EP1233992A1 - Compositions d'epoxy, d'isocyanate, et de melamine a teneur elevee en solides - Google Patents

Compositions d'epoxy, d'isocyanate, et de melamine a teneur elevee en solides

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Publication number
EP1233992A1
EP1233992A1 EP00918020A EP00918020A EP1233992A1 EP 1233992 A1 EP1233992 A1 EP 1233992A1 EP 00918020 A EP00918020 A EP 00918020A EP 00918020 A EP00918020 A EP 00918020A EP 1233992 A1 EP1233992 A1 EP 1233992A1
Authority
EP
European Patent Office
Prior art keywords
composition
weight percent
melamine
acid
epoxy compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00918020A
Other languages
German (de)
English (en)
Inventor
Isao Nagata
Peter William Uhlianuk
Donald A. White
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1233992A1 publication Critical patent/EP1233992A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G18/30—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
    • 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
    • C08G18/4009—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
    • 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
    • C08G18/4244—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
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • 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

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.
  • Basecoat-clearcoat systems have found wide acceptance in the past decade as automotive finishes. Continuing effort has been directed to such coating systems to improve the overall appearance, the clarity of the topcoat, and the resistance to deterioration. Further effort has been directed to the development of coating compositions having low volatile organic content (NOC).
  • NOC non volatile organic content
  • compositions used to form a protective coatings include those disclosed in U.S. Patent No. 4,533,716 (Okoshi et al.). These compositions are prepared using a triazine-type resin formed by a co-condensation reaction with formaldehyde, a polyol, and as required a monohydric alcohol.
  • the polyols used in the condensation reaction may be prepared by an esterification reaction between higher fatty acids and epoxy compounds having a number average molecular weight of 174 to 4,000.
  • the polyols used in the 4,533,716 invention do not include epoxy compounds.
  • the 4,533,716 coating compositions are disclosed to include a triazine- type resin and a polyisocianate.
  • the present invention is directed to a clear coating composition
  • a clear coating composition comprising isocyanate, melamine, and epoxy components wherein the 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 ,melamine, and epoxy components wherein the isocyanate component comprises an aliphatic polyisocyanate having on an average 2 to 6 isocyanate functionalities, and curing the layer into the clear coating.
  • One of the advantages of the present invention is its low VOC, significantly below the current guidelines of Environment Protection Agency (EPA) of the United States.
  • Another advantage is etch and mar resistance 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 potlife typically of minutes (5 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 cure-baked 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.
  • desired coating properties such as high gloss, mar-resistance and resistance to environmental etching.
  • Low NOC coating composition means a coating composition that includes less then 0.48 kilograms of organic solvent per liter (4 pounds per gallon) of the composition, as determined under the procedure provided in ASTM D3960.
  • High solids composition means a coating composition having 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) and 20° gloss of more than 70.
  • “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 the adduct contain functionality which react within the composition of the invention to give a coating of good appearance, durability, hardness and mar resistance.
  • Applicants have unexpectedly discovered that contrary to conventional approaches used in typical thermoset coating compositions, i.e., those involving a film forming polymer and crosslinking component, a very viable route lies in a combination of what would traditionally be considered crosslinking agents for producing a unique low NOC high solids clear coating composition which provides coatings with superior properties, such as mar and etch resistance.
  • the clear coating composition includes isocyanate, melamine, and epoxy 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 65 percent and more preferably in the range of from 45 percent to 60 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, dodecamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate, 1 ,4-cyclohexane diisocyanate, isophorone diisocyanate, 4-methy 1-1,3 - diisocyanatocyclohexane, trans-vinylidene diisocyanate, dicyclohexylmethane
  • the isocyanate funtionalities of the polymeric isocyanate may be capped with a monomeric alcohol, isopropanol or isobutanol to prevent premature crosslinking in a one-pack composition.
  • a monomeric alcohol include methanol, ethanol, propanol, butanol and hexanol.
  • blockers include lactams, oximes, malonic esters, alkylacetoacetates, triazoles, pyrazoles (e.g. dimethyl pyrazole), phenols and amines.
  • Compositions of the present invention include one or more melamine.
  • a melamine used in the present invention includes, in part, alkylated melamine-formaldehyde resin.
  • the alkylated melamine formaldehyde resin maybe partially or fully alkylated.
  • partially alkylated melamines Cymel 1158 Cymel 324, Cymen 327 (from Cytec Ind., from West Paterson, NJ), Resimine BM 9539 (from Solutia, Inc., St. Louis, Mo.) can be mentioned.
  • fully aklykated melamines Cymel 350, and Cymel 301 (from Cytec Co., from Cytec. Ind., West Paterson, NJ) and Resimine 764 (from Solutia Inc., St. Louis, Mo.) can be mentioned.
  • a composition of the present invention may comprise from about 10 weight percent to about 40 weight percent of a melamine, preferably from about 15 weight percent to 35 weight percent of a melamine.
  • compositions of the present invention include one or more oligomeric epoxy compounds, preferably containing at least two epoxy functionalities.
  • Suitable oligomeric epoxy compounds containing a hydroxy functionality or (OH) group used in the practice of the present invention include, among others, sorbitol polyglycidyl ether such as DCE 358 (form Dixie Chemical Co., Houston, TX), diglycerol polyglycidy ether such as Denacol EX 421 (from Nagase Cehmical Co., Hyogo, Japan), glycerol polyglycidyl ether such as Denacol Ex 313 and EX 314 (from Nagase Chemical Co., Hyogo, Japan), and triglycidyl tris(2-hydroxyethyl) isocyanurate such as Denacol EX 421 (from Nagase Chemical Co., Hyogo, Japan).
  • Suitable oligomeric epoxy compounds which typically do not contain significant hydroxy functionality used in the practice of the present invention include, among others, di- and polyglycidyl ethers of polycarboxylic acid and di- and polyglycidyl ester of acids such as Araldite CY 184 (from Ciba-Geigy, Brewster, N.Y.), cycloaliphatic epoxide such as ERL 4221 (from Union Carbide, Danbury, CT), and polyglycol diepoxide such as DER 736 (from Dow Chemical Co., Midland, MI).
  • a composition of the present invention comprises from about 10 weight percent to about 40 weight percent of an eopxy compound, preferably from about 15 weight percent to 35 weight percent of an epoxy compound.
  • the coating composition preferably includes one or more catalysts to enhance crosslinking of the components on curing.
  • a preferable catalyst is an organotin catalyst such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide, and dibutyltin bis(acetoacetate) in an amount of generally ranges from 0.001 percent to 1.0 percent, preferably from 0.01 percent to 0.5 percent and more preferably from 0.05 percent to 0.2 percent, the percentages being in weight percentages based on the total weight of composition solids.
  • organotin catalyst such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide, and dibutyltin bis(acetoacetate) in an amount of generally ranges from 0.001 percent to 1.0 percent, preferably from 0.01 percent to 0.5 percent and more preferably from 0.05 percent to 0.2 percent, the percentages being in weight percentages based on the total weight of composition solids.
  • the above coating composition can include other suitable catalysts, such as conventional acid catalysts, for example blocked or unblocked phosphoric acid and sulfonic acid in an amount ranging from 0.1 percent to 2 percent, preferably in the range of from 0.2 percent to 1.0 percent.
  • acid catalysts phenyl acid phosphate, butyl acid phosphate, octyl acid phosphate, dodecylbenzenesulfonic acid, para-toluenesulfonic acid and dinonylnaphthalene sulfonic acid, which are optionally blocked with amines such as dimethyl oxazolidine and 2-amino-2-methyl- 1 - propanol can be mentioned.
  • the coating composition of the present invention which is formulated into high solids coating systems may also contain 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.
  • 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
  • glycol ether esters such as propylene glycol monomethyl ether acetate.
  • the amount of organic solvent added depends
  • the amount of organic solvent used results in the composition having a VOC of less than 0.48 kilogram/liter (4 pounds per gallon), preferably in the range of 0.1 kilogram/liter to 0.4 kilogram/liter (1 pound to 3 pounds per gallon) of an organic solvent per liter of the composition.
  • 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. To improve weatherability of the clear finish of the coating composition, about 0.1-5%, by weight, based on the weight of the composition solids, of an ultraviolet light stabilizer or a combination of ultraviolet light stabilizers may be added.
  • UV light absorbers such as hydroxydodecyclbenzo-phenone, 2,4-dihydroxybenzophenone
  • triazoles such as 2- phenyl-4-(2'-4'-dihydroxybenzoyl)triazoles
  • triazines such as 3,5-dialkyl-4- hydroxyphenyl derivatives of triazine and triazoles such as 2-(benzotriazole-2-yl)- 4,6-bis(methylethyl-l -phenyl ethyl)phenol, 2-(3-hydroxy-3,5'-di-tert amyl phenyl) benzotriazole, 2-(3 ',5 '-bis( 1 , 1 -dimethylpropyl
  • 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.
  • Particularly useful blend 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 , 1 -dimethylethyl)-4-hydroxy-,C7-9-branched alkyl esters.
  • the coating composition of the present invention optionally contains, in the range of 0.5 weight percent to 15 weight percnt, preferably 1 weight percent to 10 weight percent of polyhydroxy functional compounds such as polycarbonate polyol (formula shown in the example), 2-ethyl-l,3-hexanediol, polycaprolactone triol, and the adduct of epsilon caprolactone and l,3,5-tris( 2-hydroxyethyl) cyanuric acid, all percentages being based on the total weight composition solids.
  • polyhydroxy functional compounds such as polycarbonate polyol (formula shown in the example), 2-ethyl-l,3-hexanediol, polycaprolactone triol, and the adduct of epsilon caprolactone and l,3,5-tris( 2-hydroxyethyl) cyanuric acid, all percentages being based on the total weight composition solids.
  • the coating composition of the present invention optionally contains in the range of from 0.5 percent to 30 percent, preferably in the range of from 1 percent to 20 percent, stabilized crossslinked polymer particles, non-aqueous dispersion (NAD) ( as described in detail in U.S. Patent 4,960,828), all percentages being based on the total weight of composition solids.
  • NAD non-aqueous dispersion
  • the clear coating composition of the present invention may be supplied in the form of a two-pack coating composition in which a first pack includes the polyisocyanate and a second-pack includes the melamine, epoxy compounds and other additives.
  • the first and the second pack are stored in separate containers and mixed before use.
  • the containers are preferrably sealed air tight to prevent reactions during storage.
  • the isocyanate funtionalities of the polyisocyanate are blocked, all components of the composition can be stored in the same containers in the form of a one-pack coating composition.
  • the first-pack of the two-pack coating composition containing the polyisocyanate and the second-pack containing the melamine, epoxy compounds, and other additiaves are mixed just prior to use for about 1 to 15 minutes before use to form a pot mix, which has limited pot life, in range of from 5 minutes to 6 hours, before it becomes too viscous to permit application through conventional application systems, such as spraying.
  • the first pack and the second pack are mixed together at the plural spray gun with or without electrostastics, before applied to a substrate.
  • the layer of the coating composition then cures under ambient conditions or preferably at higher temperatures in the range of 80-160°C for 10 minutes to 3 hours, preferably in the range of 20 minutes to 1 hour to form a coating on the substrate having the desired coating properties.
  • 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 10 to 60 minutes It is understtood that actual baking temperature would vary depending upon the catalyst and the amount thereof, thickness of the layer being cured, the blocked isocyanate functionalities and the melamine utilized in the coating composition.
  • the use of the foregoing baking step is particularly useful under Original Equipment Manufature (OEM) condition.
  • OEM Original Equipment Manufature
  • Part A was prepared by combining the following ingredients: 20 parts of ARALDITE CY 184; 25 parts of CYMEL 1158; 2.0 parts of TINUVIN 384; 1.5 parats of TINUVIN 292; 0.68 parts of a solution comprising 10 weight percent of BYK 301 in propylene monoetheyl ether acetate; 5.0 parts of a solution of 1 weight percent of dibutyltin dilaurate in butyl acetate; 0.67 parts of a solution of 75 weight percent of phenyl acid phosphate in butanol; 2.0 parts of PL1015, and 5.26 parts of 2- ethylhexyl acetate.
  • Protective Coating 2 was prepared as follows: Parts A was prepared by combining 22.0 parts of ARALDITE CY 184, 25.0 parts of CYMEL 1158, 2.0 parts of TINUVIN 384, 1.5 parts of TINUVIN 292, 0.68 parts of a solution of 10 weight percent of BYK 301 in propylene ethyl ether acetate, 5.0 parts of a solution of 1 weight percent dibutyltin dilaurate in butyl acetate, 0.67 parts of a solution of 75 weight percent of phenyl acid phosphate in butanol and 5.26 parts of 2-ethylhexyl acetate.
  • the above part A mixture was then combined with 54.7 parts of TOLONATE HDT-LV as a part B to form a clear composition.
  • the composition had a solid content of 85.6 weight percent, and a volatile organic compounds concentration of 1.29 lbs/gal. (0.15 Kg/liter).
  • composition was then sprayed over a conventional silver metallic waterborne basecoat which had been applied to the similar substrate as described in Example 1 and prebaked at 82°C for 10 minutes, and baked at 140°C for 30 minutes similar to Example 1.
  • the coating exhibited gloss 95, DOI 95 and Tukon hardness 11.3.
  • Protective Coating 3 was prepared as follows: Part A was prepared by mixng 20.0 parts of ARALDITE CY 184, 12.5 parts of CYMEL 1158, 10.0 parts of CYMEL 350, 2.0 parts of TINUVIN 384, 1.5 parts of TINUVIN 292, 0.68 parts of a solution of 10 weight percent of BYK 301 in propylene monoetheyl ether acetate, 0.5 parts of a solution of 10 weight percent of dibutyltin dilaurate in Butyl acetate, 0.67 parts of a solution of 75 weight percent of phenyl acid phosphate in butanol, 2.0 parts of PL1015 and 10.26 parts of 2-ethylhexyl acetate.
  • This part A mixture was then combined with 54.7 parts of TOLONATE HDT-LV as part B to form a clear composition.
  • the clear composition had a solid content of 87.1 weight percent, and a volatile organic compounds concentration of 1.18 lbs/gal. (0.14 Kg/liter).
  • Example 4 The composition was then sprayed over a conventional silver metallic waterborne basecoat which had been applied to the similar substrate as described in Example 1 and prebaked at 82°C for 10 minutes, and baked at 140°C for 30 minutes similar to Example 1. The coating exhibited gloss 94, DOI 94 and Tukon hardness 1 1.4.
  • Protective Coating Example 4 The composition was then sprayed over a conventional silver metallic waterborne basecoat which had been applied to the similar substrate as described in Example 1 and prebaked at 82°C for 10 minutes, and baked at 140°C for 30 minutes similar to Example 1. The coating exhibited gloss 94, DOI 94 and Tukon hardness 1 1.4.
  • Protective Coating Example 4 The composition was then sprayed over a conventional silver metallic waterborne basecoat which had been applied to the similar substrate as described in Example 1 and prebaked at 82°C for 10 minutes, and baked at 140°C for 30 minutes similar to Example 1. The coating exhibited gloss 94, DOI 94 and Tukon hardness 1 1.4.
  • Protective Coating 4 was prepared as follows: Part A was prepared by mixing 20 parts of ERL 4221, 25 parts of CYMEL 1158, 2.0 parts of TINUVIN 384, 1.5 parts of TINUVIN 292, 0.68 parts of a solution of 10 weight percent of BYK 301 in propylene monoethyl ether acetate, 0.5 parts of a solution of 10 weight percent dibutyltin dilaurate in butyl acetate, 1.4 parts of dodecylbenzenesulfonic acid salt of amionefhylpropanol, 2.0 parts of PL 1015, and 5.26 parts of 2-ethylhexyl acetate.
  • This part A mixture was then combined with 54.7 parts of TOLONATE HDT-LV as a part B to form a clear composition.
  • the clear composition had a solid content of 88.44 weight percent, and a volatile organic compounds concentration of 1.05 lbs/gal (0.12 Kg/liter].
  • composition was then sprayed over a conventional silver metallic waterborne basecoat which had been applied to the similar substrate as described in Example 1 and prebaked at 82°C for 10 minutes, and baked at 140°C for 30 minutes similar to Example 1.
  • the coating exhibited gloss 90, DOI 90 and Tukon hardness 4.6.
  • Protective Coating 5 was prepared as follows: Part A was prepared by mixing 20.0 parts of DER 736 20.0 parts of CYMEL 350, 2.0 parts of TINUVIN 384,
  • This part A mixture was then combined with 52.5 parts of TOLONATE HDT-LV as a part B to form a clear composition.
  • the composition had solid content of 88.0 weight percent, and a volatile organic compounds concentration of 1.09 lbs/gal.(0.13 Kilograms/liter).
  • composition was then sprayed over a conventional silver metallic waterborne basecoat which had been applied to the similar substrate as described in Example 1 and prebaked at 82°C for 10 minutes, and baked at 140°C for 30 minutes similar to Example 1.
  • the coating exhibited gloss 87, DOI 90 and Tukon hardness

Abstract

L'invention concerne une composition de revêtement incolore à faible teneur en composants organiques volatiles (VOC), comprenant un composant d'époxy, un composant de mélamine, et un polyisocyanate aliphatique possédant en moyenne 2 à 6 fonctionnalités isocyanate, et contenant éventuellement un catalyseur (par exemple, des catalyseurs d'organotine, des catalyseurs acides et des combinaisons); un composé fonctionnel pollyhydroxyle (par exemple, un polycarbonate polyol); ou d'autres additifs (par exemple des absorbants de lumière et des stabilisateurs de lumière). L'invention concerne également un article recouvert dudit revêtement incolore, un procédé de préparation de ladite composition, et un procédé d'application de cette composition, par exemple, sur un corps d'automobile.
EP00918020A 1999-03-17 2000-03-16 Compositions d'epoxy, d'isocyanate, et de melamine a teneur elevee en solides Withdrawn EP1233992A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US12485099P 1999-03-17 1999-03-17
US124850P 1999-03-17
US13114599P 1999-04-27 1999-04-27
US13114699P 1999-04-27 1999-04-27
US131145P 1999-04-27
US131146P 1999-04-27
PCT/US2000/006960 WO2000055231A1 (fr) 1999-03-17 2000-03-16 Compositions d'epoxy, d'isocyanate, et de melamine a teneur elevee en solides

Publications (1)

Publication Number Publication Date
EP1233992A1 true EP1233992A1 (fr) 2002-08-28

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EP00918020A Withdrawn EP1233992A1 (fr) 1999-03-17 2000-03-16 Compositions d'epoxy, d'isocyanate, et de melamine a teneur elevee en solides

Country Status (9)

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EP (1) EP1233992A1 (fr)
JP (1) JP2003525966A (fr)
KR (1) KR20020000781A (fr)
CN (1) CN1152901C (fr)
AU (1) AU773223B2 (fr)
BR (1) BR0010382A (fr)
CA (1) CA2361302A1 (fr)
NZ (1) NZ514217A (fr)
WO (1) WO2000055231A1 (fr)

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WO2004031306A1 (fr) * 2002-10-01 2004-04-15 Ppg Industries Ohio, Inc. Compositions de revetement pouvant etre appliquees par electrodeposition et procedes associes
WO2008100548A1 (fr) * 2007-02-13 2008-08-21 Basf Corporation Système de revêtement pour obtenir une excellente adhérence de mvss
CN104073141B (zh) * 2014-06-24 2016-10-05 华南理工大学 一种高固体分双组分聚氨酯涂料及其制备方法
CN104211899B (zh) * 2014-08-25 2016-10-05 华南理工大学 聚醛改性羧酸‐非离子型聚氨酯水分散体及其制备方法与在涂料中的应用
JP7385983B2 (ja) * 2016-10-06 2023-11-24 株式会社ダイセル 硬化性樹脂組成物及びその硬化物、プリプレグ、並びに繊維強化複合材料
JP7110606B2 (ja) * 2017-02-27 2022-08-02 東ソー株式会社 熱可塑性ポリウレタン樹脂組成物、および該樹脂組成物を用いた成形体
WO2018155396A1 (fr) * 2017-02-27 2018-08-30 東ソー株式会社 Composition de résine polyuréthane thermoplastique, et corps moulé mettant en œuvre cette composition de résine
CN116348298B (zh) * 2020-10-16 2024-04-09 东曹株式会社 聚碳酸酯多元醇及其制造方法、组合物及其制造方法、氨基甲酸酯树脂、以及水性氨基甲酸酯树脂分散体

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US4623481A (en) * 1984-09-21 1986-11-18 E. I. Du Pont De Nemours & Company Conductive primers
AU670570B2 (en) * 1992-03-24 1996-07-25 Nippon Paint Co., Ltd. Polyfunctional polycarbonate polyol
JPH06256714A (ja) * 1993-03-04 1994-09-13 Kansai Paint Co Ltd 塗料組成物
JP2691864B2 (ja) * 1994-02-24 1997-12-17 昭和アルミニウム株式会社 エポキシ系樹脂組成物
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KR20020000781A (ko) 2002-01-05
NZ514217A (en) 2004-02-27
CA2361302A1 (fr) 2000-09-21
AU773223B2 (en) 2004-05-20
CN1344285A (zh) 2002-04-10
WO2000055231A1 (fr) 2000-09-21
AU3890000A (en) 2000-10-04
JP2003525966A (ja) 2003-09-02
CN1152901C (zh) 2004-06-09
BR0010382A (pt) 2003-07-22

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