WO2003000761A1 - Panneaux de fibre revetus a densite moyenne, leur procede de production et leur utilisation - Google Patents

Panneaux de fibre revetus a densite moyenne, leur procede de production et leur utilisation Download PDF

Info

Publication number
WO2003000761A1
WO2003000761A1 PCT/EP2002/006677 EP0206677W WO03000761A1 WO 2003000761 A1 WO2003000761 A1 WO 2003000761A1 EP 0206677 W EP0206677 W EP 0206677W WO 03000761 A1 WO03000761 A1 WO 03000761A1
Authority
WO
WIPO (PCT)
Prior art keywords
groups
acid
group
density fiberboard
medium
Prior art date
Application number
PCT/EP2002/006677
Other languages
German (de)
English (en)
Inventor
Wolfgang Bremser
Hans-Peter Steiner
Frank Strickmann
Peter-Eduard Kunze
Original Assignee
Basf Coatings Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Coatings Ag filed Critical Basf Coatings Ag
Priority to EP02743217A priority Critical patent/EP1401908A1/fr
Publication of WO2003000761A1 publication Critical patent/WO2003000761A1/fr

Links

Classifications

    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/06—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood
    • B05D7/08—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood using synthetic lacquers or varnishes

Definitions

  • the present invention relates to new coated mitrichicht fibreboards.
  • the present invention also relates to a new method for producing coated medium-density fiberboard.
  • the present invention relates to the use of the new coated medium-density fiberboard for the production of doors, wooden cassettes, furniture and rear walls of furniture.
  • Coated medium-density fibreboards and their use for the production of doors, wooden cassettes, furniture and back walls of furniture are known per se. Because of the porous structure of the medium density fiberboard, however, their coating often causes problems. The aim is to produce scratch-resistant, glossy coatings that have a uniform flow and a smooth surface without faults, such as craters or pinholes, are free of light-dark shades (clouds) and against all household chemicals , including active chlorine, are stable. With the coating materials previously used for this purpose, however, it is not easy to produce coatings that easily meet all of these requirements.
  • Pigmented coating materials are known from German patent applications DE 199 30 665 A 1 and DE 199 30 067 A 1
  • 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 with the proviso that at least two of the variables R 1 , R 2 , R 3 and R 4 are substituted or unsubstituted aryl, arylalkyl or
  • Arylcycloalkyl radicals in particular substituted or unsubstituted aryl radicals
  • the pigmented coating materials can be two- or multi-component systems which contain polyisocyanates as crosslinking agents.
  • the pigmented coating materials can be customary and known binders, such as linear and / or branched and / or block-like, comb-like and / or random (meth) acrylate (co) polymers, polyesters, alkyds, aminoplast resins, polyurethanes, acrylated polyurethanes, acrylated polyesters , Polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth) acrylate diols, preferably in an amount of 1 to 50, preferably 2 to 40, particularly preferably 3 to 30 and in particular 5 to 25% by weight, in each case based on the total solids content of the coating material. It is not specified which of these customary and known binders are preferably used. In addition, it is not proposed to use the binders in the form of their dispersions.
  • Suitable substrates are all surfaces to be painted, which are not damaged by curing the paintwork thereon using heat and optionally actinic radiation.
  • the fiber composites are not specified in more detail.
  • the known coating materials are basically 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.
  • the Basecoat according to the invention also for painting furniture. But above all, they are used for automotive painting.
  • the object of the present invention is to provide new coated medium-density fiberboard which are suitable for the production of doors in the interior, of wooden cassettes, furniture and furniture rear walls and which have scratch-resistant, glossy coatings which have a uniform flow and a smooth surface without defects, such as Craters or pinholes, have no light-dark shades (clouds) and are resistant to all household chemicals, including those containing active chlorine.
  • the new coated medium-density fiberboard should be easy to manufacture.
  • the new medium-density fiberboard which is coated on at least one of its 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
  • At least one further monomer (a) is polymerized in the presence of the copolymer formed in the first stage without the addition of free radical initiators (co);
  • the coating materials on the medium-density fiberboard provided scratch-resistant, glossy coatings, which had a uniform course and a smooth surface without defects, such as craters or pinholes, were free from light-dark shades (clouds) and against all household chemicals , including active chlorine, were stable.
  • the medium-density fiberboard to be coated is the usual and known medium-density fiberboard, as is known to be used for the production of doors in the interior, wooden cassettes, cheap furniture and furniture back panels.
  • the medium-density fiberboard is coated on at least one surface, in particular at least two surfaces.
  • the two surfaces are preferably the front and the back of the medium-density fiberboard.
  • at least one of the four lateral surfaces can also be coated. Which embodiment is chosen depends on the intended use of the new coated medium-density fiberboard.
  • 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.
  • the first coating material being a customary and known, preferably physically curing, coating material based on organic solvents, in particular methyl ethyl ketone, and (meth) acrylate copolymers as used in the field of medium density Fiberboard is commonly used to make primers.
  • (Meth) acrylate copolymers which are suitable for this purpose are commercially available products and are sold, for example, by DSM under the brand Uracron®, for example Uracron® CY476E.
  • At least one of the further coating materials or the further coating material which is applied to the primer 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 ( alky! enoxid) -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,
  • 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, he
  • 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
  • Reaction products from cyclic esters such as' e.g. epsilon-caprolactone and these hydroxyalkyl esters;
  • 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; 5
  • Carboxylic acids with glycidyl esters of an alpha-branched monocarboxylic acid with 5 to 18 carbon atoms in the molecule are included in the molecule.
  • 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 is preferred 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-methiol and N, N-dimethylol-aminoethyl acrylate, aminoethyl ethacrylate,
  • 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, NN-dimethyl, N-ethyl, N, N-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 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, 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, iso-butyl, 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.
  • 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, line
  • 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.
  • 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
  • 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.
  • 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 A 1, DE 40 15 155 A 1, 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 may also contain at least one, in particular one, primary aqueous dispersion (C) of at least one (meth) acrylate copolymer which is different from the aqueous dispersion (A).
  • Primary aqueous dispersions (C) are common and known products and are sold, for example, by Zeneca under the Neocryl® brand, for example Neocryl® XK 90.
  • the primary aqueous dispersions (C) are preferably used to grind the pigments described below.
  • the coating material to be used according to the invention can also give color and / or effect, fluorescent, electrically conductive and / or magnetically shielding pigments, metal powder, organic and inorganic, transparent or opaque fillers and / or nanoparticles (collectively “pigments (D)”) contain.
  • 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 as well as 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, uitramarin 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 color pigments are monoazo pigments, bisazo pigments, anthraquinone pigments, and
  • Benzimidazole Pigments Quinacridone Pigments, Quinophthalone Pigments, Diketopyrroiopyrrole Pigments, Di ⁇ xazine Pigments, In ⁇ anthron 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 titanium dioxide / tin oxide pigments.
  • magnétiqueally shielding pigments are 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.
  • 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 powders, in particular made of polylamide or polyacrylonitrile.
  • silicates such as talc, mica or kaolin
  • silicas oxides such as aluminum hydroxide or magnesium hydroxide
  • organic fillers such as plastic powders, 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, are also particularly preferred for example, sold by Südchemie under the Optigel ® brand or by Laporte under the Laponite ® brand.
  • the coating material to be used according to the invention may also contain at least one further additive.
  • Suitable further additives are other crosslinking agents, such as blocked, other than the polyisocyanates (B)
  • HALS reversible radical scavengers
  • thermolabile free radical initiators thermally curable reactive thinners
  • adhesion promoters leveling agents
  • film-forming aids film-forming aids
  • rheology aids thickeners
  • the production of the coating materials to be used according to the invention has no peculiarities, but instead takes place by mixing the components described above in conventional and known mixing units, such as stirred kettles, Ultraturrax, inline dissolvers, extruders or kneaders.
  • the coating materials to be used according to the invention are also not peculiar, but can be carried out by all customary application methods, such as, for example, spraying, knife coating, brushing, pouring, dipping, trickling or rolling.
  • 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.
  • the new coated medium-density fibreboards have scratch-resistant, glossy coatings, which have a uniform flow and a smooth surface without faults, such as craters or pinholes, are free of light-dark shades (clouds) and against all household chemicals, including active chlorine are resistant.
  • the new coated medium-density fibreboards are therefore ideally suited for the production of interior doors, wooden cassettes, cheap furniture and furniture back panels.
  • Dispersions was used, equipped with a stirrer, a reflux condenser and 3 feed vessels, 1,591, 1 part by weight VE- Submitted water and heated to 70 ° C. 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).
  • the base coating was mixed with 13.25 parts by weight of a polyisocyanate (trimeric hexamethylene diisocyanate of the isocyanurate type, Basonat® P LR 8878 from BASF Aktiengesellschaft, 56 percent in 1-methoxypropylacetate-2 / acetone).
  • a polyisocyanate trimeric hexamethylene diisocyanate of the isocyanurate type, Basonat® P LR 8878 from BASF Aktiengesellschaft, 56 percent in 1-methoxypropylacetate-2 / acetone.
  • the coating material was applied with the aid of cup guns to medium-density fibreboards which were provided with a primer, prepared from a solution of a commercially available methacrylate copolymer (Uracron® CY476E from DSM) in methyl ethyl ketone.
  • a primer prepared from a solution of a commercially available methacrylate copolymer (Uracron® CY476E from DSM) in methyl ethyl ketone.
  • the wet layer thickness was adjusted such that after the layers had hardened for 60 minutes at 40 ° C., dry layer thicknesses of 50 to 70 ⁇ m resulted.
  • the coatings had a uniform flow and a smooth surface.
  • the gloss was 14 to 18 ° with a measuring angle of 60 °.
  • the scratch resistance and chemical resistance to chlorine-containing cleaning agents were excellent.

Landscapes

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

Abstract

L'invention concerne des panneaux de fibres à densité moyenne, revêtus sur au moins une de leurs surfaces, ledit revêtement pouvant être produit par application sur les surfaces d'au moins une matière de recouvrement, et durcissement de la ou des couches résultantes. Au moins une des matières de revêtement contient (A) la dispersion aqueuse d'un copolymère en bloc comprenant des groupes fonctionnels réactifs aux isocyanates, obtenus par copolymérisation en bloc radicale contrôlée s'effectuant en deux ou plusieurs étapes dans un milieu aqueux ou organique. Au cours d'une première étape (1), (a) au moins un monomère insaturé oléfinique et (b) au moins un monomère insaturé oléfinique, différent du monomère insaturé oléfinique (a), et de formule générale (I) : R?1R2C=CR3R4¿ sont copolymérisés. Au cours d'une seconde étape (2), un autre monomère (a) est (co)polymérisé en présence du copolymère formé lors de la première étape sans addition d'initiateurs radicaux. Une des matières de revêtement comprend en outre un polyisocyanate.
PCT/EP2002/006677 2001-06-21 2002-06-18 Panneaux de fibre revetus a densite moyenne, leur procede de production et leur utilisation WO2003000761A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02743217A EP1401908A1 (fr) 2001-06-21 2002-06-18 Panneaux de fibre revetus a densite moyenne, leur procede de production et leur utilisation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10129875.7 2001-06-21
DE2001129875 DE10129875A1 (de) 2001-06-21 2001-06-21 Beschichtete mitteldichte Faserplatten, Verfahren zu ihrer Herstellung und ihre Verwendung

Publications (1)

Publication Number Publication Date
WO2003000761A1 true WO2003000761A1 (fr) 2003-01-03

Family

ID=7688913

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/006677 WO2003000761A1 (fr) 2001-06-21 2002-06-18 Panneaux de fibre revetus a densite moyenne, leur procede de production et leur utilisation

Country Status (3)

Country Link
EP (1) EP1401908A1 (fr)
DE (1) DE10129875A1 (fr)
WO (1) WO2003000761A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7812090B2 (en) 2006-06-02 2010-10-12 Valspar Sourcing, Inc. High performance aqueous coating compositions
US7834086B2 (en) 2006-06-02 2010-11-16 Valspar Sourcing, Inc. High performance aqueous coating compositions
US8057893B2 (en) 2006-01-31 2011-11-15 Valspar Sourcing, Inc. Coating system for cement composite articles
US8057864B2 (en) 2006-01-31 2011-11-15 Valspar Sourcing, Inc. Method for coating a cement fiberboard article
US8133588B2 (en) 2006-05-19 2012-03-13 Valspar Sourcing, Inc. Coating system for cement composite articles
US8202581B2 (en) 2007-02-16 2012-06-19 Valspar Sourcing, Inc. Treatment for cement composite articles
US8277934B2 (en) 2006-01-31 2012-10-02 Valspar Sourcing, Inc. Coating system for cement composite articles
US8932718B2 (en) 2006-07-07 2015-01-13 Valspar Sourcing, Inc. Coating systems for cement composite articles
AT508686B1 (de) * 2009-07-27 2015-02-15 Mikowitsch Herbert Verfahren zur oberflächenbehandlung einer pressholzplatte
US8993110B2 (en) 2005-11-15 2015-03-31 Valspar Sourcing, Inc. Coated fiber cement article with crush resistant latex topcoat
US9133064B2 (en) 2008-11-24 2015-09-15 Valspar Sourcing, Inc. Coating system for cement composite articles
US9175187B2 (en) 2008-08-15 2015-11-03 Valspar Sourcing, Inc. Self-etching cementitious substrate coating composition
CN106861437A (zh) * 2017-03-28 2017-06-20 天津大学 一种稳定高通量超滤膜的制备方法
US9783622B2 (en) 2006-01-31 2017-10-10 Axalta Coating Systems Ip Co., Llc Coating system for cement composite articles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013190777A1 (fr) * 2012-06-19 2013-12-27 パナソニック株式会社 Moulage de la bagasse

Citations (2)

* 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
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

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
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

Patent Citations (2)

* 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
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

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8993110B2 (en) 2005-11-15 2015-03-31 Valspar Sourcing, Inc. Coated fiber cement article with crush resistant latex topcoat
US8277934B2 (en) 2006-01-31 2012-10-02 Valspar Sourcing, Inc. Coating system for cement composite articles
US8057893B2 (en) 2006-01-31 2011-11-15 Valspar Sourcing, Inc. Coating system for cement composite articles
US8057864B2 (en) 2006-01-31 2011-11-15 Valspar Sourcing, Inc. Method for coating a cement fiberboard article
US8293361B2 (en) 2006-01-31 2012-10-23 Valspar Sourcing, Inc. Coating system for cement composite articles
US9783622B2 (en) 2006-01-31 2017-10-10 Axalta Coating Systems Ip Co., Llc Coating system for cement composite articles
US8133588B2 (en) 2006-05-19 2012-03-13 Valspar Sourcing, Inc. Coating system for cement composite articles
US7812090B2 (en) 2006-06-02 2010-10-12 Valspar Sourcing, Inc. High performance aqueous coating compositions
US9359520B2 (en) 2006-06-02 2016-06-07 Valspar Sourcing, Inc. High performance aqueous coating compositions
US8658286B2 (en) 2006-06-02 2014-02-25 Valspar Sourcing, Inc. High performance aqueous coating compositions
US7834086B2 (en) 2006-06-02 2010-11-16 Valspar Sourcing, Inc. High performance aqueous coating compositions
US8932718B2 (en) 2006-07-07 2015-01-13 Valspar Sourcing, Inc. Coating systems for cement composite articles
US10640427B2 (en) 2006-07-07 2020-05-05 Axalta Coating Systems IP Co. LLC Coating systems for cement composite articles
US9593051B2 (en) 2006-07-07 2017-03-14 Valspar Sourcing, Inc. Coating systems for cement composite articles
US8202581B2 (en) 2007-02-16 2012-06-19 Valspar Sourcing, Inc. Treatment for cement composite articles
US9175187B2 (en) 2008-08-15 2015-11-03 Valspar Sourcing, Inc. Self-etching cementitious substrate coating composition
US9133064B2 (en) 2008-11-24 2015-09-15 Valspar Sourcing, Inc. Coating system for cement composite articles
AT508686B1 (de) * 2009-07-27 2015-02-15 Mikowitsch Herbert Verfahren zur oberflächenbehandlung einer pressholzplatte
CN106861437A (zh) * 2017-03-28 2017-06-20 天津大学 一种稳定高通量超滤膜的制备方法
CN106861437B (zh) * 2017-03-28 2019-12-20 天津大学 一种稳定高通量超滤膜的制备方法

Also Published As

Publication number Publication date
DE10129875A1 (de) 2003-01-09
EP1401908A1 (fr) 2004-03-31

Similar Documents

Publication Publication Date Title
EP1196507B1 (fr) Peinture d'appret et son utilisation pour la production de peintures d'appret et de peintures multicouches a coloration ou a effet
EP1309637B1 (fr) Polyurethane et polymerisats mixtes greffes a base de polyurethane et leur utilisation pour produire des matieres de recouvrement, des adhesifs et des matieres d'etancheite
EP1425326A1 (fr) Polyurethanes et copolymeres greffes a base de polyurethane, et leur utilisation pour preparer des matieres de revetement, des matieres adhesives et des matieres d'etancheite
EP1368441B1 (fr) Substance de recouvrement aqueuse sensiblement ou entierement exempte de substances organiques volatiles, procedes permettant de la produire et son utilisation
WO2003000761A1 (fr) Panneaux de fibre revetus a densite moyenne, leur procede de production et leur utilisation
EP1373385B1 (fr) Dispersions aqueuses libres ou essentiellement libres de composes organiques volatils, procede de fabrication et utilisation
EP1194494B1 (fr) Substance de revetement aqueuse, son procede de production et son utilisation
WO2002064652A1 (fr) Dispersion primaire aqueuse pratiquement ou totalement exempte de matieres organiques volatiles, son procede de production et son utilisation
DE10257377A1 (de) Wässriger farb- und/oder effektgebender Beschichtungsstoff und seine Verwendung
EP1301547B1 (fr) Dispersions primaires et substances de revetement aqueuses, leur procede de production et leur utilisation
DE10048670A1 (de) Beschichtungsstoffsystem für die Herstellung farb- und/oder effektgebender Mehrschichtlackierungen auf der Basis von Mehrkomponentenbeschichtungsstoffen
EP1373344B1 (fr) Copolymeres modifies au moyen de polyurethannes, procede de production et utilisation de ces copolymeres
DE19959927A1 (de) Wäßrige Primärdispersionen und Beschichtungsstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1200203B1 (fr) Peinture multicouche de coloration et/ou a effets, son procede de realisation et son utilisation
DE10005819A1 (de) Wäßrige Primärdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1368399B1 (fr) Substance de revetement aqueuse a plusieurs composants, procede de production et utilisation de cette substance
DE10010405A1 (de) Wäßrige (Meth)Acrylatcopolymerisat-Dispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2003000762A1 (fr) Pieces de bois enduites riches en constituants, procede de fabrication et utilisation desdites pieces
DE10010416A1 (de) Pysikalisch oder thermisch und/oder mit aktinischer Strahlung härtbarer Beschichtungsstoff und seine Verwendung
DE10126650B4 (de) Funktionale organische Pulver, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10128886B4 (de) Thermisch oder thermisch und mit aktinischer Strahlung härtbarer, wäßriger, farb- und/oder effektgebender Beschichtungsstoff und seine Verwendung
DE10146483A1 (de) Farb- und/oder effektgebender wäßriger Beschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2002743217

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2004103743

Country of ref document: RU

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2004103864

Country of ref document: RU

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 2002743217

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP

WWW Wipo information: withdrawn in national office

Ref document number: 2002743217

Country of ref document: EP