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    • 专利摘要:
    ITEM, METHOD, AND, COATING COMPOSITION. The present invention provides a polymer that is useful in a variety of applications, including as a polymer binder in a coating composition, and especially a coating composition for packaging. Packaging articles (e.g., containers) comprising the polymer and methods of making such packaging articles are also disclosed.
    公开号:BR112012026240A2
    申请号:R112012026240-8
    申请日:2011-04-15
    公开日:2020-07-28
    发明作者:Richard H. Evans；Jeffrey Niederst；Robert M. O'Brien；Benoit Prouvost；Kevin Romagnoli；Grant Schutte；Paul Stenson；Tom Van Kuren
    申请人:Valspar Sourcing, Inc.；
    IPC主号:
    专利说明:

    “ARTICLE, METHOD, AND, COATING COMPOSITION”
    CROSS-REFERENCE TO RELATED ORDER This application claims the benefit of US provisional application serial number 61/324,997, filed April 16, 2010 and titled —"COATING COMPOSITIONS FOR CONTAINERS AND METHODS OF COATING", and US provisional application number No. 61/333,133, filed May 10, 2010 and titled "COATING COMPOSITIONS FOR CONTAINERS AND METHODS OF COATING", each of which is incorporated herein by reference in their entirety.
    FUNDAMENTALS The application of coatings to metals to delay 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 these containers to prevent the contents from coming into contact with the metal of the container. Contact between 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 inside of food and beverage containers to prevent corrosion in the container headspace between the food product fill line and the container lid. Packaging coatings preferably need to be capable of high speed application to the substrate, in addition to providing the necessary properties, when hardened, to perform well for this demanding purpose. For example, the coating should preferably be safe for food contact, should not adversely affect the flavor of the packaged food or beverage, have excellent adhesion to the substrate, resist staining and other coating defects such as "pops", "blushing", " and/or "bubbling", and resist degradation over long periods of time, even when exposed to harsh environments. In addition, the coating generally needs to be able to maintain adequate film integrity during manufacture of the container, and be able to withstand the processing conditions to which the container may be subjected during the product packaging process.
    Various coatings have been used as internal protective coatings for cans, including polyvinyl chloride-based coatings and epoxy-based coatings incorporating bisphenol A ("BPA"). Each of these types of coating, however, has potential disadvantages. For example, recycling of materials containing polyvinyl chloride or related halide-containing 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.
    What the market needs is an improved binder system for use in coatings such as packaging coatings.
    SUMMARY This invention provides a coating composition useful in coating a variety of substrates, including metallic substrates of packaging articles. In preferred embodiments, the coating composition is useful for coating one or more external or internal surfaces of a food or beverage container, or a portion thereof, including the interior of food-contacting surfaces.
    In preferred embodiments, the coating composition includes an effective amount (e.g., a film-forming amount) of a polymer, preferably a polyether polymer, which is free of structural units derived from bisphenol A ("BPA'"). or BPA diglycidyl ether ("BADGE"). In certain preferred embodiments, the polymer: (1) has a glass transition temperature ("Tg") of at least 70°C, and more preferably 70 to 150°C, and/or (ii) includes at least one, and most preferably a plurality of polycyclic groups. In some embodiments, the polymer has a Tg of at least 70°C and includes one or more polycyclic groups. In addition, the polymer preferably includes one or more segments of Formula I below: -O-Ar- (R 1 -Ar), -O-, OD wherein: each Ar is independently an aryl or heteroaryl group (typically a arylene or divalent heteroarylene group), each n is independently O or 1, R, if present, is a divalent organic group, and the two oxygen atoms shown in Formula I are preferably each an ether oxygen.
    In some embodiments, the polyether polymer may have a Tg of less than 70°C, for example, if the coating composition is intended for use on an external surface of a food or beverage container or is intended for use in packaging food products. food or drink that is not chemically aggressive.
    The R in Formula 1, when present, may vary depending on what is particularly required of the polymer. In some embodiments, R is preferably a group other than -C(CH; 3 );-. In some embodiments, R includes one or more quaternary carbon atoms, which may optionally be present in a cyclic group. In such an embodiment, R includes a cyclic group, more preferably a six-membered carbon ring (e.g., a substituted or unsubstituted cyclohexane group, which is preferably divalent), most preferably a ring of six-element carbon in which a ring carbon atom is a quaternary carbon atom present in a chain linking the pair of Ar groups. In some embodiments (for example, where the segment of Formula 1 is derived from 1,1 -bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-di(4-hydroxyphenyl)-cyclohexane, or a substituted variant thereof), the quaternary carbon atom of the group cyclic can be directly attached to a carbon atom of each Ar group.
    In preferred embodiments, the polymer includes secondary hydroxyl groups, and more preferably one or more -CH 1 -CH(OH)-CH 2 - segments, which are preferably derived from an ethylene oxide.
    The coating compositions of the present invention preferably include at least a film-forming amount of the polymer described herein and may optionally include additional ingredients such as, for example, an optional carrier and/or an optional crosslinker. If desired, the polymer and coating composition can be formulated to be suitable for use as a coating for a 15" food contact package. It is also contemplated that the coating composition may have utility in a variety of coating uses. end outside the food or beverage packaging coating industry.
    In one embodiment, the present invention provides a container that includes a food contact surface, wherein at least a portion of the food contact surface is coated with a coating composition described herein.
    In one embodiment, a method of preparing a container is provided that includes a substrate having a food contact surface. The method includes: providing a coating composition described herein, which preferably includes a liquid carrier, and applying the coating composition to at least a portion of the food contact surface of the substrate before or after forming the substrate into a container. Typically, the substrate is a metallic substrate.
    In one embodiment, a method for forming a food or beverage can, or a portion thereof, is provided, which includes: applying a coating composition described herein to a metallic substrate (e.g., applying the composition to the metallic substrate in the form of a coil or flat sheet), curing the composition, and forming the substrate into a food or beverage can, or a portion thereof.
    In certain embodiments, forming the substrate in an article includes forming the substrate at an end of the can or a body of the can. In certain embodiments, the article is a two-piece stretched food can, a three-piece food can, one end of a food can, a closure system for a food or beverage container, a food or beverage can. stretched and smoothed, one end of a beverage can, and the like. Suitable metallic substrates include, for example, steel or aluminum.
    In certain embodiments, the coating composition is substantially free of BPA and mobile and/or bonded BADGE. More preferably, the coating composition is completely free of BPA and BADGE.
    The above summary of the present invention is not intended to describe each disclosed embodiment or each implementation of the present invention. The following description more particularly exemplifies the illustrative embodiments. At various points throughout this application, guidance is provided through lists of examples, examples of which may be used in various combinations. In each case, the reported list serves only as a representative group and should not be interpreted as an exclusive list.
    DEFINITIONS For use in the present invention, the term "organic group"
    means a substituted or unsubstituted 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 a combination of aliphatic and cyclic groups (eg example, alkaryl and arylalkyl groups). A 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 "portion" are used to differentiate chemical species that allow substitution or that can be substituted, and those that do not or may not. be replaced.
    Thus, when the term "group" is used to describe a chemical substituent, the chemical material described includes the unsubstituted group and the group with O, N, Si, or S atoms, for example, in the chain (such as in an alkoxy group) as well as -carbonyl or other conventional substitution groups.
    When the term "moiety" is used to describe a chemical compound or substituent, only an unsubstituted chemical material must be included.
    For example, the phrase "alkyl group" is intended to include not only pure open-chain saturated alkyl hydrocarbon substituents such as methyl, ethyl, propyl, t-butyl, and the like, but also alkyl substituents containing additional substituents known in the art. technique, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc.
    Thus, "alkyl group" includes ether, haloalkyl, nitroalkyl, carboxy alkyl, hydroxy alkyl, sulfoalkyl, etc. groups.
    On the other hand, the phrase "alkyl moiety" is limited to the inclusion only of pure open-chain saturated alkyl hydrocarbon substituents such as methyl, ethyl, propyl, t-butyl, and the like.
    For use in the present invention, the term "group" is intended to refer to both the specific portion and the broader class of substituted and unsubstituted structures that includes the portion.
    The term "cyclic group" means a closed-ring organic group which is classified as an alicyclic group or an aromatic group, both of which may include heteroatoms.
    The term "alicyclic group" means a cyclic organic group that has properties reminiscent of those of aliphatic groups.
    The term "polycyclic" when used in the context of a group refers to an organic group that includes at least two cyclic groups in which one or more atoms (and, more typically, two or more atoms) are present in the rings of both at least two cyclic groups. Thus, for example, a group consisting of two cyclohexane groups connected by a single methylene group is not a polycyclic group.
    The term "tricyclic" group refers to a polycyclic group that includes three cyclic groups in which the ring of each cyclic group shares one or more atoms with one or both rings of other cyclic groups.
    The term "Ar" refers to a divalent aryl group (e.g., an arylene group), which refers to an aromatic or closed-ring ring system such as phenylene, naphthylene, biphenylene, fluorenylene, and indenyl, as well as heteroarylene groups (i.e., a closed aromatic or hydrocarbon-like aromatic ring or a 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, tetrazoyl, 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 called "arylene" or "heteroarylene" groups (e.g. furylene, pyridylene, etc.)
    A group that can be the same or different is called an "independently" something.
    The term "polyhydric phenol", for use in the present invention, broadly refers to any compound that has at least two groups -total hydroxylan, each attached to one or more rings of one or more aryl or heteroaryl groups, plus typically one or more phenylene groups. Thus, for example, hydroquinone and 4,4'-biphenol are both considered to be polyhydric phenols. For use in the present invention, polyhydric phenols typically have six carbon atoms in an aryl ring, although it is contemplated that aryl or heteroaryl groups that have rings of other sizes may be used.
    The term "phenylene", for use in the present invention, refers to an aryl group of six carbon atoms (e.g., as in a benzene group) that may have any substituent groups (including, for example, hydrogen atoms, halogens, hydrocarbon groups, oxygen atoms, hydroxyl groups, etc.). Thus, for example, the following aryl groups are each phenylene rings: -C'Hy-, -C'H3(CH;3) -, and -CsH(CH;3),Cl-. Also, for example, each of the aryl rings of a naphthalene group are phenylene rings.
    The term "substantially free" of a particular mobile compound means that said polymer and/or composition contains less than 100 parts per million (ppm) of said mobile compound. The term "essentially free" of a particular mobile compound means that said polymer and/or composition contains less than 5 parts per million (ppm) of said mobile compound. The term "completely free" of a particular mobile compound means that said polymer and/or composition contains less than 20 parts per billion (ppb) of said mobile compound.
    The term "mobile" means that the compound can be extracted from the cured coating when a coating (typically -1 mg/cm° (6.5 mg/in ) of thickness) is exposed to a test medium for some defined set of conditions. , depending on the purpose. An example of these test conditions is exposing the cured coating to HPLC grade acetonitrile for 24 hours at 25°C. If the above phrases are used without the term "mobile" (e.g. "substantially BPA free"), then the aforementioned 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.
    The term "crosslinker" refers to a molecule capable of forming a covalent bond between polymers or between two different regions of the same polymer.
    The term "on", when used in the context of a coating applied to a surface or substrate, includes coatings applied directly or indirectly to the surface or substrate. Thus, for example, a coating applied to a primer layer covering a substrate constitutes a coating applied to the substrate.
    Unless otherwise noted, the term "polymer" includes both homopolymers and copolymers (ie, polymers of two or more different monomers). Similarly, unless otherwise noted, use of a term designating a polymer class, such as "polyether", is intended to include both homopolymers and copolymers (e.g., polyether-ester polymers).
    The terms "comprises" and variations thereof do not have a limiting meaning when such terms appear in the description and claims.
    The terms "preferred" and "preferred" refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other modalities may also be preferred, under the same or different circumstances. Furthermore, mention 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.
    For use in the present invention, "a", "an", "the", "a", "at least one", "at least one", "one or more" and "one or more" are used interchangeably . Therefore, for example, a coating composition comprising "a" polyether can be interpreted to mean that the coating composition includes "one or more" polyethers.
    In the present invention, references to extreme number ranges include all numbers contained within this range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.) . Also, the description of a range includes the description of all sub-ranges included in the wider range (for example, | to 5 shows 1 to 4, 1.5 to 4.5, 1 to 2, etc.).
    DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS This invention provides a polymer that preferably has: (1) a Tg of at least 70°C and/or (11) one or more polycyclic groups. In preferred embodiments, the polymer is a polyether polymer. For convenience, the polymer of the present invention will be referred to hereinafter as a polyether polymer.
    The polyether polymer may have utility in multiple different end uses. In preferred embodiments, the polyether polymer is particularly useful as a binder polymer for a coating composition. Thus, in another aspect, the present invention provides a coating composition that preferably includes at least a film-forming amount of the polymer. While any suitable curing mechanism can be used, thermosetting coating compositions are preferred. Preferred coating compositions include one or more liquid carriers and are water-based and/or solvent-based coating compositions. While coating compositions that include a liquid carrier are currently preferred, it is contemplated that the polyether polymer may have utility in other coating application techniques such as, for example, powder coating.
    In preferred embodiments, the coating composition of the present invention is suitable for use as a cling wrap coating and, more preferably, as a coating on an inner and/or outer surface of a food or beverage container. Thus, in certain preferred embodiments, the coating composition is suitable for use as a food contact liner. It is also within the scope of the present invention to use the coating composition in drug-contacting packaging applications, for example, on an inner surface of a metal can of a metered-dose inhaler.
    In preferred embodiments, the polyether polymer preferably includes one or more secondary hydroxyl groups attached to a polymer backbone, and more preferably a plurality of such groups. In preferred embodiments, the backbone includes one or more -CH 2 -CH(OH)-CH 2 - segments, which are preferably derived from an ethylene oxide group. For example, such segments can be formed by reacting an ethylene oxide group with a hydroxyl group (more preferably, a hydroxyl group of a polyhydric phenol).
    If desired, the polyether polymer backbone may include stepwise growth or condensation bonds in addition to ether bonds (i.e., in addition to or in place of ether bonds) such as, for example, amide bonds, carbonate bonds, ester bonds, urea bonds, urethane bonds, etc. In some embodiments, the backbone includes both ester and ether bonds.
    In order to have a suitable balance of coating properties for use as a food contact coating, including adequate corrosion resistance when in prolonged contact with — packaged food or beverage products, the polyether polymer preferably has a temperature of glass transition ("Tg") of at least 60°C, more preferably at least 70°C, and most preferably at least 80°C. In preferred embodiments, the Tg is less than 150°C, more preferably less than 130°C, and most preferably less than 110°C. Without being bound by any theory, it is believed that it is especially 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 high temperature retort processing (e.g. (e.g. at temperatures greater than or equal to about 100°C, and sometimes accompanied by pressures above atmospheric pressure), and particularly when retorting products that have a more chemically aggressive nature. It is contemplated that in some embodiments, for example where the coating composition is intended for use as an external varnish on a food or beverage container, the Tg of the polymer may be less than described above (eg for example, as low as about 30°C) and the coating composition may still have an adequate balance of end-use properties.
    Preferred polyether polymers may have a backbone that includes any suitable end groups, including, for example, epoxy and/or hydroxyl groups (e.g., a hydroxyl group attached to a terminal aryl or heteroaryl group). Polymers can be produced in a variety of molecular weights. Preferred polyether polymers have a number average molecular weight ("Mn") of at least
    2,000, more preferably at least 3,000, and most preferably at least 4,000. The molecular weight of the polymer can be as high as necessary for the desired application. Depending on the particular embodiment, the polyether polymer can be amorphous or at least semi-crystalline.
    The polyether polymer may include branching if desired. In preferred embodiments, however, the polyether polymer is a linear or substantially linear polymer.
    In preferred embodiments, the polyether polymer includes a plurality of aryl or heteroaryl groups, with divalent aryl groups currently being preferred. Phenylene groups are particularly preferred. Aryl and/or heteroaryl groups may be present in the polymer in one or more segments of Formula I above, one or more other segments, or a combination thereof. In some embodiments, the polymer can be formed by reacting ingredients that include one or more of: (1) a polyepoxide that has one or more aryl or heteroaryl groups, (11) a polyhydric phenol that has one or more groups aryl or heteroaryl, or (111) a comonomer having one or more aryl or heteroaryl groups.
    Without being bound by any theory, it is believed that the inclusion of a sufficient number of aryl and/or heteroaryl groups in the polyether polymer is an important factor in achieving adequate coating performance for food contact coatings, especially when the product to be packaged is a so-called "hard to contain" food or beverage product. Sauerkraut (sauerkraut) is an example of a product that is difficult to contain. In preferred embodiments, aryl and/or heteroaryl groups constitute at least 20 percent by weight ("% by weight,"), more preferably at least 30% by weight, and most preferably at least 45% by weight of the polymer. , based on the total weight of aryl and heteroaryl groups in the polymer relative to the weight of the polymer. The maximum concentration of aryl/heteroaryl groups is not particularly limited, but preferably the amount of such groups is configured such that the Tg of the polymer does not exceed the Tg ranges discussed above. The total amount of aryl and/or heteroaryl groups in the polymer will typically constitute less than about 80% by weight, more preferably less than about 70% by weight, and most preferably less than 60% by weight of the polymer from polyether. The total amount of aryl and/or heteroaryl groups in the polymer can be determined based on the weight of the aryl or heteroaryl-containing monomer incorporated into the polymer and the weight fraction of such monomer that constitutes the aryl or heteroaryl groups.
    In preferred embodiments, the polyether polymer includes one or more segments (and more preferably, a plurality) of Formula I below: -O-Ar- (R 1 -Ar), -O-OD wherein: and each Ar is independently an aryl group (e.g. an arylene group) or a heteroaryl group (e.g. a heteroarylene group), and each is independently O or 1, and R, if present, is a divalent organic group, with the proviso that in In certain embodiments, R is preferably a group other than -C(CH;3)x-, and each of the two oxygen atoms shown in Formula [ is preferably ether oxygen (as opposed, for example, to an —oxygen from an ester bond).
    In Formula 1, each Ar preferably has less than 20 carbon atoms, more preferably less than 11 carbon atoms, and even more preferably less than 8 carbon atoms. Preferably, each Ar has at least 4 carbon atoms, more preferably at least 5 carbon atoms, and most preferably at least 6 carbon atoms. In certain embodiments, each Ar is a phenylene group. In certain embodiments, each Ar is a phenylene group of the following formula -C(R')1-, wherein each R' is independently hydrogen, a halogen, or an organic group, and wherein two R' groups can be joined. to form an organic ring which may optionally contain one or more heteroatoms. Preferably, each R' is hydrogen.
    The molecular weight of R in Formula I may be any suitable molecular weight. In certain preferred embodiments, R has a molecular weight of less than 500, less than 200, less than 150, or less than
    100. In some embodiments, R has a molecular weight greater than that of a -C(CH;3);- group, or greater than 75. In some embodiments, the R of Formula I includes one or more cyclic groups (such as, for example, one or more alicyclic groups (which may optionally include heteroatoms), aryl, and/or heteroaryl)). In some embodiments, the R of Formula I does not include one or both of: ester bonds or other gradually growing bonds (eg, condensation bonds). In some embodiments, R includes a divalent cyclic group of structure —CAR), wherein: (1) q is from 2 to 10, more typically from 6 to 10, even more typically from 8 to 10, and most typically still 10, and (ii) each Rº is independently hydrogen, a halogen, or an organic group (eg, an alkyl group such as a methyl group, ethyl group, propyl group, etc.) and two R groups can join together to form a ring. The one or more cyclic groups may be present in a chain connecting the two Ar groups of the —Formula or a pendant group attached to the chain. Typically, the total number of atoms in the chain connecting the two Ar groups (not counting any hydrogen or substituent atoms attached to the chain) is less than 10, more typically less than 6, even more typically less than 3, and in some embodiments, 1. In some embodiments, all atoms in the chain connecting the two Ar groups are carbon atoms.
    In some embodiments, the R of Formula I includes at least one carbon atom in a chain connecting the two groups Ar which is at least one tertiary carbon atom, and more preferably a quaternary carbon atom. In such embodiments, the R of Formula I is a segment having the following structure: -(X), -C(R5)-(X),-, wherein: each X is independently a divalent organic group, which may include, optionally, one or more heteroatoms (e.g. O, N, S, Si), each R is independently a hydrogen, a halogen, or an organic group, and wherein (i) at least one Ri group (and more preferably both R groups ) is an organic group having at least one carbon atom and (ii) two R° groups may join together to form a ring, for example a six-membered ring (for example, a six-membered carbon ring which may be saturated or unsaturated, more typically, saturated). A preferred example of such a ring group is a substituted or unsubstituted cyclohexane group (e.g. -Cs(R2)1o- wherein: each R' is independently as previously described, and two R' groups may join to form a ring).
    Currently preferred materials for forming a segment of Formula I with an R having a quaternary carbon atom include 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1- di(4-hydroxyphenyl)-cyclohexane, 1,1-di(4-hydroxy-3-methylphenyl)-cyclohexane, 1,1-di(4-hydroxy-3,5-dimethylphenyl)-cyclohexane , — variants — substituted — thereof, and diepoxides thereof, whose structures are shown below.
    1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane
    E 1,1-di(4-hydroxyphenyl)-cyclohexane HO' | | oH 1,1-di(4-hydroxy-3-methylphenyl)-cyclohexane HO' oH 1,1-di(4-hydroxy-3,5-dimethylphenyl)-cyclohexane.
    In certain preferred embodiments, the polyether polymer includes one or more of the above segments of Formula 1, wherein: each n is 1 and R includes one or more polycyclic groups.
    In another embodiment, R does not include a polycyclic group and the one or more polycyclic groups are either not present in the polymer or included in different segments of the polymer.
    In preferred embodiments, the polyether polymer includes a plurality of segments of Formula 1, which are preferably dispersed throughout the polymer backbone, more preferably a polyether backbone.
    In preferred embodiments, the segments of Formula I constitute a substantial portion of the general structural units of the polymer.
    Typically, the segments of Formula I constitute by weight at least 10% by weight, preferably at least 30% by weight, and most preferably at least 40% by weight of polymer.
    The weight percentage of the segments of Formula I in the polyether polymer may, in certain situations, be below the proportions mentioned above, and may even be substantially below. By way of example, the concentration of the segments of Formula I may be outside the ranges mentioned above if the polyether polymer includes a broad molecular weight of additional components, as may occur, for example, when the polymer is a copolymer such as a copolymer containing acrylic (for example, an acrylic polyether copolymer formed by grafting acrylic onto a polyether polymer of the present invention). In such embodiments, the weight percentage of the Formula I segments present in the polymer is as described above, based on the weight percentage of the Formula I segments relative to the total polyether fraction of the polymer (not considering the total weight of the portions of non-polyether such as, for example, the acrylic portions). In general, the total polyether fraction of the polymer can be calculated based on the total weight of the polyepoxide and polyhydric phenol reactants (e.g., polyhydric monophenols and/or diphenols) incorporated into the polymer.
    Any suitable reagents can be used to form the polyether polymer. In preferred embodiments, the polyether polymer is a reaction product of reactants including a polyepoxide compound (i.e., a compound having two or more ethylene oxide groups) and a polyhydric phenol. The polyether polymer is typically a reaction product of one or more diepoxide compounds reacted with one or more dihydric phenol compounds.
    Examples of dihydric phenols suitable for use in forming a polyether polymer include compounds of Formula II below: HO-Ar-(R,;-Ar),-OH, - (ID where Ar, R, and n are as defined above for the Formula I.
    Thus, in some embodiments, compounds of Formula II can be used to incorporate segments of Formula I into the polymer of the invention.
    Examples of suitable dihydroxy phenols of Formula II include hydroquinone, catechol, resorcinol, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-di(4-hydroxyphenyl) -cyclohexane, 1,1-di(4-hydroxy-3-methylphenyl)-cyclohexane, 1,1-di(4-hydroxy-3,5-dimethylphenyl)-cyclohexane, dihydroxynaphthalene, 4 ,4º-biphenol, diphenol compounds of Formula III below, or a mixture thereof.
    The polyether polymers of the present invention can be prepared by methods that involve advancing the molecular weight of the compounds of Formula II.
    In certain embodiments, compounds of Formula II can be reacted with a polyepoxide (more preferably a diepoxide) to advance molecular weight.
    For example, compounds of Formula II can be reacted with non-BPA-based diepoxides to form polyether polymers preferably having backbone-attached secondary hydroxyl groups that can be formulated with crosslinkers and coating additives for rigid packaging.
    Alternatively, compounds of Formula II can be reacted with epichlorohydrin to form a diepoxide analog of compounds of Formula II, which can then be reacted with other compounds of Formula II to form a polymer that includes -CH;-CH(OH)- segments. CH;-. By way of example, a polyether polymer of the present invention can be formed by reacting 1,1-di(4-hydroxyphenyl)-cyclohexane (or a substituted variant thereof) with a 1,1-di (4-hydroxyphenyl)-cyclohexane (or a substituted variant thereof). Conditions for such reactions are generally carried out using standard techniques which are known to the person skilled in the art, or which are exemplified in the Examples Section.
    Any suitable technique can be used to produce diepoxide analogs of the compounds of Formula II. For example, diepoxide analogues (e.g., glycidyl ethers or esters of dihydric phenols) can be prepared by reacting required proportions of a compound of Formula II (e.g., dihydric phenol) and epichlorohydrin in an alkaline medium. . The desired alkalinity is typically obtained by adding basic substances such as sodium or potassium hydroxide, preferably in stoichiometric excess with respect to the epichlorohydrin. The reaction is preferably achieved at temperatures from 50°C to 150°C. Heating is typically continued for several hours to affect the reaction and the product is —then washed to remove salt and base. Procedures for such reactions are generally well known and shown, for example, in the US patent.
    2,633,458.
    For use in the present invention, preferred diepoxides are BPA-free diepoxides, preferably with one or more ether linkages, and more preferably BPA-free diglycidyl ether compounds. Also within the scope of the invention is the use of BPA-free diglycidyl ester compounds. Examples of suitable diepoxides for use in forming a polyether polymer include diepoxide analogues of compounds of FormulaII above. Examples of such compounds include: the diglycidyl ester or diglycidyl ether of: hydroquinone, catechol, resorcinol, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, — 1,1-di( 4-hydroxyphenyl)-cyclohexane, — 1,1-di(4-hydroxy-3-methylphenyl)-cyclohexane, — 1,1-di(4-hydroxy-3,5-dimethylphenyl)-cyclohexane , dihydroxynaphthalene, 4,4'-biphenol, or a mixture thereof), 1,4-cyclohexane dimethanol diglycidyl ether (CHDMDGE), diglycidyl phthalic ester, diglycidyl terephthalic ester, diglycidyl isophthalic ester, diglycidyl ester hexahydrophthalic, neopentyl glycol diglycidyl ether, 2-methyl-1,3-propandiol diglycidyl ether, tetramethyl cyclobutanediol diglycidyl ether (e.g. 1,3-dihydroxy-2,2,4,4,tetramethyl cyclobutane), tricyclodecane dimethanol diglycidyl ether, diepoxides derived from the compound of Formula III below, diepoxides derived from the compound of Formula VI below, or derivatives or mixtures thereof.
    If desired, one or more comonomers and/or co-oligomers may be included in the reagents used to generate the polymer of the invention.
    Some non-limiting examples of such materials include adipic acid, azelaic acid, terephthalic acid, isophthalic acid, and combinations thereof.
    The comonomers and/or co-oligomers may be included in the initial reaction mixture of the polyepoxide and polyhydric phenol and/or may be post-reacted with the resulting polyether oligomer/polymer.
    In a presently preferred embodiment, a comonomer and/or co-oligomer is not used to produce the polyether polymer of the present invention.
    The molecular weight advancement of the polyether polymer can be enhanced through the use of a catalyst in the reaction of a diepoxide (either a Formula II analog diepoxide or another diepoxide) with a Formula II compound.
    Typical catalysts useful in advancing the molecular weight of the epoxy material of the present invention include amines, hydroxides (e.g., potassium hydroxide), phosphonium salts, and the like.
    A currently 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.
    Alternatively, epoxy-terminated polymers of the present invention can be reacted with fatty acids to form polymers that have unsaturated (e.g., air-oxidizable) reactive groups, or with acrylic acid or methacrylic acid to form free-radical curable polymers.
    The advancement of polymer molecular weight can also be enhanced by reacting an epoxy terminated polymer of the present invention with a suitable diacid (such as adipic acid).
    When intended for use in a food contact coating or other application where good corrosion resistance is desired (for example, certain drug contact coatings such as those used inside metered dose inhaler containers), the —diepoxide and the compound of Formula II are preferably selected such that the resulting polymer has a Tg within one of the preferred ranges described above.
    Table 1 below includes measured Tg values of polyether polymers produced from the indicated combinations of diepoxides and dihydric phenols.
    Each of the polymers has a number average molecular weight ("Mn") of 3,000 to 6,000. Tg values were measured by differential scanning calorimetry (DSC) using the methodology presented in the Test Methods section.
    Polyether polymers produced from BPA and BADGE are included in Table 1 for purposes of comparison.
    As discussed above, preferred polymers of the invention are not derived from BPA or BADGE.
    Preferred polymers in Table 1 include those free of BPA and BADGE that have a Tg of at least 70°C.
    Table 1 Tg(°C) | Resorcil 44'- |BP 1,1-Bis(4-1,1-di(4-1,5-di-9-fluoren-nol |diphenol | A | hydroxyphenyl)- | hydroxyphenyl)- | hydroxy- | bisphenol 3,3,5-trimethyl- | cyclohexane | naphthalene cyclohexane NPGDGE | 8 | 9 6 — | 25 | 32 | 59 | CHDMDGE| 19 [| 30 [31] 6& [| 53 | an [| 7 | RDGE =| - | 6 65 98 | 7480 BADGE | 7 |/8 8 —- [| 8 | % | 106 |) * Two different samples were tested. **NPDGE is neopentyl glycol diglycidyl ether, CHDMDGE is cyclohexane dimethanol diglycidyl ether, RDGE is resorcinol diglycidyl ether, and BADGE is bisphenol A diglycidyl ether.
    Not shown in Table 1, a polyether polymer having a similar molecular weight to those in Table 1 was prepared from 1,1-di(4-hydroxy-3-methylphenyl)-cyclohexane and diglycidyl ether of
    4,4º butylidenebis(6-t-butyl-3-methylphenol) and the resulting polymer had a Tg of 72°C.
    As previously discussed, in some embodiments, the backbone includes both ester and ether bonds. In some such embodiments, the polyether polymer includes one or more segments of Formula I wherein R is a segment -R$,-C(0)-OR$-O-C(O)-R",-, wherein: R° is a divalent organic group, each R6, if present, is independently a divalent organic group, and each t is independently O or 1. In such embodiment, R° includes at least one divalent cyclic group as, for example , a divalent polycyclic group, a divalent aryl or heteroarylene group (for example, a substituted or unsubstituted phenylene group), or a divalent alicyclic group (for example, a substituted or unsubstituted cyclohexane or cyclohexene group). A further discussion of suitable segments containing ester linkages and materials for incorporating such segments into the polyether polymer is provided in the US patent.
    7,910,170.
    An example of a material suitable for forming a segment of Formula I that includes a segment -R6--C(O)-OR*-O-C(O)-Ri.- which has a polycyclic group at R* is a compound of Formula III below, or a diepoxide analog thereof: oH SS ” oH (II) In one embodiment, the compound of Formula III is formed by the reaction of two moles of a phenol-containing compound that has a hydroxyl group and a hydroxyl group reactive (e.g., a carboxylic group) with one mole of a diol compound including a polycyclic group. An example of the same is the reaction product of 2 moles of 4-hydroxy phenylacetic acid (HPAA) with 1 mole of tricyclodecane dimethanol (TCDM), which — yields a reaction product that has a structure of Formula III.
    In some embodiments, it may be advantageous to include one or more polycyclic groups in a backbone of the polyether polymer. In such embodiments, one or more polycyclic groups are provided in the R of Formula IL. The polycyclic groups may be any suitable organic polycyclic groups. For example, polycyclic groups can be saturated or unsaturated: bicyclic groups, tricyclic groups, or polycyclic groups consisting of four or more fused rings. Preferred polycyclic groups include bicyclic groups and tricyclic groups. The ring atoms of the polycyclic group are typically carbon atoms, although it is contemplated that the rings may include one or more heteroatoms (e.g., N, S, O, Si, etc.). In some embodiments, the polycyclic group includes at least one bridge that has one or more atoms (typically one or more carbon atoms) situated between the bridgehead atoms, wherein both (i) the one or more atoms are and ( 11) bridgehead atoms are shared by at least two rings. Thus, for example, bicyclo[4.4.0]decane does not include such a bridge, while norbornane does include such a bridge.
    Some non-limiting examples of suitable polycyclic groups are given below:
    AO sy tricyclodecane
    O Bicyclo[4.4.0]decane norbornane
    Y O. o
    Y isosorbide Each of the above polycyclic groups is represented as a divalent unit of the polymer (e.g. a divalent unit of the main chain) wherein each "Y" independently denotes another portion of the polymer which can be attached to any suitable atom of the polycyclic group (with the exception of the isosorbide group shown) and where a Y can be a final group.
    It is also contemplated that variants of any of the above polycyclic structures may be used, such as, for example, substituted variants thereof or unsaturated variants thereof. An example of an unsaturated variant of a norbornane group and a norbornene group. Additional examples of polycyclic groups suitable for use in the polymer of the present invention are provided in PCT Application No. PCT/US2010/0030584, filed April 9, 2010 and titled "Polymer Having Unsaturated Cycloaliphatic Functionality and Coating Compositions — Formed — Therefrom", and in PCT application No. PCT/US2010/0030576, filed on April 9, 2010 and entitled
    "Polyester Coating Composition." In some embodiments, the polymer may include one or more polycyclic groups comprising an unsaturated structure that is at least bicyclic, more preferably bicyclic, and represented by the IUPAC (International Union of Pure and Applied Chemistry) nomenclature of Expression (IV) below: bicyclo[xyz]alkene (IV) In Expression (IV), and x is an integer that has a value of 2 or more, and y is an integer that has a value of | or more, and 7z is an integer having a value of 0 or more, and the term alkene refers to the IUPAC nomenclature designation (e.g., hexene, heptene, heptadiene, octene, etc.) for a given bicyclic molecule and denotes that the bicyclic group includes one or more double bonds (more typically one or more carbon-carbon double bonds).
    In certain preferred embodiments, the z in Expression (IV) is 1 or more. In other words, such bicyclic groups include a bridge with at least one atom (typically one or more carbon atoms) interdisposed between a pair of bridgehead atoms, where the at least one atom is shared by at least two rings. . By way of example, bicyclo[4.4.0]decane does not include such a bridge.
    In certain preferred embodiments, x has a value of 2 or 3 (most preferably 2) and each of y and z independently has a value of | or 2.
    The bicyclic structures represented by Expression (IV) include one or more carbon-carbon double bonds (eg, 1,2, 3, etc.). Some non-limiting examples of some suitable unsaturated bicyclic groups represented by Expression (IV) include bicyclo[2.1.1]hexene, bicyclo[2.2.1]heptene (i.e. norbornene), bicyclo[2.2.2]octene, bicyclo[ 2.2.1]heptadiene, and bicyclo[2.2.2]octadiene.
    It is contemplated that the bicyclic groups represented by Expression (IV) may contain one or more heteroatoms (e.g., nitrogen, oxygen, sulfur, etc.) and may serve as substituents to contain one or more additional substituents. For example, one or more cyclic groups (including, for example, pendant cyclic groups and ring groups fused to a ring of a bicyclic group) or acyclic groups may be attached to the bicyclic group represented by Expression (IV). Thus, for example, in some embodiments the bicyclic group of Expression (IV) may be present in a tricyclic or larger group.
    In some embodiments, some or all of the bicyclic groups of Expression (IV) may be saturated. Some non-limiting examples of saturated bicyclics include saturated homologues of the structures represented by Expression (IV) (i.e. bicyclo[xyz]Jalkane, with x, y, and z as described above) such as, for example, bicyclo[2.1.1] hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, and bicyclo[3.2.1]octane, bicyclo[4.3.2 Jundecane, bicyclo[5.2.0]nonane.
    As discussed above, in some embodiments, the polyether polymer includes at least one polycyclic group or a plurality of polycyclic groups (e.g., >2, >3, >4, >5, >10, etc.). A useful measurement for evaluating the number of polycyclic groups in the polymer is the % by weight of the polycyclic groups relative to the total weight of the polymer. In certain embodiments, the polycyclic groups constitute at least about 5, at least about 15, or at least about 25% by weight of the polyether polymer. While the upper limit is not especially limited, in some embodiments, the polycyclic groups constitute less than about 75, less than about 50, or less than about 35% by weight of the polyether polymer. Care must be taken when interpreting the %
    weight of polycyclic groups due to the fact that direct measurement of the weight of polycyclic groups may not be feasible. Consequently, it may be necessary to determine the total amount of polycyclic groups present in the polymer by theoretical calculation based on the weight of the polycyclic-containing monomer(s) incorporated into the polymer and the weight fraction of such monomer constituting the polycyclic groups.
    When present, the one or more polycyclic groups may be located at any position within the polymer backbone (e.g., on the backbone and/or pendant sites).
    Optional polycyclic groups may be incorporated into the polyether polymer using any suitable reagent or combination of reagents. For example, polycyclic groups can be incorporated into the polymer using a polycyclic-containing polyepoxide and/or a polyhydric phenol compound. It is also contemplated that one or more other polycyclic reagents may be used, as, for example, a polycyclic comonomer that has at least two functional groups, preferably capable of reacting with a phenol hydroxyl group and/or an oxide group. of ethylene to form a covalent bond.
    As discussed above, in some embodiments, the R of Formula and/or II includes one or more polycyclic groups. In such embodiments, R has the structure -Rº-Y-Rº-, wherein each Y is a divalent organic group that includes at least one polycyclic group and each Rº is independently a divalent organic group. In some embodiments, one or both R6 groups include a stepwise polymeric linkage, such as an amide, carbonate, ester, ether, urea, or urethane linkage, with ester linkages being preferred. In one embodiment, each R$ group includes an ester bond.
    By way of example, a polycyclic-containing compound of Formula II can be formed by reacting (a) a suitable amount
    (e.g., about 2 moles) of a Compound A that has 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 difunctional Compound B or taller that has one or more polycyclic groups 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, 4-hydroxy benzoic acid, and derivatives or mixtures thereof.
    Examples of preferred Compounds B include polycyclic-containing diols such as tricyclodecane dimethanol (TCDM), nadic acid and/or anhydride, a polycyclic anhydrosugar such as isosorbide, isomanide, or isoidide, and derivatives or mixtures thereof.
    In some embodiments, the polycyclic group may be formed after the reaction of Compounds A and B.
    For example, a Diels-Alder reaction (using, for example, cyclopentadiene as a reactant) could be used to incorporate an unsaturated bicyclic group such as a norbornene group into Compound B, where Compound B, in its unreacted form, would require the inclusion of 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 related to such Diels-Alder reactions, see, for example, PCT Application No. PCT/US2010/0030584, filed April 9, 2010 and titled "Polymer Having Unsaturated Cycloaliphatic Functionality and Coating Compositions Formed Therefrom" and PCT Application No. PCT/US2010/0030576, filed April 9, 2010 and titled "Polyester Coating Composition". In some embodiments, it may be advantageous for the polyether polymer to include one or more polycyclic-containing backbone segments that have the following structure (Formula V):
    —Y-R-Y-, (V) wherein: and eachY is independently a polycyclic group,
    and R' is a divalent organic linking group (typically a substituted or unsubstituted hydrocarbyl linking group which may include one or more heteroatoms in the chain), and and the two polycyclic groups are preferably closely spaced.
    Without being bound by any theory, it is believed that the inclusion of such backbone segments in the polyether polymer can impart one or more beneficial coating properties to coatings incorporating the polymer. R preferably has a chain length of 100 or fewer atoms (more preferably, a chain length of <5, <A, <3, <2, or | atoms) in the backbone connecting the two X groups. In one embodiment, R has the structure -C(Rº$).-, where each Rº is independently a hydrogen, a halogen, or an organic group (for example, a methyl group or a substituted or unsubstituted hydrocarbon group that may include one or more heteroatoms ), and where the two R* groups can both be present in a ring-shaped group.
    Segments having a structure of Formula V can be incorporated into a polymer of the present invention using any suitable compound. For example, a difunctional dimer compound of the following Formula VI can be used: Z-(R)-YRY-(Rº).-Z, (VD where: and YeR' are as described above for Formula V, and each is independently O or 1, and each R, if present, is independently a divalent organic group (more preferably a substituted or unsubstituted C1-C10 hydrocarbon group which may include one or more heteroatoms), and each Z is independently a reactive functional group ,
    more preferably a functional group capable of reacting with a complementary functional group to form a stepwise growth bond such as, for example, an amide, carbonate, ether, ester, urea, or urethane bond. Hydroxyl groups and ethylene oxide groups (for example, an ethylene oxide group of a glycidyl ether or glycidyl ester group) are preferred reactive functional groups. An example of a representative compound of Formula VI is given below: DD”
    HO AT OL wherein the linking groups are a 2,2 isopropylidene group — which can independently bond to any suitable carbon atom of the tricyclodecane groups. Functional ethylene oxide groups can be included in the compound of Formula VI above by, for example, reacting the hydroxyl groups with epichlorohydrin. In certain preferred compounds, each of Y and R' of Formulas V and VI is independently selected such that the unit length of the structure -Y-R'-Y- is similar to that of a main chain of the epoxy unit produced. by bisphenol A (e.g., within 30%, 20%, 10%, etc. of the bisphenol A unit length). The polyether 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 can be water, organic solvent, or mixtures of several of these liquid carriers. Examples of organic solvents include glycol ethers, alcohols, aromatic or aliphatic hydrocarbons, dibasic esters, ketones, esters, and the like, and mixtures thereof. Preferably, such liquid carriers are selected to provide a dispersion or solution of the polyether polymer for further formulation. It is within the scope of the present invention to formulate a packaging coating composition by replacing a polyether polymer described herein with any conventional epoxy polymer present in a packaging coating composition known in the art (including any of those disclosed in publications patent mentioned here). Thus, for example, the polyether polymer of the present invention can serve as a substitute, for example, for a BPA/BADGE containing polymer of an epoxy/acrylic latex coating system, for a BPA/BADGE containing polymer of a epoxy coating system containing solvent, etc.
    If a water-based system is desired, techniques can be used such as those described in US patents 3,943,187, 4,076,676,
    4,247,439, 4,283,428, 4,285,847, 4,413,015, 4,446,258, 4,476,262, 4,963,602,
    5,296,525, 5,527,840, 5,830,952, 5,922,817, 6,034,157, 7,037,584, 7,189,787, and in US patent application 20100068433. The water-based coating system of the present invention may optionally include one or more organic solvents, which will typically be selected to be water miscible. The liquid carrier system of the waterborne coating compositions will typically include at least 50% by weight of water, more typically at least 75% by weight of water, and in some embodiments more than 90% by weight, or more than 95% by weight of water. Any suitable means can be used to make the polyether polymer of the present invention water miscible. For example, the polymer may include a suitable amount of salt groups such as ionic or cationic salt groups to render the polymer water miscible (or groups capable of forming such salt groups). A neutralized acidic or basic group are preferred saline groups. Thus, in one embodiment, a water-dispersible polymer of the present invention can be formed from preformed polymers (e.g., an ethylene oxide-functionalized polymer that preferably has at least one segment of Formula I and an acid-functionalized polymer) in the presence of a tertiary amine. In another embodiment, a water dispersible polymer of the present invention can be formed from an ethylene oxide functionalized polymer, preferably having at least one segment of Formula I which is reacted with ethylenically unsaturated monomers to form a functionalized polymer. with acid, which can then be neutralized, for example, with a tertiary amine. Thus, for example, in one embodiment a water dispersible polymer which preferably has at least one segment of Formula I may be formed in accordance with the acrylic polymerization teachings of the US patents
    4,285,847 and/or 4,212,781. In another embodiment, polymerization of the acrylic can be achieved through the reaction of ethylenically unsaturated monomers with unsaturation present in the polymer, preferably containing at least one segment of Formula LI. See, for example, the US patent
    4,517,322 and/or US Patent Application No. 2005/0196629, assigned to Bariatinsky, et al., for examples of such techniques. If desired, an acid-functionalized polymer can be combined with an amine, more preferably a tertiary amine, to at least partially neutralize it prior to reaction with the ethylene oxide-functionalized polymer, preferably having at least a segment of the Formula I. In addition to water-based coating compositions, epoxy-containing solvent-based packaging coating compositions are known in the art. See, for example, US patents
    3,943,187 and 3,997,694, which teach epoxy-containing solvent-based packaging coating compositions. In one embodiment, the coating composition of the present invention is an organic solvent-based system that includes no more than a minimal amount of water (e.g., less than about 2% by weight of water).
    In another embodiment, a polymer preferably containing segments of Formula I and including -CH 2 -CH(OH)-CH 2 - segments, which are derived from an ethylene oxide, 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.
    The amount of polyether polymer included in the coating compositions of the present invention can 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 or solvent based, etc. For liquid-based coating compositions, however, the polyether polymer of the present invention will typically constitute at least about 10% by weight, at least about 30% by weight, or at least about 50% by weight, of the coating composition, based on the total weight of resin solids in the coating composition. For such liquid-based coating compositions, the binder polyether polymer will typically constitute less than about 90% by weight, less than about 80% by weight, or — less than about 70% by weight, of the coating composition. coating, based on the total weight of resin solids in the coating composition.
    A coating composition of the present invention may also include other optional ingredients that do not adversely affect the coating composition or a resulting cured coating composition. Such optional ingredients are typically included in a coating composition to improve the aesthetics of the composition, to facilitate manufacture, processing, handling, and application of the composition, and to further optimize a particular functional property of a coating composition or a coating composition. cured coating resulting therefrom. For example, the composition comprising the polyether polymer of the present invention may optionally include crosslinkers, fillers, catalysts, lubricants, pigments, surfactants, dyes, toners, binders, extenders, anticorrosion agents, flow control agents, thixotropic agents. , dispersing agents, antioxidants, oxygen scavenging materials, adhesion promoters, light stabilizers, and mixtures thereof, as needed to provide the desired film properties. Each optional ingredient is preferably included in an amount sufficient to serve its intended purpose, but not in an amount that adversely affects a coating composition or a cured coating composition resulting therefrom.
    Preferred polyether polymers and coating compositions of the present invention are substantially free of mobile and/or bonded BPA and BADGE, and more preferably are essentially free of these compounds, and most preferably completely free of these compounds.
    It has been found that coating compositions using the aforementioned polymer-containing compositions can be formulated using one or more optional curing agents (i.e., crosslinking resins, sometimes called "crosslinkers"). The choice of a particular crosslinker typically depends on the particular product being formulated. For example, some coating compositions are highly colored (eg gold colored coatings). These coatings can typically be formulated using crosslinkers which themselves tend to have a yellowish color.
    In contrast, white coatings are generally formulated using a non-yellowing crosslinker, or only a small amount of a yellowing crosslinker.
    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-reacting curing resins such as phenoplastic and aminoplastic.
    Phenoplastic 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-tert-amylphenol, cyclopentylphenol, and compounds of Formula II.
    Aminoplastic resins are the condensation products of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, and benzaldehyde with substances containing amino or an amido group such as urea, melamine, and benzoguanamine.
    Examples of suitable aminoplastic crosslinking resins include, but are not limited to, benzoguanamine-formaldehyde resins, melamine-formaldehyde resins, etherified melamine-formaldehyde, and urea-formaldehyde resins.
    Examples of other generally suitable curing agents are blocked or unblocked aliphatic, cycloaliphatic or aromatic di-, tri-, or polyvalent isocyanates such as hexamethylene diisocyanate, cyclohexyl-1,4-diisocyanate, and the like.
    Some other non-limiting examples of generally suitable blocked isocyanates include isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, tetramethyl xylene diisocyanate, xylylene diisocyanate, and mixtures thereof.
    In some embodiments, blocked isocyanates are used which have a Mn of at least about 300, more preferably at least about 300.
    650, and most preferably at least about 1,000.
    Blocked polymeric isocyanates may be used in certain embodiments. Some examples of suitable blocked polymeric 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. of 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. of Pittsburgh, PA, USA), or combinations thereof. Examples of suitable trimers may include a trimerization product prepared from an average of three molecules of diisocyanate or a trimer prepared from an average of three moles of diisocyanate (e.g. HMDI) reacted with a mol of another compound such as a triol (eg trimethylolpropane).
    The level of curing agent (i.e., crosslinker) required — will depend on the type of curing agent, the time and temperature of the curing, the molecular weight of the polyether polymer, and the desired film properties. If used, a crosslinker is typically present in an amount of up to 50% by weight, preferably up to 30% by weight, and most preferably up to 15% by weight. If used, the crosslinker is preferably present in an amount of at least 0.1% by weight, more preferably at least 1% by weight, and most preferably at least 1.5% by weight. These weight percentages are based on the total weight of resin solids in the coating composition.
    A coating composition of the present invention can,
    also, include other optional polymers that do not adversely affect the coating composition or a resulting cured coating composition.
    These optional polymers are typically included in a coating composition as a filler material, although they may be included as a crosslinking material, or provide desirable properties.
    One or more optional polymers (e.g. filler polymers) may be included in an amount sufficient to serve the purpose for which they are intended, but not in an amount such as to adversely affect a coating composition or a resulting cured coating composition. .
    Such additional polymeric materials may be non-reactive and therefore simply function as fillers.
    Such optional non-reactive filler polymers include, for example, polyesters, acrylics, polyamides, polyethers, and novalac.
    Alternatively, such polymeric materials or additional monomers may be reactive with other components of the composition (eg, an acid functionalized polymer). If desired, reactive polymers can be incorporated into compositions of the present invention to provide additional functionality for various purposes, including cross-linking.
    Examples of such reactive polymers include, for example, polyesters, acrylics, polyamides, and functionalized polyethers.
    Preferred optional polymers are substantially free of mobile BPA and BADGE, and more preferably completely free of such compounds.
    A 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. dodecyl benzene sulfonic acid (DDBSA), available under the tradename CYCAT 600 from Cytec), methane sulfonic acid (MSA), p-toluene sulfonic acid (pTSA), dinonylnaphthalene disulfonic acid (DNNDSA), and triflic acid), quaternary ammonium compounds, phosphorous compounds, and tin, titanium, and zinc compounds, and mixtures thereof.
    Specific examples include, but are not limited to, a tetraalkylammonium halide, a tetraalkyl or tetraaryl phosphonium iodide or acetate, tin octoate, zinc octoate, triphenylphosphine, and similar catalysts known to those skilled in the art.
    If used, a catalyst will preferably be present in an amount of at least 0.01% by weight and more preferably at least 0.1% by weight, based on the weight of the non-volatile material in the composition of coating.
    If used, a catalyst will preferably be present in an amount of not more than 3% by weight, and more preferably, not more than 1% by weight, based on the weight of the non-volatile material in the coating composition.
    Another useful optional ingredient is a lubricant (e.g. a wax), which facilitates the manufacture of articles made from metal (e.g. food or beverage can lids and ends) by providing lubricity to the metal coated substrate blades. .
    Non-limiting examples of suitable lubricants include, for example, natural waxes such as carnauba wax or lanolin wax, polytetrafluorethane (PTFE) and polyethylene type lubricants.
    If used, a lubricant is preferably present in the coating composition in an amount of at least 0.1% by weight, and preferably, not more than 2% by weight, and more preferably, not more than 1%. by weight, based on the total weight of non-volatile material in the coating composition.
    Another useful optional ingredient is a pigment, such as titanium dioxide.
    If used, a pigment is preferably present in the coating composition in an amount of not more than 70% by weight, more preferably not more than 50% by weight, and most preferably not more than 40% by weight, based on the total weight of solids in the coating composition.
    Surfactants may optionally be added to the coating composition to aid in flow and substrate wetting. Examples of surfactants include, but are not limited to, polyethers and nonylphenol salts and similar surfactants known to those skilled in the art. If used, a surfactant will preferably be present in an amount of at least 0.01% by weight and more preferably at least 0.1% by weight, based on the weight of resin solids. If used, a surfactant is preferably present in an amount of not more than 10% by weight, and more preferably, not more than 5% by weight, based on the weight of resin solids.
    The coating composition of the present invention may be present as one layer of a single-layer coating system or one or more layers of a multi-layer coating system. The coating composition can be used as a base coat, an intermediate coat, a top coat, or a combination thereof. The coating thickness of a particular layer and the total coating system will vary depending on the coating material used, the substrate, the method of applying the coating, and the purpose of the coated article. Single-layer or multi-layer coil coating systems that include 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 about 2 to about 60 microns, and more typically from about 3 to about 12 microns. The coating composition of the present invention can be applied to a substrate either before 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 metallic substrate (e.g., applying the composition to the metallic substrate in the form of a coil or flat sheet), curing the composition, and forming (e.g. by stamping) the substrate into a packaging can or a portion thereof (e.g. a food or beverage can or a portion thereof). For example, riveted beverage can ends that have a cured coating of the present invention on a surface thereof can be formed in such a process. After application of the coating composition to a substrate, the composition may be cured using a variety of processes, including, for example, oven baking using conventional or convectional methods, or any other method that provides a temperature high suitable for curing the coating. The curing process can be carried out in distinct or combined stages. For example, substrates can be dried at room temperature to leave the coating compositions in a largely uncrosslinked state. The coated substrates can then be heated to fully cure the compositions. In certain examples, the coating compositions of the present invention can be dried and cured in one step.
    Curing conditions will vary depending on the application method and intended purpose. The curing process can be done at any suitable temperature, including, for example, oven temperatures in the range from about 100°C to about 300°C, and more typically from about 177°C to about 250°C. If the metal coil is the substrate to be coated, curing the applied coating composition can be conducted, for example, by heating the coated metal substrate over a suitable period of time to a peak temperature of the metal (" PMT") preferably greater than about 177°C (350°F). More preferably, the coated metal coil is heated for a suitable period of time (e.g., about 5 to 900 seconds) to a PMT of at least about 218°C (425°P).
    The coating compositions of the present invention are particularly useful for coating metallic substrates. The coating compositions can 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 metallic substrate. The polymer can be applied to a metal substrate either before or — after the substrate is formed into a can (e.g. a two-piece can, three-piece can) or portions thereof, which can be a can end or body. from the can. Preferred polymers of the present invention are suitable for use in food contact situations and can be used inside such cans. Coating compositions are particularly useful inside the ends and frames of two-piece or three-piece cans.
    The coating compositions may be suitable for spray coating, coil coating, reactive coating, blade coating, and side seam coating (e.g. food can side seam coating). A more detailed discussion of these application methods is provided below. It is contemplated that the coating compositions of the present invention may suitably be used in each of these application methods discussed further below, including the end uses associated therewith.
    Spray coating includes introducing the coated composition into a preformed packaging container. Typical pre-formed packaging containers for spray coating include food cans, beer and beverage containers, and the like. The spray preferably uses a spray nozzle capable of uniformly coating the inside of the packaging container. The sprayed preformed container is then subjected to heat to remove any residual carriers (eg water or solvents) and harden the coating.
    A coil coating is described as the coating of a continuous coil composed of a metal (eg steel or aluminum). Once coated, the coating coil is subjected to a short thermal, ultraviolet, and/or electromagnetic curing cycle, for a process to quench (e.g., dry and cure) the coating. Coil coatings provide metal coated substrates (e.g. steel and/or aluminum) that can be manufactured into shaped articles such as two-piece stretch food cans, three-piece food cans, food can ends, straightened and flattened, beverage can ends, and the like.
    A reactive coating is commercially described as the outer coating of two-piece stretched and smoothed ("D&I") cans with a thin layer of protective coating. The exterior of these D&I cans is "wash coated" by passing the cans into two preformed D&I pieces under a coating composition curtain. The cans are inverted, that is, the open end of the can is "down" as it passes through the curtain. This curtain from the coating composition resembles a "waterfall". Once these cans pass through this coating composition curtain, the liquid coating material effectively coats the outside of each can. Excess coating is removed — through the use of an "air knife". Once the desired amount of coating is applied to the outside of each can, each can is passed through a thermal, ultraviolet, and/or electromagnetic curing oven for hardening (e.g., drying and curing) the coating. The residence time of the coated can within the curing oven is typically 1 minute to 5 minutes. The curing temperature within this oven will typically be in the range of 150°C to 220°C.
    A blade coating is described as coating separate pieces of a variety of materials (eg steel or aluminum) that have been pre-cut into square or rectangular "blades". Typical dimensions of these blades are approximately one square meter. Once coated, each blade is cured. Once hardened (eg, dried and cured), the coated substrate sheets are collected and prepared for subsequent fabrication. Blade coatings provide a metal coated substrate (e.g. steel or aluminum) that can be correctly fabricated into shaped articles such as stretched two-piece food cans, three-piece food cans, food can ends, straightened and flattened, beverage can ends (including, for example, riveted beverage can ends that have a rivet for attaching a ring thereto), and the like.
    A side seam coating is described as spraying a liquid coating onto the welded area of food cans in three shaped pieces. When three-piece food cans are being prepared, a rectangular piece of coated substrate is formed into a cylinder. The forming of the cylinder becomes permanent due to the welding of each side of the rectangle by heat welding. Once welded together, each can typically needs a coating layer, which protects the exposed "weld" from corrosion — subsequent or other effects of the contained food. Liners that function in this function are called "side seam strips". Typical side seam strips are spray applied and cured quickly through waste heat from the welding operation in addition to a small thermal, ultraviolet, and/or electromagnetic oven.
    Other commercial coating application and curing methods are also contemplated, for example, electrocoating, extrusion coating, lamination, powder coating, and the like. In one embodiment, the coating composition of the present invention is an organic solvent-based composition that preferably has at least 20% by weight of non-volatile (i.e. "solids") components, and more preferably at least 20% by weight. at least 25% by weight of non-volatile components. In one embodiment, the coating composition is an organic solvent-based composition that preferably has no more than 40% by weight of non-volatile components (i.e., " solids"), and more preferably not more than 35% by weight of non-volatile components. In such embodiments, the non-volatile film-forming components preferably include at least 50% by weight of the polyether polymer of the present invention, more preferably at least 55% by weight of the polymer, and most preferably at least 55% by weight. least 60% by weight of the polymer. In such embodiments, the non-volatile film-forming components preferably include not more than 95% by weight of the polyether polymer of the present invention, and more preferably not more than 85% by weight of the polymer.
    In one embodiment, the coating composition is a water-based composition that preferably has at least 15% by weight non-volatile (i.e., "solids") components. In one embodiment, the coating composition is a water-based composition that preferably has no more than 50% by weight of non-volatile (i.e. "solids") components, and more preferably no more than 40 % by weight of non-volatile components In such embodiments, the non-volatile film-forming components preferably include at least 25% by weight of the polyether polymer of the present invention, more preferably at least % by weight of the polymer, and more preferably at least 40% by weight of the polymer In such embodiments, the non-volatile film-forming components preferably include not more than 60% by weight of the polyether polymer of the present invention, and with more preferably not more than 70% by weight of the polymer.
    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 metallic substrate of at least 8, more preferably at least 9, and ideally 10 (10 being perfect), when subjected to the test described below in the Examples section using 3% by weight acetic acid in deionized water in place of " Aggressive Food Product".
    Some additional non-limiting embodiments of the present invention are provided below to further exemplify certain aspects of the present invention.
    1. A coating composition comprising: a film-forming amount of a polyether polymer having a backbone that includes a polycyclic group (and more preferably a plurality of such groups), an optional crosslinker, and a liquid carrier optional.
    2. The coating composition of modality 1 which is at least substantially free of BPA or BADGE.
    3. The coating composition of embodiment 1 or 2 in which the polyether polymer includes one or more pendant hydroxyl groups attached to backbone carbon atoms.
    4. The coating composition of any one of embodiments 1 to 3, wherein the backbone includes the segments -CH1;-CH(OH)-CH;-.
    5. The coating composition of any one of embodiments 1 to 4 in which the aryl or heteroaryl groups constitute at least 20% by weight of the polyether polymer, based on the total weight of the aryl and heteroaryl groups present in the polymer relative to to the weight of the polymer.
    6. The coating composition of any one of embodiments 1 to 5 in which the backbone includes a plurality of ester linkages.
    7. The coating composition of any of the | to 6 in which the polyether polymer includes one or more of the following segments of Formula LI: -O-Ar- (R 1 -Ar), -O-, wherein: each Ar is independently an aryl or heteroaryl group (more preferably a divalent phenylene group), each n is independently O or 1, R, if present, is a divalent organic group, and each of the two oxygen atoms is ether oxygen.
    8. The coating composition of embodiment 7 in which each n is | and R includes the polycyclic group.
    9. The coating composition of embodiment 7 or 8 in which the R includes at least one ester linkage.
    10. The coating composition of embodiment 9 in which the R includes a segment having the structure of Formula III below: -RÍ-C(0)-OR*-O-C(O)-R”;- wherein: R° is a divalent organic group that includes a polycyclic group, each R is a divalent organic group, and cadatéOoul.
    11. The coating composition of any one of embodiments 1 to 10 in which the polyether polymer has a glass transition temperature (Tg) of at least about 30°C, more preferably about 50°C, and most preferably at least about 30°C. minus about 70°C, even more preferably from about 80°C to 110°C.
    12. The coating composition of any one of embodiments 1 to 11 that includes the liquid carrier and the polyether polymer has a number average molecular weight of at least 2,000.
    13. The coating composition of any of the | at 12 in which the polyether polymer is a reaction product of ingredients including a polyepoxide and a polyhydric phenol, more preferably a diepoxide and a dihydric phenol.
    14. The coating composition of embodiment 13 in which one or both of the polyepoxide and the polyhydric phenol include a polycyclic group.
    15. The coating composition of any one of embodiments 1 to 14 in which polycyclic includes a tricyclodecane group.
    16. The coating composition of embodiment 13 in which one or both of the polyepoxide or polyhydric phenol are derived from -isosorbide.
    17. The coating composition of any one of embodiments 1 to 16 which is a water-based system.
    18. The coating composition of any one of embodiments 1 to 17 which is a solvent based system.
    19. The coating composition of any one of embodiments 1 to 18 which is suitable for use as a food contact coating.
    20. An article having the coating composition of any one of embodiments 1 to 19 applied to at least a portion of a surface thereof.
    The article of claim 20 which is a metal food or beverage container or a portion thereof.
    22. A method comprising: providing a metallic substrate, providing a coating composition of any one of embodiments 1 to 19, and applying the coating composition to at least a portion of a major surface of the substrate before, or after , the formation of the substrate in a food or beverage container or a portion thereof.
    23. A coating composition comprising: a polyether polymer (preferably in a film-forming amount) having: one or more segments of the following Formula [: -O-Ar- (R1-Ar),-O -, wherein: each Ar is independently an aryl or heteroaryl group (more preferably a divalent phenylene group), each n is independently O or 1, R, if present, is a divalent organic group, and each of the two atoms of oxygen is ether oxygen, and preferably having a glass transition temperature (Tg) of at least 30°C, more preferably at least 50°C, and most preferably at least 70°C, and wherein the coating composition is at least substantially free of BPA or BADGE.
    24. The coating composition of modality 23 in which
    R, if present, is not -C(CH;3), ;-.
    25. The coating composition of embodiment 23 or 24 in which the polyether polymer has a Tg of 70 to 150°C.
    26. The coating composition of any of — embodiments 23 to 25 in which the polyether polymer has a Tg of 80 to 110°C.
    27. The coating composition of any one of embodiments 23 to 26 in which the polyether polymer includes one or more pendant hydroxyl groups attached to backbone carbon atoms.
    28. The coating composition of any one of embodiments 23 to 27 in which a polyether polymer backbone includes -CH;-CH(OH)-CH;- segments.
    29. The coating composition of any one of embodiments 23 to 28 in which aryl or heteroaryl groups constitute at least 20% by weight of the polyether polymer, based on the total weight of aryl and heteroaryl groups present in the polymer relative to the polymer weight.
    30. The coating composition of any one of embodiments 23 to 29 in which the polyether polymer is a reaction product of ingredients including a polyepoxide and a polyhydric phenol, more preferably a diepoxide and a dihydric phenol.
    31. The coating composition of any one of embodiments 23 to 30 in which each of polyepoxide and polyhydric phenol independently includes an aryl or heteroaryl group.
    32. The coating composition of any one of embodiments 23 to 31 in which one or more of the polyepoxide or polyhydric phenol is selected from: 1,1-di(4-hydroxyphenyl)-cyclohexane, 1 ,1-di(4-hydroxy-3-methylphenyl)-cyclohexane, 1,1-di(4-hydroxy-3,5-
    dimethylphenyl)-cyclohexane, a mixture thereof, the diglycidyl ether of any of these, or combinations thereof.
    33. The coating composition of any one of embodiments 23 to 32 in which one or more of the polyepoxide or polyhydric phenol is selected from: 1,1-bis(4-hydroxyphenyl)-3,3,5 - trimethyl-cyclohexane, the diglycidyl ether of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, or combinations thereof.
    33.5. The coating composition of any one of embodiments 23 to 33 wherein the polyether polymer has a number average molecular weight of at least 2000.
    34. The coating composition of any one of embodiments 23 to 33.5 in which n is 1 and R includes a quaternary carbon atom on a main chain segment of R connecting the two Ar groups shown in Formula L.
    35. The coating composition of any one of embodiments 23 to 34 in which R includes at least one cyclic group.
    36. The coating composition of embodiment 35 in which the cyclic group is a pendant or backbone alicyclic group.
    37. The coating composition of embodiment 35 or 36 in which the cyclic group includes a six-membered carbon ring (e.g., a cyclic group -CK(Rº)- wherein: (1) q is from 2 to 10, more typically from 6 to 10, more typically from 8 to 10, and still but typically 10, and (ii) each R' group is independently hydrogen, a halogen, or an organic group and two R' groups can join to form a ring.
    38. The coating composition of any one of embodiments 35 to 37 in which the cyclic group is a substituted or unsubstituted divalent cyclohexane group.
    39. The coating composition of any one of embodiments 35 to 38 in which the cyclic group includes a quaternary carbon atom present on an R backbone connecting the two Ar groups of Formula L.
    40. The coating composition of any one of embodiments 35 to 39 in which the R of Formula I does not include any — ester linkages in an R backbone connecting the two Ar groups.
    41. The coating composition of any one of embodiments 23 to 40 in which the polyether polymer includes a plurality of ester linkages.
    42. The coating composition of any one of embodiments 23 to 39 and 41 in which n is 1 and R includes at least one ester linkage.
    43. The coating composition of embodiment 42 wherein the R comprises a segment having the structure of Formula III below: -R6-C(0)-OR*-O-C(O)-R”;- wherein: Rº is a divalent organic group, each Rº is a divalent organic group, and each is Ooul.
    44. The coating composition of embodiment 43 wherein —R° includes at least one aryl or divalent heteroaryl group.
    45. The coating composition of any one of embodiments 23 to 40 in which the polyether polymer is free of ester linkages.
    46. The coating composition of any of the — embodiments of 23 to 4S5 which is a water-based system.
    47. The coating composition of any one of embodiments 23 to 45 which is a solvent based system.
    48. The coating composition of any one of embodiments 23 to 47 which is suitable for use as a food contact coating.
    49. An article that includes a metal substrate of a food or beverage container, or a portion thereof, and a coating composition of any one of embodiments 23 to 48 applied to at least a portion of a major surface of the metal substrate.
    50. A method comprising: providing a metallic substrate, providing a coating composition of any one of embodiments 23 to 48, and applying the coating composition to at least a portion of a major surface of the substrate before, or after , the formation of the substrate in a food or beverage container or a portion thereof.
    51. The method of embodiment 50 further comprising: forming a metallic substrate having the coating composition applied thereto in a food or beverage container or a portion thereof.
    52. The method of embodiment 50 wherein the metallic substrate includes a portion of a preformed food or beverage container.
    53. The method of any one of embodiments 50 to 52 wherein the main surface includes a food contact surface.
    54. The coating composition, method, or article of any of embodiments 1 to 53 in which the polyether polymer — includes at least: 1% by weight, 5% by weight, 10% by weight, 20% by weight , % by weight, or 50% by weight, of the segments of Formula I.
    TEST METHODS Unless otherwise noted, the following test methods were used in the examples that follow.
    Differential Scanning Calorimetry Samples for the differential scanning calorimetry ("DSC") test were prepared by first applying the liquid resin composition onto aluminum foil panels.
    The panels were baked in a Fisher Isotemp electric oven for 20 minutes at 149ºC (300ºF) 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 heat-cool-heat method of DSC.
    The samples were equilibrated to -60°C, then heated at 20°C per minute to 200°C, cooled to -60°C, and then heated again at 20°C per minute to 200°C.
    The glass transitions were calculated from the thermogram of the last heating cycle.
    The glass transition was measured at the inflection point of the transition.
    Adhesion Adhesion testing is performed to assess whether the coating compositions adhere to the coated substrate.
    The adhesion test was performed according to ASTM D 3359 - test method B, using SCOTCH 610 tape (available from the 3M Company of Saint Paul, Minnesota, USA). Adhesion is generally rated on a scale of 0 to 10 where a rating of "10" does not indicate failure of adhesion, a rating of "9" indicates that 90% of the coating remains adhered, an "8" rating indicates that 80 % of the coating remains adhered, and so on.
    Adhesion scores of 10 are typically desired for commercially viable coatings. — Blur Resistance Blur resistance measures the ability of a coating to resist attack from various solutions.
    Typically, blush is measured by the amount of water absorbed in a coated film.
    When the film absorbs water, it often becomes cloudy or appears white.
    Blushing is usually measured visually using a scale of 0 to 10, where an index of "10" indicates no blushing and an index of "O" indicates complete bleaching of the film. Blush indices of at least 7 are typically desired for commercially viable coatings and optimally 9 or more. — Corrosion Resistance Corrosion resistance is a measure of the coating's ability to resist a corrosive/acidic environment. It is generally measured on a scale of 0 to 10. An "O" indicates that the coating is completely corroded, which is observed through bubbling or blistering of the film in all areas. A "10" indicates that the coating does not change after being subjected to the corrosive environment. Stain Resistance Stain resistance is a measure of a coating's ability to resist stains from a medium. It is generally measured on a scale of 0 to 10. An "O" indicates that the coating is completely stained with a complete color change of the film seen in all areas. A "10" indicates that the coating color remains unchanged after being subjected to the staining environment. Solvent Resistance Test The extent of "cure" or crosslinking of a coating is measured as a resistance to solvents such as methyl ethyl ketone (MEK) or isopropyl alcohol (IPA). This test is performed as described in ASTM D5402-93. The double friction number (i.e. a back and forth motion) is reported. Preferably, the MEK solvent resistance is at least 30 double rubs.
    EXAMPLES The following examples are offered to aid in the understanding of the present invention and should not be considered to limit its scope. Unless otherwise noted, all parts and percentages are by weight.
    List of Raw Materials and Ingredients The following table lists some of the raw materials and ingredients used in the following examples.
    Alternative materials or suppliers may serve as substitutes, as will be appreciated by those skilled in the art.
    Phenolic Crosslinker PRENODUR PR Smyrna, Georgia, USA 612 Diglycidyl! cyclohexane ether | CVC Thermoset | Moorestown, NJ, USA dimethanol ERISYS GE-22 Specialties 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethyl- | Honshu Chemical Tokyo, Japan Cyclohexane Polymerization Catalyst | Shell Houston, Texas, USA CATALYST 1201 1,1-Di(4-hydroxyphenyl)-cyclohexane Honshu Chemical Resorcinol Diglycidyl Ether ERISYS CVC Thermoset | Moorestown, NJ, USA Specialties Bisphenol A Diglycidyl Ether EPON Houston, Texas, USA 828 Bisphenol A Dow Chemical Midland, MI, USA Example 1: Polyether Polymers Test 1: A 4 neck round bottom flask equipped with a mechanical stirrer , a water-cooled condenser, and a thermocouple connected to a heating control device and a heating mantle, 138.4 parts of ERISYS GE-22, 140.3 parts of 1,I-bis(4-hydroxyphenyl )-3,3,5-trimethyl-cyclohexane, 0.26 parts OF CATALYST 1201 and 13.4 parts of methyl isobutyl ketone.
    Stirring and heating were started and continued until the batch reached 130°C, at which point heating was stopped and the batch was allowed to exotherm to 158°C.
    The batch was heated to 155°C for 180 minutes, at which time the epoxy value was 0.038 equivalents/100 grams.
    At this point, the heating was stopped and 84.2 parts of ethylene glycol butyl ether were slowly added, followed by 42.1 parts of butanol.
    The final resin had a non-volatile content of 66.9%, an epoxy value of 0.036, a Brookfield viscosity of 75,000 centipoise at -27°C (80°F), and a Tg of 60°C.
    Based on a theoretical calculation, the final resin included 20.6% by weight of aryl groups, based on the total weight of aryl groups in the polymer versus the weight of the polymer.
    Test 2:
    To a 4-neck round-bottom flask equipped with a mechanical stirrer, a water-cooled condenser, and a thermocouple connected to a heating control device and a heating mantle, 169.8 parts of ERISYS GE-22 were added, 130.2 parts of 1,1-di(4-hydroxyphenyl)-cyclohexane, 0.30 parts of 1201 catalyst and 15.9 parts of methyl isobutyl ketone.
    Stirring and heating were started and continued until the batch reached 125°C, at which time heating was stopped and the batch was allowed to exotherm to 166°C.
    The batch was heated to 155°C for 120 minutes, at which time the epoxy value was 0.035 equivalents/100 grams.
    At this point, the heating was stopped and 122 parts of ethylene glycol butyl ether were slowly added, followed by 60.6 parts of butanol.
    The final resin had a non-volatile content of 60.2%, an epoxy value of 0.035, and a Tg of 38°C.
    Based on a theoretical calculation, the final resin included 24.6% by weight of aryl groups, based on the total weight of aryl groups in the polymer relative to the weight of the polymer.
    Test 3:
    A 4-neck, round-bottomed flask equipped with a mechanical stirrer, a water-cooled condenser, and a thermocouple
    — connected to a heating control device and a heating mantle, 233.4 parts of RDGE, 266.6 parts of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclo- hexane, 0.5 parts of CATALYST 1201 and 26.3 parts of methyl isobutyl ketone.
    Stirring and heating were started and continued until the batch reached 130°C, at which time heating was stopped and the batch was allowed to exotherm to 162°C. The batch was heated to 155°C for 60 minutes, at which time the epoxy value was 0.034 equivalents/100 grams. At this point, the heating was stopped and 205.6 parts of ethylene glycol butyl ether were slowly added, followed by 101.2 parts of butanol. The final resin had a non-volatile content of 59.6%, an epoxy value of 0.031, and a Tg of 98°C. Based on a theoretical calculation, the final resin included 42% by weight of aryl groups, based on the total weight of aryl groups in the polymer relative to the weight of the polymer. Tested4: To a 4-neck round-bottom flask equipped with a mechanical stirrer, a water-cooled condenser, and a thermocouple connected to a heating control device and a heating mantle, 250.7 parts of RDGE, 249 .3 parts of 1,1-di(4-hydroxyphenyl)-cyclohexane, 0.50 parts of CATALYST 1201 and 33.5 parts of methyl isobutyl ketone. Stirring and heating were started and continued until the batch reached 125°C, at which point heating was stopped and the batch was allowed to exotherm to 171°C. The batch was heated to 155°C for 45 minutes, at which time the epoxy value was 0.037 —equivalents/100 grams. At this point, the heating was stopped and 205 parts of ethylene glycol butyl ether were slowly added, followed by 101 parts of butanol. The final resin had a non-volatile content of 60.2%, an epoxy value of 0.032, and a Tg of 80°C. Based on a theoretical calculation, the final resin included 45.4% by weight of aryl groups, based on the —total weight of aryl groups in the polymer relative to the weight of the polymer.
    Comparative Test 5: To a 4-neck round-bottom flask equipped with a mechanical stirrer, a water-cooled condenser, and a thermocouple connected to a heating control device and a heating mantle, 259.8 parts of EPON were added. 828, 140.3 parts of bisphenol A, 04 parts of CATALYST 1201 and 30.2 parts of methyl isobutyl ketone. Stirring and heating were started and continued until the batch reached 130°C, at which point heating was stopped and the batch was allowed to exotherm to 162°C. The batch was heated to 155°C for 75 minutes, at which time the epoxy value was 0.039 equivalents/100 grams. At this point, the heating was stopped and 369.4 parts of ethylene glycol butyl ether were slowly added. The final resin had a non-volatile content of 51.4%, an epoxy value of 0.038, a Brookfield viscosity of 39,000 centipoise at -27°C (80°F), and a Tg of 78°C. Based on a theoretical calculation, the final resin included 52% by weight of aryl groups, based on the total weight of aryl groups in the polymer relative to the weight of the polymer.
    Examples 2 to 6: Coating Compositions To produce the coating compositions of Examples 2 to 6, each of the polyether polymers of Example 1, Tests 1 to 5, were cut to a non-volatile content of 35%, with a 1:1 ratio of cyclohexane:aromatic solvent 150. Then 20% solids in solids of PHENODUR PR 612 was added, followed by the addition of 0.1% solids in solids of H2PO, as a solution of 10% in butanol. Thus, for each of Tests 1 to 5, 80/20 polyether/phenolic acid catalyzed formulations were provided. Table 2 below indicates the particular polyether polymer of Example 1, Tests 1 to 5, present in each of Examples 2 to 6.
    — Coating Properties The coating compositions of Examples 2 through 6 were each weathered with appropriately sized metal wires to obtain a dry film thickness of 7 — 7.8 grams per square meter (with a metric equivalent being of 4.5-5.0 milligrams/square inch). The coating compositions were applied to a 75tt tin plate ("ETP") and a 75t tin free plate ("TFS") of 0.25 and baked to cure the coating. Baking took place for 12 minutes at -206°C (403°F) in a gas-heated forced draft oven. 202 sanitary food can ends were formed from the coated plates. A 1.58 Nm (14 inch-pound) reverse impact (using a 0.91 kg (two pound) weight dropped from a suitable height) was applied to each can end at the center of the uncoated side of the end. The ends were immersed in two different aggressive food products (i.e. the — aggressive food products | and 2 in Table 2) that have an initial temperature of 82ºC (180ºF) and stored for 2 weeks at -49ºC (120ºF). After 2 weeks the ends were removed from the food product, rinsed with water, and evaluated for adhesion, corrosion, staining, and flushing. The results are shown in Table 2 below.
    As shown in Table 2, the RDGE-containing formulations of Examples 4 and 5 perform similarly to the BPA-containing formulation of Comparative Example 6. The lower Tgs of the CHDMDGE-containing formulations of Examples 2 and 3 were lower in this test than the Tgs. higher than the RDGE-containing formulations of Examples 4 and 5.
    Table 2 Composition of — [Example 2nd [Example 3rd [Example 4. [Example 5" [Example coating |Comparative 6 Resin Example 1,Example 1, Example 1,/IExample 1,/Example 1, Test Test 1 Test 2 Test 1 Test 2 5 Aggressive Food Product 1 Adhesion/Rush [8/10 Stain/Corrosion [7/7*——-—- 187 ————H10/10 10/10 10/10 Aggressive Food Product 2 Adhesion/Rash /8 /10 8/10 10/10 10/10 10/10
    Stain/Corrosion 10/9 10/10 Aggressive Food Product 1 Stick/Rush 8/7 ——— |87 [1010 10/10 10/10 Stain/Corrosion 9/7 /—-—- /gy5 ——— [10 /10 10/10 10/10 Aggressive Food Product 2 Adhesion/Rash [8/5 === |85 — [1010 10/10 10/10 Stain/Corrosion Examples 7 to 13 below refer to embodiments of the present invention which include a polyether polymer having optional polycyclic groups.
    Example 7: Adduct of 2 mol of 4-hydroxy phenyl acetic acid (HPAA) with 1 mol of tricyclodecane dimethanol (TCDM) to a 4-necked round-bottomed flask equipped with a mechanical stirrer, a water-cooled condenser over a Dean trap -Stark, and a thermocouple connected to the heating control device and a heating mantle, 705.6 parts of TCDM (available from OXEA), 1094.4 parts of HPAA (available from Aceto), 1.8 parts of CATALYST 4201 polymerization CATALYST (dibutyl tin oxide, available from Atofina). Stirring and heating was started for 4 hours until the batch reached 230°C. The batch was heated to 230°C for a further 4 hours, at which time the acid value was 2.0 mg KOH/gram. At this point, heating was stopped until the batch reached 120°C, at which point the batch was unloaded. The material was a sticky semi-solid at room temperature.
    Example 8: Adduct of 2 moles of 4-hydroxy phenyl acetic acid (HPAA) with 1 — isosorbide mold A a 4 neck round bottom flask equipped with a mechanical stirrer, a water cooled condenser over a trap
    Dean-Stark, and a thermocouple connected to the heating control device and a heating mantle, were added 162.2 parts of isosorbide (polymer grade, available from ADM), 337.8 parts of HPAA, and 0.5 parts of CATALYST 4201 polymerization CATALYST. Stirring and heating was started for 5 hours until the batch reached 240°C.
    At this time the acid value was 2.0 mg KOH/gram.
    Heating was stopped until the batch reached 150°C, at which point the batch was unloaded.
    The material was a sticky solid at room temperature.
    Example 9: Polyether Polymer Incorporating the Adduct of Example 7 Into a 4-neck, round-bottomed flask equipped with a mechanical stirrer, a water-cooled condenser, and a thermocouple connected to a heating control device and a heating mantle, 80.5 parts of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane diglycidyl ether (from Sachem, The Netherlands), 73.4 parts of the HPAA-TCDM adduct from Example were added. 7.0.15 parts CATALYST 1201 polymerization catalyst (available from Shell) and 8 parts methyl isobutyl ketone.
    Stirring and heating were started until the batch reached 125°C, at which point the batch was allowed to exotherm to 147°C. —The batch was left to return to the temperature of 120ºC and kept that way for 2 hours, at which time the epoxy value was 0.040 equivalents/100 grams.
    At this point, the heating was stopped and 140 parts of a 2:1:1 mixture of xylene:cyclohexanone:propylene glycol methyl ether acetate were added.
    The final resin composition had a non-volatile content of 52.2%, an epoxy value of 0.033, a viscosity of 3,800 centipoise, and a Tg of 88°C.
    Example 10: Polyether Polymer Incorporating the Adduct of Example 7 Into a 4-neck, round-bottomed flask equipped with a mechanical stirrer, a water-cooled condenser, and a thermocouple connected to a heating control device and a heating mantle, 55.4 parts of hydroquinone diglycidyl ether, 94.7 parts of the HPAA-TCDM adduct from Example 7, 0.15 parts of CATALYST 1201 (available from Shell) and 16.7 parts of -methyl isobutyl ketone were added.
    Stirring and heating were started until the batch reached 120°C, at which time the batch remained between 125 and 130°C for 3 hours, at which time the epoxy value was 0.041 equivalents/100 grams.
    At this time, the heating was stopped and 136 parts of cyclohexanone were slowly added.
    The final resin composition had a non-volatile content of 50.7%, an epoxy value of 0.034, and a Tg of 48°C.
    Example 11: Polyether Polymer Incorporating the Adduct of Example 8 Into a 4-neck, round-bottomed flask equipped with a mechanical stirrer, a water-cooled condenser, and a thermocouple connected to a heating control device and a heating mantle, 68.1 parts of 1,4-cyclohexane dimethanol diglycidyl ether (CHDMDGE, available from Emeral Materials, New Jersey, USA), 89.2 parts of the HPAA-isosorbide adduct from Example 8, 0, were added. 15 parts of CATALYST 1201 POLYMERIZATION CATALYST and 8 parts of methyl isobutyl ketone.
    Stirring and heating were started until the batch reached 130°C, at which time the batch remained between 125 and 130°C for 4 hours, at which time the epoxy value was 0.033 equivalents/100 grams.
    At this point, heating was stopped and 23 parts of cyclohexanone were slowly added, followed by 23 parts of propylene glycol methyl ether acetate and 46 parts of xylene.
    The final resin composition had a non-volatile content of 61.9%, an epoxy value of 0.034, and a Tg of 36°C.
    Example 12: Coating Composition The polyether polymer composition of Example 9 was cut to a non-volatile content of 35% using a 1:1 cyclohexane: AROMATIC 150 blend. Then 20% solids on solids of phenolic crosslinker PHENODUR PR 612 (available from Cytec, of Smyrna, Georgia, USA) was added, followed by 0.1% solids on solids of H3PO;, added as a 10% solution in butanol.
    In this way, an 80:20 polyether:phenolic acid catalyzed coating composition was provided. The coating composition of Example 12, along with an industry standard BPA-based polyether coating composition, were each applied to both ETP and TFS.
    The coatings were scraped with appropriately sized metal wires to obtain coatings having a dry film thickness of 0.69 to 0.78 mg/cm (from 4.5 to 5.0 milligrams/square inch ("msi")). The coated metal samples were then baked for 12 minutes in a gas heated oven to -206°C (403°F). 202 sanitary can ends were formed from the resulting coated boards.
    A 1.58 Nm (14 inch-pound) reverse impact was applied to each end to the center of the uncoated side of the end.
    The ends were then immersed in two different aggressive food products (i.e., the aggressive food products | and 2 in Table 2) which have an initial temperature of 82°C (180°F) and stored for 2 weeks at -49°C (120°F). After 2 weeks the ends were removed from the food product, rinsed with water, and evaluated for adhesion, corrosion, staining, and flushing.
    The results are shown in Table 3 below.
    Table 3 | — Aggressive Food Product 2 | |
    RR MO O | — Aggressive Food Product 1 [| | — Aggressive Food Product 2 pj As shown in the data in Table 3, the coating composition of Example 12 showed similar performance to that of the commercial BPA-based control. Example 13: Coating Composition The CHDMDGE/HPAA-isosorbide polyether polymer composition of Example 11 was reduced to 40% solids with cyclohexanone. An outer coating formulation for metal packaging was produced by mixing 90 parts of the reduced polymer blend, 8.6 parts of CYMEL 1054 crosslinker (available from Cytec), 0.45 parts of Lanco TF1780 wax (available from Lubrizol) , and 0.99 parts of Lanocerin product (available from Lubrizol). This formulation had a solids content of 41.9% by weight and a ratio of polyether to crosslinker (on solids) of 87.5:12.5. The coating was scraped with a metal wire over a flat metal substrate to obtain a coating with a dry film thickness of 0.54 to 0.62 mg/cm (from 3.5 to 4.0 msi) on a TFS metal foil and double-baked using 10-minute bakes in an oven at -204ºC (400ºF), and various film properties were tested. A BPA-based commercial epoxy packaging coating product was used as a control and applied and cured in the same manner.
    The cured coated substrate was then subjected to a variety of tests to evaluate various coating properties. Data from these tests are recorded below in Table 4. As shown in the data in Table 4, the experimental coating composition performed equivalently to that of the commercial control, except for resistance to MEK (although 55-60 MEK rubs is considered acceptable). Table 4 Coated Panel Appearance 3.16 Nm (28 10 10 inch-lbs) Reverse Impact Crack 3.16 Nm (28 10 10 inch-lbs) Reverse Impact Grip Resistance to MEK 55-60 Stretch Can Manufacturing 100% Ticket | 100% Pass Drawn Can Manufacturing + 90 minutes Crimped IRetort at 121ºC (250ºF) (Test for loss of Adhesion after retorting a can 100% Pass | 100% Drawn Pass) The coating data in Table 4 suggests that the coating composition of Example 13 may be suitable for use in forming an outer coating on certain packaging coating articles.
    The complete description of all patents, patent applications, publications, and electronically available material cited in the present invention are incorporated herein by reference. The detailed description and examples mentioned above have been offered solely for the sake of clarity of understanding. No unnecessary limitations should be inferred from them. The invention is not limited to the exact details shown and described, as variations obvious to one skilled in the art will be included in the invention defined by the claims.
    权利要求:
    Claims (20)
    [1]
    1. Article, characterized in that it comprises: a metallic substrate of a food or beverage container or a portion thereof, and a coating applied to at least a portion of a main surface of the metallic substrate, wherein the coating comprises: a film-forming amount of a polyether polymer having: one or more segments of the following Formula [: -O-Ar- (R1-Ar), -O-, wherein: each Ar is independently an aryl or heteroaryl group , each n is independently O or 1, R, if present, is a divalent organic group, and each of the two oxygen atoms is ether oxygen, and a glass transition temperature (Tg) of at least 70°C, and in that the coating composition is at least substantially free of bisphenol A and bisphenol A diglycidyl ether.
    [2]
    2. Article according to claim 1, characterized in that the polyether polymer has a Tg of 70 to 150ºC.
    [3]
    An article according to claim 1, characterized in that the polyether polymer has a Tg of 80 to 110°C.
    [4]
    4. Article according to any one of the claims | to 3, characterized in that the main chain includes segments -CH,-CH(OH)-CH,;-.
    [5]
    5. Article according to any one of claims 1 to
    4, characterized in that the aryl or heteroaryl groups constitute at least 20% by weight of the polyether polymer, based on the total weight of the aryl and heteroaryl groups present in the polymer in relation to the weight of the polymer.
    [6]
    Article according to any one of claims 1 to 5, characterized in that the polyether polymer is a reaction product of ingredients including a polyepoxide and a polyhydric phenol.
    [7]
    7. Article according to claim 6, characterized in that each of polyepoxide and polyhydric phenol includes, —independently, an aryl or heteroaryl group.
    [8]
    An article according to any one of claims 1 to 7, characterized in that the polyether polymer has a number average molecular weight of at least 2,000.
    [9]
    9. Article according to any one of the claims | to 8, characterized by the fact that R, if present, is a divalent group other than —-C(CH;3),-.
    [10]
    10. An article according to any one of claims 1 to 9, characterized in that n is 1 and R includes a quaternary carbon atom in a main chain segment connecting the two Ar groups
    [11]
    11. Article according to claim 10, characterized in that R includes at least one cyclic group.
    [12]
    12. Article according to claim 10, characterized in that: (1) R is free of ester bonds and (11) the at least one group — cyclic is a divalent alicyclic group.
    [13]
    13. Article according to any one of claims 1 to 12, characterized in that n is 1 and R comprises a segment with the formula below: —R*-C(0)-OR*-0-C(O)- R-
    wherein: R° is a divalent organic group, each R* is a divalent organic group, and each is Ooul.
    [14]
    14. Article according to any one of claims 1 to 11, characterized in that the polyether polymer is free of ester bonds.
    [15]
    15. Article according to any one of claims 1 to 14, characterized in that the coating composition is a — food contact coating.
    [16]
    16. Article according to claim 1, characterized in that R is present and includes a main chain alicyclic group.
    [17]
    17. Article according to claim 6, characterized in that the polyepoxide comprises tetramethyl diglycidyl ether - cyclobutanediol or a derivative thereof.
    [18]
    18. Method, characterized in that it comprises: providing a metallic substrate, providing a coating composition, which comprises: a polyether polymer having: one or more segments with the following Formula [: -O-Ar- (R1-Ar ),-O-, where: each Ar is independently an aryl or heteroaryl group, each n is independently O or 1, R, if present, is a divalent organic group, and each of the two oxygen atoms is oxygen of ether, and a glass transition temperature (Tg) of at least 70°C, and wherein the coating composition is at least substantially free of bisphenol A and the diglycidyl ether of bisphenol A, and applying the coating composition over at least a portion of a main surface of the substrate before, or after, formation of the substrate in a food or beverage container or a portion thereof.
    [19]
    19. Coating composition, characterized in that it comprises: a film-forming amount of a —polyether polymer having: one or more segments with the following Formula [: -O-Ar- (R,-Ar),- O-, where: each Ar is independently an aryl or heteroaryl group, each n is independently O or 1, R, if present, is a divalent organic group, and each of the two oxygen atoms is ether oxygen, and a glass transition temperature (Tg) of at least 70°C and a number average molecular weight of at least 2000; and a liquid carrier, wherein the coating composition is at least substantially free of bisphenol A and bisphenol A diglycidyl ether.
    [20]
    Coating composition according to claim 19, characterized in that the polyether polymer is a reaction product of ingredients including tetramethyl cyclobutanediol diglycidyl ether.
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    同族专利:
    公开号 | 公开日
    AU2011239491B2|2016-02-25|
    CA2793541C|2018-05-08|
    EP2558543A4|2014-07-30|
    EP2558543B1|2017-08-30|
    WO2011130671A2|2011-10-20|
    US20210024774A1|2021-01-28|
    CN102858893A|2013-01-02|
    BR112012026240B1|2021-08-03|
    CA2793541A1|2011-10-20|
    CN102858893B|2016-08-03|
    US11130881B2|2021-09-28|
    KR20180037316A|2018-04-11|
    AU2011239491A1|2012-09-27|
    EP2558543A2|2013-02-20|
    KR20130061132A|2013-06-10|
    JP2013529226A|2013-07-18|
    CN106085168B|2018-10-16|
    PL2558543T3|2018-01-31|
    US20180112102A1|2018-04-26|
    RU2544676C2|2015-03-20|
    US20130280455A1|2013-10-24|
    RU2012140144A|2014-05-27|
    MX2012011843A|2012-11-12|
    JP5752784B2|2015-07-22|
    US20180112101A1|2018-04-26|
    EP3263664A1|2018-01-03|
    CN106085168A|2016-11-09|
    WO2011130671A3|2012-03-15|
    EP3611235A1|2020-02-19|
    ES2642061T3|2017-11-15|
    EP3263664B1|2020-11-04|
    KR102032749B1|2019-10-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL84498C|1936-10-28|
    NL68367C|1948-03-29|
    BE495432A|1949-04-29|1900-01-01|
    NL173809B|1951-11-17|Rca Corp|IMAGE RECORDING DEVICE WITH COLOR CODING STRIP FILTER SYSTEM.|
    US2694694A|1952-10-17|1954-11-16|Devoe & Raynolds Co|Manufacture of epoxide resins|
    NL103227C|1953-04-06|
    US2824855A|1954-12-20|1958-02-25|Freeman Chemical Corp|Preparation of epoxide resins|
    US3153008A|1955-07-05|1964-10-13|Gen Electric|Aromatic carbonate resins and preparation thereof|
    US3275601A|1956-01-04|1966-09-27|Bayer Ag|Manufacture of polycarbonates using tertiary amines, quaternary amines and salts thereof as catalysts|
    US3102043A|1958-01-30|1963-08-27|Fluidized bed coating method |
    US2951778A|1958-06-05|1960-09-06|Grace W R & Co|High temperature adhesive containing polyepoxide resin mixture|
    US3220974A|1959-01-02|1965-11-30|Gen Electric|Epoxy modified polycarbonate resinous compositions|
    BE586968A|1959-01-27|
    US3041300A|1959-10-06|1962-06-26|Martin Marietta Corp|Polyglycidyl ethers of ether anhydro hexitols, method of production, and aqueous solutions thereof|
    US3085992A|1960-05-31|1963-04-16|Dow Chemical Co|Alkyl amine terminated polycarbonates|
    BE609222A|1960-10-17|
    US3297724A|1961-03-07|1967-01-10|Eastman Kodak Co|Diepoxides|
    NL296913A|1962-08-23|
    US3321424A|1964-01-06|1967-05-23|Swift & Co|Coating compositions comprising styrene-maleic anhydride copolymer and polyepoxide|
    US3404102A|1964-04-09|1968-10-01|Union Carbide Corp|Polycyclic epoxide compositions and presins produced therefrom|
    US3379684A|1964-04-29|1968-04-23|Wiesner Ivo|Method of preparing high-molecular polyhydroxyethers|
    US3366600A|1964-06-02|1968-01-30|Grace W R & Co|Process for preparing amine-phenol curing agent epoxy resin compositions|
    US3288884A|1964-07-20|1966-11-29|Dow Chemical Co|Resinous composition comprising a vinyl chloride polymer and a halogenated polyepoxide|
    BE671444A|1964-10-28|1900-01-01|
    US3480695A|1965-12-14|1969-11-25|Union Carbide Corp|Polyhydroxyether compositions containing polycarbonates|
    USRE28862E|1966-10-17|1976-06-15|Owens-Illinois, Inc.|Easy open means for bottles and the like|
    US3491112A|1967-01-30|1970-01-20|Ncr Co|3--3--phthalides|
    US3509174A|1967-01-30|1970-04-28|Ncr Co|3--phthalides|
    US3477990A|1967-12-07|1969-11-11|Shell Oil Co|Process for reacting a phenol with an epoxy compound and resulting products|
    US3578615A|1968-04-08|1971-05-11|Shell Oil Co|Epoxy resin coatings having improved cathodic disbonding resistance|
    US3553119A|1968-12-18|1971-01-05|Cook Paint & Varnish Co|Epoxy resin ester production|
    US3769302A|1969-01-21|1973-10-30|T Hoover|Aliphatic amino-substituted flourans|
    US3642828A|1970-11-03|1972-02-15|Ncr Co|Alkyl or halo substituted tetrahalofluorans|
    US3681390A|1970-11-16|1972-08-01|Ncr Co|Dialkylamino fluoran chromogenic compounds|
    US3879348A|1970-12-22|1975-04-22|Bayer Ag|Saponification-resistant polycarbonates|
    US3950451A|1971-02-27|1976-04-13|Asahi Denka Kogyo K.K.|Hardenable epoxy resin composition|
    BE791793A|1971-12-06|1973-03-16|Ncr Co|CHROMOGENIC COMPOUNDS|
    CH603738A5|1972-07-25|1978-08-31|Hoechst Ag|
    JPS4934526A|1972-08-01|1974-03-30|
    DE2323803C3|1973-05-11|1983-12-01|Basf Ag, 6700 Ludwigshafen|Spirodipyrans and their use as color formers for copying processes|
    JPS5138245B2|1973-05-22|1976-10-20|
    US4172103A|1973-06-09|1979-10-23|Bayer Aktiengesellschaft|Polycarbonate moulding compounds|
    US3876606A|1973-06-14|1975-04-08|Minnesota Mining & Mfg|Thermosetting epoxy resin powder highly filled with barium sulfate, calcium carbonate and mica|
    US4247439A|1973-11-06|1981-01-27|E. I. Du Pont De Nemours And Company|Water-borne coating composition made from epoxy resin, polymeric acid and tertiary amine|
    US3997694A|1973-12-12|1976-12-14|E. I. Du Pont De Nemours And Company|Container coated with a ductile coating of an acrylic polymer having reactive sites and an epoxy resin|
    US3943187A|1973-12-12|1976-03-09|E. I. Du Pont De Nemours And Company|Ductile coating composition of an acrylic polymer having reactive sites and an epoxy resin|
    US3984363A|1973-12-14|1976-10-05|Alelio Gaetano F D|Polymerizable lignin derivatives|
    US3905926A|1973-12-14|1975-09-16|Alelio Gaetano F D|Polymerizable lignin derivatives|
    GB1508420A|1974-03-28|1978-04-26|Shell Int Research|Compositions comprising bitumens andpolymers and products comprising bitumens chemically coupled withpolymers and their preparation|
    US4076676A|1975-02-04|1978-02-28|E. I. Du Pont De Nemours And Company|Aqueous coating composition from aminoplast and reaction product of tertiary amine and polymer containing terminal epoxy groups|
    US4173594A|1975-02-24|1979-11-06|Lord Corporation|Thermosetting lacquer compositions|
    US4009224A|1975-08-11|1977-02-22|Minnesota Mining And Manufacturing Company|Epoxy resin powder including ethylene vinyl acetate|
    US4051195A|1975-12-15|1977-09-27|Celanese Polymer Specialties Company|Polyepoxide-polyacrylate ester compositions|
    US4111910A|1976-07-12|1978-09-05|The Dow Chemical Company|Polycarbonates having carbamate terminal groups|
    US4076764A|1976-07-22|1978-02-28|Shell Oil Company|Epoxy resin composition having improved physical properties|
    US4283428A|1977-03-08|1981-08-11|Ppg Industries, Inc.|Beverage containers coated with a water-based liner|
    US4212781A|1977-04-18|1980-07-15|Scm Corporation|Modified epoxy resins, processes for making and using same and substrates coated therewith|
    US4122060A|1977-06-16|1978-10-24|E. I. Du Pont De Nemours And Company|Epoxy resin powder coating composition|
    US4285847A|1979-04-11|1981-08-25|Scm Corporation|Polymerization process and product|
    US4413015A|1979-06-21|1983-11-01|Mobil Oil Corporation|Storage stable water-dilutable acid adducted epoxy based coating for metal food contact surfaces|
    DE2930787A1|1979-07-28|1981-02-12|Bayer Ag|CROSSLINKABLE POLYCARBONATE ELASTOMERS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR MEDICAL PACKAGING AFTER CROSSLINKING|
    US4399241A|1980-03-21|1983-08-16|Scm Corporation|Base for a graft polymer, novel graft polymer compositions, solvents and water-reducible coatings incorporating the novel graft polymers, and processes for making them|
    JPS6317104B2|1980-06-23|1988-04-12|Asahi Denka Kogyo Kk|
    US4374233A|1981-04-02|1983-02-15|General Electric Company|Block copolymers of polyphenylene oxides and non-sterically-hindered high molecular weight aromatic polycarbonates|
    US4368315A|1981-04-27|1983-01-11|General Electric Company|Catalyzed interfacial polycondensation polycarbonate process|
    JPS6320251B2|1981-07-31|1988-04-27|Daicel Chem|
    US4446258A|1982-12-30|1984-05-01|Mobil Oil Corporation|Aqueous coating comprising dispersible epoxy resin-acid polymer ester and diluent polymer, and method of preparation|
    US4476262A|1982-12-30|1984-10-09|Mobil Oil Corporation|Aqueous coatings comprising ionic polymer ester and diluent polymer with reduced monomer residue and method of preparation|
    JPH0338997B2|1983-04-14|1991-06-12|Hodogaya Chemical Co Ltd|
    US4468483A|1983-05-05|1984-08-28|Texaco Inc.|Aromatic polyester polycarbonates from polyols derived from recycled polyethylene terephthalate|
    US4517322A|1983-09-22|1985-05-14|Ppg Industries, Inc.|Acrylated alkyd and polyester resins|
    US4487861A|1983-11-28|1984-12-11|Scm Corporation|Aqueous polymeric blends|
    US4600737A|1983-12-21|1986-07-15|Inmont Corporation|Water dilutable acrylated epoxy-phenolic coating compositions|
    US4552814A|1984-05-21|1985-11-12|The Dow Chemical Company|Advanced epoxy resins having improved impact resistance when cured|
    US4564655A|1984-12-10|1986-01-14|General Electric Company|Polycarbonate compositions|
    EP0185118B1|1984-12-21|1995-09-20|Dainippon Ink And Chemicals, Inc.|A method for coating a substrate with a coating film|
    US4622368A|1985-05-13|1986-11-11|General Electric Company|Plasticized polyetherimide blends|
    JPH0422155B2|1985-07-10|1992-04-15|Jujo Paper Co Ltd|
    US4665149A|1985-11-08|1987-05-12|The Dow Chemical Company|Triazine containing epoxy resins having improved thermal stability|
    US4647612B1|1985-12-30|1990-10-23|Ppg Industries Inc|
    US5591788A|1987-07-16|1997-01-07|The Dow Chemical Company|Cationic, advanced epoxy resin compositions incorporating glycidyl ethers of oxyalkylated aromatic or cycloaliphatic diols|
    US4757132A|1986-10-20|1988-07-12|General Electric Company|Cyclic polyester oligomer polymerization|
    EP0265791A3|1986-10-31|1988-08-24|General Electric Company|Polycarbonate and copolyester carbonate resin compositions exhibiting a high flexural modulus|
    US4707534A|1986-12-09|1987-11-17|Minnesota Mining And Manufacturing Company|Glycidylethers of fluorene-containing bisphenols|
    JPH0588871B2|1987-06-03|1993-12-24|Sekisui Chemical Co Ltd|
    US4794156A|1987-08-04|1988-12-27|The Dow Chemical Company|Two stage catalytic production of high molecular weight polyhalobisphenol polycarbonates|
    MX169357B|1987-08-13|1993-09-30|Valspar Corp|COATING COMPOSITION IN AQUEOUS COMPOSITION|
    US4880892A|1987-08-31|1989-11-14|Ciba-Geigy Corporation|Composition comprising an epoxy resin, a phenol and an advancement catalyst|
    US4794102A|1987-09-03|1988-12-27|Appleton Papers Inc.|Thermally-responsive record material|
    US5080961A|1987-10-13|1992-01-14|Macy Richard J|Coextruded structures|
    US4806597A|1987-10-29|1989-02-21|General Electric Company|Composition comprising aromatic polycarbonate, polyolefin, ethylene vinyl alcohol copolymer, and a modified hydrogenated alkylidene vinyl aromatic block copolymer|
    US5162406A|1987-12-17|1992-11-10|The Dow Chemical Company|Polymer stabilizing compositions|
    US4849502A|1988-02-22|1989-07-18|General Electric Company|Method of regulating the polymerization of cyclic polycarbonate with initiator and polyhydric phenol|
    JPH0255727A|1988-08-19|1990-02-26|Mitsui Petrochem Ind Ltd|Polyhydroxy polyether and use thereof|
    US4994217A|1988-12-29|1991-02-19|General Electric Company|Low odor polyphenylene ether/polystyrene process|
    DE3935639A1|1989-02-01|1990-08-02|Bayer Ag|POLYCARBONATE RESIN MIXTURES|
    US5201436A|1989-11-13|1993-04-13|The Glidden Company|Can coating of epoxy resin, acrylic copolymer and acrylic surfactant|
    US4963602A|1989-11-13|1990-10-16|Hi-Tek Polymers, Inc.|Aqueous epoxy resin-acrylic resin coating compositions containing also phenoxy, novolac and resole resin combination|
    NL9000006A|1990-01-03|1991-08-01|Stamicarbon|METHOD FOR MANUFACTURING ARTICLES FROM POLYCARBONATE.|
    US5264503A|1990-01-29|1993-11-23|Shell Oil Company|Phenol-terminated epoxy resin with functional elastomer|
    US5115082A|1990-04-17|1992-05-19|Raychem Corporation|Fluorinated poly|
    US5212241A|1990-05-25|1993-05-18|The Glidden Company|Glycidyl-epoxy-acrylic copolymers|
    US5068284A|1990-08-03|1991-11-26|General Electric Company|Blocked amine terminated polycarbonates and products obtained therefrom|
    DE69129052T2|1990-09-10|1998-11-12|Hitachi Chemical Co Ltd|Process for the preparation of high molecular weight epoxy resins|
    US5571907A|1990-12-07|1996-11-05|Hawaiian Sugar Planters' Association|Epoxy monomers from sucrose|
    JPH04366124A|1991-06-12|1992-12-18|Kansai Paint Co Ltd|Epoxy resin composition|
    JP2924985B2|1991-06-28|1999-07-26|日本ジーイープラスチックス株式会社|Method for producing polycarbonate|
    IT1251489B|1991-09-17|1995-05-15|Enichem Sintesi|DIOLOTHERMINATED POLYCARBONATES|
    JP2681907B2|1992-11-20|1997-11-26|日本製紙株式会社|Thermal recording medium|
    DE69418308T2|1993-01-29|1999-09-23|Valspar Corp|COATING COMPOSITION OF A HYDROXY-FUNCTIONAL BLOCKCOPOLYMER POLYESTER|
    JPH06298902A|1993-04-16|1994-10-25|Toto Kasei Kk|Epoxy resin composition|
    JP3428695B2|1993-08-20|2003-07-22|ジャパンエポキシレジン株式会社|Modified liquid epoxy resin composition|
    JPH07126574A|1993-10-29|1995-05-16|Nippon Steel Chem Co Ltd|Epoxy resin composition for powder coating|
    JP3484546B2|1993-11-13|2004-01-06|東都化成株式会社|Powder coating composition|
    JPH07196770A|1993-12-28|1995-08-01|Nippon Kayaku Co Ltd|Epoxy resin, epoxy resin composition and its cured product|
    WO1995026997A1|1994-03-31|1995-10-12|Ppg Industries, Inc.|Epoxy/amine barrier coatings|
    US5576413A|1994-04-25|1996-11-19|General Electric Company|Flame retardant polycarbonate compositions|
    US5527840B1|1994-10-04|1999-08-10|Valspar Corp|Aqueous coating composition|
    JP3554626B2|1994-11-09|2004-08-18|富士写真フイルム株式会社|Thermoresponsive microcapsules, and thermosensitive recording materials and multicolor thermosensitive recording materials using the same|
    US5718352A|1994-11-22|1998-02-17|Aluminum Company Of America|Threaded aluminum cans and methods of manufacture|
    JP3509236B2|1994-11-28|2004-03-22|大日本インキ化学工業株式会社|Epoxy resin composition and semiconductor encapsulating material|
    JPH08183852A|1994-12-28|1996-07-16|Nippon G Ii Plast Kk|Copolycarbonate, copolycarbonate composition and production thereof|
    JP3481338B2|1995-02-01|2003-12-22|ジャパンエポキシレジン株式会社|Liquid epoxy resin composition|
    US5639806A|1995-03-28|1997-06-17|Borden Chemical, Inc.|Bisphenol-containing resin coating articles and methods of using same|
    US5677398A|1995-04-13|1997-10-14|Mitsui Toatsu Chemicals, Inc.|Epoxy acrylate resins and their uses|
    US5803301A|1996-09-12|1998-09-08|Toyo Seikan Kaisha, Ltd.|Seamless can and process for making the same|
    DE19536381A1|1995-09-29|1997-04-03|Hoechst Ag|Epoxy and epoxy polyacrylate dispersions containing reactive diluents, process for their preparation and their use|
    EP0861873B1|1995-11-09|2006-07-12|Kaneka Corporation|Polycarbonate resin composition|
    US6376021B1|1996-02-12|2002-04-23|Polymer Alloys Llc|Heat treatment of polyphenylene oxide-coated metal|
    US5830952A|1996-02-22|1998-11-03|The Dexter Corporation|Water-dispersible polymer and coating composition containing the same|
    US5718353A|1996-05-08|1998-02-17|Gojo Industries, Inc.|Towelette dispensing closure assembly|
    US6472472B2|1996-05-17|2002-10-29|The Valspar Corporation|Powder coating compositions and method|
    ZA973692B|1996-05-17|1997-11-25|Dexter Corp|Extrusion coating compositions and method.|
    US5686185A|1996-06-28|1997-11-11|Morton International, Inc.|Disbondment resistant epoxy powder coating composition|
    US6043333A|1996-08-23|2000-03-28|Nippon Kayaku Kabushiki Kaisha|Modified epoxy resin, epoxy resin composition and cured product thereof|
    US5807912A|1996-10-03|1998-09-15|General Electric Company|Ortho esters as BPA scavenger in polycarbonate product|
    US6201070B1|1996-11-20|2001-03-13|Union Carbide Chemicals & Plastics Technology Corporation|Method for enhancing the toughness of cycloaliphatic epoxide-based coatings|
    EP1542273B1|1997-03-31|2013-09-25|Hitachi Chemical Co., Ltd.|Circuit-connecting material and circuit terminal connected structure and connecting method|
    US5811498A|1997-04-16|1998-09-22|The Dexter Corporation|α-glycol endcapped resins, their method of manufacture, and compositions containing the same|
    GB9708825D0|1997-05-01|1997-06-25|Ici Plc|Process for producing a coating composition|
    US6008273A|1997-05-09|1999-12-28|The Dexter Corporation|Waterborne coating compositions for metal containers|
    JPH10316717A|1997-05-16|1998-12-02|Kishimoto Akira|Epoxy resin emulsion and production of water-based coating material|
    GB9807213D0|1998-04-04|1998-06-03|Ici Ltd|Aqueous coating composition|
    JP2000007757A|1998-04-22|2000-01-11|Asahi Chiba Kk|New epoxy resin|
    JP2000007891A|1998-04-22|2000-01-11|Asahi Chiba Kk|New liquid epoxy resin composition, its cured product and semiconductor sealing device|
    US5994462A|1998-06-11|1999-11-30|The Dexter Corporation|Solid coating compositions for powder and extrusion applications|
    JP2000005019A|1998-06-24|2000-01-11|Ritsuchieru:Kk|Food and drink container for infant|
    US6133402A|1998-08-04|2000-10-17|Cornell Research Foundation, Inc.|Polycarbonates made using high activity catalysts|
    US7635662B2|1998-09-04|2009-12-22|Chemipro Kasei Kaisha, Ltd.|Compound for color-producing composition, and recording material|
    US6469127B1|1999-01-12|2002-10-22|Space Environmental Technology Company, Inc,|Polycarbonate resin having low tendency of releasing environmental endocrine disruptors|
    US6359062B1|1999-03-02|2002-03-19|The Valspar Corporation|Coating compositions|
    FR2791065A1|1999-03-16|2000-09-22|Seb Sa|NON-STICK COATING HAVING IMPROVED SCRATCH RESISTANCE|
    US6060577A|1999-03-18|2000-05-09|General Electric Company|Polycarbonates derived from alicyclic bisphenols|
    JP4195145B2|1999-04-01|2008-12-10|出光興産株式会社|Method for producing polycarbonate|
    US6451926B1|1999-05-04|2002-09-17|Eastman Chemical Company|Coating compositions based on polyether alcohols prepared from 3,4-epoxy-1-butene|
    AU5046300A|1999-05-26|2000-12-12|Henkel Corporation|Autodeposition coatings and process therefor|
    JP3348040B2|1999-06-04|2002-11-20|群栄化学工業株式会社|Novolak type phenolic resin|
    MXPA02000341A|1999-07-14|2002-07-02|Vantico Ag|Curable composition.|
    CA2280409C|1999-08-16|2008-05-20|Henry Degraaf|Aqueous coating composition and process|
    US6576718B1|1999-10-05|2003-06-10|General Electric Company|Powder coating of thermosetting resin and poly)|
    KR20010090730A|2000-03-27|2001-10-19|사토 아키오|Developer composition and heat sensitive recording material|
    US6225436B1|2000-04-07|2001-05-01|The Dow Chemical Company|Polycarbonate preparation process|
    US6660688B2|2000-05-31|2003-12-09|Ricoh Company Ltd.|Thermosensitive recording medium|
    CA2421205A1|2000-09-04|2003-03-03|Nippon Steel Chemical Co., Ltd.|Separator for fuel cell, process for producing the same, and material therefor|
    JP3511136B2|2000-09-25|2004-03-29|日立化成工業株式会社|Epoxy resin molding material for sealing and semiconductor device|
    JP2002097409A|2000-09-25|2002-04-02|Kansai Paint Co Ltd|Coating composition|
    JP2002097250A|2000-09-26|2002-04-02|Asahi Kasei Epoxy Kk|Epoxy resin, its reaction product, and curable resin composition using the same|
    JP2002220563A|2000-10-20|2002-08-09|Kansai Paint Co Ltd|Water-based coating composition for inner surface of can|
    US20040044101A1|2000-10-20|2004-03-04|Yuji Hirose|Water-based coating composition for can inner surfaces|
    JP2002194274A|2000-10-20|2002-07-10|Kansai Paint Co Ltd|Coating composition|
    JP2002138245A|2000-11-01|2002-05-14|Kansai Paint Co Ltd|Aqueous coating composition|
    JP2002155727A|2000-11-21|2002-05-31|S & S Engineering:Kk|Particulate filter|
    JP2002206017A|2001-01-10|2002-07-26|Kansai Paint Co Ltd|Epoxy resin composition|
    US6608163B2|2001-01-17|2003-08-19|General Electric Company|Polycarbonate copolymers having improved hydrolytic stability|
    JP2002316963A|2001-02-15|2002-10-31|Osaka Gas Co Ltd|Bisphenol with low activity as endocrine disruptor|
    WO2003000751A1|2001-05-10|2003-01-03|Bittner George D|Endocrine disruptive chemical free additives and method|
    FI110314B|2001-05-25|2002-12-31|Jujo Thermal Oy|Process for preparing thermosensitive recording material and thermosensitive recording material|
    JP5131506B2|2001-06-27|2013-01-30|新日鉄住金化学株式会社|Epoxy resin|
    JP4421145B2|2001-07-02|2010-02-24|Ｓａｂｉｃイノベーティブプラスチックスジャパン合同会社|Piping material|
    US6784228B2|2001-07-12|2004-08-31|Dainippon Ink And Chemicals, Inc.|Epoxy resin composition, cured article thereof, novel epoxy resin, novel phenol compound, and process for preparing the same|
    US6924328B2|2001-09-06|2005-08-02|Valspar Sourcing, Inc.|Stabilized coating compositions|
    US6916874B2|2001-09-06|2005-07-12|Valspar Sourcing, Inc.|Coating compositions having epoxy functional stabilizer|
    KR100878415B1|2001-09-28|2009-01-13|스미토모 베이클리트 컴퍼니 리미티드|Epoxy resin compositions and semiconductor devices|
    AU2002344461B2|2001-11-07|2007-07-12|Toray Industries, Inc.|Epoxy resin compositions for fiber-reinforced composite materials, process for production of the materials and fiber-reinforced composite materials|
    JP2003155420A|2001-11-22|2003-05-30|Nippon Shokubai Co Ltd|Aqueous resin composition|
    US7214742B2|2001-11-30|2007-05-08|Ciba Specialty Chemicals Corp.|2-hydroxyphenyl-s-triazine crosslinkers for polymer networks|
    JP2003178348A|2001-12-07|2003-06-27|Birukon Kk|Paper sheet discriminating counter and discriminating counting method|
    JP2003176348A|2001-12-11|2003-06-24|Uchu Kankyo Kogaku Kenkyusho:Kk|Polycarbonate and method of producing the same|
    US6716955B2|2002-01-14|2004-04-06|Air Products And Chemicals, Inc.|Poly polymer with low temperature crosslinking grafts and adhesive comprising the same|
    US6730361B2|2002-02-12|2004-05-04|Valspar Sourcing, Inc.|Method of coating a packaging container using crosslinkable polyester-polyurethane|
    JP4455886B2|2002-03-08|2010-04-21|バルスパーソーシング，インコーポレイティド|Coating with low content of volatile organic compounds|
    WO2003080706A1|2002-03-25|2003-10-02|Bayer Materialscience Ag|Polycarbonate having a high extensional viscosity|
    DE10216896A1|2002-04-17|2003-11-13|Goldschmidt Ag Th|Aqueous polysiloxane-polyurethane dispersion, its production and use in coating materials|
    US7008979B2|2002-04-30|2006-03-07|Hydromer, Inc.|Coating composition for multiple hydrophilic applications|
    JP2004010874A|2002-06-11|2004-01-15|Uchu Kankyo Kogaku Kenkyusho:Kk|Polycarbonate and its manufacturing method|
    US7157119B2|2002-06-25|2007-01-02|Ppg Industries Ohio, Inc.|Method and compositions for applying multiple overlying organic pigmented decorations on ceramic substrates|
    US20040005420A1|2002-07-08|2004-01-08|Burgoyne William Franklin|Fluid containment vessels with chemically resistant coatings|
    US20050267286A1|2003-10-20|2005-12-01|Shinya Nakamura|Curing accelerator for curing resin, curing resin composition, electronic component device and method for producing phosphine derivative|
    US7141627B2|2002-10-31|2006-11-28|Dainippon Ink And Chemicals, Inc.|Epoxy resin composition|
    DE10252627A1|2002-11-11|2004-05-27|Surface Specialties Germany Gmbh & Co. Kg|Binder and its application as a coating material for the coating of metal containers|
    JP3565831B2|2002-11-26|2004-09-15|新日鐵化学株式会社|Thermosetting resin composition|
    EP1572776B1|2002-12-04|2009-03-25|Blue Goo L.L.C.|Metal-acylates as curing agents for polybutadiene, melamine and epoxy compounds|
    CN1742236A|2002-12-06|2006-03-01|三菱化学株式会社|Electrophotographic photoreceptor|
    DE10304341A1|2003-02-03|2004-08-12|Basf Ag|Hydrolysis-resistant polyester|
    JP3986445B2|2003-02-17|2007-10-03|東都化成株式会社|Method for producing high-purity epoxy resin and epoxy resin composition|
    MXPA05010454A|2003-04-02|2005-11-04|Valspar Sourcing Inc|Aqueous dispersions and coatings.|
    TW200726784A|2003-04-07|2007-07-16|Hitachi Chemical Co Ltd|Epoxy resin molding material for sealing use and semiconductor device|
    US7060739B2|2003-04-25|2006-06-13|Milliken & Company|Antimicrobial fluoroelastomer rubber articles and compositions|
    US6844416B2|2003-05-02|2005-01-18|Xerox Corporation|Polycarbonates|
    US6939592B2|2003-05-08|2005-09-06|Ppg Industries Ohio, Inc.|Carbamated polyols, and compositions and methods using the same|
    WO2005000597A1|2003-06-25|2005-01-06|Asahi Kasei Chemicals Corporation|Developer for recording materials|
    US6984262B2|2003-07-16|2006-01-10|Transitions Optical, Inc.|Adhesion enhancing coating composition, process for using and articles produced|
    DE10332723A1|2003-07-18|2005-02-03|Degussa Ag|Solvent-containing coating compositions|
    AU2004261560A1|2003-07-28|2005-02-10|Valspar Sourcing, Inc.|Metal containers having an easily openable end and method of manufacturing the same|
    DE10338909A1|2003-08-23|2005-03-17|Bayer Materialscience Ag|Aromatic formals as additives for reducing the water absorption of polycarbonates|
    US6844071B1|2003-10-06|2005-01-18|General Electric Company|Multilayer articles comprising polycarbonate and polypropylene and method for their preparation|
    US7256228B2|2003-11-21|2007-08-14|General Electric Company|Stabilized polycarbonate polyester composition|
    US7675185B2|2003-12-11|2010-03-09|Hitachi Chemical Co., Ltd.|Epoxy resin molding material for sealing and electronic component|
    US7022765B2|2004-01-09|2006-04-04|General Electric|Method for the preparation of a poly-polyolefin composition, and composition prepared thereby|
    US20050196629A1|2004-02-12|2005-09-08|Valspar Sourcing, Inc.|Methods of coating interior container surfaces and containers containing internal coatings|
    CN100523046C|2004-03-03|2009-08-05|日立化成工业株式会社|Encapsulation epoxy resin material and electronic component|
    US7261843B2|2004-03-04|2007-08-28|Transitions Optical, Inc.|Photochromic optical article|
    US20050215670A1|2004-03-29|2005-09-29|Akihiko Shimasaki|Coating composition and article coated therewith|
    EP1584638A1|2004-03-29|2005-10-12|Imperial Chemical Industries Plc.|Coating composition based on modified epoxy resins|
    CA2561414A1|2004-03-31|2005-10-13|Asahi Kasei Chemicals Corporation|Hardener for epoxy resin and epoxy resin composition|
    EP1739116A4|2004-04-05|2008-10-22|Sekisui Chemical Co Ltd|Hollow resin fine particles, organic/inorganic hybrid fine particles, and method for producing hollow resin fine articles|
    US7150902B2|2004-04-07|2006-12-19|Pepsico, Inc.|High Tg coatings|
    JP4665425B2|2004-04-08|2011-04-06|東洋製罐株式会社|Aqueous coating composition, process for producing the same, and can body and can lid having coating film made of the aqueous coating composition|
    JP2005320446A|2004-05-10|2005-11-17|Sumitomo Bakelite Co Ltd|Epoxy resin composition for sealing semiconductor and semiconductor device|
    DE102004031158A1|2004-06-28|2006-01-19|Basf Ag|Use of polymers containing ether groups as solubilizers|
    MY139524A|2004-06-30|2009-10-30|Ciba Holding Inc|Stabilization of polyether polyol, polyester polyol or polyurethane compositions|
    CN101018536A|2004-07-14|2007-08-15|3M埃斯佩股份公司|Dental composition containing epoxy functional polymerizable compounds|
    DE602005026946D1|2004-07-16|2011-04-28|Mitsubishi Chem Corp|ELECTRO-PHOTOGRAPHIC LIGHT-SENSITIVE BODY|
    DE102004036757A1|2004-07-29|2006-03-23|Bayer Materialscience Ag|Cyclic oligoformals in polycarbonate|
    US7368171B2|2004-09-03|2008-05-06|H.B. Fuller Licensing & Financing, Inc.|Laminating adhesive, laminate including the same, and method of making a laminate|
    AU2005295228B2|2004-10-20|2012-02-16|Swimc Llc|Coating compositions for cans and methods of coating|
    DE102004054498A1|2004-11-11|2006-05-24|Bayer Materialscience Ag|Polycarbonate / polyformal blend as material for optical data storage with reduced water absorption|
    WO2006059363A1|2004-11-30|2006-06-08|Matsushita Electric Works, Ltd.|Epoxy resin composition for prepreg, prepreg, and multilayered printed wiring board|
    JP4760010B2|2004-12-22|2011-08-31|三菱化学株式会社|Polyether polyol resin, curable resin composition and cured product thereof|
    US7585904B2|2005-01-26|2009-09-08|Hitachi Chemical Company, Ltd.|Curing accelerator, curable resin composition and electronic parts device|
    CA2595969A1|2005-01-28|2006-08-03|Basf Aktiengesellschaft|Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces|
    WO2006087906A1|2005-02-18|2006-08-24|Hitachi Chemical Co., Ltd.|Novel curable resin, method for producing same, epoxy resin composition and electronic component device|
    WO2006090794A1|2005-02-23|2006-08-31|Asahi Kasei Chemicals Corporation|Latent hardener for epoxy resin and epoxy resin composition|
    US20060287479A1|2005-06-17|2006-12-21|Crawford Emmett D|Polyester compositions containing cyclobutanediol and articles made therefrom|
    EP2447059B1|2005-08-11|2018-05-30|Valspar Sourcing, Inc.|Bisphenol A and aromatic glycidyl ether-free coatings|
    DE102005038608A1|2005-08-16|2007-02-22|Basf Ag|Polymer composition for corrosion protection|
    DE102005045034A1|2005-09-21|2007-03-29|Rasselstein Gmbh|Method for passivating the surface of coated metal strips and device for applying the passive layer to a metal-coated steel strip|
    US7446234B2|2005-09-27|2008-11-04|Council Of Scientific And Industrial Research|Bisphenol compound and process for preparation thereof|
    US7910170B2|2005-10-18|2011-03-22|Valspar Sourcing, Inc.|Coating compositions for containers and methods of coating|
    US9156996B2|2005-10-21|2015-10-13|Valspar Sourcing, Inc.|Powder coloring system|
    UA91243C2|2005-11-10|2010-07-12|Ппг Б.В.|Metal substrate with epoxy based coating, process of coating, two layer coating system and use|
    DE102005056959A1|2005-11-29|2007-05-31|W.R. Grace & Co. Conn.|Metal-coating composition, especially for steel or aluminum food or drink cans, is based on PVC, acrylic resin, crosslinker and solvent, and contains no Bisphenol A or its diglycidyl ether|
    EP1798267A1|2005-12-15|2007-06-20|Dupont Powder Coatings France S.A.S.|Powder coating composition suitable for coil coating|
    TWI444406B|2006-01-12|2014-07-11|Nippon Steel & Sumikin Chem Co|An aromatic ether type polymer, a method for producing the same, and a polymer composition|
    EP1992655B9|2006-02-28|2012-03-07|DIC Corporation|Method of producing phenol resin and method of producing epoxy resin|
    GB0608560D0|2006-05-02|2006-06-07|Victrex Mfg Ltd|Polymeric materials|
    IL175638D0|2006-05-15|2007-08-19|Bromine Compounds Ltd|Flame retardant composition|
    US8865783B2|2006-05-15|2014-10-21|Bromine Compounds Ltd.|Flame retardant composition|
    US7981515B2|2006-05-30|2011-07-19|Ppg Industries Ohio, Inc.|Bis epoxy polyesters and food cans coated with a composition comprising same|
    US7619056B2|2006-06-02|2009-11-17|New Jersey Institute Of Technology|Thermoset epoxy polymers from renewable resources|
    GB2451395B|2006-06-14|2011-06-29|Sanyo Chemical Ind Ltd|Method for producing resin dispersions and resin particles|
    JP5279176B2|2006-06-29|2013-09-04|エアプロダクツアンドケミカルズインコーポレイテッド|Curing agent for epoxy resin and coating composition|
    JP4088337B2|2006-07-20|2008-05-21|積水化学工業株式会社|Adhesive for electronic parts and method for producing semiconductor chip laminate|
    JP5261896B2|2006-07-27|2013-08-14|ダイキン工業株式会社|Coating composition|
    US20080064795A1|2006-09-08|2008-03-13|George Bittner|Materials free of endocrine disruptive activity|
    EP2089225B1|2006-09-19|2018-08-22|Valspar Sourcing, Inc.|Food and beverage containers and methods of coating|
    BRPI0717071B1|2006-09-19|2018-12-04|Valspar Sourcing Inc|food and drink coated article|
    JP5134233B2|2006-11-29|2013-01-30|出光興産株式会社|ADAMANTAN DERIVATIVE, PROCESS FOR PRODUCING THE SAME AND RESIN COMPOSITION CONTAINING ADAMANTAN DERIVATIVE|
    JP4909049B2|2006-12-19|2012-04-04|ダイニチ工業株式会社|Combustion device|
    DE102007013273A1|2007-03-16|2008-09-18|Bayer Materialscience Ag|Method for producing multilayer containers|
    JP4845129B2|2007-03-28|2011-12-28|国立大学法人京都大学|Flexible substrate and manufacturing method thereof|
    WO2008121959A1|2007-04-02|2008-10-09|Valspar Sourcing, Inc.|Stabilizer polymer and coating compositions thereof|
    US8075812B2|2007-04-04|2011-12-13|Sabic Innovative Plastics Ip B.V.|Method of separating a poly composition from a solvent, and poly composition prepared thereby|
    WO2008137562A1|2007-05-02|2008-11-13|Valspar Sourcing, Inc.|Coating system|
    DE102007022130B4|2007-05-11|2015-02-19|Bayer Intellectual Property Gmbh|Process for the preparation of polycarbonate after the melt transesterification process|
    US8740692B2|2007-05-15|2014-06-03|Shfl Entertainment, Inc.|Method and apparatus for variable contribution progressive jackpots|
    CN101755328B|2007-07-19|2011-08-31|积水化学工业株式会社|Adhesive for electronic component|
    WO2009015493A1|2007-07-27|2009-02-05|Eth Zurich|Compositions comprising carbon coated, non-noble metal nanoparticles|
    WO2009036790A1|2007-09-21|2009-03-26|Henkel Ag & Co. Kgaa|Primer compositions for adhesive bonding systems and coatings|
    US8501287B2|2007-11-21|2013-08-06|Eastman Chemical Company|Plastic baby bottles, other blow molded articles, and processes for their manufacture|
    CN101244290A|2007-11-30|2008-08-20|顾其胜|Method for preparing crosslinked hyaluronic acid microgel for tissue filling|
    WO2009089145A1|2008-01-08|2009-07-16|Dow Global Technologies Inc.|High tg epoxy systems for composite application|
    EP2113534B8|2008-04-01|2011-09-21|Mitsubishi Gas Chemical Company, Inc.|Resin composition, prepreg and metal-foil-clad laminate|
    US8346576B2|2008-07-29|2013-01-01|Hartford Fire Insurance Company|Apparatus, method, program and computer-readable recording medium for providing guaranteed minimum accumulated benefit contract funded with matching bond investments|
    US20100030576A1|2008-07-30|2010-02-04|Mclane Advanced Technologies, Llc|System and Method for Pain Management|
    US20100056721A1|2008-09-03|2010-03-04|Kathryn Wright|Articles prepared from certain hydrogenated block copolymers|
    JP2010064293A|2008-09-09|2010-03-25|Furukawa-Sky Aluminum Corp|Coated aluminum plate and aluminum can lid|
    AU2009319890B2|2008-11-26|2015-09-10|Swimc Llc|Polyester-carbamate polymer and coating compositions thereof|
    EP2373751A1|2008-12-10|2011-10-12|Valspar Sourcing, Inc.|Polyester polymer having phenolic functionality and coating compositions formed therefrom|
    US8168721B2|2009-02-06|2012-05-01|Eastman Chemical Company|Coating compositions containing tetramethyl cyclobutanediol|
    AU2010216270B2|2009-02-19|2013-03-07|3M Innovative Properties Company|Fusion bonded epoxy coating compositions that include magnesium oxide|
    MX338773B|2009-04-09|2016-05-02|Valspar Sourcing Inc|Polymer having unsaturated cycloaliphatic functionality and coating compositions formed therefrom.|
    BRPI1014962B1|2009-04-09|2020-03-03|Swimc Llc|COATING COMPOSITION, METHOD, AND, COATED ARTICLE|
    JP5492883B2|2009-05-22|2014-05-14|旭化成ケミカルズ株式会社|Car lamp peripheral parts|
    FR2946049B1|2009-05-27|2013-01-18|Chaire Europ De Chimie Nouvelle Pour Un Dev Durable|NATURAL PHENOLIC COMPOUNDS AND THEIR ACTIVATION MODE FOR THE FORMULATION OF THERMOSETTING RESINS|
    US8273849B2|2009-12-30|2012-09-25|Sabic Innovative Plastics Ip B.V.|Isosorbide-based polycarbonates, method of making, and articles formed therefrom|
    WO2011130671A2|2010-04-16|2011-10-20|Valspar Sourcing, Inc.|Coating compositions for packaging articles and methods of coating|
    US8526919B2|2010-11-17|2013-09-03|Tip Solutions, Inc.|Message injection system and method|
    US9018335B2|2010-12-29|2015-04-28|Empire Technology Development Llc|Substances for use as bisphenol a substitutes|
    MX351419B|2010-12-29|2017-10-13|Akzo Nobel Coatings Int Bv|Adhesion promoter resin compositions and coating compositions having the adhesion promoter resin compositions.|
    EP2812404B1|2012-02-07|2019-11-06|Swimc Llc|Containers and other articles coated with compositions|
    PL2673323T3|2011-02-07|2018-08-31|Valspar Sourcing, Inc.|Coating compositions for containers and other articles and methods of coating|
    WO2012149340A1|2011-04-27|2012-11-01|University Of Massachusetts Lowell|Bisphenol a free epoxy resins|
    US10125288B2|2011-05-02|2018-11-13|Ppg Industries Ohio, Inc.|Coating compositions comprising 2,2′-biphenol|
    US20120282475A1|2011-05-05|2012-11-08|Ppg Industries Ohio, Inc.|Non-aqueous dispersions comprising a polyester stabilizer and their use in coatings|
    US9670378B2|2011-05-23|2017-06-06|Ppg Industries Ohio, Inc.|Coating compositions with improved adhesion to containers|
    US20120301646A1|2011-05-23|2012-11-29|PPG Insdustries Ohio, Inc.|Coating compositions for containers|
    US20120301647A1|2011-05-23|2012-11-29|Ppg Industries Ohio, Inc.|Phosphatized polyesters and coating compositions containing the same|
    BR112013030102A2|2011-05-25|2016-09-20|Solvay Specialty Polymers Usa|polymers with reduced estrogenic activity|
    US20120302690A1|2011-05-27|2012-11-29|Ppg Industries Ohio, Inc.|Grafted acrylic comprising water soluble and water insoluble portions and lattices and coatings comprising the same|
    US20130052381A1|2011-08-22|2013-02-28|Robert R. Gallucci|Polyepoxides and epoxy resins and methods for the manufacture and use thereof|
    US9605177B2|2012-03-29|2017-03-28|Blue Cube Ip Llc|Waterborne dispersions|
    EP2847288B1|2012-05-09|2018-05-23|Dow Global Technologies LLC|A polyester composition and method of producing the same|
    CN104540744B|2012-08-09|2017-08-25|威士伯采购公司|Container coating system|
    MY180067A|2012-08-09|2020-11-20|Valspar Sourcing Inc|Compositions for containers and other articles and methods of using same|
    WO2014025410A1|2012-08-09|2014-02-13|Valspar Sourcing, Inc.|Stabilizer and coating compositions thereof|
    ES2644018T3|2013-03-15|2017-11-27|Akzo Nobel Coatings International B.V.|Acrylic grafted polyether resins based on phenolestearic acid and coating compositions formed therefrom|
    BR112015023366A2|2013-03-15|2017-07-18|Akzo Nobel Coatings Int Bv|polyether resin, coating composition, and substrate coating method|
    EP2997094B1|2013-05-16|2019-04-03|The Coca-Cola Company|Polymer compositions and coatings for food and beverage packaging|
    EP3725767A1|2013-10-17|2020-10-21|Swimc Llc|Diphenol) compounds and polymers formed therefrom|JPS60109760A|1983-11-18|1985-06-15|Toshiba Corp|Phase controller of power converter|
    WO2011130671A2|2010-04-16|2011-10-20|Valspar Sourcing, Inc.|Coating compositions for packaging articles and methods of coating|
    PL2673323T3|2011-02-07|2018-08-31|Valspar Sourcing, Inc.|Coating compositions for containers and other articles and methods of coating|
    EP2812404B1|2012-02-07|2019-11-06|Swimc Llc|Containers and other articles coated with compositions|
    US9321935B2|2011-05-23|2016-04-26|Ppg Industries Ohio, Inc.|Container coating compositions|
    EP2882401A4|2012-08-09|2016-03-30|Valspar Sourcing Inc|Dental materials and method of manufacture|
    CN104541210A|2012-08-09|2015-04-22|威士伯采购公司|Developer for thermally responsive record materials|
    WO2014025410A1|2012-08-09|2014-02-13|Valspar Sourcing, Inc.|Stabilizer and coating compositions thereof|
    CN104540874B|2012-08-09|2018-05-01|威士伯采购公司|Makrolon|
    MY180067A|2012-08-09|2020-11-20|Valspar Sourcing Inc|Compositions for containers and other articles and methods of using same|
    CN104540744B|2012-08-09|2017-08-25|威士伯采购公司|Container coating system|
    MX2015011304A|2013-03-01|2015-12-03|Valspar Sourcing Inc|Aqueous coating compositions including phenolic resin.|
    CN105144422B|2013-03-25|2019-05-10|大日本印刷株式会社|Battery use packing material|
    WO2015050755A1|2013-10-02|2015-04-09|Valspar Corporation|Removable closure and coating system|
    MX2016004086A|2013-10-02|2016-06-06|Valspar Sourcing Inc|Removable closure and coating system.|
    EP3725767A1|2013-10-17|2020-10-21|Swimc Llc|Diphenol) compounds and polymers formed therefrom|
    US10023586B2|2013-12-19|2018-07-17|Archer Daniels Midland Company|Enhanced regio-selectivity in glycol acylation|
    KR101418026B1|2014-02-06|2014-08-08|동우 화인켐 주식회사|Thermosetting ink composition|
    JP6746501B2|2014-04-14|2020-08-26|ヴァルスパー・ソーシング・インコーポレーテッド|Method of preparing compositions for containers and other articles and methods of use thereof|
    US10793742B2|2014-05-19|2020-10-06|Valspar Sourcing, Inc.|Polyethers containing non-bisphenolic cyclic groups|
    US10442572B2|2014-10-20|2019-10-15|Ppg Industries Ohio, Inc.|Coated food-contacting containers|
    US20160107818A1|2014-10-20|2016-04-21|Ppg Industries Ohio. Inc.|Polyethers derived from benzene dimethanol|
    TWI614275B|2015-11-03|2018-02-11|Valspar Sourcing Inc|Liquid epoxy resin composition for preparing a polymer|
    EP3559127A4|2016-12-21|2020-05-13|Swimc Llc|Polymers containing reactive carbonyl groups and coating compositions containing such polymers|
    US20190345359A1|2016-12-28|2019-11-14|Swimc Llc|Packaging coating resins derived from reactions of phenols with polyolefinic terpenes|
    EP3604157A4|2017-03-22|2020-07-15|Toyo Seikan Co., Ltd.|Metallic bottle can and method for manufacturing same|
    CN110662814B|2017-05-15|2021-11-16|陶氏环球技术有限责任公司|Water-based adhesive composition|
    EP3684871A4|2017-09-19|2021-03-24|Swimc LLC|Coating compositions including a furan-containing polyester, articles, and methods of coating|
    WO2021097308A1|2019-11-14|2021-05-20|Swimc Llc|Metal packaging powder coating compositions, coated metal substrates, and methods|
    US20210348338A1|2020-05-05|2021-11-11|Actega North America, Inc|Environmentally-friendly heat sealable aqueous barrier coating for cellulosic substrate and methods of making and using the same|
    法律状态:
    2020-08-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-08-18| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-15| B25A| Requested transfer of rights approved|Owner name: ENGINEERED POLYMER SOLUTIONS, INC. (US) |
    2020-09-29| B25A| Requested transfer of rights approved|Owner name: THE VALSPAR CORPORATION (US) |
    2020-10-13| B25A| Requested transfer of rights approved|Owner name: THE SHERWIN-WILLIAMS COMPANY (US) |
    2020-10-27| B25A| Requested transfer of rights approved|Owner name: THE SHERWIN-WILLIAMS HEADQUARTERS COMPANY (US) |
    2020-11-10| B25A| Requested transfer of rights approved|Owner name: SWIMC LLC (US) |
    2021-01-05| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/04/2011, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |
    优先权:
    申请号 | 申请日 | 专利标题
    US32499710P| true| 2010-04-16|2010-04-16|
    US61/324,997|2010-04-16|
    US61/324997|2010-04-16|
    US33313310P| true| 2010-05-10|2010-05-10|
    US61/333,133|2010-05-10|
    US61/333133|2010-05-10|
    PCT/US2011/032738|WO2011130671A2|2010-04-16|2011-04-15|Coating compositions for packaging articles and methods of coating|
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