Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D139/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
• • 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
  • C09D131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
  • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
• • 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
  • C09D135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D135/02—Homopolymers or copolymers of esters
• • 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
  • C09D135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D135/08—Copolymers with vinyl ethers
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular

Definitions

• the present invention relates to the use of copolymers which in copolymerized form contain, among other monomers, from 10 to 90% by weight of monomers containing heterocyclic basic groups and contain no vinylpyrrolidone as the monomer component, as additives in paints for improving the adhesion of the solid paint film to a substrate.
• copolymers which in copolymerized form contain, among other monomers, from 10 to 90% by weight of monomers containing heterocyclic basic groups and contain no vinylpyrrolidone as the monomer component, as additives in paints for improving the adhesion of the solid paint film to a substrate.
• the term "solid paint film” includes all types of physically or chemically cured paint coatings.
• Paints and coatings serve decorative purposes, as well as the protection of the substrate from harmful influences. In order to perform this function, it is very important that these coatings adhere to the substrate on which they are applied by the usual means such as spraying, rolling, dipping, etc.
• EP 09 288 20 describes this problem very clearly and proposes a solution which is intended to eliminate the problem by subsequently adding products containing cyclic ureas to the emulsion polymer as an additive, these additives likewise being emulsion polymers.
• This proposal does not completely solve the pending problem and there is still a great shortage of adhesion-promoting additives to aqueous dispersion coating systems, especially for difficult substrates, such as aged organic coatings based on, for example, filled and / or pigmented alkyd or acrylate resins or substrates such as filled and / or fiber-reinforced thermoplastics, thermosets, elastomers such.
• PE Polyethylene
• PP polypropylene
• PVC polyvinyl chloride
• PS polystyrene
• PC polymethyl methacrylate
• PMMA polymethyl methacrylate
• ABS acrylonitrile-butadiene-styrene graft copolymer
• PA polyamide
• POM polyoxymethylene
• UP unsaturated polyesters
• EP epoxy resins
• MF melamine resins
• PF polyurethane
• EPDM ethylene-propylene-diene elastomer
• WO 2004/081128 describes nitrogen-containing polymers for the surface treatment of metals. This process requires intensive pretreatment of the metals, including a thin coating of aqueous solutions of the nitrogen-containing polymers. Thereafter, the adhesion of paints on this pretreated metal to be improved. This is essentially a passivation of the metals to be coated, a side effect is the better adhesion of optionally applied paint layers on the passivated surfaces.
• DE 100 05 113 A1 describes a process for the corrosion protection treatment of metal surfaces, which is characterized in that the metal surface is brought into contact with a homo- or copolymer of vinylpyrrolidone.
• the improvement of the adhesion of an optionally later applied organic coating on the passivated metal surface is only a secondary effect, in the foreground is the anti-corrosive effect of homopolymers or copolymers of vinylpyrrolidone on metal substrates.
• the BASF brochure "PVP and more” describes copolymers of vinylpyrrolidone and vinylimidazole as adhesion promoters in corrosion protection.
• EP 0171850 likewise describes adhesion-improving additives to PVC plastisols based on polyaminoamides of unsaturated polycarboxylic acids, in essentially dimerized and trimerized fatty acids, and piperazine derivatives. These compounds are very hydrophobic and accordingly only effective in non-polar systems, which are baked at temperatures not below 120 0 C.
• copolymers with heterocyclic basic groups, preferably imidazole groups in the molecule, which contain no polyvinylpyrrolidone can solve this problem if they are added directly to the paint system as adhesion-improving compounds.
• the copolymers to be used according to the invention contain from 10 to 90% by weight, preferably from 20 to 80% by weight and more preferably from 40 to 70% by weight of monomers containing heterocyclic basic groups in addition to other monomers, such as, for example, As (meth) acrylic acid esters, aromatic vinyl compounds, vinyl esters, itaconic acid esters, maleic anhydride, maleic acid esters, vinyl ethers and other vinyl compounds with the exception of vinylpyrrolidone.
• monomers containing heterocyclic basic groups in addition to other monomers, such as, for example, As (meth) acrylic acid esters, aromatic vinyl compounds, vinyl esters, itaconic acid esters, maleic anhydride, maleic acid esters, vinyl ethers and other vinyl compounds with the exception of vinylpyrrolidone.
• (meth) acrylic acid esters it is possible to use compounds which are prepared by esterification of the (meth) acrylic acid with different alcohols, such as, for example, B. linear and branched alcohols having a chain length of C 1 - C 4, cyclic, substituted and unsubstituted alcohols having 6 - 15 carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate , i-butyl (meth) acrylate, fe / t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate or aryl (meth) acrylates such as benzyl methacrylate or phenyl acrylate, where the aryl radicals are each unsubstituted or up to fourfold may be substituted such as 4-nitrophenyl methacrylate.
• Hydroxyalkyl (meth) acrylates of straight-chain, branched or cycloaliphatic diols having 2 to 36 C atoms for example 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl monomethacrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl methacrylate,
• Methoxymethoxyethyl methacrylate benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 1-ethoxybutyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate, poly (ethylene glycol) methyl ether (meth) acrylate, poly (propylene glycol) methyl the methacrylate; caprolactone and / or valerolactone-modified hydroxyalkyl (meth) acrylates having a mean
• Aminoethylethyleneurea are also suitable.
• Perfluoroalkyl (meth) acrylates having 6 to 20 carbon atoms; Oxiranyl (meth) acrylates, such as 2,3-epoxybutyl methacrylate, 3,4-
• Copolymerizable, heterocyclic basic group-containing monomers can not be prepared without major effort and are commercially available, therefore, essentially in the copolymers, the readily available N-vinylimidazole or 2- and
• the monomers mentioned can also be prepared in mixtures together with N-
• aromatic vinyl compounds are preferably styrene, ⁇ -methyl styrene,
• Vinyltoluene or 5-vinyl-2-norbornene in question are special
• Vinyl acetate suitable but it can also be used vinyl crotonate.
• vinyl ethers ethyl vinyl ether and n-butyl vinyl ether, but also isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether and 4-hydroxybutyl vinyl ether can be used.
• Other vinyl compounds useful as comonomers are N-vinyllactams such as N-vinylcaprolactam and N-vinylpiperidone, but not the toxic vinylpyrrolidone, or vinyl heteroaromatics such as e.g. B. 2- and 4-vinylpyridine N-oxide.
• the prerequisite is that the monomers can be copolymerized with the co-used comonomers and the heterocyclic basic groups which are absolutely necessary for the polymers according to the invention, in the predetermined amounts in the polymers copolymerize.
• macromonomers can be used as comonomers. These macromonomers can be prepared by known methods, such. See, for example, U.S. Patent 5,770,646, U.S. 5,310,813, Russian Chemical Reviews, 56 (8), 1987 and XXIV International Conference in Organic Coatings, June 6-10, 1998, Application of Graft Copolymers by Macromonomer method to 2. component polyurethane coatings (Kansai Paint Co. Ltd.).
• Methyl (meth) acrylate ethyl (meth) acrylate, n- and i-butyl (meth) acrylate.
• cycloaliphatic (meth) acrylates can be used, such as. B.
• Other suitable monomers are, for. As styrene, ⁇ - methyl styrene, acrylonitrile and alkyl vinyl ethers, as already mentioned above. It can, however, too
• macromonomers are also suitable as comonomers.
• monovinyl-terminated polydimethylsiloxanes which are obtained, for example, by reaction of monohydroxy-functional polysiloxanes (obtainable, for example, from Shin Etsu) with (meth) acrylic acid.
• These macromonomers have a number average molecular weight (Mn) of from 200 to 5000 g / mol, and preferably from 500 to 1000 g / mol. To ensure that these macromonomers carry essentially only one ethylenically unsaturated end group, special synthetic procedures are necessary.
• these can be prepared with the aid of so-called "chain transfer agents", as described in US Pat. No. 5,770,646 using cobalt complexes in concentrations of 5-1000 ppm, preferably pentacyanocobaltate (II) or diaquabis (borodifluorodimethylphenylglyoximato
• cobalt complexes in concentrations of 5-1000 ppm, preferably pentacyanocobaltate (II) or diaquabis (borodifluorodimethylphenylglyoximato
• the corresponding Co (III) complexes are likewise used, and the polymerization can then be carried out in solvents such as aromatics, ketones, acetates, alcohols or glycol ethers.
• these macromonomers can be prepared by free-radical polymerization in the presence of a mercapto-functional carboxylic acid as a chain regulator, such as mercaptoacetic acid or mercaptopropionic acid This terminal carboxyl function is further reacted with glycidyl methacrylate to give the methacrylic functional polymerizable macromonomer ow.
• a mercapto-functional carboxylic acid as a chain regulator, such as mercaptoacetic acid or mercaptopropionic acid
• Hydroxy functional chain regulators e.g. Mercaptoethanol or mercaptopropanol are also usable.
• the polymers obtained using these agents then carry at one end a hydroxy function which is further reacted with (meth) acryloyl chloride to form the (meth) acrylic functional polymerizable macromonomer.
• These macromonomers are preferably used in amounts of from 0.5 to 15% by weight, particularly preferably from 2 to 10% by weight, in the polymers according to the invention.
• RAFT Reversible Addition Fragmentation Chain Transfer Process
• MADIX MADIX
• addition fragmentation chain transfer using certain polymerization regulators which will be referred to herein only as RAFT, for example, in Polym , 49, 993, Aust. J. Chem 2005, 58, 379, J. Polym., Part A: Polym. Chem., 2005, 43, 5347, US 6,291,620, WO 98/01478, WO 98/58974
• NMP controlled polymerization with nitroxyl compounds as polymerization regulators
• Atom Transfer Radical Polymerization (ATRP) is described, for example, in Chem. Rev. 2001, 101 , 2921.
• Group transfer polymerization (GTP) is described, for example, by OW Webster in "Group Transfer Polymerization", “Encyclopedia of Polymer Science and Engineering”, Volume 7, HF Mark, NM Bikales, CG Overberger and G. Menges , Eds., Wiley Interscience, New York 1 987, page 580 et seq. Disclosed.
• the controlled radical polymerization with tetraphenylethane is described for example in Macromol. Symp.
• the number-average molecular weights (Mn) of the polymers according to the invention are preferably in the range from 1000 to 50000 g / mol, more preferably 2000 to 25000 g / mol, very particularly preferably in the range from 3000 to 15000 g / mol.
• the number average molecular weight (Mn) can be determined by gel permeation chromatography with polymethyl methacrylate standards.
• the heterocyclic basic groups of the branched polymers according to the invention can also be salified.
• monocarboxylic acids such as acetic acid, propionic acid, stearic acid, oleic acid
• hydroxycarboxylic acids such as ricinol fatty acid, hydroxystearic acid
• sulfonic acids of the general formula HOSO2R 1 sulfuric acid esters
• the radicals R 1 and R 2 are characterized in that they contain at least one alkyl, aryl or aralkyl radical having more than 5 carbon atoms and / or a carboxylic ester function (-COO-) and / or a urethane group (-NHCOO-) ,
• the salification component can also, at least partially, already in the copolymerization as z. B.
• (meth) acrylic acid are polymerized with.
• Other copolymerizable acids are, for. Crotonic acid, allylacetic acid and vinylacetic acid.
• monoethylenically unsaturated dicarboxylic acids are suitable, such as. For example, maleic acid, fumaric acid, itaconic acid and maleic anhydride.
• sulfonic acid group-containing monomers such as.
• vinylsulfonic acid allylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, as well as phosphonic acid-containing monomers such as vinylphosphonic acid are used.
• the acids can be used either alone or as mixtures.
• the acidic monomers are used in amounts of between 1 and 5%, preferably between 1 and 3%, based on the total monomer content. If the polymerization in an aqueous medium, the acid-containing monomers can also be used as salts, such. B. as sodium or potassium salt.
• N-vinylimidazole with the listed copolymers is radically copolymerized in a suitable solvent, which does not interfere with the later application.
• the polymers according to the invention are prepared in a manner known to the person skilled in the art, preferably by means of free radical polymerization in organic form Solvents using radical formers (initiators), such as peroxides or azo compounds.
• radical formers initiators
• Suitable solvents are esters such as ethyl acetate, n-butyl acetate or 1-methoxy-2-propyl acetate and alcohols such as ethanol, i-propanol, n-butanol or 1-methoxy-2-propanol and glycol ethers such as 2-ethoxyethanol, 2 -Propoxyethanol, 2-butoxyethanol, 2- (2-ethoxyethoxy) ethanol or 2- (2-butoxyethoxy) ethanol, in question. It is also possible to use aromatic solvents, for example toluene, xylene or higher boiling alkylbenzenes.
• esters and glycol ethers are preferably employed, particularly preferred are Texanol ® (2,2,4-trimethyl-1, 3-diol monoisobutyrate), 1-methoxy-2-propyl acetate and 2-butoxyethanol.
• the usual peroxidic initiators such as tert - butyl peroxobenzoate or dibenzoyl peroxide or azo initiators such as azoisobutyronitrile (AIBN) or preferably 2,2 * -Azobis (2-methylbutyronitrile) (AMBN) can be used.
• azo initiators such as azoisobutyronitrile (AIBN) or preferably 2,2 * -Azobis (2-methylbutyronitrile) (AMBN)
• chain stoppers such as dodecyl mercaptan, mercaptoethanol or other thiols can be used to control the molecular weight in the desired manner.
• the polymerization is conducted at temperatures of about 60 0 C to 180 0 C, preferably at 70 ° C to 150 ° C, particularly preferably at 75 ° C to 13O 0 C.
• the polymerization can also be carried out in bulk, if solvents are undesirable or the solvents used in the polymerization, such as alcohols, esters, glycol ethers and ketones, such as.
• ethanol, butyl acetate, ethyl acetate, Texanol ® , butyl glycol, propylene glycol monomethyl ether, diisobutyl ketone and methyl ethyl ketone are distilled off completely or partially after the polymerization and the polymer in a suitable carrier medium, which is suitable for aqueous emulsion paints, added.
• a suitable carrier medium which is suitable for aqueous emulsion paints, added.
• esters glycol ethers, alcohols such as Texanol ® , 2-butoxyethanol or ethanol / water or higher molecular weight glycol ethers, which are not classified as volatile organic solvents (VOC).
• the comonomers used in the copolymerization depend on the later field of application of the polymers. Thus, it makes sense to choose the monomer composition so that there is good compatibility in the emulsion polymer, and also to the substrate, which is to be coated, there is a certain affinity. Should z. B. the adhesion of a hydrophilic coating system can be improved on a substrate, as comonomers are preferably hydrophilic monomers such.
• polyethylene glycol monomethyl ether methacrylate 400 the number indicates the approximate molecular weight used in addition to N-vinylimidazole.
• Hydrophilic monomers have a solubility parameter greater than or equal to 22 J 1/2 / cm 3/2 , whereas hydrophobic monomers have a solubility parameter of less than 22 J 1/2 / cm 3/2 (classification according to WO 97/28200).
• the heterocyclic basic group can also be introduced into the polymer by polymer-analogous reaction.
• reactions are suitable which the heterocyclic basic group, by z.
• This reaction when carried out by means of a primary amine group-bearing heterocyclic basic group, such as aminopropylimidazole, can also be carried on to the imide.
• base polymers for carrying out such polymer-analogous reaction z. Styrene-maleic anhydride copolymers (MSA), which are commercially available in various molecular weights and styrene / MSA ratios. In addition to the commercial styrene / MSA copolymers, other alkene / MSA copolymers are available such.
• poly (meth) acrylates preferably poly (alkyl acrylates), more preferably poly (n-butyl acrylates) and their copolymers as base polymers having molecular weights between 1000 and 20,000 g / mol, preferably 2000 and 10,000 g / mol, and more preferably between 3000 and 7500 g / mol, wherein the heterocyclic group-containing basic compounds such as hydroxyethyl imidazole or aminopropyl imidazole are introduced by transesterification or transamidation with release of alkanols, preferably n-butanol in the polymer.
• transesterifications or transamidations can be carried out by conventional methods using customary catalysts such as, for example, tetraisopropyl titanate or para-toluenesulfonic acid (PTS), as described in the patent DE 197 21 728, or else by enzymatic reaction, as described in the patent DE 198 50 507 ,
• customary catalysts such as, for example, tetraisopropyl titanate or para-toluenesulfonic acid (PTS), as described in the patent DE 197 21 728, or else by enzymatic reaction, as described in the patent DE 198 50 507 ,
• Epoxy group-containing base polymers can also be reacted with ring-opening compounds containing primary or secondary amino groups containing heterocyclic basic groups.
• z. B. hydroxy-functional derivatives are also prepared by z. B. hydroxyalkyl acrylates in a Michael addition with z. B. aminopropylimidazole be implemented adding. Further such reactive compounds can be prepared in a simple manner by heterocyclic basic compounds such. Imidazole, 2-methylimidazole, 2-ethylimidazole, 4-methylimidazole, 2-ethyl-4-methylimidazole, pyrazole, N-methylpiperazine, N-ethylpiperazine, and N- (2-aminoethyl) morpholine with e.g. B. hydroxyethyl in a Michael addition to the corresponding hydroxy compounds. This reaction obeys, by way of example, the following mechanism:
• MSA-containing copolymers are reacted with aminopropylimidazole, optionally with the aid of catalysts such as, for example, para-toluenesulfonic acid, to give amide- and / or imide-containing polymers.
• the molecular weights of the MSA-containing copolymers are between 1000 and 10000 g / mol, preferably between 2000 and 5000 g / mol.
• These polymer-analogous reactions can be carried out solvent-free or in aprotic solvents such as, for example, ethyl acetate, butyl acetate, PMA or aromatics such as xylene.
• the solvents used for the synthesis may remain in the reaction mixture or be completely or partially removed and optionally replaced by other solvents or carrier media.
• the solvent can be removed, for example, by distilling off, if appropriate under reduced pressure and / or azeotropically with the addition of water, in whole or in part.
• the active substance obtained by one of these methods can then be dissolved in a solvent suitable for the respective field of application.
• compounds containing heterocyclic basic groups are reacted with acrylates to form Michael adducts and these are added in a further step to MSA-containing copolymers to form ester groups.
• the present invention relates to the use of copolymers with heterocyclic basic groups, preferably imidazole groups, as adhesion-promoting additives to preferably aqueous dispersion coating systems, especially for difficult substrates, such as aged organic coatings based on, for example, filled and / or pigmented alkyd or acrylate resins or Substrates such as filled and / or fiber-reinforced thermoplastics, duromers, elastomers such.
• PE Polyethylene
• PP polypropylene
• PVC polyvinyl chloride
• PS polystyrene
• PC polymethyl methacrylate
• PMMA polymethyl methacrylate
• ABS acrylonitrile-butadiene-styrene graft copolymer
• PA polyamide
• POM polyoxymethylene
• UP unsaturated polyesters
• EP epoxy resins
• MF melamine resins
• PF polyurethanes
• EPDM ethylene-propylene-diene elastomers
• the amount of copolymers of the invention containing heterocyclic basic groups, preferably imidazole groups, as adhesion-promoting additives to preferably aqueous dispersion coating systems is preferably from 0.05 to 5.0% by weight of active substance, more preferably from 0.1 to 3.0% by weight of active substance and very particularly preferably 0.2 to 2.0% by weight of active substance, based on the weight of the overall formulation.
• the invention further provides hardened and uncured polymer compositions containing one or more of the copolymers with heterocyclic basic groups, preferably imidazole groups, as adhesion-improving additives.
• PEG-MA 400 polyethylene glycol monomethyl ether methacrylate 400 (number indicates approximate molecular weight)
• Tone TM M 100 addition product of hydroxyethyl acrylate with 2 mol ⁇ -caprolactone
• Example 7
• Example 8-10 are prepared analogously to Example 7:
• Dropping funnels are filled at room temperature 50 g XyIoI and 36 g of aminopropylimidazole and heated to 135 0 C under a nitrogen atmosphere. To this solution is added a mixture of 25 g SMA2000 resin (copolymer of styrene and
• Dropping funnels are initially charged at room temperature with 38.71 g of hydroxyethyl acrylate. Under nitrogen atmosphere is then added dropwise in about 30 minutes 41, 72 g of aminopropylimidazole. The reaction is highly exothermic, the exothermic reaction temperature of 70 0 C is reached. After complete addition of the Aminopropylimidazols the temperature is maintained for two hours at 7O 0 C. An NMR study then shows a nearly quantitative conversion to the desired Michael addition product. This gives a clear yellow oil.
• HPA hydroxypropyl acrylate
• a pigmented aqueous dispersion was prepared and incorporated after 1 day storage at RT compounds of the invention at low shear rates.
• the varnish was also conditioned for 7 days
• the parts by weight of raw materials stated in the tables below are weighed into a 100 ml double-walled disperse pot.
• the amount of raw material weighed in is the same amount of glass beads with 1mm diameter added and then dispersed with a 45mm Teflon disk under city water cooling.
• the dispersion time is 30 minutes at a peripheral speed (Teflon disk) of 23m / s. After cooling, the other raw materials are stirred.
• the paints prepared in this way are screened through a paper sieve (mesh size 80 ⁇ m) and filled into glass bottles.

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• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Paints Or Removers (AREA)
• Macromonomer-Based Addition Polymer (AREA)
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• 2006
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