EP1490447A1 - Liants resineux en dispersion reticulables contenant un monomere d'ether allylique - Google Patents

Liants resineux en dispersion reticulables contenant un monomere d'ether allylique

Info

Publication number
EP1490447A1
EP1490447A1 EP03708199A EP03708199A EP1490447A1 EP 1490447 A1 EP1490447 A1 EP 1490447A1 EP 03708199 A EP03708199 A EP 03708199A EP 03708199 A EP03708199 A EP 03708199A EP 1490447 A1 EP1490447 A1 EP 1490447A1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
polymerizable monomers
aqueous
ethylene glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03708199A
Other languages
German (de)
English (en)
Inventor
Martin Melchiors
Rolf Gertzmann
Sandra Hackbarth
Raul Pires
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1490447A1 publication Critical patent/EP1490447A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/635—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto unsaturated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D157/04—Copolymers in which only the monomer in minority is defined
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the invention relates to aqueous, crosslinkable binder dispersions containing hydroxy-functional copolymers based on ethylene glycol monoallyl ether, a process for their preparation and the use of the dispersions in paints.
  • binders based on hydroxy-functional copolymers in coating systems. These binders can be used in organically dissolved form, as an aqueous dispersion and in water-thinnable form in solvent-based or aqueous lacquers. Crosslinking of these copolymers in the coating is possible via the OH groups, e.g. with melamine resins or (blocked) polyisocyanates to one-component - or two-component to processable paints.
  • Aqueous coating systems are increasingly used to reduce the emissions of volatile organic compounds (VOC).
  • VOC volatile organic compounds
  • Such lacquers contain a significantly lower proportion of organic solvents (“co-solvents”) than the solvent-based lacquers.
  • co-solvents organic solvents
  • the switch to aqueous coating systems has the deterioration of other coating properties, e.g. the resistance to solvents and chemicals. The reason for this is the higher hydrophilicity of the aqueous or water-dilutable binders compared to their solvent-based counterpart.
  • a particularly difficult requirement to meet is the so-called anti-graffiti resistance, ie the commercially available paint sprays, colored pencils or paint sticks leave color spots in the paint layer that cannot be removed by cleaning agents without damaging the paint layer (e.g. deterioration in gloss) (the Requirements are described, for example, in TL 918 300, item 4.11, of Irish Bahn AG).
  • the resistance of aqueous coatings based on hydroxy-functional copolymer dispersions can be improved by combining them in the lacquer with polyisocyanates with free NCO groups as crosslinkers to form aqueous two-component polyurethane lacquers (2K-PUR).
  • Such coatings are described, for example, in EP-A 0 358 979 or in EP-A 0 947 557.
  • the copolymers on which these coating dispersions are based are produced by radical polymerization of vinyl monomers in an aqueous phase, so-called primary dispersions or in an organic phase with subsequent dispersion in water, so-called secondary dispersions.
  • the monomer mixtures generally contain hydroxy (meth) acrylate monomers as building blocks for the OH functionality of the resin. This gives paint films with an overall high level of paint technology, but the anti-graffiti resistance of these paint films does not meet the requirements.
  • EP-A 0 900 243 and WO-A 00/00527 describe water-dilutable, hydroxy-functional resins for coating compositions, the OH groups being introduced into the resins by incorporating propoxylated allyl alcohol.
  • WO-A 99/51658 discloses aqueous two-component polyurethane paints containing aqueous dispersions of polyisocyanates with free NCO groups and hydroxy-functional resins, based on allyl alcohol or an alkoxylated allyl alcohol.
  • the object of the present invention was to provide binder dispersions based on hydroxy-functional resins, with which aqueous 2-component PU lacquers with good film appearance and good resistance properties, in particular very good anti-graffiti resistance, can be produced.
  • This object was achieved in that the lacquers contain aqueous binder dispersions based on hydroxyl- and acid-functional copolymersates which contain at least ethylene glycol monoallyl ether as the hydroxymonomer.
  • the invention thus relates to aqueous crosslinkable binder dispersions containing hydroxyl- and acid-functional copolymers (A) and / or (A 1 ), characterized in that the copolymer (A) or (A ') contains ethylene glycol monoallyl ether (al).
  • the copolymer (A) preferably contains
  • the copolymer (A) particularly preferably contains
  • ethylene glycol monoallyl ether (a2) 0.5 to 10% by weight, preferably 1 to 5% by weight, particularly preferably 1.5 to 4% by weight, one or more acid-functional polymerizable monomers, (a3) 5 to 60% by weight .%, preferably 10 to 50% by weight, particularly preferably 15 to 40
  • % By weight of one or more polymerizable monomers with cyclic groups, (a4) 5 to 60% by weight, preferably 10 to 50% by weight, particularly preferably 15 to 40
  • % By weight of one or more further polymerizable monomers, (a5) 0 to 40% by weight, preferably 0 to 25% by weight, particularly preferably 0 to 10% by weight one or more OH and / or NH-functional polymerizable monomers the sum of the components adding up to 100% by weight, and (a4) being different from (al) to (a3) and (a5).
  • a copolymer (A ') is also preferred
  • a copolymer (A ') containing is particularly preferred
  • copolymer (A) or (A '), contained in the binders according to the invention contains as the monomer (al) ethylene glycol monoallyl ether.
  • Component (a1) can, for example, in accordance with US Pat. No. 4,618,703 (column 2, line 56 - column 3, line 56) or Jungk et al., Organic Preparations and Procedures International 1983, 15 (3), 152 f getting produced.
  • Unsaturated, free-radically polymerizable compounds with carboxyl / carboxylate groups or sulfonic acid / sulfonate groups are suitable as component (a2).
  • acid-functional monomers (A2) are e.g. Acrylic acid, methacrylic acid, ß-carboxyethyl acrylate, crotonic acid, fumaric acid, maleic acid (anhydride),
  • Itaconic acid monoalkyl esters of dibasic acids / anhydrides such as Maleic acid monoalkyl esters, and the olefinically unsaturated monomers containing sulfonic acid / sulfonate groups described in WO-A 00/39181 (page 8 line 13 - page 9 line 19), including 2-acrylamido-2-methylpropanesulfonic acid as examples be.
  • Carboxy-functional monomers are preferably used, particularly preferably acrylic acid and / or methacrylic acid.
  • Examples of polymerizable monomers with cyclic groups (a3) are Cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylates substituted with alkyl groups on the ring, isobornyl (meth) acrylate or norbornyl (meth) acrylate in question, but also styrene, vinyl toluene or ⁇ -methylstyrene. Isobornyl (meth) acrylate and / or styrene are preferably used.
  • Suitable monomers (a4) are, for example, (meth) acrylic acid esters with C 1 to C 8 hydrocarbon radicals in the alcohol part, for example ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2- Ethylhexyl methacrylate, but also vinyl esters, vinyl monomers containing alkylene oxide units such as, for example, condensation products of (meth) acrylic acid with oligoalkylene oxide monoalkyl ethers and monomers with other functional groups such as epoxy groups, alkoxysilyl groups, urea groups, urethane groups,
  • di- or higher functional (meth) acrylate Monomers and / or vinyl monomers such as hexanediol di (meth) acrylate can be used in amounts of 0-2% by weight, based on the sum of the monomers (al) to (a6). Methyl methacrylate, n-butyl acrylate, n-butyl methacrylate or 2-ethylhexyl acrylate are preferably used.
  • Suitable hydroxy-functional monomers (a5) are e.g. Hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate or hydroxy monomers containing alkylene oxide units, such as e.g. Addition products of ethylene oxide, propylene oxide or butylene oxide with (meth) acrylic acid. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate or hydroxybutyl methacrylate are preferably used.
  • % By weight, preferably 0.2 to 0.4% by weight.
  • the polyesters used as component (a6) are from 0 to 40% by weight, preferably 0 to 20% by weight and particularly preferably 0 to 0, by a polycondensation of (I) known per se
  • Monocarboxylic acids with 8-30 C atoms (II) 0.6 to 5% by weight, preferably 0.6 to 2% by weight> of an ⁇ , ⁇ -unsaturated
  • Mono- or dicarboxylic acid with 3 to 8 carbon atoms or their anhydrides (III) 20 to 60% by weight, preferably 25 to 55% by weight, of one or more aliphatic, cycloaliphatic or aromatic di-, tri- or tetracarboxylic acids with 2 to 40 C atoms or their anhydrides,
  • (VI) 0 to 10% by weight, preferably 0 to 5% by weight of further COOH or OH-reactive compounds such as e.g. Epoxides, isocyanates, amines or oxazolines with 1 to 4, preferably 1.9 to 2.5 functional groups per molecule,
  • COOH or OH-reactive compounds such as e.g. Epoxides, isocyanates, amines or oxazolines with 1 to 4, preferably 1.9 to 2.5 functional groups per molecule
  • reaction of components (I) to (VI) can optionally be carried out with the aid of conventional esterification catalysts, preferably according to the principle of melt or azeotropic condensation at temperatures from 140 ° C. to 240 ° C. with elimination of water. * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * *
  • As component (I) contains the polyester component (a6) of the invention
  • Binder dispersion optionally one or more aliphatic monocarboxylic acids with 8 to 30 carbon atoms.
  • saturated monocarboxylic acids with 8 to 30 carbon atoms are 2-ethylhexanoic acid, octanoic acid (caprylic acid), decanoic acid (capric acid), dodecanoic acid (lauric acid), hexadecanoic acid (cetylic acid) or ocadecanoic acid (stearic acid).
  • aliphatic, mono- or polyunsaturated monocarboxylic acids with 8 to 30 carbon atoms such as oleic acid, linoleic acid or linolenic acid.
  • monocarboxylic acids such as those formed in the saponification of natural oils and fats are preferably used.
  • fatty acids are soybean oil fatty acid, tall oil fatty acid, linseed oil fatty acid, castor oil fatty acid, coconut oil fatty acid, peanut oil fatty acid or safflower oil fatty acid.
  • Monocarboxylic acids which occur naturally due to saponification are particularly preferred non-drying oils and or fats can be obtained.
  • oils and fats are coconut oil, palm kernel oil and peanut oil.
  • monocarboxylic acids with 8 to 30 carbon atoms are hydrogenated fatty acids, synthetic fatty acids, for example from paraffin oxidation or Koch synthesis (J. Falbe, New Syntheses with Carbon Monoxide, Berlin, Heidelberg, New York (1980), see. 372 ff).
  • the polyester component (a6) contains ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids with 3 to 8 carbon atoms.
  • carboxylic acids are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid or tetrahydrophthalic acid.
  • derivatives of carboxylic acids such as e.g. Anhydrides or esters can be used as starting materials for polyester production. Maleic anhydride is preferred.
  • Suitable components (III) for the polyester component (a6) are aliphatic, cycloaliphatic or aromatic di-, tri- or tetracarboxylic acids with 2 to 40 C-
  • Atoms such as Phthalic acid, isophthalic acid or terephthalic acid as well as pyromellitic acid, trimellitic acid and succinic acid, adipic acid, sebacic acid, azelaic acid.
  • Dimer fatty acids made from natural or synthetic fatty acids are also suitable. Instead of the free carboxylic acids, derivatives of carboxylic acids such as e.g. Anhydrides or esters can be used as starting materials for polyester production.
  • Dicarboxylic acids such as e.g. Phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid or azelaic acid are used.
  • Aliphatic monoalcohols such as butanol, pentanol or 2-ethylhexanol, for example, can be used as OH components (IV) with 1 to 4 OH groups per molecule.
  • OH components (IV) with 1 to 4 OH groups per molecule.
  • 'Fatty alcohols' such as those formed during the reduction of fatty acids, are also suitable.
  • alcohol components with 2 OH groups are ethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylpentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tripropylene glycol or hydrogenated bisphenol.
  • Preferred OH components (IN) are three and higher alcohol components, optionally used in combination with dihydric alcohols. Pentaerythritol, glycerol or trimethylolpropane may be mentioned as examples.
  • Examples of monocarboxylic acids (V) include Benzoic acid or alkylbenzoic acids in
  • the polyester component (a6) is usually prepared by polycondensation as in the literature (R. Dhein, K. Reuter, G. Ruf in 'Houben-Weyl, Methods of Organic Chemistry Vol E20 / 2 ⁇ Ed .: H Bartl, J. Falbe, 4th edition p.
  • Suitable polyisocyanates are preferably aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-isocyanatocyclohexane), tetramethylxylylene diisocyanate or modified aliphatic types such as polyisocyanates containing isocyanurate, uretdione or biuret groups.
  • aromatic polyisocyanates such as
  • Suitable epoxides are for example epoxy resins based on bisphenol A diglycyidylether or Cardura ® E 10 (glycidyl ester of a mixture of highly branched monocarboxylic acids having 10 carbon atoms; Versatic ® 10, from Resolution Nederland BV, Hoogvliet, the Netherlands.).
  • Suitable amines are, for example, hexamethylenediamine, isophoronediamine, diethylenetriamine or ethylenediamine.
  • the aqueous binder dispersions according to the invention are prepared by converting components (a1) to (a5) into a copolymer (A) or components (a1) to (a6) into a copolymer (A ') and sat (A) or (A ') is converted into the aqueous phase, the acid groups being at least partially neutralized before or during the dispersion.
  • the copolymers (A) or (A ') containing the binder dispersions according to the invention can be prepared by polymerization processes known per se. However, the preparation is preferably carried out by polymerization in the organic phase with subsequent dispersion of the resin in the aqueous phase, the acid groups being at least partially neutralized before or during the process of dispersing the resin. It is particularly preferred to prepare the copolymer (A) or (A ') using a multi-stage polymerization process, such as e.g. in the
  • EP-A 0 947 557 page 3 line 2 - page 4 line 15
  • EP-A 1 024 184 page 2 line 53 - page 4 line 9
  • a monomer mixture which is relatively hydrophobic or free of acid groups and then a more hydrophilic monomer group containing acid groups is metered in at a later point in the polymerization.
  • component (a6) is used in the preparation of the copolymer (A '), it can be dissolved in the hydrophobic part, but also partly in the hydrophilic part.
  • component (a6) is preferably initially introduced.
  • Component (a6) is particularly preferably initially introduced together with component (al), component (a6) may contain cosolvent, but is preferably free of cosolvent.
  • Components (a2) to (a4) and optionally (a5) are then as described in EP-A 0 947 557 (page 3 line 2 - page 4 line 15) or in EP-A 1 024 184 ( P. 2 line 53 - p. 4 line 9) as metered in to the component (a6) and polymerized.
  • the hydrophilic polymer is in the presence of the hydrophobic
  • a multi-stage polymerization process it is also preferred to carry out the process continuously (gradient polymerization), ie a monomer mixture or monomer-polyester mixture with changing composition is used. added, the hydrophilic monomer proportions being higher towards the end of the feed than at the beginning.
  • component (a1) can also be metered in (with a correspondingly lower incorporation rate) at the same time as the other monomers.
  • the incorporation rate of (al) can also be influenced by the reaction conditions (pressure, temperature). Any remaining contents of unincorporated (a1) can optionally be easily removed by distillation after the end of the polymerization and used again.
  • the copolymerization is generally at 90 to 180 ° C, preferably at 100 to
  • the reaction can be carried out in the presence of organic solvents.
  • organic solvents Any solvents known in coating technology are suitable as such, preference is given to those which are usually used as cosolvents in aqueous dispersions, such as, for example, alcohols, ethers, alcohols containing ether groups, esters, ketones, N-methylpyrrolidone or nonpolar hydrocarbons or mixtures of these solvents.
  • the solvents are used in amounts such that their content in the finished dispersion is 0-12% by weight, preferably 0-6% by weight, particularly preferably 0-1% by weight. If necessary, the solvents used can also partially removed by distillation if particularly low levels of organic solvents are required.
  • Suitable initiators for the polymerization reaction are organic peroxides such as Di-tert-butyl peroxide or tert-butyl peroxy-2-ethylhexanoate and azo compounds.
  • the amounts of initiator used depend on the desired molecular weight. For reasons of process reliability and easier handling, peroxide initiators can also be used as a solution in suitable organic solvents of the above. Be used.
  • the number average molecular weight M n of the copolymers (A) or (A ') can be controlled by carefully selecting the process parameters, for example the molar monomer-initiator ratio, the reaction time or the temperature, and is generally between 500 and 30,000, preferably between 500 and 20,000, particularly preferably between 500 and 15,000.
  • (A) is 2 to 10% by weight o, preferably 2.5 to 8.5% by weight, particularly preferably 3 to 7% by weight o and is determined by the relative amount of the hydroxy-functional monomers (al) and ( a5) and (a6).
  • the content of acid groups, which forms the sum of carboxyl / carboxylate and sulfonic acid / sulfonate groups, in the 100% copolymer (A) or (A ') is 5 to 100 mequ./lOO g, preferably 10 to 80 mequ./lOO g and particularly preferably 20 to 60 mequ./lOOg and is determined by the relative amount of the acid-functional monomers (a2) used and the amount (a6) to be used for copolymer (A ').
  • the copolymer (A) or (A ') for the hydrophilization may contain, in addition to the acid groups, monomer units containing alkylene oxide in built-in form or else external emulsifiers. However, the copolymers (A) or (A 1 ) are preferably only hydrophilized by acid groups.
  • organic amines or water-soluble inorganic bases for example soluble metal hydroxides
  • suitable amines are N-methylmo ⁇ holin, triethylamine, diisopropylethylamine, dimethylethanolamine, dimethylisopropanolamine, methyldiethanolamine, diethylethanolamine, butanolamine, mo ⁇ holin, 2-aminomethyl-2-methylpropanol or isophoronediamine.
  • Ammonia can also be used.
  • the neutralizing agent is added in amounts such that there is a degree of neutralization (ie the molar ratio of neutralizing agent to acid) of 40 to 150%, preferably 60 to 120%.
  • the pH of the aqueous binder dispersion according to the invention is 6.0 to 11.0, preferably 6.5 to 9.0. ,
  • the aqueous, crosslinkable binder dispersions according to the invention have a solids content of 25 to 60%, preferably 30 to 50%, and an organic solvent content of 0 to 12%, preferably 0 to 6%.
  • the present invention also makes it possible to prepare quasi-co-solvent-free aqueous dispersions.
  • the binder dispersions according to the invention may, in addition to the copolymer (A) or (A '), optionally also other binders or dispersions, e.g. based on polyesters, polyurethanes, polyethers, polyepoxides or polyacrylates and optionally pigments and other auxiliaries and additives known in the coatings industry.
  • the binder dispersions according to the invention can be processed into aqueous coating compositions.
  • Aqueous coating compositions comprising the binder dispersions according to the invention and at least one crosslinking agent, preferably a polyisocyanate crosslinking agent, particularly preferably a polyisocyanate crosslinking agent with free NCO groups, are therefore also a subject of the present invention.
  • both one-component and two-component paints can be produced.
  • coating agents are to be understood in which the binder component and the crosslinking component can be stored together without a crosslinking reaction taking place to an appreciable extent or harmful to later application.
  • the crosslinking reaction only takes place after application after activation of the crosslinker. This activation can be done, for example, by
  • Two-component paints in the sense of the present invention are coating compositions in which the binder component and crosslinker component have to be stored in separate containers due to their high reactivity. The two components are mixed shortly before application and then generally react without additional activation. To accelerate the crosslinking reaction, however, catalysts can also be used or higher temperatures can be used.
  • Suitable crosslinkers are, for example, polyisocyanate crosslinking agents, amide and amine formaldehyde resins, phenolic resins, aldehyde and ketone resins, such as e.g. Phenol-formaldehyde resins, resols, furan resins, urea resins, carbamic acid ester resins, triazine resins, melamine resins, benzoguanamine resins, cyanamide resins, aniline resins, as described in "Lackbuchharze”, H. Wagner, H.F. Sarx, Carl Hanser Verlag Kunststoff, 1971.
  • Polyisocyanates with free and / or blocked NCO groups are preferably used as crosslinking agents, since the aqueous one-component and two-component polyurethane coatings obtained have a particularly high level of coating technology.
  • Blocked polyisocyanates for example based on isophorone diisocyanate, hexamethylene diisocyanate, 1,4-diisocyanatocyclohexane, bis (4-isocyanatocyclohexane) methane or 1,3-diisocyanatobenzene or based on lacquer polyisocyanates such as biuret or isocyanurate groups, are suitable as such crosslinking resins containing polyisocyanates of 1, 6-diisocyanatohexane, isophorone diisocyanate or bis- (4-isocyanatocyclohexane) methane or urethane-containing lacquer polyisocyanates based on 2,4- and / or 2,6-
  • Suitable blocking agents for these polyisocyanates are, for example, monohydric alcohols such as methanol, ethanol, butanol, hexanol, cyclohexanol, benzyl alcohol, oximes such as acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, lactams such as ⁇ -caprolactam, phenols, amines such as diisopropylamine or dibutylamine, dimethylpy- razole or triazole and dimethyl malonate, diethyl malonate or dibutyl malonate.
  • monohydric alcohols such as methanol, ethanol, butanol, hexanol, cyclohexanol, benzyl alcohol, oximes such as acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, lactams such as ⁇ -caprolactam,
  • low-viscosity, hydrophobic or hydrophilized polyisocyanates with free isocyanate groups based on aliphatic, cycloaliphatic, aromatic lipatic and / or aromatic isocyanates, preferably aliphatic or cycloaliphatic isocyanates, since a particularly high level of resistance of the paint film can be achieved in this way.
  • These polyisocyanates generally have a viscosity of 10 to 3500 mPas at 23 ° C. If necessary, the polyisocyanates can be used in admixture with small amounts of inert solvents in order to lower the viscosity to a value within the stated range.
  • Triisocyanatononan can also be used alone or in mixtures as a crosslinking component.
  • copolymer (A) or (A ') described here is generally sufficiently hydrophilic so that the dispersibility of the crosslinking resins, insofar as they are not water-soluble or water-dispersible substances, is ensured.
  • Water-soluble or dispersible, blocked polyisocyanates are obtainable, for example, by modification with carboxylate and / or polyethylene oxide groups and / or polyethylene oxide / polypropylene oxide groups. Hydrophilization of the polyisocyanates is possible, for example, by reaction with undersized amounts of monohydric, hydrophilic polyether alcohols. The preparation of such hydrophilic polyisocyanates is described, for example, in EP-A 0 540 985, page 3, line 55 - page 4 line 5. The allophanate groups described in EP-A-959087, page 3 lines 39-51, which are prepared by reacting low-monomer polyisocyanates with polyethylene oxide polyether alcohols under allophanatization conditions, are also very suitable.
  • the water-dispersible polyisocyanate mixtures based on triisocyanatononane described in DE-A 100 078 21, page 2 line 66 - page 3 line 5 are also suitable. Hydrophilization is also possible by adding commercially available emulsifiers.
  • non-hydrophilic, low-viscosity polyisocyanate crosslinking agents since a very high level can be achieved in particular with regard to resistance to graffiti.
  • the customary auxiliaries and Additives of paint technology are added, such as Defoamers, thickeners, pigments, dispersing aids, catalysts, skin-preventing agents, anti-settling agents or emulsifiers.
  • Binder dispersions are suitable for all areas of application in which aqueous coating and coating systems with high demands on the resistance of the
  • Films are used, e.g. coating of mineral building material surfaces, Painting and sealing of wood and wood-based materials, coating of metallic surfaces (metal coating), coating and painting of asphalt or bituminous coverings, painting and sealing of various plastic surfaces (plastic coating) as well as high-gloss paints.
  • the present application also relates to substrates coated with aqueous coating compositions comprising the binder dispersions according to the invention.
  • aqueous coating compositions containing the binder dispersions according to the invention are used for the production of primers, fillers, pigmented or transparent topcoats, clearcoats and high-gloss lacquers, and single-layer lacquers which are used in single and series application, e.g. can be used in the field of industrial painting, automotive initial and repair painting.
  • aqueous coating compositions comprising the binder dispersions according to the invention, preferably in combination with polyisocyanates or particularly preferably in combination with low-viscosity non-hydrophilized polyisocyanates, are the coating or coating of metallic surfaces or plastics at room temperature to 140 ° C. With very good film optics, these coatings have a high level of resistance to solvents and chemicals, in particular excellent resistance to graffiti.
  • the coating can be produced using the various spraying processes, such as air pressure, airless or electrostatic spraying processes, using one- or, if appropriate, two-component spraying systems.
  • the lacquers and coating compositions containing the binder dispersions according to the invention can also be applied by other methods, for example by brushing, rolling or knife coating. Examples
  • Viscosity measurements were carried out in a cone-plate viscometer according to DIN 53019 at a shear rate of 40 s "1 .
  • Example 1 Preparation of a dispersion containing hydroxyl groups according to the invention
  • Mixture (I) from 990 g of ethylene glycol monoallyl ether, 83.2 g of methyl methacrylate, 83.3 g of isobornyl methacrylate, 3.5 g of acrylic acid and 10.8 g of di-tert-butyl peroxide are introduced and heated to 143 ° C.
  • a mixture (II) of 407.2 g of methyl methacrylate and 407.3 g of isobornyl methacrylate and, in parallel, 39.2 g of di-tert-butyl peroxide are then metered in over the course of 4.5 hours at the same temperature with stirring.
  • a mixture (IV) of 217.5 g of methyl methacrylate, 190 g of butyl acrylate and 60 g of acrylic acid and again, in parallel, a solution of 8 g of di-tert-butyl peroxide in 16 g of Solvent Naphtha ® 100 metered in evenly within 1.5 h, and more
  • the dispersion is quasi-solvent free.
  • the OH content of the resin (100%) is 6.1% (OH number 201 mg KOH / g), the acid number (100%) 21.5 mg KOH / g.
  • Example 2 Preparation of a dispersion containing hydroxyl groups according to the invention
  • Example 1 is repeated with the difference that 990.5 g of the resin obtained after distillation are mixed with 87.4 g of Solvent Naphtha ® 100 and 87.4 g of butylglycol at 95 ° C. Then is neutralized with 29.0 g of dimethylethanolamine at 95 ° C and by adding 1850 g of dist. Dispersed water to a stable aqueous dispersion with a solids content of 32.3% at a viscosity of 1560 mPas and a pH of 7.9. The dispersion has a co-solvent content of 5.7%. The OH content of the resin (100%) is 6.1% (OH number
  • Example 3 Preparation of a dispersion containing hydroxyl groups according to the invention
  • a mixture (I) of 750 g of ethylene glycol monoallyl ether, 83.2 g of methyl methacrylate, 83.3 g of isobornyl methacrylate, 10.8 g of di-tert-butyl peroxide and 78 g of butyl glycol is placed in a 6-liter reaction vessel with a stirring, cooling and heating device submitted and heated to 143 ° C.
  • Mixture (I) from 990 g of ethylene glycol monoallyl ether, 83.2 g of methyl methacrylate, 83.3 g of isobornyl methacrylate, 3.5 g of acrylic acid and 10.8 g of di-tert.butyl peroxide are introduced and heated to 143 ° C.
  • This resin melt is then dissolved in 195.8 g of solvent naphtha 100, neutralized with 54.3 g of dimethylethanolamine at 95 ° C., and 4550 g of dist. Water too.
  • a stable aqueous dispersion is obtained with a solids content of 33.2%> at a viscosity of 2400 mPas and a pH of 8.0.
  • the dispersion has a cosolvent content of 2.7%.
  • the OH content of the resin (100%) is 5.9% (OH number 195 mg KOH / g), the acid number (100%) 15 mg KOH / g.
  • Example 5 Preparation of a dispersion containing hydroxyl groups according to the invention
  • a mixture (I) of 450 g of ethylene glycol monoallyl ether, 700 g of the polyester resin a), 13.3 g of methyl methacrylate, 8.7 g of styrene, 1.3 g of n- is in a 6 1 reaction vessel with a stirring, cooling and heating device.
  • An initiator solution of 39.0 g of di-tert-butyl peroxide dissolved in 78.0 g of butyl glycol is added dropwise to the mixture (I) over the course of 4 hours, the temperature being kept at 140.degree.
  • a mixture (II) of 120.0 g of methyl methacrylate, 78.0 g of styrene, 12.0 g of n-butyl acrylate and 264.0 g of hydroxypropyl acrylate is metered in at 2 ° C. at a reaction temperature of 2 hours.
  • the resin melt is neutralized with 61.8 g of dimethylethanolamine at 95 ° C and then gives 2070 g of dist. Water too.
  • a stable aqueous dispersion is obtained with a solids content of 43.2%, a viscosity of 2400 mPas and a pH of 7.6.
  • the dispersion is free of cosolvents.
  • the OH content of the resin (100%) is 7.7% (OH number 253 mg KOH / g), the acid number (100%) 26 mg KOH / g.
  • Example 6 Preparation of a dispersion not containing hydroxyl groups according to the invention (comparison)
  • binder dispersion I and additives II-IV are rubbed with a stirrer (approx. 10 minutes at approx. 2000 rpm) to form an aqueous base lacquer component and left to vent for 1 day. After the setting with dist. Allow water to viscosity (approx. 40 s DIN 6 cup) and vent again for 1 day.
  • Spray viscosity diluted by approx. 25 s (DIN 4 cup). After application (HVLP NR 2000 spray gun; 3.0-3.5 bar) on coil coating sheets coated with a commercially available water-dilutable or solvent-based basecoat (e.g. Permahyd or Permacron; Spies Hecker), the paints are applied for 30 minutes RT flashed off, 30 min at 60 ° C in the oven and then 7-10
  • a commercially available water-dilutable or solvent-based basecoat e.g. Permahyd or Permacron; Spies Hecker
  • aqueous 2-component PU lacquers based on the dispersions according to the invention from Examples 1 and 2 combine very good film optics, high hardness, very good resistance to solvents and chemicals with excellent resistance to graffiti.
  • Coatings based on the dispersions from Examples 5 and 6 not according to the invention likewise show a good level of properties, but with weaknesses in gloss and hardness (Disp. 5) and resistance to solvents and chemicals (Disp. 6). While the paints based on the dispersions from Ex. 1 and 2 the graffiti test of

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)
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Abstract

L'invention concerne des dispersions aqueuses de liants réticulables, ces dispersions contenant des copolymères à fonction hydroxy à base d'éther monoallylique d'éthylèneglycol. L'invention concerne en outre un procédé de production de ces dispersions et leur utilisation dans des peintures ou vernis.
EP03708199A 2002-03-21 2003-03-10 Liants resineux en dispersion reticulables contenant un monomere d'ether allylique Withdrawn EP1490447A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10212545 2002-03-21
DE2002112545 DE10212545A1 (de) 2002-03-21 2002-03-21 Vernetzbare Bindemitteldispersionen
PCT/EP2003/002403 WO2003080751A1 (fr) 2002-03-21 2003-03-10 Liants resineux en dispersion reticulables contenant un monomere d'ether allylique

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EP1490447A1 true EP1490447A1 (fr) 2004-12-29

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EP (1) EP1490447A1 (fr)
JP (2) JP2005520913A (fr)
KR (1) KR20050007443A (fr)
CN (1) CN1656185A (fr)
AU (1) AU2003212320A1 (fr)
CA (1) CA2479772A1 (fr)
DE (1) DE10212545A1 (fr)
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JP4157853B2 (ja) * 2003-08-13 2008-10-01 ローム アンド ハース カンパニー 硬化性組成物およびバインダーとしての使用
US20050214534A1 (en) * 2004-03-29 2005-09-29 Adamo Joseph R Extended curable compositions for use as binders
WO2007008959A2 (fr) * 2005-07-11 2007-01-18 Wood Coatings Research Group, Inc. Dispersions aqueuses utilisant des esters de cellulose de carboxyalkyle et polymeres reductibles dans l'eau
DE102005050823A1 (de) * 2005-10-24 2007-04-26 Basf Coatings Ag Von organischen Lösemitteln im Wesentlichen oder völlig freie, strukturviskose, härtbare, wässrige Pulverdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
JP5398153B2 (ja) * 2007-02-16 2014-01-29 関西ペイント株式会社 着色塗料組成物
DE102007059090A1 (de) * 2007-12-07 2009-06-10 Benecke-Kaliko Ag Polymermischung
CN103073974B (zh) * 2012-12-12 2016-05-04 优利康达（天津）科技有限公司 一种能快速施工的不饱和树脂涂层封闭剂及使用方法
JP6602611B2 (ja) * 2015-09-08 2019-11-06 株式会社日本触媒 結合剤
CN112352002B (zh) * 2018-06-19 2022-10-14 3M创新有限公司 包含聚酯颗粒的水分散体、光致聚合型组合物、制品和方法

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AU2003212320A1 (en) 2003-10-08
CN1656185A (zh) 2005-08-17
KR20050007443A (ko) 2005-01-18
JP2009144163A (ja) 2009-07-02
US20060122329A1 (en) 2006-06-08
US7408001B2 (en) 2008-08-05
US20030181576A1 (en) 2003-09-25
US7022760B2 (en) 2006-04-04
WO2003080751A1 (fr) 2003-10-02
JP2005520913A (ja) 2005-07-14
DE10212545A1 (de) 2003-10-02
CA2479772A1 (fr) 2003-10-02

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