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WO2003000762A1 - Pieces de bois enduites riches en constituants, procede de fabrication et utilisation desdites pieces - Google Patents

Pieces de bois enduites riches en constituants, procede de fabrication et utilisation desdites pieces Download PDF

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Publication number
WO2003000762A1
WO2003000762A1 PCT/EP2002/006700 EP0206700W WO03000762A1 WO 2003000762 A1 WO2003000762 A1 WO 2003000762A1 EP 0206700 W EP0206700 W EP 0206700W WO 03000762 A1 WO03000762 A1 WO 03000762A1
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Prior art keywords
groups
acid
group
radicals
ingredients according
Prior art date
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German (de)
English (en)
Inventor
Wolfgang Bremser
Hans-Peter Steiner
Frank Strickmann
Ralf Robert
Jorge Prieto
Andreas Hartel
Patricia Schneider
Reinhold Clauss
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BASF Coatings GmbH
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BASF Coatings GmbH
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Priority to EP02743222A priority Critical patent/EP1406940A1/fr
Publication of WO2003000762A1 publication Critical patent/WO2003000762A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy 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

Definitions

  • the present invention relates to new coated, ingredient-rich wooden parts.
  • the present invention relates to a new method for producing coated, high-content wooden parts.
  • the present invention relates to the use of the new coated, ingredient-rich wooden parts for the production of interior fittings, in particular doors, ceiling and wall panels, parquet floors and furniture.
  • the decoratively sophisticated and protective coating of wood parts rich in ingredients in the form of solid wood or veneer creates numerous problems because of the fibrous structure of the substrate and the exudation, bleeding and outgassing of liquid and / or volatile wood components such as resin or tannins. These occur increasingly in woods such as oak, teak, rosewood, wenge, eucalyptus and European softwoods
  • the aim is to produce decoratively sophisticated, protective, scratch-resistant, transparent, clear, glossy or matt coatings with as few application steps as possible, which have a uniform course and a smooth closed-pore or open-pore surface without defects, such as craters or pinholes (pin holes ), and are resistant to household chemicals in accordance with DIN 68861/1 B.
  • coating materials previously used for this purpose however, it is not easy to produce coatings that easily meet all of these requirements. From the German patent application DE 199 30 664 A 1 coating materials are known which
  • radicals R 1 , R 2 , R 3 and R 4 each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals provided that at least two of the variables R 1 , R 2 , R 3 and R 4 represent substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;
  • the coating materials can be two- or multi-component systems which contain at least one polyisocyanate as crosslinking agent.
  • the coating materials can contain customary and known paint additives.
  • Suitable substrates are all surfaces to be painted, which are not damaged by curing the paintwork thereon using heat and optionally actinic radiation.
  • the type of wood to be coated is not specified.
  • the known coating materials are therefore also suitable for applications outside of automotive painting, for example in industrial painting, including coil coating and container coating.
  • industrial painting they are suitable for painting practically all parts and objects for private or industrial use, such as radiators, household appliances, small parts made of metal, hubcaps or rims. They can also be used for painting furniture. But above all, they are used for automotive painting.
  • the painting of wood or wooden parts rich in ingredients and the related problems are not addressed in the German patent application.
  • the object of the present invention is to provide new coated, ingredient-rich wooden parts which are particularly suitable for the production of wooden interiors, in particular doors, ceiling and wall panels, parquet floors and furniture, and which are decoratively sophisticated, protective, scratch-resistant, transparent, clear , have glossy or matt coatings that have a uniform flow and a smooth closed-pore or an open-pore surface without defects, such as craters or pinholes, and are resistant to household chemicals in accordance with DIN 68861/1 B.
  • the new coated wooden parts rich in ingredients should be easy to produce.
  • the new ingredient-rich wooden parts have been found which are coated on at least one of their surfaces, the coating being producible by applying at least one coating material to at least one surface and curing the resulting layer or layers, at least one of the coating materials
  • radicals R 1 , R 2 , R 3 and R 4 are each independently of one another hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl,
  • Arylcycloalkyl radicals in particular substituted or unsubstituted aryl radicals
  • the coating materials to be used according to the invention delivered decoratively sophisticated, protective, scratch-resistant, transparent, clear, shiny or matt coatings in just a few application steps, which had a uniform course and a smooth closed-pore or an open-pore surface without defects, such as craters or pinholes ( pin holes), and were resistant to household chemicals according to DIN 68861/1 B.
  • the ingredient-rich wooden parts to be coated are, in particular, solid wooden parts or veneered chipboard, as are usually used for the production of interior fittings, in particular doors, ceiling and wall panels, parquet floors or furniture.
  • woods rich in ingredients are oak, teak, rosewood, wenge, eucalyptus and European softwoods.
  • woods from deciduous trees such as beech, cherry, maple or walnut, in which the problems described are not so pronounced, can be coated with the coating materials to be used according to the invention.
  • the ingredient-rich wooden parts are coated on at least one surface, in particular at least two surfaces, or on all surfaces. Which embodiment is chosen depends on the intended use of the new, coated, ingredient-rich wooden parts.
  • the coating on at least one of the surfaces can be produced by applying at least one coating material to the surface in question and curing the resulting layer or layers.
  • At least one of the coating materials or the one coating material contains the aqueous dispersion (A) of at least one block copolymer.
  • the block copolymer contains on average at least two, preferably at least three, in particular at least four isocyanate-reactive functional groups.
  • suitable isocyanate-reactive groups are hydroxyl groups, primary and secondary amino groups (if not neutralized), thiol groups and imino groups. After their neutralization, the primary and secondary amino groups can also serve as dispersing functional groups (ii). Hydroxyl groups are preferably used.
  • the block copolymer can be prepared by two-stage or multi-stage, in particular two-stage, controlled radical copolymerization of at least one olefinically unsaturated monomer (a) with at least one monomer (b).
  • the monomers (a) are preferably selected from the group consisting of hydrophilic and hydrophobic olefinically unsaturated monomers.
  • hydrophilic and hydrophobic reference is made to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 294, “Hydrophilie”, and pages 294 and 295, “Hydrophobie”.
  • Suitable hydrophilic monomers (a) contain at least one, in particular one, dispersing functional group which consists of the group consisting of
  • the functional groups (i) from the group consisting of carboxylic acid, sulfonic acid and phosphonic acid groups, acidic sulfuric acid and phosphoric acid ester groups and carboxylate, sulfonate, phosphonate, sulfate ester and phosphate ester groups are preferably the functional groups (ii) from the Group consisting of primary, secondary and tertiary amino groups, primary, secondary, tertiary and quaternary ammonium groups, quaternary phosphonium groups and tertiary sulfonium groups, and the functional groups (iii) from the group consisting of omega-hydroxy and omega-alkoxy poly ( alkylene oxide) -1-yl groups.
  • the primary and secondary amino groups can also serve as isocyanate-reactive functional groups.
  • hydrophilic monomers (a) with functional groups (i) are acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; olefinically unsaturated sulfonic or phosphonic acids or their partial esters; or maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono no (meth) acryloyloxyethyl ester, especially acrylic acid and methacrylic acid.
  • Examples of highly suitable hydrophilic monomers (a) with functional groups (ii) are 2-aminoethyl acrylate and methacrylate or allylamine.
  • Examples of highly suitable hydrophilic monomers (a) with functional groups (iii) are omega-hydroxy or omega-methoxy-polyethylene oxide-1-yl-, omega-methoxy-polypropylene-oxide-1-yl- or omega-methoxy-poly (ethylene oxide) -co-polypropylene oxide) -1 -yl acrylate or methacrylate.
  • hydrophilic monomers (a) When selecting the hydrophilic monomers (a), care must be taken that the hydrophilic monomers (a) with functional groups (i) and the hydrophilic monomers (a) with functional groups (ii) are not combined with one another, because this is insoluble to form them Salts and polyelectrolyte complexes can lead. In contrast, the hydrophilic monomers (a) with functional groups (i) or with functional groups (ii) with the hydrophilic monomers (a) with functional groups (iii) can be combined as desired.
  • the monomers (a) with the functional groups (i) are particularly preferably used.
  • the neutralizing agents for the functional groups (i) which can be converted into anions are preferably selected from the group consisting of ammonia, trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, 2-aminomethylpropanol, dimethylisopropylamine, dimethylisopropylamine, dimethylisopropylamine , Diethylenetriamine and Triethylenetetramine, and the neutralizing agents for the functional groups convertible into cations (ii) selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic acid and citric acid.
  • esters of olefinically unsaturated acids such as (meth) acrylic acid, crotonic acid, ethacrylic acid, vinylphosphonic acid or vinylsulfonic acid alkyl or cycloalkyl esters with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n Butyl, sec-butyl, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate, methacrylate,
  • minor amounts of higher-functional monomers (1) are to be understood here as amounts which do not lead to crosslinking or gelling of the block copolymers, unless they should be in the form of crosslinked microgel particles;
  • Hydroxyalkyl esters of alpha.beta-olefinically unsaturated carboxylic acids such as hydroxyalkyl esters of acrylic acid, methacrylic acid and ethacrylic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-
  • Methyl propanediol monoacrylate monomethacrylate, monoethacrylate or monocrotonate
  • olefinically unsaturated alcohols such as allyl alcohol
  • Allyl ethers of polyols such as trimethylolpropane monoallyl ether or pentaerythritol mono-, di- or triallyl ether.
  • the higher functional monomers (a1) are generally used only in minor amounts. In the context of the present invention are subordinate Amounts of higher-functional monomers are to be understood as amounts which do not lead to crosslinking or gelling of the block copolymers, unless they should be in the form of crosslinked microgel particles;
  • Carboxylic acids with glycidyl esters of an alpha-branched monocarboxylic acid with 5 to 18 carbon atoms in the molecule The reaction of acrylic or methacrylic acid with the glycidyl ester
  • Carboxylic acid with a tertiary alpha carbon atom can take place before, during or after the polymerization reaction.
  • the reaction product of acrylic and / or methacrylic acid with the glycidyl ester of Versatic® acid is preferably used as monomer (2).
  • Glycidyl ester is commercially available under the name Cardura® E10. In addition, reference is made to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 605 and 606;
  • Formaldehyde adducts of aminoalkyl esters of alpha-beta-olefinically unsaturated carboxylic acids and of alpha, beta-unsaturated carboxamides such as N-methylol and N, N-dimethylol-aminoethyl acrylate, aminoethyl methacrylate, acrylamide and methacrylamide; such as
  • Olefinically unsaturated monomers containing acryloxysilane groups and hydroxyl groups can be prepared by
  • vinyl esters of monocarboxylic acids with 5 to 18 carbon atoms in the molecule which are branched in the alpha position such as the vinyl esters of Versatic® acid which are sold under the brand VeoVa®;
  • cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbones,
  • amides of alpha.beta-olefinically unsaturated carboxylic acids such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, NN-diethyl, N-propyl, N, N- Dipropyl, N-butyl, N, N-dibutyl and / or
  • epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid;
  • vinyl aromatic hydrocarbons such as styrene, vinyl toluene or alpha-alkylstyrenes, especially alpha-methylstyrene;
  • nitriles such as acrylonitrile or methacrylonitrile
  • Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene dichloride,
  • vinylidene Vinyl amides such as N-vinyl pyrrolidone
  • Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n- Butyl vinyl ether, isobutyl vinyl ether and vinyl cyclohexyl ether; as well as vinyl esters such as vinyl acetate, vinyl propionate, and vinyl butyrate;
  • allyl compounds selected from the group consisting of allyl ether and esters such as propyl allyl ether, butyl allyl ether,
  • polysiloxane macromonomers which have a number average molecular weight Mn from 1,000 to 40,000 and on average 0.5 to 2.5 ethylenically unsaturated double bonds per molecule exhibit; in particular polysiloxane macromonomers which have a number average molecular weight Mn of 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, as in the DE
  • the radicals R 1 , R, R 3 and R 4 each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or Arylcycloalkyl radicals, with the proviso that at least two of the variables R 1 , R 2 , R 3 and R 4 stand for substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals.
  • alkyl radicals examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.
  • Suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.
  • alkylcycloalkyl radicals examples include methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane.
  • Suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylcyclohex-1-yl.
  • Suitable aryl radicals are phenyl, naphthyl or biphenylyl.
  • alkylaryl radicals examples include benzyl or ethylene or propane-1,3-diyl-benzene.
  • suitable cycloalkylaryl radicals are 2-, 3-, or 4-phenylcyclohex-1-yl.
  • Suitable arylalkyl radicals are 2-, 3- or 4-methyl, ethyl, propyl or butylphen-1-yl.
  • Suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1 -yl.
  • radicals R 1 , R 2 , R 3 and R 4 described above can be substituted.
  • electron-withdrawing or electron-donating atoms or organic residues can be used.
  • Suitable substitutes are halogen atoms, in particular chlorine and fluorine, nitrile groups, nitro groups, partially or completely halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and Arylcycloalkyl radicals, including those exemplified above, in particular tert-butyl; Aryloxy, alkyloxy and cycloalkyloxy radicals, in particular phenoxy, naphthoxy, methoxy, ethoxy, propoxy, butyloxy or cyclohexyloxy; Arylthio, alkylthio and cycloalkylthio radicals, in particular phenylthio, naphthylthio, methylthio, ethylthio, propylthio, butylthio
  • Examples of monomers (b) used with particular preference in accordance with the invention are diphenylethylene, dinaphthaleneethylene, eis or trans-stilbene, vinylidene-bis (4-N, N-dimethylaminobenzene), vinylidene-bis (4-aminobenzene) or vinylidene-bis (4- nitrobenzene).
  • the monomers (b) can be used individually or as a mixture of at least two monomers (b).
  • diphenylethylene is of very particular advantage and is therefore used with very particular preference according to the invention.
  • Each of the above-mentioned monomers (a) can be polymerized alone with the monomer (b). According to the invention, however, it is advantageous to use at least two monomers (a) because this allows the profile of properties of the resulting block copolymers to vary very widely in a particularly advantageous manner and can be adapted very specifically to the particular intended use of the aqueous dispersions (A).
  • the monomers (a) are preferably selected such that the property profile of the block copolymers is essentially determined by the (meth) acrylate monomers described above, the monomers (a), which come from other monomer classes, advantageously and widely varying this property profile.
  • dispersing functional groups (i) or (ii) and / or (iii) or are preferably incorporated into the block copolymers, by means of which the block copolymers become hydrophilic, so that they can be dispersed or dissolved in aqueous media. Installation is preferably carried out in the first stage of the production of the block copolymer
  • isocyanate-reactive functional groups are incorporated which can crosslink with the polyisocyanates described below.
  • the block copolymers are prepared by reacting at least one monomer (b) with at least one monomer (a), in particular at least one hydrophilic monomer (a), in a first stage (1) to give a copolymer or a macroinitiator. After its isolation or directly in the reaction mixture, preferably directly in the reaction mixture, this copolymer or this macroinitiator is then reacted in at least one further stage (2) with at least one further, preferably hydrophobic, monomer (a) under radical conditions. The reaction is preferably carried out in the absence of an initiator of the radical polymerization.
  • Steps (1) and (2) can also be carried out in succession in one reactor.
  • the monomer (b) is first reacted completely or partially with at least one monomer (a) depending on the desired application and the desired properties, after which at least one further monomer (a) is added and polymerized by free radicals.
  • at least two monomers (a) are used from the start, the monomer (b) first reacting with one of the at least two monomers (a) and then the resulting copolymer above a certain molecular weight also with the further monomer (a) responding.
  • the weight ratio of the copolymer or macroinitiator formed in the first stage (1) to the further monomer (s) (a) in the further stage (s) (2) is preferably 1:25 to 5: 1, preferably 1:22 to 4: 1, particularly preferably 1:18 to 3: 1, very particularly preferably 1:16 to 2: 1 and in particular 1:15 to 1: 1.
  • block copolymers with block, multiblock, gradient (co) polymer, star and branch structures, which may also be functionalized at the end groups.
  • initiators of free-radical polymerization which can be used are: dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; Potassium, sodium or ammonium peroxodisulfate; Azodinitriles such as azobisisobutyronitrile; C-C-cleaving initiators such as benzpinacol silyl ether; or a combination of a non-oxidizing initiator with hydrogen peroxide. Further examples of suitable initiators are described in German patent application DE 196 28 142 A1, page 3, line 49, to page 4,
  • Comparatively large amounts of free-radical initiator are preferably added, the proportion of the initiator in the reaction mixture, based in each case on the total amount of the monomers (a) and (b) and of the initiator, particularly preferably 0.5 to 50% by weight, being very particular is preferably 1 to 20% by weight and in particular 2 to 15% by weight.
  • the weight ratio of initiator to monomers (b) is preferably 4: 1 to 1: 4, particularly preferably 3: 1 to 1: 3 and in particular 2: 1 to 1: 2. Further advantages result if the initiator within the specified limits Excess is used.
  • the two-stage or multi-stage radical copolymerization or block copolymerization is carried out in an aqueous or an organic medium.
  • the resulting organic solution or dispersion of the block copolymer or the block copolymers is dispersed in an aqueous medium, resulting in a secondary dispersion (A).
  • the organic solvents contained therein are optionally distilled off.
  • aqueous primary dispersions (A) which, as such, can be used directly for the preparation of the coating materials to be used according to the invention.
  • the block copolymerization is preferably carried out in an aqueous medium.
  • the aqueous medium essentially contains water.
  • the aqueous medium can contain minor amounts of the additives described below and / or other dissolved solid, liquid or gaseous, low and / or high molecular weight substances, especially bases, provided that these do not negatively influence or even inhibit the copolymerization and / or more volatile for emission organic compounds.
  • the term “minor amount” is understood to mean an amount which does not cancel out the aqueous character of the aqueous medium.
  • the aqueous medium can also be pure water.
  • suitable bases are low molecular weight bases such as sodium hydroxide solution, potassium hydroxide solution, ammonia, diethanolamine, triethanolamine, mono-, di- and triethylamine, and / or dimethylethanolamine, in particular ammonia and / or di- and / or triethanolamine.
  • the reactors for the (co) polymerization processes are the customary and known stirred tanks, stirred tank cascades, tubular reactors, loop reactors or Taylor reactors, as described, for example, in the patents DE 198 28 742 A1 or EP 0 498 583 A1 or in the article by K. Kataoka in Chemical Engineering Science, Volume 50, No. 9, 1995, pages 1409 to 1416.
  • the radical copolymerization is preferably carried out in stirred tanks or Taylor reactors, the Taylor reactors being designed so that the conditions of the Taylor flow are met over the entire length of the reactor, even if the kinematic viscosity of the reaction medium changes greatly due to the copolymerization, in particular increases (cf. German patent application DE 198 28 742 A 1).
  • the copolymerization is advantageously carried out at temperatures above room temperature and below the lowest decomposition temperature of the monomers used in each case, preferably a temperature range from 10 to 150 ° C. 50 to 120 ° C and in particular 55 to 110 ° C is very particularly preferably selected.
  • the copolymerization can also be carried out under pressure, preferably under 1.5 to 3000 bar, preferably 5 to 1500 and in particular 10 to 1000 bar.
  • the block copolymer is not subject to any restrictions.
  • the copolymerization is advantageously carried out so that a
  • Standard of ⁇ 4 preferably particularly preferably ⁇ 2 and in particular ⁇ 1, 5 and in individual cases also ⁇ 1, 3 results.
  • Ratio of monomer (a) to monomer (b) to radical initiator controllable within wide limits the content of monomer (b) determines the molecular weight, in such a way that the greater the proportion of monomer (b), the lower the amount obtained
  • the proportion of block copolymers in the aqueous dispersions (A) can vary widely. It is preferably 10 to 70, preferably 15 to 65, particularly preferably 20 to 60, very particularly preferably 25 to 55 and in particular 30 to 50% by weight, in each case based on the aqueous dispersion (A).
  • the content of the aqueous dispersions (A) of the coating material to be used according to the invention can in any case vary widely depends on the requirements of the individual case.
  • the content is preferably 10 to 80, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 30 to 60% by weight, based on the coating material.
  • the coating material to be used according to the invention further contains at least one crosslinking agent component which contains or consists of at least one polyisocyanate.
  • the crosslinking agent component can contain inert organic solvents in order to lower the viscosity of the polyisocyanates so that they can be more easily mixed with the other constituents of the coating material to be used according to the invention
  • the statistical average of the polyisocyanates contains 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.
  • polyisocyanates are polyurethane prepolymers containing isocyanate groups, which can be prepared by reacting polyols with an excess of diisocyanates and are preferably low-viscosity.
  • Diisocyanatocyclopentane 1,3-diisocyanatocyclopentane, 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-
  • polyisocyanates are used which are prepared in a customary and known manner from the diisocyanates described above.
  • Examples of suitable production processes and polyisocyanates are, for example, from the patents CA 2,163,591 A, US-A-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 1, EP 0 496 208 A 1, EP 0 524 500 A 1, EP 0 566 037 A 1, US 5,258,482 A 1, US 5,290,902 A 1, EP 0 649 806 A 1, DE 42 29 183 A 1 or EP 0 531 820 A1.
  • the content of the coating materials to be used according to the invention in the polyisocyanates described above can vary very widely.
  • the content depends in particular on the functionality of the polyisocyanates on the one hand and the number of isocyanate-reactive functional groups in the binders on the other hand and on the crosslinking density which the coatings should have.
  • the content is preferably 1 to 30, preferably 2 to 28, particularly preferably 3 to 24, very particularly preferably 3 to 22 and in particular 3 to 20% by weight, in each case based on the coating material.
  • the coating material to be used according to the invention can additionally contain at least one customary and known pigment from the group consisting of coloring and / or effect-imparting, fluorescent, electrically conductive and magnetically shielding pigments, metal powders, organic and inorganic, transparent or opaque fillers and nanoparticles.
  • suitable effect pigments are metal plate pigments such as commercially available aluminum bronzes, chromated according to DE 36 36 183 A1
  • non-metallic effect pigments such as pearlescent or Interference pigments, platelet-shaped effect pigments based on iron oxide, which have a color from pink to brown-red, 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, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, azomethane pigments, iso-pigment pigments, iso-pigment pigments
  • Thioindigo pigments metal complex pigments, perinone pigments, and
  • fluorescent pigments are bis (azomethine) pigments.
  • Suitable electrically conductive pigments are titanium dioxide / tin oxide pigments.
  • magnétiqueally shielding pigments examples include pigments based on iron oxides or chromium dioxide.
  • suitable metal powders are powders made from metals and metal alloys aluminum, zinc, copper, bronze or brass.
  • suitable 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 polylamide or polyacrylonitrile.
  • suitable transparent fillers are those based on silicon dioxide, aluminum oxide or zirconium oxide.
  • Suitable nanoparticles are selected from the group consisting of hydrophilic and hydrophobic, in particular hydrophilic, nanoparticles based on silicon dioxide, aluminum oxide, zinc oxide, zirconium oxide and the polyacids and heteropolyacids of transition metals, preferably of molybdenum and tungsten, with a primary article size ⁇ 50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm.
  • the hydrophilic nanoparticles preferably have no matting effect. Nanoparticles based on silicon dioxide are particularly preferably used.
  • Hydrophilic pyrogenic silicon dioxides are very particularly preferably used, the agglomerates and aggregates of which have a chain-like structure and which can be produced by flame hydrolysis of silicon tetrachloride in a detonating gas flame. These are sold, for example, by Degussa under the brand Aerosil ®. Precipitated water glasses, such as nanohectorites, which are sold, for example, by Südchemie under the Optigel ® brand or by Laporte under the Laponite ® brand, are also used with particular preference.
  • the coating material to be used according to the invention can also contain at least one customary and known additive.
  • suitable additives are primary aqueous dispersion of customary and known binders, which are different from aqueous dispersion (A); other, different from the polyisocyanates (B) Crosslinking agents, such as blocked polyisocyanates, aminoplast resins, or tris (alkoxycarbonylamino) triazines, provided that these do not have excessively high injury temperatures; molecularly dispersible dyes, light stabilizers, such as UV absorbers and reversible radical scavengers (HALS); antioxidants; low and high boiling ("long”) organic solvents, deaerating agents; Wetting agents; emulsifiers; slip additives;
  • A aqueous dispersion
  • B polyisocyanates
  • Crosslinking agents such as blocked polyisocyanates, aminoplast resins, or tris (alkoxycarbonylamino) triazines, provided that these do not have excessively high injury temperatures
  • the coating materials to be used according to the invention should preferably be completely or almost free of volatile organic compounds (VOC)
  • VOC volatile organic compounds
  • the coating materials to be used according to the invention are preferably used to produce transparent matt or clear coatings.
  • the additives should be selected so that the transparency or clarity of the coatings is not impaired.
  • the production of the coating materials to be used according to the invention has no peculiarities, but instead takes place by mixing the constituents described above in usual and known mixing units, such as stirred kettles, Ultraturrax, inline dissolvers, extruders or kneaders.
  • the application of the coating materials to be used according to the invention also has no peculiarities, but can be done by all customary application methods, such as Spraying, knife coating, brushing, pouring, dipping, trickling, rolling or Vacumat® coating (manufacturer: Schiele company).
  • Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), if appropriate combined with hot spray application, such as hot air hot spraying.
  • the curing of the applied coating materials also has no special features in terms of method, but instead takes place according to the customary and known thermal methods, such as heating in a forced-air oven or irradiation with IR lamps, or by air curing at room temperature.
  • the new coated, ingredient-rich wooden parts have decoratively sophisticated, protective, scratch-resistant, transparent, clear, glossy or matt coatings that have a uniform flow and a smooth, closed-pore or open-pore surface without defects, such as craters or
  • the advantageous coatings can be produced in just a few application steps.
  • the coatings are grippable and grindable just 15 minutes after their application and curing.
  • the new ones can be used after only half an hour coated ingredient-rich wooden parts can be easily painted over. Since the coatings effectively prevent liquid and / or volatile substances from escaping from the wood, the new, coated, ingredient-rich wooden parts are ideally suited for the production of interior fittings, especially doors, ceiling and wall panels, parquet floors and furniture.
  • a steel reactor as is usually used for the production of dispersions, equipped with a stirrer, a reflux condenser and 3 feed vessels, 1,591, 1 part by weight of demineralized water were placed and heated to 70.degree. 308.2 parts by weight of acrylic acid, 555.2 parts by weight of methyl methacrylate and 45.2 parts by weight of diphenylethylene were placed in the first feed vessel. 300.1 parts by weight of 25 percent ammonia solution were placed in the second feed vessel. 159 parts by weight of demineralized water and 68.2 parts by weight of ammonium peroxodisulfate were placed in the third feed vessel. The three feeds were started simultaneously with vigorous stirring of the initial charge in the steel reactor.
  • the first and second feed were metered in within four hours.
  • the third feed was metered in over 4.5 hours.
  • the resulting reaction mixture was kept at 70 ° C. for four hours and then cooled to below 40 ° C. and filtered through a 100 ⁇ m GAF bag.
  • the resulting dispersion had a solids content of 33 to 34% by weight (1 hour, 130 ° C.) and a free monomer content of less than 0.2% by weight (determined by gas chromatography).
  • the resulting dispersion was then cooled below 40 ° C. and filtered through a 50 ⁇ m GAF bag.
  • the dispersion (A) had a solids content of 42 to 43% by weight (1 hour, 130 ° C.) and a free monomer content of less than 0.2% by weight (determined by gas chromatography).
  • dispersion (A) from preparation example 2 181 parts by weight of dispersion (A) from preparation example 2, 3.0 parts by weight of a commercially available wax (Poligen ® WE from BASF Aktiengesellschaft),
  • the base lacquer was mixed with 10.0 parts by weight of a polyisocyanate (trimeric hexamethylene diisocyanate of the isocyanurate type, Basonat® P LR 8878 from BASF Aktiengesellschaft, 56 percent in 1-methoxypropyl acetate-2 / acetone).
  • a polyisocyanate trimeric hexamethylene diisocyanate of the isocyanurate type, Basonat® P LR 8878 from BASF Aktiengesellschaft, 56 percent in 1-methoxypropyl acetate-2 / acetone.
  • the coating material was applied with the help of cup guns to veneered chipboard and solid woods made of oak, teak, rosewood, wenge, eucalyptus, spruce, fir and pine.
  • the wet layer thickness was adjusted such that after the layers had cured for 15 minutes at room temperature, dry layer thicknesses of 50 to 80 ⁇ m resulted, as is usually the case with physical wood protection (cf.Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998 , »Physical Wood Protection «, page 450) can be used.
  • the new coated wooden parts rich in ingredients showed decoratively sophisticated, protective, scratch-resistant, transparent, clear, glossy coatings with a very good pore pattern.
  • the coatings had a uniform course and a smooth closed-pore or an open-pore surface without defects, such as craters or pinholes, and were resistant to household chemicals in accordance with DIN 68861/1 B.
  • the coatings were grippable and grindable after only 15 minutes. After just half an hour they could easily be painted over. Since the coatings effectively prevented the escape of liquid and / or volatile ingredients from the woods, the new coated, ingredient-rich wooden parts were ideally suited for the production of interior fittings, in particular doors, ceiling and wall panels, parquet floors and furniture.

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

Abstract

L'invention concerne des pièces de bois riches en constituants, enduites sur au moins une de leurs surfaces. On peut réaliser cette enduction, en appliquant sur les surfaces au moins une substance d'enduction et en durcissant la ou les couches obtenues. Selon cette invention, au moins une des substances d'enduction renferme (A) la dispersion aqueuse d'un copolymérisat séquencé, contenant des groupes fonctionnels réactifs aux isocyanates et pouvant être obtenu par copolymérisation séquencée radicalaire contrôlée en deux ou plusieurs étapes dans un milieu aqueux ou organique, (1) dans une première étape (a) au moins un monomère oléfiniquement insaturé et (b) au moins un monomère oléfiniquement insaturé, différent du monomère oléfiniquement insaturé (a), de formule générale R<1>R<2>C=CR<3>R<4> (I) étant copolymérisés et (2) dans une deuxième étape (a) un autre monomère (a) étant (co)polymérisé en présence du copolymérisat formé dans la première étape sans addition d'initiateurs radicalaires, et (B) un polyisocyanate.
PCT/EP2002/006700 2001-06-21 2002-06-18 Pieces de bois enduites riches en constituants, procede de fabrication et utilisation desdites pieces Ceased WO2003000762A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02743222A EP1406940A1 (fr) 2001-06-21 2002-06-18 Pieces de bois enduites riches en constituants, procede de fabrication et utilisation desdites pieces

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2001129898 DE10129898A1 (de) 2001-06-21 2001-06-21 Beschichtete inhaltsstoffreiche Holzteile, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10129898.6 2001-06-21

Publications (1)

Publication Number Publication Date
WO2003000762A1 true WO2003000762A1 (fr) 2003-01-03

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EP (1) EP1406940A1 (fr)
DE (1) DE10129898A1 (fr)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003059035A3 (fr) * 2002-01-15 2003-12-04 Vkr Holding As Procede permettant de traiter un substrat en bois contenant de la resine et composition permettant de recouvrir et de remplir les irregularites dudit substrat
CN103370178A (zh) * 2010-12-17 2013-10-23 巴斯夫欧洲公司 具有低甲醛排放的多层含木素纤维素模制品
WO2022006703A1 (fr) * 2020-07-06 2022-01-13 Dic Corporation Composition, formulation de revêtement et corps multicouche

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0625529A1 (fr) * 1993-05-18 1994-11-23 Bayer Ag Mélange de liants et son utilisation
WO2000012579A1 (fr) * 1998-08-31 2000-03-09 Ppg Industries Ohio, Inc. Compositions thermodurcissables, contenant des polymeres fonctionnels a groupes hydroxy prepares par polymerisation radicalaire a transfert d'atome
WO2000037507A1 (fr) * 1998-12-18 2000-06-29 Basf Coatings Ag Procede de production d'un produit de reaction polymere
DE19930664A1 (de) * 1999-07-02 2001-01-11 Basf Coatings Ag Klarlack und seine Verwendung zur Herstellung von Klarlackierungen und farb- und/oder effektgebenden Mehrschichtlackierungen

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19930067A1 (de) * 1999-06-30 2001-01-11 Basf Coatings Ag Beschichtungsstoff und seine Verwendung zur Herstellung von Füllerschichten und Steinschlagschutzgrundierungen
DE19930665A1 (de) * 1999-07-02 2001-01-11 Basf Coatings Ag Basislack und seine Verwendung zur Herstellung von farb- und/oder effektgebenden Basislackierungen und Mehrschichtlackierung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0625529A1 (fr) * 1993-05-18 1994-11-23 Bayer Ag Mélange de liants et son utilisation
WO2000012579A1 (fr) * 1998-08-31 2000-03-09 Ppg Industries Ohio, Inc. Compositions thermodurcissables, contenant des polymeres fonctionnels a groupes hydroxy prepares par polymerisation radicalaire a transfert d'atome
WO2000037507A1 (fr) * 1998-12-18 2000-06-29 Basf Coatings Ag Procede de production d'un produit de reaction polymere
DE19930664A1 (de) * 1999-07-02 2001-01-11 Basf Coatings Ag Klarlack und seine Verwendung zur Herstellung von Klarlackierungen und farb- und/oder effektgebenden Mehrschichtlackierungen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003059035A3 (fr) * 2002-01-15 2003-12-04 Vkr Holding As Procede permettant de traiter un substrat en bois contenant de la resine et composition permettant de recouvrir et de remplir les irregularites dudit substrat
CN103370178A (zh) * 2010-12-17 2013-10-23 巴斯夫欧洲公司 具有低甲醛排放的多层含木素纤维素模制品
WO2022006703A1 (fr) * 2020-07-06 2022-01-13 Dic Corporation Composition, formulation de revêtement et corps multicouche

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EP1406940A1 (fr) 2004-04-14
DE10129898A1 (de) 2003-01-09

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