SA112340118B1 - Solvent-based coating compositions - Google Patents

Abstract

Coating compositions are disclosed. In some embodiments, the coating compositions are used to coat substrates such as packaging materials and the like for the storage of food and beverages. The coating compositions can be prepared by reacting an epoxidized vegetable oil and a hydroxyl functional material in the presence of an acid catalyst to form a hydroxyl functional oil polyol, mixing the hydroxyl functional oil polyol (with or without epoxidized polybutadiene) with a functional polyolefin copolymer to form a mixture, reacting the mixture with an ethylenically unsaturated monomer component in the presence of an initiator to form a graft copolymer, and crosslinking the graft copolymer with a crosslinker to form the coating composition.

Description

1 Solvent-based paint formulations

Solvent-based coating compositions Full Description BACKGROUND The present invention relates to coating compositions; methods for coating substrates with coating compositions; and substrates coated with paint formulations. The current technology relies primarily on epoxy resin technology (dalled) © with amino resins and phenolics. Paint formulations consisting of @pOXY resins oS su have been used based on bisphenol A A and polyvinyl chloride for coat packaging and containers 0018065 Food and Beverages Beverages However; There is a desire among some consumers and brand owners for coatings compositions free; or null to a large extent 0; Bisphenol A and polyvinyl chloride for food and beverage packages and containers. The publicly owned patent publication (Yo) Ve ITY describes the composition of a coating comprising a hydroxyl functional oil polyol by a method comprising the reaction of epoxidized vegetable oil (epoxidized) with a substance with a hydroxyl group hydroxyl functional material having 1 acid catalyst .acid catalyst GP Sell Publication 171001010 describes a coating composition comprising a copolymer doped with an acrylic alcohol hydroxyl functional oil polyol acrylic graft with hydroxyl functional group prepared by a method comprising the reaction of an epoxide vegetable oil with a material having a hydroxyl functional group in the presence of an acidic catalyst to form an oily polyhydroxyalcohol ‎To having a hydroxyl functional group; Reaction of an oily polyhydric alcohol with a hydroxyl functional group with an ethylenically unsaturated monomer component

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A 00000014 in the presence of an initiator to form a copolymer doped with an acrylic alcohol polyhydroxyl oil with a hydroxyl functional group; The copolymer doped acrylic polyhydric alcohol oil with a hydroxyl functional group was crosslinked with a crosslinker to form a coating composition. However; Some oil polyol technology does not have good flexibility © in basa It can benefit from other modifications when the material to be used is a coating compound on Bae Description of the British patent application 4 1797.6 aluminum can Aluminum or steel plated with tin © 10060-518_Soft Drinks Beverages 081001138160 Protected by formulation aqueous coating of copolymer 1 + © 7/00 A6000 Polyethylene - maleic acid. Vo solution 80016015 as applied preferably contains from —0 + NY% by weight weight solids which is too low for applications ending in beverage can 8005-080 .beverage The coating applied to the 56 substrate has also been heat-cured at 100°C for VY minutes which is too long and not applicable for ALE 080-8005 case finish applications. There is a desire for Ve to produce coating compositions for packaging which do not contain BPA-8 or PVC or are largely free of them. The coating compositions of the invention may be used; While gin is used as a filling coating for food and beverage cans and containers. Can be formulated to provide application lef stiffness and improved toughness Corrosion resistance (St) flexibility Peal blush resistance and retort resistance compared to some coating formulations 0 Commercial coating compositions. General description of the invention The technology of the present invention has the ability to provide coatings that are more rigid and durable; abrasion resistance; flexibility; redness resistance; better retort resistance than some coating compositions of the present technology. The higher Yo ratio of solids allows a range of Wider coating in a .single pass operation Evy

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Coating formulations may contain 9675 or ye Jes J renewable oil polyol, which contributes to sustainability and meets the needs of global consumers. The functional polyolefin copolymers of the invention provide film flexibility and good adhesion to the substrates.

© .metal substrates The easy-to-open ends for beer and beverage cans for sale are manufactured by first coating a flat sheet 181 of a metal substrate “heating the coated substrate” and then Molding stamping or shaping 9 The coated substrate into the desired shape. Coil coating lines are required

High speed High speed often coating compound that will dry and cure within seconds peak metal large to peak metal temperature depen low as the substrate is heated 0 Aggie can be applied 700 degrees to about 001 Which may range from about temperature coating compositions of the present invention on the ends of beer and beverage cans and may be applied in weights

Film weights Approx. 1 mg per square inch to Approx. 01 mg per square inch

On the high speed coil coating line. The Jal invention provides an alternative to combinations

Vo mil epoxy resin-based coatings that still allow for a formaldehyde free cure; The blush resistance has the ability to retort and can handle tough drinks. The present invention includes processes for producing coating compositions; like combinations

Solvent-based coatings and coating compositions formed by this process “These processes can be performed in a single reactor or in reactors

0 multiple reactors in some embodiments of the invention; The coating compositions are prepared in a way that includes the steps of reacting an epoxide vegetable oil with a substance with a hydroxyl functional group in the presence of

Acid catalyst (eg Lewis acid catalyst and solvent Jas pl oily polyhydroxyl with hydroxyl functional group; mixing of an oily polyhydric alcohol with hydroxyl functionalized copolymer of an olefin functionalized

epoxidized (with or without functional polyolefin copolymer Yo; the mixture reacted with an unsaturated ethylene mixture to form a polybutadiene mixture

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In amy, an initiator _ to form a graft copolymer and crosslink 9 grafted copolymer to form the coating composition. In some embodiments of the invention; The coating composition is prepared by a method comprising mixing an oily polyhydric alcohol with a hydroxyl functional group (with or without polybutadiene epoxide) and a copolymer of polyethylene (meth Au)acrylic in the presence of an acidic catalyst (e.g. Lewis acid catalyst) to form a mixture; Then grafting the unsaturated monomer component ethylene in the presence of an initiator to form a .graft copolymer in some embodiments of the invention; The paint composition is prepared by mixing an oily polyhydric alcohol with a hydroxyl functional group and a copolymer of polyethylene(meth)acrylic acid (with or without polybutadiene epoxide) Sl 0 mixture; Then the inoculation of the unsaturated ethylene monomer component to form a grafted copolymer and the interaction of the grafted copolymer with a BPA free epoxide crosslinker to form an aqueous microgel polymeric coating is useful in can coating applications 008100. An alcohol may dissolve an oily polyhydroxyl of the hydroxyl functional group in a polyolefin functionalized copolymer solvent at 0 high temperature (eg 061 °C). or butyl; It can be polymerized in the presence of a starter. Acrylic monomers can be grafted onto an oil polyol backbone or onto formed acrylic copolymers. It was discovered that polyethylene acid as a functional polyolefin copolymer was more suitable with the acrylate polymer. 0 . in the presence of an oily polyhydric alcohol; And that the polyethylene acid provided good adhesion and elasticity for the film performance. Sometimes the copolymer of the functional polyolefin has a separate layer (separate phase) with the acrylate polymer and produced an opaque hazy film without the presence of

Oily polyhydric alcohol. In some embodiments of the invention; Polybutadiene Yo epoxide coating polymers AS can; such as 001750600 in solvent; The acidic copolymer of polyethylene

for etc

High temperature (such as 040°C). The unsaturated monomer component (Jie basi) can be polymerized styrene or butyl acrylate; in the initial existence. Say the grafting of acrylic monomers onto the epoxy butadiene structure or the acrylic copolymers formed. The epoxy polybutadiene contains an epoxy group and an unsaturated group. The EPOXY group may react with an acid group of a polyethylene acid and may react The unsaturated group with the unsaturated monomer component is ethylene and crosslinks to form a coating composition using Jie crosslinkers phenolic crosslinkers and BPA-free epoxy-based crosslinkers BPA 5-©» A10A0055.Coating Polymers Consisting of Oily Polyhydroxyl Alcohol;0 A Functional Polyolefin Copolymer and an Ethylene Unsaturated Monomer Component May Be Crosslinked to Form a Coating Composition Using Crosslinks Such as a BPA-Free Phenolic Crosslinker or Epoxy-Based Crosslinker Showing Coating Compositions The present invention has very good film performance when coated on Jie BSH easy-open—ends for beer and beverages.In some embodiments, the invention Jal includes methods for coating a substrate by applying a coating composition A on the substrate. 1 Substrates coated with coating compositions are also described. in some embodiments; The substrate is can or .packaging ssc Detailed Description: As used in the previously discussed embodiments and other embodiments of the description and claims described here The following terms generally have the meaning indicated (card) but these meanings are not intended by 0 Limiting the scope of the invention if the utility of the invention is realized by inference in a broader sense of the following terms. The invention (Jal) includes substrates that are at least partially coated with the coating composition of the invention and methods for coating the substrates. The term 'substrate' as used herein includes; without limitation; Cans; metal cans; Easy Open Ends » Packages; ded calla or any parts thereof use Bla to touch or come into contact with any type of food or drink. also; the terms 'pillar'; 'can (le) food'; Yo "food containers" and the like include; Unlimited eg; Evy

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"can ends", which can be molded from the raw material can end stock for the end of the can and can be used to fill food and drinks. The present invention includes methods for preparing compositions

Coating by reaction of vegetable oil epoxide with a substance with a hydroxyl functional group in the presence of an acidic catalyst to form an oily polyhydric alcohol with a hydroxyl functional group; Mixing multiple alcohols

© oily hydroxyl of a hydroxyl functional group (with or without a polybutadiene epoxide) with a polyolefin functional copolymer to form a mixture; the mixture was reacted with an ethylene unsaturated monomer component in the presence of an initiator to form a bait copolymer; The grafted copolymer is crosslinked with a material

crosslinking to form the composition of the coating; paint formulations may be used; led among others; In preparing coatings for food and beverage packages and containers. In some embodiments of the invention »

(0) preparation of the coating composition by a method comprising the reaction of an oily polyhydric alcohol with a hydroxyl functional group − or without a polybutadiene epoxide; Jie 001750600 or available from Cray Valley or a copolymer of polyethylene (meth)acrylic and an ethylene unsaturated monomer component in the presence of an acid catalyst (such as a Lewis acid catalyst) and an initiator to form a bait copolymer; crosslinking of the graft copolymer with crosslinking material to form

1 Apply the paint. In some embodiments of the invention, the coating composition is a solvent-based coating composition. Solvent-based coating formulations may contain an unfunctionalized monomer and/or have a functionalized hydroxyl group; Optionally with higher levels of the acid functionalized monomer to put the composition in a 50 O 1000 solution. For example unlimited; The composition of the solvent-based paint may include an unsaturated ethylene monomer component containing non-polymers

unlimited butyl; Butyl acrylate JB is unfunctional eg; for example bully) saturated Yo methacrylate » styrene ; Stearin methyl methacrylate Methyl methacrylate ¢ acrylate

benzyl methacrylate and the like and mixtures terminated and optionally in smaller quantities

of functional monomers such as; Unlimited eg; hydroxy propyl methacrylate “hydroxy ethyl acrylate” yo glycidyl methacrylate ¢ £1 “acrylic acidell” methacrylic acid ; acetoacetoxy ethyl methacrylate

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phosphate esters mono-methacrylate phosphate esters and the like and mixtures thereof. In some embodiments of the invention; Monomethacrylate is added to the monomer with the functional hydroxyl group at a level of about 9678 of the weight of the unsaturated ethylene component mixture. The monomer component mixture is added to the monomer.

© is acidic functionalized to a level of approximately 70760 by weight of the ethylene unsaturated monomer component mixture. in some embodiments; Acetoacetoxyethyl methacrylate is added at a level of up to

Approximately 96,708 by weight of the unsaturated ethylene monomer component mixture. Mono-methacrylate phosphate esters can be added (PamM=400 5 Sipomer 080-100, 08:07-200 Jie) at the level of

It amounts to about 9670 by weight of the unsaturated ethylene monomer component mixture. In some

0 solidifications; Approximately 01 to about 9656 by weight of the unsaturated monomer component mixture is ethylenediaminetreally an acid functional monomer in some embodiments; The monomer is acidic. The function is methacrylic acid. The epoxy vegetable oil can be used alone or in combination with other vegetable oils. Epoxy vegetable oils can be prepared from vegetable oils by; for example

formic or acetic Addition of hydrogen peroxide and formic or acetic acid smal eg Gale Vo to vegetable oil; Then contain the mixture at a high temperature until some or all of the 0 is converted into epoxide groups. Carbon-carbon double bonds, which are primarily glycerides. Vegetable oils primarily contain Glycerides in degrees of fatty acids and fatty acids triesters of glycerol

Yo varies varying degrees of unsaturation 105810178100. eg unbounded; Epoxy vegetable oils for use in the invention can be prepared from vegetable oils (glycerides

Jie (fatty acid triglycerides) without limitation; esters of glycerol and fatty acids with an alkyl chain of about 11 to about

;? A carbon atom. Fatty acid glycerides, which

unsaturated in unsaturated glyceride oils triglycerides form triglycerides Yo

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Oils 9170661106 are generally referred to as dried or semi-dried oils 56001017/109. Drying oils include but are not limited to 0115 Drying Oil; linseed oil; Perilla oil 8671/18 and blends (gis combinations) while semi-dried oils; no pas include tall oil; soy bean oil; safflower oil and blends. of which Triglyceride oils in some embodiments contain identical or alternatively different fatty acid chains attached to the same glycerol molecule in some embodiments; oils contain fatty acid chains containing bonds 000 conjugated double bonds In some embodiments conjugated double fatty acid chains or a single double bond 0 are used in small quantities The unsaturation of the double bond in glycerides can be measured by the value Iodine 0 degree (number) double bond unsaturation in chains which indicates the degree of iodine value of the fatty acid Unsaturated fatty acid glyceride oils used in some embodiments of .701 and about 001 and alternatively between about The YO of the invention has a YO value greater than approx

1 Vegetable oils existing in nature for use in the invention may be JE Unlimited; Mixtures of fatty acid chains present as glycerides; Gen peal is a limiting distribution of glyceride fatty acid esters; Where the distribution of the fatty acid may be random, but within the subject range, which may vary moderately based on the growth conditions of the vegetable source. Soybean oil is used in some embodiments, which

0 contains approximately 9611 Ja palmitic fatty acids ; Je 964 stearic »about © 967 oleic »; About 9651 linolenic » and about 969 linoleic

dlinoleic where is oleic ; Linoleic and linolenic are unsaturated fatty acids 0015810138180. Includes unsaturated vegetable oils used in some embodiments of the invention; Without an glyceride oils containing non-fatty acid glyceride esters

YO saturated unpaired quot; Without limitation, linoleic and linolenic fatty acids.

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Contains unsaturated glyceride oils; without limitation; com oil, HA 5% cotton oil

cottonseed oll; rapeseed oil ‎rapeseed oil; hempseed oil; oil

linseed oil; wild mustard oil; Peanut oil

peanut oll « perilla oil; poppyseed oil; Seed oil

‎0 turnip; safflower oil; safflower oil,; sesame oil; sunflower oil; canola oil; pine resinous tall oil; and mixtures thereof. The fatty acid glycerides for use in the invention include;

For example, but not limited to those containing linoleic and linolenic fatty acid chains; oils

For example, but not limited to hemp seed oil; Linseed oil; Perilla seed oil

- poppy; safflower oil; soybean oil; sunflower oil; canola oil; pine resinous oil»; grape seed oil»; rattonseed oil; corn oil; and similar oils, which contain higher levels of linoleic and linolenic fatty acid glycerides. May contain glycerides

Contains less saturated fatty acids in some embodiments. For example, but not limited to;

Soybean oil can be used, which contains glycerides of linoleic and linolenic fatty acids

Mostly. Combinations of these oils are used in some embodiments of the invention. Vegetable oils may be fully or partially epoxidized by known methods; Jie, to name a few; using acids such as; without limitation; Peroxy acid for epoxidation of unsaturated double bonds of unsaturated vegetable oil. The unsaturated glyceride oils used in some embodiments include monoglycerides; Bis and mixtures thereof with ADE glycerides or acid esters

0 fatty acids, saturated or unsaturated. in some embodiments; Epoxy vegetable oil includes corn oil; cottonseed oil; grapeseed oil; hemp seed oil; linseed oil, wild mustard oil, groundnut oil, perilla oil, poppy seed oil; rapeseed oil; safflower oil; Sesame oil; soybean oil; sunflower oil; canola oil; pine spruce oil; fatty acid ester; 00009708106 Monoglyceride or SE Glyceride

Yo 0191706008 of these oils; or a mixture thereof. Commercially available sources of epoxy vegetable oils are used in some embodiments of the invention such as; For example, but not limited to soybean oil

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Epoxidized soy oil sold under the brand names "VIKOLOX" "VIKOFLEX 7170" Available from 'DRAPEX 6.8' (Arkema, Inc) Available from Chemtura

“PLAS-CHECK 775” “Corporation is available from Ferro Corp. Other epoxy vegetable oils included for use in the invention” include but are not limited to linseed oil.

© epoxidized linseed oil sold under the brand names “VIKOFLEX 7190” available from Arkema, Inc. and “DRAPEX 10.4” available from Chemtura Corporation.

Cottonseed csuuSsuyl epoxidized cotton seed oil

epoxidized carthamus oil and mixtures thereof. Epoxy soybean oil is used in

Some embodiments. In some embodiments of the invention; The substance includes a hydroxyl functional group;

“ethylene glycol” propylene glycol without limitation propylene glycol 0 ; tri-neopentyl glycol 1,3-propane diol ¢ 1,3-propane diol ; Diethylene glycol, trimethylol propane

polyetherglycol; polyester; polycarbonate »

polyolefin a polyolefin with a hydroxyl functional group; and combinations thereof. The article includes a group

n-butanol Butanol —N _hydroxyl functional is an alcohol in some embodiments such as; without limitation” 15; and the like; benzyl alcohol; benzyl alcohol 2—ethyl hexanol ethyl hexanol —Y “ polyols or polyhydric alcohol diols alone; Or in combination with dihydroxyalcohol

in some embodiments; The material has a hydroxyl functional group in an amount of about 94:1 to J 0:30 at a weight ratio of __ Sle hydroxyl functional group to epoxide vegetable oil

Geert and alternatively from about 950:5 to about cepoxidized vegetable oil 0 for the hydroxyl function of the substance with the 6011/8601 ratio set some embodiments; The equivalent ratio in vegetable oil epoxide is about the hydroxyl functional oxirane to the oxiran functional

01 to approx. VF some solidifications; The equivalent ratio of the hydroxyl function to

The function of oxyran in epoxy vegetable oils ranged from about 0:07 to about ?:1. In some

Yo anthropomorphisms; The equivalent ratio of the hydroxyl function to the oxyrane function in the vegetable oil

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-117- An epoxide of about .0:0.7 acid catalyst may be without limitation an acid catalyst (ug) a strong acid catalyst such as; For example, but not limited to; one or more 5 sulfonic acid or an al strong acid (an acid with a pKa value of approx ? or less); acid 11116; Triflat salt 1111816 for metal A101818 group HA, 118, IA, © 18 or VIIA from the Periodic Table of Elements (according to IUPAC 0) mixture of triflate salts mentioned, or a combination thereof.In some embodiments, the amount of acidic catalyst may range from about 1 ppm to about 0 ed per million; alternatively from about 01 ppm to about 0001 ppm per million” based on the total weight of the reaction mixture, including factors

HA, for example, but not limited to, catalysts for group metal triflats 0 - catalysts for magnesium ftriflate such as without limitation zinc and magnesium ftriflates without limitation Ji 118 group metal triflate catalysts without limitation Jie HA; catalysts for group metal triflate cadmium triflate without limitation Jie IB catalysts for group metal triflate « lanthanum triflate

Jie VIHA; and catalysts for aluminum triflate of the group Ve; and combinations thereof. The amount of cobalt triflate catalyst may range from but not limited to cobalt triflate parts per 00001 to about 10 triflates per metal but not limited to from about parts per million; On a total weight basis of approx 001 to approx 01 ele of the reaction mixture. Some embodiments of the invention utilize a metal triflate catalyst in the form of a solution in 00 organic solvent solvent 098010. Examples of solvents include; without limitation water; alcohols such as n-butanol; and the like; In addition to aromatic hydrocarbon solvents «cycloaliphatic polar solvents (Jie polar solvents, for example, but not limited to cycloaliphatic ketones, for example, cyclohexanone dls); polar aliphatic solvents (Jie « aliphatic solvents © to name butl alkoxyalkanols —Y ¢ alkoxyalkanols 2—methoxyethanol ¢ solvents without an Evy group

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functional hydroxyl; and mixtures thereof. in some embodiments; The epoxy vegetable oil is heated

and a substance with a functional hydroxyl group in the presence of an acidic catalyst and a solvent (such as propylene glycol) to a temperature of about 0 © to about 060 °C. Optionally, another solvent (such as ethylene glycol) may be included. monobutyl ether

© ether or diethylene glycol monoethyl ether in the composition of vegetable oil epoxide and the substance with the hydroxyl functional group to aid in viscosity control. In some embodiments; a solvent is present during the alcohol reaction

A polyhydroxyl with a hydroxyl functional group with a copolymer of a functionalized polyolefin and the unsaturated monomer component (Lili) such as but not limited to a ketone such as; without

Vo cui » methyl amyl ketone aromatic solvent 810013116 xylene or 100 aromatic ester solvent or non—hydroxyl functional AT solvent; and mixtures of leis is used

up to about 9640 solvents dependent on the total weight of the reaction mixture in the various embodiments of the invention; Alternatively, about © is used to about 96358 after about 7 to about ?

Vo hours; >90960 epoxide groups are consumed in some embodiments. Selected solvents from these described Gl may be added as well as other solvents including; Without ran solvents with a hydroxyl functional group on cooling 179a000. in some embodiments; It is desirable

in which it has an NV (non-volatile weight content) of about 1 to 560 Ja. In some applications; a functionalized polyolefin copolymer and a component of

0 unsaturated monomer ethylene with an oleoretical polyhydric alcohol with a hydroxyl functional group to form a mixture (optionally in the presence of an acid catalyst; such as the acid catalysts described above). in some embodiments; Functional polyolefin copolymers may include, but are not limited to;

polyethylene methacrylic acid, polyethylene acrylic acid; Copolymers of ethylene and maleic anhydride

ethylene and maleic anhydride vo « copolymers of propylene and maleic anhydride; and combinations thereof. These copolymers may be Primacor 5980i available from Dow

for etc

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Chemical or 925 Nucrel available from DuPont .in some embodiments; Polybd605 may include epoxidized polybutadiene

polybd 700 “polybd600E and combinations thereof are available from Cray Valley. The water dispersion may have a higher solids content and better stability in the presence of a polybutadiene epoxide. The mixture may react

© with an ethylene unsaturated monomer component in the presence of an initiator to form a bait copolymer. (Say) Addition of the ethylene unsaturated monomer component and the initiator after the mixture has cooled. In some embodiments;

The unsaturated monomer component ethylene and the initiator within about 2 hours. in some embodiments; Complete

quenching of the reaction product of the oleic polyhydric alcohol with the hydroxyl functional group; The unsaturated monomer component was ethylenediaminetized and the starter after approximately 1 hour of incubation to form a bait copolymer.

Yo The term Gl SF can be used to describe the donated copolymer as an acrylic-doped copolymer; however, the word acrylic is used in its broadest sense to include all components of the ethylene unsaturated monomer. The component of the ethylene unsaturated monomer may consist of a single monomer or a mixture of monomers. The unsaturated monomer component (adi) includes without limitation one or more compounds or mixtures

of vinyl monomers; acrylic monomers; allylic monomers; acrylamide monomers; vinyl esters

“vinyl propionate vinyl acetate included without limitation” vinyl acetate VO; 560203165 vinyl acetate “vinyl benzoate” similar vinyl butyrates; halides, vinyl esters, and vinyl esters « vinyl isopropyl acetates

vinyl, vinyl halides, including but not limited to vinyl chloride; vinyl fluoride and vinylidene chloride » vinyl aromatic hydrocarbons | 0 810123116 including but not limited to styrene; Methylstyrene compounds except 761 and similar low alkyl styrenes; chlorostyrene ¢ vinyl toluene » vinyl naphthalene « vinyl aliphatic hydrocarbon monomers included

without limitation alpha olefins 81008 such as for example unlimited; ethylene

; propylene isobutylene; and cyclohexene “in addition to conjugated dienes such as, for example, non-endl

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-?.1 « methyl-2-butadiene methyl -? - Butadiene « 1,3-butadiene Butadiene -.1 « 2,3 dimethyl butadiene 7.? Dimethylbutadiene ¢ 1,3—piperylene Pipereline “cyclopentadiene”; cyclohexane; Cyclohexane isoprene Vinyl alkyl isoprene Including (alkyl phenyl ethers. dicyclopentadiene als and dipentadiene; n-butyl vinyl ether butyl vinyl ether —n « isopropyl vinyl ether includes but not limited to acrylic monomers; monomers such as Lisobutyl vinyl ether without limitation; low alkyl esters of acrylic or methacrylic acid having an alkyl portion "carbon atoms" in addition to aromatic derivatives 01 to approx 1 ester containing approx 0 of acrylic and methacrylic acid. Acrylic monomers include, but not limited to; 0 ethyl ethyl acrylate and methyl methacrylate. acrylate methyl acrylate and methacrylate butyl acrylate methacrylate butyl acrylate 2-61 hexyl acrylate and methacrylate? "candy stag" and "methacrylate" cycloacrylates; benzyl isodecylacrylate and methacrylate”; Various decyl acrylate Vo glycidyl ethers Glycidyl ethers “edly Stag benzyl acrylate Acrylates reacted with acrylic and methacrylic acids; hydroxyl alkyl acrylates and methacrylates such as without hydroxyethyl and hydroxypropyl acrylates and methacrylates; glycidyl acrylate uaa

glycidyl acrylate and methacrylate; Amino acrylates and methacrylates. 0 in some embodiments; The das weight ratio of oleic polyhydric alcohol to functional polyolefin copolymer may be from about 0:48807 to about Avie alternatively from about 10:56 to about cert each on a total solids basis. in some embodiments; The weight ratio of the ethylene unsaturated monomer component to oleoretical polyhydric alcohol dese hydroxyl functional to copolymer_of functional polyolefin may be of about

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01 to approx. 0:10:01 alternatively from 15:15:76 da to approx.

:> alternatively from about 70:40:40 to about .001:001:500 in some embodiments; The weight ratio of oleoretical polyhydric alcohol to copolymer of functional polyolefin to polybutadiene epoxide may be from about teen to about 0 1:15:85 alternatively from about 00:90:56 to about 5:75:75 ; All on a total solids basis. in some embodiments; The weight ratio of the unsaturated monomer component may be ethylene to oleoretical polyhydroxyal alcohol with a hydroxyl functional group to the copolymer of functional polyolefin to polybutadiene epoxide from about 0 to about 0 alternatively from about 19:77:1680: ? to about 8070:78:17 and 0 to about hay from about 2:70:785:45+0 to about .7:001:77:5 0 in some embodiments; The weight ratio of the functionalized polyolefin to epoxy-polybutadiene copolymer may be from about 00 to about anion alternatively from about 50:70 to about 40:750; All on a total solids basis. in some embodiments; The weight ratio of the ethylene unsaturated monomer component to the epoxide-polybutadiene to the olefin-functionalized copolymer may be from about Vo 9:1:906 to 10:70:71 daa alternatively from about 17:17:86 to about 7:19:55 eg towards an alternative from about 4:75:1? to Yer eve Mes the use of the various initiators alone or in union in some embodiments of the invention. in some embodiments; Primers are used with high grafting efficiencies. Prefixes include without limitation; azo compounds such as, for example, Unlimited; Valeronitrile ¢ (2,4-dimethylvaleronitrile, 1-T-butyl-azocyanocyclohexane 1-t-butyl- 382007/800070106); hydroperoxide compounds such as butyl tertiary hydroperoxide t-butyl hydroperoxide and cumene hydroperoxide; peroxide compounds, Jie peroxides, for example, Unlimited Yo; benzoyl 560720 peroxide; caprylyl peroxide.

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-11- di—t-butyl peroxide; ethyl-v.v-3,3 ethyl (t-butylperoxy butyrate ; ?.- ethyl 3,3'di (t-butylperoxy (t-amylperoxy butyrate; triamyl Y= mS gpm = ethylhexanoate -7.7.010 » t-amylperoxy-2-ethyl hexanoate tetramethylbutyl-© peroxy-7?- 1,1-ethylhexanoate ,3,3-tetramethylbutyl-peroxy—2—- ethylhexanoate + t-butylperoxy bivilate « peresters such as for example JB Unlimited; t-butyl (peracetate, t-butyl perphthalate; and tributyl perbenzoate-] butyl perbenzoate; in addition to the percarbonates; Jie on Vo for example unlimited; bi-1 Cyano-1-methylethyl (1-cyano-1-methylethyl) peroxy dicarbonate; perphosphates « t-butyl peroctoate ; and the like and their mixtures. In some embodiments; the initiator is present in a quantity from about 0100 to about 70615; and on n alternate ho from about 1 to about 965; based on the weight of the monomer mixture. The temperature chosen for inoculation of the 15-unsaturated ethylene monomer component may vary with the half-life of the chosen initiator in some embodiments of the invention. Unlimited eg; At 181 °C the tert-butyl peroxybenzoate has a half-life of about 1 min and may be used for vaccination. Dibenzoyl peroxide has a half-life of 1? minute at 100 degrees Celsius; 001 degrees Lhe may be the temperature for doping an oily polyhydric alcohol with a hydroxyl functional group with dibenzoyl peroxide in some embodiments of the invention. and on a large scale; Depending on the half-life of the initiator used; The reaction can be carried out from about 0 to about Yoo degrees Celsius. in some embodiments; One or more mixtures of a starter with or without a solvent are added after forming a copolymer doped with an acrylic alcohol polyhydroxyl oil with a hydroxyl functional group to reduce the free monomer content. The compositions of the starter and the solvent in one or more of these mixtures may be the same or Different from Yo, the combinations of these components used to form the copolymer doped with an acrylic alcohol polyhydroxyl oil with a hydroxyl functional group.

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in some embodiments; The grafted copolymer is mixed with a crosslinker to form a coating composition

Curable coating composition. A crosslinked coating composition may provide excellent film performance in very short baking for coil applications. Applications An unlimited list of crosslinked materials for use in the invention includes epoxides

© Free of A= Jib Diglycidyl Methacrylate Copolymer; Sorbitol A5015150 converted to cas gu benzoguanamine » benzoguanamine formaldehyde ¢ glycoluril ¢ melamine formaldehyde » phenolic crosslinker ¢ phenol formaldehyde formaldehyde urea formaldehyde isocyanate 0 disabled isocyanate Sakuranomiya Chemical Company's blocked isocyanate MC-16, Cytec's EP-560, PH2028, PH2013/65B, PR899/60MPC, (Hexion's PF6535LB, SI Group's SFC112/65, Ruters' 7700 LB and mixtures thereof. In some embodiments; a glycidyl methacrylate copolymer is used as a crosslinker to help improve resistance to retort and chemicals. Copolymer synthesis may involve

sald 1 crosslinking without matting styrene acrylate; methacrylate; meth(acrylates) functional; Acrylic monomers included without “aan” low alkyl esters from LST or methacrylic acid with part

An alkyl ester contains between about 1 and about 10 carbon atoms; aromatic derivatives of LL ST and methacrylic acid; methyl acrylates and methacrylates; ethyl acrylates and methacrylates; butyl acrylate and methacrylate; propyl acrylates and methacrylates; 7- Ethylhexyl acrylate and methacrylate;

0 - hexyl als acrylates and methacrylates; (Ll Acrylates and Methacrylates; Isodecyl Acrylates edly Slag Benzyl Acrylates and Methacrylates; Various Glycidyl Ethers Reacted with Acrylic and Methacrylic Acids; Hydroxyl Alkyl Acrylates and Methacrylates such as but not limited to; Hydroxy

Ji, hydroxypropyl acrylate and methacrylate; glycidyl acrylates and methacrylates; Amino acrylates and methacrylates. The temperature chosen for crosslinking of the copolymer may be different for the monomer component

YO is ethylenedially unsaturated with half of the initiating jee selected in some embodiments of the invention. Unlimited eg; At 171 °C the tert-butyl peroxybenzoate has a half-life

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-14- About Th is a minute and may be used for vaccination. Dibenzoyl peroxide has a half-life of Vo min at 0° die and 100°C may be the temperature for doping an oily polyhydric alcohol having a hydroxyl group with dibenzoyl peroxide in some embodiments of the invention. and on a large scale; Depending on the half-life of the initiator used; The reaction can be carried out from about 50 to about 101 °C. in different incarnations; The ratio of crosslinker to graft copolymer is about 995:1 to about 960:100; alternatively about 56:01 to about 0:70 3. Optionally mixtures of polymers and crosslinkers may occur In the presence of a curing catalyst. Cure catalysts include; Unlimited eg; dodecyl benzene sulfonic acid; p-toluene sulfonic acid; phosphoric acid » and the like, and their mixtures. in some embodiments; Other polymers may be blended into the paint formulation; Such as without limitation polyethers «hil Jo ¢ polyesters ¢ polycarbonates ¢ polyurethanes Wy polyurethanes and the like; In addition to their mixtures. Curing conditions for can coatings in some embodiments are about © to about 10 seconds at D0 about 500 degrees Fahrenheit to about 100 degrees Fahrenheit; Alternatively about © seconds to about 10 seconds at about 4060 degrees Fahrenheit to about 900 degrees Fahrenheit. The copolymers and coating compositions of the invention may include conventional additives known to those experts in the art; Jie without pan flow agents; csurface active agents, defoamers; Additives for anti-cracking ‎additives | 0 201-01816109 .; lubricants ¢ meat-release additives; and catalysts for processing. In some embodiments of the invention; One or more coating compositions are applied to the substrate” Jie eg Unlimited; cans; metal cans; the ends are easy to open; packages; containers; vessels; The ends of cans” or any parts thereof used to hold or touch any type of food or beverage. in some embodiments; YO apply one or more coating materials in addition to the coating formulations of the invention Jie call without limitation; A primer coating may be applied between the substrate and the coating composition. may apply

Evy

1. Coating formulations on substrates by any method known to SEY experts in the field. in some embodiments; Coating compositions are sprayed or roll coated onto a substrate. when applied; Coating formulations contain; Unlimited eg; Between about 70,718 and about 706,406 by weight polymeric solids with respect to about 907,080 to about 96,860 © solvent. For some applications other than spraying; The solvent carried in the polymeric solutions may contain; Unlimited eg; Between about 9678 and about 9660 by weight polymeric solids solutions 7006+16a00. Organic solvents are used in some embodiments to facilitate roll coating or other application methods and may include these solvents; Without limitation—N-butanol; = butoxy-Jl = xylene” propylene glycol; -1!0 butyl ethers glycol; Diethylene glycol mono (Ji) ether and other aromatic and esterification solvents and their mixtures. in some embodiments; A1-butyl ether glycol is used in combination with propylene glycol. The resulting coating compositions are applied in some embodiments by conventional methods known in the coating industry. thus” by way of the indefinite JB; Spray paint application methods may be used; rolling » dipping; Dipping and flow 10 008008. In some embodiments; after application to a substrate; The coating composition is heat-cured at temperatures in the range of about Yeu °C to about You °C; Alternatively, for a period sufficient to effect complete curing in addition to volatilizing any fugitive components, the coating compositions of the present invention may be tinted and/or darkened by pigments and 0. Opacity 008611655 known in some renderings. For many uses; including unlimited use of foodstuffs; The pigment may be zinc oxide, carbon black or titanium dioxide. The resulting paint compositions are applied in some embodiments by conventional methods known in the paint industry. And therefore; Unlimited eg; Spray paint application methods may be used; Yo-cooling and flowing for both clear and pigmented films.

Evy yy in some embodiments; after application to a substrate; The paint composition is thermally cured at degrees Celsius; Alternatively higher than 750°C to about 181°F in the range of about, long enough to effect complete curing as well as vaporize any volatile components. For substrates intended as beverage containers; The coating is applied in some embodiments at a rate of in mg per square inch of polymer coating per square inch of about 11 to about 15 range from about © of the exposed substrate surface. in some embodiments; The water dispersible coating is applied at 0.0101 mg per square inch and approximately 6.1 in thickness between approx. for substrates prepared as soft-open beverage ends; The coating is applied in some embodiments of 15 mg per square inch of polymer coating to about 0.5 at a rate in the range of about 1 square inch of the exposed substrate surface. Conventional package coating formulations are applied to metals to a high degree. Some coating formulations of the present invention achieve VEY at about 777 to about °C or less. 701 provides good results at approx. Jie or less; 771 Le score gives good results at approx. Coater No. 60619 may allow this low-temperature coating device to save energy. tin—plated steel; Like tinned steel differentalloys using different alloys recycled ends along with Lal body used for easy open ends. This allows Vo « metal 001018108! When used as a coating for the easy-open finish of a metal container .can body The acidified can body Patent coatings show resistance to retort-cured beverages; acidified coffee, and the like. In some “isotonic drinks”; Isotonic drinks 5 9676 for coating composition greater than approx. solids content solids; The solids content is 9670 centipoise solids 0.01 to about TO and the coating composition has a viscosity of about 0 (mg per square inch) Msi A to about 1 film weights lie or more to produce a weight so that the membrane has good resistance to chemicals Over blister so that excess blisters are reduced aluminum pick-up resistance End applications are easy to open. Yo

Evy

— \ \ — Examples The invention will also be described with reference to the following unlimited ABA. It should be understood that changes and modifications may be made to these examples by those experts in the art without departing from the spirit and scope of the invention. © Example 1 Preparation of an oily polyhydric alcohol with a hydroxyl functional group TeV g propylene glycol mixed; ©?? 0 grams of epoxidized soy bean oil, converted to epoxide, 0 grams of ybutanol + 218-8 grams of Nacure Super (available from King Industries) in a nitrogen atmosphere and heated to Vie 0 °C The initial exotherm was controlled and the mixture was kept at 0 °C for approximately 2 hours The epoxy equivalent weight was 707730 The mixture was cooled To 001 degrees Celsius, 94 grams of butyl ether glycol was added. Example Y 1. Preparation of a glycidyl methacrylate copolymer crosslinker. 80 grams of butyl ether glycol and aha 1.87 butyl tertiary peroctoate were heated. tert-butyl 4168m to 001 degree hydrogen in the reactor was pumped aha Tr glycidyl YY » glycidyl methacrylate “dy Sti g butyl acrylate” Fo g methyl methacrylate £07 g tert-butyl per octoate in the reactor within 1 hour.After that, 001 da 0 butyl tertiary per octoate 05 g butyl ether glycol was added to the ee lily reactor for an hour. M 001 grams of butyl tertiary peroctoate and * grams of butyl ether glycol were added to the reactor and kept sad for an hour. duals 9 g of butyl ether glycol was added to the reactor and the reactor was cooled to 0 0 °C. The final solids content was Yoo 0 Evy

_ \ —

Example ?

Preparation of a glycidyl methacrylate copolymer crosslinker

Av gram butyl ether glycol AY gram butyl tert peroctoate was heated to 001

boiling point in a reactor. YO g glycidyl methacrylate was infused; YO grams of butyl acrylate; Ov

© jam styrene and aha £.Y butyl tertiary peroctoate in the reactor within 1 hour. and then; It was completed

Add pha 001 butyl tertiary peroctoate and 7 g butyl ether glycol to the reactor and keep it

for an hour. and then; aba 001 of butyl terpeoctoate Yo gram of butyl was added

glycol ethers to the reactor and kept for 1 hour. uals pha 11 butyl ethers added

glycol to the reactor and the reactor was cooled to 0 5°C. The final solids content was Sotho 0

Example ;

Prepare the grafted copolymer and then Lala 5.7 g of oily polyhydric alcohol

with a hydroxyl functional group previously prepared with 0 lb ethylene glycol monobutyl ether

and 1.7 ala 5980 +0000800. The mixture was heated to 048 °C and kept for 1 hour. Then the mixture was cooled to 10 degrees YEP. Then feed 0.79 grams of styrene » 101 grams of butyl

Acrylates ¢ 7 . 1 gm Hydroxypropyl Methacrylate 6 0 *. 1 gram of methacrylic acid and 77. Y grams

Aztec benzoyl peroxide (%Vo) in water) to the mixture at Veo

dap Celsius in Yoo hours. after that; 1.7 grams of butyl tertiary peroctoate was added and retained

for 0.5 hours at 015°C. after that; 0 aha 17-butyl tere-per-octoate was added. coli was treated for 600 minutes. Then aha 1765 ethylene glycol monobutyl ether was added and done

Cool the reactor to 500 degrees Celsius. The final solids content was Sova

or example

Preparation of the grafted copolymer A 0 pha £ of oily polyhydric alcohol was mixed with a group

Hydroxyl functionalized prepared with 100 grams of ethylene glycol mono-butyl ether ethylene

Lalt

No Y1.7 5 glycol monobutyl ether g 5980i 000018007. The mixture was heated to Yeo °C and kept for 1 hour. The mixture was cooled to 120°C. ©? Benzyl Methacrylate Sipomer 800-200 ala 01 (651615 phosphate esters of PPG monomethacrylate aha 0.1 ((Monomethacrylate) hydroxypropyl methacrylate; 1 0g methacrylic acid f*.7 gram Aztec benzoyl peroxide (9675 in water) to the mixture at Veo dap C during Yoo hour.After that, 1.7 gram butyl tere peroctoate was added and kept for 0.5 hour at 015° C. After that, AHA 17 Butyl Tertiary Peroctoate was added and kept for © min. After that, You added gram ethylene glycol monobutyl ether and the reactor was cooled to 560° C. The material content was final solids content 00 9070 Example 6+ Preparation of grafted copolymer A £0.0g oily polyhydric alcohol with a hydroxyl functional group as prepared was mixed with £0g ethylene glycol monobutyl ether TTT 5980g +00001300. The mixture was heated to 0460 °C and kept for 1 hour The mixture was cooled to 1015 °C Fo gram styrene was fed to © aha butyl acrylate Tov gram hydr 1.6 g methacrylic propyl methacrylate (VF g Sad) ABEM acetoacetoxyethyl methacrylate and Y.0 g Bl benzoyl peroxide (9675 in water) were added to the mixture at Veo °C Celsius in Yoo hours. after that; 107 grams of butyl tertiary peroctoate was added and was sol) for 0.5 hours at 015°C. 0 - after that; 107 grams of butyl tertiary peroctoate was added and kept for 500 minutes. and then; You gram ethylene glycol monobutyl ether was added and the reactor was cooled to 500°C. The final solids content was 9 9767. Example Vv etc

Ag \ — Preparation of the grafted copolymer 45.5 g of oily polyhydric alcohol with a hydroxyl functional group previously prepared was mixed with £0 g ethylene glycol monobutyl ether and 7707 g 5980 +00101300. The mixture was heated to 1400 degrees Augie and kept sad for an hour. The mixture was cooled to 10 an hour. then feed ¢y gram Jie methacrylate; VY g butyl acrylate 0 1.1 g hydroxypropyl methacrylate”; 1.76 g methacrylic acid 5 7.5 g Aztec benzoyl peroxide (%oVo) in water) to the mixture at YO degree YEP within Yoo hour. After that, 107 grams of butyl terti-per-octoate was added and soli) was added for 0.5 hours at 015°C. after that; Then add 1 gram of butyl tert per octoate (cola) As for $v min. Then Yoo 1 gram ethylene glycol monobutyl ether was added and the reactor was cooled to −1°C. 001 final solids content was NAK

A Example Preparation of grafted copolymer 45.5 grams of oily polyhydric alcohol with a hydroxyl functional group previously prepared were mixed with 00 grams of ethylene glycol monobutyl ether TTT grams of Nucrel 2806 (from Dupont) 5. Heat the mixture to ‎ 0618 °C and kept for an hour, then the mixture was cooled to Yao, the degree of YEP, then .71 grams of styrene » 101 grams of butyl acrylate 7 grams of hydroxypropyl methacrylate » 1.6 grams of acid cll Sle 5 0.¥ gram Aztec benzoyl peroxide (%oVo) in water) to the mixture at YO degree YEP within Yoo hour. Then, 107 grams of butyl terti-per-octoate was added and soli) was added for 0.5 hours at 015°C. after that; Then add 1 gram of butyl tert per octoate (cola) As for $v min. Then YS was added 188g ethylene glycol monobutyl ether and the reactor was cooled to 500°C. Was the final solids content Gove example? Preparation of paint compositions for Lal

— A \ — The six coating formulations shown in Table 1 below have been formulated with a variety of solvents; Crosslinks and waxes The resulting films were coated on TFS 211 substrates using YA applicator that produced 1.25 mg per square inch. Film thicknesses lie Table 1 (Coating formulations) Example 7 Example 7 Example ¢ Example 7 Example + Example o Polymer Hut OA.VY aba 1g 2g 0 1g .] | grams. 2 2g sak tangle 0.17 Marge 0.61g 50.1g 1g 1g 1g Erisys 0357 No : : : Example 1 Example 1 Example Y Example Y Glymo GE-60 sorbitol ds to epoxide butyl ethers ale 011 insoluble Ha 1.1 insoluble Aa 1.1 inapplicable glycol applicable to applicable Y A aba Y A aba Y A EP-560 g Y A aba Y A aba Y A Phenolic oo g Cytec Wax AY aba AY 0 g JY gram AY aba AY g AY gram Carnauba oo Testing Films of Paint Formulations Measuring Redness Resistance Blush resistance The ability of the paint to resist the attack of various solutions. Bale Redness is measured by the amount of water absorbed into a film coated with Lae .008160 film The film absorbs water; It generally becomes cloudyaile or appears white. Coating compositions were evaluated by deionized water retort, Evy.

to

(44 minutes immersed in water at Yoo degrees Fahrenheit). The redness of the retort blush was measured visually on scale zero-e. A blush of zero means that there is no blush. Red © means the film is completely white. Solvent resistance is measured as resistance to solvents; Such as Ji) Jie ketone (MEK) methyl ethyl ketone or acetone. © This test was performed as described in ASTM D 5402-93 Double-rubs (ie one back-and forth motion Lbs 006) are recorded. MEK was used in the current tests. The manufacture of an Ericksen beaded mug measures the ability to retain the integrity of a coated substrate as the ply forming process mimics the end of a beverage can. It is a measure of the presence of cracks or fractures in beads 06805. YX (0 inch) drown cups were manufactured by Cupper 0105807. Adhesion test was performed on decorated Ericksen cups. with beads to assess whether the paint sticks to the cups A No. (sha) Adhesion tested in accordance with 8 D 3359-1851 Method 8511/4 using tape (SCOTCH 610 available from 3M Company of Saint Paul, Minnesota). Adhesion is generally rated on a scale of ja 0 where A grade of "0" indicates adhesion failure and a grade of 1 "5" indicates that the film was completely off the substrate. Blisters were measured by MEIJI Techno Microscopes and referenced by D714 /511. Graded Blisters are none; few or dense in this application.Some coated films showed excellent flex/adhesion with good curing response with short residence times on both aluminum and 211 TFS.Water retort did not appear. Ericksen beaded cups have no sores

blistering 00 or tape off The test results are summarized in a table? below.

Yds grams | .£6 gram £0.01 ala 10 gram £70) SAVY | ala the resin, uh, uh, uh, uh, uh, uh, uh, uh, uh, uh, uh, uh, uh, uh, uhhhhhhhhhhhhhhhhhhhhhhhhhhhh)

Resistance 1 Y 1 0 0 Submerged 0 80 Addy at F You is crooked) Frictions Yer < A Yeo Ye oe—0n 0 Y MEK Cup None | There are no | None Ericksen |cracked or |cracked The six paint shown in the table? below with different crosslinking materials as summarized in a table? below. © schedule? Play # Y 1 1 ¢ > 1 ex ¢ ex Jha A s ex Jha A s ex A EV

q — \ — resin (£0 g thousands g). Zero zero zero zero aa Ya zero example? Zero Zero Zero Zero Yt EP-560 phenolic 2 g 2 g AY 2 g AY g AY g Y.A g Y.A g TY Carnauba xed 1.17 g AY gm 17 gm IY gm TY gm Then coating the coating compositions, as in Table 7, on TFS substrates 1 21 to produce no mg per square inch of film thicknesses. The wrapper on one of the AA506 Press has been converted into 0007 beverage ends. The endings were evaluated in several tests and the results are summarized in Table 0

5 Then measure the redness of the PRN by measuring the amount of PRA absorbed into the coated film when the film is immersed in water. Water vapor blush was measured. Coating formulations were evaluated with a deionized water retort (90 minutes immersed in water at You degrees Fahrenheit). The redness of the retort was measured using an Enamel Rater 800 //A. Coated can ends were placed on a Waco Enamel Rater to test the coating coverage on beverage cans.

0 This test displays an indication of the amount of metal exposed by incomplete paint coverage on the

clear LED; My number is easy to read. When the can is inverted it becomes an electrode and an end

The can is immersed in the electrolyte and the reading is displayed on the Enamel Rater. Resistance was used

Copper chloride resistance to measure the ability of the coated substrate after the Evy water retort

=« So

to maintain its integrity as it undergoes a formation process to produce the end of dle

Beverages 080-800 .beverage 4 This test. The ends of the manufactured case were exposed

fabricated can ends to a solution of copper chloride 0000a56 CcOpper chloride . will

Copper is deposited in creaks or fractures that may be present at the end.

© Preparation of the copper sulfate testing solution las by 1000 grams

Ter ela a gram of copper sulfate Yeo + copper sulfate a gram of hydrochloric acid

hydrochloric acid and 1 gram Dowfax 2A1 copper sulfate was dissolved in distilled water

distilled water in a beaker flask 4,060,860 ml; Then hydrochloric acid was added

Dowfax 1. The test method was as follows: (1) plate to a depth of Y/Y Vo inch with the copper sulfate solution; (1) float the ends with the inside side down on the solution; (7) )

timer setting for 791 minutes; And 2 (after A) minutes, remove the ends and dip them in glaze

Tap water Redness was measured visually using a zero-scale. redness

Zero means that there is no copper chloride stain on the end. Heal © means that the membrane

It was completely stained with copper chloride. The %Y citric acid test 05 simulated acidic beverages Beverage 801016 was used. The ends of the cans were immersed in NY solution.

Citric acid for Te min an Yo. die Fahrenheit . The results of the A test are summarized in the Lg table

Retort redness and adhesion were measured in the same way as the previous examples.

schedule;

1 2 ¢ 1 1

The retort at F yo. with water vapor AR A “Net 101

(Enamel Rater)

Water retort immersed 0 min at 7.7 oY EY.) 1.10 confirm to unscrew

(Enamel Rater) F Yo.

Evy

Exposure of the metal to copper sulfate A fine rivet blush resistance 1< 1 1“ 1<0 zero degree > 1 > 1 > 1 .+ . . 7 citric acid 1 min at F ye.

ua ha 1 1 1 zero redness

There is no there is no there is no there is no there is no pimples d : v 1 : : adhesion

will not?

Claims (1)

Addition of protection elements 1- A coating composition prepared in a manner that includes: (I) Reaction of epoxidized vegetable oil with a material with a hydroxyl functional group in the presence of an acid catalyst and a solvent to form an oily polyhydric alcohol with a hydroxyl functional oil polyol©; b) mixing an oily polyhydric alcohol with a hydroxyl functional oil polyol with a copolymer of a functional polyolefin copolymer to form a mixture ¢ c) reaction of the mixture with an ethylenically unsaturated monomer component 0 in the presence of an initiator to form a graft copolymer; and (a 0205510009 graft copolymer with a crosslinker to form the coating composition. Vo ?-la, coating composition of element 1; in which vegetable oil is derived The ow epoxidized vegetable oil is an unsaturated fatty acid glyceride .unsaturated fatty acid glyceride *- coating composition (according to Gua) vegetable oil 0 epoxidized Ss epoxidized vegetable 1 to 90 ein based on total weight Hydroxyl functionalized oil-acrylic grafted copolymer .hydroxyl functional oil acrylic graft copolymer ¢— coating composition according to the element ¢ where the material includes the hydroxyl functional group Yo hydroxyl functional material propylene glycol Evy aa «ethylene glycol; (ethylene glycol 1,3—propane diol propane diol -7,1 » glycol neopentyl glycol; trimethylol propane « second diethylene glycol; polyether glycol; Benzyl alcohol benzyl alcohol » “- ethyl hexanol 2—ethyl hexanol polyester ; urine © polycarbonate ¢ polyolefin with a hydroxyl functional group polyolefin; or a mixture of them. —o coating composition (according to Gua) The material is in a group Hydroxyl functional material in an amount of 1 to 95 parts of 0 epoxidized vegetable oil. = the coating composition according to the Gua element is the weight ratio 60 An oily polyhydric alcohol with a hydroxyl functional group Functional polyolefin copolymer to functional polyolefin copolymer oil polyol total solids 70:80 on a total solids basis Vo acid according to element 1; Where the catalyst includes coating composition -1 acid catalyst on strong acid Jie strong acid sulfonic acid; acid 11116; Triflat salt 1111816 of the metal A101818 group HA, 118, IA, 0 8AA or VIIA from the Periodic Table of the Elements (according to the Convention IUPAC) “Mixture of the aforementioned triflate salts” or its combination Coating composition (according to Cua) is the ratio of the weight of the YO ethylenically unsaturated monomer component to An oily polyhydric alcohol with the hydroxyl functional oil group Evy Dio "polyol" to a copolymer of a functional polyolefin copolymer from 1? to Nabtla 4- The coating composition according to element 1, where the alcohol reacts with the hydroxyl functional oil polyol And the copolymer of the functional polyolefin copolymer with epoxidized polybutadiene -0 coating composition according to element 9, where the alcohol ratio is 0 oil polyol to the polymer Functional polyolefin copolymer to epoxidized polybutadiene 01:50:96 to AVA -11 coating composition according to element 9; Gua Ratio Weight of the VO ethylenically unsaturated monomer component to the hydroxyl functional oil polyol to the functional polyolefin copo copolymer lymer to epoxidized polybutadiene from 1:0:19:760 to 1:08 0 VY - coating composition according to item 1 where the unsaturated monomer component is ethylenically unsaturated monomer component on butyl acrylate; methyl methacrylate; styrene; benzyl methacrylate «hydroxy propyl methacrylate Yo» hydroxy ethyl acrylate; glycidyl methacrylate “acrylic acid”; Evy methacrylic acid —yvo- acetoacetoxy ethyl methacrylate Ji) acetoxy gull + methacrylic acid phosphate ester “methacrylate” of it. mixtures; or monomethacrylate initiator (initiator includes Gua) according to coating composition -1“3 0 [-]; t-butyl peroxy benzoate on tetramethyl butyl peroxybenzoate - 7.7.010; dibenzoyl peroxide SG; butyl peroctoate 1,1,3,3-tetramethylbutyl-peroxy —2—- hexanoate Ji) butyl — peroxy-?- of them. mixture; Or a mixture of ethylhexanoate ye initiator Cua) according to the coating composition -6 unsaturated monomer component 7 weight of monomer component 15 to 6.1 in the amount of ethylenically. unsaturated solvent include Gua 1 depending on coating composition -1 reaction reaction mixture total weight up to 96560 Vo mixture sale include Cua) according to the coating composition -75 melamine formaldehyde “phenol-formaldehyde on a phenol-formaldehyde crosslinker; formaldehyde urea formaldehyde urea formaldehyde ¢ melamine formaldehyde | 00 isocyanate 500/80816a “isocyanate” benzoguanamine formaldehyde A bisphenol-A free — ; bisphenol-free epoxides blocked isocyanate blocking copolymer; phenolic crosslinker; A phenolic crosslinking material epoxides epoxidized sorbitol epoxide glycidyl acrylate meth acrylate mixture or a mixture of “glycoluril glycolyl” benzoguanamine “sorbitol Yo” of which. Evy +1 1"-7 coating composition (Gua) incorporating copolymer A functional polyolefin copolymer on acidic polyethylene polyethylene methacrylic acid » polyethylene maleic and maleic anhydride copolymer of ethylene; A copolymer of ethylene, acrylic acid anhydride©; Copolymers of propylene and maleic anhydride maleic anhydride” or a combination thereof. VA — method for coating a substrate comprising: (I) Reaction of epoxidized vegetable oil with a hydroxyl functional material in the presence of an acid catalyst aca And a solvent to form an oily polyhydric alcohol with a hydroxyl functional group. functional oil polyol; b) Mixing the oily polyhydric alcohol with the hydroxyl functional group functional polyolefin with functional oil polyol ¢ mixture to form a copolymer 10 The reaction of the mixture with a saturated pe monomer component graft to form a doped copolymer 701118100 in the presence of an ethylenically unsaturated initiator copolymer; c) crosslinking the graft copolymer with crosslinker | 0 to create the coating composition; And d) The coating composition is applied to the .substrate 1) The method according to the element (VA) where the copolymer includes a functionalized polyolefin polyethylene on poly(ethylene methacrylic acid) functional polyolefin copolymer « polyethylene acrylic acid cmethacrylicacid, Yo Copolymer of ethylene and maleic anhydride « Polymers Evy — 7 as copolymers of propylene and maleic anhydride » or a combination thereof. -0 substrate coated with coating composition according to element 1 lo} substrate 535, -71 coated by method AA Evy element 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