US20060142473A1 - Polytrimethylene ether diol containing coating compositions - Google Patents

Polytrimethylene ether diol containing coating compositions Download PDF

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Publication number
US20060142473A1
US20060142473A1 US10/545,828 US54582805A US2006142473A1 US 20060142473 A1 US20060142473 A1 US 20060142473A1 US 54582805 A US54582805 A US 54582805A US 2006142473 A1 US2006142473 A1 US 2006142473A1
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coating composition
meth
group
groups
weight
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Hari Sunkara
Patricia Sormani
James Oneil
Joseph Kurian
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EIDP Inc
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Priority to US10/545,828 priority Critical patent/US20060142473A1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: O'NEIL, JAMES WILLIAM, SORMANI, PATRICIA MARY ELLEN, KURIAN, JOSEPH V., SUNKARA, HARI BABU
Publication of US20060142473A1 publication Critical patent/US20060142473A1/en
Abandoned legal-status Critical Current

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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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08G18/4063—Mixtures of compounds of group C08G18/62 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two 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
    • C08G18/78—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • Y10T428/20—Patched hole or depression
    • 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]
    • 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]
    • Y10T428/31547—Of polyisocyanurate
    • 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]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31605—Next to free metal
    • 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
    • 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]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31859—Next to an aldehyde or ketone condensation product
    • Y10T428/3187—Amide-aldehyde
    • Y10T428/31873—Urea or modified urea-aldehyde

Definitions

  • This invention is directed to coating compositions, in particular, to coating composition useful as interior and exterior top coats, base coats, primers, primer surfacers and primer fillers having excellent physical properties, such as, flexibility, hardness, chip resistance and when used as a primer, a primer surfacer or a primer filler also has a combination of excellent sandability and chip resistance.
  • the multi-layer finishes on automobile and truck bodies and parts typically utilize the following: (1) an electrocoat layer applied over a substrate, typically, a phosphatized cold rolled steel, (2) a primer layer, (3) a colored layer, typically pigmented, and (4) a clear layer.
  • a colored top coat layer may be used in place of the colored layer and clear layer.
  • a suitable primer, primer surfacer or primer filler coating is applied over the multi-layer finish that usually is sanded thereby exposing one or more layers or is applied over a filler material that has been used to fill in surface imperfections.
  • This primer, primer surfacer or primer filler herein after, “prime”, has many requirements. It must have adhesion to the substrate and provide a surface to which the colored layer or top coat will adhere. It must be readily sandable in a reasonably short period of time after application, for example, about three hours after application. It must provide the resulting multi-layer finish with good impact resistance, in particular, stone chip resistance.
  • Coatings used to form finishes on appliances, flexible and rigid thermoset or thermoplastic substrates, industrial equipment, exterior structures, and the like may be applied directly to the substrate which may be untreated, primed or surface treated.
  • the resulting finish must have the required properties for its intended use.
  • a coating composition comprising a film forming binder of
  • the coating composition can be used as a clear coating composition, can contain pigments and be used as a pigmented top coating, a pigmented base coating, a primer, primer filler, or primer surfacer coating and is useful for coating, for example, automobile and truck bodies and parts, industrial equipment, appliances, and interior and exterior structures.
  • the novel coating composition of this invention preferably is a solvent-borne coating composition containing a film forming binder of at least one polymer that has pendant groups, such as, hydroxyl, carboxyl glycidyl, amine, amide, silane or mixtures of these groups that are reactive with a crosslinking component utilized in the composition and the polymer has a glass transition temperature (Tg) of 10 to 80° C.
  • the binder contains a polytrimethylene ether diol having a Mn (number average molecular weight) of 500 to 5,000; and also, a crosslinking component and optionally, the composition can contain pigment(s).
  • the coating composition can be used as a clear coating composition in combination with a pigmented base coat or color coat, which optionally, also may be the novel composition or another composition.
  • the composition can be pigmented and used as a top coating, primer coating, primer surfacer, primer filler coating and the like.
  • the coating composition is particularly useful for coating automobile and truck bodies and parts but can also be used for appliances, industrial equipment, home use items, such as, shelves, cabinets and various furniture items and can be used on a variety of rigid and flexible thermoset and thermoplastic substrates and composite substrates and can be used as an architectural paint for the interior and exterior of homes, office buildings, industrial buildings and the like.
  • substrates over-which the coating composition, may be applied may be untreated, treated, primed and the like to improve adhesion.
  • Typical substrates include aluminum, magnesium, copper, tin, zinc, galvanized steel, stainless steel, alloys of steel, cold rolled steel, phosphatized cold rolled steel, phosphatized cold rolled steel having an electrodeposited primer thereon, plastics, such as, polypropylene and copolymers thereof, polyurethanes, polycarbonate, ABS, plastic fiber reinforced substrates, such as RIM, SMC (sheet molding compound) and the like.
  • One particularly useful coating composition is a primer that is used for refinishing or repairing automobile and truck bodies or parts.
  • This primer has a particular advantage that after a relatively short time after application, it is sufficiently cured and can be sanded.
  • This primer in combination with a topcoat of a color coat and clear coat or a pigmented mono-coat provides a finish that has improved chip resistance.
  • binder refers to the film forming constituents of the composition that include the polymer having reactive groups, polytrimethylene ether diol, and the crosslinking component and any other polymers, reactive oligomers and/or reactive diluents. Solvents, pigments, catalysts, rheology modifiers, antioxidants, UV stabilizers, leveling agents, antifoaming agents, anti-cratering agents, adhesion promoting agents are not included in the term.
  • the binder of the novel coating composition typically contains (a) 10 to 80% by weight, preferably, 20 to 70% by weight, of the polymer(s) having pendant reactive groups, (b) 1 to 50% by weight, preferably 5 to 40% by weight of polytrimethylene ether diol, and (c) 10 to 50% by weight, preferably 15 to 45% by weight of the crosslinking component. All weight percentages are based on the total weight of the binder of the coating composition and the sum of the percentages of (a), (b) and (c) is 100%
  • the polymer used in the composition has a weight average molecular weight of about 1,000 to 100,000, a Tg of 10 to 80° C. and contains reactive moieties, such as, hydroxyl, carboxyl, glycidyl, amine, amide, silane or mixtures of such groups.
  • the Tg of the binder when cured is greater than 30° C.
  • Theses polymers. can be straight chain polymers, branched polymers, graft copolymers, graft terpolymers and core shell polymers. Typical of these polymers are acrylic polymers, acrylourethane polymers, polyesters, polyesterurethanes, polyetherurethanes, poly(meth)acrylamides, polyepoxides and polycarbonates.
  • acrylic polymers are used having a weight average molecular weight of 5,000 to 50,000 and more preferably, of 10,000 to 25,000 and a Tg preferably, of 30° C. to 80° C.
  • typically useful acrylic polymers are those known in the art and are polymers of the following: linear alkyl (meth)acrylates having 1 to 12 carbon atoms in the alkyl group, cyclic or branched alkyl (meth)acrylates having 3 to 12 carbon atoms in the alkyl group, including isobomyl (meth)acrylate, and the polymer can contain styrene, alpha methyl styrene, vinyl toluene, and (meth)acrylonitrile, (meth)acryl amides and monomers that provide pendant reactive groups like, hydroxy alkyl (meth)acrylates having 1 to 6 carbon atoms in the alkyl group, glycidyl (meth)acrylate, hydroxy amino alkyl (meth)acrylate having
  • hydroxy functional acrylic polymers having a hydroxy equivalent weight (on a solids basis) of 300 to 800, preferably, 380 to 750 and more preferably, 450 to 580 and are polymers of hydroxy alkyl (meth)acrylates and one or more of the aforementioned monomers.
  • the hydroxyl equivalent weight is the grams of resin per equivalent of hydroxyl groups.
  • One preferred hydroxy containing acrylic polymer contains 35 to 40% by weight styrene, 15 to 25% by weight ethylhexyl methacrylate and 15 to 20% by weight isobornyl methacrylate and 20 to 30% by weight hydroxyethyl methacrylate.
  • a particularly preferred acrylic polymer contains 37% styrene, 20% by weight 2-ethylhexyl methacrylate and 17.5% by weight isobornyl methacrylate and 25.5% by weight hydroxyethyl methacrylate
  • Suitable hydroxyl-functional unsaturated monomers that are used to introduce hydroxyl groups into the acrylic polymer are, for example, hydroxyalkyl esters of alpha,beta-olefinically unsaturated monocarboxylic acids with primary or secondary hydroxyl groups. These may, for example, comprise the hydroxyalkyl esters of acrylic acid, methacrylic acid, crotonic acid and/or isocrotonic acid. The hydroxyalkyl esters of (meth)acrylic acid are preferred.
  • Suitable hydroxyalkyl esters of alpha, beta-olefinically unsaturated monocarboxylic acids with primary hydroxyl groups are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyamyl (meth)acrylate, hydroxyhexyl (meth)acrylate.
  • suitable hydroxyalkyl esters with secondary hydroxyl groups are 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate.
  • Additional useful hydroxy-functional unsaturated monomers are reaction products of alpha,beta-unsaturated monocarboxylic acids with glycidyl esters of saturated monocarboxylic acids branched in alpha position, for example with glycidyl esters of saturated alpha-alkylalkanemonocarboxylic acids or alpha,alpha′-dialkylalkanemonocarboxylic acids.
  • These preferably comprise the reaction products of (meth)acrylic acid with glycidyl esters of saturated alpha,alpha-dialkylalkanemonocarboxylic acids with 7 to 13 carbon atoms per molecule, particularly preferably with 9 to 11 carbon atoms per molecule.
  • These reaction products may be formed before, during or after the copolymerization reaction.
  • hydroxy-functional unsaturated monomers are reaction products of hydroxyalkyl (meth)acrylates with lactones.
  • Hydroxyalkyl (meth)acrylates which may be used are, for example, those stated above.
  • Suitable lactones are, for example, those that have 3 to 15 carbon atoms in the ring, wherein the rings may also comprise different substituents.
  • Preferred lactones are gamma-butyrolactone, delta-valerolactone, epsilon-caprolactone, beta-hydroxy-beta-methyl-delta-valerolactone, lambda-laurolactone or mixtures thereof. Epsilon-caprolactone is particularly preferred.
  • the reaction products preferably comprise those prepared from 1 mole of a hydroxyalkyl ester of an alpha,beta-unsaturated monocarboxylic acid and 1 to 5 moles, preferably on average 2 moles, of a lactone.
  • the hydroxyl groups of the hydroxyalkyl esters may be modified with the lactone before, during or after the copolymerization reaction.
  • Suitable unsaturated monomers that can be used to provide the acrylic polymer with carboxyl groups are, for example, olefinically unsaturated monocarboxylic acids, such as, for example, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid. Acrylic acid and methacrylic acid are preferably used.
  • Suitable unsaturated monomers that can be used to provide the acrylic polymer with glycidyl groups are, for example, allyl glycidyl ether, 3,4-epoxy-1-vinylcyclohexane, epoxycyclohexyl (meth)acrylate, vinyl glycidyl ether and glycidyl (meth)acrylate. Glycidyl (meth)acrylate is preferably used.
  • Free-radically polymerizable, olefinically unsaturated monomers which, apart from at least one olefinic double bond, do not contain additional functional groups that can be used to form the acrylic polymer are, for example, esters of unsaturated carboxylic acids with aliphatic monohydric branched or unbranched as well as cyclic alcohols with 1 to 20 carbon atoms.
  • the unsaturated carboxylic acids which may be considered, are acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid. Esters of (meth)acrylic acid are preferred.
  • Examples of (meth)acrylic acid esters are methyl acrylate, ethyl acrylate, isopropyl acrylate, tert.-butyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate and the corresponding methacrylates.
  • Examples of (meth)acrylic acid esters with cyclic alcohols are cyclohexyl acrylate, trimethylcyclohexyl acrylate, 4-tert.-butylcyclohexyl acrylate, isobomyl acrylate and the corresponding methacrylates.
  • Further useful unsaturated monomers that do not contain additional functional groups are, for example, vinyl ethers, such as, isobutyl vinyl ether and vinyl esters, such as, vinyl acetate, vinyl propionate, vinyl aromatic hydrocarbons, preferably those with 8 to 9 carbon atoms per molecule.
  • vinyl ethers such as, isobutyl vinyl ether and vinyl esters, such as, vinyl acetate, vinyl propionate, vinyl aromatic hydrocarbons, preferably those with 8 to 9 carbon atoms per molecule.
  • vinyl ethers such as, isobutyl vinyl ether
  • vinyl esters such as, vinyl acetate, vinyl propionate, vinyl aromatic hydrocarbons, preferably those with 8 to 9 carbon atoms per molecule.
  • vinyl ethers such as, isobutyl vinyl ether
  • vinyl esters such as, vinyl acetate, vinyl propionate, vinyl aromatic hydrocarbons, preferably those with 8 to 9 carbon atoms per molecule.
  • vinyl ethers such as, isobut
  • olefinically polyunsaturated monomers may also be used. These are monomers having at least 2 free-radically polymerizable double bonds per molecule. Examples of these are divinylbenzene, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, glycerol dimethacrylate.
  • the hydroxy-functional (meth)acrylic polymers generally are formed by free-radical copolymerization using conventional processes well known to those skilled in the art, for example, bulk, solution or bead polymerization, in particular by free-radical solution polymerization using free-radical initiators.
  • Acrylourethanes also can be used to form the novel coating composition of this invention.
  • Typical useful acrylourethanes are formed by reacting the aforementioned acrylic polymers with an organic polyisocyanate. Generally, an excess of the acrylic polymer is used so that the resulting acrylourethane has terminal acrylic segments having reactive groups as described above. These acrylourethanes can have reactive end groups and/or pendant groups such as hydroxyl, carboxyl, amine, glycidyl, amide, silane or mixtures of such groups.
  • Useful organic polyisocyanates are described hereinafter as the crosslinking component but also can be used to form acrylourethanes useful in this invention.
  • Typically useful acrylourethanes are disclosed in Stamegna et al. U.S. Pat. No. 4,659,780, which is hereby incorporated by reference.
  • Hydroxy containing polyesters can be used to form the novel coating composition of this invention.
  • Typical polyesters that can be used have an acid value of 15 to 60, a hydroxyl value of not more than 95 and have a number average molecular weight from 1500 to 10,000.
  • the polyesters may be saturated or unsaturated and optionally, may be modified with fatty acids.
  • These polyesters are the esterification product of one or more polyhydric alcohols, such as, alkylene diols and glycols; monocarboxylic acids and a polycarboxylic acids or anhydrides thereof, such as, dicarboxylic and/or tricarboxylic acids or tricarboxylic acid anhydrides.
  • polyhydric alcohols used to form the polyester include triols and tetraols, such as, trimethylol propane, triethylol propane, trimethylol ethane, glycerine, and dihydric alcohols and diols that include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexane dimethanol, hydrogenated bisphenols A and F, Esterdiol 204 (Trademark of Union Carbide) and highly functional polyols, such as, trimethylolethane, trimethylolpropane, and pentaerythritol.
  • Polyhydric alcohols having carboxyl groups may
  • Typical acids and anhydrides that can be used to form the polyester are aliphatic or aromatic carboxylic acids and anhydrides thereof, such as, adipic acid, azelaic acid, sebacic acid, dimerized fatty acids, maleic acid, maleic anhydride, succinic acid, succinic anhydride, isophthalic acid, terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylic acid, tetrahydro- and hexahydrophthalic anhydride, tetrachlorophthalic acid, terephthalic acid bisglycol ester, benzophenone dicarboxylic acid, trimellitic acid and trimellitic anhydride.
  • One useful polyester is the estrification product of neopentyl glycol, trimethylol propane, 1,6 hexane diol, adipic acid, isophthalic acid and trimellitic anhydride.
  • Polyesterurethanes also can be used to form the novel coating composition of this invention.
  • useful polyesterurethanes are formed by reacting the aforementioned polyesters with an organic polyisocyanate. Generally, an excess of the polyester is used so that the resulting polyesterurethane has terminal polyester segments having reactive hydroxyl groups.
  • Carboxy functional polyesterurethanes can also be used.
  • Useful organic polyisocyanates are described hereinafter as the crosslinking component but can be used to form polyesterurethanes useful in this invention.
  • useful coating compositions that utilize polyesterurethanes are disclosed in Johnson U.S. Pat. No. 5,122,522, which is hereby incorporated by reference.
  • Polycarbonate polyols can be used as to form the novel coating composition and are the esters of carbonic acid which are obtained by the reaction of carbonic acid derivatives, e.g., diphenyl carbonate or phosgene with polyols, preferably diols. Suitable diols are any of those mentioned above.
  • Polyetherurethanes can be used to form the novel coating composition and are the reaction product of a polyetherpolyol and/or polylactonepolyol and an organic polyisocyanate.
  • the R 1 groups may be identical or different.
  • polyetherpolyols are poly(oxypropylene) glycols, poly(oxymethylene) glycols, poly(oxyethylene) glycols, or mixtures thereof, block copolymers that contain different glycols or mixed block copolymers that contain different oxytetramethylene, oxyethylene and/or oxypropylene units.
  • Polylactone polyols that can be used to form a useful polyetherurethane are polyols that are derived from lactones, preferably caprolactones and can be obtained, for example, by reacting epsilon caprolactone with a diol.
  • Diols that can be used to react with lactones are, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol and dimethylolcyclohexane.
  • Preferred polyepoxides are polyglycidyl ethers of cyclic polyols. Particularly preferred are polyglycidyl ethers of ployhydric phenols, such as, bisphenol A or bisphenol F.
  • Such polyepoxides can be produced by the etherification of polyhydric phenols with epihalohydrin or dihalohydrin, such as, epichlorohydrin or dichlorohydrin in the presence of alkali.
  • polyhydric phenols examples include 2,bis-(4-hydroxyphenyl)ethane, 2-methyl-1,1-bis-(4-hydroxyphenyl)propane and the like.
  • polyhydric phenols other cyclic polyols can be used to prepare the polyglycidyl ethers, such as, alicyclic phenols, particularly, cycloaliphatic polyols, and hydrogenated bisphenol A.
  • Polyepoxides can be chain extended with polyether or polyester polyols, such as, polycaprolactone diols and with ethoxylated bisphenol A.
  • Poly(meth)acrylamides can be used to form the novel coating composition, such as, polymers of (meth)acrylamide and alkyl (meth)acrylates, hydroxy alkyl (meth)acrylates, (meth)acrylic acid and or one of the aforementioned ethylenically unsaturated polymerizable monomers.
  • the polytrimethylene ether diol used in the coating composition has a number average molecular weight (Mn) in the range of 500 to 5,000, preferably 1,000 to 3,000.
  • Mn number average molecular weight
  • the polytrimethylene ether diol has a Tg of about ⁇ 75° C., a polydispersity in the range of 1.1 to 2.1 and a hydroxyl number in the range of 20 to 200.
  • the polytrimethylene ether diol is prepared by an acid-catalyzed polycondensation of 1,3-propanediol, preferably, as described in US. Published Patent Application Numbers 2002/7043 A1 and 2002/10374 A1, both of which are hereby incorporated by reference.
  • the polytrimethylene ether diol also can be prepared by a ring opening polymerization of a cyclic ether, oxetane, as described in J. Polymer Sci., Polymer Chemistry Ed. 28, 449 to 444 (1985) which is also incorporated by reference.
  • 1,3-propanediol is preferred over the use of oxetane since it is a less hazardous, very stable, low cost, commercially available material and can be prepared by use of petro chemical feed-stocks or renewable resources.
  • a bio-route via fermentation of a renewable resource is used to obtain the 1,3-propanediol.
  • a renewable resource is corn since it is readily available and has a high rate of conversion to 1,3-propanediol and can be genetically modified to improve yields to diol.
  • Typical bio-conversion processes are shown in U.S. Pat. No. 5,686,276, U.S. Pat. No. 5,633,362 and U.S. Pat. No. 5,821,092.
  • U.S. Pat. No. '276 teaches a bio-conversion process of a fermentable carbon source to 1,3-propanediol by a single microorganism.
  • Copolymers of polytrimethylene ether diol also can be used.
  • such copolymers are prepared by copolymerizing 1,3-propanediol with another diol, such as, ethane diol, hexane diol, 2-methyl 1,3-propanediol, 2,2-dimethyl-1,3-propanediol. At least 50% of the copolymer must be from 1,3-propanediol.
  • a blend of a high and low molecular weight polytrimethylene ether diol can be used wherein the high molecular weight diol has an Mn of 1,000 to 4,000 and the low molecular weight diol has an Mn of 150 to 500.
  • the average Mn of the diol should be in the range of 1,000 to 4,000.
  • the diol can contain polytrimethylene ether triols and other higher functionality polytrimethylene ether polyols in an amount of 1 to 20% based on the weight of the polytrimethylene ether diol.
  • Blends of the polytrimethylene ether diol and other cycloaliphatic hydroxyl containing either branched or linear oligomers can be used.
  • Such oligomers are disclosed in Barsotti, et al. U.S. Pat. No. 6,221,494, which is hereby incorporated by reference. Up to 30% by weight, based on the weight of the diol, of such oligomers can be used.
  • Coatings formed from compositions of this invention containing polytrimethylene ether diols in particular have better chip resistance properties in comparison to coating prepared from conventional diols, for example, polytetramethylene ether diols and polyoxypropylene diols.
  • crosslinking agents can be used in the novel composition of this invention, such as, organic polyisocyanates, melamine formaldehydes, alkylated melamine formaldehydes, benzoquanamine formaldehyde, urea formaldehyde, polyepoxides, silane resins and any mixtures thereof.
  • organic polyisocyanates crosslinking agents that can be used include aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates and isocyanate adducts.
  • Suitable aliphatic, cycloaliphatic and aromatic polyisocyanates include the following: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate (“TDI”), 4,4-diphenylmethane diisocyanate (“MDI”), 4,4′-dicyclohexyl methane diisocyanate, (“H 12 MDI”), 3,3′-dimethyl-4,4′-biphenyl diisocyanate (“TODI”), 1,4-benzene diisocyanate, trans-cyclohexane-1,4-diisocyanate, 1,5-naphthalene diisocyanate (“NDI”), 1,6-hexamethylene diisocyanate (“HDI”), 4,6-xylene diisocyanate, isophorone diisocyanate, (“IPDI”), other aliphatic or cycloaliphatic di-, tri- or tetra-isocyan
  • Tri-functional isocyanates also can be used, such as, triphenyl methane triisocyanate, 1,3,5-benzene triisocyanate, 2,4,6-toluene triisocyanate.
  • Trimers of diisocyanates such as, the trimer of hexamethylene diisocyanate sold as Tolonate® HDT from Rhodia Corporation and the trimer of isophorone diisocyanate are also suitable.
  • An isocyanate functional adduct can be used, such as, an adduct of an aliphatic polyisocyanate and a polyol or an adduct of an aliphatic polyisocyanate and an amine. Also, any of the aforementioned polyisocyanates can be used with a polyol to form an adduct.
  • Polyols such as, trimethylol alkanes, particularly, trimethylol propane or ethane can be used to form an adduct.
  • a particularly useful coating composition useful for the interior of automobiles and truck that forms a finish with a soft leather like touch or feel comprises the polytrimethylene ether diol and an organic polyisocyanate crosslinking agent.
  • such compositions comprise a binder of about 40 to 90% by weight of the polytrimethylene ether diol and 10 to 60% by weight of an organic polyisocyanate crosslinking agent.
  • O'Neil U.S. Pat. No. 6,207,224 and O'Neil U.S. Pat. No. 6,436,478 disclose such compositions and are hereby incorporated by reference.
  • the polytrimethylene ether glycol can be the polyol component of the coating compositions disclosed in these patents.
  • Such compositions have excellent appearance, good adhesion to thermoplastic substrates, have a soft feel but still have sufficient hardness to avoid scratching and marring and are comparable to commercially available compositions of this type.
  • Typical alkylated melamines that can be used as the cross linking component are monomeric or polymeric and have a relatively low molecular weight.
  • Alkoxy monomeric melamines that can be used are low molecular weight melamines that contain on an average three or more methylol groups reacted with a monohydric alcohol having 1 to 5 carbon atoms, such as, methanol, propanol, n-butanol and isobutanol and have an average degree of polymerization of less than 2 and preferably, in the range of about 1.1 to 1.8.
  • Suitable monomeric melamines include highly alkylated melamines, such as, methylated melamines, methylated and butylated melamines, butylated melamines, isobutylated melamines and mixtures thereof. More particularly, hexamethoxymethylol melamine, butylated melamines and mixed methylated and butylated melamines are preferred. Particularly preferred alkylated melamines include hexamethoxymethylol melamines, such as, Cymel® 301 and 303 and Resimene® 747, Cymel® 1156 which is reported to be a 100% butylated melamine having a degree of polymerization of 2.9. A particularly preferred mixture of melamines is Cymel® 1156 and Resimene® CE-4514 which is reported to be a 50/50 methylated/butylated melamine.
  • a typically useful polymeric melamine is Cymel® 327 which is a highly methylated melamine having a degree of polymerization of 1.8.
  • Other polymeric melamines, such as, Cymel® 328 can also be used.
  • melamines are supplied commercially; for example, by Cytec Industries Inc., Stamford, Conn., and by Solutia Inc., Springfield, Mass.
  • Polyepoxide resins also can be used as the crosslinking component. Any of the aforementioned polyepoxide resins can be used as the crosslinking agent. Generally, if a polyepoxide is used as the crosslinking agent, it is not used as component a. of the novel composition.
  • crosslinking components are melamine formaldehyde, benzoguanamine formaldehyde, and urea formaldehyde.
  • a silane crosslinking component also can be used.
  • One useful silane crosslinking component is an aminofunctional silane crosslinking agent usually in an amount of 0.1 to 50% by weight, based on the weight of the binder; preferably, 0.5 to 10.0% by weight of silane is used.
  • Typical useful aminofunctional silanes have the formula (X n R) a Si—(—OSi) y —(OR 3 ) b wherein X is selected from the group of —NH 2 , —NHR 4 , and SH, n is an integer from 1-5, R is a hydrocarbon group contain 1 to 22 carbon atoms, R 3 is an alkyl group containing 1 to 8 carbon atoms, a is at least 1, y is from 0 to 20, b is at least 2 and R 4 is an alkyl group having 1 to 4 carbon atoms.
  • aminofunctional silanes are aminomethyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyidiethoxysilane, gamma-aminopropylethyldiethoxysilane, gamma-aminopropylphenyldiethoxyysilane, N-beta(aminoethyl)gamma-aminopropyltrimethoxysilane, delta-aminobutyltriethoxysilane, delta-aminobutylethyldiethoxysilane and diethylene triamino propylaminotrimethoxysilane.
  • N-beta(aminoethyl)gamma-aminopropyltrimethoxysilane commercially sold as Silquest® A 1120 and diethylene triamino propylaminotrimethoxysilane that is commercially sold as Silquest® A 1130. Both of theses silanes are sold by OSi Specialties, Inc. Danbury, Conn.
  • amino silane crosslinking agent When an amino silane crosslinking agent is used, additional amino functional curing agents, such as, primary, secondary and tertiary amines, that are well known in the art are usually added. Typically, aliphatic amines containing a primary amine group, such as, diethylene triamine, and triethylene tetramine can be added. Tertiary amines, such as, tris-(dimethyl aminomethyl)-phenol can also be used.
  • the novel composition can contain 1 to 50% by weight, preferably, 20 to 40% by weight, based on the weight of the binder of acrylic NAD (non-aqueous dispersed) resins.
  • NAD resins typically are high molecular weight resins having a crosslinked acrylic core with a Tg between 20 to 100° C. and attached to the core are low Tg stabilizer segments.
  • a description of such NAD resins is in Antonelli et al. U.S. Pat. No. 4,591,533, Antonelli et al. U.S. Pat. No. 5,010,140 and in Barsofti et al. U.S. Pat. No. 5,763,528. These patents are hereby incorporated by reference.
  • a catalyst is used in the novel composition to reduce curing time and temperature and allow curing of the coating at ambient temperatures.
  • Typical catalysts include dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dichloride, dibutyl tin dibromide, triphenyl boron, tetraisopropyl titanate, triethanolamine titanate chelate, dibutyl tin dioxide, dibutyl tin dioctoate, tin octoate, aluminum titanate, aluminum chelates, zirconium chelate, hydrocarbon phosphonium halides, such as, ethyl triphenyl phosphonium iodide and other such phosphonium salts, and other catalysts or mixtures thereof known to those skilled in the art.
  • the novel composition typically is solvent based and has a solids content of 30 to 90% by weight, preferably, 50 to 80% by weight and more preferably, 60 to 80% by weight, of binder of a ready to spray composition.
  • the novel composition may be formulated at 100% solids by using reactive diluents of low molecular weight resin(s), such as, an acrylic resin.
  • Typical solvents include aromatic hydrocarbons, such as, toluene, xylene; ketones, such as, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and diisobutyl ketone; esters, such as, ethyl acetate, n-butyl acetate and isobutyl acetate.
  • Typical alcohols that can be used are ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, and diacetone alcohol and mixtures of any of the above. Alcohols are not used in the presence of isocyanate crosslinking agents.
  • An advantage of the novel coating composition of this invention is that it has a low VOC (volatile organic content) and can readily be formulated to have a VOC of less than 334 g/l (2.8 pounds per gallon) and in particular can be formulated to a VOC less than 240 g/l (2 pound per gallon) that meets current governmental air pollution regulations.
  • the composition can contain pigments in a pigment to binder weight ratio of 1/100 to 350/100.
  • conventional primer pigments are used in a pigment to binder weight ratio of 50/100 to 350/100.
  • Typical of such pigments that are useful in primers are titanium dioxide, zinc phosphate, iron oxide, carbon black, amorphous silica, high surface area silica, barium sulfate, talc, chromate pigments for corrosion resistance, such as, calcium chromate, strontium chromate, zinc chromate, magnesium chromate, barium chromate and hollow glass spheres.
  • the coating composition is used as a base coat or topcoat coating composition
  • metallic flakes and powders such as, aluminum flake and aluminum powders
  • special effects pigments such as, coated mica flakes, coated aluminum flake, colored pigments and inorganic or organic colored pigments may be used usually in combination with one of the aforementioned pigments.
  • Suitable pigments and extenders that can be used are, for example, inorganic or organic coloring pigments like titanium dioxide, micronised titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone or pyrrolopyrrole pigments.
  • special effect pigments are metal pigments, for example made from aluminium or copper, interference pigments, such as, titanium dioxide coated aluminium, coated mica; graphite special effect pigments and iron oxide in flake form.
  • Examples of extenders are silicon dioxide, barium sulfate, talcum, aluminium silicate and magnesium silicate.
  • novel coating composition is to be used as an exterior coating or as a coating that is subject to weathering and/or exposure to UV light
  • weatherability and UV durability of the coating can be improved by the addition of an ultraviolet light stabilizer or a combination of ultraviolet light stabilizers in the amount of 0.1% to 10% by weight, based on the weight of the binder.
  • ultraviolet light stabilizers include ultraviolet,light absorbers, screeners, quenchers, and specified hindered amine light stabilizers.
  • An antioxidant also can be added, in the amount of 0.1% to 5% by weight, based on the weight of the binder.
  • Typical ultraviolet light stabilizers that are useful include benzophenones, triazoles, triazines, benzoates, hindered amines and mixtures thereof. Specific examples of ultraviolet stabilizers are disclosed in Antonelli et al. U.S. Pat. No. 4,591,533, the entire disclosure of which is incorporated herein by reference. For good durability, a blend of Tinuvin® 928 and Tinuvin® 123 (hindered amine light stabilizers), all commercially available from Ciba Specialty Chemicals, Tarrytown, N.Y. is preferred.
  • the coating compositions may contain conventional coating additives.
  • the additives comprise the conventional additives usable in the coatings.
  • Examples of such additives are leveling agents based on (meth)acrylic homopolymers, Theological agents, such as highly disperse silica or polymeric urea compounds, thickeners, such as partially cross-linked polycarboxylic acid or polyurethanes, antifoaming agents, wetting agents, catalysts for the cross-linking reaction of the OH-functional binders, for example organic metal salts, such as, dibutyltin dilaurate, zinc naphthenate and compounds containing tertiary amino groups, such as, triethylamine, for the cross-linking reaction with polyisocyanates.
  • the additives are used in conventional amounts familiar to the person skilled in the art.
  • the novel coating composition may also contain other conventional formulation additives, such as, wetting agents, leveling and flow control agents, for example, Resiflow®S (polybutylacrylate), BYK® 320 and 325 (high molecular weight polyacrylates), BYK® 347 (polyether-modified siloxane) and rheology control agents, such as, fumed silica.
  • wetting agents for example, Resiflow®S (polybutylacrylate), BYK® 320 and 325 (high molecular weight polyacrylates), BYK® 347 (polyether-modified siloxane) and rheology control agents, such as, fumed silica.
  • the coating compositions according to the invention may contain further reactive low molecular weight compounds as reactive diluents that are capable of reacting with the cross-linking component c.
  • low molecular weight polyhydroxyl compounds such as, ethylene glycol, propylene glycol, trimethylolpropane and 1,6-dihydroxyhexane may be used.
  • the coating compositions according to the invention may be transparent or pigmented coating compositions.
  • Pigmented coating compositions are produced by mixing the individual constituents with one another and homogenizing or grinding them in conventional manner. It is, for example, possible to proceed by initially mixing a proportion of component a. and/or component b. with the pigments and/or extenders and the additives and solvents conventional in coatings and grinding the mixture in grinding units.
  • the novel composition may be formulated as a single-component or two-component coating compositions.
  • the coating compositions are two-component systems, i.e. components a. and b. may be mixed with the polyisocyanate component only shortly before application.
  • blocked polyisocyanates and/or amino resins are, for example, used as the cross-linking agent, the coating compositions may be formulated as a single component composition.
  • the coating compositions may, in principle, additionally be adjusted to spraying viscosity with organic solvents before being applied.
  • the two components are mixed together shortly before application.
  • the first component contains the polymer having pendant reactive groups, such as, an acrylic polymer having reactive hydroxyl groups, and the polytrimethylene ether diol and pigments.
  • the pigments can be dispersed in the first component using conventional dispersing techniques, such as, ball milling, sand milling attritor grinding, and the like.
  • the second component contains the crosslinking agent, such as, a polyisocyanate crosslinking agent, and an optional amino functional silane crosslinking agent and an optional additional amine curing agents and solvents.
  • the coating compositions according to the invention are suitable for vehicle and industrial coating and may be applied by using known processes, in particular spray application.
  • the coating compositions may be used both for vehicle original coating and for repair or refinish coating of vehicles and vehicle parts.
  • Curing temperatures depend on the crosslinking agent used.
  • the crosslinking agent is a polyisocyanate
  • cure can be accomplished at ambient temperatures but the composition also can be force dried at elevated temperature of 50 to 150° C.
  • Typical baking temperatures used for heat crosslinkable agents, such as, alkylated melamines are 60 to 160° C., preferably of 100 to 140° C. and are generally used for original vehicle coatings.
  • Curing temperatures of 20° C. to 80° C., in particular of 20 to 60° C. are used for vehicle repair or refinish coating in which the crosslinking agent typically is a polyisocyanate.
  • the coating compositions according to the invention may be formulated as pigmented or transparent coatings. They may be used for the production of the outer pigmented top coat layer of a multi-layer coating and for the production of the filler and/or primer coat of a multi-layer coating.
  • the present invention also relates to the use of the coating compositions according to the invention as top coat coating compositions and as filler and primer coating compositions and to a process for the production of multi-layer coatings, wherein, in particular, the pigmented top coat and the filler and primer coats of multi-layer coatings are produced by the coating compositions according to the invention.
  • Heat activated crosslinking agents such as, alkylated melamine formaldehydes, can be added directly to the coating composition containing the polymer having pendant reactive groups and the polytrimethylene ether diol at any time prior to application since there is no reaction between the crosslinking agent and the other components until after the coating is applied and baked at an elevated temperature.
  • the coating composition can be applied by conventional techniques, such as, spraying, electrostatic spraying, dipping, brushing, and flow coating.
  • the coating is applied to a dry film thickness of 50 to 300 microns and preferably, 75 to 200 microns.
  • Cured clear films (non-pigment containing films) of the novel coating composition formulated with a polymer, for example, an acrylic polymer, have excellent elastic and hardness properties and the Tg of the cured film is greater than 50° C. which is surprising since the diol used in the composition has a Tg of ⁇ 75° C. While not wishing to be bound by a theory, it is believed the polymer provides the hardness to the coating while the polytrimethylene ether diol segment provides improved flexibility and thus provides a coating with improved chip resistance and desired hardness.
  • the composition of this invention forms finishes having a high excellent flexibility, good adhesion to metal substrates, provides good filling of surface imperfections, can easily be sanded in a short time after application and curing and provides excellent stone chip resistance.
  • the coating composition has a good cure response at ambient temperatures and excellent cure response at elevated temperature curing conditions.
  • Gravelometer similar to test method ASTM D3170. A 90 degree panel angle is used, with panels and stones conditioned in a freezer held at ⁇ 26° C. to ⁇ 36° C. for a minimum of 2 hours prior to testing. One pint of such frozen stones is used in the test. Additionally, 3 pints of room-temperature stones are used on panels stored at room temperature to provide additional information. Panels are rated from 1 to 9 with 1 being the worst (very severe chipping) and 9 being the best (almost no chipping). Optionally, the area (in square millimeters) of the largest chip is also considered in assessing the performance of the coating.
  • Persoz Hardness Test the change in film hardness of the coating was measured with respect to time after application by using a Persoz Hardness Tester Model No. 5854 [ASTM D4366] supplied by Byk-Mallinckrodt, Wallingford, Conn. The number of Oscillations [referred as Persoz No.] are recorded.
  • Hardness was measured using a Fischerscope® Hardness Tester. [The measurement is in Newtons per square millimeter.]
  • Tg glass transition temperature
  • Molecular weights Mw and Mn and the polydispersity (Mw/Mn) of the acrylic polymer and other polymers are determined by GPC (Gel Permeation Chromatography) using polystyrene standards and tetrahydrofuran as the solvent.
  • Percent strain to break and energy to break were obtained on a Model 1122 Instron electromechanical test machine modified for computer control and data reduction and maintained according the standards of ISO 9001.
  • Test sample width was 12.7 mm and thickness was approximately 0.1 mm; the exact thickness was determined with a calibrated micrometer.
  • the gage length was 12.7 mm and test speed was 5.0 mm/min. All results were obtained under ambient laboratory conditions.
  • 1,3-Propanediol (3.4 kg) and concentrated sulfuric acid (30.4 g) were placed in a 5 L three neck round bottom flask fitted with a nitrogen inlet, mechanical stirrer and a distillation head. Nitrogen gas was bubbled through the reaction mixture for 15 minutes. The polymerization was carried out at 160° C. with stirring under a nitrogen atmosphere. After collecting 525 g of water distillate in a receiving flask, the flask was connected to a vacuum pump and the pressure was slowly reduced to 1-5 mm Hg. The molecular weight of the resulting reaction product was monitored by analyzing the samples at different time intervals using an NMR end group analysis method. The polymerization was stopped after obtaining the desired molecular weight (approximately 2,000) and the polymer was purified as described below.
  • Primer millbase compositions A, B, and C were prepared by charging the following ingredients into a mixing vessel: Primer Millbase Compositions A B C Description of Material PBW PBW PBW Portion 1 Butyl acetate 130.90 84.38 52.17 Xylene 21.30 21.81 22.21 Methyl amyl ketone 23.20 23.81 24.25 Methyl isobutyl ketone 75.30 77.09 78.50 Polytrimethylene ether diol B Mn 2738 75.70 38.75 — (prepared above) Ethylene oxide oligomer (1) 0.0 48.44 98.64 Hydroxy acrylic polymer (2) 295.20 305.97 — Hydroxy acrylic polymer (3) — — 307.9 BYK-320 dispersion (Polysiloxane resin 3.80 3.88 3.95 available from Byk Chemie) Anti-Terra U (salt of a long chain 2.80 2.82 2.87 polyamine-amide and high molecular weight este
  • Hydroxy acrylic polymer (2) acrylic polymer of 37 parts styrene, 17.5 parts isobornyl methacrylate, 25.5 parts hydroxyethyl methacrylate, 20 parts 2-ethylhexyl methacrylate having a Mw of 15,000 and a Tg of 68° C.
  • Hydroxy acrylic polymer (3) acrylic polymer of 37 parts styrene, 23 parts hydroxyethyl acrylate, 40 parts 2-ethylhexyl methacrylate having a Mw of 15,000 and a Tg of 20° C.
  • Primer Millbase Compositions A, B and C In the preparation of each of the Primer Millbase Compositions A, B and C, Portion 1 was charged into the mixing vessel and stirred for 15 minutes. Portion 2 was premixed and slowly added to the mixing vessel with stirring and stirred for 30 minutes. Portion 3 was premixed and slowly added to the mixing vessel with stirring and stirred for 60 minutes. Portion 4 was added and stirred for 15 minutes and the resulting mixture was ground 3 passes in a top feed sand mill using glass media for 3 passes. Since Primer Millbase Composition C does not contain polytrimethylene ether diol, it is considered to be a comparative composition.
  • Primer Millbases A to C have the following properties: Primer Millbase A B C Weight % solids 70.2 72.0 73.4 Volume % solids 49.8 51.6 53.3 Pigment/Binder ratio 312.85/100 309.71/100 309.7/100 Pigment Vol. Concentration (%) 53.7 54.2 54.0 Gallon Weight (#/gal) 12.09 12.36 12.49
  • Activated Primer Compositions A to C were prepared by blending the following ingredients together shortly before spray application: Activated Primer Comp. A B C Primer Mill Base 166.40 161.95 157.69 Reducer (3) 18.80 18.32 17.84 Activator (4) 14.80 19.73 24.46 Total 200.00 200.00 200.00 Reducer (3) - 12375S - blend of hydrocarbon solvents commercially available from E.I. DuPont de Nemours and Company, Wilmington, Delaware. Activator (4) - 12305S - Tolonate ® HDT trimer of hexamethylene diisocyanate (Rhodia Inc.) activator is commercially available from E.I. DuPont de Nemours and Company, Wilmington, Delaware.
  • the above prepared Activated Primer Compositions A to C were each applied by spraying onto separate cold rolled steel panels coated with about 0.3 to 0.6 mils (7.5 to 15 microns) of a commercial refinish wash primer (described below) and the Activated Primer Composition was cured at ambient temperature. After curing, the resulting dry film thickness of the primer composition was in the range of 4 to 7 mils (100 to 178 microns).
  • the Persoz Hardness and the Fischer Hardness were measured for each of the panels and shown in Tables 2 and 3 below.
  • Primer C panels were retested (Primer C did not contain the polytrimethylene ether diol). TABLE 2 Persoz Hardness of Activated Primer Compositions A to C Primer 3 Hours 1 Day A 30 66 B 30 51 C 34 36 C (retest) 34 36
  • the commercial refinish wash primer utilized to prime the above steel panels is formulated by mixing Variprime® 615S (pigmented component) and Variprime® 616S (reducer component) in a 1/1 volume ratio (weight ratio of 120 g of 615S/80 g of 616S) to form a composition having a total solids content of 28.43%, binder solids of 8.39%, pigment to binder weight ratio of 239/100, VOC (#/gal) 5.891 and a gallon weight (#/gal) of 5.42.
  • the binder of the primer is a combination of phenolic/polyvinyl butyral/nitrocellulose resin.
  • the pigment portion of 615S contains zinc chromate pigment in the amount of 5.3% on the total formula composition by weight.
  • the reducer (616S) contains phosphoric acid in the amount of 2.2% by weight based the total formula weight.
  • 615S and 616S are commercial products available from E.I. DuPont de Nemours and Company, Wilmington
  • a set of panels primed with Primer Compositions A to C was prepared as above.
  • the panels were allowed to cure overnight at about 24° C. and 50% relative humidity, and were then sanded with 400 grit sandpaper to give a film build of about 4.0 to 4.5 mils (102 to 114 microns).
  • Each of the panels was coated with an un-activated blue metallic base coat—ChromaBase® Blue Metallic basecoat N 8112K (hydroxy functional acrylic polymer dispersion containing dispersed aluminum flake pigments, phthalocyanine blue pigment and carbon black pigment) and Chromasystems Basemaker 7175S (acrylic resin in organic solvents—available from E.I. DuPont de Nemours and Company, Wilmington, Delaware).
  • Another panel was prepared as above with Primer Composition C and the blue metallic base coat was activated with ChromaPremier® 12305S isocyanate activator.
  • a second set of panels coated with Primer Composition A to C and prepared as described above was coated with an unactivated red base coat—ChromaBase® Red Basecoat B8713K (hydroxyfunctional acrylic polymer dispersion containing Monastral® Magenta pigment dispersion and Perrindo® red dispersion) and Chromasystems Basemaker 7175S (acrylic resin in organic solvents).
  • ChromaBase® Red Basecoat B8713K hydroxyfunctional acrylic polymer dispersion containing Monastral® Magenta pigment dispersion and Perrindo® red dispersion
  • Chromasystems Basemaker 7175S acrylic resin in organic solvents.
  • One part of B8731K was mixed with one part of 7175S.
  • Each of the panel was coated with a clear top-coat (described above).
  • Clear Coating Composition F is a comparative composition that was formulated with a low Tg acrylic polymer (Tg 20° C.).
  • Clear Coating Composition E is a comparative composition that was formulated with a high Tg acrylic polymer (Tg 68° C.).
  • Clear Coating Composition D is a preferred composition of the invention and was also formulated with the same high Tg acrylic polymer. Clear Coating Composition D has acceptable hardness values (Persoz and Fischer) but significantly higher % Strain to Break and Energy to Break which typically translates into a more durable clear coating composition that is useful on automobiles and truck in comparison to Clear Coating Compositions E and F.
  • Clear Coating Composition E that used the same high Tg acrylic polymer as Clear Coating Composition D but did not use the polytrimethylene ether diol but rather a ethylene oxide oligomer had high hardness but significantly lower % Strain to Break and Energy to Break in comparison to Clear Coating Composition D which represents the invention.
  • Clear Coating Composition F that used the low Tg acrylic polymer and the ethylene oxide oligomer had significantly lower % Strain to Break and Energy to Break in comparison to Clear Coating Composition D which represents the invention.
  • PPG 2000 Polypropylene glycol having a molecular weight of 2000 from Aldrich Chemical Company (product no. 81380).
  • Terathane ® 2000 polyether glycol having a molecular weight of 2023 from E.I. DuPont de Nemours and Company.
  • Activator (4) described in Example 1.
  • the above prepared Clear Coating Compositions G to K were each applied with a draw-down bar on electrocoated steel panels.
  • the clear coating compositions were cured at an ambient temperature of about 24° C.
  • the resulting dry film thickness of each of the clear coating compositions was in the range of 1.8 to 2.2 mils (46 to 56 microns).
  • Primer millbase compositions L to P were prepared by charging the following ingredients into a mixing vessel: Primer Millbase Compositions L M N O P Description of Material PBW PBW PBW PBW PBW Portion 1 Butyl acetate 131.0 131.0 131.0 130.9 127.3 Xylene 21.3 21.3 21.3 21.3 20.7 Methyl amyl ketone 23.3 23.3 23.3 23.2 22.5 Methyl isobutyl ketone 75.3 75.3 75.2 73.2 Polytrimethylene ether diol Mn 2753 75.7 — — — — PPG 2000 (5) described in — 75.7 — — — —
  • Example 3 Terathane ® 2000 (6) — — 75.7 — — described in Example 3
  • the resulting Primer Millbases L to P have the following properties: Primer Millbase L M N O P Weight % solids 69.9 69.9 69.9 69.9 67.8 Volume % solids 49.1 49.1 52.7 48.9 46.3 Pigment/Binder 318.5/100 318.5/100 318.5/100 318.5/ 321.7/ ratio 100 100 Pigment Vol. 54.61 54.47 47.2 55.01 55.58 Concentration (%) Gallon Weight 12.13 12.13 11.26 12.17 11.98 (#/gal)
  • Activated Primer Compositions L to P were prepared by blending the following ingredients together shortly before spray application: Activated Primer Comp. L M N O P Primer Mill Base 250 249.8 249.1 159.4 163.3 Reducer (3) 28.3 28.3 28.2 18.0 18.5 Activator (4) 21.7 21.9 22.7 22.5 17.9 Total 300.0 300.0 300.0 199.9 199.7 Reducer (3) - described in Example 1. Activator (4) - described in Example 1
  • the above prepared Activated Primer Compositions L to P were each applied by spraying onto separate cold rolled steel panels coated with about 0.3 to 0.6 mils (7.5 to 15 microns) of a commercial refinish wash primer (described in Example 1) and the Activated Primer Composition was cured at ambient temperature. The resulting dry film thickness of the primer composition was in the range of 4 to 7 mils (100 to 178 microns).
  • the Persoz Hardness and the Fischer Hardness were measured for each of the panels and shown in Tables 9 and 10 below. TABLE 9 Persoz Hardness of Activated Primer Compositions L to P Primer 3 Hours 1 Day L 34 86 M 39 93 N 41 85 O 35 46 P 30 61
  • a set of panels primed with Primer Compositions L to P was prepared as above.
  • the panels were allowed to cure overnight at about 24° C. and 50% relative humidity and were then sanded with 400 grit sandpaper and the resulting film build was about 4.0 to 4.5 mils (102 to 114 microns).
  • Each of the panels was coated with an un-activated red metallic base coat (described in Example 1).
  • Each panel was top coated with a clear top coat (DuPont ChromaClear® V-7500S described in Example 1) and cured.

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US20100267892A1 (en) * 2007-11-13 2010-10-21 Patrick Henry Corcoran Isocyanate terminated polytrimethylene ether polyol and process for making same
WO2010078232A1 (fr) * 2008-12-30 2010-07-08 E. I. Du Pont De Nemours And Company Composition de revêtement à l'eau contenant un polytriméthylène éther diol
WO2012024402A1 (fr) * 2010-08-17 2012-02-23 E. I. Du Pont De Nemours And Company Composition de revêtement durcissable aux uv présentant une résistance améliorée aux rayures
WO2013090398A1 (fr) * 2011-12-12 2013-06-20 U.S. Coatings Ip Co. Llc Composition de revêtement à base d'eau contenant un polyol de poly(éther de triméthylène) provenant d'une ressource biologique
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CN108368335A (zh) * 2015-12-11 2018-08-03 株式会社钟化 机械强度优异的含有聚合物微粒的聚氨酯系固化性组合物

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US7268182B2 (en) 2007-09-11
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