WO2010112288A1 - Agent de revêtement, procédé de fabrication d'un revêtement et article revêtu - Google Patents

Agent de revêtement, procédé de fabrication d'un revêtement et article revêtu Download PDF

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WO2010112288A1
WO2010112288A1 PCT/EP2010/052662 EP2010052662W WO2010112288A1 WO 2010112288 A1 WO2010112288 A1 WO 2010112288A1 EP 2010052662 W EP2010052662 W EP 2010052662W WO 2010112288 A1 WO2010112288 A1 WO 2010112288A1
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meth
octa
coating composition
composition according
ethyl
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PCT/EP2010/052662
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German (de)
English (en)
Inventor
Bardo Schmitt
Wolfgang Klesse
Martina Ebert
Thorben SCHÜTZ
Mario Gomez
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Evonik Röhm Gmbh
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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters

Definitions

  • Coating composition process for producing a coating and coated article
  • the present invention relates to a coating agent.
  • the present invention is directed to a method for producing a coating carried out using the coating agent and a coated article obtainable by the method.
  • Coating agents in particular paints, have been produced synthetically for a long time.
  • An important group of these agents is based on aqueous dispersions which often comprise (meth) acrylate polymers.
  • aqueous dispersions which often comprise (meth) acrylate polymers.
  • the publication DE-A-41 05 134 describes aqueous dispersions which contain alkyl methacrylates as binders.
  • paints from US 5,750,751, EP-A-1 044 993 and WO 2006/013061 are known.
  • DE-A-27 32 693 discloses coating compositions based on solvents which can be crosslinked by polyisocyanates.
  • reactive coatings form another group of known coating compositions.
  • paints are known for example from EP-O 693 507.
  • compositions are known which comprise so-called reactive diluents.
  • the document EP-A-546 417 describes coating compositions which comprise in particular octadienyl ethers.
  • coating compositions described above already show a good property spectrum. However, there is a permanent need to improve this property spectrum. Thus, coatings obtainable from some of the coating agents set forth above exhibit insufficient resistance to chemicals, in particular polar solvents, for elevated demands.
  • a high stability compared to many different solvents and to bases and acids should be achieved.
  • a very good resistance to methyl ethyl ketone (MEK) should be given.
  • the hardness of the coatings obtainable from the coating compositions should be able to be varied over a wide range.
  • particularly hard, scratch-resistant coatings should be able to be obtained from the coating compositions.
  • coatings which are obtainable from the coating compositions according to the invention, based on the hardness should have a relatively low brittleness.
  • Weathering resistance in particular have a high UV resistance.
  • the coating agents should show good processability over a wide range of temperature and humidity.
  • the coating compositions should show improved environmental compatibility.
  • the smallest possible amounts of organic solvents should be released into the environment by evaporation.
  • the present invention accordingly provides a coating composition comprising at least one (meth) acrylic polymer and at least one reactive diluent, which is characterized in that the reactive diluent comprises at least one octadienyl group and the (meth) acrylic polymer units derived from (meth) acrylic Monomers are derived which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical, and
  • the coatings available from the coating compositions of the present invention show high chemical resistance. In this case, a high stability compared to many different solvents and to bases and acids can be achieved. In particular, a very good resistance to methyl ethyl ketone (MEK) is often given. Likewise, a very good resistance to water can be achieved. Therefore, these coating agents can be used for the production of protective coatings. Furthermore, the hardness of the coatings obtainable from the coating compositions can be varied over a wide range. In particular, particularly hard, scratch-resistant coatings can be obtained. Furthermore, coatings which are obtainable from the coating compositions according to the invention, based on the hardness and the chemical resistance, a relatively low brittleness.
  • MEK methyl ethyl ketone
  • the coating compositions of the invention have good processability over a wide range of temperature and humidity.
  • the coating compositions show improved environmental compatibility.
  • extremely small amounts of organic solvents are released into the environment through evaporation.
  • Particularly preferred embodiments show no release of organic solvents into the atmosphere.
  • the coating compositions may comprise a high solids content.
  • coating compositions of the invention lead to coatings with a high gloss.
  • the coating compositions of the present invention exhibit particularly long shelf life and durability.
  • the coatings obtainable from the coating compositions show a high weather resistance, in particular a high UV resistance.
  • novel coating compositions are particularly cost-effective and commercially available.
  • the coating composition according to the invention comprises at least one reactive diluent which has at least one octadienyl group.
  • These compounds accordingly comprise at least one group of the formula -R, in which R represents a residue with exactly 8 carbon atoms, which has two carbon-carbon atoms. Has double bonds.
  • the preferred radicals having exactly 8 carbon atoms and 2 double bonds include in particular octa-2,7-dienyl groups, octa-3,7-dienyl groups, octa-4,7-dienyl groups, octa-5,7-dienyl groups, octa-2,4 -dienyl groups, octa-2,5-dienyl groups, octa-2,6-dienyl groups, octa-3,5-dienyl groups, octa-3,6-dienyl groups and octa-4,6-dienyl groups.
  • the compounds preferably to be used as reactive diluents may have a molecular weight in the range from 140 g / mol to 2000 g / mol, preferably 140 g / mol to 1000 g / mol and very particularly preferably 140 g / mol to 500 g / mol.
  • the dynamic viscosity of the reactive diluent can be in a wide range.
  • reactive diluents having a boiling point of at least 180 ° C., preferably at least 250 ° C., particularly preferably at least 280 ° C. at atmospheric pressure (1024 mbar), are of particular interest.
  • the boiling point of the reactive diluent at atmospheric pressure in the range of 180 to 350 0 C, more preferably in the range of 250 to 300 0 C.
  • the reactive diluent having at least one octadienyl group is an alcohol, an amine, an ether or an ester.
  • the preferred alcohols include in particular octa-2,7-dienol, octa-3,7-dienol, octa-4,7-dienol, octa-5,7-dienol, octa-2,4-dienol, octa-2, 5-dienol, octa-2,6-dienol, octa-3,5-dienol, octa-3,6-dienol and octa-4,6-dienol.
  • Particularly preferred ethers include compounds having an ether group derived from monoalcohols having preferably 1 to 10 carbon atoms.
  • These monoalcohols may be linear, cyclic or branched.
  • unsaturated, saturated or aromatic alcohols can be used to prepare the ethers. These include, in particular, the methyl, ethyl, propyl, butyl, pentyl and hexyl ethers of the octadienols set forth above. Examples of these ethers are in particular methoxyocta-2,7-diene (methyl octa-2,7-dienyl ether), ethoxy octa-2,7-diene and propoxy octa-2,7-diene.
  • the molecular weight of preferred ethers derived from monoalcohols having preferably 1 to 10 carbon atoms is preferably 140 to 300 g / mol, more preferably 140 to 250 g / mol.
  • ethers of alcohols having two, three or more hydroxy groups may be used.
  • These polyhydric alcohols preferably have 2 to 10 carbon atoms, which alcohols may be linear, branched, cyclic, saturated, unsaturated or aromatic.
  • These include in particular the ethers of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, di-pentaerythritol, mannitol, sorbitol, sucrose or mixtures of such alcohols.
  • the ethers of the polyhydric alcohols with octadienols set forth herein may have one, two, three or more octadienyl groups.
  • the preferred compounds include in particular monoocta-4,6-dienoxyethanol, 1,2-diocta-4,6-dienoxyethane, monoocta-4,6-dienoxy-propanediol, diocta-4,6-dienoxy-propanol, triocta-2, 7-dienoxypropane, monoocta-2,7-dienoxyethanol, 1, 2-diocta-2,7-dienoxyethane, monoocta-2,7-dienoxy-propanediol, diocta-2,7-dienoxy-propanol and triocta-2,7- dienoxypropan.
  • These ethers may be used singly or as a mixture of two or more.
  • Molecular weight of preferred ethers derived from polyhydric alcohols having preferably 2 to 10 carbon atoms is preferably 170 to 800 g / mol, more preferably 170 to 600 g / mol.
  • amines can also be used.
  • compounds with one, two or more amine groups can be used.
  • Preferred amines comprise 8 to 20 carbon atoms.
  • the preferred amines include in particular octa-2,7-dienylamine, octa-3,7-dienylamine, octa-4,7-dienylamine, octa-5,7-dienylamine, octa-2,4-dienylamine, octa-2, 5-dienylamine, octa-2,6-dienylamine, octa-3,5-dienylamine, octa-3,6-dienylamine, octa-4,6-dienylamine, (methyl (octa-2,7-dienyl) amino) -ethanol , (Ethyl (octa-2,7-dienyl) amino) ethanol, 2-octa-2,7-dienyloxyethanol and (methyl (octa-2,7-dienyl) amino) ethylamine.
  • esters having one or more octadienyl groups are preferred reactive diluents to be used.
  • Suitable carboxylic acids from which the esters are derived may be linear, branched, cyclic, saturated or unsaturated.
  • aliphatic acids and aromatic acids can be used. These include, in particular, esters of the above-described octadienols which are derived from monocarboxylic acids.
  • Preferred monocarboxylic acids have 1 to 20, preferably 1 to 10 and particularly preferably 1 to 4 carbon atoms.
  • the preferred monocarboxylic acids include in particular formic acid, acetic acid, propionic acid, butyric acid, acrylic acid and methacrylic acid.
  • These reactive diluents preferably have exactly one octadienyl group.
  • the molecular weight of preferred esters derived from monocarboxylic acids preferably having 1 to 20 carbon atoms is preferably 150 to 500 g / mol, more preferably 150 to 300 g / mol.
  • esters of carboxylic acids having two, three or more carboxylic acid groups may also be used, such as the esters of oxalic acid, citric acid, terephthalic acid, fumaric acid, maleic acid or adipic acid.
  • Preferred polycarboxylic acids have 1 to 20, preferably 1 to 10 and particularly preferably 1 to 6 carbon atoms.
  • esters of polycarboxylic acids which have one, two or more octadienyl groups.
  • the molecular weight of preferred esters derived from polycarboxylic acids preferably having 1 to 20 carbon atoms is preferably 200 to 1000 g / mol, more preferably 300 to 600 g / mol.
  • telomerization means the reaction of compounds with conjugated double bonds in the presence of nucleophiles.
  • the telomerization of 1, 3-butadiene using metal compounds comprising metals of the 8th to 10th group of the Periodic Table of the Elements can be carried out as a catalyst, wherein palladium compounds, in particular Palladiumcarbenkomplexe, which are set forth in more detail in the above-mentioned documents, can be used with particular preference.
  • Ethylaminopropanol, or carboxylic acids in particular the previously detailed mono- and polycarboxylic acids are used.
  • the nucleophiles set forth in WO 2004/002931, WO 03/031379 and WO 02/100803 are incorporated herein by reference for purposes of disclosure.
  • the temperature at which the telomerization reaction is carried out is between 10 and 180 ° C., preferably between 30 and 120 ° C., more preferably between 40 and 100 ° C.
  • the reaction pressure is 1 to 300 bar, preferably 1 to 120 bar, especially preferably 1 to 64 bar and most preferably 1 to 20 bar.
  • the preparation of isomers from compounds having an octa-2,7-dienyl group can be accomplished by isomerization of the double bonds contained in the compounds having an octa-2,7-dienyl group.
  • Reactive diluents which are particularly suitable according to the invention are obtained by reacting alcohols having octadienyl ether groups with monocarboxylic or polycarboxylic acids or with polycarboxylic anhydrides in the sense of an ester formation reaction.
  • telomeres which are based on at least trihydric alcohols or randomly at least trifunctional alcohol mixtures, and which have on average per molecule at least one free hydroxyl group.
  • a coating composition according to the invention comprises at least one (meth) acrylic polymer having units derived from (meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical.
  • (Meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group are esters or amides of (meth) acrylic acid whose alkyl group has at least one carbon-carbon double bond and 8 to 40 carbon atoms.
  • the alkyl or alcohol or amide radical may preferably have 10 to 30 and more preferably 12 to 20 carbon atoms, which radical may comprise heteroatoms, in particular oxygen, nitrogen or sulfur atoms.
  • the alkyl group may have one, two, three or more carbon-carbon double bonds.
  • the polymerization conditions in which the (meth) acrylic polymer is prepared are preferably selected so that the largest possible proportion of the double bonds of the alkyl radical is maintained during the polymerization. This can be done for example by steric hindrance of the double bonds contained in the alcohol radical.
  • At least a part, preferably all of the double bonds contained in the alkyl radical of the (meth) acrylic monomer has a lower reactivity in a free-radical polymerization than a (meth) acrylic group, so that preferably no further (meth) acrylic groups in the alkyl radical are included.
  • the iodine number of the (meth) acrylic monomers to be used for the preparation of the (meth) acrylic polymers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical is preferably at least 50, more preferably at least 100, and most preferably at least 125 g of iodine / 100 g of (meth) acrylic monomer.
  • Such (meth) acrylic monomers generally correspond to the formula (I)
  • radical R is hydrogen or methyl
  • X is independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6
  • Carbon atoms and R 1 is a linear or branched radical having 8 to 40, preferably 10 to 30 and particularly preferably 12 to 20 carbon atoms having at least one CC double bond.
  • (Meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can be obtained, for example, by esterification of (meth) acrylic acid, reaction of (meth) acryloyl halides or transesterification of (meth) acrylates with alcohols which are at least have a double bond and 8 to 40 carbon atoms. Accordingly, (meth) acrylamides can be obtained by reaction with an amine. These reactions are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry 5th Edition on CD-ROM or F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation I", Journal of Applied Polymer Science, Vol. 30, 4571-4582 (1985).
  • Suitable alcohols include octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, nonadecenol, icosenol, docosenol, octadiene-ol, nonanoedia-ol, deca- dien-ol, undecadiene-ol, dodecadiene-ol, trideca-dien-ol, tetradeca-dien-ol, pentadeca-dien-ol, hexadeca-dien-ol, heptadeca-dien-ol, octadeca-diene ol, Nonadeca-dien-ol, Ikosa-dien-ol and
  • the preferred (meth) acrylates obtainable by this process include, in particular, octadiene-yl (meth) acrylate, octadeca-diene-yl (meth) acrylate, octadecanetrienyl (meth) acrylate, Hexadecenyl (meth) acrylate, octadecenyl (meth) acrylate and hexadecadienyl (meth) acrylate.
  • (meth) acrylates which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can also be obtained by reacting unsaturated fatty acids with (meth) acrylates which have reactive groups in the alkyl radical, in particular alcohol radical.
  • the reactive groups include in particular hydroxy groups and epoxy groups. Accordingly, for example, hydroxyalkyl (meth) acrylates, such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate,
  • Suitable fatty acids for reaction with the abovementioned (meth) acrylates are often commercially available and are obtained from natural sources. These include undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid and / or cervonic acid.
  • Preferred (meth) acrylates obtainable by this process include in particular (meth) acryloyloxy-2-hydroxypropyl linoleic acid ester, (Meth) acryloyloxy-2-hydroxypropyl-linolenic acid ester and (meth) acryloyloxy-2-hydroxypropyl-oleic acid ester.
  • R is hydrogen or a methyl group
  • X 1 and X 2 are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X 1 and X 2 a group of the formula NR ', where R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R 2 is an unsaturated radical having 9 to 25 carbon atoms, are used.
  • R is hydrogen or a methyl group
  • X 1 is oxygen or a group of the formula NR ', in which R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a bonding group, R is hydrogen or a radical having 1 to 6 carbon atoms and R 2 is an unsaturated radical having 9 to 25 carbon atoms.
  • radical having 1 to 6 carbon atoms means a group having 1 to 6 carbon atoms and includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups
  • the groups mentioned may be branched or unbranched, and these groups may also have substituents, in particular halogen atoms or hydroxyl groups.
  • the radicals R ' are preferably alkyl groups.
  • the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl group.
  • the group Z preferably represents a linking group comprising 1 to 10, preferably 1 to 5 and most preferably 2 to 3 carbon atoms. These include in particular linear or branched, aliphatic or cycloaliphatic radicals, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, wherein the Ethylene group is particularly preferred.
  • the group R 2 in formula (II) represents an unsaturated radical having 9 to 25 carbon atoms.
  • These groups include in particular alkenyl, cycloalkenyl, alkenoxy, cycloalkenoxy, alkenoyl and heteroalipatic groups. Furthermore, these groups may have substituents, in particular halogen atoms or hydroxyl groups.
  • the preferred groups include in particular alkenyl groups, such as, for example, the nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, , Docosenyl, octadiene-yl, nonanediazyl, decadiene-yl, undecanediazyl, dodecadienyl, tridecadienyl, tetradecadienyl -, Pentadeca-dien-yl-, Hexadeca- dien-yl, heptadeca-dien-yl, octadeca-dien-yl, nonadeca-dien-yl
  • the preferred (meth) acrylic monomers of the formula (II) or (III) include heptadecenyloyloxy-2-ethyl (meth) acrylamide, heptadecadienyloxy-2-ethyl (meth) acrylamide, heptadeca- trienyloxy-2-ethyl (meth) acrylamide, heptadecenyloyloxy-2-ethyl (meth) acrylamide, (meth) acryloyloxy-2-ethyl-palmitoleic acid amide, (meth) acryloyloxy-2-ethyl-oleic acid amide, (meth) acryloyloxy 2-ethyl-icosenoic acid amide, (meth) acryloyloxy-2-ethyl-cetolenic acid amide,
  • the notation (meth) acryl stands for acrylic and methacrylic radicals, with methacrylic radicals being preferred.
  • Particularly preferred monomers according to formula (II) or (III) are methacryloyloxy-2-ethyl-oleic acid amide, methacryloyloxy-2-ethyl-linolenic acid amide and / or methacryloyloxy-2-ethyl-linolenic acid amide.
  • the (meth) acrylic monomers of the formula (II) or (III) can be obtained in particular by multistage processes.
  • a first step for example, one or more unsaturated fatty acids or fatty acid esters can be reacted with an amine, for example, ethylenediamine, ethanolamine, propylenediamine or propanolamine, to form an amide.
  • an amine for example, ethylenediamine, ethanolamine, propylenediamine or propanolamine
  • the hydroxy group or the amine group of the amide is reacted with a (meth) acrylate, for example methyl (meth) acrylate, to obtain the monomers of the formula (II) or (III).
  • intermediates obtained for example carboxamides which have hydroxyl groups in the alkyl radical
  • intermediates obtained can be purified.
  • intermediates obtained can be reacted without expensive purification to the (meth) acrylic monomers of the formula (II) or (III).
  • the (meth) acrylic monomers having 8 to 40, preferably 10 to 30 and particularly preferably 12 to 20 carbon atoms and at least one double bond in the alkyl radical in particular include monomers of the general formula (IV)
  • R is hydrogen or a methyl group
  • X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms
  • R 3 is an alkylene group having 1 to 22 carbon atoms
  • Y is oxygen, sulfur or a group of the formula NR ", where R" is hydrogen or a radical having 1 to 6 carbon atoms. represents nitrogen atoms
  • R 4 is an unsaturated radical having at least 8 carbon atoms and at least two double bonds.
  • the radical R ⁇ > 3 is an alkylene group having 1 to 22 carbon atoms, preferably 1 to 10, particularly preferably 2 to 6 carbon atoms.
  • the radical R 3 represents an alkylene group having 2 to 4, more preferably 2 carbon atoms.
  • the alkylene groups having 1 to 22 carbon atoms include in particular the methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexyl groups, with the ethylene group being particularly preferred.
  • the radical R 4 comprises at least two CC double bonds which are not part of an aromatic system.
  • the radical R 4 represents a group with exactly 8 carbon atoms, which has exactly two double bonds.
  • the radical R 4 preferably represents a linear hydrocarbon radical which has no heteroatoms.
  • the radical R 4 in formula (IV) may comprise a terminal double bond.
  • the radical R 4 in formula (IV) can not comprise a terminal double bond.
  • the double bonds contained in the radical R 4 may preferably be conjugated. According to a further preferred embodiment of the present invention, the double bonds contained in the radical R 4 are not conjugated.
  • Preferred R 4 radicals having at least two double bonds include, among others, octa-2,7-dienyl group, octa-3,7-dienyl group, octa-4,7-dienyl group, octa-5,7-dienyl group, octa 2,4-dienyl group, octa-2,5-dienyl group, octa-2,6-dienyl group, octa-3,5-dienyl group, octa-3,6-dienyl group and octa-4,6-dienyl group.
  • the (meth) acrylic monomers of the general formula (IV) include, inter alia, 2 - [((2-E) octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [( (2-Z) octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [((3-E) octa-3,7- dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [((4-Z) octa-4,7-dienyl) methylannino] ethyl 2-methylprop-2-enoate, 2 - [(octa-2 , 6-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [(octa-2,4-dienyl) -methyl
  • the (meth) acrylic monomers of the formula (IV) set out above can be obtained in particular by processes in which (meth) acrylic acid or a (meth) acrylate, in particular methyl (meth) acrylate or ethyl (meth) acrylate with an alcohol and / or an amine is reacted. These reactions have been previously stated.
  • the starting material to be reacted with the (meth) acrylic acid or the (meth) acrylate may advantageously correspond to the formula (V),
  • X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R 3 is an alkylene group having 1 to 22 carbon atoms, Y is oxygen, sulfur or a group of the formula NR ", where R "Represents hydrogen or a radical having 1 to 6 carbon atoms, and R 4 is an at least double unsaturated radical having at least 8 carbon atoms.
  • the preferred starting materials of the formula (V) include (methyl (octa-2,7-dienyl) amino) ethanol, (ethyl (octa-2,7-dienyl) amino) ethanol, 2-octa-2,7-dienyloxyethanol, (methyl octa-2,7-dienyl) amino () ethylamine,
  • telomerization means the reaction of compounds with conjugated double bonds in the presence of nucleophiles
  • the telomerization of 1, 3-butadiene using metal compounds comprising metals of the 8th to 10th group of the Periodic Table of the Elements can be carried out as a catalyst, wherein palladium compounds, in particular Palladiumcarbenkomplexe, which are set forth in more detail in the above-mentioned documents, can be used with particular preference.
  • nucleophiles are dialcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol; Diamines such as ethylenediamine, N-methyl-ethylenediamine, N 1 N'Dimethylethylendiannin or hexamethylenediamine; or aminoalkanols, such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol.
  • dialcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol
  • Diamines such as ethylenediamine, N-methyl-ethylenediamine, N 1 N'Dimethylethylendiannin or hexamethylenediamine
  • aminoalkanols such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol,
  • (meth) acrylic acid for example octadienyl (meth) acrylates can be obtained, which are particularly suitable as (meth) acrylic monomers having 8 to 40 carbon atoms.
  • the preparation of isomers from compounds having an octa-2,7-dienyl group can be carried out by isomerization of the double bonds contained in the compounds having an octa-2,7-dienyl group.
  • the (meth) acrylic polymer to be used according to the invention preferably comprises 0.5 to 60% by weight, preferably 1 to 30% by weight, particularly preferably 1.5 to 20% by weight and very particularly preferably 2 to 15% by weight. -% of units derived from (meth) acrylic monomers having in the alkyl radical at least one double bond and 8 to 40 carbon atoms, based on the weight of the (meth) acrylic polymer.
  • the (meth) acrylic polymers can preferably be obtained by free-radical polymerization. Accordingly, the proportion by weight of the respective units comprising these polymers results from the proportions by weight of corresponding monomers used to prepare the polymers, since the proportion by weight of groups derived from initiators or molecular weight regulators can usually be neglected.
  • the above-mentioned (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group may be used singly or as a mixture of two or more monomers.
  • the (meth) acrylic polymer to be used in the coating agent according to the invention comprises units derived from hydroxyl-containing monomers.
  • Hydroxyl-containing monomers are compounds which have at least one hydroxyl group in addition to a carbon-carbon double bond. These compounds have preferably 3 to 30, particularly preferably 4 to 20 and very particularly preferably 5 to 10 carbon atoms.
  • the carbon group of these compounds may be linear, branched or cyclic. Furthermore, these compounds may have aromatic or heteroaromatic groups.
  • olefinic alcohols such as allyl alcohol, these compounds include in particular unsaturated esters and ethers having a hydroxy group.
  • These preferably include (meth) acrylates having a hydroxy group in the alkyl radical, in particular 2-hydroxyethyl (meth) acrylate, preferably 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl (meth) acrylate, for example 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth ) acrylate, preferably hydroxypropyl methacrylate (HPMA), hydroxybutyl (meth) acrylate, preferably hydroxybutyl methacrylate (HBMA), 3,4-dihydroxybutyl (meth) acrylate, 2,5-dimethyl-1,6-hexanediol mono (meth) acrylate 1, 10 Decandiol mono (meth) acrylate and glycerol mono (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate preferably 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl (meth)
  • the (meth) acrylic polymer may be from 1 to 70% by weight, more preferably from 5 to 60% by weight, and most particularly preferably 10 to 40 wt .-% units derived from hydroxyl-containing monomers, based on the weight of the (meth) acrylic polymer.
  • (meth) acrylic polymers to be used according to the invention may have units derived from further monomers .
  • These comonomers include inter alia (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical. In this case, (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical are preferred.
  • the (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical include, inter alia, (meth) acrylates having a linear or branched alkyl radical, such as, for example
  • Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylates having at least one substituent on the ring, such as tert-butylcyclohexyl (meth) acrylate and trimethylcyclohexyl (meth) acrylate, norbornene nyl (meth) acrylate, methylnorbornyl (meth) acrylate and dimethylnorbornyl (meth) acrylate, bornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, menthyl (meth) acrylate and isobornyl (meth) acrylate.
  • the (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical set forth above can be used singly or as a mixture.
  • Surprising advantages are shown in particular by (meth) acrylic polymers, which are preferably 5% by weight to 95% by weight, preferably 10% by weight to 70% by weight and very particularly preferably 20% by weight to 60% by weight.
  • the (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical which do not have double bonds or heteroatoms in the alkyl radical set out above can be selected such that a (meth) acrylic polymer consisting of these (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical has a glass transition temperature of at least 40 0 C, preferably at least 50 0 C and particularly preferably at least 60 ° C.
  • the glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calohmetry (DSC), in particular according to DIN EN ISO 11357.
  • DSC differential scanning calohmetry
  • the glass transition temperature can be determined as the center of the glass stage of the second heating curve at a heating rate of 10 0 C per minute.
  • the glass transition temperature Tg can also be calculated approximately in advance by means of the Fox equation. After Fox TG, Bull. Am. Physics Soc. 1, 3, page 123 (1956): 1 x, X 1 x "
  • Tg Tg 1 Tg Tg n 2 wherein X n is the mass fraction designated n (wt .-% / 100) of monomer n and Tg n is the glass transition temperature in Kelvin of the homopolymer of the monomer. Further helpful information can be found by the person skilled in the art in Polymer Handbook 2 nd Edition, J. Wiley & Sons, New York (1975), which indicates Tg values for the most common homopolymers.
  • poly (methyl methacrylate) has a glass transition temperature of 378 K, poly (butyl methacrylate) of 297 K, poly (isobornyl methacrylate) of 383 K, poly (isobornyl acrylate) of 367 K and poly (cyclohexyl methacrylate) of 356 K up.
  • the glass transition temperature may be the polymer consisting of (meth) acrylates having 1 to 12 carbon atoms in the alkyl group having no double bonds or heteroatoms in the alkyl group, a weight average molecular weight of at least 100,000 g / mol and a number average molecular weight of at least 80,000 g / mol.
  • Acid group-containing monomers are compounds which can be preferably radically copolymerized with the previously set forth (meth) acrylic monomers. These include, for example, monomers having a sulfonic acid group, such as, for example, vinylsulfonic acid; Monomers having a phosphonic acid group, such as, for example, vinylphosphonic acid and unsaturated carboxylic acids, such as, for example, methacrylic acid, acrylic acid, fumaric acid and maleic acid. Particularly preferred are methacrylic acid and acrylic acid.
  • the acid group-containing monomers can be used individually or as a mixture of two, three or more acid group-containing monomers.
  • (meth) acrylic polymers which contain 0 to 10% by weight, preferably 0.5 to 8% by weight and more preferably 1 to 5% by weight, of units derived from acid groups Monomers are derived, based on the total weight of the (meth) acrylic polymer.
  • Another class of comonomers are (meth) acrylates having at least 13 carbon atoms in the alkyl radical, which are derived from saturated alcohols, such as 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl ( meth) acrylate, pentadecyl (meth) acrylate, Hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-iso-propylheptadecyl (meth) acrylate, 4-tert-butyl-octadecyl (meth) acrylate, ⁇ -ethyl-octadecylmethacrylate, S-isopropyl-octadecylmethacrylate , Oct
  • Cycloalkyl (meth) acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (neth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (neth) acrylate; heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (neth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate, 1- (2-methacryloyloxyethyl) -2-pyrrolidone;
  • Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as N- (methacryloyloxyethyl) diisobutylketimine, N- (methacryloyloxyethyl) dihexadecylketimine, methacryloylamidoacetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethylmethacrylate;
  • Aryl (meth) acrylates such as benzyl (meth) acrylate or phenyl (meth) acrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four times; polyalkoxylated derivatives of (meth) acrylic acid, in particular polypropylene glycol mono (meth) acrylate having 2 to 10, preferably 3 to 6 propylene oxide units, preferably polypropylene glycol monomethacrylate with about 5 propylene oxide units (PPM5), polyethylene glycol mono (me
  • the comonomers also include vinyl esters such as vinyl acetate, vinyl chloride, vinyl versatate, ethylene vinyl acetate, ethylene vinyl chloride;
  • vinyl esters such as vinyl acetate, vinyl chloride, vinyl versatate, ethylene vinyl acetate, ethylene vinyl chloride;
  • Maleic acid derivatives such as, for example, maleic anhydride, esters of maleic acid, for example dimethyl maleate, methylmaleic anhydride; and fumaric acid derivatives such as dimethyl fumarate.
  • styrenic monomers such as styrene, substituted styrenes having an alkyl substituent in the side chain, such as e.g. As ⁇ -methyl styrene and ⁇ -ethyl styrene, substituted styrenes having an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
  • styrenic monomers such as styrene, substituted styrenes having an alkyl substituent in the side chain, such as e.g. As ⁇ -methyl styrene and ⁇ -ethyl styrene, substituted styrenes having an alkyl substituent on the ring, such as vinyl toluen
  • Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles; Maleimide, methylmaleimide;
  • Vinyl and isoprenyl ethers are further examples of comonomers.
  • the (meth) acrylic polymer may contain from 0 to 60% by weight, more preferably from 5 to 50% by weight and most preferably from 10 to 40% by weight of units derived from styrenic monomers , in particular of styrene, substituted styrenes having an alkyl substituent in the side chain, substituted styrenes having an alkyl substituent on the ring and / or halogenated styrenes, based on the total weight of the (meth) acrylic polymer.
  • the proportion of compounds having two or more (meth) acrylic groups is preferably at most 5 wt .-%, in particular at most 2 wt .-%, particularly preferably at most 1 wt .-%, particularly preferred at most 0.5% by weight and very particularly preferably at most 0.1% by weight, based on the total weight of the monomers.
  • the molecular weight of (meth) acrylic polymers to be used according to the invention can be within a wide range.
  • the weight-average molecular weight is usually at least 1000 g / mol, preferably at least 2000 g / mol and very particularly preferably at least 5000 g / mol.
  • (meth) acrylic polymers having a relatively high molecular weight can be used.
  • These (meth) acrylic polymers can be obtained in particular by emulsion polymerization, these (meth) acrylic polymers, for example, having a weight-average molecular weight.
  • low molecular weight (meth) acrylic polymers may also be used. These (meth) acrylic polymers may, for example, exhibit a weight average molecular weight in the range from 1000 to 150000 g / mol, in particular 4000 to 100000 g / mol, particularly preferably in the range from 5000 to 50 000 g / mol.
  • the number-average molecular weight of preferred (meth) acrylic polymers is in the range from 1000 to 10000 g / mol, more preferably in the range from 1500 to 5000 g / mol. Also of particular interest are (meth) acrylic polymers which have a polydispersity index M w / M n in the range from 1 to 5, particularly preferably in the range from 2 to 3.
  • the molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard.
  • the (meth) acrylic polymer may have a molecular weight distribution having at least 2 peaks, as measured by gel permeation chromatography.
  • the glass transition temperature of the (meth) acrylic polymer is preferably in the range from 20 0 C to 90 0 C., particularly preferably in the range of 25 to 80 ° C and very particularly preferably in the range of 30 to 80 0 C.
  • the glass transition temperature may be about the type and the proportion of monomers used to prepare the (meth) acrylic polymer.
  • the glass transition temperature Tg of the (meth) acrylic polymer can be determined in a known manner by means of differential scanning calorimetry (DSC), in particular according to DIN EN ISO 11357.
  • DSC differential scanning calorimetry
  • the glass transition temperature can be determined as the center of the glass stage of the second heating curve at a heating rate of 10 0 C per minute.
  • the glass transition temperature Tg can also be calculated approximately in advance by means of the previously described Fox equation.
  • the iodine number of preferably used (meth) acrylic polymers is preferably in the range of 1 to 300 g of iodine per 100 g of polymer, preferably in the range of 2 to 250 g of iodine per 100 g of polymer, more preferably 5 to 100 g of iodine per 100 g of polymer and very particularly preferably 10 to 50 g of iodine per 100 g of polymer, measured in accordance with DIN 53241-1.
  • the hydroxyl number of the polymer may preferably be in the range of 3 to 300 mg KOH / g, more preferably 20 to 200 mg KOH / g, and most preferably in the range of 40 to 150 mg KOH / g.
  • the hydroxyl number can be determined according to DIN EN ISO 4629.
  • the (meth) acrylic polymers to be used according to the invention can be obtained, in particular, by solution polymerizations, bulk polymerizations or emulsion polymerizations, it being possible to achieve surprising advantages by free-radical solution polymerization. These are set forth in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition.
  • ATRP Atom Transfer Radical Polymerization
  • NMP Non-mediated polymerization
  • RAFT Reversible Addition Fragmentation Chain Transfer
  • the useful initiators include the azo initiators well known in the art, such as AIBN and 1, 1-azobiscyclohexanecarbonitrile, as well as peroxide.
  • xy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2) ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-t
  • the initiators mentioned can be used both individually and in mixtures. They are preferably used in an amount of 0.05 to 10.0 wt .-%, particularly preferably 5 to 8 wt .-%, based on the total weight of the monomers. It is also preferable to carry out the polymerization with a mixture of different polymerization initiators having a different half-life.
  • the sulfur-free molecular weight regulators include, but are not limited to, dimeric ⁇ -methylstyrene (2,4-diphenyl-4-methyl-1-pentene), enol ethers of aliphatic and / or cycloaliphatic aldehydes, terpenes, ⁇ -terpinene, Terpinolene, 1,4-cyclohexadiene, 1,4-dihydronaphthalene, 1, 4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran, 2,5-dimethylfuran and / or 3,6-dihydro-2H-pyran, is preferred dimeric ⁇ -methylstyrene.
  • Mercury compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides can preferably be used as sulfur-containing molecular weight regulators.
  • the following polymerization regulators are exemplified: di-n-butylsulfide, di-n-octylsulfide, diphenylsulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide and dimethyl sulfoxide.
  • Preferred compounds used as molecular weight regulators are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides.
  • examples examples of these compounds are ethylthioglycolate, 2-ethylhexyl thioglycolate, cysteine, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol , Thioacetic acid, thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan.
  • Particularly preferably used polymerization regulators are mercapto alcohols and mercaptocarboxylic acids.
  • the molecular weight regulators are preferably used in amounts of 0.05 to 10, more preferably 0.1 to 5 wt .-% and most preferably in the range of 0.5 to 2, based on the monomers used in the polymerization.
  • mixtures of polymerization regulators can also be used in the polymerization.
  • the polymerization can be carried out at atmospheric pressure, lower or higher pressure.
  • the polymerization temperature is not critical. In general, however, it is in the range of -20 ° - 200 0 C, preferably 50 ° - 150 0 C and particularly preferably 80 ° - 130 0 C.
  • the polymerization can be carried out with or without solvent.
  • the term of the solvent is to be understood here broadly.
  • the preferred solvents include in particular aromatic hydrocarbons, such as toluene, xylene; Esters, in particular acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone; Alcohols, especially isopropanol, n-butanol, isobutanol; Ethers, in particular glycolomethyl ether, glycol monoethyl ether, glycol monobutyl ether; Aliphatics, preferably pentane, hexane, cycloalkanes and substituted cycloalkanes, for example cyclohexane; Mixtures of aliphatics and / or aromatics, preferably naphtha; Gas
  • coating compositions which are preferably 40 to 80% by weight, more preferably 50 to 75% by weight, of at least one (meth) acrylic polymer having units derived from (meth) acrylic monomers which are described in US Pat Alkyl radical at least one double bond and 8 to 40 carbon atoms have.
  • the weight ratio of reactive diluent to (meth) acrylic polymer may be in the range of 10 to 90 to 90 to 10, more preferably in the range of 20 to 80 to 40 to 60.
  • the coating compositions according to the invention can be crosslinked in particular by crosslinking agents which can react with the hydroxyl groups of the (meth) acrylic polymer to be used according to the invention.
  • the present polymers having hydroxy groups can be crosslinked with compounds having two or more N-methylolamide groups, such as polymers having repeating units derived from N-methylolmethacrylamide.
  • temperatures of at least 100 ° C., preferably at least, are used for crosslinking.
  • polymers according to the invention can be crosslinked with hydroxyl groups with polyanhydrides, such as, for example, dianhydrides, in particular pyromellitic dianhydride, or polymers with two or more units derived from maleic anhydride.
  • polyanhydrides such as, for example, dianhydrides, in particular pyromellitic dianhydride, or polymers with two or more units derived from maleic anhydride.
  • the crosslinking with polyanhydrides may preferably be at an elevated temperature, for example at least 100 0 C., preferably at least 120 ° C.
  • crosslinking agents are melamine or urea derivatives.
  • the crosslinking with melamine or urea derivatives may preferably be at elevated Temperature of for example at least 100 0 C, preferably at least 120 0 C take place.
  • the preferred crosslinking agents include in particular polyisocyanates or compounds which release polyisocyanates.
  • Polyisocyanates are compounds having at least 2 isocyanate groups.
  • the polyisocyanates which can be used according to the invention may comprise any desired aromatic, aliphatic, cycloaliphatic and / or (cyclo) aliphatic polyisocyanates.
  • the preferred aromatic polyisocyanates include 1, 3 and 1, 4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, tolidine diisocyanate, 2,6-toluene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,4 ' Diphenylmethane diisocyanate (2,4'-MDI), 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates (MDI) and oligomeric diphenylmethane diisocyanates (polymeric MDI), xylylene diisocyanate, tetramethylxylylene diisocyanate and triisocyanatotoluene.
  • MDI monomeric diphenylmethane diisocyanates
  • polymeric MDI oligomeric diphenylmethane diisocyanates
  • Preferred aliphatic polyisocyanates have 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical.
  • suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical.
  • (cyclo) aliphatic diisocyanates the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z. B. is the case with isophorone diisocyanate. In contrast, is meant by cycloaliphatic diisocyanates those which have only directly attached to the cycloaliphatic ring NCO groups, for. B.
  • H 12 MDI examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate.
  • socyanate heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate, such as 4-isocyanatomethyl-1, 8-octane diisocyanate (TIN), decane and triisocyanate, undecanediol and triisocyanate, dodecanedi and triisocyanates.
  • TIN 4-isocyanatomethyl-1, 8-octane diisocyanate
  • decane and triisocyanate undecanediol and triisocyanate
  • dodecanedi and triisocyanates dodecanedi and triisocyanates.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • H 12 MDI diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-thmethylhexamethylene diisocyanate / 2,4,4-thmethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • aliphatic, cycloaliphatic and araliphatic, d. H. Aryl-substituted aliphatic diisocyanates are described for example in Houben-Weyl, Methods of Organic Chemistry, Volume 14/2, pages 61-70 and in the article by W. Siefken, Justus Liebigs Annalen der Chemie 562, 75-136.
  • mixtures of the polyisocyanates can be used.
  • oligoisocyanates or polyisocyanates which are prepared from the abovementioned diisocyanates or polyisocyanates or mixtures thereof by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, Uretonimine, oxadiazinetrione or Iminooxadiazindion structures produce.
  • This preferred class of polyisocyanates can be prepared by dimerization, thimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates compounds having more than two isocyanate groups per molecule, for example, the reaction products of these simple diisocyanates, such as z. B. IPDI, TMDI, HDI and / or H 12 MDI with polyhydric alcohols (eg., Glycerin, trimethylolpropane, pentaerythritol) or polyhydric polyamines, or the Triisocyanura- te by trimerization of simple diisocyanates, such as IPDI , HDI and H 12 MDI.
  • polyhydric alcohols eg., Glycerin, trimethylolpropane, pentaerythritol
  • Triisocyanura- te by trimerization of simple diisocyanates, such as IPDI , HDI and H 12 MDI.
  • Coating agents which preferably contain from 0.5 to 10% by weight, particularly preferably from 2 to 7% by weight, of crosslinking agent are therefore of particular interest.
  • the reaction of the (meth) acrylic polymers with the organic polyisocyanates can be carried out here with 0.5 to 1.1 NCO group per hydroxyl group, depending on the intended use of the reaction products.
  • the reaction is preferably carried out in such a way that the amounts of the organic polyisocyanate, based on the total hydroxy content of the components present in the reaction mixture per hydroxyl group, are present in an amount of from 0.7 to 1.0 isocyanate groups.
  • the coating compositions of the invention do not require siccatives, but these may be included as an optional ingredient in the compositions.
  • siccatives include in particular organometallic compounds, for example metal soaps of transition metals, such as cobalt, manganese, lead, zirconium, iron, cerium; Alkali or alkaline earth metals, such as lithium, potassium and calcium.
  • transition metals such as cobalt, manganese, lead, zirconium, iron, cerium
  • Alkali or alkaline earth metals such as lithium, potassium and calcium.
  • cobalt naphthalate and cobalt acetate can be used individually or as a mixture, with particular preference being given to mixtures containing cobalt, zirconium and lithium salts.
  • the proportion of siccatives in preferred coating compositions may preferably be in the range of greater than 0 to 5% by weight, more preferably in the range of greater than 0 to 3% by weight and most preferably in the range of greater than 0 to 0.1% by weight. %, Based on the weight of the polymer.
  • the novel coating compositions may comprise solvents. Examples of preferred solvents have previously been presented in the context of a radical polymerization, so that reference is hereby made.
  • the proportion of solvent in preferred coating compositions may in particular be in the range from 0 to 50, particularly preferably in the range from 1 to 20.
  • the coating compositions according to the invention may also contain customary auxiliaries and additives such as rheology modifiers, defoamers, water scavengers (moisture-removing additives, orthoesters), deaerators, pigment wetting agents, dispersing additives, substrate wetting agents, lubricants and leveling additives, preferably each in an amount of 0 wt. % to 3% by weight, based on the total formulation, and of water repellents, plasticizers, thinners, in particular further reactive diluents, UV stabilizers and adhesion promoters, preferably each in an amount of from 0% by weight to 20 wt .-%, based on the total formulation may be included.
  • auxiliaries and additives such as rheology modifiers, defoamers, water scavengers (moisture-removing additives, orthoesters), deaerators, pigment wetting agents, dispersing additives, substrate wetting agents, lubricants and leveling additive
  • the coating compositions of the invention may contain conventional fillers and pigments, e.g. Talc, calcium carbonate, titanium dioxide, carbon black, etc. in an amount of up to 50% by weight of the total composition.
  • conventional fillers and pigments e.g. Talc, calcium carbonate, titanium dioxide, carbon black, etc. in an amount of up to 50% by weight of the total composition.
  • the coating compositions according to the invention are distinguished by an outstanding property spectrum, which in particular comprises excellent processability and excellent quality of the coating obtained.
  • Preferred coating agents can be processed in a wide temperature window, which preferably has a width of at least 20 ° C., in particular at least 30 ° C., without impairing the quality of the coating, which is distinguished, in particular, by high solvent and water resistance , Accordingly, a preferred coating agent at a temperature of 15 ° C, 20 °, 30 0 C or 40 0 C are processed without a significant deterioration in quality is measurable.
  • the dynamic viscosity of the coating agent is dependent on the solids content and the nature of the reactive diluent and may include a wide range. So this can be more than 20,000 mPas at high polymer content. Expediently, a dynamic viscosity in the range from 10 to 10000 mPas, preferably 100 to 8000 mPas and very particularly preferably 1000 to 6000 mPas, measured according to DIN EN ISO 2555 at 25 ° C (Brookfield) is usually.
  • a surprisingly good processability shows coating compositions whose solids content is preferably at least 50% by weight, more preferably at least 60% by weight.
  • the coating compositions of the invention can be processed over a much wider temperature range than previously known coating compositions. With comparable processing properties, the coating compositions of the invention are characterized by a surprisingly high solids content, so that the coating compositions of the invention are particularly environmentally friendly.
  • the present invention provides a process for producing a coating in which a coating composition of the invention is applied to a substrate and cured.
  • the coating composition of the invention can be applied by conventional application methods such as dipping, rolling, flooding, casting, in particular by brushing, rolling, spraying (high pressure, low pressure, airless or electrostatic (ESTA)).
  • the curing of the coating agent is carried out by drying and by oxidative crosslinking by means of atmospheric oxygen.
  • crosslinking with a crosslinking agent, in particular a polyisocyanate can be carried out.
  • the substrates which can preferably be provided with a coating agent according to the invention include, in particular, metals, in particular iron and steel, zinc and galvanized steels, and also plastics and concrete substrates.
  • the present invention provides coated articles obtainable by a method according to the invention.
  • the coating of these objects is characterized by an excellent property spectrum.
  • Preferred coatings obtained from the coating compositions of the invention exhibit high mechanical resistance.
  • the pendulum hardness is preferably at least 30 s, preferably at least 50 s and very particularly preferably at least 100 s, measured in accordance with DIN ISO 1522.
  • preferred coatings which are obtainable from the coating compositions of the invention have a surprisingly high adhesive strength, which can be determined in particular according to the cross-cut test.
  • a classification of 0-1, particularly preferably of 0 according to the standard DIN EN ISO 2409 can be achieved.
  • the coatings obtainable from the coating compositions according to the invention generally exhibit high solvent resistance, with only small amounts in particular being dissolved out of the coating by solvents.
  • Preferred coatings exhibit excellent resistance in particular to polar solvents, in particular alcohols, for example 2-propanol, or ketones, for example methyl ethyl ketone (MEK), nonpolar solvents, for example diesel fuel (alkanes).
  • polar solvents in particular alcohols, for example 2-propanol, or ketones, for example methyl ethyl ketone (MEK), nonpolar solvents, for example diesel fuel (alkanes).
  • MEK methyl ethyl ketone
  • nonpolar solvents for example diesel fuel (alkanes).
  • preferred coatings according to the present invention show a pendulum hardness according to DIN ISO 1522 of at least 120 s, preferably at least 150 s.
  • the coating compositions of the invention can be designed so that they show a high resistance to acids and bases.
  • coatings show a surprisingly good cupping.
  • coatings show a depression of at least 4.5 mm, more preferably at least 5.0 mm, measured according to DIN 53156 (Erichsen).
  • the fatty acid methyl ester mixture comprised 6% by weight of saturated C12 to C16 fatty acid methyl ester, 2.5% by weight of saturated C17 to C20 fatty acid methyl ester, 52% by weight of monounsaturated C18 fatty acid methyl ester, 1.5% by weight of monounsaturated C20 to C24 fatty acid methyl esters , 36% by weight of polyunsaturated C18 fatty acid methyl ester, 2% by weight of polyunsaturated C20 to C24 fatty acid methyl esters.
  • the reaction mixture was heated to 150 0 C. Within 2 h, 19.5 ml of methanol were distilled off. The resulting reaction product contained 86.5% fatty acid ethanolamides. The resulting reaction mixture was further processed without purification. After cooling, 1919 g (19.2 mol) of methyl methacrylate, 3.1 g of LiOH and an inhibitor mixture consisting of 500 ppm hydroquinone monomethyl ether and 500 ppm phenothiazine were added.
  • reaction apparatus While stirring, the reaction apparatus was purged with nitrogen for 10 minutes. Thereafter, the reaction mixture was heated to boiling. The methyl methacrylate / methanol azeotrope was separated and then the head temperature gradually increased to 100 0 C. After completion of the reaction, the reaction mixture was cooled to about 70 0 C and filtered.
  • a reaction mixture comprising 17.37 g of di-tert-butyl peroxide (DTBP), 46.64 g of isobornyl methacrylate (IBOMA), 69.97 hydroxyethyl methacrylate (HEMA), 23.32 g of ethylhexyl methacrylate (EHMA), 23.32 g methacryloyloxy-2-ethyl-fatty acid amide (MUMA), 69.97 g of styrene and 4.17 g of 2-mercaptoethanol were added over a period of 4 hours.
  • DTBP di-tert-butyl peroxide
  • IBOMA isobornyl methacrylate
  • HEMA 69.97 hydroxyethyl methacrylate
  • EHMA ethylhexyl methacrylate
  • MUMA methacryloyloxy-2-ethyl-fatty acid amide
  • the polymer content was adjusted to 65% by adding 18.75 g of n-butyl acetate and 69.2 g of 2,7-octadienylmethyl ether.
  • the properties of the coating agent thus obtained were examined.
  • a film having a thickness of about 50 microns was formed on an aluminum plate, wherein the polymer film by adding polyisocyanate (hexamethylene diisocyanate, HDI 50/60 NCO / OH) and dibutyltin dilaurate (DBTL, 0.01 wt .-%, based on the Polymer weight).
  • polyisocyanate hexamethylene diisocyanate
  • DBTL dibutyltin dilaurate
  • the hardness or scratch resistance of the crosslinked polymer film was examined by determining the pendulum hardness.
  • the chemical resistance was examined by treating the polymer film with methyl ethyl ketone. Subsequently, the pen hardness of the film was measured. As a criterion, in particular a softening of the film by the treatment with the solvent is used.
  • the brittleness of the film was examined by creep tests according to Erichsen.
  • the adhesive strength of the coating was determined by a crosshatch test.
  • reaction vessel 50.01 g of solvent (Solvesso 100) were introduced and heated to 140 0 C. Oxygen in the reaction vessel was removed by introducing nitrogen. Subsequently, a reaction mixture comprising 15.33 g of di-tert-butyl peroxide (DTBP), 41.15 g of isobornyl methacrylate (IBOMA), 61.
  • DTBP di-tert-butyl peroxide
  • IBOMA isobornyl methacrylate
  • HEMA hydroxyethyl methacrylate
  • EHMA ethylhexyl methacrylate
  • MUMA methacryloyloxy-2-ethyl-fatty acid amide
  • 61, 73 g of styrene and 3.69 g of 2-mercaptoethanol were added over a period of 4 hours. Subsequently, the reaction was continued for 30 minutes with stirring. Thereafter, the mixture was cooled to 80 0 C.
  • Example 1 From the obtained coating agent, a film was prepared according to the method set forth in Example 1. The properties of the coatings obtained were determined by the test methods set out above, the results of which are shown in Table 1.
  • reaction mixture comprising 30.66 g of di-tert-butyl peroxide (DTBP), 82.31 g of isobornyl methacrylate (IBOMA), 123.46 hydroxyethyl methacrylate (HEMA), 82.31 g of ethylhexyl methacrylate (EHMA), 123.46 g of styrene and 7.38 g of 2-mercaptoethanol were added over a period of 4 hours. Subsequently, the reaction was continued for 30 minutes with stirring.
  • DTBP di-tert-butyl peroxide
  • IBOMA isobornyl methacrylate
  • HEMA 123.46 hydroxyethyl methacrylate
  • EHMA ethylhexyl methacrylate
  • 2-mercaptoethanol 123.46 g of styrene
  • the polymer content was adjusted to 65% by adding 92.31 g of n-butyl acetate.
  • the (meth) acrylic polymers containing MUMA show a somewhat higher pendulum hardness, although the number of carbon atoms in the alkyl radical of the methacrylate is significantly greater than in EHMA. Furthermore, the (meth) acrylic polymers containing MUMA show a significantly increased solvent resistance to polar solvents. When using a reactive diluent, this resistance can be increased to a surprising degree.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un agent de revêtement contenant un polymère de (méth)acryle et au moins un diluant réactif. Le diluant réactif contient au moins un groupe octadiényle et le polymère de (méth)acryle contient des unités dérivées de monomères de (méth)acryle, présentant au moins une double liaison et 8 à 40 atomes de carbone dans le radical alkyle, et des unités dérivées de monomères renfermant des groupes hydroxy. L'invention concerne également un procédé de fabrication d'un revêtement, et un article revêtu présentant un revêtement fabriqué au moyen du procédé selon l'invention.
PCT/EP2010/052662 2009-03-30 2010-03-03 Agent de revêtement, procédé de fabrication d'un revêtement et article revêtu WO2010112288A1 (fr)

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DE102009001965A DE102009001965A1 (de) 2009-03-30 2009-03-30 Beschichtungsmittel, Verfahren zur Herstellung einer Beschichtung und beschichteter Gegenstand

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Publication number Priority date Publication date Assignee Title
DE102011088149A1 (de) 2011-12-09 2013-06-13 Evonik Industries Ag Beschichteter Verbundkörper, umfassend ein Verbundmaterial

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Publication number Priority date Publication date Assignee Title
DE102012203362A1 (de) 2012-03-05 2013-09-05 Evonik Röhm Gmbh Stabilisierte (Meth)acrylmonomere

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011088149A1 (de) 2011-12-09 2013-06-13 Evonik Industries Ag Beschichteter Verbundkörper, umfassend ein Verbundmaterial
WO2013083362A2 (fr) 2011-12-09 2013-06-13 Evonik Industries Ag Corps composite enrobé comportant un matériau composite

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