according to the invention.
  • prepolymers containing such isocyanate groups which are obtainable by reacting one of the abovementioned low molecular weight di- or polyisocyanates with at least one of the compounds of component C1, the equivalent ratio of the isocyanate groups to the reactive groups of component C1 being in particular about 2: 1
  • compounds containing isocyanate groups selected from isocyanurates and biurets of aliphatic or aromatic diisocyanates.
  • Component C further includes compounds C2, which cause a flexibilization of the UV-cured coating.
  • a flexibilization can also be achieved by reacting at least a portion of the free isocyanate groups of the binder with hydroxyalkyl esters and / or alkylaminamides of relatively long-chain dicarboxylic acids, preferably aliphatic dicarboxylic acids having at least 6 carbon atoms. Examples of suitable dicarboxylic acids are adipic acid, sebacic acid, dodecanedioic acid and / or dimer fatty acids.
  • the flexibilization reactions can each be carried out before or after the addition of component B to the prepolymers containing isocyanate groups. Flexibilization is also achieved when using as chain extender C1 longer-chain aliphatic diols and / or diamines, in particular aliphatic diols and / or diamines having at least 6 carbon atoms.
  • the coating compositions may contain one or more reactive diluents.
  • Reactive diluents are low molecular weight, liquid compounds which have at least one, polymerizable, ethylenically unsaturated double bond.
  • An overview of Reactiwer Pressner can be found z. In J.P. Fouassier (ed.), Radiation Curing in Polymer Science and Technology, Elsevier Science Publisher Ltd., 1993, Vol. 1, p 237-240. They usually serve to influence the viscosity and the coating properties, such as the crosslinking density.
  • the coating compositions used according to the invention preferably contain reactive diluents in an amount of up to 70% by weight, particularly preferably from 15 to 65% by weight, based on the total weight of P1 and reactive diluent in the coating composition.
  • reactive diluent classes include (meth) acrylic acid and its esters with diols, polyols and aminoalcohols, maleic acid and its esters or half esters, vinyl esters of saturated and unsaturated carboxylic acids, vinyl ethers and vinylureas.
  • C 2 -C 12 -alkylene glycol di (meth) acrylates such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and 1,12-dodecyl diacrylate, esters of acrylic acid or methacrylic acid with (poly ) ether diols such as di- or Tripropylenglykoldi (meth) acrylate, triethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate, esters of acrylic acid or methacrylic acid with olefinically unsaturated alcohols such as vinyl (meth) acrylate, allyl (meth) acrylate and dicyclopentadienyl, esters acrylic acid or methacrylic acid with higher-valued alcohols such as glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, esters of acrylic
  • reactive diluents based on esters of acrylic acid or of methacrylic acid and, among these, preferably mono- and diacrylates and also mono- and dimethacrylates, in particular isobornyl acrylate, hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and Laromer® 8887 from BASF AG.
  • the coating compositions according to the invention contain photoinitiators or photoinitiator combinations, as are customarily used in radiation-curable coating compositions, and which can initiate the polymerization of ethylenically unsaturated double bonds on exposure to UV radiation.
  • Radiation-curable coating compositions generally contain, based on the total weight of P1 and optionally the reactive diluents, at least 0.1% by weight, preferably at least 0.5% by weight and up to 10% by weight, preferably 0.5 to 6 wt .-%, in particular 1 to 4 wt .-%, of at least one photoinitiator.
  • photoinitiators examples include benzophenone and benzophenone derivatives, such as 4-phenylbenzophenone and 4-chlorobenzophenone, Michler's ketone, anthrone, acetophenone derivatives, such as 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone, benzoin and benzoin ethers such as methyl, ethyl and butyl benzoin ethers, benzil ketals such as benzil dimethyl ketal, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -on, anthraquinone and its derivatives such as ⁇ -methylanthraquinone and tert-butylanthraquinone, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethoxy
  • Such initiators are, for example, the products available commercially under the trademarks Irgacure® 184, Darocure® 1173 from Ciba Geigy, Genocure® from Rahn or Lucirin® TPO from BASF AG.
  • Preferred photoinitiators are also phenylglyoxalic acid, its esters and their salts, which can also be used in combination with one of the abovementioned photoinitiators.
  • the coating compositions may also contain customary auxiliaries and / or additives, for example light stabilizers (for example HALS compounds, benzotriazoles, oxalanilides and the like), slip additives, polymerization inhibitors, matting agents, defoamers, leveling agents and film-forming auxiliaries, e.g. Cellulose derivatives, or other commonly used in topcoats additives.
  • light stabilizers for example HALS compounds, benzotriazoles, oxalanilides and the like
  • slip additives for example HALS compounds, benzotriazoles, oxalanilides and the like
  • polymerization inhibitors for example HALS compounds, benzotriazoles, oxalanilides and the like
  • matting agents for example HALS compounds, benzotriazoles, oxalanilides and the like
  • defoamers for example HALS compounds, benzotriazoles, oxalanilides and the like
  • leveling agents e.g. Cellu
  • Flowable or liquid coating compositions are preferably used in the process according to the invention. These can be sprayed or sprayed or applied to the surfaces of the article to be coated by conventional methods, for example by dip coating, spraying or doctoring.
  • the still moist coating may be subjected to a drying step prior to curing with UV radiation.
  • the still moist coating can also be first cross-linked and then cured with UV radiation.
  • the coating composition of the invention is applied in an amount of 3 to 200 g / m 2 , preferably 5 to 150 g / m 2 .
  • coating thicknesses in the cured state of 3 to 200 microns, preferably 5 to 150 microns are generated.
  • the coating compositions are often used in the form of clearcoats, so that they usually have no or only transparent fillers and opaque Contain pigments.
  • the coating compositions contain from 2 to 40% by weight, based on the total weight of the coating agent, of one or more pigments.
  • the coating agents may contain from 1 to 30% by weight, based on the total weight of the coating agent, of one or more fillers.
  • UV-curable coating compositions in the process according to the invention in the form of aqueous preparations.
  • binder dispersion or emulsions are virtually free of environmentally harmful volatiles, such as monomers or cosolvents.
  • the crosslinking according to the process described here under a protective gas atmosphere is carried out after complete evaporation of the water or in spray application additionally after complete escape of the trapped air.
  • a wide variety of substrates can be coated, for example glass, metal substrates, such as aluminum, steel and other iron alloys, furthermore wood, paper, plastics and mineral substrates, for. B. concrete roof tiles and fiber cement boards.
  • the method according to the invention is also suitable for coating packaging containers and for coating films for the furniture industry.
  • the inventive method is characterized in particular by the fact that except planar or largely planar objects and body, d. H. Objects with a three-dimensional design, can be provided with scratch-resistant coatings.
  • the coating compositions according to the invention are preferably applied to primed or basecoat-coated metal surfaces, e.g. As metal sheets or metal bands, three-dimensionally designed metal objects, eg. As molded metal sheets, such as body parts, housing, frame profiles for windows o. ⁇ ., Applied.
  • primers the commonly used basecoats can be used.
  • the basecoat used is both conventional and aqueous basecoats.
  • Equipment for the curing of radiation-curable coatings under normal atmospheric conditions as well as under strict exclusion of oxygen are known to the person skilled in the art (cf., for example, BR Holmes, UV and EB Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kingdom 1984).
  • the process according to the invention can basically be carried out in both plant types.
  • the equipment for curing under normal atmospheric conditions are then provided with additional means by which the areas of the system in which the coating is cured, for example the curing unit in a painting line, with an inert gas or a mixture of inert gas and oxygen or air Reaching the desired oxygen concentration rinse at the cure site.
  • the protective gas supply in the area of the UV source.
  • conventional UV curing equipment which includes a UV curing unit having an entrance and an exit opening and a conveyor which passes the still wet coated article through the entrance opening into the curing unit, past the W source, and then through the exit opening transported out of the curing unit, you can see at least one device for purging with inert gas, for.
  • a nozzle bar in the inlet and the outlet opening and optionally other devices for purging with inert gas in the interior of the curing unit, z. B. in close proximity to the UV source before.
  • the surfaces of uniformly shaped body, z. As bodies and body panels, one can pass similar to the drying zone of a car wash, through an enriched with inert gas region of a UV source. It is also possible to extend the contour of a body which is in the enriched with inert gas region, with a movably arranged UV source.
  • Systems for UV curing of bodies, in particular bodies with a complex three-dimensional shape are known for example from US 4,208,587 and WO 98/53008.
  • the plant types described there can be used in the manner described above be retrofitted in the process according to the invention with suitable flushing devices for inert gas.
  • the UV source used for curing can be provided with nozzles or slots through which, during curing, i. H. of exposing the object provided with the moist coating agent, protective gas constantly flows, so that at the location of the radiation curing, the oxygen concentration is reduced to the value according to the invention.
  • the nozzles or slots are preferably arranged as a ring or ring around the UV source.
  • suitable devices for example by means of a robotic arm (cf. also WO 98/53008).
  • the curing of the coated surfaces by means of UV radiation can of course also take place in externally sealed rooms or chambers with reduced oxygen content in the atmosphere.
  • An advantage of the method according to the invention is that the desired oxygen concentrations can be realized without great technical effort. Also, the amount of inert gas used is less than the amount usually required to achieve a strict exclusion of oxygen, since rinsing with an inert gas sufficient for the establishment of the oxygen concentrations of the invention, which does not lead to complete displacement of the oxygen from the atmosphere located in the curing zone.
  • the process according to the invention can also be described as a process for UV curing of UV-curable coatings under reduced or restricted inert gas atmosphere.
  • the coatings obtained by the process according to the invention have a significantly improved scratch resistance.
  • High scratch resistance is to be understood as a good performance in the Scotch-Brite test.
  • the coatings obtainable according to the invention often have delta-gloss values of not more than 30, whereby values of not more than 20 or not more than 10 are achieved without a complete exclusion of oxygen being required.
  • Example 1 (coating based on a urethane acrylate)
  • Laromer® LR 8987 commercially available mixture of an aliphatic urethane acrylate with 30% by weight of hexanediol diacrylate from BASF AG. Molecular weight about 650 g / mol, Functionality about 2.8 double bonds / mol (about 4.5 mol / kg), Viscosity 2-6 Pa.s (DIN EN ISO 3219).
  • Irgacure I 184 commercially available photoinitiator from Ciba-Geigy.
  • Table 1 Test results of the coating Example 1 when cured under different oxygen levels oxygen content Scratch resistance (loss of gloss) sway 10 DH 50 DH (S) 21% (air) * 50.0 56.4 175 15% 9.5 15.8 183 10% 6.5 11.8 185 7% 6.7 9.3 181 5% 6.7 8.7 183 3% 4.4 8.4 182 1.3% 4.2 9.1 182 0.5% 3.9 8.0 188 340 ppm (inert) * 4.2 9.2 189 * Verglechsbeispiel
  • Laromer® LR 8800 commercial mixture of a polyester acrylate modified with an aromatic epoxy acrylate from BASF AG. Polyester acrylate based on trimethylolpropane and maleic acid. Molecular weight about 900 g / mol, Functionality about 3.5 (about 3.9 mol double bond / kg). Viscosity 4-8 Pa.s (DIN EN ISO 3219). 2 parts Irgacure 1 184: commercially available photoinitiator from Ciba-Geigy.
  • Example 3 (coating based on an oligoether acrylate)
  • Laromer® LR 8863 commercially available oligoether acrylate from BASF AG. Molecular weight about 500 g / mol, Functionality about 3 (about 6.0 mol double bonds / kg), Viscosity about 0.1 Pa.s (DIN EN ISO 3219). 2 parts Irgacure I 184: commercially available photoinitiator from Ciba-Geigy.
  • Table 3 Test results of the coating Example 3 when cured under different oxygen levels oxygen content Scratch resistance (loss of gloss) sway 10 DH 50 DH (S) 21% (air) * nB nB nB 15% nB nB nB 11% 60.3 67.9 164 7% 29.0 51.7 160 5% 2, 3 5.1 175 3% 2.6 6.7 174 1.4% 1.4 3.4 175 0.5% 1.7 4.5 173 340 ppm (inert) * 1.0 3,3 174 * Comparative Example nB: not measurable, because the surface is too soft.
  • Example 4 (coating based on an amine-modified oligoether acrylate)
  • Laromer® LR 8869 commercially available, amine-modified oligoether acrylate from BASF AG. Molecular weight about 550 g / mol, Functionality approx. 3. Viscosity 0.08-0.12 Pa.s (DIN EN ISO 3219). 2 parts Irgacure I 184: commercially available photoinitiator from Ciba-Geigy.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (9)

  1. Procédé de préparation de revêtements antirayures comprenant les étapes suivantes :
    - une application d'au moins un produit de revêtement durcissable par rayonnement U.V. sur au moins une surface d'un objet à revêtir, le produit de revêtement contenant au moins un polymère et/ou oligomère P1 présentant en moyenne au moins une double liaison éthyléniquement insaturée par molécule,
    - un durcissement du produit de revêtement par action du rayonnement U.V.,

    caractérisé en ce qu'on effectue le durcissement du produit de revêtement sous un gaz de protection contenant de l'oxygène qui présente une pression partielle d'oxygène de l'ordre de 0,5 à 18 kPa.
  2. Procédé suivant la revendication 1, caractérisé en ce que le polymère et/ou oligomère P1 présente une teneur en doubles liaisons de l'ordre de 0,01 à 1 mole/100 g de P1.
  3. Procédé suivant l'une des revendications précédentes, caractérisé en ce que le poids moléculaire moyen numérique de P1 est de l'ordre de 400 à 10.000 Daltons.
  4. Procédé suivant l'une des revendications précédentes, caractérisé en ce que les doubles liaisons éthyléniques dans P1 se présentent sous la forme de groupes acrylate, méthacrylate, acrylamido ou méthacrylamido.
  5. Procédé suivant la revendication 4, caractérisé en ce que P1 est choisi parmi des (méth)acrylates d'uréthanne, des (méth)acrylates de polyester, des (méth)acrylates d'oligoéther et des (méth)-acrylates d'époxyde.
  6. Procédé suivant l'une des revendications précédentes, caractérisé en ce que les produits de revêtement durcissables par rayonnement U.V. contiennent, outre P1, un ou plusieurs diluants réactifs.
  7. Procédé suivant la revendication 6, caractérisé en ce que le diluant réactif est choisi parmi des composés comportant un ou deux groupes acrylate et/ou méthacrylate.
  8. Procédé suivant l'une des revendications précédentes, caractérisé en ce que l'objet à revêtir est un corps.
  9. Procédé suivant l'une des revendications précédentes, caractérisé en ce qu'on balaye à l'aide d'un gaz de protection la zone d'une installation dans laquelle le revêtement durcit par action du rayonnement U.V.
EP00967627A 1999-08-25 2000-08-24 Procede de realisation de revetements antirayures Revoked EP1218462B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19940312 1999-08-25
DE19940312A DE19940312A1 (de) 1999-08-25 1999-08-25 Verfahren zur Herstellung kratzfester Beschichtungen
PCT/EP2000/008284 WO2001014483A1 (fr) 1999-08-25 2000-08-24 Procede de realisation de revetements antirayures

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EP1218462A1 EP1218462A1 (fr) 2002-07-03
EP1218462B1 true EP1218462B1 (fr) 2006-02-15

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US (1) US6777458B1 (fr)
EP (1) EP1218462B1 (fr)
DE (2) DE19940312A1 (fr)
WO (1) WO2001014483A1 (fr)

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EP1218462A1 (fr) 2002-07-03
WO2001014483A1 (fr) 2001-03-01
US6777458B1 (en) 2004-08-17
DE19940312A1 (de) 2001-03-01

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