EP1551896A1 - Matiere de revetement thermodurcissable et durcissable par des rayons actiniques et procede de revetement de surfaces microporeuses - Google Patents

Matiere de revetement thermodurcissable et durcissable par des rayons actiniques et procede de revetement de surfaces microporeuses

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Publication number
EP1551896A1
EP1551896A1 EP03757894A EP03757894A EP1551896A1 EP 1551896 A1 EP1551896 A1 EP 1551896A1 EP 03757894 A EP03757894 A EP 03757894A EP 03757894 A EP03757894 A EP 03757894A EP 1551896 A1 EP1551896 A1 EP 1551896A1
Authority
EP
European Patent Office
Prior art keywords
coating material
actinic radiation
material according
groups
thermally
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Withdrawn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
EP03757894A
Other languages
German (de)
English (en)
Inventor
Yvonne Lichte
Heinrich Wonnemann
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 EP1551896A1 publication Critical patent/EP1551896A1/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Withdrawn legal-status Critical Current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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • 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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a new coating material which is curable thermally and with actinic radiation.
  • the present invention relates to a new method for coating, in particular for sealing, microporous surfaces of all kinds, especially the microporous surfaces of moldings made of wood, glass, leather, plastics, metals, minerals, in particular fired and unfired clay, ceramics, nature - and artificial stone or cement; Fiber materials, in particular glass fibers, ceramic fibers, carbon fibers, textile fibers, plastic fibers or metal fibers and composites of these fibers; or fiber-reinforced materials, in particular plastics reinforced with the fibers mentioned above, especially the porous surfaces of SMC (Sheet Molded Compounds) and BMC (Bulk Molded Compounds).
  • SMC Sheet Molded Compounds
  • BMC Bulk Molded Compounds
  • SMC and BMC have long been used for the production of complex shaped sanitary articles, household appliances and components, in particular for the automotive industry, such as mudguards, fenders, doors or reflectors of lamps. Due to their structure and material composition based on glass fibers, the SMC and BMC are highly temperature-resistant and can withstand temperatures of 190 to 200 ° C. They show only a slight deformation. In addition, the complex articles can be manufactured more easily and with greater accuracy with this technology than with reinforced thermoplastic materials.
  • SMC and BMC are microporous and therefore cannot be coated directly, because microbubbles are formed in the coating at 70 to 80 ° C by outgassing monomers such as styrene.
  • the coating material known from the German patent application and curable with actinic radiation contains
  • (a1) at least one constituent, for example a urethane (meth) acrylate, with (a11) at least two functional groups, for example acrylate groups, which are used for crosslinking with actinic radiation, and if appropriate
  • (a12) at least one functional group, in particular hydroxyl groups, which can undergo thermal crosslinking reactions with a complementary functional group (a22) in component (a2),
  • (a22) at least one functional group, in particular an isocyanate group, which can undergo thermal crosslinking reactions with a complementary functional group (a12) in component (a1),
  • the coating material contains at least one thermally curable component (a7) if the component (a1) has no functional group (a12).
  • the known coating material may contain, as constituents (a7), thermally curable binders and / or crosslinking agents, for example blocked polyisocyanates. Unblocked polyisocyanates are not used as components (a7).
  • the known coating material can contain electrically conductive pigments as a paint additive (a6).
  • the well-known coating material provides coatings and seals that effectively suppress the formation of microbubbles without great effort and have a smooth surface free of surface structures such as orange peel, which does not require post-treatment, and can be easily and safely overpainted without problems of interlayer adhesion thereafter result.
  • the ability to be overpainted is retained even if the seal or primer layer on electrically conductive surfaces is overpainted with an electrocoat. This enables the corresponding SMC or BMC to be directly coated in, for example, uncoated Install car bodies and coat them electrophoretically in the same way as the metal parts.
  • the known coating material and the coatings produced from it have to be further improved by means of electrostatic high-rotation processes (ESTA) or by means of electrophoretic dip coating, despite the high technological level already achieved with regard to sandability and polishability, mechanical flexibility, adhesion, interlayer adhesion and overpaintability. to meet the increased demands of the market.
  • ESA electrostatic high-rotation processes
  • electrophoretic dip coating despite the high technological level already achieved with regard to sandability and polishability, mechanical flexibility, adhesion, interlayer adhesion and overpaintability. to meet the increased demands of the market.
  • the coating of complex shaped molded parts does not yet fully meet the increasing demands of the market.
  • the hardening of the coatings in the shadow zones of the molded parts is often not sufficient to ensure good sandability and polishability of the coatings, in particular the seals.
  • this is particularly disadvantageous in the production of particularly high-quality SMC and BMC.
  • Coating materials curable thermally and with actinic radiation are known from German patent applications DE 199 30 665 A1, DE 199 30 067 A1 and DE 199 30 664 A1 or DE 199 24 674 A1 which contain at least one thermally curable constituent with at least two Isocyanate-reactive groups, which are necessarily copolymers of olefinically unsaturated monomers with 1, 1-diphenylethylene and its derivatives. Problems associated with the coating of a microporous surface and possible solutions for this are not addressed.
  • the coating material can contain an electrically conductive pigment, such as a pigment based on mica (Minatec® 40th CM from Merck).
  • an electrically conductive pigment such as a pigment based on mica (Minatec® 40th CM from Merck).
  • the use of saturated aromatic polyisocyanates is not described, but it is specifically only emphasized on the (cyclo) aliphatic polyisocyanates.
  • the new coating material should allow thermal curing to be carried out at temperatures of ⁇ 120 ° C.
  • the new coatings and seals should be of high mechanical flexibility and have very good adhesion to a wide variety of substrates. In addition, they should be easy to paint over.
  • the new thermally and actinic radiation-curable coating material has been found to contain
  • the new coating material curable thermally and with actinic radiation is referred to as “coating material according to the invention”.
  • the new process for coating microporous surfaces has been found, in which the surfaces in question are coated with at least one thermally and actinic radiation-curable coating material, after which the resulting layer (s) are thermally cured and with actinic radiation, where as Coating material at least one coating material according to the invention is used.
  • the new process for coating microporous surfaces is referred to below as the “process according to the invention”.
  • molded parts according to the invention The new coated, in particular sealed, molded parts are referred to below as “molded parts according to the invention” and the corresponding SMC and BMC as “compounds according to the invention”.
  • the coating material according to the invention had a particularly wide processing window and therefore can be carried out without problems even under difficult technical and climatic conditions with technologically outdated devices and systems and / or at comparatively high or low temperatures and / or comparatively low or high air humidity caused improved curing properties, especially in the shadow zones of complex shaped three-dimensional moldings, and provided coatings, in particular seals, on a wide variety of microporous surfaces that had excellent sandability and polishability.
  • the coatings and seals of the invention were high mechanical flexibility and had excellent adhesion to a wide variety of substrates and excellent interlayer adhesion.
  • the coating material of the invention is curable thermally and with actinic radiation.
  • thermal hardening means the heat-initiated hardening of a layer of a coating material, in which a crosslinking agent that is usually present is used. Usually this is referred to by experts as external crosslinking.
  • actinic radiation means electromagnetic radiation such as near infrared (NIR), visible light, UV radiation or X-rays, in particular UV radiation, or corpuscular radiation such as electron beams.
  • NIR near infrared
  • UV radiation visible light
  • UV radiation UV radiation
  • X-rays UV radiation
  • corpuscular radiation such as electron beams.
  • the coating material of the invention contains at least one constituent (a1) with a statistical average of at least two, in particular at least three, functional groups (a11) per molecule which contain at least one, in particular one, bond which can be activated with actinic radiation and which serves for crosslinking with actinic radiation , and optionally at least one, in particular at least two, isocyanate-reactive group (s) (a12). It is preferred that the radiation-curable binders are UV-curable. It is further preferred if component (a1) contains essentially no, particularly preferably none, groups (a12).
  • Component (a1) preferably contains on average no more than six, in particular no more than five functional groups (a11) per molecule.
  • bonds which can be activated with actinic radiation are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds.
  • bonds in particular the carbon-carbon double bonds, are preferably used.
  • Suitable carbon-carbon double bonds are, for example, in (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isoprenyl, isopropenyl, allyl - or butenyl groups; Ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups.
  • (meth) acrylate groups, in particular acrylate groups are of particular advantage and are therefore used with very particular preference in accordance with the invention.
  • Suitable isocyanate-reactive groups (a12) are thiol, primary or secondary amino, imino or hydroxyl groups, especially hydroxyl groups.
  • the component (a1) is oligomeric or polymeric.
  • an oligomer is understood to mean a compound which generally has on average 2 to 15 basic structures or monomer units.
  • a polymer is understood to mean a compound which generally has on average at least 10 basic structures or monomer units.
  • Compounds of this type are also referred to by experts as binders or resins.
  • a low-molecular compound is to be understood as a compound which essentially derives only from a basic structure or a monomer unit.
  • Compounds of this type are generally referred to by the experts as reactive thinners.
  • the polymers or oligomers used as binders (a1) usually have a number average molecular weight of 500 to 50,000, preferably 1,000 to 5,000. They preferably have a double bond equivalent weight of 400 to 2,000, particularly preferably 500 to 900. In addition, they preferably have a viscosity of 250 to 11,000 mPas at 23 ° C.
  • binders or resins (a1) come from the oligomer and / or polymer classes of the (meth) acrylic-functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and phosphazene acrylates and the corresponding methacrylates.
  • Binders (a1) which are free from aromatic structural units are preferably used. Urethane (meth) acrylates, phosphazene (meth) acrylates are therefore preferred and / or polyester (meth) acrylates, particularly preferred
  • Urethane (meth) acrylates in particular aliphatic urethane (meth) acrylates, are used.
  • the urethane (meth) acrylates (a1) are obtained by reacting a di- or polyisocyanate with a chain extender from the group consisting of diols / polyols and / or diamines / polyamines and / or dithiols / polythiols and / or alkanolamines and then reacting the remaining free ones Isocyanate groups with at least one hydroxyalkyl (meth) acrylate or hydroxyalkyl ester of other ethylenically unsaturated carboxylic acids.
  • chain extenders di- or polyisocyanates and hydroxyalkyl esters are preferably chosen so that
  • the equivalent ratio of the NCO groups to the reactive groups of the chain extender is between 3: 1 and 1: 2, preferably 2: 1, and
  • the OH groups of the hydroxyalkyl esters of the ethylenically unsaturated carboxylic acids are present in a stoichiometric amount with respect to the free isocyanate groups of the prepolymer of isocyanate and chain extender.
  • the urethane (meth) acrylates by first reacting part of the isocyanate groups of a di- or polyisocyanate with at least one hydroxyalkyl ester and then reacting the remaining isocyanate groups with a chain extender.
  • the amounts of chain extender, isocyanate and hydroxyalkyl ester become so selected that the equivalent ratio of the NCO 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 NCO groups to the OH groups of the hydroxyalkyl ester is 1: 1.
  • all intermediate forms of these two processes are also possible.
  • part of the isocyanate groups of a diisocyanate can first be reacted with a diol, then another part of the isocyanate groups can be reacted with the hydroxyalkyl ester and then the remaining isocyanate groups can be reacted with a diamine.
  • the urethane (meth) acrylates (a1) can be made more flexible, for example, by reacting corresponding isocyanate-functional prepolymers or oligomers with longer-chain, aliphatic diols and / or diamines, in particular aliphatic diols and / or diamines with at least 6 C atoms , This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
  • Viaktin® VTE 6160 from Vianova, Austria
  • Laromer® 8861 from BASF AG as well as test products developed from it.
  • Urethane (meth) acrylates (a1) containing hydroxyl groups are known, for example, from US Pat. Nos. 4,634,602 A or 4,424,252 A.
  • polyphosphazene (meth) acrylate (a1) is the phosphazene dimethacrylate from Idemitsu, Japan.
  • Ebecryl® 8210, Laromer® LR8987 and Laromer® UA19T are particularly preferably used.
  • component (a1) in an amount of 5 to 50% by weight, preferably 6 to 45% by weight, particularly preferably 7 to 40% by weight, very particularly preferably 8 to 35% by weight and in particular 9 up to 30 wt .-%, each based on the solid of the coating material of the invention applied.
  • the coating material contains at least one thermally curable component (a2) with at least two, in particular at least three, isocyanate-reactive groups.
  • thermally curable component (a2) with at least two, in particular at least three, isocyanate-reactive groups.
  • isocyanate-reactive groups are those described above, especially hydroxyl groups.
  • the component (a2) is oligomeric or polymeric.
  • Suitable constituents (a2) are linear and / or branched and / or block-like, comb-like and / or randomly constructed oligomers or polymers, such as (meth) acrylate (co) polymers, polyesters, alkyds,
  • Aminoplast resins polyurethanes, polylactones, polycarbonates, polyethers, Epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters or polyureas, of which the (meth) acrylate copolymers, the polyesters, the polyurethanes, the polyethers and the epoxy resin-amine adducts, but especially the polyesters, are advantageous.
  • Suitable binders (a2) are, for example, under the trade names Desmophen® 650, 2089, 1100, 670, 1200 or 2017 from Bayer, under the trade names Priplas or Pripol® from Uniqema, under the trade names Chempol® polyester or polyacrylate polyol from the company CCP, under the trade names Crodapol® 0-25, 0-85 or 0-86 from the company Croda, Setal® 1615 or 1715 from the company Akzo, under the trade name Dobeckan ® IU 080014 from the company Schenectady-Beck Elektroisoliersysteme or sold by Witco under the trade name Formrez® ER417.
  • the binders (a2) preferably have a mass-average molecular weight of 500 to 10,000 daitons, preferably 1000 to 5000 daltons, and a hydroxyl number of 80 to 160 mg KOH / g.
  • Setal® 1615, Setal® 1715, Desmophen® 650 and Desmophen® 670 are preferably used as binders (a2).
  • the proportion of constituents (a2) in the coating materials can vary widely and depends on the requirements of the individual case. They are preferably used in an amount of 5 to 90% by weight, preferably 6 to 80% by weight, particularly preferably 7 to 70% by weight, very particularly preferably 8 to 60% by weight and in particular 9 to 50% by weight. %, each based on the solids of the coating material, applied.
  • the coating material further contains at least one aromatic polyisocyanate (a3) free of functional groups (a11).
  • the aromatic polyisocyanates (a3) contain on average at least 2.0, preferably more than 2.0 and in particular more than 3.0 isocyanate groups per molecule. There is basically no upper limit to the number of isocyanate groups; According to the invention however, it is advantageous if the number of 15, preferably 12 ⁇ more preferably 10, most preferably 8.0, and especially does not exceed 6.0.
  • Suitable aromatic polyisocyanates (a3) are polyurethane prepolymers containing isocyanate groups, which can be prepared by reacting polyols with an excess of aromatic diisocyanates and are preferably of low viscosity.
  • aromatic diisocyanates 1, 2- 1, 3- and 1, 4-benzene diisocyanate, 2,4- and 2,6-toyulenediisocyanate, 4,4 ' -
  • Biphenylene diisocyanate bis (4 ⁇ isocyanatophenyl) methane, 2,2-bis (4-isocyanatophenyl) propane and the positional isomers
  • Naphthalene diisocyanates in particular the technical mixtures of 2,4- and 2,6-tolylene diisocyanate.
  • aromatic polyisocyanates (a3) which contain isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide and / or uretdione groups and are prepared in a customary and known manner from the aromatic diisocyanates described above , Example more suitable
  • aromatic polyisocyanates described in German patent application DE 196 09 617 A1 with aromatic isocyanate-reactive functional groups containing dioxanes, dioxolanes and oxazolidines, which still contain free isocyanate groups, are suitable as aromatic polyisocyanates (a3).
  • the aromatic polyisocyanates (a3) can be used together with cycloaliphatic and / or aliphatic polyisocyanates free of functional groups (a11), resulting in the mixture (a3).
  • the cycloaliphatic and aliphatic polyisocyanates free of functional groups (a11) also contain on average at least 2.0, preferably more than 2.0 and in particular more than 3.0 isocyanate groups per molecule. There is basically no upper limit to the number of isocyanate groups; According to the invention, however, it is advantageous if the number does not exceed 15, preferably 12, particularly preferably 10, very particularly preferably 8.0 and in particular 6.0.
  • Suitable aliphatic and cycloaliphatic polyisocyanates are isocyanate-containing polyurethane prepolymers which are obtained by reacting polyols with an excess of aliphatic and Cycloaliphatic diisocyanates can be prepared and are preferably low viscosity.
  • aliphatic and cycloaliphatic polyisocyanates which contain isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide and / or uretdione groups and which are prepared in a customary and known manner from the aliphatic and cycloaliphatic diisocyanates described above become.
  • suitable production processes are also from the patent specifications CA 2,163,591 A, US 4,419,513, US 4,454,317 A, EP 0 646 608 A, US 4,801, 675 A, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A.
  • EP 0 496 208 A1 EP 0 524 500 A1, EP 0 566 037 A1, US 5,258,482 A1, US 5,290,902 A1, EP 0 649 806 A1, DE 42 29 183 A1, EP 0 531 820 A 1 or DE 100 05 228 A 1 known.
  • the aromatic polyisocyanates (a3) are preferably selected from the group of polyisocyanates based on the technical mixtures of 2,4- and 2,6-toluenediisocyanate.
  • the (cyclo) aliphatic polyisocyanates are preferably selected from the group consisting of polyisocyanates based on hexamethylene diisocyanate and based on isophorone diisocyanate.
  • a minor part of the aromatic polyisocyanates (a3) and / or the (cyclo) aliphatic polyisocyanates can be blocked with customary and known blocking agents.
  • a subordinate part is to be understood as meaning amounts which vary the technological profile of properties of the polyisocyanates (a3) in an advantageous manner, but do not characterize them.
  • 5 to 80 mol%, in particular 20 to 45 mol%, of the aromatic polyisocyanates (a3) and / or the (cyclo) aliphatic polyisocyanates are preferably blocked.
  • the (cyclo) aliphatic polyisocyanate hardeners preferably have an NCO content of 15 to 25%.
  • the aromatic polyisocyanate hardeners preferably have an NCO content of 10 to 15%.
  • the content of aromatic polyisocyanates (a3) or of the mixture (a3) of at least one aromatic polyisocyanate (a3) and at least one aliphatic and / or cycloaliphatic polyisocyanate in the coating materials according to the invention can vary very widely and depends on the requirements of the individual case, in particular the content of components (a2) and optionally (a1) in isocyanate-reactive groups.
  • the content is preferably 5 to 60 % By weight, preferably 5 to 55% by weight, particularly preferably 5 to 50% by weight, very particularly preferably 5 to 45% by weight and in particular 5 to 40% by weight, in each case based on the solids content of the coating material of the invention.
  • the quantitative ratio of aromatic polyisocyanate (a3) to (cyclo) aliphatic polyisocyanate in the mixture (a3) is 95: 5 to 5:95, preferably 85:15 to 15:85 and in particular 80:20 to 20:80.
  • the coating material of the invention can also contain at least one pigment and / or a filler. These can be coloring and / or effect-giving, fluorescent, electrically conductive and / or magnetically shielding pigments, metal powder, scratch-resistant pigments, organic dyes, organic and inorganic, transparent or opaque fillers and / or nanoparticles.
  • the coating material of the invention is used to produce electrically conductive seals, it preferably contains at least one electrically conductive pigment and / or at least one electrically conductive filler.
  • Suitable effect pigments are platelet pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes and non-metallic effect pigments, such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide and brown, a shade of pink has or liquid crystalline effect pigments.
  • suitable inorganic color pigments are white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron-manganese black or spinel black; Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.
  • white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone
  • Black pigments such as carbon black, iron-manganese black or spinel black
  • suitable organic coloring pigments are monoazo pigments, bisazo pigments, anthraquinone pigments, and
  • Benzimidazole pigments quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments,
  • Thioindigo pigments metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments or aniline black.
  • fluorescent pigments are bis (azomethine) pigments.
  • Suitable electrically conductive pigments are e.g. Pigments with a pigment content of 20 to 25 wt .-%, based on the total solids of the composition, from one
  • Dry film layer thickness of 60 ⁇ m cause opacity to black / white contrast.
  • These pigments are preferably transparent to actinic radiation, in particular UV radiation.
  • Particularly suitable electrically conductive pigments of this type are pigments based on mica or mica, which are coated with metal oxide layers, in particular antimony-tin mixed oxide layers.
  • Particularly suitable conductive mica pigments are marketed by Merck under the brand Minatec ® 40 CM, 31 CM or 30 CM ("Conductive Mica").
  • magnétiqueally shielding pigments examples include pigments based on iron oxides or chromium dioxide.
  • suitable metal powders are powders made of metals and metal alloys such as aluminum, zinc, copper, bronze or brass.
  • Suitable soluble organic dyes are lightfast organic
  • the specialist can determine the tendency to migrate assess his general specialist knowledge and / or determine it with the help of simple preliminary tests, for example in the context of tinting tests.
  • organic and inorganic fillers are chalk, calcium sulfates, barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular made of polyamide or polyacrylonitrile.
  • silicates such as talc, mica or kaolin
  • silicas oxides such as aluminum hydroxide or magnesium hydroxide
  • organic fillers such as plastic powder, in particular made of polyamide or polyacrylonitrile.
  • suitable transparent fillers are those based on silicon dioxide, aluminum oxide or zirconium oxide, but in particular nanoparticles based on this.
  • Fillers which are transparent to actinic radiation, in particular UV radiation, such as Mircavor® 20, Mistron® Monomix and Blancfix® N or F are particularly preferably used.
  • the electrically conductive coating materials according to the invention very particularly preferably comprise at least one of the electrically conductive mica pigments described above and at least one of the fillers described above which are transparent to UV radiation.
  • the content of the pigments and / or fillers described above in the coating material according to the invention can vary very widely and depends on the requirements of the individual case. Based on the solids content of the coating material, it is preferably 5 to 50, more preferably 5 to 45, particularly preferably 5 to 40, very particularly preferably 5 to 35 and in particular 5 to 30% by weight.
  • the coating material of the invention can contain at least one tackifier.
  • Tackifiers are polymeric additives for adhesives that increase their tack, i.e. their inherent stickiness or self-adhesion, so that they adhere firmly to surfaces after a short pressure (cf.Ullmann 's Encyclopedia of Industrial Chemistry, CD-ROM, Wiley VCH, Weinheim, 1997, "tackifier").
  • Suitable tackifiers are highly flexible resins selected from the group consisting of
  • alkyl (meth) acrylates especially alkyl acrylates, such as poly (isobutyl acrylate) or poly (2-ethylhexyl acrylate), which are sold under the Acronal® brand by BASF Aktiengesellschaft, under the Elvacite® brand by Dupont, under the Brand Neocryl® from Avecia and Plexigum® from Roehm;
  • linear polyesters as are used in the usual way for coil coating and are sold, for example, under the Dynapol® brand by Dynamit Nobel, under the Skybond® brand by SK Chemicals, Japan, or under the trade name LTW by Degussa ;
  • non-reactive urethane-urea oligomers made from bis (4,4-isocyanatophenyl) methane, N, N-dimethylethanolamine and diols such as propanediol, hexanediol or dimethylpentanediol and e.g. are marketed by Swift Reichold under the Swift Range® brand or Mictchem Chemicals under the Surkopack® or Surkofilm® brands.
  • the tackifiers are preferably used in an amount of 0.1 to 10% by weight, preferably 0.2 to 9% by weight, particularly preferably 0.3 to 8% by weight, very particularly preferably 0.4 to 7% by weight. % and in particular 0.56% by weight, based in each case on the solids of the coating material of the invention.
  • the coating material of the invention can contain at least one photoinitiator. If the coating material is to be crosslinked with UV radiation, the use of a photoinitiator is generally necessary. If they are also used, they are preferably in the coating material in proportions of 0.1 to 10% by weight, preferably 0.2 to 8% by weight, particularly preferably 0.3 to 7% by weight, very particularly preferred 0.4 to 6 wt .-% and in particular 0.5 to 5 wt .-%, each based on the solids of the coating material.
  • photoinitiators examples include those of the Norrish II type, the mechanism of which is based on an intramolecular variant of the hydrogen abstraction reactions, as occurs in a variety of ways in photochemical reactions (examples here are from Römpp Chemie Lexikon, 9th extended and revised edition, Georg Thieme Verlag Stuttgart, Vol. 4, 1991) or cationic photoinitiators (for example, refer to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446), in particular benzophenones, benzoins or benzoin ethers or phosphine oxides.
  • Irgacure® 184 Irgacure® 1800 and Irgacure® 500 from Ciba Geigy
  • Grenocure® MBF from Rahn
  • Lucirin® TPO from BASF AG
  • the coating material of the invention can contain at least one initiator of the thermal crosslinking. From 80 to 120 ° C, these form radicals that start the crosslinking reaction.
  • thermolabile free-radical initiators are organic peroxides, organic azo compounds or CC-cleaving initiators such as dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.
  • CC-cleaving initiators are particularly preferred, since during their thermal cleavage no gaseous decomposition products are formed which could lead to disturbances in the sealing.
  • the coating material according to the invention can contain at least one reactive thinner that is curable with actinic radiation and / or thermally.
  • thermally curable reactive diluents are positionally isomeric diethyloctanediols or hydroxyl group-containing hyperbranched compounds or dendrimers, as described in patent applications DE 198 09 643 A1, DE 198 40 605 A1 or DE 198 05421 A1.
  • Suitable reactive diluents are polycarbonate diols, polyester polyols, poly (meth) acrylate diols or polyadducts containing hydroxyl groups.
  • reactive solvents which can be used as reactive diluents 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 ether, diethylene glycol monobutyl ether,
  • Reactive diluents which can be crosslinked with actinic radiation are, for example, (meth) acrylic acid and its esters, maleic acid and its esters or half esters, vinyl acetate, vinyl ether, vinyl ureas and others.
  • examples include alkylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate,
  • reactive thinners curable with actinic radiation are those described in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword “reactive thinners”.
  • the reactive diluents are used in an amount of preferably 2 to 70% by weight, particularly preferably 10 to 65% by weight and in particular 15 to 50% by weight, in each case based on the solids content of the coating material ,
  • the coating material of the invention can also contain at least one customary and known isocyanatoacrylate.
  • isocyanatoacrylates are described in European patent application EP 0
  • the coating material of the invention can also contain at least one crosslinking agent, as is usually used for thermal crosslinking in one-component systems.
  • crosslinking agents are aminoplast resins, as described, for example, in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, page 29, “Aminoharze”, the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff., The book “Paints, Coatings and Solvents", second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP-B-0 245 700 A1 as well as in the article by B.
  • the coating material of the invention may further contain water and / or at least one inert inorganic or organic solvent.
  • inorganic solvents are liquid nitrogen and supercritical carbon dioxide.
  • suitable organic solvents are the low-boiling solvents or high-boiling ("long") solvents usually used in the paint field, such as ketones such as methyl ethyl ketone, methyl isoamyl ketone or methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate, ethyl ethoxypropionate, methoxypropyl acetate or butyl glycol acetate, ethers or ethylene dibutyl acetate, ethers such as dibutyl glycol acetate, Diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol or dibutylene glycol dimethyl, diethyl or dibutyl ether, N-methylpyrrolidone or xylenes or mixtures of aromatic and / or aliphatic hydrocarbons such as solvent naphtha®,
  • the coating material of the invention can contain at least one customary and known paint additive in effective amounts, i.e. in amounts of preferably up to 40% by weight, particularly preferably up to 30% by weight and in particular up to 20% by weight, in each case based on the solids content of the coating material.
  • paint additives examples include UV absorbers, light stabilizers, free radical scavengers, catalysts for crosslinking such as dibutyltin dilaurate or lithium decanoate, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents, adhesion promoters, flow control agents, film-forming aids such as cellulose derivatives, flame retardants, sag control. rheology-controlling additives or matting agents.
  • the coating material of the invention can be in various forms. With a corresponding choice of its components (a1), (a2) and (a3) described above and any other components that may be present, it can be present as a liquid coating material which is essentially free of organic solvents and / or water (100% system ). However, the coating material can be a solution or dispersion of the components described above in water and / or organic solvents. A further advantage of the aqueous and the conventional coating material is that solids contents of up to 80% by weight, based on the coating material, can be set.
  • the coating material according to the invention can be a powder clearcoat if the components described above are selected accordingly.
  • This powder clearcoat can optionally be dispersed in water, resulting in a powder slurry clearcoat.
  • the coating material of the invention allows the coating material of the invention to be a one-component system. However, if there is a risk that the constituents mentioned will thermally crosslink prematurely, it is advisable to design the coating material of the invention as a two- or multicomponent system in which at least constituent (a3) is stored separately from the other constituents and only shortly before use in the process according to the invention is added.
  • the production of the coating material according to the invention does not offer any special features in terms of method, but instead takes place in a customary and known manner by mixing the components described above in suitable mixing units, such as stirred kettles, dissolvers, Ultraturrax, inline dissolvers, gear rim dispersing units. Pressure relief homogenizers, microfluidizers, agitator mills or extruders. It is important to ensure that there is no premature crosslinking induced by visible light or other actinic radiation.
  • the process according to the invention is used for coating, in particular sealing, microporous surfaces which generally have pores with a width of 10 to 1,500, preferably 20 to 1,200 and in particular 50 to 1,000 nm.
  • the surfaces can be electrically conductive or electrically insulating.
  • the electrically conductive surfaces are metallic or non-metallic.
  • Non-metallic conductive surfaces consist, for example, of electrically conductive ceramic materials, in particular oxides and chalcogenides, or electrically conductive polymers.
  • microporous surfaces are preferably the surfaces of molded parts made of materials selected from the group consisting of wood, glass, leather, plastics, minerals, foams, fiber materials and fiber-reinforced materials, metals and metallized materials.
  • Foams i. S. of DIN 7726: 1982-05 are materials with open and / or closed cells distributed over their entire mass and a bulk density that is lower than that of the framework substance.
  • elastic and soft elastic foams i. S. of DIN 53580 see also Römpp Lexikon Chemie, CD-ROM: Version 2.0, Georg Thieme Verlag, Stuttgart, New York, 1999, "Foams").
  • the metallized materials are preferably wood, glass, leather, plastics, minerals, foams, fiber materials and fiber-reinforced materials.
  • the minerals are preferably fired and unfired clay, ceramics, natural or artificial stone or cement
  • the fiber materials are glass fibers, ceramic fibers, carbon fibers, textile fibers, plastic fibers or metal fibers and composites of these fibers
  • the fiber-reinforced materials are plastics that are reinforced with the above fibers.
  • the metals are preferably reactive consumer metals, in particular iron, steel, zinc, aluminum, magnesium, titanium and the alloys of at least two of these metals.
  • the molded parts are preferred
  • Components for motor vehicle construction in particular parts of motor vehicle bodies, such as mudguards, fenders, spoilers, bonnets, doors or reflectors of lamps,
  • the molded parts are SMC (sheet molded compounds) or BMC (bulk molded compounds).
  • SMC and BMC can have a wide variety of technological properties and a wide variety of properties.
  • "Semi-finished products" ie the mixture that has not yet been processed in the mold
  • SMC and BMC contain unsaturated polyesters, fillers of all kinds, glass fibers and additives such as inhibitors to improve storage stability and initiators to start the polymerization as well as mold release agents.
  • About the choice of SMC / BMC pigments can also be made conductive. Due to the fillers, SMC / BMC can draw moisture.
  • the processing of the semifinished product into the molded part sets the viscosity, density, strength and other factors via the exact composition of possible porosity, additive concentration on the surface of the molded part and structure, these features generally having a negative effect on the adhesion of coatings. It is a particular merit of the coating materials according to the invention and the method according to the invention that the seals and Beschic attachments to a wide variety of SMC and BMC.
  • the coating material to be used according to the invention is applied to the surface of the moldings, in particular the BMC and SMC.
  • One or more layers of the coating material according to the invention can be used in the process according to the invention be applied. If several layers are applied, coating materials of different material composition according to the invention can be used. In most cases, however, the desired property profile of the molded parts and compounds according to the invention is achieved with a coating made of a coating material.
  • the layer of the coating material is applied in a wet layer thickness that results in a dry layer thickness of the seal of 10 to 100, preferably 10 to 75, particularly preferably 10 to 55 and in particular 10 to 50 ⁇ m after curing in the finished molded part or compound according to the invention.
  • the application of the coating material according to the invention can be carried out by all customary application methods, e.g. Spraying, knife coating, painting,
  • Spray application possibly combined with hot spray application such as hot air hot spraying.
  • the application can be used for
  • Temperatures of max. 70 to 80 ° C are carried out so that suitable application viscosities are achieved without a change in the short-term thermal load or
  • hot spraying can be designed in such a way that the coating material is only heated very briefly in or shortly before the spray nozzle.
  • the spray booth used for the application can be operated, for example, with a circulation that can be tempered if necessary a suitable absorption medium for the overspray, e.g. B. the coating material of the invention itself is operated.
  • the application is preferably carried out when illuminated with visible light of a wavelength of over 550 ⁇ m or with exclusion of light. This avoids material changes or damage to the coating material according to the invention and the overspray.
  • the layer of the coating material according to the invention is cured thermally and with actinic radiation after its application, so that the sealing according to the invention results.
  • Curing can take place after a certain period of rest. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 30 min.
  • the idle time is used, for example, for the course and degassing of the layer from the coating material or for the evaporation of volatile constituents such as solvents, water or carbon dioxide if the coating material has been applied with supercritical carbon dioxide as a solvent.
  • the drying that takes place during the rest period can be supported and / or shortened by using elevated temperatures of up to 80 ° C, provided that there is no damage or changes to the coating material layer, such as premature complete crosslinking.
  • Curing is preferably carried out using UV radiation or electron beams.
  • work is preferably carried out under an inert gas atmosphere or an oxygen-depleted atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the layer made of the coating material according to the invention. Even in the case of curing with UV radiation, in order to avoid the formation of ozone, work can be carried out under an inert gas or in an oxygen-depleted atmosphere.
  • the usual and known radiation sources and optical auxiliary measures are used for curing with actinic radiation.
  • suitable radiation sources are high-pressure or low-pressure mercury lamps or electron beam sources.
  • Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters.
  • shadow areas such as cavities, folds and other undercuts due to construction, can be combined with point, small area or all-round emitters with an automatic movement device for irradiating cavities or Edges are (partially) cured.
  • the curing can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, curing alternately with UV radiation and electron radiation.
  • the thermal curing also has no special features in terms of method, but is carried out according to the customary and known methods, such as heating in a forced air oven or irradiation with IR lamps. As with actinic radiation curing, thermal curing can also be carried out in stages.
  • the thermal curing is advantageously carried out at a temperature of up to 120 ° C., particularly preferably up to 110 ° C., very particularly preferably up to 100 ° C. and in particular up to 90 ° C., preferably for a time of 1 min to 2 h, preferably 2 min to 1 h and in particular 3 to 30 min.
  • Thermal curing and curing with actinic radiation can be used simultaneously or alternately. If the two curing methods are used alternately, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, it may prove advantageous to start with the end of curing with actinic radiation.
  • the person skilled in the art can determine the hardening method which is most advantageous for the individual case on the basis of his general specialist knowledge, if necessary with the aid of simple preliminary tests.
  • the layers of the coating materials according to the invention can also be cured excellently in the shadow zones of the molded parts.
  • the moldings and SMC and BMC coated with the coating material according to the invention can be immediately overpainted after drying and irradiation with actinic radiation, preferably in a state which is not fully cured, which is important for the production of the inventive Molded parts and the SMC and BMC according to the invention means significant time, energy and cost savings.
  • an electrically non-conductive coating material according to the invention is applied to the SMC and BMC.
  • the applied layers are partially hardened with actinic radiation, in particular UV radiation.
  • the partially hardened layers are then coated with a customary and known electrically conductive two-component coating material (two-component guide primer), or with an electrically conductive coating material according to the invention, in particular a two-component guide primer, after which the two layers are thermally cured together.
  • the molded parts and SMC and BMC coated with the coating material according to the invention can be thermally post-cured after drying and irradiation with actinic radiation, for example for 20 minutes at 90 ° C., after which the molded parts according to the invention and the SMC and BMC according to the invention until further processing, in particular for overpainting, can be stored in stacks without problems of sticking or deforming.
  • the electrically conductive coatings and seals according to the invention are outstandingly suitable for the application of further coating materials with the aid of electrostatic high rotation (ESTA) or with the aid of electrophoretic application processes such as anodic or cathodic electrocoating.
  • the molded parts and compounds according to the invention obtained in the procedure according to the invention show no signs of microbubbles (microbubbling or blistering). Their surface is smooth and free from interference. Their thermal stability is excellent: the surface is not damaged even after several hours of thermal stress at high temperatures.
  • the molded parts and compounds according to the invention can therefore, for example, be installed directly in uncoated automobile bodies and, together with them in the line - also electrophoretically - painted.
  • the coatings and seals obtained in the process according to the invention have excellent flexibility and excellent adhesion to a wide variety of substrates, so that the moldings and compounds according to the invention can be easily deformed without the coatings thereon being mechanically damaged. They are also extremely easy to grind and polish, so that damaged areas can be repaired very easily.
  • the coatings and seals can be applied with all customary and known aqueous or conventional, liquid or solid, anhydrous and solvent-free, physically or thermally and / or with actinic radiation-primers, electrocoat materials, fillers or stone chip protection primers, color and / or effect uni-paint or basecoats as well as clear coats.
  • the resulting multicoat paint systems have excellent intercoat adhesion.
  • a mixed lacquer was first prepared by mixing and homogenizing the following components in the order given:
  • the coating material of preparation example 1 was prepared shortly before application by mixing and homogenizing 100 parts by weight of the mixed lacquer and 10 parts by weight of a 75% by weight solution of a technical mixture of 2,4- and 2,6-tolylene diisocyanate in ethyl acetate (Desmodur® L 75 manufactured by Bayer AG (isocyanate content: 11.5 to 13%).
  • the coating material of preparation example 2 was prepared shortly before application by mixing and homogenizing 100 parts by weight of the mixed lacquer, 5 parts by weight of a 75% by weight solution of a technical mixture of 2,4- and 2,6-tolylene diisocyanate in ethyl acetate (Desmodur® L 75 from Bayer AG (isocyanate content: 11.5 to 13%) and 5 parts by weight of a 90% by weight solution of the trimers of hexamethylene diisocyanate in solvent naphtha® (Desmodur® N3300 from Bayer diluted to a 90% solution) ,
  • a mixed lacquer was first produced by mixing and homogenizing the following components in the order given:
  • the coating material of manufacturing example 3 was shortly before
  • the coating material of preparation example 4 was prepared shortly before application by mixing and homogenizing 100 parts by weight of the mixed lacquer, 5 parts by weight of a 75% by weight solution of a technical mixture of 2,4- and 2,6-tolylene diisocyanate in ethyl acetate (Desmodur ⁇ L 75 from Bayer AG (isocyanate content: 11.5 to 13%) 5 parts by weight of a 90% by weight solution of the trimers of hexamethylene diisocyanate in solvent naphtha® (Desmodur® N3300 from Bayer diluted to a 90% solution).
  • Example 1 to 4 the coating materials of preparation examples 1 to 4 were applied to a wide variety of porous surfaces, in particular SMC and BMC, using customary pneumatic or electrostatic methods.
  • the resulting layers of the coating materials were flashed off and dried and then irradiated with UV radiation.
  • the resulting layers of the coating materials of preparation examples 1 and 2 were flashed off and dried and then irradiated with UV radiation. They were then thermally hardened at 90 ° C. for 20 minutes. This resulted in hardened, electrically conductive (Examples 1 and 2) and non-conductive (Examples 3 and 4) seals with a dry layer thickness between 10 and 50 ⁇ m. They were characterized by the complete absence of microbubbles. They were also fully cured in the shadow zones of the molded parts, especially the SMC and BMC. They had excellent flexibility and hardness. The coated molded parts, in particular the SMC and BMC, could easily be stored in stacks until further processing without mechanical damage to the seals or their sticking.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un matériau de revêtement thermodurcissable et durcissable par des rayons actiniques. Ce matériau comprend (a1) au moins un constituant contenant (a11), dans une moyenne statistique, au moins deux groupes fonctionnels par molécule, ces groupes ayant au moins une liaison activable par un rayon actinique et cette liaison servant à la réticulation par un rayon actinique, et éventuellement (a12) au moins un groupe réactif à l'isocyanate, (a2) au moins un constituant thermodurcissable contenant au moins deux groupes réactifs à l'isocyanate et (a3) au moins un polyisocyanate aromatique exempt des groupes fonctionnels (a11) ou un mélange contenant au moins un polyisocyanate aromatique exempt de groupes fonctionnels (a11) et au moins un polyisocyanate (cyclo)aliphatique exempt de groupes fonctionnels (a11). L'invention concerne également l'utilisation pour revêtir des surfaces microporeuses, notamment de SMC et BMC.
EP03757894A 2002-10-17 2003-09-29 Matiere de revetement thermodurcissable et durcissable par des rayons actiniques et procede de revetement de surfaces microporeuses Withdrawn EP1551896A1 (fr)

Applications Claiming Priority (3)

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DE10248324 2002-10-17
DE10248324A DE10248324A1 (de) 2002-10-17 2002-10-17 Thermisch und mit aktinischer Strahlung härtbarer Beschichtungsstoff und Verfahren zum Beschichten miktoporöser Oberflächen
PCT/EP2003/010791 WO2004035651A1 (fr) 2002-10-17 2003-09-29 Matiere de revetement thermodurcissable et durcissable par des rayons actiniques et procede de revetement de surfaces microporeuses

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EP (1) EP1551896A1 (fr)
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AU2003273927A1 (en) 2004-05-04

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