SA516371673B1 - Acrylic resins and powder coating compositions and powder coated substrates including the same - Google Patents

Abstract

An epoxy functional acrylic resin having a Tg of greater than 85°C and a calculated solubility parameter from about 9.20 to about 9.30 (cal/cm3)1/2, powder coating compositions including the same and coated substrates coated with the powder coating composition is described. The resin includes, as copolymerized monomers, from about 10 wt.% to about 40 wt.% of one or more epoxy functional unsaturated monomers; from about 10 wt.% to about 20 wt.% of one or more hydrophobic acrylic monomers, and from greater than 50 wt.% to about 75 wt.% of at least one nonionic copolymer that is different from the hydrophobic acrylic monomers ii), each monomer wt.% based on the total weight of copolymerized monomers in the resin.

Description

1 Acrylic resins and powder coating compositions and powder-coated substrates incorporating them

Acrylic resins and powder coating compositions and powder coated substrates including the same Full Description Background of the invention Acrylic resins powder coating compositions and Thermosetting epoxy clear The rates mentioned in this document. when formulated into a clear powder coating such as substrates and when such coating is applied to substrates powder coating © 718001760; Provides aluminum automotive wheels powder formulations of formed aluminum epoxy functional acrylic coating includes acrylic resins with functional epoxy group

Copper This resists hairline corrosion and corrosion by accelerating copper-accelerated acetic acid salt spray 5 Excellent while maintaining excellent appearance (CASS) Accelerated Acetic Acid Salt Spray and resistance to collision. 0 by metal vehicle wheels Exposed parts can be corroded from Rigid and tough metal composite wheels to protect the film surface of gravel and other debris from road surfaces. Foil Required Foil must be non-porous and must show wheel surface Superior adhesion to metal. These properties can prevent the spread of corrosion to the metal. These visible craters can prevent Jie properties at the junction of the wafer and the metal. however; The appearance of hair wear;0 with paint is not necessary to increase hair wear. by the time"; Appropriate wafer thicknesses Acrylic and polyurethane protective clear coat protective clear coat powder coatings for hairline coatings even though conventional SSE coatings on aluminum polyester wheels appear acceptable. Predominantly Aluminum Over Clear Coats Surface Treatments Apply Yo-Cleaning Monolayer Self-Assembly 56-7 wheel surface pretreatments Primer Wheel

Assembled monolayer (5/1/4). Surface pretreatment with self-assembled monolayers can preserve the bright color and appearance of aluminum without the introduction of chrome~—containing compounds however; Clean-up coatings can be left over failed self-assembled monolayer pre-treats to provide suitable capillary corrosion© coating materials. Polyester clear coats over pre-treated aluminum wheels and rims may provide adequate hairline corrosion resistance if the clear coat is coated with a liquid coating to provide adhering chemical resistance; Scratch materials and weather fluctuations. Compositions of acrylic powder containing epoxy are also common. 0 US patent identification numbers 76 identifiable “(-Simeone, et al) describe powder coating formulations comprising epOXy functional acrylate polymers. These formulations may provide an acceptable appearance when painted. Over a color coat material but lacks tolerance to acceptable climatic fluctuations.German Patent No. 1 (Ford Werke AG) YY 11 YY discloses powders composed of 1 glycidyl acrylic copolymers. For flexible moulds, 5 .., powders are not suitable for coatings and do not provide a weather resistant mould.(Lu, et al) 11 008778/710097 discloses powder coating compositions comprising copolymers of glycidyl (meth)acrylate and caprolactone (meth)acrylate .0 powder coating formulations do not show better hair abrasion resistance than powder coatings with an acrylic clear cleaning agent coat with a conventional functional epoxy combination.US Patent Disclosure R Qom 1,771,777 for powder coating resins | powder coating resins comprising from 01 to 7 00 by weight of glycidyl acrylate (GA) or glycidyl methacrylate (GMA) preferably Yo to or Yo 7 wt.; And from ? to 7 01 by weight of at least one selected from the group comprising

This is isobutyl methacrylate (2//8a)” isobornyl acrylate (IBOA) acrylate and isobornyl methacrylate (IBOMA) preferably 15 Yo 7 wt” and from YO to 15 7 wt. of at least ethylenically unsaturated monomer (Ladi) copolymerizable; Preferably 0 01 to 2 50 wt. These resins do not exhibit high glass transition temperatures (eo) Jad (Ty) glass transition temperature greater than AS (ia) in combination with the solubility parameter Exceeding 9.12 kcal/JP (as EP No. 5115097 discloses the preparation and use of a cathodic electrodeposition paint that exhibits defects in the absence of 0 cationic acrylic copolymer 0800010. However 55% copolymer has a negative effect on paint adhesion unless the copolymer exhibits a hydroxyl number greater than 660. Accordingly, there is still a need for suitable epoxy functional group acrylic resins for powder coating formulations that can provide lattice abrasion resistance and precipitated acetic acid salt spraying. Improved copper for aluminium; forged alloy or metal substrates without degradation Vo smoothness of powder coating “purity or stability of powder coating composition and impact resistance” particularly in powder coatings for forged aluminum or alloy wheels and rims Previous car leveling to process using; For example; hexavalent chromium—free pretreatments .general description of the invention Embodiments according to the present disclosure are directed to an epoxy-functionalized acrylic resin comprising; as copolymerized monomers from about 01 wt. percent (7 by weight) to about 7 Er by weight of one or more unsaturated monomers of an epoxy functional group; From about 7 01 wt to about 7 0 wt of one or SST of hydrophobic acrylic monomers Yo 000000858 and from greater than 7 en by wt to about 7 Ve by wt non-copolymer

Coe is at least different from hydrophobic acrylic monomers; nonionic copolymer Each monomer has a #7 by weight based on the total weight of the copolymer monomers in the resin. The resin °C (°C) and the AC solubility variable from ST also has a glass transition temperature of

Com (price/~$5.71 to approx. 5.01 calculated from approx. Some embodiments of acrylic resins with epoxy functional group may be included in a © powder coating formulation suitable for coating JB surfaces) may include powder paint. For example, bare or uncured on acrylic resin with epoxy functional metal surfaces. These coatings can be used as crosslinkers and one or more powdered Jal crosslinking compounds to protect corrosion-prone metal surfaces or corrosive environments. For example, using powder coating compositions comprising acrylic resin with an epoxy functional group according to disclosure 0 aluminum alloy for cast aluminum coating, casting, aluminum alloy substrate Jal wheel or vehicle surfacing. Jie Substrate Detailed description: Embodiments are described Acrylic resins in a functionalized epoxy group capable of providing improved capillary and copper-accelerated acetic acid salt spray resistance and used for SE 5 powder coating compositions for clean-up paint or tinted clean-up coatings herein. TO 01 Acrylic Resins with Epoxy Functional Group may include; as copolymer monomers; a) of about 7 56 by weight of one or more unsaturated monomers of an epoxy functional group; by weight from 1 0 7 # by weight to about 1 0 7 eg glycidyl (meth) acrylates; aa) from approx

Love by weight to about 7 51 of (iis one or more hydrophobic acrylic monomers 0 wt of one or more ethylene unsaturated monomers different from the hydrophobic acrylic monomer AA). Resins with the functionalized epoxy group have a higher glass transition temperature

LY of 85° elevation; hydroxyl number of yellow; and a calculated solubility variable from about to about 9.30 (kcal/cm"). In some embodiments the vinyl acrylic resin by weight or less of 7 11 aromatic vinyl monomer of the epoxy functional group may also comprise YO a

sl (iv aromatic monomer) over the total weight of the copolymer monomers in this epoxy functionalized acrylic resin. This epoxy functionalized acrylic resin provides improved resistance to capillary corrosion and copper-accelerated acetic acid salt spraying in sald clean or sale powder coating formulations Tinted Cleaning Coating.Furthermore » No Shown © Powder Coating Compositions Resins have a coarse microtexture or 'orange-peel' appearance ALE This distinguishes other resins with a glass transition temperature of Ao°C or higher. Acrylic resin embodiments of the epoxy functional group described herein can be embedded in powder coating compositions.Powder coating compositions can be applied to metal substrates either pre-treated, lie-coated or bare.For example (Ji) can be applied 0 Embodiments of the powder coating compositions described herein on forged aluminum or alloy substrates. Such substrates may be cleaned and pretreated with zine phosphate iron phosphate 1200 or other suitable pretreatments. Suitable substrates include aluminum wheels auto flattening. Some embodiments of these powder coating formulations may include one or more adjuvants selected from non-Call 1 hydrophobic submicron particle adhesion promoter light stabilizer and an absorber of ultraviolet (UV) waves in some embodiments; The powder coating composition may include an acrylic resin with a functional epoxy group; or a mixture of two or more resins; and one or more crosslinker 0 resin mixtures may include an acrylic resin with an epoxy functional group and one or more second resins. Non-exhaustive examples of a second resin include an acrylic resin with a second epoxy functional group; Copolymerization product of one or more monomers of a carboxylic acid functional group and one or more nonionic ccOmoOnomers "©" copolymer of one or more It is a monomer of a phosphoric acid group

A functional phosphorus acid and one or more nonionic “comonomers” and mixtures or combinations thereof. in some embodiments; The second resin is preferably JA largely hydrophobic acrylic copolymer monomer (a); i.e. hydrophobic acrylic monomer (ii hydrophobic acrylic monomer) comprising 7.0 7 by weight or JH Based on the total weight of the copolymer monomer in the copolymer In some embodiments the powder coating composition may include one or more adhesion enhancers Jie epoxy resin epOXy resin in some embodiments LUST resin includes a combination Preferably functionalized epoxy mixtures of one or more acrylic resins of the epoxy functionalized group that are substantially 0 free of aromatic monomer o(iV) and one or more of the second resin comprises a copolymerization product of 70 7 by weight or less of one or more aromatic vinylyl co-monomers (iv) eg styrene or Jad sly vinyl toluene over the total weight of the copolymer monomers in the second copolymer(s). Another embodiment epoxy functional group acrylic resin preferably comprises Vo acrylic resin with a group functionalized epoxy and one or more LY resins) with a second epoxy functionalized group substantially free of hydrophobic acrylic copolymer (oil) where laa) ranges from the amount of hydrophobic acrylic copolymer (i) from 7 0001 wt to 7 01 wt” based on the total weight of the copolymer monomers in the epoxy functional group acrylic resin. in one embodiment; Acrylic resin with epoxy functional group 0 more preferably also comprises as copolymer to up to Fe 7 by weight; One or more aromatic vinyl monomersly (iV) on the total weight of the copolymer monomers in the acrylic resin of the epoxy functional group. In some embodiments, one or more of the crosslinking compounds may comprise an organic dicarboxylic acid anhydride anhydride or an excess of it with Js Yo polyester ester or Js isocyanate polyisocyanate YAY

—A— Embodiments of acrylic resins with the epoxy functional group described herein can be used to produce

Jane Clear or tinted powder coatings that exhibit excellent lattice corrosion and acetic acid salt spray resistance on forged aluminum or alloy substrates;_such as Galas 80100017/6 automobile wheel spokes;_using conventional coating application techniques. Powder coating wheel substrates formulations provide lattice corrosion resistance and improved copper-acidified acetic acid salt spraying; Conjugation© Good color and excellent blocking resistance. The powder coating compositions described herein provide ¢ Slice with a lattice appearance and a sprinkling of copper-accelerated acetic acid used for coating SB surfaces; resistant coatings and magnesium alloy substrates; steel surfaces of iron .brass substrates hardener Powder coating compositions described herein include acrylic resin with epoxy functional group 0 comprising copolymer or copolymer mixture comprising based on total weight of monomers acrylic copolymer component copolymerizing into acrylic copolymer component by weight from one or more of 7 Ee to about 10 of about (i) of an epoxy functional group; (il) an unsaturated monomer of an epoxy functional group; eg glycidyl(meth)acrylates; One or more non-ionic acrylic monomers 7 71 by weight to about 7 0 1 about ge Vo residue One or more non-ionic co-monomer different from the non-ionic acrylic monomer (ils waterproof; polymer component includes acrylic The joint of the functional epoxy group in the form of (ii waterproof Cady)

IY in the amount of © // wt. or more or additional IV (IV) on a diethyl aromatic monomer copolymerized on the total weight of the monomers sly wt. or less; #7 8.5 (Jamie wt. or less OR; in copolymer form Polymerization into the acrylic copolymer component of the epoxy functional group. 0 resin mill comprising mixtures of one or more clay components to be formed at any time after polymerization; or Jl) mixing of resins can be polymerized; eg (Se “components) co-resined in the presence of an already formed resin. Suitable second copolymers for mixing with epoxy functionalized acrylic copolymer can be selected from epoxy functionalized acrylic copolymers;

_q- acrylic with an epoxy functional group; vinyl copolymers copolymers with a carboxylic acid functional group; vinyl copolymers with a 635-carboxylic acid functional group; Acrylic copolymers with a phosphoric acid functional group; quinyl copolymers with a phosphoric acid functional group; mixtures and combinations thereof. The quantity of one or more of the second acrylic copolymers can range; Based on total weight of acrylic copolymers in 5 wt.; in another embodiment as 7 610 to about 1 mixture of in one embodiment of about by weight; or; in another embodiment also more favourably; 7 510 to about 100 favourites; by weight or less. 7 506 approx. In embodiments in which the second acrylic copolymer comprises the copolymerization product from one or more monomers of a carboxylic acid functional group and one or more co-monomers; 0 7 01 The monomer with the carboxylic acid functional group may be used in amounts up to about wt. or more; preferred; about © #7 by weight or less; based on #7 0.1 wt.; or; Approximately the total weight of the copolymer monomers in the copolymer. In embodiments in which the second acrylic copolymer comprises the copolymer product from one or more monomers of a phosphoric acid functional group and one or more copolymers; 1 may use the monomer of the phosphoric acid functional group in amounts up to 7 © by weight; preferably by weight or more; or 7 7 by weight or less; Based on a total weight of 7 1.1 OR; the copolymer monomers in the copolymer. In one embodiment; The epoxy functionalized copolymer component comprises a mixture of one or more epoxy functionalized acrylic copolymers with one or more 0 second copolymers that are substantially free of non-acrylic copolymer (i The second copolymer comprises the Jamie copolymer product as (if hydrophilic by weight; based on total weight of the copolymers” one or more than 7 Av © to iil group unsaturated monomer epoxy-functionalized; and one or more non-ionic copolymer ye In another embodiment; the epoxy-functionalized acrylic copolymer component comprises one or more epoxy-functionalized acrylic copolymers substantially free of monomer

Lad and one or more second copolymers. In another embodiment (IV) thinyl aromatic copolymer wt or 7 Yo preferably; the second copolymer comprises from ? to +7 // wt; or, depending on the total weight of the monomers (iV less of diethyl aromatic copolymer 0 copolymerization into the second copolymer. On mixtures of one or (JU) Other suitable polymer mixtures may comprise; for example, more than one epoxy-functionalized acrylic copolymer with a second copolymer Selected Epoxy Functionalized Acrylic Copolymer Substantially Free of Vinyl Aromatic Monomer aa Acrylic Carboxylic Acid Functional Free to oiV Copolymer 0 Acrylic Acid Copolymer (Large IV of Monomer) Aromatic vinyl copolymer phosphoric functionalization is substantially free of aromatic vinylyl copolymer 7a) and mixtures thereof. eg; one or more (0-85 0-8 Luly) unsaturated glycicarboxylic acids dyl ester glycidyl ester 0 0 “(methacrylic as cethylenically unsaturated carboxylic acids allyl glycidyl or itaconic 11800016 and maleic glycidyl ethers maleic acid preferably; The monomer is chosen with the glycidyl (meth) epoxy functional group .5 or the 11 aR? Acrylate monomers of the formula *110-0)890)0(05 where the glycidyl end of the alkylene residue is less and 47 is an alkyl structural unit, alkyl group 00 i.e., “carbon atoms” to 4 carbon atoms 1 branched or Unbranched Containing from a terminal at the distal end of the saturation metal The explanatory compounds are a glycidyl ring A glycidyl (meth) glycidyl ring within the definition of formula (a) is a 1,2-epoxy glycidyl acrylate butyl acrylate -7 ¢) 5 glycidyl (meth)acrylate acrylate is preferably methyl RY; glycidyl (meth) acrylates in the formula; where cepoxybutylacrylate ©

Tian

-11- except 610 no 9. Can include methylene group is a methylene glycidyl group R? ; methyl glycidyl acrylate monomers on a mixture of monomers of Formula A. can get

The Dow Chemical Company from a commercial source of edly < I glycidyl (meth) or glycidyl (meth) acrylate monomer can be prepared under conventional (Midland, MI) reaction conditions for those skilled in the art. oo The quantity of monomers varies Unsaturated epoxy functional group (i) used to obtain the epoxy functionalized acrylic resin ranged from about 7 01 wt to about 7 500 wt unsaturated epoxy functionalized monomer; based on the total weight of the copolymers in the acrylic copolymer component In the OAT embodiment the amount of 0 unsaturated monomers of the epoxy functional group used is from about 7 01 wt to about 7 75 wt; and in the HAT embodiment also from about 7 Yo by wt to about 7 71 wt. If the amount of unsaturated monomer of the epoxy functional group used is less than about 7 01 wt. based on total weight of the copolymer monomers” it does not contribute significantly to the improvement of the solvent resistance and mechanical toughness. (on the AV side) if the quantity exceeds about 0 5 7 by weight; 0. No further improvement in corrosion resistance is obtained. Suitable hydrophobic acrylic monomers efi e.g. oJ may comprise one or more selected monomers of isobornyl (Cue) la dsobornyl acrylate (methacrylate) cyclopentadienyl (meth) gla ddicyclopentadienyl (meth) 2-ethylhexyl (methacrylate) cyclohexyl (meth)acrylate Benzyl (meth)acrylate phenyl (meth) acrylate —ts phenyl (methacrylate) t-butyl (meth)acrylate These monomers improve the capillary corrosion resistance of coatings Jie aluminum wheels.In one embodiment the hydrophilic acrylic monomer Yo is chosen preferably from bicyclic cycloalkyl(meth)acrylates.

-117- Dicyclopentadienyl (meth) acrylate J «cycloalkyl (meth) isobornyl acrylates | dicyclopentadienyl (meth)acrylates (meth)acrylates is also HAT and in embodiment oJ l or faa 3.5 mass solubility in water of ALE © homogeneous 100700010162 with jails transformation temperature: l or less; where it can form by itself °C; and in embodiment preferably other" about 1175 °C to 0 0 glass in the range of °C. In some embodiments the monomers of 175 °C to about 8 hydroxyl hydrophobic aa) can be free to Lots of hydroxyl groups. 0 and has a hydroxyl number of functional groups | 0 used to obtain the acrylic resin (ii) the amount of hydrophobic acrylic monomers by weight based on the total 7 Yo of the epoxy functional group ranges from about © 7 by weight to about the weight of the copolymers in the acrylic copolymer component of the group Functional epoxy. In another embodiment the amount of hydrophobic acrylic monomers used is preferably from 7 71 wt. to about 7 01 wt. ) comprising one or more of any non-ionic acrylic;kenyl or allyl monomer; such as, for example, ama-8; cyclo(meth)acrylates and one or more selected monomers of alkyl(meth)acrylates Alkyl aryl (meth) ceycloalkyl acrylates (01610(8017/18165) Amides (meth)acrylonitriles (meth)acrylonitriles 65 Non-dibasic acids dialkyl esters Dialkyl esters ((meth)acrylamides alkyl (meth) a Polyalkoxylated acrylates ) 0 dibasic acids saturated alkoxy group 01 to 1 of polyalkoxylated alkyl (meth)acrylates and mixtures thereof. unless otherwise indicated; Non-ionic co-monomers include groups Yo

A on the hydrophobic co-monomers AA) and phenylaromatic (7a) monomers. in one embodiment; The non-ionic co-monomer preferably has a mass water solubility of fan© liter or less; or; Preferably » Yo g/l or less. in some embodiments; The non-ionic co-monomer aa) can be devoid of up to an large number of hydroxyl groups and have a © hydroxyl number of 0 . in some embodiments; Non-ionic co-monomers (iil) of cycloalkyl(meth)acrylates (iiia) can be selected; e.g.,© to Coy(cyclo)alkyl esters of 6a07/010(8) of (methic) acid acrylic acid 16a/0161(8017); ((meth)acrylate 0 isobutyl (meth)acrylate 7-ethylhexyl (meth)acrylate 01610(801/1848) Al61o10©-2; cyclohexyl acrylate 1686 laurel ( lauryl (methacrylate) stearyl acrylate ¢ (meth)acrylate eicosyl (meth)acrylate and cetyl (meth)acrylate plus tri Decyl(meth)tridecyl acrylate (((meth)acrylate 0) and mixtures thereof. In one embodiment; preferably (jia) co-monomers comprising one or more © to Cg (cyclo)alkyl ester (cycloalkyl ester of (meth)acrylic acid) such as butyl (meth)acrylate and methyl methacr. ylate in some embodiments (AY) resins of the epoxy functional group may also comprise 0-vinyl monomers (iv) including alkyl aryl (meth) acrylates Jad alkyl aryl (meth)acrylates vinyl esters Jad esters and alkyl vinyl ethers in one embodiment; The quinyl monomers are preferably aromatic vinyl monomers selected from styrene” =o methylstyrene —o co—methyl styrene a—ethylstyrene and styrenes substituted with ©-alkyl 51/160865 “gyal g —alkyl substituted vinyl toluene | © Die Jus benzene divinyl benzene vinyl esters at

For example Jad “vinyl acetates are vinyl ethers allyl 65; Callyl alcohols and mixtures thereof. in one embodiment; The amount of co-monomer varies from the Jud copolymerized (iv) vinyl comonomer used; from about 6.5 7 wt to about 11 7 wt; and in another embodiment from about A 7 wt. to about A 7 wt.; Based on the total weight of the copolymer monomers in the epoxy functional group acrylic copolymer component. In the AT embodiment the amount of dimethyl co-monomer JS(IV) is preferred from about 7 7 wt to dim wt. Acrylic resins of the epoxy functional group have a calculated glass transition temperature greater than 0 85 °C; and in some embodiments may have a preferably calculated glass transition temperature of about 90 °C or greater; In other embodiments also it may more preferably have a calculated glass transition temperature of about 90° C to about 100° Asie Jada ensures a suitable acrylic copolymer suitable glass transition temperature resistant glass Adequate obstruction or stability when packing while preserving adequate flow and Vo wafer forming properties. Acrylic resins with epoxy functional group may also have a calculated solubility variable SP of about 5.18 (cal/cm)” or greater. In another embodiment the resin is preferably .50 from about 9.71 to about 0 9.9; In yet another embodiment, from about 9.77 to about 01, SP is defined by: SP, = W1xSPl W2xSP2 W3xSP3 wl Ww2 Ww3 Ft + [lot Fog tt ——( Yo where SPC is the calculated solubility variable of the resin; W2 WIT 3//a... is the weight percentage of each independent monomer; .d3 002 dl m” is the specific gravity of each independent monomer; “SP1

AG \ — 2, 503... is the solubility variable of the homopolymer of each monomer reduced: The solubility variable used for the calculations “dled” can be obtained eg” in the monomer supplier data sheet or a published document such as “Polymer Handbook” (4th Edition, John Wiley, New York, 1999) eo A list of monomer—homopolymer glass transition temperature and 50 for free radical polymerizable monomers is included in Table 1 next. Table 1 Homopolymer Homopolymer: monomer transformation temperature | Variable susceptibility (lsd) (price / 1 specific gravity of glass. (degree for 0" cm decantation) Butyl acrylate ASE a, acrylate Butyl methacrylate Butyl AA Al acid methacrylate Ethyl a lo ,71 methacrylate glycidyl methacrylate q,¢0 £1 Glycidyl no methacrylate 1-octyl methacrylate n— VA Ag Y. Octyl methacrylate TYAY

_ a \ _ Isobornyl acrylate AY a Isobornyl acrylate Isobornyl methacrylate «,4vAa AY YY Isobornyl methacrylate ¢A Iso butyl 7L ANE methacrylate lauryl methacrylate AY lo- to Lauryl methacrylate Yao 5 #176" Methyl methacrylate Stearyl methacrylate YA No ATE Stearyl methacrylate In some embodiments; epoxy functionalized acrylic resins can be free to aa has a large hydroxyl functional group and has a calculated hydroxyl number of 0. In some embodiments epoxy functionalized acrylic resins can have (f/M) functionality per molecule of less than VE other embodiment © The resin preferably has a functional group value per molecule from about © to about 07.5 In another embodiment a clad functional group value per molecule from about 01 to about Te A functional group value per molecule is calculated from E to W//A/ Molecular Weight Say MW Determination of MW Molecular Weight by Gel Permeation Chromatography

-11-

(GPC) EEW can be determined by the acetic acid 808116/perchloric acid method (ASTMD 4-1687 +) using the Metrohm Autotitrator

Supplied with unit 1108000 808 5 Dosimat 805. Acrylic copolymers with a carboxylic acid functional group suitable for use in an epoxy functionalized acrylic copolymer powder coating formulation may include any copolymer having a weighted average molecular weight of between about 0001 and about © and an equivalent carboxylic acid weight from about ,Fo to about 1,000; preferably at least about 0 ; copolymerization product from 1.5 to 75 7 by weight; Based on the total weight of the copolymer monomers; of one or more ethylene unsaturated carboxylic acid

0 8 and one or more non-ionic co-monomers. Examples of suitable acrylic copolymers with a carboxylic acid functional group are 9 Joneryl™ and 821 Joneryl™ from BASF Corporation, Wyandotte, BASF Corporation, Wyandotte, AA. Suitable 0-8 unsaturated carboxylic acid monomers suitable for the manufacture of acrylic copolymer can include with a carboxylic acid functional group; For example (JU on acid

Vo-acrylic acid cmethacrylic acid cacryloxypropionic acid crotonic acid acid 01010016”; fumaric cacid monoalkyl esters of fumaric acid maleic acid monoalkyl esters of maleic acid; Itaconic acid 1800016 is a monoalkyl ester of itaconic acid and mixtures thereof.

0 Acrylic phosphoric acid functionalized copolymers suitable for use in the epoxy functionalized acrylic copolymer component may comprise a copolymerization product of (i) from 1.5 to 7 01 by weight; preferably; 1 to © 7 by weight; based on the total weight of the copolymers; of one or more phosphoric acid 01105000115 cacid monomer and one or more nonionic copolymer. May include polymer

Yo acrylic co-phosphorous acid functional group also contains the copolymerization product of Ma

M1- up to 7 01 by weight; preferred; 1 to © 7 by weight; Based on the total weight of the copolymers” of one or more ethylene unsaturated carboxylic acid 0B the acrylic copolymer may comprise mixtures of one or more acrylic copolymers with a phosphoric acid functional group and one or more acrylic copolymers with a phosphoric acid functional group © Functional Epoxy. Phosphorous acid monomers suitable for the manufacture of an acrylic copolymer with a phosphorus acid functional group can be any unsaturated ethylene 0-8 monomer having a phosphoric acid group and can be in the acid form or in the salt form of a phosphoric acid group. phosphorus acid group 0 monomers of phosphorus acid (JU) can include phosphoalkyl (Meth)acrylates such as phosphoethyl (meth)acrylate phosphopropyl (meth)acrylate and phosphobutyl (meth) acrylate phosphoalkyl crotonate phosphoalkyl 0105; phosphoalkyl maleate 008168168 phosphoalkyl phosphoalkyl fumarate phosphoalkyl fumarate 0018:8168 Yo phosphodialkyl (((meth)acrylates) phosphodialkyl crotonate 0101003165 Jud (phosphodialkyl phosphates “vinyl phosphates” and (meth)allyl phosphate. Phosphoalkyl methacrylates are preferred. Phosphoalkyl methacrylates may include and other suitable phosphoric acid monomers on dihydrogen phosphate-functional monomers 0 such as allyl phosphate mono or diphosphate from bis(hydroxy-methyl) fumarate fumarate or titaconate monomers e.g. eli (phosphonate functional monomers); Jad vinyl phosphonic acid “allyl phosphonic acid” Yo acid ?- Acrylamido - ?- Methylpropane Phosphonic 2-acrylamido—2— -o <methylpropanephosphonic acid Phosphonostyrene -1 “a—phosphonostyrene TYAY

“yao 2-methylacrylamido—2- meheylacrylamido-?- methylpropanephosphonic acid monomers (hydroxy) phosphenylalkyl (meth) acrylates sMethylpropanephosphonic acid 1,2-ethylenically unsaturated (0) ?- ethylene ¢ (hydroxy)phosphinylalkyl (meth) acrylate monomers Ji «oligomeric phosphorus acid monomers phosphorus acid monomers cdiphosphomonoalkyl (meth)acrylates Triphosphomonoalkyl (meth) ((meth)acryloyloxyalkyl diphosphate alkyl diphosphate ctriphosphomonoalkyl (meth)acrylates metaphosphomonoalkyl (meth) acrylates acrylates

polyphosphomonoalkyl (meth)acrylates 0. Acrylic copolymers with a suitable phosphoric acid functional group can be prepared by first preparing a co-reactive epoxy production polymer containing a suspended first co-reactive epoxy group where it can react with a compound It contains a second co-reactive group and a phosphoric acid group. For example a production polymer can be prepared using glycidyl (meth) acrylate. The appropriate second co-reactive groups on the compound are Vo amine which includes a second co-reactive group and a phosphoric acid group that is an amine Say phosphoric acid anhydride hydroxyl reacts; And phosphoric acid anhydride or “polyphosphoric acid” is a production polymer with an epoxy functional group with polyphosphoric acid to generate an acrylic copolymer with a phosphoric acid functional group using glyphosate glyphosate

0 is an endosomal phosphoric acid group. Any suitable acrylic copolymers may be formed by conventional polymerization methods in the presence of a thermal or oxidizing-reducing initiator. Organic solvent polymerization 714 can be carried out in the case of acrylic copolymers with an epoxy functional group. in other cases; .aqueous emulsion polymerization can be carried out M7

Cy.

POWDER COATING COMPOSITIONS » In addition to the acrylic resin with the epoxy functional group; also on one or more crosslinking compounds; Preferably sale flexibilizing crosslinker (crosslinker) sale crosslinker is added in a stoichiometric of about 1.7 to about ?,0:1 acid to epoxy in the acrylic copolymer; preferably Approximately 1.95 to Approx. 0.15 5 1 Appropriate amounts of sale crosslinking can range from © to Ye 7 by weight Blu on the total weight of the powder coating composition May include Suitable crosslinking compounds on any material that will react with epoxy groups / 60077 without yellowing the product coating, for example binary acids or Gar aie anhydrides or dianhydrides 05. In one embodiment, the crosslinking compounds may include preferably over 0 organic dicarboxylic acids and their anhydrides; Jie sebacic acid 5658016 adipic acid azelaic acid dodecanedioic acid and excess adducts Made by esterification of organic dicarboxylic acids or anhydrides using polyesters or polyols 7015a00. Crosslinking material can help to improve

. For coatings made of powder coating composition chip resistance Vo chip resistance The powder coating composition may additionally include one or more adhesion enhancer or an isocyanate compound comprising any epoxy resin or isocyanate compound (Jia) resins have a glass transition temperature of 50°C or higher; like; For example, cepoxy—phenolic novolac resins epoxy dimers; Nogolac epoxy-phenolic resin isophorone diisocyanate trimers and dimers 0 or (HMDI) hexamethylene diisocyanate (1001) 5160680 (5160680) | toluene diisocyanate retarded isofuron diisocyanate; and caprolactam polymers such as caprolactam 45-diisocyanate “isocyanate terminated prepolymers with glycol or polyol glycols or dimers or trimers thereof using a polyol Yo diisocyanates Preferred are bisphenol epoxy resins adhesion promoters yy

F sid or more preferably Bis A are bisphenol epoxy resins by weight to about 7 1.1 epoxy. Appropriate amounts of adhesion promoter can range from approximately preferably HAT to total weight of the powder coating formulation; in embodiment Bl wt; 7 7 0 1 to approx 1.1 more preferably than approx AT to 9 7 wt; and in an embodiment of 1" wt. Amounts greater than about 7 7 wt. © In order to help resist capillary corrosion, powder coating formulations may also include approx. (+ 7 wt.) to about 71,0 by weight; based on total weight of hydrophobic submicron powder composition Gall coating of one or more non-metal submicrons eg metal oxide 00398010 oxide such as inorganic oxide 6 eg corganosilicon compound or silica 51168"; organosilicone compound 0 oxide treated with PDMS polydimethyl siloxane eg polydimethylsiloxane fume silica eg chydrolyzable silanes optionally hydrolyzable silanes can be used 7 to about ? 0.00 also by an amount of about ? 0.00 calkoxysilanes eg alkoxysilanes sla wt.; in another embodiment preferably; about 0.09 7 wt. to about 6.7 7 wt; fillers based on the total weight of the powder coating formulation for coupling fillers Examples of silanes include .008109 matrix Ino coating matrix rganic oxide pigments and suitable glycidyl alkoxy silanes on glycidyl trimethoxy glycidyl trimethoxysilane Jie camino alkoxy silanes .silane 00 Powder coating formulations also optionally include one or more light stabilizers of Ultraviolet rays can even help absorbers or light stabilizers withstand weather fluctuations. A light stabilizer or UV light absorbent can be used preferably to 1.1 to 003 of about 11 phr to about 1.1 violet in amounts of about 1.1 hindered on amines hindered JE approx © 007 Suitable light fixtures include; For Yo

For “Jie camines” poly(alkanoyl piperidine alcohols) eg oligomers of dimethyl succinate using 4-hydroxy tetramethyl piperidine ethanol hindered phenols or combinations thereof Suitable UV light absorbers include, for example, benzotriazoles coxalic acid diarylamides and 7-hydroxybenzophenone 2.—hydroxy benzophenone Small quantities may be included; eg from about 0.009 7 wt. to about 7 Yee by wt., depending on the total weight of the powder coating composition; preferably from about 0.001 0 17 wt. to about 5 0.001 wt. .,.7 by weight of organic pigments such as phthalo-cyanines to control yellowing The composition of the powder coating may additionally include from about 0.000 to about 7 01 by weight, based on the total Weight of the powder coating composition; optical brighteners and/or or upgrade factors for leveling tagents from about 1.1 to about phn 01 based on total powder coating formula weight; 0 of one or more flatting agents 89801 flatting calkyl (meth)acrylate copolymers from about 0.00 001 to about 6 phr of one or more waxes 8785/»; and from about 0.00 to about 7 01 by weight; Based on the total weight of the powder coating formula; of pre-mixed additives | Post blends such as dry flow aids such as LLY and smoked alumina fume 0 csunnal. Powder coating formulations are produced according to traditional methods. ingredients can be mixed; and then mix it closely; like; For example; By melt-assembly so that no noticeable hardening occurs. molten compound 0101180 can be extruded; after ejaculation; rapid cooling; followed by a tahwa; as necessary; Classification of particles according to size. laa) in the OAT embodiment assemblies can be produced

Agglomerate powder coating by aggregating particles comprising an acrylic copolymer with a non-call hydrophilic micron particle to form agglomerate particles. Powder coating formulations can be used by conventional means. For electrostatic coating

Yoo average particle size can range from about © to about electrostatic coating © µm; in another embodiment preferably of about μm or greater; and about Vo micrometers or less. Once set DHA coatings harden eg" at a temperature of about 90 to about You°C for a period of about 0 * sec to about 90 min. The heat for thermal hardening can come from a convection source; Infrared (IR) infrared or near-0 infrared source. Suitable substrates may include; for example aluminium; on forged alloys cna calloys steel; magnesium alloy; Jie electronic goods and brass hardware Jie cbrass Lock and door hardware. Aluminum substrates can include; For example JB on aluminum lithium aluminum alloys caluminum silicon alloys aluminum aluminum magnesium dithium alloys Yo 060 aluminum manganese 1180980656 0 aluminum copper base alloys base alloys such as caluminum bronze and the like The alloys may be monomeric, bimetallic, or more than two metals In one embodiment the bases are preferably pretreated Aluminum alloys may be 0 and dyed are pretreated with “(JU) self-assembled monolayer of sale organic material The layer is self-assembled phosphor; acrylic modified zirconium or zirconium titanates passivating Steel and iron substrates can be pre-treated with Witanate iron phosphate or zinc phosphate agents.

— ¢ \ — in one of the embodiments»; The resin has a glass transition temperature greater than 85°C; and in the AT embodiment preferably about 90°C or greater; In another embodiment also more preferably from about 0 °C to about 100 °C Aggie preservation of an appropriate acrylic copolymer ensures glass transition temperature De-blocking resistance or stability when packing while proper flow and wafer-forming properties are maintained. . The examples listed below are provided to illustrate the embodiments of the functionalized epoxy-group acrylic resins and powder coating formulations described herein and are not intended to limit the protected scope of the invention. Examples 0 Resin Synthesis Examples Synthesis Example 1 (Comparative Example) 0150 grams of butyl acetate was charged into a 0000 o liter bottom glass reactor of ; Necks equipped with mechanical lie “mechanical stirrer” condenser nitrogen inlet and means for forming 10 bubbles bubbler measuring probe temperature sails feeding monomer / starting material monomer initiator feed tube The flask was heated under recurrent (at approximately 10°C) with nitrogen atmosphere. A monomer mixture was prepared by dla (£2 g) of butyl methacrylate 10.7 g of glycidyl methacrylate (7917 aba 083,4 (hls) of isobornyl methacrylate (bli ZAA) Isobornyl methacrylate Yo 75 g of methyl Af cody Sle 5 g of styrene 777.7 g of 156 butyl acetate in a © liter container An initiator solution was prepared by mixing 01 g of 215 sale TRIGONOX® (tert-butyl peroxy-?-ethylhexanoate) YTV, (tert-butyl peroxy—-2-ethylhexanoate) initiator grams of butyl acetate. The monomer mixture and the starter mixture were collected in one container TYAS streaming has been stopped

c \ — nitrogen Nitrogen flow to the reactor The monomer and starting material mixture was fed to the reactor over a cycle; hours. When the monomer and starter had been fed complete the feed line was flushed with 4.0 lb of ign acetate. The reaction mixture was cooled to approximately 111 °C and kept at the same temperature for a combined time of 0 yo min. A mixture of © 11 gram of 218 TRIGONOX® in 1 011 gram of butyl acetate into the beaker over the course of To 1 minute. When complete upon addition of TRIGONOX® 215 solution the line was rinsed with 0.0 g of butyl acetate. The reaction was kept at approximately 111 °C for an additional 1 min and then cooled to room temperature. Glass transition temperature (calculated) VY, v= °C = Mw 0 0 ÷ 0110 = Mn EEW = 25 NY - SP Functional group per molecule - 8_ Synthesis example? (Comparative example) 0050 grams of butyl acetate is charged into a © liter round bottom glass reactor with ; necks equipped with mechanical lia; capacitor; Nitrogen inlet and bubbler; Temperature measuring probe and monomer/starter feed tube. The flask was heated under reflux (at approximately YY °C) with nitrogen atmosphere. A monomer mixture was prepared by adding (8 lb 9 g of butyl methacrylate » carat g of glycidyl methacrylate Y) 74 activity) yate g of isoborneyl methacrylate 7A (activity A) » g of Je methacrylate with 1 gram of styrene and 777.7 grams of butyl acetate in a 0 liter container. A starting solution was prepared by mixing 155.6 grams of TRIGONOX® 215 starting material (tert-butyl peroxy-?-

ethyl hexanoate) and; pha Vo is from butyl acetate. The monomer mixture and the starting material mixture were collected in one container. The flow of nitrogen to the reactor has been stopped. The mixture of monomer and starting material was fed into the reactor over an orbit; hours. When the monomer and starter were fully fed, the feed line was rinsed with 58.28 grams of 0-butyl acetate. The reaction mixture was cooled to approximately © 111 °C and kept at the same temperature for a combined period of 300 minutes. A mixture of 11.8 aha of TRIGONOX® 215 in aha 011 of butyl acetate was added to the beaker over Te ae min. When complete upon addition of TRIGONOX® 218 solution the line was rinsed with 01.5 g of butyl acetate. The reaction was kept at approximately 111 °C for an additional 31 minutes and then cooled to room temperature. 0 glass transition temperature (calculated) = 1.1°C Mw = ducats YYY. = Mn EEW - d SP = 7 Functional group per molecule - 0 Ex. 0 ly 9" (according to {according to} amperage current) 0050 grams of butyl acetate was charged into a round bottom glass reactor Capacity © litres, necks equipped with mechanical lia, condenser, nitrogen inlet and bubbler, temperature probe and monomer/starter feed tube. A nitrogen atmosphere The monomer mixture was prepared by Alia (17 g glycidyl methacrylate 79V activity) TOA 1 g isobornyl methacrylate 7AA activity 1111 g methyl methacrylate 84 g of styrene and YYV,Y g of butyl acetate in a 0 L container A starting solution was prepared by mixing VEY (g) of M7

TRIGONOX® 5 Starter (Tert-Butyl Peroxy Y = Ethyl Hexanoate) and 108 grams of Butyl Acetate. The monomer mixture and the starting material mixture were collected in one container. The flow of nitrogen to the reactor has been stopped. The mixture of monomer and starting material was fed into the reactor over an orbit; hours. When the monomer and starter feed is complete, Calas is finished feeding the line with 58.5 g of butyl acetate. The reaction mixture was cooled to approximately 11 °C and kept at the same temperature for a combined period of 310 minutes. A mixture of 1,0 aya of TRIGONOX® 5 in aba 011 of butyl acetate was added to the beaker over 10 ae minutes. When complete upon addition of TRIGONOX® 215 solution the line was rinsed with 01g of butyl acetate. The reaction was kept at approximately 11 °C for an additional Fo min and then cooled to room temperature. Glass transition temperature (calculated) = 37.9 °C Mw = 174 yyay = Mn oY. - EEW q,Y¢ = SP 0 Functional group per molecule - 01 Synthesis Example 4 (according to the present invention) 0150 grams of butyl acetate was charged into a © liter round bottom glass reactor of ; necks equipped with mechanical lia; capacitor; Nitrogen inlet and bubbler; Probe 0 temperature measurement and monomer/starter feed tube. The flask was heated under reflex aie (approximately 111 °C) using a nitrogen atmosphere. A monomer mixture was prepared by adding ala 7 of glycidyl methacrylate (YATE 79) activity (YATE) 176 g of isobornyl methacrylate (alia 7) g of methyl cD Sle 84 g of styrene and 777, 4 grams of

A —_ \ _ butyl acetate in a © liter container. The teal solution was prepared by mixing 157.4 pba of sal TRIGONOX® 5 starter (tert-butyl peroxy-?-ethylhexanoate) with 10,5 g of butyl acetate. The monomer mixture and the starting material mixture were collected in one container. The flow of nitrogen to the reactor has been stopped. The mixture of monomer and starting material was fed into the reactor over an orbit; © Hours. When the monomer and starter feed was complete the feed line was rinsed with 58.5 g of butyl acetate. The reaction mixture was cooled to approximately 111 °C and held at the same temperature for a combined time of 0 © min. A mixture of 1.0 grams of TRIGONOX® 5 in 0.011 grams of butyl acetate was added to the beaker over the course of 10 minutes. When complete upon addition of TRIGONOX® 215 solution the line was rinsed with aba 01 butyl acetate. The reaction was kept at approximately 111 °C for an additional F min and then cooled to room temperature. Glass transition temperature (calculated) = 17.7 °C Mw = 11771 Mn = .91 oo. = EEW 10 ,YA - SP functional group per molecule - 11 Synthesis Example © (according to the present invention) 0050 g of butyl acetate was charged into a © liter round bottom glass reactor of ; Yo necks equipped with a mechanical lie “capacitor”; Nitrogen inlet and bubbler; Temperature measuring probe and monomer/starter feed tube. The flask was heated under rewind (at approximately 111 °C) with a nitrogen atmosphere. A monomer mixture was prepared by adding ala 7 of glycidyl methacrylate (79Y activity) - YATE grams of isoborneyl methacrylate

q —_ \ _ ZAA) activity) — 0111 g of methyl methacrylate” 011 g of butyl methacrylate” 84 g of styrene TOYLY 5 g of butyl acetate in a © liter container. A starting solution was prepared by mixing 147.1 grams of 215 sale TRIGONOX® starter (tert-butylperoxy-?-ethylhexanoate) and; pha 15 from butyl acetate. The monomer mixture and the initiator mixture© were collected in one container. The flow of nitrogen to the reactor has been stopped. The monomer and starting material mixture was fed into the reactor over a period of 8 hours. When the monomer and starter feed was complete the feed line was rinsed with 58.5 g of butyl acetate. The reaction mixture was cooled to approximately 111 °C and kept at the same temperature for a combined period of 0 Yo min. A mixture of © 11 g of TRIGONOX® 215 in 0 aha VT of butyl acetate was poured into the beaker over the course of 0 to 1 min. When complete upon addition of TRIGONOX® 215 solution the line was rinsed with aba 01 butyl acetate. The reaction was kept at approximately 111°C for an additional 10 minutes and then cooled to room temperature. Glass transition temperature (calculated) = AVY °C Mw = 4 =Mn 10 75 CR = EEW q,Y¢ - SP Functional group per molecule - “0” Contents displayed Each of the examples of the 0-1 synthesis in Table OF is associated with their properties. TYAY

for NY la, for ASTM © 1400-00 “Standard Test Method for Nondestructive Measurement of Dry Film Thickness of Nonconductive (Coatings Applied to a Nonferrous Metal Base”, 2000 Record the wafer thickness as banding (low to high) for the three readings measured in the center portion of the sheet © Cross Adhesion: Crossshatch Adhesion Coatings were tested in accordance with the adhesion test method published by the American Society for Testing And Materials (ASTM) using the method "Standard Test Methods for Measuring Adhesion by D3359-02 ‎Tape Test, Test Method B--Cross-Cut Tape Test (2002) 99 8A100006; and then quick removal of the tap. The cutting area is then checked to determine if the coating has loosened or peeled off; the area is marked with a rating. A grade of Be is excellent; requires no removal of the coating. An 80 degree can indicate indicates that 765 or more coatings have been removed thus showing poor adhesion to the substrate Acceptable adhesion grade is BY GMW14458 (ISO 9227: General Motors Copper Accelerated Acetic Acid Salt Spray Test Vo) The Copper Accelerated Acetic Acid Salt Spray Resistance Test for Powder Coatings was performed on 20065) by Lede (done). Obtaining machined aluminum plaques

Custom Alloy Light Metals, City of Industry, CA USA of aluminum alloy 1 mm notch by cutting a notch through the coating to the bottom of the substrate (approximately the length of A356 ingot 0 - perpendicular to the machining lines using a tool / scribing tool fixture MA-08+0106 per 2634L SAE A continuous check was carried out along the entire length of the scribing to ensure detection of base metal 0858. The slitted plates were placed in an accelerated salt spray chamber (Q-Lab) accelerated salt spray chamber equipped with an air pressurized atomizer for a solution of fan 0 + 5 0 L sodium chloride (NaCl) sodium chloride Yo and 7 + fas 1 L copper chloride ( I) Dihydrate

yy in deionized water having the number (CuCl, - 2H,0) copper(ll) chloride dihydrate

VIA sad at 00°C + ? °C VV of 1,? To pH on each type using a metric measuring ruler and hourly filaments. The lengths of all the filaments were measured Maximum creepage Recording the maximum elongation Capillary corrosion test for greased aluminum wheels 0011 (AUG) SAE EE 2635L

Painted Aluminum and Painted Aluminum Wheels Wheel Trim resistance test was carried out on powder coatings

Custom Alloy Light Metals, City of Forged Aluminum (obtained by Industry, CA U.S.A. of aluminum alloy A356 ingot mm grooving length) based on 171 grooving tool/forming lines Plating under the substrate (approx. 0 carbide bits per 2634L]/5. A continuous check was carried out along the entire length of the notch to ensure detection of base metal. The plates with the notches were placed in a precipitated acetic acid salt spray chamber so that they were ASTM B 368-97 (2003) (001”) 597-714 Copper per ASTM B non-metallic plaque and groove approximately 0° horizontal on a non-metallic rack Plaques exposed for 7 hours In a chamber spraying a copper-accelerated acetic acid salt as Vo 806 (lady Jame after spraying an acetic acid salt 97-7378 (0017). Described as ASTM 900 clad) seconds sad A oscillating spin rinse was performed min after rinsing Every 11 was placed on each plate The plates were placed in a humidity chamber through the plates in the humidity chamber so that the moisture droplets partially end at approximately 0°C Courier detected I. 177 sad Plaques inside the humidity chamber, 0 hours. The lengths of all filaments were measured on each VIA. The maximum increase of filaments per plaque of each type was evaluated using a metric ruler. The average elongation (filament length) and maximum elongation (the longest filament length) were recorded.

BYK Heavy-Duty Impact: Impact resistance testing was performed using BYK Heavy-Duty Impact

ASTM D 2794-93 'Standard Test' following standard 'model G1120 (Tester Yo

TYAY

Ad \ — — Method for Resistance of Organic Coatings to the Effect of Rapid Deformation (Impact) A four pound weight was used for testing. Obstruction resistance: The test method provides an assessment of the resistance of a powder coating to obstruction; kneading or flocculation; 2 Assemble equipment containing a glass test tube You mm long Yo mm in diameter A nylon or ceramic cylinder approximately 01 mm in height and approximately 0.77 mm in diameter such that the cylinder should slide freely in the tube; A lead shot shell and an oven capable of storing 1 011 + degrees Fahrenheit. The test tube was filled with powder to a height of 1" mm. The cylinder was placed on top of the powder sample in the test tube so as not to damage the integrity of the sample and to avoid premature compression. A lead shell was placed on the top of the cylinder so that ea) Weight of shell and cylinder assembled 1 + 100 g. The entire assembly with test tube oriented vertically was placed in an oven with internal air temperature of 1 + 110 degrees F. After “YE” hours A) the test tube containing Weighed powder sample from furnace and allowed to cool to room temperature Cylinder and lead shot were carefully poured out of test tube so as not to damage the powder Exposed powder sample was assessed visually for obstruction and grade determined by means of the scale described in Table Y The test can also be extended over a longer period of time, with the extent of obstruction checked in YE hour intervals. The maximum acceptable obstruction resistance is 1H after VE test. The powder is free-flowing; no sign of lumps or bulges

Agglomerations .agglomeration . The powder is free flowing; But it has a few bulges or clumps, as it is easy to break it into the powder. The powder is free flowing; But it contains an average number of bulges or EAS nw where 3 | 1 Friability into a powder: The powder is fractured but easily friable into the powder upon removal from the test tube. the powder is broken; It is of moderate difficulty to break into a powder upon removal from the test tube. The powder is fraction 3 and is very friable within the powder + upon removal from the test tube. the powder is broken; It can be broken down; But not inside the powder, which is free from clumps. 1 The powder is melted into a hard lump that can be broken with difficulty in The powder is melted into a hard lump that can be broken with difficulty in large pieces SU The powder is melted into a hard lump and no longer longer in an adjustable form Va as if it were not a powder. Milling A0: Milling was carried out on an ICM 11 2.4 95/158 CX/System 110-PSR (Neuman & Esser, 06801-08160069, Germany) using an A-bolt mill and an impact classifier. 1010801 has a 71-pound tooth with a speed setting of 84 m/s

Duo "mill speed mill and 11 m/sec for classifier with intake air flow of 111-90 ft"/min. Examples 1 to Formulation and Application The powder coating formulations of Examples 1-5 of the ingredients listed in Table ¢ were performed according to a method whereby the raw ingredients are mixed with a Prism Mixer for Ve seconds at 0 RPM after ejaculation in Coperion Werner & Pfleiderer, Stuttgart, ( ZSK-30 (Germany) at 5000 rpm; 6-71 77 Torque f /97/A-111 °C ( 1976- 77 degrees Fahrenheit) barrel temperature settings. The resulting molten extruded mixture was fed through cooled chill-rolls to form a solid sheet which was then granulated into strip form. Mixing the pre-mixed additives (dry flow) with the slides by shaking in a bag for 0,75-5, min. The pre-mixed slides were then ground to fine powder in a laboratory mill Wuppertal, Retsch ZM lab mill (Haan, Germany at Yo, ere) rpm using a 0.1 mm sieve. The resulting BES! powder 900000 was ground through a VE micrometer sieve. Yor Mesh) for use thereafter to form coatings and T.T Apply to the indicated substrate using Versa— (Nordson Corp., Westlake, OH) Spray an electrostatic spray gun to the indicated thickness and then solidify at 117.6° with YVO (°F) for 10 minutes in an electrically heated lab oven Blue (SPX Thermal Product Solutions, White Deer, PA) M DC-206G Ye Table oF Synthesis Examples Synthesis Example | Synthesis example Example example Synthesis example

Ag Ad _ Calculated Glass Transition Temperature AVY ay, ¥ v4 YY, YY, (Degree) SPc (qr/q,v¢ 1,YA 71 47 47 AFA / 7 cm set Functional VY, 0 0" 0,1 per molecule Table ;: Examples Powder formulation CC Raw material Amount (percentage by weight) achieved

#1

HERE i | > i z 0 ntm kk na a 7 i > i z 0

BE = > i z 0 a 7 i > i z 0 he ” Acrylate copolymer 3 flow modifier T#1 “” T#1 “” T#1” 'T#1' 'T#1' 'polyester ghd oo methyl succinate 'Polyester of dimethyl 9001368 using 4-hydroxy bE 4-hydroxy tetramethyl tA tA tA tA tA piperidine ethanol Organophosphite © Ye Ye Ye Ye Ye Ye antioxidant Ye Ye Ye Ye Ye YES . y alias 50.83 Phenolic TYAY

The issue is that we are an an benzoxazoles Bis “Dioxazine violet* Dioxazine Ye Ye Ye Ye Ye Ye ?Glycidyl trimethoxy silane Smoked aluminum oxide - flow Gala Fumed aluminum oxide - Dry flow ZZ ZZ ZZ Sebacic Acid, ICC Chemical Corp., Warrenville, IL. 1 Mi Won benzoin, GCA Chemical Corp., Bradenton, FL. Y. Resiflow™ PL 200, Estron Chemical, Calvert City, KY. ¥ UVAsorb™ HA22, 3V Inc, Charlotte, NC ¢ © Tinuvin™ 405, BASF Pigments and Resins, Ludwigshafen, Germany. .o Ultranox™ 626, Addivant, Inc, Middlebury, CT. 5. Irganox™ 1076, BASF Plastic Additives, Basel, Switzerland. .1; Optiblanc™ PL, 3V Inc, Weehawken, NJ. Hostaperm™ 14-4006 Violet RL SP, Clariant, Charlotte, NC. .A 1

Since Xiameter™ OFS-6040 Silane, Dow Corning Corp., Midland, MI. 4. Airoxide™ C, Evonik Corp., Parsippany, NJ.\ .on 0 ut The aluminum substrate used for corrosion resistance testing (filament© and spraying copper-accelerated acetic acid salt) was prepared in the following manner. Raw Aluminum die cut (wo aluminum ingot) Alloy A356 (Lhe obtained from Custom Alloy Light (Metals, City of Industry, CA) 1,7" oxy, e Then forming on both sides using a diamond tipped lathe with an approximate width of 001 microns for each machining line. Surface treatment dallas dat 0 for aluminum plaques. by a commercial primary dallas using the following 4 stages in a haley pattern with deionized water rinsing between steps: Mild alkaline cleaner acid deoxidizer aes 007 discoloration of zirconium titanate titanate and a self-assembled monolayer of phosphorous organic material an final drying was done 156 °C VO sad min in an electric oven to ensure that the substrate was completely dry before packaging.Then the plates were sealed Pre-dalled aluminum vacuum bagged and powder coated within YE 1 hour of initial curing. T for Vo min to reach a substrate surface temperature (Ls day) of 11.1 degrees Fahrenheit (You) for flakes of thickness 0.75-5 μm (approximately Woo mY, mm). 0 - Table io Results Example 1 1 ¢ TYAS

q —_ since collision resistance; Direct (in. lb) (sheet of | Ye \E Ye Ye 01 steel) Cross Adhesion (Grade (Al #5)) 8 dela VE snagging resistance 1¢ VIA hour snagging resistance A 1 Filiform 2635L SAE (Average (pe AY) 1,85 p 11 (formed Al plate) Filiform 2635L SAE (maximum elongation 1,0 mm 1, 0 0 Suction Y,e (formed Al plaque) H 61/144568 v¢. Alllain ail) CASS | ¢ 8 and 0 mm) (formed Al plain) BYK Wavescan on 1 L N 1 &Y=L|K XY = Ll “S (L .8) Lab Grind (FLA values — 5 A, . = 8 FY 5 = B 5 = A (R 9 watery watery AM = R| H 01 = R | AT (average of 7 times)

=« _ (A plate (-Al =R 5,2 BYK Wavescan on ¢S iL ad) ICM Grind c i=Lp YA=S| yv=8 (R ( Average (1 times test) 0. =R|V+) =R((-Al) plate As shown in Table 0 Examples oF;05 show that a polymer has a glass transition ha greater than AS °C provides significant improvement in acetic acid salt spraying with copper and capillary corrosion resistance compared to commercial epoxy-functionalized copolymer acrylic powder coatings of Examples 1 and which have a glass transition temperature of less than 85°C. Furthermore, this improvement is achieved while maintaining impact resistance and cross-adhesion that can be expected to be sustained when using a polymer having a higher glass transition temperature. Using a laboratory abrasive shal compared to commercial functionalized epoxy group copolymer powder coatings in Example 1 and as indicated by the relevant BYK Wavescan values of 0. Wavescan values could be further improved using a range abrasive Experimental pilot—grinding equipment 6a508; As shown by the example; As it does not show a decrease in softness characteristics compared to Yall in addition; As shown in the table M illustrates the example? Significant improvement in resistance to disability over that produced by Example 1. Hence; il) of the present invention demonstrates a relatively high Sha Vo glass transition (97.9 degrees (Ashe) resisting retardation discernible at conventional and extended test lengths when subjected to heating conditions not exhibited by a resin having a transition temperature Much lower glass YY glass transition temperature (Basie

— \ ¢ — The contents of all documents mentioned are included in the detailed description of the invention; in a relevant part; in this document for reference; The mention of any document shall not be construed as an acknowledgment that it is the prior domain in relation to the present invention. Although particular embodiments of the present invention are shown and described herein, it is not intended to limit the invention to the details shown. Instead of that; Various adjustments can be made in the details within a scope

And the scope of the equivalents of the claims and without deviating from the content and scope of the invention. All phases with exclusive clauses indicate any or both of the included clauses and their absence. For example, the term “(co)polymer” includes alternatively 1 1 copolymer 1 copolymer and mixtures thereof.

10 unless otherwise noted; All indicated operations and each ARG) were carried out under standard temperature and pressure (STP) conditions. All ranges listed here are inclusive and can be aggregated. For example; if an ingredient is present in a quantity in quantities of 0.05 7 wt or more than 0.1 / wt; in quantities up to 0.5 7 by weight; Then the ingredient may be present in amounts from 105 to 7 01 by weight; From 1*9 to 7 01 by weight or from 0.06

1 to Zoe by weight. As used here the expression 'mean particle size' should indicate; unless otherwise indicated; refers to the particle diameter or the largest particle dimension in a particle distribution as determined by laser light scattering using the Malvern Mastersizer™ 2000 instrument.

(Instruments Inc., Southboro, MA) per manufacturer-recommended procedure. Y 0 As used here ¢ The term 'powder coating' refers to a coating formed from a powder coating composition. As used here the expression ads! co" to any polymer made of two or more different monomers. TYAS

_ \ —_ as used herein unless otherwise indicated; The expression 'glass transition temperature' or Ty is calculated for any resin or (co)polymer as described by Fox in Bull.

Amer. Physics. Soc., 1, 3, page 123 (1956) as used ols The term “hybrid” of any (co)polymer or resin shall refer to materials (ald5) grafts or templates of copolymers block copolymers and compatible or compatible blends of such (co-)polymers or resins, such as epoxy polyester hybrids.

Advanced Chemistry Development (ACD/Labs) is specified using dime of Chemical and is available in “Software V9.04 (© 1994-2007 ACD/Labs) 0

Abstracts’ Registry as used herein The term “(meth)acrylates” refers to any acrylate or methacrylate and the term “(meth)acrylate” refers to either an acrylic or a methacrylic. as used herein unless otherwise indicated » The expression ‘StS weight’ refers to the weighted average Vo of a polymer as measured by a calibrated gel-transfer chromatography using polystyrene standards as used herein. The expression ‘monomer a non-ionic conjugate” to monomers that do not have acidic groups or salts; basic groups or salts; condensation if. polyahl groups or crosslinking groups “(NH SHOH eg Juan le). Syntax used here The expression 'oligoorganosilicon' denotes any number from 1 to Yo a unit containing silicon and the prefix 'polyorganosilicon' includes more than one Yo unit containing silicone.

As used cla the expression 'phosphorus acid group' refers to an phosphorus oxo acid having a GuaPOH moiety in which the hydrogen atom is ionizable. The expression 'acid group' is also included Phosphorous "salts of phosphorus oxo acid, i.e. where it has a Jie cation © metal ion or ammonium ion replaces the acid proton

the least proton. Examples of phosphoric acid groups include formed groups of phosphinic acid phosphonic acid phosphoric acid aes phosphoric acid pyrophosphinic acid pyrophosphoric acid partial esters terminator and salts thereof.

Ye as used la The expression 1m refers to the quantity; Polymer! on random copolymers; stereotyped segmented and grafted; and any mixture or combination thereof.

Vo As used here the terms 'resin' and 'polymer' are interchangeable. As used here 'resin system' refers to an aggregate epoxy resin; ly toughening resin; crosslinking compound; curing agent or a sale hardener (but not a catalyst) that becomes an integral part of the cross—linked structure.

Je YS Syntax used here The expression “substantially free of copolymerized monomer (designated)” indicates that an acrylic copolymer comprising ? 7 wt. or less of the given copolymer monomer; Based on the total weight of the copolymer monomers. in this document; unless otherwise stated; All percentages are by weight.

Claims (1)

M. Cement elements - 1 acrylic resin with a functional epoxy group, epoxy functional acrylic resin includes; as copolymerized monomers (i) from 7 01 wt to 7 560 wt of ¢tepoxy functional unsaturated monomers (ii © from 7 01 wt to Yo 7 wt. Hydrophobic acrylic monomers “acrylic monomers and (i) from 50 7 wt. to # 7 wt. of a nonionic copolymer different from hydrophobic acrylic monomers (ii hydrophobic acrylic monomers) each monomer monomer 7 by weight based on the total weight of the copolymer monomers tresin BLY in copolymerized monomers 0 °C to 95 °C; And 500 temperatures transform glass from resin, where the resin has, to 9.01 calculated from the solubility parameter, the solubility parameter of resin, where the resin has oe (cal/A | 7?- Acrylic resin with the epoxy functional acrylic resin according to claim 1 wherein it is hydrophobic acrylic monomers (ii hydrophobic acrylic monomers) with a mass solubility in water of 7.0 faa L and where it can It forms a homopolymer with a (Ty) glass transition temperature from 00°C to 175°C. 01 According to the element of epoxy functional acrylic resin, acrylic resin with the epoxy functional group - (ii hydrophobic acrylic monomers, where hydrophobic acrylic monomers 1) Protection .bicycloalkyl (meth)acrylate C ¢ — ;- 1 acrylic resin epoxy functional acrylic resin of claim (FF) wherein bicycloalkyl (meth) acrylate is isoborneyl (meth) acrylate .isobornyl (meth)acrylate 0 *#- acrylic resin of epoxy functional acrylic resin according to claim 1 in which there are hydrophobic acrylic monomers in an amount of 14 7 by weight to 72 010 wt. = epoxy functional acrylic resin of 0 claim 1 wherein the iii copolymerized monomer is Ci to Cg ( Cyclo-alkyl ester of (meth)acrylic acid .acid aul -1 acrylic with epoxy functional acrylic resin according to No protection element 0 where the iii nonionic copolymer is butyl (meth) acrylate or methyl methacrylate A = . epoxy functional acrylic resin of claim 0; also comprising 1,5 7 wt. to 11 7 wt. of thienyl monomer Aromatic vinyl eli ¢(iv aromatic monomer 0 over total weight of copolymerized monomers 5 in 1-group 1 acrylic resin . epoxy functional acrylic resin - 1-group acrylic resin epoxy functional acrylic resin according to claim 1 wherein the vinyl aromatic monomer 0 is styrene .styrene YO PR includes: powder coating composition -0 according to epoxy functional acrylic resin component protection 1; and resin zB) crosslinkers o where Vv is according to the element of protection powder coating composition 11-organic powder coating composition is organic dicarboxylic acid crosslinkers that are crosslinking compounds or polyester or an excess thereof with polyester anhydride or anhydride dicarboxylic acid polyisocyanate isocyanate 01 of claim 10; Powder coating composition The powder coating composition -1 selected from the group that includes adjuvants also includes auxiliary materials, adhesion, chydrophobic submicron particle, hydrophobic, ultraviolet waves, absorber. light stabilizer promoter and combination thereof (UV) ultraviolet 0 powder coating Coated with a coated substrate =) mentioned: powder coating composition Coating ccomposition according to epoxy functional acrylic resin epoxy functional acrylic resin protection 1; And Yo resin zB) crosslinkers crosslinking substrates where the substrate is VY according to the coated substrate -64 forged alloy or aluminum alloy The validity period of this patent is twenty years from the date of filing the application, provided that the annual financial fee is paid for the patent and that it is not invalid or forfeited for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties, and industrial designs, or its executive regulations issued by King Abdulaziz City for Science and Technology; Saudi Patent Office P.O. Box TAT Riyadh 57??11 ¢ Kingdom of Saudi Arabia Email: Patents @kacst.edu.sa