WO2010127910A1 - Agent de revêtement, procédé pour produire un revêtement et objet revêtu - Google Patents

Agent de revêtement, procédé pour produire un revêtement et objet revêtu Download PDF

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Publication number
WO2010127910A1
WO2010127910A1 PCT/EP2010/053964 EP2010053964W WO2010127910A1 WO 2010127910 A1 WO2010127910 A1 WO 2010127910A1 EP 2010053964 W EP2010053964 W EP 2010053964W WO 2010127910 A1 WO2010127910 A1 WO 2010127910A1
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meth
acrylate
polymer
coating composition
monomers
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PCT/EP2010/053964
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German (de)
English (en)
Inventor
Bardo Schmitt
Reinhold Martin
Martina Ebert
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Evonik Röhm Gmbh
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Publication of WO2010127910A1 publication Critical patent/WO2010127910A1/fr

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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
    • 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
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

Definitions

  • Coating composition process for producing a coating and coated article
  • the present invention relates to a coating agent, a process for producing a coating and a coated article.
  • Coating agents in particular paints, have been produced synthetically for a long time. Based on their economic importance, considerable efforts have been made to adapt the properties of these coating compositions to different needs. For this purpose, additives are often used or the binder modified as such. However, an optimization of a certain property often leads to disadvantages with respect to other features of these coating compositions.
  • prior art coating compositions comprising compounds having oxazolidine groups are known.
  • the prior art includes documents DE-A 26 10 406, EP-A 0 409 459, EP-A-0 728 822, US 5,672,379, US 3,037,006 and EP-A-0 302 373.
  • the document DE-A 26 10 406 relates to compositions containing at least one oxazolidine and at least one polyanhydride and to harden in the presence of water, harden chemically resistant polymer materials.
  • a variety of different oxazolidines and polyanhydrides are enumerated, wherein the proportion of oxazolidine groups or anhydride groups in these compounds is not specified.
  • polyanhydrides are used which by reaction of maleic anhydride with wood oil.
  • a coating agent comprising copolymers with acid anhydride groups and copolymers with oxazolidine groups is not explicitly stated.
  • only polymers which have been prepared in solvents are described.
  • the document EP-A 0 409 459 describes aqueous dispersions comprising a polyfunctional amine polymer and an anionically stabilized emulsion polymer.
  • homopolymers obtained by polymerization of oxazolidine ethyl methacrylate (OXEMA) in particular are used in combination with copolymers comprising acid groups.
  • Polymers with a low content of oxazolidine groups are not explicitly listed in this publication, wherein the proportion of comonomers is limited to 80 wt .-%.
  • EP-A-0 728 822 discloses coating compositions comprising at least one film-forming polymer having anionic properties and at least one water-soluble or water-dispersible polymer having amino groups.
  • the amino group-containing polymer comprises at least 20% by weight of units derived from monomers having an amino group.
  • mixtures of acid group-containing polymers and homopolymers obtained by polymerization of oxazolidine ethyl methacrylate (OXEMA) are set forth.
  • aqueous dispersions which can serve in particular for the production of road markings.
  • these aqueous dispersions may include polymers with acid groups and polymers with amino groups.
  • the polymers containing amino groups contain at least 20%, preferably min. at least 50% units derived from amino group-containing monomers.
  • only homopolymers of oxazolidine ethyl methacrylate are used.
  • the published patent application EP-A-0 302 373 describes moisture-curing binder compositions of polymers with maleic anhydride units and oxazolanes.
  • the oxazolanes have a molecular weight in the range of 87 to 10,000.
  • Polymers with a low content of oxazolidine groups are not listed in this document.
  • the compositions presented include larger amounts of organic solvents.
  • coating compositions described above already show a good property spectrum.
  • coatings obtainable from previously disclosed coating compositions exhibit relatively high swelling to organic solvents or water.
  • solvents or water can be improved by an additional crosslinking, for example with polyisocyanates.
  • this other properties of the coating materials in particular the processability, durability and, depending on the type of crosslinking agents used, the environmental impact reduced.
  • the coatings obtainable from the coating compositions should become dust-dry and tack-free after a very short time. Furthermore, the coating compositions should show a long pot life, based on the dust drying time, so that the coating composition can be processed for a relatively long time after opening the container.
  • the coatings obtainable from the coating compositions should achieve high stability against many different solvents as well as with respect to water, bases and acids.
  • MIBK methyl isobutyl ketone
  • 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 obtainable from the coating compositions of the invention should have a relatively low brittleness in terms of hardness.
  • a coating composition which has a particularly long shelf life and durability.
  • Another object is to provide coating compositions which are useful in coatings lead to a high gloss.
  • the coatings obtainable from the coating compositions should have a high weather resistance, in particular a high UV resistance.
  • the coating compositions should show improved environmental compatibility.
  • the smallest possible amounts of organic solvents should be released into the environment by evaporation.
  • the coating compositions should have a low residual monomer content.
  • a coating composition according to the invention comprises at least one amino-containing (meth) acrylate polymer which comprises from 0.1 to 15% by weight of units derived from monomers containing oxazolidine groups, and 20 to 99.9 wt .-% of units derived from alkyl (meth) acrylates having 1 to 12 carbon atoms.
  • A represents an ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, with the ethylene group being particularly preferred.
  • ⁇ M) 'R 4 , R 5 , R 6 independently of one another, are hydrogen or methyl
  • n is an integer from 0 to 100, preferably 1 to 50
  • o and p independently of one another are an integer from 0 to 2.
  • (Meth) acrylate stands for esters of methacrylic acid and esters of acrylic acid and mixtures of these esters.
  • Monomers having oxazolidine groups are described, for example, in DE-A 26 10 406 filed on 12.03.1976 with the German Patent Office with the application number P 2610406.3; EP-A 0 409 459 filed on 09.07.1990 with the European Patent Office with the application number EP 90307464.9; EP-A-0 728 822, filed on 28.08.1996 at the European Patent Office with the application number EP 96300938.6; U.S. 5,672,379, filed Jul. 26, 1996, in the United States Patent Office (USPTO), Serial No. 687,851; and US 3,037,006 filed on Jul. 5, 1996 with the United States Patent Office (USPTO), application number 40,562; in which reference is made to these documents for the purpose of disclosure and the monomers comprising oxazolidine groups set out therein and their preparation are incorporated into the present application.
  • the monomers with oxazolidine groups set forth above can be obtained, for example, by transesterification of hydroxyl-containing oxazolidines with (meth) acrylates. Hydroxy-containing oxazolidines can be obtained, for example, by reacting amines with carbonyl compounds. Such reactions are described in the prior art set forth above, in particular in DE-A 26 10 406 and US 3,037,006.
  • the amino group-containing (meth) acrylate polymer comprises from 0.1 to 15% by weight, preferably from 1 to 8, and most preferably from 2 to 5% by weight of units derived from monomers having oxazolidine groups, based on Weight of the amino group-containing (meth) acrylate polymer.
  • the (meth) acrylate 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 amino group-containing (meth) acrylate polymer comprises from 20 to 99.9% by weight, preferably from 30 to 98% by weight and most preferably from 60 to 96% by weight. % of units derived from alkyl (meth) acrylates having 1 to 12 carbon atoms, based on the weight of the amino group-containing (meth) acrylate polymer.
  • the alkyl (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical include (meth) acrylates having a linear or branched alkyl radical, such as, for example, methyl (meth) acrylate, ethyl (meth acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 3-isopropyl-propyl (meth) acrylate, nonyl (meth) acryl
  • 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, Norbornyl (meth) acrylate, methylnorbornyl (meth) acrylate and
  • Adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, menthyl (meth) acrylate and isobornyl (meth) acrylate may be used singly or as a mixture.
  • (Meth) acrylate polymer include units derived from comonomers. These include, inter alia, (meth) acrylates having a hydroxy group in the
  • Alkyl radical in particular
  • 2-hydroxyethyl (meth) acrylate preferably 2-hydroxyethyl methacrylate
  • Hydroxypropyl (meth) acrylate for example, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, preferably hydroxypropyl methacrylate
  • amino-containing (meth) acrylate polymers which have from 0 to 10% by weight, preferably from 0.5 to 8% by weight and more preferably from 1 to 5% by weight, of units derived from Derived acid group-containing monomers, based on the total weight of the polymer.
  • 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 with 2 to 10, preferably 3 to 6 propylene oxide units, preferably polypropylene glycol monomethacrylate with about 5 propylene oxide units (PPM5), polyethylene glycol mono (meth) acrylate with 2 to 10, preferably 3 to 6 ethylene oxide units, preferably
  • Polybutylene glycol mono (meth) acrylate polyethylene glycol polypropyleneglycol mono (meth) acrylate;
  • (Meth) acrylamides in particular N-methylol (meth) acrylamide, N 1 N- dimethylaminopropyl (meth) acrylamide, tert-butylaminoethyl methacrylate, methacrylamide and acrylamide; and
  • the polymerization conditions in which a polymer to be used according to the invention is prepared are preferably selected such that the largest possible proportion of the double bonds of the alkyl radical is retained during the polymerization. This can be done for example by steric hindrance of the double bonds contained in the alcohol radical. Furthermore, 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.
  • R 1 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 8 is a linear or branched radical having 8 to 40, preferably 10 to 30 and more preferably 12 to 20 carbon atoms, which has at least one CC double bond.
  • Suitable alcohols include octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, nonadecenol, ikosenol, 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, Ikos
  • 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.
  • the 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 1 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 represents a group of the formula NR 'in which R' represents hydrogen or a radical having 1 to 6 carbon atoms, Z 1 represents a linking group and R 9 is an unsaturated radical having 9 to 25 carbon atoms.
  • R 1 is hydrogen or a methyl group
  • X 1 is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z 1 is a linking group, R is hydrogen or a radical having 1 to 6 carbon atoms and R 9 is an unsaturated group 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 heteroaliphatic groups may be branched or unbranched, furthermore these groups may have substituents, in particular halogen atoms or hydroxyl groups.
  • the radicals R ' are preferably alkyl groups.
  • Preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl group.
  • the group Z 1 in formulas (IV) and (V) 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 9 in formula (IV) and (V) 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.
  • Particularly preferred monomers according to formula (IV) or (V) 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 (IV) or (V) 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 (IV) or (V).
  • 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 formula (IV) or (V).
  • 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 include in particular monomers of the general formula (VI)
  • R 1 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 10 is an alkylene group having 1 to 22 carbon atoms
  • Y is oxygen, sulfur or a group of Formula NR ", wherein R" is hydrogen or a radical having 1 to 6 carbon atoms
  • R 11 is an unsaturated radical having at least 8 carbon atoms and at least two CC double bonds.
  • the radical R 10 is an alkylene group having 1 to 22 carbon atoms, preferably 1 to 10, particularly preferably 2 to 6 carbon atoms.
  • the radical R 10 represents, according to a particular embodiment of the present invention, 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, isopropylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, with the ethylene group being particularly preferred.
  • the radical R 11 comprises at least two CC double bonds which are not part of an aromatic system.
  • the radical R 11 represents a group with exactly 8 carbon atoms, which has exactly two carbon-carbon double bonds.
  • the radical R 11 preferably represents a linear hydrocarbon radical which has no heteroatoms.
  • the radical R 11 in formula (VI) may comprise a terminal double bond.
  • the radical R 11 in formula (VI) can not comprise a terminal carbon-carbon double bond.
  • the double bonds contained in the radical R 11 may preferably be conjugated. According to another preferred embodiment of the present invention, the double bonds contained in the radical R 11 are not conjugated.
  • the (meth) acrylic monomers of the general formula (VI) 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-methylpropyl 2-enoate,
  • X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R 10 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 11 is an at least double unsaturated radical having at least 8 carbon atoms.
  • the preferred starting materials of the formula (VII) 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,
  • 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.
  • dialcohols such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol; Diamines such as ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediannine or hexamethylenediamine; or aminoalkanols, such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol.
  • Diamines such as ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediannine or hexamethylenediamine
  • aminoalkanols such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol.
  • 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.
  • Examples of monomers having at least one carboxylic anhydride group are maleic anhydride, derivatives of maleic anhydride, such as methylmaleic anhydride, dimethylmaleic anhydride or phenylmaleic anhydride, and itaconic anhydride.
  • maleic anhydride is particularly preferred.
  • monomer mixtures which comprise monomers having at least one carboxylic acid group and monomers having at least one carboxylic acid anhydride group.
  • functional polymers comprising a higher proportion of units derived from monomers having at least one carboxylic acid group than units derived from monomers having at least one carboxylic anhydride group.
  • the molar ratio of carboxylic acid groups to carboxylic anhydride groups in the functional polymer is greater than 1.5, more preferably greater than 2, and most preferably greater than 5.
  • Alkyl (meth) acrylates having 1 to 12 carbon atoms have been previously set forth, so reference is hereby made.
  • An amino-containing (meth) acrylate polymer and / or a functional polymer to be used according to the invention may preferably be from 0 to 60% by weight, preferably from 0.5 to 30% by weight, more preferably from 1 to 20% by weight and completely most preferably comprise from 2 to 15% by weight of units derived from (meth) acrylic monomers having in the alkyl radical at least one double bond and from 8 to 40 carbon atoms, based on the weight of the respective 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 not more than 0.5% by weight and very particularly preferably not more than 0.1% by weight, based on the total weight of the monomers.
  • the molecular weight of the amino group-containing (meth) acrylate polymers and the functional polymers can be in 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.
  • polymers having a relatively high molecular weight can be used.
  • amino-containing (meth) acrylate polymers or functional polymers can be obtained in particular by emulsion polymerization, the weight-average molecular weight of these polymers being, for example, in the range from 100,000 to 10,000,000 g / mol, particularly preferably in the range from 200,000 to 500,000 g / mol can lie.
  • Emulsion polymers are notable in particular for their high environmental compatibility, since they often require no organic solvents and can have a particularly low residual monomer content.
  • low molecular weight polymers to be used according to the invention may also be used.
  • These amino group-containing (meth) acrylate polymers or functional polymers may, for example, have 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.
  • Low molecular weight polymers are widely used in organic solvent coating compositions. Coating compositions comprising organic solvents show good processability over a wide range of temperature and humidity.
  • the ratio of the weight average molecular weight of the amino group-containing (meth) acrylate polymer to the weight average molecular weight of the functional polymer can be in the range of 5: 1 to 1: 5, more preferably in the range of 2: 1 to 1: 2 lie.
  • amino-containing (meth) acrylate polymers or functional 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 glass transition temperature of the polymers to be used according to the invention namely the amino group-containing (meth) acrylate polymers and the functional polymers, is preferably in the range from -60 0 C to 100 0 C, in particular -30 ° C to 70 0 C particularly preferred in the range of -20 to 40 ° C, and most preferably in the range of 0 to 25 ° C.
  • the glass transition temperature can be influenced by the type and proportion of monomers used to make the polymer.
  • the glass transition temperature Tg of the 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 Fox equation. After Fox TG, Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:
  • Tg n the glass transition temperature in Kelvin of the homopolymer of the monomer n.
  • poly (methyl methacrylate) has a glass transition temperature of 378K, poly (butyl methacrylate) of 297K, poly (isobornyl methacrylate) of 383K, poly (isobornyl acrylate) of 367K, and poly (cyclohexyl methacrylate) of 356K.
  • the polymer may have one or more different glass transition temperatures. This information therefore applies to at least one segment which satisfies the characteristics of the amino group described above. pen-containing (meth) acrylate polymer or the functional polymer.
  • the architecture of the polymers to be used according to the invention is not critical for many applications and properties.
  • the polymers in particular the emulsion polymers, can represent random copolymers, gradient copolymers, block copolymers and / or graft copolymers.
  • Block copolymers or gradient copolymers can be obtained, for example, by discontinuously changing the monomer composition during chain growth.
  • the emulsion polymer in particular the amino group-containing (meth) acrylate polymer and / or the functional polymer is a random copolymer in which the monomer composition is substantially constant via the polymerization.
  • the monomers may have different copolymerization parameters, the exact composition may vary across the polymer chain of the polymer.
  • the polymers to be used according to the invention can be homogeneous polymers which, for example, form particles with a constant composition in an aqueous dispersion.
  • the amino group-containing (meth) acrylate polymer and the functional polymer, which are preferably an emulsion polymer may be one or more Segments exist, each of which is obtainable by polymerization of a monomer mixture.
  • the polymers to be used according to the invention can be a core-shell polymer which can have one, two, three or more shells.
  • the shell may be connected to the core or inner shells via covalent bonds.
  • the shell can also be polymerized on the core or an inner shell.
  • the iodine number of polymers to be used according to the invention can preferably be in the range from 0 to 300 g of iodine per 100 g of polymer, preferably in the range from 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 most preferably 10 to 50 g of iodine per 100 g of polymer, measured in accordance with DIN 53241-1.
  • coating compositions in which the functional polymer differs from the amino group-containing (meth) acrylate polymer. can become.
  • coating agents are preferred in which the difference between the acid number of the functional polymer and the acid number of the amino group-containing (meth) acrylate polymer is at least 0.1 mg KOH / g and more preferably at least 1 mg KOH / g.
  • the hydroxyl number of the polymers to be used according to the invention may preferably be in the range from 0 to 150 mg KOH / g, more preferably 20 to 120 mg KOH / g and most preferably in the range from 40 to 100 mg KOH / g.
  • the hydroxyl number can be determined according to DIN EN ISO 4629.
  • the 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 means of a radical-elastic emulsion polymerization. These are set forth in LJII-Mann's Encyclopaedia of Industrial Chemistry, Sixth Edition.
  • ATRP Atom Transfer Radical Polymerization
  • NMP Non-mediated polymerization
  • RAFT Reversible Addition Fragmentation Chain Transfer
  • emulsion polymerization Methods of emulsion polymerization are set forth, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition.
  • an aqueous phase is prepared, the usual addition to water additives, especially emulsifiers and protective colloids for stabilizing the emulsion.
  • the emulsion polymerization can be carried out, for example, as a miniemulsion or as a microemulsion, described in detail in Chemistry and Technology of Emulsion Polymerization, A.M. van Herk (editor), Blackwell Publishing, Oxford 2005 and J. O'Donnell, E.W. Kaier, Macromolecular Rapid Communications 2007, 28 (14), 1445-1454.
  • a miniemulsion is customary characterized by the use of costabilizers or swelling agents, many of which use long-chain alkanes or alkanols.
  • the droplet size in miniemulsions is preferably in the range of 0.05 to 20 microns.
  • the droplet size in the case of microemulsions is preferably in the range below 1 ⁇ m, whereby particles below a size of 50 nm can be obtained in this way.
  • Microemulsions often use additional surfactants, for example hexanol or similar compounds.
  • the dispersing of the monomer-containing phase in the aqueous phase can be carried out by known means. These include, in particular, mechanical methods and the use of ultrasound.
  • core-shell polymers can also be prepared.
  • the composition of the monomer mixture can be changed stepwise, wherein before changing the composition Polymerization is preferably up to a conversion of at least 80 wt .-%, more preferably at least 95 wt .-%, in each case based on the total weight of the monomer mixture used, polymehsiert.
  • Core-shell polymer here stands for a polymer which has been prepared by a two-stage or multistage emulsion polymerization, without the core-shell structure having been demonstrated, for example, by electron microscopy.
  • the tracking of the progress of the polymerization in each step may be carried out in a known manner, for example gravimetrically or by gas chromatography.
  • the monomer composition for producing the core preferably comprises from 50 to 100% by weight of (meth) acrylates, with a mixture of acrylates and methacrylates being used with particular preference.
  • the weight ratio of acrylates to methacrylates in the core may be greater than or equal to 1, more preferably greater than or equal to 2.
  • a monomer mixture may preferably be grafted onto it or polymerized onto the core, which contains 0.5 to 20% by weight, particularly preferably 2 to 15% by weight, in particular 5 to 10% by weight.
  • Monomer with oxazolidine groups Monomer with oxazolidine groups.
  • the emulsion polymerization is preferably carried out at a temperature in the range from 0 to 120 ° C., more preferably in the range from 30 to 100 ° C.
  • polymerization temperatures in the range from greater than 60 to less than 90 ° C., expediently in the range from greater than 70 to less than 85 ° C., preferably in the range from greater than 75 to less than 85 ° C., have proven to be particularly favorable.
  • the initiation of the polymerization takes place with the customary for the emulsion polymerization initiators. Suitable organic initiators are, for example, hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide.
  • Suitable inorganic initiators are hydrogen peroxide and the alkali metal and ammonium salts of peroxodisulfuric acid, in particular ammonium, sodium and potassium peroxodisulfate.
  • Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulfite and alkali metal and the ammonium salts of peroxodisulfuric acid, in particular sodium and potassium peroxodisulfate. Further details can be found in the specialist literature, in particular H. Rauch-Puntigam, Th. Völker, "Acrylic and Methacrylic Compounds", Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopaedia of Chemical Technology, Vol. 1, p. 386ff, J. Wiley, New York, 1978. In the context of the present invention, the use of organic and / or inorganic initiators is particularly preferred.
  • the initiators mentioned can be used both individually and in mixtures. They are preferably used in an amount of 0.05 to 3.0 wt .-%, based on the total weight of the monomers of each stage. It is also preferable to carry out the polymerization with a mixture of different polymerization initiators having a different half-life, in order to keep the radical stream constant during the polymerization and at different polymerization temperatures.
  • the stabilization of the approach is preferably carried out by means of emulsifiers and / or protective colloids.
  • the emulsion is stabilized by emulsifiers to obtain a low dispersion viscosity.
  • the total amount of emulsifier is preferably 0.1 to 15 wt .-%, in particular 1 to 10 Wt .-% and particularly preferably 2 to 5 wt .-%, based on the total weight of the monomers used.
  • a part of the emulsifiers may be added during the polymerization.
  • emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, in particular
  • Alkyl sulfates preferably those having 8 to 18 carbon atoms in the alkyl radical, alkyl and alkylaryl ether sulfates having 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units;
  • Sulfonates preferably alkyl sulfonates having 8 to 18 carbon atoms in the alkyl radical, alkylaryl sulfonates having 8 to 18 carbon atoms in the alkyl radical, esters and half-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms in the alkyl radical; optionally, these alcohols or alkylphenols may also be ethoxylated with 1 to 40 ethylene oxide units;
  • Partial phosphoric acid esters and their alkali metal and ammonium salts preferably alkyl and alkylaryl phosphates having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 1 to 5 ethylene oxide units;
  • alkylpolyglykolether preferably having 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units;
  • Alkylarylpolyglykolether preferably having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 8 to 40 ethylene oxide units; Ethylene oxide / propylene oxide copolymers, preferably block copolymers, desirably with 8 to 40 ethylene oxide or propylene oxide units, respectively.
  • Particularly preferred anionic emulsifiers include in particular fatty alcohol ether sulfates, diisooctyl sulfosuccinate, lauryl sulfate, C15- Paraffin sulfonate, which compounds can generally be used as the alkali metal salt, in particular as the sodium salt.
  • These compounds can in particular be obtained commercially under the trade names Disponil® FES 32, Aerosol® OT 75, Texapon® K1296 and Statexan® K1 from the companies Cognis GmbH, Cytec Industries, Inc. and Bayer AG.
  • Useful nonionic emulsifiers include tert-octylphenol ethoxylate with 30 ethylene oxide units and fatty alcohol polyethylene glycol ethers which preferably have 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units. These emulsifiers are commercially available under the trade names Triton® X 305 (Fluka), Tergitol® 15-S-7 (Sigma-Aldrich Co.), Marlipal® 1618/25 (Sasol Germany) and Marlipal® O 13/400 (Sasol Germany) available.
  • the weight ratio of anionic emulsifier to nonionic emulsifier in the range of 20: 1 to 1: 20, preferably 2: 1 to 1: 10 and more preferably 1: 1 to 1: 5 are.
  • Mixtures comprising a sulfate, in particular a fatty alcohol ether sulfate, a lauryl sulfate, or a sulfonate, in particular a diisooctyl sulfosuccinate or a paraffin sulfonate as anionic emulsifier and an alkylphenol ethoxylate or a fatty alcohol polyethylene glycol ether, each preferably 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units have proven particularly useful as a nonionic emulsifier.
  • the emulsifiers can also be used in admixture with protective colloids.
  • Suitable protective colloids include, among others, partially hydrolyzed polyvinyl acetates, polyvinylpyrrolidones, carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins, poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, melamine-formaldehyde sulfonates,
  • Naphthalene formaldehyde sulfonates, styrene-maleic acid and vinyl ether maleic copolymers If protective colloids are used, this is preferably carried out in an amount of 0.01 to 1, 0 wt .-%, based on the total amount of the monomers.
  • the protective colloids can be initially charged or added before the start of the polymerization.
  • the initiator can be initially charged or added. Furthermore, it is also possible to submit a portion of the initiator and to meter in the remainder.
  • the polymerization is preferably started by heating the batch to the polymerization temperature and initially and / or adding the initiator, preferably in aqueous solution.
  • a part of the monomers can be initially charged in the reactor and the remainder added over a certain period of time.
  • the feed may be interrupted for a few minutes after e.g. 1-5% of the monomers are added.
  • the dosages of emulsifier and monomers can be carried out separately or preferably as a mixture, in particular as an emulsion in water.
  • the emulsion polymerization can be carried out in a wide pH range. It is preferably between 2 and 9. In a particular embodiment, the polymerization is carried out at pH values between 4 and 8, in particular between 6 and 8. Likewise, the dispersion after the polymerization can be adjusted to a preferred pH range for the application. For pigmented coating systems, the range is generally 8 - 9 or above.
  • the molecular weight of the polymers is initially uncritical within wide limits.
  • Preferred emulsion polymers having a high content of polymers which are insoluble in THF may be obtained in the manner set forth above.
  • the reaction parameters to obtain a high molecular weight are known.
  • the use of molecular weight regulators can be dispensed with.
  • Coating compositions that are particularly easy and easy to process may also have lower molecular weight polymers, with the solvent resistance and hardness of these coatings reaching a relatively high level.
  • these polymers having a particularly good processability, a molecular weight below 1 000 000 g / mol, preferably below 500 000 g / mol and more preferably below 250 000 g / mol.
  • the molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard.
  • Low molecular weight polymers especially emulsion polymers, can be obtained by the addition of molecular weight regulators to the reaction mixture before or during polymerization.
  • molecular weight regulators for this Sulfur-free molecular weight regulators and / or sulfur-containing molecular weight regulators may be used.
  • 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.
  • the sulfur-containing molecular weight regulators used may preferably be mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides.
  • the following polymerization regulators are given by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-n-butyl sulfide.
  • Preferred compounds used as molecular weight regulators are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides. Examples of these compounds are ethyl thioglycolate, 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 alkyl mercaptans such as n-butylmercaptan, n- Hexylmercaptan or n-dodecylmercaptan.
  • Particularly preferred polymerization regulators are mercaptoalcohols and mercaptocarboxylic acids.
  • the molecular weight regulators are preferably used in amounts of 0.05 to 10, more preferably 0.1 to 5 wt .-%, based on the monomers used in the polymerization. Of course, mixtures of polymerization regulators can also be used in the polymerization.
  • polymerizations using molecular weight regulators can be used to reduce the minimum film-forming temperature (MFT) of the polymers obtainable thereby.
  • the proportion of molecular weight regulators can be dimensioned such that the polymers or the coating compositions of the invention have a minimum film-forming temperature (MFT) of at most 60 ° C., more preferably at most 50 ° C., and very particularly preferably at most 40 ° C, which can be measured according to DIN ISO 2115. The higher the proportion of molecular weight regulators, the lower the minimum film-forming temperature.
  • the adjustment of the particle radii can be influenced inter alia by the proportion of emulsifiers. The higher this proportion, especially at the beginning of the polymerization, the smaller the particles are obtained.
  • the emulsion polymer in particular the amino group-containing (meth) acrylate polymer or the functional polymer is uncrosslinked or crosslinked so low that the soluble in tetrahydrofuran (THF) at 20 0 C content above 60 wt .-% based on the weight of Emulsion polymers is.
  • the emulsion polymer may contain from 2 to 60% by weight, more preferably from 10 to 50% by weight, and most preferably 20 to 40 wt .-%, based on the weight of the emulsion polymer which is soluble in THF at 20 0 C.
  • soluble portion of a dried sample of polymethyl risats is stored in a 200-fold amount of solvent, based on the weight of the sample, at 20 0 C for 4 h.
  • the drying is carried out so that no possible self-crosslinking occurs. This can be done for example by freeze-drying.
  • the solution is separated from the insoluble fraction, for example by filtration.
  • the weight of the residue is determined. For example, a 0.5 g sample of a vacuum-dried emulsion polymer can be stored in 150 ml of THF for 4 hours.
  • coating compositions with amino group-containing (meth) acrylate polymers and functional polymers which have a very similar solubility behavior in THF.
  • the difference between the solubility of the amino group-containing (meth) acrylate polymer and the solubility of the functional polymer in tetrahydrofuran (THF) at 20 ° C. in preferred coating compositions is preferably at most ⁇ 20%, more preferably at most ⁇ 10%, and most especially preferably at most ⁇ 5%.
  • the particle radius of the emulsion polymers can be in a wide range.
  • emulsion polymers having a particle radius in the range of 10 to 500 nm, preferably 10 to 100 nm, particularly preferably 20 to 60 nm can be used.
  • particle radii below 50 nm can be advantageous for the film formation and the coating properties.
  • the radius of the particles can be determined by PCS (Photon Correla- tion spectroscopy), the data given refer to the r50 value (50% of the particles are smaller, 50% are larger).
  • PCS Photon Correla- tion spectroscopy
  • a Beckman Coulter N5 Submicron Particle Size Analyzer can be used for this purpose.
  • the difference between the particle radius of the amino group-containing (meth) acrylate polymer and the particle radius of the functional polymer in preferred coating compositions is preferably at most ⁇ 30 nm, more preferably at most ⁇ 20 nm, and most preferably at most ⁇ 10 nm.
  • coating compositions which preferably contain from 40 to 80% by weight, particularly preferably from 50 to 75% by weight, of polymers to be used according to the invention.
  • Coating agents in which the weight ratio of amino group-containing (meth) acrylate polymer to functional polymer is in the range from 10: 1 to 1:10, preferably from 5: 1 to 1: 5 and particularly preferably in the range from 2: 1 to 1: 2 is located.
  • the present coating compositions show the tendency of self-crosslinking.
  • self-crosslinking in this context refers to a possible reaction of the oxazolidine groups or the amino groups derived therefrom with the carboxylic acid or carboxylic anhydride groups of the functional polymer be accelerated in particular by heat treatment of the films at temperatures above 60 0 C, more preferably above 100 0 C.
  • the time over which the films are crosslinked at temperatures above room temperature is, for example, the pH of the film and the nature and amount of the oxazolidine group-bearing or carboxylic acid or carboxylic anhydride group-comprising repeat units and the desired one mechanical strength of the coating or chemical resistance dependent.
  • This self-crosslinking can preferably be carried out to tack-free according to DIN 53150 or beyond, wherein according to another embodiment, the self-crosslinking to exactly the freedom from gluten according to DIN 53150 takes place.
  • Crosslinked films are often characterized by high solvent resistance and excellent mechanical properties.
  • Coatings which have been subjected to a heat treatment have clear advantages in terms of chemical resistance and mechanical properties, in particular tensile strength and pendulum hardness. Thus, chemical resistance and mechanical properties can be improved to an unexpected degree by annealing.
  • the coating compositions according to the invention can be crosslinked in particular by crosslinking agents which can react with the amino groups of the (meth) acrylate polymer to be used according to the invention and / or the acid or acid anhydride groups of the functional polymer.
  • 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
  • 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. isophorone diisocyanate is the case.
  • cycloaliphatic diisocyanates are understood to be those which have only NCO groups bonded directly to the cycloaliphatic ring, eg. B. H 12 MDI.
  • Examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclo hexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate, such as 4-isocyanatomethyl-1, 8-octane diisocyanate (TIN), decane diisocyanate and triisocyanate, undecaned
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • H 12 MDI diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-thmethylhexamethylene diisocyanate / 2,4,4-thymethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • aliphatic, cycloaliphatic and araliphatic, d. H. Aryl-substituted aliphatic diisocyanates are described, for example, in Houben-Weyl, Methoden der organischen Chemie, 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.
  • This preferred class of polyisocyanates can be prepared by dimerization, trimerization, 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. B. IPDI, TMDI, HDI and / or H 12 MDI with polyhydric alcohols (eg, glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines, or the triisocyanurates, by trimerization of simple diisocyanates, such as IPDI, HDI and H 12 MDI.
  • polyhydric alcohols eg, glycerol, trimethylolpropane, pentaerythritol
  • polyhydric polyamines eglycerol, trimethylolpropane, pentaerythritol
  • trimerization of simple diisocyanates such
  • 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 may in this case be carried out with 0.5 to 1.1 NCO group per reactive 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 reactive group, are present in an amount of from 0.7 to 1.0 isocyanate groups.
  • the term "reactive group” means a group which is reacted with an isocyanate. can be set. These include in particular hydroxy groups and / or amino 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, vanadium, lead, zirconium; Alkali or alkaline earth metals, such as lithium, potassium and calcium.
  • transition metals such as cobalt, manganese, vanadium, lead, zirconium
  • Alkali or alkaline earth metals such as lithium, potassium and calcium.
  • cobalt naphthalate and cobalt acetate cobalt naphthalate and cobalt acetate.
  • the siccatives 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 from greater than 0 to 5% by weight, more preferably in the range from 1 to 3% by weight, based on the polymer content.
  • the coating agents may comprise solvents. These coating agents can be processed over a particularly broad temperature and humidity range.
  • 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 glycol monomethyl ether, glycol monoethyl ether, glycol monobutyl ether; Aliphatic, preferably pentane, hexane, cycloalkane and substituted cycloalkanes, for example cyclohexane; Mixtures of alipha
  • coating compositions whose solids content is preferably at least 50% by weight, more preferably at least 60% by weight, exhibit surprisingly good processability. This information applies in particular to coating compositions comprising organic solvents.
  • the coating compositions of the invention comprise a relatively high proportion of water, with aqueous dispersions being particularly preferred coating compositions.
  • the aqueous dispersions preferably have a solids content in the range from 10 to 70% by weight, particularly preferably from 20 to 60% by weight.
  • These coating compositions often comprise only a very small, preferably no fraction of organic solvents.
  • Preferred aqueous dispersions contain at most 5% by weight, more preferably at most 2
  • VOC volatile organic compounds
  • the coating compositions of the invention may contain conventional additives, in particular UV stabilizers, flow control agents and biocides.
  • the dynamic viscosity of the coating agent is dependent on the solids content and may include a wide range. So this can be more than 10,000 mPas at high polymer content.
  • the present invention provides a method for producing a coating in which a coating composition of the invention is applied to a substrate and cured.
  • the coating composition according to the invention can be applied by conventional application methods, in particular by roller application or spraying. Furthermore, dipping methods are also suitable for applying the coating composition.
  • the present coating composition can be used in particular for the production of paints, varnishes, sealants, adhesives and printing inks.
  • the substrates which can preferably be provided with a coating composition according to the invention include in particular metals, in particular iron and steel, zinc and galvanized steels, wood, plastics and concrete substrates.
  • the present invention provides coated articles obtainable by a method according to the invention.
  • Thieves- The layering of these objects is characterized by an outstanding range of properties.
  • the coatings obtainable from the coating compositions according to the invention show a high resistance to solvents, with only small amounts in particular being dissolved out of the coating by solvents.
  • Preferred coatings show a high resistance, in particular to methyl isobutyl ketone (MIBK).
  • MIBK methyl isobutyl ketone
  • the weight loss after treatment with MIBK is preferably at most 50% by weight, preferably at most 35% by weight.
  • the uptake of MIBK is preferably at most 1000 wt .-%, more preferably at most 600 wt .-%, based on the weight of the coating used. These values are measured at a temperature of about 25 ° C and an exposure time of at least 4 hours, whereby a completely dried coating is measured, which was preferably crosslinked.
  • the coatings obtained from the coating compositions of the invention show high mechanical resistance.
  • the pendulum hardness is preferably at least 15 s, preferably at least 25 s, measured according to DIN ISO 1522.
  • coatings show surprisingly good mechanical properties.
  • coatings which have a nominal elongation at break of preferably at least 200%, more preferably at least 300%, measured in accordance with DIN EN ISO 527 Part 3.
  • coatings are furthermore preferred which have a tensile strength, measured in accordance with DIN EN ISO 527 Part 3, of at least 2 MPa, more preferably at least 4 MPa.
  • preferred coatings which are obtainable from the coating compositions according to the invention are distinguished by 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 dispersion prepared had a solids content of 40 ⁇ 1 wt .-%.
  • the dispersion prepared had a solids content of 40 ⁇ 1 wt .-%.
  • the dispersion prepared had a solids content of 40 ⁇ 1 wt .-%.
  • 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 ethanol amides. The resulting reaction mixture was further processed without purification.
  • 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.
  • the prepared dispersion had a solids content of 39 ⁇ 1% by weight.
  • example 1 A mixture was prepared comprising the polymer set forth above with oxazolidine groups and the polymer set forth above with acid groups. For this purpose, the corresponding dispersions were mixed, wherein the OXEMA content was adjusted to 2.5 wt .-% (based on the solids content).
  • the swelling properties of the coating composition thus obtained were examined.
  • a 1000 .mu.m-thick film (wet) was applied to a silikonumran- finished glass plate and dried for seven days at room temperature or for 6 hours at 145 0 C.
  • the required mass of the dispersion was calculated.
  • a blend was prepared comprising the previously described oxazolidine polymer and the acid anhydride group polymer set forth above.
  • the corresponding dispersions were mixed, wherein the OXEMA content was adjusted to 2.5 wt .-% (based on the solids content).
  • a homopolymer based on oxazolidinylethyl methacrylate was prepared according to Example 9 of the publication US Pat. No. 3,037,006, whereby a 25% strength aqueous solution was obtained.
  • This aqueous solution was mixed with the acid anhydride group polymer set forth above to adjust the OXEMA content to 2.5% by weight (based on the solid content).
  • the dispersion prepared had a solids content of 40 ⁇ 1 wt .-%.
  • the properties of the coating composition thus obtained were investigated by the methods set forth in Example 1, with only one drying at 145 ° C for 6 hours.
  • the true swelling in MIBK was 459%; the true swelling in water is 13.0% and the pendulum hardness is 6 s.
  • coating compositions comprising a polymer having a high content of oxazolidine groups and a polymer having a lower content of oxazolidine groups accordingly exhibit higher pendulum hardness and less swelling in water than coating agents comprising only polymers having oxazolidine groups and acid groups.
  • the coating composition of Example 3 based on the solids content, comprised twice as many oxazolidine groups with 5% by weight as the coating composition of Example 1.
  • the coating agent obtained in Example 1 was provided with a crosslinking agent.
  • a crosslinking agent 40.0 g of the dispersion described in Example 1 were admixed with 1.0 g of a solution of hexamethylene diisocyanate (HDI) and n-butyl acetate (6/1).
  • Example 5 The properties of the coating composition thus obtained were investigated by the methods set forth in Example 1, with only drying at 145 ° C for 6 hours.
  • the true swelling in MIBK was 413%; the true swelling in water 7.0% and the pendulum hardness 21 s.
  • Example 5 The true swelling in MIBK was 413%; the true swelling in water 7.0% and the pendulum hardness 21 s.
  • the coating agent obtained in Example 3 was provided with a crosslinking agent.
  • a crosslinking agent 40.0 g of the dispersion described in Example 3 were admixed with 1.0 g of hexamethylene diisocyanate (HDI) and dibutyltin dilaurate (DBTL, 0.01% by weight, based on the polymer weight).
  • HDI hexamethylene diisocyanate
  • DBTL dibutyltin dilaurate
  • the properties of the coating composition thus obtained were investigated by the methods set forth in Example 1, with only drying at 145 ° C for 6 hours.
  • the true swelling in MIBK was 341%; the true swelling in water 11, 4% and the pendulum hardness 9 s.
  • a blend was prepared comprising the above-described oxazolidine group polymer and the polymer set forth above having groups derived from methacryloyloxy-2-ethyl-fatty acid amides.
  • the corresponding dispersions were mixed, wherein the OXEMA content was adjusted to 2.5 wt .-% (based on the solids content).
  • the properties of the coating composition thus obtained were investigated by the methods set forth in Example 1, with only drying at 145 ° C for 6 hours.
  • the true swelling in MIBK was 270% and the true swelling in water was 3%.

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  • Chemical & Material Sciences (AREA)
  • 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)

Abstract

La présente invention concerne un agent de revêtement comprenant au moins un polymère de (méth)acrylate contenant des groupes amino et comprenant 0,1 à 15 % en poids de motifs dérivés de monomères ayant des groupes oxazolidine et 20 à 99,9 % en poids de motifs dérivés de (méth)acrylates d'alkyle ayant 1 à 12 atomes de carbone, et au moins un polymère fonctionnel ayant des groupes acide carboxylique ou anhydride d'acide carboxylique. La présente invention concerne également un procédé pour produire un revêtement. La présente invention concerne en outre un objet revêtu comprenant un revêtement qui peut être obtenu au moyen de ce procédé.
PCT/EP2010/053964 2009-05-07 2010-03-26 Agent de revêtement, procédé pour produire un revêtement et objet revêtu WO2010127910A1 (fr)

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DE102009002888.9 2009-05-07
DE102009002888A DE102009002888A1 (de) 2009-05-07 2009-05-07 Beschichtungsmittel, Verfahren zur Herstellung einer Beschichtung und beschichteter Gegenstand

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US687851A (en) 1897-11-05 1901-12-03 Frederick C Austin Impact-tool.
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WO2004002931A1 (fr) 2002-06-29 2004-01-08 Oxeno Olefinchemie Gmbh Procede pour la telomerisation d'olefines non cycliques

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TW201114856A (en) 2011-05-01
DE102009002888A1 (de) 2010-11-11

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