WO2000055229A1 - High solids acid etch resistant clear coating composition - Google Patents
High solids acid etch resistant clear coating composition Download PDFInfo
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- WO2000055229A1 WO2000055229A1 PCT/US2000/006963 US0006963W WO0055229A1 WO 2000055229 A1 WO2000055229 A1 WO 2000055229A1 US 0006963 W US0006963 W US 0006963W WO 0055229 A1 WO0055229 A1 WO 0055229A1
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- silane
- melamine
- isocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4261—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups prepared by oxyalkylation of polyesterpolyols
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4291—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from polyester forming components containing monoepoxy compounds
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
- C08G18/58—Epoxy resins
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- 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
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- 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
- C08G18/6295—Polymers of silicium containing compounds having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- 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
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention generally relates to high solids, low VOC (volatile organic component) coating compositions and more particularly to low VOC clear coating compositions suited for multi-layered coatings used in automotive OEM and refinish applications.
- VOC volatile organic component
- Basecoat-clearcoat systems have found wide acceptance in the automotive finishes market. Continuing effort has been directed to improve the overall appearance, the clarity of the topcoat, and the resistance to deterioration of these coating systems at ever-higher application solids levels. Further effort has also been directed to the development of coating compositions having low VOC. A continuing need still exists for clear coating formulations having an outstanding balance of performance characteristics after application, particularly gloss and distinctness of image (DOI) at high solids levels.
- DOI gloss and distinctness of image
- Melamine/acrylic polyol crosslinked or melamine self-condensed coatings may provide coatings having acceptable mar but such coatings have poor acid etch resistance and decreased appearance at higher solids levels.
- isocyanate/acrylic polyol based 2K urethane coatings generally provide acceptable acid-etch resistance but such coatings have poor mar resistance. Therefore, a need still exists for coatings that not only provide acceptable mar and acid-etch resistance but also high gloss and DOI at the lowest VOC possible.
- the present invention is directed to a clear coating composition comprising isocyanate, silane and melamine components wherein said isocyanate component comprises an aliphatic polyisocyanate having on an average 2 to 6 isocyanate functionalities.
- the present invention is also directed to a method of producing a clear coating on a substrate comprising: applying a layer of a clear coating composition comprising isocyanate, silane and melamine components wherein said isocyanate component comprises an aliphatic polyisocyanate having on an average 2 to 6 isocyanate functionalities; and curing said layer into said clear coating.
- One of the advantages of the present invention is its low VOC, which is below the current guidelines of Environment Protection Agency (EPA) of the United States.
- Another advantage is the mar and etch resistance and hardness of the coating resulting from the coating composition of the present invention.
- thermo-pack coating composition means a thermoset coating composition comprising two components stored in separate containers. These containers are typically sealed to increase the shelf life of the components of the coating composition. The components are mixed prior to use to form a pot mix. The pot mix has a limited pot life typically a few minutes (15 minutes to 45 minutes) to a few hours (4 hours to 6 hours). The pot mix is applied as a layer of desired thickness on a substrate surface, such as an autobody. After application, the layer is cured under ambient conditions or bake cured at elevated temperatures to form a coating on the substrate surface having desired coating properties, such as high gloss, mar-resistance and resistance to environmental etching.
- thermoset coating composition means a thermoset coating composition comprising two components that are stored in the same container. However, one component is blocked to prevent premature crosslinking. After the application of the one-pack coating composition on a substrate, the layer is typically exposed to elevated temperatures to unmask the blocked component. Thereafter, the layer is bake-cured at elevated temperatures to form a coating on the substrate surface having desired coating properties, such as high gloss, mar- resistance and resistance to environmental etching.
- Low VOC coating composition means a coating composition that includes in the range of from 0 to 0.472 kilogram of organic solvent per liter (4 pounds per gallon), preferably in the range of from 0.118 (1 pound per gallon) to 0.178 kilogram of organic solvent per liter (1.5 pounds per gallon) of the composition, as determined under the procedure provided in ASTM D3960.
- High solids composition means a coating composition having a solid component in the range of from 65 to 100 percent and preferably greater than 70 percent, all in weight percentages based on the total weight of the composition.
- “Clear coating composition” means a clear coating composition that produces upon cure, a clear coating having DOI (distinctness of image) rating of more than 80 and 20° gloss rating of more than 80.
- GPC weight average molecular weight and GC number average molecular weight means a weight average molecular weight and a weight average molecular weight, respectively measured by utilizing gel permeation chromatography.
- HPLC high performance liquid chromatograph
- Polymer particle size means the diameter of the polymer particles measured by using a Brookhaven Model BI-90 Particle Sizer supplied by Brookhaven Instruments Corporation, Holtsville, N.Y.
- the sizer employs a quasi- elastic light, scattering technique to measure the size of the polymer particles.
- the intensity of the scattering is a function of particle size.
- the diameter based on an intensity weighted average is used. This technique is described in Chapter 3, pages 48-61, entitled Uses and Abuses of Photon Correlation Spectroscopy in Particle Sizing by Weiner et al. 1987 edition of American Chemical Society Symposium series.
- Polymer solids or “composition solids” means a polymer or composition in its dry state.
- Aliphatic as employed herein includes aliphatic and cycloaliphatic materials.
- Crosslinkable means that the individual components of an adduct contain functionalities which react within the composition of the invention to give a coating of good appearance, durability, hardness and mar resistance.
- Acid etch resistance refers to the resistance provided by a coated surface against chemical etching action by the environment, such as for example acid rain.
- Mar resistance refers to the resistance provided by coating to mechanical abrasions, such as, for example, the abrasion of a coated surface, such as an automotive body, that typically occurs during washing and cleaning of the coated surface.
- Applicants have unexpectedly discovered that contrary to conventional approaches used in typical thermoset coating compositions, i.e., those involving polymers and crosslinking components, a very viable route lies in a combination of what would traditionally be considered as crosslinking agents for producing a unique low VOC high solids clear coating composition that produces coatings having superior coating properties, such as clarity, and mar and etch resistance.
- Applicants have further unexpectedly discovered that by including a silane component in a clear coating composition, the solids level can be further increased without sacrificing the etch and mar resistance, gloss, DOI, and other desired coating properties. It is believed that the silane component acts as a substitute for a solvent typically used in a coating composition and reacts upon cure to generate a stable and durable crosslinking structure.
- the clear coating composition includes isocyanate, silane and melamine components.
- the isocyanate component includes an aliphatic polyisocyanate having on an average 2 to 6, preferably 2.5 to 6 and more preferably 3 to 4 isocyanate functionalities.
- the coating composition includes in the range of from 35 percent to 70 percent, preferably in the range of from 40 percent to 60 percent, and most preferably in the range of 45 percent to 55 percent of the aliphatic polyisocyanate, the percentages being in weight percentages based on the total weight of composition solids.
- Suitable aliphatic polyisocyanates include aliphatic or cycloaliphatic di-, tri- or tetra-isocyanates, which may or may not be ethylenically unsaturated, such as 1,2-propylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 2,3-butylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, dodecamethylene diisocyanate, omega -dipropyl ether diisocyanate, 1,3-cyclopentane diisocyanate, 1 ,2-cyclohexane diisocyanate, 1 ,4-cyclohexane diisocyanate, isophorone diisocyanate, 4-methyl- 1 ,3-diisocyan
- Aromatic polyisocyanates are not suitable for use in the present invention as the clear coatings resulting therefrom are too light sensitive and tend to yellow with age and crack upon long term exposure to sunlight. As a result such clear coatings are not durable.
- the isocyanate functionalities of the polymeric isocyanate may be capped with a monomeric alcohol to prevent premature crosslinking in a one-pack composition.
- suitable monomeric alcohols include methanol, ethanol, propanol, butanol, isopropanol, isobutanol, hexanol, 2-ethylhexanol and cyclohexanol.
- the melamine component of the coating composition includes suitable monomeric or polymeric melamines or a combination thereof. Alkoxy monomeric melamines are preferred.
- the coating composition includes in the range of from 10 percent to 40 percent, preferably in the range of from 15 percent to 35 percent, and most preferably in the range of from of 20 percent to 30 percent of the melamine, the percentages being in weight percentages based on the total weight of composition solids.
- alkoxy monomeric melamine means a low molecular weight melamine which contains, on an average three or more methylol groups etherized with a d to 5 monohydric alcohol such as methanol, n-butanol, or isobutanol per triazine nucleus, and has an average degree of condensation up to about 2 and preferably in the range of about 1.1 to about 1.8, and has a proportion of mononuclear species not less than about 50 percent by weight.
- the polymeric melamines have an average degree of condensation of more than 1.9
- Suitable monomeric melamines include highly alkylated melamines, such as methylated, butylated, isobutylated melamines and mixtures thereof. More particularly hexamethylol melamine, trimethylol melamine, partially methylated hexamethylol melamine, and pentamethoxymethyl melamine are preferred. Hexamethylol melamine and partially methylated hexamethylol melamine are more preferred and hexamethylol melamine is most preferred. Many of these suitable monomeric melamines are supplied commercially.
- Cytec Industries Inc. West Patterson, New Jersey supplies Cymel ® 301 (degree of polymerization of 1.5, 95% methyl and 5% methylol), Cymel ® 350 (degree of polymerization of 1.6, 84% methyl and 16% methylol), 303, 325, 327 and 370, which are all monomeric melamines.
- Suitable polymeric melamines include high amino (partially alkylated, -N, -H) melamine known as ResimeneTM BMP5503 (molecular weight 690, polydispersity of 1.98, 56% buytl, 44 % amino), which is supplied by Solutia Inc., St.
- Cytec Industries Inc. also supplies Cymel ® 1130 @ 80 percent solids (degree of polymerization of 2.5), Cymel ® 1133 (48% methyl, 4 % methylol and 48 % butyl), both of which are polymeric melamines.
- the coating composition preferably includes one or more catalysts to enhance crosslinking of the components on curing.
- the coating composition includes in the range of from 0.1 percent to 5 percent, preferably in the range of from 0.1 to 2 percent, more preferably in the range of from 0.5 percent to 2 percent and most preferably in the range of from 0.5 percent to 1.2 percent of the catalyst, the percentages being in weight percentages based on the total weight of composition solids .
- the suitable catalysts include the conventional acid catalysts, such as aromatic sulfonic acids, for example dodecylbenzene sulfonic acid, para- toluenesulfonic acid and dinonylnaphthalene sulfonic acid, all of which are either unblocked or blocked with an amine, such as dimethyl oxazolidine and 2-amino- 2-methyl- 1 -propanol, n,n-dimethylethanolamine or a combination thereof.
- Other acid catalysts that can be used are strong acids, such as phosphoric acids, more particularly phenyl acid phosphate, which may be unblocked or blocked with an amine.
- the coating composition preferably includes a small amount of one or more organo tin catalysts, such as dibutyl tin dilaurate, dibutyl tin diacetate, stannous octate, and dibutyl tin oxide.
- organo tin catalysts such as dibutyl tin dilaurate, dibutyl tin diacetate, stannous octate, and dibutyl tin oxide.
- Dibutyl tin dilaurate is preferred.
- the amount of organo tin catalyst added generally ranges from 0.001 percent to 0.5 percent, preferably from 0.05 percent to 0.2 percent and more preferably from 0.1 percent to 0.15 percent, the percentages being in weight percentages based on the total weight of composition solids.
- the silane component of the coating composition generally includes a polymer provided with at least one reactive silane group.
- the coating composition includes in the range of from 5 percent to 45 percent, preferably in the range of from 10 percent to 40 percent, and most preferably in the range of from of 15 percent to 35 percent of the silane component, the percentages being in weight percentages based on the total weight of composition solids.
- the silane polymers suitable for use in the present invention have weight average molecular weight in the range of about 100 to 30,000, preferably in the range of about 120 to 25,000 and more preferably in the range of about 150 to 7,500. All molecular weights disclosed herein are determined by gel permeation chromatography using a polystyrene standard.
- the silane polymer suitable herein is a polymerization product of about 30 to 95%, preferably 40 to 60%, by weight of ethylenically unsaturated non-silane containing monomers and about 5 to 70%, preferably 40 to 60%, by weight of ethylenically unsaturated silane containing monomers, based on the weight of the silane polymer.
- Suitable ethylenically unsaturated non-silane containing monomers are alkyl acrylates, alkyl methacrylates and any mixtures thereof, where the alkyl groups have 1 to 12 carbon atoms, preferably 3 to 8 carbon atoms.
- Suitable alkyl methacrylate monomers used to form the silane polymer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, and lauryl methacrylate.
- suitable alkyl acrylate momomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, and lauryl acrylate.
- Cycloaliphatic methacrylates and acrylates also can be used, for example, such as trimethylcyclohlexyl methacrylate, trimethylcyclohexl acrylate, iso-butyl methacrylate, t-butyl cyclohexyl acrylate, or t-butyl cyclohexyl methacrylate.
- Aryl acrylate and aryl methacrylates such as, for example, benzyl acrylate and benzyl methacrylate can be also used. It is understood that combinations of the foregoing monomers are also suitable.
- alkyl acrylates or methacrylates other polymerizable non-silane-containing monomers, up to about 50% by weight of the polymer, can be used in the silane polymer for the purpose of achieving the desired properties such as hardness, appearance, and mar resistance.
- exemplary of such other monomers are styrene, methyl styrene, acrylamide, acrylonitrile and methacrylonitrile.
- Styrene may be used in the range of 0 to 50%, preferably 5% to 30% by weight of the silane polymer.
- a suitable silane containing monomer useful in forming the silane polymer is an alkoxysilane having the following structural formula:
- H 2 C — COCH 2 — (CH 2 ) n CH 2 — Si OR
- R is either CH 3 , CH 3 CH 2 , CH 3 O, or CH 3 CH 2 O;
- Rj and R 2 are CH 3 or CH 3 CH ;
- R 3 is either H, CH 3 , or CH CH 2 ;
- n is 0 or a positive integer from 1 to 10, preferably from 1 to 4.
- R is CH 3 O or CH 3 CH 2 O and n is l.
- alkoxysilanes are the acrylatoalkoxy silanes, such as gamma-acryloxypropyltrimethoxy silane and the methacrylatoalkoxy silanes, such as gamma-methacryloxypropyltrimethoxy silane, and gamma-methacryloxypropyltris(2-methoxyethoxy) silane.
- H 2 CH— (CH 2 ) ⁇ CH 2 — Si OR
- R, Ri and R are as described above and n is a positive integer from 1 to 10, preferably from 1 to 4.
- alkoxysilanes are the vinylalkoxy silanes, such as vinyltrimethoxy silane, vinyltriethoxy silane and vinyltris(2- methoxyethoxy) silane.
- silane containing monomers are acyloxysilanes, including acrylatoxy silane, methacrylatoxy silane and vinylacetoxy silanes, such as vinylmethyldiacetoxy silane, acrylatopropyltriacetoxy silane, and methacrylatopropyltriacetoxy silane. It is understood that combinations of the above-mentioned silane containing monomers are also suitable.
- one particular example of a silane polymer useful in the coating composition of this invention may contain the following constituents: about 15 to 25% by weight styrene, about 30 to 60% by weight methacryloxypropyltrimethoxy silane, and about 25 to 50% by weight trimethylcyclohexyl methacrylate.
- One preferred silane polymer contains about 30% by weight styrene, about 50% by weight methacryloxypropyl trimethoxy silane, and about 20% by weight of nonfunctional acrylates or methacrylates such as trimethylcyclohexyl methacrylate, butyl acrylate, and iso-butyl methacrylate and any mixtures thereof.
- Silane functional macromonomers also can be used in forming the silane polymer.
- These macromonomers are the reaction product of a silane containing compound, having a reactive group such as epoxide or isocyanate, with an ethylenically unsaturated non-silane containing monomer having a reactive group, typically a hydroxyl or an epoxide group, that is co-reactive with the silane monomer.
- An example of a useful macromonomer is the reaction product of a hydroxy functional ethylenically unsaturated monomer such as a hydroxyalkyl acrylate or methacrylate having 1 to 4, preferably 2 to 3 carbon atoms in the alkyl group and an isocyanatoalkyl alkoxysilane such as isocyanatopropyl triethoxysilane.
- a hydroxy functional ethylenically unsaturated monomer such as a hydroxyalkyl acrylate or methacrylate having 1 to 4, preferably 2 to 3 carbon atoms in the alkyl group and an isocyanatoalkyl alkoxysilane such as isocyanatopropyl triethoxysilane.
- silane functional macromonomers are those having the following structural formula:
- H 2 C C O R 3 OCN— (CH 2 ) n Si OR
- R, R 1? and R 2 are as described above; t is H or CH 3 , R 3 is an alkylene group having 1 to 8, preferably 1 to 4 carbon atoms and n is a positive integer from 1 to 8, preferably from 1 to 4.
- the coating composition of the present invention which is formulated into high solids coating systems further contains at least one organic solvent typically selected from the group consisting of aromatic hydrocarbons such as petroleum naphtha or xylenes; ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone or acetone; esters such as butyl acetate or hexyl acetate; and glycol ether esters, such as propylene glycol monomethyl ether acetate.
- the amount of organic solvent added depends upon the desired solids level as well as the desired amount of VOC of the composition. If desired, the organic solvent may be added to both components of the binder.
- the coating composition of the present invention may also contain conventional additives such as stabilizers, and rheology control agents, flow agents, and toughening agents. Such additional additives will, of course, depend on the intended use of the coating composition. Any additives that would adversely effect the clarity of the cured coating will not be included as the composition is used as a clear coating. The foregoing additives may be added to either component or both, depending upon the intended use of the coating composition.
- the clear coating composition of the present invention may be supplied in the form of a two-pack coating composition in which the first-pack includes the polyisocyanate component and the second-pack includes the melamine component.
- the first and the second pack are stored in separate containers and mixed before use.
- the containers are preferably sealed air tight to prevent degradation during storage.
- the mixing may be done, for example, in a mixing nozzle or in a container.
- both the components of the coating composition can be stored in the same container in the form of a one-pack coating composition.
- an ultraviolet light stabilizer or a combination of ultraviolet light stabilizers and absorbers may be added.
- These stabilizers include ultraviolet light absorbers, screeners, quenchers and specific hindered amine light stabilizers.
- an antioxidant can be added.
- Typical ultraviolet light stabilizers that are useful include benzophenones, such as hydroxydodecyclbenzo-phenone, 2,4- dihydroxybenzophenone; triazoles, such as 2-phenyl-4-(2'-4'- dihydroxybenzoyl)triazoles; and triazines, such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine and triazoles such as 2-(benzotriazole-2-yl)-4,6- bis(methylethyl- 1 -phenyl ethyl)phenol, 2-(3-hydroxy-3 ,5 '-di-tert amyl phenyl) benzotriazole, 2-(3 ' ,5 ' -bis( 1 , 1 -dimethylpropyl)-2 ' -hydroxyphenyl)-2H- benzotriazole, benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(l,l- dimethylethy
- Typical hindered amine light stabilizers are bis(2,2,6,6- tetramethylpiperidinyl)sebacate, bis(N-methyl-2,2,6,6- tetramethylpiperidinyl)sebacate and bis(N-octyloxy-2,2,6,6- tetramethylpiperidynyl)sebacate.
- One of the useful blends of ultraviolet light absorbers and hindered amine light stabilizers is bis(N-octyloxy-2,2,6,6- tetramethylpiperidynyl)sebacate and benzenepropanoic acid, 3-(2H-benzotriazol- 2-yl)-5-(l,l-dimethylethyl)-4-hydroxy-,C7-9-branched alkyl esters.
- Another useful blend of ultraviolet light absorbers and hindered amine light stabilizers is 2- (3 ' , 5 ' -bis( 1 -methyl- 1 -phenylethyl)-2 ' -hydroxypheny l)benzotriazole and decanedioc acid,bis(2,2,6,6,-tetramethyl-4-piperidinyl)ester both supplied by Ciba Specialty Chemicals, Tarrytown, New York under the trademark Tinuvin ® 900 and Tinuvin ® 123, respectively.
- the coating composition of the present invention optionally contains in the range of from 0.1 percent to 40 percent, preferably in the range of from 5 percent to 35 percent, and more preferably in the range of from 10 percent to 30 percent of a flow modifying resin, such as a non-aqueous dispersion (NAD), all percentages being based on the total weight of composition solids.
- a flow modifying resin such as a non-aqueous dispersion (NAD)
- NAD non-aqueous dispersion
- the weight average molecular weight of the flow modifying resin generally varies in the range of from 20,000 to 100,000, preferably in the range of from 25,000 to 80,000 and more preferably in the range from 30,000 to 50,000.
- the non-aqueous dispersion-type resin is prepared by dispersion- polymerizing at least one vinyl monomer in the presence of a polymer dispersion stabilizer and an organic solvent.
- the polymer dispersion stabilizer may be any of the known stabilizers used commonly in the field of non-aqueous dispersions, and may include the following substances (1) through (9) as examples:
- a hydroxy-containing acrylic copolymer prepared by copolymerizing at least 20 percent by weight of (meth)acrylic ester of a monohydric alcohol containing 4 or more carbon atoms.
- An acrylic copolymer obtainable by producing at least 0.3 double bond per molecule based on its number average molecular weight, into the copolymer mentioned under (4).
- a method for introducing double bonds may, for example, comprise copolymerizing the acrylic polymer with a small amount of glycidyl (meth)acrylate and then adding (meth)acrylic acid to the glycidyl group.
- An alkyd resin with an oil length not less than 15 percent and/or a resin obtainable by introducing polymerizable double bonds into the alkyd resin may, for example, comprise addition reaction of glycidyl (meth)acrylate to the carboxyl groups in the alkyd resin.
- An exemplary method of introducing double bonds comprises addition reaction of isocyanatoethyl methacrylate to cellulose acetate butyrate.
- the acrylic copolymers mentioned under (4) and (5) are desirable in that they not only lend themselves well to adjustment of molecular weight, glass transition temperature, polarity (polymer SP value), hydroxyl value, acid value and other parameters but are excellent in weatherability. More desirable are acrylic copolymers containing an average of about 0.2 to about 1.2 polymerizable double bonds, per molecule, which are graft copolymerized with dispersed particles.
- the non-aqueous dispersion-type resin used in accordance with this invention can be easily prepared by dispersion-polymerizing at least one vinyl monomer in the presence of the aforedescribed polymer dispersion stabilizer and an organic solvent, which mainly contains an aliphatic hydrocarbon.
- the dispersion stabilizer and the vinyl monomer are soluble in the organic solvent.
- the polymer particles formed by the vinyl monomer are not soluble in the solvent.
- the monomer component forming the acrylic copolymer suitable as the polymer dispersion stabilizer and the vinyl monomer forming the dispersed particles may be virtually any radical-polymerizable unsaturated monomer.
- a variety of monomers can be utilized for the purpose. Typical examples of such monomers include the following.
- Cj-is alkyl esters of acrylic or methacrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, and stearyl methacrylate; glycidyl acrylate and glycidyl methacrylate; C 2 - 8 alkenyl esters of acrylic or methacrylic acid, such as allyl acrylate, and allyl methacrylate; C 2 - 8 hydroxyalkyl esters of acrylic or methacrylic acid, such
- (b) Ninyl aromatic compounds, such as, for example, styrene, ⁇ - methylstyrene, vinyltoluene, p-chlorostyrene, and vinylpyridine.
- (c) ⁇ , ⁇ -Ethylenically unsaturated acids, such as, for example, acrylic acid, methacrylic acid, itaconic acid and crotonic acid
- (d) -Amides of acrylic or methacrylic acid such as, for example, acrylamide, methacrylamide, n-butoxymethylacrylamide, N-methylolacrylamide, n-butoxymethylmethacrylamide, and N-methylolmethacrylamide.
- the following materials can be used with particular advantage for the preparation of the acrylic copolymer used as a dispersion stabilizer:
- the dispersion stabilizer may be one prepared by adding glycidyl (meth)acrylate or isocyanatoethyl methacrylate to a copolymer of the monomers for introduction of polymerizable double bonds.
- the acrylic copolymer used as the dispersion stabilizer can be easily prepared using a radical polymerization initiator in accordance with the known solution polymerization process.
- the number average molecular weight of the dispersion stabilizer is preferably in the range of about 1,000 to about 50,000 and, for still better results, about 3,000 to about 20,000.
- particularly preferred vinyl monomers for the formation of the dispersed polymer particles predominantly contain comparatively high-polarity monomers, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and acrylonitrile, supplemented as necessary with (meth)-acrylic acid, and 2-hydroxyethyl (meth)acrylate.
- gel particles as cross-linked in molecules by copolymerizing a small amount of polyfunctional monomers, such as divinylbenzene, and ethylene glycol dimethacrylate, by copolymerizing a plurality of monomers having mutually reactive functional groups, such as glycidyl methacrylate and methacrylic acid, or by copolymerizing an auto-reactive monomer, such as N- alkoxymethylated acrylamides, and ⁇ -methacryloyloxypropyl trimethoxy silanes.
- polyfunctional monomers such as divinylbenzene, and ethylene glycol dimethacrylate
- an auto-reactive monomer such as N- alkoxymethylated acrylamides, and ⁇ -methacryloyloxypropyl trimethoxy silanes.
- the ratio of the dispersion stabilizer to the vinyl monomer forming dispersed particles is selected from the range of about 5/95 to about 80/20 by weight, preferably about 10/90 to about 60/40 by weight, and the dispersion polymerization can be conducted in the presence of a radical polymerization initiator by a known procedure.
- particle size of the resulting non-aqueous dispersion type acrylic resin is generally in the range of about 0.05 ⁇ m to about 2 ⁇ m, the range of about 0.1 ⁇ m to about 0.7 ⁇ m is preferable from the stability of shelf life and the gloss, smoothness and weatherability of the film.
- the first-pack of the two-pack coating composition containing the polyisocyanate and the second-pack containing the melamine and silane component are mixed just prior to use or about 5 to 30 minutes before use to form a pot mix, which has limited pot life of about 10 minutes to about 6 hours.
- a layer of the pot mix is typically applied to a substrate by conventional techniques, such as spraying, electrostatic spraying, roller coating, dipping or brushing.
- a clear coat layer having a thickness in the range of from 25 micrometers to 75 micrometers is applied over a metal substrate, such as automotive body, which is often pre-coated with other coating layers, such as an electrocoat, primer and a basecoat.
- the two pack coating composition may be baked upon application for about 60 to 10 minutes at about 80°C to 160°C.
- the one-pack coating composition containing the blocked polyisocyanate When the one-pack coating composition containing the blocked polyisocyanate is used, a layer thereof applied over a substrate using aforedescribed application techniques, is cured at a baking temperature in the range of from 80°C to 200°C, preferably in the range of 80°C to 160°C, for about 60 to 10 minutes. It is understood that actual baking temperature would vary depending upon the catalyst and the amount thereof, thickness of the layer being cured and the blocked isocyanate functionalities and the melamine utilized in the coating composition. The use of the foregoing baking step is particularly useful under OEM (Original Equipment Manufacture) conditions.
- the clear coating composition of the present invention is suitable for providing clear coatings on variety of substrates, such as metal, wood and concrete substrates.
- the present composition is especially suitable for providing clear coatings in automotive OEM or refinish applications. These compositions are also suitable as clear coatings in industrial and maintenance coating applications.
- Silane Polymer 1 In a flask fitted with a mixer and a condenser, 158 parts of aliphatic solvent were heated to reflux. A mixture of 140 parts of styrene, 140 parts of isobornyl methacrylate, 304 parts of methacryloxypropylrimethoxysilane (UCARSIL ® A-174 by Witco), 82 parts of aliphatic solvent and 16 parts of tertiary butyl peracetate were added over a period of 240 minutes. The reaction mixture was held for 1 hour to yield a polymer containing methacryloxypropylrimethoxysilane. Silane Polymer 2 (Silane functional Polyurethane Polymer)
- Aromatic 100 solvent 1035.7 parts of Aromatic 100 solvent, 206.48 parts of propylene carbonate (supplied by Huntsman Corporation, Austin, Texas), and 340.2 parts aminopropyl trimethoxy silane (supplied by OSI Corporation, Tarrytown, New York) were charged.
- the reaction mixture was heated under agitation to 120°C, held 4 hours and then cooled to 100°C.
- a shot of 570.49 parts of cyclohexanol supplied by Aldrich Chemical Company, Milwaukee, Wisconsin
- 40 parts of Aromatic 100 solvent 0.3 parts of dibutyltin dilaurate catalyst (supplied by Air Products, AUentown, Pennsylvania) was added.
- Cymel® 1168 methylated butylated melamine from Cytec Industries Inc., West Patterson, New York
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Abstract
Description
Claims
Priority Applications (11)
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KR1020017011745A KR20020007330A (en) | 1999-03-17 | 2000-03-16 | High solids acid etch resistant clear coating composition |
AU37532/00A AU772837B2 (en) | 1999-03-17 | 2000-03-16 | High solids acid etch resistant clear coating composition |
CA 2361299 CA2361299A1 (en) | 1999-03-17 | 2000-03-16 | High solids acid etch resistant clear coating composition |
NZ51336300A NZ513363A (en) | 1999-03-17 | 2000-03-16 | High solids acid etch resistant clear coating composition |
BR0010514A BR0010514A (en) | 1999-03-17 | 2000-03-16 | Composition of transparent coating of high solids content resistant to acid corrosion and method of producing a transparent coating on a substrate |
US09/913,054 US6607833B1 (en) | 1999-03-17 | 2000-03-16 | High solids acid etch resistant clear coating composition |
DE2000616906 DE60016906T2 (en) | 1999-03-17 | 2000-03-16 | ACID-RESISTANT CLEAR LACQUER COMPOSITION WITH HIGH SOLIDS CONTENT |
JP2000605654A JP2002539305A (en) | 1999-03-17 | 2000-03-16 | High solids acid corrosion resistant transparent coating composition |
DK00916425T DK1171498T3 (en) | 2000-03-16 | 2000-03-16 | Acid-resistant clear coating composition with high solids content |
EP20000916425 EP1171498B1 (en) | 1999-03-17 | 2000-03-16 | High solids acid etch resistant clear coating composition |
AT00916425T ATE285424T1 (en) | 1999-03-17 | 2000-03-16 | ACID-RESISTANT CLEAR COAT COMPOSITION WITH HIGH SOLIDS CONTENT |
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US (1) | US6607833B1 (en) |
EP (1) | EP1171498B1 (en) |
JP (1) | JP2002539305A (en) |
KR (1) | KR20020007330A (en) |
CN (1) | CN1165561C (en) |
AT (1) | ATE285424T1 (en) |
AU (1) | AU772837B2 (en) |
BR (1) | BR0010514A (en) |
CA (1) | CA2361299A1 (en) |
DE (1) | DE60016906T2 (en) |
ES (1) | ES2233354T3 (en) |
NZ (1) | NZ513363A (en) |
PT (1) | PT1171498E (en) |
WO (1) | WO2000055229A1 (en) |
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- 2000-03-16 CN CNB00805150XA patent/CN1165561C/en not_active Expired - Fee Related
- 2000-03-16 JP JP2000605654A patent/JP2002539305A/en active Pending
- 2000-03-16 NZ NZ51336300A patent/NZ513363A/en unknown
- 2000-03-16 AU AU37532/00A patent/AU772837B2/en not_active Ceased
- 2000-03-16 ES ES00916425T patent/ES2233354T3/en not_active Expired - Lifetime
- 2000-03-16 WO PCT/US2000/006963 patent/WO2000055229A1/en not_active Application Discontinuation
- 2000-03-16 US US09/913,054 patent/US6607833B1/en not_active Expired - Fee Related
- 2000-03-16 KR KR1020017011745A patent/KR20020007330A/en not_active Application Discontinuation
- 2000-03-16 EP EP20000916425 patent/EP1171498B1/en not_active Revoked
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WO2004014991A1 (en) * | 2002-08-07 | 2004-02-19 | E.I. Du Pont De Nemours And Company | One-pack primer sealer compositions for smc automotive body panels |
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Also Published As
Publication number | Publication date |
---|---|
US6607833B1 (en) | 2003-08-19 |
DE60016906T2 (en) | 2005-12-08 |
EP1171498A1 (en) | 2002-01-16 |
CN1165561C (en) | 2004-09-08 |
CN1370188A (en) | 2002-09-18 |
NZ513363A (en) | 2003-03-28 |
AU3753200A (en) | 2000-10-04 |
BR0010514A (en) | 2002-01-08 |
DE60016906D1 (en) | 2005-01-27 |
ATE285424T1 (en) | 2005-01-15 |
ES2233354T3 (en) | 2005-06-16 |
PT1171498E (en) | 2005-02-28 |
CA2361299A1 (en) | 2000-09-21 |
EP1171498B1 (en) | 2004-12-22 |
KR20020007330A (en) | 2002-01-26 |
JP2002539305A (en) | 2002-11-19 |
AU772837B2 (en) | 2004-05-06 |
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