US 2010.0099806A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0099806 A1 Houze et al. (43) Pub. Date: Apr. 22, 2010

(54) PROCESS FOR PRODUCING DIMETHYL (22) Filed: Oct. 22, 2009 CARBONATE CONTAINING COMPOSITIONS Related U.S. Application Data (75) Inventors: Eric C. Houze, Mullica Hill, NJ (US); Laura Ann Lewin, (60) Provisional application No. 61/196,987, filed on Oct. Greenville, NJ (US) 22, 2008. Correspondence Address: Publication Classification E DUPONT DE NEMOURS AND COMPANY (51) Int. C. LEGAL PATENT RECORDS CENTER CSK 5/04 (2006.01) BARLEY MILL PLAZA 25/1122B, 4417 LAN U.S. Cl...... 524/28O CASTER PIKE (52) WILMINGTON, DE 19805 (US) (57) ABSTRACT (73) Assignee: E. I. DUPONT DE NEMOURS The present invention is directed to a process for producing AND COMPANY, Wilmington compositions containing dimethylcarbonate alone or in com (DE) bination with other co-solvent and more particularly directed to low VOC coating compositions used in automotive refinish (21) Appl. No.: 12/604,144 applications. US 2010/00998.06 A1 Apr. 22, 2010

PROCESS FOR PRODUCING DIMETHYL toxy ethoxy 222-propanol. 1-methyl naphthalene, 1-nitro CARBONATE CONTAINING COMPOSITIONS propane, 2.4-pentane dione, 2-ethylhexanol, 2-ethylhexyl acetate, 2-methyl-1-butanol, acetic anhydride, butyl acetate, FIELD OF INVENTION di-isoamyl ketone, diacetone alcohol, diethylene glycol monobutyl ether acetate, diethylene glycol, diisobutyl 0001. The present invention is directed to compositions ketone, ethylene glycol monoethyl ether acetate, glycol containing dimethyl carbonate and more particularly directed monopropyl ether acetate benzyl alcohol. 1,2-dichloroet to coating compositions directed to automotive refinish appli hane, 1,3-dioxane, 1,2-dimethoxyethane, 1-butanol. 1-me cations containing low VOCs (volatile organic compounds). thyl-2-pyrrolidinone, 1-propanol, 2-butanol, 2-ethylhexanol, 2-methoxyethanol. 2-propanol, acetone, acetonitrile, ben BACKGROUND OF INVENTION Zene, bis(2-methoxyethyl)ether, butyl cellosolve, carbon tet 0002 Many types of coating compositions, such as those rachloride, chlorobenzene, chlorobenzene, cyclohexane, used in the Industrial OEM (original equipment manufac cyclohexanol, cyclohexanone, dibasic ester, dichlo turer) and automotive refinish market utilize liquid coatings romethane, diethyl ether, diethylene glycol monobutyl ether, that contain organic solvents some of which upon evaporation diisopropyl ether, dimethyl ether, dimethylpropyleneurea, in the atmosphere can, depending upon the content of VOCs, dimethylsulphoxide, ethanol, ethyl acetate, ethyl benzene, be harmful to the environment and health. Generally VOCs ethylene glycol, ethyl amylketone, ethylbenzene, ethyl pro are considered to be those organic chemical compounds that pionate, ethylene glycol diacetate, ethylene glycol monobutyl have high enough vapor pressures under normal conditions to ether, ethylene glycol monoethyl ether, ethylene glycol significantly vaporize and enter the atmosphere, and to be monohexyl ether, ethylene glycol monomethyl ether, ethyl photochemically reactive, leading to the formation of tropho ene glycol monopropyl ether, fluorobenzene, formamide, fur spheric oZone. Thus, the manufacturers of coating composi fural, heptane, hexane, hexylene glycol, hexylene glycol tions endeavor to reduce the content of organic solvents in diacetate, iso-butyl acetate, iso-butyl isobutyrate, isoamyl their compositions. Alternatively, the manufacturers of coat alcohol, isobutanol, isopropanol, isopropyl acetate, 1,3,5-tri ing compositions employ certain solvents, such as acetone, methylbenzene, methane Sulphonic acid, methanol, methyl methyl acetate, Oxsol(R) 100 (1-chloro, 4-trifluoromethylben acetate, methyl celloSolve, methyl cyclohexane, methyl ethyl Zene) and t-butyl acetate, which have been considered exempt ketone, methyl amyl ketone, methyl amyl acetate, methyl VOC solvents by the United States Environmental Protection hexyl ketone, methyl n-propyl ketone, methylene chloride, Agency. However, each of these exempt solvents has signifi n-butyl propionate, n-heptyl acetate, n-hexyl acetate, n-nonyl cant issues in coatings formulations. Acetone and methyl acetate, n-octyl acetate, n-pentyl propionate, primary amyl acetate are extremely volatile, limiting the amount that can be acetate, propylene glycol monoethyl ether acetate, propylene used in a given formula and t-butyl acetate is not accepted as glycol t-butyl ether, propylene glycol isobutyl ether, propy VOC exempt by all Air Quality Management Districts (e.g., lene glycol monobutyl ether, propylene glycol monothyl California does not accept t-butyl acetate as a VOC exempt ether, propylene glycol monopropyl ether, methyl isobutyl Solvent) and is also unstable in Some coatings formulations. ketone, methyl tertbutyl ether, m-xylene, n,n-dimethyl for OxsolR 100 is a very poor coatings solvent due to its high mamide, n,n-dimethylacetamide, N,N-dimethylaniline, specific gravity (1.34) and weak solubility characteristics, so n-butanol, n-propyl acetate, o-Xylene, pentane, petroleum it is very expensive to use. Thus, a need still exists for a ether, propionic acid, p-Xylene, pyridine, sec-butyl alcohol, VOC-exempt solvent more suitable for use in coating com sec-butyl acetate, tert-butyl alcohol, tetrachloroethylene, tet positions, such as industrial and automotive refinish paints rahydrofuran, terpene, toluene, trichloroethylene, triethy that has a lower vapor pressure than acetone and methyl lamine, triethylene glycol monobutyl ether, triethylene gly acetate and is also an effective solvent compatible with vari col, monoethyl ether triethylene glycol, monomethyl ether, ous components, such as binder component, of a typical coat triethylene glycol diacetate, and a combination thereof, and ing composition. 0005 (B) mixing the solvent component with the binder component to form said composition. STATEMENT OF INVENTION DETAILED DESCRIPTIONS 0003. The present invention is directed to a process for producing a composition consisting essentially of a binder 0006. Unless stated otherwise: component and a solvent component, said process compris 0007. These and other features and advantages of the ing the steps of present disclosure will be more readily understood, by those 0004 (A) preparing the solvent component by mixing a of ordinary skill in the art, from a reading of the following solvent dimethyl carbonate with a co-solvent selected from detailed description. It is to be appreciated those certain fea the group consisting of aromatic hydrocarbon (135-146C), tures of the disclosure, which are, for clarity, described above aromatic hydrocarbon (150-190C), aromatic hydrocarbon and below in the context of separate embodiments, may also (182-219C), aliphatic hydrocarbon (100-150C), aliphatic be provided in combination in a single embodiment. Con hydrocarbon (100-163C), aliphatic hydrocarbon (115-149C), versely, various features of the disclosure that are, for brevity, aliphatic hydrocarbon (138-177C), aliphatic hydrocarbon described in the context of a single embodiment, may also be (138-185C), aliphatic hydrocarbon (145-205C), aliphatic provided separately or in any Sub-combination. In addition, hydrocarbon (150-205C), aliphatic hydrocarbon (150-210C), references in the singular may also include the plural (for aliphatic hydrocarbon (155-190C), aliphatic hydrocarbon example, “a” and “an may refer to one, or one or more) (170-210C), aliphatic hydrocarbon (180-210C), aliphatic unless the context specifically states otherwise. hydrocarbon (182-266C), aliphatic hydrocarbon (90-110C), 0008. The use of numerical values in the various ranges mineral spirit, 1,1,1-trichloroethane, 1,1,2-trichloroethane, specified in this application, unless expressly indicated oth 1.2-propylene glycol. 1,3-butanediol. 1,4-butanediol. 1-bu erwise, are stated as approximations as though the minimum US 2010/00998.06 A1 Apr. 22, 2010

and maximum values within the stated ranges were both a coating on the Substrate Surface having the desired coating preceded by the word “about.” In this manner, slight varia properties. Such as high gloss, mar-resistance and resistance tions above and below the stated ranges can be used to achieve to environmental etching. Substantially the same results as values within the ranges. 0013 “One-pack coating composition” means a thermo Also, the disclosure of these ranges is intended as a continu set coating composition comprising a crosslinkable compo ous range including every value between the minimum and nent and a crosslinking component that are stored in the same maximum values. container. However, crosslinkable functionalities on a crosslinkable polymer in the crosslinkable component are 0009. The crosslinkable functionalities are chemically blocked to prevent premature crosslinking, i.e., curing. After reactive functionalities provided on the backbone, atterminal the application of the one-pack coating composition on a end(s) or pendant from the backbone of a polymer chain. Substrate, the layer is typically exposed to elevated tempera When a crosslinkable polymer is mixed with a crosslinking tures to unmask the blocked crosslinkable functionalities. agent, crosslinkable functionalities on the crosslinkable poly Thereupon, the unmasked crosslinkable functionalities on the mer react with the crosslinking functionalities on the crosslinkable polymer in the layer react with the crosslinking crosslinking agent to form a network, i.e., a process of curing functionalities on the crosslinking agent in the layer, which is that leads to the formation of a coating having the desired bake-cured at elevated temperatures to form a coating on the coating properties, such as high gloss, mar-resistance and Substrate Surface having the desired coating properties. resistance to environmental etching. Typical crosslinkable 0014 “Low VOC coating composition” means a coating functionalities can include hydroxyl, acetoacetoxy, thiol, car composition that is less than about 0.6 kilogram of organic boxyl, primary amine, secondary amine, epoxy, anhydride, Solvent per liter (4.8 pounds per gallon) of the composition, as imino, ketimine, and aldimine functionalities. determined under the procedure provided in ASTM D3960. 0010. The crosslinking functionalities in a crosslinking (0015 “GPC weight average molecular weight” and “GPC component are chemically reactive functionalities provided number average molecular weight' means a weight average molecular weight and a weight average molecular weight, on the back bone, at terminal end(s) or pendant from the respectively measured by utilizing gel permeation chroma backbone of a polymer chain, a compound, or an oligomer. tography. A high performance liquid chromatograph (HPLC) When a crosslinking component is mixed with a crosslink supplied by Hewlett-Packard; Palo Alto, Calif. is typically able component, crosslinkable functionalities react with the used. Unless stated otherwise, the liquid phase used was crosslinking functionalities to form a network. Typical tetrahydrofuran and the standard is typically polymethyl crosslinking functionalities can include isocyanate, amine, methacrylate. ketimine, melamine, epoxy, polyacid, anhydride, and a com 0016. The applicants have made an unexpected discovery bination thereof. that by including dimethyl carbonate, propylene carbonate or 0011. It would be clear to one of ordinary skill in the art in combination with other co-solvents in a solvent borne that generally certain crosslinking functionalities from the composition, Such as an automotive paint, it is possible to crosslinking components crosslink with certain crosslinkable reduce the VOC of the composition without sacrificing the functionalities from the crosslinkable components. Some of desired solvent properties, such as compatibility with other those paired combinations include: (1) ketimine crosslinking components in a composition, such as polymers in the binder functionalities generally crosslink with acetoacetoxy, epoxy, component. The following embodiments are illustrative of or anhydride crosslinkable functionalities; (2) isocyanate and the applicants invention. melamine crosslinking functionalities generally crosslink 0017. One embodiment of the coating composition of the with hydroxyl, thiol, primary and secondary amine, ketimine, present invention consists essentially of a binder component or aldimine crosslinkable functionalities; (3) epoxy and a solvent component, wherein the solvent component crosslinking functionalities generally crosslink with car consists of dimethyl carbonate, propylene carbonate or a boxyl, primary and secondary amine, ketimine, or anhydride combination thereof. crosslinkable functionalities; (4) amine crosslinking func 0018. The proportion of dimethyl carbonate to propylene tionalities generally crosslink with acetoacetoxy crosslink carbonate when used in combination in the solvent compo able functionalities; (5) polyacid crosslinking functionalities nent ranges from 100/0 to 0/100, preferably from 100/0 to generally crosslink with epoxy crosslinkable functionalities; 80/20 and more preferably from 97/3 to 90/10. and (6) anhydride crosslinking functionalities generally 0019. It should be understood that commercially produced crosslink with epoxy and ketimine crosslinkable functional dimethyl carbonate or propylene carbonate can contain impu ities. rities or Small quantities of other solvents, which are gener 0012 “Two-pack coating composition” means a thermo ally less than 0.5% weight percent based on the total of the set coating composition comprising a crosslinkable compo dimethyl carbonate or propylene carbonate contained in the nent and a crosslinking component that are stored in separate composition. containers. These containers are typically sealed to increase 0020. In another embodiment of the coating composition the shelf life of the components of the composition. The of the present invention consists essentially of a binder com crosslinkable component and crosslinking component are ponent and a solvent component, wherein the solvent com mixed prior to use to form a pot mix. The pot mix has a limited ponent consists of: potlife, typically a few minutes (15 minutes to 45 minutes) to 0021 (A) dimethyl carbonate; and a few hours (4 hours to 6 hours). The pot mix is conventionally 0022 (B) a co-solvent selected from the group consisting applied, generally by means of a spray gun or roller, as a layer of aromatic hydrocarbon (135-146C), aromatic hydrocarbon of a desired thickness on a Substrate Surface. Such as an (150-190C), aromatic hydrocarbon (182-219C), aliphatic autobody. After the application, the layer is cured under ambi hydrocarbon (100-150C), aliphatic hydrocarbon (100-163C). ent conditions or bake cured at elevated temperatures to form aliphatic hydrocarbon (115-149C), aliphatic hydrocarbon US 2010/00998.06 A1 Apr. 22, 2010

(138-177C), aliphatic hydrocarbon (138-185C), aliphatic acetate, ethyl acetate, propyl acetate, n-butyl acetate, t-butyl hydrocarbon (145-205C), aliphatic hydrocarbon (150-205C), acetate, 2-ethylhexyl acetate, methoxy propyl acetate, 1-me aliphatic hydrocarbon (150-210C), aliphatic hydrocarbon thyl-2-pyrrolidinone, aromatic hydrocarbon (135-146C), (155-190C), aliphatic hydrocarbon (170-210C), aliphatic aromatic hydrocarbon (150-190C), aromatic hydrocarbon hydrocarbon (180-210C), aliphatic hydrocarbon (182-266C), (182-219C), heptane, aliphatic hydrocarbon (100-150C), ali aliphatic hydrocarbon (90-110C), mineral spirit, 1,1,1- phatic hydrocarbon (100-163C), aliphatic hydrocarbon (115 trichloroethane, 1,1,2-trichloroethane, 1,2-propylene glycol, 149C), aliphatic hydrocarbon (138-177C), aliphatic hydro 1,3-butanediol, 1,4-butanediol, 1-butoxy ethoxy 222-pro carbon (138-185C), aliphatic hydrocarbon (145-205C), panol. 1-methyl naphthalene, 1-nitro propane, 2.4-pentane aliphatic hydrocarbon (150-205C), aliphatic hydrocarbon dione, 2-ethyl hexanol, 2-ethyl hexyl acetate, 2-methyl-1- (150-210C), aliphatic hydrocarbon (155-190C), or a combi butanol, acetic anhydride, butyl acetate, di-isoamyl ketone, nation thereof. diacetone alcohol, diethylene glycol, monobutyl ether 0026. The solvent component in the aforedescribed acetate, diethylene glycol, diisobutyl ketone, ethylene glycol, embodiment consists in the range of 5 weight percent to 100 monoethyl ether acetate, glycol monopropyl ether acetate weight percent, preferably in the range of 10 to 90 and more benzyl alcohol. 1,2-dichloroethane, 1,3-dioxane, 1.2- preferably in the range of 40 to 80 of dimethyl carbonate, all dimethoxyethane, 1-butanol, 1-methyl-2-pyrrolidinone, percentages based on the total weight of the composition. 1-propanol, 2-butanol, 2-ethylhexanol, 2-methoxyethanol, 0027. The solvent component in the aforedescribed 2-propanol, acetone, acetonitrile, benzene, bis(2-methoxy embodiment consists in the range of 0.01 weight percent to 95 ethyl)ether, butyl cellosolve, carbon tetrachloride, chloroben weight percent, preferably in the range of 15 to 90 and more Zene, chlorobenzene, cyclohexane, cyclohexanol, cyclohex preferably in the range of 20 to 60 of the co-solvent, all anone, dibasic ester, dichloromethane, diethyl ether, percentages based on the total weight of the composition. diethylene glycol monobutyl ether, diisopropyl ether, dim 0028. The amount of solvent component in the foregoing ethyl ether, dimethylpropyleneurea, dimethylsulphoxide, embodiment of the composition can be adjusted to provide ethanol, ethyl acetate, ethylbenzene, ethylene glycol, ethyl the composition with a VOC of less than 0.576 kilogram (4.8 amylketone, ethylbenzene, ethylpropionate, ethylene glycol pounds per gallon) and preferably in the range of 0.012 kilo diacetate, ethylene glycol monobutyl ether, ethylene glycol gram to 0.576 kilogram (0.1 pound to 4.8 pounds per gallon), monoethyl ether ethylene glycol monohexyl ether, ethylene more preferably in the range of from 0.12 kilogram to 0.42 glycol monomethyl ether, ethylene glycol monopropyl ether, kilogram (1.0 to 3.5 pounds per gallon), and most preferably fluorobenzene, formamide, furfural, heptane, hexane, hexy in the range of from 0.012 kilogram to 0.252 kilogram (0.1 to lene glycol, hexylene glycol diacetate, iso-butyl acetate, iso 2.1 pounds per gallon) of solvent per liter of the composition. butyl isobutyrate, isoamyl alcohol, isobutanol, isopropanol, The solids level of the coating of the present invention varies isopropyl acetate, 1,3,5-trimethylbenzene, methane Sul in the range of from 5 percent to 100 percent, preferably in the phonic acid, methanol, methyl acetate, methyl celloSolve, range of from 10 percent to 95 percent and more, preferably methyl cyclohexane, methyl ethyl ketone, methyl amyl in the range of from 25 percent to 85 percent, all percentages ketone, methyl amyl acetate, methylhexyl ketone, methyl being based on the total weight of the composition. n-propyl ketone, methylene chloride, n-butyl propionate, 0029. The solvent component consists in the range of 0.01 n-heptyl acetate, n-hexyl acetate, n-nonyl acetate, n-octyl weight percent to 95 weight percent, preferably in the range acetate, n-pentyl propionate, primary amylacetate, propylene of 5 to 90 and more preferably in the range of 15 to 75 of glycol monoethyl ether acetate, propylene glycol t-butyl dimethyl carbonate, propylene carbonate, or a combination ether, propylene glycol isobutyl ether, propylene glycol thereof, all percentages based on the total weight of the com monobutyl ether, propylene glycol monothyl ether, propylene position. glycol monopropyl ether, methyl isobutyl ketone, methylter 0030 The binder component in the compositions of the thutyl ether, m-Xylene, n,n-dimethyl formamide, n,n-dim present invention can include a crosslinkable component and ethylacetamide, N,N-dimethylaniline, n-butanol, n-propyl a crosslinking component, wherein the crosslinkable compo acetate, o-Xylene, pentane, petroleum ether, propionic acid, nent includes one or more crosslinkable polymers having one p-Xylene, pyridine, Sec-butyl alcohol, sec-butyl acetate, t-bu to fifteen crosslinkable functionalities. The crosslinking com tyl acetate, propylene carbonate, tert-butyl alcohol, tetrachlo ponent includes one or more crosslinking agents having two roethylene, tetrahydrofuran, terpene, toluene, trichloroethyl to six crosslinking functionalities. ene, triethylamine, triethylene glycol monobutyl ether, 0031. Some suitable crosslinkable polymers are an acrylic triethylene glycol, monoethyl ether triethylene, glycol polymer, polyester, polyurethane, polyether, polyvinylbu monomethyl ether triethylene glycol diacetate, and a combi tyral, polyvinylchloride, polyolefin, epoxy, silicone, vinyl nation thereof. ester, phenolic, alkyd or a combination thereof, all of which 0023 The foregoing numerals in parenthesis, such as, for are typically provided with crosslinkable functionalities. example, (90-110C) refer to an aromatic hydrocarbon having 0032. The binder component can include 0.1% to 50% by a boiling point range of 90° C. to 110°C. weight, based on the total weight of the binder component 0024 Preferably, one or more co-solvents in the solvent Solids, of acrylic polymers. Some of the typical acrylic poly component in the aforedescribed embodiment can be esters, mers include acrylic polymers which are the polymerization ketones, ether alcohols, ether esters, alcohols, aromatic hyro product of methacrylate, and acrylate monomers having carbons, aliphatic hydrocarbons listed above, 1-methyl-2- weight average molecular weights ranging from 1,000 to pyrrolidinone, or a combination thereof. 20,000. Styrene and other C.B ethylenically unsaturated 0025 More preferably, one or more co-solvents in the monomers can also be used with the above monomers in the solvent component in the aforedescribed embodiment can be acrylic polymer. acetone, methyl propyl ketone, methyl amyl ketone, 2-pro 0033 Typical acrylic polymers are prepared by polymer panol. 1-butanol, methoxy propanol, butoxyethanol, methyl izing a monomer mixture containing one or more following US 2010/00998.06 A1 Apr. 22, 2010

group of monomers, such as, for example, acrylic ester mono hydrolysis, Such as ketimine, aldimine or oxazoline and any mer including methyl acrylate, ethyl acrylate, butyl acrylate, combination of Such functional groups. Hydroxyl function 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, alities are preferred. At least one of the monomer in the ethyl methacrylate, butyl methacrylate, lauryl (meth)acry monomer mixture provides the crosslinkable acrylic polymer late, isobornyl(meth)acrylate, isodecyl(meth)acrylate, oleyl or polyester with one or more crosslinkable functionalities. (meth)acrylate, palmityl(meth)acrylate, Stearyl(meth)acry Alternatively, crosslinkable functionalities can also be pro late, hydroxyethyl(meth)acrylate, and hydroxypropyl(meth) vided by reacting the resulting polymer, after polymerization, acrylate; acrylamide or Substituted acrylamides; styrene or with a monomer or a polymer that provides the resulting alkyl substituted styrenes; butadiene; ethylene; vinyl acetate; polymer with crosslinkable functionalities. vinyl ester of “Versatic acid (a tertiary monocarboxylic acid 0038. Some of the suitable crosslinking agents for the having Co., Co and C chain length, the vinyl ester is also aforedescribed crosslinkable acrylic polymers and polyesters known as “vinyl versataten), or other vinyl esters: vinyl include polyisocyanates, melamines, urea formaldehyde monomers, such as, for example, vinyl chloride, vinylidene polymers, or a combination thereof. chloride, vinyl pyridine, N-Vinyl pyrrolidone; amino mono 0039 Suitable polyisocyanates have on an average 2 to 10, mers, such as, for example, N,N'-dimethylamino(meth)acry preferably 2.5 to 6 and more preferably 3 to 4 crosslinking late; chloroprene and acrylonitrile or methacrylonitrile. functionalities, i.e., isocyanates. The composition can include Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, in the range of from 0.01 percent to 70 percent, preferably in fumaric acid, maleic acid, monomethyl itaconate, monom the range of from 10 percent to 50 percent, and more prefer ethyl fumarate, monobutyl fumarate, maleic anhydride, ably in the range of 20 percent to 40 percent of the polyiso 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium cyanate, the percentages being in weight percentages based vinyl Sulfonate, and phosphoethyl methacrylate. on the total weight of composition Solids. 0034 Preferably, the acrylic polymer is polymerized from 0040. The following polyisocyanates are suitable: a monomer mixture of about 5% to 30% by weight styrene, 0041 Aliphatic polyisocyanates, which include aliphatic 10% to 40% by weight butyl methacrylate, 10% to 40% by or cycloaliphatic di-, tri- or tetra-isocyanates, which may or weight butylacrylate, 15% to 50% by weight of hydroxyethyl may not be ethylenically unsaturated. Such as 1,2-propylene acrylate or hydroxy propyl acrylate, all weight percentages diisocyanate, trimethylene diisocyanate, tetramethylene based on the total weight of monomer solids. The acrylic diisocyanate, 2,3-butylene diisocyanate, hexamethylene polymer preferably has a weight average molecular weight of diisocyanate, octamethylene diisocyanate, 2,2,4-trimethyl about 3,000 to 15,000. The acrylic polymer can be prepared hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene by Solution polymerization, typically at elevated tempera diisocyanate, dodecamethylene diisocyanate, omega-dipro tures, in which the monomer mixture, conventional Solvents, pyl ether diisocyanate, 1.3-cyclopentane diisocyanate, 1.2- thermal initiators, such as 2,2'-azobis(isobutyronitrile) or per cyclohexane diisocyanate, 1.4-cyclohexane diisocyanate, oxyacetate, are heated to about 70° C. to 175° C. for about 1 isophorone diisocyanate, 4-methyl-1,3-diisocyanatocyclo to 12 hours. hexane, trans-Viny-lidene diisocyanate, dicyclohexyl 0035. The binder component of the coating composition methane-4,4'-diisocyanate, 3,3'-dimethyl-dicyclohexyl of the present invention can contain from about 0.01% to 40% methane 4,4'-diisocyanate, and meta-tetramethylxylylene by weight of a polyester polymer which is the esterification diisocyanate. The polyisocyanates can include those having product of analiphatic or aromatic dicarboxylic acid, a polyol isocyanurate structural units, such as the isocyanurate of hex having at least three reactive hydroxyl groups, a diol, an amethylene diisocyanate and isocyanurate of isophorone aromatic or aliphatic cyclic anhydride and a cyclic alcohol. diisocyanate, the adduct of 2 molecules of a diisocyanate, One preferred polyester is the esterification product of adipic Such as hexamethylene diisocyanate, uretidiones of hexam acid, trimethylol propane, hexanediol, hexahydrophathalic ethylene diisocyanate, uretidiones of isophorone diisocyan anhydride and cyclohexane dimethylol. The weight percent ate or isophorone diisocyanate; and diols, such as ethylene ages are based on total weight of the binder component Solids. glycol, the adduct of 3 molecules of hexamethylene diisocy 0036 Typically to prepare the aforedescribed polymers, a anate and 1 molecule of water (available under the trademark monomer mixture in conventional Solvents polymerized, at Desmodur R N of Bayer Corporation, Pittsburgh, Pa.). The elevated temperatures, with one or more conventional ther polyisocyanates can also include Suitable aromatic polyiso mal initiators. Some of the suitable thermal initiators include cyanates for use in coatings not requiring high levels of sta 2,2'-aZobis(2-methylpropanenitrile), 2,2'-azobis(2-meth bility to UV light. Some of such suitable aromatic polyisocy ylbutanenitrile), 1,1'-azobis(cyclohexanecarbonitrile), tert anates can include toluene diisocyanate and diphenylmethane butyl peroxy-2-ethylhexanoate, tert-butylperoxydiethyl diisocyanate. If desired, the isocyanate functionalities of the acetate, tert-butyl peroxyisobutyrate, 1,1-di-tert-butylper polyisocyanate can be blocked with a monomeric alcohol to oxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycy prevent premature crosslinking in a one-pack composition. clohexane, tert-butyl peroxy-3.5.5-trimethylhexanoate, tert Some of the suitable monomeric alcohols include methanol, butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, ethanol, propanol, butanol, isopropanol, isobutanol, hexanol, tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl 2-ethylhexanol and cyclohexanol. cumyl peroxide, di-tert-butyl peroxide and di-tert-amyl per 0042. The crosslinking component of the binder compo oxide. nent when containing polyisocyanate can also contain a cata 0037. As noted earlier, the aforedescribed crosslinkable lyst component, which preferably includes one or more cata acrylic polymers and polyesters are provided with one or lysts to enhance crosslinking of during the curing. Suitable more crosslinkable functionalities such as, hydroxy function catalysts include one or more organo tin catalysts, such as alities; or functionalities that can form hydroxy functional dibutyl tin dilaurate, dibutyl tin diacetate, Stannous octoate, ities on hydrolysis, such as carbonate and orthoester, amine and dibutyl tin oxide. Dibutyl tin dilaurate is preferred. The functionality; or groups that can form amine functionality on amount of organo tin catalyst added generally ranges from US 2010/00998.06 A1 Apr. 22, 2010

0.001 percent to 0.5 percent, preferably from 0.05 percent to 0047. Some of the suitable crosslinking agents can also 0.2 percent and more preferably from 0.01 percent to 0.1 include a silane polymer or oligomer provided with at least percent, the percentages being in weight percentages based one reactive silane group. The coating composition can on the total weight of composition Solids. include in the range of from 0.1% to 45%, preferably in the 0043 The following melamines are suitable: range of from 10% to 40%, and most preferably in the range 0044) Monomeric or polymeric melamine-formaldehyde of from of 15% to 35% of the silane polymer, the percentages resin (melamine) or a combination thereof. The composition being in weight percentages based on the total weight of can include in the range of from 0.1 percent to 40%, prefer composition Solids. The silane polymers suitable for use in ably in the range of from 15% to 35%, and most preferably in the present invention have weight average molecular weight the range of 20 percent to 30 percent of the melamine, the in the range of about 500 to 30,000, preferably in the range of percentages being in weight percentages based on the total about 750 to 25,000 and more preferably in the range of about weight of composition Solids. The monomeric melamines 1000 to 7,500. All molecular weights disclosed herein are include low molecular weight melamines which contain, on determined by gel permeation chromatography using a poly an average, three or more methylol groups etherized with a C styrene standard. The silane polymer Suitable herein is a to C monohydric alcohol such as methanol, n-butanol, or polymerization product of about 30 to 95%, preferably 40 to isobutanol per triazine nucleus, and have an average degree of 60%, by weight of ethylenically unsaturated non-silane con condensation up to about 2 and preferably in the range of taining monomers and about 5 to 70%, preferably 40 to 60%, about 1.1 to about 1.8, and have a proportion of mononuclear by weight of ethylenically unsaturated silane containing species not less than about 50 percent by weight. By contrast monomers, based on the weight of the silane polymer. Suit the polymeric melamines have an average degree of conden able ethylenically unsaturated non-silane containing mono sation of more than 1.9. Some such suitable monomeric mers are: alkyl acrylates, alkyl methacrylates and any mix melamines include alkylated melamines, such as methylated, tures thereof, where the alkyl groups have 1 to 12 carbon butylated, isobutylated melamines and mixtures thereof. atoms, preferably 3 to 8 carbon atoms. Many of these Suitable monomeric melamines are Supplied 0048. In addition to alkyl acrylates or methacrylates, other commercially. For example, Cytec Industries Inc., West polymerizable non-silane-containing monomers, up to about Patterson, N.J. supplies Cymel R. 301 (degree of polymeriza 50% by weight of the polymer, can be used in the silane tion of 1.5, 95% methyl and 5% methylol), Cymel(R) 350 polymer for the purpose of achieving the desired properties (degree of polymerization of 1.6, 84% methyl and 16% such as, hardness, appearance, and mar resistance. Exem methylol), 303, 325, 327 and 370, which are all monomeric plary of Such other monomers are styrene, methyl styrene, melamines. Suitable polymeric melamines include high acrylamide, acrylonitrile and methacrylonitrile. Styrene can amino (partially alkylated, —N. —H) melamine known as be used in the range of 0.1 to 50%, preferably 5% to 30% by ResimeneR BMP5503 (molecular weight 690, polydisper weight of the silane polymer. Typical examples of silane sity of 1.98, 56% butyl, 44% amino), which is supplied by containing monomers for silane polymerization are the acry Solutia Inc., St. Louis, Mo., or Cymel(R1158 provided by latoalkoxy silanes, such as Y-macryloxypropyltrimethoxy Cytec Industries Inc., West Patterson, N.J. Cytec Industries silane and the methacrylatoalkoxy silanes, such as Y-meth Inc. also supplies Cymel(R) 1130 (a) 80 percent solids (degree acryloxypropyltrimethoxysilane, and Y-methacryloxypropy of polymerization of 2.5), Cymel(R) 1133 (48% methyl, 4% ltris(2-methoxyethoxy) silane. Other suitable alkoxy silane methylol and 48% butyl), both of which are polymeric monomers are vinylalkoxy silanes, such as vinyltrimethoxy melamines. silane, vinyltriethoxy silane and vinyltris(2-methoxyethoxy) 0045. The crosslinking component of the binder compo silane. Still other Suitable silane containing monomers are nent when containing melamine can also contain a catalyst acyloxysilanes, including acrylatoxy silane, methacrylatoxy component, which preferably includes one or more catalysts silane and vinylacetoxy silanes, such as vinylmethyldiac to enhance crosslinking of the components on curing. Gen etoxy silane, acrylatopropyltriacetoxy silane, and methacry erally, the coating composition includes in the range of from latopropyltriacetoxy silane. It is understood that combina 0.1 percent to 5 percent, preferably in the range of from 0.1 to tions of the above-mentioned silane containing monomers are 2 percent, more preferably in the range of from 0.5 percent to also suitable. 2 percent and most preferably in the range of from 0.5 percent 0049. One preferred example of a silane polymer useful in to 1.2 percent of the catalyst, the percentages being in weight the coating composition is polymerized from about 15 to 25% percentage based on the total weight of composition Solids. by weight styrene, about 30 to 60% by weight methacrylox Some Suitable catalysts include the conventional acid cata ypropyltrimethoxy silane, and about 25 to 50% by weight lysts, such as aromatic sulfonic acids, for example dodecyl trimethylcyclohexyl methacrylate. Another preferred silane benzene Sulfonic acid, para-toluenesulfonic acid and polymer contains about 30% by weight styrene, about 50% by dinonylnaphthalene sulfonic acid, all of which are either weight methacryloxypropyltrimethoxy silane, and about unblocked or blocked with an amine, such as dimethyl oxazo 20% by weight of nonfunctional acrylates or methacrylates lidine and 2-amino-2-methyl-1-propanol, n,n-dimethyletha Such as trimethylcyclohexylmethacrylate, butyl acrylate, and nolamine or a combination thereof. Other acid catalysts that iso-butyl methacrylate and any mixtures thereof. can be used are strong acids, such as phosphoric acids, more 0050 Silane functional monomers also can be used in particularly phenyl acid phosphate, which may be unblocked forming the silane polymer. These monomers are the reaction or blocked with an amine. product of a silane containing compound, having a reactive 0046. Some of the suitable urea formaldehyde polymers group Such as epoxide or isocyanate, with an ethylenically include methylated urea formaldehyde Resimene.R. 980 and unsaturated non-silane containing monomer having a reactive butylated urea formaldehyde U-6329, which are supplied by group, typically a hydroxyl, acid or an epoxide group, which Solutia Inc., St. Louis, Mo. is co-reactive with the silane monomer. US 2010/00998.06 A1 Apr. 22, 2010

0051 Suitable silane oligomers, such as 1-trimethoxysi preferably in the range of from 0.5 percent to 2 percent and lyl-4-trimethoxysilylmethylcyclohexane, useful in the most preferably in the range of from 0.5 percent to 1.2 percent present coating composition include, but are not limited to, of the catalyst, the percentages being in weight percentage those taught in U.S. Pat. No. 5,527,936. based on the total weight of composition solids. Some Suit 0052. The crosslinking component of the binder compo able catalysts include tertiary amines such as triethylene nent when containing silane can also contain a catalyst com diamine, bis(2-dimethyl aminoethyl)ether and N.N.N.N'- ponent, which preferably includes one or more catalysts to tetramethylethylenediamine and onium compounds includ enhance crosslinking of the silane moieties of the silane poly ing quaternary phosphonium and quaternary ammonium. mer with itself and with other components of the composi Examples of phosphonium catalysts which can be used in tion. Typical of such catalysts are dibutyl tin dilaurate, dibutyl catalyst blends are benzyl triphenyl phosphonium chloride: tin diacetate, dibutyl tin dioxide, dibutyl tin dioctoate, tin ethyl triphenyl phosphonium bromide; tetra butyl phospho acetate, titanates such as tetraisopropyl titanate, tetrabutyl nium chloride; tetra butyl phosphonium bromide; benzyl titanate (Tyzor R. RTM supplied by DuPont Company, Wilm triphenyl phosphonium iodide; benzyl triphenyl phospho ington, Del.), aluminum titanate, aluminum chelates, and Zir nium bromide; and ethyl triphenyl phosphonium iodide. conium chelate. Amines and acids, or combinations thereof, 0057. It should be generally understood that in the forego are also useful for catalyzing silane bonding. Preferably, ing examples, ketimine crosslinking agent generally these catalysts are used in the amount of about 0.1 to 5.0% by crosslinks with acetoacetoxy crosslinkable functionalities; weight of the composition. polyisocyanate crosslinking agent generally crosslinks with 0053 Some of the crosslinkable polymers suitable for the hydroxyl, primary and secondary amine, and ketimine aforedescribed silane crosslinking agent include polymers crosslinkable functionalities; epoxy crosslinking agent gen and oligomers containing hydroxy functionality, or groups erally crosslinks with carboxyl, anhydride, primary and sec that can form hydroxy groups such as carbonate and orthoe ondary amine crosslinkable groups; polyamine crosslinking ster, alkoxysilicates and any combination of Such groups. agent generally crosslinks with acetoacetoxy, and epoxy 0054 The crosslinking component can also include from crosslinkable functionalities; polyacid crosslinking agent about 0.1 to 40% by weight of an epoxy crosslinking agent generally crosslinks with epoxy crosslinkable functionalities; containing at least two epoxy groups and having a molecular and Melamine crosslinking agents generally crosslink with weight of less than about 2500. Some of the suitable epoxy hydroxyl, carboxyl, and amide crosslinkable functionalities. crosslinker include Sorbitol polyglycidyl ether, mannitol 0058. The composition of the present invention can polyglycidyl ether, pentaerythritol polyglycidyl ether, glyc optionally contain, in the range of from 0.1 percent to 50 erol polyglycidyl ether, low molecular weight epoxy resins, percent, a modifying resin, Such as a well known non-aqueous Such as epoxy resins of epichlorohydrin and bisphenol-A, di dispersion (NAD), all percentages being based on the total and polyglycidyl esters of polycarboxylic acids, polyglycidyl weight of composition solids. The weight average molecular ethers of isocyanurates, such as DENECOLOR EX301 polyg weight of the modifying resin generally varies in the range of lycidyl ether from Nagase in Japan; Sorbitol polyglycidyl from 20,000 to 100,000, preferably in the range of from ether, such as DEC-358(R) polyglycidyl ether from Dixie 25,000 to 80,000 and more preferably in the range from Chemical in Texas, and di- and polyglycidyl esters of acids, 30,000 to 50,000. such as ARALDITER) CY-184 polyglycidyl ester from Ciba 0059. In yet another embodiment, the binder component Geigy in New York, or XU-71950 polyglycidyl ester from of the composition can containa film forming polymer, which Dow Chemical company in Michigan. Cycloaliphatic typically a high molecular weight thermoplastic polymer, epoxies can also be used, such as ERL-4221 from Union which is dissolved in the Solvent component. Such a compo Carbide. sition is conventionally applied over a substrate and upon 0055. The crosslinking component of the composition can evaporation of the solvent component, a coating of the film include from about 0.1 to 40% by weight of an epoxy forming polymer is then produced over the Substrate crosslinking agent containing at least two epoxy groups and 0060. The composition of the present invention can also having a molecular weight of less than about 2500. Some of contain conventional additives, such as, pigments, UV the Suitable epoxy crosslinking agents include Sorbitol polyg absorbers, stabilizers, rheology control agents, flow agents, lycidyl ether, mannitol polyglycidyl ether, pentaerythritol metallic flakes, toughening agents and fillers. Such additional polyglycidyl ether, glycerol polyglycidyl ether, low molecu additives will, of course, depend upon the intended use of the lar weight epoxy resins, such as epoxy resins of epichlorohy coating composition. Fillers, pigments, and other additives drin and bisphenol-A, di- and polyglycidyl esters of polycar that would adversely affect the clarity of the cured coating are boxylic acids, polyglycidyl ethers of isocyanurates, such as typically not included if the composition is intended as a clear DENECOLOR EX301 polyglycidyl ether from Nagase in coating. Japan; sorbitol polyglycidyl ether, such as DEC-358(R) polyg 0061. To improve weatherability of the clear finish of the lycidyl ether from Dixie Chemical in Texas, and di- and composition, about 0.1 to 5% by weight, based on the weight polyglycidyl esters of acids, such as ARALDITER) CY-184 of the composition solids, of an ultraviolet light stabilizer or polyglycidyl ester from Ciba-Geigy in New York, or a combination of ultraviolet light stabilizers and absorbers XU-71950 polyglycidyl ester from Dow Chemical company may be added. These stabilizers include ultraviolet light in Michigan. Cycloaliphatic epoxies can also be used, such as absorbers, screeners, quenchers and specific hindered amine ERL-4221 from Union Carbide. light stabilizers. Also, about 0.1 to 5% by weight, based on the 0056. The epoxy crosslinking agent containing composi weight of the composition solids, of an antioxidant can be tion preferably includes one or more catalysts to enhance added. Most of the foregoing stabilizers are supplied by Ciba crosslinking of the components on curing. Generally, the Specialty Chemicals, Tarrytown, N.Y. composition includes in the range of from 0.1 percent to 5 0062. In use, the first-pack of the two-pack composition percent, preferably in the range of from 0.1 to 2 percent, more containing the crosslinkable component and other additives, US 2010/00998.06 A1 Apr. 22, 2010

and the second-pack containing the crosslinkable component Such truck bodies, buses, farm and construction equipment, are mixed just prior to use for about 1 to 15 minutes before use truck caps and covers, commercial trailers, consumer trailers, to form a pot mix, which has limited pot life, in range of from recreational vehicles, including but not limited to, motor 5 minutes to 6 hours, before it becomes too viscous to permit homes, campers, conversion vans, vans, pleasure vehicles, application through conventional application systems, such pleasure craft Snow mobiles, all terrain vehicles, personal as spraying. Alternatively, the first pack and the second pack watercraft, motorcycles, boats, and aircraft. The Substrate are mixed together at the plural spray gun with or without further includes industrial and commercial new construction electrostastics, before applied to a substrate. Other methods and maintenance thereof; cement and wood floors; leather; of applications include roller coating, dipping or brushing and walls of commercial and residential structures, such office other conventional application methods. The layer of the buildings and homes; amusement park equipment; concrete composition then cures under ambient conditions or prefer Surfaces, such as parking lots and drive ways; asphalt and ably at higher temperatures in the range of 80°C.-160° C. for concrete road Surface, wood Substrates, marine Surfaces; out 10 minutes to 3 hours, preferably in the range of 20 minutes to door structures. Such as bridges, towers; coil coating; railroad 1 hour to form a coating on the Substrate having the desired cars; printed circuit boards; machinery; OEM tools; signage; coating properties. fiberglass structures; sporting goods; and sporting equip 0063. When the one-pack composition containing the ment. blocked crosslinking agent is used, a layer thereof, applied 0069. This invention further directed to a process for pro over a Substrate using aforedescribed application techniques, ducing a composition consisting essentially of a binder com is cured at a baking temperature in the range of from 80° ponent and a solvent component. The process can comprise C.-200° C., preferably in the range of 80° C.-160° C., for the steps of: about 10 to 60 minutes. It is understood that the actual baking temperature would vary depending upon the type of catalyst 0070 (A) preparing the solvent component by mixing a solvent dimethyl carbonate with a co-solvent selected from and the amount thereof is used, the thickness of the layer the group consisting of aromatic hydrocarbon (135-146C), being cured, the blocked crosslinking functionalities and the aromatic hydrocarbon (150-190C), aromatic hydrocarbon type of crosslinking agent utilized in the composition. The (182-219C), aliphatic hydrocarbon (100-150C), aliphatic use of the foregoing baking step is particularly useful under hydrocarbon (100-163C), aliphatic hydrocarbon (115-149C), Original Equipment Manufature (OEM) condition. aliphatic hydrocarbon (138-177C), aliphatic hydrocarbon 0064. It is further understood that the actual curing time (138-185C), aliphatic hydrocarbon (145-205C), aliphatic depends upon the presence or absence of any suitable drying hydrocarbon (150-205C), aliphatic hydrocarbon (150-210C), devices, such as, fans that assist in continuously flowing air aliphatic hydrocarbon (155-190C), aliphatic hydrocarbon over the coated substrate to accelerate the cure rate. Gener (170-210C), aliphatic hydrocarbon (180-210C), aliphatic ally, a clearcoat layer having a thickness in the range of from hydrocarbon (182-266C), aliphatic hydrocarbon (90-110C), 25 micrometers to 75 micrometers applied over a metal sub mineral spirit, 1,1,1-trichloroethane, 1,1,2-trichloroethane, strate, such as automotive body, which is often pre-coated 1.2-propylene glycol. 1,3-butanediol. 1,4-butanediol. 1-bu with other coating layers, such as electro-coat, primer and toxy ethoxy 222-propanol. 1-methyl naphthalene, 1-nitro basecoat, cures in 20 to 60 minutes at baking temperatures propane, 2.4-pentane dione, 2-ethylhexanol, 2-ethylhexyl ranging from 80°C.-160° C. acetate, 2-methyl-1-butanol, acetic anhydride, butyl acetate, 0065. In the alternative, the binder component of the com di-isoamyl ketone, diacetone alcohol, diethylene glycol position can include one or more conventional photoinitia monobutyl ether acetate, diethylene glycol, diisobutyl tors. The layer of such a composition when exposed to actinic ketone, ethylene glycol monoethyl ether acetate, glycol radiation, such as ultraviolet light, can trigger the crosslink monopropyl ether acetate benzyl alcohol. 1,2-dichloroet ing of the crosslinkable crosslinking functionalities in the hane, 1,3-dioxane, 1,2-dimethoxyethane, 1-butanol. 1-me applied layer to produce a coating on the Substrate. thyl-2-pyrrolidinone, 1-propanol, 2-butanol, 2-ethylhexanol, 0.066. In another embodiment of the invention, the binder 2-methoxyethanol. 2-propanol, acetone, acetonitrile, ben component of the composition can be a conventional thermo Zene, bis(2-methoxyethyl)ether, butyl cellosolve, carbon tet plastic polymer, Such as a high molecular weight polymer, rachloride, chlorobenzene, chlorobenzene, cyclohexane, which is dissolved in the aforedescribed solvent component. cyclohexanol, cyclohexanone, dibasic ester, dichlo A layer of Such a composition can be conventionally applied romethane, diethyl ether, diethylene glycol monobutyl ether, over a Substrate. Upon evaporation of the solvent component, diisopropyl ether, dimethyl ether, dimethylpropyleneurea, a film of the thermoplastic polymer is formed over the sub dimethylsulphoxide, ethanol, ethyl acetate, ethyl benzene, Strate as a coating. ethylene glycol, ethyl amylketone, ethylbenzene, ethyl pro 0067. The compositions of the aforedescribed embodi pionate, ethylene glycol diacetate, ethylene glycol monobutyl ments can be formulated as a coating composition, an adhe ether, ethylene glycol monoethyl ether, ethylene glycol sive, or a printing ink. The coating composition can be an monohexyl ether, ethylene glycol monomethyl ether, ethyl automotive OEM paint, automotive refinish paint, architec ene glycol monopropyl ether, fluorobenzene, formamide, fur tural paint or an industrial paint. fural, heptane, hexane, hexylene glycol, hexylene glycol 0068. The suitable substrates for applying the coating diacetate, iso-butyl acetate, iso-butyl isobutyrate, isoamyl composition of the present invention include automobile bod alcohol, isobutanol, isopropanol, isopropyl acetate, 1,3,5-tri ies, any and all items manufactured and painted by automo methylbenzene, methane Sulphonic acid, methanol, methyl bile Sub-Suppliers, frame rails, commercial trucks and truck acetate, methyl celloSolve, methyl cyclohexane, methyl ethyl bodies, including but not limited to beverage bodies, utility ketone, methyl amyl ketone, methyl amyl acetate, methyl bodies, ready mix concrete delivery vehicle bodies, waste hexyl ketone, methyl n-propyl ketone, methylene chloride, hauling vehicle bodies, and fire and emergency vehicle bod n-butyl propionate, n-heptyl acetate, n-hexyl acetate, n-nonyl ies, as well as any potential attachments or components to acetate, n-octyl acetate, n-pentyl propionate, primary amyl US 2010/00998.06 A1 Apr. 22, 2010 acetate, propylene glycol monoethyl ether acetate, propylene 0076. The forgoing results obtained by using EPA Method glycol t-butyl ether, propylene glycol isobutyl ether, propy 24 clearly show elimination of VOC obtained by using dim lene glycol monobutyl ether, propylene glycol monothyl ethyl carbonate. ether, propylene glycol monopropyl ether, methyl isobutyl ketone, methyl tertbutyl ether, m-xylene, n,n-dimethyl for TABLE 2 mamide, n,n-dimethylacetamide, N,N-dimethylaniline, n-butanol, n-propyl acetate, o-Xylene, pentane, petroleum Comparative ether, propionic acid, p-Xylene, pyridine, sec-butyl alcohol, Composition ingredients Example 2 Example 2 sec-butyl acetate, tert-butyl alcohol, tetrachloroethylene, tet Crosslinkable component rahydrofuran, terpene, toluene, trichloroethylene, triethy Crosslinkable Polymer' 37.7 37.7 lamine, triethylene glycol monobutyl ether, triethylene gly Additive’ O.1 O.1 col, monoethyl ether triethylene glycol, monomethyl ether, Hindered amine light O6 O6 triethylene glycol diacetate, and a combination thereof, and stabilizer 0071 (B) mixing the solvent component with the binder UV Absorber' O6 O6 component to form said composition. Solvent component added 0072 The composition can be produced as a coating com to crosslinkable component position, such as an automotive OEM paint, automotive refin n-propyl acetate O 22.7 Dimethyl carbonate 22.7 ish paint, architectural paint or an industrial paint; an adhe Methyl Amyl Ketone 13.2 13.2 sive; or a printing ink. 2-ethylhexyl acetate 4.4 4.4 Crosslinking component Test Procedures 0073. The following test procedures were used for gener Polyisocyanate" 20.7 20.7 ating data reported in the examples below: Total 100 1OO 0074 USEPA Method 24 entitled as “Determination of Weight % Solids 59.7 59.7 Volatile Matter Content, Water Content, Density, Volume Sol VOC by EPA Method 24 2.1% 3.5 ids, And Weight Solids Of Surface Coatings”. USEPA Joncryl(R) 587 hydroxy-functional acrylic copolymer, supplied by BASF Method 24 was established by United States Environmental Corporation, Sturtevant, Wisconsin. Protection Agency and is incorporated herein by reference. °Modaflow (R) acrylic flow and levelling agent, supplied Cytec Surface Spe cialties,'Tinuvin Stamford, (R 292 Bis Connecticut. (1.2.2,6,6-pentamethylpiperidyl) sebacate, supplied Examples Ciba'Tinuvin Chemicals, (R 328 2-(2-H-benzotriazol-2-yl)-4,6-ditertpentylphenol, Ardsley, New York. supplied 0075) Ciba Chemicals, city name, state name. Supplied by Aldrich Chemicals in Milwaukee, Wisconsin. Supplied by Eastman Chemicals, Kingsport, Tennessee. TABLE 1. Tolonate (R) HDT mixture of isocyanurate oligomers of 1,6-diisocyanato hexane, Supplied Rhodia Inc., Cranbury, New Jersey. Comparative *On the basis of the application filed by Kowa American Corporation, New Composition ingredients Example 1 Example 1 York, New York on Jul. 29, 2004 to United States Environmental Protection Agency to make dimethyl carbonate as a VOC exempt solvent, said applica Crosslinkable component tion being incorporated herein by reference. Crosslinkable Polymer 37.7 37.7 0077. The forgoing results obtained by using EPA Method Additive’ (Provide chemical O.1 O.1 24 clearly show reduction of VOC obtained by using dimethyl name) Hindered amine light O6 O.6 carbonate. stabilizer What is claimed is: Solvent component added 1. A process for producing a composition consisting essen to crosslinkable component tially of a binder component and a solvent component, said n-propyl acetate O 40.3 process comprising the steps of Dimethyl carbonate' 40.3 (A) preparing the solvent component by mixing a solvent (Aldrich) dimethyl carbonate with a co-solvent selected from the Crosslinking component group consisting of aromatic hydrocarbon (135-146C), Polyisocyanate 20.7 20.7 aromatic hydrocarbon (150-190C), aromatic hydrocar bon (182-219C), aliphatic hydrocarbon (100-150C), ali Total 100 1OO phatic hydrocarbon (100-163C), aliphatic hydrocarbon Weight % Solids 59.7 59.7 (115-149C), aliphatic hydrocarbon (138-177C), ali VOC by EPA Method 24 O* 3.5 phatic hydrocarbon (138-185C), aliphatic hydrocarbon Joncryl(R) 587 hydroxy-functional acrylic copolymer, supplied by BASF (145-205C), aliphatic hydrocarbon (150-205C), ali Corporation, Sturtevant, Wisconsin. phatic hydrocarbon (150-210C), aliphatic hydrocarbon °Modaflow (R) acrylic flow and levelling agent, supplied Cytec Surface Spe (155-190C), aliphatic hydrocarbon (170-210C), ali cialties,'Tinuvin Stamford, (R 292 Bis Connecticut. (1.2.2,6,6-pentamethylpiperidyl) sebacate, supplied phatic hydrocarbon (180-210C), aliphatic hydrocarbon Ciba Chemicals, Ardsley, New York. 'Supplied by Aldrich Chemicals, city name, state name. (182-266C), aliphatic hydrocarbon (90-110C), mineral Tolonate (R) HDT mixture of isocyanurate oligomers of 1,6-diisocyanato spirit, 1,1,1-trichloroethane, 1.1.2-trichloroethane, 1.2- hexane, Supplied Rhodia Inc., Cranbury, New Jersey. propylene glycol, 1,3-butanediol. 1,4-butanediol. 1-bu *On the basis of the application filed by Kowa American Corporation, New toxyethoxy 222-propanol. 1-methyl naphthalene, 1-ni York, New York on Jul. 29, 2004 to United States Environmental Protection Agency to make dimethyl carbonate as a VOC exempt solvent, said applica tro propane, 2.4-pentane dione, 2-ethylhexanol, 2-ethyl tion being incorporated herein by reference. hexyl acetate, 2-methyl-1-butanol, acetic anhydride, butyl acetate, di-isoamyl ketone, diacetone alcohol, US 2010/00998.06 A1 Apr. 22, 2010

diethylene glycol monobutyl ether acetate, diethylene (150-205C), aliphatic hydrocarbon (150-210C), aliphatic glycol, diisobutyl ketone, ethylene glycol monoethyl hydrocarbon (155-190C), and a combination thereof. ether acetate, glycol monopropyl ether acetate benzyl 3. The process of claim 1, wherein said solvent component alcohol. 1,2-dichloroethane, 1,3-dioxane, 1.2- consists in the range of 5 weight percent to 100 weight percent dimethoxyethane, 1-butanol. 1-methyl-2-pyrrolidinone, of dimethyl carbonate, all percentages based on the total 1-propanol, 2-butanol, 2-ethylhexanol, 2-methoxyetha weight of the composition. nol, 2-propanol, acetone, acetonitrile, benzene, bis(2- 4. The process of claim 1, wherein said solvent component methoxyethyl)ether, butyl cellosolve, carbon tetrachlo consists in the range of 0.01 weight percent to 95 weight ride, chlorobenzene, chlorobenzene, cyclohexane, percent of said co-solvent, all percentages based on the total cyclohexanol, cyclohexanone, dibasic ester, dichlo weight of the composition. romethane, diethyl ether, diethylene glycol monobutyl 5. The process of claim 1, wherein said binder component ether, diisopropyl ether, dimethyl ether, dimethylpropy comprises a crosslinkable component and a crosslinking leneurea, dimethylsulphoxide, ethanol, ethyl acetate, component, wherein said crosslinkable component com ethylbenzene, ethylene glycol, ethyl amylketone, ethyl prises one or more crosslinkable polymers having one or more crosslinkable groups; and wherein said crosslinking benzene, ethyl propionate, ethylene glycol diacetate, component comprises one or more crosslinking agents hav ethylene glycol monobutyl ether, ethylene glycol mono ing two or more crosslinking groups. ethyl ether, ethylene glycol monohexyl ether, ethylene 6. The process of claim 5, wherein said binder component glycol monomethyl ether, ethylene glycol monopropyl comprises a catalyst component. ether, fluorobenzene, formamide, furfural, heptane, hex ane, hexylene glycol, hexylene glycol diacetate, iso 7. The process of claim 6, wherein said catalyst component butyl acetate, iso-butyl isobutyrate, isoamyl alcohol, consists essentially of one or more organo Zinc catalysts, one isobutanol, isopropanol, isopropyl acetate, 1,3,5-trim or more organo tin catalysts, and one or more C to Cs car ethylbenzene, methane Sulphonic acid, methanol, boxylic acids. methyl acetate, methyl celloSolve, methyl cyclohexane, 8. The process of claim 5, wherein a portion of said solvent methyl ethyl ketone, methyl amylketone, methyl amyl component is included in said crosslinkable component and acetate, methylhexyl ketone, methyl n-propyl ketone, remainder of said solvent component is included in said methylene chloride, n-butyl propionate, n-heptyl crosslinking component. acetate, n-hexyl acetate, n-nonyl acetate, n-octylacetate, 9. The process of claim 5, wherein said binder component n-pentyl propionate, primary amyl acetate, propylene comprises pigments, UV absorbers, stabilizers, rheology glycol monoethyl ether acetate, propylene glycol t-butyl control agents, flow agents, metallic flakes, toughening ether, propylene glycol isobutyl ether, propylene glycol agents, fillers, or a combination thereof. monobutyl ether, propylene glycol monothyl ether, pro 10. The process of claim 5, wherein said composition is pylene glycol monopropyl ether, methyl isobutyl formulated as a two-pack composition wherein said ketone, methyl tertbutyl ether, m-xylene, n,n-dimethyl crosslinkable component is stored separately from said formamide, n,n-dimethylacetamide, N,N-dimethyla crosslinking component. niline, n-butanol, n-propyl acetate, o-Xylene, pentane, 11. The process of claim 5, wherein said composition is petroleum ether, propionic acid, p-Xylene, pyridine, sec formulated as a one-pack composition wherein said butyl alcohol, sec-butyl acetate, tert-butyl alcohol, tet crosslinking groups are blocked. rachloroethylene, tetrahydrofuran, terpene, toluene, 12. The process of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, trichloroethylene, triethylamine, triethylene glycol wherein said composition is formulated as a coating compo monobutyl ether, triethylene glycol, monoethyl ether sition, an adhesive, or a printing ink. triethylene glycol, monomethyl ether, triethylene glycol 14. The process of claim 13, wherein said coating compo sition is an automotive OEM paint, automotive refinish paint, diacetate, and a combination thereof, and architectural paint or an industrial paint. (B) mixing the solvent component with the binder compo 15. The process of claim 1, 2, 3 or 4, wherein said binder nent to form said composition. component comprises one or more film forming polymers. 2. The process of claim 1, wherein said co-solvent is 16. The process of claim 15, wherein said binder compo selected from the group consisting of acetone, methyl propyl nent comprises pigments, UV absorbers, stabilizers, rheology ketone, methyl amylketone, 2-propanol, 1-butanol, methoxy control agents, flow agents, metallic flakes, toughening propanol, butoxyethanol, methyl acetate, ethyl acetate, pro agents, fillers, or a combination thereof. pyl acetate, n-butyl acetate, t-butyl acetate, 2-ethyl hexyl 17. The process of claim 16, wherein said composition is acetate, methoxy propyl acetate, 1-methyl-2-pyrrolidinone, formulated as a coating composition, an adhesive, or a print aromatic hydrocarbon (135-146C), aromatic hydrocarbon ing ink. (150-190C), aromatic hydrocarbon (182-219C), heptane, ali 18. The process of claim 17 wherein said coating compo phatic hydrocarbon (100-150C), aliphatic hydrocarbon (100 sition is an automotive OEM paint, automotive refinish paint, 163C), aliphatic hydrocarbon (115-149C), aliphatic hydro architectural paint or an industrial paint. carbon (138-177C), aliphatic hydrocarbon (138-185C), aliphatic hydrocarbon (145-205C), aliphatic hydrocarbon c c c c c