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
  • C09D175/02—Polyureas
• • 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than 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
  • C08G18/30—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
  • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl 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
  • C08G18/4866—Polyethers having a low unsaturation value
• • 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
  • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
  • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
  • C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits

Definitions

• compositions based on isocyanate chemistry find utility as components in coatings, such as, for example, paints, primers, and the like.
• Isocyanate-based coating compositions may include, for example, polyurethane or polyurea coatings formed from resins comprising components, such as, for example, diisocyanates, polyisocyanates, and/or isocyanate reaction products. These resins may cure by various mechanisms so that covalent bonds form between the resin components, thereby producing a cross-linked polymer network.
• the present invention is directed to a polyurea coating composition
• a polyurea coating composition comprising the reaction product of:
• an isocyanate-functional component (A) comprising:
• the present invention is directed to a polyurea coating composition consisting essentially of the reaction product of:
• an isocyanate-functional component (A) comprising:
• an aliphatic isocyanate functional material a) an aliphatic isocyanate functional material; and b) a cycloaliphatic isocyanate functional material; and an isocyanate-reactive component (B) comprising at least one polyaspartic acid ester component.
• the present invention is directed to a polyurea coating composition consisting of the reaction product of:
• an isocyanate-functional component (A) comprising:
• an aliphatic isocyanate functional material a) an aliphatic isocyanate functional material; and b) a cycloaliphatic isocyanate functional material; and an isocyanate-reactive component (B) comprising at least one polyaspartic acid ester component.
• compositions and methods according to the present disclosure should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
• any numerical range recited herein is intended to include all sub-ranges subsumed therein.
• a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
• grammatical articles "one,” “a,” “an,” and “the,” as used herein, are intended to include “at least one” or “one or more,” unless otherwise indicated.
• the articles are used herein to refer to one or more than one (i.e., to at least one) of the grammatical objects of the article.
• a component means one or more components, and thus, possibly, more than one component is contemplated and may be employed or used.
• aliphatic refers to organic compounds characterized by substituted or un-substituted straight, branched, and/or cyclic chain arrangements of constituent carbon atoms. Aliphatic compounds do not contain aromatic rings as part of the molecular structure of the compounds.
• cycloaliphatic refers to organic compounds characterized by arrangement of carbon atoms in closed ring structures. Cycloaliphatic compounds do not contain aromatic rings as part of the molecular structure of the compounds.
• an aliphatic composition may comprise an aliphatic
• diisocyanate refers to a compound containing two isocyanate groups.
• diisocyanate refers to a compound containing two isocyanate groups.
• polyisocyanate refers to a compound containing two or more isocyanate groups. Hence, diisocyanates are a subset of polyisocyanates.
• the isocyanate component (A) may comprise a combination of an aliphatic isocyanate functional material and a cycloaliphatic isocyanate functional material.
• the aliphatic isocyanate functional material may comprise a reaction product of an aliphatic diisocyanate and a hydroxy- functional ether compound.
• the cycloaliphatic isocyanate functional material may comprise a reaction product of a cycloaliphatic diisocyanate and a mono-functional alcohol compound.
• the aliphatic isocyanate functional material and the cycloaliphatic isocyanate functional material may each comprise at least one functional group selected from the group consisting of isocyanurate, iminooxadiazine, uretdione, allophanate, biuret, and combinations of any thereof.
• the aliphatic and cycloaliphatic isocyanate functional materials may be produced from and/or comprise polyisocyanates having an isocyanate functionality greater than 2.
• Isocyanurates may be prepared by the cyclic trimerization of polyisocyanates. Trimerization may be performed, for example, by reacting three (3) equivalents of a polyisocyanate to produce 1 equivalent of isocyanurate ring.
• the three (3) equivalents of polyisocyanate may comprise three (3) equivalents of the same polyisocyanate compound, or various mixtures of two (2) or three (3) different polyisocyanate
• trimerization catalysts such as, for example, phosphines, Mannich bases and tertiary amines, such as, for example, 1 ,4-diaza- bicyclo[2.2.2]octane, dialkyl piperazines, and the like, may be used as trimerization catalysts.
• Iminooxadiazines may be prepared by the asymmetric cyclic trimerization of polyisocyanates.
• Uretdiones may be prepared by the dimerization of a polyisocyanate.
• Allophanates may be prepared by the reaction of a polyisocyanate with a urethane.
• Biurets may be prepared via the addition of a small amount of water to two equivalents of polyisocyanate and reacting at slightly elevated temperature in the presence of a biuret catalyst. Biurets may also be prepared by the reaction of a polyisocyanate with a urea.
• isocyanurates, iminooxadiazines, biurets, uretdiones and allophanates, and which may find utility in the production of aliphatic and cycloaliphatic isocyanate functional materials for use in the disclosed engineered resin, may include aliphatic and cycloaliphatic diisocyanates, such as, for example, ethylene diisocyanate; 1 ,4-tetramethylene diisocyanate; 1 ,6- hexamethylene diisocyanate ("HDI"); 2,2,4-trimethyl-1 ,6-hexamethylene diisocyanate; 1 ,12-dodecamethylene diisocyanate; 1 -isocyanato-3- isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or "IPDI"); bis-(4-isocyanatocyclohexyl)methane ("H 12 MDI"); bis-(4- is
• Additional polyisocyanates (including various diisocyanates) that may also find utility in the production of aliphatic and cycloaliphatic isocyanate functional materials may include the polyisocyanates described in U.S. Patent Nos. 4,810,820; 5,208,334; 5,124,427; 5,235,018;
• isocyanate functional materials comprising an adduct of a polyisocyanate and a hydroxy-functional compound may find utility in the isocyanate component (A).
• Isocyanate functional materials may be formed, for example, by reacting an aliphatic or cycloaliphatic polyisocyanate with a hydroxy-functional compound, such as, for example, a mono-functional alcohol ("monoalcohol” or "monol"), a poly-functional alcohol (“polyol”), a mixture of monols, a mixture of polyols, or a mixture of monols and polyols.
• a polyisocyanate may be reacted with a hydroxy-functional compound to produce a polyisocyanate-hydroxyl compound adduct comprising urethane groups and/or allophanate groups, for example.
• polyisocyanates may be reacted with hydroxy-functional compounds at an OH:NCO molar ratio of 1 :1.5 to 1 :20.
• polyisocyanates may be reacted with hydroxy-functional compounds at an OH:NCO molar ratio of 1 :2 to 1 :15, or 1 :5 to 1 :15.
• Polyisocyanates that may be used to produce aliphatic and cycloaliphatic isocyanate functional materials may include, for example, the aliphatic and cycloaliphatic diisocyanates described above.
• Polyisocyanates that may be used to produce isocyanate functional materials may also include, for example, compounds produced from the diisocyanates described above and comprising at least one functional group selected from the group consisting of isocyanurate,
• iminooxadiazine uretdione, allophanate, biuret, and combinations of any thereof.
• hydroxy-functional polymeric and/or oligomeric polyethers may be used to produce the aliphatic isocyanate functional material.
• polyether refers to both polymeric and oligomeric compounds containing ether groups.
• Polyethers that may find utility in producing aliphatic isocyanate functional materials may include polyethers having from one to four free hydroxyl groups.
• Polyethers may be prepared, for example, by the oligomerization or polymerization of epoxides.
• epoxides may include, for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin.
• Each epoxide may be reacted alone (e.g., in the presence of boron trifluoride), as a mixture with a starting component having reactive hydrogen atoms, or by successive addition of the epoxide to a starting component having reactive hydrogen atoms.
• Starting components that may find utility in preparing polyethers may include, for example, water, alcohols, and phenols. Suitable starting components may include ethylene glycol; (1 ,3)- and (1 ,2)-propylene glycol; and
• the isocyanate component (A) comprises a) an aliphatic isocyanate functional material comprising a reaction product of a diisocyanate and a hydroxy-functional polyether.
• Hydroxy-functional polyethers that may find utility in the production of aliphatic isocyanate functional materials may include, for example, hydroxy-functional alkylene ether polyols, such as, for example, hydroxy-functional poly(tetra- methylene glycol), poly(propylene oxide), poly(ethylene oxide), and poly(ethylene-co-propylene oxide).
• Polyether polyols that may find utility in the production of aliphatic isocyanate functional materials may also include, for example, ethylene oxide and/or propylene oxide adducts of polyols, such as, for example, the ethylene oxide and/or propylene oxide adducts of ethylene glycol or butylene glycol.
• polycaprolactone which may function similarly to a hydroxy-functional polyether, may find utility in the production of an aliphatic isocyanate functional material.
• hydroxy-functional compounds that may be used to produce b) cycloaliphatic isocyanate functional materials may include, for example, one or more mono-functional alcohols, such as, for example, methanol, ethanol, n-propanol, isopropanol, butanol isomers, pentanol isomers, hexanol isomers, heptanol isomers, octanol isomers, nonanol isomers, decanol isomers, 2-ethylhexanol, trimethyl hexanol, cyclohexanol, fatty alcohols having 11 to 20 carbon atoms, vinyl alcohol, allyl alcohol, and combinations of any thereof.
• mono-functional alcohols such as, for example, methanol, ethanol, n-propanol, isopropanol, butanol isomers, pentanol isomers, hexanol isomers, hept
• mono-functional alcohols that may be used to produce cycloaliphatic isocyanate functional materials may include linear, branched, or cyclic alcohols containing 6 to 9 carbon atoms. In certain embodiments, the mono-functional alcohols may contain ether groups.
• the a) aliphatic isocyanate functional material may comprise an HDI-based aliphatic isocyanate functional material.
• the HDI-based aliphatic isocyanate functional material may comprise at least one allophanate group, for example.
• the HDI-based aliphatic isocyanate functional material may comprise, for example, a reaction product of a hydroxy-functional ether compound and HDI.
• the ether compound may comprise a hydroxy-functional polyether, for example.
• a hydroxy-functional polyether may comprise, for example, a polyetherpolyol as described in U.S. Patent No. 7,038,003, incorporated in its entirety by reference herein.
• a hydroxy-fu notional polyether may have a number-average molecular weight (M n ) of from 300 to 20000 g/mol. In certain embodiments, a hydroxy-functional polyether may have a number- average molecular weight (M n ) of from 1000 to 12000 g/mol, and in other embodiments 1000 to 4000 g/mol.
• hydroxy-functional polyethers may contain less than or equal to 0.02 milliequivalent of unsaturated end groups per gram of polyol (meq/g), in some embodiments less than or equal to 0.015 meq/g, and in other embodiments less than or equal to 0.01 meq/g (determined according to ASTM D 2849-69, incorporated by reference herein).
• hydroxy-functional polyethers may have a relatively narrow molecular weight distribution (e.g., a polydispersity (M w /M n ) of from 1.0 to 1.5) and/or an OH functionality of >1.9.
• hydroxy- functional polyethers may have OH functionalities of less than 6, or less than 4, for example.
• Hydroxy-functional polyethers that may find utility in the disclosed engineered resins may be prepared by alkoxylating suitable starter molecules, for example, using double metal cyanide catalysts (DMC catalysis), which is described, for example, in U.S. Patent No. 5,158,922 and E.P. Publication No. A 0 654 302, each of which is incorporated in its entirety by reference herein.
• DMC catalysis double metal cyanide catalysts
• the HDI-based aliphatic isocyanate functional material may be prepared by reacting HDI with a polyether prepared using DMC catalysis.
• the HDI-based aliphatic isocyanate functional material comprises a reaction product of HDI and polypropylene glycol, characterized in that the reaction product comprises allophanate groups.
• the HDI-based aliphatic isocyanate functional material may comprise an average isocyanate functionality of at least 4, a glass transition temperature of less than -40 °C, and/or a %NCO of less than 10%.
• the HDI-based aliphatic isocyanate functional material may be essentially free of HDI isocyanurate trimer.
• An HDI-based aliphatic isocyanate functional material comprising a reaction product of a hydroxy-functional compound and HDI, and having at least one allophanate group, may be prepared according to the processes described, for example, in U.S. Patent No. 7,038,003.
• the b) cycloaliphatic isocyanate functional material may comprise an IPDI-based cycloaliphatic isocyanate functional material.
• the IPDI-based cycloaliphatic isocyanate functional material may comprise at least one allophanate group and at least one
• the IPDI-based cycloaliphatic isocyanate functional material may comprise, for example, a reaction product of a mono-functional alcohol and IPDI.
• the mono-functional alcohol may comprise a monoalcohol as described in U.S. Patent Nos. 5,124,427; 5,235,018; 5,208,334; and 5,444,146, each of which is incorporated in its entirety by reference herein.
• the IPDI-based cycloaliphatic isocyanate functional material may be prepared by reacting IPDI with a monoalcohol to produce a polyisocyanate mixture having an NCO content of 10% to 47% by weight, a viscosity of less than 10,000 mPa.s, and containing isocyanurate and allophanate groups in a molar ratio of
• the IPDI-based cycloaliphatic isocyanate functional material comprises a reaction product of IPDI and a monoalcohol selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, butanol isomers, pentanol isomers, hexanol isomers, heptanol isomers, octanol isomers, nonanol isomers, decanol isomers, 2-ethylhexanol, trimethyl hexanol, cyclohexanol, fatty alcohols having 11 to 20 carbon atoms, vinyl alcohol, allyl alcohol, and combinations of any thereof.
• a monoalcohol selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, butanol isomers, pentanol isomers, hexanol isomers, heptanol is
• the monoalcohol may be selected from the group consisting of methanol, ethanol, 1-butanol, 2-butanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, isocetyl alcohol, 1-dodecanol, and a mono- hydroxy poly(ethylene oxide), characterized in that the IPDI reaction product comprises isocyanurate and allophanate groups in a molar ratio of monoisocyanurates to monoallophanates of 10:1 to 1 :5.
• the IPDI-based cycloaliphatic isocyanate functional material may comprise an average isocyanate functionality of at least 2.3, a glass transition temperature between 25 °C and 65 °C, and/or a %NCO of 10% to 47% by weight.
• the b) cycloaliphatic isocyanate functional material e.g., an IPDI-based cycloaliphatic isocyanate functional material
• the a) aliphatic isocyanate functional material e.g., an HDI-based aliphatic isocyanate functional material
• the isocyanate component (A) may comprise 95:5 to 50:50 cycloaliphatic isocyanate functional material to aliphatic isocyanate functional material, by weight.
• the isocyanate component (A) may comprise 75:25 to 65:35 cycloaliphatic isocyanate functional material to aliphatic isocyanate functional material, by weight. In certain other embodiments, the isocyanate component (A) may comprise 73:27 to 69:31 cycloaliphatic isocyanate functional material to aliphatic isocyanate functional material, by weight.
• the isocyanate component (A) may comprise from 50 weight percent to 100 weight percent b) cycloaliphatic isocyanate functional material (e.g., an IPDI-based cycloaliphatic isocyanate functional material).
• the isocyanate component (A) may comprise from 0 weight percent to 50 weight percent a) aliphatic isocyanate functional material (e.g., an HDI-based aliphatic isocyanate functional material).
• the isocyanate component (A) may comprise 50%-99%, 50%-95%, 50%-90%, 50%-80%, 50%-70%, or 50%-60%, by weight, b) cycloaliphatic isocyanate functional material.
• the isocyanate component (A) may comprise 1%-50%, 5%-50%, 10%-50%, 20%-50%, 30%-50%, or 40%-50%, by weight, a) aliphatic isocyanate functional material.
• the isocyanate component (A) may comprise 60%-99%, 60%-95%, 60%-90%, 60%-80%, or 60%-70%, by weight, b) cycloaliphatic isocyanate functional material. In certain other embodiments, the isocyanate component (A) may comprise 70%-99%, 70%-95%, 70%-90%, or 70%-80%, by weight, b) cycloaliphatic isocyanate functional material. In certain other embodiments, the isocyanate component (A) may comprise 65%-75%, by weight, b) cycloaliphatic isocyanate functional material.
• the isocyanate component (A) may comprise 1 %-40%, 5%-40%, 10%-40%, 20%-40%, or 30%-40%, by weight, a) aliphatic isocyanate functional material. In certain other embodiments, the isocyanate component (A) may comprise 1%-30%, 5%- 30%, 10%-30%, or 20%-30%, by weight, a) aliphatic isocyanate functional material. In certain other embodiments, the isocyanate component (A) may comprise 25%-35%, by weight, a) aliphatic isocyanate functional material. In certain embodiments, the isocyanate-reactive component (B) may comprise polyaspartic acid esters prepared in accordance with U.S. Patent No.
• Suitable polyaspartic acid esters for use in accordance with the present invention include those corresponding to the formula:
• X represents an organic group which has a valency of n and is inert towards isocyanate groups at a temperature of 100°C or less, preferably the group obtained, more preferably the hydrocarbon group obtained, by removing the amino groups from an aliphatic, araliphatic or cycloaliphatic polyamine, more preferably a diamine, and
• Ri and R 2 may be the same or different and represent organic groups which are inert towards isocyanate groups at a temperature of 100°C or less, preferably an alkyl group containing 1 to 9 carbons and more preferably methyl, ethyl or butyl groups, or Ri and R 2 together with the ⁇ -carbon atom form a cycloaliphatic or heterocyclic ring,
• R3 and R 4 may be identical or different and represent hydrogen or
• organic groups which are inert towards isocyanate groups at a temperature of 100°C or less and n has a value of at least 2, preferably 2 to 6, more preferably 2
• polyaspartic acid esters may be prepared by reacting optionally substituted maleic or fumaric acid esters with polyamines.
• Suitable optionally substituted maleic or fumaric acid esters are those corresponding to the formula
• optionally substituted maleic or fumaric acid esters suitable for use in the preparation of the polyaspartates include dimethyl, diethyl and dibutyl (e.g., di-n-butyl) esters of maleic acid and fumaric acid and the corresponding maleic or fumaric acid esters substituted by methyl in the 2- and/or 3-position.
• Suitable polyamines for preparing the polyaspartic acid esters include those corresponding to the formula
• the polyamines include high molecular weight amines having molecular weights of 400 to about 10,000, preferably 400 to about 6,000, and low molecular weight amines having molecular weights below 400.
• the molecular weights are number average molecular weights (M n ) and are determined by end group analysis (NH number). Examples of these polyamines are those wherein the amino groups are attached to aliphatic, cycloaliphatic, araliphatic and/or aromatic carbon atoms.
• Suitable low molecular polyamines include ethylene diamine, 1 ,2- and 1 ,3-propane diamine, 2-methyl-1 ,2-propane diamine, 2,2-dimethyl-1 ,3- propane diamine, 1 ,3- and 1 ,4-butane diamine, 1 ,3- and 1 ,5-pentane diamine, 2-methyl-1 ,5-pentane diamine, 1 ,6-hexane diamine, 2,5-dimethyl- 2,5-hexane diamine, 2,2,4-and/or 2,4,4-trimethyl-1 ,6-hexane diamine, 1 ,7- heptane diamine, 1 ,8-octane diamine, 1 ,9-nonane diamine,
• triaminononane 1 , 10-decane diamine, 1 ,11 -undecane diamine, 1 ,12- dodecane diamine, 1-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane, 2,4- and/or 2,6-hexahydrotoluylene diamine, 2,4'- and/or 4,4'-diamino- dicyclohexylmethane, 3,3'-dialkyl-4,4'-diamino-dicyclohexyl methanes (such as 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane and 3,3'-diethyl- 4,4'-diamino-dicyclohexyl methane), 1 ,3- and/or 1 ,4-cyclohexane diamine,
• Preferred polyamines are 1-amino-3-aminomethyl-3,5,5-trimethyl- cyclohexane (isophorone diamine or IPDA), bis-(4-aminocyclo-hexyl)- methane, bis-(4-amino-3-methylcyclohexyl)-methane, 1 ,6-diamino-hexane, 2-methyl pentamethylene diamine, ethylene diamine, triamino-nonane, 2,4- and/or 2,6-toluylene diamine and 4,4'- and/or 2,4'-diamino-diphenyl methane.
• IPDA isophorone diamine or IPDA
• Suitable high molecular weight polyamines include those prepared from the known polyhydroxyl compounds of polyurethane, especially the polyethers.
• the polyamines may be prepared by reacting the polyhydroxyl compounds with an excess of the previously described
• polyisocyanates to form NCO prepolymers and subsequently hydrolyzing the terminal isocyanate group to an amino group.
• the polyamines are prepared by converting the terminal hydroxy groups of the polyhydroxyl compounds to amino groups, e.g., by amination.
• Preferred high molecular weight polyamines are amine-terminated polyethers such as the Jeffamine ® resins available from Huntsman International, LLC.
• the preparation of the polyaspartic acid esters from the above mentioned starting materials may be carried out, for example, at a temperature of 0 to 100°C using the starting materials in such proportions that at least 1 , preferably 1 , olefinic double bond is present for each primary amino group. Excess starting materials may be removed by distillation after the reaction. The reaction may be carried out solvent-free or in the presence of suitable solvents such as methanol, ethanol, propanol, dioxane and mixtures of such solvents.
• the polyurea coating composition may be prepared by mixing the isocyanate component (A) and the polyaspartic acid ester (B) at an NCO.NH ratio of from about 20:1 to 1 :20, in some embodiments from about 10:1 to 1 :10, in some embodiments from about 5:1 to 1 :5, in some embodiments from about 3:1 to 1 :3, in some
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more aldimines or ketimines as disclosed in U.S. Patent Nos. 6,164,141 and 5,623,045, respectively, each of which is incorporated in its entirety herein by reference.
• the polyurea coating composition does not include aldimines or ketimines.
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more organic acids, as disclosed in U.S. Patent No. 5,580,945, which is incorporated in its entirety herein by reference.
• the polyurea coating composition does not include any such organic acids.
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more silane adhesion promoters as disclosed in U.S. Patent Nos. 6,444,325 and 6,887,964, respectively, each of which is incorporated in its entirety herein by reference.
• the polyurea coating composition does not include such silane adhesion promoters.
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and additional components.
• the moisture-curable coating composition may comprise, for example, the isocyanate component (A), the polyaspartic acid ester (B), additive resins, pigments, tint pastes, pigment wetting agents, pigment dispersants, light stabilizers, UV-absorbers, rheology modifiers, defoamers, dehydrators, solvents, catalysts, or additives to affect, for example, substrate wetting, film leveling, coating surface tension, pigment grinding, pigment deflocculation, or gloss.
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more additive resins, such as, for example, Joncryl ® 611 (BASF Corporation) and/or Neocryl B-734TM (DSM N.V.).
• Joncryl ® 611 is a styrene-acrylic acid copolymer resin.
• Joncryl ® 611 may be used as an additive resin in a polyurea coating composition to affect pigment dispersion and film-forming properties, for example.
• Neocryl B-734TM is a methyl methacrylate, n-butyl methacrylate copolymer resin.
• Neocryl B- 734TM may be used as an additive resin to affect pigment dispersion and film-forming properties, for example.
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more pigments, such as, for example, titanium dioxide.
• the disclosed polyurea coating composition may include, for example, KronosTM 2310 (Kronos Worldwide, Inc.) and/or Ti-Pure ® R-706 (DuPont).
• the disclosed polyurea coating composition may comprise one or more fillers. Fillers that may find utility in the disclosed polyurea coating composition may include, for example, Imsil ® A-10 (Unimin Corporation) and/or Nytal ® 3300 (R. T. Vanderbilt Company).
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more pigment wetting agents or dispersants.
• Pigment wetting agents and dispersants that may find utility in the disclosed polyurea coating composition may include, for example, Disperbyk ® -110 (BYK- Chemie GmbH), Disperbyk ® -192(BYK-Chemie GmbH), and/or Anti-Terra U (BYK-Chemie GmbH).
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more rheology modifiers.
• Rheology modifiers that may find utility in the disclosed polyurea coating composition may include, for example, Byk ® 430, Byk ® 431 (BYK-Chemie GmbH), Bentonite clays, and/or castor oil derivatives.
• a polyurea coating composition may comprise the disclosed engineered resin and one or more defoamers. Defoamers that may find utility in the disclosed polyurea coating composition may include, for example, Byk ® 077 (BYK-Chemie GmbH).
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more light stabilizers and/or UV-absorbers.
• Light stabilizers that may find utility in the disclosed polyurea coating composition may include, for example, Tinuvin ® 292 (Ciba/BASF).
• UV-absorbers that may find utility in the disclosed polyurea coating composition may include, for example, Tinuvin ® 1130 (Ciba/BASF).
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more dehydrators.
• Dehydrators that may find utility in the polyurea coating composition may include, for example, p-toluenesulfonyl isocyanate, isophorone
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more catalysts, such as, for example, dibutyltin dilaurate or a tertiary amine.
• Catalysts that may find utility in the disclosed polyurea coating composition may include, for example, Dabco ® T-12 (Air Products and Chemicals, Inc.) and/or 1 ,4-diazabicyclo[2.2.2]octane.
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more additional additives.
• the polyurea coating composition may comprise the isocyanate component (A), the polyaspartic acid ester (B) and one or more solvents.
• Solvents that may find utility in the disclosed polyurea coating composition may include, for example, methyl n-amyl ketone ("MAK”), AromaticTM 100 (ExxonMobile Chemical), AromaticTM 150 (ExxonMobile Chemical), xylene, methyl isobutyl ketone (“MIBK”), ethyl 3- ethoxypropionate (EastmanTM EEP solvent, Eastman Chemical Company), and/or methyl ethyl ketone (“MEK”).
• MAK methyl n-amyl ketone
• MIBK methyl isobutyl ketone
• MEK methyl ethyl 3- ethoxypropionate
• the application of the polyurea coating composition of the present invention to the substrate to be coated takes place with the methods known and customary in coatings technology, such as spraying, knife coating, curtain coating, vacuum coating, rolling, pouring, dipping, spin coating, squeegeeing, brushing or squirting or by means of printing techniques such as screen, gravure, flexographic or offset printing and also by means of transfer methods.
• coatings technology such as spraying, knife coating, curtain coating, vacuum coating, rolling, pouring, dipping, spin coating, squeegeeing, brushing or squirting or by means of printing techniques such as screen, gravure, flexographic or offset printing and also by means of transfer methods.
• the polyurea coating composition of the present invention finds particular utility in the coating of metal substrates.
• the polyurea coating composition shows improved adhesion over known coating compositions with respect to new or weathered galvanized steel, treated or untreated steel, treated or untreated aluminum and metal alloys.
• Suitable substrates also include, for example, wood, plastic, including plastic in the form of films, especially ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM, and UP (abbreviations according to DIN 7728T1), paper, leather, textiles, felt, glass, wood, wood materials, cork, inorganically bonded substrates such as wooden boards and fiber cement slabs, electronic assemblies or mineral substrates.
• plastic including plastic in the form of films, especially ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET,
• Desmophen ® NH 1420 - Polyaspartic acid ester prepared from bis-(4- aminocyclohexyl)-methane (amine number of 195-205) available from Bayer MaterialScience LLC.
• Desmodur ® N-75 BA Aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI) and dissolved in n-butyl acetate and xylene (1 :1), having an NCO content of 16.5 wt.%, available from Bayer
• the isocyanate functional material comprised 30 weight percent of an HDI-based aliphatic isocyanate functional material (the "HDI- based material”) and 70 weight percent of an IPDI-based cycloaliphatic isocyanate functional material (the "IPDI-based material”).
• the HDI-based material comprised an allophanate reaction product of HDI and a hydroxy-functional polyether prepared using DMC catalysis.
• the HDI was reacted with the polyether using the processes described in U.S. Patent No. 7,038,018.
• the HDI-based material had an average isocyanate functionality of greater than or equal to 4, a glass transition temperature of less than -40 °C, and a %NCO of less than 10% by weight.
• the HDI-based material was essentially free of HDI isocyanurate trimer.
• the IPDI-based material comprised an allophanate-modified isocyanurate trimer reaction product of IPDI and a monol.
• the IPDI was reacted with the monol using the processes described in U.S. Patent Nos. 5,124,427 and 5,235,018.
• the IPDI-based material had an average isocyanate functionality of at least 2.3, a glass transition temperature between 25 °C and 65 °C, and a %NCO of 10% to 20% by weight.
• Coating compositions were made according to the procedure of Example 2, with the specific formulations listed in each respective Example.
• Desmophen NH-1420, Byk 307 and Kronos 2310 are charged into the high speed grinding vessel and milled to a Hegman 6.5. Tinuvins 292 and 1130 along with DBE-9 are added in the letdown. The coating
• Tinuvin 292 1.36 0.16 1.36 0.16 Tinuvin 1130 2.72 0.28 2.72 0.28 DBE-9 70.78 7.74 0 0 SubTotal I 261.59 20.24 187.74 12.08
• Example 6 A commercially available system utilizing Desmophen NH 1420 and Desmodur N-75 BA/X indexed at an NCO:NH ratio of 1 :1 was tested in accordance with Examples 2-5 above.
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