US20100015344A1 - Coating compositions with high scratch resistance and weathering stability - Google Patents

Coating compositions with high scratch resistance and weathering stability Download PDF

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Publication number
US20100015344A1
US20100015344A1 US12/519,466 US51946607A US2010015344A1 US 20100015344 A1 US20100015344 A1 US 20100015344A1 US 51946607 A US51946607 A US 51946607A US 2010015344 A1 US2010015344 A1 US 2010015344A1
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coating composition
coating
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groups
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Matthijs Groenewolt
Andreas Poppe
Gunter Klein
Manuela Niemeier
Elke Westhoff
Wilfried Stubbe
Simone Hesener
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BASF Coatings GmbH
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BASF Coatings GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated 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
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • 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
    • C08G18/70—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
    • C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
    • 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
    • C08G18/80—Masked polyisocyanates
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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

Definitions

  • the present invention relates to thermally curable coating compositions, based on aprotic solvents and comprising polyols and polyisocyanates with hydrolyzable silane groups which lead to coatings which combine a high scratch resistance with high gloss and high weathering stability.
  • WO-A-01/98393 describes 2K (2-component) coating compositions comprising a polyol binder component and a polyisocyanate crosslinker component partly functionalized with alkoxysilyl groups. These coating compositions are used as primers and are optimized for adhesion to metallic substrates, especially aluminum substrates. Over these coating compositions, as part of an OEM finish or a refinish, it is possible to apply basecoat/clearcoat systems. In terms of scratch resistance and weathering stability, the coating compositions of WO 01/98393 are not optimized.
  • EP-A-0 994 117 describes moisture-curable mixtures comprising a polyol component and a polyisocyanate component which may partly have been reacted with a monoalkoxysilylalkylamine that has undergone reaction preferably to an aspartate.
  • coatings formed from such mixtures do have a certain hardness, they are nevertheless of only limited suitability for OEM applications in terms of their weathering stability and, in particular, their scratch resistance.
  • US-A-2006/0217472 describes coating compositions which can comprise a hydroxy-functional acrylate, a low molecular mass polyol component, a polyisocyanate, and an amino-functional alkoxysilyl component, preferably bisalkoxysilylamine.
  • Such coating compositions are used as clearcoat material in basecoat/clearcoat systems and lead to scratchproof coatings.
  • Coating compositions of this kind have only very limited storage qualities, and the resulting coatings have low weathering stability, particularly with respect to UV radiation in a wet/dry cycle.
  • WO 2006/042585 describes clearcoat materials which are suitable for OEM finishing and which as their main binder component comprise polyisocyanates whose isocyanate groups, preferably to an extent of more than 90 mol %, have undergone reaction with bisalkoxysilylamines. Clearcoat materials of this kind combine excellent scratch resistance with high chemical and weathering resistance. But there is still a need for a further improvement in the weathering stability, particularly with respect to cracking under UV irradiation in a wet/dry cycle, with retention of the high level of scratchproofing.
  • EP-A-1 273 640 describes 2K coating compositions composed of a polyol component and of a crosslinker component consisting of aliphatic and/or cycloaliphatic polyisocyanates, 0.1 to 95 mol % of the free isocyanate groups originally present having undergone reaction with bisalkoxysilylamine.
  • These coating compositions can be used for OEM finishing and, after their curing is complete, combine good scratch resistance with effective resistance to environmental influences. Nevertheless, these coating compositions have a particularly strong propensity toward post-crosslinking, which—straight after final thermal curing—results in only inadequate scratch resistance of the coatings.
  • the strong post-crosslinking also has a negative impact particularly on the weathering stability as it entails an increased risk of tearing under tension.
  • the coating compositions ought to lead to coatings which already have a high degree of scratchproofing straight after thermal curing and in particular a high retention of gloss after scratch exposure.
  • the coatings and coating systems, especially the clearcoat systems ought to be able to be produced even in film thicknesses>40 ⁇ m without stress cracks occurring. This is a key requirement for the use of the coatings and coating systems, particularly of the clearcoat systems, in the technologically and esthetically particularly demanding field of automotive OEM finishing.
  • the intention in particular was to provide clearcoat systems featuring high resistance, particularly to cracking, under weathering with UV radiation in a wet/dry cycle, in combination with outstanding scratch proofing.
  • the new coating compositions ought to be preparable easily and with very good reproducibility, and ought not to present any environmental problems during application of the coating material.
  • the finally cured coating obtained from the coating composition has a post-crosslinking index (PCI) of less than 2, wherein
  • the components of the invention can be prepared particularly easily and with very good reproducibility, and do not cause any significant toxicological or environmental problems during application of the coating material.
  • the coating compositions of the invention produce new coatings and coating systems, especially clearcoat systems, which are highly scratchproof and, in contrast to common, highly crosslinked scratchproof systems, are acid-resistant. Moreover, the coatings and coating systems of the invention, especially the clearcoat systems, can be produced even in film thicknesses>40 ⁇ m without stress cracks occurring. Consequently the coatings and coating systems of the invention, especially the clearcoat systems, can be used in the technologically and esthetically particularly demanding field of automotive OEM finishing. In that context they are distinguished by particularly high carwash resistance and scratchproofing. The high scratch resistance straight after the final curing of the coatings is given such that the coatings can be handled without problems straight after the final curing.
  • PCI Post-Crosslinking Index
  • the coating compositions cure as far as possible under the applied curing conditions, in other words exhibit low post-crosslinking after the coating has been cured. This low post-crosslinking is expressed through the post-crosslinking index (PCI).
  • PCI post-crosslinking index
  • the post-crosslinking index is defined as the ratio of the storage modulus E′(200) of the finally cured coating, measured at 200° C., to the minimum of the storage modulus E′(min) of the finally cured coating, measured at a temperature directly above the measured glass transition temperature Tg, i.e., E′(min) is the minimum of the storage modulus which occurs during the DMTA measurement when the measuring temperature is greater than Tg and less than 200° C.
  • finally cured coating is meant a coating which is cured for 20 minutes at an article temperature of 140° C. and stored at 25° C. for 8 days after curing before the DMTA measurements are carried out.
  • the coating compositions of the invention can also be cured under other conditions, differing in accordance with the intended use. Furthermore, it will be appreciated that the coating compositions of the invention can also be stored for less than 8 days after final curing before the storage moduli are measured. Naturally, in that case, generally speaking, the post-crosslinking index in the case of shorter storage of, say, just 1 day at 25° C. will be somewhat higher than in the case of storage at 25° C. for 8 days. To determine the post-crosslinking index by means of DMTA measurements with the objective of ascertaining whether the coating compositions in question are in accordance with the invention, however, it is necessary to cure and store the coating under the reproducible, precisely specified conditions.
  • the storage moduli E′(200) and E′(min) and also the glass transition temperature Tg, which are required for the determination of the post-crosslinking index, are measured by dynamic-mechanical thermo-analysis (DMTA) at a heating rate of 2 K/min and at a frequency of 1 Hz.
  • DMTA dynamic-mechanical thermo-analysis
  • Dynamic-mechanical thermo-analysis is a widely known measurement method for determining the viscoelastic properties of coatings and is described for example in Murayama, T., Dynamic Mechanical Analysis of Polymeric Material, Elsevier, N.Y., 1978 and Loren W. Hill, Journal of Coatings Technology, vol. 64, no. 808, May 1992, pages 31 to 33.
  • the measurements can be carried out, for example, using the DMTA V instrument from Rheometrics Scientific at a frequency of 1 Hz and an amplitude of 0.2%.
  • the heating rate is 2 K per minute.
  • the DMTA measurements are carried out on free films with a thickness of 40 ⁇ m ⁇ 10 ⁇ m.
  • the coating composition of the invention is applied to substrates to which the coating obtained does not adhere.
  • suitable substrates include glass, Teflon, polyethylene terephthalate and polypropylene.
  • the resulting coating is cured for 20 minutes at an article temperature of 140° C. and stored at 25° C. for 8 days after curing, before the DMTA measurements are carried out.
  • a further feature of the coating compositions of the invention is that they can be finally cured to a coating which has statistically distributed regions of the Si—O—Si network. This means that there is no deliberate accumulation or depletion of the Si—O—Si network in particular regions of the coating, including, in other words, the near-surface coating zone accumulation that is described in the as yet unpublished German patent application P102007013242.
  • the finally cured coating obtained from the coating composition has a post-crosslinking index (PCI) of less than 2, preferably of less than or equal to 1.8, more preferably less than or equal to 1.7, and very preferably less than or equal to 1.5.
  • PCI post-crosslinking index
  • the low post-crosslinking index (PCI) to be set in accordance with the invention of less than 2, preferably less than or equal to 1.8, more preferably less than or equal to 1.7, and very preferably less than or equal to 1.5, can be set by means of a multiplicity of measures, which are elucidated in more detail below.
  • PCI post-crosslinking index
  • the coating compositions of the invention are distinguished at the same time by very good resistance properties on the part of the coatings of the invention with respect to cracking under UV radiation and wet/dry cycling in the CAM180 test (to DIN EN ISO 11341 February 98 and DIN EN ISO 4892-2 November 00), a high gloss, and high gloss retention after weathering.
  • One preferred measure for controlling the post-crosslinking index (PCI) is the catalyst (D) for the crosslinking of the silane groups.
  • catalyst for the crosslinking of the silane groups and/or the alkoxysilyl units and also for the reaction between the hydroxyl groups of the compound (A) and the free isocyanate groups of the compound (B) it is possible to use compounds that are known per se, if at the same time the low post-crosslinking index is ensured by virtue of the other measures specified further below.
  • Lewis acids such as, for example, tin naphthenate, tin benzoate, tin octoate, tin butyrate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide, lead octoate, and also catalysts as described in WO-A-2006/042585.
  • catalyst (D) In order to set a low post-crosslinking index, however, it is preferred as catalyst (D) to employ phosphorus-containing, more particularly phosphorus- and nitrogen-containing, catalysts. In this context it is also possible to use mixtures of two or more different catalysts (D).
  • Suitable phosphorus-containing catalysts (D) are substituted phosphonic diesters and diphosphonic diesters, preferably from the group consisting of acyclic phosphonic diesters, cyclic phosphonic diesters, acyclic diphosphonic diesters and cyclic diphosphonic diesters. Catalysts of this kind are described for example in German patent application DE-A-102005045228.
  • substituted phosphoric monoesters and phosphoric diesters preferably from the group consisting of acylic phosphoric diesters and cyclic phosphoric diesters, more preferably amine adducts of the phosphoric acid monoesters and diesters.
  • acyclic phosphoric diesters (D) are selected more particularly from the group consisting of acyclic phosphoric diesters (D) of the general formula (IV):
  • radicals R 10 and R 11 are selected from the group consisting of:
  • substituted and unsubstituted alkyl having 1 to 20, preferably 2 to 16, and more particularly 2 to 10 carbon atoms, cycloalkyl having 3 to 20, preferably 3 to 16, and more particularly 3 to 10 carbon atoms, and aryl having 5 to 20, preferably 6 to 14, and more particularly 6 to 10 carbon atoms,
  • alkylaryl substituted and unsubstituted alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyl, arylcycloalkylalkyl, arylalkylcycloalkyl, cycloalkylalkylaryl, and cycloalkylarylalkyl, the alkyl, cycloalkyl, and aryl groups present therein each containing the aforementioned number of carbon atoms, and
  • substituted or unsubstituted radical of the aforementioned kind containing at least one, more particularly one, heteroatom selected from the group consisting of oxygen atom, sulfur atom, nitrogen atom, phosphorus atom, and silicon atom, more particularly oxygen atom, sulfur atom and nitrogen atom,
  • catalyst (D) of the corresponding amine-blocked phosphoric esters and more particularly here amine-blocked phosphoric acid ethylhexyl esters and amine-blocked phosphoric acid phenyl esters, especially amine-blocked bis(2-ethylhexyl)phosphate.
  • amines with which the phosphoric esters are blocked are, more particularly, tertiary amines, an example being triethylamine.
  • tertiary amines which ensure high efficacy of the catalyst under the curing conditions of 140° C.
  • Certain amine-blocked phosphoric acid catalysts are also available commercially (e.g., Nacure products from King Industries). Mention may be made for example of Nacure 4167 from King Industries as a particularly suitable catalyst on the basis of an amine-blocked phosphoric acid partial ester.
  • the catalysts are used preferably in fractions of 0.01% to 20% by weight, more preferably in fractions of 0.1% to 10% by weight, based on the nonvolatile constituents of the coating composition of the invention.
  • the amount of catalyst used also has a certain influence on the post-crosslinking index, since a relatively low catalyst efficacy can be compensated in part by correspondingly higher amounts employed.
  • one or more constituents of the coating composition comprise hydrolyzable silane groups. These hydrolyzable silane groups lead to the construction of the Si—O—Si network which is distributed statistically in the finally cured coating.
  • Suitable more particularly here are coating compositions in which one or more constituents of the coating composition contain at least partly one or more identical or different structural units of the formula (I)
  • silane radicals also has an influence on the reactivity and hence also on the maximally extensive reaction during the curing of the coating, in other words on the setting of a maximally low post-crosslinking index (PCI).
  • PCI maximally low post-crosslinking index
  • the hydrolyzable groups G may be selected from the group of halogens, more particularly chlorine and bromine, from the group of alkoxy groups, from the group of alkylcarbonyl groups, and from the group of acyloxy groups. Particular preference is given to alkoxy groups (OR′).
  • the alkoxy radicals (OR′) that are preferred in each case may be alike or different; critical for the structure of the radicals, however, is the extent to which they influence the reactivity of the hydrolyzable silane groups.
  • R′ is an alkyl radical, more particularly having 1 to 6 C atoms.
  • radicals R′ which increase the reactivity of the silane groups, i.e., which represent good leaving groups.
  • a methoxy radical is preferred over an ethoxy radical, which is preferred in turn over a propoxy radical.
  • R′ ethyl and/or methyl, more particularly methyl.
  • organofunctional silanes may also be influenced considerably by the length of the spacers X between silane functionality and organic functional group that serves for reaction with the modifying constituent.
  • methacryloyloxymethyltrimethoxysilane (“alpha” silane, e.g., commercial product Geniosil® XL 33 from Wacker) is used with preference over methacryloyloxypropyltrimethoxysilane (“gamma” silane, e.g., commercial product Geniosil® GF 31 from Wacker) in order to introduce the hydrolyzable silane groups into the coating composition.
  • alpha silane e.g., commercial product Geniosil® XL 33 from Wacker
  • gamma silane e.g., commercial product Geniosil® GF 31 from Wacker
  • spacers which increase the reactivity of the silanes are preferred over spacers which reduce the reactivity of the silanes.
  • the functionality of the silanes also has an effect on the post-crosslinking index.
  • functionality in this context is meant the number of radicals of the formula (I) per molecule.
  • a monofunctional silane is therefore a silane of the kind which for each silane molecule introduces one radical of the formula (I) into the constituent that is to be modified.
  • a difunctional silane is a silane of the kind which for each silane molecule introduces in each case two radicals of the formula (I) into the constituent.
  • compositions in which the constituents have been modified with a mixture of a monofunctional silane and a difunctional silane are more particularly the amino-functional disilanes of the formula (IIa) that are described further below, and monofunctional silanes used are the silanes of the formula (IIIa) that are described further below.
  • the post-crosslinking index decreases as the proportion of monofunctional silane goes up, but at the same time there is also a decrease in the scratch resistance.
  • PCI post-crosslinking index
  • the degree of silanization overall can be lowered; in other words, in the case of the below-described modification of the polyisocyanate component (B) with a (bis-silyl)amine of the formula (IIa), the fraction of isocyanate groups reacted overall with a silane can be chosen to be correspondingly low.
  • nonfunctional substituents on the organofunctional silane that is used to introduce the structural units (I) and/or (II) and/or (III) to influence the reactivity of the hydrolyzable silane group.
  • This may be illustrated by way of example taking as an example bulky, voluminous substituents on the amine function, which can reduce the reactivity of amine-functional silanes.
  • N-(n-butyl)-3-aminopropyltrimethoxysilane is preferred over N-cyclo-hexyl-3-aminopropyltrimethoxysilane for the introduction of the structural units (III).
  • radicals which increase the reactivity of the silanes are preferred over radicals which lower the reactivity of the silanes.
  • the structural units of the formula (I) can be introduced into the constituents of the coating composition.
  • the introduction of the structural units takes place via a reaction of the functional groups of the constituents to be modified with complementary functional groups of the silane.
  • secondary aminosilanes such as, for example, bis(2-trimethoxysilylethyl)amine, bis(2-triethoxysilylethyl)amine, bis(3-triethoxysilylpropyl)amine (available under the trade name Dynasylan® 1122 from Degussa), bis(3-trimethoxysilylpropyl)amine (available under the trade name Dynasylan® 1124 from Degussa), bis(4-triethoxysilylbutyl)amine, N-(n-butyl)-3-aminopropyltrimethoxysilane (available under the trade name Dynasylan® 1189 from Degussa), N-(n-butyl)-3-aminopropyltriethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane (available under
  • Epoxy-functional silanes can be used more particularly for addition to compounds with carboxylic acid or anhydride functionality.
  • suitable epoxy-functional silanes are 3-glycidyloxypropyltrimethoxysilane (available from Degussa under the trade name Dynasylan® GLYMO), 3-glycidyloxypropyltriethoxysilane (available from Degussa under the trade name Dynasylan® GLYEO), and the like.
  • Anhydride-functional silanes can be used more particularly for addition to epoxy-functional compounds.
  • An example that may be mentioned of a silane with anhydride functionality is 3-(triethoxysilyl)propylsuccinic anhydride (available from Wacker Chemie under the trade name Geniosil® GF 20).
  • Silanes of this kind can be used in the context of Michael reactions or else in the context of metal-catalyzed reactions.
  • Those exemplified are 3-methacryloyloxypropyltrimethoxysilane (available for example from Degussa under the trade name Dynasilan® MEMO, or from Wacker Chemie under the trade name Geniosil® GF 31), 3-methacryloyloxypropyltriethoxysilane, vinyltrimethoxysilane (available, among others, from Wacker Chemie under the trade name Geniosil® XL 10), vinyldimethoxymethylsilane (available, among others, from Wacker Chemie under the trade name Geniosil® XL 12), vinyltriethoxysilane (available, among others, from Wacker Chemie under the trade name Geniosil® GF 56), (methacryloyloxymethyl)methyldimethoxysilane (available, among others, from Wacker Chemie under the trade name
  • Silanes with isocyanato function or carbamate function are employed in particular in the context of reactions with hydroxy-functional compounds. Examples of silanes with isocyanato function are described in WO 07/03857, for example.
  • Suitable isocyanatoalkyltrialkoxysilanes are isocyanatopropyltrimethoxysilane, isocyanatopropylmethyldimethoxysilane, isocyanatopropylmethyldiethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropyltriisopropoxysilane, isocyanatopropylmethyldiisopropoxysilane, isocyanatoneohexyltrimethoxysilane, isocyanatoneohexyldimethoxysilane, isocyanatoneohexyldiethoxysilane, isocyanatoneohexyltriethoxysilane, isocyanatoneohexyltriisopropoxysilane, isocyanatoneohexyldiisopropoxysilane, isocyanatoisoamyltrimethoxysilane, isocyanatois
  • the isocyanatopropylalkoxysilane used preferably has a high degree of purity, more particularly a purity of at least 95%, and is preferably free from additives, such as transesterification catalysts, which can lead to unwanted side reactions.
  • compositions comprising at least one hydroxyl-containing compound (A) and at least one isocyanato-containing compound (B), wherein one or more constituents of the coating composition comprise, as additional functional components, between
  • n 0 to 2
  • m 0 to 2
  • m+n 2
  • x,y 0 to 2
  • coating compositions wherein one or more constituents of the coating composition contain between 5 and 95 mol %, more particularly between 10 and 90 mol %, more preferably between 20 and 80 mol %, and especially between 30 and 70 mol %, based in each case on the entirety of the structural units (II) and (III), of at least one structural unit of the formula (II), and between 5 and 95 mol %, more particularly between 10 and 90 mol %, more preferably between 20 and 80 mol %, and especially between 30 and 70 mol %, based in each case on the entirety of the structural units (II) and (III), of at least one structural unit of the formula (III).
  • hydroxyl-containing compound (A) it is preferred to use both low molecular mass polyols and also oligomeric and/or polymeric polyols.
  • Low molecular mass polyols used are, for example, diols, such as, preferably, ethylene glycol, neopentyl glycol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and 1,2-cyclohexanedimethanol, and also polyols, such as, preferably, trimethylolethane, trimethylolpropane, trimethylolhexane, 1,2,4-butanetriol, pentaerythritol, and dipentaerythritol. Low molecular mass polyols of this kind are preferably admixed in minor proportions to the oligo
  • the preferred oligomeric and/or polymeric polyols (A) have mass-average molecular weights Mw>500 daltons, as measured by means of GPC (gel permeation chromatography), preferably between 800 and 100 000 daltons, in particular between 1000 and 50 000 daltons.
  • Particularly preferred are polyester polyols, polyurethane polyols, polysiloxane polyols, and, in particular, polyacrylate polyols and/or polymethacrylate polyols, and their copolymers, referred to as polyacrylate polyols below.
  • the polyols preferably have an OH number of 30 to 400 mg KOH/g, in particular between 100 and 300 KOH/g.
  • the glass transition temperatures, as measured by DSC (differential thermoanalysis), of the polyols are preferably between ⁇ 150 and 100° C., more preferably between ⁇ 120° C. and 80° C.
  • Suitable polyester polyols are described for example in EP-A-0 994 117 and EP-A-1 273 640.
  • Polyurethane polyols are prepared preferably by reacting polyester polyol prepolymers with suitable di- or polyisocyanates and are described in EP-A-1 273 640, for example.
  • Suitable polysiloxane polyols are described for example in WO-A-01/09260, and the polysiloxane polyols recited therein can be employed preferably in combination with further polyols, especially those having relatively high glass transition temperatures.
  • the polyacrylate polyols that are very particularly preferred in accordance with the invention are generally copolymers and preferably have mass-average molecular weights Mw of between 1000 and 20 000 daltons, in particular between 1500 and 10 000 daltons, in each case measured by means of gel permeation chromatography (GPC) against a polystyrene standard.
  • the glass transition temperature of the copolymers is generally between ⁇ 100 and 100° C., in particular between ⁇ 50 and 80° C. (measured by means of DSC measurements).
  • the polyacrylate polyols preferably have an OH number of 60 to 250 mg KOH/g, in particular between 70 and 200 KOH/g, and an acid number of between 0 and 30 mg KOH/g.
  • the hydroxyl number indicates how many mg of potassium hydroxide are equivalent to the amount of acetic acid bound by 1 g of substance during acetylation.
  • the sample is boiled with acetic anhydride-pyridine and the acid formed is titrated with potassium hydroxide solution (DIN 53240-2).
  • the acid number here indicates the number of mg of potassium hydroxide consumed in neutralizing 1 g of the respective compound of component (b) (DIN EN ISO 2114).
  • hydroxyl-containing binders as well may be used to influence the post-crosslinking index.
  • degree of silanization i.e., the amount of structural units of the formula (I) and/or (II) and/or (III), which in turn results in a lower post-crosslinking index.
  • Hydroxyl-containing monomer units used are preferably hydroxyalkyl acrylates and/or hydroxyalkyl methacrylates, such as, in particular, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, and, in particular, 4-hydroxybutyl acrylate and/or 4-hydroxybutyl methacrylate.
  • alkyl methacrylates and/or alkyl methacrylates such as, preferably, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, 3,3,5-trimethylhexyl acrylate, 3,3,5-trimethylhexyl methacrylate, stearyl acrylate, stearyl methacrylates, stearyl methacrylates, stearyl me
  • Further monomer units which can be used for the polyacrylate polyols are vinylaromatic hydrocarbons, such as vinyltoluene, alpha-methylstyrene or, in particular, styrene, amides or nitriles of acrylic or methacrylic acid, vinyl esters or vinyl ethers, and, in minor amounts, in particular, acrylic and/or methacrylic acid.
  • vinylaromatic hydrocarbons such as vinyltoluene, alpha-methylstyrene or, in particular, styrene, amides or nitriles of acrylic or methacrylic acid, vinyl esters or vinyl ethers, and, in minor amounts, in particular, acrylic and/or methacrylic acid.
  • the hydroxyl-containing compound A as well as the hydroxyl groups, comprises structural units of the formula (I) and/or of the formula (II) and/or of the formula (III).
  • Structural units of the formula (II) can be introduced into the compound (A) by incorporation of monomer units containing such structural units, or by reaction of polyols containing further functional groups with a compound of the formula (IIa)
  • the polyol For the reaction of the polyol with the compound (IIa), the polyol, correspondingly, has further functional groups which react with the secondary amino group of the compound (IIa), such as acid or epoxy groups in particular.
  • Inventively preferred compounds (IIa) are bis(2-ethyltrimethoxysilyl)amine, bis(3-propyltrimethoxysilyl)amine, bis(4-butyltrimethoxysilyl)amine, bis(2-ethyltriethoxysilyl)amine, bis(3-propyltriethoxysilyl)amine and/or bis(4-butyltriethoxysilyl)amine.
  • bis(3-Propyltrimethoxysilyl)amine is especially preferred.
  • Aminosilanes of this kind are available for example under the trade name DYNASILAN® from DEGUSSA or Silquest® from OSI.
  • Monomer units which carry the structural elements (II) are preferably reaction products of acrylic and/or methacrylic acid or of epoxy-functional alkyl acrylates and/or methacrylates with the abovementioned compounds (IIa).
  • Structural units of the formula (III) can be introduced into the compound (A) by incorporation of monomer units containing such structural units or by reaction of polyols containing further functional groups with a compound of the formula (IIIa)
  • the polyol for the reaction of the polyol with the compound (IIIa) the polyol, correspondingly, has further functional groups which react with the functional group -ZH of the compound (IIIa), such as acid, epoxy or ester groups in particular.
  • Inventively preferred compounds (IIIa) are omega-aminoalkyl- or omega-hydroxyalkyltrialkoxysilanes, such as, preferably, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, and 4-hydroxybutyltriethoxysilane.
  • Particularly preferred compounds (IIIa) are N-(2-(trimethoxysilyl)ethyl)alkylamines, N-(3-(trimethoxysilyl)propyl)alkylamines, N-(4-(trimethoxysilyl)butyl)alkylamines, N-(2-(triethoxysilyl)ethyl)alkylamines, N-(3-(triethoxysilyl)propyl)alkylamines and/or N-(4-(triethoxysilyl)butyl)alkylamines.
  • N-(3-(Trimethoxysilyl)propyl)butylamine is especially preferred.
  • Aminosilanes of this kind are available for example under the trade name DYNASILAN® from DEGUSSA or Silquest® from OSI.
  • Monomer units which carry the structural elements (III) are preferably reaction products of acrylic and/or methacrylic acid or of epoxy-functional alkyl acrylates and/or methacrylates, and also, in the case of hydroxy-functional alkoxysilyl compounds, transesterification products of alkyl acrylates and/or methacrylates, especially with the abovementioned hydroxy- and/or amino-functional alkoxysilyl compounds (IIIa).
  • the coating compositions of the invention comprise one or more compounds having free, i.e., nonblocked, and/or blocked isocyanate groups.
  • the coating compositions of the invention comprise compounds (B) having free isocyanate groups.
  • the free isocyanate groups of the isocyanate-group-containing compounds B may also, however, be used in blocked form. This is preferably the case when the coating compositions of the invention are employed in the form of one-component systems.
  • the di- and/or polyisocyanates which serve as parent structures for the isocyanato-containing compounds (B) used with preference in accordance with the invention are preferably conventional substituted or unsubstituted aromatic, aliphatic, cycloaliphatic and/or heterocyclic polyisocyanates.
  • polyisocyanates examples are as follows: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane 4,4′-diisocyanate, diphenylmethane 2,4′-diisocyanate, p-phenylene diisocyanate, biphenyl diisocyanates, 3,3′-dimethyl-4,4′-diphenylene diisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, isophorone diisocyanate, ethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate, methyl
  • Particularly preferred polyisocyanates PI are hexamethylene 1,6-diisocyanate, isophorone diisocyanate, and 4,4′-methylenedicyclohexyl diisocyanate, their biuret dimers and/or isocyanurate trimers.
  • polyisocyanates are polyisocyanate prepolymers containing urethane structural units which are obtained by reacting polyols with a stoichiometric excess of aforementioned polyisocyanates.
  • Polyisocyanate prepolymers of this kind are described for example in U.S. Pat. No. 4,598,131.
  • the isocyanato-functional compounds (B) that are especially preferred in accordance with the invention, functionalized with the structural units (II) and (III), are prepared with particular preference by reacting the aforementioned di- and/or polyisocyanates with the aforementioned compounds (IIa) and (IIIa), by reacting
  • the total fraction of the isocyanate groups reacted with the compounds (IIa) and (IIIa) in the polyisocyanate compound (B) is between 5 and 95 mol %, preferably between 10 and 90 mol %, more preferably between 15 and 85 mol % of the isocyanate groups in the core polyisocyanate structure.
  • the isocyanate groups are advantageously reacted with a mixture of the compounds (IIa) and (IIIa).
  • Particularly preferred compounds (IIa) are bis(2-ethyltrimethoxysilyl)amine, bis(3-propyltrimethoxysilyl)amine, bis(4-butyltrimethoxysilyl)amine, bis(2-ethyltriethoxysilyl)amine, bis(3-propyltriethoxysilyl)amine and/or bis(4-butyltriethoxysilyl)amine.
  • bis(3-Propyltrimethoxysilyl)amine is especially preferred.
  • Aminosilanes of this kind are available for example under the trade name DYNASILAN® from DEGUSSA or Silquest® from OSI.
  • Preferred compounds (IIIa) are 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, and 4-hydroxybutyltriethoxysilane.
  • Particularly preferred compounds (IIIa) are N-(2-(trimethoxysilyl)ethyl)alkylamines, N-(3-(trimethoxysilyl)propyl)alkylamines, N-(4-(trimethoxysilyl)butyl)alkylamines, N-(2-(triethoxysilyl)ethyl)alkylamines, N-(3-(triethoxysilyl)propyl)alkylamines and/or N-(4-(triethoxysilyl)butyl)alkylamines.
  • N-(3-(Trimethoxysilyl)propyl)butylamine is especially preferred.
  • Aminosilanes of this kind are available for example under the trade name DYNASILAN® from DEGUSSA or Silquest® from OSI.
  • isocyanato-containing compounds (B) are reaction products of hexamethylene 1,6-diisocyanate and/or isophorone diisocyanate, and/or their isocyanurate trimers, with bis(3-propyltrimethoxysilyl)amine and N-(3-(trimethoxysilyl)propyl)butylamine.
  • the reaction of the isocyanato-containing compounds (B) with the compounds (IIa) and (IIIa) takes place preferably in inert gas at temperatures of not more than 100° C., preferably at not more than 60° C.
  • the free isocyanate groups of the isocyanato-containing compounds B can also be used in blocked form. This is preferably the case when the coating compositions of the invention are used as one-component systems.
  • blocking it is possible in principle to use any blocking agent which can be used for blocking polyisocyanates and which has a sufficiently low unblocking temperature. Blocking agents of this kind are very familiar to the skilled worker. It is preferred to use blocking agents as described in EP-A-0 626 888 and EP-A-0 692 007.
  • the weight fraction of hydroxyl-containing compounds A to be employed, based on the weight fraction of the isocyanato-containing compounds B, is dependent on the hydroxy equivalent weight of the polyol and on the equivalent weight of the free isocyanate groups of the polyisocyanate B.
  • the coating composition of the invention there is one or more constituents between 2.5 to 97.5 mol %, based on the sum of structural units (II) and (III), of at least one structural unit (II) and between 2.5 to 97.5 mol %, based on the sum of structural units (II) and (III), of at least one of structural units (III).
  • the coating compositions of the invention contain preferably between 2.5% and 97.5%, more preferably between 5% and 95%, very preferably between 10% and 90%, and in particular between 20% and 80%, by weight, based on the amount of nonvolatile substances in the coating composition, of the hydroxyl-containing compounds (A), and preferably between 2.5% and 97.5%, more preferably between 5% and 95%, very preferably between 10% and 90%, and in particular between 20% and 80%, by weight, based on the amount of nonvolatile substances in the coating composition, of the isocyanato-containing compounds (B).
  • the structural elements (I) and/or (II) and/or (III) are present preferably in fractions of 2.5 to 97.5 mol %, more preferably between 5 and 95 mol %, and very preferably between 10 and 90 mol %.
  • the silane content in % by mass of Si is determined arithmetically from the amounts of the compounds with the structural unit (I) and, respectively, the compounds (IIa) and/or (IIIa) that are used.
  • the structural elements (I), (II) and/or (III) may additionally also be part of one or more further components (C), different than the components (A) and (B), in which case the criteria to be applied are those specified above.
  • component (C) it is possible as component (C) to use oligomers or polymers containing alkoxysilyl groups, such as, for example, the poly(meth)acrylates specified in patents and patent applications U.S. Pat. No. 4,499,150, U.S. Pat. No. 4,499,151 or EP-A-0 571 073, as carriers of structural elements (III), or to use the compounds specified in WO-A-2006/042585, as carriers of structural elements (II).
  • components (C) of this kind are used in fractions of up to 40%, preferably up to 30%, more preferably up to 25%, by weight, based on the nonvolatile constituents of the coating composition.
  • the weight fractions of the polyol A and of the polyisocyanate B are preferably selected such that the molar equivalent ratio of the unreacted isocyanate groups of the isocyanate-containing compounds (B) to the hydroxyl groups of the hydroxyl-containing compounds (A) is between 0.9:1 and 1:1.1, preferably between 0.95:1 and 1.05:1, more preferably between 0.98:1 and 1.02:1.
  • compositions are one-component coating compositions
  • isocyanato-containing compounds (B) whose free isocyanate groups have been blocked with the blocking agents described above.
  • a coating component comprising the hydroxyl-containing compound (A) and also further components, described below is mixed conventionally with a further coating component, comprising the isocyanato-containing compound (B) and, where appropriate, further of the components described below, this mixing taking place shortly before the coating composition is applied; generally speaking, the coating component that comprises the compound (A) comprises the catalyst and also part of the solvent.
  • Solvents suitable for the coating compositions of the invention are in particular those which, in the coating composition, are chemically inert toward the compounds (A) and (B) and also do not react with (A) and (B) when the coating composition is being cured.
  • solvents are aliphatic and/or aromatic hydrocarbons such as toluene, xylene, solvent naphtha, Solvesso 100 or Hydrosol® (from ARAL), ketones, such as acetone, methyl ethyl ketone or methyl amyl ketone, esters, such as ethyl acetate, butyl acetate, pentyl acetate or ethyl ethoxypropionate, ethers, or mixtures of the aforementioned solvents.
  • the aprotic solvents or solvent mixtures preferably have a water content of not more than 1%, more preferably not more than 0.5%, by weight, based on the solvent.
  • binders (E) which preferably are able to react and form network points with the hydroxyl groups of the compound (A) and/or with the free isocyanate groups of the compound (B) and/or with the alkoxysilyl groups of the compounds (A), (B) and/or (C).
  • amino resins and/or epoxy resins are the typical, known amino resins, some of whose methylol and/or methoxymethyl groups may have been defunctionalized by means of carbamate or allophanate groups.
  • Crosslinking agents of this kind are described in patents U.S. Pat. No. 4,710,542 and EP-B-0 245 700 and also in the article by B. Singh and coworkers, “Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry” in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207.
  • such components (E) are used in fractions of up to 40%, preferably up to 30%, more preferably up to 25%, by weight, based on the nonvolatile constituents of the coating composition.
  • the coating composition of the invention may further comprise at least one typical, known coatings additive in effective amounts, i.e. in amounts preferably up to 30%, more preferably up to 25%, and in particular up to 20% by weight, in each case based on the nonvolatile constituents of the coating composition.
  • Suitable coatings additives are:
  • the coating composition of the invention may additionally comprise further pigments and/or fillers and may serve for producing pigmented topcoats.
  • the pigments and/or fillers employed for this purpose are known to the skilled worker.
  • the coatings of the invention produced from the coating compositions of the invention adhere excellently even to electrocoats, surfacer coats, basecoat systems or typical, known clearcoat systems that have already cured, they are outstandingly suitable not only for use in automotive OEM finishing but also for automotive refinish or for the modular scratchproofing of automobile bodies that have already been painted.
  • the coating compositions of the invention can be applied by any of the typical application methods, such as spraying, knife coating, spreading, pouring, dipping, impregnating, trickling or rolling, for example.
  • the substrate to be coated may itself be at rest, with the application equipment or unit being moved.
  • the substrate to be coated in particular a coil, may be moved, with the application unit at rest relative to the substrate or being moved appropriately.
  • spray application methods such as compressed-air spraying, airless spraying, high-speed rotation, electrostatic spray application (ESTA), alone or in conjunction with hot spray application such as hot-air spraying, for example.
  • spray application methods such as compressed-air spraying, airless spraying, high-speed rotation, electrostatic spray application (ESTA), alone or in conjunction with hot spray application such as hot-air spraying, for example.
  • ESA electrostatic spray application
  • the applied coating compositions of the invention can be cured after a certain rest time.
  • the rest time serves, for example, for the leveling and devolatilization of the coating films or for the evaporation of volatile constituents such as solvents.
  • the rest time may be assisted and/or shortened by the application of elevated temperatures and/or by a reduced humidity, provided this does not entail any damage or alteration to the coating films, such as premature complete crosslinking, for instance.
  • the thermal curing of the coating compositions has no peculiarities in terms of method but instead takes place in accordance with the typical, known methods such as heating in a forced-air oven or irradiation with IR lamps.
  • the thermal cure may also take place in stages.
  • Another preferred curing method is that of curing with near infrared (NIR) radiation.
  • NIR near infrared
  • the thermal cure takes place advantageously at a temperature of 30 to 200° C., more preferably 40 to 190° C., and in particular 50 to 180° C. for a time of 1 min up to 10 h, more preferably 2 min up to 5 h, and in particular 3 min to 3 h, although longer cure times may be employed in the case of the temperatures that are employed for automotive refinish, which are preferably between 30 and 90° C.
  • the coating compositions of the invention produce new cured coatings, especially coating systems, more particularly clearcoat systems; moldings, especially optical moldings; and self-supporting films, all of which are highly scratchproof and in particular are stable to chemicals and to weathering.
  • the coatings and coating systems of the invention, especially the clearcoat systems can in particular be produced even in film thicknesses>40 ⁇ m without stress cracks occurring.
  • coating compositions of the invention are of excellent suitability as decorative, protective and/or effect-imparting, highly scratchproof coatings and coating systems on bodies of means of transport (especially motor vehicles, such as motor cycles, buses, trucks or automobiles) or parts thereof; on buildings, both interior and exterior; on furniture, windows, and doors; on plastics moldings, especially CDs and windows; on small industrial parts, on coils, containers, and packaging; on white goods; on films; on optical, electrical, and mechanical components; and on hollow glassware and articles of everyday use.
  • bodies of means of transport especially motor vehicles, such as motor cycles, buses, trucks or automobiles
  • parts thereof on buildings, both interior and exterior; on furniture, windows, and doors; on plastics moldings, especially CDs and windows; on small industrial parts, on coils, containers, and packaging; on white goods; on films; on optical, electrical, and mechanical components; and on hollow glassware and articles of everyday use.
  • the coating compositions and coating systems of the invention are employed in particular in the technologically and esthetically particularly demanding field of automotive OEM finishing and also of automotive refinish.
  • the coating compositions of the invention are used in multistage coating methods, particularly in methods where a pigmented basecoat film is first applied to an uncoated or precoated substrate and thereafter a film with the coating compositions of the invention is applied.
  • basecoat materials are described for example in EP-A-0 692 007 and in the documents cited there in column 3 lines 50 et seq.
  • the applied basecoat material is preferably first dried, i.e., at least some of the organic solvent and/or water is stripped from the basecoat film in an evaporation phase. Drying is accomplished preferably at temperatures from room temperature to 80° C. Drying is followed by the application of the coating composition of the invention. Subsequently the two-coat system is baked, preferably under conditions employed for automotive OEM finishing, at temperatures from 30 to 200° C., more preferably 40 to 190° C., and in particular 50 to 180° C., for a time of 1 min up to 10 h, more preferably 2 min up to 5 h, and in particular 3 min to 3 h, although longer cure times may also be employed at the temperatures employed for automotive refinish, which are preferably between 30 and 90° C.
  • the coats produced with the coating composition of the invention are notable in particular for an especially high chemical stability and weathering stability and also for a very good carwash resistance and scratchproofing, in particular for an excellent combination of scratchproofing and weathering stability with respect to UV radiation in a wet/dry cycle.
  • the coating composition of the invention is used as a transparent clearcoat material for coating plastics substrates, especially transparent plastics substrates.
  • the coating compositions include UV absorbers, which in terms of amount and type are also designed for effective UV protection of the plastics substrate.
  • the coating compositions are notable for an outstanding combination of scratchproofing and weathering stability with respect to UV radiation in a wet/dry cycle.
  • the plastics substrates thus coated are used preferably as a substitute for glass components in automobile construction, the plastics substrates being composed preferably of polymethyl methacrylate or polycarbonate.
  • a three-neck glass flask equipped with a reflux condenser and a thermometer is charged with 57.3 parts by weight of trimerized hexamethylene diisocyanate (HDI) (Basonat HI 100 from BASF AG) and 88.0 parts by weight of solvent naphtha.
  • HDI trimerized hexamethylene diisocyanate
  • IIa N-[3-(trimethoxysilyl)propyl]butylamine
  • IIIa dinasilan® 1189 from Degussa
  • the reaction temperature is held at 50 to 60° C. until the isocyanate mass fraction as determined by titration is at the theoretically calculated 70 mol %.
  • the solution of the partly silanized polyisocyanate has a solids content of 47.1% by weight.
  • a three-neck glass flask equipped with a reflux condenser and a thermometer is charged with 57.3 parts by weight of trimerized hexamethylene diisocyanate (HDI) (Basonat HI 100 from BASF AG) and 69.7 parts by weight of solvent naphtha.
  • HDI trimerized hexamethylene diisocyanate
  • the solution of the partly silanized polyisocyanate has a solids content of 53.9% by weight.
  • a three-neck glass flask equipped with a reflux condenser and a thermometer is charged with 57.3 parts by weight of trimerized hexamethylene diisocyanate (HDI) (Basonat HI 100 from BASF AG) and 69.7 parts by weight of solvent naphtha.
  • HDI trimerized hexamethylene diisocyanate
  • the solution of the partly silanized polyisocyanate has a solids content of 55.0% by weight.
  • a three-neck glass flask equipped with a reflux condenser and a thermometer is charged with 57.3 parts by weight of trimerized hexamethylene diisocyanate (HDI) (Basonat HI 100 from BASF AG) and 88.0 parts by weight of solvent naphtha.
  • HDI trimerized hexamethylene diisocyanate
  • IIa bis[3-(trimethoxysilyl)propyl]amine
  • the solution of the partly silanized polyisocyanate has a solids content of 63.0% by weight.
  • a three-neck glass flask equipped with a reflux condenser and a thermometer is charged with 57.3 parts by weight of trimerized hexamethylene diisocyanate (HDI) (Basonat HI 100 from BASF AG) and 88.0 parts by weight of solvent naphtha.
  • HDI trimerized hexamethylene diisocyanate
  • IIIa N-[3-(trimethoxysilyl)propyl]butylamine
  • Dynasilan® 1189 from Degussa are metered in at a rate such that 50 to 60° C. are not exceeded.
  • the reaction temperature is held at 50 to 60° C. until the isocyanate mass fraction as determined by titration is at the theoretically calculated 30 mol %.
  • the solution of the partly silanized polyisocyanate has a solids content of 54.8% by weight.
  • a three-neck glass flask equipped with a reflux condenser and a thermometer is charged with 57.3 parts by weight of trimerized hexamethylene diisocyanate (HDI) (Basonat HI 100 from BASF AG) and 69.7 parts by weight of solvent naphtha.
  • HDI trimerized hexamethylene diisocyanate
  • the solution of the partly silanized polyisocyanate has a solids content of 61.9% by weight.
  • a three-neck glass flask equipped with a reflux condenser and a thermometer is charged with 57.3 parts by weight of trimerized hexamethylene diisocyanate (HDI) (Basonat HI 100 from BASF AG) and 88.0 parts by weight of solvent naphtha.
  • HDI trimerized hexamethylene diisocyanate
  • the solution of the partly silanized polyisocyanate has a solids content of 58.2% by weight.
  • a mixture a2 consisting of 4.97 parts by weight of styrene, 16.91 parts by weight of tert-butyl acrylate, 19.89 parts by weight of 2-hydroxypropyl methacrylate, 7.45 parts by weight of n-butyl methacrylate, and 0.58 part by weight of acrylic acid is added at a rate such that the addition of the mixture a2 is concluded after 6 h.
  • the reaction mixture is held at 140° C. for a further 2 h and then cooled to below 100° C.
  • reaction mixture is diluted additionally with a mixture a3 of 3.70 parts by weight of 1-methoxyprop-2-yl acetate, 3.06 parts by weight of butyl glycol acetate, and 6.36 parts by weight of butyl acetate 98/100.
  • the resulting solution of the polyacrylate polyol A has a solids content of 52.4% (1 h, 130° C., forced-air oven), a viscosity of 3.6 dPas (ICI cone/plate viscometer, 23° C.), a hydroxyl number of 155 mg KOH/g, and an acid number of 10-13 mg KOH/g.
  • the coating compositions were formulated as follows:
  • Component 1 containing component A (polyol) and commercial additives and catalyst and solvent, is combined shortly before application with component 2, containing component B (modified polyisocyanate), and the components are stirred together until a homogeneous mixture is formed.
  • component A polyol
  • component B modified polyisocyanate
  • Application takes place pneumatically at 2.5 bar in three spray passes. Thereafter the coating is flashed off at room temperature for 5 minutes and subsequently baked at 140° C. for 22 minutes.
  • Table 1 lists all of the inventive coating compositions B1 to B7 in terms of the proportions of the components:
  • Example B1 B2 B3 B4 B5 B6 B7 Component B B1 B2 B3 B4 B5 B6 B7 Parts by weight of 45.0 45.0 45.0 45.0 45.0 polyacrylate polyol A of example Parts by weight of 52.0 47.2 48.3 43.7 144.9 133.0 153.0 component B Parts by weight of 2.1 2.2 2.3 2.4 6.9 7.2 7.8 catalyst 1 (Nacure 4167, King Industries) nonvolatile fraction 25% Parts by weight of BYK 0.2 0.2 0.2 0.2 0.2 0.2 0.2 301 (flow control agent, Byk Chemie) Parts by weight of 0.9 0.9 0.9 0.9 0.9 Tinuvin 384.2 (Ciba) Parts by weight of 0.8 0.8 0.8 0.8 0.8 0.8 Tinuvin 292 (Ciba) Parts by weight of 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Solventnaphtha
  • the storage moduli E′(200) and E′(min) and also the glass transition temperature Tg of the respective cured coating are measured by dynamic-mechanical thermo-analysis (DMTA) at a heating rate of 2 K/min using the DMTA V instrument from Rheometrics Scientific at a frequency of 1 Hz and an amplitude of 0.2%.
  • the DMTA measurements are carried out on free films with a thickness of 40 ⁇ m ⁇ 10 ⁇ m.
  • the coating composition under test is applied to substrates to which the coating obtained does not adhere.
  • suitable substrates include glass, Teflon, polyethylene terephthalate and polypropylene.
  • the resulting coating is cured for 20 minutes at an article temperature of 140° C. and is stored at 25° C. for 8 days after curing, before the DMTA measurements are carried out.
  • the scratchproofing of the surfaces of the resultant coatings was tested by means of the Crockmeter test (in general in accordance with EN ISO 105-X12, with 10 double rubs and an applied force of 9 N, using 9 ⁇ m abrasive paper (3M 281Q, using wetordryTMproductionTM), with subsequent determination of the residual gloss at 20° using a commercially customary gloss meter), and by means of the hammer test (10 or 100 double rubs with steel wool (RAKSO®00(fine)) with an applied weight of 1 kg, implemented with a hammer.
  • Table 2 shows the properties of the coatings of examples B1 to B7, prepared from the inventive coating compositions comprising an isocyanurate adduct B originating from the reaction of the HDI isocyanurate with, in each case, a mixture of a component IIa and a component IIIa (Examples B2, B3, B6 and B7), in comparison to coating compositions comprising an isocyanurate adduct B originating from the reaction with the HDI isocyanurate, referred to as HDI for short below, and exclusively one component IIa (example B4) or IIIa (examples B1 and B5).
  • examples B1 and B2 with a very low proportion of silane crosslinking (conversion of the isocyanate groups of the HDI of 30 mol % and high fraction of monofunctional silane structural units of 100 mol % structural units III in example B1 and 70 mol % structural units III in example B2) lower degrees of post-crosslinking are obtained than in example 7, with a high proportion of silane crosslinking (conversion of the isocyanate groups of the HDI of 70 mol % and high fraction of difunctional silane structural units of 70 mol % structural units II in example B7).
  • B1 and B4 may be contrasted with B2 and B3 in the group with 30 mol % conversion of the isocyanate functions.
  • B1 achieves high weathering values, but the scratchproofing is moderate.
  • B4 has good scratchproofing values, but is weaker in weathering.
  • Both examples B2 and B3 have better scratchproofing than B1 and better weathering times than B4.
  • Examples 1 to 7 were repeated, albeit with the sole difference that this time, instead of the catalyst based on amine-blocked phosphoric acid partial esters, blocked para-toluenesulfonic acid was used as the catalyst.
  • Table 3 lists all of the coating compositions of the comparative examples, in terms of the proportions of the components:
  • the comparison of the inventive examples 1 to 7 with the comparative examples VB1 to VB7 shows that the inventive coatings of examples B1 to B7 exhibit good scratchproofing directly after final curing, whereas the corresponding coatings of the comparative examples VB1 to VB7, with a high post-crosslinking index PCI>2, all exhibit a significantly poorer scratchproofing after the final 20-minute 140° C. cure. More particularly, therefore, the coatings of comparative examples VB1 to VB4, with a low degree of silanization, must be given an additional thermal aftertreatment following the cure, in order to obtain the good scratchproofing that is required in the field of OEM finishing; to do so, however, is very costly and inconvenient and therefore impracticable.
  • the coatings can be handled to a limited extent at best, given the risk of damage. Even the polishability of the resulting coatings, as is required for line refinishing, is present only conditionally for the coatings of the comparative examples.
  • the inventive coatings more particularly those of examples B3 to B7, also exhibit a better gloss than the coatings of the corresponding comparative examples.
  • the inventive example B1 using the high-activity catalyst based on the amine-blocked phosphoric acid partial ester, exhibits a PCI of 1.1, whereas the corresponding comparative example, using the corresponding amount of the substantially less effective catalyst based on blocked p-toluenesulfonic acid, has an excessively high PCI of 2.9.
  • the coating of comparative example VB1 has the aforementioned completely inadequate scratchproofing.
  • PCI post-crosslinking index
  • the coating of comparative example VB1 has the aforementioned completely inadequate scratchproofing.

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  • Polymers & Plastics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
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  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080245999A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Silane-Functional, Curable Mixtures Comprising Phosphonic and Diphosphonic Diesters
US20080245998A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Thermally Curable Mixtures Comprising Phosponic and Diphosphonic Diesters
US20090223631A1 (en) * 2006-05-29 2009-09-10 Basf Coatings Ag Use of curable mixtures comprising silane compounds and also phosphonic diesters or diphosphonic diesters as coupling agents
US20100028544A1 (en) * 2006-12-19 2010-02-04 Basf Coatings Ag Coating compositions with high scratch resistance and weathering stability
US20100120952A1 (en) * 2007-03-23 2010-05-13 Basf Coatings Ag Phosphonate containing two-component coating system and the production and use thereof
US20110027489A1 (en) * 2007-12-19 2011-02-03 Basf Coatings Gmbh Coating agent having high scratch resistance and high weathering resistance
US20110045190A1 (en) * 2007-12-19 2011-02-24 Basf Coatings Gmbh Coating agent with high scratch resistance and weathering resistance
US20110059251A1 (en) * 2007-12-19 2011-03-10 Basf Coatings Gmbh Coating composition having a high scratch resistance and weathering stability
US20120100380A1 (en) * 2009-06-24 2012-04-26 Basf Coatings Gmbh Coating compositions and coatings produced from them and featuring high scratch resistance in association with good results in the erichsen cupping test and good antistonechip properties
US20130136865A1 (en) * 2010-04-21 2013-05-30 Basf Coatings Gmbh Coating materials with high solids content and good levelling, multi-coat paint systems produced therefrom and use thereof
US8486539B2 (en) 2008-12-05 2013-07-16 Basf Coatings Gmbh Coating compositions and coatings produced from them with high scratch resistance, weathering stability, and good optical properties
CN103429684A (zh) * 2010-12-22 2013-12-04 技术研究院 防污涂层组合物、涂层及其制备方法和应用
WO2014016019A1 (de) * 2012-07-25 2014-01-30 Basf Coatings Gmbh Polyurethan-beschichtungsmittelzusammensetzung, mehrstufige beschichtungsverfahren
US8658752B2 (en) 2008-06-25 2014-02-25 Basf Coatings Gmbh Use of partially silanized polyisocyanate-based compounds as crosslinking-agents in coating compositions, and coating compositions comprising the compounds
US20140245270A1 (en) * 2013-02-26 2014-08-28 Red Hat, Inc. Systems and methods for providing context simulation
US20140308451A1 (en) * 2011-03-14 2014-10-16 Basf Coatings Gmbh Polyurethane coating material composition, multistage coating methods using these coating material compositions, and also the use of the coating material composition as clearcoat material and pigmented coating material, and application of the coating method for automotive refinish and/or for the coating of plastics substrates and/or of utility vehicles
US20140322448A1 (en) * 2011-03-14 2014-10-30 Basf Coatings Gmbh Polyurethane coating agent composition, multistage coating method using said coating agent compositions, and use of the coating agent compositions as clear coating or pigmented coating material, and use of the coating method for automotive repair painting and/or for coating plastics substrates and/or of commercial vehicles
US9035082B2 (en) 2011-10-10 2015-05-19 Cytonix, Llc Low surface energy touch screens, coatings, and methods
US20150344728A1 (en) * 2012-12-03 2015-12-03 Basf Coatings Gmbh Multicoat Effect And/Or Color Paint System And Method For Producing It, And Its Use
RU2581975C1 (ru) * 2014-12-10 2016-04-20 Федеральное государственное бюджетное образовательное учреждение высшего образования "Юго-Западный государственный университет" (ЮЗГУ) Устройство автоматизированного регулирования расхода тепла на отоплениев системах теплоснабжения
US20160122583A1 (en) * 2012-12-03 2016-05-05 BASF Coating GmbH Coating Material Compositions And Coatings Produced Therefrom Combining High Scratch Resistance With Good Polishability And Good Optical Properties, And Use Thereof
CN107001854A (zh) * 2014-12-08 2017-08-01 巴斯夫涂料有限公司 涂料组合物和由其制备的涂层及其用途
US10144198B2 (en) 2014-05-02 2018-12-04 Corning Incorporated Strengthened glass and compositions therefor
WO2019068083A1 (en) 2017-09-29 2019-04-04 Dow Global Technologies Llc ISOCYANATE-BASED ADHESIVE BONDING WITHOUT PRIMER LAYER WITH SILAN ACRYLIC POLYOL COATING
US20220025233A1 (en) * 2018-12-05 2022-01-27 Sunstar Engineering Inc. Urethane-based adhesive for automobile
US12331214B2 (en) 2019-07-03 2025-06-17 Covestro Intellectual Property Gmbh & Co. Kg Resistant 2K-PUR coatings

Families Citing this family (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4829837B2 (ja) * 2007-04-27 2011-12-07 関西ペイント株式会社 複層塗膜形成方法
DE102008043218A1 (de) 2008-09-24 2010-04-01 Evonik Goldschmidt Gmbh Polymere Werkstoffe sowie daraus bestehende Kleber- und Beschichtungsmittel auf Basis multialkoxysilylfunktioneller Präpolymerer
DE102009016195A1 (de) * 2009-04-03 2010-10-07 Basf Coatings Ag Feuchtigkeitshärtende Beschichtungsmittel auf der Basis aprotischer Lösemittel enthaltend Bindemittel mit Alkoxysilangruppen und deren Verwendung
DE102009022631A1 (de) 2009-05-25 2010-12-16 Evonik Goldschmidt Gmbh Härtbare Silylgruppen enthaltende Zusammensetzungen und deren Verwendung
DE102009041380A1 (de) * 2009-09-12 2011-03-24 Basf Coatings Gmbh Bindemittelmischung und sie enthaltende Beschichtungsmittel sowie daraus hergestellte Beschichtungen mit hoher Kratzbeständigkeit und Witterungsstabilität sowie guten optischen Eigenschaften
DE102009054071A1 (de) * 2009-11-20 2011-05-26 Basf Coatings Gmbh Beschichtungsmittel mit guter Lagerbeständigkeit und daraus hergestellte Beschichtungen mit hoher Kratzfestigkeit bei gleichzeitig guter Witterungsbeständigkeit
DE102010015675A1 (de) 2010-04-21 2011-10-27 Basf Coatings Gmbh Beschichtungsmittel mit verbesserter Ablaufneigung
DE102010015683A1 (de) 2010-04-21 2011-10-27 Basf Coatings Gmbh Beschichtungsmittel mit hohem Festkörpergehalt und gutem Verlauf sowie daraus hergestellte Mehrschichtlackierungen und deren Verwendung
KR101906618B1 (ko) 2010-11-19 2018-10-10 바스프 코팅스 게엠베하 높은 고형물 함량 및 양호한 레벨링을 갖는 코팅 조성물, 및 이로부터 형성된 다층 표면 코팅, 및 이들의 용도
CN103298847B (zh) * 2011-01-20 2015-11-25 巴斯夫涂料有限公司 水性聚氨酯涂布剂和由其制得的具有高耐划伤性和良好耐化学性的涂层
KR101962493B1 (ko) * 2011-06-09 2019-03-26 바스프 코팅스 게엠베하 높은 내스크래치성 및 우수한 연마성을 나타내는 코팅제 조성물, 이로부터 제조된 코팅, 및 이의 용도
EP2718342B1 (de) * 2011-06-09 2016-08-03 BASF Coatings GmbH Beschichtungsmittelzusammensetzungen und daraus hergestellte beschichtungen mit hoher kratzfestigkeit bei gleichzeitig guter polierbarkeit sowie deren verwendung
US9371469B2 (en) 2011-06-09 2016-06-21 Basf Coatings Gmbh Coating agent compositions, coatings made therefrom and exhibiting high scratch resistance and good polishability, and use thereof
ES2684145T3 (es) 2011-11-17 2018-10-01 Basf Coatings Gmbh Materiales de recubrimiento que contienen diésteres de glicerina y su uso en pinturas de varias capas
US9493661B2 (en) 2011-11-17 2016-11-15 Basf Coatings Gmbh Glycerol diesters, method for producing same, and use of same in coatings materials
US9090797B2 (en) * 2011-12-02 2015-07-28 Ppg Industries Ohio, Inc. Method of mitigating ice build-up on a substrate
DE102012204290A1 (de) 2012-03-19 2013-09-19 Evonik Degussa Gmbh Addukte aus Isocyanatoalkyl-trialkoxysilanen und aliphatischen, alkyl-verzweigten Diolen oder Polyolen
WO2013146705A1 (ja) * 2012-03-30 2013-10-03 太陽ホールディングス株式会社 ポリ（メタ）アクリレートの製造方法、これにより得られたポリ（メタ）アクリレート、モノマー組成物、その硬化物、およびこれを含むプリント配線板
MX2015000947A (es) 2012-07-25 2015-10-08 Basf Coatings Gmbh Composicion de agente de revestimiento de poliuretano y uso de la misma, metodos de revestimiento de multiples etapas.
WO2014026780A1 (en) 2012-08-16 2014-02-20 Basf Coatings Gmbh Coating compositions containing benzotrizol based uv-absorbers
KR101392725B1 (ko) * 2013-02-08 2014-05-08 전북대학교산학협력단 수용성 방염액, 목재의 방염 공정처리 방법, 이에 의한 방염목재
MX380707B (es) 2013-12-18 2025-03-12 Basf Coatings Gmbh Metodo de produccion de un sistema de pintura multicapa.
US9868134B2 (en) 2013-12-18 2018-01-16 Basf Coatings Gmbh Method for producing a multicoat paint system
EP2886207A1 (de) 2013-12-18 2015-06-24 BASF Coatings GmbH Verfahren zur Herstellung einer Mehrschichtlackierung
KR102368390B1 (ko) 2013-12-18 2022-02-28 바스프 코팅스 게엠베하 멀티코트 페인트 시스템을 금속 기판 상에 제조하는 방법 및 이에 의해 제조되는 멀티코트 페인트 시스템
EP2896639A1 (de) 2014-01-15 2015-07-22 BASF Coatings GmbH Beschichtete metallisierte Oberflächen
JP2017509901A (ja) * 2014-03-17 2017-04-06 プリズム・アナリティカル・テクノロジーズ・インコーポレーテッドＰｒｉｓｍ Ａｎａｌｙｔｉｃａｌ Ｔｅｃｈｎｏｌｏｇｉｅｓ，Ｉｎｃ． 高速試料分析方法及び高速試料分析システム
WO2016045839A1 (de) 2014-09-24 2016-03-31 Basf Coatings Gmbh Haftvermittler für zur herstellung von füllerschichten geeignete beschichtungszusammensetzungen
BR112017011795A2 (pt) 2014-12-02 2018-02-27 Basf Coatings Gmbh agente de revestimento pigmentado e revestimentos produzidos com o mesmo.
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RU2017129589A (ru) * 2015-01-22 2019-02-25 БАСФ Коатингс ГмбХ Система покровного средства на основе полиолов с низким кислотным числом
WO2016146474A1 (de) 2015-03-17 2016-09-22 Covestro Deutschland Ag Silangruppen enthaltende polyisocyanate auf basis von 1,5-diisocyanatopentan
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CN107636096B (zh) 2015-05-21 2020-06-05 科思创德国股份有限公司 聚氨酯涂料组合物
ES2742182T3 (es) * 2015-06-15 2020-02-13 Basf Coatings Gmbh Composiciones de agente de revestimiento de poliuretano así como su uso para la preparación de lacados de múltiples capas
JP2018524161A (ja) * 2015-06-15 2018-08-30 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 車輪リムをコーティングする方法、並びに得られる防汚性及び耐ブレーキダスト性のコーティング
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WO2017042175A1 (en) 2015-09-09 2017-03-16 Covestro Deutschland Ag Scratch-resistant aqueous 2k pu coatings
KR102555281B1 (ko) 2015-09-09 2023-07-14 코베스트로 도이칠란트 아게 스크래치-내성 2-성분 폴리우레탄 코팅
WO2017055418A1 (de) 2015-09-30 2017-04-06 Evonik Degussa Gmbh Mit silikonharzen modifizierte isocyanatoalkylalkoxysilan-addukte und ihre verwendung
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WO2020074297A1 (de) 2018-10-12 2020-04-16 Basf Coatings Gmbh Verfahren zur herstellung einer mehrschichtlackierung durch post- additivierung mindestens eines basislacks mit einer wässrigen dispersion, enthaltend polyamide und/oder amidwachse
CA3125931A1 (en) 2019-01-23 2020-07-30 Basf Coatings Gmbh Polycarboxylic acid-containing aqueous coating agent having an improved effect pigment alignment
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US20220213346A1 (en) * 2019-05-06 2022-07-07 Basf Coatings Gmbh Silane-based coating composition
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KR20220064406A (ko) 2019-10-23 2022-05-18 바스프 코팅스 게엠베하 핀홀에 대한 개선된 안정성을 갖는 안료처리된 수성 코팅 조성물
EP4093826A1 (en) 2020-01-21 2022-11-30 BASF Coatings GmbH Aqueous polycarboxylic acid containing coating composition with improved leveling properties
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JP2024517763A (ja) 2021-04-28 2024-04-23 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング ヒドロキシル官能性チオエーテル化合物、及び硬化性組成物におけるその使用方法
EP4108694A1 (de) 2021-06-21 2022-12-28 Covestro Deutschland AG Beschichtungsmittel und daraus erhältliche beschichtungen mit verbesserten anschmutzungsresistenzen und (selbst-)reinigungseigenschaften
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Citations (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3168483A (en) * 1961-01-17 1965-02-02 Air Prod & Chem Diazabicyclooctane-alkylene oxide catalyst compositions
US3707521A (en) * 1970-03-05 1972-12-26 Essex Chemical Corp Polyurethane sealant-primer system isocyanate-reactive surface primer composition for polyurethane sealants
US3718614A (en) * 1971-02-23 1973-02-27 American Cyanamid Co Polymeric viscosity control additives for silica thixotropic compositions
US3959403A (en) * 1975-03-31 1976-05-25 General Electric Company Process for making silarylenesilanediol, silarylenesiloxanediol and silarylenesiloxane-polydiorganosiloxane block copolymers
US4278783A (en) * 1978-09-05 1981-07-14 Mitsubishi Gas Chemical Company Inc. Method of curing an organoalkoxysilane compound
US4499151A (en) * 1983-03-29 1985-02-12 Ppg Industries, Inc. Color plus clear coating method utilizing addition interpolymers containing alkoxy silane and/or acyloxy silane groups
US4499150A (en) * 1983-03-29 1985-02-12 Ppg Industries, Inc. Color plus clear coating method utilizing addition interpolymers containing alkoxy silane and/or acyloxy silane groups
US4598131A (en) * 1984-12-19 1986-07-01 Ppg Industries, Inc. Catalysts for curable coating vehicle based upon aminoalkyloxy silanes and organic isocyanates
US4710542A (en) * 1986-05-16 1987-12-01 American Cyanamid Company Alkylcarbamylmethylated amino-triazine crosslinking agents and curable compositions containing the same
US4853146A (en) * 1987-01-24 1989-08-01 Akzo N.V. Thickening compositions and thickened aqueous acid solutions
US5225248A (en) * 1991-05-13 1993-07-06 E. I. Du Pont De Nemours And Company Method of curing a topcoat
US5238993A (en) * 1992-10-02 1993-08-24 The Dow Chemical Company Primer composition for improving the bonding of urethane adhesives to acid resistant paints
US5250605A (en) * 1990-12-17 1993-10-05 E. I. Du Pont De Nemours And Company Coating compositions comprising an organosilane polymer and reactive dispersed polymers
US5516559A (en) * 1992-02-15 1996-05-14 Basf Lacke+Farben, Ag Process for the production of a two-coat finish, and nonaqueous coatings suitable for this process
US5691439A (en) * 1996-12-16 1997-11-25 Bayer Corporation Low surface energy polyisocyanates and their use in one- or two-component coating compositions
US5716678A (en) * 1993-03-31 1998-02-10 Basf Lacke + Farben, Ag Process for the production of a two-coat finish on a substrate surface
US5719251A (en) * 1995-03-08 1998-02-17 E. I. Du Pont De Nemours And Company Reactive organosilicon compounds
US5747166A (en) * 1991-09-28 1998-05-05 Basf Corporation Aqueous coatings and processes for the production of automobile finishes
US5747590A (en) * 1996-12-04 1998-05-05 E. I. Du Pont De Nemours And Company Acrylic-melamine-functionalized oligomer coating composition
US5908895A (en) * 1996-06-22 1999-06-01 Herberts Gesellschaft Beschrankter Haftung Aqueous dispersion of silane-functional polyurethane resins, coating compositions and use thereof
US5985463A (en) * 1998-06-24 1999-11-16 E.I. Du Pont De Nemours And Company Coating containing hydroxy containing acrylosilane polymer to improve mar and acid etch resistance
US6379807B1 (en) * 2000-11-07 2002-04-30 E. I. Du Pont De Nemours And Company Coating composition having improved acid etch resistance
US6403699B1 (en) * 1993-03-31 2002-06-11 Basf Coatings Ag Nonaqueous coating and process for producing a two-coat finish
US20020142169A1 (en) * 2001-01-24 2002-10-03 Steffen Hofacker Two-component polyurethane binders as primers
US6492482B2 (en) * 2000-09-30 2002-12-10 Deguss-Huels Aktiengesellschaft Nonaqueous, heat-curable two-component coating
US20030027921A1 (en) * 2001-07-06 2003-02-06 Degussa Ag Nonaqueous thermosetting two-component coating composition
US6607833B1 (en) * 1999-03-17 2003-08-19 E. I. Du Pont De Nemours And Company High solids acid etch resistant clear coating composition
US20040106726A1 (en) * 2002-08-06 2004-06-03 Joshi Ravi R. Pultrusion systems and process
US20050165177A1 (en) * 2002-04-30 2005-07-28 Basf Aktiengesellschaft Method for producing highly functional, hyperbranched polyesters
US20050238899A1 (en) * 2004-04-27 2005-10-27 Isao Nagata High solids clearcoat compositions containing silane functional compounds
US20060045965A1 (en) * 2004-08-30 2006-03-02 Jun Lin Method for achieving a durable two-tone finish on a vehicle
US20060217472A1 (en) * 2005-03-11 2006-09-28 Staunton Thomas J Scratch resistant curable coating composition
US20070059532A1 (en) * 2005-09-15 2007-03-15 Basf Corporation Thermosetting coating compositions with multiple cure mechanisms
US20070213501A1 (en) * 2004-06-01 2007-09-13 Basf Aktiengesellschaft Highly functional, highly branched or hyperbranched polyesters, the production thereof and the use of the same
US20080047469A1 (en) * 2004-10-19 2008-02-28 Basf Coatings Ag Highly Scratch-Resistant and Highly Elastic Coating Agents Based on Alkoxysilane Functional Components
US20080075871A1 (en) * 2006-09-21 2008-03-27 Ppg Industries Ohio, Inc. Low temperature, moisture curable coating compositions and related methods
US20080245999A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Silane-Functional, Curable Mixtures Comprising Phosphonic and Diphosphonic Diesters
US20090223631A1 (en) * 2006-05-29 2009-09-10 Basf Coatings Ag Use of curable mixtures comprising silane compounds and also phosphonic diesters or diphosphonic diesters as coupling agents
US20100028544A1 (en) * 2006-12-19 2010-02-04 Basf Coatings Ag Coating compositions with high scratch resistance and weathering stability
US20110027489A1 (en) * 2007-12-19 2011-02-03 Basf Coatings Gmbh Coating agent having high scratch resistance and high weathering resistance
US20110045190A1 (en) * 2007-12-19 2011-02-24 Basf Coatings Gmbh Coating agent with high scratch resistance and weathering resistance
US20110059251A1 (en) * 2007-12-19 2011-03-10 Basf Coatings Gmbh Coating composition having a high scratch resistance and weathering stability
US20110245406A1 (en) * 2008-12-05 2011-10-06 Basf Coatings Gmbh Coating compositions and coatings produced from them with high scratch resistance, weathering stability, and good optical properties
US20110263789A1 (en) * 2007-06-06 2011-10-27 Basf Coatings Ag Clear paint compositions comprising hyperbranched, dendritic, hydroxyl- functional polyesters
US20110269897A1 (en) * 2008-06-25 2011-11-03 Basf Coatings Gmbh Use of partially silanized polyisocyanate-based compounds as crosslinking-agents in coating compositions, and coating compositions comprising the compounds
US20120100380A1 (en) * 2009-06-24 2012-04-26 Basf Coatings Gmbh Coating compositions and coatings produced from them and featuring high scratch resistance in association with good results in the erichsen cupping test and good antistonechip properties
US20120189858A1 (en) * 2009-06-06 2012-07-26 BASF Coating GmbH Coating compositions and resultant coatings with high scratch resistance and stability to solvent popping

Family Cites Families (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2835451C2 (de) 1978-08-12 1985-10-24 Saarbergwerke AG, 6600 Saarbrücken Verfahren zum Verfestigen von Kohle und/oder Gestein im Bergbau
US4479990A (en) * 1982-07-30 1984-10-30 Westinghouse Electric Co. Arc and track resistant articles utilizing photosensitive sag resistant cycloaliphatic epoxy resin coating compositions
JPS59124954A (ja) * 1982-12-30 1984-07-19 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
US4508887A (en) * 1983-08-01 1985-04-02 Dow Corning Corporation Method and novel catalyst compositions for preparing polyorganosiloxanes
EP0249201A3 (en) 1986-06-10 1989-07-19 Union Carbide Corporation High solids sag resistant cycloaliphatic epoxy coatings containing low molecular weight high tg organic polymeric sag resisting additives
SU1654318A1 (ru) * 1987-09-30 1991-06-07 Московский Инженерно-Строительный Институт Им.В.В.Куйбышева Способ приготовлени композиций дл нанесени покрытий спортивных площадок
JP2719420B2 (ja) * 1989-10-19 1998-02-25 鐘淵化学工業株式会社 加水分解性シリル基含有ビニル系重合体の製造方法
JP3086737B2 (ja) 1992-01-17 2000-09-11 鐘淵化学工業株式会社 塗料用硬化性組成物
US5344879A (en) 1992-01-17 1994-09-06 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Curable composition for paint
JP3144872B2 (ja) 1992-02-27 2001-03-12 鐘淵化学工業株式会社 硬化性組成物
GB9210653D0 (en) 1992-05-19 1992-07-01 Ici Plc Silane functional oligomer
JP3482569B2 (ja) 1994-06-14 2003-12-22 鐘淵化学工業株式会社 塗料用樹脂組成物、及び耐汚染性に優れた塗膜の形成方法
WO1997012945A1 (en) 1995-10-06 1997-04-10 Cabot Corporation Aqueous thixotropes for waterborne systems
JPH10306251A (ja) 1997-05-07 1998-11-17 Kanegafuchi Chem Ind Co Ltd 塗料用硬化性組成物およびそれを塗布してなる塗装物
SE510128C2 (sv) 1997-06-26 1999-04-19 Perstorp Ab Förfarande för framställning av dendritisk polyol
JPH11116847A (ja) 1997-10-09 1999-04-27 Kanegafuchi Chem Ind Co Ltd 上塗り塗料組成物およびその塗膜の形成方法
US5952445A (en) * 1998-04-09 1999-09-14 Bayer Corporation Water dispersible compounds containing alkoxysilane groups
US6046270A (en) 1998-10-14 2000-04-04 Bayer Corporation Silane-modified polyurethane resins, a process for their preparation and their use as moisture-curable resins
DE19855619A1 (de) * 1998-12-02 2000-06-08 Wacker Chemie Gmbh Unter Abspaltung von Alkoholen zu Elastomeren vernetzbare Organopolysiloxanmassen
AU771282B2 (en) 1999-07-30 2004-03-18 Ppg Industries Ohio, Inc. Coating compositions having improved scratch resistance, coated substrates and methods related thereto
US6239211B1 (en) * 2000-01-24 2001-05-29 Dow Corning Corporation Emulsions containing silicone polymers
EP1263828B1 (en) * 2000-03-13 2005-10-19 Akzo Nobel Coatings International B.V. Compositions comprising an isocyanate-functional compound, an isocyanate-reactive compound, and a co-catalyst
WO2001098393A1 (en) 2000-06-22 2001-12-27 Basf Corporation Coating compositions having improved adhesion to aluminum substrates
EP1197506B1 (en) 2000-10-13 2006-01-25 Tosoh Corporation Catalyst for production of a two component polyurethane sealant
US6642309B2 (en) * 2001-08-14 2003-11-04 Kaneka Corporation Curable resin composition
AT412090B (de) 2002-01-29 2004-09-27 Surface Specialties Austria Hydroxyfunktionelle polyester
US20040077778A1 (en) 2002-08-07 2004-04-22 Isidor Hazan One-pack primer sealer compositions for SMC automotive body panels
DE10352907A1 (de) 2002-11-15 2004-08-05 Henkel Kgaa Silylgruppen enthaltende Präpolymere, deren Herstellung und Verwendung in Montageschäumen
JP4360811B2 (ja) * 2003-02-04 2009-11-11 新日本製鐵株式会社 プレス成形性と加工部耐食性に優れたプレコート金属板
DE10323206A1 (de) 2003-05-22 2004-12-09 Consortium für elektrochemische Industrie GmbH Schäumbare Mischungen
EP1496114A1 (de) 2003-07-07 2005-01-12 Margraf, Stefan, Dr.med. Verfahren zur Inaktivierung von Mikroorganismen
EP1502927A1 (de) 2003-07-31 2005-02-02 Sika Technology AG Isocyanatfreie Primerzusammensetzung für Glas und Glaskeramiken
DE10344448A1 (de) 2003-09-25 2005-04-28 Henkel Kgaa Bindemittel mit Barriere-Eigenschaft
US20050208312A1 (en) 2004-03-17 2005-09-22 Isidor Hazan One-pack primer surfacer composition for SMC automotive body panels
DE102004050748A1 (de) 2004-10-19 2006-04-20 Basf Coatings Aktiengesellschaft Hochkratzfeste und hochelastische Beschichtungsmittel auf Basis von Alkoxysilanen
DE102004050747A1 (de) 2004-10-19 2006-04-27 Basf Coatings Ag Beschichtungsmittel enthaltend Addukte mit Alkoxysilanfunktionalität
DE102005003299A1 (de) 2005-01-24 2006-07-27 Goldschmidt Gmbh Nanopartikel für die Herstellung von Polyurethanschaum
FR2886284B1 (fr) 2005-05-30 2007-06-29 Commissariat Energie Atomique Procede de realisation de nanostructures
DE102005026085A1 (de) 2005-06-07 2006-12-14 Construction Research & Technology Gmbh Silan-modifizierte Harnstoff-Derivate, Verfahren zu ihrer Herstellung und deren Verwendung als Rheologiehilfsmittel
FR2887996B1 (fr) 2005-06-30 2007-08-17 Prismaflex Internat Sa Panneau de communication retroeclaire
WO2007016234A2 (en) 2005-07-29 2007-02-08 E. I. Du Pont De Nemours And Company Method for producing damage resistant multi-layer coatings on an automotive body or part thereof
DE102007013242A1 (de) 2007-03-15 2008-09-18 Basf Coatings Ag Hochkratzfeste Beschichtung mit guter Witterungs- und Rissbeständigkeit

Patent Citations (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3168483A (en) * 1961-01-17 1965-02-02 Air Prod & Chem Diazabicyclooctane-alkylene oxide catalyst compositions
US3707521A (en) * 1970-03-05 1972-12-26 Essex Chemical Corp Polyurethane sealant-primer system isocyanate-reactive surface primer composition for polyurethane sealants
US3718614A (en) * 1971-02-23 1973-02-27 American Cyanamid Co Polymeric viscosity control additives for silica thixotropic compositions
US3959403A (en) * 1975-03-31 1976-05-25 General Electric Company Process for making silarylenesilanediol, silarylenesiloxanediol and silarylenesiloxane-polydiorganosiloxane block copolymers
US4278783A (en) * 1978-09-05 1981-07-14 Mitsubishi Gas Chemical Company Inc. Method of curing an organoalkoxysilane compound
US4499150A (en) * 1983-03-29 1985-02-12 Ppg Industries, Inc. Color plus clear coating method utilizing addition interpolymers containing alkoxy silane and/or acyloxy silane groups
US4499151A (en) * 1983-03-29 1985-02-12 Ppg Industries, Inc. Color plus clear coating method utilizing addition interpolymers containing alkoxy silane and/or acyloxy silane groups
US4598131A (en) * 1984-12-19 1986-07-01 Ppg Industries, Inc. Catalysts for curable coating vehicle based upon aminoalkyloxy silanes and organic isocyanates
US4710542A (en) * 1986-05-16 1987-12-01 American Cyanamid Company Alkylcarbamylmethylated amino-triazine crosslinking agents and curable compositions containing the same
US4853146A (en) * 1987-01-24 1989-08-01 Akzo N.V. Thickening compositions and thickened aqueous acid solutions
US5041239A (en) * 1987-01-24 1991-08-20 Akzo N. V. Premix compositions for the preparation of thickened aqueous acid solutions
US5250605A (en) * 1990-12-17 1993-10-05 E. I. Du Pont De Nemours And Company Coating compositions comprising an organosilane polymer and reactive dispersed polymers
US5225248A (en) * 1991-05-13 1993-07-06 E. I. Du Pont De Nemours And Company Method of curing a topcoat
US5747166A (en) * 1991-09-28 1998-05-05 Basf Corporation Aqueous coatings and processes for the production of automobile finishes
US5516559A (en) * 1992-02-15 1996-05-14 Basf Lacke+Farben, Ag Process for the production of a two-coat finish, and nonaqueous coatings suitable for this process
US5238993A (en) * 1992-10-02 1993-08-24 The Dow Chemical Company Primer composition for improving the bonding of urethane adhesives to acid resistant paints
US5716678A (en) * 1993-03-31 1998-02-10 Basf Lacke + Farben, Ag Process for the production of a two-coat finish on a substrate surface
US6403699B1 (en) * 1993-03-31 2002-06-11 Basf Coatings Ag Nonaqueous coating and process for producing a two-coat finish
US5719251A (en) * 1995-03-08 1998-02-17 E. I. Du Pont De Nemours And Company Reactive organosilicon compounds
US5908895A (en) * 1996-06-22 1999-06-01 Herberts Gesellschaft Beschrankter Haftung Aqueous dispersion of silane-functional polyurethane resins, coating compositions and use thereof
US5747590A (en) * 1996-12-04 1998-05-05 E. I. Du Pont De Nemours And Company Acrylic-melamine-functionalized oligomer coating composition
US5691439A (en) * 1996-12-16 1997-11-25 Bayer Corporation Low surface energy polyisocyanates and their use in one- or two-component coating compositions
US5985463A (en) * 1998-06-24 1999-11-16 E.I. Du Pont De Nemours And Company Coating containing hydroxy containing acrylosilane polymer to improve mar and acid etch resistance
US6607833B1 (en) * 1999-03-17 2003-08-19 E. I. Du Pont De Nemours And Company High solids acid etch resistant clear coating composition
US6492482B2 (en) * 2000-09-30 2002-12-10 Deguss-Huels Aktiengesellschaft Nonaqueous, heat-curable two-component coating
US6379807B1 (en) * 2000-11-07 2002-04-30 E. I. Du Pont De Nemours And Company Coating composition having improved acid etch resistance
US20020142169A1 (en) * 2001-01-24 2002-10-03 Steffen Hofacker Two-component polyurethane binders as primers
US20030027921A1 (en) * 2001-07-06 2003-02-06 Degussa Ag Nonaqueous thermosetting two-component coating composition
US20050165177A1 (en) * 2002-04-30 2005-07-28 Basf Aktiengesellschaft Method for producing highly functional, hyperbranched polyesters
US20040106726A1 (en) * 2002-08-06 2004-06-03 Joshi Ravi R. Pultrusion systems and process
US20050238899A1 (en) * 2004-04-27 2005-10-27 Isao Nagata High solids clearcoat compositions containing silane functional compounds
US20070213501A1 (en) * 2004-06-01 2007-09-13 Basf Aktiengesellschaft Highly functional, highly branched or hyperbranched polyesters, the production thereof and the use of the same
US7858732B2 (en) * 2004-06-01 2010-12-28 Basf Aktiengesellschaft Highly functional, highly branched or hyperbranched polyesters, the production thereof and the use of the same
US20090275680A1 (en) * 2004-06-01 2009-11-05 Basf Aktiengesellschaft Highly functional, highly branched or hyperbranched polyesters, the production thereof and the use of the same
US20090281271A1 (en) * 2004-06-01 2009-11-12 Basf Aktiengesellschaft Highly functional, highly branched or hyperbranched polyesters, the production thereof and the use of the same
US20060045965A1 (en) * 2004-08-30 2006-03-02 Jun Lin Method for achieving a durable two-tone finish on a vehicle
US20080047469A1 (en) * 2004-10-19 2008-02-28 Basf Coatings Ag Highly Scratch-Resistant and Highly Elastic Coating Agents Based on Alkoxysilane Functional Components
US7772320B2 (en) * 2004-10-19 2010-08-10 Basf Corporation High scratch-resistance and high elasticity coating materials based on alkoxysilane functional components
US20060217472A1 (en) * 2005-03-11 2006-09-28 Staunton Thomas J Scratch resistant curable coating composition
US20070059532A1 (en) * 2005-09-15 2007-03-15 Basf Corporation Thermosetting coating compositions with multiple cure mechanisms
US20080245999A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Silane-Functional, Curable Mixtures Comprising Phosphonic and Diphosphonic Diesters
US8013099B2 (en) * 2005-09-22 2011-09-06 Basf Coatings Ag Use of phosphonic acid diesters and diphosphonic acid diesters and silane group containing, curable mixtures containing phosphonic acid diesters and diphosphonic acid diesters
US20090223631A1 (en) * 2006-05-29 2009-09-10 Basf Coatings Ag Use of curable mixtures comprising silane compounds and also phosphonic diesters or diphosphonic diesters as coupling agents
US20080075871A1 (en) * 2006-09-21 2008-03-27 Ppg Industries Ohio, Inc. Low temperature, moisture curable coating compositions and related methods
US20100143596A1 (en) * 2006-12-19 2010-06-10 Basf Coatings Ag Coating agents having high scratch resistance and weathering stability
US20100028544A1 (en) * 2006-12-19 2010-02-04 Basf Coatings Ag Coating compositions with high scratch resistance and weathering stability
US20110263789A1 (en) * 2007-06-06 2011-10-27 Basf Coatings Ag Clear paint compositions comprising hyperbranched, dendritic, hydroxyl- functional polyesters
US20110027489A1 (en) * 2007-12-19 2011-02-03 Basf Coatings Gmbh Coating agent having high scratch resistance and high weathering resistance
US20110045190A1 (en) * 2007-12-19 2011-02-24 Basf Coatings Gmbh Coating agent with high scratch resistance and weathering resistance
US20110059251A1 (en) * 2007-12-19 2011-03-10 Basf Coatings Gmbh Coating composition having a high scratch resistance and weathering stability
US20110269897A1 (en) * 2008-06-25 2011-11-03 Basf Coatings Gmbh Use of partially silanized polyisocyanate-based compounds as crosslinking-agents in coating compositions, and coating compositions comprising the compounds
US20110245406A1 (en) * 2008-12-05 2011-10-06 Basf Coatings Gmbh Coating compositions and coatings produced from them with high scratch resistance, weathering stability, and good optical properties
US20120189858A1 (en) * 2009-06-06 2012-07-26 BASF Coating GmbH Coating compositions and resultant coatings with high scratch resistance and stability to solvent popping
US20120100380A1 (en) * 2009-06-24 2012-04-26 Basf Coatings Gmbh Coating compositions and coatings produced from them and featuring high scratch resistance in association with good results in the erichsen cupping test and good antistonechip properties

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
International Preliminary Report on Patentability for PCT/EP2007/011191, 07 July 2009, 14 pgs. *

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10294389B2 (en) * 2005-09-22 2019-05-21 Basf Coatings Gmbh Use of phosphonic acid diesters and diphosphonic acid diesters and thermally curable mixtures containing phosphonic acid diesters and diphosphonic acid diesters
US20080245998A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Thermally Curable Mixtures Comprising Phosponic and Diphosphonic Diesters
US20080245999A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Silane-Functional, Curable Mixtures Comprising Phosphonic and Diphosphonic Diesters
US8013099B2 (en) 2005-09-22 2011-09-06 Basf Coatings Ag Use of phosphonic acid diesters and diphosphonic acid diesters and silane group containing, curable mixtures containing phosphonic acid diesters and diphosphonic acid diesters
US20090223631A1 (en) * 2006-05-29 2009-09-10 Basf Coatings Ag Use of curable mixtures comprising silane compounds and also phosphonic diesters or diphosphonic diesters as coupling agents
US9018330B2 (en) 2006-05-29 2015-04-28 Basf Coatings Gmbh Use of curable mixtures comprising silane group-containing compounds and phosphonic acid diester or diphosphonic acid diester as adhesives
US20100028544A1 (en) * 2006-12-19 2010-02-04 Basf Coatings Ag Coating compositions with high scratch resistance and weathering stability
US20100143596A1 (en) * 2006-12-19 2010-06-10 Basf Coatings Ag Coating agents having high scratch resistance and weathering stability
US8569438B2 (en) 2006-12-19 2013-10-29 Basf Coatings Gmbh Coating agents having high scratch resistance and weathering stability
US9353287B2 (en) 2006-12-19 2016-05-31 Basf Coatings Gmbh Coating agents having high scratch resistance and weathering stability
US8138249B2 (en) 2007-03-23 2012-03-20 Basf Coatings Japan Ltd. Phosphonate-containing two-component coating system and the production and use thereof
US20100120952A1 (en) * 2007-03-23 2010-05-13 Basf Coatings Ag Phosphonate containing two-component coating system and the production and use thereof
US8808805B2 (en) 2007-12-19 2014-08-19 Basf Coatings Gmbh Coating agent with high scratch resistance and weathering resistance
US20110059251A1 (en) * 2007-12-19 2011-03-10 Basf Coatings Gmbh Coating composition having a high scratch resistance and weathering stability
US20110045190A1 (en) * 2007-12-19 2011-02-24 Basf Coatings Gmbh Coating agent with high scratch resistance and weathering resistance
US9090732B2 (en) 2007-12-19 2015-07-28 Basf Coatings Gmbh Coating composition having a high scratch resistance and weathering stability
US20110027489A1 (en) * 2007-12-19 2011-02-03 Basf Coatings Gmbh Coating agent having high scratch resistance and high weathering resistance
US8679589B2 (en) 2007-12-19 2014-03-25 Basf Coatings Gmbh Coating agent having high scratch resistance and high weathering resistance
US8658752B2 (en) 2008-06-25 2014-02-25 Basf Coatings Gmbh Use of partially silanized polyisocyanate-based compounds as crosslinking-agents in coating compositions, and coating compositions comprising the compounds
US8486539B2 (en) 2008-12-05 2013-07-16 Basf Coatings Gmbh Coating compositions and coatings produced from them with high scratch resistance, weathering stability, and good optical properties
US9017818B2 (en) * 2009-06-24 2015-04-28 Basf Coatings Gmbh Coating compositions and coatings produced from them and featuring high scratch resistance in association with good results in the Erichsen cupping test and good antistonechip properties
US20120100380A1 (en) * 2009-06-24 2012-04-26 Basf Coatings Gmbh Coating compositions and coatings produced from them and featuring high scratch resistance in association with good results in the erichsen cupping test and good antistonechip properties
US20130136865A1 (en) * 2010-04-21 2013-05-30 Basf Coatings Gmbh Coating materials with high solids content and good levelling, multi-coat paint systems produced therefrom and use thereof
US8790752B2 (en) * 2010-04-21 2014-07-29 Basf Coatings Gmbh Coating materials with high solids content and good levelling, multicoat paint systems produced therefrom and use thereof
US9029491B2 (en) 2010-12-22 2015-05-12 Teknologisk Institut Repellent coating composition and coating, method for making and uses thereof
CN103429684A (zh) * 2010-12-22 2013-12-04 技术研究院 防污涂层组合物、涂层及其制备方法和应用
US20140308451A1 (en) * 2011-03-14 2014-10-16 Basf Coatings Gmbh Polyurethane coating material composition, multistage coating methods using these coating material compositions, and also the use of the coating material composition as clearcoat material and pigmented coating material, and application of the coating method for automotive refinish and/or for the coating of plastics substrates and/or of utility vehicles
US20140322448A1 (en) * 2011-03-14 2014-10-30 Basf Coatings Gmbh Polyurethane coating agent composition, multistage coating method using said coating agent compositions, and use of the coating agent compositions as clear coating or pigmented coating material, and use of the coating method for automotive repair painting and/or for coating plastics substrates and/or of commercial vehicles
US9340638B2 (en) * 2011-03-14 2016-05-17 Basf Coatings Gmbh Polyurethane coating material composition, multistage coating methods using these coating material compositions, and also the use of the coating material composition as clearcoat material and pigmented coating material, and application of the coating method for automotive refinish and/or for the coating of plastics substrates and/or of utility vehicles
US9340703B2 (en) * 2011-03-14 2016-05-17 Basf Coatings Gmbh Polyurethane coating agent composition, multistage coating method using said coating agent compositions, and use of the coating agent compositions as clear coating or pigmented coating material, and use of the coating method for automotive repair painting and/or for coating plastics substrates and/or of commercial vehicles
US9035082B2 (en) 2011-10-10 2015-05-19 Cytonix, Llc Low surface energy touch screens, coatings, and methods
US9249050B2 (en) 2011-10-10 2016-02-02 Cytonix, Llc Low surface energy touch screens, coatings, and methods
AU2013295294B2 (en) * 2012-07-25 2016-02-25 Basf Coatings Gmbh Polyurethane coating agent compositions, multi-stage coating methods
US9644111B2 (en) 2012-07-25 2017-05-09 Basf Coatings Gmbh Polyurethane coating material composition, multi-stage coating methods
WO2014016019A1 (de) * 2012-07-25 2014-01-30 Basf Coatings Gmbh Polyurethan-beschichtungsmittelzusammensetzung, mehrstufige beschichtungsverfahren
US20160122583A1 (en) * 2012-12-03 2016-05-05 BASF Coating GmbH Coating Material Compositions And Coatings Produced Therefrom Combining High Scratch Resistance With Good Polishability And Good Optical Properties, And Use Thereof
US10081738B2 (en) * 2012-12-03 2018-09-25 Basf Coatings Gmbh Multicoat effect and/or color paint system and method for producing it, and its use
US10100222B2 (en) * 2012-12-03 2018-10-16 Basf Coatings Gmbh Coating material compositions and coatings produced therefrom combining high scratch resistance and good polishability and good optical properties, and use thereof
US20150344728A1 (en) * 2012-12-03 2015-12-03 Basf Coatings Gmbh Multicoat Effect And/Or Color Paint System And Method For Producing It, And Its Use
US20140245270A1 (en) * 2013-02-26 2014-08-28 Red Hat, Inc. Systems and methods for providing context simulation
US10144198B2 (en) 2014-05-02 2018-12-04 Corning Incorporated Strengthened glass and compositions therefor
CN107001854A (zh) * 2014-12-08 2017-08-01 巴斯夫涂料有限公司 涂料组合物和由其制备的涂层及其用途
RU2581975C1 (ru) * 2014-12-10 2016-04-20 Федеральное государственное бюджетное образовательное учреждение высшего образования "Юго-Западный государственный университет" (ЮЗГУ) Устройство автоматизированного регулирования расхода тепла на отоплениев системах теплоснабжения
WO2019068083A1 (en) 2017-09-29 2019-04-04 Dow Global Technologies Llc ISOCYANATE-BASED ADHESIVE BONDING WITHOUT PRIMER LAYER WITH SILAN ACRYLIC POLYOL COATING
US11499075B2 (en) 2017-09-29 2022-11-15 Ddp Specialty Electronics Materials Us, Llc Isocyanate functional adhesive which bonds primerless to silanated acrylic polyol based coatings
US20220025233A1 (en) * 2018-12-05 2022-01-27 Sunstar Engineering Inc. Urethane-based adhesive for automobile
US12234386B2 (en) * 2018-12-05 2025-02-25 Sunstar Engineering Inc. Urethane-based adhesive for automobile
US12331214B2 (en) 2019-07-03 2025-06-17 Covestro Intellectual Property Gmbh & Co. Kg Resistant 2K-PUR coatings

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