US20100015344A1 - Coating compositions with high scratch resistance and weathering stability - Google Patents
Coating compositions with high scratch resistance and weathering stability Download PDFInfo
- 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
- Authority
- US
- United States
- Prior art keywords
- coating composition
- coating
- mol
- iii
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 0 O=PO.[10*]O.[11*]O Chemical compound O=PO.[10*]O.[11*]O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006059951 | 2006-12-19 | ||
DE102006059951.9 | 2006-12-19 | ||
PCT/EP2007/011191 WO2008074490A1 (de) | 2006-12-19 | 2007-12-19 | Beschichtungsmittel mit hoher kratzbeständigkeit und witterungsstabilität |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100015344A1 true US20100015344A1 (en) | 2010-01-21 |
Family
ID=39199992
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/519,449 Active 2029-05-11 US9353287B2 (en) | 2006-12-19 | 2007-12-19 | Coating agents having high scratch resistance and weathering stability |
US12/519,458 Active 2029-12-06 US8569438B2 (en) | 2006-12-19 | 2007-12-19 | Coating agents having high scratch resistance and weathering stability |
US12/519,466 Abandoned US20100015344A1 (en) | 2006-12-19 | 2007-12-19 | Coating compositions with high scratch resistance and weathering stability |
US14/036,367 Abandoned US20140023789A1 (en) | 2006-12-19 | 2013-09-25 | Coating agents having high scratch resistance and weathering stability |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/519,449 Active 2029-05-11 US9353287B2 (en) | 2006-12-19 | 2007-12-19 | Coating agents having high scratch resistance and weathering stability |
US12/519,458 Active 2029-12-06 US8569438B2 (en) | 2006-12-19 | 2007-12-19 | Coating agents having high scratch resistance and weathering stability |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/036,367 Abandoned US20140023789A1 (en) | 2006-12-19 | 2013-09-25 | Coating agents having high scratch resistance and weathering stability |
Country Status (13)
Country | Link |
---|---|
US (4) | US9353287B2 (zh) |
EP (3) | EP2102263B1 (zh) |
JP (3) | JP5631004B2 (zh) |
KR (3) | KR20090094377A (zh) |
CN (3) | CN101583643B (zh) |
AT (1) | ATE515523T1 (zh) |
BR (3) | BRPI0721070A2 (zh) |
CA (3) | CA2671662C (zh) |
ES (3) | ES2369110T3 (zh) |
MX (3) | MX2009005613A (zh) |
PL (3) | PL2091987T3 (zh) |
RU (3) | RU2467026C2 (zh) |
WO (3) | WO2008074491A1 (zh) |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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 |
Families Citing this family (68)
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 |
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 |
DE102010015675A1 (de) * | 2010-04-21 | 2011-10-27 | Basf Coatings Gmbh | Beschichtungsmittel mit verbesserter Ablaufneigung |
WO2012065942A1 (de) | 2010-11-19 | 2012-05-24 | Basf Coatings Gmbh | Beschichtungsmittel mit hohem festkörpergehalt und gutem verlauf sowie daraus hergestellte mehrschichtlackierungen und deren verwendung |
US9777190B2 (en) | 2011-01-20 | 2017-10-03 | Basf Coatings Gmbh | Aqueous polyurethane coating material and coatings produced therefrom and having high scratch resistance and good chemicals resistance |
WO2012168014A1 (de) | 2011-06-09 | 2012-12-13 | Basf Coatings Gmbh | Beschichtungsmittelzusammensetzungen und daraus hergestellte beschichtungen mit hoher kratzfestigkeit bei gleichzeitig guter polierbarkeit sowie deren verwendung |
EP2718343B1 (de) * | 2011-06-09 | 2015-04-29 | 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 |
WO2013072480A1 (de) | 2011-11-17 | 2013-05-23 | Basf Coatings Gmbh | Glyceroldiester enthaltende beschichtungsmittel und deren verwendung in mehrschichtlackierungen |
ES2666364T3 (es) | 2011-11-17 | 2018-05-04 | Basf Coatings Gmbh | Uso de diésteres de glicerina como diluyentes reactivos y materiales de recubrimiento que los contienen |
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 |
CN104203992B (zh) * | 2012-03-30 | 2016-08-24 | 太阳控股株式会社 | 聚(甲基)丙烯酸酯及制造方法、单体组合物、固化物和印刷电路板 |
WO2014016026A1 (de) | 2012-07-25 | 2014-01-30 | Basf Coatings Gmbh | Polyurethan-beschichtungsmittelzusammensetzung und ihre verwendung, mehrstufige beschichtungsverfahren |
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 |
EP2886207A1 (de) | 2013-12-18 | 2015-06-24 | BASF Coatings GmbH | Verfahren zur Herstellung einer Mehrschichtlackierung |
KR102351172B1 (ko) | 2013-12-18 | 2022-01-13 | 바스프 코팅스 게엠베하 | 금속 기판 위에 멀티코트 페인트 시스템을 제조하는 방법 및 상기 방법에 의해 제조된 멀티코트 페인트 시스템 (method for producing a multicoat paint system on a metallic substrate and multicoat paint system produced thereby) |
RU2675915C1 (ru) | 2013-12-18 | 2018-12-25 | БАСФ Коатингс ГмбХ | Способ получения многослойной красочной системы |
MX2016008064A (es) | 2013-12-18 | 2016-09-16 | Basf Coatings Gmbh | Metodo de produccion de un sistema de pintura multicapa. |
EP2896639A1 (de) | 2014-01-15 | 2015-07-22 | BASF Coatings GmbH | Beschichtete metallisierte Oberflächen |
KR20160132467A (ko) * | 2014-03-17 | 2016-11-18 | 프리즘 애널리티컬 테크놀로지스, 인크. | 신속한 시료 분석을 위한 공정 및 시스템 |
US10870764B2 (en) | 2014-09-24 | 2020-12-22 | Basf Coatings Gmbh | Adhesion promoter for coating compositions suitable for producing surfacer coats |
KR20170088971A (ko) | 2014-12-02 | 2017-08-02 | 바스프 코팅스 게엠베하 | 안료처리 코팅제 및 그로부터 제조된 코팅 |
JP6893470B2 (ja) | 2014-12-02 | 2021-06-23 | 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BASF Coatings GmbH | コポリマーおよび当該コポリマーを含有する顔料入りコーティング剤 |
KR101953499B1 (ko) * | 2014-12-08 | 2019-02-28 | 바스프 코팅스 게엠베하 | 비수성 코팅 물질 조성물, 개선된 접착력 및 내스크래치성을 갖는 그로부터 제조된 코팅, 및 그의 용도 |
CA2972550C (en) * | 2015-01-22 | 2019-10-29 | Basf Coatings Gmbh | Coating material system based on polyols of low acid number |
RU2017129590A (ru) * | 2015-01-22 | 2019-02-22 | БАСФ Коатингс ГмбХ | Система покровного средства на основе li/bi катализаторов |
WO2016146474A1 (de) | 2015-03-17 | 2016-09-22 | Covestro Deutschland Ag | Silangruppen enthaltende polyisocyanate auf basis von 1,5-diisocyanatopentan |
ES2707979T3 (es) | 2015-04-09 | 2019-04-08 | Evonik Degussa Gmbh | Aductos de isocianatoalquiltrimetoxisilanos y agentes ignífugos reactivos con éstos |
EP3085719A1 (de) | 2015-04-21 | 2016-10-26 | Covestro Deutschland AG | Hydrophob modifizierter polyisocyanuratkunststoff und verfahren zu dessen herstellung |
BR112017023621A2 (pt) | 2015-05-06 | 2018-07-24 | Basf Coatings Gmbh | processo para produzir um sistema de pintura de multirrevestimentos sobre um substrato de metal, e, sistema de pintura de multirrevestimentos. |
EP3298058B1 (de) | 2015-05-21 | 2019-04-17 | Covestro Deutschland AG | Polyurethan-beschichtungszusammensetzungen |
US20180171175A1 (en) * | 2015-06-15 | 2018-06-21 | Basf Coatings Gmbh | Method for coating wheel rims, and resultant dirt-repellent and brake dust-resistant coatings |
MX2017016472A (es) * | 2015-06-15 | 2018-05-17 | Basf Coatings Gmbh | Composiciones de un material de recubrimiento de poliuretano y su uso para producir sistemas de pintura de multiples recubrimientos. |
EP3307834A1 (de) | 2015-06-15 | 2018-04-18 | BASF Coatings GmbH | Verfahren zur beschichtung von radfelgen sowie die hierbei erhaltenen schmutz abweisenden und bremsstaubresistenten beschichtungen |
JP6712314B2 (ja) | 2015-09-09 | 2020-06-17 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトCovestro Deutschland Ag | 耐引掻性水性2k puコーティング |
CN108026237B (zh) | 2015-09-09 | 2020-12-22 | 科思创德国股份有限公司 | 耐划伤的双组分聚氨酯涂料 |
JP6756821B2 (ja) | 2015-09-30 | 2020-09-16 | エボニック オペレーションズ ゲーエムベーハー | シリコーン樹脂で変性されたイソシアナトアルキルアルコキシシラン付加物およびその使用 |
RU2700867C1 (ru) | 2015-11-26 | 2019-09-23 | БАСФ Коатингс ГмбХ | Способ получения многослойной красочной системы |
KR20190010876A (ko) | 2016-05-24 | 2019-01-31 | 바스프 코팅스 게엠베하 | 개선된 내오염성 및 (자기)세정 특성을 갖는 코팅제 및 그로부터 제조된 코팅 및 그의 용도 |
KR102442964B1 (ko) | 2016-08-09 | 2022-09-14 | 코베스트로 도이칠란트 아게 | 실란-관능성 중합체성 폴리우레탄 |
WO2018046494A1 (en) | 2016-09-06 | 2018-03-15 | Oxis Energy Limited | Anode for an electrochemical cell |
WO2020040738A1 (en) | 2018-08-21 | 2020-02-27 | Evonik Degussa Gmbh | Heat-curable coating compositions containing silane-functional polyurethane resins catalyzed by amidine salts |
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 |
BR112021012807A2 (pt) | 2019-01-23 | 2021-11-03 | Basf Coatings Gmbh | Composição de revestimento aquoso, método de produção de um sistema de tinta de múltiplos revestimentos em um substrato, sistema de tinta de múltiplos revestimentos, e, uso de pelo menos um ácido policarboxílico em uma composição de revestimento aquoso |
KR20220002426A (ko) | 2019-04-26 | 2022-01-06 | 바스프 코팅스 게엠베하 | 수계 코팅 조성물 및 상기 조성물을 사용하여 다층 코팅 필름을 형성하는 방법 |
EP3760658A1 (de) | 2019-07-03 | 2021-01-06 | Covestro Deutschland AG | Beständige 2k-pur-beschichtungen |
JP7318109B2 (ja) | 2019-07-29 | 2023-07-31 | 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 | 光輝コート層を含む多層コーティングの生成方法及び前記方法で得られる多層コーティング |
KR20220064406A (ko) | 2019-10-23 | 2022-05-18 | 바스프 코팅스 게엠베하 | 핀홀에 대한 개선된 안정성을 갖는 안료처리된 수성 코팅 조성물 |
MX2022008964A (es) | 2020-01-21 | 2022-08-15 | Basf Coatings Gmbh | Composicion de recubrimiento acuosa que contiene acido policarboxilico con propiedades de nivelacion mejoradas. |
US20230211530A1 (en) | 2020-07-02 | 2023-07-06 | Covestro Deutschland Ag | Coatings from polyisocyanurate coatings (rim) and their use in injection molding processes |
WO2022167173A1 (en) | 2021-02-03 | 2022-08-11 | Basf Coatings Gmbh | Method for forming a multilayer coating and object coated with such a multilayer coating |
WO2022229304A1 (en) | 2021-04-28 | 2022-11-03 | Basf Coatings Gmbh | Hydroxyl-functional thioether compounds and their use in curable compositions |
EP4108694A1 (de) | 2021-06-21 | 2022-12-28 | Covestro Deutschland AG | Beschichtungsmittel und daraus erhältliche beschichtungen mit verbesserten anschmutzungsresistenzen und (selbst-)reinigungseigenschaften |
EP4108695A1 (de) | 2021-06-21 | 2022-12-28 | Covestro Deutschland AG | Beschichtungsmittel und daraus erhältliche beschichtungen mit verbesserten anschmutzungsresistenzen und (selbst-)reinigungseigenschaften |
EP4108697A1 (de) | 2021-06-21 | 2022-12-28 | Covestro Deutschland AG | Beschichtungsmittel und daraus erhältliche beschichtungen mit verbesserten anschmutzungsresistenzen und (selbst-)reinigungseigenschaften |
EP4186951A1 (de) | 2021-11-30 | 2023-05-31 | BASF Coatings GmbH | Verfahren zur herstellung einer mehrschichtlackierung |
EP4198094A1 (de) | 2021-12-20 | 2023-06-21 | Covestro Deutschland AG | Mehrschichtaufbau auf metallischen untergründen basierend auf polyaspartatbeschichtungen |
WO2023117926A1 (en) | 2021-12-21 | 2023-06-29 | Basf Se | Environmental attributes for nitrogen containing chemicals |
WO2024052234A1 (en) | 2022-09-05 | 2024-03-14 | Basf Coatings Gmbh | Aqueous coating material containing cellulose nanofibers |
CN115433508B (zh) * | 2022-09-16 | 2023-04-18 | 天津森聚柯密封涂层材料有限公司 | 一种单组分高强度弹性涂料及其制备方法和应用 |
EP4357420A1 (en) | 2022-10-17 | 2024-04-24 | BASF Coatings GmbH | Process for sustainably coating automotive substrates |
Citations (47)
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 |
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)
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 |
EP0554684B1 (en) | 1992-01-17 | 1996-01-03 | 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 |
ES2280235T3 (es) | 1999-07-30 | 2007-09-16 | Ppg Industries Ohio, Inc. | Composiciones de recubrimiento que tienen resistencia al rayado mejorada, sustratos recubiertos y metodos relacionados con los mismos. |
US6239211B1 (en) * | 2000-01-24 | 2001-05-29 | Dow Corning Corporation | Emulsions containing silicone polymers |
KR20020081408A (ko) * | 2000-03-13 | 2002-10-26 | 아크조 노벨 엔.브이. | 이소시아네이트-관능기 화합물, 이소시아네이트-반응성화합물 및 공촉매를 포함하는 조성물 |
WO2001098393A1 (en) | 2000-06-22 | 2001-12-27 | Basf Corporation | Coating compositions having improved adhesion to aluminum substrates |
DE60116825T2 (de) | 2000-10-13 | 2006-07-27 | Tosoh Corp., Shinnanyo | Katalysator zur Herstellung von einer Zwei-Komponenten Polyurethandichtungsmasse |
DE60203973T2 (de) * | 2001-08-14 | 2006-02-23 | Kaneka Corp. | Härtbares Harz |
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 |
DE102004050747A1 (de) | 2004-10-19 | 2006-04-27 | Basf Coatings Ag | Beschichtungsmittel enthaltend Addukte mit Alkoxysilanfunktionalität |
DE102004050748A1 (de) | 2004-10-19 | 2006-04-20 | Basf Coatings Aktiengesellschaft | Hochkratzfeste und hochelastische Beschichtungsmittel auf Basis von Alkoxysilanen |
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 |
-
2007
- 2007-12-19 WO PCT/EP2007/011192 patent/WO2008074491A1/de active Application Filing
- 2007-12-19 MX MX2009005613A patent/MX2009005613A/es active IP Right Grant
- 2007-12-19 BR BRPI0721070-1A2A patent/BRPI0721070A2/pt not_active IP Right Cessation
- 2007-12-19 BR BRPI0721288-7A2A patent/BRPI0721288A2/pt not_active Application Discontinuation
- 2007-12-19 PL PL07856913T patent/PL2091987T3/pl unknown
- 2007-12-19 WO PCT/EP2007/011190 patent/WO2008074489A1/de active Application Filing
- 2007-12-19 KR KR1020097015003A patent/KR20090094377A/ko not_active Application Discontinuation
- 2007-12-19 ES ES07856915T patent/ES2369110T3/es active Active
- 2007-12-19 CA CA2671662A patent/CA2671662C/en active Active
- 2007-12-19 CN CN2007800466688A patent/CN101583643B/zh not_active Expired - Fee Related
- 2007-12-19 AT AT07856915T patent/ATE515523T1/de active
- 2007-12-19 US US12/519,449 patent/US9353287B2/en active Active
- 2007-12-19 MX MX2009005495A patent/MX2009005495A/es active IP Right Grant
- 2007-12-19 KR KR1020097015002A patent/KR101500460B1/ko active IP Right Grant
- 2007-12-19 KR KR1020097015004A patent/KR101500462B1/ko active IP Right Grant
- 2007-12-19 ES ES07856914T patent/ES2408171T3/es active Active
- 2007-12-19 CA CA002671663A patent/CA2671663A1/en not_active Abandoned
- 2007-12-19 JP JP2009541879A patent/JP5631004B2/ja active Active
- 2007-12-19 PL PL07856914T patent/PL2091988T3/pl unknown
- 2007-12-19 JP JP2009541877A patent/JP5637687B2/ja active Active
- 2007-12-19 US US12/519,458 patent/US8569438B2/en active Active
- 2007-12-19 ES ES07856913T patent/ES2409182T3/es active Active
- 2007-12-19 MX MX2009005536A patent/MX2009005536A/es active IP Right Grant
- 2007-12-19 RU RU2009127635/04A patent/RU2467026C2/ru active
- 2007-12-19 EP EP07856915A patent/EP2102263B1/de not_active Revoked
- 2007-12-19 CN CN2007800467267A patent/CN101563382B/zh active Active
- 2007-12-19 RU RU2009127638/04A patent/RU2467027C2/ru active
- 2007-12-19 CA CA2671516A patent/CA2671516C/en active Active
- 2007-12-19 PL PL07856915T patent/PL2102263T3/pl unknown
- 2007-12-19 EP EP07856913A patent/EP2091987B1/de not_active Revoked
- 2007-12-19 CN CN2007800466781A patent/CN101568565B/zh active Active
- 2007-12-19 WO PCT/EP2007/011191 patent/WO2008074490A1/de active Application Filing
- 2007-12-19 EP EP07856914A patent/EP2091988B1/de not_active Revoked
- 2007-12-19 US US12/519,466 patent/US20100015344A1/en not_active Abandoned
- 2007-12-19 BR BRPI0721292-5A2A patent/BRPI0721292A2/pt not_active IP Right Cessation
- 2007-12-19 RU RU2009127640/04A patent/RU2467028C2/ru not_active IP Right Cessation
- 2007-12-19 JP JP2009541878A patent/JP2010513617A/ja active Pending
-
2013
- 2013-09-25 US US14/036,367 patent/US20140023789A1/en not_active Abandoned
Patent Citations (54)
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 |
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)
Title |
---|
International Preliminary Report on Patentability for PCT/EP2007/011191, 07 July 2009, 14 pgs. * |
Cited By (46)
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 |
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 |
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 |
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 |
US8569438B2 (en) | 2006-12-19 | 2013-10-29 | Basf Coatings Gmbh | 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 |
US20100143596A1 (en) * | 2006-12-19 | 2010-06-10 | Basf Coatings Ag | 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 |
US20100120952A1 (en) * | 2007-03-23 | 2010-05-13 | Basf Coatings Ag | Phosphonate containing two-component coating system and the production and use thereof |
US8138249B2 (en) | 2007-03-23 | 2012-03-20 | Basf Coatings Japan Ltd. | Phosphonate-containing two-component coating system and the production and use thereof |
US8679589B2 (en) | 2007-12-19 | 2014-03-25 | Basf Coatings Gmbh | Coating agent having high scratch resistance and high weathering resistance |
US8808805B2 (en) | 2007-12-19 | 2014-08-19 | Basf Coatings Gmbh | Coating agent with high scratch resistance and weathering resistance |
US20110027489A1 (en) * | 2007-12-19 | 2011-02-03 | Basf Coatings Gmbh | Coating agent having high scratch resistance and high weathering resistance |
US9090732B2 (en) | 2007-12-19 | 2015-07-28 | 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 |
US20110059251A1 (en) * | 2007-12-19 | 2011-03-10 | Basf Coatings Gmbh | Coating composition having a high scratch resistance and weathering stability |
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 |
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 |
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 |
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 |
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 |
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 |
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 |
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 |
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 |
US9249050B2 (en) | 2011-10-10 | 2016-02-02 | Cytonix, Llc | Low surface energy touch screens, coatings, and methods |
US9035082B2 (en) | 2011-10-10 | 2015-05-19 | 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 |
WO2014016019A1 (de) * | 2012-07-25 | 2014-01-30 | Basf Coatings Gmbh | Polyurethan-beschichtungsmittelzusammensetzung, mehrstufige beschichtungsverfahren |
US9644111B2 (en) | 2012-07-25 | 2017-05-09 | Basf Coatings Gmbh | Polyurethane coating material composition, multi-stage coating methods |
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 |
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 |
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 |
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 |
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 |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8569438B2 (en) | Coating agents having high scratch resistance and weathering stability | |
US8679589B2 (en) | Coating agent having high scratch resistance and high weathering resistance | |
US9090732B2 (en) | Coating composition having a high scratch resistance and weathering stability | |
US8808805B2 (en) | Coating agent with high scratch resistance and weathering resistance | |
US9017818B2 (en) | 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 | |
US8486539B2 (en) | Coating compositions and coatings produced from them with high scratch resistance, weathering stability, and good optical properties | |
US9777190B2 (en) | Aqueous polyurethane coating material and coatings produced therefrom and having high scratch resistance and good chemicals resistance | |
AU2011244543A1 (en) | Coating materials with high solids content and good levelling, multi-coat paint systems produced therefrom and use thereof | |
US9266995B2 (en) | Binding agent mixture, coating agents containing said binding agent mixture, and coatings produced from said coating agents, said coatings having a high scratch resistance, high weathering stability, and good optical properties |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BASF COATINGS AG,GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GROENEWOLT, MATTHIJS;POPPE, ANDREAS;KLEIN, GUENTER;AND OTHERS;SIGNING DATES FROM 20090602 TO 20090618;REEL/FRAME:023259/0875 |
|
AS | Assignment |
Owner name: BASF COATINGS GMBH, GERMANY Free format text: CHANGE OF NAME;ASSIGNORS:GROENEWOLT, MATTHIJS;POPPE, ANDREAS;KLEIN, GUENTER;AND OTHERS;SIGNING DATES FROM 20090602 TO 20090618;REEL/FRAME:028642/0378 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |