阅读说明：本技术 聚合聚噁唑啉 (Polymeric polyoxazolines ) 是由 周宏英 D·A·辛普森 C·P·库兹 T·米兹哈拉 于 2018-12-14 设计创作，主要内容包括：公开了具有以下结构的聚合聚噁唑啉(I)：<Image he="134" wi="700" file="DDA0002532540250000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>,其中X是与二羧酸/酸酐反应后的聚合多元醇的残基；其中R<Sub>5</Sub>是有机部分；其中Y是含有一个或多个噁唑啉基的有机部分；并且其中每个R<Sub>10</Sub>独立地是氢或有机部分。制作此种聚噁唑啉并将其用于涂料中的方法以及用其涂覆的封装体也在本发明的范围内。(Disclosed is a polymeric polyoxazoline (I) having the structure: wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is 5 Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups(ii) a And wherein each R 10 Independently hydrogen or an organic moiety. Methods of making such polyoxazolines and using them in coatings and packages coated therewith are also within the scope of the invention.)

1. A polymeric polyoxazoline having the structure:

wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is₅Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups; and wherein each R₁₀Independently hydrogen or an organic moiety.

2. A polymeric polyoxazoline according to claim 1, wherein X is the residue of a polyether polyol.

3. A polymeric polyoxazoline according to claim 1, wherein each Y independently contains one or two oxazoline groups.

4. The polymeric polyoxazoline of claim 1, wherein R₅Is C₂H₄Or C₆H₁₀。

5. The polymeric polyoxazoline of claim 1, wherein R₁₀Is hydrogen.

6. A method of making the polymeric polyoxazoline of claim 1, comprising:

(a) reacting a polymeric polyol having terminal and/or pendant hydroxyl groups with a dicarboxylic acid/anhydride to form a carboxylic acid functional polymer, and

(b) reacting the carboxyl functional polymer with a polyoxazoline containing at least two oxazoline groups.

7. The method of claim 6, wherein the polymeric polyol comprises a polyester polyol, a polyether polyol, a polyurethane polyol, or mixtures thereof.

8. The process according to claim 6, wherein the dicarboxylic acid/anhydride is an anhydride containing from 2 to 30 carbon atoms.

9. The method of claim 8, wherein the anhydride comprises hexahydrophthalic anhydride.

10. The method of claim 7, wherein the polymeric polyol comprises a polyether polyol.

11. The method of claim 6, wherein the polyoxazoline comprises phenylene-bis-oxazoline.

12. The method of claim 11, wherein the phenylene-bis-oxazoline comprises 1, 3-phenylene-bis-oxazoline.

13. The method of claim 6, wherein the polyoxazoline comprises 2, 2', 2 "- (hexane-1, 3, 6-triyl) tris (4, 5-dihydrooxazole).

14. A coating composition comprising:

(a) a polymer comprising an acidic functional group, and

(b) a polymeric polyoxazoline crosslinker having the structure:

wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is₅Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups(ii) a And wherein each R₁₀Independently hydrogen or an organic moiety.

15. The coating composition of claim 14, wherein the polymer comprising acidic functional groups comprises a polyester polymer and/or a (meth) acrylic polymer.

16. The coating composition of claim 14, wherein (a) and (b) are dispersed in an aqueous medium.

17. The coating composition of claim 14, wherein the molar ratio of polyoxazoline to carboxylic acid is 0.05: 1 to 2: 1.

18. A package comprising a coating composition applied to at least a portion of a surface of the package, the coating composition comprising:

(a) a polymer comprising an acidic functional group, and

(b) a polymeric polyoxazoline crosslinker having the structure:

wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is₅Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups; and wherein each R₁₀Independently hydrogen or an organic moiety.

19. The package of claim 18, wherein the package is a metal can.

20. The package of claim 18, wherein the coating is applied to a food-contact surface of the package.

21. The enclosure of claim 19, wherein the coating composition is applied to the surface of a can lid.

22. The package of claim 18, wherein the coating composition is a water-based composition, and (a) and (b) are dispersed in an aqueous medium.

23. The package of claim 18, wherein the polymer comprising acidic functional groups comprises a carboxyl-containing (meth) acrylic polymer, a carboxyl-containing polyester polymer, or a mixture thereof.

24. The coating composition of claim 14, wherein the composition is substantially free of formaldehyde.

25. The coating composition of claim 14, wherein the composition is substantially free of BPA.

26. A method of coating an encapsulant comprising applying the coating of claim 14 to at least a portion of the encapsulant.

27. The method of claim 8, wherein the acid comprises adipic acid.

Technical Field

The present invention relates to polymeric polyoxazolines and methods of making and using the same.

Background

Various coatings have been used to coat the surfaces of food and beverage packaging. For example, metal cans are sometimes coated using coil coating or sheet coating operations; that is, a coil or sheet of steel or aluminum is coated with a suitable composition and cured. The coated substrate is then formed into a can body or can lid. Alternatively, the coating composition may be applied to the formed can, for example, by spraying and dipping, and then cured. Coatings for food and beverage packaging are typically capable of high speed application to a substrate and provide the necessary properties upon curing to function in demanding end use environments. For example, the coating should be safe for food contact. It is increasingly desirable to use coatings made without the use of formaldehyde.

Disclosure of Invention

The present invention relates to a polymeric polyoxazoline having the structure:

wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is₅Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups; and wherein each R₁₀Independently hydrogen or an organic moiety.

The present invention also relates to a method of making a polymeric polyoxazoline, the method comprising:

(a) reacting a polymeric polyol having terminal and/or pendant hydroxyl groups with a 1, 2 dicarboxylic acid/anhydride to form a carboxylic acid functional polymer, and

(b) reacting a carboxylic acid functional polymer with a polyoxazoline.

The present invention also relates to a coating composition comprising:

(a) a polymer comprising an acidic functional group, and

(b) a polymeric polyoxazoline crosslinker having the structure:

wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is₅Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups; and wherein each R₁₀Independently hydrogen or an organic moiety.

The present invention also relates to a package comprising a coating composition applied to at least a portion of a surface of the package, the coating composition comprising:

(a) a polymer comprising an acidic functional group, and

(b) a polymeric polyoxazoline crosslinker having the structure:

wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is₅Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups; and wherein each R₁₀Independently hydrogen or an organic moiety.

Detailed Description

As used herein, the terms "carboxylic acid" and "carboxyl group" are used interchangeably. By "carboxylic acid functional polymer" is meant a polymer having at least one unreacted carboxylic acid group, which is prepared by reacting a polymeric polyol with a dicarboxylic acid/anhydride as described herein. "polymer comprising acidic functional groups" also means a polymer having at least one unreacted carboxylic acid group, but which can be prepared by any means known in the art.

The term "organic moiety" or "organyl" as used herein means a hydrocarbon group (with optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that is classified as aliphatic, cyclic (including alicyclic and aromatic), or a combination of aliphatic and cyclic (e.g., alkaryl and aralkyl). The term "aliphatic group" means a saturated or unsaturated straight or branched chain hydrocarbon group. The term "alkyl" means a saturated straight or branched chain hydrocarbon group including, for example, methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, pentyl, 2-ethylhexyl, and the like.

Groups that may be the same or different are referred to as "independent" things.

Substitutions may be made in the organic portion of the compounds according to the invention. Thus, when the term "group" is used to describe a chemical substituent, the chemical material being described includes the unsubstituted group and the group having, for example, O, N, Si or S atoms in the chain (as in an alkoxy group) as well as a carbonyl group or other conventional substituent. For example, the phrase "alkyl" is intended to include not only pure open-chain saturated hydrocarbon alkyl groups consisting of only hydrogen and carbon, such as methyl, ethyl, propyl, tert-butyl, and the like, but also alkyl groups bearing further substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, and the like. Thus, "alkyl" includes ether groups, haloalkyl groups, nitroalkyl groups, carboxyalkyl groups, hydroxyalkyl groups, sulfoalkyl groups, and the like.

The term "polyoxazoline" as used herein means a compound containing at least two (2) oxazoline groups.

The term "crosslinker", "curing agent" or "crosslinker" refers to a molecule capable of forming a covalent linkage between two or more moieties (e.g., two moieties present in two different polymer molecules) or between two different regions of the same polymer.

The term "dispersed in an aqueous medium" means that the polymer comprising acidic functional groups and the polymeric polyoxazoline crosslinker can be mixed into an aqueous medium to form a stable mixture; that is, when left to stand at room temperature (23 ℃), the mixture does not separate into immiscible layers within one hour after mixing.

The term "latex" means a polymer that is polymerized in an aqueous medium by free radical initiated emulsion polymerization techniques. The polymer is in particulate form and is dispersed in an aqueous medium.

The term "food-contact surface" refers to a surface of a package, such as an interior surface of a food or beverage package that is in contact with or intended to be in contact with a food or beverage product. For example, the inner surface of the metal substrate of a food or beverage package, or a portion thereof (such as a can lid or can body), is the food-contact surface even though the inner metal surface is coated with the coating composition.

The term "colorant" means any substance that imparts color and/or other opacity and/or other visual effect to the composition. The term "colorant" as used herein means any substance that imparts color and/or other opacity and/or other visual effect (e.g., gloss) to the composition. The colorant can be added to the coating in any suitable form, such as in the form of discrete particles, dispersions, solutions, and/or flakes. A single colorant or a mixture of two or more colorants can be used in the coating of the present invention. Particularly suitable for use as the encapsulating coating are those coatings approved for food contact, such as titanium dioxide; iron oxides, such as black iron oxide; carbon black; ultramarine; phthalocyanines such as phthalocyanine blue and phthalocyanine green; iron yellow; quinacridone red; and combinations thereof, and those listed in federal regulation, clause 178.3297, which is incorporated herein by reference.

The term "at … …" when used in the context of a coating being applied to a surface or substrate includes the coating being applied directly or indirectly to the surface or substrate. Thus, for example, a coating applied to a primer layer overlying a substrate constitutes a coating applied to a substrate.

Acrylic and methacrylic monomers and polymers are designated as (meth) acrylic monomers and polymers.

Unless otherwise indicated, molecular weights are all based on number average ("Mn") and determined by gel permeation chromatography using polystyrene standards.

As used herein, unless otherwise expressly specified, all numbers (such as those expressing values, ranges, amounts, or percentages) are to be understood as beginning with the word "about", even if the term does not expressly appear. Moreover, any numerical range recited herein is intended to include all sub-ranges subsumed therein. Singular encompasses plural and vice versa. For example, although reference is made herein to "a" polymeric polyoxazoline, "a" film-forming resin, "an" isocyanate, "an" alkanolamine, "a" … … residue, and the like, each of these and one or more of any other components may be used. The term "polymer" as used herein refers to oligomers and both homopolymers and copolymers, and the prefix "poly" refers to two or more. Including for example and similar terms is meant to include, for example and without limitation.

Also herein, reference to numerical ranges by endpoints includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). Further, disclosure of a range includes disclosure of all sub-ranges encompassed within the broader range (e.g., 1 to 5 discloses 1 to 4, 1.5 to 4.5, 4 to 5, etc.).

The present invention relates to a polymeric polyoxazoline having the following structure (a):

wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is₅Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups; and wherein each R₁₀Independently hydrogen or an organic moiety.

The polymeric polyoxazolines of the present invention may be prepared by reacting a polymeric polyol with a dicarboxylic acid/anhydride and then further reacting the resulting product with polyoxazoline. It is understood that the "-O-X-O" moiety in Structure A is the residue of a polymeric polyol, which means the portion of the polyol remaining after reaction with the carboxylic acid/anhydride;the moiety is the residue of a dicarboxylic acid/anhydride, which means the moiety remaining after reaction with the polymeric polyol, andthe moiety is the residue of the polyoxazoline, which means the moiety of the polyoxazoline remaining after reaction with the carboxylic acid functional polymer.

Examples of suitable polymeric polyols are polyether polyols, polyester polyols and polyurethane polyols.

Examples of suitable polyether polyols include polyalkylene ether polyols such as those having the following structural formula:

wherein the substituent R⁶Is hydrogen or lower alkyl containing 1 to 5 carbon atoms, and n has a value of 2 to 6, and m has a value of 8 to 100 or higher. Exemplary polyalkylene ether polyols include poly (oxytetramethylene) glycol, poly (oxytetraethylene) glycol, poly (oxyethylene) glycol, poly (oxy-1, 2-propane) glycol, and poly (oxy-1, 2-butane) glycol.

Also useful are polyether polyols formed from the alkoxylation of various polyols, for example, glycols such as ethylene glycol, 1, 6-hexanediol, and the like, one common alkoxylation process is to react a polyol with an alkylene oxide (e.g., propylene oxide or ethylene oxide) in the presence of an acidic or basic catalyst.

The hydroxy-functional polyether polymer or oligomer can have an Mn of 250 to 5000 (such as 500 to 3200) and a hydroxyl number of 20 to 500.

Linear polyester polyols may also be used, and may be prepared by polyesterification of polycarboxylic acids or anhydrides thereof with excess polyols and or epoxides using any polymerization technique known to those skilled in the art. Typically, the polycarboxylic acids and polyols are aliphatic or aromatic dibasic acids and diols. Transesterification of the polycarboxylates may also be carried out.

Polyols useful in making polyesters include, for example, alkanediols such as ethylene glycol, propylene glycol, neopentyl glycol, and other diols such as trimethylpentanediol, hydrogenated bisphenol a, cyclohexanediol, cyclohexanedimethanol, caprolactone diol, the reaction product of caprolactone and ethylene glycol, hydroxyalkylated bisphenols, polyether diols (e.g., poly (oxytetramethylene) glycol, and the like). Higher functionality polyols may also be used. Examples include trimethylolpropane, trimethylolethane, pentaerythritol, and the like.

The acid component of the polyester may be comprised of monomeric carboxylic acids or anhydrides thereof having from 2 to 18 carbon atoms per molecule in addition to the carbon atoms of the carboxylic acid or anhydride moiety. Included among the acids that may be used are cycloaliphatic acids and anhydrides such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, 1, 3-cyclohexanedicarboxylic acid, and 1, 4-cyclohexanedicarboxylic acid. Other suitable acids include adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, decanedioic acid, dodecanedioic acid, and other various types of dicarboxylic acids. Lower alkyl diacids, i.e., acids having less than about 10 carbon atoms (such as adipic acid), are particularly suitable. The polyester may include small amounts of monobasic acids such as benzoic acid, stearic acid, acetic acid, and oleic acid. In addition, higher carboxylic acids such as trimellitic acid and trimesic acid can be used. When reference is made to an acid in this paragraph, it is understood that the anhydride present may be used in place of or in addition to the acid. Likewise, lower alkyl esters of diacids such as dimethyl glutarate and dimethyl terephthalate may be used. Cycloaliphatic acids and anhydrides are particularly suitable.

The hydroxy-functional polyester polymer can have an Mn of 400 to 3500, such as 800 to 2000, and a hydroxyl number of 20 to 300.

Polyurethanes may also be used. Among the polyurethanes that can be used are polymeric or oligomeric polyols obtained by reacting diols, alkanediols or triols with polyisocyanates such that the OH/NCO equivalent ratio is greater than 1: 1, so that free hydroxyl groups are present in the product. Polyols useful in making polyurethanes include those disclosed above in making polyesters.

The organic polyisocyanate used to prepare the hydroxy-functional polyurethane may be an aliphatic or aromatic polyisocyanate or a mixture of both. Diisocyanates are particularly suitable, but higher polyisocyanates can be used instead of or in combination with diisocyanates.

Examples of suitable aromatic diisocyanates are 4, 4' -diphenylmethane diisocyanate and toluene diisocyanate. Examples of suitable aliphatic diisocyanates are linear aliphatic diisocyanates such as 1, 6-hexamethylene diisocyanate. In addition, cycloaliphatic diisocyanates may be employed. Examples include isophorone diisocyanate and 4, 4' -methylene-bis- (cyclohexyl isocyanate). Examples of suitable higher polyisocyanates are 1, 2, 4-benzene triisocyanate and polymethylene polyphenyl isocyanates.

The hydroxy-functional polyurethane polymer may have a number average molecular weight of 300 to 3000, such as 300 to 600, and a hydroxyl number of 20 to 200.

As mentioned above, according to the present invention, a polymeric polyol is reacted with a dicarboxylic acid/anhydride. Any dicarboxylic acid/anhydride may be used. Dicarboxylic acids/anhydrides refer to dicarboxylic acids, dicarboxylic anhydrides and mixtures thereof. The dicarboxylic acid anhydride may be a 1, 2-dicarboxylic acid anhydride. Any suitable dicarboxylic acid/anhydride may be used, including any of those listed above for preparing the polyester polyols. Particularly suitable are dicarboxylic acids/anhydrides having from 4 to 12 carbons. "R₅The value of "will vary depending on the dicarboxylic acid/anhydride used. For example, if the dicarboxylic acid is adipic acid, R₅Will be a six carbon alkyl moiety; if the dicarboxylic anhydride is succinic anhydride, R₅Will be a two carbon alkyl moiety (vinyl).

Other suitable acids/anhydrides that can be used to form the desired polyester are acids/anhydrides having from 2 to 30 carbon atoms in addition to the carbon atoms of the anhydride moiety. Examples include aliphatic, including cycloaliphatic, olefinic and cyclic olefinic anhydrides, and aromatic anhydrides. Substituted aliphatic and aromatic anhydrides are also included within the definition of aliphatic and aromatic, so long as the substituents do not adversely affect the reactivity of the anhydride or the properties of the resulting polyester. Examples of substituents are chlorine, alkyl and/or alkoxy. Examples of the acid anhydride include succinic anhydride, methylsuccinic anhydride, dodecenylsuccinic anhydride, octadecenylsuccinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylhexahydrophthalic anhydride (such as methylhexahydrophthalic anhydride), tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, itaconic anhydride, citraconic anhydride, maleic anhydride, and norbornene anhydride.

The polymeric polyol and the dicarboxylic acid/anhydride are reacted under conditions sufficient to cause reaction between the hydroxyl groups of the polyol and the acid groups of the dicarboxylic acid/anhydride. For example, when an anhydride is used, the conditions should be sufficient to ring-open the anhydride to form the half-ester, and generally substantially no polyesterification occurs. Such reaction products have relatively low molecular weights with narrow molecular weight distributions and low viscosities, and provide lower volatile organic content in the coating composition while still providing excellent properties in the resulting coating. By essentially no polyesterification is meant that the carboxyl groups formed by the anhydride reaction are not further esterified by the polyol in a reiterative manner. This means that less than 10 wt%, such as less than 5 wt% of high molecular weight polyester is formed; high molecular weight in this context means 2500, 3000 or even higher.

To effect the reaction, the dicarboxylic acid anhydride and the polymeric polyol are contacted with each other, typically by mixing the two components together in a reaction vessel. The reaction may be carried out in the presence of an inert atmosphere such as nitrogen and in the presence of a solvent to dissolve solid components and/or reduce the viscosity of the reaction mixture. Examples of suitable solvents are high boiling point materials and include, for example, ketones such as methyl pentanone, diisobutyl ketone, methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; and other organic solvents such as dimethylformamide and N-methyl-pyrrolidone.

The reaction temperature may be low, i.e. not higher than 160 ℃, such as lower than 120 ℃, and may range from 70 ℃ to 135 ℃, such as from 90 ℃ to 120 ℃.

The reaction time may vary depending mainly on the reaction temperature. The reaction time may be as low as 10 minutes up to 24 hours.

The equivalent ratio of anhydride groups to hydroxyl groups of the polymeric polyol can be from 0.8: 1 to 1.2: 1 (anhydrides are considered monofunctional) to obtain maximum conversion to the desired half-ester; the equivalent ratio of acid groups (if diacid is used) to hydroxyl groups can be 1.6: 1 to 2.4: 1.

After the half-ester is formed, the resulting carboxylic acid functional polymer is reacted with polyoxazoline. The polyoxazoline may contain two, three or four oxazoline groups.

Examples of polyoxazolines are those having the following structure:

wherein n is¹Is an integer from 2 to 4; r is an n-valent organic radical such as an arylene or alkylene radical; r₁、R₂、R₃And R₄May be the same or different and are each independently selected from hydrogen and C₁To C₄Alkyl groups such as methyl, ethyl, propyl and butyl. When polyoxazoline is structure (1), it is understood that R₁R4 corresponds to R shown in Structure A₁₀. Specific examples of compounds of structure 1 are as follows:

1, 2-phenylene-bis-oxazolines

1, 3-phenylene-bis-oxazolines

1, 4-phenylene-bis-oxazolines

1, 2-bis (oxazolinyl-4-methyl) benzene

1, 3-bis (oxazolinyl-4-methyl) benzene

1, 4-bis (oxazolinyl-4-methyl) benzene

1, 2-bis (oxazolinyl-5-ethyl) benzene

1, 3-bis (oxazolinyl-5-methyl) benzene

1, 3-bis (oxazolinyl-5-ethyl) benzene

1, 4-bis (oxazolinyl-5-ethyl) benzene

1, 2, 4-tris (oxazolinyl) benzene

1, 3, 5-tris (oxazolinyl) benzene

1, 2, 4, 5-tetra (oxazolinyl) benzene

Examples of other polyoxazolines are those having the following structure:

R＝C₄H₈、C₆H₁₂

the reaction of the polyoxazoline with the carboxylic acid functional polymer can generally be achieved by simply adding the polyoxazoline to the half-ester reaction mixture after the half-ester forming reaction is complete. The reaction mixture comprising the carboxylic acid functional polymer and polyoxazoline can be heated to a temperature of 60 ℃ to 160 ℃ and held at this temperature until an acid number of less than 2 is obtained.

As described above, in partRepresents a residue of polyoxazoline; one of the oxazoline rings of the polyoxazoline will react with the carboxylic acid functional polymer and Y is an organic moiety. Since polyoxazoline has 2 to 4 oxazoline groups, Y will contain at least one, but possibly two oxazoline groups.

The resulting polymeric polyoxazoline can have the following structure:

wherein X is the residue of the polymeric polyol after reaction with a 1, 2-dicarboxylic anhydride, and wherein Y is an organic moiety containing one or more oxazoline groups.

Examples of such polymeric polyoxazolines are, for example, those prepared from polytetrahydrofuran (polythf) (TERETHANE 650) reacted with phthalic anhydride and 1, 3-phenylene-bis-oxazoline, i.e.

An example of a higher functionality polymeric polyoxazoline can be made using 2, 2', 2 "-hexane-1, 3, 6-triyl (4, 5-dihydrooxazole), i.e.,

the polymeric polyoxazoline may be used as a curing agent with a polymer containing acid functional groups. The curable compositions are useful as coating compositions, such as inks for automotive and industrial applications, floor finishes, protective and decorative coating compositions.

Examples of polymers containing acid functional groups are the above-mentioned carboxylic acid functional polyethers, polyesters and polyurethanes. In addition, carboxylic acid functional (meth) acrylic polymers may be used.

The carboxyl group-containing (meth) acrylic polymer can be obtained in a conventional manner, specifically by solution or emulsion polymerization.

For example, the carboxyl group-containing (meth) acrylic polymer can be obtained from a carboxyl group-containing ethylenically unsaturated monomer and another ethylenically unsaturated monomer.

The carboxyl group-containing ethylenically unsaturated monomer may include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, half esters thereof such as ethyl maleate, ethyl fumarate and ethyl itaconate, mono (meth) acryloyloxyethyl succinate, mono (meth) acryloyloxyethyl phthalate and the like. The carboxyl group-containing ethylenically unsaturated monomer may comprise two or more species.

Other ethylenically unsaturated monomers can include hydroxyl-containing ethylenically unsaturated monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate non-functional ethylenically unsaturated monomers such as styrene, α -methyl styrene, acrylic esters (e.g., methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate) and methacrylic esters (e.g., methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate) are typically present.

The calculated molar ratio of polyoxazoline to carboxylic acid in the composition can be 0.05: 1 to 5: 1, such as 0.5: 1 to 2: 1.

The polymeric polyoxazoline and/or coating composition of the present invention can be substantially free, and/or can be completely free of bisphenol a and epoxy compounds derived from bisphenol a ("BPA"), such as bisphenol a diglycidyl ether ("BADGE"). Such polymeric polyoxazolines and/or coating compositions are sometimes referred to as "unintended BPA" because BPA comprising derivatives or residues thereof is not intentionally added, but may be present in trace amounts due to impurities or unavoidable contamination from the environment. The polymeric polyoxazoline and/or the coating composition can also be substantially free, can be substantially free, and/or can be completely free of bisphenol F ("BPF") and epoxy compounds derived from bisphenol F, such as bisphenol F diglycidyl ether ("BFDGE"). The term "substantially free" as used in this context means that the polymeric polyoxazoline and/or the coating composition contains less than 1000 parts per million (ppm), "substantially free" means less than 100 parts per million, and "completely free" means less than 20 parts per billion (ppb) of any of the above compounds, derivatives or residues thereof.

Further, the polymeric polyoxazoline and/or coating composition of the invention may be substantially free, and/or may be completely free of formaldehyde. The term "substantially free" as used in this context means that the polymeric polyoxazoline and/or the coating composition contains and/or releases less than 1000 parts per million (ppm) when cured, "substantially free" means less than 100 parts per million, and "completely free" means less than 100 parts per billion (ppb) of formaldehyde compounds, derivatives or residues thereof.

Typically, the coating composition will contain a diluent such as water or an organic solvent or a mixture of water and an organic solvent to dissolve or disperse the resin binder. The organic solvent can be selected to be sufficiently volatile to evaporate substantially completely from the coating composition during the curing process. Examples of suitable organic solvents are aliphatic hydrocarbons such as mineral spirits and high flash point VM & P naphtha; aromatic hydrocarbons such as benzene, toluene, xylene and solvent naphtha 100, 150, 200, etc.; alcohols such as ethanol, n-propanol, isopropanol, n-butanol, etc.; ketones such as acetone, cyclohexanone, methyl isobutyl ketone, and the like; esters such as ethyl acetate, butyl acetate, and the like; glycols such as butanediol, glycol ethers such as methoxypropanol, and ethylene glycol monomethyl and monobutyl ethers, and the like. Mixtures of various organic solvents may also be used. For aqueous compositions, polymers containing acidic functional groups, such as acid-functional (meth) acrylic polymers, the acid groups are at least partially neutralized with an amine to aid in the dispersion or dissolution of the resin binder in the aqueous medium. When present, the amount of diluent used in the coating composition can be 20 to 80 weight percent, such as 30 to 70 weight percent, based on the total weight of the coating composition.

The compositions of the present invention can be applied to any substrate known in the art, for example, automotive substrates, marine substrates, industrial substrates, packaging substrates, lumber, wood flooring and furniture, apparel, electronic products including housings and circuit boards and including consumer electronic products (housings such as computers, notebooks, smartphones, tablets, televisions, gaming devices, computer accessories, MP3 players, and the like), glass and transparent films, sports equipment including golf balls, and the like. These substrates may be, for example, metallic or non-metallic. Metal substrates include tin, steel, tin-plated steel, chrome-passivated steel, galvanized steel, aluminum, and aluminum foil. As used herein, sheet metal refers to both flat sheet metal and coiled sheet metal that is coiled, uncoiled for coating, and then rewound for shipment to the manufacturer. Non-metallic substrates include polymers, plastics, polyesters, polyolefins, polyamides, celluloses, polystyrenes, polyacrylics, poly (ethylene naphthalate), polypropylene, polyethylene, nylons, EVOH, polylactic acid, other "green" polymer substrates, poly (ethylene terephthalate) ("PET"), polycarbonate acrylonitrile butadiene styrene ("PC/ABS"), polyamides, wood, veneers, wood composites, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles, synthetic and natural leather, and the like. The substrate may be one that has been treated in some way, such as to impart a visual and/or color effect.

The compositions of the present invention may be applied by any means standard in the art, such as electrocoating, spraying, electrostatic spraying, dipping, rolling, brushing, and the like.

The compositions of the present invention may be used alone or in combination with one or more other compositions, such as a coating system having two or more layers. For example, the compositions of the present invention may or may not contain a colorant and may be used as a primer, basecoat, and/or topcoat. For substrates coated with multiple coatings, one or more of these coatings may be a coating as described herein. The coatings of the present invention may also be used as encapsulating "size" coatings, seal coats, spray coats, end coats, and the like.

It is to be understood that the compositions described herein can be one component ("1K") or a multi-component composition, such as two components ("2K") or more. A 1K composition will be understood to mean a composition in which all coating components remain in the same package after manufacture, during storage, etc. The 1K composition can be applied to a substrate and cured by any conventional means, such as by heating, forced air, and the like. The composition of the invention may also be multi-component, which is to be understood as a composition in which the various components are kept separately until the coating.

The composition may be a varnish. A varnish is to be understood as a substantially transparent or translucent coating. Thus, the varnish may have a degree of color as long as it does not opacify the varnish or otherwise affect the ability to view the underlying substrate to any significant degree. The clearcoats of the invention can be used, for example, in combination with pigmented basecoat coats. The varnish may be formulated as known in the coatings art.

The composition may also contain a colorant, such as a pigmented basecoat paint used in combination with a clearcoat paint, or as a pigmented monocoat paint. Such coating layers are used in various industries to impart decorative and/or protective finishes. Such a paint or paint system may be applied to a vehicle, for example. "vehicle" is used herein in its broadest sense and includes all types of vehicles such as, but not limited to, cars, trucks, buses, vans, golf carts, motorcycles, bicycles, rail vehicles, boats, ships, airplanes, helicopters, and the like. It should be understood that the portion of the vehicle coated according to the present invention may vary depending on the coating used. For example, a stone chip resistant primer may be applied to certain portions of the vehicle. When used as a colored base coat or a single coat paint, the coating of the present invention will typically be applied to those visible portions of a vehicle, such as the roof, hood, trunk lid, etc. of a car, but may also be applied to other areas, such as the interior of a trunk, the door, etc., particularly when the composition is formulated as a sealant or adhesive; for example, the compositions may be formulated to have a viscosity such that they provide sound and/or vibration damping for the vehicle. The compositions of the present invention may also be applied to those parts of the vehicle that come into contact with the driver and/or passengers, such as the steering wheel, the dashboard, the gear shift lever, the controls, the door handle, etc. The varnish will typically be applied to the exterior of the vehicle.

The invention further relates to a package at least partially coated with any of the above coating compositions. A "package" is anything used to contain another item, particularly an item that is shipped from a point of manufacture to a consumer and then stored by the consumer. Thus, a package will be understood to be something that is sealed to keep its contents from deteriorating until opened by the consumer. The manufacturer will typically determine the length of time that the food or beverage will not spoil, which is typically in the range of months to years. Thus, the "package" of the present invention is distinct from a storage package or baking appliance in which a consumer can make and/or store a food product; such a package will only maintain the freshness or integrity of the food item for a relatively short period of time. As used herein, "package" means the completed package itself or any component thereof, such as an end, lid, cap, etc. For example, a "package" coated with any of the coating compositions described herein may include a metal can in which only the can end or a portion thereof is coated. The package according to the present invention may be made of metal or nonmetal (e.g., plastic or laminate), and may be in any form. An example of a suitable package is a laminated tube. Another example of a suitable package is a metal can. The term "metal can" includes any type of metal can, package, or any type of container or portion thereof that is sealed by a food/beverage manufacturer to minimize or eliminate spoilage of the contents prior to opening of such package by a consumer. One example of a metal can is a food can; the term "food can" as used herein refers to a can, package, or any type of container or portion thereof for holding any type of food and/or beverage. "beverage can" may also be used to refer more specifically to food cans that enclose a beverage. The term "metal can" specifically includes food cans, including beverage cans, and also specifically includes "can lids," including "E-Z open lids," which are typically stamped from can lid stock and used in conjunction with the packaging of food and beverages. The term "metal can" also includes in particular metal caps and/or closures, such as bottle caps, screw caps and lids of any size, lug caps, etc. The metal can may also be used to hold other items including, but not limited to, personal care products, spray insecticides, spray paint, and any other compound suitable for encapsulation in an aerosol can. Cans can include "two-piece cans" and "three-piece cans" as well as thin-walled drawn monolithic cans; such monolithic canisters are commonly used in aerosol products. The packages coated according to the invention may also include plastic bottles, plastic tubes, laminates and soft packages, such as packages made of PE, PP, PET or the like. Such packaging may hold, for example, food, toothpaste, personal care products, and the like.

The coating may be applied to the inside and/or outside of the package. For example, the coating may be roll coated onto the metal used to make two-piece food cans, three-piece food cans, can lid stock and/or can lid/closure stock. Applying the coating to the coil or sheet by roll coating; the coating is then cured by radiation, and the can lid is stamped out and made into the finished product, i.e., can lid. The paint may also be applied to the bottom of the can as an edge paint; such coating may be performed by roll coating. During continuous fabrication and/or handling of the cans, edge painting is used to reduce friction to improve handling. The coating may be applied to the "side bars" of the metal can, which will be understood as the seams formed during the manufacture of the three-piece can. The coating may also be applied to the overcap and/or closure; such coatings may include, for example, protective varnish applied before and/or after the overcap/closure is formed and/or colored enamel posts applied to the overcap, particularly those having a scored seam at the bottom of the overcap. The decorated can stock can also be partially coated on the outside with the coatings described herein, and the decorated, coated can stock is used to form various metal cans. The coating may be applied to the can stock prior to forming the can or can part, or may be applied to the can or can part after forming.

Any material used to form food cans can be processed according to the method of the present invention. Particularly suitable substrates include tin-plated steel, tin-free steel and black plated steel.

Accordingly, the present invention further relates to a method of coating an encapsulation comprising applying any of the above coating compositions on at least a portion of the encapsulation and curing the coating. Two-piece cans are manufactured by joining a can body (typically a drawn metal body) and a can lid (typically a drawn metal lid) together. The coating of the present invention is suitable for food contact situations and can be used on the inside of such cans. They are particularly useful for spray-applied liquid coatings on the interior of two-piece thin-walled drawn beverage cans and for coil coating of food can ends. The invention also provides utility in other applications. These additional applications include, but are not limited to, block coating, sheet coating, and side seam coating (e.g., food can side seam coating).

Spraying includes introducing the coating composition into the interior of the preformed package. Typical prefabricated packages suitable for spray coating include food cans, beer and beverage packages, and the like. Spraying may utilize a nozzle capable of uniformly coating the inside of the prefabricated package. The sprayed preformed package is then heated to remove residual solvent and harden the coating. For food in-line spraying, the curing conditions involve maintaining the temperature measured at the top of the can at 350 ° F to 500 ° F for 0.5 to 30 minutes.

Coil coating is described as coating a continuous coil composed of metal (e.g., steel or aluminum). Once coated, the coated web is subjected to a short thermal, ultraviolet, and/or electromagnetic curing cycle to harden (e.g., dry and cure) the coating. Coil coating provides a coated metal (e.g., steel and/or aluminum) substrate that can be fabricated into shaped articles, such as two-piece drawn food cans, three-piece food cans, food can lids, thin-walled drawn cans, and the like.

Seal coating is commercially described as applying a thin layer of protectant coating to the exterior of a two-piece thin-walled drawn ("D & I") can. The exterior of these D & I cans are "block coated" by passing a preformed two-piece D & I can under a curtain of coating composition. The can is inverted, that is, the open end of the can is in a "down" position when passing through the curtain. The curtain of such coating compositions presents a "waterfall" appearance. Once the cans are passed under the curtain of coating composition, the liquid coating material effectively coats the exterior of each can. Excess coating is removed by using an "air knife". Once the desired amount of coating is applied to the exterior of each can, each can is passed through a thermal, ultraviolet, and/or electromagnetic curing oven to harden (e.g., dry and cure) the coating.

Sheet coating is described as coating individual sheets of various materials (e.g., steel or aluminum) that have been pre-cut into square or rectangular "sheets". Typical dimensions for these panels are about one square meter. Once coated, each sheet is cured. Once hardened (e.g., dried and cured), the coated substrate sheet is collected and ready for subsequent fabrication. Sheet coating provides a coated metal (e.g., steel or aluminum) substrate that can be successfully fabricated into shaped articles, such as two-piece drawn food cans, three-piece food cans, food can lids, thin-walled drawn cans, and the like.

Side seam coating is described as spray coating a liquid coating over the welded area of a formed three-piece food can. When preparing three-piece food cans, a rectangular piece of coated substrate is formed into a cylinder. The formation of the cylinder is permanent due to the welding of each side of the rectangle via thermal welding. Once welded, each can typically requires a layer of liquid coating to protect the exposed "weld" from subsequent corrosion or other effects on the contained foodstuff. The liquid coating that serves this function is called a "side seam strip". In addition to small thermal, ultraviolet, and/or electromagnetic ovens, typical side seam strips are spray coated and cured quickly by residual heat from the welding operation.

Aspects of the invention

Non-limiting aspects of the invention include:

1. a polymeric polyoxazoline having the structure:

wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is₅Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups; and wherein each R₁₀Independently hydrogen or an organic moiety.

2. The polymeric polyoxazoline of aspect 1, wherein X is the residue of a polyester polyol, polyether polyol, or polyurethane polyol polymer.

3. A polymeric polyoxazoline according to any preceding aspect, wherein Y independently contains one or two oxazoline groups.

4. The polymeric polyoxazoline of any preceding aspect, wherein R₅Comprising ethylene (C)₂H₄) Or cyclohexane (C)₆H₁₀)。

5. The polymeric polyoxazoline of any preceding aspect, wherein R₁₀Including hydrogen.

6. A method of making a polymeric polyoxazoline, comprising:

(a) reacting a polymeric polyol having terminal and/or pendant hydroxyl groups with a dicarboxylic acid/anhydride to form a carboxylic acid functional polymer, and

(b) reacting the carboxylic acid functional polymer with a polyoxazoline containing at least two oxazoline groups.

7. The method of aspect 6, wherein the polymeric polyol comprises a polyester polyol, a polyether polyol, a polyurethane polyol, or a mixture thereof.

8. The method of aspect 6 or aspect 7, wherein the dicarboxylic acid/anhydride contains 2 to 30 carbon atoms.

9. The method according to any preceding aspect, wherein the dicarboxylic acid/anhydride comprises phthalic anhydride.

10. The method of any of aspects 6-9, wherein the polymeric polyol comprises a polyether polyol.

11. The method of any one of aspects 6 to 10, wherein the polyoxazoline comprises phenylene-bis-oxazoline.

12. The method of aspect 11, wherein the phenylene-bis-oxazoline comprises a 1, 3-phenylene-bis-oxazoline.

13. The method of any one of aspects 6-10, wherein the polyoxazoline comprises 2, 2', 2 ″ - (hexane-1, 3, 6-triyl) tris (4, 5-dihydrooxazole).

14. A coating composition comprising:

(a) a polymer comprising an acidic functional group, and

(b) a polymeric polyoxazoline crosslinker having the structure:

wherein X is the residue of a polymeric polyol after reaction with a dicarboxylic acid/anhydride; wherein R is₅Is an organic moiety; wherein Y is an organic moiety containing one or more oxazolinyl groups; and wherein each R₁₀Independently hydrogen or an organic moiety.

15. The coating composition of aspect 14, wherein the polymer comprising acidic functional groups comprises a polyester polymer and/or a (meth) acrylic polymer.

16. The coating composition of aspect 14 or aspect 15, wherein (a) and (b) are dispersed in an aqueous medium.

17. The coating composition of any one of aspects 14 to 16, wherein the molar ratio of polyoxazoline to carboxylic acid is 0.05: 1 to 2: 1.

18. The coating composition according to any one of aspects 14 to 17, wherein the polymeric polyoxazine cross-linking agent comprises a polymeric polyoxazine having a structural unit according to any one of aspects 1 to 5 and/or made by a method according to any one of aspects 6 to 13.

19. A package at least partially coated on a surface thereof with a coating composition comprising any one of the coating compositions of aspects 14 to 18.

20. The coated package of aspect 19, wherein the package is a metal can.

21. The coated package of aspect 19 or aspect 20, wherein the coating is applied to at least a portion of a food-contact surface of the package.

22. The coated package of any one of aspects 19-21, wherein the coating composition is applied to the surface of a can lid.

23. The coated package of any one of aspects 19-22, wherein the composition is an aqueous composition in which (a) and (b) are dispersed in an aqueous medium.

24. The coated package of any one of aspects 19-23, wherein the polymer comprising an acidic functional group comprises a carboxyl-containing (meth) acrylic polymer, a carboxyl-containing polyester polymer, or a mixture thereof.

25. The coated package of any one of aspects 19-24, wherein the coating composition is the coating composition of any one of claims 14-18.

26. The coating composition of any one of aspects 14 to 18, wherein the coating composition is substantially free, and/or completely free of BPA, BADGE, BPF, BFDGE, and/or formaldehyde.

27. A method of coating an encapsulant comprising coating at least a portion of an encapsulant with any of the coating compositions of aspects 14-18.

Examples of the invention

The following examples are provided to aid the understanding of the present invention and should not be construed as limiting the scope of the invention. All parts and percentages are by weight unless otherwise indicated.

Example 1: synthesis of 2, 2' - (Hexane-1, 3, 6-triyl) tris (4, 5-dihydrooxazole)

To a 1000m L four-necked reaction flask was added 161.2g of hexane-1, 3, 6-trimethylnitrile, 4.8g of zinc octoate and 150.7g of xylene then the flask was equipped with a thermocouple, water condenser, stirring blade and 0.5SCFH nitrogen blanket, the contents of the flask were heated to 130 ℃ while stirring, 244.6g of monoethanolamine was added dropwise to the flask at 127 ℃ after which the reaction mixture was held at reflux for 10 hours using Thermoscientific Nicolet iS5 FT-IR until the IR spectrum showed the absence of a characteristic nitrile band (2244cm 4 cm)^-1). Excess ethanolamine was removed by azeotropic distillation using Dean Stark. After removal of the ethanolamine, xylene was distilled off. The reaction mixture was cooled to 60 ℃ and poured off.

Example 2

The polymeric polyoxazoline as shown in the above structure (7) is prepared as follows:

to a 500m L four-necked reaction flask was added 79.6g TERETHANE 650 and 37.7g hexahydrophthalic anhydride then the flask was assembled with a thermocouple, water condenser, stirring blade and 0.2SCFH nitrogen blanket the contents of the flask were heated to 150 ℃ and held for 1 hour while stirring after which the reaction mixture was cooled to 120 ℃ after which 71.9g polyoxazoline from example 1 was added to the reaction mixture at 120 ℃ the reaction mixture was held at 150 ℃ for 2 hours then heated to 200 ℃ for 3 hours until a solution of 0.1NKOH in methanol was used as a reagent to obtain an acid number of less than 2 with Metrohm 888Titrando then the reaction mixture was cooled to 60 ℃ and 100g 1-methoxy-2-propanol was added to the reaction mixture the final product was poured through a filter bag.

Example 3

The polymeric polyoxazoline as shown in the above structure (6) is prepared as follows:

to a 500m L four-necked reaction flask was added 79.6g TERETHANE 650 and 37.7g hexahydrophthalic anhydride then the flask was set up with a thermocouple, water condenser, stirring blade and 0.2SCFH nitrogen blanket the contents of the flask were heated to 150 ℃ and held for 1 hour while stirring after which 66.2g 1, 3-phenylene-bis-oxazoline was added to the reaction mixture and the reaction mixture was held at 150 ℃ for 5 hours until an acid value of less than 2 was obtained with a Metrohm 888Titrando using a 0.1N solution of KOH in methanol as a reagent then the reaction mixture was cooled to 60 ℃ and poured.

Example 4

A water-based coating composition containing a polymer comprising an acidic functional group component and the polymeric polyoxazoline polymer of example 2 was prepared from the following mixture of ingredients:

material	Gram number of material
		Acrylic latex1	78.05
Acrylic acid solution2	5.61
		Example 2Of (a) a polymeric polyoxazoline	2.54
Phosphoric acid-DMEA solution3	0.69
		Butanol	6.87
Pentanol (amyl alcohol)	2.75
		2-butoxyethanol	2.75
Dimethylethanolamine	0.74
		Total of	100.00
Viscosity of #4 Ford cup at 21 deg.C (seconds)	19.3
		pH	7.8
Theoretical weight solids of paint	27.5

¹Acrylic latex having a composition of 5% acrylic, 40% BMA, 30% BA and 25% MMA made using 0.44% ammonium persulfate initiator on monomer solids at 29.5% solids in deionized water and MA L VERN Z-average particle size of 355nm the latex was neutralized to 25% with dimethylethanolamine and contained 25% on monomer solidsThere was 0.12% sodium bicarbonate.

²An acrylic solution polymer of 21% acrylic acid, 35% butyl acrylate and 44% butyl methacrylate made at 49% solids weight in a solvent blend of 40% butanol, 50% 2-butoxyethanol and 10% deionized water, having a GPC number average molecular weight of 4,115 and a weight average molecular weight of 12,047. A solution polymer was prepared using a total of 1.25% t-butyl peroxy-3, 5, 5-trimethylhexanoate on monomer solids as initiator. The solution polymer was neutralized to 50% using dimethylethanolamine.

³Phosphoric acid, neutralized with dimethylethanolamine in deionized water, was made using 2.35 grams of phosphoric acid (85%), 3.2 grams of dimethylethanolamine, and 14.45 grams of deionized water.

The coating was pulled down onto flat aluminum beverage cans using a #9 rod to obtain a coating at 5 to 6g/m²The target film weight within the range, the coating was baked in a box oven set at 215 ℃ for one forty five seconds, the film weight was measured using a Strand gage (Strand Gauge). A2L b.Hammer program with gauze and a double rub program were used to determine MEK resistance.A set of panels was exposed to boiling 3% acetic acid for 30 minutes and then soaked in 3% acetic acid for ten days at 40 ℃ for coating adhesion to an aluminum substrate, the panels were tested using a BYK Cross-Cut Tester Kit (BYK Cross-Cut Tester Kit) #5127 with 1.5mm blades.

¹The control group was a commercial coating for the interior of the beverage can. The coating is an epoxy acrylic paint containing bisphenol a.

While specific embodiments of the invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims.