Compositions for containers and other articles and methods of using same
Abstract
The present invention provides a polymer that is preferably a polyether polymer for use in coating compositions. Furthermore, packages comprising the polymer and methods for making such packages are provided. The present invention further provides powder coating compositions that include the polymer, which are useful in a wide variety of coating end uses including, for example, valve and pipe coatings.

Term
7.9 yearsleft in the term
Expires 5 August 2034.
- Priority
- Filed
- Granted
- Today
- Expires
39 claims: 11 independent, 28 dependent
- 1INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL REIVINDICACIONES Habiéndose descrito la invención como antecede, se reclama como propiedad lo contenido en las siguientes reivindicaciones:1. Un artículo caracterizado porque comprende: un recipiente de envasado, o una porción de este, que tiene un sustrato metálico y una composición de revestimiento dispuesta en al menos una porción del sustrato, en donde la composición de revestimiento incluye un polímero de poliéter que está sustancialmente libre de bisfenol A, bisfenol F, bisfenol S y epóxidos de estos y es un producto de reacción de ingredientes que incluye: (i) un diepóxido que incluye un segmento de Fórmula (II), (Π) en donde: H denota un átomo de hidrógeno, si está presente, cada R 1 , si está presente, es independientemente un átomo o grupo que tiene un peso atómico de al menos 15 Daltons, v es 1 a 4, y INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL IMPI en donde dos o más grupos R 1 pueden unirse para formar uno o más grupos cíclicos;y (ii) un monofenol polihídrico.
- 2Un artículo caracterizado porque comprende:un recipiente de envasado, o una porción de este, que tiene: un sustrato metálico;una composición de revestimiento dispuesta en al menos una porción del sustrato, la composición de revestimiento que comprende: un polímero de poliéter que incluye al menos 25% en peso de grupo arilo o heteroarilo y es sustancialmente libre de monómero de bisfenol ligado, o un diepóxido de estos, e incluye uno o más segmentos de Fórmula (II) , en donde: H denota un átomo de hidrógeno, si está presente, cada R 1 , si está presente, es independientemente un átomo o grupo que tiene un peso atómico de al menos 15 Daltons, v es 1 a 4, y 112 IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL en donde dos o más grupos R 1 pueden unirse para formar uno o más grupos cíclicos.
- 3El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque el recipiente envasado, o una porción de este, es un recipiente para alimentos o bebidas o una porción de este que tiene la composición de revestimiento dispuesta en al menos una porción de una superficie interna.
- 4El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque cada uno de los átomos de oxígeno descritos en la Fórmula (II) está presente en un enlace éter.
- 5El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque el polímero incluye uno o más de los segmentos -CH2-CH(OH) -CH2- o -CH2CH 2 -CH(OH)-.
- 6El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque v es 2 a 4.
- 7El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque al menos un R 1 se une al anillo de fenileno en una posición orto con relación a al menos uno de los átomos de oxígeno descritos en la Fórmula (II).
- 8El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque cada átomo de 113 IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL oxígeno descrito en la Fórmula (II) tiene al menos un R 1 en posición orto a él en el anillo de fenileno.
- 9El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque cada R 1 es, independientemente, seleccionado de un grupo orgánico, un grupo que contiene azufre o un grupo que contiene nitrógeno.
- 10El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque cada R 1 es un grupo orgánico.
- 11El artículo de conformidad con la reivindicación 10, caracterizado porque cada R 1 es una entidad de hidrocarburo que incluye de uno a cuatro átomos de carbono.
- 12El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque el polímero de poliéter es un producto de reacción de reactantes que incluyen un diepóxido y un monofenol dihídrico.
- 13El artículo de conformidad con la reivindicación 12, caracterizado porque cada uno del diepóxido y el monofenol dihídrico incluye un segmento de la Fórmula (II) .
- 14El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque el polímero de poliéter es un producto de reacción de reactantes que incluyen un primer monofenol dihídrico y un diepóxido de un 114 IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL segundo monofenol dihídrico, y en donde el primer y segundo monofenoles dihídricos son iguales o diferentes.
- 15El artículo de conformidad con la reivindicación 14, caracterizado porque el diepóxido es un éter diglicidilo del segundo monofenol dihídrico.
- 16El artículo de conformidad con cualquiera de las reivindicaciones 1 ó 12 a 15, caracterizado porque el diepóxido es no genotóxico.
- 17El artículo de conformidad con cualquiera de las reivindicaciones 1 ó 12 a 16, caracterizado porque el diepóxido es un compuesto de la Fórmula (IV):en donde: H y R 1 son como se describió en la Fórmula (II);v es 1 a 4;s es 0 a 1;R 3 , si está presente, es un grupo divalente;y cada R 4 es independientemente un átomo de hidrógeno, un átomo de halógeno, o un grupo orgánico que puede incluir uno o más heteroátomos. 115 IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL
- 18El artículo de conformidad con cualquiera de las reivindicaciones 14 a 17, caracterizado porque el primer monofenol dihídrico se selecciona de uno o más de catecol, resorcinol o hidroquinona.
- 19El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque el segmento de la Fórmula (II) se deriva de un diepóxido de 2,5-di-tbutilhidroquinona.
- 20El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque el polímero de poliéter, presenta una temperatura de transición vitrea de al menos 60 °C.
- 21El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque los grupos fenilenos constituyen al menos 25 por ciento en peso del polímero de poliéter.
- 22El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque los grupos fenilenos constituyen al menos 45 por ciento en peso del polímero de poliéter.
- 23El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque el polímero de poliéter tiene un índice de polidispersidad de 2 a 3.5 antes de cualquier cura de la composición de revestimiento.
- 24El artículo de conformidad con cualquier 116 IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL reivindicación anterior, caracterizado porque el polímero de poliéter no incluye ningún halógeno.
- 25El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque el polímero de poliéter tiene un peso molecular promedio en número de al menos 2,000 y una temperatura de transición vitrea de al menos 30°C, y en donde la composición de revestimiento incluye al menos 10 por ciento en peso del polímero de poliéter, con base en los sólidos de resina totales en la composición de revestimiento.
- 26El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque una cadena principal del polímero de poliéter está libre de enlaces éster.
- 27El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque la composición de revestimiento contiene menos de 1000 partes por millón (ppm) de bisfenol A, bisfenol F, bisfenol S y diepóxidos de estos.
- 28El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque la composición de revestimiento contiene menos de 1000 partes por millón (ppm) de monómeros de bisfenol y diepóxidos de estos.
- 29El artículo de conformidad con cualquier reivindicación anterior, caracterizado porque el artículo es 117 IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL un artículo de envasado para alimentos o bebidas que incluye un producto de alimentos o bebidas envasado en él.
- 30Una composición de revestimiento, caracterizada porque es como se define en cualquier reivindicación anterior.
- 31Un método caracterizado porque comprende, proporcionar una composición de revestimiento de conformidad con cualquier reivindicación anterior, y aplicar la composición de revestimiento a al menos una porción de un sustrato metálico antes o después de formar el sustrato metálico en un recipiente para alimentos o bebidas o una porción de este.
- 32El método de conformidad con la reivindicación 31, caracterizado porque la composición de revestimiento se aplica a al menos una porción de una superficie interior de un recipiente para alimentos o bebidas, o una porción de este.
- 33Una composición de revestimiento en polvo, caracterizada porque comprende un polvo base que incluye el polímero de poliéter de conformidad con cualquier reivindicación anterior.
- 34La composición de revestimiento en polvo de conformidad con la reivindicación 33, caracterizada porque la composición de revestimiento en polvo es, sustancialmente, libre de cualquiera de los monómeros de bisfenol móvil o 118 IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL ligado y diepóxidos de este.
- 35Un método, caracterizado porque comprende:proporcionar un sustrato metálico;aplicar la composición de revestimiento en polvo de conformidad con la reivindicación 33 ó 34 al sustrato metálico;calentar el sustrato metálico antes, durante o después de la aplicación de la composición de revestimiento en polvo para formar un revestimiento curado a partir de la composición de revestimiento en polvo.
- 36El método de conformidad con la reivindicación 35, caracterizado porque el sustrato metálico se incluye en un artículo para almacenar o transportar líquido.
- 37El método de conformidad con la reivindicación 36, caracterizado porque el revestimiento curado se ubica en una superficie prevista para estar en contacto con agua potable.
- 38Un artículo caracterizado porque es el resultado de un método de conformidad con cualquiera de las reivindicaciones 35 a 37.
- 39El artículo de conformidad con la reivindicación 38, caracterizado porque el artículo es una válvula o conexión para agua.
Independent claims39
476 paragraphs in 140 sections, as filed
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
COMPOSITIONS FOR CONTAINERS AND OTHER ARTICLES AND METHODS
TO USE THEM
BACKGROUND OF THE INVENTION
The application of coatings on metals to retard or inhibit corrosion has been established. This is particularly true in the area of packaging containers, such as metal cans for food and beverages. 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 the metal and the packaged product can cause corrosion of the metal container and consequently contaminate the packaged product. This is particularly true when the contents of the container are chemically aggressive in nature. Protective coatings are also applied to the interior of food and beverage containers to prevent corrosion in the void space of the container between the food product fill line and the container lid.
Preferably, packaging coatings should allow for high speed application to the substrate and provide the necessary properties when cured to meet end use requirements. For example, the coating must be safe for food contact, must not adversely affect the taste of the
Ref. 249932
<img file="MX373246B_D0001.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY A packaged food or beverage product must have excellent adhesion to the substrate, resist staining and other coating defects, such as bursting, opacity, and/or bubbling, and must resist degradation over prolonged periods, even when are exposed to harsh environments. Additionally, the liner generally must be able to maintain adequate film integrity during container manufacture and withstand the processing conditions to which the container may be exposed during product packaging.
Various coatings have been used as protective coatings for can interiors, including polyvinyl chloride-based coatings and epoxy-based coatings incorporating bisphenol A (BPA). Each of these types of coatings, however, has potential drawbacks. For example, the recycling of materials containing polyvinyl chloride polymers or related halide-containing vinyl polymers can be problematic. Additionally, some prefer to reduce or eliminate certain BPA-based compounds commonly used to formulate epoxy food contact coatings.
What is needed on the market is an improved binder system for use in coatings, such as, for example, packaging coatings.
<img file="MX373246B_D0002.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
BRIEF DESCRIPTION OF THE INVENTION
The present invention provides a polymer useful for a wide variety of applications, such as, for example, as a binder polymer in a coating composition. While the polymer of the present invention may have any chemical backbone, the polymer is a polyether polymer, preferably including aromatic ether segments. The polymer is preferably substantially free or completely free of one or both: (i) linked bisphenol A, bisphenol F, bisphenol S, and diepoxides thereof, and (ii) one or more of linked polyhydric phenol monomers, and epoxides thereof, that have estrogen agonist activity for a human estrogen receptor greater than or equal to that of bisphenol S, greater than or equal to that of 4,4'(propane-2,2-diyl)bis(2,6-dibromophenol), or greater than or equal to that of 2,2-bis(4-hydroxyphenyl) )propanoic. In preferred embodiments, the polymer is substantially free, more preferably essentially free, even more preferably essentially completely free, and optionally completely free of: bound bisphenol monomers and epoxides thereof. In some embodiments, the polymer is substantially free, more preferably completely free, of any bound polyhydric polyphenol or epoxide thereof.
Preferred polymers of the present invention are
<img file="MX373246B_D0003.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY suitable for use in a variety of end uses including, for example, as a coating film-forming material. In some embodiments, the polymer has a glass transition temperature of at least 30°C, more preferably 60°C, and an average molecular weight of at least 1000, more preferably 2000. The aryl or heteroaryl groups preferably constitute , at least 25 percent by weight of the polymer.
In preferred embodiments, the polymer further includes pendant hydroxyl groups (eg, secondary hydroxyl groups), and more preferably one or more -CH segments<sub>2</sub>-CH(OH)-CH<sub>2</sub>- or -CH<sub>2</sub>-CH<sub>2</sub>-CH(OH)-, which are preferably derived from an oxirane group and are located in a main chain of the polymer.
The polymer preferably includes one or more segments, and more preferably a plurality of segments having one or more aryl or heteroaryl groups in a backbone portion of the segment. The polymer preferably includes a plurality of segments of Formula (I) below:
-O-Ar-Oen where Ar represents an aryl or heteroaryl group and each described oxygen is bonded to an atom of the aryl or heteroaryl group and is preferably part of an ester or ether bond, more preferably an ether bond.
<img file="MX373246B_D0004.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
In some embodiments, the aryl or heteroaryl group described in Formula (I) includes one or more, more preferably two or more, substituent groups (i.e., other than hydrogen) that are bonded to the ring, preferably at a position ortho relative to one of the described oxygen atoms.
In preferred embodiments, the polymer includes one or more, and even more preferably a plurality of segments of Formula (I) as depicted in Formula (II):
<img file="MX373246B_D0005.tif" />
Formula (II) where:
• H denotes a hydrogen atom, if present, • each R<sup>1</sup>, if present, is, independently, an atom or group having an atomic weight of at least 15 daltons, • v is 0 to 4, and • wherein two or more R groups<sup>1</sup> they can join together to form one or more cyclic groups.
Non-limiting examples of R groups<sup>1</sup> include groups having at least one carbon atom, one halogen atom, one sulfur-containing group, or any other suitable group, preferably having an atomic weight of at least
<img file="MX373246B_D0006.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY at least 15 daltons, which is preferably practically non-reactive with an epoxy group. Currently, organic groups, particularly organic groups free of halogen atoms, are preferred.
Typically, the polymer is a reaction product of ingredients including a diepoxide and a diol. In some embodiments, the polyether polymer of the present invention is a reaction product of ingredients including a first dihydric monophenol and a second dihydric monophenol diepoxide (which is preferably non-genotoxic), wherein the first and second monophenols dihydrics are the same or different compound. In one embodiment, the polyether polymer is a reaction product of ingredients that include one or more of: (i) substituted or unsubstituted catechol, resorcinol, hydroquinone, or a mixture of these and (ii) a diepoxide (eg ., a diglycidyl ether) of substituted or unsubstituted catechol, resorcinol, hydroquinone, or a mixture of these.
The present invention further provides a coating composition that includes the polymer described herein, more preferably a polyether polymer described herein. The coating composition preferably includes at least a film-forming amount of the polymer and may optionally include one or more additional polymers. The
<img file="MX373246B_D0007.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY coating composition is useful for coating a wide variety of substrates, including an internal or external coating on metal containers for packaging or portions thereof.
In preferred embodiments, the coating composition is useful as a food contact coating on a food or beverage container. The coating composition is preferably substantially free of mobile or bound BPA or BPA diglycidyl ether (BADGE), and more preferably completely free of BPA or BADGE. More preferably, the coating composition is substantially free, and most preferably completely free, of mobile or bound polyhydric phenols having estrogen agonist activity greater than or equal to that of: 4,4'-(propane-2,2- diyl)diphenol, more preferably BPS, still more preferably 4,4<sup>1</sup> -(propane2,2-diyl)bis(2,6-dibromophenol) and optimally 2,2bis(4-hydroxyphenyl)propanoic acid. In certain preferred embodiments, the coating composition is substantially free, more preferably completely free, of bound biphenol monomers and epoxides thereof. In some embodiments, the coating composition is substantially free, more preferably completely free, of bound polyhydric polyphenol monomers and
<img file="MX373246B_D0008.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY epoxides of these.
The coating composition may further have utility in a variety of coating end uses including, for example, coatings for valves and fittings, especially valves and fittings for use with potable water; pipes for transporting liquids, especially pipes for drinking water; and liquid storage tanks, especially potable water tanks such as, for example, bolted steel water tanks.
In one embodiment, the coating composition of the present invention is a powder coating composition, preferably including a base powder, formed at least in part from the polymer of the present invention. The coating composition may include one or more optional ingredients in the base powder particles and/or in separate particles. Such optional ingredients may include, for example, crosslinker, cure accelerator, color pigment, filler, flow additives, etc.
The present invention further provides packaging articles having a coating composition of the present invention applied to a surface of the packaging article. In one embodiment, the article for packaging is a container, such as a food or beverage container, or a portion thereof (for example, a lid).
<img file="MX373246B_D0009.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY thread, an end of a beverage can, an end of a food can, etc.), where at least a portion of an internal surface of the container is coated with a coating composition described in the present disclosure suitable for prolonged contact with a beverage or food product or other packaged product.
In one embodiment, a method of preparing a container including an inner food contact liner of the present invention is provided. The method includes: providing a coating composition described herein that includes a binder polymer and, optionally, a liquid carrier; and applying the coating composition to at least a portion of a surface of a substrate before or after forming the substrate in a container or a portion thereof having the coating composition disposed on an internal surface. Typically, the substrate is a metal substrate, although the coating composition can be used to coat other substrate materials, if desired. Examples of other substrate materials may include cardboard, plastics (eg, polyesters such as polyethylene terephthalates; nylons; polyolefins such as, eg, polypropylene, polyethylene, and the like; ethylene vinyl alcohol; polyvinylidene chloride; and copolymers of these) and paper.
<img file="MX373246B_D0010.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
In one embodiment, a method of forming food or beverage cans, or a portion thereof, is provided; the method includes: applying a coating composition described herein to a metal substrate (for example, applying the coating composition to the metal substrate in the form of a flat coil or sheet), curing the coating composition, and forming the substrate in a food or beverage can or a portion thereof.
In certain embodiments, forming the substrate into an article includes forming the substrate into an end of a can or a can body. In certain embodiments, the article is a two-piece stretched food can, a three-piece food can, a food can end, a drawn and pressed food or beverage can, a beverage can end, the end of a cap opens easily, a screw cap and the like. Suitable metal substrates include, for example, steel or aluminum.
In certain embodiments, a packaging container is provided having: (a) a coating composition of the present invention disposed on at least a portion of an internal or external surface of the container and (b) a product packaged therein, such as as a food, beverage, cosmetic, or medicinal product.
<img file="MX373246B_D0011.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
In one embodiment, a packaging container is provided having a coating composition of the present invention disposed on an inner surface that includes a packaged product intended for human contact or consumption, for example, a food or beverage product, a cosmetic product or a medicinal product.
The above brief description of the present invention is not intended to describe every described embodiment or every implementation of the present invention. The following description more specifically exemplifies the illustrative embodiments. Lists of examples are used as a guide in various parts of the application, and the examples may be used in various combinations. In each case, the indicated list is used only as a representative group and should not be construed as an exclusive list. Unless otherwise indicated, structural representations included in this description are not intended to indicate any particular stereochemistry and are intended to include all stereoisomers.
DEFINITIONS
As used herein, the term "organic group" means a hydrocarbon group (with optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that is classified as an aliphatic group, cyclic group, or a combination of
<img file="MX373246B_D0012.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY aliphatic and cyclic groups (eg, alkaryl and aralkyl groups).
The term "cyclic group" means a closed ring hydrocarbon group which is classified as an alicyclic group or an aromatic group; both can include heteroatoms.
The term "alicyclic group" refers to a cyclic hydrocarbon group having properties similar to those of aliphatic groups.
The term aryl group (eg, an arylene group) refers to a closed aromatic ring or ring system, such as phenylene, naphthylene, biphenylene, fluorenylene, and indenyl, as well as heteroarylene groups (eg, a hydrocarbon). aromatic or aromatic-like closed ring or ring system, wherein one or more of the atoms in the ring are elements other than carbon (eg, nitrogen, oxygen, sulfur, etc.)). Suitable heteroaryl groups include furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, 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.
<img file="MX373246B_D0013.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
When such groups are divalent, they are typically referred to as arylene or heteroarylene groups (eg, furylene, pyridylene, etc.)
A group that can be the same or a different group is specified as independently.
Substitution on the organic groups of the compounds of the present invention is contemplated. In order to simplify the description and narration of certain terminology used throughout this application, the terms group and portion are used to differentiate between chemical species that allow substitution or that can be substituted and those that do not allow or that cannot be substituted in that way. way. Thus, when the term group is used to describe a chemical substituent, the chemical material described includes the unsubstituted group and that group with O, N, Si, or S atoms, for example, in the pad (as in an alkoxy group) in addition of carbonyl groups or other conventional substitution. When the term "portion" is used to describe a chemical compound or substituent, it is intended to include only an unsubstituted chemical material. For example, the phrase "alkyl group" is intended to include pure open-chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like, as well as alkyl substituents containing other substituents known in the art, such as hydroxy, alkoxy,
<img file="MX373246B_D0014.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, "alkyl group" includes ether, haloalkyl, nitroalkyl, carboxyalkyl, hydroxyalkyl, sulfoalkyl, etc. groups. On the other hand, the phrase, "alkyl moiety" is limited only to the inclusion of pure open-chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like. As used in the present description, the term "group" is intended to be a narrative, both of the particular portion and of the broader class of substituted and unsubstituted structures, which includes the entity.
The term polyhydric phenol, as used herein, refers broadly to any compound having one or more aryl or heteroaryl groups (most often one or more phenylene groups) and at least two hydroxyl groups attached to the compound. same or different aryl or heteroaryl group. Thus, for example, both hydroquinone and 4,4'-biphenol are considered polyhydric phenols. As used herein, polyhydric phenols typically have six carbon atoms in an aryl ring, although it is contemplated that aryl or heteroaryl groups having other ring sizes may be used.
The term polyhydric monophenol refers to a polyhydric phenol that (i) includes an aryl or heteroaryl (more
<img file="MX373246B_D0015.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY typically, a phenylene group) that has at least two hydroxyl groups attached to the aryl or heteroaryl ring and (ii) does not include any other aryl or heteroaryl ring that has a hydroxyl group attached to the ring. The term "dihydric monophenol" refers to a polyhydric monophenol that includes only two hydroxyl groups attached to the aryl or heteroaryl ring.
The term polyhydric polyphenol (including bisphenols) refers to a polyhydric phenol that includes two or more aryl or heteroaryl groups, each having at least one hydroxyl group attached to the aryl or heteroaryl ring.
The term bisphenol refers to a polyhydric polyphenol having two phenylene groups each including six carbon rings and a hydroxyl group attached to a ring carbon atom, wherein the rings of the two phenylene groups share no atoms in common.
The term phenylene, as used herein, refers to an aryl ring with six carbon atoms (eg, as in a benzene group) which may have any substituent group (including, eg, hydrogen atoms, halogens, hydrocarbon groups, hydroxyl groups, ether bonds, ester bonds, etc.). Thus, for example, each of the following aryl groups is a phenylene ring: -C<sub>6</sub>H<sub>4</sub>-, -C<sub>6</sub>H<sub>3</sub>(CH<sub>3</sub>)- and -C<sub>6</sub>H(CH<sub>3</sub>) <sub>2</sub>C1-. Furthermore, for example, each of the aryl rings in a group of
<img file="MX373246B_D0016.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY Naphthalene is a phenylene ring.
The term "substantially free of a bound or mobile compound" means that the recited material or composition contains less than 1000 parts per million (ppm) of bound or mobile compound. The term "essentially free of a bound or mobile compound" means that the recited material or composition contains less than 100 parts per million (ppm) of bound or mobile compound. The term "essentially completely free" of a particular mobile or bound compound means that the recited material or composition contains less than 5 parts per million (ppm) of the mobile or bound compound. The term "completely free of a bound or mobile compound" means that the recited material or composition contains less than 20 parts per billion (ppb) of bound or mobile compound. If the phrases mentioned above are used without the mobile or bound term (eg. g., substantially free of BPA), then the recited material or composition contains less than the aforementioned amount of the compound, whether the compound is mobile or bound.
The term mobile refers to the fact that the compound can be extracted from the cured coating when a coating (typically ~1 mg/cm<sup>2</sup>) is exposed to a test medium for a set of defined conditions, depending on the end use. An example of these test conditions is the exposure of the
<img file="MX373246B_D0017.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY coating cured to HPLC-grade acetonitrile for 24 hours at 25 °C.
The term bound when used in combination with one of the phrases mentioned in the context, for example, of a bound compound of a polymer or other ingredient of a coating composition (eg, a polymer that is substantially free of bound BPA) refers to the polymer or other ingredient containing less than the aforementioned amount of structural units derived from the compound. For example, a polymer that is substantially free of bound BPA includes less than 1000 ppm (or 0.1% by weight), if any, of structural units derived from BPA.
When the phrases include none, free from (outside the context of the aforementioned phrases) and the like are used in the present description, the phrases are not intended to exclude the presence of trace amounts of the relevant structure or compound that may be present due to environmental contaminants.
The term "estrogenic activity" or "estrogenic agonist activity" refers to the ability of a compound to mimic hormone-like activity through interaction with an endogenous estrogen receptor, typically a human endogenous estrogen receptor.
The term food contact surface is
<img file="MX373246B_D0018.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY refers to the substrate surface of a container (typically, an internal surface of a food or beverage container) that comes into contact with, or is made to come into contact with, a food or beverage product. By way of example, an internal surface of a metal substrate of a food or beverage container, or a portion thereof, is a food contact surface even if the internal metal surface is coated with a polymeric coating composition.
The term "unsaturated" when used in the context of a compound refers to a compound that includes at least one non-aromatic double bond.
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 an overlying first layer of a substrate constitutes an applied coating on the substrate.
Unless otherwise indicated, the term "polymer" includes both homopolymers and copolymers (ie, polymers of two or more different monomers). Of
<img file="MX373246B_D0019.tif" />
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Likewise, unless otherwise indicated, the use of a term indicating a class of polymers such as, for example, polyether, is intended to include both homopolymers and copolymers (for example, polyether copolymers). -ester).
The terms "comprise" and "variations" thereof do not have a limiting meaning, where such terms appear in the description and in the claims.
The terms preferred and preferably refer to embodiments of the invention that might have certain benefits under certain circumstances. However, other modalities might also be preferred, under the same or different circumstances. Furthermore, the disclosure of one or more preferred embodiments does not imply that the other embodiments are not useful and is not intended to exclude other embodiments from the scope of the invention.
As used herein, a, one, the, at least one, and one or more are used interchangeably. Thus, for example, a coating composition comprising a polyether can be interpreted as meaning that the coating composition includes one or more polyethers.
In the present description, moreover, the numeric ranges by minimum and maximum values include all numbers within the range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. .). In addition, the description of an interval includes the description of
<img file="MX373246B_D0020.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY all subranges within the larger range (eg, 1 to 5 describes la4, 1.5 to 4.5, 4a5, etc.).
DETAILED DESCRIPTION OF THE INVENTION
In one aspect, the present invention provides a coating composition that includes a polymer, more preferably a binder polymer, and even more preferably a polyether binder polymer. Although the following description focuses primarily on coating end uses, it is contemplated that the polymer of the present invention, as well as intermediates thereof, may be useful in a wide variety of additional end uses, such as, for example, in adhesives. or compounds.
The coating compositions of the present invention preferably include at least a film-forming amount of the polymer described herein. In addition to the polymer, the coating composition may further include one or more additional ingredients, such as, for example, a crosslinker, a liquid carrier, and any other suitable optional additives. Although any suitable curing mechanism may be used, thermosetting coating compositions are preferred. In addition, while coating compositions that include a liquid carrier are presently preferred, it is contemplated that the polymer of the present invention may be useful in coating application techniques. solid coatings such as,
<img file="MX373246B_D0021.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY for example, powder coating, laminated coatings, etc.
The coating compositions of the present invention may be useful in a wide variety of end uses including packaging coating end uses. Other coating end uses may include industrial coatings, marine coatings (eg, for ship hulls), storage tanks (eg, metal or concrete), architectural coatings (eg, metal or concrete). g., in metal siding, metal roofing, ceilings, garage doors, etc.), garden tools and equipment, toys, automotive siding, metal furniture siding, coil siding for home applications, floor coverings, and the like.
In preferred embodiments, the coating composition is suitable for use as an adherent packaging coating, and more preferably as an adherent coating on an internal and/or external surface of a food or beverage container. Thus, in preferred embodiments, the coating composition is suitable for use as a food contact coating. It is further contemplated that the coating composition may be useful for cosmetic or medical product packaging coating end uses, and as a coating that enters into
<img file="MX373246B_D0022.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY contact with the drug, particularly (for example, as an inner lining of a metered-dose inhaler can, commonly called an MDI container). It is further contemplated that the coating composition may be useful in coating applications where the coated substrate comes into contact with bodily fluids, such as, for example, as an inner liner of a blood vial.
In preferred embodiments, the polymer of the present invention, which is preferably a polyether polymer, includes one or more segments of Formula (I) below:
-O-Ar-O- Formula (I) wherein each Ar in Formula (I) represents an aryl or heteroaryl group and each of the described oxygen atoms is bonded to an aryl or heteroaryl ring atom and are presented, preferably an ether or ester bond, more preferably an ether bond.
Ar groups having six-membered rings are preferred, and Ar groups having six-membered carbon rings are particularly preferred.
Preferred Ar groups include less than 20 carbon atoms, more preferably less than 11 carbon atoms, and even more preferably less than 8 carbon atoms. Ar groups preferably have at least 4 carbon atoms, more preferably at least 5 carbon atoms.
<img file="MX373246B_D0023.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY carbon and, even more preferably, at least 6 carbon atoms. Preferred Ar groups are substituted or unsubstituted phenylene groups.
In some embodiments, the Ar group of Formula (I) can be two or more fused aryl rings. A naphthalene group is an example of the Ar group.
In some embodiments, the group Ar described in Formula (I) includes one or more, more preferably two or more, substituent groups (most preferably bulky substituent groups). Suitable substituent groups are described in further detail hereinafter. In some embodiments, one or more substituent groups are preferably attached to the ring preferably in an ortho or meta position, more preferably an ortho position, relative to at least one of the described oxygen atoms.
The segments of Formula (I) may be of any suitable size. Typically, the segments of Formula (I) will have an atomic weight of less than 1000, preferably less than 600, more preferably less than 400 Daltons, even more preferably less than 350 Daltons. In some embodiments, the segments of Formula (I) have an atomic weight of less than 250 Daltons.
The segments of Formula (I) are preferably found in a polymer backbone.
<img file="MX373246B_D0024.tif" />
In preferred embodiments, Ar is a phenylene group. A segment of Formula (I) in which Ar is a phenylene group is described below in Formula (II).
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
<img file="MX373246B_D0025.tif" />
Formula (II) where:
• H denotes a hydrogen atom, if present;
• each R<sup>1</sup>, if present, is preferably independently an atom or group preferably having an atomic weight of at least 15 Daltons which is preferably not substantially reactive with an epoxy group;
• v is 0 to 4; and • two or more R groups<sup>1</sup> they may optionally join to form one or more cyclic groups.
The oxygen atoms shown in Formula (II) can be located in any position on the ring, including ortho, meta, or para positions.
- O-, H, and R<sup>1</sup> of the phenylene group may be located at any position on the ring relative to each other. In some embodiments, where v is 1 to 4, one or more R<sup>1</sup> are located in an ortho position on the ring relative to the
<img file="MX373246B_D0026.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY minus one of the oxygen atoms described. Depending on the position of the described oxygen atoms relative to one another (eg, ortho, meta, or para), the segment of Formula (II) may include up to two ortho R<sup>1</sup>, up to three ortho R<sup>1</sup> or up to four ortho R<sup>1</sup> relative to the two oxygen atoms. In one embodiment, each disclosed oxygen includes at least one R group.<sup>1</sup> located an ortho position relative to it.
Without theoretical limitation, it is believed that in the case of polyhydric monophenol compounds (i) the absence of a second phenol ring and (ii) the presence of additional polar groups on the phenol ring may help prevent estrogenic activity. Furthermore, it is contemplated that the presence of one or more substituent groups on the phenol ring of polyhydric monophenol compounds, and particularly ortho substituent groups relative to oxygen atoms, may further help prevent estrogenic activity.
The optical chemical constituents, size, and/or configuration (eg, linear, branched, etc.) of one or more R groups<sup>1</sup>, if present, may depend on a variety of factors including, for example, the location of the R group<sup>1</sup> on the aryl group. To avoid any ambiguity, the term group when used in the context of groups R<sup>1</sup> refers to a single atom (eg, a halogen atom) or molecules (ie, two or more atoms).
<img file="MX373246B_D0027.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
Certain preferred segments of Formula (II) include up to four R groups<sup>1</sup> having an atomic weight of at least 15 Daltons. In some embodiments, segments of Formula (II) include up to four R groups<sup>1</sup> having an atomic weight of at least 25, at least 40 or at least 50 Daltons. Although the maximum suitable size of the R<sup>1</sup> is not particularly limited, typically less than 500 daltons, more often less than 100 daltons, and even more often less than 60 daltons. Non-limiting examples of R groups<sup>1</sup> they include groups having at least one carbon atom (eg, organic groups), halogen atoms, sulfur-containing groups, or any other suitable group that is preferably substantially non-reactive with an epoxy group.
In some embodiments, each R<sup>1</sup>, if present, preferably includes at least one carbon atom, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms. R<sup>1</sup> is typically a saturated or unsaturated, most often saturated, hydrocarbon group, which may optionally include one or more heteroatoms other than carbon or hydrogen atoms (e.g., N, O, S, Si, a halogen, etc.) . Examples of suitable hydrocarbon groups may include: alkyl groups (eg, methyl, ethyl, propyl, butyl groups, etc., including isomers of these), alkenyl groups,
<img file="MX373246B_D0028.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY alkynyl groups, alicyclic groups, substituted or unsubstituted aryl groups, or combinations of these.
In some embodiments, the phenylene group described in Formula (II) includes at least one R group<sup>1</sup> I rent. As mentioned above, any suitable isomer can be used. Therefore, for example, a linear butyl group or a branched isomer such as isobutyl group or tert-butyl group can be used. In one embodiment, a preferred group is the tert-butyl group (and, more preferably, R<sup>1</sup> a portion of tert-butyl).
It is contemplated that R<sup>1</sup> it may include one or more cyclic groups. Also, R.<sup>1</sup> can form a cyclic or polycyclic group with one or more R groups<sup>1</sup>.
In some embodiments, the segments of Formula (II) may include one or more halogen atoms (such as the R group<sup>1</sup>) located ortho to one or both of the oxygen atoms described. However, in certain preferred embodiments, the segments of Formulas (I) and (II) do not include any halogen atoms. Furthermore, in certain preferred embodiments, the polymer that includes one or more segments of Formulas (I) or (II) are preferably free of halogen atoms.
In preferred embodiments, each R<sup>1</sup>, if present, is preferably unreactive with an oxirane group at a temperature less than about 200°C.
<img file="MX373246B_D0029.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
Presently preferred segments of Formula (II) include only one phenylene group and further preferably include only one aryl group.
The segments of Formula (II) can be of any suitable molecular weight, including any of those described in conjunction with Formula (I). Typically, however, the segments of Formula (II) will have an atomic weight of from about 100 to about 400 Daltons. In some embodiments, the segments of Formula (II) have an atomic weight of less than 250 Daltons.
In preferred embodiments, the polymer of the present invention includes a plurality of segments of Formula (II), which are preferably dispersed throughout a polymer backbone, more preferably a polyether backbone. In preferred embodiments, the segments of Formula (II) make up a substantial portion of the overall mass of the polymer. Typically, the segments of Formula (II) make up at least 10 weight percent (wt%), preferably at least 30 wt%, more preferably at least 40 wt%, still more preferably at least 50% by weight and optimally at least 55% by weight of the polymer.
The percentage weight of the segments of Formula (II) in the polymer of the present invention may be less than the amounts mentioned above in certain
<img file="MX373246B_D0030.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY situations and may even be substantially less. By way of example, the concentration of the segments of Formula (II) may be outside the ranges mentioned above if the polymer of the present invention, which is preferably a polyether polymer, includes additional high molecular weight components such as can occur, for example, when the polymer is a copolymer, such as an acrylic-containing copolymer (eg. g ., an acrylic polyether copolymer formed by grafting acrylic to a polyether polymer of the present invention). In embodiments, the weight percent of Formula (II) segments present in the polymer is preferably as described above (p. g., 10 wt%, 30 wt%, 40 wt%, 50 wt%, 55 wt%), based on the percentage weight of the segments of Formula (II) relative to the polyether moiety total polymer (without taking into account the total weight of non-polyether portions such as, for example, acrylic portions). Generally, the total polyether fraction of the polymer can be calculated based on the total weight of the polyepoxide and polyhydric phenol reactants incorporated into the polymer.
Depending on the particular embodiment, the polymer of the present invention is preferably amorphous or semi-crystalline.
The polymer may include branching, if preferred.
<img file="MX373246B_D0031.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
However, in preferred embodiments, the polymer of the present invention is a linear or substantially linear polymer.
If preferred, the polymer backbone may include step-growth linkages (eg, condensation linkages) other than ether linkages (eg, in addition to or instead of ether linkages) such as eg amide linkages, carbonate linkages, ester linkages, urea linkages, urethane linkages, etc. Thus, for example, in some embodiments, the backbone may include ester linkages and ether linkages. In some embodiments, the polymer is a polyether polymer that is free of backbone condensation linkages or stage growth linkages other than ether linkages. In one embodiment, the polymer is free of backbone ester linkages.
The polymer of the present invention preferably includes hydroxyl groups. In preferred embodiments, the polymer includes a plurality of hydroxyl groups attached to the backbone. In preferred embodiments, the polyether portions of the polymer backbone include fully distributed secondary hydroxyl groups. Preferred secondary hydroxyl groups are present on the -CH segments<sub>2</sub>-CH(OH)-CH<sub>2</sub>- or -CH<sub>2</sub>CH<sub>2</sub>-CH(OH)-, which are preferably derived from a group
<img file="MX373246B_D0032.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY oxirano. The segments can be formed, for example, by the reaction of an oxirane group and a hydroxyl group (preferably a hydroxyl group of a polyhydric monophenol). In some embodiments, segments of CH<sub>2</sub>5 CH(OH- or -CH<sub>2</sub>-CH<sub>2</sub>-CH(OH) )-CH<sub>2</sub>- are attached to each of the ether oxygen atoms of the preferred segments of Formula (I).
The polymer backbone of the present invention may include any suitable terminal groups, including, for example, epoxy and/or hydroxyl groups (eg, a hydroxyl group attached to a terminal aryl or heteroaryl ring).
In preferred embodiments, the polymer of the present invention is formed using reactants that include at least one polyepoxide compound, most often at least one diepoxide compound. The polyepoxide compound can be enriched to form a binder polymer, more preferably a polyether binder polymer, of a suitable molecular weight with a suitable enhancer or combinations of enhancers. Polyhydric monophenol and dihydric monophenol extenders are particularly preferred. Examples of other suitable enhancers may include polyacids (and diacids, particularly) or phenol compounds having both a phenol hydroxyl group and a carboxylic group (for
<img file="MX373246B_D0033.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY example, hydroxybenzoic acid for and/or hydroxyphenyl acetic acid for). Conditions for such reactions are generally carried out using standard techniques well known to one of skill in the art or exemplified in the Examples section.
In certain preferred embodiments, the polymer of the present invention does not include any structural units derived from a bisphenol monomer. To avoid the inclusion of any bisphenol monomer in the materials used to make the preferred polymers of the present invention, there is no potential for any residual unreactive bisphenol monomer to be present in a composition containing the polyether polymer.
The bisphenol monomers typically have a molecular weight of less than 500 Daltons, more typically less than 400 Daltons, even more typically less than 350 Daltons, etc. Examples of bisphenol monomers include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol I, bisphenol M, bisphenol P, bisphenol PH, bisphenol S, bisphenol TMC, bisphenol Z, 4,4'-(propane-2,2-diyl)bis(2,6-dibromophenol), 2,2bis(4-hydroxyphenyl)propanoic acid, and the like. Bisphenol monomers are typically synthesized by the reaction of a phenol compound with a ketone (eg. , formaldehyde, acetalaldehyde, acetone, cyclohexanone, acetophenone, etc.).
<img file="MX373246B_D0034.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
Bisphenol A, for example, is synthesized by reacting two equivalents of phenol with one equivalent of acetone.
The term bisphenol monomer, as used in the present description, does not include adducts of dihydric monophenols and linker compounds such as diacids or diepoxides that do not include any structural unit derived from a bisphenol monomer. Thus, for example, a polyether polymer formed by the reaction of the following ingredients is free of structural units derived from a bisphenol monomer: (i) a diepoxide of Formulas (IV) and (ii) an adduct of two equivalents of hydroquinone reacted with one equivalent of 1,4-cyclohexanedimethanol diglycidyl ether (CHDMDGE).
In some embodiments, the polymer of the present invention does not include any structural units derived from a polyhydric polyphenol monomer.
While any suitable ingredient may be used to form the polymer, in presently preferred embodiments, the polymer was formed through the reaction of ingredients including: (a) a polyepoxide of a first polyhydric monophenol, more preferably a diepoxide of a first dihydric monophenol, even more preferably a diglycidyl ether of a first dihydric monophenol and (b) a second polyhydric monophenol, more preferably a
<img file="MX373246B_D0035.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY dihydric monophenol, where the first and second dihydric/polyhydric monophenols are the same or different. In certain preferred embodiments, components (a) and (b) include a segment of Formula (I), and more preferably a segment of Formula (II).
A useful dihydric monophenol compound for incorporating segments of Formula (II) into the polymer of the present invention is described in Formula (III) below, wherein R<sup>1</sup> and v are as indicated in Formula (II):
<img file="MX373246B_D0036.tif" />
Formula (II)
Examples of dihydric monophenol compounds of Formula (III) include catechol and substituted catechols (eg, 3-methylcatechol, 4-methylcatechol, 4-tert-butyl catechol, and the like); hydroquinone and substituted hydroquinones (eg. g., methylhydroquinone, 2,5-dimethylhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, ethylhydroquinone, 2,5-diethylhydroquinone, triethylhydroquinone, tetraethylhydroquinone, tert-butylhydroquinone, 2,5-di-tertbutylhydroquinone, and the like); resorcinol and substituted resorcinols (eg, 2-methylresorcinol, 4-methyl resorcinol.
<img file="MX373246B_D0037.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
2,5-dimethylresorcinol, 4-ethylresorcinol, 4-butylresorcinol, 4,6-di-tert-butylresorcinol, 2,4,6-tri-tert-butylresorcinol and the like); and variants and mixtures of these.
In a preferred embodiment, the polyether polymer of the present invention is formed using a 2,5-di-t-butylhydroquinone diepoxide, described below.
<img file="MX373246B_D0038.tif" />
Preferred compounds of Formula (III) do not show appreciable estrogenic activity. Substantially preferred non-estrogenic compounds exhibit a degree of estrogen agonist activity, in an in vitro component human estrogen receptor assay, that is less than that exhibited by ginesteine in the assay, more preferably less than that exhibited by 4, 4'-(propane-2,2-diyl)diphenol in the assay, even more preferably less than that exhibited by bisphenol S in the assay, even more preferably less than that exhibited by 4,4<sup>1</sup> -(propane-2,2diiDbis(2,6-dibromophenol) in the assay and optionally less than that exhibited by 2,2-bis(4-
<img file="MX373246B_D0039.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY hydroxyphenyl) propanoic in the test. It has been found, for example, that 2,5-di-t-butylhydroquinone has no appreciable estrogenic activity in an in vitro assay; the results are known to correlate directly with the results of the MCF-7 cell proliferation assay (MCF-7 assay) through analysis of common reference compounds. Furthermore, hydroquinone was determined to be substantially non-estrogenic.
The MCF-7 assay is a useful test to assess whether a polyhydric phenol compound is appreciably non-estrogenic. The MCF-7 assay uses MCF-7, clone WS8 cells to determine whether a substance induces cell proliferation via estrogen receptor (ER)-mediated pathways. The method is described in Test Method Nomination: MCF-7 Cell Proliferation Assay of Estrogenic Activity submitted for validation by CertiChem, Inc. to the North American Toxicology Program Interagency Center for the Evaluation of Alternative Toxicology Methods (NICEATM) on January 19, 2006 (available online at http://iccvam.niehs.nih.gov/methods/endocrine/endodocs/SubmDo c. pdf).
A brief summary of the MCF-7 assay method is provided below. MCF-7 cells, clone WS8, are kept at 37 °C in RMPI (Roswell Park Memorial Institute medium) that
<img file="MX373246B_D0040.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY contain phenol red (eg, GIBCO catalog number 11875119) and are supplemented with additives indicated for routine cultivation. An aliquot of cells maintained at 37°C was cultured for 2 days in phenol-free medium containing 5% charcoal-depleted fetal bovine serum in a 25-cm tissue culture flask.<sup>2</sup>. Using a robotic dispenser such as an epMotion 5070 unit, MCF-7 cells are then seeded at 400 cells per well in 0.2 ml of hormone-free growth medium in 96-well Corning plates. Cells are adapted for three days in hormone-free culture medium before adding test chemical to assess activity. The medium containing the test chemical is replaced, daily, for 6 days. At the end of day 7 exposed to the test chemical, the medium is removed, the wells are washed once with 0.2 mL HBSS (Hank's Balanced Salt Solution), and then the amounts of DNA per well are assessed using a modification of the diphenylamine assay (DPA) microplate described by Burton, which is used to calculate the level of cell proliferation.
Examples of appreciably non-estrogenic polyhydric phenols include polyhydric phenols which when tested using the MCF-7 assay show a relative proliferative effect (RPE) having a value
<img file="MX373246B_D0041.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY logarithmic (base 10) less than about -2.0, more preferably, an RPE of -3 or less, and even more preferably, an RPE of -4 or less. RPE is the ratio of the EC50 of the test chemical to the EC50 of the control substance estradiol 17-beta times 100, where EC50 is a 50% effective concentration or one-half maximal stimulating concentration for cell proliferation measured as total DNA in the MCF-7 assay.
A table is provided below that includes some illustrative preferred polyhydric compounds of Formula (III) and their measured or expected log RPE values in the MCF-7 assay.
<td>Dihydric monophenol compound of Formula (III)</td><td>Reference compound</td><td>Log EPR</td>
<td></td><td>173-estradiol</td><td> 2.00</td>
<td></td><td>bisphenol S</td><td> -2</td>
<td></td><td>4,4'-(propane-2,2- diyl)bis(2,6- dibromophenol)</td><td> -3</td>
<td></td><td>2,2-bis(4- hydroxyphenyl)propanoic</td><td>less than -4</td>
<td>2,5-di-t-butylhydroquinone</td><td></td><td>less than -4</td>
Although 2,5-di-t-butylhydroquinone and 2,2-bis(4-
<img file="MX373246B_D0042.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY hydroxyphenyl)propanoic acid were shown in the table above with RPE values less than -4, it is believed that the RPE value of 2,5-dit-butylhydroquinone is less than the RPE value of 2,2bis(4) acid. -hydroxyphenyl)propanoic.
The use of a polyhydric monophenol that does not have appreciable estrogenic activity may be beneficial in the event that any residual unreacted polyhydric phenol may be present in a cured coating composition. Although the balance of scientific data does not indicate that the presence in cured coatings of very small amounts of polyhydric phenols with estrogenic activity in an in vitro recombinant cell assay presents a human health concern, the use of polyhydric monophenols that do not have appreciable estrogenic activity in the assay may be desirable from a public perception standpoint. Thus, in preferred embodiments, the polymer of the present invention is preferably formed using polyhydric monophenol compounds that do not show appreciable estrogenic activity in the MCF-7 test.
The dihydric monophenol compounds of Formula (III) may be converted to a diepoxide using any suitable process and material. The use of epichlorohydrin in the epoxidation process is currently preferred.
<img file="MX373246B_D0043.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
The epoxy groups (also commonly called oxirane groups) of the polyepoxide compound may be attached to the compound via any suitable linkage, including, for example, ether-containing linkages or ester-containing linkages. Glycidyl ethers of polyhydric phenols and glycidyl esters of polyhydric phenols are the preferred polyepoxide compounds, particularly diglycidyl ethers.
A preferred polyepoxide compound for use in incorporating segments of Formula (II) into the polymer of the present invention is depicted in Formula (IV) below:
<img file="MX373246B_D0044.tif" />
where:
•R<sup>1</sup> and v are as represented, above, for Formula (II);
• s is 0 to 1, more preferably 1;
•R<sup>3</sup>, if present, is a divalent group, more preferably a divalent organic group; and • preferably, each R<sup>4</sup>, if present, is,
<img file="MX373246B_D0045.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY independently, a hydrogen atom, a halogen atom, or a hydrocarbon group that may include one or more heteroatoms; more preferably, each R<sup>4</sup> it is a hydrogen atom.
R<sup>3</sup> is typically a hydrocarbyl group, which may optionally include one or more heteroatoms. Preferred hydrocarbyl groups include groups having from one to four carbon atoms; methylene groups are particularly preferred. In some embodiments, R<sup>3</sup> includes a carbonyl group. In the modality, R<sup>3</sup> includes a carbonyl group that is bonded to the oxygen atom depicted in Formula (IV) (eg, as in an ester bond).
In currently preferred embodiments, R<sup>4</sup> it is a hydrogen atom.
Diepoxides have been successfully produced using dihydric monophenol compounds of Formula (III) and polyether polymers have been successfully produced from these.
Preferably, v of Formula (IV) is 1 or greater (eg, 1, 2, 3, or 4), more preferably at least 2. In certain preferred embodiments, the phenylene group of Formula (IV) includes an R<sup>1</sup> at one or both ortho ring positions for each oxygen atom described.
Preferred diepoxide compounds of Formula (IV) are non-mutagenic and more preferably non-genotoxic.
<img file="MX373246B_D0046.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
A useful test for evaluating genotoxicity and mutagenicity is the in vivo mammalian test known as the in vivo alkaline single cell gel electrophoresis assay (known as the comet assay). The method is described in: Tice, RR The single cell gel/comet assay: a microgel electrophoretic technique for the detection of DNA damage and repair in individual cells. Environmental Mutagenesis. Eds. Phillips, DH and Venitt, S. Bios Scientific, Oxford, UK, 1995, pgs. 315-339. A negative test result in the comet assay indicates that a compound is non-genotoxic and therefore non-mutagenic, although a positive test does not definitively indicate otherwise and in cases a more definitive test may be used (eg . , a two-year rat feeding study).
Without being limited by theory, it is believed that the presence of one or more R groups<sup>1</sup>, more preferably, one or more R groups<sup>1</sup> ortho, on the phenylene ring of a diepoxide compound of Formula (IV) may contribute to the diepoxide being non-genotoxic. Illustratively, 2,5-di-t-butylhydroquinone is non-genotoxic.
It is further contemplated that the polymer of the present invention may be formed by the reaction of ingredients including the dihydric monophenol compound of Formula (III) and a diepoxide other than that of Formula (IV). Examples of the diepoxide compounds may include ether
<img file="MX373246B_D0047.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY 1,4-cyclohexanedimethanol diglycidyl (CHDMDGE), neopentyl glycol diglycidyl ether, 2-methyl-l,3-propanediol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, and combinations of these. Without being limited by theory, aliphatic diepoxides (eg. g ., CHDMDGE and neopentyl glycol diglycidyl ether) that tend to produce polymers with lower glass transition temperature (Tg) values may not be suitable for certain packaging liner applications in which a relatively high Tg polymer is desired for purposes of corrosion resistance, although they may be suitable for exterior coating applications for packaging or other end uses.
Any suitable polyhydric phenol can be used to improve the molecular weight of the diepoxides of Formula (IV) to form polyether polymers. However, the use of bisphenol A or polyhydric phenols that exhibit estrogen agonist activity equivalent to or greater than that of BPS is not preferred. In certain preferred embodiments, polyepoxides of Formula (IV) are replaced with polyhydric monophenols of Formula (III). Hydroquinone is a preferred replacement material.
Without theoretical limitations, it is believed that it is more difficult to form a polyether polymer (using reasonable process conditions and times) by using,
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY as an extender, of a polyhydric monophenol compound of Formula (III) substituted in multiple ortho ring positions with large substituent groups. For example, it has been difficult for the inventors to use conventional industrial processes to effectively react 2,5-di-t-butylhydroquinone with diepoxide monomer to form a polyether polymer. (However, it is somewhat surprising that 2,5-di-t-butylhydroquinone can survive a reaction with epichlorohydrin to form a diepoxide that reacts with dihydric monophenols that do not include ortho substitution). Without theoretical limitation, it is believed that the hydroxyl groups of certain ortho substituted dihydric monophenol compounds are not sufficiently accessible to react efficiently with an oxirane group of a diepoxide monomer and form an ether linkage.
Thus, in certain embodiments, a dihydric monophenol that is preferably unblocked by any bulky group substituent in an ortho position is used as an extender. In some embodiments, it may be advantageous to use, as an extender, a dihydric monophenol that: (i) does not include any R groups<sup>1</sup> or (ii) does not include any R groups<sup>1</sup> in an ortho position.
If preferred, one or more comonomers and/or co-oligomers may be included in the reactants used to generate the
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY polymer of the present invention. Non-limiting examples of such materials include adipic acid, azelaic acid, terephthalic acid, isophthalic acid, and combinations of these. The comonomers and/or cooligomers can be included in an initial reaction mixture of polyepoxide and polyhydric phenol and/or can be further reacted with the resulting polyether oligomer or polymer. In presently preferred embodiments, a comonomer and/or cooligomer is not used to produce a polyether polymer of the present invention.
Preferred polymers of the present invention can be made in a wide variety of molecular weights. Preferred polyether polymers of the present invention have a number average molecular weight (Mn) of at least 2000, more preferably at least 3000, and even more preferably at least 4000. The molecular weight of the polymer of polyether can be as high as necessary for the desired application. Typically, however, the Mn of the polyether polymer, when adapted for use in a liquid coating composition, is no greater than about 11,000. In some embodiments, the polyether polymer has an Mn of from about 5,000 to about 8,000. In embodiments where the polymer of the present invention is a copolymer, such as, for example, a polyether acrylic copolymer, while the
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY molecular weight of the general polymer may be greater than the ranges mentioned above, the molecular weight of the polyether polymer portion will be greater than that mentioned above. Typically, however, such copolymers have an Mn of less than about 20,000.
Polymer molecular weight gain can be enhanced by the use of a catalyst in the reaction of a diepoxide with one or more enhancing comonomers, such as, for example, a dihydric monophenol of Formula (III). Typical catalysts that can be used in advancing the molecular weight of the epoxy material of the present invention include amines, hydroxides (eg, potassium hydroxide), phosphonium salts, and the like. A currently preferred catalyst is a phosphonium salt catalyst. The catalyst useful in the present invention is preferably present in an amount sufficient to facilitate the desired condensation reaction.
Alternatively, the epoxy-terminated polymers of the present invention can be reacted with fatty acids to form polymers having unsaturated reactive groups (eg, air-oxidizable) or with acrylic acid or methacrylic acid to form free radically curable polymers.
The molecular weight advancement of the polymer can be further enhanced by reacting a polymer
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hydroxyl or epoxy terminated of the present invention with a suitable diacid (such as adipic acid).
The polymer of the present invention may exhibit any suitable polydispersity index (PDI). In embodiments in which the polymer is a polyether polymer intended for use as a binder polymer in a liquid applied to a packaging liner (eg. g., a food or beverage can liner), the polyether polymer will typically have a PDI of about 1.5 to 5, more typically about 2 to 3.5, and in some cases about 2.2 to 3 or so. about 2.4 to 2.8.
As mentioned above, in certain preferred embodiments, the coating composition of the present invention is suitable for use in the production of a food contact packaging coating. To exhibit an adequate balance of coating properties for use as a coating for food contact packaging, including adequate corrosion resistance when in prolonged contact with packaged food or beverage products that may Having a corrosive nature, the polymer of the present invention preferably has a glass transition temperature (Tg) of at least 60 °C, more preferably, at least 70 °C and, even with
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY higher preference, at least 80 °C. In preferred embodiments the Tg is less than 150°C, more preferably less than 130°C and even more preferably less than 110°C. Tg can be determined by differential scanning calorimetry (DSC) using the methodology described in the Test Methods section. In preferred embodiments, the polymer is a polyether polymer exhibiting a Tg in accordance with the Tg values mentioned above.
While not intending to be bound by theory, it is believed that it is important that the polymer exhibit a Tg such as that described above in applications where the coating composition comes into contact with food or beverage products during retort processing. high temperature (for example, at temperatures of or greater than about 100 °C and sometimes accompanied by pressures exceeding atmospheric pressure) and, particularly, with retort processing food or beverage products that are more chemically aggressive in nature. It is contemplated that in some embodiments, such as, for example, when the coating composition is intended to be used as an exterior varnish on a food or beverage container, the Tg of the polymer may be lower than described above (for example, as low as about 30 °C), where the composition of
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY coating still present an adequate balance of properties in the final use.
When referring to the Tg of a polymer herein in the context of a coating composition including the polymer or an article coated with a coating composition, the stated Tg values for the polymer refer to the Tg of the polymer before from any cure of a coating composition that includes the polymer.
While not intending to be bound by theory, it is believed that the inclusion of a sufficient number of aryl and/or heteroaryl groups (typically phenylene groups) in the binder polymer of the present invention is an important factor in achieving coating performance. suitable for packaging liners that come into contact with food, especially when the product to be packaged is the known hard-to-contain food or beverage product. Sauerkraut is an example of a product that is difficult to contain. In preferred embodiments, the aryl and/or heteroaryl groups make up at least 25% by weight, more preferably at least 30% by weight, even more preferably at least 35% by weight, and optimally at least 45% by weight. by weight of the polyether polymer, based on the total weight of the aryl and heteroaryl groups in the polymer relative to the weight of the polyether polymer. It is not particularly limited to
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY higher concentration of the aryl/heteroaryl groups, but preferably the amount of the groups is configured such that the Tg of the polyether polymer does not exceed the Tg ranges previously described. The total amount of aryl and/or heteroaryl groups in the polyether polymer is typically less than about 80% by weight, more preferably less than about 75% by weight, even more preferably less than 70% by weight. weight and, optimally, less than about 60% by weight of the polyether polymer. The total amount of the aryl and/or heteroaryl groups in the polyether polymer can be determined based on the weight of the aryl or heteroaryl containing monomer incorporated into the polyether polymer and the fraction by weight of such monomer which constitutes the aryl or heteroaryl groups. . In embodiments where the polymer is a polyether copolymer (eg, a polyether acrylic copolymer), the weight fraction of aryl or heteroaryl groups in the polyether polymer portion(s) of the copolymer is generally as described. above, although the weight fraction relative to the total weight of the copolymer may be less. Therefore, in preferred embodiments, the polyether moiety of the polymer includes an amount of phenylene groups in accordance with the amounts mentioned above.
In one embodiment, the polymer of the present invention
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY does not include any structural unit derived from hydrogenated bisphenol A or a hydrogenated bisphenol A diepoxide.
The polymers of the present invention can be applied to a substrate as part of a coating composition that includes a liquid carrier. The liquid carrier can be water, organic solvent, or mixtures of several such liquid carriers. Therefore, the liquid coating compositions of the present invention can be water-based or solvent-based systems. Examples of suitable organic solvents include glycol ethers, alcohols, aromatic or aliphatic hydrocarbons, dibasic esters, ketones, esters, and the like, and combinations of these. Preferably, such carriers are selected to produce a dispersion or solution of the polymer for further formulation.
It is anticipated that a polyether polymer of the present invention may be substituted for any conventional epoxy polymer present in a packaging coating composition that is known in the art. Thus, for example, the polyether polymer of the present invention may be replaced, for example, by a BPA/BADGE-containing polymer of an epoxy/acrylic latex coating system, by a BPA/BADGE-containing polymer of a solvent-based epoxy coating system,
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY etc.
The amount of binder polymer of the present invention included in coating compositions can vary widely depending on a wide variety of considerations, such as, for example, method of application, presence of other film-forming materials, whether the coating composition is it a water-based or solvent-based system, etc. However, for liquid-based coating compositions the binder polymer of the present invention typically constitutes at least 10% by weight, more often at least 30% by weight, and even more often by weight. at least 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 polymer typically constitutes less than about 90% by weight, more often less than about 80% by weight, and even more often less than about 70% by weight. of the coating composition, based on the total weight of resin solids in the coating composition.
In one embodiment, the coating composition is an organic solvent-based composition that preferably has at least 20% by weight non-volatile (solid) components, and more preferably at least 25% by weight.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY by weight of non-volatile components. Organic solvent-based compositions preferably have no more than 40% by weight of non-volatile components, and more preferably no more than 35% by weight of non-volatile components. For this embodiment, the nonvolatile components preferably include at least 50% by weight of the polymer of the present invention, more preferably at least 55% by weight of the polymer, and even more preferably at least 60%. % by weight of the polymer. For this embodiment, the non-volatile components preferably include no more than 95% by weight of the polymer of the present invention, and more preferably no more than 85% by weight of the polymer.
In some embodiments, the coating composition of the present invention is a solvent-based system that includes no more than a de minimis amount of water (eg, less than 2% by weight of water), if any. An example of the coating composition is a solvent-based coating composition that includes no more than a de minimis amount of water and includes, on a solid basis, from about 30 to 99% by weight, more preferably about 50 to 85% by weight of the polyether polymer of the present invention; a suitable amount of crosslinking agents (eg, a phenolic crosslinker or anhydrous crosslinker); and, optionally, inorganic filler (eg,
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
Uncle<sub>2</sub>) or other optional additives. In the solventborne coating composition of the present invention, the polyether polymer is a high molecular weight polyether polymer preferably having an Mn of from about 7,500 to about 10,500, more preferably about 8,000 to 10,000 and , even more preferably, about 8,500 to about 9,500.
In one embodiment, the coating composition is a water-based composition, preferably having at least 15% by weight of non-volatile (solid) components. In one embodiment, the coating composition is a water-based composition preferably having no more than 50% by weight non-volatile components, and more preferably no more than 40% by weight non-volatile components. For this embodiment, the non-volatile components preferably include at least 5% by weight of the polymer of the present invention, more preferably at least 25% by weight of the polymer, even more preferably at least 30%. by weight of the polymer and, optimally, at least 40% by weight of the polymer. For this embodiment, the non-volatile components preferably include no more than 70% by weight of the polymer of the present invention, and more preferably no more than 60% by weight of the polymer.
If a water-based system is desired, techniques such as those described in the U.S. patents may be used.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
United States no. 3,943,187; 4,076,676; 4,247,439; 4,285,847; 4,413,015; 4,446,258; 4,963,602; 5,296,525;
5,527,840; 5,830,952; 5,922,817; 7,037,584; and 7,189,787. The waterborne coating systems of the present invention may optionally include one or more organic solvents that are typically selected to be miscible with water. Liquid carrier systems of waterborne coating compositions typically include at least 50% by weight water, more often at least 75% by weight water, and in some embodiments greater than 90%. by weight or 95% by weight of water. Any suitable means may be used to render the polymer of the present invention miscible with water. For example, the polymer may include a suitable amount of salt groups, such as ionic salt groups or cationic salt groups to render the polymer water-miscible (or groups with the ability to form such salt groups). Preferred salt groups are neutralized acid or base groups.
In some embodiments, the polymer of the present invention is covalently bonded to one or more materials (eg, oligomers or polymers) having salts or salt-forming groups to render the polymer water-dispersible. The salt or salt-forming group containing material may be, for example, oligomers or polymers that (i) are formed in situ before, during or after the formation of the
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polymer of the present invention or (ii) are supplied as preformed materials that are reacted with a preformed, or emerging, polymer of the present invention. Covalent bonding can be achieved through any suitable means including, for example, by reactions involving carbon-carbon double bonds, hydrogen abstraction (eg, eg, by a reaction involving benzoyl peroxide-mediated grafting by hydrogen abstraction such as, for example, described in US Pat. 4,212,781), or the reaction of complementary reactive functional groups such as occurs, for example, in condensation reactions. In one embodiment, a linker compound is used to covalently link the polyether polymer and the salt- or salt-forming group-containing material. In certain preferred embodiments, the one or more materials having salt or salt-forming groups is an acrylic material, more preferably an acid or anhydride functional acrylic material.
In one embodiment, a water-dispersible polymer can be formed from preformed polymers (eg, (a) an oxirane-functional polymer such as, for example, a polyether polymer preferably having at least one segment of Formula (I) and (b) an acid-functional polymer such as, eg, an acid-functional acrylic polymer) in the presence of an amine, more preferably a tertiary amine. If desired, an acid-functional polymer may be combined with an amine, more preferably a tertiary amine, to at least partially neutralize it prior to reaction with an oxirane-functional polymer preferably having at least one segment. of Formula (I).
In another embodiment, a water-dispersible polymer can be formed from an oxirane-functional polymer (more preferably, a polyether polymer described herein) preferably having at least one segment of Formula (I ) that is reacted with ethylenically unsaturated monomers to form an acid-functional polymer, which can then be neutralized with, for example, a base such as a tertiary amine. Thus, for example, in one embodiment, a water-dispersible polymer preferably having at least one segment of Formula (I) can be formed in accordance with the acrylic polymerization teachings of U.S. patents United no. 4,285,847 and/or 4,212,781, which describe techniques for grafting acid-functional acrylic groups (eg, through the use of benzoyl peroxide) onto epoxy-functional polymers. In another embodiment, the polymerization of acrylics can be carried out through the reaction of ethylenically unsaturated monomers with the unsaturation
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY present in the polymer containing, preferably, at least one segment of Formula (I). See, for example, US Pat. 4,517,322 and/or published US patent application no. 2005/0196629 for examples of such techniques.
In another embodiment, a water-dispersible polymer having the structure ELA can be formed, wherein E is an epoxy portion of the polymer formed from a polyether polymer described herein, A is a polymerized acrylic portion of the polymer, and L is a linking portion of the polymer that covalently joins E and A. The polymer can be prepared, for example, from (a) a polyether polymer described herein preferably having about two epoxy groups, (b) an unsaturated bond compound preferably having (i) one nonaromatic carbon-carbon double bond, conjugated nonaromatic carbon-carbon double bonds, or a carbon-carbon triple bond, and (ii) a functional group with the ability to react with an epoxy group (eg . , a carboxylic group, a hydroxyl group, an amino group, an amido group, a mercapto group, etc.). Preferred linking compounds include 12 or fewer carbon atoms, with sorbic acid being an example of such a preferred linking compound. The acrylic portion preferably includes one or more salt groups or
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY salt formers (for example, acid groups, such as those present in α,β-ethylenically saturated carboxylic acid monomers). The polymers can be formed, for example, by using a BPA- and BADGE-free polyether polymer of the present invention in combination with the materials and techniques described in US Pat. 5,830,952 or US patent application no. 2010/0068433.
In some embodiments, the coating composition of the present invention is substantially free of acrylic components. For example, in some embodiments, the coating composition includes less than about 5% by weight or less than about 1% by weight of polymerized acrylic monomers (eg, a mixture of ethylenically unsaturated monomers that includes at least some selected monomers). of acrylic acid, methacrylic acid or esters of these).
If desired, an acid-functional polymer can be combined with a base (more preferably an amine, even more preferably a tertiary amine) to at least partially neutralize it prior to reaction with an oxirane-functional polymer having, preferably, at least one segment of Formula (I).
In another embodiment, a polymer preferably containing segments of Formula (I) and including
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY segments -CH<sub>2</sub>-CH(OH)-CH<sub>2</sub>- or -CH<sub>2</sub>-CH<sub>2</sub>-CH(OH)-, which are derived from an oxirane, is reacted with an anhydride. This provides an acid functionality which when combined with an amine or other suitable base to at least partially neutralize the acid functionality is water dispersible.
In some embodiments, the coating composition of the present invention is a low VOC coating composition that preferably includes no more than 0.4 kilograms (kg) of volatile organic compounds (VOCs) per liter of solids. , more preferably no more than 0.3 kg VOC per liter of solids, even more preferably no more than 0.2 kg VOC per liter of solids, and optionally no more than 0.1 kg VOC per liter of solids.
Reactive diluents can optionally be used to produce the low VOC coating compositions. The reactive diluent preferably functions as a solvent or otherwise lowers the viscosity of the reactant mixture. The use of one or more reactive diluents as a solvent eliminates or reduces the need to incorporate a substantial amount of other co-solvents (such as butanol) during processing.
Suitable reactive diluents for use in the present invention preferably include monomers and
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY reactive oligomers free of radicals. A small amount of reactive diluent that can undergo reaction with the polymer of the present invention may be used (eg, hydroxyl monomers such as 2-hydroxyl ethyl methacrylate, amide monomers such as acrylamide, and N-methylol monomers such as N-methylol acrylamide). Suitable reactive diluents include, for example, vinyl compounds, acrylate compounds, methacrylate compounds, acrylamides, acrylonitriles, and the like, and combinations of these. Suitable vinyl compounds include, for example, vinyl toluene, vinyl acetate, vinyl chloride, vinylidene chloride, styrene, substituted styrenes, and the like, and combinations of these. Suitable acrylate compounds include butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, tert-butyl acrylate, methyl acrylate, 2-hydroxyethyl acrylate, poly(ethylene glycol) acrylate, isobornyl acrylate, and combinations of these. Suitable methacrylate compounds include, for example, butyl methacrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate, poly(ethylene glycol) methacrylate, poly(propylene glycol) methacrylate, and the like, and combinations of these. Preferred reactive diluents include styrene and butyl acrylate. United States patent no. 7,037,584 provides additional description of
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY Appropriate materials and methods regarding the use of reactive diluents in low VOC packaging coating compositions.
Any suitable amount of one or more reactive diluents may optionally be employed in the coating compositions of the present invention. For example, an amount of one or more reactive diluents sufficient to meet the VOC content of the aforementioned low VOC coating compositions may be used. In some embodiments, the coating composition includes at least about 1% by weight, at least about 5% by weight, or at least 10% by weight of the polymerized reactive diluent.
In one embodiment, a polyether polymer of the present invention is mixed, in any suitable order, with an acrylic component (eg, acrylic resin) and reactive diluent. The polyether polymer and acrylic resin are preferably reacted with each other (although they may be used as a simple mixture), before or after the addition of reactive diluents, to form a polyether acrylate copolymer. The polyether acrylate and the reactive diluents are also preferably dispersed in water. The reactive diluent is then preferably polymerized in the presence of the polyether-acrylate copolymer to form a coating composition having the desired low VOC content.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
In this context, the term "reactive diluent" refers to monomers and oligomers that are preferably substantially non-reactive with the polyether resin or any carboxylic acid entities (or other functional groups) that might be present, for example, in the polyether resin. acrylic resin, under contemplated mixing conditions. Reactive diluents are furthermore preferably capable of undergoing a reaction to form a polymer, described as an interpenetrating network with the polymer of the present invention, or with unsaturated entities which may optionally be present, for example, in a acrylic resin.
A coating composition of the present invention may further include other optional ingredients that do not adversely affect the coating composition or a resulting cured coating composition thereof. Such optional ingredients are typically included in a coating composition to improve the aesthetics of the composition, to facilitate manufacturing, processing, handling and application of the composition; or to further improve the particular functional property of a coating composition or a resulting cured coating composition thereof. For example, the composition including a polymer of the present invention may optionally include crosslinkers, fillers,
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY catalysts, lubricants, pigments, surfactants, dyes, colorants, toners, coalescents, extenders, anticorrosive agents, flow control agents, thixotropic agents, dispersing agents, antioxidants, oxygen scavenging materials, adhesion promoters, light stabilizers, antifoam agents, and mixtures of these, as needed to provide desired film properties. Each optional ingredient is preferably included in an amount sufficient for its intended purpose, but preferably not in such an amount as to adversely affect a coating composition or a resulting cured coating composition thereof.
Preferred coating compositions of the present invention are substantially free of mobile BPA or mobile BADGE or both, more preferably essentially free of these compounds, even more preferably essentially completely free, and optionally completely free of these compounds. The coating composition is further preferably substantially free of bound BPA or bound BADGE or both, more preferably essentially free of these compounds, even more preferably essentially completely free and optionally completely free of these compounds. Furthermore, preferred compositions are also substantially free, more preferably,
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY essentially free, even more preferably essentially completely free and optionally completely free of one or more, or all, of: bisphenol S, bisphenol F, and the diglycidyl ether of bisphenol F or bisphenol S. In some embodiments, the composition is substantially free, more preferably essentially free, still more preferably essentially completely free, and optionally completely free of bound biphenol monomers and epoxides thereof.
The ingredients used to make the polymer of the present invention are preferably free of any corresponding dihydric phenol or diepoxide monomers (e.g., diglycidyl ethers), which exhibit estrogen agonist activity in the MCF-7 assay greater than or equal to than that exhibited by 4,4'-(propane-2,2 diyl)diphenol in the assay. More preferably, the aforementioned ingredients are free of any dihydric phenol, or corresponding diepoxides, that exhibit estrogen agonist activity in the MCF-7 assay greater than or equal to that of bisphenol S. Even more preferably, the aforementioned ingredients are free of any corresponding dihydric phenol or diepoxide monomers, which exhibit an estrogen agonist activity in the MCF-7 assay greater than or equal to that of 4.4<sup>1</sup> -(propane-2,2-diyl)bis(2,6-dibromophenol). Optimally, the
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The polymer does not include any structural unit derived from a dihydric phenol monomer (or preferably any other polyhydric phenol monomer), or a diepoxide of these, which has an estrogen agonist activity greater than 2,2-bis acid. (4-hydroxyphenyl)propanoic. The same is preferably true for any other component of a composition that includes the polymer.
The coating compositions of the present invention may be formulated using one or more optional curing agents (eg, crosslinking resins, sometimes referred to as crosslinkers). The choice of a particular crosslinking agent typically depends on the specific product being formulated. For example, some coating compositions are highly colored (eg, gold-colored coatings). These coatings can typically be formulated with the use of crosslinkers which themselves tend to have a yellowish color. In contrast, white coatings are generally formulated with non-yellowing crosslinkers or only a small amount of a yellowing crosslinker.
Suitable examples of such curing agents are hydroxyl-reactive curing resins, such as phenoplasts, aminoplasts, blocked or deblocked isocyanates or mixtures of these.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
Suitable phenoplast resins include the condensation products of aldehydes with phenols. Preferred aldehydes are formaldehyde and acetaldehyde. Various phenols can be used, such as phenol, cresol, pphenylphenol, p-tert-butylphenol, p-tert-amylphenol, cyclopentylphenol, and compounds of Formula (III).
Suitable aminoplast resins are the condensation products of aldehydes, such as formaldehyde, acetaldehyde, crotonaldehyde, and benzaldehyde, with substances containing amino groups or amido groups, such as urea, melamine, and benzoguanamine. Examples of suitable aminoplast crosslinking resins include, but are not limited to, benzoguanamine-formaldehyde resins, melamine-formaldehyde resins, etherified melamine-formaldehyde resins, and urea-formaldehyde resins.
Examples of other generally suitable curing agents are blocked or unblocked di-, tri- or polyvalent aliphatic, cycloaliphatic or aromatic isocyanates, such as hexamethylene diisocyanate, cyclohexyl-1,4-diisocyanate and the like. Additional non-limiting examples of generally suitable blocked isocyanates include isophorone diisocyanate isomers, dicyclohexylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, tetramethyl xylene diisocyanate,
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY xylylene and mixtures of these. Blocked isocyanates having an Mn of at least about 300, more preferably at least about 650, and even more preferably at least about 1000 are used in some embodiments.
Polymeric blocked isocyanates are useful in certain embodiments. Some examples of suitable polymeric blocked isocyanates include a biuret or isocyanurate of a diisocyanate, a trifunctional trimer, or a mixture of these. Examples of suitable blocked polymeric isocyanates include TRIXENE BI 7951, TRIXENE BI 7984, TRIXENE BI 7963, TRIXENE BI 7981 (TRIXENE materials are available from Baxenden Chemicals, Ltd. , Accrington, Lancashire, England), DESMODUR BL 3175A, DESMODUR BL3272, DESMODUR BL3370, DESMODUR BL 3475, DESMODUR BL 4265, DESMODUR PL 340, DESMODUR VP LS 2078, DESMODUR VP LS 2117 and DESMODUR VP LS 2352 DESMODUR (These are materials of available from Bayer Corp., Pittsburgh, Pa, USA) or combinations of these. Examples of suitable trimers may include a trimerization product made from an average of three diisocyanate molecules or a trimer made from an average of three moles of diisocyanate (eg, HMDI) reacted with one mole of another compound, such as, for example, a triol (eg trimethylolpropane).
The concentration of curing agent (eg ,
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY crosslinker) to be used typically depends on the type of curing agent, the baking time and temperature, the molecular weight of the polymer binder, and the desired properties of the coating. If used, the crosslinker is typically present in an amount of up to 50% by weight, preferably up to 30% by weight, and more preferably up to 15% by weight. If used, a crosslinker is preferably present in an amount of at least 0.1% by weight, more preferably at least 1% by weight, and even more preferably at least 1.5% by weight. These percent weights are based on the total weight of resin solids in the coating composition.
In some embodiments, the coating composition of the present invention is formaldehyde-free coatings that include, or release as a result of the curing process, not more than 1% by weight of formaldehyde, not more than 0.5% by weight of formaldehyde, not more than 0.25% by weight of formaldehyde or not more than 5 ppm of formaldehyde. The absence of phenolic resin and/or melamine 20 is believed to contribute to a coating composition that is substantially free of formaldehyde.
As described above, in some embodiments, the coating composition of the present invention includes an acrylic component that may be optionally covalently bonded to the polyether polymer.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY described in the present invention. In some embodiments, the acrylic component may be present as a separate polymer mixed with the polyether polymer (in addition to any acrylic component that may optionally be covalently bonded to the polyether polymer).
The coating composition of the present invention may include any amount of acrylic component suitable to produce the desired coating or film properties. In preferred embodiments containing acrylic components, the coating composition includes an amount of acrylic component of at least about 5% by weight, more preferably at least about 10% by weight, and even more preferably at least about 15%. % by weight, as determined by an amount of a monomeric mixture used to prepare the acrylic component and based on the total weight of resin solids in the coating system. In preferred embodiments, the coating composition preferably includes less than about 95% by weight of the acrylic component, more preferably less than about 75% by weight, and even more preferably less than about 30 to 40%. % by weight, as determined by an amount of a monomeric mixture used to prepare the acrylic component and based on the total resin solids in the system of
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY coating.
In certain water-based embodiments in which at least some of the acrylic component is covalently bonded to the polyether polymer, at least a portion of the acrylic monomers used to form the acrylic component are preferably capable of producing the polyether polymer. dispersible in water. In embodiments, the acrylic component is preferably formed from an ethylenically unsaturated monomeric mixture including one or more α,β-unsaturated carboxylic acids. The one or more α,β-unsaturated carboxylic acids preferably produce the water-dispersible polymer after neutralization with a base. Suitable α,β unsaturated carboxylic acid monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, mesaconic acid, citraconic acid, sorbic acid, fumaric acid, and mixtures of these. The acrylic monomer may further include, for example, acrylamide or methacrylamide which can produce the water-dispersible polymer. Preferred acrylic components for use in packaging coating applications are substantially free or completely free of acrylamide or methacrylamide monomers.
The acrylic monomers used to form the acrylic component can include from 0% to about 95%,
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY in the total weight of monomers, of vinyl monomers.
The acrylic component preferably includes one or more non-functional monomers and one or more functional monomers (more preferably acid-functional monomers and even more preferably acid-functional acrylic monomers). In presently preferred embodiments, the acrylic component includes one or more vinyl monomers. The acrylic component is preferably prepared through chain growth polymerization using one or more ethylically unsaturated monomers. Examples of suitable ethylically unsaturated monomers include non-functional monomers such as styrene®, halostyrenes, α-methylstyrene, acrylic acid alkyl esters (eg, methyl acrylate, ethyl acrylate, butyl acrylate, etc.), methacrylic acid alkyl esters and/or crotonic acid (eg . , methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl methacrylates and crotonates), vinyl cyclohexane, vinyl cyclooctane, vinyl cyclohexane, hexanediol diacrylate, dimethyl maleate, dibutyl fumarate and similar diesters, vinyl naphthalene, vinyl toluene, vinyl acetate, vinyl propionate, vinyl cyclooctane, alli methacrylate, 2-ethylhexyl acrylate, and diesters of maleic anhydride; and functional monomers such as acid functional monomers (eg. , acrylic acid, methacrylic acid, crotonic acid, itaconic acid, anhydride
<img file="MX373246B_D0076.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY maleic acid and esters of these, mesaconic acid, citraconic acid, fumaric acid and sorbic acid), amide functional monomers (eg acrylamide, methacrylamide, etc.), hydroxyl functional monomers (eg . , hydroxyalkyl acrylate or methacrylate monomers such as hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HPA), hydroxypropyl methacrylate (HPMA), etc.); and variations and combinations of these. Preferred non-functional monomers include styrene, ethyl acrylate, butyl methacrylate, and combinations of these. Preferred functional monomers include acrylic acid, methacrylic acid, and combinations of these.
In some embodiments, the acrylic component is at least substantially free of styrene.
The combination and/or ratio(s) of the above monomers can be adjusted to provide a desired coating or film property. Preferably, at least a portion of the above monomers is capable of rendering the resin system dispersible in an aqueous carrier. Examples of monomers capable of rendering the resin system dispersible in an aqueous carrier include monomers functional with acid to form salt groups upon neutralization with a base.
Without being limited by theory, it is believed that, for certain embodiments of the present invention, the Tg of the
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY The acrylic component is a contributing factor for coating compositions that exhibit adequate resistance to replicate processes associated with certain food and beverage products. Generally, the Fox equation can be used to calculate the theoretical Tg of the acrylic component. In some embodiments, the acrylic component has a Tg of at least about 40°C, preferably at least about 60°C, more preferably at least about 80°C, and even more preferably at least about 90°C. . Illustratively, a water-dispersible polymer having an ELA structure described above herein may include an acrylic component having the Tg. The acrylic component preferably has a Tg of less than about 280°C, more preferably less than about 220°C, even more preferably less than about 180°C, even more preferably less than about 160°C. and optimally less than about 150°C. In some embodiments, the acrylic component has a Tg of less than about 130°C or less than about 120°C. In some embodiments, the acrylic component has a Tg greater than about 100°C, more preferably from about 100°C to about 120°C.
In other modalities (eg, where resistance to
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY replication processes of astringents is not a problem) it may be beneficial to use an acrylic component with a Tg lower than 50 °C, lower than 40 °C or even lower than 30 °C.
A coating composition of the present invention may further include other optional polymers that do not adversely affect the coating composition or a resulting cured coating composition thereof. Such optional polymers are typically included in a coating composition as a filler material, although they may also be included, for example, as a binder polymer, a crosslinking material, or to produce desired properties. One or more optional polymers (eg, filler polymers) may be included in an amount sufficient for the intended purpose, but not in an amount such as to adversely affect a coating composition or a resulting cured coating composition thereof.
Such additional polymeric materials may be non-reactive and thus function simply as fillers. Such optional non-reactive filler polymers include, for example, polyesters, acrylics, polyamides, polyethers, and novalacs. Alternatively, such additional monomeric or polymeric materials may be reactive with other components of the composition (eg, an acid-functional or unsaturated polymer). Whether
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If desired, the reactive polymers may be incorporated into the compositions of the present invention to provide additional functionality for various purposes, including crosslinking or dispersing the polymer of the present invention in water. Examples of such reactive polymers include, for example, functionalized polyesters, acrylics, polyamides, and polyethers.
A preferred optional ingredient is a catalyst to increase the cure ratio. Examples of catalysts include, but are not limited to, strong acids (eg. g., phosphoric acid, dodecylbenzene sulfonic acid (DDBSA), available as 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 compounds of tin, titanium and zinc. Specific examples include, but are not limited to, a tetraalkyl ammonium halide, a tetraalkyl or tetraaryl phosphonium iodide or acetate, tin octoate, zinc octoate, triphenylphosphine, and similar catalysts known to persons skilled in the art. If a catalyst is used, it is preferably 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. coating. Whether
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The MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY uses a catalyst, this is present, preferably, in an amount not greater than 3% by weight and, more preferably, not greater than 1% by weight, based on the weight of the non-volatile material in the coating composition.
Another useful optional ingredient is a lubricant (eg, a wax), which facilitates the processing of fabricated metal articles (eg, stoppers and ends of food or beverage cans) by imparting lubricity to sheets of coated metal substrate. Non-limiting examples of suitable lubricants include, for example, natural waxes, such as carnauba wax or lanolin wax, polytetrafluoroethane (PTFE) type lubricants, and polyethylene. 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. 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 a pigment is used, it is present in the coating composition in an amount of not more than 70% by weight, more preferably not more than 50% by weight, and even more preferably not more than 40% by weight. weight, based on the total weight of solids in the
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY coating composition.
Surfactants may optionally be added to the coating composition, for example, to aid flow and wetting of the substrate. Examples of surfactants include, but are not limited to, nonylphenol polyesters and similar salts and surfactants known to those skilled in the art. If a surfactant is used, it is preferably 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 a surfactant is used, it 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.
In some embodiments, the polyether polymer of the present invention is included in a monolayer or multilayer coating system layer that includes a layer incorporating a thermoplastic dispersion (e.g., a halogenated polyolefin dispersion such as, for example, example, a polyvinyl chloride (PVC) organosol). In one embodiment, the polyether polymer is included in a first layer of the multilayer coating system that includes another layer (eg. g., a top layer) incorporating a thermoplastic dispersion. Multi-layer coating systems are described in the provisional patent application of
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY United States no. 61/681,590 entitled Container Coating System (file number 160-P-2218USP1) filed August 9, 2012. In another embodiment, the polyether polymer is included in the layer incorporating the thermoplastic dispersion, for example, as a stabilizer for PVC and/or as a ceresin, which is described in US provisional patent application no. 61/681,602 entitled Stabilizer and Coating Compositions Thereof (file number 160P-2207USP1) filed August 9, 2012.
In some embodiments, the coating composition is free of PVC. That is, in some embodiments, the coating composition preferably contains less than 2% by weight of vinyl chloride or other halogenated vinyl materials, more preferably less than 0.5% by weight of the materials, and even more preferably, less than 1 ppm of the materials.
The coating composition of the present invention may be present as one layer of a single layer coating system or as one or more layers of a multilayer coating system. The coating composition can be used as a primer coat, an intermediate coat, a top coat, or a combination of these. The coating thickness of a particular layer and the total coating system vary by material.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY of the coating used, the substrate, the method of applying the coating, and the end use for the coated article. Single-layer or multi-layer coating systems that include one or more layers formed from a coating composition of the present invention may have any suitable total coating thickness, but typically have a total dry coating thickness average from about 1 to about 60 microns and, more typically, from about 2 to about 15 microns. Typically, the total coating thickness for rigid metal food or beverage can applications will be from about 3 to about 10 microns. Coating systems for closure applications can have an average total coating thickness up to approximately 15 microns. In certain embodiments in which the coating composition is used as an internal coating on a drum (eg. g., a drum for use with food or beverage products), the total coating thickness may be approximately 25 microns.
The coating compositions of the present invention are particularly useful for coating metal substrates.
The coating composition of the present invention can be applied to a substrate either before or after
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY convert the substrate into an article (such as, for example, a container for food or beverages or a portion thereof). In one embodiment, a method is provided that includes: applying a coating composition described herein to a metal substrate (eg, applying the composition to the metal substrate in the form of a flat coil or sheet), curing the composition, and converting (eg, by die-cutting) the substrate into a packaging container or portion thereof (eg, a food or beverage can or portion thereof). For example, beverage can ends (e.g., riveted beverage can ends having a rivet for attaching a pull tab thereof) with a cured coating of the present invention on one surface thereof may be formed into the process. In another embodiment, the coating composition is applied to a preformed metal food or beverage can or a portion thereof. For example, in some embodiments, the coating composition is spray-applied to an inner surface of a preformed food or beverage can (eg, as is typically the case with two-piece food or beverage cans).
In one embodiment, the coating composition of the present invention is a water-based internal spray coating suitable for spray application to
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY the internal surfaces of a two-piece can for food or beverages, which preferably includes from about 15 to about 40% by weight of non-volatile materials, more preferably from 15 to 25% by weight non-volatile materials for internal spraying of two-piece food or beverage cans (eg, two-piece steel or aluminum food or beverage can).
The metal substrate used in forming rigid food or beverage cans or portions thereof typically has a thickness in the range of about 0.13 mm (0.005 inches) to about 0.64 mm (0.025 inches). Electrochromic tin steel, cold-rolled steel, and aluminum are commonly used as metal substrates for food or beverage cans, or portions thereof. In embodiments in which a metal foil substrate is used in the forming of, for example, a packaging article, the thickness of the metal foil substrate may be even thinner than that described above.
After the coating composition is applied to a substrate, the composition may be cured by a variety of processes including, for example, conventional or convection oven baking or any other method that provides a suitable elevated temperature for curing the coating. The curing process can
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MEXICAN INSTITUTE
OF THE PROPERTY
INDUSTRIAL carried out in different or combined stages. For example, the substrates can be dried at room temperature so that the coating compositions are substantially uncrosslinked. The coated substrates can then be heated to fully cure the compositions. In some cases, the coating compositions of the present invention can be dried and cured in one step.
Curing conditions vary depending on application method and intended end use. The curing process can be performed at any suitable temperature, including, for example, oven temperatures in the range of from about 100°C to about 300°C, and most often from about 177°C to about 250°C. . If the substrate to be coated is a metal coil, curing of the applied coating composition can be conducted, for example, by heating the crosslinked metal substrate for a suitable period of time to a peak metal temperature (PMT), preferably higher than approximately 177 °C (350 °F) . More preferably, the coated metal coil is heated for a suitable period of time (eg. g., about 5 to 900 seconds, more typically about 5 to 30 seconds) to a PMT of at least about 218°C (425°F).
The coating compositions of the present invention may be suitable, for example, for the
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY spray coating, coil coating, wash coating, sheet coating, and side seam coating (for example, side seam coating of food cans). Ά A further description of such application methods is provided below. It is contemplated that the coating compositions of the present invention may be suitably used in each of these application methods further described below, including the end uses associated therewith.
Spray coating includes the introduction of the coated composition into a preformed packaging container. Typical preformed packaging containers suitable for spray coating include food cans, beer and beverage containers, and the like. The spray process preferably uses a spray nozzle with the ability to evenly coat the interior of the preformed packaging container. The sprayed preformed container is then subjected to heat to remove any residual carrier (eg, water or solvents) and to harden the coating.
A coil coating is described as the coating of a continuous coil composed of a metal (for example, steel or aluminum). Once coated, the coil
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY of the coating is subjected to a short thermal curing cycle, ultraviolet and/or electromagnetic, for the hardening (for example, drying and curing) of the coating. Coil liners provide coated metal (e.g., steel and/or aluminum) substrates that can be made into formed articles, such as two-piece deep drawn food cans, three-piece deep drawn food cans, food can ends, deep drawn cans. and ironed, beverage can ends and the like. In one embodiment, the coating composition of the present invention is a water-based coating composition that is applied to aluminum or steel coatings from which the riveted beverage can ends are subsequently made.
A liner is commercially described as coating the exterior of drawn and ironed (D&I) two-piece cans with a thin layer of protective coating. The exterior of these D&I cans is coated by passing the preformed two-piece D&I cans through a curtain of coating composition. The cans are inverted, i.e. the closed end of the can is facing down when passed through the curtain. This lining composition curtain takes on a waterfall-like appearance. Once these cans pass under this
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY curtain of coating composition, the liquid coating material effectively covers the exterior of each can. Excess coating is removed with the use of an air knife. After 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 to harden (eg, dry and cure) the coating. The residence time of the coated can within the confines of the curing oven is typically from 1 minute to 5 minutes. The curing temperature in this oven will typically range from 150°C to 220°C.
Sheet cladding is described as cladding separate pieces of a wide variety of materials (eg, steel or aluminum) that have been pre-cut, typically into square or rectangular sheets. The typical dimensions of these sheets are approximately one square meter. Upon completion of the coating process, the coating hardens (ie, dries and cures) and the coated sheets are collected and prepared for further manufacturing. Sheet liners provide a coated metal (e.g., steel or aluminum) substrate that can be successfully converted into formed articles, such as two-piece drawn food cans, three-piece food cans, food can ends, stuffed and ironed,
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY ends of beverage cans (including, for example, riveted ends of beverage cans that have a rivet to fix the ring) and the like. In one embodiment, the coating composition of the present invention is a solvent-based coating composition that is applied to steel or aluminum sheets that are subsequently fabricated into the packaging articles described above.
A side seam coating is described as the application of a powder coating or the spray application of a liquid coating over the welded area of three-piece formed food cans. In preparing three-piece food cans, a rectangular piece of coated substrate is made into a cylinder. The formation of the cylinder is permanent due to the welding of each side of the rectangle by means of thermal welding. Once welded, each can typically requires a coating layer that protects the exposed welded portion from subsequent corrosion or other effects on the contained food product. Coatings that perform this function are called side seam strips. Typical side seam strips are spray applied and rapidly cured by residual heat from the welding operation in addition to a small thermal, ultraviolet and/or electromagnetic oven.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
The application of other commercial coatings and curing methods, eg, electrocoating, extrusion coating, laminating, powder coating, and the like, is further envisioned.
In embodiments in which the coating composition is intended to be used as an inner coating for packaging, the coating composition, when properly cured, preferably has a corrosion resistance to withstand prolonged contact with the packaged product, as well as any processing condition, without improper degradation. Inner coating compositions for packaging, when applied to suitable metal substrates (eg. , a metal substrate used in the examples section below) in a coating thickness consistent with that typically used in the particular packaging end use and properly cured, is preferably capable of withstanding immersion in a 2% NaCl aqueous solution for 90 minutes at a temperature of 121°C and a pressure of 1.05 kilograms per square centimeter without exhibiting any reduction in inadequate film integrity such as bubbling or loss of adhesion (eg, by using methods in the test methods section) . Beverage can end liners is preferably able to pass the above test by
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY the use of a 1% aqueous citric acid solution instead of the 2% NaCl solution.
The polymer of the present invention can be used in p powder coating applications for use in the formation of an adherent polymeric coating. Thus, in some embodiments, the coating composition of the present invention is a powder coating composition that preferably does not include a liquid carrier (although it may include trace amounts of residual water or organic solvent). The powder coating composition is preferably in the form of a finely divided, free-flowing powder. In preferred embodiments, the powder composition is a thermosetting powder composition that forms a thermosetting coating when properly cured. The following description relates to the embodiments of the powder coating of the present invention.
The powder coating composition of the present invention may be particularly useful in end uses where the coated substrate is intended to come into contact with substances for human consumption or intimate contact with humans. For example, the powder coating compositions can be used to coat: surfaces of food or beverage containers, cosmetic containers, or medicinal product containers; surfaces
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY of valves and connections, including surfaces made to come into contact with drinking water or other consumable liquids; pipe surfaces, including internal surfaces of pipes for water or other pipes for carrying liquids; and tank surfaces, which include the internal surfaces of water tanks, such as bolted steel tanks. For powder coatings that come into contact with potable water, the cured powder coating composition should preferably meet ANSI/NSF Standard 61. Some examples of connections include items for use in systems for conveying liquids (for example, for use in the transportation of potable water), such as connectors (for example, threaded or flanged connectors), elbows, flow dividers (for example, , tees, etc.), backflow preventers, pipe end plugs, and the like.
The powder coating composition preferably includes at least a film-forming amount of the polymer of the present invention, which in preferred embodiments is a polyether polymer having segments of Formula (I). To facilitate stability of the powder coating composition during storage prior to use, a polymer of the present invention is preferably selected having a Tg of at least
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY at least about 40°C, more preferably at least about 50°C, and even more preferably at least about 60°C. The powder coating composition preferably includes at least about 50% by weight, more preferably at least 70% by weight, and even more preferably at least 90% by weight of the polymer of the present invention. , based on total resin solids.
Powder coating compositions typically use binder polymers having a different molecular weight (typically a lower molecular weight) compared to liquid packaging coating compositions for use in metal food or beverage cans. When used in powder coating compositions, the polymer of the present invention preferably has a number average molecular weight (Mn) of at least about 1000, more preferably at least about 1200, and even more preferably at least about 1200. preferably at least about 1500. In such applications, the polymer of the present invention preferably has an Mn of less than about 6000, more preferably less than about 5000, and even more preferably less than about 4000.
The powder coating composition preferably includes at least one base powder that includes the
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY polymer of the present invention. The base powder may further include one or more optional ingredients, which may include any of the suitable ingredients described herein. The base powder preferably includes the polymer of the present invention as a major component on a weight basis, and more preferably includes at least 50% by weight of the polymer. In some embodiments, the polymer of the present invention comprises all or substantially all of the base powder.
The base powder particles may be of any suitable size. Preferably, the base powder particles exhibit a particle size diameter of from about 1 micron to about 200 microns, more preferably from about 10 to about 150 microns.
The base powder may exhibit any suitable particle size distribution. In some embodiments, the average particle size of the base powder is preferably at least about 20 microns, more preferably at least about 30 microns, and even more preferably at least about 40 microns. In some embodiments, the average particle size is preferably less than about 150 microns, more preferably less than about 100 microns, and even more preferably
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY less than approximately 60 microns. The average particle sizes mentioned in this paragraph are average particle diameter sizes expressed on a volume basis, which can be determined, for example, by diffraction of laser radiation.
The powder compositions of the present invention may further contain one or more other optional ingredients. The optional ingredients preferably do not adversely affect the powder compositions or the articles formed from them. Such optional ingredients may be included, for example, to improve aesthetics; to facilitate the manufacture, processing and/or handling of the powder compositions or the articles formed from them; and/or to further improve a particular property of powder compositions or articles formed thereof. Each optional ingredient is preferably included in an amount sufficient for its intended purpose, but not in such an amount as to adversely affect a powder composition or a resulting cured coating thereof. The optional ingredient(s) may be present in a particle the same as or different from the polymer of the present invention, or a combination of these. In preferred embodiments, one or more optional ingredients are present in the base powder particles together with the polymer of the present invention. If it is present in particles
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Other than those of the base powder, the particles of the optional ingredient or ingredients preferably have a particle size in the general range of the particle sizes of the base powder.
The powder composition preferably includes one or more optional curing agents (eg, crosslinkers). Suitable curing agents may include phenolic crosslinkers, preferably BPA-free phenolic crosslinkers; dicyandiamide, which may be optionally substituted; carboxyl-functional compounds, such as, for example, carboxyl-functional polyester resins or carboxyl-functional acrylic resins; and combinations of these. The powder composition may include any suitable amount of the crosslinker(s). In some embodiments, the crosslinker is present in the powder composition in an amount of up to about 15% by weight, preferably up to about 10% by weight, and more preferably up to about 5% by weight, based on total weight. of the powder coating composition. If used, the crosslinker is preferably present in an amount of at least about 0.1% by weight, more preferably at least about 0.5% by weight, and even more preferably at least about 1% by weight. weight, based on the total weight of the powder coating composition.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
An optional cure accelerator may be present in the powder coating composition to facilitate curing. When used, the powder coating composition typically includes from about 0.1% by weight to about 3% by weight of one or more cure accelerators. 2-Methylimidazole is an example of a preferred cure accelerator. Other suitable cure accelerators may include imidazoles, phosphonium salts, tertiary amines, quaternary ammonium salts, anhydrides, polyamides, aliphatic amines, epoxy resin amine adducts, and combinations of these.
The powder coating composition may optionally include one or more flow control agents to improve the flow, wetting, and/or leveling properties of the cured film. If used, the flow control agents are typically present in an amount of from about 0.01 wt% to about 5 wt%, more often from about 0.2 wt% to about 2 wt%, based on to the total weight of the powder coating composition. Examples of suitable flow control agents include polyacrylates, such as poly(2-ethylhexyl acrylate) and various 2-ethylhexyl acrylate copolymers.
The powder coating composition may optionally include one or more flow agents to
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY facilitate the preparation of a free-flowing powder composition. If used, the fluidizing agent is typically present in an amount of from about 0.01 wt% to about 5 wt%, more often from about 0.05 wt% to about 0.5 wt%, based on total weight. of the powder coating composition. Suitable fluidizing agents include, for example, fumed silicas of suitable particle size. Such fluidizing agents may preferably be added after the melt blending process, such as for the extruded flake before or after milling.
The inorganic filler and/or color pigment may optionally be included in the powder coating compositions. Examples of such suitable materials may include calcium silicates, such as, for example, wollastonite; barium sulfate; calcium carbonate; mica; talcum powder; silica; iron oxide; titanium dioxide; carbon black; phthalocyanines; chrome oxide; and combinations of these.
The powder coating compositions can be prepared by any suitable method. In one embodiment, some or all of the ingredients are melt blended, which can be achieved, for example, with the use of conventional single or twin screw extruders.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY screw. The temperature of the melt blending step is preferably controlled to avoid any appreciable crosslinking. Typically, a melt blending temperature is selected such that the melt blend temperature is no greater than about 100°C to about 150°C. The ingredients may optionally be premixed prior to melt blending. After melt blending and cooling, the resulting blend, which is typically an extrudate, can be processed into a powder using conventional milling techniques. Optionally, the resulting milled powder can be sieved to remove particles that are not in the desired particle size range. The powder may optionally be mixed with one or more additional powders to form the finished powder coating composition. For example, in some embodiments, the milled powder is combined with powdered flow agent either before or after optional screening.
The powder coating compositions can be applied to the substrate using any suitable method. Typically, the substrate is a metal substrate (eg, cast iron, steel, etc.), which may be pure metal or optionally pre-treated and/or primed. One such suitable method is spray application.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY electrostatic powder charged on the substrate. Alternatively, the substrate can be applied, for example, by immersing the substrate in a fluidized bed for powder. In a preferred embodiment, the powder is applied to a hot substrate that has been heated to 190°C-240°C. Upon contact with the hot metal substrate, the powder melts, reacts and forms a continuous coating that is preferably smooth and uniform. In another embodiment, the powder is applied to a substrate at near room temperature, and then the powder-coated substrate is heated to a temperature sufficient to cause the powder to melt, react, and form a continuous coating that is preferably smooth. and uniform.
Melting and curing (eg, crosslinking) of the powder composition can be carried out in combined or discontinuous heating steps. In presently preferred embodiments, a co-heating step is used in which the powder coating composition is heated to a temperature sufficient to both melt the powder and cure the resulting continuous coating. Firing temperature and cooking duration vary based on a wide variety of factors, including, for example, end use. To cure the coating, the firing temperature is typically at least about
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
150 °C and, more often, at least about 200 °C. Generally, a lower cure temperature can be used if a longer cure time is used. Typically, the curing temperature is no greater than about 240°C. Curing time can range from, for example, about 30 seconds to about 30 minutes, depending on the curing temperature and end use.
The thickness of the cured powder coating varies depending on the particular end use. Typically, however, the cured powder coating has an average coating thickness in the range of from about 25 to about 1500 microns, and more often from about 50 to about 500 microns. In some embodiments, an average coating thickness in the range of about 125 to about 300 microns is used. test methods
Unless otherwise indicated, the test methods listed below were used in the following examples.
Differential Scanning Calorimetry
Samples for Differential Scanning Calorimetry (DSC) testing were prepared by first applying the liquid resin composition onto
<img file="MX373246B_D0103.tif" />
100
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY aluminum sheet panels. The panels were then baked in a Fisher Isotemp electric oven for 20 minutes at 300°F (149°C) to remove volatile materials. After cooling to room temperature, samples were removed from the panels, weighed into standard sample containers, and analyzed using the standard DSC hot-cold-hot method. Samples were equilibrated at -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. Glass transition temperatures were calculated from the thermogram of the last heat cycle. The glass transition was determined at the inflection point of the transition. Accession
Adhesion testing is done to assess if the coating adheres to the coated substrate. Adhesion testing was performed in accordance with ASTM D 3359 - Test Method B with a SCOTCH 610 tape available from 3M Company of Saint Paul, Minnesota.
Adhesion is generally rated on a scale of 0 to 10 where a value of 10 indicates optimal adhesion, a value of 9 indicates 90% of the coating remains adhered, a value of 8 indicates 80% of the coating remains adhered. sticks, etc. The ratings of
<img file="MX373246B_D0104.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY 10 adhesion are typically preferred for commercially viable coatings.
Opacity resistance
The haze resistance test measures the ability of a coating to resist attack from various solutions. Typically, opacity is measured by the amount of water absorbed into a coated film. Generally, when the film absorbs water it becomes cloudy or white in color. Haze is generally determined visually using a scale of 0-10, where a rating of 10 indicates no haze and a rating of 0 indicates complete whitening of the film. Typically, opacity ratings of at least 7 are preferred for commercially viable coatings, and optimally 9 or more.
Reverse impact and crack resistance
Reverse impact measures the ability of the coating substrate to resist given deformation when impacted by a steel punch with a hemispherical head and can be a predicate, for example, for the ability of a food and beverage can coating to survive a can drop event. For the present evaluation, a coated substrate was subjected to 4.07 N m (36 in-lbs) of force using
<img file="MX373246B_D0105.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY BYKGardner general bending and impact test apparatus and evaluated, visually, for micro-disintegration or micro-fracturing, commonly referred to as cracking. The test pieces were impacted on the reverse or uncoated side. A rating of 10 indicates no cracking and suggests sufficient flexibility and curing. A rating of 0 indicates total failure. Commercially viable coatings preferably show little or no cracking in a reverse impact test. In the data reported below in Table 1, w refers to portions of the coated strip immersed in water and wv refers to portions of the coated strip that were exposed to water vapor in void space.
process resistance
The process test determines a coating's ability to withstand elevated temperatures and pressures while in contact with water. The conditions are frequently encountered in pasteurization processes used in conjunction with food and beverage products. A coated substrate is typically tested in the following manner. Coated metal substrate strips (eg . 3.8 cm (1.5 in) by 17.8 cm (7 in) strips of electrochromic tin ETP are partially submerged in water
<img file="MX373246B_D0106.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY deionized and partially immersed strips are placed in a pressure oven and subjected for 90 minutes at adequate elevated pressure to reach a temperature of 121 °C (-250 °F). The coated strips are then tested for coating adhesion and opacity as described above. Commercially available coatings preferably provide adequate process resistance with perfect adhesion (rating of 10) and haze rating of at least 5, optimally at least 9. Solvent resistance
The extent of cure or crosslinking of a coating is measured as resistance to solvents such as methyl ethyl ketone (MEK) or isopropyl alcohol (IPA). This test is performed as described in ASTM method D 5402-93. The number of double rubs (ie a back and forth motion) is reported. Preferably, the solvent resistance of MEK is at least 30 double rubs.
EXAMPLES
The following examples are offered to aid in the understanding of the present invention and are not to be construed as limiting the scope thereof. Unless otherwise indicated, all parts and percentages are by weight.
<img file="MX373246B_D0107.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
Example 1. Synthesis of 2,5-di-t-butyl hydroquinone diglycidyl ether and a polyether polymer of this
2,5-di-tert-butylhydroquinone (30 g, 0.135 mol) was dissolved in 2-propanol (500 mL) and epichlorohydrin (100 g, 1.08 mol) at room temperature. Sodium hydroxide (16.2 g, 0.405 mol) in water (63 mL) was added in 5-10 minute portions. After stirring for 30 minutes the purple solution was heated to 70°C. The mixture was stirred overnight at 70°C. After 20 hours, the solution was cooled to room temperature and filtered. The 2-propanol was removed on a rotary evaporator at 30°C. The remaining mixture was diluted with water (400 mL) and extracted with ethyl acetate (1 L). The organic extract was dried over sodium sulfate. After filtration and concentration under reduced pressure, the remaining oil was dried under high vacuum at room temperature until constant weight was obtained. The crude product (48.4 g, orange solid) was mixed with hot methanol (200 mL) for 30 min. The methanol was allowed to cool to room temperature, while mixing. The solid product was filtered and resuspended in hot methanol (150 mL). After cooling and filtering, the semi-purified product (30.1 g, 90-95% pure by NMR) was crystallized from hot ethyl acetate (50 mL). The ethyl acetate was cooled to room temperature and then
<img file="MX373246B_D0108.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY refrigerated for 4 hours at -10 °C. The crystallized product was filtered and dried under high vacuum at room temperature until constant weight was obtained. The experiment generated 2,5-di-tert-butylhydroquinone diglycidyl ether (19.4 g, 43% yield) as a white solid. The epoxy value was 0.577 equivalents per 100 grams of material.
15.34 parts of 2,5-di-tert-butylhydroquinone diglycidyl ether, 4.54 parts of hydroquinone, 0.018 parts of CATALYST 1201 catalyst and 1.05 parts of ethyl carbitol. This mixture was heated with stirring to 125°C, allowed to exotherm to 169°C, then heated at 160°C for 3 hours until the epoxy value was 0.034 equivalents per 100 grams. At this point, 18.8 parts of cyclohexanone was added to the mixture, while the mixture was cooled to 70 °C. The batch was discharged supporting a solvent-based polymer with a non-volatile content (NVC) of 50% and an epoxy value of 0.034 equivalents per 100 grams of polymer. The polymer had an Mn of 6,520, a
<img file="MX373246B_D0109.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
PDI of 2.47 and presented a Tg of 74 °C.
Example 2. Coating compositions
A packaging coating composition, and more specifically a packaging coating composition suitable for use on the interior or exterior of a food or beverage can, can be formulated for the methods and materials included in the present invention by use of the polymer of polyether. Table 1 below shows the film properties of the resin, when formulated with a cresol-based thermosetting phenolic resin with or without a catalyst. The coating compositions from each of runs 1-3 were applied to
0.25 of ETP substrate no. 75 and cured for 10 minutes in a box oven at 204°C (-400°F) to produce a cured coating having dry film weight.
Table 1
<td>Ingredients</td><td>Test 1 % in weigh</td><td>test 2 % in weigh</td><td>test 3 % in weigh</td>
<td>Resin of Example 1 (35.0% solids)</td><td> 100.00</td><td> 73.02</td><td> 70.80</td>
<td>Phenolic resin (80.0% solids)</td><td> —</td><td> 11.32</td><td> 10.97</td>
<td>C i chlorohexanone</td><td> —</td><td> 15.06</td><td> 14.60</td>
<td>BYK-310*</td><td> —</td><td> 0.60</td><td> 0.58</td>
<img file="MX373246B_D0110.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
<td>Phosphoric acid catalyst (10% in butyl cellosolve)</td><td></td><td></td><td> 3.05</td>
<td>Total:</td><td> 100.00</td><td> 100.00</td><td> 100.00</td>
<td>CNV</td><td> 35.0 %</td><td> 34.6 %</td><td> 33.9 %</td>
<td>Resin: Crosslinking Agent (solids on solids)</td><td> 100: 0</td><td> 74: 26</td><td> 74: 26</td>
<td>Dry film weight (microns)</td><td> 4.9</td><td> 4.3</td><td> 4.5</td>
<td>Accession</td><td> 10</td><td> 10</td><td> 10</td>
<td>Solvent resistance (double frictions)</td><td> < 3</td><td> 35</td><td> 90 - 100</td>
<td>Rev. Imp. Cracking (36 in-lbs)</td><td>Serious</td><td>Moderate (“7”)</td><td>Nothing (“10”)</td>
<td>Process Resistance (90 minutes at 250°F):</td><td></td><td></td><td></td>
<td>Opacity (p/pv)</td><td></td><td> 8/10</td><td> 10 / 10</td>
<td>Adhesion (w/pv)</td><td> —</td><td> 10 / 10</td><td> 10 / 10</td>
* BYK-310 is a siloxane flow modifier.
It can be seen from Table 1 that when the resin is formulated with a crosslinking agent and catalyst, excellent cure and film properties are obtained.
This application incorporates as references the
<img file="MX373246B_D0111.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY descriptions of each of the following: United States patent application no. 13/570,632 entitled COATING COMPOSITIONS FOR CONTAINERS AND OTHER ARTICLES AND METHODS OF COATING (file number 06-2085-0101) filed on August 9, 2012; United States patent application no. 13/570,743 entitled COATING COMPOSITIONS FOR CONTAINERS AND OTHER ARTICLES AND METHODS OF COATING (file number 06-2085-0102) filed on August 9, 2012; and United States patent application no. 61/681,434 entitled COMPOSITIONS FOR CONTAINERS AND OTHER ARTICLES AND METHODS OF COATING (file number 06-2224-010A) filed on August 9, 2012.
The complete description of all patents, patent applications and publications and electronic material mentioned in the present invention are hereby incorporated by reference. The above detailed description and examples are included for ease of understanding only. Therefore, they do not constitute a limitation to the present invention. The invention is not limited to the precise details shown and described as variations that are apparent to those of skill in the industry are included within the invention defined by the claims. The present invention illustratively described herein
<img file="MX373246B_D0112.tif" />
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY description can be practiced adequately, in some modalities, in the absence of any element that has not been specifically described in this description.
It is stated that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is the one that is clear from the present description of the invention.
Contents140
123 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56 Sheet 57 Sheet 58 Sheet 59 Sheet 60 Sheet 61 Sheet 62 Sheet 63 Sheet 64 Sheet 65 Sheet 66 Sheet 67 Sheet 68 Sheet 69 Sheet 70 Sheet 71 Sheet 72 Sheet 73 Sheet 74 Sheet 75 Sheet 76 Sheet 77 Sheet 78 Sheet 79 Sheet 80 Sheet 81 Sheet 82 Sheet 83 Sheet 84 Sheet 85 Sheet 86 Sheet 87 Sheet 88 Sheet 89 Sheet 90 Sheet 91 Sheet 92 Sheet 93 Sheet 94 Sheet 95 Sheet 96 Sheet 97 Sheet 98 Sheet 99 Sheet 100 Sheet 101 Sheet 102 Sheet 103 Sheet 104 Sheet 105 Sheet 106 Sheet 107 Sheet 108 Sheet 109 Sheet 110 Sheet 111 Sheet 112 Sheet 113 Sheet 114 Sheet 115 Sheet 116 Sheet 117 Sheet 118 Sheet 119 Sheet 120 Sheet 121 Sheet 122 Sheet 123
99 members in 13 offices
Priority claims7
| Document | Office | Kind | Date |
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| 2012024191 | United States of America | W | |
| 2012024193 | United States of America | W | |
| PCTUS2012024191 | World Intellectual Property Organization (WIPO) | – | |
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| 201261681394 | United States of America | P | |
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| 2013024960 | United States of America | W |
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Numbers
- Publication
- 373246
- Application
- 9453
Titles2
- Spanish
- COMPOSICIONES PARA CONTENEDORES Y OTROS ARTICULOS Y METODOS PARA USARLOS.
- English
- COMPOSITIONS FOR CONTAINERS AND OTHER ITEMS AND METHODS TO USE THEM.
Classification
- CPC, 10
- C09D171/00
- A47J47/02
- C08L71/00
- C08G59/063
- C08G59/066
- C08G59/1444
- C08G59/245
- C08G2650/56
- C23C2/00
- B65D25/14
- IPC, 5
- A47J47 02
- B65D25 14
- C08L71 00
- C09D171 00
- C23C2 00