Coating compositions for containers and other articles and methods of coating

COATING COMPOSITIONS FOR CONTAINERS AND OTHER ARTICLES AND METHODS OF COATING

CROSS-REFERENCE TO RELATED APPLICATIONS

[001] This application claims the benefit of U.S. Provisional Application No.

61/440,085 filed on February 7, 2011 and entitled “COATING COMPOSITION FOR CONTAINERS AND OTHER ARTICLES AND METHODS OF COATING,” and U.S. U.S. Provisional Application No. 61/579,072 filed on December 22, 2011 and entitled “COATING COMPOSITION FOR CONTAINERS AND OTHER ARTICLES AND METHODS OF COATING,” each of which is incorporated herein by reference in its entirety.

BACKGROUND

[002| The application of coatings to metals to retard or inhibit corrosion is well established. This is particularly true in the area of packaging containers such as metal food and beverage cans. Coatings are typically applied to the interior of such containers to prevent the contents from contacting the metal of the container. Contact between the metal and the packaged product can lead to corrosion of the metal container, which can contaminate the packaged product. This is particularly true when the contents of the container are chemically aggressive in nature. Protective coatings are also applied to the interior of food and beverage containers to prevent corrosion in the headspace of the container between the fill line of the food product and the container lid.

[003] Packaging coatings should preferably be capable of high-speed application to the substrate and provide the necessary properties when hardened to perform in this demanding end use. For example, the coating should be safe for food contact, not adversely affect the taste of the packaged food or beverage product, have excellent adhesion to the substrate, resist staining and other coating defects such as “popping,” “blushing” and/or “blistering,” and resist degradation over long periods of time, even when exposed to harsh environments. In addition, the coating should generally be capable of maintaining suitable film integrity during container fabrication and be capable of withstanding the processing conditions that the container may be subjected to during product packaging.

[004] Various coatings have been used as interior protective can coatings, including polyvinyl-chloride-based coatings and epoxy-based coatings incorporating bisphenol A (“BPA”). Each of these coating types, however, has potential shortcomings. For

2020201397 26 Feb 2020 example, the recycling of materials containing polyvinyl chloride or related halidecontaining vinyl polymers can be problematic. There is also a desire by some to reduce or eliminate certain BPA-based compounds commonly used to formulate food-contact epoxy coatings.

[005] What is needed in the marketplace is an improved binder system for use in coatings such as, for example, packaging coatings.

SUMMARY

[006] This invention provides a polymer useful in a variety of applications such as, for example, as a binder polymer of a coating composition. The polymer preferably includes one or more segments having two or more aryl or heteroaryl groups in which each aryl or heteroaryl group includes an oxygen atom attached to the ring and a substituent group (preferably a “bulky” substituent group) attached to the ring preferably at an ortho or meta position relative to the oxygen atom. An example of such a segment is: -O-Ar(R²)_n-Ar-O-, wherein “Ar” represents an aryl or heteroaryl group preferably having at least one R¹ group attached to the ring at an ortho or meta position relative to the depicted oxygen atom, which preferably belongs to an ether linkage, and wherein R¹, R², and n are as defined herein for Formula (I). In preferred embodiments, the polymer is a polyether polymer.

[007] In preferred embodiments, the polymer includes one or more segments, and even more preferably a plurality of segments, of the below Formula (I):

<img file="AU2020201397B2_D0001.tif" />

wherein:

• each of the pair of oxygen atoms depicted in Formula (I) is preferably present in an ether or ester linkage, more preferably an ether linkage;

· “H” denotes a hydrogen atom, if present;

• each R¹ is independently an atom or group preferably having an atomic weight of at least 15 daltons, wherein each of the phenylene groups depicted in Formula (I) preferably includes at least one R¹ attached to the ring at an ortho or meta position relative to the oxygen atom;

2020201397 26 Feb 2020 • v is independently 1 to 4;

• w is 4;

• R², if present, is preferably a divalent group;

• n is 0 or 1, with the proviso that if n is 0, the phenylene groups depicted in

Formula (I) can optionally join to form a fused ring system with each other (e.g., a substituted naphthalene group), in which case w is 3 (as opposed to 4); and • wherein two or more R¹ and/or R² groups can join to form one or more cyclic groups.

[008] The segment of Formula (I) preferably includes at least one R¹ that is capable of 10 providing steric hindrance to a phenol hydroxyl group. More preferably, each phenylene group depicted in Formula (I) includes at least one such R¹ group. Preferred such R¹groups arc sufficiently “bulky” so that, when located at an ortho or meta position (more typically an ortho position) relative to a phenol hydroxyl group, the R¹ group provides sufficient steric hindrance to reduce the accessibility and/or reactivity of such a phenol 15 hydroxyl group.

[009] In preferred embodiments, one or both of the following are true: (i) at least one R^s attached to each phenylene ring depicted in Formula (I) at an ortho position relative to the depicted oxygen atom and (ii) at least one R¹ attached to the ring at an ortho or meta position relative to the depicted oxygen atom includes one or more carbon atoms.

Non-limiting examples of R¹ groups include groups having at least one carbon atom, a halogen atom, a sulfur-containing group, or any other suitable group preferably having an atomic weight of at least 15 daltons that is preferably substantially non-reactive with an epoxy group. Organic groups are presently preferred, with organic groups that are free of halogen atoms being particularly preferred.

[010] While the polymer of the present invention can have any suitable backbone chemistry, in preferred embodiments the polymer is a polycther polymer.

[Oil] The polymer preferably does not include any structural units derived from bisphenol A (“BPA”) or the diglycidyl ether of BPA (“BADGE”).

[012] In preferred embodiments, the polymer also includes pendant hydroxyl groups (e.g., secondary hydroxyl groups) and, more preferably, one or more -CH2-CH(OH)CH₂- segments, which arc preferably derived from an oxirane and located in a backbone of the polymer.

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[013] The present invention also provides a coating composition that includes the polymer described herein, more preferably a polyether polymer described herein. The coating composition preferably includes at least a film-forming amount of the polymer and may optionally include one or more additional polymers. The coating composition is useful in coating a variety of substrates, including as an interior or exterior coating on metal packaging containers or portions thereof. In preferred embodiments, the coating composition is useful as a food-contact coating on a food or beverage container. In preferred embodiments, the coating composition is at least substantially free of mobile BPA or BADGE, and more preferably is completely free of BPA or BADGE. The coating composition may also have utility in a variety of other coating end uses, including, for example, coatings for valves and fittings, especially valves and fittings for use with potable water; pipes for conveying liquids, especially potable water pipes; and liquid storage tanks, especially potable water tanks such as, e.g., bolted steel water tanks. [014] In one embodiment, the coating composition of the present invention is a powder coating composition that preferably includes a base powder, formed at least in part, from the polymer of the present invention. The coating composition may include one or more optional ingredients in the particles of the base powder and/or in separate particle. Such optional ingredients may include, for example, crosslinker, cure accelerator, colored pigment, filler, flow additives, etc.

[015] The present invention also provides packaging articles having a coating composition of the present invention applied to a surface of the packaging article. In one embodiment, the packaging article is a container such as a food or beverage container, or a portion thereof (e.g., a twist-off closure lid, beverage can end, food can end, etc.), wherein at least a portion of an interior surface of the container is coated with a coating composition described herein that is suitable for prolonged contact with a food or beverage product or other packaged product.

[016] In one embodiment, a method of preparing a container is provided that includes an interior, food-contact coating of the present invention. The method includes: providing a coating composition described herein that includes a binder polymer and optionally a liquid carrier; and applying the coating composition to at least a portion of a surface of a substrate prior to or after forming the substrate into a container or a portion thereof having the coating composition disposed on an interior surface. Typically, the

2020201397 26 Feb 2020 substrate is a metal substrate, although the coating composition may be used to coat other substrate materials if desired.

[017] In one embodiment, a method of forming food or beverage cans, or a portion thereof, is provided that includes: applying a coating composition described herein to a 5 metal substrate (e.g., applying the coating composition to the metal substrate in the form of a planar coil or sheet), hardening the coating composition, and forming the substrate into a food or beverage can or a portion thereof.

[018] In certain embodiments, forming the substrate into an article includes forming the substrate into a can end or a can body. In certain embodiments, the article is a two-piece 10 drawn food can, three-piece food can, food can end, drawn and ironed food or beverage can, beverage can end, twist-off closure lid, and the like. Suitable metal substrates include, for example, steel or aluminum.

[019] In certain embodiments, a packaging container is provided having: (a) a coating composition of the present invention disposed on at least a portion of an interior or 15 exterior surface of the container and (b) a product packaged therein such as a food, beverage, cosmetic, or medicinal product.

[020] The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list. Unless otheiwise indicated, the structural representations included herein are not intended to indicate any particular stereochemistry and are intended to encompass all stereoisomers.

DEFINITIONS

[021] As used herein, the term “organic group” means a hydrocarbon group (with optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that is classified as an aliphatic group, a cyclic group, or combination of aliphatic and cyclic groups (e.g., alkaryl and aralkyl groups). The term “cyclic group” means a 30 closed ring hydrocarbon group that is classified as an alicyclic group or an aromatic group, both of which can include heteroatoms. The term “alicyclic group” means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.

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[022] The term “aryl group” (e.g., an arylene group) refers to a closed aromatic ring or ring system such as phenylene, naphthylene, biphenylene, fluorenylene, and indenyl, as well as heteroarylene groups (i.e., a closed aromatic or aromatic-like ring hydrocarbon or ring system in which one or more of the atoms in the ring is an element other than carbon (e.g., nitrogen, oxygen, sulfur, etc.)). Suitable heteroaryl groups include furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tctrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, pyrazinyl, 1-oxidopyridyl, pyridazinyl, triazinyl, tetrazinyl, oxadiazolyl, thiadiazolyl, and so on. When such groups are divalent, they are typically referred to as “arylene” or “heteroarylene” groups (e.g., furylene, pyridylene, etc.)

[023] A group that may be the same or different is referred to as being “independently” something.

[024] Substitution is anticipated on the organic groups of the compounds of the present invention. As a means of simplifying the discussion and recitation of certain terminology used throughout this application, the terms “group” and “moiety” are used to differentiate between chemical species that allow for substitution or that may be substituted and those that do not allow or may not be so substituted. Thus, when the term “group” is used to describe a chemical substituent, the described chemical material includes the unsubstituted group and that group with Ο, N, Si, or S atoms, for example, in the chain (as in an alkoxy group) as well as carbonyl groups or other conventional substitution. Where the term “moiety” is used to describe a chemical compound or substituent, only an unsubstituted chemical material is intended to be included. For example, the phrase “alkyl group” is intended to include not only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like, but also alkyl substituents bearing further substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, “alkyl group” includes ether groups, haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls, etc. On the other hand, the phrase “alkyl moiety” is limited to the inclusion of only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like. As used herein, the term “group” is intended

2020201397 26 Feb 2020 to be a recitation of both the particular moiety, as well as a recitation of the broader class of substituted and unsubstituted structures that includes the moiety.

[025] The term “polyhydric phenol” as used herein refers broadly to any compound having one or more aryl or heteroaryl groups (more typically one or more phenylene 5 groups) and at least two hydroxyl groups attached to a same or different aryl or heteroaryl ring. Thus, for example, both hydroquinone and 4,4’-biphcnol arc considered to be polyhydric phenols. As used herein, polyhydric phenols typically have six carbon atoms in an aryl ring, although it is contemplated that aryl or heteroaryl groups having rings of other sizes may be used.

[026] The term “phenylene” as used herein refers to a six-carbon atom aryl ring (e.g., as in a benzene group) that can have any substituent groups (including, e.g., hydrogen atoms, halogens, hydrocarbon groups, oxygen atoms, hydroxyl groups, etc.). Thus, for example, the following aryl groups are each phenylene rings: -C6H4-, -CeHXCH})-, and -C6H(CH3)₂C1-. In addition, for example, each of the aryl rings of a naphthalene group are phenylene rings.

[027] The term “substantially free” of a particular mobile compound means that the recited polymer and/or composition contains less than 100 parts per million (ppm) of the recited mobile compound. The term “essentially free” of a particular mobile compound means that the recited polymer and/or composition contains less than 5 parts per million 20 (ppm) of the recited mobile compound. The term “completely free” of a particular mobile compound means that the recited polymer and/or composition contains less than 20 parts per billion (ppb) of the recited mobile compound.

[028] The term “mobile” means that the compound can be extracted from the cured coating when a coating (typically ~1 mg/cm²) is exposed to a test medium for some defined set of conditions, depending on the end use. An example of these testing conditions is exposure of the cured coating to HPLC-grade acetonitrile for 24 hours at 25°C. If the aforementioned phrases are used without the term “mobile” (e.g., “substantially free of BPA”) then the recited polymer and/or composition contains less than the aforementioned amount of the compound whether the compound is mobile in the coating or bound to a constituent of the coating.

[029] The term “estrogenic activity” refers to the ability of a compound to mimic hormone-like activity through interaction with an endogenous estrogen receptor, typically an endogenous human estrogen receptor.

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[030] The term “food-contact surface” refers to the substrate surface of a container (typically an inner surface of a food or beverage container) that is in contact with, or intended for contact with, a food or beverage product. By way of example, an interior surface of a metal substrate of a food or beverage container, or a portion thereof, is a 5 food-contact surface even if the interior metal surface is coated with a polymeric coating composition.

[031] The term “crosslinker” refers to a molecule capable of forming a covalent linkage between polymers or between two different regions of the same polymer.

[032] The term “on,” when used in the context of a coating applied on a surface or substrate, includes both coatings 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 on the substrate.

[033] Unless otherwise indicated, the term “polymer” includes both homopolymers and copolymers (e.g., polymers of two or more different monomers). Similarly, unless otherwise indicated, the use of a term designating a polymer class such as, for example, “polyether” is intended to include both homopolymers and copolymers (e.g., polyetherester copolymers).

[034] The terms “comprises” and variations thereof do not have a limiting meaning where these terms appear in the description and claims.

[035] The terms “preferred” and “preferably” refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

[036] As used herein, “a,” “an,” “the,” “at least one,” and “one or more” are used interchangeably. Thus, for example, a coating composition that comprises “a” polyether can be interpreted to mean that the coating composition includes “one or more” poly ethers.

[037] Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). Furthermore, disclosure of a range includes disclosure of all subranges included within the broader range (e.g., 1 to 5 discloses 1 to 4, 1.5 to 4.5, 4 to 5, etc.).

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DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[038] In one aspect, the present invention provides a coating composition that includes a polymer, more preferably a binder polymer, and even more preferably a polyether binder polymer. Although the ensuing discussion focuses primarily on coating end uses, 5 it is contemplated that the polymer of the present invention, as well as intermediates thereof, may have utility in a variety of other end uses such as, for example, in adhesives or composites.

[039] Coating compositions of the present invention preferably include at least a filmforming amount of the polymer described herein. In addition to the polymer, the coating 10 composition may also include one or more additional ingredients such as, for example, a crosslinker, a liquid carrier, and any other suitable optional additives. Although any suitable cure mechanism may be used, thermoset coating compositions are preferred.

Moreover, although coating compositions including a liquid carrier are presently preferred, it is contemplated that the polymer of the present invention may have utility in 15 solid coating application techniques such as, for example, powder coating.

[040] Coating compositions of the present invention may have utility in a variety of coating end uses, and especially packaging coating end uses. Preferred coating compositions of the present invention exhibit a superior combination of coating attributes such as good flexibility, good substrate adhesion, good chemical resistance and corrosion 20 protection, good fabrication properties, and a smooth and regular coating appearance free of blisters and other application-related defects. In preferred embodiments, the coating composition is suitable for use as an adherent packaging coating and, more preferably, as an adherent coating on an interior and/or exterior surface of a food or beverage container. Thus, in preferred embodiments, the coating composition is suitable for us as a food25 contact coating. It is also contemplated that the coating composition may have utility in cosmetic packaging or medical packaging coating end uses, and as a drug-contact coating in particular (e.g., as an interior coating of a metered dose inhaler can commonly referred to as an “MDI” container). It is also contemplated that the coating composition may have utility in coating applications in which the coated substrate will contact bodily fluids such as, e.g., as an interior coating of a blood vial.

[041] In preferred embodiments, the polymer of the present inx^ention, which is preferably a polyether polymer, includes one or more segments of the below Formula (I):

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<img file="AU2020201397B2_D0002.tif" />

Formula (D wherein:

• each of the pair of oxygen atoms depicted in Formula (I) is preferably present in an ether or ester linkage, more preferably an ether linkage;

• “H” denotes a hydrogen atom, if present;

· each R¹ is preferably independently an atom or group preferably having at atomic weight of at least 15 daltons that is preferably substantially non-reactive with an epoxy group;

• v is independently 1 to 4;

• w is 4;

· each of the phenylene groups depicted in Formula (I) includes at least one R¹ attached to the ring preferably at an ortho or meta position relative to the oxygen atom;

• R², if present, is preferably a divalent group;

• n is 0 or 1, with the proviso that if n is 0, the phenylene groups depicted in

Formula (I) can optionally join to form a fused ring system (e.g., a substituted naphthalene group) in which case w is 3 (as opposed to 4); and • two or more R¹ and/or R² groups can optionally join to form one or more cyclic groups.

[042] In preferred embodiments, each R^l and R², if present, are preferably not reactive with an oxirane group at a temperature of less than about 200°C.

[043] As depicted in the above Formula (I), the segment includes a pair of phenylene groups (and may optionally include one or more additional phenylene or other aryl or heteroaryl groups). Although aryl groups having a six-carbon aromatic ring are presently preferred, it is contemplated that any other suitable aryl or heteroaryl groups may be used in place of the phenylene groups depicted in Formula (I). As depicted in the above Formula (I), the substituent groups (i.e., -Ο-, H, R¹, and R²) of each phenylene group can be located at any position on the ring relative to one another, although in preferred embodiments at least one R¹ is positioned on the ring immediately adjacent to the

2020201397 26 Feb 2020 oxygen atom. In other embodiments in which other aryl or heteroarylene groups are used in place of the depicted phenylene groups in Formula (I), it is contemplated that the same would hold true for the substituent groups of such other aryl or heteroarylene groups.

[044] In preferred embodiments, R¹ is attached to the phenylene ring at a carbon atom immediately adjacent to the carbon atom to which the depicted oxygen atom is attached. In other words, R^l is preferably located at an ortho position on the ring relative to the oxygen atom. In some embodiments, an R¹ is located immediately adjacent to the oxygen on either side. That is, in some embodiments, an R^l is located at each ortho position on the ring relative to the oxygen atom. While not intending to be bound by any theory, it is believed that the positioning of one or more R¹ groups at an ortho position relative to the oxygen atom depicted in Formula (I) may be beneficial, for example, in the event that monomer used to make the segment of Formula (I) is not fully reacted into the polymer. Such unreacted monomer could potentially migrate out of a cured coating composition including the polymer. The benefits of R¹ with regards to an absence of appreciable estrogenic activity in certain such potential migrants are discussed in greater detail below.

[045] While not intending to be bound by any theory, it is believed that a polyhydric phenol compound is less likely to exhibit appreciable estrogenic activity if the one or 20 more hydroxyl groups present on each aryl ring (typically phenol hydroxyl groups) are sterically hindered by one or more other substituents of the aryl ring, as compared to a similar polyhydric phenol compound having hydrogen atoms present at each ortho position. It is believed that it may be preferable to have substituent groups positioned at each ortho position relative to the aforementioned hydroxyl groups to provide optimal steric effect to reduce accessibility and/or reactivity of the hydroxyl group. While it is preferred to position the substituent groups at one or both ortho positions, a sufficiently “bulky” substituent group(s) located at one or both meta positions may also provide the desired effect.

[046] Preferred R¹ groups are sufficiently “bulky” to provide a suitable level of steric hindrance for the aforementioned hydroxyl groups to achieve the desired effect. To avoid any ambiguity, the term “group” when used in the context of R¹ groups refers to both single atoms (e.g., a halogen atom) or molecules (i.e., two or more atoms). The optimal chemical constituents, size, and/or configuration (e.g., linear, branched, etc.) of

2020201397 26 Feb 2020 the one or more R¹ groups may depend on a variety of factors, including, for example, the location of the R¹ group on the aryl group.

[047] Preferred segments of Formula (I) include one or more R¹ groups having an atomic weight of at least 15 daltons. In some embodiments, the segments of Formula (I) 5 include one or more R¹ groups having an atomic weight of at least 25, at least 40, or at least 50. While the maximum suitable size of R¹ is not particularly limited, typically it will be less than 500 daltons, more typically less than 100 daltons, and even more typically less than 60 daltons. Non-limiting examples of R¹ groups include groups having at least one carbon atom (e.g., organic groups), halogen atoms, sulfur-containing 10 groups, or any other suitable group that is preferably substantially non-reactive with an epoxy group.

[048] In presently preferred embodiments, one or more R¹ groups of each phenylene group includes at least one carbon atom, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms. R¹ will typically be a saturated or unsaturated 15 hydrocarbon group, more typically saturated, that may optionally include one or more heteroatoms other than carbon or hydrogen atoms (e.g., N, O, S, Si, a halogen atom, etc.). Examples of suitable hydrocarbon groups may include substituted or unsubstituted: alkyl groups (e.g., methyl, ethyl, propyl, butyl groups, etc., including isomers thereof), alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, or 20 combinations thereof.

[049] In certain preferred embodiments, each phenylene group depicted in Formula (I) includes at least one alkyl R¹ group. As discussed above, any suitable isomer may be used. Thus, for example, a linear butyl group may be used or a branched isomer such as an isobutyl group or a tert-butyl group. In one embodiment, a tert-butyl group (and more 25 preferably a tert-butyl moiety) is a preferred R¹ group.

[050] As previously mentioned, it is contemplated that R¹ may include one or more cyclic groups. In addition, R^l may form a cyclic or polycyclic group with one or more other R¹ groups and/or R².

[051] In some embodiments, one or both phenylene groups depicted in Formula (I) 30 includes an R¹ located ortho to the oxygen that is a halogen atom, more preferably a higher molecular weight halogen such as bromine or iodine. However, in preferred embodiments, the segment of Formula (I) does not include any halogen atoms.

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Moreover, in presently preferred embodiments, the polymer including one or more segments of Formula (I) is preferably free of halogen atoms.

[052] R² is present or absent in the segment of Formula (I) depending on whether n is 0 or 1. When R² is absent, either (i) a carbon atom of one phenylene ring is covalently attached to a carbon atom of the other phenylene ring (which occurs when w is 4) or (ii) the phenylene groups depicted in Formula (1) join to form a fused ring system (which occurs when w is 3 and the two phenylene groups are so fused). In some embodiments, R² (or the ring-ring covalent linkage if R² is absent) is preferably attached to at least one, and more preferably both, phenylene rings at a para position (i.e., 1,4 position) relative to the oxygen atom depicted in Formula (I). An embodiment of the segment of Formula (I), in which n is 0 and w = 3 such that the two phenylene groups have joined to form a naphthalene group, is depicted below:

<img file="AU2020201397B2_D0003.tif" />

[053] R² can be any suitable divalent group including, for example, carbon-containing groups (which may optionally include heteroatoms such as, e.g., N, O, S, Si, a halogen 15 atom, etc.), sulfur-containing groups (including, e.g., a sulfur atom), oxygen-containing groups (including, e.g., an oxygen atom, a ketone group, etc.), nitrogcn-containing groups, or a combination thereof. In preferred embodiments, R² is present and is typically an organic group containing less than 15 carbon atoms, more typically 1 to 10 carbon atoms. R² will typically be a saturated or unsaturated hydrocarbon group, more typically a saturated alkyl group. In some embodiments, R² may include one or more cyclic groups, which may be aromatic or alicyclic and can optionally include hetcroatoms. The one or more optional cyclic groups of R² can be present, for example, (i) in a chain connecting the two phenylene groups depicted in Formula (I) and/or (ii) in a pendant group attached to a chain connecting the two phenylene groups.

[054] The atomic weight of the R² group of Formula (I), if present, may be any suitable atomic weight, although in preferred embodiments, R² has an atomic weight of less than about 500 daltons, more preferably less than about 200 daltons, even more preferably less than 150 daltons, and optimally less than 100 daltons.

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[055] In some embodiments, R² includes a carbon atom that is attached to a carbon atom of each of the phenylene groups depicted in Formula (I). For example, R² can have a structure of the formula -C(R⁷R⁸)-, wherein R⁷ and R⁸ are each independently a hydrogen atom, a halogen atom, an organic group, a sulfur-containing group, a nitrogen5 containing group, or any other suitable group that is preferably substantially non-reactive with an epoxy group, and wherein R⁷ and R⁸ can optionally join to form a cyclic group. In an embodiment, R is a divalent methylene group (i.e., -CH₂-).

[056] The oxygen atom of a phenylene ring depicted in Formula (I) can be positioned on the ring at any position relative to R² (or relative to the other phenylene ring if R² is 10 absent). In some embodiments, the oxygen atom (which is preferably an ether oxygen) and R² are located at para positions relative to one another.

[057] The segments of Formula (I) can be of any suitable size. Typically, the segments of Formula (I) will have an atomic weight of less than 1,000, preferably less than 600, more preferably less than 400 daltons. More typically, the segments of Formula (I) will 15 have an atomic weight of about 250 to about 400 daltons.

[058] In preferred embodiments, the substituted phenylene groups of Formula (I) are symmetric relative to one another. Stated otherwise, the substituted phenylene groups are preferably formed from the same phenol compound, thereby resulting in the same substituent groups on each ring located at the same ring positions. An example of a 20 compound having symmetric phenylene groups is provided below.

[059] An example of a compound having phenylene groups that are not symmetric is provided below, in which a methyl group is at a meta position on one ring and at an ortho position on the other.

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<img file="AU2020201397B2_D0004.tif" />

[060] In preferred embodiments, the polymer of the present invention includes a plurality of segments of Formula (I), which are preferably dispersed throughout a backbone of the polymer, more preferably a polyethcr backbone. In preferred embodiments, the segments of Formula (I) constitute a substantial portion of the overall mass of the polymer. Typically, segments of Formula (I) constitute at least 10 weight percent (“wt-%”), preferably at least 30 wt-%, more preferably at least 40 wt-%, even more preferably at least 50 wt-%, and optimally at least 55 wt-% of the polymer.

[061] The weight percent of segments of Formula (I) in the polymer of the present invention may be below the amounts recited above in certain situations, and can even be substantially below. By way of example, the concentration of segments of Formula (I) may be outside the ranges recited above if the polymer of the present invention, which is preferably a polyether polymer, includes large molecular weight additional components such as may occur, for example, when the polymer is a copolymer such as an acrylic15 containing copolymer (e.g., an acrylic-polyether copolymer formed by grafting acrylic onto a polyethcr polymer of the present invention). In such embodiments, the weight percent of segments of Formula (I) present in the polymer is preferably as described above (i.e., > 10 wt-%, > 30 wt-%, > 40 wt-%, > 50 wt-%, > 55 wt-%), based on the weight percent of segments of Formula (I) relative to the total polyether fraction of the polymer (while not considering the total weight of non-polyether portions such as, for example, acrylic portions). Tn general, the total polyether fraction of the polymer can be calculated based on the total weight of polyepoxide and polyhydric phenol reactants (e.g., polyhydric monophenols and/or diphenols) incorporated into the polymer.

[062] Depending upon the particular embodiment, the polymer of the present invention 25 may be amorphous or semi-crystalline.

[063] The polymer can include branching, if desired. In preferred embodiments, however, the polymer of the invention is a linear or substantially linear polymer.

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[064] If desired, the backbone of the polymer may include step-growth linkages (e.g., condensation linkages) other than ether linkages (i.e., in addition to, or in place of, the ether linkages) such as, for example, amide linkages, carbonate linkages, ester linkages, urea linkages, urethane linkages, etc. Thus, for example, in some embodiments, the 5 backbone may include both ester and ether linkages.

[065] The polymer of the present invention preferably includes hydroxyl groups. In preferred embodiments, the polymer includes a plurality of hydroxyl groups attached to the backbone. In preferred embodiments, polyether portions of the polymer backbone include secondary hydroxyl groups distributed throughout. Preferred secondary hydroxyl groups are present in -CH2-CH(OH)-CH₂- segments, which are preferably derived from an oxirane group. Such segments may be formed, for example, via reaction of an oxirane group and a hydroxyl group (preferably a hydroxyl group of a polyhydric phenol). In some embodiments, CH₂-CH(OH)-CH₂- segments are attached to each of the ether oxygen atoms of preferred segments of Formula (I).

[066] The backbone of the polymer of the present invention may include any suitable terminal groups, including, for example, epoxy and/or hydroxyl groups (e.g., a hydroxyl group attached to a terminal aryl or heteroaryl ring).

[067] In preferred embodiments, the polymer of the present invention is formed using reactants that include at least one polyepoxide compound, more typically at least one diepoxide compound. Although any suitable ingredients may be used to form the polymer, in presently preferred embodiments, the polymer is formed via reaction of ingredients that include: (a) one or more polyepoxides, more preferably one or more diepoxides, and (b) one or more polyols, more preferably one or more polyhydric phenols, and even more preferably one or more dihydric phenols. The polymer is preferably derived from ingredients including a diepoxide having one or more “hindered” aryl or heteroaryl groups, and more preferably one or more “hindered” phenylene groups described herein (e.g., as depicted in Formula (I)).

[068] While it is contemplated that the segments of Formula (I) may be incorporated into the polymer using ingredients other than a polyepoxide compound, in preferred embodiments some, or all, of the segments of Formula (I) are incorporated into the polymer using a polyepoxide compound, and more preferably a diepoxide compound. The polyepoxide compound may be upgraded to form a binder polymer, more preferably a polyether binder polymer, of a suitable molecular weight using any suitable extender or

2020201397 26 Feb 2020 combinations of extenders. As discussed above, polyhydric phenols, and dihydric phenols in particular, are preferred extenders. Examples of other suitable extenders may include polyacids (and diacids in particular) or phenol compounds having both a phenol hydroxyl group and a carboxylic group (e.g., para hydroxy benzoic acid and/or para hydroxy phenyl acetic acid). Conditions for such reactions are generally carried out using standard techniques that arc known to one of skill in the art or that are exemplified in the examples section.

[069] The epoxy groups (also commonly referred to as “oxirane” groups) of the polyepoxide compound may be attached to the compound via any suitable linkage, including, for example, ether-containing or ester-containing linkages. Glycidyl ethers of polyhydric phenols and glycidyl esters of polyhydric phenols are preferred polyepoxide compounds, with diglycidyl ethers being particularly preferred.

[070] A preferred polyepoxide compound for use in incorporating segments of Formula (I) into the polymer of the present invention is depicted in the below Formula (II):

<img file="AU2020201397B2_D0005.tif" />

wherein:

• R¹, R², n, v, and w are as described above for Formula (I);

• each of the phenylene groups depicted in Formula (II) includes at least one R¹that is preferably attached to the ring at a position immediately adjacent to the oxygen atom (i.e., ortho);

• s is 0 to 1, more preferably 1;

• R³, if present, is a divalent group, more preferably a divalent organic group; and • preferably each R⁴ is independently a hydrogen atom, a halogen atom, or a hydrocarbon group that may include one or more heteroatoms; more preferably each R⁴ is a hydrogen atom.

[071] R³ is typically a hydrocarbyl group, which may optionally include one or more heteroatoms. Preferred hydrocarbyl groups include groups having from one to four

2020201397 26 Feb 2020 carbon atoms, with methylene groups being particularly preferred. In some embodiments, R³ includes a carbonyl group. In one such embodiment, R³ includes a carbonyl group that is attached to the oxygen atom depicted in Formula (II) (e.g., as in an ester linkage).

[072] In presently preferred embodiments, R⁴is a hydrogen atom.

1073] Preferred polycpoxidc compounds of Formula (II) arc non-mutagcnic. A useful test for assessing mutagenicity is the mammalian in vivo assay known as the in vivo alkaline single cell gel electrophoresis assay (referred to as the “comet” assay). The method is described in: Tice, R.R. “The single cell gel/comet assay: a microgel electrophoretic technique for the detection of DNA damage and repair in individual cells.” Environmental Mutagenesis. Eds. Phillips, D.H and Venitt, S. Bios Scientific, Oxford, UD, 1995, pp. 315-339. A negative test result in the comet assay indicates that a compound is non-mutagenic.

[074] In some embodiments, the polyepoxide compound of Formula (II) is formed via epoxidation of a diphenol compound (e.g., via a condensation reaction using epichlorohydrin or any other suitable material). Such a diphenol compound is depicted in the below Formula (III), wherein R.¹, R², n, v, and w are as in Formula (I):

Formula (III)

[075] Preferred compounds of Formula (III) do not exhibit appreciable estrogenic activity. Preferred appreciably non-estrogenic compounds exhibit a degree of estrogen agonist activity, in a competent in vitro human estrogen receptor assay, that is less than that exhibited by genistein in the assay, and more preferably less than that exhibited by 4,4'-(propane-2,2-diyl)diphenol in the assay. It has been found that compounds such as 4,4’-methylenebis(2,6-di-t-butylphenol), 2,2’-methylenebis(4-methyl-6-t-butylphenol),

4,4’-methylenebis(2,6-dimethylphenol), 4,4’butylidenebis(2-t-butyl-5-methylphenol), and 4,4’-(ethane-l,2-diyl)bis(2,6-dimethylphenol) do not exhibit appreciable estrogenic activity in a suitable in vitro assay whose results arc known to be directly correlated to the results of the MCF-7 cell proliferation assay (“MCF-7 assay”) through analysis of common reference compounds. The MCF-7 assay is a useful test for assessing whether a

2020201397 26 Feb 2020 polyhydric phenol compound is appreciably non-estrogenic. The MCF-7 assay uses MCF-7 WS8 cells to measure whether and to what extent a substance induces cell proliferation via estrogen receptor (ER)-mediated pathways. The method is generally described in NICEATM Pre-Screen Evaluation of the In Vitro Endocrine Disruptor

Assay, National Toxicology Program Interagency Center for the Evaluation of Alternative Toxicological Methods (NICEATM). Examples of appreciably nonestrogenic polyhydric phenols include polyhydric phenols that when tested using the MCF-7 assay exhibit a Relative Proliferative Effect (“RPE”) having a logarithmic value (with base 10) of less than about -2.0, more preferably less than about -3.0, and even more preferably less than about -4.0. The RPE, which is specifically defined in the aforementioned MCF-7 reference, is the ratio between the highest cell yield obtained with the test compound in the MCF-7 assay to that obtained with 17-beta estradiol in the MCF-7 assay multiplied by 100. A Table is provided below including various polyhydric compounds of Formula (III) and their anticipated logarithmic RPE values in the MCF-7 assay.

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<td> Poly hydric Compound of Formula (III)</td><td> Reference Compound</td><td> Log RPE</td>

<td></td><td> 17p-estradiol</td><td> 2.00</td>

<td></td><td> Genistein</td><td> -1.85</td>

<td> 4,4'-(propane-2,2-diyl)bis(2,6dimethylphenol)</td><td></td><td> -2.2</td>

<td> 4,4’-methylenebis(2,6-dimethylphenol)</td><td></td><td> about -4</td>

<td> 4,4’-(ethane-1,2-diy l)bis (2,6dimethylphenol)</td><td></td><td> in the range of -2 to - 3</td>

<td> 4,4’-butylidenebis(2-t-butyl-5mcthylphenol)</td><td></td><td> in the range of -3 to - 5</td>

<td> 4,4’-methylenebis(2,6-di-t-butylphcnol)</td><td></td><td> in the range of -3.5 to -5</td>

<td> 2,2’-methylenebis(4-methyl-6-tbutylphenol</td><td></td><td> In the range of -4 to 5</td>

<td> 4,4’-(ethane-1,2-diy l)bis(2,6dimethylphenol)</td><td></td><td> in the range of -4 to - 5</td>

<td> Ή Tetrabromobisphenol A</td><td></td><td> less than -5</td>

*A bromine is located at each ortho position.

[076] A diphenol having no appreciable estrogenic activity may be beneficial in the event that any unreacted, residual diphenol may be present in a cured coating composition. While the balance of scientific data does not indicate that the presence in cured coatings of very small amounts of residual diphenols having estrogenic activity in an in vitro recombinant cell assay pose a human health concern, the use of diphenols having no appreciable estrogenic activity in such an assay may nonetheless be desirable from a public perception standpoint. Thus, in preferred embodiments, the polymer of the present invention is preferably formed using polyhydric phenol compounds that do not exhibit appreciable estrogenic activity in the MCF-7 test.

[077] While not intending to be bound by any theory, as previously discussed, it is believed that the presence of substituent groups (i.e., a group other than a hydrogen atom) at one or more of the ortho and/or meta positions of each phenylene ring of the

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Formula (III) compound, relative to the phenol hydroxyl group of each ring, can reduce or effectively eliminate any estrogenic activity. It is believed that the inhibition/elimination of estrogenic activity may be attributable to one or both of the following: (a) steric hindrance of the phenol hydroxyl group and/or (b) the compound having a higher molecular weight due to the presence of the one or more substituent groups. Substitution at one or both of the ortho positions of each phenylene ring is presently preferred as it is believed that ortho substitution can provide the greatest steric hindrance for the hydroxyl group.

[078] Preferred compounds of Formula (III) include the below listed diphenol compounds (with the chemical name indicated below each structure).

<img file="AU2020201397B2_D0006.tif" />

4,4’-Methylenebis(2,6-di-t-butylphenol);

<img file="AU2020201397B2_D0007.tif" />

<img file="AU2020201397B2_D0008.tif" />

4,4’Butylidenebis(2-t-butyl-5-methylphenol)

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<img file="AU2020201397B2_D0009.tif" />

2,2’-Methylenebis(6-t-butyl-4-methylphenol)

<img file="AU2020201397B2_D0010.tif" />

4,4’-isopropylidenebis(2,6-dimethylphenol)

<img file="AU2020201397B2_D0011.tif" />

4,4’-methylenebis(2,6-dimethylphenol)

<img file="AU2020201397B2_D0012.tif" />

2,2’-methylenebis(4-methyl-6-t-butylphenol)

[079] The below compounds of Formula (III) may also be used in certain embodiments if desired.

2020201397 26 Feb 2020

<img file="AU2020201397B2_D0013.tif" />

4,4’-(ethane-l,2-diyl)bis(2,6-dimethylphenol)

<img file="AU2020201397B2_D0014.tif" />

4,4’-Isobutylidenebis(2-t-butyl-5-methylphenol)

<img file="AU2020201397B2_D0015.tif" />

4,4’-isopropylidenebis(2-methylphenol)

<img file="AU2020201397B2_D0016.tif" />

4,4’-isopropylidcnebis(2-isopiOpylphenol)

<img file="AU2020201397B2_D0017.tif" />

4,4’-isopropylidenebis(2-phenylphenol)

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<img file="AU2020201397B2_D0018.tif" />

2,5-di-t-butylhydroquinone

<img file="AU2020201397B2_D0019.tif" />

4,4^?-cyclohexylidenebis(2-methylphenol)

<img file="AU2020201397B2_D0020.tif" />

4,4’-cyclohexylidenebis(2,b-dimethylphenol)

[080] In certain embodiments, bis(4-hydroxy-3-methylphenyl) methane may be used if desired, which is shown below.

<img file="AU2020201397B2_D0021.tif" />

[081] The diphenol compounds of Formula (III) can be converted to a diepoxide using any suitable process and materials. The use of epichlorohydrin in the epoxidation process is presently preferred. By way of example, below is a diepoxide formed via an epichlorohydrin epoxidation of 4,4’-methylenebis(2,6-di-t-butylphenol).

2020201397 26 Feb 2020

<img file="AU2020201397B2_D0022.tif" />

[082] Numerous diepoxides have been successfully generated using various diphenol compounds of Formula (111), and polycthcr polymers have been successfully produced therefrom. In general, it is much more difficult to successfully form a polyether polymer 5 (using reasonable process times and conditions) using, as a diphenol component, a compound of Formula (III) substituted at the ortho ring positions. For example, the inventors have found it difficult using conventional industrial processes to efficiently react 4,4’-methylenebis(2,6-di-t-butylphenol) with diepoxide monomer to form a polyethcr polymer. (Somewhat surprisingly, however, diphcnol compounds such as 10 4,4’-methylenebis(2,6-di-t-butylphenol) can undergo a condensation reaction with epichlorohydrin to form a diepoxide that is reactive with conventional dihydric phenols that are not substituted at the ortho or meta positions.) While not wishing to be bound by theory, it is believed that the hydroxyl groups of such diphenol compounds are generally not sufficiently accessible to efficiently react with an oxirane group of a diepoxide monomer and form an ether linkage. Nonetheless, it is contemplated that a “hindered” diphcnol compound of Formula (III) may be selected such that the hydroxyl groups arc sufficiently sterically hindered so that the compound does not exhibit appreciable estrogenic activity, while the hydroxyl groups are still sufficiently accessible so that the compound can react with a diepoxide and build molecular weight under reasonable process times and conditions (e.g., less than 24 hours of reaction time at a reaction temperature of less than about 240°C).

[083] In certain preferred embodiments, the diphenol compound of Formula (III) is substituted at one or both ortho ring positions of each depicted phenylene group with an R¹ group that includes from 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms, and even more preferably 1 to 2 carbon atoms. In some embodiments, substituted or unsubstituted methyl groups are preferred ortho R¹ groups, with the methyl moiety (i.e., -CH3) being particularly preferred. While not intending to be bound by any theory, it has been observed that the presence of large ortho substituent groups can sometimes

2020201397 26 Feb 2020 affect the efficiency by which certain diphenol compounds of Formula (III) are converted into diepoxides using epichlorohydrin and, moreover, the efficiency by which the resulting diepoxide can be upgraded into a polyether polymer having segments of Formula (I).

[084] Any suitable polyhydric phenol may be used to upgrade the molecular weight of polyepoxidcs of Formula (II) to form polyethcr polymers. However, the use of bisphenol A is not preferred. Preferred polyhydric phenols are dihydric phenols that are free of bisphenol A and preferably do not exhibit appreciable estrogenic activity. In certain preferred embodiments, a polyhydric phenol is used that has a molecular weight greater than that of bisphenol A (i.e., greater than about 228 grams/mole).

[085] Examples of suitable dihydric phenols for use in forming the polyether polymer include compounds of the below Formula (IV):

HO-Ar- (Y_u-Ar)_t-OH, wherein:

· each Ar is independently an aryl group or heteroaryl group, more preferably a phenylene group (and typically an unsubstituted phenylene group, i.e., -C6H4-);

• Y, if present, is a divalent group;

• u is independently 0 or 1; and • t is independently 0 or 1.

[086] In some embodiments, Y includes one or more cyclic groups (e.g., alicyclic and/or aromatic groups), which may be monocyclic or polycyclic groups (e.g., a divalent: norbomanc, norbomenc, tricyclodecanc, bicyclo[4.4.0] decane, or isosorbidc group, or a combination thereof).

[087] In some embodiments, Y includes one or more ester linkages. For example, in some embodiments, Y is a -R⁶W-Z-R⁵-Z-R⁶W- segment, where: R⁵ is a divalent organic group; each R⁶, if present, is independently a divalent organic group; each Z is independently an ester linkage that can be of either directionality (i.e., -C(O)-O- or -OC(O)-; and each w is independently 0 or 1. In one such embodiment, R⁵ includes at least one divalent cyclic group such as, for example, a divalent polycyclic group, a divalent aryl or heteroarylene group (e.g., a substituted or unsubstituted phenylene group) or a divalent alicyclic group (e.g., a substituted or unsubstituted cyclohexane or cyclohexene group) such as, for example, any of those described herein. In one embodiment, Y is 26

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R⁶W-C(O)-O-R⁵-O-C(O)-R⁶W-. A further discussion of suitable segments containing ester linkages and materials for incorporating such segments into the polymer of the invention is provided in U.S. Published Application No. 2007/0087146 by Evans et. al. and Published International Application No. WO 2011/130671 by Niederst et al.

[088] If present, Y typically has a molecular weight of less than about 500, and more typically less than about 300.

[089] Examples of suitable dihydric phenols include hydroquinone, catechol, p-tertbutyl catechol, resorcinol, l,l-bis(4-hydroyphenyl)-3,3,5-trimethyl-cyclohexane, l,l-di(4-hydroxyphenyl)-cyclohexane, dihydroxynaphthalene, biphenol, or a mixture 10 thereof.

[090] By way of example, a cyclic-group-containing compound of Formula (IV) may be formed by reacting (a) a suitable amount (e.g., about 2 moles) of a Compound A having a phenol hydroxyl group and a carboxylic acid or other active hydrogen group with (b) a suitable amount (e.g., about 1 mole) of a di-functional or higher Compound B having one or more cyclic groups (monocyclic and/or polycyclic) and two or more active hydrogen groups capable of reacting with the active hydrogen group of Compound A. Examples of preferred Compounds A include 4-hydroxy phenyl acetic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, and derivatives or mixtures thereof.

Examples of preferred Compounds B include cyclic-containing diols such as cyclohexane dimethanol (CHDM); tricyclodecane dimethanol (TCDM); nadic acid and/or anhydride; a polycyclic anyhydrosugar such as isosorbide, isomannide, or isoidide; and derivatives or mixtures thereof. In some embodiments, the cyclic group may be formed after reaction of Compounds A and B. For example, a Diels-Alder reaction (using, e.g., cyclopentadiene as a reactant) could be used to incorporate an unsaturated bicyclic group such as a norbornene group into Compound B, in which case Compound B in its unreacted form would need to include at least one non-aromatic carbon-carbon double bond in order to participate in the Diels-Alder reaction. For further discussion of suitable materials and techniques relating to such Diels-Alder reactions see, for example, Published International App. Nos. WO 2010/118356 by

Skillman et al. and WO 2010/118349 by Hayes et al.

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[091] An additional example of a suitable Compound B is provided below:

<img file="AU2020201397B2_D0023.tif" />

[092] Some examples of cyclic-group-containing dihydric phenol compounds are provided below. These compounds are discussed in further detail in the previously referenced Published International Application No. WO 2011/130671 by Niederst et al.

<img file="AU2020201397B2_D0024.tif" />

<img file="AU2020201397B2_D0025.tif" />

[093] If desired, one or more comonomers and/or co-oligomers may be included in the reactants used to generate the polymer of the present invention. Non-limiting examples of such materials include adipic acid, azelaic acid, terephthalic acid, isophthalic acid, and 10 combinations thereof. The comonomers and/or cooligomers may be included in an initial reaction mixture of polyepoxide and polyhydric phenol and/or may be post-reacted with the resulting polyether oligomer or polymer. In presently preferred embodiments, a comonomer and/or co-oligomer is not utilized to produce a polyether polymer of the present invention.

[094] Preferred polymers of the present invention may be made in a variety of molecular weights. Preferred polyether polymers of the present invention have a number average molecular weight (Mn) of at least 2,000, more preferably at least 3,000, and even more preferably at least 4,000. The molecular weight of the polyether polymer may be as high as is needed for the desired application. Typically, however, the Mn of the polyether polymer, when adapted for use in a liquid coating composition, will not exceed

2020201397 26 Feb 2020 about 10,000. In embodiments where the polymer of the present invention is a copolymer, such as for example a polyether-acrylic copolymer, while the molecular weight of the polyether polymer is typically within the ranges recited above, the molecular weight of the overall polymer may be higher than that recited above.

Typically, however, such copolymers will have an Mn of less than about 20,000.

1095] Advancement of the molecular weight of the polymer may be enhanced by the use of a catalyst in the reaction of a diepoxide with one or more upgrade comonomers such as, e.g., a polyhydric phenol of Formula (IV). Typical catalysts usable in the advancement of the molecular weight of the epoxy material of the present invention include amines, hydroxides (e.g., potassium hydroxide), phosphonium salts, and the like. A presently preferred catalyst is a phosphonium catalyst. The phosphonium catalyst useful in the present invention is preferably present in an amount sufficient to facilitate the desired condensation reaction.

[096] Alternatively, epoxy-terminated polymers of the present invention may be reacted with fatty acids to form polymers having unsaturated (e.g., air oxidizable) reactive groups, or with acrylic acid or methacrylic acid to form free-radically curable polymers.

[097] Advancement of the molecular weight of the polymer may also be enhanced by the reaction of a hydroxyl- or epoxy-terminated polymer of the present invention with a 20 suitable diacid (such as adipic acid).

[098] As discussed above, in certain preferred embodiments, the coating composition of the present invention is suitable for use in forming a food-contact packaging coating. In order to exhibit a suitable balance of coating properties for use as a food-contact packaging coating, including suitable corrosion resistance when in prolonged contact 25 with packaged food or beverage products which may be of a corrosive nature, the polymer of the present invention preferably has a glass transition temperature (“Tg”) of at least 60°C, more preferably at least 70°C, and even more preferably at least 80°C. In preferred embodiments, the Tg is less than 150°C, more preferably less than 130°C, and even more preferably less than 110°C. Tg can be measured via differential scanning calorimetry (“DSC”) using the methodology disclosed in the Test Methods section. In preferred embodiments, the polymer is a poly ether polymer exhibiting a Tg pursuant to the aforementioned Tg values.

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[099] While not intending to be bound by any theory, it is believed that it is important that the polymer exhibit a Tg such as that described above in applications where the coating composition will be in contact with food or beverage products during retort processing at high temperature (e.g., at temperatures at or above about 100°C and sometimes accompanied by pressures in excess of atmospheric pressure), and particularly when retort processing food or beverage products that are more chemically aggressive in nature. It is contemplated that, in some embodiments, such as, for example, where the coating composition is intended for use as an exterior varnish on a food or beverage container, the Tg of the polymer may be less than that described above 10 (e.g., as low as about 30°C) and the coating composition may still exhibit a suitable balance of properties in the end use.

[0100] While not intending to be bound by any theory, it is believed that the inclusion of a sufficient number of aryl and/or heteroaryl groups (typically phenylene groups) in the binder polymer of the present invention is an important factor for achieving suitable coating performance for food-contact packaging coatings, especially when the product to be packaged is a so called “hard-to-hold” food or beverage product. Sauerkraut is an example of a hard-to-hold product. In preferred embodiments, aryl and/or heteroaryl groups constitute at least 20 wt-%, more preferably at least 30 wt-%, and even more preferably at least 45 wt-% of the polyether polymer, based on the total weight of aryl and heteroaryl groups in the polymer relative to the weight of the polyether polymer. The upper concentration of aryl/heteroaryl groups is not particularly limited, but preferably the amount of such groups is configured such that the Tg of the polyether polymer does not exceed the Tg ranges previously discussed. The total amount of aryl and/or heteroaryl groups in the polyether polymer will typically constitute less than about 80 wt-%, more preferably less than about 70 wt-%, and even more preferably less than 60 wt-% of the polyether polymer. The total amount of aryl and/or heteroaryl groups in the polyether polymer can be determined based on the weight of aryl- or heteroaryl-containing monomer incorporated into the polyether polymer and the weight fraction of such monomer that constitutes aryl or heteroaiyl groups. In embodiments where the polymer is a polyether copolymer (e.g., a polyether-acrylic copolymer), the weight fraction of aryl or hcteroaryl groups in the polyether polymer portion(s) of the copolymer will generally be as described above, although the weight fraction relative to the total weight of the copolymer may be less.

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[0101] Preferred aryl or heteroaryl groups include less than 20 carbon atoms, more preferably less than 11 carbon atoms, and even more preferably less than 8 carbon atoms. The aryl or heteroaryl groups preferably have at least 4 carbon atoms, more preferably at least 5 carbon atoms, and even more preferably at least 6 carbon atoms. Substituted or unsubstituted phenylene groups are preferred aryl or heteroaryl groups. Thus, in preferred embodiments, the polyethcr fraction of the polymer includes an amount of phenylene groups pursuant to the amounts recited above.

[0102] The polymers of the present invention can be applied to a substrate as part of a coating composition that includes a liquid carrier. The liquid carrier may be water, organic solvent, or mixtures of various such liquid carriers. Accordingly, liquid coating compositions of the present invention may be either water-based or solvent-based systems. Examples of suitable organic solvents include glycol ethers, alcohols, aromatic or aliphatic hydrocarbons, dibasic esters, ketones, esters, and the like, and combinations thereof. Preferably, such carriers are selected to provide a dispersion or solution of the polymer for further formulation.

[0103] It is anticipated that a polyether polymer of the present invention may be substituted for any conventional epoxy polymer present in a packaging coating composition known in the art. Thus, for example, the polyether polymer of the present invention may be substituted, for example, for a BPA/BADGE-containing polymer of an epoxy/acrylic latex coating system, for a BPA/BADGE containing polymer of a solvent based epoxy coating system, etc.

[0104] The amount of binder polymer of the present invention included in coating compositions may vary widely depending on a variety of considerations such as, for example, the method of application, the presence of other film-forming materials, whether the coating composition is a water-based or solvent-based system, etc. For liquid-based coating compositions, however, the binder polymer of the present invention will typically constitute at least 10 wt-%, more typically at least 30 wt-%, and even more typically at least 50 wt-% of the coating composition, based on the total weight of resin solids in the coating composition. For such liquid-based coating compositions, the binder polymer will typically constitute less than about 90 wt-%, more typically less than about 80 wt-%. and even more typically less than about 70 wt-% of the coating composition, based on the total weight of resin solids in the coating composition.

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[0105] In one embodiment, the coating composition is an organic solvent-based composition preferably having at least 20 wt-% non-volatile components (i.e., “solids”), and more preferably at least 30 wt-% non-volatile components. In one embodiment, the coating composition is an organic solvent-based composition preferably having no greater than 40 wt-% non-volatile components (i.e., “solids”), and more preferably no greater than 30 wt-% non-volatile components. For this embodiment, the non-volatile film-forming components preferably include at least 50 wt-% of the polymer of the invention, more preferably at least 55 wt-% of the polymer, and even more preferably at least 60 wt-% of the polymer. For this embodiment, the non-volatile film-forming components preferably include no greater than 95 wt-% of the polymer of the invention, and more preferably no greater than 85 wt-% of the polymer.

[0106] In one embodiment, the coating composition of the present invention is a solventbased system that includes no more than a de minimus amount of water (e.g., less than 2 wt-% of water), if any.

[0107] In one embodiment, the coating composition is a water-based composition preferably having at least 15 wt-% non-volatile components (i.e., “solids”). In one embodiment, the coating composition is a water-based composition preferably having no greater than 50 wt-% non-volatile components (i.e., “solids”), and more preferably no greater than 40 wt-% non-volatile components. For this embodiment, the non-volatile film-forming components preferably include at least 5 wt-% of the polymer of the present invention, more preferably at least 25 wt-% of the polymer, even more preferably at least 30 wt-% of the polymer, and optimally at least 40 wt-% of the polymer. For this embodiment, the non-volatile film forming components preferably include no greater than 70 wt-% of the polymer of the present invention, and more preferably no greater than 60 wt-% of the polymer.

[0108] If a water-based system is desired, techniques may be used such as those described in U.S. Pat. Nos. 3,943,187; 4,076,676; 4,247,439; 4,285,847; 4,413,015; 4,446,258; 4,963,602; 5,296,525; 5,527,840; 5,830,952; 5,922,817; and U.S. Published Pat. Application No. 2004/0259989. Water-based coating systems of the present invention may optionally include one or more organic solvents, which will typically be selected to be miscible in water. The liquid carrier system of water-based coating compositions will typically include at least 50 wt-% of water, more typically at least 75 wt-% of water, and in some embodiments more than 90 wt-% or 95 wt-% of water.

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Any suitable means may be used to render the polymer of the invention miscible in water. For example, the polymer may include a suitable amount of salt groups such as ionic or cationic salt groups to render the polymer miscible in water (or groups capable of forming such salt groups). Neutralized acid or base groups are preferred salt groups.

[0109] tn one embodiment, a water-dispersible polymer may be formed from preformed polymers (e.g.,(a) an oxirane-functional polymer, such as, e.g., a polycthcr polymer, preferably having at least one segment of Formula (I) and (b) an acid-functional polymer such as, e.g., an acid-functional acrylic polymer) in the presence of a tertiary amine. [0110] In another embodiment, a water-dispersible polymer may be formed from an oxirane-functional polymer (more preferably a polyether polymer) preferably having at least one segment of Formula (I) that is reacted with ethylenically unsaturated monomers to form an acid-functional polymer, which may then be neutralized, for example, with a tertiary amine. Thus, for example, in one embodiment, a water-dispersible polymer preferably having at least one segment of Formula (I) may be formed pursuant to the acrylic polymerization teachings of U.S. Pat. Nos. 4,285,847 and/or 4,212,781, which describe techniques for grafting acid-functional acrylic groups (e.g., via use of benzoyl peroxide) onto epoxy polymers. In another embodiment, acrylic polymerization may be achieved through reaction of ethylenically unsaturated monomers with unsaturation present in the polymer preferably containing at least one segment of Formula (I). See, for example, U.S. Pat. No. 4,517,322 and/or U.S. Published Pat. Application No. 2005/0196629 for examples of such techniques.

[0111] In another embodiment, a water-dispersible polymer may be formed having the structure E-L-A, wherein E is an epoxy portion of the polymer formed from a polyether polymer described herein, A is a polymerized acrylic portion of the polymer, and L is a linking portion of the which covalently links E to A. Such a polymer can be prepared, for example, from (a) a polyether polymer described herein preferably having about two epoxy groups, (b) an unsaturated linking compound preferably having (i) either conjugated carbon-carbon double bonds or a carbon-carbon triple bond and (ii) a functional group capable of reacting with an epoxy group (e.g., a carboxylic group, a hydroxyl group, an amino group, an amido group, a mercapto group, etc.). Preferred linking compounds include 12 or less carbon atoms, with sorbic acid being an example of a preferred such linking compound. The acrylic portion preferably includes one or more salt groups or salt-forming groups (e.g., acid groups such as present in α,β-

2020201397 26 Feb 2020 ethylenically saturated carboxylic acid monomers). Such polymers may be formed, for example, using a BPA- and BADGE-free polyether polymer of the present invention in combination with the materials and techniques disclosed in U.S. Pat. No. 5,830,952. [0112] In some embodiments, the coating composition of the present invention is substantially free of acrylic (e.g., includes less than about 1 wt-% of polymerized acrylic monomers).

[0113] If desired, an acid-functional polymer can be combined with a tertiary amine to at least partially neutralize it prior to reaction with an oxirane-functional polymer preferably having at least one segment of Formula (I).

[0114] In another embodiment, a polymer preferably containing segments of Formula (I) and including -CH2-CH(OH)-CH2- segments, which are derived from an oxirane, is reacted with an anhydride. This provides acid functionality which, when combined with an amine or other suitable base to at least partially neutralize the acid functionality, is water dispersible.

[0115] A coating composition of the present invention may also include other optional ingredients that do not adversely affect the coating composition or a cured coating composition resulting therefrom. Such optional ingredients are typically included in a coating composition to enhance composition esthetics; to facilitate manufacturing, processing, handling, and application of the composition; and to further improve a particular functional property of a coating composition or a cured coating composition resulting therefrom. For example, the composition that includes a polymer of the present invention may optionally include crosslinkers, fillers, catalysts, lubricants, pigments, surfactants, dyes, colorants, toners, coalescents, extenders, anticorrosion agents, flow control agents, thixotropic agents, dispersing agents, antioxidants, oxygen-scavenging materials, adhesion promoters, light stabilizers, and mixtures thereof, as required to provide the desired film properties. Each optional ingredient is preferably included in a sufficient amount to serve its intended purpose, but not in such an amount to adversely affect a coating composition or a cured coating composition resulting therefrom.

[0116] Preferred compositions are substantially free of mobile BPA and BADGE, and more preferably essentially free of these compounds, and most preferably completely free of these compounds. The coating composition is also preferably substantially free of bound BPA and BADGE, more preferably essentially free of these compounds, and optimally completely free of these compounds. In addition, preferred compositions are

2020201397 26 Feb 2020 also substantially free, more preferably essentially free, and most preferably completely free of: bisphenol S, bisphenol F, and the diglycidyl ether of bisphenol F or bisphenol S. [0117] It has been discovered that coating compositions using the aforementioned polymer-containing compositions may be formulated using one or more optional curing agents (i.e., crosslinking resins, sometimes referred to as “crosslinkers”). The choice of particular crosslinker typically depends on the particular product being formulated. For example, some coating compositions are highly colored (e.g., gold-colored coatings). These coatings may typically be formulated using crosslinkers that themselves tend to have a yellowish color. In contrast, white coatings are generally formulated using non10 yellowing crosslinkers, or only a small amount of a yellowing crosslinker.

[0118] Preferred curing agents are substantially free of mobile BPA and BADGE and more preferably completely free of bound BPA and BADGE. Suitable examples of such curing agents are hydroxyl-reactive curing resins such as phenoplasts, aminoplast, blocked or unblocked isocyanates, or mixtures thereof.

[0119] Suitable phenoplast resins include the condensation products of aldehydes with phenols. Formaldehyde and acetaldehyde are preferred aldehydes. Various phenols can be employed such as phenol, cresol, p-phenylphenol, p-tert-butylphenol, p-tertamylphenol, cyclopentylphenol, and compounds of Formula (III).

[0120] Suitable aminoplast resins are the condensation products of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, and benzaldehyde with amino- or amidogroup-containing substances such as urea, melamine, and benzoguanamine. Examples of suitable aminoplast crosslinking resins include, without limitation, benzoguanamineformaldehyde resins, melamine-formaldehyde resins, etherified melamine-formaldehyde, and urea-formaldehyde resins.

[0121] Examples of other generally suitable curing agents are the blocked or nonblocked aliphatic, cycloaliphatic or aromatic di-, tri-, or poly-valent isocyanates, such as hexamethylene diisocyanate, cyclohexyl-1,4-diisocyanate, and the like. Further nonlimiting examples of generally suitable blocked isocyanates include isomers of isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, tetramethyl xylene diisocyanate, xylylenc diisocyanate, and mixtures thereof. In some embodiments, blocked isocyanates are used that have an Mn of at least about 300, more preferably at least about 650, and even more preferably at least about 1,000.

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[0122] Polymeric blocked isocyanates are useful in certain embodiments. Some examples of suitable polymeric blocked isocyanates include a biuret or isocyanurate of a diisocyanate, a trifunctional “trimer,” or a mixture thereof. Examples of suitable blocked polymeric isocyanates include TRIXENE BI 7951, TRIXENE BI 7984, TRIXENE BI

7963, TRIXENE BI 7981 (TRIXENE materials are available from Baxenden Chemicals,

Ltd., Accrington, Lancashire, England), DESMODUR BL 3175A, DESMODUR BL3272, DESMODUR BL3370, DESMODUR BL 3475, DESMODUR BL 4265, DESMODUR PL 340, DESMODUR VP LS 2078, DESMODUR VP LS 2117, and DESMODUR VP LS 2352 (DESMODUR materials are available from Bayer Corp.,

Pittsburgh, PA, USA), or combinations thereof Examples of suitable trimers may include a trimerization product prepared from on average three diisocyanate molecules or a trimer prepared from on average three moles of diisocyanate (e.g., HMDI) reacted with one mole of another compound such as, for example, a triol (e.g., trimethylolpropane). [0123] The level of curing agent (i.e., crosslinker) used will typically depend on the type of curing agent, the time and temperature of the bake, the molecular weight of the binder polymer, and the desired coating properties. If used, the crosslinker is typically present in an amount of up to 50 wt-%, preferably up to 30 wt-%, and more preferably up to 15 wt-%. If used, a crosslinker is preferably present in an amount of at least 0.1 wt-%, more preferably at least 1 wt-%, and even more preferably at least 1.5 wt-%. These weight percentages are based upon the total weight of the resin solids in the coating composition.

[0124] A coating composition of the present invention may also include other optional polymers that do not adversely affect the coating composition or a cured coating composition resulting therefrom. Such optional polymers are typically included in a 25 coating composition as a filler material, although they can also be included, for example, as a binder polymer, a crosslinking material, or to provide desirable properties. One or more optional polymers (e.g., filler polymers) can be included in a sufficient amount to serve an intended purpose, but not in such an amount to adversely affect a coating composition or a cured coating composition resulting therefrom.

[0125] Such additional polymeric materials can be nonreactive, and hence, simply function as fillers. Such optional nonreactive filler polymers include, for example, polyesters, acrylics, polyamides, polyethers, and novalacs. Alternatively, such additional polymeric materials or monomers can be reactive with other components of the

2020201397 26 Feb 2020 composition (e.g., an acid-functional or unsaturated polymer). If desired, reactive polymers can be incorporated into the compositions of the present invention, to provide additional functionality for various purposes, including crosslinking or dispersing the polymer of the present invention into water. Examples of such reactive polymers include, for example, functionalized polyesters, acrylics, polyamides, and polyethers. Preferred optional polymers are substantially free or essentially free of mobile BPA and BADGE, and more preferably completely free of mobile and bound such compounds. [0126] One preferred optional ingredient is a catalyst to increase the rate of cure. Examples of catalysts, include, but are not limited to, strong acids (e.g., phosphoric acid, 10 dodecylbenzene sulphonic acid (DDBSA), available as CYCAT 600 from Cytec), methane sulfonic acid (MSA), p-tohiene sulfonic acid (pTSA), dinonylnaphthalene disulfonic acid (DNNDSA), and triflic acid); quaternary ammonium compounds; phosphorous compounds; and tin, titanium, and zinc compounds. Specific examples include, but are not limited to, a tetraalkyl ammonium halide, a tetraalkyl or tetraaryl phosphonium iodide or acetate, tin octoate, zinc octoate, triphenylphosphine, and similar catalysts known to persons skilled in the art. If used, a catalyst is preferably present in an amount of at least 0.01 wt-%, and more preferably at least 0.1 wt-%, based on the weight of nonvolatile material in the coating composition. If used, a catalyst is preferably present in an amount of no greater than 3 wt-%, and more preferably no greater than 1 wt-%, based on the weight of nonvolatile material in the coating composition.

[0127] Another useful optional ingredient is a lubricant (e.g., a wax), which facilitates manufacture of fabricated metal articles (e.g., closures and food or beverage can ends) by imparting lubricity to sheets of coated metal substrate. Non-limiting examples of suitable lubricants include, for example, natural waxes such as Carnauba wax or lanolin wax, polytetrafluoroethane (PTFE) and polyethylene-type lubricants. If used, a lubricant is preferably present in the coating composition in an amount of at least 0.1 wt-%, and preferably no greater than 2 wt-%, and more preferably no greater than 1 wt-%, based on the total weight of nonvolatile material in the coating composition.

[0128] Another useful optional ingredient is a pigment, such as titanium dioxide. If used, a pigment is present in the coating composition in an amount of no greater than 70 wt-%, more preferably no greater than 50 wt-%, and even more preferably no greater than 40 wt-%, based on the total weight of solids in the coating composition.

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[0129] Surfactants can be optionally added to the coating composition to aid in flow and wetting of the substrate. Examples of surfactants, include, but are not limited to, nonylphenol polyethers and salts and similar surfactants known to persons skilled in the art. If used, a surfactant is preferably present in an amount of at least 0.01 wt-%, and more preferably at least 0.1 wt-%, based on the weight of resin solids. If used, a surfactant is preferably present in an amount no greater than 10 wt-%, and more preferably no greater than 5 wt-%, based on the weight of resin solids.

[0130] The coating composition of the present invention can be present as a layer of a mono-layer coating system or one or more layers of a multi-layer coating system. The coating composition can be used as a primer coat, an intermediate coat, a top coat, or a combination thereof The coating thickness of a particular layer and the overall coating system will vary depending upon the coating material used, the substrate, the coating application method, and the end use for the coated article. Mono-layer or multi-layer coil coating systems including one or more layers formed from a coating composition of the present invention may have any suitable overall coating thickness, but will typically have an overall average dry coating thickness of from about 2 to about 60 microns and more typically from about 3 to about 12 microns.

[0131] The coating composition of the present invention may be applied to a substrate either prior to, or after, the substrate is formed into an article (such as, for example, a food or beverage container or a portion thereof). In one embodiment, a method is provided that includes: applying a coating composition described herein to a metal substrate (e.g., applying the composition to the metal substrate in the form of a planar coil or sheet), hardening the composition, and forming (e.g., via stamping) the substrate into a packaging container or a portion thereof (e.g., a food or beverage can or a portion thereof). For example, riveted beverage can ends having a cured coating of the present invention on a surface thereof can be formed in such a process. In another embodiment, the coating composition is applied to a preformed metal food or beverage can, or a portion thereof. For example, in some embodiments, the coating composition is spray applied to an interior surface of a preformed food or beverage can (e.g., as typically occurs with “two-piece” beverage cans.).

[0132] After applying the coating composition onto a substrate, the composition can be cured using a variety of processes, including, for example, oven baking by either conventional or convectional methods, or any other method that provides an elevated

2020201397 26 Feb 2020 temperature suitable for curing the coating. The curing process may be performed in either discrete or combined steps. For example, substrates can be dried at ambient temperature to leave the coating compositions in a largely un-crosslinked state. The coated substrates can then be heated to fully cure the compositions. In certain instances, 5 coating compositions of the present invention can be dried and cured in one step.

[0133] The cure conditions will vary depending upon the method of application and the intended end use. The curing process may be performed at any suitable temperature, including, for example, oven temperatures in the range of from about 100°C to about 300°C, and more typically from about 177°C to about 250°C. If metal coil is the substrate to be coated, curing of the applied coating composition may be conducted, for example, by heating the coated metal substrate over a suitable time period to a peak metal temperature (“PMT”) of preferably greater than about 350°F (177°C). More preferably, the coated metal coil is heated for a suitable time period (e.g., about 5 to 900 seconds) to a PMT of at least about 425°F (218°C).

[0134] The coating compositions of the present invention are particularly useful for coating metal substrates. The coating compositions may be used to coat packaging articles such as a food or beverage container, or a portion thereof In preferred embodiments, the container is a food or beverage can and the surface of the container is the surface of a metal substrate. The polymer can be applied to a metal substrate either before or after the substrate is formed into a can (e.g., two-piece cans, three-piece cans) or portions thereof, whether it be a can end or can body. Preferred polymers of the present invention are suitable for use in food-contact situations and may be used on the inside of such cans. They are particularly useful on the interior of two-piece or threepiece can ends or bodies.

[0135] The coating compositions of the present invention may be suitable, for example, for spray coating, coil coating, wash coating, sheet coating, and side seam coating (e.g., food can side seam coating). A further discussion of such application methods is provided below. It is contemplated that coating compositions of the present invention may be suitably used in each of these application methods discussed further below, 30 including the end uses associated therewith.

[0136] Spray coating includes the introduction of the coated composition into the inside of a preformed packaging container. Typical preformed packaging containers suitable for spray coating include food cans, beer and beverage containers, and the like. The

2020201397 26 Feb 2020 spray process preferably utilizes a spray nozzle capable of uniformly coating the inside of the preformed packaging container. The sprayed preformed container is then subjected to heat to remove any residual carriers (e.g., water or solvents) and harden the coating.

[0137] A coil coating is described as the coating of a continuous coil composed of a metal (e.g., steel or aluminum). Once coated, the coating coil is subjected to a short thermal, ultraviolet, and/or electromagnetic curing cycle, for hardening (e.g., drying and curing) of the coating. Coil coatings provide coated metal (e.g., steel and/or aluminum) substrates that can be fabricated into formed articles, such as two-piece drawn food cans, 10 three-piece food cans, food can ends, drawn and ironed cans, beverage can ends, and the like.

[0138] A wash coating is commercially described as the coating of the exterior of twopiece drawn and ironed (“D&amp;I”) cans with a thin layer of protectant coating. The exterior of these D&amp;I cans are ‘‘wash-coated” by passing pre-formed two-piece D&amp;I cans 15 under a curtain of a coating composition. The cans are inverted, that is, the open end of the can is in the “down” position when passing through the curtain. This curtain of coating composition takes on a “waterfall-like” appearance. Once these cans pass under this curtain of coating composition, the liquid coating material effectively coats the exterior of each can. Excess coating is removed through the use of an “air knife.” Once 20 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. The residence time of the coated can within the confines of the curing oven is typically from 1 minute to 5 minutes. The curing temperature within this oven will typically range from 150°C to 220°C.

[0139] A sheet coating is described as the coating of separate pieces of a variety of materials (e.g., steel or aluminum) that have been pre-cut into square or rectangular “sheets.” Typical dimensions of these sheets are approximately one square meter. Once coated, each sheet is cured. Once hardened (e.g., dried and cured), the sheets of the coated substrate are collected and prepared for subsequent fabrication. Sheet coatings provide coated metal (e.g., steel or aluminum) substrate that can be successfully fabricated into formed articles, such as two-piece drawn food cans, thrce-piecc food cans, food can ends, drawn and ironed cans, beverage can ends (including, e.g., riveted beverage can ends having a rivet for attaching a pull tab thereto), and the like.

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[0140] A side seam coating is described as the application of a powder coating or the spray application of a liquid coating over the welded area of formed three-piece food cans. When three-piece food cans are being prepared, a rectangular piece of coated substrate is formed into a cylinder. The formation of the cylinder is rendered permanent due to the welding of each side of the rectangle via thermal welding. Once welded, each can typically requires a layer of coating, which protects the exposed “weld” from subsequent corrosion or other effects to the contained foodstuff. The coatings that function in this role are termed “side seam stripes.” Typical side seam stripes are spray applied and cured quickly via residual heat from the welding operation in addition to a 10 small thermal, ultraviolet, and/or electromagnetic oven.

[0141] Other commercial coating application and curing methods are also envisioned, for example, electrocoating, extrusion coating, laminating, powder coating, and the like.

[0142] In certain preferred embodiments, the coating composition of the present invention is capable of exhibiting one or more (and in some embodiments all) of the following coating properties: a blush resistance, corrosion resistance, stain resistance, and/or adhesion to metal substrate of at least 8, more preferably at least 9, and optimally 10 (10 being perfect), when subjected to the testing described below in Example 5 using 3 wt-% acetic acid in deionized water in place of the “Aggressive Food Product.”

[0143] The polymer of the present invention can be used in powder coating applications for use in forming an adherent polymeric coating. Thus, in some embodiments, the coating composition of the present invention is a powder coating composition that preferably does not include a liquid carrier (although it may include trace amounts of residual water or organic solvent). The powder coating composition is preferably in the form of a finely divided, free flowing powder. In preferred embodiments, the powder composition is a thermosettable powder composition that forms a thermoset coating when suitably cured. The discussion that follows relates to powder coating embodiments of the present invention.

[0144] The powder coating composition of the present invention may be particularly useful in end uses in which a coated substrate is intended to contact substances for consumption by humans or intimate contact with humans. For example, the powder coating compositions may be used to coat: surfaces of food or beverage containers, cosmetic containers, or medicinal containers; surfaces of valves and fittings, including surfaces intended for contact with potable water or other consumable liquids; surfaces of

2020201397 26 Feb 2020 pipes, including internal surfaces of water pipes or other liquid conveying pipes; and surfaces of tanks, including internal surfaces of water tanks such as bolted steel tanks. For powder coatings that will contact potable water, the cured powder coating composition should preferably comply with ANSI/NSF standard 61. Some examples of 5 fittings include articles for use in liquid conveying systems (e.g., for use in conveying potable water) such as connectors (e.g., threaded or flanged connectors), elbows, flow splitters (e.g., T-fittings, etc.), backflow preventers, pipe end caps, and the like.

[0145] The powder coating composition preferably includes at least a film-forming amount of the polymer of the present invention, which in preferred embodiments is a polyether polymer having segments of Formula (I). In order to facilitate stability of the powder coating composition during storage prior to use, a polymer of the present invention is preferably selected that has a Tg of at least about 40°C, more preferably at least about 50°C, and even more preferably at least about 60°C. The powder coating composition preferably includes at least about 50 wt-%, more preferably at least

70 wt-%, and even more preferably at least 90 wt-% of the polymer of the present invention, based on total resin solids.

[0146] Powder coating compositions typically utilize binder polymers having a different molecular weight (typically a lower molecular weight) than those of liquid packaging coating compositions for use on metal food or beverage cans. When used in powder coating compositions, the polymer of the present invention preferably has a number average molecular weight (Mn) of at least about 1,000, more preferably at least about 1,200, and even more preferably at least about 1,500. In such applications, the polymer of the present invention preferably has an Mn of less than about 6,000, more preferably less than about 5,000, and even more preferably less than about 4,000.

[0147] The powder coating composition preferably includes at least one base powder that includes the polymer of the present invention. The base powder may further include one or more optional ingredients, which may include any suitable ingredients disclosed herein. The base powder preferably includes the polymer of the present invention as a major component on a weight basis, and more preferably includes at least 50 wt-% of the polymer. In some embodiments, the polymer of the present invention comprises all or substantially all of the base powder.

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[0148] The particles of the base powder may be of any suitable size. Preferably, the particles of the base powder exhibit a particle size diameter of from about 1 micron to about 200 microns, more preferably from about 10 to about 150 microns.

[0149] The base powder may exhibit any suitable distribution of particle sizes. The median particle size of the base powder is preferably at least about 20 microns, more preferably at least about 30 microns, and even more preferably at least about 40 microns. In preferred embodiments, the median particle size is less than about 150 microns, more preferably less than about 100 microns, and even more preferably less than about 60 microns. The median particle sizes referenced in this paragraph are median diameter particle sizes expressed on a volume basis, which may be determined, for example, via laser diffraction.

[0150] Powder compositions of the present invention may also contain one or more other optional ingredients. The optional ingredients preferably do not adversely affect the powder compositions or articles formed therefrom. Such optional ingredients may be 15 included, for example, to enhance aesthetics; to facilitate manufacturing, processing, and/or handling of powder compositions or articles formed therefrom; and/or to further improve a particular property of powder compositions or articles formed therefrom.

Each optional ingredient is preferably included in a sufficient amount to serve its intended purpose, but not in such an amount to adversely affect a powder composition or a cured coating resulting therefrom. The one or more optional ingredients may be present in a same or different particle than the polymer of the present invention, or a combination thereof. In preferred embodiments, one or more optional ingredients are present in the particles of the base powder along with the polymer of the present invention. If present in particles other than those of the base powder, the particles of the optional ingredient(s) preferably have a particle size in the general range of the particles sizes of the base powder.

[0151] The powder composition preferably includes one or more optional curing agents (i.e., cross linkers). Suitable curing agents may include phenolic crosslinkers, preferably BPA-free phenolic crosslinkers; dicyandiamide, which may be optionally substituted;

carboxyl-functional compounds such as, e.g., carboxyl-functional polyester resins or carboxyl-functional acrylic resins; and combinations thereof. The powder composition may include any suitable amount of the one or more crosslinkers. In some embodiments, crosslinker is present in the powder composition in an amount of up to about 15 wt-%,

2020201397 26 Feb 2020 preferably up to about 10 wt-%, and more preferably up to about 5 wt-%, based on the total weight of the powder coating composition. If used, crosslinker is preferably present in an amount of at least about 0.1 wt-%, more preferably at least about 0.5 wt-%, and even more preferably at least about 1 wt %, based on the total weight of the powder 5 coating composition.

[0152] An optional cure accelerator may be present in the powder coating composition to facilitate cure. When used, the powder coating composition typically includes from about 0.1 wt-% to about 3 wt-% of one or more cure accelerators. 2-methylimidazole is an example of a preferred cure accelerator. Other suitable cure accelerators may include 10 imidazoles, phosphonium salts, tertiary amines, quaternary ammonium salts, anhydrides, polyamides, aliphatic amines, epoxy resin-amine adducts, and combinations thereof.

[0153] The powder coating composition may optionally include one or more flow control agents to improve the flow, wetting, and/or leveling properties of the cured film. If used, flow control agents are typically present in an amount of about 0.01 wt-% to 15 about 5 wt-%, more typically from about 0.2 wt-% to about 2 wt-%, based on the total weight of the powder coating composition. Examples of suitable flow control agents include polyacrylates such as poly(2-ethylhexyl acrylate) and various co-polymers of 2-ethylhexyl acrylate.

[0154] The powder coating composition may optionally include one or more fluidizing 20 agents to facilitate the preparation of a free-flowing powder composition. If used, fluidizing agent is typically present in an amount of about 0.01 wt-% to about 5 wt-%, more typically from about 0.05 wt-% to about 0.5 wt-%, based on the total weight of the powder coating composition. Suitable fluidizing agents include, for example, fumed silicas of a suitable particle size. Such fluidizing agents may preferably be added after 25 the melt blending process, such as to the extruded flake before or after grinding.

[0155] Inorganic filler and/or colored pigment may optionally be included in the powder coating compositions. Examples of suitable such materials may include calcium silicates such as, e.g., wollastonite; barium sulfate; calcium carbonate; mica; talc; silica; iron oxide; titanium dioxide; carbon black; phthalocyanines; chromium oxide; and 30 combinations thereof.

[0156] The powder coating compositions can be prepared via any suitable methods. In one embodiment, some or all of the ingredients are melt-blended together, which may be accomplished, for example, using conventional single-screw or twin-screw extruders.

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The temperature of the melt-blending step is preferably controlled to avoid any appreciable cross-linking. Typically, a melt-blending temperature is selected such that the temperate of the molten blend does not exceed about 100°C to about 150°C. The ingredients may optionally be pre-mixed prior to melt blending. After melt blending and 5 cooling, the resulting blend, which is typically an extrudate, can be processed into powder using conventional milling techniques. The resulting milled powder can optionally be sieved to remove particles falling outside the desired particle size range. The powder can optionally be mixed with one or more additional powders to form the finished powder coating composition. For example, in some embodiments, the milled 10 powder is combined with fluidizing agent powder either before or after optional sieving.

[0157] The powder coatings compositions can be applied to substrate using any suitable method. Typically, the substrate is a metal substrate (e.g., cast iron, steel, etc.), which may be bare metal or may be optionally pretreated and/or primed. One suitable such method is the electrostatic spray application of charged powder to substrate.

Alternatively, the substrate may be applied, for example, by dipping the substrate in a fluidized powder bed. In a preferred embodiment, the powder is applied to heated substrate that has been heated to between 190°C and 240°C. Upon contacting the heated metal substrate, the powder melts, reacts, and forms a continuous coating that is preferably smooth and uniform. In another embodiment, the powder is applied to a near ambient temperature substrate and the powder coated substrate is then heated to a temperature sufficient to cause the powder to melt, react, and form a continuous coating that is preferably smooth and uniform.

[0158] The melting and curing (i.e., crosslinking) of the powder composition may be performed in combined or discrete heating steps. In presently preferred embodiments, a 25 combined heating step is used in which the powder coating composition is heated to a temperature sufficient to both melt the powder and cure the resulting continuous coating. The bake temperature and the duration of the bake will vary depending upon a variety of factors, including, for example, the end use. For purposes of curing the coating, the bake temperature is typically at least about 150°C, and more typically at least about 200°C. In 30 general, a lower cure temperature may be used if a longer cure time is employed. The cure temperature typically will not exceed about 240°C. The cure time may range, for example, from about 30 seconds to about 30 minutes, depending upon the cure temperature and the end use.

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[0159] The thickness of the cured powder coating will vary depending upon the particular end use. However, typically the cured powder coating will have an average coating thickness in the range of about 25 to about 1,500 microns, and more typically about 50 to about 500 microns. In some embodiments, an average coating thickness in the range of about 125 to about 300 microns is used.

EMBODIMENTS

[0160] Some additional non-limiting embodiments are provided below to further exemplify the present invention.

[0161] Embodiment 1: A polymer, more preferably a polycther polymer having one or more segments of the below Formula (I):

<img file="AU2020201397B2_D0026.tif" />

wherein:

• each of the pair of oxygen atoms depicted in Formula (I) is preferably present in an ether or ester linkage, more preferably an ether linkage;

· “H” denotes a hydrogen atom, if present;

• each R^l is independently an atom or group preferably having an atomic weight of at least 15 daltons, wherein each of the phenylene groups depicted in Formula (I) preferably includes at least one R¹ attached to the ring at an ortho or meta position relative to the oxygen atom;

· v is independently 1 to 4;

• w is 4;

• R², if present, is preferably a divalent group;

• n is 0 or 1, with the proviso that if n is 0, the phenylene groups depicted in Formula (I) can optionally join to form a fused ring system with each other (e.g., 25 a substituted naphthalene group), in which case w is 3;

• wherein two or more R¹ and/or R² groups can join to form one or more cyclic groups; and • the polymer is preferably free of BPA or BADGE.

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[0162] Embodiment 2: A polyether polymer that is the reaction product of ingredients including:

<img file="AU2020201397B2_D0027.tif" />

wherein:

• R¹, R², n, v, and w are as described above for Formula (1);

· each of the phenylene groups depicted in Formula (1) includes at least one R¹ that is preferably attached to the ring at an ortho or meta position relative to the depicted oxygen atom, more preferably an ortho position;

• s is 0 to 1;

• R³, if present, is a divalent group, more preferably a divalent organic group; and 10 · preferably each R⁴ is independently a hydrogen atom, a halogen atom, or a hydrocarbon group that may include one or more heteroatoms.

[0163] Embodiment 3: A coating composition comprising the polymer of Embodiments 1 or 2 (preferably in at least a film-forming amount) and one or more optional ingredients selected from a crosslinker and a liquid carrier.

[0164] Embodiment 4: An article (preferably a packaging article, more preferably a food or beverage container or a portion thereof) having a substrate (preferably a metal substrate), wherein the coating composition of Embodiment 3 is applied on at least a portion of the substrate.

[0165] Embodiment 5: A method comprising: providing a substrate (preferably a metal substrate) and applying the coating composition of Embodiment 3 on at least a portion of the substrate.

[0166] Embodiment 6: A polymer, coating composition, article, or method of any preceding embodiment, wherein the polymer and/or coating composition is at least substantially free of BPA or BADGE.

[0167] Embodiment 7: A polymer, coating composition, article, or method of any preceding embodiment, wherein each of the depicted phenylene groups in Formula (T) or

2020201397 26 Feb 2020

Formula (ΙΓ) has at least one ortho or meta R¹ (relative to the depicted oxygen) that is an organic group, more preferably an organic group that includes from 1 to 4 carbon atoms, even more preferably 1 to 2 carbon atoms.

[0168] Embodiment 8: A polymer, coating composition, article, or method of any preceding embodiment, wherein each of the depicted phenylene groups in Formula (I) or Formula (II) has at least one ortho or meta R¹ (relative to the depicted oxygen) that is independently a group selected from substituted or unsubstituted methyl groups, ethyl groups, propyl groups, butyl groups, or an isomer thereof.

[0169] Embodiment 9: A polymer, coating composition, article, or method of any preceding embodiment, wherein each phenylene group depicted in Formula (I) or Formula (II) includes R¹ s attached to the ring at both ortho positions relative to the depicted oxygen atom.

[0170] Embodiment 10: A polymer, coating composition, article, or method of any preceding embodiment, wherein the segment of Formula (I) is derived from 4,4’15 methylenebis(2,6-di-t-butylphenol); 2,2'-methylenebis(4-methyl-6-t-butylphenol);

4,4’-methylenebis(2,6-dimethylphenol); 4,4’butylidenebis(2-t-butyl-5-methylphenol), a derivative thereof, or a diepoxide thereof (more preferably a diglycidyl ether thereof). [0171] Embodiment 11: A polymer, coating composition, article, or method of any preceding embodiment, wherein each phenylene group depicted in Formula (I) or

Formula (II) includes at least one R¹ attached to the ring at an ortho position relative to the depicted oxygen atom.

[0172] Embodiment 12: A polymer, coating composition, article, or method of any preceding embodiment, wherein n is 1.

[0173] Embodiment 13: A polymer, coating composition, article, or method of any preceding embodiment, wherein n is 1 and R² has a atomic mass of less than 500, more preferably less than 200, even more preferably less than 100.

[0174] Embodiment 14: A polymer, coating composition, article, or method of any preceding embodiment, wherein R² is an organic group containing less than 15 carbon atoms, more preferably 1 to 10 carbon atoms, and in certain embodiments 1 to 2 carbon 30 atoms .

[0175] Embodiment 14.5: A polymer, coating composition, article, or method of any preceding embodiment, wherein n is 1 and R² is an organic group of the formula C(R⁷R⁸) -, wherein R⁷ and R^s are each independently a hydrogen atom, a halogen atom,

2020201397 26 Feb 2020 an organic group, a sulfur-containing group, a nitrogen-containing group, or any other suitable group that is preferably substantially non-reactive with an epoxy group, and wherein R⁷ and R^s can optionally join to form a cyclic group.

[0176] Embodiment 15: A polymer, coating composition, article, or method of any preceding embodiment, wherein the polymer (preferably a polyether polymer) includes one or more pendant hydroxyl groups attached to backbone carbon atoms.

[0177] Embodiment 16: A polymer, coating composition, article, or method of any preceding embodiment, wherein a backbone of the polymer includes -CH₂-CH(OH)CH₂- segments.

[0178] Embodiment 17: A polymer, coating composition, article, or method of any preceding embodiment, wherein -CH₂-CH(OH)-CH₂- segments are attached to each of the ether oxygen atoms depicted in Formula (I).

[0179] Embodiment 18: A polymer, coating composition, article, or method of any preceding embodiment, wherein the polymer (preferably a poly ether polymer) has a Tg 15 of at least 60°C, more preferably at least 70°C, even more preferably at least 80°C.

[0180] Embodiment 19: A polymer, coating composition, article, or method of any preceding embodiment, wherein aryl or heteroaryl groups (more typically phenylene groups) constitute at least 20 wt-% of the polyether polymer, based on the total weight of aryl and heteroaryl groups present in the polymer relative to the weight of the polymer.

[0181] Embodiment 20: A polymer, coating composition, article, or method of any preceding embodiment, wherein the polymer includes a plurality of segments of Formula (I) and, in some embodiments, includes at least: 1 wt-%, 5 wt-%, 10 wt-%, 20 wt-%, 30 wt-%, or 50 wt-% of the segments of Formula (T).

[0182] Embodiment 21: A polymer, coating composition, article, or method of any preceding embodiment, wherein the polymer is a polyether polymer and the polyether polymer (or polyether polymer fraction of a copolymer such as a polyether-acrylic copolymer) includes at least 20 wt-%, at least 30 wt-%, or at least 50 wt-% of segments of Formula (I).

[0183] Embodiment 22: A polymer, coating composition, article, or method of any preceding embodiment, wherein the polymer and/or coating composition is at least substantially free of acrylic (i.e., includes less than 1 wt-% of polymerized acrylic monomers, if any).

2020201397 26 Feb 2020

[0184] Embodiment 23: A polymer, coating composition, article, or method of any preceding embodiment, wherein the polymer includes a plurality of segments of the below Formula (IV):

-O-Ar-(Y_U-Ar)_t-O5 wherein:

• each Ar is preferably a phenylene group, more preferably an unsubstituted phenylene group;

• u is independently 0 or 1;

• t is independently 0 or 1;

· Y, if present, is a divalent group; and • the two oxygen atoms arc preferably each ether oxygen.

[0185] Embodiment 24: A polymer, coating composition, article, or method of Embodiment 23, wherein Y is a divalent organic group having a molecular weight of less than 500.

[0186] Embodiment 25: A polymer, coating composition, article, or method of

Embodiments 24 or 25, wherein the segment of Formula (IV) has a molecular weight greater than that of bisphenol A.

[0187] Embodiment 26: A polymer, coating composition, article, or method of any of Embodiments 23-25 wherein t and u are each 1 and Y_u includes one or more ester linkages.

[0188] Embodiment 27: A polymer, coating composition, article, or method of any of Embodiments 23-26, wherein Y includes one or more monocyclic or polycyclic groups. [0189] Embodiment 28: A polymer, coating composition, article, or method of any preceding embodiment, wherein the polymer comprises a polyether polymer that is a 25 reaction product of ingredients including (i) a polyepoxide having a segment of

Formula (I) or a polyepoxide compound of Formula (II) and (ii) a polyhydric phenol. [0190] Embodiment 28.5: A polymer, coating composition, article, or method of Embodiment 28, wherein one or more (and more preferably all) of the following are true: (a) the polyepoxidc of (i) is formed from a polyhydric phenol that docs not exhibit appreciable estrogenic activity (e.g., when tested using the MCF-7 assay it preferably exhibits an RPE having a logarithmic value of less than about -2.0);

2020201397 26 Feb 2020 (b) the polyepoxide of (i) does not exhibit mutagenicity or any other unsuitable genotoxicity (i.e., the polyepoxide is non-genotoxic in, e.g., the comet assay); and (c) the polyhydric phenol of (ii) does not exhibit appreciable estrogenic activity.

[0191] Embodiment 29: A polymer, coating composition, article, or method of

Embodiment 28, wherein the poly hydric phenol is of the formula:

HO—Ar—(R⁵)w—Z—R⁶—Z— (R⁵)w —Ar—OH wherein:

• each Ar is independently a divalent aryl group or heteroaryl group (more typically a substituted or unsubstituted phenylene group);

· each R⁵, if present, is independently a divalent organic group;

• R⁶ is a divalent organic group;

• each Z is independently an ester linkage of either directionality (i.e., -C(O)-O- or -O-C(O)-) and • each w is 0 or 1.

[0192] Embodiment 30: A polymer, coating composition, article, or method of any preceding embodiment, wherein the polymer has an Mn of from 2,000 to 20,000. [0193] Embodiment 31: A coating composition, article, or method of any preceding embodiment, wherein the coating composition, by weight total resin solids, includes at least 5 wt-% or 10 wt-% of the polyether polymer.

[0194] Embodiment 32: A coating composition, article, or method of any preceding embodiment, wherein the coating composition is a food-contact coating.

[0195] Embodiment 33: A coating composition, article, or method of any preceding embodiment, wherein the coating composition is one of: a solvent-based coating composition or a water-based coating composition.

[0196] Embodiment 34: A coating composition, article, or method of any preceding embodiment, wherein the coating composition is a water-based coating composition that is at least substantially free of acrylic.

[0197] Embodiment 35: A method of any preceding embodiment, wherein the substrate is formed into a packaging container or a portion thereof (e.g., a food or beverage container or a portion thereof) after application of the coating composition.

[0198] Embodiment 36: A method or article of any preceding embodiment, wherein the coated article comprises a metal food or beverage container, a cosmetic container, a pharmaceutical container, or a portion thereof (e.g., a can end) having the coating

2020201397 26 Feb 2020 composition applied to one or more of: an exterior surface or an interior (i.e., productcontact) surface.

[0199] Embodiment 37: A coating composition, article, or method of any of Embodiments 1-32, 35, and 36, wherein the coating composition comprises a powder 5 coating composition.

[0200] Embodiment 38: The article or Embodiment 37, wherein the article is an article for conveying or storing potable water (e.g., a water valve, water fitting, water pipe, a bolted steel water tank or a panel for use therein, etc.).

[0201] Segments of Formula (I) and compounds of Formulas (II) or (III) wherein each of the depicted phenylene groups include one or two ortho X groups (relative to the depicted oxygen atom) are presently preferred. To further illustrate such structures, below is a table exemplifying some non-limiting combinations of one or more ortho X and R“ for a given phenylene group. The table is non-limiting with respect to the ring position of R² (e.g., ortho, meta, para), although typically R² will be located at a para position relative to the oxygen atom. The columns labeled “Ortho Position A” and “Ortho Position B” indicate the group present at each ortho position of the phenylene group (assuming R² is not located at an ortho position). Positions “A” or “B” can be either ortho position relative to the depicted oxygen atom. If R² is located at an ortho position of the phenylene group, then the group listed in the “Ortho Position B” column is not present. Typically, the phenylene groups in a given segment of Formula (I) or compound of Formula (II) or (III) will be “symmetric” relative to the second phenylene group such that the same ortho group (as delineated in the ortho position column “A” or “B”) is located on each ring at the same ortho position.

[0202] The below table is also intended as a listing of independent examples of X or R², 25 as well as examples of combinations of X and R² (regardless of whether X is ortho or meta relative to the oxygen atom, whether other X are present in a particular phenylene group, or whether the one or more X are the same for both of the phenylene groups). This additional purpose is the reason for the additional qualifier “or X” in the legend of the first column.

Ortho Position “A^M (or X)

Butyl Butyl Butyl Butyl

Ortho Position “B”

Hydrogen Methyl Ethyl Propyl

2-Butylidene

2-Butylidene

2-Butylidene

2-Butylidene

2020201397 26 Feb 2020

<td> Ortho Position “A” (or X)</td><td> Ortho Position “B”</td><td> R²</td>

<td> Butyl</td><td> isopropyl</td><td> 2-Butylidcnc</td>

<td> Butyl</td><td> Butyl</td><td> 2-Butylidene</td>

<td> Ethyl</td><td> Hydrogen</td><td> 2-Butylidcne</td>

<td> Ethyl</td><td> Methyl</td><td> 2-Butylidene</td>

<td> Ethyl</td><td> Ethyl</td><td> 2-Butylidene</td>

<td> Isopropyl</td><td> Hydrogen</td><td> 2-Butylidene</td>

<td> Isopropyl</td><td> Methyl</td><td> 2-Butylidcnc</td>

<td> Isopropyl</td><td> Ethyl</td><td> 2-Butylidene</td>

<td> Isopropyl</td><td> Propyl</td><td> 2-Butylidene</td>

<td> Isopropyl</td><td> isopropyl</td><td> 2-Butylidene</td>

<td> Methyl</td><td> Hydrogen</td><td> 2-Butylidene</td>

<td> Methyl</td><td> Methyl</td><td> 2-Butylidene</td>

<td> Propyl</td><td> Hydrogen</td><td> 2-Butylidcnc</td>

<td> Propyl</td><td> Methyl</td><td> 2-Butylidene</td>

<td> Propyl</td><td> Ethyl</td><td> 2-Butylidene</td>

<td> Propyl</td><td> Propyl</td><td> 2-Butylidene</td>

<td> scc-Butyl</td><td> Hydrogen</td><td> 2-Butylidcne</td>

<td> sec-Butyl</td><td> Methyl</td><td> 2-Butylidene</td>

<td> sec-Butyl</td><td> Ethyl</td><td> 2-Butylidene</td>

<td> sec-Butyl</td><td> Propyl</td><td> 2-Butylidene</td>

<td> scc-Butyl</td><td> isopropyl</td><td> 2-Butylidcnc</td>

<td> sec-Butyl</td><td> Butyl</td><td> 2-Butylidene</td>

<td> sec-Butyl</td><td> sec-Butyl</td><td> 2-Butylidene</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> 2-Butylidene</td>

<td> tert-Butyl</td><td> Methyl</td><td> 2-Butylidene</td>

<td> tert-Butyl</td><td> Ethyl</td><td> 2-Butylidene</td>

<td> tert-Butyl</td><td> Propyl</td><td> 2-Butylidene</td>

<td> tert-Butyl</td><td> isopropyl</td><td> 2-Butylidene</td>

<td> tert-Butyl</td><td> Butyl</td><td> 2-Butylidene</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> 2-Butylidene</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> 2-Butylidene</td>

<td> Butyl</td><td> Hydrogen</td><td> Butylene</td>

<td> Butyl</td><td> Methyl</td><td> Butylene</td>

<td> Butyl</td><td> Ethyl</td><td> Butylene</td>

<td> Butyl</td><td> Propyl</td><td> Butylene</td>

<td> Butyl</td><td> isopropyl</td><td> Butylene</td>

<td> Butyl</td><td> Butyl</td><td> Butylene</td>

<td> Ethyl</td><td> Hydrogen</td><td> Butylene</td>

<td> Ethyl</td><td> Methyl</td><td> Butylene</td>

<td> Ethyl</td><td> Ethyl</td><td> Butylene</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Butylene</td>

<td> Isopropyl</td><td> Methyl</td><td> Butylene</td>

<td> Isopropyl</td><td> Ethyl</td><td> Butylene</td>

<td> Isopropyl</td><td> Propyl</td><td> Butylene</td>

2020201397 26 Feb 2020

<td> Ortho Position “A” (or X)</td><td> Ortho Position “B”</td><td> R²</td>

<td> Isopropyl</td><td> isopropyl</td><td> Butylene</td>

<td> Methyl</td><td> Hydrogen</td><td> Butylene</td>

<td> Methyl</td><td> Methyl</td><td> Butylene</td>

<td> Propyl</td><td> Hydrogen</td><td> Butylene</td>

<td> Propyl</td><td> Methyl</td><td> Butylene</td>

<td> Propyl</td><td> Ethyl</td><td> Butylene</td>

<td> Propyl</td><td> Propyl</td><td> Butylene</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Butylene</td>

<td> sec-Butyl</td><td> Methyl</td><td> Butylene</td>

<td> sec-Butyl</td><td> Ethyl</td><td> Butylene</td>

<td> sec-Butyl</td><td> Propyl</td><td> Butylene</td>

<td> sec-Butyl</td><td> isopropyl</td><td> Butylene</td>

<td> sec-Butyl</td><td> Butyl</td><td> Butylene</td>

<td> sec-Butyl</td><td> sec-Butyl</td><td> Butylene</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> Butylene</td>

<td> tert-Butyl</td><td> Methyl</td><td> Butylene</td>

<td> tert-Butyl</td><td> Ethyl</td><td> Butylene</td>

<td> tert-Butyl</td><td> Propyl</td><td> Butylene</td>

<td> tert-Butyl</td><td> isopropyl</td><td> Butylene</td>

<td> tert-Butyl</td><td> Butyl</td><td> Butylene</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> Butylene</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> Butylene</td>

<td> Butyl</td><td> Hydrogen</td><td> Cyclohexylidene</td>

<td> Butyl</td><td> Methyl</td><td> Cyclohexylidene</td>

<td> Butyl</td><td> Ethyl</td><td> Cyclohexylidene</td>

<td> Butyl</td><td> Propyl</td><td> Cyclohexylidene</td>

<td> Butyl</td><td> isopropyl</td><td> Cyclohexylidene</td>

<td> Butyl</td><td> Butyl</td><td> Cyclohexylidene</td>

<td> Ethyl</td><td> Hydrogen</td><td> Cyclohexylidene</td>

<td> Ethyl</td><td> Methyl</td><td> Cyclohexylidene</td>

<td> Ethyl</td><td> Ethyl</td><td> Cyclohexylidene</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Cyclohexylidene</td>

<td> Isopropyl</td><td> Methyl</td><td> Cyclohexylidene</td>

<td> Isopropyl</td><td> Ethyl</td><td> Cyclohexylidene</td>

<td> Isopropyl</td><td> Propyl</td><td> Cyclohexylidene</td>

<td> Isopropyl</td><td> isopropyl</td><td> Cyclohexylidene</td>

<td> Methyl</td><td> Hydrogen</td><td> Cyclohexylidene</td>

<td> Methyl</td><td> Methyl</td><td> Cyclohexylidene</td>

<td> Propyl</td><td> Hydrogen</td><td> Cyclohexylidene</td>

<td> Propyl</td><td> Methyl</td><td> Cyclohexylidene</td>

<td> Propyl</td><td> Ethyl</td><td> Cyclohexylidene</td>

<td> Propyl</td><td> Propyl</td><td> Cyclohexylidene</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Cyclohexylidene</td>

<td> sec-Butyl</td><td> Methyl</td><td> Cyclohexylidene</td>

2020201397 26 Feb 2020

<td> Ortho Position “A” (or X)</td><td> Ortho Position “B”</td><td> R²</td>

<td> scc-Butyl</td><td> Ethyl</td><td> Cyclohcxylidcne</td>

<td> sec-Butyl</td><td> Propyl</td><td> Cyclohexylidene</td>

<td> scc-Butyl</td><td> isopropyl</td><td> Cyclohcxylidcne</td>

<td> sec-Butyl</td><td> Butyl</td><td> Cyclohexylidene</td>

<td> scc-Butyl</td><td> sec-Butyl</td><td> Cyclohcxylidcne</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> Cyclohexylidene</td>

<td> tcrt-Butyl</td><td> Methyl</td><td> Cyclohcxylidcne</td>

<td> tert-Butyl</td><td> Ethyl</td><td> Cyclohexylidene</td>

<td> tert-Butyl</td><td> Propyl</td><td> Cyclohexylidene</td>

<td> tert-Butyl</td><td> isopropyl</td><td> Cyclohexylidene</td>

<td> tcrt-Butyl</td><td> Butyl</td><td> Cyclohcxylidcne</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> Cyclohexylidene</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> Cyclohcxylidcne</td>

<td> Butyl</td><td> Hydrogen</td><td> Cyclopentylidene</td>

<td> Butyl</td><td> Methyl</td><td> Cyclopentylidene</td>

<td> Butyl</td><td> Ethyl</td><td> Cyclopentylidene</td>

<td> Butyl</td><td> Propyl</td><td> Cyclopentylidcnc</td>

<td> Butyl</td><td> isopropyl</td><td> Cyclopentylidene</td>

<td> Butyl</td><td> Butyl</td><td> Cyclopentylidene</td>

<td> Ethyl</td><td> Hydrogen</td><td> Cyclopentylidene</td>

<td> Ethyl</td><td> Methyl</td><td> Cyclopentylidcne</td>

<td> Ethyl</td><td> Ethyl</td><td> Cyclopentylidene</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Cyclopentylidene</td>

<td> Isopropyl</td><td> Methyl</td><td> Cyclopentylidene</td>

<td> Isopropyl</td><td> Ethyl</td><td> Cyclopentylidene</td>

<td> Isopropyl</td><td> Propyl</td><td> Cyclopentylidene</td>

<td> Isopropyl</td><td> isopropyl</td><td> Cyclopentylidene</td>

<td> Methyl</td><td> Hydrogen</td><td> Cyclopentylidene</td>

<td> Methyl</td><td> Methyl</td><td> Cyclopentylidene</td>

<td> Propyl</td><td> Hydrogen</td><td> Cyclopentylidene</td>

<td> Propyl</td><td> Methyl</td><td> Cyclopentylidene</td>

<td> Propyl</td><td> Ethyl</td><td> Cyclopentylidene</td>

<td> Propyl</td><td> Propyl</td><td> Cyclopentylidene</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Cyclopentylidene</td>

<td> sec-Butyl</td><td> Methyl</td><td> Cyclopentylidene</td>

<td> sec-Butyl</td><td> Ethyl</td><td> Cyclopentylidene</td>

<td> sec-Butyl</td><td> Propyl</td><td> Cyclopentylidene</td>

<td> sec-Butyl</td><td> isopropyl</td><td> Cyclopentylidene</td>

<td> sec-Butyl</td><td> Butyl</td><td> Cyclopentylidene</td>

<td> sec-Butyl</td><td> sec-Butyl</td><td> Cyclopentylidene</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> Cyclopentylidene</td>

<td> tert-Butyl</td><td> Methyl</td><td> Cyclopentylidene</td>

<td> tert-Butyl</td><td> Propyl</td><td> Cyclopentylidene</td>

<td> tert-Butyl</td><td> isopropyl</td><td> Cyclopentylidene</td>

2020201397 26 Feb 2020

<td> Ortho Position “A” (or X)</td><td> Ortho Position “B”</td><td> R²</td>

<td> tcrt-Butyl</td><td> Butyl</td><td> Cyclopcntylidcne</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> Cyclopentylidene</td>

<td> tcrt-Butyl</td><td> tert-Butyl</td><td> Cyclopcntylidenc</td>

<td> Butyl</td><td> Hydrogen</td><td> Ethylidene</td>

<td> Butyl</td><td> Methyl</td><td> Ethylidcne</td>

<td> Butyl</td><td> Ethyl</td><td> Ethylidene</td>

<td> Butyl</td><td> Propyl</td><td> Ethylidcne</td>

<td> Butyl</td><td> isopropyl</td><td> Ethylidene</td>

<td> Butyl</td><td> Butyl</td><td> Ethylidene</td>

<td> Ethyl</td><td> Hydrogen</td><td> Ethylidene</td>

<td> Ethyl</td><td> Methyl</td><td> Ethylidene</td>

<td> Ethyl</td><td> Ethyl</td><td> Ethylidene</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Ethylidene</td>

<td> Isopropyl</td><td> Methyl</td><td> Ethylidene</td>

<td> Isopropyl</td><td> Ethyl</td><td> Ethylidene</td>

<td> Isopropyl</td><td> Propyl</td><td> Ethylidene</td>

<td> Isopropyl</td><td> isopropyl</td><td> Ethylidene</td>

<td> Methyl</td><td> Hydrogen</td><td> Ethylidene</td>

<td> Methyl</td><td> Methyl</td><td> Ethylidene</td>

<td> Propyl</td><td> Hydrogen</td><td> Ethylidene</td>

<td> Propyl</td><td> Methyl</td><td> Ethylidcne</td>

<td> Propyl</td><td> Ethyl</td><td> Ethylidene</td>

<td> Propyl</td><td> Propyl</td><td> Ethylidene</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Ethylidene</td>

<td> sec-Butyl</td><td> Methyl</td><td> Ethylidene</td>

<td> sec-Butyl</td><td> Ethyl</td><td> Ethylidene</td>

<td> sec-Butyl</td><td> Propyl</td><td> Ethylidene</td>

<td> sec-Butyl</td><td> isopropyl</td><td> Ethylidene</td>

<td> sec-Butyl</td><td> Butyl</td><td> Ethylidene</td>

<td> sec-Butyl</td><td> sec-Butyl</td><td> Ethylidene</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> Ethylidene</td>

<td> tert-Butyl</td><td> Methyl</td><td> Ethylidene</td>

<td> tert-Butyl</td><td> Ethyl</td><td> Ethylidene</td>

<td> tert-Butyl</td><td> Propyl</td><td> Ethylidene</td>

<td> tert-Butyl</td><td> isopropyl</td><td> Ethylidene</td>

<td> tert-Butyl</td><td> Butyl</td><td> Ethylidene</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> Ethylidene</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> Ethylidene</td>

<td> Butyl</td><td> Hydrogen</td><td> Iso-Propylidene</td>

<td> Butyl</td><td> Methyl</td><td> Iso-Propylidene</td>

<td> Butyl</td><td> Ethyl</td><td> Iso-Propylidene</td>

<td> Butyl</td><td> Propyl</td><td> Iso-Propylidene</td>

<td> Butyl</td><td> isopropyl</td><td> Iso-Propylidene</td>

<td> Butyl</td><td> Butyl</td><td> Iso-Propylidene</td>

2020201397 26 Feb 2020

<td> Ortho Position “A” (or X)</td><td> Ortho Position “B”</td><td> R²</td>

<td> Ethyl</td><td> Hydrogen</td><td> Iso-Propylidenc</td>

<td> Ethyl</td><td> Methyl</td><td> Iso-Propylidene</td>

<td> Ethyl</td><td> Ethyl</td><td> Iso-Propylidenc</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Iso-Propylidene</td>

<td> Isopropyl</td><td> Methyl</td><td> Iso-Propylidcnc</td>

<td> Isopropyl</td><td> Ethyl</td><td> Iso-Propylidene</td>

<td> Isopropyl</td><td> Propyl</td><td> Iso-Propylidcnc</td>

<td> Isopropyl</td><td> isopropyl</td><td> Iso-Propylidene</td>

<td> Methyl</td><td> Hydrogen</td><td> Iso-Propylidene</td>

<td> Methyl</td><td> Methyl</td><td> Iso-Propylidene</td>

<td> Propyl</td><td> Hydrogen</td><td> Iso-Propylidene</td>

<td> Propyl</td><td> Methyl</td><td> Iso-Propylidene</td>

<td> Propyl</td><td> Ethyl</td><td> Iso-Propylidene</td>

<td> Propyl</td><td> Propyl</td><td> Iso-Propylidene</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Iso-Propylidene</td>

<td> sec-Butyl</td><td> Methyl</td><td> Iso-Propylidene</td>

<td> sec-Butyl</td><td> Ethyl</td><td> Iso-Propylidcnc</td>

<td> sec-Butyl</td><td> Propyl</td><td> Iso-Propylidene</td>

<td> sec-Butyl</td><td> isopropyl</td><td> Iso-Propylidene</td>

<td> sec-Butyl</td><td> Butyl</td><td> Iso-Propylidene</td>

<td> sec-Butyl</td><td> sec-Butyl</td><td> Iso-Propylidcnc</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> Iso-Propylidene</td>

<td> tert-Butyl</td><td> Methyl</td><td> Iso-Propylidene</td>

<td> tert-Butyl</td><td> Ethyl</td><td> Iso-Propylidene</td>

<td> tert-Butyl</td><td> Propyl</td><td> Iso-Propylidene</td>

<td> tert-Butyl</td><td> isopropyl</td><td> Iso-Propylidene</td>

<td> tert-Butyl</td><td> Butyl</td><td> Iso-Propylidene</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> Iso-Propylidene</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> Iso-Propylidene</td>

<td> Butyl</td><td> Hydrogen</td><td> Methylidene</td>

<td> Butyl</td><td> Methyl</td><td> Methylidene</td>

<td> Butyl</td><td> Ethyl</td><td> Methylidene</td>

<td> Butyl</td><td> Propyl</td><td> Methylidene</td>

<td> Butyl</td><td> isopropyl</td><td> Methylidene</td>

<td> Butyl</td><td> Butyl</td><td> Methylidene</td>

<td> Ethyl</td><td> Hydrogen</td><td> Methylidene</td>

<td> Ethyl</td><td> Methyl</td><td> Methylidene</td>

<td> Ethyl</td><td> Ethyl</td><td> Methylidene</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Methylidene</td>

<td> Isopropyl</td><td> Methyl</td><td> Methylidene</td>

<td> Isopropyl</td><td> Ethyl</td><td> Methylidene</td>

<td> Isopropyl</td><td> Propyl</td><td> Methylidene</td>

<td> Isopropyl</td><td> isopropyl</td><td> Methylidene</td>

<td> Methyl</td><td> Hydrogen</td><td> Methylidene</td>

2020201397 26 Feb 2020

<td> Ortho Position “A” (or X)</td><td> Ortho Position “B”</td><td> R²</td>

<td> Methyl</td><td> Methyl</td><td> Methylidene</td>

<td> Propyl</td><td> Hydrogen</td><td> Methylidene</td>

<td> Propyl</td><td> Methyl</td><td> Methylidene</td>

<td> Propyl</td><td> Ethyl</td><td> Methylidene</td>

<td> Propyl</td><td> Propyl</td><td> Methylidene</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Methylidene</td>

<td> sec-Butyl</td><td> Methyl</td><td> Methylidene</td>

<td> sec-Butyl</td><td> Ethyl</td><td> Methylidene</td>

<td> sec-Butyl</td><td> Propyl</td><td> Methylidene</td>

<td> sec-Butyl</td><td> isopropyl</td><td> Methylidene</td>

<td> sec-Butyl</td><td> Butyl</td><td> Methylidene</td>

<td> sec-Butyl</td><td> scc-Butyl</td><td> Methylidene</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> Methylidene</td>

<td> tert-Butyl</td><td> Methyl</td><td> Methylidene</td>

<td> tert-Butyl</td><td> Ethyl</td><td> Methylidene</td>

<td> tert-Butyl</td><td> Propyl</td><td> Methylidene</td>

<td> tert-Butyl</td><td> isopropyl</td><td> Methylidene</td>

<td> tert-Butyl</td><td> Butyl</td><td> Methylidene</td>

<td> tert-Butyl</td><td> scc-Butyl</td><td> Methylidene</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> Methylidene</td>

<td> Butyl</td><td> Hydrogen</td><td> Propylidcne</td>

<td> Butyl</td><td> Methyl</td><td> Propylidene</td>

<td> Butyl</td><td> Ethyl</td><td> Propylidene</td>

<td> Butyl</td><td> Propyl</td><td> Propylidene</td>

<td> Butyl</td><td> isopropyl</td><td> Propylidene</td>

<td> Butyl</td><td> Butyl</td><td> Propylidene</td>

<td> Ethyl</td><td> Hydrogen</td><td> Propylidene</td>

<td> Ethyl</td><td> Methyl</td><td> Propylidene</td>

<td> Ethyl</td><td> Ethyl</td><td> Propylidene</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Propylidene</td>

<td> Isopropyl</td><td> Methyl</td><td> Propylidene</td>

<td> Isopropyl</td><td> Ethyl</td><td> Propylidene</td>

<td> Isopropyl</td><td> Propyl</td><td> Propylidene</td>

<td> Isopropyl</td><td> isopropyl</td><td> Propylidene</td>

<td> Methyl</td><td> Hydrogen</td><td> Propylidene</td>

<td> Methyl</td><td> Methyl</td><td> Propylidene</td>

<td> Propyl</td><td> Hydrogen</td><td> Propylidene</td>

<td> Propyl</td><td> Methyl</td><td> Propylidene</td>

<td> Propyl</td><td> Ethyl</td><td> Propylidene</td>

<td> Propyl</td><td> Propyl</td><td> Propylidene</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Propylidene</td>

<td> sec-Butyl</td><td> Methyl</td><td> Propylidene</td>

<td> sec-Butyl</td><td> Ethyl</td><td> Propylidene</td>

<td> sec-Butyl</td><td> Propyl</td><td> Propylidene</td>

2020201397 26 Feb 2020

<td> Ortho Position “A” (or X)</td><td> Ortho Position “B”</td><td> R²</td>

<td> sec-Butyl</td><td> isopropyl</td><td> Propylidcne</td>

<td> sec-Butyl</td><td> Butyl</td><td> Propylidene</td>

<td> scc-Butyl</td><td> sec-Butyl</td><td> Propylidcne</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> Propylidene</td>

<td> tert-Butyl</td><td> Methyl</td><td> Propylidcne</td>

<td> tert-Butyl</td><td> Ethyl</td><td> Propylidene</td>

<td> tert-Butyl</td><td> Propyl</td><td> Propylidene</td>

<td> tert-Butyl</td><td> isopropyl</td><td> Propylidene</td>

<td> tert-Butyl</td><td> Butyl</td><td> Propylidene</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> Propylidene</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> Propylidcne</td>

<td> Butyl</td><td> Hydrogen</td><td> Trimethyl Cyclohexylidene</td>

<td> Butyl</td><td> Methyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Butyl</td><td> Ethyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Butyl</td><td> Propyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Butyl</td><td> isopropyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Butyl</td><td> Butyl</td><td> Trimcthyl Cyclohexylidenc</td>

<td> Ethyl</td><td> Hydrogen</td><td> Trimethyl Cyclohexylidene</td>

<td> Ethyl</td><td> Methyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Ethyl</td><td> Ethyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Trimcthyl Cyclohcxylidene</td>

<td> Isopropyl</td><td> Methyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Isopropyl</td><td> Ethyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Isopropyl</td><td> Propyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Isopropyl</td><td> isopropyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Methyl</td><td> Hydrogen</td><td> Trimethyl Cyclohexylidene</td>

<td> Methyl</td><td> Methyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Propyl</td><td> Hydrogen</td><td> Trimethyl Cyclohexylidene</td>

<td> Propyl</td><td> Methyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Propyl</td><td> Ethyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Propyl</td><td> Propyl</td><td> Trimethyl Cyclohexylidene</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Trimethyl Cyclohexylidene</td>

<td> sec-Butyl</td><td> Methyl</td><td> Trimethyl Cyclohexylidene</td>

<td> sec-Butyl</td><td> Ethyl</td><td> Trimethyl Cyclohexylidene</td>

<td> sec-Butyl</td><td> Propyl</td><td> Trimethyl Cyclohexylidene</td>

<td> sec-Butyl</td><td> isopropyl</td><td> Trimethyl Cyclohexylidene</td>

<td> sec-Butyl</td><td> Butyl</td><td> Trimethyl Cyclohexylidene</td>

<td> sec-Butyl</td><td> sec-Butyl</td><td> Trimethyl Cyclohexylidene</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> Trimethyl Cyclohexylidene</td>

<td> tert-Butyl</td><td> Methyl</td><td> Trimethyl Cyclohexylidene</td>

<td> tert-Butyl</td><td> Ethyl</td><td> Trimethyl Cyclohexylidene</td>

<td> tert-Butyl</td><td> Propyl</td><td> Trimethyl Cyclohexylidene</td>

<td> tert-Buty]</td><td> isopropyl</td><td> Trimethyl Cyclohexylidene</td>

<td> tert-Butyl</td><td> Butyl</td><td> Trimethyl Cyclohexylidene</td>

2020201397 26 Feb 2020

<td> Ortho Position “A” (or X)</td><td> Ortho Position “B”</td><td> R²</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> Trimcthyl Cyclohcxylidcne</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> Trimethyl Cyclohexylidene</td>

<td> Butyl</td><td> Hydrogen</td><td> Acetophenone</td>

<td> Butyl</td><td> Methyl</td><td> Acetophenone</td>

<td> Butyl</td><td> Ethyl</td><td> Acetophenone</td>

<td> Butyl</td><td> Propyl</td><td> Acetophenone</td>

<td> Butyl</td><td> isopropyl</td><td> Acetophenone</td>

<td> Butyl</td><td> Butyl</td><td> Acetophenone</td>

<td> Ethyl</td><td> Hydrogen</td><td> Acetophenone</td>

<td> Ethyl</td><td> Methyl</td><td> Acetophenone</td>

<td> Ethyl</td><td> Ethyl</td><td> Acetophenone</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Acetophenone</td>

<td> Isopropyl</td><td> Methyl</td><td> Acetophenone</td>

<td> Isopropyl</td><td> Ethyl</td><td> Acetophenone</td>

<td> Isopropyl</td><td> Propyl</td><td> Acetophenone</td>

<td> Isopropyl</td><td> isopropyl</td><td> Acetophenone</td>

<td> Methyl</td><td> Hydrogen</td><td> Acetophenone</td>

<td> Methyl</td><td> Methyl</td><td> Acetophenone</td>

<td> Propyl</td><td> Hydrogen</td><td> Acetophenone</td>

<td> Propyl</td><td> Methyl</td><td> Acetophenone</td>

<td> Propyl</td><td> Ethyl</td><td> Acetophenone</td>

<td> Propyl</td><td> Propyl</td><td> Acetophenone</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Acetophenone</td>

<td> sec-Butyl</td><td> Methyl</td><td> Acetophenone</td>

<td> sec-Butyl</td><td> Ethyl</td><td> Acetophenone</td>

<td> sec-Butyl</td><td> Propyl</td><td> Acetophenone</td>

<td> sec-Butyl</td><td> isopropyl</td><td> Acetophenone</td>

<td> sec-Butyl</td><td> Butyl</td><td> Acetophenone</td>

<td> sec-Butyl</td><td> sec-Butyl</td><td> Acetophenone</td>

<td> tert-Butyl</td><td> Hydrogen</td><td> Acetophenone</td>

<td> tert-Butyl</td><td> Methyl</td><td> Acetophenone</td>

<td> tert-Butyl</td><td> Ethyl</td><td> Acetophenone</td>

<td> tert-Butyl</td><td> Propyl</td><td> Acetophenone</td>

<td> tert-Butyl</td><td> isopropyl</td><td> Acetophenone</td>

<td> tert-Butyl</td><td> Butyl</td><td> Acetophenone</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> Acetophenone</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> Acetophenone</td>

<td> Butyl</td><td> Hydrogen</td><td> Benzophenone</td>

<td> Butyl</td><td> Methyl</td><td> Benzophenone</td>

<td> Butyl</td><td> Ethyl</td><td> Benzophenone</td>

<td> Butyl</td><td> Propyl</td><td> Benzophenone</td>

<td> Butyl</td><td> isopropyl</td><td> Benzophenone</td>

<td> Butyl</td><td> Butyl</td><td> Benzophenone</td>

<td> Ethyl</td><td> Hydrogen</td><td> Benzophenone</td>

2020201397 26 Feb 2020

<td> Ortho Position “A” (or X)</td><td> Ortho Position “B”</td><td> R²</td>

<td> Ethyl</td><td> Methyl</td><td> Benzophenone</td>

<td> Ethyl</td><td> Ethyl</td><td> Benzophenone</td>

<td> Isopropyl</td><td> Hydrogen</td><td> Benzophenone</td>

<td> Isopropyl</td><td> Methyl</td><td> Benzophenone</td>

<td> Isopropyl</td><td> Ethyl</td><td> Benzophenone</td>

<td> Isopropyl</td><td> Propyl</td><td> Benzophenone</td>

<td> Isopropyl</td><td> isopropyl</td><td> Benzophenone</td>

<td> Methyl</td><td> Hydrogen</td><td> Benzophenone</td>

<td> Methyl</td><td> Methyl</td><td> Benzophenone</td>

<td> Propyl</td><td> Hydrogen</td><td> Benzophenone</td>

<td> Propyl</td><td> Methyl</td><td> Benzophenone</td>

<td> Propyl</td><td> Ethyl</td><td> Benzophenone</td>

<td> Propyl</td><td> Propyl</td><td> Benzophenone</td>

<td> sec-Butyl</td><td> Hydrogen</td><td> Benzophenone</td>

<td> sec-Butyl</td><td> Methyl</td><td> Benzophenone</td>

<td> sec-Butyl</td><td> Ethyl</td><td> Benzophenone</td>

<td> sec-Butyl</td><td> Propyl</td><td> Benzophenone</td>

<td> sec-Butyl</td><td> isopropyl</td><td> Benzophenone</td>

<td> sec-Butyl</td><td> Butyl</td><td> Benzophenone</td>

<td> sec-Butyl</td><td> sec-Butyl</td><td> Benzophenone</td>

<td> tcrt-Butyl</td><td> Hydrogen</td><td> Benzophenone</td>

<td> tert-Butyl</td><td> Methyl</td><td> Benzophenone</td>

<td> tert-Butyl</td><td> Ethyl</td><td> Benzophenone</td>

<td> tert-Butyl</td><td> Propyl</td><td> Benzophenone</td>

<td> tert-Butyl</td><td> isopropyl</td><td> Benzophenone</td>

<td> tert-Butyl</td><td> Butyl</td><td> Benzophenone</td>

<td> tert-Butyl</td><td> sec-Butyl</td><td> Benzophenone</td>

<td> tert-Butyl</td><td> tert-Butyl</td><td> Benzophenone</td>

TEST METHODS

[0203] Unless indicated otherwise, the following test methods were utilized in the Examples that follow.

Differential Scanning Calorimetry

[0204] Samples for differential scanning calorimetry (“DSC”) testing were prepared by first applying the liquid resin composition onto aluminum sheet panels. The panels were then baked in a Fisher Isotemp electric oven for 20 minutes at 300°F (149°C) to remove volatile materials. After cooling to room temperature, the samples were scraped from the panels, weighed into standard sample pans and analyzed using the standard DSC heatcool-hcat method. The samples were equilibrated at -60°C, then heated at 20°C per

2020201397 26 Feb 2020 minute to 200°C, cooled to -60°C, and then heated again at 20°C per minute to 200°C. Glass transitions and melt points were calculated from the thermogram of the last heat cycle. The glass transition was measured at the inflection point of the transition and the melt point was measured at the peak maximum of the melting peak.

Adhesion

[0205] Adhesion testing is performed to assess whether the coating adheres to the coated substrate. The adhesion test was performed according to A STM D 3359 - Test Method B, using SCOTCH 610 tape (available from 3M Company of Saint Paul, Minnesota). Adhesion is generally rated on a scale of 0-10 where a rating of “10” indicates no adhesion failure, a rating of “9” indicates 90% of the coating remains adhered, a rating of “8” indicates 80% of the coating remains adhered, and so on. Adhesion ratings of 10 are typically desired for commercially viable coatings.

Blush Resistance

[0206] Blush resistance measures the ability of a coating to resist attack by various solutions. Typically, blush is measured by the amount of water absorbed into a coated film. When the film absorbs water, it generally becomes cloudy or looks white. Blush is generally measured visually using a scale of 0-10 where a rating of “10” indicates no blush and a rating of “0” indicates complete whitening of the film. Blush ratings of at least 7 are typically desired for commercially viable coatings and optimally 9 or above.

Corrosion

[0207] Corrosion is a measure of a coatings ability to resist a corrosive/acidic environment. It is generally measured on a scale of 0-10. A “0” indicates the coating is completely corroded, observed by bubbling or blistering of the film in all areas. A “10” indicates the coating is unchanged from before it was subjected to the corrosive environment.

Stain

[0208] Stain is a measure of a coating’s ability to resist staining by a media. It is generally measured on a scale of 0-10. A “0” indicates that the coating is completely stained with a complete color change of the film observed in all areas. A “10” indicates 30 that the coloration of the coating is unchanged from before it was subjected to the staining environment.

2020201397 26 Feb 2020

Pencil Hardness

[0209] This test measures the hardness of a cured coating. Pencil hardness was assessed using ASTM D3363, with the test run against metal grain. The data is reported in the form of the last successful pencil prior to film rupture. Thus, for example, if a coating does not rupture when tested with a 2H pencil, but ruptures when tested with a 3H pencil, the coating is reported to have a pencil hardness of 2H.

Metal Exposure

[0210] This test measures the ability of a coated substrate to retain its integrity as it undergoes the formation process necessary to produce a fabricated article such as a beverage can end. It is a measure of the presence or absence of cracks or fractures in the formed end. The end is typically placed on a cup filled with an electrolyte solution. The cup is inverted to expose the surface of the end to the electrolyte solution. The amount of electrical current that passes through the end is then measured. If the coating remains intact (no cracks or fractures) after fabrication, minimal current will pass through the end.

[0211] For the present evaluation, fully converted riveted 202 standard opening beverage ends were exposed for a period of approximately 4 seconds to a room-temperature electrolyte solution comprised of 1% NaCl by weight in deionized water. The coating evaluated was present on the interior surface of the beverage end. Metal exposure was measured using a WACO Enamel Rater II (available from the Wilkens-Anderson Company, Chicago, IE) with an output voltage of 6.3 volts. The measured electrical current, in milliamps, is reported. End continuities were tested initially and then after the ends were subjected to a boiling Dowfax detergent solution (the Dowfax product is available from Dow Chemical) for 60 minutes. After cooling and drying, the milliamps of current passing through the end was measured again.

[0212] Preferred coatings of the present invention initially pass less than 10 milliamps (mA) when tested as described above, more preferably less than 5 mA, most preferably less than 2 mA, and optimally less than 1 mA. After Dowfax, preferred coatings give continuities of less than 20 mA, more preferably less than 10 mA, and even more preferably less than 5 mA.

2020201397 26 Feb 2020

Solvent Resistance

[0213] The extent of “cure” or crosslinking of a coating is measured as a resistance to solvents, such as methyl ethyl ketone (MEK) (available from Exxon, Newark, NJ). This test is performed as described in ASTM D 5402-93. The number of double-rubs (i.e., 5 one back-and forth motion) is reported. This test is often referred to as “MEK

Resistance.”

EXAMPLES

[0214] The following examples are offered to aid in understanding of the present invention and are not to be construed as limiting the scope thereof. Unless otherwise indicated, all parts and percentages are by weight. The constructions cited were evaluated by tests as follows:

Example 1: Diepoxides of Ortho-Substituted Diphenols

Run I: Diglycidyl ether of 4,4’-methylenebis(2,6-di-tert-butylphenol)

[0215] A solution of 4,4’-methylenebis(2,6-di-t-butylphenol) (500 grams, 1.076 moles obtained from Albemarle Corporation) in anhydrous dimethylformamide (1.5 liters) was cooled to -10°C and a solution of sodium /e/7-pentoxide (374 grams, 3.23 moles) in anhydrous dimethylformamide (1.5 liters) was added drop wise at -10 to -5°C. The mixture was stirred for 30 minutes at -10°C. Epichlorohydrin (1.9 liters, 24.2 moles) was added via dropping funnel at -10 to -5°C. The solution was allowed to warm up to room temperature and then was heated for 16 hours at a temperature of from 75 to 82°C. After cooling down to ambient temperature, the mixture was added to cold tap water (12 liters). Ethyl acetate (5 liters) was added to the mixture, which was stirred for 10 minutes and separated. The aqueous layer was extracted again with additional ethyl acetate (3 liters). The combined ethyl acetate extracts were washed twice with brine (2 x

6 liters), dried over anhydrous sodium sulfate (600 grams), and filtered. The solvent was removed under reduced pressure to give 887 grams of crude product as a purple oil. The crude product was dissolved in toluene (600 milliliters) and passed over a silica gel pad (1.4 kilograms), and eluted with a mixture of toluene and heptane (8 parts toluene to 2 parts heptane). The fractions containing product were combined and evaporated under reduced pressure. The product was mostly the desired diepoxidc (756 grams, yellow oil which crystallizes in time), with some monoepoxide present. The purified material (756 grams) was dissolved at 70°C in 2-propanol (2.3 liters) and then allowed to cool down to

2020201397 26 Feb 2020 room temperature overnight. The flask was kept in an ice-water bath for 3 hours, filtered and the solids were washed three times with cold 2-propanol (3 x 400 milliliters). The obtained solid was dried under high vacuum at ambient temperature to give the final product as a white solid (371 grams having an HPLC purity of 95.2%, and a yield of

60%). The epoxy value of the final product was 0.367 equivalents per 100 grams. The resulting diglycidyl ether of 4,4’-methylenebis(2,6-di-t-butylphenol) was tested using suitable genotoxicity assays (e.g., Ames II assay) and was found to be non-genotoxic.

Run II: Diglycidyl ether of 4,4^,Butylidenebis(2-t-butyl-5-methylphenol))

[0216] A 20-gram batch of the diglycidyl ether of 4,4’-butylidenebis(2-t-butyl-510 methylphenol) was prepared by reacting epichlorohydrin with 4,4’-butylidenebis(2-tbutyl-5-methylphenol). Multiple purification steps were required to obtain a suitably pure batch. The purified batch exhibited an epoxy value of 0.402 equivalents per 100 grams. The resulting diglycidyl ether of 4,4^?-butylidenebis(2-t-butyl-5-methylphenol) was tested using suitable genotoxicity assays (e.g., Ames II assay) and was found to be non-genotoxic.

Run III: Diglycidyl ether of 4,4^,-methylenebis(2,6-dimethylphenol)

[0217] 4,4’-Methylenebis(2,6-dimethylphenol) (32 grams, 0.125 moles), epichlorohydrin (140 milliliters, 1.79 moles), and 2-propanol (150 milliliters) were heated to 80°C in an oil bath. Sodium hydroxide (12.5 grams, 0.313 moles) in water (20 milliliters) was added in portions over 5 minutes. The purple solution was heated for 2 hours at 80°C. The mixture was cooled to room temperature, filtered, and concentrated on a rotary evaporator at a temperature of about 30-40°C. The remaining oil was mixed with dichloromethane (50 milliliters) and heptane (100 milliliters) and allowed to stir for 30 minutes at ambient temperature. The salts were removed by filtration and the filtrate was concentrated on a rotary evaporator at 30-40°C. The remaining oil was dried under high vacuum at ambient temperature until a constant weight was obtained. The crude product was crystallized twice from methanol (250 milliliters) and dried under high vacuum at ambient temperature until a constant weight was obtained. The experiment generated diglycidyl ether of 4,4’-methylenebis(2,6-dimethylphenol) (28 grams, 60% yield) as a white solid. The epoxy value was 0.543 equivalents per 100 grams.

[0218] The diphenols used to make the diglycidyl ethers of each of Runs I-III were assayed for estrogenic activity by an outside toxicology laboratory using a suitable assay

2020201397 26 Feb 2020 whose results are known to be directly correlatable to the MCF-7 assay based on common reference compounds.

Example!: Dihydric Phenol Adducts

Run I: Dihydric Phenol Adduct of 1 mole 4,85 Bis(hydroxymethyl)tricyclor5.2.l.Ojdecane with 2 moles of 3-hydroxy benzoic acid [0219] To a 4-neck round-bottom flask equipped with a mechanical stirrer, a watercooled condenser on top of a Dean-Stark Trap, and a thermocouple connected to heating control device and a heating mantle was added 249.24 parts of tricyclodecane dimethanol or “TCDM” (from OXEA), 350.76 parts of 3-hydroxybenzoic acid (from Aldrich), and

0.6 parts of a polymerization catalyst. Stirring and heating was begun over 4 hours until the batch reached 230°C. The batch was heated at 230°C for 4 more hours, at which time about 43 parts of water was collected and the acid value was 2.0 mg KOH/gram. At that time, heating was discontinued until the batch reached 120°C, at which time the batch was discharged. The material was a solid at room temperature that could be broken up.

Run IT: Dihydric Phenol Adduct of 1 mole 4,8Bis(hydroxymethyl)tricyclor5.2.1.01decane with 2 moles of 4-hydroxy phenylacetic acid [0220] To a 4-neck round-bottom flask equipped with a mechanical stirrer, a watercooled condenser on top of a Dean-Stark Trap, and a thermocouple connected to heating control device and a heating mantle was added 235.3 parts of TCDM (from OXEA), 364.7 parts of 4-hydroxy phenyl acid (from Aceto), and 0.65 parts of polymerization catalyst. Stirring and heating was begun over 7 hours until the batch reached 230°C. The batch was heated at 230°C for 8 more hours, at which time a total of 40 parts of water were collected and the acid value was 1.8 milligrams KOH/gram. At that time, heating was discontinued until the batch reached 120°C, at which time the batch was discharged. The material was a tacky semisolid at room temperature.

Run III: Dihydric Phenol Adduct of 1 mole 1,4-Cyclohexanedimethanol (CHDM) with 2 moles of 3-hydroxy benzoic acid

[0221] To a 4-neck round-bottom flask equipped with a mechanical stirrer, a water30 cooled condenser on top of a Dean-Stark Trap, and a thermocouple connected to heating control device and a heating mantle was added 228.6 parts of the CHDM-90 product (90% cyclohexane dimcthanol in water from Eastman), 394.2 parts of 3-hydroxybenzoic

2020201397 26 Feb 2020 acid (from Aceto), and 0.6 parts polymerization catalyst. Stirring and heating was begun over 4 hours until the batch reached 230°C. The batch was heated at 230°C for 8 more hours, at which time 70 parts of water were collected and the acid value was 1.6 milligrams KOH/gram. At that time, heating was discontinued until the batch reached

120°C, at which time the batch was discharged. The material was a solid at room temperature that could be broken up.

Run TV: Dihydric Phenol Adduct of 1 mole 1,4-Cyclohexanedimethanol (CHDM) with 2 moles of 4-hydroxy phenylacetic acid

[0222] To a 4-ncck round-bottom flask equipped with a mechanical stirrer, a water- cooled condenser on top of a Dean-Stark Trap, and a thermocouple connected to heating control device and a heating mantle was added 214.3 parts of the CHDM-90 product, 407.1 parts of 4-hydroxy phenylacetic acid (from Aceto), and 0.6 parts polymerization catalyst. Stirring and heating was begun over 4 hours until the batch reached 230°C.

The batch was heated at 230°C for 6 more hours, at which time 65 parts of water were collected and the acid value was 3.0 milligrams KOH/gram. At this time, heating was discontinued until the batch reached 120°C, at which time the batch was discharged. The material was a solid at room temperature that could be broken up.

Example 3: Poly ether Polymers

[0223] As indicated in the below Table 1,15 different polyether polymers (i.e., Runs 1 to 15) were made by upgrading various diepoxides (“DGE” in Table 1) of Example 1 with various diphenols of Example 2.

[0224] The following general procedure was used to prepare each of the polyether polymers of Runs 1-10 in Table 1: To a 4-neck round-bottom flask equipped with a mechanical stirrer, a water-cooled condenser, and a thermocouple connected to heating control device and a heating mantle was added the diepoxide of Example 1, Run I (i.e., the diglycidyl ether of 4,4’-methylenebis(2,6-di-t-butylphenol)) and a specified amount of a diphenol of Example 2, 0.1% parts CATALYST 1201 polymerization catalyst (from Shell), and an amount of methylisobutylketone (from Ashland) suitable to take the batch to 95 wt-% solids. Stirring and heating was begun until the batch became homogeneous and reached the temperature indicated Table 1. The batch was held at that temperature until the target epoxy value (“EV”) was reached. At that time, heating was discontinued and cyclohexanone (from Ashland) was slowly added until the weight percent solids (or

2020201397 26 Feb 2020 weight percent nonvolatile material) indicated in Table 1 was achieved. The batch was discharged when the temperature was below 70°C. As indicated in the below Table 1, all of polymers Runs 1-10 exhibited good molecular weight build and a high Tg.

[0225] The aforementioned methodology can also be used to formulate polyether polymers using the diepoxides of Example 1, Runs II, III, and IV.

Table 1

<td> Run</td><td> Ex. 1 DGE</td><td> Weight Parts</td><td> Diphenol</td><td> Weight Parts</td><td> Reaction Temp (°C)</td><td> Target EV</td><td> Act. EV</td><td> ** NV</td><td> Mn</td><td> Mw</td><td> Tg (°C)</td>

<td> 1</td><td> Run 1</td><td> 45.3</td><td> Ex. 2, Run I</td><td> 29.7</td><td> 120</td><td> 0.036</td><td> 0.036</td><td> 45.6</td><td> 4280</td><td> 10780</td><td> 91</td>

<td> 2</td><td> Run I</td><td> 44.3</td><td> Ex. 2, Run Π</td><td> 30.7</td><td> 120</td><td> 0.036</td><td> 0.034</td><td> 41.7</td><td> 4240</td><td> 15680</td><td> 82</td>

<td> 3</td><td> Run 1</td><td> 47.4</td><td> Ex. 2, Run ΠΙ</td><td> 27.6</td><td> 120</td><td> 0.036</td><td> 0.032</td><td> 40.4</td><td> 5200</td><td> 15330</td><td> 94</td>

<td> 4</td><td> Run 1</td><td> 46.2</td><td> Ex. 2, Run IV</td><td> 28.8</td><td> 120</td><td> 0.036</td><td> 0.034</td><td> 43.3</td><td> 5560</td><td> 17800</td><td> 82</td>

<td> 5</td><td> Run 1</td><td> 46</td><td> Ex. 2, Run HI</td><td> 29</td><td> 120</td><td> 0.02</td><td> 0.18</td><td> 30.9</td><td> 7380</td><td> 29540</td><td> 99</td>

<td> 6</td><td> Run I</td><td> 45.2</td><td> Ex. 2, Run HI</td><td> 29.8</td><td> 120</td><td> 0.01</td><td> 0.007</td><td> 31.2</td><td> 5870</td><td> 28620</td><td> 97</td>

<td> 7</td><td> Run I</td><td> 145.4</td><td> Ex. 2, Run IV</td><td> 94.6</td><td> 120</td><td> 0.032</td><td> 0.032</td><td> 42.8</td><td> 5230</td><td> 14970</td><td> 80</td>

<td> 8</td><td> Run I</td><td> 142.3</td><td> Ex. 2, Run IV</td><td> 97.7</td><td> 120</td><td> 0.021</td><td> 0.021</td><td> 41.9</td><td> 6460</td><td> 26900</td><td> 82</td>

<td> 9</td><td> Run 1</td><td> 203</td><td> * HQ</td><td> 36.96</td><td> 160</td><td> 0.032</td><td> 0.032</td><td> 40.8</td><td> 4700</td><td> 10650</td><td> 100</td>

<td> 10</td><td> Run I</td><td> 201.8</td><td> Ψ HQ</td><td> 38.2</td><td> 160</td><td> 0.021</td><td> 0.019</td><td> 40.4</td><td> 6100</td><td> 14280</td><td> 105</td>

<td> 11</td><td> Run II</td><td> 339.2</td><td> HQ</td><td> 60.8</td><td> 160</td><td> 0.028</td><td> 0.029</td><td> 40.8</td><td> 5700</td><td> 13280</td><td> 98</td>

<td> 12</td><td> Run II</td><td> 244.5</td><td> Ex. 2, Run IV</td><td> 155.5</td><td> 130</td><td> 0.028</td><td> 0.027</td><td> 41.0</td><td> 3800</td><td> 8320</td><td> 82</td>

<td> 13</td><td> Run II</td><td> 250.8</td><td> Ex. 2, Run HI</td><td> 149.2</td><td> 130</td><td> 0.028</td><td> 0.028</td><td> 40.8</td><td> 6130</td><td> 17570</td><td> 91</td>

<td> 14</td><td> Run III</td><td> 63.2</td><td> * HQ</td><td> 16.8</td><td> 160</td><td> 0.035</td><td> 0.033</td><td> 39.3</td><td> 5400</td><td> 12900</td><td> 95</td>

<td> 15</td><td> Run III</td><td> 41.9</td><td> Ex. 2, Run III</td><td> 38.1</td><td> 130</td><td> 0.029</td><td> 0.023</td><td> 42.2</td><td> 7600</td><td> 48900</td><td> 90</td>

HQ stands for hydroquinone.

**NV stands for wt-% non-volatile material.

Example 4: Coating Compositions

[0226] The polyether polymer composition of Example 3, Run 2 and Example 3, Run 4 were each cut to a non-volatile content of 35 wt-% using cyclohexanone. Then 20 wt-% (solids on solids) of phenolic crosslinker was added, followed by 0.1 wt-% H3PO4 (solids on solids) added as a 10% solution in butanol. Thus, were provided two acid-catalyzed

80:20 polyethecphenolic formulations. The coating composition formulated using

Example 3, Run 2 is referred to herein as Example 4, Run 1, whereas the coating

2020201397 26 Feb 2020 composition formulated using Example 3, Run 4 is referred to herein as Example 4, Run 2.

Example 5: Coated Substrate

[0227] The two coating compositions above, along with an industry standard BPA-based 5 polyether coating composition, were each applied to both 75# tinplate (ETP) and tin-free steel (TFS). The coatings were drawn down with the appropriate-sized wire bars to obtain coatings having a dry-film thickness of 4.5-5.0 milligrams/square-inch (msi). The coated metal samples were then baked for 12 minutes in a 403°F (~206°C) gas-fired oven. 202 sanitary food can ends were formed from the resulting coated plates. Each 10 can end was given a 14-inch-pound reverse impact in the center of the uncoated side of the can end. The can ends were then immersed in two different aggressive food products (i.e., Aggressive Food Products 1 and 2 in Table 2) having an initial temperature of 180°F (82°C) and stored for 2 weeks at 120°F (~49°C). After 2 weeks, the can ends were removed from the food product, rinsed with water, and evaluated for adhesion, corrosion, stain, and blush. The results are shown in Table 2 below. The coating compositions of Example 4 exhibited coating properties equal to or better than that of the industry standard epoxy coating.

Table 2

<td> Coating Composition</td><td> Commercial Control</td><td> Example 4, Run 1</td><td> Example 4, Run 2</td>

<td colspan="3"> ETP</td><td></td>

<td> Aggressive Food Product 1</td><td></td><td></td><td></td>

<td> Adhesion / Blush</td><td> 10/10</td><td> 10/10</td><td> 10/10</td>

<td> Stain / Corrosion</td><td> 10/10</td><td> 10/10</td><td> 10/10</td>

<td> Aggressive Food Product 2</td><td></td><td></td><td></td>

<td> Adhesion / Blush</td><td> 10/10</td><td> 10/10</td><td> 10/10</td>

<td> Stain / Corrosion</td><td> 10/10</td><td> 10/10</td><td> 10/10</td>

<td> TFS</td><td></td><td></td><td></td>

<td> Aggressive Food Product 1</td><td></td><td></td><td></td>

<td> Adhesion / Blush</td><td> 10/10</td><td> 10/10</td><td> 10/10</td>

<td> Stain / Corrosion</td><td> 10/10</td><td> 10/10</td><td> 10/10</td>

<td> Aggressive Food Product 2</td><td></td><td></td><td></td>

<td> Adhesion / Blush</td><td> 10/10</td><td> 10/10</td><td> 10/10</td>

<td> Stain / Corrosion</td><td> 10/9</td><td> 10/10</td><td> 10/10</td>

2020201397 26 Feb 2020

Example 6: Water-Dispersible Polyether Polymers

Run 1:

[0228] To a 4-neck round-bottom flask equipped with a mechanical stirrer, a nitrogen inlet to maintain a nitrogen blanket, a water-cooled condenser, and a thermocouple connected to heating control device and a heating mantle was added 65.34 parts of the diepoxide of Example 1, Run III (i.e., the diglycidyl ether of 4,4’-methylenebis(2,6dimethylphenol), 17.61 parts of hydroquinone, 0.054 parts CATALYST 1201 catalyst (from Shell), 0.305 parts sorbic acid, and 1.96 parts ethyl carbitol. This mixture was heated with stirring to 125°C, allowed to exotherm to 152°C, then heated at 155°C for 4 10 hours until the epoxy value was 0.025 eq/100 g. A water-dispersible polymer was then produced using a mixture of styrene, ethyl acrylate, methylmethacrylate, acrylic acid, and methacrylic acid in combination with a linking compound pursuant to the teachings of U.S. Pat. No. 5,830,952, with the above polyether polymer used in place of the polyether polymer taught in U.S. Pat. No. 5,830,952. The water-dispersible polymer yielded a water-based dispersion having a nonvolatile content of about 40% and an acid value of 15-45 mg KOH/gram.

[0229] The resin was formulated into an aqueous finish in the same fashion as a commercial epoxy polymer based on BPA and BADGE and baked on chrome-treated aluminum substrate for 60 seconds at 465°F (241°C) to a dry film thickness of 7 msi.

The properties of the cured coating including the Example 6, Run 1 resin were similar to that of the commercial epoxy control coating. Table 4 below illustrates some of the coating properties of the Example 6, Run 1 coating relative to the control coating.

2020201397 26 Feb 2020

Table 3

<td rowspan="2"> Coating</td><td colspan="2"> Metal Exposure (milliamps)</td><td colspan="2"> DI Water Retort</td><td rowspan="2"> MEK Double Rubs</td><td rowspan="2"> Pencil Hardness</td>

<td> Before Boiling Dowfax</td><td> After Boiling Dowfax</td><td> Blush (W/V)‘</td><td> Adh. (W/V)‘</td>

<td> BADGE/BPA Control</td><td> 0.2</td><td> 0.9</td><td> 10/10</td><td> 10/10</td><td> 20-50</td><td> 4H</td>

<td> Example 6, Run 1</td><td> 0.1</td><td> 3.1</td><td> 10/10</td><td> 10/10</td><td> 20-50</td><td> 3H</td>

Strips of coated aluminum were placed in a pressure cooker filled with deionized water and processed for 90 minutes at 250°F (121°C). Afterward, the coated strips were rated for blush and adhesion both in the area where the coated strip was immersed in the liquid (“W”) and where the area of the strip was in the vapor phase (“V”).

Run 2:

[0230] To a 4-ncck round-bottom flask equipped with a mechanical stirrer, a nitrogen 5 inlet to maintain a nitrogen blanket, a water-cooled condenser, and a thermocouple connected to heating control device and a heating mantle was added 59.96 parts of the diepoxide of Example 1, Run II (i.e., the diglycidyl ether of 4,4’-butylidenebis(2-t-butyl5-methylphenol)), 0.08 parts CATALYST 1201 catalyst, and 2.22 parts xylene. This mixture was stirred and heated to 130°C and held for 3 hours, at which time the epoxy value was 0.034 equivalents per 100 grams. 25.05 parts of butyl cellosolve were added, followed by 10.53 parts primary amyl alcohol and 14.47 parts n-butanol while the temperature was stabilized at 120°C. A premixture of methacrylic acid, styrene, and benzoyl peroxide was then added while maintaining the temperature. At the end of the addition, the addition device was flushed with butyl cellosolve. After holding at temperature for 2 hours after the end of the feed, deionized water was added and the temperature was stabilized at 90°C. A room-temperature premix of deionized water and dimethylethanol amine was added over time and the batch was held, followed by subsequent additions of deionized water. The resulting water-based dispersion had a nonvolatile content of about 20% and an acid value of 80-120 mg KOH/gram.

[0231] A finish was made by mixing the water-based resin of Example 6, Run 2 with a solution consisting of suitable amounts of phenol-based phenolic resin, t-butyl-phenolbased phenolic resin, and organic solvent. This was followed by an additional let-down of organic solvent and deionized water to yield a spray coating having a # 4 Ford cup

2020201397 26 Feb 2020 viscosity of 20 seconds and a nonvolatile content of about 20%. This water-based finish was sprayed on drawn and ironed ETP food cans and baked for 3.5 minutes at 425°F (218°C), yielding a cured coating having a dry film weight of 275 milligrams per can. When tested against a similar BADGE/BPA-based control coating, the coating properties of the coating formulated using the Example 6, Run 2 resin were similar, including corrosion resistance.

Example 7- Preparation of solid resin from advancement of diglycidvl ether with hydroquinone

[0232] A reaction flask equipped with a mechanical stirrer, thermocouple, nitrogen inlet 10 and vacuum outlet was charged with 900.0 parts of the diglycidyl ether described in

Example 1, Run II, having a titrated epoxy value of 0.376 (epoxide equivalent wcight=266) (3.383 equivalents). The contents were gently heated under nitrogen blanket until completely melted, then agitation was started and 0.80 parts of ethyltriphenylphosphonium iodide catalyst were added, followed by 124.0 parts of hydroquinone (2.252 equivalents). Heating was continued under a reduced pressure of approximately 50 torr (to reduce the level of residual moisture or other volatiles) to a temperature of 130°C, then heating was continued under atmospheric pressure. When the temperature reached 140°C, external heating was discontinued and the reaction was allowed to exotherm. Over a period of approximately 25 minutes, the reaction temperature increased to a peak exotherm temperature of 181°C. The contents were held for an additional 90 minutes at 180°C, then discharged to shallow aluminum pans and allowed to cool to form a friable solid. The product gave a titrated epoxide equivalent weight of 952 (theoretical target^ 907), and a melt viscosity of 19.3 P (150°C, 900 RPM, Brookfield CAP 2000).

Example 8- Preparation of the bis(3-hvdroxybenzoate) of Cyclohexanedimethanol [0233] A reaction flask equipped with mechanical stirrer, thermocouple, nitrogen inlet, and a Dean-Stark trap under a reflux condenser was charged with 259.6 parts of 1,4-cyclohexanedimethanol (CHDM, 1.8 mol). Agitation was started under a nitrogen blanket, and 497.2 parts of 3-hydroxybenzoic acid (3.6 mol), 3.4 parts of p-tolucncsulfonic acid monohydrate (0.018 mol), and 200 parts of xylene were successively added. The contents were heated gradually to reflux and the water of esterification was collected as a lower layer in the Dean-Stark trap. After approximately

2020201397 26 Feb 2020 hours at 145-150°C, approximately 94% of the theoretical quantity of water had been collected, and additional collection of water in the trap had ceased. The bulk of the xylene was removed at ambient pressure, and then vacuum was gradually applied while holding the product at 150°C. When only minimal evolution of volatiles was observed at 5 approximately 50 torr, the product was discharged into a shallow aluminum pan and allowed to cool to ambient temperature.

Example 9- Preparation of Solid Resin from Advancement of Diglycidyl Ether with the bis(3-hydroxybenzoate) of CHDM

[0234] A reaction flask equipped with mechanical stirrer, thermocouple, nitrogen inlet, 10 and vacuum outlet was charged with 750.0 parts of the diglycidyl ether described in

Example 1, Run II having a titrated epoxy value of 0.376 (epoxide equivalent wcight=266) (2.819 epoxide equivalents), followed by 315.0 parts of the bis(3hydroxybenzoate) of CHDM which was prepared according to the procedure of Example 8 (calculated theoretical phenolic equivalent weight of 192.2) (1.639 equivalents), and 15 1.30 parts of ethyltriphenylphosphonium iodide catalyst. The contents were gradually heated until fully melted at about 90°C, then agitation was started and the pressure was reduced to approximately 50 torr in order to remove residual volatiles. Heating was continued to a temperature of 140°C, at which point external heating was discontinued. The reaction was allowed to exotherm, and the vacuum was broken once the temperature 20 reached 145°C. The exotherm continued over the course of approximately 30 minutes to a peak temperature of 158°C. The temperature set-point was increased to 160°C and the product was held for an additional 2 hours before discharge. The final product gave a titrated epoxide equivalent weight of 1016 (theoretical target 903) and a melt viscosity of 39.0 P (150°C, 900 RPM, Brookfield CAP 2000).

Examples 10-12- Preparation of Powder Coatings

[0235] The solid resins from Examples 7 and 9 were broken into smaller flake size using a high-intensity paddle mixer (Reos Incorporated, Cleveland, Ohio) for two cycles of 10 seconds each at approximately 1,000 revolutions-per-minute (“RPM”). The resins were then combined with the additional ingredients listed in Table 4. The composition shown 30 in Example 10 is a comparative example based upon a conventional commercially available BPA-based epoxy resin. All quantities in Table 4 are expressed in parts by weight.

2020201397 26 Feb 2020

Table 4

<td> Ingredient</td><td> Comparative Example 10</td><td> Example 11</td><td> Example 12</td>

<td> Epon 2004</td><td> 900.0</td><td></td><td></td>

<td> Epoxy Upgrade from Example 7</td><td></td><td> 900.0</td><td></td>

<td> Epoxy Upgrade from Example 9</td><td></td><td></td><td> 900.0</td>

<td> DYHARD 100S</td><td> 27.0</td><td> 27.0</td><td> 27.0</td>

<td> 2-methylimidazole</td><td> 2.0</td><td> 2.0</td><td> 2.0</td>

<td> ESCAT 60</td><td> 10.0</td><td> 10.0</td><td> 10.0</td>

<td> RESIFLOW PF-67</td><td> 13.0</td><td> 13.0</td><td> 13.0</td>

<td> R2899 Red Iron Oxide</td><td> 42.0</td><td> 42.0</td><td> 42.0</td>

<td> VANSIL W-20</td><td> 325.0</td><td> 325.0</td><td> 325.0</td>

[0236] Further explanation of certain ingredients included in Table 4 is provided below.

EPON 2004 is a conventional BPA-based epoxy resin available from Hexion, Columbus, 5 OH. Dyhard 100S is a micronized grade of dicyandiamide treated with silica dry flow agent, available from Alzchcm, Trostberg, Germany. Dyhard MI is a micronized form of 2-methylimidazole available from Alzchem. Resiflow PF-67 is a polyacrylate flow control agent available from Estron Chemical, Calvert City, KY. Escat 60 is an alkyl imidazole on a silica carrier, available from Estron chemical, Calvert City, KY. R2899

Red Iron Oxide was obtained from Rockwood Pigments, Beltsville, MD. Vansil W-20 is a wollastonite pigment available from R.T. Vanderbilt Company, Norwalk, CT.

[0237] The ingredients in Table 4 were dry blended in a Reos high-intensity paddle mixer for two cycles of ten seconds each at approximately 1000 RPM. After dry blending, the samples were extruded in a Coperion ZSK-30 extruder operating at approximately 200 RPM with temperature set points of 90°C in zone 1 and 110°C in zone 2. The extrudate was discharged through chilled rollers, and the resulting solid flake was ground in a Mikropul Bantam laboratory mill and then sieved through a 94 mesh screen.

2020201397 26 Feb 2020

[0238] Samples of the finished powder coatings were electrostatic sprayed at approximately 70 kilovolts onto 0.5 mm thick cold rolled steel panels and baked for 30 minutes at 220°C. Film properties were as shown in Table 5. The test method for impact resistance can be found in ASTM D2794.

Table 5

<td> Test</td><td> Comparative Example 10</td><td> Example 11</td><td> Example 12</td>

<td> Adhesion</td><td> 9</td><td> 9</td><td> 10</td>

<td> Pencil Hardness</td><td> 3H</td><td> 3H</td><td> 3H</td>

<td> Impact Resistance (direct)</td><td> 80 inch-pounds</td><td> 80 inch-pounds</td><td> 80 inch-pounds</td>

<td> Solvent Resistance (MEK Double Rubs)</td><td> 50</td><td> 20</td><td> 50</td>

Example 13: Powder Coating Composition

[0239] The powder compositions as described in Examples 10-12 are repeated except the dicyandiamide is increased to 36 parts and the accelerators are replaced with triphenyl phosphine.

Example 14: Powder Coating Composition

[0240] The powder compositions as described in Examples 10-12 are repeated except the dicyandiamide is increased to 36 parts and the accelerators are replaced with Curezol C17Z accelerator (available from Air Products, Allentown, PA).

[0241] The complete disclosure of all patents, patent applications, and publications, and electronically available material cited herein are incorporated by reference. The foregoing detailed description and examples have been given for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described, for variations obvious to one skilled in the art will be included within the invention defined by the claims. The invention illustratively disclosed herein suitably may be practiced, in some embodiments, in the absence of any element which is not specifically disclosed herein.