HK1133029B - Coatings comprising terpene - Google Patents

Description

Terpene-containing coating

Technical Field

The present invention relates generally to terpene containing polymers and terpene containing coatings.

Background

The prices of raw materials used in many manufacturing processes continue to rise, especially those whose prices rise and fall with oil prices. For this reason, and due to the predicted consumption of oil reserves, raw materials derived from renewable or alternative resources may be desirable. The increased demand for environmentally friendly products, along with the uncertainty of the variable and volatile petrochemical market, has driven the development of raw materials from renewable and/or inexpensive sources.

Disclosure of Invention

The present invention relates to coatings comprising a polymer comprising a terpene and a monomer polymerized with the terpene by free radical polymerization, wherein the monomer is not maleic acid/maleic anhydride.

The invention further relates to a cured coating comprising terpenes in an amount of more than 30 wt% on solids basis, wherein the terpenes are not in the form of copolymers with phenol, cresol or maleic acid/anhydride and glycol esters (glycol ester).

The invention further relates to a coating comprising terpene and urea, wherein the urea is formed from a reaction mixture comprising an isocyanate functional component and an amine functional component, wherein the ratio of equivalents of isocyanate groups to equivalents of amine groups is greater than 1 and the isocyanate functional component and the amine functional component can be applied to a substrate in a volume mixing ratio of 1: 1.

The invention further relates to a polymer comprising 30 wt% or more of a terpene and less than 20 wt% of an ethylenically unsaturated mono-and/or dicarboxylic acid containing 3 to 5 carbon atoms or anhydride thereof, wherein the wt% is based on total solids weight and wherein the polymer is prepared by free radical polymerization.

Detailed Description

The present invention relates to coatings comprising a polymer comprising a terpene and a monomer polymerized with the terpene by free radical polymerization. The polymer does not contain maleic acid/anhydride. In certain embodiments, the polymer specifically excludes methacrylates, and in certain embodiments, the copolymer is not a copolymer of a terpene with phenol, cresol, or isomers thereof.

Terpenes as used herein include alpha-pinene, beta-pinene, terpinolene, limonene (dipentene), beta-terpinene, gamma-terpinene, alpha-thujene, sabinene, delta-³Carene, camphene, beta-cadinene, beta-caryophyllene, cedrene, beta 0-bisalbone, beta-bisalbone, gamma-bisalbone, zingiberene, carene, (alpha-caryophyllen-1-ene), alpha-citronellol, linalool, geraniol, nerol, ips enol (ipsenol), alpha-terpineol, D-terpineol- (4), dihydrocarveol, nerolidol, farnesol, alpha-cineol, beta-cineol, citral, D-citronellal, carvone, D-pulegone, menthone, carvone, sesquiterpene (bisabolene), beta-apine, alpha-santal, vitamin A, abietic acid and mixtures of these compounds.

As described above, the terpene is polymerized with a monomer that polymerizes with the terpene by free radical polymerization. Such monomers include, for example, acrylic monomers having the following structure (I)Wherein Y is-NR¹ ₂、-O-R²-O-C(＝O)-NR¹ ₂OR-OR³；R¹Is H, linear or branched C₁-C₂₀Alkyl, or linear or branched C₁-C₂₀A hydroxyalkyl group; r²Is methyl, linear, acyclic or branched C₁-C₂₀Alkyl, alkenyl, aryl, alkaryl or aralkyl, and R³Is H, poly (ethylene oxide) radical, poly (propylene oxide) radical, linear or branched C₁-C₂₀Alkyl, hydroxyalkyl, aryl and aralkyl, linear or branched C₁-C₂₀Fluoroalkyl, fluoroaryl and fluoroarylAn alkyl group, a siloxane group, a polysiloxane group, an alkylsiloxane group, an ethoxylated trimethylsilyloxy group, or a propoxylated trimethylsilyloxy group. One particularly useful class of acrylic monomers are those described by structure (I), wherein Y comprises at least one functional group of epoxy, oxirane (oxirane), carboxylic acid, hydroxyl, amide, oxazoline, acetoacetate (acetoacetate), isocyanate, or carbamate, R²Is divalent linear or branched C₁-C₂₀An alkyl linking group.

Examples of suitable monomers belonging to structure (I) include, but are not limited to, hydroxyethyl acrylate, hydroxypropyl acrylate, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, isobornyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, acrylamide, perfluoromethylethyl acrylate, perfluoroethyl acrylate, perfluorobutylethyl acrylate, trifluoromethylbenzyl acrylate, perfluoroalkylethyl acrylate, acryloyloxyalkyl terminated polydimethylsiloxane, acryloyloxyalkyl tris (trimethylsiloxysilane), acryloyloxyalkyl trimethylsiloxy terminated polyethylene oxide, chlorotrifluoroethylene, glycidyl acrylate, 2-ethylhexyl acrylate, and n-butoxy methacrylamide.

Other suitable monomers that can be polymerized with terpenes in the present invention include, but are not limited to, acrylonitrile, methacrylonitrile, vinyl halides, crotonic acid, vinyl alkyl sulfonates, and acrolein. Vinyl halides include, but are not limited to, vinyl chloride and vinylidene fluoride. Others also include ethylenically unsaturated monomers such as isobutylene and its derivatives, methacrylates, and styrenes.

The terpene and monomer are typically mixed together in the presence of a free radical polymerization initiator. Any standard free radical polymerization method may be used. In certain embodiments, a continuous process is employed for preparing polymers at high temperatures (i.e., greater than 200 ℃) and high pressures (i.e., greater than 500psi) using a small amount of initiator (i.e., less than 10 weight percent). In certain embodiments, the polymerization is conducted in the substantial absence of lewis acids and/or transition metals.

Any suitable free radical polymerization initiator may be used in the present invention. Suitable free radical initiators are typically thermal free radical initiators. Suitable thermal free radical initiators include, but are not limited to, peroxy compounds, azo compounds, and persulfate compounds.

Examples of suitable thermal free radical initiator peroxides include, but are not limited to, hydrogen peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, diacyl peroxide, decanoyl peroxide, lauroyl peroxide, peroxydicarbonate, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals, and mixtures thereof.

Examples of suitable thermal free radical initiator azo compounds include, but are not limited to, 4-4 ' -azobis (4-cyanovaleric acid) (4-4 ' -azobis (4-cyanovaleric acid)), 1-1 ' -azobiscyclohexanecarbonitrile, 2-2 ' -azobisisobutyronitrile, 2-2 ' -azobis (2-methylpropionamidine) dihydrochloride, 2-2 ' -azobis (2-methylbutyronitrile), 2-2 ' -azobis (propionitrile), 2-2 ' -azobis (2, 4-dimethylvaleronitrile), 2-2 ' -azobis (valeronitrile), 2 ' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 4 ' -azobis (4-cyanovaleric acid) (4, 4 '-azobis (4-cyanopentanic acid)), 2' -azobis (N, N '-dimethyleneisobutyramidine), 2' -azobis (2-amidinopropane) dihydrochloride, 2 '-azobis (N, N' -dimethyleneisobutyramidine) dihydrochloride, 2- (carbamoylazo) -isobutyronitrile, and mixtures thereof.

It will be further appreciated by those skilled in the art that the polymers used in accordance with the present invention are random or alternating polymers. That is, the polymer of the present invention is different from, for example, polymers prepared by methods other than radical polymerization known in the art (e.g., cationic polymerization, group transfer polymerization, and atom transfer radical polymerization). Such methods can produce different polymer configurations as "designed," for example, block copolymers.

Typically, the terpene comprises from 10 to 60 weight percent, for example from 30 to 50 weight percent, of the total solids weight of the polymer. In certain embodiments, the terpene comprises 30 wt% or more, such as 50 wt% or more, of the polymer. The monomer may constitute from 90 to 40 wt%, for example from 70 to 50 wt% of the polymer. It should be understood that while reference is made throughout the specification and claims to "a" terpene and "a" monomer polymerized with a terpene by free radical polymerization, terpenes and/or mixtures of such monomers may be used.

"coating" according to the present invention shall generally be understood as a composition that when cured may form a substantially continuous film forming a surface layer providing decorative and/or protective functionality and that when cured is not tacky or sticky. Thus, in certain embodiments, a coating according to the present invention will not include a binder.

The coatings of the present invention may comprise from 5 to 100 wt% (e.g., 10 to 70 or 10 to 40 wt%), based on total solids weight, of a polymer comprising a terpene and a monomer polymerized with the terpene by free radical polymerization. For example, the coating can comprise 10 wt% or more (e.g., 20 wt% or more or 30 wt% or more) terpene, where wt% is based on total solids weight.

It will be appreciated that when a terpene is used in the coating according to the invention, either alone or in polymeric form, it may form part of the film-forming resin of the coating and in certain embodiments crosslink with other film-forming components. It is not added as a solvent (e.g., a solvent that evaporates during curing), chain transfer agent, adhesion promoter, or other additive. Those skilled in the art will appreciate that cured coatings in which terpenes or polymers thereof are used as solvents, chain transfer agents, or tackifiers or other additives will have lower amounts of terpenes therein. In certain embodiments, compositions wherein the terpene content of the cured coating is less than 10 wt%, e.g., 5 wt% or less, are specifically excluded.

In certain embodiments, one or more additional film-forming resins are also used in the coating. For example, the coating composition may comprise any of a wide variety of thermoplastic and/or thermosetting ingredients known in the art. The coating composition may be a water-based or solvent-based liquid composition, or alternatively may be in the form of solid particles, i.e. a powder coating.

Thermosetting or curable coating compositions typically comprise film-forming polymers or resins having functional groups that are reactive with themselves or with crosslinking agents. The film-forming resin may be selected from, for example, acrylic polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyether polymers, bisphenol a based epoxy polymers, polysiloxane polymers, copolymers thereof, and mixtures thereof. In general, these polymers may be any of these types of polymers made by any method known to those skilled in the art. These polymers may be solvent-based or water dispersible, emulsifiable or have limited water solubility. The functional groups on the film-forming resin may be selected from any of a number of reactive functional groups including, for example, carboxylic acid groups, amine groups, epoxy groups, hydroxyl groups, thiol groups, carbamate groups, amide groups, urea groups, isocyanate groups (including blocked isocyanate groups and tri-alkylcarbamoyltriazine) thiol groups, anhydride groups, acetoacetic acid acrylates, uretdiones, and combinations thereof.

Thermosetting coating compositions typically comprise a crosslinker that can be selected from, for example, aminoplasts, polyisocyanates including blocked isocyanates, polyepoxides, beta hydroxyalkylamides, polyacids, anhydrides, organometallic acid-functional materials, polyamines, polyamides, and mixtures of any of the foregoing.

The coating composition may also include a solvent. Suitable solvents include water, organic solvents and/or mixtures thereof. Suitable solvents include glycols, glycol ether alcohols, ketones, aromatics, such as xylene and toluene, acetates, mineral spirits, naphtha and/or mixtures thereof. "acetate" includes glycol ether acetates. In certain embodiments, the solvent is a non-aqueous solvent. "non-aqueous solvent" and like terms mean that less than 50% of the solvent is water. For example, less than 10%, or even less than 5% of the solvent may be water. It is to be understood that solvent mixtures that include water or exclude water in amounts less than 50% may constitute "non-aqueous solvents".

If desired, the coating composition may contain other optional materials well known in the art of coating formulation, such as plasticizers, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow control agents, thixotropic agents, colorants, fillers, organic co-solvents, reactive diluents, catalysts, and other conventional adjuvants.

As used herein, "colorant" and like terms refer to any substance that imparts color and/or other opacity and/or other visual effect to the composition. The colorant may be added to the coating in any suitable form, such as discrete particles, dispersions, solutions, and/or flakes. A single colorant or a mixture of two or more colorants can be used in the present coatings.

Examples of colorants include pigments, dyes, and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. The colorant may comprise, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use. The colorant may be an organic or inorganic colorant and may be aggregated or non-aggregated. The colorants can be incorporated into the coating by utilizing a grind vehicle, such as an acrylic grind vehicle, the use of which is well known to those skilled in the art.

Examples of pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketopyrrolopyrrole red ("DPPBO red"), titanium dioxide, carbon black, and mixtures thereof. The terms "pigment" and "colored filler" are used interchangeably.

Examples of dyes include, but are not limited to, those that are solvent and/or aqueous based such as pthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum, and quinacridone.

Examples of tints include, but are not limited to, pigments dispersed in an aqueous or water-miscible carrier such as AQUA-CHEM 896 commercially available from Degussa, inc, CHARISMA COLORANTS and maxiner inclusion COLORANTS commercially available from Accurate Dispersions of Eastman Chemical, inc.

As noted above, the colorant can be in the form of a dispersion, including but not limited to in the form of a nanoparticle dispersion. Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect. The nanoparticle dispersion may include a colorant such as a pigment or dye having a particle size of less than 150nm, such as less than 70nm or less than 30 nm. Nanoparticles can be produced by milling raw organic or inorganic pigments with grinding media having a particle size of less than 0.5 mm. Examples of nanoparticle dispersions and their methods of manufacture are described in U.S. Pat. No. 6,875,800B 2, incorporated herein by reference. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and chemical attrition (i.e., partial dissolution). To minimize re-aggregation of the nanoparticles in the coating, a dispersion of resin-coated nanoparticles may be used. As used herein, a "dispersion of resin-coated nanoparticles" refers to a continuous phase in which are dispersed discrete "composite particles" comprising nanoparticles and a resin coating on the nanoparticles. Examples of dispersions of resin-coated nanoparticles and methods for their manufacture are described in U.S. application No. 10/876,031 filed 24.6.2004 (which is incorporated herein by reference) and U.S. provisional application No. 60/482,167 filed 24.6.2003 (which is incorporated herein by reference).

Examples of special effect compositions that may be used in the coatings of the present invention include pigments and/or compositions that produce one or more appearance effects such as reflectance, pearlescence, metallic sheen, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and/or color change (color-change). Additional special effect compositions may provide other perceptible properties, such as opacity or texture. In one non-limiting embodiment, special effect compositions can produce a color shift such that the color of the coating changes when the coating is viewed at different angles. Examples of color effect compositions are described in U.S. Pat. No. 6,894,086, incorporated herein by reference. Additional color effect compositions may include transparent coated mica and/or synthetic mica, coated silica, coated alumina, transparent liquid crystal pigments, liquid crystal coatings, and/or any composition in which interference is caused by refractive index differences within the material and not due to refractive index differences between the surface of the material and the air.

The coatings of the present invention may be substantially transparent. As used herein, "substantially transparent" means that an object can be seen through the coating and viewed through the coating will be visible without significant distortion. It will be appreciated that the use of certain colorants will still result in a substantially transparent coating.

In certain non-limiting embodiments, photosensitive compositions and/or photochromic compositions that reversibly change their color when exposed to one or more light sources can be used in the coatings of the present invention. Photochromic and/or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition is excited, the molecular structure changes and the changed structure exhibits a new color that is different from the original color of the composition. When removed from radiation exposure, the photochromic and/or photosensitive composition can return to a resting state in which the original color of the composition is restored. In one non-limiting embodiment, the photochromic and/or photosensitive composition can be colorless in a non-excited state and exhibit color in an excited state. A complete color change may occur within milliseconds to minutes, for example 20 seconds to 60 seconds. Examples of photochromic and/or photosensitive compositions include photochromic dyes.

In one non-limiting embodiment, the photosensitive composition and/or photochromic composition can be associated with and/or at least partially bound (e.g., by covalent bonds) to the polymer and/or polymeric material of the polymerizable component. In contrast to some coatings in which the photosensitive composition may migrate out of the coating and crystallize into the substrate, the photosensitive composition and/or photochromic composition associated with and/or at least partially bound to the polymer and/or polymerizable component according to one non-limiting embodiment of the present invention has minimal migration out of the coating. Examples of photosensitive and/or photochromic compositions and methods for their manufacture are described in U.S. application serial No. 10/892,919, filed on 7, 16, 2004, which is incorporated herein by reference.

In general, the colorant can be present in the coating composition in any amount sufficient to impart the desired visual and/or color effect. The colorant may comprise from 1 to 65 weight percent, for example from 3 to 40 weight percent or from 5 to 35 weight percent of the composition of the present invention, as a weight percent based on the total weight of the composition.

In certain particular embodiments of the invention, the coating is a thermosetting composition comprising a non-gelling, hydroxyl-functional polymer prepared by polymerizing turpentine and a monomer (e.g., an acrylate) polymerized with turpentine by free radical polymerization, as described above, and a crosslinking agent such as melamine and/or isocyanate.

The polymers described herein in connection with the crosslinker may themselves constitute the film-forming resin, or one or more additional film-forming resins may be used, such as hydroxy-functional acrylic polymers commonly used in the art, e.g., MACRYNAL 510 and JONCRYL 500. These film-forming resins may be described in U.S. Pat. Nos. 5,965,670 and 7,053,149, both of which are incorporated herein by reference.

In certain other embodiments, the coating is an electrodepositable coating composition comprising the above-described polymers alone or in combination with resins commonly used in electrodepositable coatings known in the art. Examples include cationic and anionic acrylic resins and epoxy resins.

It is further understood that the coatings described herein may be "one-component" ("1K") or "two-component" ("2K"), or even multi-component compositions. A 1K composition will be understood to mean a composition in which all coating components remain in the same container after manufacture, during storage, etc. The 1K coating may be applied to a substrate and cured by any conventional method, for example, by heating, forced air, and the like. The coating of the invention may also be a 2K coating, which is to be understood as a coating in which the various components are kept separately until immediately before application. Typically, one component of a 2K coating comprises a resin and the other component comprises a curing agent for the resin. For example, one component may comprise an isocyanate and the other component may comprise a hydroxy-functional polymer, such as a polyester or an acrylic.

As noted above, in certain embodiments, the above-described copolymers will react with other film-forming components and become part of the film-forming resin of the coating.

The coatings of the present invention can be applied to any substrate known in the art, such as automotive substrates and industrial substrates. These substrates can be, for example, metals, polymers, transparent plastic substrates, polycarbonates, wood substrates, concrete, glass, and the like.

The coatings of the present invention may be applied by any means standard in the art, such as electrocoating, spraying, electrostatic spraying, dipping, rolling, brushing, printing, and the like. The coating may be applied to a dry film thickness of 0.1 to 5 mils, e.g., 0.5 to 3.0 or 0.9 to 2.0 mils. In certain embodiments of the invention, even thicker layers are contemplated, such as 20-100 mils, or up to 150 mils. The coatings of the present invention may be used alone or in combination with other coatings. For example, the coatings may be pigmented or unpigmented, and may be used as primers, e-coats, basecoats, topcoats, automotive refinish coatings, and the like. For substrates coated with multiple coatings, one or more of the coatings may be a coating as described herein.

The invention further relates to a cured coating comprising a terpene in an amount of greater than 30 wt% on a solids basis, wherein the terpene is not a phenol, cresol or maleic acid/anhydride and glycol ester containing copolymer. The terpene may be any of those described above, and may be in the form of a polymer, such as those described above. As used herein, a "cured" coating refers to a coating that exhibits solvent resistance.

The invention further relates to a coating comprising terpene and urea, wherein the urea is formed from a reaction mixture comprising an isocyanate functional component and an amine functional component, wherein the ratio of equivalents of isocyanate groups to equivalents of amine groups is greater than 1 and the isocyanate functional component and the amine functional component can be applied to a substrate in a volume mixing ratio of 1: 1. The terpene may be added directly, or in the form of a polymer, such as those described above.

The invention further relates to a polymer comprising 30 wt% or more (e.g., 50 wt% or more) terpene and less than 20 wt% (e.g., 10 wt% or less or 5 wt% or less) ethylenically unsaturated mono-and/or dicarboxylic acid containing 3 to 5 carbon atoms or anhydride thereof, wherein wt% is based on total solids weight, wherein the polymer is prepared by free radical polymerization. Suitable monomers may include any of those described above. These polymers may be prepared according to any of the methods described above.

Unless otherwise expressly stated, all numbers such as those expressing values, ranges, amounts or percentages used herein are to be understood as being preceded by the word "about", even if the term does not expressly appear. Also, any numerical range recited herein is intended to include all sub-ranges subsumed therein. Singular encompasses plural and vice versa. For example, although reference is made herein to "a" terpene, "a" monomer, "a" polymer, and the like, one or more of each of these and any other components may also be used. The term "polymer" as used herein refers to oligomers as well as homopolymers and copolymers; the prefix "poly" refers to two or more.

Examples

The following examples are intended to illustrate the invention and should not be construed as limiting the invention in any way.

Example 1

Various polymers containing terpene were prepared as follows:

example B

Synthesis of copolymer containing turpentine/isobutene/methyl acrylate/hydroxypropyl acrylate

The following ingredients were polymerized as listed below:

	composition (I)	Parts by weight (gram)
			Feed 1	Isobutene turpentine1	127.00136.00
Feed 2	Di-tert-amyl peroxyglycol monomethyl ether	38.0038.00
			Feed 3	Methyl acrylate hydroxypropyl acrylate	110.00280.00

¹Available from Pinova (a subsidiary of Hercules Incorporated). Feeding the raw materials1 was added to a 1-liter stirred stainless steel pressure reactor. The reactor was then pressurized with nitrogen and maintained at 5 psig. The stirring of the reactor was set at 500rpm and the reactor temperature was adjusted to 170 ℃. Feed 2 was added to the reactor over 2.0 hours. Feed 3 was added to the reactor over 1.8 hours 15 minutes after the start of feed 2. During the monomer addition, the temperature was maintained at 170 ℃ at 170 PSI. After feeds 2 and 3 were in the reactor, the reaction mixture was held for 2 hours. The reactor was then cooled to 25 ℃ and vented. The resulting polymer, measured at 110 ℃ for one hour, had a solids content of 74.33%. The copolymer has a number average molecular weight M_n2430 and polydispersity M_w/M_nHydroxyl number of 2.1 (determined by gel permeation chromatography using polystyrene as standard) and 196.

Example C

Synthesis of copolymer containing beta-pinene/methyl acrylate/hydroxypropyl acrylate/acrylic acid

The following ingredients were polymerized as listed below:

	composition (I)	Parts by weight (gram)
			Feed 1	Beta-pinene2Methyl acrylate hydroxypropyl acrylate butyl acetate	127.0098.00120.00180.00
Feed 2	Di-tert-amyl peroxide	172.50
			Feed 3	Beta-pinene hydroxypropyl acrylate methyl acrylate butyl acetate	882.001365.001080.0070.00125.00

²Available from Pinova. Feed 1 was added to a 4-liter stirred stainless steel pressure reactor. Then theThe reactor was pressurized with nitrogen and maintained at 5 psig. The stirring of the reactor was set at 500rpm and the reactor temperature was adjusted to 170 ℃. Feeds 2 and 3 were added to the reactor over 2.5 hours. During the monomer addition, the temperature was maintained at 170 ℃ at 136 PSI. After feeds 2 and 3 were in the reactor, the reaction mixture was held for 2 hours. The reactor was then cooled to 25 ℃ and vented. The resulting polymer, measured at 110 ℃ for one hour, had a solids content of 74.91%. The copolymer has a number average molecular weight M_n2350 and polydispersity M_w/M_n2.6 (determined by gel permeation chromatography using polystyrene as standard) and a hydroxyl number of 137.

Example D

Synthesis of copolymer containing beta-pinene/isobutylene/methyl acrylate/hydroxypropyl acrylate/acrylic acid

The following ingredients were polymerized as listed below:

	composition (I)	Parts by weight (gram)
			Feed 1	Beta-pinene methyl acrylate hydroxypropyl acrylate isobutylene acrylate	25.7516.6620.401.1995.20
Feed 2	Di-tert-amylperoxy acetate	29.3230.62
			Feed 3	Beta-pinene hydroxypropyl acrylate methyl acrylate acrylic acid	149.94231.80183.6010.71

Feed 1 was added to a 1-liter stirred stainless steel pressure reactor. The reactor was then pressurized with nitrogen and maintained at 5 psig. The stirring of the reactor was set at 500rpm and the reactor temperature was adjusted to 170 ℃. After 2.5 hours, the mixture is cooledFeeds 2 and 3 were added to the reactor. During the monomer addition, the temperature was maintained at 170 ℃ at 262 PSI. After feeds 2 and 3 were in the reactor, the reaction mixture was held for 2 hours. The reactor was then cooled to 25 ℃ and vented. The resulting polymer, measured at 110 ℃ for one hour, had a solids content of 79.48%. The copolymer has a number average molecular weight M_n2330 and polydispersity M_w/M_n2.6 (determined by gel permeation chromatography using polystyrene as standard) and a hydroxyl number of 123.

Example E

Synthesis of copolymer containing limonene/methyl acrylate/hydroxypropyl acrylate/acrylic acid

The following ingredients were polymerized as listed below:

	composition (I)	Parts by weight (gram)
			Feed 1	Limonene3Methyl acrylate hydroxypropyl acrylate	30.0019.6024.00
Feed 2	Di-tert-amylperoxy acetate	34.5036.00
			Feed 3	Methyl acrylate hydroxypropyl citracrylate acrylic acid	176.00273.00216.007.00

³Available from Acros Organics. Feed 1 was added to a 1-liter stirred stainless steel pressure reactor. The reactor was then pressurized with nitrogen and maintained at 5 psig. The stirring of the reactor was set at 500rpm and the reactor temperature was adjusted to 170 ℃. Feeds 2 and 3 were added to the reactor over 2.5 hours. During the monomer addition, the temperature was maintained at 170 ℃ at 120 PSI. In the reactor at feeds 2 and 3After neutralization, the reaction mixture was held for 2 hours. The reactor was then cooled to 25 ℃ and vented. The solids content of the resulting polymer, determined at 110 ℃ for one hour, was determined to be 72.31%. The copolymer has a number average molecular weight M_n1920 and polydispersity M_w/M_n2.6 (determined by gel permeation chromatography using polystyrene as a standard) and a hydroxyl number of 115.

Example F

Synthesis of copolymer containing limonene/methyl acrylate/hydroxypropyl acrylate/acrylic acid

The following ingredients were polymerized as listed below:

	composition (I)	Parts by weight (gram)
			Feed 1	Citric allyl methyl acrylate hydroxypropyl acrylate	30.0019.6024.00
Feed 2	Di-tert-butyl peroxyisopropanol	50.0036.00
			Feed 3	Methyl acrylate hydroxypropyl citracrylate acrylic acid	176.00273.00216.007.00

Feed 1 was added to a 1-liter stirred stainless steel pressure reactor. The reactor was then pressurized with nitrogen and maintained at 5 psig. The stirring of the reactor was set at 500rpm and the reactor temperature was adjusted to 170 ℃. Feeds 2 and 3 were added to the reactor over 2.5 hours. During the monomer addition, the temperature was maintained at 170 ℃ at 146 PSI. After feeds 2 and 3 were in the reactor, the reaction mixture was held for 2 hours. The reactor was then cooled to 25 ℃ and vented. The resulting polymer, measured at 110 ℃ for one hour, had a solids content of 84.52%. Copolymer toolNumber average molecular weight M_n1930 and polydispersity M_w/M_n2.7 (determined by gel permeation chromatography using polystyrene as standard) and a hydroxyl number of 105.

Example G

Synthesis of copolymer containing beta-pinene/alpha-methyl styrene/methyl acrylate/hydroxypropyl acrylate/acrylic acid

The following ingredients were polymerized as listed below:

	composition (I)	Parts by weight (gram)
			Feed 1	Beta-pinene methyl acrylate hydroxypropyl acrylate alpha-methyl styrene	27.2717.6021.602.59.00
Feed 2	Di-tert-amylperoxy acetate	31.0532.40
			Feed 3	Methyl acrylate beta-pinene hydroxypropyl acrylate alpha-methyl styrene	158.40245.43194.4022.5081.00

Feed 1 was added to a 1-liter stirred stainless steel pressure reactor. The reactor was then pressurized with nitrogen and maintained at 5 psig. The stirring of the reactor was set at 500rpm and the reactor temperature was adjusted to 170 ℃. Feeds 2 and 3 were added to the reactor over 2.5 hours. During the monomer addition, the temperature was maintained at 170 ℃ at 116 PSI. After feeds 2 and 3 were in the reactor, the reaction mixture was held for 2 hours. The reactor was then cooled to 25 ℃ and vented. The resulting polymer, measured at 110 ℃ for one hour, had a solids content of 72.41%. The copolymer has a number average molecular weight M_n4330 and polydispersity M_w/M_n2.7 (by gel permeation)Chromatography was determined using polystyrene as a standard) and a hydroxyl number of 70.

Example H

Synthesis of copolymer containing beta-pinene/2-ethylhexyl acrylate/hydroxypropyl acrylate/acrylic acid

The following ingredients were polymerized as listed below:

	composition (I)	Parts by weight (gram)
			Feed 1	Beta-pinene ethyl hexyl acrylate hydroxypropyl acrylate	24.2433.3619.20
Feed 2	Di-tert-amylperoxy acetate	27.6028.80
			Feed 3	Ethylhexylacrylate beta-pinene hydroxypropyl acrylate acrylic acid	300.24218.16172.805.60

Feed 1 was added to a 1-liter stirred stainless steel pressure reactor. The reactor was then pressurized with nitrogen and maintained at 5 psig. The stirring of the reactor was set at 500rpm and the reactor temperature was adjusted to 170 ℃. Feeds 2 and 3 were added to the reactor over 2.5 hours. During the monomer addition, the temperature was maintained at 170 ℃ at 114 PSI. After feeds 2 and 3 were in the reactor, the reaction mixture was held for 2 hours. The reactor was then cooled to 25 ℃ and vented. The resulting polymer, measured at 110 ℃ for one hour, had a solids content of 77.52%. The copolymer has a number average molecular weight M_n2900 and polydispersity M_w/M_nHydroxyl number of 2.5 (determined by gel permeation chromatography using polystyrene as standard) and 104.

Example I

Synthesis of copolymer containing beta-pinene/methyl acrylate/hydroxypropyl acrylate/hydroxyethyl acrylate

The following ingredients were polymerized as listed below:

	composition (I)	Parts by weight (gram)
			Feed 1	Beta-pinene methyl acrylate hydroxypropyl acrylate hydroxyethyl acrylate butyl acetate	150.00111.5060.0053.50180.00
Feed 2	Di-tert-amyl peroxide	172.50
			Feed 3	Beta-pinene hydroxypropyl acrylate hydroxyethyl acrylate butyl acetate methyl acrylate	1000.001365.00550.00485.00125.00

Feed 1 was added to a 4-liter stirred stainless steel pressure reactor. The reactor was then pressurized with nitrogen and maintained at 5 psig. The stirring of the reactor was set at 500rpm and the reactor temperature was adjusted to 170 ℃. Feeds 2 and 3 were added to the reactor over 2.5 hours. During the monomer addition, the temperature was maintained at 170 ℃ at 135 PSI. After feeds 2 and 3 were in the reactor, the reaction mixture was held for 2 hours. The reactor was then cooled to 25 ℃ and vented. The resulting polymer, measured at 110 ℃ for one hour, had a solids content of 73.78%. The copolymer has a number average molecular weight M_n1050 and polydispersity M_w/M_nHydroxyl number of 3.3 (determined by gel permeation chromatography using polystyrene as standard) and 133.

Example J

Synthesis of copolymer containing beta-pinene/methyl acrylate/hydroxypropyl acrylate

The following ingredients were polymerized as listed below:

	composition (I)	Parts by weight (gram)
			Feed 1	Beta-pinene methyl acrylate hydroxypropyl acrylate	1000800200
Feed 2	DTAP4	60
			Feed 3	DTAP	20

⁴Free radical initiator, di (t-amyl) peroxide, available from Arkema, inc

Charge 1 was added to a stainless steel reaction vessel at nominal pressure under a nitrogen atmosphere and heated to 175 ℃. An initial charge of DTAP (feed 2) was fed to the vessel over a period of 1 hour. When the feed was complete, the reaction mixture was held at 175 ℃ for an additional 2 hours. A second feed of DTAP (feed 3) was fed to the vessel over a period of 30 minutes. When the feed was complete, the reaction mixture was held at 175 ℃ for an additional 2 hours. At the end of the hold, the reaction mixture was cooled to 40 ℃ and the material was collected. The material had a measured solids of 73.06%.

Example K

Synthesis of copolymer containing beta-pinene/methyl acrylate/hydroxypropyl acrylate

A mixture of 38.7% β -pinene, 25.0% methyl acrylate, 30.7% hydroxypropyl acrylate, 0.8% acrylic acid, and 4.8% di-t-butyl peroxide was continuously fed to a 5 gallon continuously stirred tank reactor at a rate calculated to obtain an average residence time of 20 minutes. The reactor was maintained at a pressure of 500psig and a temperature of 365 ° F. The reaction product was continuously pumped to a 30 gallon flash tank maintained at a 20% fill level, along with di-tert-amyl peroxide (4 wt% based on the reaction product). The contents of the flash tank were maintained at 300 ° F. The output of the flash tank was mixed with sufficient butyl acetate in a static mixer to reduce the solids content to 81% and discharged into storage. The reaction was run for a period of 6.5 hours. The resulting resin had a weight average molecular weight of 5000.

Example 2

Resin for melamine crosslinked clear coat: preparing a transparent film-forming composition by mixing together the following ingredients in order; each formulation (F1-F5) consisted of 46% crosslinker and 54% polymer. F1 represents the control formulation.Melamine crosslinked clear coat systemWeight (g) of component solution F1F 2F 3F 4F 5 methyl n-amyl 7.257.257.257.257.25 xylene 2.202.202.202.202.20 Aromatic 1007.487.487.487.487.48 ethylene glycol monohexyl 0.710.710.710.710.71 ethanol 3.313.313.313.313.31 RESIMINE 757⁵47.4247.4247.4247.4247.42 example a 79.41-example B, prepared as described in example 1. -72.65 — example C, prepared as described in example 1. - -72.09- -example D, prepared as described in example 1. - - -67.92Example E, prepared as described in example 1. -74.68 dodecylbenzylsulfonic acid solution⁶1.431.431.431.431.43 Total 149.21142.45141.89137.72144.48⁵Fully alkylated methoxy/butoxy functional aminoplasts are available from Solutia, inc.⁶Available from Nusil Technology. Hydroxypropyl acrylate, n-butyl methacrylate, n-butyl acrylate, styrene, methyl methacrylate, acrylic acid. The polymer was 68 wt% solids in 38/57/5 weight ratio of aromatic solvent-form 100/methyl ether propylene glycol acetate/acetone CP.

More specifically, each component was mixed in turn under stirring. The final viscosity, measured on a #4 ford cup available from Paul n. gardner Company, inc., was adjusted to 27 "± 1" at room temperature with 1/1/1 parts by weight of aromatic solvent type 100/methyl-n-amyl ketone/xylene and 4/1 methyl-n-amyl ketone/2-butoxyethanol acetate. The test substrates were 10.16cm x 30.48cm ACT cold rolled steel sheets available as APR45583 from ACT Laboratories, inc. Clear coat compositions F1-F5 were applied to the steel panels at ambient temperature using an 8-pass Wet FilmApplicator #14 available from Paul n. The target dry film thickness was about 30 microns (1.6 mils). The steel panels prepared from each coating were air flashed for 10 minutes and baked at 285F (141 c) for 30 minutes. And baking the steel plate along the horizontal position. The initial specular Gloss was measured at 20 degrees using a Novo Gloss Statistical Gloss meter from Gardco, where higher values indicate better performance.

The fischer scope H100 microhardness test system measures hardness in newtons per square millimeter. More specifically, coating test specimens in newtons (N)/mm²Microhardness in units is determined as follows: the preparation for each example was carried out at 100 millinewton loads with 30 step loads and 0.5 second dwell between step load stepsAt a depth of 2 microns in the central region of the test sample of (1) measurement was taken. Scratch gloss retention was tested by subjecting the coated panels to a scratch test performed as follows: the coated surface was linearly scratched with weighted sandpaper for ten double rubs using Atlas AATCC Scratcratchtester model CM-5 available from Atlas electric Devices Company of Chicago, Illinois. The sandpaper used was a 3M 281Q WETORDRY PRODUCTION 9 micron polished paper sheet, commercially available from the 3M Company of St.Paul, Minnesota. The panels were then rinsed with tap water and patted dry carefully with paper towels. 20 degree gloss (mar gloss) was measured on the scratched area of each test panel. The scratch results are reported as% scratch retention using the following calculation using the lowest 20 degree gloss read from the scratch area: scratch gloss/initial gloss × 100. Higher retained gloss percentage values are desirable.

The performance data are summarized in table 1.TABLE 1F1F 2F 3F 4F 520 ° gloss 9290919292 Fischer microhardness ("FMH") 137145148148149% scratch retention 5554574441

As can be seen from table 1, the hardness of the inventive formulation (F2-F5) is higher than that of the control sample (F1), and the% scratch retention is comparable for samples F2 and F3 and slightly lower for F4 and F5.Example 3

A transparent film-forming composition was prepared by mixing the following ingredients together in order. Each formulation contains one equivalent weight of isocyanate and one equivalent weight of polymer. F6 represents a control sample.2K isocyanate-crosslinked systems

Composition (I)	Weight of solution (g)
							F6	F7	F8	F9	F10
Example L	89.29	-	-	-	-
						Example B	-	70.55	-	-	-
Example C	-	-	81.43	-	-
						Example D	-	-	-	81.75	-
Example E		-	-	-	89.08
						3-Ethoxypropionic acid ethyl ester	30	30	30	30	30
Methyl ether propylene glycol acetate	10	10	10	10	10
						DESMODUR N 33007	37.5	47.79	39	35.01	35.58
Dibutyl tin dilaurate8	0.05	0.05	0.05	0.05	0.05
						Polybutyl acrylate9	1.1	1.1	1.1	1.1	1.1
2-ethylhexyl acrylate10	0.53	0.53	0.53	0.53	0.53
						Total of	168.47	160.02	162.11	158.44	166.34

⁷Polyisocyanate, available from Bayer.⁸Catalyst, available from Atofina.⁹Flow additives, available from DuPont.¹⁰A flow additive, available from Solutia, inc. Hydroxypropyl acrylate, n-butyl methacrylate, n-butyl acrylate, styrene, methyl methacrylate, acrylic acid. The polymer was 71 wt% solids in an aromatic solvent of 46/54-type 100/xylene.

Formulations were prepared and tested as discussed in example 2, except that the final viscosity of the formulation was adjusted to 24 "-26" at room temperature with ethyl 3-ethoxypropionate, as measured on a #4 ford cup available from Paul n.TABLE 2

	F6	F7	F8	F9	F10
						20 degree gloss	84	82	84	83	85
FMH	125	122	139	140	142
						% scratch retention	10	18	12	9	8

As demonstrated in table 2, the inventive formulations have comparable or higher hardness and% scratch retention compared to the control samples.

Example 4

Preparing a transparent film-forming composition by mixing together the following ingredients; each component was mixed in turn with stirring:TABLE 3

Composition (I)	Parts by weight (gram)	Solid weight (g)
			Xylene	3.9	-
3-Ethoxypropionic acid ethyl ester	3.51	-
			Aromatic solvent type-150	10.54	-
Butyl Cellosolve acetate11	1.83	-
			Butyl carbitol12	2.93	-
Butyl carbitol acetate13	3.51	-
			Tridecanol	3.51	-
Aromatic solvent-100 type	1.78	-
			Testbenzin	1.83	-
TINUVIN 92814	1.95	1.95
			TINUVIN 29215	0.78	0.78
TINUVIN 12316	0.78	0.78
			Acid catalyst17	0.68	0.48
SETAMINE US-13818	41.6	29.10
			LAROTACT LR 901819	9.17	4.63
Sagging control agent208	42.0	25.21
			ADDITOL XL 12121	0.02	0.003
WORLEE 31522	0.39	0.05
			EFKA 678123	0.78	0.59
And (3) simplifying information:
			aromatic solvent-100 type
Viscosity of spray coating24(sec)	30
			Paint spraying temperature (finish temperature, F.)	72

¹¹2-butoxyethyl acetate solvent, available from Union Carbide Corp.¹²Diethylene glycol monobutyl ether, available from Union Carbide corp.¹³2- (2-butoxyethoxy) ethyl acetate, available from Union Carbide Corp.¹⁴UV absorbers, available from Ciba Specialty Chemicals Corp.¹⁵Sterically hindered amine light stabilizers, available from Ciba Additives.¹⁶Sterically hindered amine light stabilizers, available from Ciba Additives.¹⁷Dodecyl benzene sulfonic acid solution, available from chemcental.¹⁸Melamine formaldehyde Resins, available from Nuplex Resins.¹⁹Tris (alkylcarbamoyl) triazine, available from BASF AG.²⁰SCA acrylic Resins, available from Nuplex Resins.²¹Polysiloxane diols, available from Cytec Surface Specialties.²²Water soluble silicone additives, available from Worlee Chemie.²³Halogen-free cationic compounds, available from Efka Chemicals.²⁴Viscosity in seconds measured with a #4 ford flow cup at ambient temperature.

Various formulations were then prepared using the transparent film-forming compositions described in table 3 above, and to this was added an acrylic resin and/or copolymer of the present invention prepared as described in example 1. F11 represents a control sample.

Composition (I)	F11	F12	F13	F14	F15	F16	F17	F18	F19
										The clear compositions described in Table 3 above	131.5(63.6)	131.5(63.6)	131.5(63.6)	131.5(63.6)	131.5(63.6)	131.5(63.6)	131.5(63.6)	131.5(63.6)	131.5(63.6)
Acrylic resin25	63.7(41.1)	48.2(31.1)	32.7(21.1)	17.2(11.1)	-	-	-	-	-
										Example C	-	12.5(10)	25.0(20)	37.5(30)	51.4(41.1)	-	-	-	-
Example D	-	-	-	-	-	51.7(41.1)	-	-	-
										Example G	-	-	-	-	-	-	57.2(41.1)	-	-
Example F	-	-	-	-	-	-	-	49.1(41.1)	-
										Example H	-	-	-	-	-	-	-	-	53.0(41.1)

²⁵Solids-based having a weight average molecular weight ("Mw") of about 8000 for Cardura E, styrene, hydroxyethyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, and a weight average molecular weight ("Mw") of 370 hydroxyl equivalent weight ("EW"). The polymer was 65 wt% solids in a weight ratio of 34/66 xylene/Solvesso 100 (available from Exxon).

The film-forming compositions F11-F19 were spray applied to a colored basecoat to form a color-plus-clear composite coating on a primed electrocoated steel sheet. The sheet material used was a cold-rolled steel sheet (10.16 cm. times.30.48 cm). The panels were coated with ED6060 electrocoat and 1177225a primer (both available from PPG Industries, inc.), followed by Obsidian Schwartz (black metal-pigment pigmented water-based basecoat, also available from PPG Industries, inc.). The base coat was automatically sprayed onto the electrocoated and primed steel panels at ambient temperature (approximately 70F (21 c)). The target dry film thickness of the basecoat is about 0.6 to 0.8 mils (about 15 to 20 microns). The basecoated panels were dewatered at 176 ° F (80 ℃) for 10 minutes prior to clearcoat application.

The clear coat composition was each sprayed automatically onto the basecoat plate in two coats at ambient temperature with ambient flash between applications. The target dry film thickness of the clearcoat is 1.6-1.8 mils (about 41-46 microns). All coatings were allowed to air flash at ambient temperature prior to oven treatment. The panels were baked at 285F (141 c) for thirty minutes to fully cure the coating. The panels are prepared for a horizontal baking position and a vertical baking position. And carrying out appearance observation on the horizontal and vertical plates. The horizontal sheets were also tested for physical properties such as scratch resistance, acid resistance and hardness. The properties of the coatings are reported in table 4 below.TABLE 4 ²⁶The 20 ° Gloss was measured with a statistical novo-Gloss 20 ° Gloss meter available from Paul n.²⁷Image Distinctiveness (DOI) was measured using a Hunter Associates DORIGON II DOI meter.²⁸Long Wave (LW) and Short Wave (SW) measurements were performed using BYK Wavescan DOI.²⁹The acid resistance was evaluated triply by placing 50. mu.l of a pH 2 sulfuric acid solution drop-wise on the plate. The panels were then placed in a 120 ° F oven at 20' to allow the solution to evaporateAnd (4) sending. This constitutes one cycle. This cycle was repeated two more times. The board was then washed with soap and water and wiped dry with a towel. A comparison with a set of known standard samples gives a rating of 0-10. A rating of 1 indicates no visible damage and a rating of 10 indicates complete loss of the coating.³⁰The procedure is as described in example 2.³¹The scratch test was performed by subjecting the coated panels to: the coated surface was linearly scratched with weighted sandpaper for ten double rubs using an atlas AATCC Scratch Tester model CM-5 available from atlas electric Devices Company of Chicago, Illinois. The sandpaper used was a 3M 281Q WETORDRY PRODUCTION 2 micron polished paper sheet, commercially available from 3M Company of St.Paul, Minnesota.³²10 cycles car washes measured after 10 double passes in a car wash plant from Amtec Kistler³³% gloss retention (% GR) -% gloss retention is reported as the percentage of the initial gloss retained after the scratch test using the following calculation, using the lowest 20 degrees gloss read from the scratched area: 100% × scratched gloss/initial gloss. Higher retained gloss percentage values are desirable.

As demonstrated in table 4, F12-F18 generally had comparable performance compared to the control sample (F11).Example 5

This example describes the preparation of a cationic resin prepared from the following ingredients:

composition (I)	Parts by weight
		EPON 82834	614.68
bisphenol-A	265.42
		Example J	205.31
Ethyl triphenyl phosphonium iodide	0.6
		Methyl isobutyl ketone	13.52
Crosslinking agent35	277.33
		Diethanolamine (DEA)	8.4
Diketimines36	45.62
		EPON 828	14.84

³⁴Available from Resolution.³⁵An amine-functional crosslinker prepared as follows.³⁶The diketoimine was derived from bis (hexamethylene) triamine (DYTEK BHMT-HP, available from Invista) and methyl isobutyl ketone (69.65% solids in methyl isobutyl ketone, yielding 39.5% hydrolyzed solids).

EPON 828, bisphenol a and the example a copolymer prepared as described in example 1 were charged to a reaction vessel and heated to 125 ℃ under a nitrogen atmosphere. Ethyltriphenylphosphonium iodide was then added and the reaction mixture was allowed to heat exothermically to about 140 ℃. The reaction was held at 135 ℃ for 2 hours and 30 minutes and an epoxy equivalent was obtained. At this point, a charge of methyl isobutyl ketone was added and the reaction mixture was cooled to 98 ℃. The crosslinker and diethanolamine were added sequentially. The mixture was allowed to heat up exothermically and then heated until a temperature of 122 ℃ was reached. The mixture was held at 122 ℃ for 15 minutes. The diketoimine is then added and the mixture is held at 121 ℃ for a further 25 minutes. EPON 828 was added thereto and the mixture was held at 125 ℃ for an additional 45 minutes. The resin mixture (1624.86 parts) was dispersed in an aqueous medium by adding it to a mixture of 45.87 parts sulfamic acid and 863.94 parts deionized water. The dispersion was further diluted in stages with 506.94 parts deionized water and 960.51 parts deionized water and vacuum stripped to remove organic solvent to yield a dispersion with a solids content of 46.6%.Crosslinking agent

The cross-linking agent was prepared from the following ingredients:

composition (I)	Weight (D)Portions are
		Bis (hexamethylene) triamine37	107.7
Propylene carbonate38	102.09

³⁷Available from Invista as DYTEK BHMT-HP.³⁸Available from Sigma-Aldrich co.

Bis (hexamethylene) triamine was added to the reaction vessel and heated under a nitrogen atmosphere. The propylene carbonate was added over 3 hours. The reaction mixture was allowed to heat exothermically to 66 ℃ and then cooled and maintained at 59 ℃. The mixture was held at 59 ℃ for an additional 2 hours and then allowed to cool. The material had a MEQ amine of 2.308 and the mixture was collected.

The electrodeposition bath composition according to the present invention was prepared using the resin prepared as described above. The electrodeposition bath was prepared from a mixture of the following ingredients:

composition (I)	Parts by weight
		Cationic resins	1407.9
Plasticizer39	34.5
		Solvent(s)40	19
Pigment paste prepared as described below	230.8
		Deionized water	2107.8

³⁹Mazo-1651 is a plasticizer based on butyl carbitol and formaldehyde, available from BASF.⁴⁰Ethylene glycol monohexyl ether, available from Dow.

The bath is formed by adding the plasticizer and solvent to the resin with stirring. The blend was then diluted with 500 parts deionized water. The pigment paste was diluted with 300 parts of deionized water and then blended into the diluted resin mixture with stirring. The remainder of the deionized water was then added with stirring. The final bath solids was about 22% with a pigment to resin ratio of 0.15: 1.0. The paint was allowed to stir for at least two hours. 20% of the total paint weight was removed by ultrafiltration and replaced with deionized water.

The pigment paste used in the electrodeposition bath composition of the present invention (prepared as described above) was prepared from a mixture of the following ingredients:

composition (I)	Parts by weight
		Cationic grinding resin41	439.6
SURFYNOL GA42	9.1
		Catalyst paste43	190.8
Aluminium silicate44	121.4
		CSX-33345	7.3
KRONOS 231046	417.5
		Deionized water	95.5

⁴¹As described in example 2 of US 4,715,898, plus 2 wt% (solids basis) icomen T-2 available from BASF.⁴²Nonionic surfactants, available from Air Products and Chemicals, inc.⁴³A dibutyltin oxide catalyst paste was prepared as follows.⁴⁴Available from Engelhard Corporation.⁴⁵Carbon black beads, available from Cabot Corp.⁴⁶Titanium dioxide pigment, available from Kronos Worldwide, inc.

The above ingredients were added sequentially under high shear stirring. After the ingredients were fully blended, the pigment paste was transferred to a vertical sand mill and ground to a Hegman value of about 7.25. The pigment paste was then collected. The solids measured after 1 hour at 110 ℃ were 63%.

A catalyst paste for preparing the pigment paste was prepared from a mixture of the following ingredients:

composition (I)	Parts by weight
		Cationic grinding resin 47	527.7
N-butoxy propanol	6.9
		FASCAT 420148	312.0
Deionized water	59.8

⁴⁷As described in example 2 of US 4,715,898, plus 2 wt% (solids basis) icoment-2.⁴⁸Dibutyl tin oxide, available from Arkema, inc.

The above ingredients were added sequentially under high shear stirring to prepare a catalyst paste. After the ingredients were fully blended, the pigment paste was transferred to a vertical sand mill and ground to a Hegman value of about 7.25. The catalyst paste was then collected. The solids measured after 1hr at 110 ℃ were 51%.Electrocoating process

The electrodeposition bath composition prepared above was electrodeposited onto phosphated electrogalvanized panels (commercially available from ACT laboratories). A phosphate salt commercially available from PPG Industries, inc. is CHEMFOS 700 with CHEMSEAL 59 wash. The conditions for cationic electrodeposition were 3 minutes at 250 volts DC at 99 ° F to produce a cured film of 0.85 mil thickness. The electrocoated substrate was cured in an electric oven at 340 ° F for 30 minutes. The electrocoated substrate is then top-coated with a commercially available basecoat/clearcoat system available from PPG industries, Inc. The commercially available topcoat systems are a white base coat of BWB8554R and a WTKR 20002K ISO clearcoat. The appearance and chipping (chip) of the electrocoats described in these examples were evaluated against standard samples. The standard control system was ED-6100H electrocoat and 1177-225AR primer topcoat.

Appearance was measured as described above using a BYK Gardner wave scan and the results are given in table 5. Chipping was evaluated as described in PPG Cleveland ETP QWI-0630.0, but 2 pints of gravel were used instead of the 1 pint specified. The results are given in table 2.TABLE 5

Electrocoat/primer surface coating agent	LW	SW	Grade of shattering (10-best, 0-worst)
				Electrocoating/electroless of this example	2.2	15.0	7
ED-6100H/1177-225AR	2	13.9	6

As demonstrated in table 5, the present system has higher LW and SW and better chip resistance compared to the control sample without the use of a primer surface.

Example 6

Two different 2k systems were prepared using example G prepared as described in example 1. The 2K systems are all isocyanate-packaged crosslinked clearcoats, the first at an isocyanate/hydroxyl ratio (NCO/OH) of 1.1/1 (hereinafter referred to as F20) and the second at an NCO/OH ratio of 1.3/1 (hereinafter referred to as F21).

The ingredients of each package 1 described below (clearcoat package) were blended and mixed together and left for use. The ingredients of package 2 (hardener or hardener package) are blended together and left to use. Pack 1 and pack 2 are mixed together just prior to spraying. The clear coat was applied over the DBC 18492 blue metal basecoat using a DeVilbissGTI spray gun. The clearcoat was applied in two coats to achieve a dry film thickness of about 2.5 mils. The applied coating was allowed to cure overnight at room temperature before testing.

The substrate used was an APR 43741ED primed and sealed panel from ACT Laboratories, Hillsdale, MI; the panels were sanded with 400 grit sandpaper prior to priming.

A primer (of DBC 18492 light blue metal) available from ppginindustries, inc. was diluted 100% with D870 diluent prior to application on a substrate.

F20	Weight of the formulation	Solid resin
			Packaging 1:
example G	79.20	65.20
			BYK 30049	0.50	0.25
TINUVIN 29250	1.20	1.20
			CHISORB 32851	1.00	1.00
DBTDL52	0.20	0.20
			PM ACETATE53	20.83
Solvent blends54	30.00
			Small counter	132.93	67.94
And (3) packaging 2:
			Z4470 BA55	22.90	16.03
DESMODUR 340056	16.03	16.03
			MIBK57	1.14
small counter	40.07	32.06
			In total:	173.00	100.00

% Wt solids	VOC	Wt/Gal	Eq ratio NCO/OH
				57.80	3.52	8.35	1.10

F21	Weight of the formulation	Solid resin
			Packaging 1:
example G	74.71	61.59
			BYK 30047	0.50	0.25
TINUVIN 29248	1.20	1.20
			CHISORB 32849	1.00	1.00
DBTDL50	0.20	0.20
			PM ACETATE51	20.69
Solvent blends52	30.00
			Small counter	128.30	64.24
And (3) packaging 2:
			Z4470 BA53	25.54	17.88
DESMODUR 340054	17.88	17.88
			MIBK55	1.28
small counter	44.70	35.76
			In total:	173.00	100.00

% Wt solids	VOC	Wt/Gal	Eq ratio NCO/OH
				57.80	3.53	8.35	1.30

⁴⁷Available from BYK Chemie.⁴⁸Available from Ciba.⁴⁹Available from Chitec Chemical.⁵⁰DBTDL (dibutyltin dilaurate), available from Air Products.⁵¹Available from Dow Chemical.⁵²Solvent blends, available from PPG Industries.⁵³Available from BA Bayer Chemical.⁵⁴Available from Bayer Chemical.⁵⁵MIBK (methyl isobutyl ketone), available from Eastman Chemical.TABLE 6

Test of	F20	F21
			Initial viscosity58	87.5cps	78.5cps
Cotton time59	50 minutes	40 minutes
			Gloss 2060	88	88
Hardness of Kenixi61(24 hours)	18	21
			Kenixi hardness (1 week cure)	32	36

⁵⁸The viscosity was measured by brookfield LVT viscometer using a #2 spindle at 60 rpm.⁵⁹Cotton time was measured as follows: a cotton ball was dropped on the coating, waiting 5 seconds and the panel was turned over to see if the cotton ball fell. Record from spray to cotton ball complete from coatTime (minutes) when the layer fell.⁶⁰Gloss was measured by Byk-Gardner micro-TRI-gloss.⁶¹The Konig hardness was measured using a Konig pendulum impact hardness machine from Byk-Gardner after twenty four hours cure and 1 week cure.

Example 7

Clear coat 2K formulations containing abrasion resistant particles were prepared using the following ingredients. Each of the components shown in the following table was mixed in turn with stirring to form pack 1 and pack 2. Pack 1 and pack 2 are then mixed together with agitation to form a clear coating composition. The amounts shown in the table are parts by weight (in grams).F22

Composition (I)	Solid weight (g)	Weight (gram)
			Package 1
Acetic acid pentyl ester	---	7.85
			SOLVESSO 10062	---	18.13
Butyl Cellosolve acetate	---	4.80
			Butyl carbitol acetate	---	2.40
TINUVIN 123	0.50	0.50
			TINUVIN 928	2.00	2.00
Treated colloidal silica63	1.50	10.42
			Siloxane borate esters64	0.50	1.00
Example C, prepared as described in example 1	45.11	60.22
			Polyester polyols65	5.00	5.00
CYMEL 20266	5.00	6.25
			BYK 33767	0.02	0.10
NACURE 416768	1.00	4.00
			TMP/Empol Polyol69	5.00	5.65
			Package 2
Acetic acid pentyl ester	---	10.00
			SOLVESS0100	---	1.62
DESMODUR N 3300	25.83	25.83
			DESMODUR Z 4470 BA	13.56	19.37
Total of	105.02	185.14

⁶²Aromatic solvent type-100, available from Exxon.⁶³"II" prepared as described in U.S. patent No. 11/145,812 filed on 6/2005Silica B ", which is incorporated herein by reference.⁶⁴Prepared as described in U.S. patent No. 6,623,791B2, incorporated herein by reference.⁶⁵M containing C36 dibasic acid, neopentyl glycol, cyclohexanedimethanol-1, 4-trimethylolpropane_wAbout 1300 deg.f based on a solid polymer having a hydroxyl EW of 189. The polymer was 100% solids.⁶⁶Melamine formaldehyde resin available from CYTEC Industries, Inc.⁶⁷Solution of polyether modified poly-dimethyl-siloxane, available from BYK-Chemie.⁶⁸Latent catalysts, available from King Industries, inc.⁶⁹A solids-based polymer having a hydroxy EW of 199 containing trimethylolpropane and EMPOL 1008 (available from Cognis Corporation) having a Mw of about 4500. The polymer was 89% solids in n-butyl acetate.F23

Composition (I)	Solid weight (g)	Weight (gram)
			Package 1
Acetic acid pentyl ester	---	7.85
			SOLVESSO 100	---	18.13
Butyl Cellosolve acetate	---	4.80
			Butyl carbitol acetate	---	2.40
TINUVIN 123	0.50	0.50
			TINUVIN 928	2.00	2.00
Treated colloidal silica	1.50	10.42
			Siloxane borate (siloxane borate)	0.50	1.00
Example D, prepared as described in example 1.	48.24	60.69
			Polyester polyols	5.00	5.00
CYMEL 202	5.00	6.25
			BYK 337	0.02	0.10
NACURE 4167	1.00	4.00
			Polyester polyol described in footnote 65	5.00	5.65
			Component 2
Acetic acid pentyl ester	---	13.75
			SOLVESSO 100	---	1.62
DESMODUR N 3300	23.66	23.66
			DESMODUR Z 4470BA	12.61	18.01
Total of	105.03	185.83

F24

Composition (I)	Solid weight (g)	Weight (gram)
			Component 1
Acetic acid pentyl ester	---	14.00
			SOLVESSO 100	---	10.00
Butyl Cellosolve acetate	---	4.50
			Butyl carbitol acetate	---	3.00
TINUVIN 123	0.25	0.25
			TINUVIN 292	0.25	0.25
TINUVIN 928	3.00	3.00
			Treated colloidal silica	2.00	13.89
Siloxane borate esters	0.50	1.00
			Example I, prepared as described in example 1	48.70	63.84
CYMEL 202	5.00	6.25
			BYK 30670	0.02	0.15
NACURE 4167	0.50	2.00
			Polyester polyol described in footnote 65	7.79	8.76
			Component 2
Acetic acid pentyl ester	---	10.00
			Phenyl acid phosphate71	0.25	0.33
DESMODUR N 3300	27.35	27.35
			DESMODUR Z 4470BA	10.67	15.24
Total of	106.28	183.81

⁷⁰Solution of polyether modified poly-dimethyl-siloxane, available from BYK-Chemie.⁷¹Phenyl acid phosphate solution, obtainable from Rhodia.F25

Composition (I)	Solid weight (g)	Weight (gram)
			Package 1
Acetic acid pentyl ester	---	14.00
			SOLVESSO 100	---	10.00
Butyl Cellosolve acetate	---	4.50
			Butyl carbitol acetate	---	3.00
TINUVIN 123	0.25	0.25
			TINUVIN 292	0.25	0.25
TINUVIN 928	3.00	3.00
			Treated colloidal silica	2.00	13.89
Siloxane borate esters	0.50	1.00
			Acrylic polyol72	44.21	69.62
CYMEL 202	5.00	6.25
			BYK 306	0.02	0.15
NACURE 4167	0.50	2.00
			Polyester polyol described in footnote 65	11.82	13.30
			Package 2
Acetic acid pentyl ester	---	9.09
			Phenyl acid phosphate71	0.25	0.33
DESMODUR N 3300	27.72	27.72
			DESMODUR Z 4470BA	10.79	15.41
Total of	106.31	193.76

⁷²In the presence of [ 95% propylene glycol methyl ether (DOWANOL PM from Dow Chemical) and 5% SOLVESSO 100 (aromatic hydrocarbon from Exxon)]14% butyl methacrylate, 15% butyl acrylate, 28% isobornyl methacrylate, 23% hydroxypropyl methacrylate, 20% hydroxyethyl methacrylate as 63.5% solids in the solvent blend. The film-forming compositions F22-F25 were spray applied to a colored basecoat to form a color-plus-clear composite coating on a primed electrocoated steel sheet. The steel sheet used was ACT E60 EZG G60 steel sheet (10.16 cm. times.30.48 cm) with an ED-6150MB electrocoat available from ACT laboratories, Inc. The steel sheet was coated with Black 40 (a Black pigmented water based primer coating available from BASF). The base coat was automatically sprayed onto the electrocoated steel sheet at ambient temperature (approximately 70F (21 c)). The target dry film thickness of the basecoat is about 0.4 to 0.5 mils (about 10 to 13 microns). The basecoated panels were dewatered at 176 ° F (80 ℃) for 5 minutes prior to clearcoat application. The clear coat composition was each sprayed automatically onto the basecoat plate in two coats at ambient temperature with ambient flash between applications. The target dry film thickness of the clearcoat is 1.5-1.7 mils (about 38-43 microns). All coatings were allowed to air flash at ambient temperature prior to oven treatment. The panels were baked at 285F (141 c) for thirty minutes to fully cure the coating. The panels are prepared for a horizontal baking position and a vertical baking position. And carrying out appearance observation on the horizontal and vertical plates. The horizontal panels were also tested for physical properties such as scratch resistance (Amtec car wash and Atlas Crockmeter) and hardness. The properties of the coatings are reported in the table below. Horizontal position

	F22	F23	F24	F25 control acrylic
					20 degree gloss	86	86	85	84
DOI	96	94	94	92
					Short wave	28	28	27	28
Long wave	5	6	4	4
					FMH	132	125	118	116
10 cycles Amtec car wash (% gloss retention)	84	78	86	88
					10 cycles Atlas Crockmeter (% gloss retention)	70	65	62	77

Vertical position

	F22	F23	F24	F25 control acrylic
					20 degree gloss	86	86	85	84
DOI	93	92	78	92
					Short wave	25	23	44	28
Long wave	16	16	16	14

As demonstrated in these tables, the inventive formulations (F22-F24) have overall comparable performance compared to the control sample (F25).Example 8This example describes the preparation of a cationic resin prepared from the following ingredients:

composition (I)	Parts by weight
		EPON 828	456.76
bisphenol-A	197.23
		Methyl isobutyl ketone (1)	30.80
Ethyl triphenyl phosphonium iodide	0.45
		Methyl isobutyl ketone (2)	33.75
Crosslinking agents, prepared as described below	283.68
		Diethanolamine (DEA)	6.98
DETA Diketimine	24.92
		EPON 828	8.95
Example K, prepared as described in example 1	782.55

EPON 828, bisphenol a, methyl isobutyl ketone (1) and ethyl triphenyl phosphonium iodide were added to the reaction vessel and heated to 135 ℃ under a nitrogen atmosphere and the reaction mixture was allowed to heat exothermically to about 140 ℃. The reaction was held at 135 ℃ for 2 hours, then a charge of methyl isobutyl ketone (2) was added and the reaction mixture was cooled to 115 ℃. The crosslinker and diethanolamine were added sequentially. The mixture was allowed to heat up exothermically and then heated until a temperature of 122 ℃ was reached. The mixture was held at 122 ℃ for 45 minutes. DETA Diketimine was then added and the mixture was held at 122 ℃ for an additional 45 minutes. EPON 828 was added thereto and the mixture was held at 125 ℃ for another 30 minutes. Example K was then added, the temperature was adjusted to 122 ℃ and the mixture was held for one hour. The resin mixture (1760 parts) was dispersed in an aqueous medium by adding it to a mixture of 34.33 parts sulfamic acid and 907.96 parts deionized water. The dispersion was further diluted in stages with 600.50 parts deionized water and 608.40 parts deionized water and vacuum stripped to remove organic solvent to yield a dispersion with a solids content of 43.3%.Crosslinking agentThe cross-linking agent was prepared from the following ingredients:

composition (I)	Parts by weight
		Bis (hexamethylene) triamine	3675.69
Propylene carbonate	2884.32
		Methyl isobutyl ketone	1640.00

Bis (hexamethylene) triamine was added to the reaction vessel and heated under a nitrogen atmosphere. Adding carbon over 3 hoursPropylene acid ester. The reaction mixture exothermically warmed to 68 ℃ and then cooled and maintained at 60 ℃. The mixture was held at 60 ℃ for a further 2 hours, then methyl isobutyl ketone was added. An electrodeposition bath composition according to the present invention was prepared from a mixture of the following ingredients, hereinafter referred to as F26.

Composition (I)	Parts by weight
		Cationic resins, prepared as described above	1440.0
The plasticizer as described in footnote 39	32.8
		Solvent as described in footnote 40	19.0
Propylene glycol monomethyl ether	9.1
		Pigment paste, prepared as described below	223.0
Deionized water	2076.1

The bath is formed by adding the plasticizer and solvent to the resin with stirring. The blend was then diluted with 500 parts deionized water. The pigment paste was diluted with 300 parts of deionized water and then blended into the diluted resin mixture with stirring. The remainder of the deionized water was then added with stirring. The final bath solids was about 20% with a pigment to resin ratio of 0.12: 1.0. The paint was allowed to stir for at least two hours. 30% of the total paint weight was removed by ultrafiltration and replaced with deionized water. The pigment paste used in the electrodeposition bath composition of the present invention prepared as described above was prepared from a mixture of the following ingredients:

composition (I)	Parts by weight
		The yang as described in footnote 41Ion milling resin	525.3
SURFYNOL GA	1.4
		Catalyst paste as described in footnote 43	175.3
Aluminium silicate as described in footnote 44	316.6
		CSX-333	4.3
TRONOX CR800E73	40.3
		Deionized water	50.3

⁷³Titanium dioxide pigment, available from Tronox inc. The above ingredients were added sequentially under high shear stirring. After the ingredients were fully blended, the pigment paste was transferred to a vertical sand mill and ground to a Hegman value of about 7.25. The pigment paste was then collected. The solids measured after 1hr at 110 ℃ were 55%.And (3) electrocoating procedure:the electrodeposition bath composition prepared above was electrodeposited onto phosphated cold rolled steel panels (commercially available from ACT laboratories). A phosphate commercially available from PPG Industries, inc. is CHEMFOS 700 with deionized water wash. The conditions for cationic electrodeposition were 2 minutes at 125 volts DC at 92 ° F to produce a cured dry film thickness of 0.80 mils. The electrocoated substrate was cured in an electric oven at 350 ° F for 25 minutes. The electrocoated panels were tested against standard electrocoated products and the results were recorded on the following table. The control product was an ED-6280 electrocoat available from ppginindustries, inc. Watch (A)

	F26	ED6280 control paint
			Outline (Profile)74	8/12	7/9.5
QCT wet adhesion75	10/10	10/10
			30 cycle corrosion test76	4.5mm scribe creep	4.25mm scribe creep

⁷⁴The profile was measured using a Taylor HobsonSurtronic 3+ profilometer with a cutoff length of 0.03 inches and 0.10 inches.⁷⁵The cross-hatch attachment was performed on a QCT condensation tester (Q-Panel Company, Cleveland, OH) before and after condensation wet exposure at 140 ℃ F. for 16 hours.⁷⁶To coat each scribe line in the panel, the coating is cut through to the metal substrate in an X pattern. The test panels were then subjected to cyclic corrosion testing by rotating the panels through a salt solution, drying at room temperature, subjecting to wetting and low temperature according to General Motors test method GM TM 54-26. Scribe creep is reported as the average distance (in millimeters) of corrosion from the scribe mark. While specific embodiments of the invention have been described above for purposes of illustration, it will be apparent to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims.

Claims (12)

1. A coating comprising a hydroxy-functional polymer comprising a terpene and a hydroxy-functional acrylic monomer polymerized with the terpene by free radical polymerization, wherein the monomer is not maleic acid/maleic anhydride, and wherein the terpene comprises 30 wt% or more of the polymer.

2. The coating of claim 1, wherein the terpene comprises α -pinene.

3. The coating of claim 1, wherein the terpene comprises β -pinene.

4. The coating of claim 1, wherein the terpene comprises limonene.

5. The coating of claim 1, wherein the terpene comprises turpentine.

6. The coating of claim 1, wherein the polymer is crosslinked to form a part of a coating film.

7. The coating of claim 1, wherein the polymer comprises 30 wt% or more of the coating, based on total solids weight.

8. The coating of claim 1, wherein the polymer comprises 50 wt% or more of the coating, based on total solids weight.

9. The coating of claim 1, wherein the coating is an electrodepositable coating.

10. The coating of claim 1, wherein the coating comprises a colorant.

11. The coating of claim 1, wherein the coating is substantially transparent.

12. The coating of claim 1, wherein the coating is a two-component coating and the polymer is in one component and the curing agent is in another component.