TW200426184A - Acetoacetylated polyvinyl polymers and curable coating compositions made therefrom - Google Patents

Abstract

The present invention relates to curable coating compositions containing acetoacetylated polyvinyl polymers obtained from polyvinyl polymers, such as polyvinyl butyrals. These coating compositions are especially suitable for use as wash primers in automotive OEM and refinish coating applications.

Description

200426184 发明 Description of the invention: [Cross-reference to related applications] This application claims priority rights under 35 USC §119 from US Provisional Patent Application No. 60 / 456,476 (filed on March 21, 2002), which is based on The citation is incorporated herein. [Technical field to which the invention belongs] The present invention relates to a coating composition suitable for automotive applications, and more particularly to a washing primer having improved coating adhesion and hardness over conventional washing primers. [Prior art] Things. It also includes anti-corruption inhibitors (eg, chromate) and rhenium metal surfaces to improve the adhesion of the primer to the underlying surface of the bare metal substrate (eg, dish acid). In contrast to the primer, the washing primer layer is generally used (such as) to spray paint to about 76 microns ⑺ · 3 mil) to Chuan Qimi (typical thickness of U mil 'and primer _ It is generally applied to a film thickness of about 2 μm to 5 μm in 0εμ applications, and is being reworked in coating applications, especially in automotive 0EM (original equipment manufacturing) or refinishing The coating system can be used for coating multiple layers of coating compositions on metal substrates, such as car bodies. Bare metal surfaces are typically coated with a wash-type primer, followed by a coating from a master lacquer composition, which is further coated with a varnish composition. If desired, a primer can be applied to the wash primer prior to the application of the main paint composition, 'and. Coating. The adhesive strength of the coating obtained from the self-cleaning primer and the overall integration of the coating system are important. The conventional strip-type primer is a coating composition generally comprising polyvinyl butyral dissolved in isopropanol — 91637 doc 200426184 in light applications up to 127 microns (5 mils). Coatings of conventional primer compositions are typically applied to wash-off primers before applying additional coatings, such as main paints and varnishes. One of the main problems associated with this primer is the existence of conventional anti-corruption inhibitors, such as zinc acetate, and female μ inhibitors are toxic and have a negative impact on the environment. Therefore, attempts have now been made to produce chromate-free, wash-resistant primers that are equivalent to or improve the corrosion resistance provided by conventional wash strip-type primers containing chlorates. Another problem associated with this conventional wash-type primer is that the paint obtained therefrom tends to crack when exposed to the crushing effects experienced by automotive cold early soil systems. The chromate-free coating composition of the present invention is not only good for the environment, but also provides improved shatter resistance over conventional washdown primers. [Summary of the Invention] The present invention proposes a curable composition including a cross-linkable and cross-linkable component, wherein the cross-linkable component includes: (a) an ethylamidine polyethylene polymer having the following formula: • CHj-CH--CH2-CH--

CH2 — CH CH, 〇,

-CH I OH

0 = CI 2_ ch2-ch- 〇I c = I ch2 I c = I ch3 p in the range of 5 mole% to about 85 mole% in the company, and radium in the range of about 0t 2G.5 mole% In the range, ⑻ is in the range of Moore W7 Moore A, and ⑷ is in the range of about! Moore% to about 88 Moore%, 91637 doc 200426184 (m), (η), (P) and The sum of (q) is 100, and its center and heart are independently η, substituted or unsubstituted (: 1 to (: 12 alkyl, substituted or unsubstituted ^ to (^ 4 aryl) , Substituted or unsubstituted & to araryl, substituted or unsubstituted 6 to CM alkylaryl, substituted or unsubstituted d to carbocyclyl, or a combination thereof, the substituent is Independently selected from the group consisting of Cisci2 alkoxy, alkynyl, carboxyl, carboxyl derivative, sulfofluorenyl, sulfofluorenyl derivative, cyano and halo; (b) ethylamidine Tritiated polyethylene polymer: H2 c

CH 丨 O H2 c H cl

2 CH CH 丨 R1 o o

H ， on on on R H2 c

CHlOH Η2 c

ο-Η 11Η211Η3 CIOICICICIC CH 丨 2 ΓΥ "(m) is in the range of about 1.5 mole% to about 85 mole%, (n) is in the range of about 0 mole% to about 20.5 mole%, (Ρ) is in the range of about 12 mol% to about 87 mol%, (q) is in the range of about 1 mol% to about 88 mol%, and (X) is in the range of about 0.5 mol% to about In the range of 6 mol%, the total of (m), (n), (p), ⑷, and (x) is 100, and the central sum of them! ^ Is independently Η, substituted or unsubstituted (: 1 To (: 12 alkyl, substituted or unsubstituted (: 6 to (:: 14 aryl, substituted or unsubstituted Q to C22 aralkyl, substituted or unsubstituted q to Cm alkane An aryl group, a substituted or unsubstituted carbocyclic group, or a combination thereof, and wherein Z is fluorene or -COOH and Y is -COOH, a-group, an unsubstituted phenyl group, or a combination thereof, the The substituents are independently selected from the group consisting of (^ to (: alkoxy, fluorenyl, carboxyl, carboxyl derivatives, sulfofluorenyl, and sulfofluorenyl derivatives 91637 doc 200426184 gas and halogen groups; C) a combination thereof; and wherein the cross-linking component includes polyamine, poly Imine, polyepoxide, polyisocyanate, melamine, CjCi2 alkanedialdehyde, CjCi2 alkyl poly (meth) acrylate, or a combination thereof. The present invention also provides a method for manufacturing a multi-coating system on a substrate. The method includes: mixing a cross-linkable component with a cross-linking component of the curable coating composition to form a can mixture, wherein the cross-linkable component includes: (a) ethyl acetate having the formula Polyethylene polymer: * CH 2 -CH: CH: CH 'I-Ο

" CH CH 2—CH Ο I o = c CH:

-CH I OH CH2—CH> I 〇c == o I ch2 c = o I ch3 where (m) is in the range of about L5 mole% to about 85 mole%, and ⑷ is in the range of about 0 mole% to about The range of 20.5 mole% is 0, (p) is in the range of about 12 mole% to about 87 mole /%, and (q) is about 1 mole%. In the range of about 88 mole%, the sum of (m), (η), (p), and (q) is 100, and & and & are independently H, substituted or unsubstituted CjCi2 alkyl, substituted or unsubstituted C6 to (^ 4 aryl, substituted or unsubstituted & to aralkyl, substituted or unsubstituted (^ to 匚! 4 alkylaryl) , Substituted or unsubstituted. To a carbocyclic group or a combination thereof, the substituent is independently selected from 6 to (: 12 alkoxy, fluorenyl, carboxyl, carboxyl derivative, sulfonyl, sulfonyl Group consisting of derivatives, 9l637.doc 200426184 murine and halo; (b) ethyl acetylated polyethylene polymer having the formula cl—ό I n2

C——R CIOH2- /

CH2-CH I 〇 I CH〇

-CH I OH

CH, a CI 〇I CH, I 2 = 0 CH—CH- CH. Where (111) is within the range of about 1.5 mol% to 85 mol%, and ^ is about mol% to 20.5 mol In the range of (%), (p) is in the range of about 12 mol% to about 87 mol% < in the range of (q) is in the range of about 1 mol% to about 88 mol%, and In the range of mol. To 6 mol%, the total spear of (m), ⑷, (p), ⑷ and ⑻ is 100, and its center and 2 are independently H, substituted or unsubstituted Cl ^ Cn alkyl, substituted or unsubstituted (^ to (:: 14 aryl, substituted or unsubstituted C7 to CM aralkyl, substituted or unsubstituted (^ to (^ 4 Alkyl, substituted or unsubstituted carbocyclyl, or a combination thereof, and Z is fluorene or -COOH and γ is -C00H, _, unsubstituted phenyl, or a combination thereof, The substituent is independently selected from the group consisting of (: 1 to (: 12 alkoxy, fluorenyl, carboxyl-derived derivatives, sulfofluorenyl, sulfofluorenyl derivatives, cyano, and hydrazone); Or (c) a combination thereof; and wherein the cross-linking component includes polyamine, polyketimine, polyepoxide, poly Isocyanate, melamine, (^ to. ^ Alkanedialdehyde, alkyl poly (meth) acrylate, or a combination thereof; (Π) coating the tank mixture layer on the substrate; 91637 doc -10- (iii) Applying a main lacquer composition layer on the tank mixture layer; 涂覆 applying a varnish composition layer on the main lacquer composition layer to form a multilayer system on the substrate; and (V) subjecting the multilayer system to ring-coating It can be cured under elevated conditions or at an elevated curing temperature to form a multi-coating system on the substrate. The present invention further proposes _plug-in # methods for manufacturing an ethyl acetate polymer from a single step, which The method includes: (i) dissolution in one or more solvents: (a) a polyethylene polymer having the formula: ~ -η _ mmmm -π -CH2 — CH — CH2 — CH · —CH2 —CH, I- CH2-CH_ 1 0 1 OH CH〆1 1 o = c R, I-1 RL n _ _ m where (m) is in the range of about 1.5 mol% to about 85 mol%, (n) is in the range of about Mol% to about 20.5 mol%, and in the range of about 13 mol% to about 98.5 mol%, (m), (η), and (〇) Sum is 100, and Ri and R2 are independently Η, substituted or unsubstituted (: 1 to (: 12 alkyl, substituted or -unsubstituted (^ to 匚! 4aryl, via Substituted or unsubstituted c; 7 to c22 aralkyl, substituted or unsubstituted COscμ alkaryl, substituted or unsubstituted c4 to c! 4 carbocyclyl, or a combination thereof, the substituent is Independently selected from the group consisting of 匸 1 to C 12 alkoxy, donkey, junki, renyl derivatives, Xiangjiu group, continuity group derivatives, gas group and hydrazine group; (b) has Polyethylene polymer of the formula: 91637 doc -11-200426184 CIO 1 H2

c1R CIO H2- / cI〇1CIR I = H2-o αιοι-Η2

C—: I Η CI where (m) is in the range of about U mole% to about 85 mole%, and ⑻ is in the range of about 0 mole% to about 20.5 mole% '⑷ is about 13 moles Ear% to about M. # Within the guilty of ear% 'and (X) is in the range of about (^ mol% to about 6mol.), The sum of () ⑷ (0) and (X) is 1 〇〇, and wherein R1 and ^ are independently: substituted or unsubstituted CJC12 alkyl, substituted or unsubstituted [6-substituted 4-aryl, substituted or unsubstituted, substituted or unsubstituted Substituted (: 6 to 0:14 aryl, substituted or unsubstituted CjC " carbocyclyl, or a combination thereof, and Z is in the mouth, and rz is Η or -c〇H and Y Is -COOH, _ group, unsubstituted phenyl group, or potion Japanese-xju, u 4 combination, the substituent is independently selected from Cl to C12 alkoxy group, alkoxy group, recording group, appetite / residue A group consisting of a carboxyl derivative, a sulfofluorenyl group, a sulfofluorenyl group derivative, a cyano group, and a group; or (C) a combination thereof to form a solution; (Π) the solution and Ci to C 丨, Enthalpy, jealous 7 a 12 Shenyl ethyl fe acetate contact to produce the ethyl acetate [Embodiment] In this document: Π double-packed coating composition "refers to 1 ancient σσ sign-σσ /, a curable coating composition with two components stored in an early grainer. One boat The Jiang Ren version seals a container containing two components to increase the storage life of the coating composition components in Ruyang ^. The components are mixed immediately before use 91637 doc • 12- 426184

Si: The mixture has a limited shelf life, usually in a few minutes ... A thick layer needs to be coated on the surface of the substrate, such as a car body. Coating the silly layer at ί 温 or 冥, and four private cards and curing to form a coating sound with coating performance on the surface of the substrate. Μ 9 such as' improved adhesion and chip resistance. Low VOC coating composition refers to a coating composition 'per liter of coating composition containing a solvent in the range of 0.1 kg (1.0 crushed / additional life) to 0.72 kg (6 rides / gallon), preferably 0.3 kg (2 · 6 Yang Magic to G. 6 kg (5 lion / plus magic and better 0.34 kg (2.8 crushed / gallon) to 0.53 kg (44 crushed / gallon). All VOCs were determined using the procedure provided in ASTMD3960. "High solids composition " A coating composition having a solid component higher than 30% 'preferably in the range of 3 :) to 90% and more preferably in the range of 40 to 80%, both based on the total weight of the composition &Quot; GPC weight average molecular weight " refers to the weight average molecular weight determined by gel permeation chromatography, such as by Hewlett-Packard, Palo Alto, California High-performance liquid chromatography (HPLC) provided. Unless otherwise specified, tetrahydrofuran was used as the liquid phase, and polystyrene standards were used. "Tgn (glass transition temperature) was measured in C and measured by DSC (differential scanning calorimetry). ) Determination. "(Methenyl) acrylate" means C Acid esters and fluorenyl acrylates. "Polymer solid" or π composition solid "refers to a polymer or composition in a dry state. Π crosslinkable component" refers to a component that includes a compound, Position 91637 doc -13- 200426184 polymer or copolymer in the polymer main chain, hanging from the polymer main chain, at the end of the polymer main chain or a combination of functional groups. Ff cross-linking component "is a component, The component includes a compound, a polymer or copolymer having a functional group located on the polymer main chain, suspended from the polymer main chain, located at the end of the polymer main chain, or a combination thereof, wherein these groups are capable of interacting with a crosslinkable group The radicals are crosslinked (during curing) to produce a coating in the form of a crosslinked structure. Π Ambient curing conditions, defined as the presence of 12 in the spray area. (: To 45 ° C (55 ° F) Temperature range to 11 (TF) and humidity range from 15% to 90%. Ethyl acetylated polyethylene polymer is suitable for the production of the ethyl acetylated polyethylene polymer of the present invention. Formula ⑴ represents: • CH2-CH—CH2—CH. 0 \ / 0 Of /

CH2—CH I CH〇

• CH · I OH 2-(I) wherein (m) is in the range of about 1.5 mol% to about 85 mol%, preferably about mol% to about 68 mol%, and more preferably about 40 mol Mol% to about 64 mol%, (n) is in the range of about mol / mol to about 20.5 mol%, preferably about mol. Mol to about mol%, and more preferably From about 2 mole% to about 4 mole% and (0) in the range of about 13 mole% to about 98.5 mole%, preferably about 32 mole% to about 0 mole%. And the spoon is 55 mol%. All the foregoing mol percentages are calculated as the sum of (m), ⑷, and (.). It should be noted that the aforementioned groups ㈣, ⑺ 91637 doc • 14- 200426184 And (〇) -like randomly distributed on the polymer backbone. R々R2 is independently H, substituted or unsubstituted Ci to clz alkyl, substituted or unsubstituted (^ to CM aryl, Substituted or unsubstituted alkyl to aryl, substituted or unsubstituted alkyl to cM alkylaryl, substituted or unsubstituted C4 to c "carbocyclyl, or a combination thereof, the substituent Is independently selected from the group consisting of Cu to alkoxy, fluorenyl, carboxyl, and carboxyl Biology, sulfofluorenyl, sulfofluorenyl derivatives, cyano, and halo groups. Some of the foregoing examples for Ri include propyl, phenyl, and alkyl-substituted benzyl (preferably methylbenzyl) And xylyl). Some of the foregoing examples for h include fluorenyl, ethyl, propyl, butyl, and phenyl. Polyvinyl butyral with Ri as propyl and R2 as methyl is more preferred. Better polyethylene polymers with Ri as the propyl group and R2 as the methyl group are generally fine-grained free-flowing powders and are provided by a number of suppliers, such as from North Carolina, Charlotte, Clare恩 公司 （Clariant c〇rporation,

(Charlotte, North Carolina) is available under the trademark Mowital®. Some examples of 5 ^ acetalol suitable for benzemin include Mowital® B2OH [(m) in 49 to 55 mole%, (n) in 1 to 5 mole% and (〇) in 4 0 to 46 mole%], B30T [(m) at 41 to 46 mole%, (n) at 1 to 5 mole% and (0) at 49 to 55 mole%] and 63 0 (111) At 50 to 55 mole%, (11) at 1 to 5 mole% and (0); at 40 to 46 mole%]. Polyethylene polymers suitable for use in the present invention may include copolymers of vinyl acetate and one or more of the following comonomers. Monocarboxylic acids, such as acrylic acid, acrylic acid, crotonic acid, preferably acrylic acid, formic acid Acrylic acid; Ethylene unsaturated ^ -Wei ^ 'such as maleic acid, fumaric acid, itaconic acid, maleic acid is better than 91637 doc -15-2426426184; anhydride monomer, such as maleic anhydride; Monoglycidyl-containing monomers, such as glycidyl glycidyl ether, (fluorenyl) glycidyl acrylate, preferably 'glycidyl (meth) acrylate; halogen-containing monomers, such as vinyl chloride, Fluorinated ethylene, fluorinated ethylene, and bromoethylene, preferably gaseous ethylene; (^ to C η olefins, preferably ethylene and propylene; and scaly ester derivatives' are preferably vinyl acetate and ethylene diacetate The aforementioned polymers containing vinyl acetate and one or more of the aforementioned comonomers are conventionally prepared by hydrolyzing vinyl acetate groups in the polymer to vinyl alcohol groups followed by an acid catalyst (eg, phosphoric acid or hydrochloric acid) In the presence of one or more acids (e.g. A combination thereof) to produce a polyethylene polymer of the following formula (ii): Η / CIO-H2 c

Η2 C CHIR1 Γ

Η2 C ο CHIOICIR2

\ — / (II

Η2 C

CHIOH CH 丨 • Υ Ri R2, (m), ⑷ and (〇) are the same as those described in formula (I) above, and ^ in Z is Η or -COOH, and Y is -COOH, halo, unsubstituted Substituted phenyl or a combination thereof, and (X) is in a range of about 0.5 mole% to about 6 mole%, preferably 91637 doc -16-200426184 about 1 mole% to about 5 mole%, more Preferably, about 2 mol% to about 4 mol%, (the sum of (n), (n), (0), and (X) is 100. By adjusting the foregoing formula (I), (Π) or a combination thereof The ratio of (m) group, (η) group and warp group (0) group on the main chain of polyethylene polymer can control the physical and chemical properties of the obtained polyethylene polymer. The degree of polymerization can also affect the obtained polymer. Thermal and mechanical properties of ethylene polymers. Therefore, the properties of the coating can be appropriately adjusted, such as light resistance, toughness, elasticity, and water resistance of the obtained polyethylene polymer. However, when used as a wash primer composition Polyethylene polymer coatings tend to have less ideal adhesion or chip resistance to the substrate. Various attempts have been made to reduce the damage to polyvinyl butyral films caused by cracking. Improve paint adhesion. For example, polyvinyl butyral, such as phenolics, epoxys, melamine, isocyanate, or dialdehyde, is used with conventional cross-linking agents to improve paint performance, but The curing of these cross-linked systems is generally performed at high baking temperatures. Therefore, it is still necessary to use room temperature curable polyethylene polymers with comparable coating properties. The applicant of the present invention has unexpectedly discovered that by providing Acetyl acetate-based polyethylene polymer, the resulting ethyl acetate polymer not only has the required anti-fragmentation and adhesion properties, but also this modified polyethylene glycol 1 composition can be used in the environment. Under conventional conditions or at high curing temperatures, a variety of conventional cross-linking components are used for parental bonding. It is believed that the presence of acetoacetate in acetoacetated polyethylene polymers provides better coating strength obtained therefrom. (Anti-split) coatings' make the coating more stable in size and provide functional groups that chelate to the metal surface to maintain adhesion to the metal and generally reduce the permeability of the coating. These 91637 doc- 17- 200426184 It is hoped to obtain a chromate-free strip-type primer with improved properties and anti-corrosion properties. _ The ethoxylated polyethylene polymer of the present invention is substituted by about 10 mole% to about 90 mol% of the hydroxyethyl (0) group on the main chain of the polyethylene polymer of the formula VII with acetamyl acetate is generated, preferably replacing about 15 mol% to about 55 mol /%, More preferably, it is about 25 mol% to about 50 mol%. The acetofluorinated polyethylene polymer obtained in the present invention has the following formula (Hj) ·· n2 c Γ, H2 c Γ1

CH—O h2 c o H2Hcih. ”CHIOIC 丨 R5

CHlOH Π2 c

CH—OICICI—CICI ο π2 ο Η3 (III) where (p) is about 12 moles. / 0 to about 87 mol%, and% to about 45 mol%, and more preferably about mol% to about 35 mol%, and (= about 1 mol% to about 88 mol% 'Preferably about 5 mole% to about 30 mole%, and more preferably about H) mole% to about 30 moles β / "All the aforementioned mole percentages are in (m), (η), (ρ) The sum of hydrazone and fluorene is 100. Alternatively, the acetamidine acetylated polyethylene polymer of the present invention can also be polymerized from a polyethylene of formula IX having an acetamidine acetate group in the range of about 10 mol% to about 90 mol. The M-based ethylene (.) Group on the main chain of the product is generated, and it is preferable to replace about 15 mol% to about 55 mol%, more preferably about 25 mol% to about 5Q mol%. Acetylated polyethylene polymer has the formula: 91637 doc -18-200426184

ch2 * ~ ch-

CH-J I ch2

(IV) wherein all functional groups and mole percentages of the ethyl (acetylene) ethylated polyvinyl group of formula (IV) are those described in formulas (I), (11) and (III) above. It should be understood that a combination of acetoethylated polyethylene polymers of formulae (III) and (IV) may also be used. The GPC weight average molecular weight of the acetoacetated polyethylene polymer of formula (III) or (IV) is in the range of about 10,000 to about 300,000, preferably about 20,000 to about 200,000, more preferably about 30,000. To about 120,000. As determined by DSC, the Tg of the ethyl acetate polymer is in the range of about 0t to about 150t, preferably about 20 ° C to about 90 ° C, more preferably about 40 ° C to about 60 ° C. The acetoacetic acid polyethylene polymer of the present invention is obtained by contacting the polyethylene polymer of the above formula (I) or (II) with acetic acid C i to C i2 (preferably acetic acid second butyl acetate). So that the polyethylene polymer is about 10 mole% to about 90 moles. It is produced by the conversion of thiol to acetic acid. The aforementioned contacting step is preferably performed at a temperature ranging from about 75 ° C to about 135 ° C, and preferably about 80. 〇 to about 125 ° C, more preferably about 90 ° C to about 120 ° C. It should be understood that those skilled in the art can perform the above reactions at high or preferably atmospheric pressure. Depending on the reaction temperature, the reaction time can be in the range of 2 minutes to 15 hours. A suitable treatment is a solution treatment, in which the polyethylene polymer is first dissolved in a solvent such as butyl acetate, N-methyl. Each pyridone, methyl ethyl ketone, fluorenyl propyl ketone, methyl pentyl ketone, or a combination thereof, and then the polyethylene polymer solution is contacted with acetoacetic acid (: 1 to 012 alkyl esters. May 91637 ^ 00 -19- 200426184 The obtained acetoacetated polyethylene polymer is separated into a free-flowing powder or stored as a solution dissolved in the above-mentioned solvent. The acetoacetated polyethylene polymer of the present invention can be used to produce extruded and molded Products, moulded floors, heat shields, paint primers on metal substrates, used for anti-corrosive paints, printing inks, temporary adhesives and adhesives. Polymerization of ethyl acetate A clear, extruded film layer of a synthetic glass plate, such as those used in automotive windshields, to produce shatter-resistant glass. Curable coating compositions The present invention also provides a curable coating composition comprising crosslinkable and crosslinkable components These components can be packaged in a container (a single-package composition) in which the cross-linking group on the cross-linking agent in the cross-linking component is blocked to prevent premature cross-linking, or the components are packaged in two Individual containers (a dual-pack combination ). Crosslinkable components The crosslinkable components include the ethyl acetate polymer of the present invention dissolved in the solvent described earlier. The ethyl acetate polymer is also available in dry powder form. The amount of acetoacetate polyethylene polymer used in the present invention is generally in the range of about 3% by weight to about 100% by weight, preferably about "% by weight" to about 70% by weight, and more preferably about 40% by weight. % To about 45% by weight, all weight percentages are based on the total weight of the crosslinkable and crosslinkable component solids. Based on the total weight of the crosslinkable and crosslinkable component solids, the crosslinkable components can be further packaged 3 About 0.1 to 50% by weight of an acrylic polymer having a GPC weight average molecular weight of about 10,000 to 10,000. The molecular weight was determined by gel permeation chromatography using polymethyl methacrylate as a standard. Acrylic acid polymers are generally prepared from one or more monomers in the alpha group. For example, acrylic ester monomers include methyl acrylate, ethyl acrylate, and butyl acrylate. Purpose, 2-ethylhexyl malate, decyl propionate | , Methyl methyl acrylic acid purpose, ethyl methyl acrylic acid purpose, ethyl butyl acrylate, (methyl methacrylate) lauryl acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate , (Meth) acrylic acid oil ester, (meth) acrylic acid palmitate, (fluorenyl) acrylic acid stearate, hydroxyethyl (meth) acrylate, ethyl methacrylate Ethoxyethyl and hydroxypropyl (meth) acrylate; acrylamide or substituted acrylamide; styrene or ethylene substituted by alkylene; butadiene; ethylene; vinyl acetate; Vinyl esters of alkanecarboxylic acids ff (tertiary monocarboxylic acids with c9, C1 () and Ch chain lengths, this ethyl ester is also known as vinyl alkanoate) or other vinyl esters; vinyl monomers such as , Ethylene, vinylidene, vinylpyridine, N-vinyl σ bilo stilbone; amine-based monomers, for example, n, N, -difluorenylamino (meth) acrylate; Chloroprene and acrylonitrile or methacrylonitrile. Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl itaconic acid, monomethyl fumarate, monobutyl fumarate, maleic anhydride, 2-propylene Amino-2 -methyl-1-propanxanthinic acid, sodium vinyl lutein and phosphoric acid ethyl methyl acrylate. The acrylic polymer is preferably from about 20 to 30% by weight of methyl methacrylate, 20 to 30% by weight of isobornyl methacrylate, and 5 to 10% by weight. / 0 acrylic acid is polymerized by a monomer mixture of ethyl acetate, 25 to 40% by weight of ethyl acetoacetoxyethyl methacrylate, and 10 to 20% by weight of n-butyl acrylate. All weight percentages are based on monomer solids. Total weight. The acrylic polymer preferably has a weight average molecular weight of about 3,000 to 35,000. Acrylic acid polymers can be prepared by solution polymerization, in which a monomer mixture, a conventional solvent, 9! 637doc -21- 200426184 polymerization initiator (eg, 2,2M azobis (isobutyronitrile) or moon phase Lice acetate) is heated to 70 ° C to 175 ° C for about 1 to 12 hours. ~ Based on the total weight of the crosslinkable and crosslinkable component solids, the crosslinkable components of the coating composition of the present invention may also contain 0.01% by weight 5 θ to ri /. To 40 weight 0 /. Polyester polymer, the polyester polymer is an aliphatic or aromatic dicarboxylic acid, a polyol having at least three reactive radicals, a diol, an aromatic or cycloaliphatic group, and an ester group: product. One preferred polyester is an esterification product of adipic acid, trimethylolpropane, hexanediol, hexahydrophthalic anhydride, and cyclohexanediethanol. Based on the total weight of the cross-linkable and cross-linkable components, the cross-linkable components can be optionally included in the range of (Mw. 50 to 50% by weight of modified resins, such as known non-aqueous dispersion (NAD) All the ratios of white and white are based on the total weight of the solids of the composition. Non-aqueous dispersion type polymer # 兹 物 系 猎 In polymer dispersion stabilizer and organic solvent It is prepared by dispersing and polymerizing at least one σ ^ ^ vinyl preform in the presence of a polymer. The polymer dispersion stabilizer may be any known stabilizer commonly used in the field of non-aqueous Fenzaki PN κ knife. ~ Π 本 发 = 可可The cross-linking component can also be blended with reactive oligomers and non-alicyclic (linear or aromatic) fund-raising polymers as required in US Patent No. 6,221,494. This patent is incorporated by reference This article is incorporated. These non-alicyclic k can be made from non-monthly anhydrides, such as succinic acid or acetic anhydride or mixed characters. The vinegar compounds described in Patent No. 5,286,782 can also be used. 5 丨 How to use-"Cross-linking component curable coating composition, and the knife includes Crosslinking component in the range of 10 wt% / 60 to 60 wt% 91637 doc -22 «200426184, preferably in the range of 15 wt% to 55 wt%, most preferably in the range of 20 wt% to 40 wt% All weight percentages are based on the total weight of the crosslinkable and crosslinkable component solids. Crosslinking components include polyamines, polyketimines, polyepoxides, polyisocyanates, melamine, CjC! 2 Dialdehyde, CjC! 2 alkyl poly (meth) acrylate or a combination thereof. Polyamine, polyketimine or a combination thereof is preferred, and polyketimine is the best. As a combination of polyamine and polyketimine When used, the weight ratio of polyamine to polyimide is in the range of 1 ·· 100 to 1 1, preferably in the range of 1 to 50: 1, and more preferably in the range of 1:20 to 20: 1 The activation ratio is about 0.77 moles to about 4.0 moles per mol of the cross-linking group in the crosslinking component. Within the range, preferably from about 1 mole to 3 moles. Polyamines have a weight average molecular weight of at least 100 as determined by gel permeation chromatography using polymethylmethacrylate standards. Gpc weight average molecular weight is in the range of about 100 to about 100,000, preferably in the range of about 2000 to about 50,000 'and more preferably in the range of about 300 to about 10,000. Polyamines have an average of at least two primary amine functional groups per molecule. Polyamines preferably have parent polyamine molecules having an average of about 2 to about 25 primary amine functional groups, more preferably in the range of about 2 to about 6, and have 2 to 200, preferably 6 to 100 and more preferably 8 to carbon atoms. These amine functional groups can exist as pendant functional groups or functional groups located in the polymer backbone. Pendant amine functional groups are more Examples of representative polyamines suitable for use in the present invention include aliphatic or cycloaliphatic amines or combinations thereof. Preferably, an aliphatic polyamine is used. Examples of suitable polyamines include ethylenediamine, propylenediamine, butylenediamine, pentamethylene 91637 doc -23-200426184

Diamine, hexamethylenediamine, decamethylenediamine, 4,7-dioxadecane-1,10-diamine, dodecamethylenediamine, 4,9-dioxane Dodecane-1,12-diamine, 7-methyl-4,10-dioxatridecane-1,13-diamine, 1,2-diaminocyclohexane, 1,4-diamine Amino group% Hexane, 4,4'-diaminodi badhexylpyrene, isophoronediamine, bis (3-methyl-4-aminocyclohexyl) pinene, 2,2'- Bis (4-aminocyclohexyl) propane, nitrile tris (ethylamine), bis (3-aminopropyl) fluorenamine, 3-amino-1- (fluorenamino) propane, 3-amino-1 -(Cyclohexylamino) propane and N- (2-Ethyl) ethylenediamine. Ethylenediamine, propylenediamine, butanediamine and 1,2-diaminocyclohexane are preferred. Other suitable polyamines include those of the formula: H2N- (R2) n-NH- (Rdn-NHs, where the Ri and R2 groups can be the same or different and represent two to six and preferably two to four carbon atoms The alkylene group, η is independently selected from a number in the range of 1 to 6, preferably in the range of 1 to 3. The alkylene group is a cycloalkylene group or an alkylene group containing an ether oxygen atom. Examples of representative polyamines include diethylenetriamine, dipropylenetriamine, and dibutyltriamine. These polyamines should preferably be alicyclic and contain 5 to 15 carbon atoms, such as isophorone diamine Amines, more particularly alkyl groups, such as bis (3-methyl_4-aminocyclohexyl) methyl and bis (3-methyl_4-aminocyclohexyl) propane. 'Contains at least two rings Some suitable polyepoxides include those in the molecule, ie,

91637 doc _24- 200426184 where η is at least 2, Rl is hydrogen or ^, and & broadly represents _ general organic-based molecules consisting of carbon, lice, oxygen and selective nitrogen, sulfur, or both polymer. There may also be hydroxy substituents and southern and ether groups. The epoxide equivalent is generally in the range of about 100 to 1500, preferably about 100 to about 12,000, and more preferably about 150 to about 600. These polyepoxides can be broadly classified as aliphatic, aromatic, cyclic, acyclic, alicyclic or heterocyclic epoxides. Another group of polyepoxides used in the present invention includes epoxy phenolic resins. These resins are prepared by reacting an epihalohydrin with a condensation product of an aldehyde and a mono- or polyhydric phenol. An example is the reaction product of epigasol and phenol formaldehyde condensate. Another particularly preferred group of polyepoxides is the polyglycidyl mystery of polyaromatic hydroxy compounds (e.g., dibasic compounds). It must be at least divalent, for example, resorcinol, catechol, hydroquinone, bis ('hydroxyphenylbenzene, isobutane; 4,4-dihydroxybenzophenone; bis ( 'Hydroxyphenyl group, ^ isobutane; 4, kernel dihydroxybenzophenone; bis (4-hydroxyphenyl benzene, ^ ethane; bis (2-hydroxynaphthyl) methane; 1,5- Kenai and 4,4'-isopropylidenediphenol, that is, bisphosphonium a. Bisphenol A is preferred. Among many possible polyepoxides, although epibromohydrin is also useful, it is the main user Is epichlorohydrin. The polyglycidyl ether especially used in the present invention is obtained by reacting epichlorohydrin and bisphenol A in the presence of a base such as sodium hydroxide or potassium hydroxide. From SheU Chemical Co., Ltd. mpany) series of epoxy resins sold under the trademark EPON is particularly useful. Another group of useful polyepoxides are polyglycidyl ethers derived from the reaction of epi-alcohols (preferably epigas alcohols) with polyols, such as ethyl alcohol Diethylene glycol, diethylene glycol, triethylene glycol; 1,2-propylene glycol; 丨, butanediol; 丨,% pentanediol; 丨, hexanetriol; glycerol and trimethylolpropane 91637 doc -25- 200426184 Polyepoxides which are polyglycidyl ethers of polycarboxylic acid are also useful. These compounds are based on the use of epoxy compounds (such as epichlorohydrin) with aliphatic or Aromatic polycarboxylic acids are prepared by reacting with "仏", such as tartaric acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and dimerized linoleic acid. Another group of polyepoxides is derived from the epoxidation of olefinic unsaturated alicyclic materials. The epoxy alicyclic esters and esters are well known in the art. It should be understood that polyepoxides can also be used. Mixture. The preferred epoxy equivalent of the polyepoxide is in the range of 87 to 6000, and more particularly in the range of 120 to 1000. Suitable polyepoxides may include oxygen-containing alkylene groups, that is, tr -0 — ^ * CH2

R wherein R is hydrogen or (6 to 6 alkyl groups, m is an integer in the range of 丨 to 4, and n is an integer in the range of 2 to 50. The proportion of the oxygen-extracted group in the polyepoxide depends on various factors , Where the size of the aerobic elongation group and the nature of the polyepoxide. Examples of suitable polyisocyanate S purposes include aliphatic, cycloaliphatic, or aromatic di-, tri-, or di-ethyl unsaturated. Or tetraisocyanate, such as propylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 2,3-butanediisocyanate, hexamethylene diisocyanate, Human methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylene hexamethylene diisocyanate 3 purposes, ten Dimethylene diisocyanate § Purpose, dipropyl bond diisocyanate, i, 3-cyclopentane diisocyanate, i, cyclohexane diisocyanate, 1,4-cyclohexyl Alkane diisocyanate, isophorone diisocyanate, " yl], 3-diisocyanatocyclohexane, trans-vinylidene diisocyanate, dicyclohexane 9l637doc -26- 200426184 methane-4 , 4, -diisocyanate, 3,3, dimethyl_dicyclohexyl Methane · 4,4, _ diisocyanate, toluene diisocyanate, 丨,% bis (1-isocyanate-: 1-methylethyl) benzene, 1,4-bis (1-isocyanate_i _Methylethyl) benzene, 13-bis (isocyanatomethyl) benzene, xylene diisocyanate, i, 5_dimethyl_2,4_bis (isocyanatomethyl) benzyl, 1,5-dimethyl-2,4-bis (2-isocyanatoethyl) benzene, 13,% dimethyl-2,4-bis (isocyanatomethyl) benzene, 4,4 __Diisocyanatobiphenyl, 3,3-monogas_4,4 · monoisohelic acid biphenyl, 3,3, dibenzyl_4,4'_diisocyanatobiphenyl Benzene, 3,3f-dimethoxy-4,4, -diisocyanatobiphenyl, 4,4, _diisocyanatodiphenylmethane, 3,3, -dimethyl_4 , 4, -Diisocyanato diphenyl methane, monoisocyanato naphthalene, polyisocyanate with isocyanurate structural units & L 酉, 2 mol diisocyanate (such as hexamethylene Adduct of dimethyl diisocyanate or isophorone diisocyanate) and a diol (eg, ethylene glycol), an adduct of 3 mol hexamethylene monoisocyanate and 1 mol of water (from Pittsburgh, PA, PA Corporation (obtained under the trademark Desmodur (R) N), an adduct of 1 mole trimethylolpropane and 3 mole toluene diisocyanate (known from Bell Corporation under the trademark Desrnodur® L ), 1 mole of trimethylol and 3 mole of isophorol_diisocyanate adduct, compounds 1,3,5-triisocyanobenzene and 2,4,6-triisocyanate Toluene, and adducts of 1 mole of tetra-pentaerythritol and 4 mole of toluene diisocyanate. Suitable melamine for use in the present invention include monomeric or polymerizable melamine-formaldehyde resin (melamine) or a combination thereof. The coating composition may be included at about 0.1 to 40% by weight. The melamine is preferably in the range of 15% to 35% by weight, and most preferably in the range of 20% to 30% by weight. The percentage is the weight percentage based on the total solid weight of the composition. Monomeric trimer 91637 doc -27- 200426184 amines include low molecular weight melamine, which on average contains three or more Ci-C5-alcohols (eg, methanol, n-butanol, or isobutanol) per triazine core ) Etherified methyl group has an average degree of condensation of up to about 2 and preferably about 1.1 to about 1 · g, and has a weight of not less than about 50 weight. /. Of single-core types. In contrast, polymerizable melamine has an average degree of condensation greater than 1-9. Some suitable monomeric melamines include alkylated melamines such as methylated, butylated, isobutylated melamine, and mixtures thereof. Much can be said about these suitable monomeric melamines. For example, Cymel Industries (Cytec Industries Inc., West Patterson, New Jersey), Cymel® 301 (degree of polymerization, 5, 95% methyl and 5% methylol), Cymel® 3 50 (1.6 degree of polymerization, 84% methyl and 160 / 〇 via methyl), 3 03, 3 25, 327 and 3 70, all of which are monomeric melamine. Suitable polymerizable melamines include high amine (partially alkylated, -N, -η) melamine 'known as Resimene® BMP5503 (molecular weight 690, polydispersity 1.98, 56% butyl, 44% amine), Provided by Solutia Inc., St. Louis, Missouri, or St. Louis, Missouri; or Cyme ⑧ 11 58, provided by Setex Industries, New Jersey, West Paterson. Sytec Industries also offers Cymel⑧1130 @ 80% solids (degree of polymerization 2.5) and € 711 ^ 101133 (48% methyl, 40 / 〇hydroxymethyl and 48% butyl), both of which are polymerizable melamine. Some suitable cross-linking components include urea polymers, such as fluorenated urea polymers

Resimene (g) 980 and butylated urea urea formaldehyde U-6329, supplied by Thuroussee, Missouri. Some suitable Ci to (2-dioxo diacids include glutaric acid, ethylene glycol and ι, 3,5-tri 91637 doc -28- 200426184 gas ring heterocyclic sintered. Some applicable <^ to (: 12 alkyl poly (Meth) acrylates include ethylene di (meth) acrylate, tris (hydroxy) propane tri (meth) acrylate. Metal ion salts can also be used to pass through the ester groups and acetate groups. The chelation between the dilute alcohol forms and the cross-linking of the ethyl alcohol and the polyethylene polymer. The chelation can improve the adhesion of the ethyl acetate polymer to the porous substrate. The metal ion compounds can be free of Cu, Co, Fe, Mn, Sn, V, Mg, Ba, Ab, Ca, Sr, Nb, γ, ~ and combinations thereof. Examples include copper acetate, calcium acetate, acetate or other aliphatic or aromatic compounds. Other suitable polyamines include primary or secondary polyamines (eg, ethylenediamine and phorone diamine) and the aforementioned polyfunctional epoxy materials, polyisocyanate, melamine, or The combined reaction product is suitable for the present invention. The polyfluorene is obtained by blocking the amine group on the polyamine with a blocking agent. A ketone having no more than 18 carbon atoms, preferably 3 carbon atoms. A ketone of the coating composition of the present invention has a weight average molecular weight in the range of 100 to 100,000. The polyamine is preferably represented by the following formula: Ketone Blocking: 〇R—C—-R · where R and R are alkyl groups having 丨 and 12. Aliphatic or cycloaliphatic or cycloaliphatic_ is more preferred., Preferably 1 to 8 Anti-atomic independent selection of ketones is preferred, aliphatic amines having 3 to 1 stone anti-atoms 9l637.doc -29- 200426184 Polyamines suitable for use in the coating composition of the present invention include--I. Bis (4-hydroxybenzyl) -2,2-propane-based adducts of diglycidyl squamylamine; II. Adducts of amines and dimethyl maleate; III. Having at least two acrylate groups per molecule and having Adducts of amines prepared from polyacrylates with a molecular weight of about 1,000 to 50,000; adducts of 1v · amine and polyisocyanate, or combinations of V. Suitable blocking agents for amine groups Examples include acetone, diethyl ketone, methyl isobutyl ketone, isobutyraldehyde, hydroxybutyraldehyde, pentanone, cyclohexanone, ethylpentyl ketone, hydroxy Citronellal, isophorone, and decanone. Depending on the type of cross-linking component selected, various catalysts can be used. For example, when using polyisocyanates, tin compounds (including dibutyltin dilaurate and diacetic acid can be used). Dibutyltin) and tertiary amines (such as triethylenediamine). These catalysts can be used alone or in combination with carboxylic acids, such as acetic acid. When melamine is used as the cross-linking component, one or more of the following catalysts can be used: Promote cross-linking of components during curing. Coating compositions generally include catalysts in the range of from 0 to 5 wt%, preferably in the range of from 0 to 2 wt%, more preferably to 0.5 wt% . /. In the range from 2 to 2% by weight and preferably in the range from 0.5 to 1.2% by weight / 0, the percentages are all weight percentages based on the total weight of the solids of the composition. Some suitable catalysts include conventional acid catalysts such as aromatic continuous acids such as undecylbenzenesulfonic acid, p-toluenesulfonic acid and dinonylnaphthalene

2-Methrenyl- 2-f-yl-1-propanol, 叩 Α is blocked with makeup such as dimethyloxazolidine and N, N-di-T-ethanolamine or a combination thereof. Available 91637 doc -30- 200426184 7 Other acid catalysts are strong acids, such as phosphoric acid, more specifically phenyl phosphate. The acid can be unblocked or blocked with an amine.

When a polyamine or a polyketimine is used for the crosslinking component, one or more of the following catalysts may be used to promote the crosslinking of the component upon curing. It is generally used at about 5% by weight to 5%. Dry catalysts, preferably in the range of 0.0% to 2% by weight, more preferably in the range of 0.01% to 丨% by weight, all based on the total weight of the solids that can be crosslinked and crosslinked. Weight percent. Also suitable catalysts include water and retarded acids such as acetic acid, benzene acid and salicylic acid.

If desired, the coating composition may include four in the range of 2% to 10% by weight = zinc lactate, preferably in the range of 3% to 8% by weight, and more preferably in the range of MW / 0 to 6% by weight. Within the range of%, all weights are based on the weight of the coating composition. Zinc tetraoxochromate can be included in the crosslinkable or another example of the coating composition, and is preferably included in the crosslinkable component. Tetrachromic acid provided under the trademark j-iw basic chromic acid phrase can be used in the present invention by Shimu Chemical Company, Bezville, Maryland (-M Chejmcals, Beltsv, e). The coating composition may include an acid in the range of 6% by weight to 6% by weight, preferably in the range of 0.5% by weight to 4% by weight and more preferably in the range of 5% by weight: to 3% by weight. All weight percentages are Weight percentage based on the weight of the coating composition. When used in a two-pack coating composition, linoleic acid: hold: the crosslinkable component and the crosslinkable component are separated, and immediately before use with the crosslinkable and crosslinkable group It can be used in this invention. Phosphoric acid provided by Rhodes, Cranbury, New Jersey under the trademark NF 85% phosphoric acid can be used in this invention. 91637 doc -31-200426184 5 substances can also contain conventional additives, such as pigments, release- !, rheology control agents, flow agents, toughening agents and additives that obviously depend on the coating composition ... Can be cross-linked or cross-linked by adding coating additives depending on coating composition / use Components or both. 3 ± :: When the coating composition is packaged as a double-packed coating composition, the parental and crosslinkable components of the two ingredients A η ^ are mixed into a jar immediately before use: two The mixture has a limited shelf life, which is generally applied to the substrate by conventional techniques, such as electrostatic spraying, light coating, dip coating or brush coating. The tank mixture is then applied at The curing conditions are in the range of 10 minutes to 4 hours, preferably in the range of 30 minutes to: in the range of 'minutes' to form a coating with the required coating properties on the substrate ^ should be understood that the actual curing time depends on the The thickness of the applied layer, the type of application used, and the type of drying device, such as a fan that promotes the continuous flow of air on the earthen material to increase the drying rate. Generally, it is applied on a metal substrate (such as a car body) In the range of 6 micrometers to 25 micrometers thick Hou Lu washing strip type primer layer in the absence of any suitable drying device in ambient conditions ^ W minutes to cure 'with 25 micron applied on a metal substrate (such as automobile body) ^ Primer layers in thicknesses up to 300 microns in the environment It can be cured within 2 hours to 4 hours without any suitable drying device. If necessary, baking the coated substrate at a temperature of about 60t for about 30 minutes can further speed up the curing rate. The foregoing baking step is performed at 0 EM. (Original Equipment Manufacture) is particularly useful. When packaging a coating composition as a single package composition, the coating composition layer is applied in a manner similar to that described earlier. However, due to the cross-linking in the cross-linking component 01637 doc • 32- 200426184 The soil mass is closed, so that the layer is subjected to baking and curing temperature to turn on the base x, so that the daggers can interact with the crosslinkable groups present in the crosslinkable component. ", L The step is generally carried out at a flooding temperature in the range of 60 ° C to 20 ° C, preferably 80 ° C to 160 ° C, for about 10 to 60 minutes. It is also encompassed by the present invention that the parental and crosslinkable components are mixed together and manufactured in the form of a conventional free-flowing powder. It is preferred to block the cross-linking, cross-linking group in the component to prevent premature cross-linking with the cross-linkable group in the cross-linkable component. The aforementioned coating composition in powder form is conventionally applied to a substrate through a fluidized bed. Alternatively, an aqueous slurry of a powder may be used, and then the aqueous slurry may be applied to a substrate. The applied powder layer may then be subjected to a bake cure temperature to turn on the shame groups &apos; so that they can crosslink with the crosslinkable groups present in the crosslinkable component and form a coating on the substrate. The present invention also proposes a method for manufacturing a multi-coating system (preferably a multi-coat automotive OEM (original equipment manufacturing) or refinishing) comprising the coating composition of the present invention as a wash-type primer. In this method, a layer of the composition of the present invention is applied to a bare metal substrate to produce a strip-type primer coating by using the steps described earlier. A coating of a conventional primary lacquer composition, which can be colored, is applied after the wash-type primer coating, followed by a conventional varnish composition coating. If necessary, an additional coating of the conventional primer coating composition can be applied to the wash-type primer coating, followed by the main paint composition layer. It should be noted that the applicant has unexpectedly discovered that a lower molecular weight ethylene polymer can be used to brew polyethylene polymers, typically in the range of 10,000 to 50,000, as it can be incorporated into B Acetate functional groups and polymer cross-linking improve performance. Therefore, the solubility of acetoacetate polyethylene polymer is improved, and the viscosity is reduced, 91637 doc -33-200426184 and therefore the voc (volatile organic compound) of the coating composition is reduced to produce a low VOC coating composition, and Does not adversely affect easy coating. The coating composition of the invention is also suitable for industrial coatings, such as coil coatings, adhesives and sealants. The coating composition of the present invention can be suitably applied to: woven or non-woven cellulosic or non-cellulosic fabrics; leather or non-leather goods, such as shoes, leatherettes, sandals, travel shoes, gloves, hats and interior decoration; various Sports and sports-related shoes, such as travel shoes, running shoes, wheel knives; Footwear, sports and recreational equipment, such as golf clubs, balls, tees, snow samples, jet skis, water bikes, snow sports Motor vehicles, ice skating, hockey rink surfaces, hockey discs and hockey sticks, bowling lanes, bowling pins and balls, imitation fruits and dried flowers; fiber optic materials; packaging materials such as bottles, beverage boxes, food bags and boxes; nails And counterfeit fingers; safety glass, shatter-resistant glass and spectacle glass; antiplasticizer migration coating on the surface of vinyl materials; appliances, including lawn appliances; roofs and roof monuments; fabrics and soft-touch wall coverings; toys , Such as Nerf® balls; light appliances and bulbs; communication equipment, such as telephones, pagers and fax machines; credit cards; luggage and accessories; touch screen TV tubes, cathodes Tubes and radar screens, LCD and flat panel displays; Mirrors' non-slip floors; sound-absorbing soundproof walls, ceilings and seats, acoustic equipment, marine surfaces such as hulls, buoys, breakwaters, ship decks, canvases, office equipment such as Computers, photocopiers, computer printers; musical instruments such as pianos, guitars, organs; costume jewelry; and shiny metal surfaces. Due to its durable nature, coatings from the composition of the present invention can be used as durable long-life traffic signs on road surfaces, including reflective road signs. 9l637doc -34- 200426184 Examples Use the following inspection steps to generate the data reported in the examples below. Persoz hardness film hardness was tested with a type 5854 (ASTM D4366) corundum hardness tester provided by Byk-Mallinckrodt, Wallingford, Connecticut. . The number of vibrations is recorded over time, also known as the Poisson number or the Poisson hardness. Fischer hardness The hardness is measured with a Fischerscope® hardness tester (measured as Newton / mm2). Molecular Weight The molecular weight of the acrylic polymer was determined by size exclusion chromatography on a Hewlett Packard 1090 high performance liquid chromatography with a 1 047A RI detector. The molecular weight was measured using a Microstyragel column from Waters Inc., using tetrahydrofuran as a mobile phase, and a polystyrene standard of known molecular weight was used. The nonvolatile matter content of the solid detection polymer solution was measured by removing the solvent from the polymer sample in a 11 ° C down-flow air supply tank. A known amount of the polymer solution was mixed with tricresylscale and acetone, and Put it in a white air supply tank maintained at 1 〇 〇 for 1 hour, and calculate the solid weight using the weight of the residue 〇 / 〇. 13c NMR (determining mole percentage) Acetyl ethyl acetate polyethylene polymer sample The mole percentage of acetamidine acetate on the surface was determined by a Bruker 91637.doc -35- 200426184 (Bruker) DRX-400 NMR spectrum equipped with a 10 mm wide band detector. The samples were gathered forever. 5 (rc dried under vacuum, dissolved in deuterium-added formaldehyde at about 5 to 10% by weight. It is known that a 30-second relaxation delay and a 90 flip pulse were passed through the spectrometer at about 34 ° C to find the transport test. In order to ensure a fixed ratio, the Mohs ratio of vinyl alcohol substituted with acetate acetate groups can be assured. 77 The ratio of the fluorene atoms in the butyl condensed ring of acetamidine acetate to oxygen atoms and the Moore test of vinyl alcohol against Ding Shujun in polymer backbone known from literature The dry, wet, and resuming adhesive effect. For dry adhesion, orthogonal and grid shadows are generated on the board, tape is attached and removed. Then the board is given two ratings. The first rating is based on the removal The amount of coating is based on a visible grade of 0 to 10, 0 is complete failure and 10 is removed without coating. The second grade is rated as the point where the failure occurred as described above. Then placed to maintain compliance with ASTM D-173 5 -02 humidity cabinet for 4 days. Remove the plate from the humidity cabinet and test for wet adhesion within 1 hour. Then store the plate at 25 ° C and 50% relative humidity for 24 hours, and then re-examine to detect recovery of adhesion Example 1 To a glass reactor equipped with a stirrer, condenser, and steamer head, 200 parts of Mowital® B20H (GPC weight average molecular weight about 35,000 to 45,000) provided by Clarion Corporation under a nitrogen atmosphere were introduced. Polyvinyl butyral was added with 606 parts of N-methylpyrrolidone. The solution was heated to 190 ° C to remove any low-boiling solvents. The solution was then cooled to between 140 ° C and 145 ° C. 68.2 parts of tert-butyl acetoacetate were added in minutes. This batch is held at this temperature 91637 doc -36- 200426184 for 30 minutes, and then heated to about 195 t: to remove the third butanol by-product to produce acetamidine ethylated polyvinyl butyral of the above formula (III) Where (p) is 32 and (q) is 11. The polymer was separated by immersion in cold water (0473 liters (1 pint) water versus 150 grams of polymer solution), filtered and dried under vacuum at 451. Examples 2 To a glass reactor equipped with a stirrer, condenser, distillation head and under a nitrogen atmosphere, 300 parts were supplied by Solutia Inc., Springfield, Massachusetts, under a nitrogen atmosphere. Butvar® B90 (GPC weight average molecular weight approximately 90,000) polyvinyl butyral was added with 2000 parts of N-methylpyrrolidone. The solution was heated to 19 ° (: to remove any low boiling solvents. The solution was cooled to 14 ° C and 145 ° C and 102.3 parts of ethyl tertiary acetic acid was added over a few minutes. This temperature is maintained for 30 minutes, and then heated to about 195 ° C to remove the third butanol by-product to produce the ethyl alcohol ethylated polyvinyl butyrin of formula (III) above, where (?) Is 35 And (q) is 8. The polymer was separated from the cold water by sinking (.473 liters (1 pint) water to 150 grams of polymer solution), filtered and dried under vacuum at 45 ° C. Example 3 Glass reactor with stirrer, condenser, distillation head and 300 parts of Mowital® B30T (GPC weight average molecular weight about 55,000) polyvinyl butyrate supplied by Clarion Company under nitrogen atmosphere was added to 909 Parts of N-fluorenylpyrrolidone. The solution was heated to between 13 ° C and 135 ° C, and 137.3 parts of tert-butylacetamidine acetate were added over a few minutes. The batch was held at this temperature for 3 hours, and then Cool to produce acetoacetylated polyvinyl butyral of formula (III) above, where (P) is 39 and (q) g 12. The polymer is Sink into cold water 91637 doc -37- 200426184 off (0.473 liters (1 pint) of water to 150 grams of polymer solution), filter, wash with cold water 'filter and dry under vacuum first at room temperature for i days, then at 45 it It was dried on the second day, and then on the third day at 80 ° C. Example 4 A glass reactor equipped with a stirrer, condenser, distillation head and nitrogen atmosphere was supplied with 250 parts by Clarion Mowital® B3 0H (GPC weight average molecular weight about 60,000) polyvinyl butyral was added to 1667 parts of N-methyl ° ratio σ each bite ketone. The solution was heated to 90.0 to remove any low boiling solvents. The solution was then cooled to 14 °. (: To 145 t, and 85.3 parts of tert-butyl acetoacetate were added over several minutes. The batch was kept at this temperature for 30 minutes, and then heated to about 195 ° C, To remove the third butanol by-product, and then cooled to produce the acetoacetated polyvinyl butyrate of the above formula (III), where (p) is 37 ′ and (q) is 6. Sink into cold water to separate (0473 liters (1 pint) water to 150 grams of polymer solution), filter, and wash with cold water , Filtered and dried at room temperature overnight 'and then dried under vacuum at 60 ° C. for about 7 hours. To a glass reactor equipped with a stirrer, condenser, distillation head and 50 parts from Michigan under a nitrogen atmosphere, Adrian, Wacker Polymer System 'Adrian, Michigan

Pioloform LL145 (GPC weight average molecular weight about 95,000 to 100,000) Polyvinyl butyral was added with 333 parts of N-methylpyrrolidone. The solution was heated to 19 ° C to remove any low-boiling solvents. The solution was then cooled to between 140 ° and 1 45 ° C, and 7.1 parts of butylacetic acid tert-butyl acetate was added over several minutes. The batch was held at this temperature for 30 minutes, and then heated to about 195. (: to remove the 9l637doc -38- 200426184 dibutanol by-product, and then cooled to produce the ethyl acetate polymer of the above formula (πι) Vinyl butyral, where (P) is 33 and (q) is 10. The polymer was separated from the cold water by sinking (0.473 liters (1 pint) water versus 50 grams of polymer solution), filtered, and filtered with Wash with cold water, filter and dry at room temperature overnight, then dry at 6 ° C under vacuum for about 7 hours. Example 6 To a glass reactor equipped with a stirrer, condenser, distillation head and 50 parts under a nitrogen atmosphere Mowital® B60H (GPC weight average molecular weight approximately 95,000) polyvinyl butyral provided by Clarion Corporation was added to 300 parts of methylpyrrolidone. The solution was heated to 190 ° C to remove any low boiling solvents The solution was then cooled to between 140 ° C and 145 ° C, and 17 · 1 parts of acetamidine was added over a few minutes. Tertiary butyl acid. The batch is held at this temperature for 30 minutes, and then heated to about 195 ° C to remove the tertiary butanol by-product and then cooled to produce the ethyl acetate of the above formula (III). Polyvinyl butyric acid, where (p) is 35 'and (q) is 7. The polymer is separated from the cold water by sinking (0.473 liters (1 pint) water to 150 grams of polymer solution), filtered, and cold water Wash, filter, and dry overnight at room temperature, then dry under vacuum at 60 ° C for about 7 hours. Example 7 A glass reactor equipped with a stirrer, condenser, distillation head and 1500 parts by watt under a nitrogen atmosphere Gram of polymer system piiofom (D LL4150 (GPC weight average molecular weight about 35,000) polyvinyl butyral was added to 1,500 parts of methyl propyl ketone. The solution was heated to 75, and 202 minutes of tert-butyl acetoacetate was added in minutes. The batch was kept at 75 for 3 hours, and then heated to about 100 ° C over about 2.5 hours to remove the third butanol by-product. 9l637 doc -39- 200426184 Then This batch is allowed to cool to produce acetoacetylated polyvinyl butyral of the above formula (πι), where (ρ ) Is 26 and ⑷ is 10. Example 8 To a glass reactor equipped with a stirrer, condenser, distillation head and under a nitrogen atmosphere, 1000 parts of Pio 丨 form® LL4150 (available from WACKER POLYMERS SYSTEMS) GPC weight average molecular weight is about 35,000) Polyvinyl butyral is added to 1000 propyl methyl propyl. The solution is heated to 75.0, and 377 parts of tert-butyl acetoacetate are added over a few minutes. The batch was held at 75 for 3 hours and then heated to about 1000 ° C over about 2.5 hours to remove the third butanol by-product. This batch was then allowed to cool to produce the acetoacetylated polyvinyl butyral of the above formula (III), where (P) was 8 and (q) was 28. Example 9 To a glass reactor equipped with a stirrer, a condenser, and a distillation head, and under a nitrogen atmosphere, 500 parts of pioioflon LL4150 (GPC weight average molecular weight about 35 (00)) Polyvinyl butyral was added to 6 11 parts of fluorenyl ethyl ketone. The solution was heated to 75. 〇, and 80.8 parts of tert-butyl acetoacetate were added over several minutes. This batch was kept at 75t for 3 hours and then cooled to produce acetamidine ethylated polyvinyl butyral of the above formula (III), where (P) was 28 and (q) was 8. Separate the polymer from the cold water into a pint of water) water to 150 grams of polymer solution), filter, wash with cold water, filter and dry under vacuum at room temperature for about 7 hours, then dry under vacuum at about 55 for about 7 hour. Example 10 To a sloped glass reactor equipped with a stirrer, condenser, and distillation head and under a nitrogen atmosphere of 91637 doc -40-200426184, 500 parts of pi〇f〇rm (g ) LL4150 (GPC weight average molecular weight about 35,000) polyvinyl butyral was added with 611 parts of N-methylpyrrolidone. The solution was heated to 13 {rc, and 255.9 parts of tert-butyl acetoacetate were added over several minutes. This batch was held at U (rc for 3 hours' and then cooled to produce acetoacetylated polyvinyl butyrate of formula (III) above where (p) was 9 and (q) was 27. Polymerization The material was separated by sinking into cold water (0.473 liters (1 pint) water to 150 grams of polymer solution), filtered, washed with cold water, filtered, and dried under vacuum at room temperature for about 7 hours, and then under vacuum at about 55 ° C was dried for about 7 hours. Example 11 To a glass reactor equipped with a stirrer, a condenser, and a distillation head, 1,000 parts of Form 1 1 4150 (0? ( ^ Weight average molecular weight is about 35,000) Polyvinyl butyric acid is used to force 1,000 parts of tert-butyl acetate. The solution is heated to 75 ° C, and 161.6 parts of tert-butyl acetate is added over a few minutes. The batch was held at 75 ° C for 3 hours, and then heated to about 115 ° C over 2.5 hours to remove the third butanol by-product. The batch was then cooled to produce the acetamidine polymer of formula (III) above Vinyl butyral, where (P) is 23 and (q) is 13. Example 12 A glass reactor equipped with a stirrer, condenser, and distillation head And in a nitrogen atmosphere, 1000 parts of Pioloform® LL415 0 (GPC weight average molecular weight about 35,000) polyvinyl butyral provided by WACKER POLYMERS SYSTEMS was added to 1000 parts of third butyl acetate. The solution was heated to 75 ° C, and 377 parts of tert-butyl acetoacetate were added over several minutes. This batch was kept at 75 ° C for 3 hours, 9l637.doc -41-200426184 and then heated to about 115 over 2.5 hours to remove The third butanol by-product. The batch is then cooled to produce the acetoacetylated polyvinyl butyral of the above formula (III), where (ρ) is 7 and (q) is 29. Coating composition Three primer compositions (Ctng example) and comparative primer compositions (comparative ctng example 1) were prepared by sequentially adding the components listed in Table 1 below: Table 1

Ctng Example 1 Ctng Example 2 Ctng Example 3 Comparative Ctng Example 1 Crosslinkable component --- Example 9 6.2 Example 1 0 6.2 12.2 Acrylic polymer 1 100.4 98.7 92 105.7 AcAc oligomer 2 66.9 65.8 61.4 70.4 Ethanol 6.5 6.2 12 0 Catalyst 3 4.2 4.2 4.1 4.2 Cross-linking component ketimine 4 115.8 118.9 118.4 119.6, * · heart σ | r 300 300 300 300 1 · Acrylic polymer from 25% by weight of methyl methacrylate, 25% by weight

Polymerization of monomer mixtures of isobornyl methacrylate, 6 weight 0/0 hydroxyethyl acrylate, 31 weight% ethylacetoxyethyl methacrylate and 13 weight% n-butyl acrylate The polymerization was initiated with 60 weight ° / o solid third butyl peroxyacetate dissolved in butyl acetate, all percentages are weight percentages based on the total weight of the monomer mixture. The polymer has a weight average molecular weight of ~ 23,000 and a calculated T g of 17 ° C. 2 · 5 5 2 E Sj &amp; milk-based nutrition ^ ^ is used as a catalyst> odorized tetraethyl sulfide as a catalyst The reaction product of 1 mol quaternary pentaerythritol, 4 mol methyl hexahydrophthalic anhydride, 4.2 mol butylene oxide and 3.6 mol tertiary butyl acetate. The third butanol by-product 91637 doc • 42-200426184 The product was removed from the steam room. The polymer had a GPC weight average molecular weight of ~ 1 475 and a measured Tg at 10 ° C (polymethylmethacrylate standard test for GPC). 3.10% by weight benzene Catalyst solution of formic acid and 13.6% by weight triethylamine dissolved in a mixture of first amyl acetate, xylene and isobutanol. 4. 4975S intermediate temperature ketimine activator, Wilmington, Delaware Available from DuPont Company (DuPont Company, Wilmington, Delaware). The crosslinkable and crosslinkable components of the primer of the coating composition described in Table 1 above are mixed to produce a can mixture with layers on an electrocoated steel sheet. Apply with a pull-down bar to a dry film thickness of 1.5 to 2 mils (38 to 59 microns). Allow the layer to dry and The number of times specified in Table 2 below was performed at 25 ° C and 50% relative humidity. The hardness of the cured coating was then tested at the specified number of times, and the results are shown in Table 2 below. Also cured for 30 days under the above conditions Thin film inspection

Tg 〇 Table 2 Poisson hardness Fisher hardness Tg. c 3 hours 24 hours 1 day 7 days 30 days Ctng instances 1 22 61 9.9 21 63 33.3 Ctng instances 2 23 65 9.3 21.1 62 38.7 Ctng instances 3 25 75 12.5 32.1 77 42.2 Ctng instances 1 19 49 7.1 13.3 46 36.7 from Table 2 It is apparent that the primer composition of the present invention provides increased coating hardness without substantially increasing the Tg of the cured film. The examples shown in Table 3 below are prepared by sequentially adding the components in Table 3 to compare the coating properties of the unmodified polyethylene polymer with the ethyl acetoacetate polyethylene water of the present invention. All the following compositions were adjusted to provide 30% solids. 01637 doc -43-200426184 Table 3 Crosslinkable components Ctng Example 2 Ctng Example 4 Ctng Example 5 Ctng Example 6 Ctng Example 7 Ctng Example 8 Polyvinyl butyral 1 Example 9 20 55 5〇 Example 1 0 \ J 56.02 30.6 44.8 Crosslinking component ketimine z 8.87 36.8 18 Ethanol 26.6 73.2 72.6 72.6 64.7 70.3 Toluene 20.1 55.2 55.7 54.7 48.8 53.1 Total 66.Ί 183.4 187.17 183.32 180.9 186.2 1 · Pioloform⑧LL4150 Polyvinyl butyral, made by WACKER Provided by Polymer Systems, Inc. 2. Setalux 10-1440 'imine' is provided by AKZO Nobel Chemical, Inc., which delivers a washable primer for the coating composition described in Table 3 above. The cross-linking and cross-linking components are mixed to produce a can mixture whose layers are coated on an electro-coated steel test plate with a pull-down bar to a thickness of 1.5 to 2 mils dry film (38 to 50 microns). The layers were dried at 25 ° C and 50% relative humidity for the number of times specified in Table 4. The hardness of the cured coating was then examined and the results are shown in Table 4 below. Films cured for 30 days under the above conditions were also tested for Tg. Table 4: Poisson hardness Fisher hardness Tg, ° c 3 hours 24 hours 1 day 7 days 14 days 21 days Comparative Ctng Example 2 97 213 51 107 127 136 64.7 Ctng Example 6 36 108 10.4 28 53 111 27.7 Ctng Example 7 94 243 68 107 120 Γ135 63.6 Ctng instances 8 89 227 60 110 119 130 61.2 Ctng instances 4 65 157 19.5 49 74 107.8 43.4 Ctng instances 5 85 177 27 67 95 129 48.5 91637 doc -44- 200426184 · 1. A coating obtained from a coating composition containing crosslinkable and crosslinkable components exhibits increased coating Tg and hardness (ctng examples 7, 8 compared to Ctng example 6, and Ctng example 5 compared to Ctng example 4) ; And 2. The coating hardness increases over time, which is highly needed. The adhesion of some coatings from the composition shown in Table 3 to various test panels was examined. Comparative Composition Example 3 (Comp. Ex. 3) was Butvai (R) BQO polyvinyl butyral. The results are shown in Table 5 below:

Table 5 Comparison of Ctng on Cold Rolled Steel Sheets in Cold-rolled Steel Sheets under the Dewet Condition under the Wet Condition # 影 线 IX 影 影 # 影 线 fx 影 线 # 影 线 X Shadow line on cold rolled steel Example 2 9 10 8 9 10 10 Comparative Ctng Examples 3 0 2 0 0 0 0 Ctng Examples 4 9 10 8 9 10 10 Ctng Examples 5 10 10 9 10 10 10 Adhesion on Aluminum Sheets #Functional Comparative Ctng Examples 2 10 10 10 10 10 10 Compare Example of Ctng 3 10 10 10 10 10 10 Example of Ctng 4 10 10 1 1 1 1 Example of Ctng 5 10 10 10 10 10 10 Comparison of Ctng with 1 spoon on galvanized steel Example 2 10 10 8 8 10 10 Compare Example of Ctng 3 0 2 0 0 5 2 Example of Ctng 4 10 10 8 10 10 10 Example 5 Ctng 5 10 10 0 0 9 10 As can be seen from Table 5, the coating composition of the present invention is applicable to various types of substrates. Even if only ethylacetinated polyvinyl butyral (Ctng example 4) has a small adhesive effect on the aluminum 91637 doc -45- 200426184 substrate, it is the same ethylacetate when crosslinked (Ctng example 5). Ethylated polyvinyl butyral has a dramatic improved adhesion to aluminum substrates. Although acetoacetate polyvinyl butyral resin has a poor wet adhesion effect on plated steel (ctng example 5), the restored adhesion effect is excellent. With the polymer of the present invention, Pu. ^. It has been used in commercially available washing primers and paints 3, which have poor coating performance, such as bad cold rolled steel.

9l637 doc -46-

Claims (1)

200426184 The scope of the patent application: a curable composition with an outer edge and a knife, wherein the ethylenizable polyethylene polymer includes a crosslinkable and crosslinkable component including: (a) a compound having the following formula乙醯 cl—0 I H2 CIR CIO H2- / plane. “N a CH2—CH · CH: —CH · _ CH, a rw 1 〇 | 1 OH ν · ✓ Gate 2 v ^ n 0 o = c | 1 c = o 1 RLP 1 L K2j n ch2 1 mc = o IL "where (m) is in the range of 1.5 mol% to 85 mol%, (11) is in the range of mol% to 20.5 mol% Within this range, (P) is in the range of 12 mol% to 87 mol%, and (q) is 1 mol% to 88 mol. Within the range, the sum of (m), (η), (ρ), and (q) is 100, and its center and R2 are independently Η, substituted or unsubstituted Ci to C! 2 alkyl, and Substituted or unsubstituted c0 to c 14 aryl, substituted or unsubstituted C7 to C22 aralkyl, substituted or unsubstituted (^ to 匚 "alkaryl, substituted or unsubstituted C4 to c14 carbocyclic group or a combination thereof, the substituent is independently selected from (^ to c12 alkoxy group, alkynyl group, end group, end group derivative, chime group, chime group derivative, cyano group And a group consisting of i groups; (b) an ethyl acetylated polyethylene polymer having the formula: CIO H2- \ c IH CIO-H2 c1R c1οICIR I II H2-o αια-π2 H2- C. C —Y ο ο-ΙΙΗ2Γ3 200426184 where (m) is in the range of 1.5 mol% to 85 mol%, (11) is in the range of 0 mol% to 20.5 mol%, and (?) Is 12 mol. In the range of mol% to 87 mol%, (q) in the range of 1 mol% to 88 mol%, and in the range of 0.05 mol% to 6 mol%, (m) The sum of), ⑷, (p), ⑷, and (χ) is ⑽, and Center and Y 2 are independently fluorene, substituted or unsubstituted (: 1 to (: 12 alkyl, substituted or unsubstituted d to (: 14aryl, substituted or unsubstituted C7 to CM Aralkyl, substituted or unsubstituted alkoxy &quot; alkaryl, substituted or unsubstituted 04 to 0:14 carbocyclyl, or a combination thereof, and wherein Z is Η or -COOH and Υ Is -C00H, halo, unsubstituted phenyl, or a combination thereof, and the substituent is independently selected from (^ to alkoxy), alkoxy, fluorenyl, carboxyl, carboxyl derivative, sulfonyl, and sulfonyl A group consisting of a derivative, a cyano group and a halo group; (c) a combination thereof; and wherein the cross-linking component includes polyamine, polyketimine, polyepoxide, polyisocyanuron, melamine, CjCi2n Poly (meth) acrylate or a combination thereof. 2. According to the oldest coating composition in the scope of the patent application, in the ethylenic ethylidized polyethylene polymer, the heart is propyl and the heart is forma According to the oldest coating composition in the scope of the patent application, the GPC weight of the ethyl alcohol-polymerized polyethylene polymer is 4 and the average molecular weight is 2 0.001 to 300,000. 4. The oldest coating composition according to the scope of the patent application, wherein 1% of the polyethylene polymer is within 40. (: to 60. (: :). 5. The coating composition according to the first scope of the patent application, wherein the ethyl alcohol brewing 91637 doc 200426184 is a polymer which is soluble in one or more solvents. 6 The coating composition according to the first scope of the patent application, wherein The cross-linking component includes a polyamine, a polyketimine, or a combination thereof. 7. The coating composition according to item 1 of the patent application range, wherein the voc of the coating composition is in the range of 01 to 0.72 kg per liter of the composition. 8. The curable coating composition according to item 1 of the patent application scope, wherein the ethyl acetate polymer is produced by the following steps: (i) dissolved in one or more solvents: (a) having the formula Polyethylene polymer: -CH2-CH—ch2- —CH- |-• CH2-CH * 1 CH2-CH * 〇, 〆〆〇0 OH CH〆1 1 o = c Ri 1 R-π -2J 1 n where (m) is in the range of 1.5 mol% to 85 mol%, (11) is in the range of 0 mol% to 20.5 mol% and (〇) is 13 mol% Within the range of 98.5 mole% 'and the sum of (m), (n), and (0) is 100, and & and &amp; are independently Η 丄 substituted or unsubstituted Ci to C! 2 alkyl, substituted or unsubstituted c: 6 to cM aryl, substituted or unsubstituted C7 to C22 aralkyl, substituted or unsubstituted C6 to Cm alkaryl, substituted or Unsubstituted 〇4 to (: 14 carbocyclic group or a combination thereof, the substituent is independently selected from the group consisting of Cl to Cu alkoxy, fluorenyl, carboxyl, carboxyl derivatives, sulfonyl, sulfonyl Consisting of compounds, cyano and _ Group; (b) a polyethylene polymer having the formula: 91637 doc 200426184 CIO H2- / c-H CIO-H2 CIR c——ο——CIR IA H2o CIO-H2 C, C——Y ο X η Where (m) is in the range of 1.5 mol / ί &gt; to 85 mol%, (n) is in the range of 0 mol% to 20.5 mol% and (0) is in the range of 13 mol% to 98.5 mol Within the range of ear% and (X) in the range of 0.5mol% to 6mol%, the sum of (m), (η), (〇), and (χ) is 100, and its center and ^ 2 is independently Η, substituted or unsubstituted (^ to Cu alkyl, substituted or unsubstituted q to aryl, substituted or unsubstituted C * 7 to C η aralkyl, Substituted or unsubstituted (: 6 to (: 14 alkaryl), substituted or unsubstituted q to carbocyclyl, or a combination thereof, and wherein Z is fluorene or -COOH and Y is -COOH, halo , Unsubstituted phenyl or a combination thereof, the substituent is independently selected from ^ to Ci2 alkoxy, fluorenyl, carboxyl, derivatives of carboxyl, sulfofluorenyl, fluorenyl derivative, aryl and _ A group of groups; or (c) a combination thereof to form a solution; (ii) contacting the solution with acetic acid CiSC! 2 alkyl ester to produce the acetic acid ethylated polyethylene polymer. 9 · The composition according to item 8 of the scope of the patent application, wherein the & is propyl It is a methyl group. 10. The coating composition according to item 1 of the patent application, which is formulated as a car refinish or OEM washing primer composition. 11. A method for manufacturing a coating on a substrate, the method comprising: 91637 doc -4- 200426184 ⑴ intermixing and cross-mixing a crosslinkable component with a curable coating composition to form a can mixture, wherein The crosslinkable component includes:-stilbene has an ethyl acetonated polyethylene polymer of the following formula: * — _ ^ —-CH2—CH—CH2—CH—-CH2—CH. I—CH2—CH. CH2—CH— 1 〇1 OH 1 〇CH, 1 I 1 0 = C c = o R, 1 _ P | 1 L \ n ch2 mc = o ch3 &quot;. Where (m) is 1.5 mole% In the range of 85 mol%, ⑻ is in the range of 0 mol% to 2.5 mol%, ⑻ is in the range of 12 mol% to 87 mol% 'and (9) is 1 mol. ear. /. In the range of 88 mol%, the sum of Q, ^, ^) and (q) is 100, and its center and heart are independently Η, substituted or unsubstituted (: 1 to (: 12 alkyl, Substituted or unsubstituted g to c &quot; aryl, substituted or unsubstituted C: 7 to CM aralkyl, substituted or unsubstituted (: 6 to (: 14 alkylaryl, substituted Or an unsubstituted c4sci4 carbocyclic group or a combination thereof, the substituent is independently selected from the group consisting of 0: 1 to (: 12 alkoxy, fluorenyl, carboxyl, carboxyl derivatives, sulfonyl, sulfonyl A group of derivatives, cyano groups, and cyano groups; * (b) Acetoethylated polyethylene polymers having the following formula:,-_ • _ »mmm -CH2-CH—CH2-CH · 1 I One CH2 one CH, I one CH2—CH · | ch2-ch— / i 1 0 1 OH 1 0 1 I 1 o = cc = o R, 1 PI 1 L RJ n CH2 — — mc = o • CH—CH -A IIZYJX ch3 q 91637 doc 200426184 where ㈣ is in the range of [5 mol% to 85 mol%, ⑻ is in the range of 0 mol% to 20.5 mol% '(()) is 12 mol./ . Within "Molar% '⑷ In the range of 1 mol% to 88 mol% and ⑷ in the range of 0.05 mol% to 6 mol%, the sum of (m), ⑷, ⑻, ⑷, and ⑻ is above 〇0, and Where R # R2 is independently Η, a substituted or unsubstituted group, a substituted or unsubstituted (: 6 to 014 aryl group, a substituted or unsubstituted C? To C22 aralkyl group, Substituted or unsubstituted q to c "alkaryl 'substituted or unsubstituted (^ to xin 4 carbocyclyl or a combination thereof, and wherein Z is fluorene or -COOH and Y is -COOH, _, Unsubstituted phenyl or a combination thereof, the substituent is independently selected from (^ to ^) alkoxy, fluorenyl, carboxyl, carboxyl derivatives, sulfofluorenyl, sulfofluorenyl derivatives, cyano and A group consisting of halo groups; (C) a combination thereof; and wherein the cross-linking component includes polyamine, polyketimine, polyepoxide, polyisofloxacin, dimer amine, Ci to Ci2 Burn the two layers, (2 to 3) to burn-based poly (meth) acrylate or a combination thereof; (ii) coat the tank mixture layer on the substrate; and (iii) place the tank mixture layer under ambient conditions or at High curing temperature Cured to form a coating on the substrate. 12. The method according to item 丨 丨 in the scope of the patent application, wherein the &amp; is propyl and &amp; is fluorenyl. 1 3. According to the scope of patent application 11 or 12 The method of claim 1, further comprising applying a main paint composition layer on the tank mixture layer before the curing step. 1 4. The method according to item 13 of the scope of patent application, which further comprises applying a varnish composition layer on the main lacquer composition layer in addition to the curing step of 91637 dooc 200426184. 15. The method according to item 4 of the patent application scope, further comprising drying the tank mixture layer before the curing step. 16. The method according to item 15 of the scope of patent application, wherein the coating composition is a washing-type primer composition. 17. A method according to item 丨 丨 in the scope of patent application, wherein the substrate is an automobile body. 18. A method of manufacturing a multi-coating system on a substrate, the method comprising: (i) mixing a crosslinkable component with a crosslinkable component of a curable coating composition to form a can mixture, Wherein, the crosslinkable component includes: (a) Acetoethylated polyethylene polymer having the following formula: — — surface — —CH2-CH ~ CH2—CH— —CH2 —CH * | —CH2 CH * ch2 -ch— 1 0 1 OH 1 0 CH 1 1 1 o = cc = o R! 1 beep_ P 1 n CH2 a mc = ot ch3 q, where () is at 1.5 Moore /. In the range from 85 to 85 mol%, (n) within the range of 0 to 20.5 mol% 'in the range of mol% to 87 mol%' and as 1 mol% to 88 Within the range of mole%, (called '叫, (口) # ⑷ 之, 心 和 100 ％' J_where ~ and independently are Η, substituted and unsubstituted Mew group, substituted or unsubstituted Substituted red 6 to ^ aryl: substituted or unsubstituted C7ic22 aralkyl, substituted or unsubstituted. 6 to .14 alkaryl, substituted or unsubstituted to c "carbofluorenyl or In combination, the substituent is independently selected from the group consisting of an oxo 19l637doc group, a carboxyl group, a derivative of a carboxyl group, a sulfofluorenyl group, a sulfofluorenyl group derivative, a cyano group, and a group; (b) having Ethyl acetylated polyethylene polymer of the formula: -CH2-CH—CH2—CH- 0 \ 〆0 CH, CH2—CH * I CH2—CH · OH ch2-ch-0 CH—CH- ”PC = 〇〒h2 c = 〇CH, where (m) is in the range of 1.5 mol% to 85 mol%, (n) is in the range of mol% to 20.5 mol%, (P) is in 12 mol% to 87 mol%, (q) is 1 mol Within the range of 88 mole% 'and () 0 in the range of 0.05 mole% to 6 mole%, the sum of (m), (n), (p), (q), and (χ) is丨 〇〇, and its center and feet 2 are independently Η, substituted or unsubstituted 01 to 012 alkyl, substituted or unsubstituted d to (: 14 aryl, substituted or unsubstituted 2 Substituted C7 to CM aralkyl, substituted or unsubstituted q to Ci4 alkylaryl, substituted or unsubstituted d to C4 carbocyclyl, or a combination thereof, and wherein Z is Η or -COOH and Y is -COOH, halo, unsubstituted benzyl or a combination thereof, and the substituent is independently selected from (: 1 to (: 12 alkoxy, fluorenyl, carboxyl, carboxyl derivative, sulfonyl, A group consisting of a sulfonyl derivative, a helium group and a halo group; (0 its combination; and, polyepoxide, poly (^ 1 to (: 12 alkyl poly (wherein the crosslinking component includes Polyamine, polyketimine isocyanate, melamine, (: 1 to (: 2 alkanedialdehyde, 200426184-based) acrylate or a combination thereof; (ii) coating the tank mixture layer on the substrate; (iii) Can mixture layer Cover the main lacquer composition layer; (iv) apply a varnish composition layer on the main lacquer composition layer to form a multi-layer system on the substrate; (v) subject the multi-layer system to ambient conditions or increased curing Temperature curing to form a multi-coating system on the substrate. 19. The method according to item 18 of the scope of the patent application, wherein the coating composition is formulated as a primer composition. 20. According to the item 18 of the claim scope The method &amp; further comprises a method of applying a primer layer 0 on the tank mixture layer before the step of applying the main paint composition layer, wherein the coating composition is a method of item 19 or 20, wherein the Substrate 21 · Formulated as a strip-type primer composition according to item 20 of the scope of the patent application. 22 · According to the scope of the patent application, it is an automobile body. 9l637 doc 200426184 柒. Designated representative maps ... (1) The designated representative maps in this case are: (none) (II) The representative symbols of the representative maps are briefly explained. If there is a chemical formula in this case, please disclose the ones that can best show the features of the invention. Chemical formula, cht IR, CH? -CH — C \ r \ 〇— CH- II 0, CH2 — CH · 1 — ch2 ~ —CH · I 1 〇 | OH 0 = C | L RJ nm CH2—CH — I0 Ic = 〇I ch2 Ic = o -1. Ch3 H / CIO I H2c 2c CH 丨 R1 CHIO 〇 = m CHo---Ⅰ-_ Turn over CH · I. Called f. CH2-CH— LI CH CH II 1 〇 | OH 1 〇I 1 1 ZYCC = 0-"1-P 1 n ch2 1 c = 〇L i J q ch3 m 01637 doc