WO2005123787A2 - Method for obtaining coating compositions having reduced voc - Google Patents
Method for obtaining coating compositions having reduced voc Download PDFInfo
- Publication number
- WO2005123787A2 WO2005123787A2 PCT/US2005/020611 US2005020611W WO2005123787A2 WO 2005123787 A2 WO2005123787 A2 WO 2005123787A2 US 2005020611 W US2005020611 W US 2005020611W WO 2005123787 A2 WO2005123787 A2 WO 2005123787A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mixture
- functional groups
- reactive
- functional
- polymer
- Prior art date
Links
Classifications
-
- 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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Definitions
- thermosetting polymers and/or oligomers for use in curable coating compositions, especially curable coating compositions having a low or reduced VOC.
- curable thermoset coating compositions are widely used in the coatings art. They are often used as topcoats in the automotive and industrial coatings industry. Such topcoats may be basecoats, clearcoats, or mixtures thereof.
- Color- plus-clear composite coatings are particularly useful as topcoats where exceptional gloss, depth of color, distinctness of image, or special metallic effect is desired.
- the automotive industry has made extensive use of these coatings for automotive body panels.
- Color-plus-clear composite coatings require an extremely high degree of clarity in the clearcoat to achieve the desired visual effect.
- High-gloss coatings also require a low degree of visual aberrations at the surface of the coating in order to achieve the desired visual effect such as high distinctness of image (DOI).
- DOI distinctness of image
- composite coatings must also simultaneously provide a desirable balance of finished film properties such as durability, hardness, flexibility, and resistance to environmental etch, scratching, marring, solvents, and/or acids.
- coating compositions In order to obtain the extremely smooth finishes that are generally required in the coatings industry, coating compositions must exhibit good flow before curing. Good flow is observed when the coating composition is fluid enough at some point after it is applied to the substrate and before it cures to a hard film to take on a smooth appearance. Some coating compositions exhibit good flow immediately upon application and others exhibit good flow only after the application of elevated temperatures.
- One way to impart fluid characteristics and good flow to a coating composition is to incorporate volatile organic solvents into the composition. These solvents provide the desired fluidity and flow during the coating process, but evaporate upon exposure to elevated curing temperatures, leaving only the coating components behind.
- VOC volatile organic content
- any such coating composition must continue to provide finished films having a good combination of properties with respect to durability, hardness, flexibility, and resistance to chipping, environmental etch, scratching, marring, solvents, and/or acids.
- film-forming components for coating compositions wherein the film-forming component is polymerized in a material that is inert with respect to polymerization but does not volatilize upon exposure to elevated curing temperature.
- a material would enter into the film-forming reaction of a thermosetting coating composition.
- the desired effect of incorporating the material into the final film would be to increase the crosslink density of the cured film and to impart positive film attributes such as etch resistance, flexibility, scratch and mar, or chip resistance.
- binders for curable coating compositions which provide all of the advantages of prior art binders, but that contribute lower levels of volatile organic solvents to the final coating composition while still providing desirable application properties as well as finished films having commercially acceptable appearance and performance properties.
- the disclosed method comprises providing a mixture (I) comprising a reactant mixture (a) and a nonvolatile solvent (b nv ), wherein reactant mixture (a) comprises one or more polymerizable components and nonvolatile solvent (b nv ) (i) is not a crystalline solid at 25 °C, (ii) is nonvolatile, (iii) comprises at least one functional group (Fi) and (iv) is a fluid solid.
- the reactant mixture (a) is subjected to polymerization conditions sufficient to polymerize reactant mixture (a) to provide a polymer (a').
- the nonvolatile solvent (b nv ) is subjected to reaction conditions wherein the at least one functional group (Fi) of nonvolatile solvent (b nv ) is reacted with at least one reactant (e) to provide a nonvolatile solvent (b' nv ) comprising at least two functional groups (F 2 ).
- the disclosed method results in a mixture (II) of a polymer (a') in a nonvolatile solvent (b' nv ) comprising at least two functional groups (F 2 ).
- the at least one functional group (Fi) is substantially nonreactive: (1) with the components of reactive mixture (a), (2) under the polymerization conditions in which reactant mixture (a) is polymerized, and (3) with polymer (a').
- a reactive polymer composition comprising an acrylic polymer or resin (a') comprising a functional group (F 3 ) that is at least one of a primary carbamate group, a primary hydroxyl group, a secondary hydroxyl group, and mixtures thereof, and a nonvolatile solvent (b' nv ) that is not a crystalline solid at 75°C but is a fluid solid at the temperature at which polymer (a') was polymerized, the nonvolatile solvent (b') comprising (i) four or more isomers, and (ii) at least two reactive functional groups (F 2) that are selected from primary carbamate, primary hydroxyl, and secondary hydroxyl, wherein no more than 10% of the sum of functional groups (F ) and (F 3 ) are primary hydroxyl groups and at least 60% of the sum of functional groups (F 2 ) and (F 3 ) are primary carbamate groups.
- the reactive polymer composition is made by a disclosed method.
- a method of making an acrylic polymer comprises providing a mixture (I) comprising a reactant mixture (a) and a solvent mixture (b) comprising a nonvolatile solvent (b nv ), wherein reactant mixture (a) comprises one or more ethylenically unsaturated monomers and nonvolatile solvent (b nv ) (i) is not a crystalline solid at 25°C, (ii) is nonvolatile, and (iii) comprises at least one functional group (Fi), polymerizing the reactant mixture (a) under free radical polymerization conditions in the solvent mixture (b) to provide an acrylic polymer (a'), and subjecting the nonvolatile solvent (b nv ) to reaction conditions wherein the at least one functional group (Fi) of nonvolatile solvent (b nv ) is reacted with at least one reactant (e) to result in at least two functional groups (F 2 ), said method producing a mixture (I) comprising a reactant mixture (a) and a solvent
- curable coating compositions comprising a mixture
- the mixture (II) comprising a polymer (a') and a nonvolatile solvent (b' nv ) comprising at least two functional groups (F 2 ), the mixture (II) made by the process comprising providing a mixture (I) comprising a reactant mixture (a) and a nonvolatile solvent (b nv ), wherein reactant mixture (a) comprises one or more polymerizable components and the nonvolatile solvent (b nv ) (i) is not a crystalline solid at 25°C, (ii) is nonvolatile, (iii) comprises at least one functional group (Fi), and (iv) is a fluid solid, polymerizing the reactant mixture (a) to provide a polymer (a'), and subjecting nonvolatile solvent (b nv ) to reaction conditions wherein the at least one functional group (F ) of nonvolatile solvent (b nv ) is reacted with at least one reactant (e) to obtain at least two functional groups (F
- the invention provides a method of making a polymer (a'), especially a mixture (II) comprising a polymer (a') and at least one nonvolatile solvent (b' nv ) comprising at least two functional groups (F 2 ).
- mixture (II) of polymer (a') and at least one nonvolatile solvent (b' nv ) comprising at least two functional groups (F 2 ) is especially suitable for use in coating compositions having low VOCs.
- mixture (II) will comprise a polymer (a') and a solvent mixture (b), wherein solvent mixture (b) comprises at least one nonvolatile solvent (b' n v) comprising at least two functional groups (F 2 ).
- the invention also provides a reactive polymer composition, comprising an acrylic resin (a') comprising a functional group (F 3 ) that is at least one of a primary carbamate group, a primary hydroxyl group, a secondary hydroxyl group, and mixtures thereof, and a nonvolatile solvent (b' nv ) that is a noncrystalline solid at 75°C and comprises (i) four or more isomers, and (ii) at least two reactive functional groups (F 2 ) that are selected from primary carbamate, primary hydroxyl, and secondary hydroxyl, wherein no more than 5% of the sum of functional groups (F 2 ) and (F 3 ) are primary hydroxyl groups and at least 60% of the sum of functional groups (F 2 ) and (F ) are primary carbamate groups.
- the reactive polymer composition may be made by the method set forth above.
- a Tow VOC polymer or coating composition' as used herein refers to polymers or coating compositions having a volatile organic content (VOC) of no more than about 3.2 lbs. of volatile organic solvent per gallon of polymer or coating composition, in some exemplary embodiments, no more than about 2.4 lbs. of volatile organic solvent per gallon of polymer or coating composition, and in some especially exemplary embodiments, no more than about 1.6 lbs. of volatile organic solvents per gallon of polymer or coating composition.
- VOC volatile organic content
- the invention provides a reactive polymer composition, comprising an acrylic resin (a') comprising a functional group (F 3 ) that is at least one of a primary carbamate group, a primary hydroxyl group, a secondary hydroxyl group, and mixtures thereof, and a nonvolatile solvent (b' nv ) that is a noncrystalline solid at 75°C and comprises (i) four or more isomers, and (ii) at least two reactive functional groups (F 2 ) that are selected from primary carbamate, primary hydroxyl, and secondary hydroxyl, wherein no more than 5% of the sum of functional groups (F 2 ) and (F ) are primary hydroxyl groups and at least 60% of the sum of functional groups (F 2 ) and (F 3 ) are primary carbamate groups.
- an acrylic resin (a') comprising a functional group (F 3 ) that is at least one of a primary carbamate group, a primary hydroxyl group, a secondary hydroxyl group, and mixtures thereof
- Mixture (II) results from a multi-step process that requires the polymerization of a reactant mixture (a) in a solvent mixture (b).
- Solvent mixture (b) will comprise at least one nonvolatile solvent (b nv ) having at least one functional group (Fi).
- the polymerization of reactant mixture (a) into polymer (a') occurs either before, after, or simultaneously with the reaction of functional group (Fi) of the nonvolatile solvent (b nv ) with at least one reactant (e) to provide a nonvolatile solvent (b' nv ) having at least two functional groups (F 2 ). That is, at least two separate reactions must occur.
- the reactant mixture (a) is subjected to polymerization conditions sufficient to polymerize reactant mixture (a) to provide a polymer (a').
- the nonvolatile solvent (b nv ) is subjected to reaction conditions wherein the at least one functional group (Fi) of nonvolatile solvent (b nv ) is reacted with at least one reactant (e) to provide a nonvolatile solvent (b' nv ) comprising at least two functional groups (F 2 ).
- the two reactions will occur simultaneously. However, it is also possible for either of the two reactions to occur first, so long as both reactions occur at some point prior to the obtainment of mixture (II). It will thus be appreciated that the at least one functional group (Fi) is not and may not be the same as functional groups (F 2 ).
- Solvent mixture (b) in which reactive mixture (a) is polymerized comprises a particular nonvolatile solvent (b nv ) that must be substantially inert in three ways to under the polymerization conditions to which reactant mixture (a) is subjected.
- substantially inert refers to a degree of reaction between the nonvolatile solvent (b nv ) and the reaction mixture (a) of less than 3% of the total functionality of nonvolatile solvent (b nv ), preferably less than 2%, and most preferably less than 1% of the total functionality of nonvolatile solvent (b Vn )- Total functionality as used herein does not include nonaromatic alkenyl groups and reactions of extractable hydrogens.
- Extractable hydrogens refers to hydrogens attached to either carbon of a carbon-carbon double bond in a nonaromatic alkenyl group.
- any reaction between nonvolatile solvent (b nv ) and reaction mixture (a) will be attributable solely to the presence of unwanted impurities and/or contaminants in nonvolatile solvent (b nv ).
- Reactions with any nonaromatic alkenyl groups or extractable hydrogens in nonvolatile solvent (b nv ) are considered to be within the scope of unwanted impurities and/or contaminants in nonvolatile solvent (b nv ).
- the nonvolatile solvent (b nv ) must be substantially inert or nonreactive with any functional groups on components of reactant mixture (a) under the polymerization conditions.
- nonvolatile solvent (b here v ) must generally be free of any functional groups that are reactive with one or more functional groups of the components of reactant mixture (a) under the conditions used to polymerize reactant mixture (a) including free radical reactions or otherwise.
- Functional groups (Fi) of nonvolatile solvent (b here v ) will thus normally be free of any groups that are reactive with one or more functional groups of the components of reactant mixture (a) under conditions used to polymerize reactant mixture (a).
- Functional group (Fi) of nonvolatile solvent (b nv ) thus does not include nonaromatic alkenyl groups or extractable hydrogens.
- the nonvolatile solvent (b nv ) must be substantially inert or nonreactive during the polymerization of reactant mixture (a). That is, nonvolatile solvent (b nv ) may not polymerize under the polymerization conditions that result in the transformation of reactant mixture (a) into polymer (a').
- the nonvolatile solvent (b nv ) must be substantially inert or nonreactive with the resulting polymer (a') while under the polymerization conditions used to polymerize reactant mixture (a).
- the nonvolatile solvent (b nv ) may not have any functional groups reactive with the secondary hydroxyl formed by the ring opening of the oxirane functional group.
- the functional group (Fi) of nonvolatile solvent (b nv ) is limited to those functional groups which may be on one or more components of reactant mixture (a) but which do not enter into the polymerization of reactant mixture (a) or any graft polymerization processes involving reactant mixture (a) or polymer (a').
- the at least one functional group (Fi) of nonvolatile solvent (b nv ) does not include nonaromatic alkenyl groups or extractable hydrogens.
- Polymer (a') may be any polymer, oligomer or mixture thereof, resulting from the polymerization of reactant mixture (a).
- polymer (a') may generally have a number average molecular weight of from 400 to 50,000 Daltons. Usually, the polymer (a') will have a number average molecular weight of from 1000 to 50,000 Daltons.
- Polymer (a') may be an acrylic polymer, a polyurethane polymer, a polyester polymer, an epoxy upgrade polymer, a dendrimer polymer, or the like.
- polymer (a') will be an acrylic polymer, a polyurethane polymer, or a polyester polymer.
- polymer (a') will be an acrylic polymer or a polyurethane polymer, with acrylic polymers being especially preferred.
- reactant mixture (a) will depend upon the desired type of polymer (a').
- reactant mixture (a) will be comprised of one or more components, preferably two or more components that can be subjected to polymerization conditions to produce a polymer (a'). More preferably the component of reactant mixture (a) will be monomers or compounds that can react with each other and/or compounds produced therefrom, to provide a polymer of increased molecular weight relative to the initial starting reactants of reactant mixture (a).
- the polymerization of reactant mixture (a) to polymer (a') may be heterogenous, i.e., aqueous emulsion or nonaqueous dispersion, or homogenous, i.e., solution polymerization. Homogenous polymerization process are preferred.
- polymer (a') is an acrylic polymer
- reactant mixture (a) will be comprised of ethylenically unsaturated monomers having at least one carbon-carbon double bond able to undergo free radical polymerization.
- Illustrative ethylenically unsaturated monomers include, without limitation, alpha, beta-ethylenically unsaturated monocarboxylic acids containing 3 to 5 carbon atoms such as acrylic, methacrylic, and crotonic acids, and the esters, nitriles, and amides of those acids; alpha, beta-ethylenically unsaturated dicarboxylic acids containing 4 to 6 carbon atoms and the anhydrides, monoesters, and diesters of those acids; vinyl esters, vinyl ethers, vinyl ketones, and aromatic or heterocylic aliphatic vinyl compounds.
- alpha, beta-ethylenically unsaturated monocarboxylic acids containing 3 to 5 carbon atoms such as acrylic, methacrylic, and crotonic acids, and the esters, nitriles, and amides of those acids
- Carbamate functional ethylenically unsaturated monomers, cyclic carbonate functional ethylenically unsaturated monomers, and/or isocyanate functional ethylenically unsaturated monomers may also be used, most preferably in combination with other ethylenically unsaturated monomers.
- esters of acrylic methacrylic, and crotonic acids include, without limitation, those esters from reaction with saturated aliphatic and cycloaliphatic alcohols containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, lauryl, stearyl, cycolhexyl, trimethylcyclohexyl, tetrahydrofurfuryl, stearyl, sulfoethyl, and isobornyl acrylates, methacrylates, and crotonates; and polyalkylene glycol acrylates and methacrylates.
- saturated aliphatic and cycloaliphatic alcohols containing 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, ter
- Representative examples of other ethylenically unsaturated polymerizable monomers include, without limitation, such compounds as fumaric, maleic, and itaconic anhydrides, monoesters, and diesters with alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and tert-butanol.
- Representative examples of polymerizable vinyl monomers include, without limitation, such compounds as vinyl acetate, vinyl propionate, vinyl ethers such as vinyl ethyl ether, vinyl and vinylidene halides, and vinyl ethyl ketone.
- aromatic or heterocylic aliphatic vinyl compounds include, without limitation, such compounds as styrene, alpha-methyl styrene, vinyl toluene, tert-butyl styrene, and 2-vinyl pyrrolidone.
- Representative examples include acrylic and methacrylic acid amides and aminoalkyl amides, acrylonitrile, and methacrylonitriles.
- Suitable examples include acrylates or methacrylates having hydroxy, epoxy, or other functional groups, such as hydroxyalkyl acrylates and methacrylates, glycidyl esters of methacrylic and acrylic acid such as glycidyl methacrylate, and aminoalkyl esters of methacrylic or acrylic acid like N,N- dimethylaminoethyl (meth)acrylate.
- Acrylic monomers having carbamate functionality in the ester portion of the monomer are well known in the art and are described, for example in U.S.
- Patents 3,479,328, 3,674,838, 4,126,747, 4,279,833, and 4,340,497, 5,356,669, and WO 94/10211 the disclosures of which are incorporated herein by reference.
- One method of synthesis involves reaction of a hydroxy ester with urea to form the carbamyloxy carboxylate (i.e., carbamate-modified acrylic).
- Another method of synthesis reacts an ⁇ , ⁇ -unsaturated acid ester with a hydroxy carbamate ester to form the carbamyloxy carboxylate.
- Yet another technique involves formation of a hydroxyalkyl carbamate by reacting a primary or secondary amine or diamine with a cyclic carbonate such as ethylene carbonate.
- the hydroxyl group on the hydroxyalkyl carbamate is then esterif ⁇ ed by reaction with acrylic or methacrylic acid to form the monomer.
- Other methods of preparing carbamate-modified acrylic monomers are described in the art, and can be utilized as well.
- the acrylic monomer can then be polymerized along with other ethylenically unsaturated monomers, if desired, by techniques well known in the art.
- Ethylenically unsaturated isocyanate monomers are well-known in the art and include meta-isopropenyl-.alpha.,.alpha.-dimethylbenzyl isocyanate (sold by American Cyanamid as TMI®) and isocyanatoethyl methacrylate.
- Cyclic carbonate ethylenically unsaturated monomers are well-known in the art and include (2-oxo-l,3-dioxolan-4-yl)methyl methacrylate.
- polymer (a') is an acrylic resin, it will generally have a number average molecular weight of from 1000 to 50,000, preferably from 10,000 to 25,000, with molecular weights of from 15,000 to 20,000 being most preferred.
- polymer (a') will be a hydroxyl or carbamate functional resin which may or may not be water dispersible.
- polymer (a') will be a water dispersible acrylic polymer having a hydroxyl equivalent weight of from 250 to 1500 g/mole and an acid equivalent weight of from 500 to 3000 g/mole.
- the polymer (a') will be a water dispersible acrylic polymer having a carbamate equivalent weight of from 250 to 1500 g/mole and an acid equivalent weight of from 500 to 3000 g/mole.
- the polymer (a') is an acrylic polymer having a hydroxyl equivalent weight of from 250 to 1500 g/mole and an acid equivalent weight greater than 3000 g/mole.
- the polymer (a') is an acrylic polymer having a carbamate equivalent weight of from 250 to 1500 g/mole and an acid equivalent weight greater than 3000 g/mole.
- the ethylenically unsaturated monomers of reactant mixture (a) will be polymerized to provide an acrylic polymer (a') having one or more functional groups (F 0 ) that are subsequently converted to functional groups (F 3 ) via reaction with one or more reactants (e').
- Functional groups (F 0 ) in this embodiment must comprise at least one functional group convertible to a primary carbamate group or to intermediate a functional group (F 0 ) convertible to a group convertible to a primary carbamate group.
- suitable functional groups (Fo) include primary and secondary hydroxyl groups, acid groups, epoxy groups, amine groups, carbonate groups, isocyanate groups, and the like.
- the ethylenically unsaturated monomers of reactant mixture (a) may comprise primary or secondary hydroxyls as well as mixtures of both, i.e., hydroxyl ethyl methyacrylate, hydroxyl propyl methacrylate, and the like, as well as mixtures thereof.
- reactant mixture (a) will comprise glycidyl esters of acrylic and methacrylic acid so that functional groups (F 0 ) will be epoxy.
- hydroxyl functional groups (F ) or intermediate hydroxyl functional groups may be obtained by the ring opening of an epoxy functional group (Fo) with an acid functional reactant (e').
- acid functional reactant (e') must have an additional functional group such as hydroxyl, carbamate, urea, amide, and the like.
- carbamate functional groups (F 3 ) may be obtained via the reaction of hydroxyl functional groups (Fo) with a reactant (e') selected from low molecular weight carbamate functional monomers such as methyl carbamate.
- carbamate functional groups (F 3 ) may be made by decomposing a reactant (e) such as urea in the presence of hydroxyl functional groups (Fo).
- carbamate functional groups (F ) may be obtained by reacting a first reactant (e') such as phosgene with a hydroxyl functional group (Fo) followed by reaction with another reactant (e') such as ammonia.
- Epoxy functional groups (Fo) useful as an intermediate functional group may be made via reaction of acid functional groups (Fo) with a reactant (e') such as peroxide.
- a reactant e'
- epoxy functional groups (F 3 ) will be obtained via the reaction of acid or hydroxyl functional groups (Fo) with a reactant (e') such as epichlorohydrin.
- Cyclic carbonate functional groups (Fo) useful as an intermediate functional group may be made via reaction of an epoxy functional group (Fo) with a reactant (e') such as carbon dioxide.
- reactant (e') may be at least one of low molecular weight carbamate functional reactants (such as simple alkyl carbamates), urea, phosgene, ammonia, carbon dioxide, acids, aldehydes, alcohols, peroxides, epichlorohydrin, mixtures thereof, and the like.
- reactant (e') when functional group (F 0 ) is hydroxyl, reactant (e') may be an alkyl carbamate, urea, or phosgene and ammonia, h one especially exemplary embodiment, reactant (e') will be an alkyl carbamate when functional group (Fo) is hydroxyl.
- the reaction conditions suitable for the reaction of functional groups (F 0 ) with at least one reactant (e') will generally be known to those of skill in the art.
- the reaction mixture (a) will comprise ethylenically unsaturated monomers having carbamate functionality in the ester portion of the monomer.
- Acrylic monomers having carbamate functionality in the ester portion of the monomer are well known in the art and are described, for example in U.S. Patents 3,479,328, 3,674,838, 4,126,747, 4,279,833, 4,340,497, and 5,356,669, and WO 94/10211, the disclosures of which are incorporated herein by reference.
- One method of synthesis involves reaction of a hydroxy ester with urea to form the carbamyloxy carboxylate (i.e., carbamate-modified acrylic).
- Another method of synthesis reacts an ⁇ , ⁇ -unsaturated acid ester with a hydroxy carbamate ester to form the carbamyloxy carboxylate.
- Yet another technique involves formation of a hydroxyalkyl carbamate by reacting a primary or secondary amine or diamine with a cyclic carbonate such as ethylene carbonate.
- a cyclic carbonate such as ethylene carbonate.
- the hydroxyl group on the hydroxyalkyl carbamate is then esterif ⁇ ed by reaction with acrylic or methacrylic acid to form the monomer.
- Other methods of preparing carbamate-modified acrylic monomers are described in the art, and can be utilized as well.
- polymer (a') is a polyester
- reactant mixture (a) will be comprised of a mixture of at least one polycarboxylic acid and/or anhydride, and at least one polyol and/or epoxide. Such reactants will be subjected to polymerization via esterification.
- the polycarboxylic acids used to prepare a polyester polymer (a') will generally be monomeric polycarboxylic acids or anhydrides thereof having 2 to 18 carbon atoms per molecule.
- Among useful acids are phthalic acid, hexahydrophthalic acid, adipic acid, sebacic acid, maleic acid, and other dicarboxylic acids of various types. Minor amounts of monobasic acids can be included in the reaction mixture (a'), for example, benzoic acid, stearic acid, acetic acid, and oleic acid. Also, higher carboxylic acids can be used, for example, trimellitic acid and tricarballylic acid. Anhydrides of the acids referred to above, where they exist, can be used in place of the acid. Also, lower alkyl esters of the acids can be used, for example, dimethyl glutarate and dimethyl terephthalate.
- Polyols that can be used to prepare a polyester polymer (a') include diols such as alkylene glycols. Specific examples include ethylene glycol, 1,6- hexanediol, neopentyl glycol, and 2,2-dimethyl-3-hydroxypropionate. Other suitable glycols include hydrogenated bisphenol A, cyclohexanediol, cyclohexanedimethanol, caprolactone-based diols such as the reaction product of e-caprolactone and ethylene glycol, hydroxy-alkylated bisphenols, polyether glycols such as poly(oxytetramethylene)glycol, mixtures thereof and the like.
- diols such as alkylene glycols. Specific examples include ethylene glycol, 1,6- hexanediol, neopentyl glycol, and 2,2-dimethyl-3-hydroxypropionate.
- Other suitable glycols include hydrogenated bisphenol A, cycl
- the polyol component of reactant mixture (a) can be comprised of all diols, polyols of higher functionality can also be used.
- the polyol component will be a mixture comprising at least one diol, and at least one polyol of higher functionality such as a triol.
- examples of polyols of higher functionality would include trimethylol ethane, trimethylol propane, pentaerythritol, and the like. Triols are preferred.
- the mole ratio of polyols of higher functionality to diol is less than 3.3/1, preferably up to 1.4/1. Limited amounts of monofunctional alcohols, such as ethylhexanol, may also be used.
- Polyurethane polymers (a') may be prepared by the polymerization of a reactant mixture (a) comprising at least one di- and/or polyisocyanate and at least one polyol. They are prepared by a chain extension reaction of a polyisocyanate (e.g., hexamethylene diisocyanate, isophorone diisocyanate, MDI, etc.) and an active hydrogen-containing chain extension agent, such as a polyol. They can be provided with active hydrogen functional groups by capping the polyurethane chain with an excess of diol, polyamine, a ino alcohol, or the like that are included in reactant mixture (a).
- a polyisocyanate e.g., hexamethylene diisocyanate, isophorone diisocyanate, MDI, etc.
- an active hydrogen-containing chain extension agent such as a polyol.
- suitable polyisocyanates can be an aliphatic polyisocyanate, including a cycloaliphatic polyisocyanate or an aromatic polyisocyanate.
- Useful aliphatic polyisocyanates include aliphatic diisocyanates such as ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,6- diisocyanatohexane, 1,4-butylene diisocyanate, lysine diisocyanate, 1,4-methylene bis- (cyclohexyl isocyanate) and isophorone diisocyanate.
- Useful aromatic diisocyanates and araliphatic diisocyanates include the various isomers of toluene diisocyanate, meta-xylened ⁇ socyanate and para-xylenediisocyanate, also 4-chloro-l,3 ⁇ phenylene diisocyanate, 1,5-tetrahydro-naphthalene diisocyanate, 4,4'-dibenzyl diisocyanate and 1,2,4-benzene triisocyanate can be used.
- the various isomers of ⁇ ', ⁇ ', ⁇ ', ⁇ -tetramethyl xylylene diisocyanate can be used.
- Active hydrogen-containing chain extension agents generally contain at least two active hydrogen groups, for example, diols, dithiols, diamines, or compounds having a mixture of hydroxyl, thiol, and amine groups, such as alkanolamines, aminoalkyl mercaptans, and hydroxyalkyl mercaptans, among others. Both primary and secondary amine groups are considered as having one active hydrogen. Active hydrogen-containing chain extension agents also include water.
- a polyol is used as the chain extension agent, to provide a polyurethane.
- Illustrative polyols are those as described above with respect to polyesters polymers (a').
- a diol is used as the chain extension agent with little or no higher polyols, to minimize brandling.
- illustrative polyols include 1,6 hexanediol, cyclohexanedimethylol, and 1,4-butanediol. While polyhydroxy compounds containing at least three hydroxyl groups may be used as chain extenders, the use of these compounds produces branched polyurethane resins. These higher functional polyhydroxy compounds include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, among other compounds.
- Monofunctional capping alcohols such as 2-ethylhexanol may also be used.
- the mono- or polyfunctional alcohol may contain additional functional groups.
- Non-limiting examples are glycidol, hydroxyalkylcarbamates such as hydroxy ethyl carbamate or hydroxy butyl carbamate, and hydroxy acids such as 1-hydroxybutylic acid.
- the polyurethane polymer (a') may be chain extended in any manner using those compounds having at least two active hydrogen groups. Accordingly, reactant mixture (a) may thus include a mixture of polyisocyanate, polyol, and multifunctional compounds. [0054] In one especially exemplary embodiment, the reactant mixture (a) is present in a mixture (I) with a solvent mixture (b) that comprises a nonvolatile solvent (b nv ). In one exemplary embodiment, the reactant mixture (a) will be soluble in nonvolatile solvent (b nv ).
- suitable nonvolatile solvents are generally those materials that may be an amorphous solid, wax, or liquid at room temperature but are nonetheless a fluid solid at the temperature that the polymerization reaction of reactant mixture (a) occurs.
- Nonvolatile refers to materials having a boiling point at least 100°C, preferably 200°C, most preferably 300°C, above the polymerization temperature.
- a "fluid solid” refers to a nonvolatile material that has a viscosity similar to a traditional solvent at the polymerization temperature.
- the nonfunctional part of suitable nonvolatile solvents (b nv ) will have from 8 to 300 carbons.
- nonvolatile solvent (b nv ) will be have at least one functional group ( ⁇ ), while in one exemplary embodiment; nonvolatile solvent (b nv ) will have at least two functional groups (Fi). In another embodiment, nonvolatile solvent (b nv ) will be substantially free of heteroatoms as discussed below.
- nonvolatile solvents include diethyl octanediol, neodecanoic acid, the glycidyl ester of neodecanoic acid, the cyclic carbonate of the glycidyl ester of neodecanoic acid, alpha polyolefmpolyols, alpha polyolefin polyacids, and the like.
- suitable nonvolatile solvents (b m ) may also comprise heteroatom containing linking groups, i.e. containing atoms other than carbon or hydrogen.
- heteroatom containing linking groups include ethers, ureas, esters, urethanes, silanes and the like.
- the nonvolatile solvent (b nv ) will be a reactive component (c).
- the non-functional part of reactive component (c) will have from 12 to 72 carbons, more preferably from 18 to 54 carbons, and most preferably from 36 to 54 carbons.
- the nonfunctional part of reactive component (c) will have 36 carbons and at least two functional groups (Fi).
- reactive component (c) will be substantially free of heteroatoms.
- Heteroatom refers to atoms other than carbon or hydrogen.
- the phrase “substantially without” heteroatoms as used herein means that the portion of reactive component (c) which does not include functional groups (Fi) will generally have no more than two atoms which are other than carbon or hydrogen, i.e., atoms such as N, O, Si, mixtures thereof, and the like. More preferably, that portion of reactive component (c) that does not include functional groups (Fi) will have no more than two atoms that are other than carbon or hydrogen.
- that portion of reactive component (c) that does not include functional groups (Fi) will have no heteratoms, i.e., will consist solely of carbon and hydrogen atoms.
- the only heteratoms in reactive component (c) will be present in functional groups (Fi).
- reactive component (c) will not be a crystalline solid at room temperature, i.e., at temperatures of from 65 to 75°F.
- Crystalstalline refers to a solid characterized by a regular, ordered arrangement of particles. Rather, in this embodiment, reactive component (c) will be an amorphous solid, a wax or a liquid at room temperature.
- Amorphous refers to a noncrystalline solid with no well-defined ordered structure.
- reactive component (c) will comprise a mixture of two or more saturated or unsaturated structures selected from the group consisting of noncyclic structures for reactive component (c), aromatic- containing structures for reactive component (c), cyclic-containing structures for reactive component (c), and mixtures thereof. Saturated structures are preferred, especially where durability issues are of concern.
- a most preferred reactive component (c) will comprise a mixture of two or more structures selected from the group consisting of aliphatic structures for reactive component (c), aromatic- containing structures for reactive component (c), cycloaliphatic-containing structures for reactive component (c), and mixtures thereof.
- reactive component (c) comprise at least two, more preferably three, of the three cited structures. If reactive component (c) comprises only two of the three cited structures for reactive component (c), then at least one of the two structures must be present as a mixture of two or more isomers thereof.
- the mixture of reactive components (c) may comprise at least one aliphatic structure for reactive component (c) and at least one other structure for reactive component (c) selected from the group consisting of aromatic-containing structures for reactive component (c), cycloaliphatic-containing structures for reactive component (c), and mixtures thereof. If the 'at least one other structure for reactive component (c)' is not a mixture of aromatic-containing structures for reactive component (c) and cycloaliphatic-containing structures for reactive component (c), either the aromatic-containing structures or the cycloaliphatic containing structures must be present as a mixture of two or more isomers.
- the mixture of reactive components (c) may comprise at least one aromatic-containing structure for reactive component (c) and at least one other structure for reactive component (c) selected from the group consisting of aliphatic structures for reactive component (c), cycloaliphatic-containing structures for reactive component (c), and mixtures thereof. If the 'at least one other structure for reactive component (c)' is not a mixture of aliphatic structures for reactive component (c) and cycloaliphatic-containing structures for reactive component (c), either the aliphatic structures or the cycloaliphatic containing structures must be present as a mixture of two or more isomers.
- reactive component (c) will comprise one or more aliphatic structures for reactive component (c), one or more aromatic- containing structures for reactive component (c), and one or more cycloaliphatic- containing structures for reactive component (c).
- Particularly advantageous mixtures of reactive component (c) will comprise from 3 to 25 %> by weight of reactive component (c) having an aliphatic structure, from 3 to 25%o by weight of reactive component (c) having an aromatic-containing structure, and 50 to 94% by weight of reactive component (c) having a cycloaliphatic-contairiing structure.
- More preferred mixtures of reactive component (c) will comprise from 3 to 18% by weight of reactive component (c) having an aliphatic structure, from 5 to 23 % by weight of reactive component (c) having an aromatic-containing structure, and 55 to 85%o by weight of reactive component (c) having a cycloaliphatic-containing structure. Most preferred mixtures of reactive component (c) will comprise from 5 to 10%> by weight of reactive component (c) having an aliphatic structure, from 10 to 20% by weight of reactive component (c) having an aromatic-containing structure, and 60 to 70% by weight of reactive component (c) having a cycloaliphatic-containing structure. [0066] In one exemplary embodiment, reactive component (c) will comprise at least two functional groups (Fi) per molecule.
- Preferred reactive components (c) may have from two to six functional groups (Fi) while most preferably reactive component (c) will have two to three functional groups (F t ).
- Functional groups (Fi) of nonvolatile solvent (b nv ) may be selected from a variety of active hydrogen containing groups and groups reactive with such active hydrogen containing groups. Examples of illustrative functional groups (Fi) are hydroxy, isocyanate (blocked or unblocked), epoxy, carbamate, aminoplast, aldehyde, acid, epoxy, amine, cyclic carbonate, urea, mixtures thereof, and the like.
- Preferred functional groups (Fi) are hydroxyl both primary and secondary, primary carbamate, isocyanate, aminoplast functional groups, epoxy, carboxyl and mixtures thereof. Most preferred functional groups (Fi) are secondary hydroxyl, primary carbamate, and mixtures thereof, with primary carbamate groups being particularly preferred.
- Suitable nonvolatile solvents (b nv ) having functional groups (Fi) which are carboxyl are fatty acids and addition reaction products thereof, such as dimerized, trimerized and tetramerized fatty acid reaction products and higher oligomers thereof.
- Suitable acid functional dimers and higher oligomers may be obtained by the addition reaction of C 1 -18 monofunctional fatty acids.
- Suitable monofunctional fatty acids may be obtained from Cognis Corporation of Ambler, PA. Such materials will be acid functional and will contain some unsaturation.
- saturated and unsaturated dimerized fatty acids are commercially available from Uniqema of Wilmington, DE.
- Hydroxyl functional nonvolatile solvents (b nv ) are commercially available as the PripolTM saturated fatty acid dimer (PripolTM 2033) supplied by Uniqema of Wilmington, DE. Hydroxyl functional nonvolatile solvents (b nv ) may also be obtained by reduction of the acid group of the above-discussed fatty acids. [0071] Nonvolatile solvents (b nv ) having two or more carbamate functional groups may be obtained via the reaction of the hydroxyl functional nonvolatile solvents (b nv ) with a low molecular weight carbamate functional monomer such as methyl carbamate under appropriate reaction conditions.
- carbamate functional nonvolatile solvents (b nv ) may be made via decomposition of urea in the presence of hydroxyl functional nonvolatile solvents (b nv ) as described above.
- carbamate functional nonvolatile solvents (b nv ) can be obtained via the reaction of phosgene with the hydroxyl functional nonvolatile solvents (b nv ) followed by reaction with ammonia.
- Amine groups suitable for use as functional group (Fi) may be primary or secondary, but primary amines are most preferred.
- Nonvolatile solvents (b nv ) having amine functional groups (Fi) may be obtained via reaction of the acid functional nonvolatile solvents (b nv ) to form an amide, followed by conversion to a nitrile and subsequent reduction to an amine.
- Nonvolatile solvents (b nv ) having isocyanate functional groups (F0 may be obtained via reaction of the amine functional nonvolatile solvent (b nv ) described above with carbon dioxide.
- Aminoplast functional groups may be defined as those functional groups resulting from the reaction of an activated amine group and an aldehyde or formaldehyde. Illustrative activated amine groups are melamine, benzoguanamine, amides, carbamates, and the like. The resulting reaction product may be used directly as functional group (F or may be etherified with a monofunctional alcohol prior to use as functional group (Fi).
- Nonvolatile solvents (b nv ) having aminoplast functional groups (F0 may be made via reaction of carbamate functional nonvolatile solvents (b nv ) as described above with fonnaldehyde or aldehyde. The resulting reaction product may optionally be etherified with low boiling point alcohols.
- Nonvolatile solvents (b nv ) having aldehyde functional groups (F0 may be made via reduction of the acid functional nonvolatile solvents (b nv ) described above.
- Nonvolatile solvents (b nv ) having urea functional groups (F0 may be made via reaction of an amine functional nonvolatile solvent (b nv ) with urea.
- amine functional nonvolatile solvents (b nv ) can be reacted with phosgene followed by reaction with ammonia to produce the desired urea functional groups (Fi).
- Nonvolatile solvents (b nv ) having epoxy functional groups (Fi) may be made using either saturated or unsaturated fatty acids described above. If an unsaturated fatty acid is used, reaction with peroxide will form internal epoxy groups. More preferably, an acid or hydroxyl functional nonvolatile solvents (b nv ) will be reacted with epichlorohydrin. Preferred epoxy functional nonvolatile solvents (b nv ) will be obtained using saturated starting materials. [0079] Nonvolatile solvents (b nv ) having cyclic carbonate functional groups
- FO may be made via carbon dioxide insertion into an epoxy functional nonvolatile solvents (b nv ) as described above.
- nonvolatile solvents (b nv ) will comprise one or more of the following structures:
- nonvolatile solvent (bddy v ) will be substantially nonreactive under the polymerization conditions: (1) with the components of reactive mixture (a), (2) in the polymerization of reactant mixture (a) and (3) with the polymer (a').
- the functional groups (Fi) of nonvolatile solvents (b nv ) discussed above must be selected so as not to participate in the polymerization reaction of reactant mixture (a).
- the functional groups (F0 must also not react with any of the functional groups of the components reactant mixture (a) and/or on polymer (a').
- nonvolatile solvent (b nv ) when nonvolatile solvent (b nv ) is used in a free radical acrylic polymerization where reactive mixture (a) comprises an isocyanate functional monomer, the functional groups (Fi) of nonvolatile solvent (b nv ) may not be hydroxy or amine.
- functional group (Fi) of nonvolatile solvents (b nv ) when high polymerization temperatures are used in an embodiment, (such as 140°C), functional group (Fi) of nonvolatile solvents (b nv ) may not be acid functional.
- nonvolatile solvents (b nv ) when nonvolatile solvents (b nv ) is used in an embodiment employing an ionic or similar polymerization, the level of non-aromatic unsaturated groups on nonvolatile solvent (b nv ) must be minimized, preferably to a level of less than 5 weight percent, more preferably less than 2 weight percent, based on the total weight of nonvolatile solvents (b nv ).
- functional groups (FO should not contain any groups that would react with the isocyanate or active proton source (usually hydroxy) when the nonvolatile solvents (b nv ) is used in a urethane polymerization.
- the typical functional groups on nonvolatile solvents (b nv ) that should be avoided in this case are hydroxy and amine groups.
- Other functional groups on nonvolatile solvents (b nv ) might also have to be avoided depending on the nature of any functional groups on the active hydrogen material. For example, if glycidol is used as a capping group in the urethane polymerization, the nonvolatile solvents (h m ) must be free of acid groups.
- nonvolatile solvents (b nv ) When the nonvolatile solvents (b nv ) is used in a polyester polymerization, functional groups (F0 should not be any groups that will react with anhydrides, acids, and alcohols. Examples of such groups to be avoided include acids, hydroxy, epoxy, unblocked isocyanates and the like. In such as case, non-limiting examples of functional groups (F0 of nonvolatile solvents (b nv ) would be carbamate, vinyl or mixtures thereof.
- solvent mixture (b) may further comprise other solvents and/or cosolvents such as water and/or organic solvents.
- Illustrative solvents include aromatic hydrocarbons, such as, petroleum naphtha or xylenes, ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone or acetone; esters such as butyl acetate or hexyl acetate; and glycol ether esters, such as propylene glycol monomethyl ether acetate.
- aromatic hydrocarbons such as, petroleum naphtha or xylenes
- ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone or acetone
- esters such as butyl acetate or hexyl acetate
- glycol ether esters such as propylene glycol monomethyl ether acetate.
- Other examples of useful solvents include, without limitation, m-amyl acetate, ethylene glycol butyl ether-acetate, xylene,
- solvent mixture (b) will comprise from 0 to 95 % by weight of nonvolatile solvent (b nv ), in another embodiment, from 0 to 75 % by weight, and in a particularly exemplary embodiment, from 0 to 20 %> by weight, all based on the total weight of solvent mixture (b).
- Coating compositions of the invention will comprise a mixture (II) made by the method of the invention wherein mixture (II) comprises polymer (a') and the solvent mixture (b) comprising a nonvolatile solvent (b' nv ).
- Coating compositions of the invention may further comprise other known film-forming binders not made by the method of the invention, but most preferably will not.
- Illustrative examples of other binders that bay be used in addition to polymer (a') include acrylic polymers, polyurethane polymers, polyester polymers, epoxy functional polymers, mixtures thereof, and the like.
- coating compositions of the invention will comprise from
- nonvolatile of polymer (a') 10 to 90 % by weight nonvolatile of polymer (a'), more preferably from 20 to 80 % by weight nonvolatile of polymer (a') and most preferably from 40 to 60 % by weight nonvolatile of polymer (a'), based on the total weight of the total nonvolatile of the coating composition.
- solvent mixture (b) will generally have from 5 to 100 % by weight of nonvolatile solvent (b' nv ), more preferably from 30 to 100 % by weight of nonvolatile solvent (b' nv ), and most preferably from 80 to 100 % by weight of nonvolatile solvent (b' nv ), all based on the total weight of solvent mixture (b).
- Nonvolatile solvent (b nv ) is reacted with at least one reactant (e) to provide a nonvolatile solvent (b' nv ) comprising at least two functional groups (F 2 ).
- such reactions may occur before, during or after the polymerization of reactant mixture (a) to polymer (a'), hi one exemplary embodiment, the reaction of nonvolatile solvent (b tine v ) with at least one reactant (e) will occur during and after the polymerization of reactant mixture (a).
- functional group (F 2 ) will be any one of a pair of reactants that would result in a thermally irreversible chemical linkage upon reaction with a crosslinking agent (f).
- thermally irreversible linkage refers to a linkage the reversal of which is not thermally favored under the traditional cure schedules used for automotive coating compositions.
- suitable thermally irreversible chemical linkages are urethanes, ureas, esters and ethers.
- Preferred thermally irreversible chemical linkages are urethanes, ureas and esters, with urethane linkages being most preferred.
- Such chemical linkages will not break and reform during the crosslinking process as is the case with the linkages formed via reaction between hydroxyl groups and aminoplast resins.
- (b'n v ) may be any of the functional groups discussed above with respect to functional group (F0 of nonvolatile solvent (b av ).
- functional groups (F 2 ) may not be the same as functional groups (FO. That is, nonvolatile solvent (b nv ) will undergo reaction with at least one reactant (e) to produce nonvolatile solvent (b'n v )- The reaction of nonvolatile solvent (b nv ) with at least one reactant (e) produces nonvolatile solvent (b' nv ) comprising at least two functional groups (F 2 ).
- functional groups (F 2 ) of nonvolatile solvent (b' nv ) will be at least one of carbamate (especially primary carbamate), hydroxyl, isocyanate, carbonate, beta-hydroxy urethane, mixtures thereof, and the like.
- functional groups (F 2 ) of nonvolatile solvent (b' nv ) will be either primary carbamate or hydroxyl.
- functional groups (F 2 ) of nonvolatile solvent (b' nv ) will be primary carbamate.
- Illustrative reactants (e) are any reactants that may be used to convert functional groups (FO of nonvolatile solvent (b nv ) to functional groups (F 2 ) of nonvolatile solvent (b' nv ). Illustrative reactions and reactants (e) are generally discussed above with respect to the formation of preferred reactive components (c). It will be appreciated that the identity of the at least one reactant (e) will be dependent upon the identity of functional group (Fi) and the desired functional groups (F 2 ). Multiple reactants (e) may be used either simultaneously or sequentially. [0097] Hydroxyl functional groups (F 2 ) or intermediate hydroxyl functional groups may be obtained by the ring opening of an epoxy functional group (Fi) with an acid functional reactant (e).
- acid functional reactant (e) When only one epoxy functional group (F0 is present, acid functional reactant (e) must have an additional functional group such as hydroxy, carbamate, urea, amide, and the like.
- carbamate functional groups (F 2 ) may be obtained via the reaction of hydroxy functional groups (F0 with a reactant (e) selected from low molecular weight carbamate functional monomers such as methyl carbamate.
- carbamate functional groups (F 2 ) may be made by decomposing a reactant (e) such as urea in the presence of hydroxyl functional groups (FO.
- carbamate functional groups (F 2 ) may be obtained by reacting a first reactant (e) such as phosgene with a hydroxyl functional group (F0 followed by reaction with another reactant (e) such as ammonia.
- a first reactant (e) such as phosgene
- a hydroxyl functional group (F0) followed by reaction with another reactant (e) such as ammonia.
- Amine functional groups (F 2 ) may be obtained via reduction of a nitrile via reaction with a reactant (e) such as hydrogen gas.
- a reactant (e) such as hydrogen gas.
- Isocyanate functional groups (F 2 ) may be obtained via reaction of an amine functional group (F0 with a reactant (e) such as phosgene or carbon dioxide, with phosgene being preferred.
- Aminoplast functional groups (F 2 ) may be obtained via the reaction of an activated amine functional group (Fi) and a reactant (e) that is an aldehyde such as formaldehyde.
- a reactant (e) that is an aldehyde such as formaldehyde.
- Illustrative activated amine groups are melamine, benzoguanamine, amides, carbamates, and the like.
- aminoplast functional groups (F 2 ) may be made via reaction of carbamate functional groups (F0 with a reactant (e) that is an aldehyde.
- the resulting aminoplast functional group may be etherified via reaction with another reactant (e) such as a monofunctional alcohol.
- Aldehyde functional groups (F 2 ) may be made via reduction of an acid functional group (FO via reaction with at least one reactant (e) such as hydrogen.
- Urea functional groups (F 2 ) may be made via reaction of an amine functional group (F0 with a reactant (e) such as urea.
- urea functional groups (F 2 ) can be obtained via reaction of amine functional groups (Fi) with a reactant (e) such as phosgene followed by additional reaction with another reactant (e) such as ammonia.
- Epoxy functional groups (F 2 ) may be made via reaction of acid functional groups (F0 with a reactant (e) such as peroxide.
- epoxy functional groups (F 2 ) will be obtained via the reaction of acid or hydroxyl functional groups (Fi) with a reactant (e) such as epichlorohydrin.
- Cyclic carbonate functional groups (F 2 ) may be made via reaction of an epoxy functional group (F0 with a reactant (e) such as carbon dioxide.
- the reaction of a reactant (e) with a nonvolatile solvent (b nv ) having only one functional group (F0 will produce a nonvolatile solvent (b' nv ) having two or more functional groups (F 2 ).
- a reactant (e) with a nonvolatile solvent (b nv ) having only one functional group (F0 will produce a nonvolatile solvent (b' nv ) having two or more functional groups (F 2 ).
- the reaction of an epoxy functional group (Fi) with a hydroxy acid reactant (e) results in a diol
- the reaction of a cyclic carbonate (F0 with ammonia (reactant (e)) results in a hydroxy carbamate (beta or higher).
- the reaction of a cyclic anhydride with a hydroxy acid results in a di-acid.
- (e) may be at least one of low molecular weight carbamate functional reactants (such as simple alkyl carbamates), urea, phosgene, ammonia, carbon dioxide, acids, aldehydes, alcohols, peroxides, epichlorohydrin, mixtures thereof, and the like, hi another exemplary embodiment, when functional group (F0 is hydroxyl, (e) may be an alkyl carbamate, urea, or phosgene and ammonia. In one especially exemplary embodiment, reactant (e) will be an alkyl carbamate when functional group (F0 is hydroxyl.
- the polymerization of reactant mixture (a) into polymer (a') may occur either before, after, or simultaneously with the reaction of functional groups (Fi) of the nonvolatile solvent (b nv ) with the least one reactant (e) to provide nonvolatile solvent (b' nv ) having at least two functional groups (F 2 ).
- the two reactions will occur simultaneously.
- the reactant mixture (a) will be polymerized either before or simultaneously with the conversion of nonvolatile solvent (b nv ) to nonvolatile solvent (b' nv )-
- some or all of any functional groups present on polymer (a') may undergo conversion simultaneously.
- the conversion of hydroxyl functional monomers (a) to carbamate functional monomers (a) may occur simultaneously with polymerization of monomers (a) and the conversion of hydroxy functional groups (Fi) to carbamate functional groups (F 2 ).
- Coating compositions of the invention will also comprise at least one crosslinking agent (f).
- Crosslinking agent (f) will comprise at least one functional group (fi) that is reactive with functional groups (F 2 ) of nonvolatile solvent (b' nv )-
- Crosslinking agent (f) may further comprise additional functional groups (fii) that are reactive with any functional groups of polymer (a').
- the disclosed coating compositions may comprise one or more crosslinking agents (f), wherein functional groups (fi) and (fii) are on the same or different crosslinking agents (f).
- a disclosed coating composition will comprise at least one crosslinking agent (f) having both functional groups (fi) and (fii).
- crosslinking agents (f) are those crosslinking agents having one or more crosslinkable functional groups.
- Such functional groups include, for example, aminoplast, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, and acetoacetate groups. These groups may be masked or blocked in such a way so that they are unblocked and available for the cross-linking reaction under the desired curing conditions, generally elevated temperatures.
- Useful crosslinkable functional groups include hydroxy, epoxy, acid, anhydride, silane, activated methylene and acetoacetate groups.
- Preferred crosslinking agents will have crosslinkable functional groups that include hydroxy functional groups and arnino fimctional groups and isocyanate groups.
- Di- and/or polyisocyanates and/or aminoplast resins are most preferred for use as crosslinking agents in coating compositions comprising the mixture (II) of the invention.
- Mixed crosslinkers may also be used.
- the reactant (e) may be an aminoplast resin, a polyisocyanate, a blocked polyisocyanate resin (including an isocyanurate, biuret, or the reaction product of a diisocyanate and a polyol having less than twenty carbon atoms), or an acid or anhydride functional crosslinking agent.
- the crosslinker (f) will have functional groups (fi), that will react with the functional groups (F 2 ) to form a crosslink that is non-reversible under cure conditions. This will help to insure that the reactive additive remains crosslinked in the film.
- Some non-limiting examples of crosslinkable functional groups pairs that fall under this category are: carbamate:aminoplast, hydroxy:epoxy, acid:epoxy, vinybvinyl, and hydroxy socyanate.
- An example of a crosslink that is reversible under cure conditions is hydroxy:aminoplast, and hydroxy: activated methylene.
- the coating compositions of the invention are particularly suitable for use in automotive coating compositions, especially primers, basecoats, and/or clearcoats, with clearcoats being especially preferred.
- the coating compositions of the invention may be powder coatings, waterborne, power slurry, or solventborne.
- Coating compositions of the present invention preferably form the outermost layer or layer of coating on a coated substrate.
- the instant coating compositions are applied over one or more layers of primer coatings.
- the coating compositions of the invention may be used as an automotive topcoat coating applied over a layer of electrocoat primer and/or primer surfacer.
- topcoat coatings When such coating compositions are used as topcoat coatings, they preferably have a 20 degree gloss, as defined by ASTM D523-89, of at least 80 or a DOI, as defined by ASTM E430-91, of at least 80, or both. Such gloss and DOI are particularly useful in providing an automotive finish that will appeal to the buyer of the vehicle.
- Topcoat coatings may be one coat pigmented coatings or may be a color- plus-clear composite coating.
- Coating compositions of the present invention if used as a one coat pigmented coating or the color coating of a color-plus-clear composite coating, will include one or more pigments well-known in the art, such as inorganic pigments like titanium dioxide, carbon black, and iron oxide pigments, or organic pigments like azo reds, quinacridones, perylenes, copper phthalocyanines, carbazole violet, monoarylide and diarylide yellows, naphthol orange, and the like.
- the coating composition of the present invention is the clearcoat of a color-plus-clear composite coating.
- the clearcoat may be applied over a color coat according to the invention or may be applied over a color coat of a formulation already known in the art.
- Pigmented color coat or basecoat compositions for such composite coatings are well known in the art and do not require explanation in detail herein.
- Polymers known in the art to be useful in basecoat compositions include acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds, and polysiloxanes.
- Such basecoats may comprise the polymer (a') of the invention.
- Preferred polymers include acrylics and polyurethanes.
- Coating compositions can be coated onto an article by any of a number of techniques well known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like. For automotive body panels, spray coating is preferred. When the coatings will be relatively thick, they are usually applied in two or more coats separated by a time sufficient to allow some of the water and/or solvent evaporate from the applied coating layer ("flash"). The coats as applied are usually from 1 to 3 mils of the coating composition, and a sufficient number of coats are applied to yield the desired final coating thickness.
- the color coat is usually applied in one or two coats, then allowed to flash, and the clear coat is then applied to the uncured color coat in one or two coats.
- the two coating layers are then cured simultaneously.
- the cured base coat layer is 0.5 to 1.5 mils thick and the cured clear coat layer is 1 to 3 mils, more preferably 1.6 to 2.2 mils thick.
- Coating compositions of the invention are preferably subjected to conditions so as to cure the coating layers.
- thermal-curing is preferred.
- thermal curing is effected by exposing the coated article to elevated temperatures provided primarily by radiative heat sources. Curing temperatures will vary depending on the particular blocking groups used in the crosslinking agents, however they generally range between 93 degree C and 177 degree C.
- the cure temperature is between 135 degree C and 165 degree C.
- a blocked acid catalyst is included in the composition and the cure temperature is between 115 degree C and 140 degree C.
- an unblocked acid catalyst is included in the composition and the cure temperature is between 80 degree C and 100 degree C.
- the curing time will vary depending on the particular components used and physical parameters, such as the thickness of the layers. Typical curing times range from 15 to 60 minutes, and preferably 15-25 minutes at the target temperature.
- EXAMPLES Example 1 Part 1A Polymerization using a reactive material (c) as a solvent and co-tranesterification of the reactive material and the acrylic polymer [0123] A mixture of 650 parts of saturated a C36 fatty dimer diol and 350 parts of xylene was heated to 140°C under an inert atmosphere.
- Part IB A coating composition was prepared by combining the materials in order as set for below in Table 1 and mixing under agitation. Table 1
- the reaction mixture was then held at 110°C for an additional hour.
- the reactor was then set up with a paced column and an extractor to remove methanol, and a mixture of 3.1 parts of dibutyl tin oxide, 487.5 parts of methyl carbamate, 6.9 parts of triisodecyl phosphite and 636.6 parts of toluene was added.
- the system was allowed to come to reflux.
- the transcarbamation was taken to its stall point where -95% of the hydroxy groups were converted into carbamate groups.
- the solvent and excess methylcarbamate were then removed by vacuum distillation. Then 500 grams of the vacuum stripped resin was dissolved into 214 grams of methyl propyl ketone.
- the final resin had a NV of 70%.
- a coating composition was prepared by combining the materials in order as set for below in Table 2 and mixing under agitation. Table 2 Ingredient
- Example 1 The curable coating compositions from Examples 1 and 2 were evaluated per the following.
- the control was E126CG2023, a 1 -component acrylic- blocked isocyanate system available from BASF Corp. of Southfield, MI. It can be seen that the composition of Example 1 shows improvements in scratch & mar and hardness. It also exhibits a higher cured film T g and crosslhik density with all other properties essentially maintained.
- Resimene 747 Melamine from UCB
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0506160-1A BRPI0506160A (en) | 2004-06-11 | 2005-06-10 | method for obtaining low VOC coating compositions |
MXPA06000035 MX274730B (en) | 2004-06-11 | 2005-06-10 | Method for obtaining coating compositions having reduced voc. |
CA002535173A CA2535173A1 (en) | 2004-06-11 | 2005-06-10 | Method for obtaining coating compositions having reduced voc |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/866,595 | 2004-06-11 | ||
US10/866,596 | 2004-06-11 | ||
US10/866,596 US7321013B2 (en) | 2000-12-19 | 2004-06-11 | Method for obtaining coating compositions having reduced VOC |
US10/866,595 US7696285B2 (en) | 2000-12-19 | 2004-06-11 | Carbamate functional reactive polymer composition |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005123787A2 true WO2005123787A2 (en) | 2005-12-29 |
WO2005123787A3 WO2005123787A3 (en) | 2006-05-04 |
Family
ID=35462121
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2005/020611 WO2005123787A2 (en) | 2004-06-11 | 2005-06-10 | Method for obtaining coating compositions having reduced voc |
Country Status (4)
Country | Link |
---|---|
BR (1) | BRPI0506160A (en) |
CA (1) | CA2535173A1 (en) |
MX (1) | MX274730B (en) |
WO (1) | WO2005123787A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009025703A1 (en) * | 2007-08-17 | 2009-02-26 | Basf Corporation | Materials and oligomers in low voc coatings |
WO2009025704A1 (en) * | 2007-08-17 | 2009-02-26 | Basf Corporation | Coating compositions containing monomeric, long-chain reactants |
EP2444461A1 (en) * | 2010-10-23 | 2012-04-25 | Jonathan Graham | Touch-up paint |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4003868A (en) * | 1971-12-08 | 1977-01-18 | Union Carbide Corporation | Ink or coating compositions of low volatility |
US4126527A (en) * | 1975-09-30 | 1978-11-21 | Mobil Oil Corporation | Radiation curable coatings containing hydroxy functional polyethers and polyesters of monoethylenic acids or hydroxy esters thereof |
US20020119253A1 (en) * | 2000-12-19 | 2002-08-29 | Ohrbom Walter H. | Coating compositions containing crosslinkable monomeric difunctional compounds having at least thirty carbon atoms |
WO2003076530A2 (en) * | 2002-03-08 | 2003-09-18 | Valspar Sourcing, Inc. | Coatings having low volatile organic compound content |
-
2005
- 2005-06-10 WO PCT/US2005/020611 patent/WO2005123787A2/en active Application Filing
- 2005-06-10 MX MXPA06000035 patent/MX274730B/en active IP Right Grant
- 2005-06-10 BR BRPI0506160-1A patent/BRPI0506160A/en not_active Application Discontinuation
- 2005-06-10 CA CA002535173A patent/CA2535173A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4003868A (en) * | 1971-12-08 | 1977-01-18 | Union Carbide Corporation | Ink or coating compositions of low volatility |
US4126527A (en) * | 1975-09-30 | 1978-11-21 | Mobil Oil Corporation | Radiation curable coatings containing hydroxy functional polyethers and polyesters of monoethylenic acids or hydroxy esters thereof |
US20020119253A1 (en) * | 2000-12-19 | 2002-08-29 | Ohrbom Walter H. | Coating compositions containing crosslinkable monomeric difunctional compounds having at least thirty carbon atoms |
WO2003076530A2 (en) * | 2002-03-08 | 2003-09-18 | Valspar Sourcing, Inc. | Coatings having low volatile organic compound content |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009025703A1 (en) * | 2007-08-17 | 2009-02-26 | Basf Corporation | Materials and oligomers in low voc coatings |
WO2009025704A1 (en) * | 2007-08-17 | 2009-02-26 | Basf Corporation | Coating compositions containing monomeric, long-chain reactants |
EP2444461A1 (en) * | 2010-10-23 | 2012-04-25 | Jonathan Graham | Touch-up paint |
Also Published As
Publication number | Publication date |
---|---|
WO2005123787A3 (en) | 2006-05-04 |
CA2535173A1 (en) | 2005-12-29 |
MX274730B (en) | 2010-03-25 |
MXPA06000035A (en) | 2006-03-21 |
BRPI0506160A (en) | 2006-10-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU691373B2 (en) | Method of preparing carbamate-functional polymer | |
US20030100687A1 (en) | Method for selective graft polymerization | |
US7691951B2 (en) | Method for obtaining coating compositions having reduced VOC | |
EP1238031B1 (en) | Curable coating compositions containing carbamate functional reactive additives | |
EP0705853A2 (en) | Copolymers with cyclic or polycyclic monomers with special distribution of monomers and their use in coatings | |
US6583212B2 (en) | Aqueous dispersions for coating compositions | |
EP1453864B1 (en) | Method for obtaining coating compositions having reduced voc | |
EP2089436B1 (en) | Polymerization of acrylic polymers in reactive diluents | |
US7696285B2 (en) | Carbamate functional reactive polymer composition | |
WO2005123787A2 (en) | Method for obtaining coating compositions having reduced voc | |
WO2015169550A1 (en) | Method using zirconium catalyst for producing carbamate- functional materials | |
WO2004031309A1 (en) | Method of providing cured coating films free of popping defects | |
US20040063850A1 (en) | Waterborne coating compositions containing monomeric difunctional compounds | |
CA2445210C (en) | Carboxy resin crosslinkers | |
US7368501B2 (en) | Method for improving environmental durability of materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2006/000035 Country of ref document: MX |
|
ENP | Entry into the national phase |
Ref document number: 2535173 Country of ref document: CA |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: PI0506160 Country of ref document: BR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase |