DE10129875A1 - Coated medium density fiberboard, process for its production and its use - Google Patents

Abstract

Medium-density fibre boards, coated on at least one surface thereof, whereby the coating may be produced by applying at least one coating material to the surfaces and hardening the resultant layer(s). At least one of the coating materials contains (A) the aqueous dispersion of a block co-polymer, comprising isocyanate-reactive functional groups obtained by the twin- or multiple-stage controlled radical block co-polymerisation in an aqueous or organic medium, whereby (1) in a first stage (a) at least one olefinic unsaturated monomer and (b) at least one olefinic unsaturated monomer, different from the olefinic unsaturated monomer (a), of general formula (I): R<1>R<2>C=CR<3>R<4> are co-polymerised, (2) in a second stage a further monomer (a) is (co-)polymerised in the presence of the co-polymer from the first stage without addition of radical initiators and (B) a polyisocyanate.

Description

The present invention relates to new coated medium density fiberboard.

The present invention also relates to a new method of production coated medium density fibreboard. Furthermore, the present concerns Invention the use of the new coated medium density fiberboard for the manufacture of doors, wooden cassettes, furniture and back panels of furniture.

Coated medium density fiberboard and its use in manufacturing of doors, wooden cassettes, furniture and back walls of furniture are in themselves known. Because of the porous structure of the medium-density fiberboard, however their coating often causes problems. So the goal is scratch-resistant, shiny Produce coatings that are even and smooth Have a surface without defects, such as craters or pinholes, are free of light-dark shades (clouds) and against everyone Household chemicals, including those containing active chlorine, are resistant. With the coating materials previously used for this purpose However, it is not easy to produce coatings, all of them easily meet these requirements.

• A) als Bindemittel oder als eines der Bindemittel mindestens ein Copolymerisat, das durch radikalische Polymerisation von
  • a) mindestens einem olefinisch ungesättigten Monomer und
  • b) mindestens einem vom olefinisch ungesättigten Monomer (a) verschiedenen olefinisch ungesättigten Monomer der allgemeinen Formel I
    
    R¹R²C=CR³R⁴ (I),
    
    worin die Reste R¹, R², R³ und R⁴ jeweils unabhängig voneinander für Wasserstoffatome oder substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkylcycloalkyl-, Cycloalkylalkyl-, Aryl-, Alkylaryl-, Cycloalkylaryl- Arylalkyl- oder Arylcycloalkylreste stehen, mit der Maßgabe, daß mindestens zwei der Variablen R¹, R², R³ und R⁴ für substituierte oder unsubstituierte Aryl-, Arylalkyl- oder Arylcycloalkylreste, insbesondere substituierte oder unsubstituierte Arylreste, stehen;
  in einem wäßrigen Medium herstellbar ist;
  sowie
• B) mindestens ein farb-und/oder effektgebendes Pigment und/oder mindestens einen Füllstoff

enthalten. Pigmented coating materials are known from German patent applications DE 199 30 665 A1 and DE 199 30 067 A1

• A) as a binder or as one of the binders at least one copolymer, which by radical polymerization of
  • a) at least one olefinically unsaturated monomer and
  • b) at least one olefinically unsaturated monomer of the general formula I which is different from the olefinically unsaturated monomer (a)
    
    R ¹ R ² C = CR ³ R ⁴ (I),
    
    wherein 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 represent} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;
  can be produced in an aqueous medium;
  such as
• B) at least one color and / or effect pigment and / or at least one filler

contain.

The pigmented coating materials can be two or Be multi-component systems, the polyisocyanates as crosslinking agents contain.

Furthermore, the pigmented coating materials can be customary and known Binders, such as linear and / or branched and / or block-like, comb-like and / or statistically constructed (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 it is not specified which of these customary and known binders are preferably used. It also does not suggest the binders use in the form of their dispersions.

All surfaces that need to be painted come through as substrates the paintwork on it using heat and if necessary, actinic radiation are not damaged, taking into account that are z. B. metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, Glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, as well as composites of these materials. However, the fiber composites are not specified in more detail.

The known coating materials are basically also for applications Suitable outside of automotive painting, for example in industrial Painting, including coil coating and container coating. As part of the Industrial paints are suitable for painting practically all parts and items for private or industrial use such as radiators, Household appliances, small parts made of metal, hubcaps or rims. Furthermore The basecoat according to the invention also comes in for painting furniture Consideration. But above all, they are used for automotive painting.

The painting of medium density fiberboard and the related Problems are not described in the German patent applications.

The object of the present invention is to provide new coated medium density To provide fiberboard that is suitable for the production of doors in the Indoor use, of wooden cassettes, furniture and back walls and the scratch-resistant, glossy coatings that have an even flow and a smooth surface with no defects, such as craters or pinholes (pin holes), are free of light-dark shades (clouds) and against everyone Household chemicals, including those containing active chlorine, are resistant. In addition, the new coated medium density fibreboard should be easier Be able to be produced.

• A) die wäßrige Dispersion mindestens eines Blockmischpolymerisats, das im statistischen Mittel mindestens zwei isocyanatreaktive funktionelle Gruppen aufweist und durch die zwei- oder mehrstufige, kontrollierte radikalische Blockmischpolymerisation in einem wäßrigen oder einem organischen Medium erhältlich ist, wobei man
  • 1. in einer ersten Sufe
    • a) mindestens ein olefinisch ungesättigtes Monomer und
    • b) mindestens ein vom olefinisch ungesättigten Monomer (a) verschiedenes olefinisch ungesättigtes Monomer der allgemeinen Formel I
      
      R¹R²C=CR³R⁴ (I),
      
      worin die Reste R¹, R², R³ und R⁴ jeweils unabhängig voneinander für Wasserstoffatome oder substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkylcycloalkyl-, Cycloalkylalkyl-, Aryl-, Alkylaryl-, Cycloalkylaryl- Arylalkyl- oder Arylcycloalkylreste stehen, mit der Maßgabe, daß mindestens zwei der Variablen R¹, R², R³ und R⁴ für substituierte oder unsubstituierte Aryl-, Arylalkyl- oder Arylcycloalkylreste, insbesondere substituierte oder unsubstituierte Arylreste, stehen;
    copolymerisiert, wonach man
  • 2. in einer zweiten Stufe mindestens ein weiteres Monomer (a) in der Gegenwart des in der ersten Stufe gebildeten Copolymerisats ohne Zugabe von radikalischen Initiatoren (co)polymerisiert;
  und
• B) mindestens eine Vernetzungsmittelkomponente mit mindestens einem Polyisocyanat

enthält. Accordingly, the new medium-density fiberboard has been found 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

• A) the aqueous dispersion of at least one block copolymer, which has on average at least two isocyanate-reactive functional groups and is obtainable by the two- or multi-stage, controlled free-radical block copolymerization in an aqueous or an organic medium, where
  • 1. in a first step
    • a) at least one olefinically unsaturated monomer and
    • b) at least one olefinically unsaturated monomer of the general formula I which is different from the olefinically unsaturated monomer (a)
      
      R ¹ R ² C = CR ³ R ⁴ (I),
      
      wherein 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 represent} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;
    copolymerized, after which
  • 2. in a second stage, 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);
  and
• B) at least one crosslinking agent component with at least one polyisocyanate

contains.

In view of the prior art, it was surprising and for the One skilled in the art could not have foreseen that the object of the present invention was based, with the help of the invention Coating materials containing an aqueous dispersion (A) at least one Contain block copolymers of monomers (a) and (b) are dissolved could. In particular, it was surprising that these coating materials in particular application-related property profile that they had for the Coating medium-density fiberboard made excellent. As a result, the coating materials delivered on the medium density fiberboard scratch-resistant, glossy coatings that have a smooth flow and a had a smooth surface with no defects, such as craters or pin holes, were free of light-dark shades (clouds) and against everyone Household chemicals, including those containing active chlorine, were resistant.

The medium-density fiberboard to be coated is the usual and known medium density fiberboard, as is known for the production of interior doors, wooden cassettes, cheap furniture and Furniture back panels are used.

The medium density fiberboard is on at least one surface, in particular at least two surfaces coated. Preferably acts the two surfaces are the front and the back of the medium density fiberboard. But it can also be at least one of the four side surfaces to be coated. Which embodiment is chosen depends on the purpose of the new coated medium density Fiberboard.

The coating on at least one of the surfaces can be produced by: applied at least one coating material to the surface in question and the resulting layer or layers harden.

Two coating materials are preferably applied to the surface in question applied, the first coating material being a conventional one and known, preferably physically curing coating material on the Based on organic solvents, especially methyl ethyl ketone, and (Meth) acrylate copolymers acts as he does 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 for example from DSM sold under the trademark Uracron ®, for example Uracron ® CY476E.

It is essential that at least one of the other coating materials or further coating material that is applied to the primer, the aqueous Dispersion (A) contains 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. Examples of suitable isocyanate-reactive groups are Hydroxyl groups, primary and secondary amino groups (if not neutralized), thiol groups and imino groups. The primary and secondary After neutralization, amino groups can also act as dispersing agents functional groups (ii) serve. Hydroxyl groups are preferred 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, selected. Lacquer is used for the terms "hydrophilic" and "hydrophobic" on Römpp and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 294, "Hydrophilicity" as well as pages 294 and 295, "Hydrophobia".

• a) funktionellen Gruppen, die durch Neutralisationsmittel in Anionen überführt werden können, und anionischen Gruppen,

oder

• a) funktionellen Gruppen, die durch Neutralisationsmittel und/oder Quaternisierungsmittel in Kationen überführt werden können, und kationischen Gruppen,

und

• a) nichtionischen hydrophilen Gruppen,

ausgewählt wird. Suitable hydrophilic monomers (a) contain at least one, in particular one, dispersing functional group which consists of the group consisting of

• a) functional groups which can be converted into anions by neutralizing agents and anionic groups,

or

• a) functional groups which can be converted into cations by neutralizing agents and / or quaternizing agents, and cationic groups,

and

• a) nonionic hydrophilic groups,

is selected.

The functional groups (i) are preferably composed of the group from carboxylic acid, sulfonic acid and phosphonic acid groups, acidic Sulfuric acid and phosphoric acid ester groups as well as carboxylate, sulfonate, Phosphonate, sulfate ester and phosphate ester groups, 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 from omega-hydroxy and omega-alkoxy-poly (alkylene oxide) -1-yl groups, selected.

Unless neutralized, the primary and secondary amino groups also serve as isocyanate-reactive functional groups.

Examples of highly suitable 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 (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-polyethyleneoxid-1-yl-, omega Methoxy-polypropylenoxid-1-yl-, or omega-methoxy-poly (ethylene oxide-copolypropylene oxide) -1-yl acrylate or methacrylate.

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 can lead to the formation of insoluble salts and polyelectrolyte complexes. 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 required.

Of the hydrophilic monomers (a) described above, the Monomers (a) with the functional groups (1) are particularly preferably used.

Preferably, the neutralizing agents for those in anions convertible functional groups (i) from the group consisting of Ammonia, trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, Triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, 2- Aminomethylpropanol, dimethylisopropylamine, dimethylisopropanolamine, Triethanolamine, diethylenetriamine and triethylenetetramine, and the Neutralizing agent for the functional groups which can be converted 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.

• 1. im wesentlichen säuregruppenfreien Ester olefinisch ungesättigter Säuren, wie (Meth)Acrylsäure-, Crotonsäure-, Ethacrylsäure-, Vinylphosphonsäure- oder Vinylsulfonsäurealkyl- oder -cycloalkylester mit bis zu 20 Kohlenstoffatomen im Alkylrest, insbesondere Methyl-, Ethyl-, Propyl-, n- Butyl-, sec.-Butyl-, tert.-Butyl-, Hexyl-, Ethylhexyl-, Stearyl- und Laurylacrylat, -methacrylat, -crotonat, -ethacrylat oder -vinylphosphonat oder vinylsulfonat; cycloaliphatische (Meth)acrylsäure-, Crotonsäure-, Ethacrylsäure-, Vinylphosphonsäure- oder Vinylsulfonsäureester, insbesondere Cyclohexyl-, Isobornyl-, Dicyclopentadienyl-, Octahydro-4,7- methano-1H-inden-methanol- oder tert.-Butylcyclohexyl(meth)acrylat, -crotonat, -ethacrylat, -vinylphosphonat oder vinylsulfonat. Diese können in untergeordneten Mengen höherfunktionelle (Meth)Acrylsäure-, Crotonsäure- oder Ethacrylsäurealkyl- oder -cycloalkylester wie Ethylengylkol-, Propylenglykol-, Diethylenglykol-, Dipropylenglykol-, Butylenglykol-, Pentan-1,5-diol-, Hexan-1,6-diol-, Octahydro-4,7-methano- 1H-indendimethanol- oder Cyclohexan-1,2-, -1,3- oder -1,4-dioldi(meth)acrylat; Trimethylolpropantri(meth)acrylat; oder Pentaerythrittetra(meth)acrylat sowie die analogen Ethacrylate oder Crotonate enthalten. Im Rahmen der vorliegenden Erfindung sind hierbei unter untergeordneten Mengen an höherfunktionellen Monomeren (1) solche Mengen zu verstehen, welche nicht zur Vernetzung oder Gelierung der Blockmischpolymerisate führen, es sei denn, sie sollen in der Form von vernetzten Mikrogelteilchen vorliegen;
• 2. Monomere, die mindestens eine Hydroxylgruppe oder Hydroxymethylaminogruppe pro Molekül tragen und im wesentlichen säuregruppenfrei sind, wie
  • - Hydroxyalkylester von alpha,beta-olefinisch ungesättigten Carbonsäuren, wie Hydroxyalkylester der Acrylsäure, Methacrylsäure und Ethacrylsäure, in denen die Hydroxyalkylgruppe bis zu 20 Kohlenstoffatome enthält, wie 2-Hydroxyethyl-, 2- Hydroxypropyl-, 3-Hydroxypropyl-, 3-Hydroxybutyl-, 4- Hydroxybutylacrylat, -methacrylat oder -ethacrylat; 1,4- Bis(hydroxymethyl)cyclohexan-, Octahydro-4,7-methano-1H-indendimethanol- oder Methylpropandiolmonoacrylat, -monomethacrylat, -monoethacrylat oder -monocrotonat; oder Umsetzungsprodukte aus cyclischen Estern, wie z. B. epsilon-Caprolacton und diesen Hydroxyalkylestern;
  • - olefinisch ungesättigte Alkohole wie Allylalkohol;
  • - Allylether von Polyolen wie Trimethylolpropanmonoallylether oder Pentaerythritmono-, -di- oder -triallylether. Die höherfunktionellen Monomeren (a1) werden im allgemeinen nur in untergeordneten Mengen verwendet. Im Rahmen der vorliegenden Erfindung sind hierbei unter untergeordneten Mengen an höherfunktionellen Monomeren solche Mengen zu verstehen, welche nicht zur Vernetzung oder Gelierung der Blockmischpolymerisate führen, es sei denn, sie sollen in der Form von vernetzten Mikrogelteilchen vorliegen;
  • - Umsetzungsprodukte von alpha,beta-olefinisch Carbonsäuren mit Glycidylestern einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 Kohlenstoffatomen im Molekül. Die Umsetzung der Acryl- oder Methacrylsäure mit dem Glycidylester einer Carbonsäure mit einem tertiären alpha-Kohlenstoffatom kann vorher, während oder nach der Polymerisationsreaktion erfolgen. Bevorzugt wird als Monomer (2) das Umsetzungsprodukt von Acryl- und/oder Methacrylsäure mit dem Glycidylester der Versatic®-Säure eingesetzt. Dieser Glycidylester ist unter dem Namen Cardura® E10 im Handel erhältlich. Ergänzend wird auf Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, Seiten 605 und 606, verwiesen;
  • - Formaldehydaddukte von Aminoalkylestern von alpha,beta-olefinisch ungesättigten Carbonsäuren und von alpha,beta-ungesättigten Carbonsäureamiden, wie N-Methylol- und N,N-Dimethylolaminoethylacrylat, -aminoethylmethacrylat, -acrylamid und -methacrylamid; sowie
  • - Acryloxysilangruppen und Hydroxylgruppen enthaltende olefinisch ungesättigte Monomere, herstellbar durch Umsetzung hydroxyfunktioneller Silane mit Epichlorhydrin und anschließender Umsetzung des Zwischenprodukts mit einer alpha,beta-olefinisch ungesättigten Carbonsäure, insbesondere Acrylsäure und Methacrylsäure, oder ihren Hydroxyalkylestern;
• 3. Vinylester von in alpha-Stellung verzweigten Monocarbonsäuren mit 5 bis 18 Kohlenstoffatomen im Molekül, wie die Vinylester der Versatic ®-Säure, die unter der Marke VeoVa ® vertrieben werden;
• 4. cyclische und/oder acyclische Olefine, wie Ethylen, Propylen, But-1-en, Pent-1-en, Hex-1-en, Cyclohexen, Cyclopenten, Norbonen, Butadien, Isopren, Cylopentadien und/oder Dicyclopentadien;
• 5. Amide von alpha,beta-olefinisch ungesättigten Carbonsäuren, wie (Meth)Acrylsäureamid, N-Methyl -, N,N-Dimethyl-, N-Ethyl-, N,N-Diethyl-, N-Propyl-, N,N-Dipropyl, N-Butyl-, N, N-Dibutyl- und/oder N,N-Cyclohexylmethyl-(meth)acrylsäureamid;
• 6. Epoxidgruppen enthaltenden Monomere, wie der Glycidylester der Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure und/oder Itaconsäure;
• 7. vinylaromatischen Kohlenwasserstoffe, wie Styrol, Vinyltoluol oder alpha- Alkylstyrole, insbesondere alpha-Methylstyrol;
• 8. Nitrile, wie Acrylnitril oder Methacrylnitril;
• 9. Vinylverbindungen, ausgewählt aus der Gruppe, bestehend aus Vinylhalogeniden wie Vinylchlorid, Vinylfluorid, Vinylidendichlorid, Vinylidendifluorid; Vinylamiden, wie N-Vinylpyrrolidon; Vinylethern wie Ethylvinylether, n-Propylvinylether, Isopropylvinylether, n-Butylvinylether, Isobutylvinylether und Vinylcyclohexylether; sowie Vinylestern wie Vinylacetat, Vinylpropionat, und Vinylbutyrat;
• 10. Allylverbindungen, ausgewählt aus der Gruppe, bestehend aus Allylethern und -estern, wie Propylallylether, Butylallylether, Ethylenglykoldiallylether Trimethylolpropantriallylether oder Allylacetat oder Allylpropionat; was die höherfunktionellen Monomere betrifft, gilt das vorstehend Gesagte sinngemäß;
• 11. Polysiloxanmakromonomere, die ein zahlenmittleres Molekulargewicht Mn von 1.000 bis 40.000 und im Mittel 0,5 bis 2,5 ethylenisch ungesättigte Doppelbindungen pro Molekül aufweisen, wie Polysiloxanmakromonomere, die ein zahlenmittleres Molekulargewicht Mn von 1.000 bis 40.000 und im Mittel 0,5 bis 2,5 ethylenisch ungesättigte Doppelbindungen pro Molekül aufweisen; insbesondere Polysiloxanmakromonomere, die ein zahlenmittleres Molekulargewicht Mn von 2.000 bis 20.000, besonders bevorzugt 2.500 bis 10.000 und insbesondere 3.000 bis 7.000 und im Mittel 0,5 bis 2,5, bevorzugt 0,5 bis 1,5, ethylenisch ungesättigte Doppelbindungen pro Molekül aufweisen, wie sie in der DE 38 07 571 A1 auf den Seiten 5 bis 7, der DE 37 06 095 A1 in den Spalten 3 bis 7, der EP 0 358 153 B1 auf den Seiten 3 bis 6, in der US 4,754,014 A1 in den Spalten 5 bis 9, in der DE 44 21 823 A1 oder in der internationalen Patentanmeldung WO 92/22615 auf Seite 12, Zeile 18, bis Seite 18, Zeile 10, beschrieben sind; und
• 12. Carbamat- oder Allophanatgruppen enthaltende Monomere, wie Acryloyloxy- oder Methacryloyloxyethyl-, propyl- oder butylcarbamat oder -allophanat; weitere Beispiele geeigneter Monomere, welche Carbamatgruppen enthalten, werden in den Patentschriften US 3,479,328 A1, US 3,674,838 A1, US 4,126,747 A1, US 4,279,833 A1 oder US 4,340,497 A1 beschrieben.

Examples of suitable hydrophobic olefinically unsaturated monomers (a) are

• 1. essentially acid group-free esters of olefinically unsaturated acids, such as (meth) acrylic acid, crotonic acid, ethacrylic acid, vinylphosphonic acid or vinylsulfonic acid alkyl or cycloalkyl esters having 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, crotonate, ethacrylate or vinyl phosphonate or vinyl sulfonate; cycloaliphatic (meth) acrylic acid, crotonic acid, ethacrylic acid, vinylphosphonic acid or vinylsulfonic acid esters, in particular cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene methanol or tert-butylcyclohexyl (meth) acrylate, crotonate, ethacrylate, vinyl phosphonate or vinyl sulfonate. These can be used in minor amounts of higher functional (meth) acrylic acid, crotonic acid or alkyl or cycloalkyl ethacrylic acid, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1,5-diol, hexane-1,6 -diol-, octahydro-4,7-methano-1H-indendimethanol- or cyclohexane-1,2-, -1,3- or -1,4-diol di (meth) acrylate; Trimethylolpropane tri (meth) acrylate; or pentaerythritol tetra (meth) acrylate and the analog ethacrylates or crotonates. In the context of the present invention, minor amounts of higher-functional monomers (1) are to be understood as those amounts which do not lead to crosslinking or gelling of the block copolymers, unless they should be in the form of crosslinked microgel particles;
• 2. Monomers which carry at least one hydroxyl group or hydroxymethylamino group per molecule and are essentially free of acid groups, such as
  • - 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-hydroxybutyl , 4-Hydroxybutyl acrylate, methacrylate or ethacrylate; 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indendimethanol or methyl propanediol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or reaction products from cyclic esters, such as. B. 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, minor amounts of higher-functional monomers are understood to mean those amounts which do not lead to crosslinking or gelling of the block copolymers, unless they should be in the form of crosslinked microgel particles;
  • - Reaction products of alpha, beta-olefinic carboxylic acids with glycidyl esters of a monocarboxylic acid with 5 to 18 carbon atoms in the molecule, branched in the alpha position. The reaction of acrylic or methacrylic acid with the glycidyl ester of a 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). This glycidyl ester is commercially available under the name Cardura® E10. In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, 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 carboxylic acid amides, such as N-methylol and N, N-dimethylolaminoethyl acrylate, aminoethyl methacrylate, acrylamide and methacrylamide; such as
  • Olefinically unsaturated monomers containing acryloxysilane groups and hydroxyl groups, which can be prepared by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the intermediate with an alpha, beta-olefinically unsaturated carboxylic acid, in particular acrylic acid and methacrylic acid, or their hydroxyalkyl esters;
• 3. 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®;
• 4. Cyclic and / or acyclic olefins, such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbones, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene;
• 5. Amides of alpha, beta-olefinically unsaturated carboxylic acids, such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N -Dipropyl, N-butyl, N, N-dibutyl and / or N, N-cyclohexylmethyl- (meth) acrylic acid amide;
• 6. monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid;
• 7. vinyl aromatic hydrocarbons, such as styrene, vinyl toluene or alpha-alkyl styrenes, especially alpha-methyl styrene;
• 8. nitriles, such as acrylonitrile or methacrylonitrile;
• 9. vinyl compounds selected from the group consisting of vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; 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 vinylcyclohexyl ether; as well as vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate;
• 10. Allyl compounds selected from the group consisting of allyl ethers and esters, such as propyl allyl ether, butyl allyl ether, ethylene glycol diallyl ether, trimethylolpropane triallyl ether or allyl acetate or allyl propionate; As far as the higher functional monomers are concerned, what has been said above applies analogously;
• 11. Polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2.5 ethylenically unsaturated double bonds per molecule, such as polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2 , Have 5 ethylenically unsaturated double bonds per molecule; 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 DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in columns 3 to 7, EP 0 358 153 B1 on pages 3 to 6, in US 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18 to page 18, line 10; and
• 12. Monomers containing carbamate or allophanate groups, such as acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; further examples of suitable monomers which contain carbamate groups are described in the patents US 3,479,328 A1, US 3,674,838 A1, US 4,126,747 A1, US 4,279,833 A1 or US 4,340,497 A1.

Compounds of the general formula I are used as monomers (b).

In the general formula I, 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.

Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso- Butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.

Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.

Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, Ethylene cyclohexane or propane-1,3-diyl-cyclohexane.

Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, Propyl or butyl cyclohex-1-yl.

Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl.

Examples of suitable alkylaryl radicals are benzyl or ethylene or Propane-1,3-diylbenzol.

Examples of suitable cycloalkylaryl radicals are 2-, 3-, or 4-phenylcyclohex-1-yl.

Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, -propyl- or -Butylphen-1-yl.

Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl.

The radicals R ¹ , R ² , R ³ and R ⁴ described above can be substituted. For this purpose, electron-withdrawing or electron-donating atoms or organic residues can be used.

Examples of suitable substitutes are halogen atoms, in particular chlorine and Fluorine, nitrile groups, nitro groups, partially or fully halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl, aryl, alkylaryl, cycioalkylaryl, arylalkyl and arylcycloalkyl radicals, including the examples mentioned 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 or cyclohexylthio; hydroxyl groups; and / or primary, secondary and / or tertiary amino groups, especially amino, N-methylamino, N-ethylamino, N-propyiamino, N-phenylamino, N-cyclohexylamino, N, N- Dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diphenylamino, N, N- Dicyclohexylamino, N-cyclohexyl-N-methylamino or N-ethyl-N-methylamino.

Examples of monomers (b) used with particular preference according to the invention are diphenylethylene, dinaphthaleneethylene, cis or trans stilbene, vinylidene bis (4- N, N-dimethylaminobenzene), vinylidene bis (4-aminobenzene) or vinylidene bis (4- nitrobenzene).

According to the invention, the monomers (b) can be used individually or as a mixture at least two monomers (b) can be used.

Regarding the reaction and the properties of the resulting Block copolymers are of particular advantage and diphenylethylene is therefore used very particularly preferably according to the invention.

Each of the above monomers (a) can be used alone with the Monomers (b) are polymerized. According to the invention, however, it is advantageous to use at least two monomers (a) because this means that Property profile of the resulting block copolymers in particular advantageously varies very widely and the particular purpose of aqueous dispersions (A) can be adapted very specifically.

The monomers (a) are preferably selected such that the Property profile of the block copolymers essentially from the (Meth) acrylate monomers described above is determined, the Monomers (a) which come from other classes of monomers, this Property profile vary advantageously in a wide and targeted manner.

In this way, preference is given to the block copolymers dispersing functional groups (i) or (ii) and / or (iii) or incorporated, through which the block copolymers become hydrophilic, so that they are in aqueous Media can be dispersed or dissolved. It is preferably installed in the first stage of the production of the block copolymer.

In addition, isocyanate-reactive functional groups are built in with the Can crosslink polyisocyanates described below.

The block copolymers are prepared by using in a first stage (1) at least one monomer (b) with at least one monomer (a), in particular at least one hydrophilic monomer (a) to one Copolymer or a macroinitiator. This copolymer or this macroinitiator is then isolated or immediately in the Reaction mixture, preferably directly in the reaction mixture, in at least one further stage (2) with at least one further, preferably hydrophobic, monomer (a) implemented under radical conditions. Reaction in the absence of an initiator of the radical is preferred Polymerization carried out.

However, stages (1) and (2) can also be carried out in succession in one reactor be performed. For this purpose, the monomer (b) is first mixed with at least a monomer (a) completely or partially depending on the desired application and the desired properties, after which at least one further monomer (a) is added and free radical is polymerized. In another embodiment, from the start at least two monomers (a) are used, the monomer (b) initially with one of the at least two monomers (a) and then the resulting copolymer above a certain molecular weight reacts with the further monomer (a).

The weight ratio of that formed in the first stage (1) is preferably Copolymer or macro initiator to the further monomer (s) (a) the further stage (s) (2) at 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 especially 1:15 to 1: 1.

Depending on the reaction, it is possible to use block copolymers Block, multiblock, gradient (co) polymer, star and branch structures, which may also be functionalized at the end groups.

Examples of usable initiators of radical polymerization are called: 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-trimethylhexanoate or tert-butyl per-2-ethylhexanoate; Potassium, sodium or ammonium peroxodisulfate; Azodinitriles such as azobisisobutyronitrile; C-C-cleaving Initiators such as benzpinacol silyl ether; or a combination of either oxidizing initiator with hydrogen peroxide. More examples more suitable Initiators are described in German patent application DE 196 28 142 A1, page 3, Line 49 to page 4, line 6.

Comparatively large amounts of radical initiator are preferred added, the proportion of the initiator in the reaction mixture, based in each case on the total amount of monomers (a) and (b) and of the initiator, especially preferably 0.5 to 50% by weight, very particularly preferably 1 to 20% by weight and is 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 is within the specified Limits are used in excess.

The two- or multi-stage radical copolymerization or Block copolymerization is carried out in an aqueous or an organic Medium performed.

If the block copolymerization is carried out in an organic medium, the resulting organic solution or dispersion of the Block copolymers or block copolymers in an aqueous Medium dispersed, resulting in a secondary dispersion (A). The organic solvents contained therein are optionally distilled off.

If the block copolymerization is carried out in an aqueous medium, result in aqueous primary dispersions (A) which, as such, are used directly for the Production of the coating materials to be used according to the invention can be used.

The block copolymerization is preferably carried out in an aqueous medium carried out.

The aqueous medium essentially contains water. Here, the aqueous Medium in minor quantities as described in detail below Additives and / or other dissolved solid, liquid or gaseous, low and / or high molecular weight substances, in particular bases, if provided do not negatively influence or even inhibit the copolymerization and / or lead to the emission of volatile organic compounds. As part of of the present invention is one under the term "minor amount" To understand amount, which the aqueous character of the aqueous medium does not cancel. The aqueous medium can also be pure Act water.

Examples of suitable bases are low molecular weight bases such as sodium hydroxide solution, Potash lye, ammonia, diethanolamine, triethanolamine, mono-, di- and Triethylamine, and / or dimethylethanolamine, especially ammonia and / or Di- and / or triethanolamine.

The usual and. Come as reactors for the (co) polymerization processes 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, number 9, 1995, pages 1409 to 1416 be considered. The radical copolymerization is preferably carried out in Stirred kettles or Taylor reactors, the Taylor reactors being so be interpreted that the conditions of the Taylor flow are satisfied 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 A1).

The copolymerization is advantageously carried out at temperatures above Room temperature and below the lowest decomposition temperature of each used monomers carried out, preferably a temperature range from 10 to 150 ° C, very particularly preferably 50 to 120 ° C and in particular 55 up to 110 ° C is selected.

When using particularly volatile monomers (a) and / or (b), the Copolymerization also under pressure, preferably under 1.5 to 3,000 bar, preferably 5 to 1,500 and in particular 10 to 1,000 bar.

With regard to the molecular weight distributions, the block copolymer is not subject to any restrictions. But it is advantageous Copolymerization carried out so that a molecular weight distribution Mw / Mn measured with gel permeation chromatography using polystyrene as the standard of ≤ 4, preferably particularly preferably ≤ 2 and in particular ≤ 1.5 and in some cases also ≤ 1.3 results. The molecular weights of the Block copolymers are selected by the choice of the ratio of monomer (a) to monomer (b) to radical initiator controllable within wide limits. there in particular the content of monomer (b) determines the molecular weight, and in such a way that the greater the proportion of monomer (b), the lower it is molecular weight obtained.

The proportion of block copolymers in the aqueous dispersions (A) can vary widely. It is preferably 10 to 70, more preferably 15 to 65, particularly preferably 20 to 60, very particularly preferably 25 to 55 and in particular 30 to 50% by weight, based in each case on the aqueous dispersion (A).

The content of the coating material to be used according to the invention in the aqueous dispersions (A) can in any case vary widely and 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 preferred 25 to 65 and in particular 30 to 60 wt .-%, based on the Coating material.

The coating material to be used according to the invention also contains at least one crosslinking agent component, the at least one polyisocyanate contains or consists of. The crosslinker component can be inert contain organic solvents to increase the viscosity of the polyisocyanates lower, so that with the other components of the invention coating material can be mixed more easily.

The statistical average of the polyisocyanates contains at least 2.0, preferably more than 2.0 and especially more than 3.0 isocyanate groups per molecule. The There is basically no upper limit to the number of isocyanate groups;

According to the invention, however, it is advantageous if the number 15, preferably 12, particularly preferably 10, very particularly preferably 8.0 and in particular 6.0 does not exceed.

Examples of suitable polyisocyanates are those containing isocyanate groups Polyurethane prepolymers obtained by reacting polyols with an excess diisocyanates can be prepared and are preferably low viscosity. Examples of suitable diisocyanates are isophorone diisocyanate (= 5-isocyanato-1- isocyanatomethyl-1,3,3-trimethyl-cyclohexane), 5-isocyanato-1- (2-isocyanatoeth-1- yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3- trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1,3,3-trimethylcyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) - cyclohexane, 1,2-diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2- Diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane, 1,2- Diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4- Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate, Trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene diisocyanate (HDI), ethyl ethylene diisocyanate, Trimethylhexane diisocyanate, heptamethylene diisocyanate or diisocyanates derived from Dimer fatty acids, such as those sold by the company under the trade name DDI 1410 Henkel sold and in the patents WO 97/49745 and WO 97/49747 be described, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -1-pentylcyclohexane, or 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4- or 1,3-bis (2-isocyanatoeth-1-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-1- yl) cyclohexane, 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-1-yl) cyclohexane or liquid bis (4-isocyanatocyclohexyl) methane with a trans / trans content of up to 30 wt .-%, preferably 25 wt .-% and in particular 20 wt .-%, as the Patent applications DE 44 14 032 A1, GB 1220717 A1, DE 16 18 795 A1 or DE 17 93 785 A1 is described, preferably isophorone diisocyanate, 5- Isocyanato-1- (2-isocyanatoeth-1-yl) -1,3,3-trimethylcyclohexane, 5-isocyanato-1- (3- isocyanatoprop-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1- yl) -1,3,3-trimethyl-cyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4- isocyanatobut-1-yl) cyclohexane or HDI, especially HDI.

Isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, Polyisocyanates containing urea, carbodiimide and / or uretdione groups are used in a conventional and known manner from the above described diisocyanates are prepared. Example more suitable Manufacturing 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 A1, EP 0 496 208 A1, EP 0 524 500 A1, EP 0 566 037 A1, US 5,258,482 A1, US 5,290,902 A1, EP 0 649 806 A1, DE 42 29 183 A1 or EP 0 531 820 A1 known.

The content of the coating materials to be used according to the invention in the The polyisocyanates described above can vary very widely. The salary 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 according to the crosslink density that the coatings have should. The content is preferably 1 to 30, more preferably 2 to 28, particularly preferably 3 to 24, very particularly preferably 3 to 22 and in particular 3 to 20 % By weight, based in each case on the coating material.

The coating material to be used according to the invention can moreover at least one, in particular one, primary aqueous dispersion (C) contain at least one (meth) acrylate copolymer, which of the aqueous Dispersion (A) is different. Primary aqueous dispersions (C) are common and well-known products and are, for example, by Zeneca under the Brand Neocryl ®, for example Neocryl ® XK 90 sold. Preferably the primary aqueous dispersions (C) serve to grind the following described pigments.

In addition, the coating material to be used according to the invention can also color and / or effect, fluorescent, electrically conductive and / or magnetically shielding pigments, metal powder, organic and inorganic, transparent or opaque fillers and / or nanoparticles (in summary "Pigments (D)" included).

Examples of suitable effect pigments are metal flake pigments such as commercially available aluminum bronzes, chromated according to DE 36 36 183 A1 Aluminum bronze, and commercially available stainless steel bronze and non-metallic Effect pigments, such as pearlescent or interference pigments, platelet-like effect pigments based on iron oxide, which has a hue from pink to brownish red or liquid crystalline effect pigments. additional is applied to Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998, Pages 176, "Effect Pigments" and Pages 380 and 381 "Metal Oxide Mica Pigments "to" Metallpigmente ", and the patent applications and patents DE 36 36 156 A1, DE 37 18 446 A1, DE 37 19 804 A1, DE 39 30 601 A1, EP 0 068 311 A1, EP 0 264 843 A1, EP 0 265 820 A1, EP 0 283 852 A1, EP 0 293 746 A1, EP 0 417 567 A1, US 4,828,826 A or US 5,244,649 A.

Examples of suitable inorganic color pigments are white pigments such as titanium dioxide, zinc white, zinc sulphide or lithopone; Black pigments like soot, 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; Brown iron oxide, 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.

Examples of suitable organic coloring pigments are Monoazo pigments, bisazo pigments, anthraquinone pigments, Benzimidazole pigments, quinacridone pigments, quinophthalone pigments, Diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, Isoindoline pigments, isoindolinone pigments, azomethine pigments, Thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, Phthalocyanine pigments or aniline black.

In addition, varnish and printing inks are used on Römpp Lexikon, Georg Thieme Verlag, 1998, pages 180 and 181, "Eisenblau-Pigments" to "Eisenoxidschwarz", pages 451 to 453 "Pigments" to "Pigment Volume Concentration", page 563 "Thioindigo Pigments", page 567 "Titanium dioxide pigments", pages 400 and 467, "Naturally occurring Pigments ", page 459" Polycyclic Pigments ", page 52," Azomethine Pigments "," Azo Pigments ", and page 379," Metal Complex Pigments ", directed.

Examples of fluorescent pigments (daylight pigments) are Bis (azomethine) pigments.

Examples of suitable electrically conductive pigments are titanium dioxide / tin oxide Pigments.

Examples of magnetically shielding pigments are pigments based on Iron oxides or chromium dioxide.

Examples of suitable metal powders are powders made of metals and Metal alloys aluminum, zinc, copper, bronze or brass.

Examples of suitable organic and inorganic fillers are chalk, Calcium sulfate, barium sulfate, silicates such as talc, mica or kaolin, Silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular made of polyamide or Polyacrylonitrile. In addition, varnish and printing inks, Georg, are added to Römpp Lexikon Thieme Verlag, 1998, pages 250 ff., "Fillers".

Examples of 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, especially hydrophilic, nanoparticles on the Base of 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 ones are preferred Nanoparticles no matting effect. Nanoparticles are particularly preferred used on the basis of silicon dioxide.

Hydrophilic fumed silicas are very particularly preferred used, whose agglomerates and aggregates have a chain-like structure and that through the flame hydrolysis of silicon tetrachloride in one Oxyhydrogen flame can be produced. These are used, for example, by the company Degussa sold under the brand Aerosil®. Be particularly preferred also precipitated water glasses, such as nano-hectorite, for example from the company Südchemie under the Optigel® brand or from Laporte under the brand Laponite® are used.

In addition to the pigments (D) described above, it can also be used according to the invention coating material using at least one further additive contain.

Examples of suitable further additives are other polyisocyanates (B) various crosslinking agents, such as blocked polyisocyanates, Aminoplast resins, or tris (alkoxycarbonylamino) triazines, molecularly dispersed soluble 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, Polymerization inhibitors, crosslinking catalysts, thermolabile radical initiators, thermally curable reactive thinners, adhesion promoters, Leveling agents, film-forming aids, rheology aids (thickeners), Flame retardants, corrosion inhibitors, pouring aids, waxes, siccatives, biocides and / or matting agents, as described, for example, in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, im Be described in detail.

From a methodological point of view, the production of the according to the invention coating materials using no special features, but takes place by mixing the ingredients described above in conventional and known mixing units, such as stirred kettles, Ultraturrax, inline dissolvers, extruders or kneader.

In terms of methodology, the application has to be used according to the invention Coating materials also have no peculiarities, but can go through everything usual application methods, such as. B. spraying, knife coating, brushing, pouring, Dipping, trickling or rolling. Preferably be Spray application methods applied, such as compressed air spraying, Airless spraying, high rotation, electrostatic spray application (ESTA), possibly connected with hot spray application such as hot air Hot spraying.

The hardening of the applied coating materials is also not methodological Special features, but takes place according to the usual 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, shiny Coatings on that have a smooth flow and a smooth surface without interference, such as craters or pinholes, free of light Are dark shades (clouds) and against all household chemicals, including active chlorine are resistant. The new coated medium-density fibreboards are therefore excellent for the production of doors suitable for indoor use, wooden cassettes, cheap furniture and rear walls of furniture.

Production Example 1 The manufacture of a markro initiator

In a steel reactor, as is usually used for the production of dispersions is used, equipped with a stirrer, a reflux condenser and 3 1,591.1 parts by weight of demineralized water were introduced into the inlet vessels and the mixture was brought to 70 ° C. heated. In the first feed vessel 308.2 parts by weight of acrylic acid, 555.2 Parts by weight of methyl methacrylate and 45.2 parts by weight of diphenylethylene submitted. 300.1 parts by weight became 25 percent in the second feed vessel Ammonia solution submitted. In the third feed tank 159 Parts by weight of demineralized water and 68.2 parts by weight of ammonium peroxodisulfate submitted. With intensive stirring of the template in the steel reactor, the three Inlets started simultaneously. The first and second inflows were within metered in for four hours. The third inflow was within 4.5 hours Hours dosed. The resulting reaction mixture was stirred for four Hours at 70 ° C and then cooled to below 40 ° C and filtered through a 100 µm GAF bag. The resulting dispersion had one Solids content of 33 to 34 wt .-% (1 hour, 130 ° C) and a content of free monomers of less than 0.2% by weight (determined by Gas chromatography).

Preparation example 2 The preparation of the dispersion (A) of a block copolymer

In a steel reactor, as is usually used for the production of dispersions is used, equipped with a stirrer, a reflux condenser and a 1,361.7 parts by weight of demineralized water and 240 parts by weight of Dispersion according to preparation example 1 submitted and heated to 80 ° C with stirring. The feed vessel then became a mixture within six hours from 260 parts by weight of n-butyl methacrylate, 208 parts by weight of styrene, 334 Parts by weight of hydroxyethyl methacrylate and 234.4 parts by weight Ethylhexyl methacrylate added. The resulting reaction mixture was stirred at 80 ° C for two hours. Then the resulting Cooled dispersion below 40 ° C and filtered through a 50 micron 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).

example 1 The production of coated medium density fiberboard

• - 150 Gewichtsteilen der Dispersion (A) des Herstellbeispiels 2,
• - 100 Gewichtsteilen einer handelsüblichen wäßrigen Primärdispersion eines Methacrylatcopolymerisats (Neocryl® XK 90 der Firma Zeneca), enthaltend Titandioxid-Weißpigment (Glasurit® Fenstercolor 30/B 03 5 der Firma BASF Coatings AG),
• - 1,5 Gewichtsteilen eines handelsüblichen Entschäumungsmittels (Agitan® E 256 der Firma Münzing Chemie),
• - 6,0 Gewichtsteilen einer handelsübüchen Polydimethylsiloxan-Dispersion (Wacker SI finish CT12E der Firma Wacker Chemie) und
• - 5 Gewichtsteilen deionisiertem Wasser hergestellt.

For the production of the coated medium-density fiberboard, a base coat was first made

• 150 parts by weight of dispersion (A) from preparation example 2,
• 100 parts by weight of a commercially available aqueous primary dispersion of a methacrylate copolymer (Neocryl® XK 90 from Zeneca), containing titanium dioxide white pigment (Glasurit® window color 30 / B 03 5 from BASF Coatings AG),
• 1.5 parts by weight of a commercially available defoaming agent (Agitan® E 256 from Münzing Chemie),
• - 6.0 parts by weight of a commercially available polydimethylsiloxane dispersion (Wacker SI finish CT12E from Wacker Chemie) and
• - 5 parts by weight of deionized water.

Shortly before application, the base coat was 13, 25 parts by weight Polyisocyanate (trimeric hexamethylene diisocyanate of the isocyanurate type, Basonat® P LR 8878 from BASF Aktiengesellschaft, 56 percent in 1- Methoxypropylacetate-2 / acetone) mixed.

The coating material was reduced to medium density using cup guns Fiberboard made with a primer made from a solution of a commercially available methacrylate copolymer (Uracron® CY476E from DSM) in methyl ethyl ketone, were applied. The wet film thickness became like this adjusted that after curing of the layers for 60 minutes at 40 ° C. Dry layer thicknesses of 50 to 70 µm resulted.

The coatings were even and smooth Surface on. The gloss was 14 to 18 ° with a measuring angle of 60 °. The Scratch resistance and chemical resistance even against chlorine Detergents were excellent.

Claims (17)

1. 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, characterized in that at least one of the coating materials A) the aqueous dispersion of at least one block copolymer, which has on average at least two isocyanate-reactive functional groups and is obtainable by the two- or multi-stage, controlled free-radical block copolymerization in an aqueous or an organic medium, where 1. in a first step 1. at least one olefinically unsaturated monomer and 2. at least one olefinically unsaturated monomer of the general formula I which is different from the olefinically unsaturated monomer (a)

R ¹ R ² C = CR ³ R ⁴ (I),

wherein 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 represent} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;
copolymerized, after which 2. in a second stage, 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); and B) at least one crosslinking agent component with at least one polyisocyanate contains. 2. Medium density fiberboard according to claim 1, characterized in that the coating material A) at least one primary aqueous dispersion of at least one (meth) acrylate copolymer different from the aqueous dispersions (A) contains. 3. Medium density fiberboard according to claim 1 or 2, characterized in that the coating material A) at least one pigment contains. 4. Medium density fiberboard according to claim 3, characterized in that the pigments from the group consisting of color and / or effect, fluorescent, electrically conductive and magnetic shielding pigments, metal powders, organic and inorganic, transparent and opaque fillers and nanoparticles, selected become. 5. Medium density fiberboard according to one of claims 1 to 4, characterized characterized in that the block copolymer (A) can be prepared by in the first stage (1) at least one monomer (b) with at least one a hydrophilic monomer (a) is converted into a copolymer. 6. Medium density fiberboard according to one of claims 1 to 5, characterized characterized in that the block copolymer (A) can be prepared by the resulting in at least one further stage (2) Copolymer with at least one hydrophobic monomer (a). 7. Medium density fiberboard according to one of claims 1 to 6, characterized in that the aryl radicals R ¹ , R ² , R ³ and / or R ^{4 of} the monomers (b) are phenyl or naphthyl radicals. 8. Medium density fiberboard according to claim 7, characterized in that it is phenyl radicals. 9. Medium density fiberboard according to one of claims 1 to 8, characterized in that the substituents in the radicals R ¹ , R ² , R ³ and / or R ^{4 of} the monomers (b) from the group consisting of electron-withdrawing or electron-donating atoms or organic residues. 10. Medium density fiberboard according to claim 9, characterized in that the substituents from the group consisting of halogen atoms, nitrile, Nitro, partially or fully halogenated alkyl, cycloalkyl, Alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; Aryloxy, alkyloxy and cycloalkyloxy radicals; Arylthio, alkylthio and cycloalkylthio residues and primary, secondary and / or tertiary amino groups. 11. Medium density fiberboard according to one of claims 5 to 10, characterized in that the hydrophilic monomer (a) contains at least one functional group consisting of the group consisting of a) functional groups which can be converted into anions by neutralizing agents and anionic groups,
or b) functional groups which can be converted into cations by neutralizing agents and / or quaternizing agents, and cationic groups,
and c) nonionic hydrophilic groups, is selected. 12. Medium density fiberboard according to claim 11, characterized in that the functional groups (1) from the group consisting of carboxylic acid, Sulphonic acid and phosphonic acid groups, acidic sulfuric acid and Phosphoric acid ester groups and carboxylate, sulfonate, phosphonate, Sulfate ester and phosphate ester groups, the functional groups (ii) 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. 13. Medium density fiberboard according to claim 11 or 12, characterized characterized in that the neutralizing agent for those in anions convertible functional groups (i) from the group consisting of Ammonia, trimethylamine, triethylamine, tributylamine, dimethylaniline, Diethylaniline, triphenylamine, dimethylethanolamine, diethylethanolamine, Methyldiethanolamine, 2-aminomethylpropanol, dimethylisopropylamine, Dimethylisopropanolamine, triethanolamine, diethylene triamine and Triethylenetetramine, and the neutralizing agent for those in cations convertible functional groups (ii) from the group consisting of Sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, Lactic acid, dimethylolpropionic acid and citric acid become. 14. Medium density fiberboard according to one of claims 5 to 13, characterized in that the hydrophobic monomers (a) from the group consisting of 1. essentially acid group-free esters of olefinically unsaturated acids; 2. monomers which carry at least one hydroxyl group or hydroxymethylamino group per molecule and are essentially free of acid groups; 3. vinyl esters of monocarboxylic acids with 5 to 18 carbon atoms in the molecule which are branched in the alpha position; 4. cyclic and / or acyclic olefins; 5. Amides of olefinically unsaturated carboxylic acids; 6. monomers containing epoxy groups; 7. vinyl aromatic hydrocarbons; 8. nitriles; 9. vinyl compounds selected from the group consisting of vinyl halides, N-vinyl amides, vinyl ethers and vinyl esters; 10. Allyl compounds selected from the group consisting of allyl ethers and esters; 11. Polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; and 12. Monomers containing carbamate or allophanate groups; to be selected. 15. Medium density fiberboard one of claims 1 to 14, characterized characterized in that the isocyanate-reactive functional groups from the Group consisting of hydroxyl groups, primary and secondary Amino groups, thiol groups and imino groups can be selected. 16. Medium density fiberboard according to claim 15, characterized in that one uses hydroxyl groups. 17. Use of the medium density fiberboard according to one of claims 1 to 16 for the manufacture of doors, wooden cassettes, furniture and Furniture rear panels.