Coating compositions for cans and methods of coating
Abstract
A method of coating a can of food or drink, the method comprises: forming a composition comprising an emulsion polymerized latex polymer and which is substantially free of bound bisphenol A and aromatic glycidyl ether compounds, comprising: forming a salt of an acidic or anhydride-functional polymer and an amine in a carrier comprising water to form an aqueous dispersion; combining an ethylenically unsaturated monomer component with the aqueous dispersion; and polymerizing the ethylenically unsaturated monomer component in the presence of the aqueous dispersion to form an emulsion polymerized latex polymer; and applying the composition comprising the emulsion polymerized latex polymer to a metal substrate before or after forming the metal substrate in a food or beverage can or part thereof.
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20 claims: 5 independent, 15 dependent
- 1ES 2 367 516 T3 REIVINDICACIONES 1. Un método de recubrimiento de una lata de comida o bebida, el método comprende:formar una composición que comprende un polímero de látex polimerizado por emulsión y que está sustancialmente libre de bisfenol A unido y compuestos de glicidil éter aromático, que comprende: formar una sal de un polímero ácido- o anhídrido-funcional y una amina en un transportador que comprende agua para formar una dispersión acuosa;combinar un componente de monómero etilénicamente insaturado con la dispersión acuosa;y polimerizar el componente de monómero etilénicamente insaturado en presencia de la dispersión acuosa para formar un polímero de látex polimerizado por emulsión;y aplicar la composición que comprende el polímero de látex polimerizado por emulsión a un sustrato de metal antes de o después de conformar el sustrato de metal en una lata de comida o bebida o parte de la misma.
- 2El método de la reivindicación 1, en el que la aplicación de la composición a un sustrato de metal comprende aplicar la composición al sustrato de metal en forma de una bobina o lámina plana, endurecer el polímero de látex polimerizado por emulsión, y formar el sustrato en una lata de comida o bebida o parte de la misma.
- 3El método de la reivindicación 1, en el que el sustrato de metal comprende acero o aluminio.
- 4El método de la reivindicación en el que el componente de monómero etilénicamente saturado comprende una mezcla de monómeros que comprende al menos un monómero que contiene un grupo funcional oxirano.
- 5El método de la reivindicación 1, en el que el polímero ácido-funcional tiene un valor de peso molecular medio de 1500 a 50.000.
- 6El método de la reivindicación 1, en el que la composición está sustancialmente libre de BPA móvil y compuestos de glicidil éter aromático.
- 7El método de la reivindicación 1, en el que polímero ácido- o anhídrido funcional comprende un polímero acrílico ácido- o anhídrido-funcional, resina alcídica ácido- o anhídrido-funcional, resina de poliéster ácido- o anhídridofuncional, poliuretano ácido- o anhídrido-funcional, o combinaciones de los mismos.
- 8El método de la reivindicación 7, en el que el polímero ácido- o anhídrido-funcional comprende un polímero acrílico ácido-funcional.
- 9El método de la reivindicación 7, en el que el polímero ácido- o anhídrido-funcional comprende un polímero de poliéster.
- 10El método de la reivindicación 9, en el que el polímero de poliéster comprende uno o más segmentos de Fórmula 1 -O-Ar-Rn-C(O)-O-R 1 -O-C(O)-Rn-Ar-Oen la que:cada Ar es independientemente un grupo arilo divalente o grupo heteroarileno;cada R es independientemente un grupo orgánico divalente;R 1 es un grupo orgánico divalente;y cada n es 0 ó 1.
- 11El método de la reivindicación 1, en el que la amina es una amina terciaria.
- 12El método de la reivindicación 1, en el que el polímero ácido- o anhídrido-funcional se neutraliza al menos al 25% con la amina en agua.
- 13El método de la reivindicación 1, en el que el componente de monómero etilénicamente insaturado se polimeriza en presencia de la dispersión acuosa con un iniciador de radicales libres soluble en agua a una temperatura de 0 °C a 100 °C.
- 14Un método de recubrimiento de una lata de comida o bebida, el método comprende:formar una composición que comprende un polímero de látex polimerizado por emulsión, que comprende: formar una sal de un polímero ácido o anhídrido-funcional y una amina terciaria en un transportador ES 2 367 516 T3 que comprende agua para formar una dispersión acuosa;combinar un componente de monómero etilénicamente insaturado que comprende del 0,1% en peso al 30% en peso de un monómero alfa, beta-etilénicamente insaturado oxirano funcional con la dispersión acuosa, en base al peso del componente de monómero;y polimerizar el componente de monómero etilénicamente insaturado en presencia de la dispersión acuosa para formar un polímero de látex polimerizado por emulsión, y aplicar la composición que comprende el polímero de látex polimerizado por emulsión a un sustrato de metal antes de o después de conformar el sustrato de metal en una lata de comida o bebida o parte de la misma.
- 15Una lata de comida o bebida preparada mediante el método de la reivindicación 1 ó 14.
- 16Una lata de comida o bebida que comprende:una parte de cuerpo o una parte de tapa que comprende un sustrato de metal;y una composición de recubrimiento dispuesta en el mismo, en el que la composición de recubrimiento comprende un polímero de látex polimerizado por emulsión y está sustancialmente libre de bisfenol A unido y compuestos de glicidil éter aromático, en la que el polímero de látex polimerizado por emulsión se prepara a partir de una sal de un polímero ácido- o anhídrido-funcional y una amina, un componente de monómero etilénicamente insaturado, y agua.
- 17La lata de la reivindicación 16, en la que el componente de monómero etilénicamente insaturado comprende una mezcla de monómeros que comprende al menos un monómero que contiene un grupo funcional oxirano.
- 18La lata de la reivindicación 15, en la que el polímero ácido- o anhídrido-funcional comprende un polímero acrílico ácido- o anhídrido-funcional, resina alcídica ácido- o anhídrido-funcional, resina de poliéster ácido- o anhídridofuncional, poliuretano ácido- o anhídrido-funcional, o combinaciones de los mismos.
- 19La lata de la reivindicación 15, en la que la amina es una amina terciaria.
- 20Una composición para su uso en el recubrimiento de una lata de comida o bebida, la composición que comprende un polímero de látex polimerizado por emulsión, en la que el polímero de látex polimerizado por emulsión se prepara a partir de una sal de un polímero ácido- o anhídrido-funcional y una amina terciaria, un componente de monómero etilénicamente insaturado que incluye una mezcla de monómeros que incluye al menos un monómero alfa, beta-etilénicamente insaturado que contiene un grupo funcional oxirano en una cantidad de al menos el 0,1% en peso y no mayor del 30% en peso, en base al peso de la mezcla de monómero, y agua. ES 2 367 516 T3 REFERENCIAS CITADAS EN LA DESCRIPCIÓN La lista de referencias citadas por el solicitante es, únicamente, para conveniencia del lector. No forma parte del documento de patente europea. Si bien se ha tenido gran cuidado al compilar las referencias, no pueden excluirse errores u omisiones y la OEP declina toda responsabilidad a este respecto. Documentos de patente citados en la descripción • US 62063904 P [0001] • US 4692491 A [0065] • US 3479310 A [0065] • US 4147679 A [0065] US 2006060043 W [0066] US 727734 P [0066] US 2633458 A [0083]
Independent claims20
756 paragraphs in 21 sections, as filed
ES 2 367 516 T3
DESCRIPTION
Coating compositions for cans and coating methods
The present application claims priority to United States Provisional Patent Application Serial No. 60 / 620,639, filed October 20, 2004, the entirety of which is incorporated herein by reference.
A wide variety of coatings have been used to coat the surfaces of packaging items (eg, food and beverage cans). For example, metal cans are sometimes coated using coil coating or foil coating operations, i.e. a flat coil or sheet of a suitable substrate (e.g. metal steel or aluminum) is coated with a suitable composition. and it hardens (for example, it cures). The coated substrate is then formed on the lid or body of the can. Alternatively, liquid coating compositions (eg, by spraying, dipping, rolling, etc.) can be applied to the formed article and then cured (eg, cured).
The packaging coatings should preferably be capable of high speed application to the substrate and provide the necessary properties when cured to perform this demanded end use. For example, the coating must be safe for food contact, have excellent adhesion to the substrate, and resist degradation over long periods of time, even when exposed to harsh environments.
Many current packaging coatings contain mobile or bound bisphenol A (BPA) or aromatic glycidyl ether compounds or PVC compounds. Although the balance of scientific evidence available to date indicates that the small trace amounts of these compounds that must be released from existing coatings do not pose any health risk to humans, these compounds are nonetheless perceived by some people to be potentially harmful. for human health. As a consequence, there is a strong desire to remove these compounds from food contact coatings.
From what has been stated above, it will be appreciated that what is necessary in the art is a container reservoir (eg, a food or beverage can) that is lined with a composition that does not contain extractable amounts of said compounds. .
This invention provides a coating composition for a food or beverage can that includes an emulsion polymerized latex polymer. This polymer is formed by combining an ethylenically unsaturated monomer component with an aqueous dispersion of a salt of an acid- or anhydride-functional polymer (i.e., a polymer containing an acid group or an anhydride group) and an amine, preferably an tertiary amine, and then polymerizing the monomer component.
The ethylenically unsaturated monomer component is preferably a mixture of monomers. At least one of the monomers in the mixture is preferably an alpha, beta-unsaturated monomer, and at least one monomer is preferably an oxirane functional monomer. More preferably, at least one of the monomers in the mixture is an alpha beta-ethylenically unsaturated monomer containing an oxirane group.
In one embodiment, a method of preparing a food or beverage can is provided. The method includes: forming a composition that includes an emulsion polymerized latex polymer and that is substantially free of bound bisphenol A and aromatic glycidyl ether compounds including: forming a salt of an acid- or anhydride-functional polymer and an amine in a carrier comprising water (and an optional organic solvent) to form an aqueous dispersion; combining an ethylenically unsaturated monomer component with the aqueous dispersion; and polymerizing the ethylenically unsaturated monomer component in the presence of the aqueous dispersion to form an emulsion polymerized latex polymer; and applying the composition including the emulsion polymerized latex polymer to a metal substrate before or after forming the metal substrate in a food or beverage can or part thereof.
In another embodiment, the method includes: forming a composition that includes an emulsion polymerized latex polymer, including: forming a salt of an acid- or anhydride-functional polymer and a tertiary amine in a carrier comprising water (and a solvent optional organic) to form an aqueous dispersion; combining an ethylenically unsaturated monomer component comprising 0.1% by weight to 30% by weight of an alpha, beta-ethylenically unsaturated oxirane functional monomer with the aqueous dispersion, based on the weight of the monomer component; and polymerizing the ethylenically unsaturated monomer component in the presence of the aqueous dispersion to form an emulsion polymerized latex polymer; and applying the composition comprising the emulsion polymerized latex polymer to a metal substrate before or after forming the metal substrate in a food or beverage can or part thereof.
In certain embodiments, the composition can include an organic solvent in the aqueous dispersion. In certain embodiments, the method may include removing at least a portion of the organic solvent, if present, from the aqueous dispersion.
ES 2 367 516 T3
In certain embodiments, applying the composition to a metal substrate includes applying the composition to the metal substrate in the form of a flat coil or sheet, curing the emulsion polymerized latex polymer, and forming the substrate in a can of food or drink or parts thereof. In certain embodiments, applying the composition to a metal substrate comprises applying the composition to the metal substrate after the metal substrate is formed into a can or part thereof.
In certain embodiments, forming the substrate into a can or part thereof includes forming the substrate into a lid or a can body. In certain embodiments, the can is a 2-piece drawn food can, a 3-piece food can, a food can lid, a pressed or pressed food or beverage can, a beverage can lid, and the like. . The metal substrate can be made of steel or aluminum.
In certain embodiments, combining an ethylenically unsaturated monomer component with the aqueous dispersion includes adding the ethylenically unsaturated monomer component to the aqueous dispersion. Preferably, the ethylenically unsaturated monomer component is increasingly added to the aqueous dispersion.
In certain embodiments, the ethylenically unsaturated monomer component includes a mixture of monomers. Preferably, the monomer mixture includes at least one monomer containing an oxirane functional group, and more preferably, at least one alpha, beta-ethylenically unsaturated monomer containing an oxirane functional group. In certain embodiments, the monomer containing an oxirane functional group is present in the ethylenically unsaturated monomer component in an amount of at least 0.1% by weight, based on the weight of the monomer mixture. In certain embodiments, the monomer containing an oxirane functional group is present in the ethylenically unsaturated monomer component in an amount of no more than 30% by weight, based on the weight of the monomer mixture.
In certain embodiments, the methods of the present invention further include combining the emulsion polymerized latex polymer with one or more crosslinkers, fillers, catalysts, dyes, pigments, developers, extenders, lubricants, anti-corrosion agents, flow control agents, thixotropic agents, dispersing agents, antioxidants, adhesion promoters, light stabilizers, organic solvents, surfactants or combinations thereof in the coating composition.
In certain embodiments, the acid-functional polymer has an average molecular weight value of 1500 to 50,000.
In certain embodiments, the composition is substantially free of mobile BPA and aromatic glycidyl ether compounds. Preferably, the composition is substantially free of binding BPA and aromatic glycidyl ether compounds.
In certain embodiments, the acid- or anhydride-functional polymer includes an acid- or anhydride-functional acrylic polymer, acid- or anhydride-functional alkyd resin, acid- or anhydride-functional polyester resin, acid- or anhydride-functional polyurethane, or combinations thereof. Preferably, the acid-functional or anhydride-functional polymer includes an acid-functional acrylic polymer.
In certain embodiments, the amine is a tertiary amine. Preferably, the tertiary amine is selected from the group consisting of trimethyl amine, dimethylethanolamine (also known as dimethylamino ethanol), methyldiethanolamine, triethanolamine, ethyl methyl ethanol amine, dimethyl ethyl amine, dimethyl propyl amine, dimethyl 3-hydroxy. 1-propyl amine, dimethylbenzyl amine, dimethyl 2-hydroxy-1-propyl amine, diethyl methyl amine, dimethyl 1-hydroxy-2-propyl amine, triethyl amine, tributyl amine, N-methyl morpholine, and mixtures thereof. Preferably, the acid- or anhydride-functional polymer is neutralized to at least 25% with the amine in water.
In certain embodiments, the ethylenically unsaturated monomer component is polymerized in the presence of the aqueous dispersion with a water soluble free radical initiator at a temperature of 0 ° C to 100 ° C. In certain embodiments, the free radical initiator includes a peroxide initiator. Preferably, the free radical initiator includes hydrogen peroxide and benzoin. Alternatively, in certain embodiments the free radical initiator includes a redox initiator system.
The present invention also provides food cans and beverage cans prepared by a method described herein.
In one embodiment, the present invention provides a food or beverage can that includes: a body portion or a lid portion that includes a metal substrate; and a coating composition disposed therein, wherein the coating composition includes an emulsion polymerized latex polymer and is substantially free of bound bisphenol A and aromatic glycidyl ether compounds, wherein the emulsion polymerized latex polymer It is prepared from a salt of an acid- or anhydride-functional polymer and an amine, an ethylenically unsaturated monomer component, and water.
In another embodiment, the present invention provides a composition for use in coating a can.
ES 2 367 516 T3 of food or drink, wherein the composition includes an emulsion polymerized latex polymer, wherein the emulsion polymerized latex polymer is prepared from a salt of an acid- or anhydride-functional polymer and a tertiary amine, an ethylenically unsaturated monomer component that includes a mixture of monomers that include at least one alpha monomer, beta-ethylenically unsaturated containing an oxirane functional group in an amount of at least 0.1% by weight and not more than 30% by weight, based on the weight of the monomer mixture, and water.
The term "substantially free of a particular mobile compound" refers to the compositions of the present invention containing less than 1000 parts per million (ppm) of the listed mobile compound. The term "substantially free of a particular mobile compound" means that the compositions of the present invention contain less than 100 parts per million (ppm) of the listed mobile compound. The term "basically completely free of a particular mobile compound" means that the compositions of the present invention contain less than 5 parts per million (ppm) of the listed mobile compound. The term "completely free of a particular mobile compound" means that the compositions of the present invention contain less than 20 parts per billion (ppb) of the enumerated mobile compound.
The term mobile refers to the fact that the compound can be extracted from the cured coating when a coating (typically, film weight about 1 mg / cm<sup>2</sup>) is exposed to a test medium for some defined set of conditions, depending on the end use. An example of these test conditions is exposure of the cured coating to a 10 weight percent ethanol solution for two hours at 121 ° C followed by exposure for 10 days in the solution at 49 ° C.
If the phrases mentioned above are used without the term mobile (for example, substantially free of compound XYZ) then the compositions of the present invention contain less than the amount mentioned above of the compound if the compound is mobile in the coating or is attached to a constituent of the coating.
As used herein, the term "organic group" refers to 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 combination. of aliphatic and cyclic groups (eg, alkaryl and aralkyl groups). The term "aliphatic group" refers to a saturated or unsaturated linear or branched hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example. The term "alkyl group" refers to a saturated straight or branched hydrocarbon group including, for example, methyl, ethyl, isopropyl, i-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like. The term "alkenyl group" refers to an unsaturated straight or branched hydrocarbon group with one or more carbon-carbon double bonds, such as a vinyl group. The term "alkynyl group" refers to an unsaturated straight or branched hydrocarbon group with one or more carbon-carbon triple bonds. The term "cyclic group" refers to a closed ring hydrocarbon group that is classified as an alicyclic group or an aromatic group, both of which can include heteroatoms. The term "alicyclic group" refers to a cyclic hydrocarbon group that has properties similar to those of aliphatic groups.
The term Ar refers to a divalent aryl group (i.e., an arylene group), which refers to a closed aromatic ring or ring system such as phenylene, naphthylene, biphenylene, fluorenylene, and indenyl, as well as heteroarylene groups (ie ie, a closed-ring hydrocarbon in which one or more of the ring atoms is an element 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, benzyrolyl, pyrimidinyl, benzyrinozolyl, pyrimidinylal isoxazolyl, isothiazolyl, purinyl, quinazolinyl, pyrazinyl, 1-oxidopyridyl, pyridazinyl, triazinyl, tetracinyl, oxadiazolyl, thiadiazolyl, and so on. When such groups are divalent, they are typically referred to as heteroarylene groups (eg, furylene, pyridylene, etc.).
A group that can be the same or different is called that it is independently something.
Substitution is anticipated on the organic groups of the compounds of the present invention. As a means of simplifying the discussion and enumeration of certain terminology used throughout this application, the terms group and remainder are used to differentiate between chemical species that allow substitution or that can be substituted and those that do not allow or cannot be substituted for this. mode. Therefore, when the term group is used to describe a chemical substituent, the disclosed chemical material includes the unsubstituted group and said group with O, N, Si or S atoms, for example, in the chain (as in a group alkoxy) as well as carbonyl groups or other conventional substitution. When the term "moiety" is used to describe a chemical compound or substituent, it is only intended to include an unsubstituted chemical material. For example, the phrase "alkyl group" is intended to include not only pure open chain saturated aromatic alkyl hydrocarbon substituents, such as methyl, ethyl, propyl, ibutyl, and the like, but also alkyl substituents that further bear substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Therefore, alkyl group includes ether, haloalkyl, nitroalkyl, carboxyalkyl, hydroxyalkyl, sulfoalkyl, etc. groups. On the other hand, the phrase "alkyl moiety" is limited to the inclusion of only pure open chain saturated aromatic alkyl hydrocarbon substituents, such as methyl, ethyl, propyl, t-butyl, and the like.
ES 2 367 516 T3
The terms comprises and variations thereof do not have a limiting meaning when these terms appear in the description and claims.
The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may also be preferred, in the same or other circumstances. Additionally, the listing of one or more preferred embodiments does not imply that other embodiments are not useful, and it is not intended to exclude other embodiments from the scope of the invention.
As used herein, a, an, the, at least one, and one or more are used interchangeably. Thus, for example, a coating composition comprising a polymer can be construed to mean that the coating composition includes one or more polymers.
Also in this document, number range enumerations using endpoints include all numbers within this range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).
The above summary of the present invention is not intended to describe every disclosed embodiment or every implementation of the present invention. The description that follows particularly exemplifies the illustrative embodiments. At various points throughout the application, guidance is provided through the lists of examples, the examples of which can be used in various combinations. In each case, the enumerated list serves only as a representative group and should not be construed as an exclusive list.
This invention provides a coating composition for use in food and beverage cans that includes a latex polymer. The polymer is prepared in an emulsion polymerization process, preferably a free radical initiated polymerization process. The latex polymer can be applied to a metal substrate either before or after the substrate is formed in a food or beverage can (e.g. two-piece cans, three-piece cans) or parts thereof, or be it a can lid or a can body. The latex polymers of the present invention are suitable for use in food contact situations and can be used inside such cans. They are particularly useful on the inside of two-piece deep-drawn and ironed beverage cans and on beverage can lids.
The latex polymer is prepared by polymerizing an ethylenically unsaturated monomer component in an aqueous medium in the presence of the salt of a polymer containing an acid group or anhydride group and an amine, preferably a tertiary amine. The ethylenically unsaturated monomer component is preferably a mixture of monomers. Preferably, at least one of the monomers in the mixture is an alpha, betaethylenically unsaturated monomer, and preferably at least one of the monomers contains an oxirane group. More preferably, at least one of the monomers is an alpha, beta-ethylenically unsaturated monomer containing an oxirane group.
The composition can optionally include crosslinkers, fillers, catalysts, dyes, pigments, developers, extenders, lubricants, anti-corrosion agents, flow control agents, thixotropic agents, dispersing agents, antioxidants, adhesion promoters, light stabilizers, surfactants, organic solvents. , and mixtures thereof as required to provide the desired film properties.
In one embodiment, the coating composition is prepared by: forming a salt of an acid-functional or anhydride-functional polymer and an amine; dispersing the salt in a carrier including water and an optional organic solvent to form an aqueous dispersion; optionally removing the organic solvent, if present, from the aqueous dispersion; combining an ethylenically unsaturated monomer component with the aqueous dispersion (preferably, the ethylenically unsaturated monomer component is added to the aqueous dispersion); and polymerizing the ethylenically unsaturated monomer component in the presence of the aqueous dispersion to form an emulsion polymerized latex polymer.
Preferred compositions are substantially free of mobile bisphenol A (BPA) and aromatic glycidyl ether compounds (eg, BADGE, BFDGE, and epoxy novalacs), more preferably basically free of these compounds, even more preferably basically completely free of these compounds , and most preferably completely free of these compounds. Preferably, the coating composition is also substantially free of binding BPA and aromatic glycidyl ether compounds, more preferably basically free of these compounds, most preferably basically completely free of these compounds, and optimally completely free of these compounds.
The ethylenically unsaturated monomer component is preferably a monomer mixture that is capable of free radical initiated polymerization in an aqueous medium. Preferably, the monomer mixture contains at least one functional oxirane monomer, and more preferably, at least one alpha, betaethylenically unsaturated monomer containing an oxirane group.
The monomer mixture preferably contains at least 0.1 weight percent (weight%), plus
ES 2 367 516 T3 preferably at least 1% by weight, of a monomer containing an oxirane group, based on the weight of the monomer mixture. Typically, at least 0.1% by weight of the monomer containing an oxirane group contributes to the stability of the latex. Although it is not intended to be bound by theory, it is believed that this is due to the reduction in the amount of quaternary salt formation between the oxirane species, a polymer containing an acid group, and amine, which can cause coagulation of the latex. . Furthermore, at least 0.1% by weight of the monomer containing an oxirane group contributes to crosslinking in the dispersed particles and during curing, resulting in improved properties of coating compositions formulated with the polymeric network structures.
The monomer mixture preferably contains not more than 30% by weight, preferably not more than 20% by weight, even more preferably not more than 10% by weight, and optimally not more than 9% by weight of the monomer containing a oxirane group, based on the weight of the monomer mixture. Typically, more than 30% by weight of the monomer containing an oxirane group in the monomer mixture can contribute to decreased film properties. Although it is not intended to be bound by theory, it is believed to be due to the mess generated by an overabundance of crosslinking.
Suitable oxirane-functional monomers include monomers having a reactive carbon-carbon double bond and an oxirane group (ie, a glycidyl). Typically, the monomer is a glycidyl ester of an alpha, beta-unsaturated acid, or anhydride thereof (ie, an alpha, beta-ethylenically unsaturated monomer containing an oxirane group). Suitable alpha, beta-unsaturated acids include monocarboxylic acids or dicarboxylic acids. Examples of such carboxylic acids include, but are not limited to, acrylic acid, methacrylic acid, alphachloroacrylic acid, alpha-cyanoacrylic acid, beta-methylacrylic acid (crotonic acid), alpha-phenylacrylic acid, beta-acryloxypropionic acid, sorbic acid, alpha-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinamic acid, beta-stearylacrylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene, maleic anhydride, and mixtures thereof.
Specific examples of suitable monomers containing a glycidyl group are glycidyl (meth) acrylate (i.e., glycidyl methacrylate and glycidyl acrylate), mono- and di-glycidyl itaconate, mono- and di-glycidyl maleate, and mono- and di-glycidyl Format. It is also envisioned that allyl glycidyl ether and vinyl glycidyl ether can be used as the oxirane functional monomer. A preferred monomer is glycidyl methacrylate (GMA).
The oxirane-functional monomer is preferably reacted with other suitable monomers within the monomer mixture. These can be ethylenically unsaturated monomer and hydroxy-functional monomers. Suitable ethylenically unsaturated monomers include alkyl (meth) acrylates, vinyl monomers, alkyl esters of maleic or fumaric acid, and the like.
Suitable alkyl (meth) acrylates include those having the structure:
CH2 = C (R<sup>1</sup>) -CO-OR<sup>2</sup> in which R<sup>1</sup> is hydrogen or methyl, and R<sup>2</sup> it is an alkyl group preferably containing one to sixteen carbon atoms. The R group<sup>2</sup> it can be substituted with one or more moieties, and typically one to three, such as hydroxy, halo, phenyl, and alkoxy, for example. Suitable alkyl (meth) acrylates thus include hydroxy alkyl (meth) acrylates. The alkyl (meth) acrylate is typically an ester of acrylic or methacrylic acid. Preferably R<sup>1</sup> is hydrogen or methyl and R<sup>2</sup> it is an alkyl group having two to eight carbon atoms. Most preferably, R<sup>1</sup> is hydrogen or methyl and R<sup>2</sup> is an alkyl group having two to four carbon atoms.
Examples of suitable alkyl (meth) acrylates include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl (meth) acrylate (HPMA).
Difunctional (meth) acrylate monomers can also be used in the monomer mixture. Examples include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, allyl methacrylate, and the like.
Suitable vinyl monomers include styrene, methyl styrene, halostyrene, isoprene, diallylphthalate, divinylbenzene, conjugated butadiene, alphamethylstyrene, vinyl toluene, vinyl naphthalene, and mixtures thereof. The vinyl aromatic monomers described below along with the acid- or anhydride-functional polymer are also suitable for use in the ethylenically unsaturated monomer component used to prepare the latex polymer. Styrene is a preferred vinyl monomer today, in part because of its relatively low cost.
Other suitable polymerizable vinyl monomers for use in the ethylenically unsaturated monomer component include acrylonitrile, acrylamide, methacrylamide, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, N-isobutoxymethyl acrylamide, acrylamide -butoxymethyl, and the like.
ES 2 367 516 T3
The monomer containing an oxirane group preferably constitutes 0.1% by weight to 30% by weight, and more preferably 1% by weight to 20% by weight, of the ethylenically unsaturated monomer component. The other monomer or monomers in the mixture make up the remainder of the monomer component, i.e. 70% by weight to 99.9% by weight, preferably 80% by weight to 99% by weight, based on the total weight of the monomer mixture.
Preferably, at least 40% by weight of the ethylenically unsaturated monomer component, more preferably at least 50% by weight, will be selected from alkyl acrylates and methacrylates. Preferably, at least 20% by weight, more preferably at least 30% by weight, will be selected from vinyl aromatics.
Preferably, at least 5% by weight, more preferably at least 25% by weight, even more preferably at least 50% by weight, and even more preferably at least 60% by weight, of the ethylenically unsaturated monomer component is used in the preparation of latex polymer. Preferably, not more than 95% by weight, more preferably not more than 90% by weight, and even more preferably not more than 85% by weight, of the ethylenically unsaturated monomer component is used in the preparation of the latex polymer. Said percentages are based on the total weight of the ethylenically unsaturated monomer component and salt of the polymer containing an acid group or containing an anhydride group (ie, acid-functional or anhydride-functional polymer).
Among the acid functional polymers that can be used in preparing the latex polymer of the present invention are virtually any acid-containing or anhydride-containing polymer that can be neutralized or partially neutralized with an appropriate amine to form a salt that can be dissolved or dispersed from stable form in aqueous medium. The choice of the acid-containing or anhydride-containing monomer (s) is dictated by the intended end use of the coating composition and is virtually limitless.
The acid-containing polymer (ie, acid-functional polymer) preferably has an acid number of at least 40, and more preferably at least 100 milligrams (mg) of KOH per gram of resin. The acid-containing polymer preferably has an acid number of no more than 400, and more preferably no more than 300 mg of KOH per gram of resin. The anhydride-containing polymer, when in water, preferably has similar acid number ranges.
Low molecular weight polymers are preferred for certain applications of the present invention. Preferably, the molecular weight of the acid- or anhydride-functional polymer is not more than 50,000 on an average molecular weight basis, and preferably not more than 20,000. Preferably, the molecular weight of the acid- or anhydride-functional polymer is at least 1500 on an average molecular weight basis, and more preferably at least 2000.
Preferred acid- or anhydride-functional polymers that can be used include acid-functional or anhydride-functional acrylic polymers, alkyd resins, polyester polymers, and polyurethanes. Combinations of such polymers can be used if desired. In this document, the term "polymer" includes both homopolymers and copolymers (that is, polymers of two or more different monomers).
Acid- or anhydride-functional polymers used in this invention include those prepared by conventional free radical polymerization techniques. Suitable examples include those prepared from unsaturated acid- or anhydride-functional monomers, or salts thereof, and other unsaturated monomers. Of these, preferred examples include those prepared from at least 15% by weight, more preferably at least 20% by weight, of unsaturated acid- or anhydride-functional monomer, or salts thereof, and balance of other polymerizable unsaturated monomer. Examples of comonomers that have been described above apply here as well.
A variety of acid- or anhydride-functional monomers, or salts thereof, can be used; their selection is dependent on the desired final polymer properties. Preferably said monomers are ethylenically unsaturated, more preferably alpha, beta-ethylenically unsaturated. Ethylenically unsaturated acid- or anhydride-functional monomers suitable for the present invention include monomers having a reactive carbon-carbon double bond and an acid or anhydride group, or salts thereof. Such preferred monomers have 3 to 20 carbons, at least 1 site of unsaturation, and at least 1 acid or anhydride group, or salt thereof.
Suitable acid functional monomers include ethylenically unsaturated (mono-protic or diprotic) acids, anhydrides or monoesters of a dibasic acid, which are copolymerized with the other optional monomers used to prepare the polymer. Illustrative monobasic acids are those represented by the structure CH2 = C (R<sup>3</sup>) -COOH, where R<sup>3</sup> it is hydrogen or an alkyl radical of 1 to 6 carbon atoms. Suitable dibasic acids are those represented by the formulas R<sup>4</sup>(COOH) C = C (COOH) R<sup>5</sup> and R<sup>4</sup>(R<sup>5</sup>) C = C (COOH) R<sup>6</sup>COOH, in which R<sup>4</sup> and R<sup>5</sup> they are hydrogen, an alkyl radical of 1-8 carbon atoms,
ES 2 367 516 T3 halogen, cycloalkyl of 3 to 7 carbon atoms or phenyl, and R<sup>6</sup> it is an alkylene radical of 1 to 6 carbon atoms. Half-esters of these acids with alkanols of 1 to 8 carbon atoms are also suitable.
Non-limiting examples of useful ethylenically unsaturated acid-functional monomers include acids such as, for example, acrylic acid, methacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-phenylacrylic acid, beta-acryloxypropionic acid, fumaric acid. , maleic acid, sorbic acid, alphachlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinamic acid, beta-stearylacrylic acid, citraconic acid, mesaconic acid, glutaconic acid, Aconitic acid, tricarboxyethylene, 2-methyl maleic acid, itaconic acid, acid
2-methyl itaconic, methylene glutaric acid, and the like, or mixtures thereof. Preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleic acid, itaconic acid, 2-methyl itaconic acid, and mixtures thereof. More preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, and mixtures thereof. More preferred unsaturated acid functional monomers include acrylic acid, methacrylic acid, maleic acid, crotonic acid, and mixtures thereof.
Non-limiting examples of suitable ethylenically unsaturated anhydride monomers include compounds derived from the above acids (eg, as pure anhydride or mixtures thereof). Preferred anhydrides include acrylic anhydride, methacrylic anhydride, and maleic anhydride. If desired, aqueous salts of the above acids can also be used.
The polymerization of the monomers to form an acid- or anhydride-functional polymer is normally conducted by organic solution polymerization techniques in the presence of a free radical initiator as is well known in the art. Although the preparation of the acid-functional or anhydride-functional polymer is conveniently carried out in solution, neat processes can be used if desired.
In addition to acid- or anhydride-functional acrylic polymers, acid- or anhydride-functional alkyd, polyester, polyurethane resins, or combinations thereof, may also be used in the practice of the invention. Such polymers are described in US Patent Nos. 4,692,491; 3,479,310; and 4,147,679. Preferably, the acid- or anhydride-functional polymers are acid-functional acrylic polymers.
In another preferred embodiment, the acid- or anhydride-functional polymers are polyester polymers. Examples of such polyester polymers are described in PCT / US2006 / 060043 which claims priority from United States Provisional Patent Application Serial No. 60 / 727,734 (Attorney Docket No. 287.00220160), filed to date attached, entitled COATING COMPOSITIONS FOR CONTAINERS AND METHODS OF COATING. In summary, the polymers described thereon have one or more segments of Formula I:
-O-Ar-Rn-C (O) -OR<sup>1</sup>-OC (O) -Rn-Ar-O wherein each Ar is independently a divalent aryl group (ie, an arylene group) or heteroarylene group; R<sup>1</sup> it is a divalent organic group; each R is independently a divalent organic group; and n is 0 or 1. Any polymer can have a variety of said segments, which can be the same or different.
Preferably R<sup>1</sup> provides hydrolytic stability to at least one of the adjacent ester bonds (-C (O) -O and -OC (O) -), and preferably both. In this context, hydrolytic stability refers to that R<sup>1</sup> the reactivity (preferably by at least half) of the adjacent ester bond with water decreases compared to a -CH2-CH2- moiety under the same conditions. This can be achieved by selecting R<sup>1</sup> which includes a sterically bulky group in proximity (preferably within two atoms distance) of the ester oxygen. The polymer preferably includes more than 70%, more preferably more than 80%, and even more preferably more than 90% hydrolytically stable ester linkages (based on the total number of ester linkages).
In the Formula I segments, R<sup>1</sup> it is a divalent organic group, preferably, having at least 3 carbon atoms, more preferably, at least 4 carbon atoms, even more preferably, at least 5 carbon atoms, and even more preferably, at least 8 carbon atoms. It is visualized that R<sup>1</sup> it can be as large as is desired for the particular application, which one of ordinary skill can easily determine.
In certain preferred embodiments of Formula I, R<sup>1</sup> is of the formula
-C (R<sup>2</sup>) 2-Yt-C (R<sup>2</sup>) 2in which each R<sup>2</sup> is independently hydrogen or an organic group (eg, an alicyclic group or a branched or unbranched alkyl group), Y is a divalent organic group, and t is 0 or 1 (preferably 1). In certain embodiments, each R<sup>2</sup> it is independently hydrogen.
In certain embodiments, Y may optionally include one or more ether or ester linkages. In certain embodiments, Y is a divalent saturated aliphatic group (i.e., a branched or unbranched alkylene group), an alicyclic group
Divalent ES 2 367 516 T3, or a divalent aromatic group (ie, an arylene group), or combinations thereof.
In certain embodiments, Y is a divalent alkyl group (i.e., an alkylene group), which may be branched or unbranched, preferably having at least 1 carbon atom, more preferably having at least 2 carbon atoms, even more. preferably having at least 3 carbon atoms, and even more preferably having at least 6 carbon atoms. In certain embodiments, Y is a divalent alicyclic group, preferably cyclohexylene. It is envisioned that Y may be as large as is desired for the particular application, which one of ordinary skill in the art can easily determine.
Preferably, Y provides hydrolytic stability to at least one of the ester linkages adjacent to R<sup>1</sup> in Formula I. This can be achieved by selecting Y which includes a sterically bulky group that is in proximity (preferably within two atoms) of at least one of the oxygen atoms of the ester in Formula I.
In certain embodiments, R<sup>1</sup> has the formula - (C (R<sup>2</sup>) 2) s- where s is at least 2, and preferably, s is at least 3, where each R<sup>2</sup> it is as defined above. Examples of such R groups<sup>1</sup> They include, for example, neopentylene, butylethylpropylene, and -CH2-CH (CH3) -CH2-.
In certain embodiments, Y has the formula
- [Zw-C (R<sup>2</sup>) 2-OC (O) -R<sup>3</sup>-C (O) -OC (R<sup>2</sup>) 2-] vZw-, where w is 0 or 1, v is from 1 to 10, each R<sup>2</sup> is as defined above, each R<sup>3</sup> is independently a divalent organic group, and each Z is independently a divalent organic group.
In certain embodiments, R<sup>3</sup> is a divalent saturated aliphatic group (ie, branched or unbranched alkylene group), a divalent alicyclic group, an arylene group, or combinations thereof. In certain embodiments, R<sup>3</sup> is a (C3-C20) alkylene group (branched or unbranched) or a phenylene group.
In certain embodiments, Z is a divalent saturated aliphatic group (ie, branched or unbranched alkylene group), a divalent alicyclic group, a divalent aromatic group (ie, an arylene group), or combinations thereof.
Preferably, Z provides hydrolytic stability to at least one of the ester bonds adjacent to R<sup>1</sup> in Formula I and / or to an adjacent ester bond contained within Y. This can be achieved by selecting Z that includes a sterically bulky group that is in proximity (preferably within two atoms apart) of at least one of the oxygen atoms of the ester.
In the Formula I segments, n is preferably 0 (ie, R is not present). If n is 1 and R is present, however, it is preferably a (C1-C4) alkylene group, and more preferably a (C1-C4) alkylene moiety.
In the Formula I segments, each Ar preferably has less than 20 carbon atoms, more preferably less than 11 carbon atoms, and even more preferably less than 8 carbon atoms. Preferably, Ar has at least 4 carbon atoms, more preferably at least 5 carbon atoms, and even more preferably, at least 6 carbon atoms.
In certain embodiments, each Ar is a phenylene group. In certain embodiments, each Ar is a phenylene group of the formula -C6 (R<sup>4</sup>) 4-, in which each R<sup>4</sup> is independently hydrogen, a halogen, or an organic group, and wherein two R groups<sup>4</sup> they can join together to form a ring optionally containing one or more heteroatoms. In certain embodiments, R<sup>4</sup> is hydrogen or an organic group, in which two R groups<sup>4</sup> they can join together to form a 6-membered ring. Preferably R<sup>4</sup> it is hydrogen.
Polyester polymers such as these can be prepared by a variety of methods from the compounds of Formula II:
HO-Ar-Rn-C (O) -OR<sup>1</sup>-OC (O) -Rn-Ar-OH where Ar, R, R<sup>1</sup> and n are as defined above. Such compounds can be prepared, for example, by the esterification reaction of one mole of a diol (for example, HO-R'-OH such as, for example, 1,4-cyclohexane dimethanol, neopentylglycol, 2-butyl-2-ethyl- 1,3-propane diol, or 2-methyl-1,3-propane diol) with two moles of an acid (eg, 4-hydroxy benzoic acid). Alternatively, such compounds can be prepared, for example, by the transesterification reaction of one mole of a diol (for example, 1,4-cyclohexane dimethanol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propane diol , or 2-methyl-1,3-propane diol) with two moles of an ester (eg, 4-hydroxy methyl benzoate, 4-hydroxy ethyl benzoate, or 4-hydroxy butyl benzoate).
Polymers of Formula I can be prepared by methods that involve developing the molecular weight of the
ES 2 367 516 T3 compounds of Formula II. In certain embodiments, compounds of Formula II (eg, dihydric phenols) can be reacted with a diepoxide to develop molecular weight. For example, compounds of Formula II (e.g. dihydric phenols) can be highly reacted with non-BPA and BPF-based diepoxides in the same way that Bisphenol A or Bisphenol F does, to generate polymers that can be formulated with crosslinkers. and additives for coatings for rigid packaging. For example, compounds of Formula II can be reacted with a diepoxide to form a polymer that includes -CH2CH (OH) -CH2- segments. Alternatively, compounds of Formula II can be reacted with epichlorohydrin to form a diepoxide analog of compounds of Formula II, which can then be reacted with other compounds of Formula II to form a polymer that includes -CH2-CH (OH) segments. -CH2-.
Diepoxide analogs of compounds of Formula II (eg, glycidyl polyethers of dihydric phenols) can be prepared by reacting the required proportions of a compound of Formula II (eg, dihydric phenol) and epichlorohydrin in an alkaline medium. The desired alkalinity is obtained by adding basic substances, such as sodium or potassium hydroxide, preferably in stoichiometric excess with respect to epichlorohydrin. The reaction is preferably achieved at temperatures of 50 ° C to 150 ° C. Heating is continued for several hours to effect the reaction and the product is then washed free of salt and base. Procedures for such reactions are generally well known and are described, for example, in US Patent No. 2,633,458.
As used in the present invention, suitable diepoxides (other than diepoxide analogs of compounds of Formula II) are diepoxides free of BPA or BPF, preferably with one or more ether linkages. Suitable diepoxides can be prepared by a variety of processes, for example, by the condensation of a dihydroxy compound and epichlorohydrin. Examples of suitable diepoxides (other than diepoxide analogs of compounds of Formula II) include, for example, 1,4-cyclohexanedimethanol diglycidyl ether (CHDMDGE), resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, and 2-methyl diglycidyl ether. -1,3-propandiol.
The resulting polymers of Formula I can be epoxy-terminated or phenoxy-terminated, for example. They can be prepared in a variety of molecular weights, such as the molecular weights of commercially available BPA-based epoxy materials (for example, those available under brand names such as EPON 828, 1001, 1007, 1009 from Resolution Performance Products, Houston , Texas). Preferred polymers of the present invention have a mean molecular weight (MW) value of at least 2,000, more preferably at least 3,000, and even more preferably at least 4,000. The molecular weight of the polymer can be as high as necessary for the desired application.
The development of the molecular weight of the polymer can be improved by the use of a catalyst in the reaction of a diepoxide (either a diepoxide analog of Formula II or another diepoxide) with a compound of Formula (II). Typical catalysts that can be used in developing 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 catalyst. The phosphonium 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 Formula I can be reacted with fatty acids to form polymers having unsaturated reactive groups (eg, oxidizable air), or with acrylic acid or methacrylic acid to form free radically curable polymers. .
Polymer molecular weight development can also be enhanced by reacting an epoxy-terminated polymer of Formula I with a suitable diacid (such as adipic acid).
A salt (which can be a complete salt or a partial salt) of the acid- or anhydride-functional polymer is formed by neutralizing or partially neutralizing the acid groups (either initially present in the acid-functional polymer or is formed upon addition of the anhydride-functional polymer). water-functional) of the polymer with a suitable amine, preferably a tertiary amine. The degree of neutralization required to form the desired polymer salt can vary considerably depending on the amount of acid included in the polymer, and the degree of solubility or dispersibility of the salt that is desired. Ordinarily, in the preparation of the water dispersible polymer, the acidity of the polymer is neutralized to at least 25%, preferably at least 30% neutralized, and more preferably at least 35% neutralized, with the amine in water.
Some examples of suitable tertiary amines are trimethyl amine, dimethyl ethanol amine (also known as dimethylamino ethanol), methyldiethanolamine, triethanolamine, ethyl methyl ethanol amine, dimethyl ethyl amine, dimethyl propyl amine, dimethyl 3-hydroxy-1-propyl amine, dimethylbenzyl amine, dimethyl 2-hydroxy-1-propyl amine, diethyl methyl amine, dimethyl
1-hydroxy-2-propyl amine, triethyl amine, tributyl amine, N-methyl morpholine, and mixtures thereof. Most preferably, triethyl amine or dimethyl ethanol amine is used as the tertiary amine.
The amount of the acid-functional or anhydride-functional polymer salt that is used in the polymerization is preferably at least 5% by weight, more preferably at least 10% by weight, and even more preferably at least 15% by weight. % in weigh. The amount of the salt of the acid-functional polymer or anhydride
The functional ES 2 367 516 T3 used in the polymerization is preferably not more than 95% by weight, preferably not more than 50% by weight, and even more preferably not more than 40% by weight. These percentages are based on the total weight of the polymerizable ethylenically unsaturated monomer component and the salt of the polymer containing an acid group.
The reaction of tertiary amines with materials containing oxirane groups, when carried out in the presence of water, can provide a product that contains both a hydroxyl group and a quaternary ammonium hydroxide. Under preferred conditions an acid group, an oxirane group, and an amine form a quaternary salt. This bonding is favored as it not only bonds the polymers but also promotes the water dispersibility of the bonded polymer. It should be noted that an acid group and an oxirane group can also form an ester. Some of this reaction is possible, although this bond is less desirable when dispersibility in water is desired.
While the exact mode of reaction is not fully understood, it is believed that competition takes place between the two reactions; however, this is not intended to be limited. In preferred embodiments, a reaction involves the tertiary amine neutralized acid-functional polymer reacting with an oxirane-functional polymer or monomer to form a quaternary ammonium salt. A second reaction involves the esterification of the oxirane-functional monomer or polymer with a carboxylic acid or salt. In the current invention it is believed that the presence of water and the level of amine favor the formation of quaternary ammonium salts on ester bonds. A high level of quaternization improves water dispersibility while a high level of esterification provides higher viscosity and possibly gel-like material.
With respect to the conditions of the emulsion polymerization, the ethylenically unsaturated monomer component is polymerized preferably in an aqueous medium with a water-soluble free radical initiator in the presence of the acid- or anhydride-functional salt of the polymer.
The polymerization temperature is typically from 0 ° C to 100 ° C, preferably from 50 ° C to 90 ° C, more preferably from 70 ° C to 90 ° C, and even more preferably from 80 ° C to 85 ° C. The pH of the aqueous medium is normally maintained at a pH of 5 to 12.
The free radical initiator can be selected from one or more water soluble peroxides that are known to act as free radical initiators. Examples include hydrogen peroxide and t-butyl hydroperoxide. Redox initiator systems well known in the art (eg, t-butyl hydroperoxide, erythorbic acid, and ferrous complexes) can also be used. It is especially preferred to use a mixture of benzoin and hydrogen peroxide. Persulfate initiators such as ammonium persulfate or potassium persulfate are not preferred as they lead to poor water resistance properties of the cured coating.
The polymerization reaction of the ethylenically unsaturated monomer component in the presence of the aqueous dispersion of the polymer salt can be conducted as a batch, intermittent, or continuous operation. While all of the polymerization ingredients can be initially charged to the polymerization vessel, better results are usually obtained with proportioning techniques.
Typically, the reactor is charged with an appropriate amount of water, polymer salt, and free radical initiator. The reactor is then heated to the free radical initiation temperature and then charged with the ethylenically unsaturated monomer component. Preferably only water, initiator, polymer salt, and some part of the ethylenically unsaturated monomer component are initially charged to the vessel. Some water-miscible solvent may also be present. After this initial charge, the reaction is allowed for a period of time at the polymerization temperature, the remaining ethylenically unsaturated monomer component is progressively added with the addition rate that is varied depending on the polymerization temperature, the particular initiator being added. uses, and the type and amount of monomers that are polymerized. After all of the monomer component has been charged, a final heating is performed to complete the polymerization. The reactor is then cooled and the latex is recovered.
It has been discovered that coating compositions using the aforementioned network structures can be formulated using one or more optional curing agents (ie, crosslinking resins, sometimes referred to as crosslinking agents). The choice of particular crosslinker typically depends on the particular product being formulated. For example, some coating compositions are highly colored (eg, gold colored coatings). These coatings can typically be formulated using crosslinkers which themselves tend to have a yellowish color. In contrast, white coatings are generally formulated using non-yellowish crosslinkers, or only a small amount of a yellowish crosslinker. Preferred curing agents are substantially free of mobile BPA and aromatic glycidyl ether compounds (eg, BADGE, BFDGE, and epoxy novalacs).
Any of the well known hydroxyl-reactive curing resins can be used. For example, phenoplast, and aminoplast curing agents can be used.
Phenoplast resins include the condensation products of aldehydes with phenols. Formaldehyde and
ES 2 367 516 T3 acetaldehyde are preferred aldehydes. Various phenols can be used such as phenol, cresol, p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, and cyclopentylphenol.
Aminoplast resins are the condensation products of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, and benzaldehyde with substances containing an amino or amido group such as urea, melamine, and benzoguanamine.
Examples of suitable crosslinking resins include, without limitation, benzoguanamine-formaldehyde resins, melamine-formaldehyde resins, esterified melamine-formaldehyde, and urea-formaldehyde resins. Preferably, the crosslinker used when practicing this invention includes a melamine formaldehyde resin. A specific example of a particularly useful crosslinker is the fully alkylated melamine-formaldehyde resin commercially available from Cytec Industries, Inc. under the trade name CYMEL 303.
Examples of other generally suitable curing agents are blocked or unblocked aliphatic, cycloaliphatic, or aromatic isocyanates di-, tri-, or polyvalent, such as hexamethylene diisocyanate, cyclohexyl-1,4-diisocyanate, and the like.
The level of curing agent (ie crosslinking) required will depend on the type of curing agent, the time and temperature of oven drying, and the molecular weight of the polymer. 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. These weight percentages are based on the total weight of the resin solids in the coating composition.
A coating composition of the present invention may also include other optional polymers that do not adversely affect the coating composition or a cured coating composition resulting therefrom. Such optional polymers are typically included in a coating composition as a filler material, although they can be included as a crosslinking material, or provide desirable properties. One or more optional polymers (eg, filler polymers) may be included in an amount sufficient to serve an intended purpose, but not in an amount such that it adversely affects a coating composition or a cured coating composition that results from them.
Such additional polymeric materials can be non-reactive, and thus simply function as fillers. Such optional non-reactive filler polymers include, for example, polyesters, acrylics, polyamides, polyethers, and novalacs. Alternatively, such additional polymeric materials or monomers can be reacted with other components of the composition (eg, the acid-functional polymer). If desired, reactive polymers can be incorporated into compositions of the present invention, to provide additional functionality for various purposes, including crosslinking. Examples of such reactive polymers include, for example, functionalized polyesters, acrylics, polyamides, and polyethers. The preferred optional polymers are substantially free of mobile BPA and aromatic glycidyl ether compounds (eg, BADGE, BFDGE, and epoxy novalacs).
A coating composition of the present invention may also include other optional ingredients that do not adversely affect the coating composition or a cured coating composition that results therefrom. Such optional ingredients are typically included in a coating composition to improve the aesthetics of the composition, to facilitate preparation, processing, handling, and application of the composition, and to further enhance a particular functional property of a coating composition or composition. of cured coating that results therefrom.
Such optional ingredients include, for example, catalysts, dyes, pigments, developers, extenders, fillers, lubricants, anti-corrosion agents, flow control agents, thixotropic agents, dispersing agents, antioxidants, adhesion promoters, light stabilizers, surfactants, and mixtures thereof. Each optional ingredient is included in an amount sufficient to serve its intended purpose, but not in an amount such that it adversely affects a coating composition or a cured coating composition that results therefrom.
An optional preferred ingredient is a catalyst to increase the cure rate. Examples of catalysts include, but are not limited to, strong acids (for example, dodecylbenzene sulfonic acid (DDBSA, available as CYCAT 600 from Cytec), methane sulfonic acid (MSA), p-toluene sulfonic acid (pTSA), dinonylnaphthalene sulfonic acid ( DNNDSA), and triflic acid), quaternary ammonium compounds, phosphorous compounds, and tin and zinc compounds. Specific examples include, but are not limited to, a tetraalkyl ammonium halide, a tetraalkyl or tetraaryl phosphonium iodide or acetate, tin octoate, zinc octoate, triphenylphosphine, and similar catalysts known to those of skill in the art. If used, a catalyst 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. If used, a catalyst is preferably present in an amount of not more than 3% by weight, and more preferably not more than 1% by weight, based on the weight of the non-volatile material.
ES 2 367 516 T3
Another useful optional ingredient is a lubricant (eg, a wax), which facilitates the preparation of metal fasteners by imparting lubricity to the coated metal substrate sheets. Preferred lubricants include, for example, Carnauba wax and polyethylene-type lubricants. If used, a lubricant is preferably present in the coating composition in an amount of at least 0.1% by weight, and preferably not more than 2% by weight, and more preferably not more than 1% by weight, in based on the weight of the non-volatile material.
Another useful optional ingredient is a pigment, such as titanium dioxide. If used, a pigment is present in the coating composition in an amount of not more than 70% by weight, more preferably not more than 50% by weight, and even more preferably not more than 40% by weight, on a weight basis. total solids in coating composition.
Surfactants can optionally be added to the coating composition to aid in flow and wetting of the substrate. Examples of surfactants include, but are not limited to, polyethers of nonylphenol and salts and similar surfactants known to those of skill in the art. If used, a surfactant 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 resin solids. If used, a surfactant is preferably present in an amount of not more than 10% by weight, and more preferably not more than 5% by weight, based on the weight of resin solids.
As described above, the coating compositions of the present invention are particularly well suited for use in food and beverage cans (eg, two-piece cans, three-piece cans, etc.). Two-piece cans are made by joining a can body (typically a drawn metal body) to a can lid (typically a drawn metal lid). The coatings of the present invention are suitable for use in food or beverage contact situations and can be used on the inside of such cans. They are particularly suitable for spray applied liquid coatings for the interior of pressed and pressed two-piece beverage cans and coil coatings for beverage can lids. The present invention offers utility in other applications as well. These additional applications include, but are not limited to, dip coating, foil coating, and side seam coatings (eg, food can side seam coatings).
Spray coating includes introducing the coated composition into a preformed container reservoir. Typical preformed packaging tanks suitable for spray coating include food cans, beer and beverage tanks, and the like. Spraying preferably uses a spray nozzle capable of uniformly coating the inside of the preformed packaging tank. The powdered preformed container is then subjected to heat to remove residual solvents and harden the coating.
A coil coating is described as the coating of a continuous coil composed of a metal (eg, steel or aluminum). Once coated, the coating coil is subjected to a short thermal, ultraviolet, and / or electromagnetic cure cycle, for hardening (eg, drying and curing) of the coating. Coil liners provide coated metal substrates (e.g. steel and / or aluminum) that can be fabricated into shaped articles, such as 2-piece deep-drawn food cans, 3-piece food cans, food can lids, cans stuffed and ironed, beverage can lids, and the like.
A wash coating is described in the marketplace as coating the exterior of two-piece deep drawn and pressed (D&I) cans with a thin layer of protective coating. The exterior of these D&I cans are wash coated by passing D&I two-piece preformed cans under a curtain of a coating composition. The cans are inverted, that is, the open lid of the can is in the down position when it is passed through the curtain. This covering composition curtain takes on a waterfall-like appearance. Once these cans pass under this curtain of coating composition, the liquid coating material effectively coats the exterior of each can. The excess coating is removed through the use of an air knife. Once the desired amount of coating is applied to the exterior of each can, each can is passed through a thermal, ultraviolet, and / or electromagnetic curing oven to harden (eg, dry and cure) the coating. The residence time of the coated can within the limits of the curing oven is typically 1 minute to 5 minutes. The curing temperature within this oven will typically range from 150 ° C to 220 ° C.
A sheet coating is described as the coating of separate pieces of a variety of materials (eg, steel or aluminum) that have been pre-cut into square or rectangular sheets. The typical dimensions of these sheets are approximately one square meter. Once coated, each sheet is cured. Once hardened (eg, dried and cured), the sheets of the cured substrate are accumulated and prepared for further fabrication. Foil liners provide a coated metal substrate (e.g. steel or aluminum) that can be successfully manufactured into shaped articles, such as 2-piece deep-drawn food cans, 3-piece food cans, food can lids , deep-drawn and ironed cans, beverage can lids, and the like.
A side seam coating is described as the spray application of a liquid coating
ES 2 367 516 T3 on the welded area of three-piece formed food cans. When the three-piece food cans are being prepared, a rectangular piece of coated substrate is formed into a cylinder. The cylinder formation is supplied permanently due to the welding of each side of the rectangle through heat welding. Once welded, each can typically requires a layer of liquid coating, which protects the exposed weld from subsequent corrosion or other effects to the contained food product. Liquid coatings that have this role are called side seam strips. Typical side seam strips are spray applied and cure rapidly through residual heat from the welding operation as well as a small thermal, ultraviolet, and / or electromagnetic oven.
Other coating application and curing methods on the market are also envisioned, for example electrocoating, extrusion coating, laminating, powder coating, and the like.
The preferred coatings of the present invention exhibit one or more of the properties that have been described in the Examples Section. The most preferred coatings of the present invention exhibit one or more of the following properties: metal exposure value of less than 3 mA; metal exposure value after drop damage less than 3.5 mA; overall extraction results of less than 50 ppm; adhesion ratio of 10; surface color alteration ratio of at least 7; slight cracking or absence in a reverse impact test; no cracking (ratio of 10) in a dome impact test; beveled below 0.51 cm (0.2 inch); COF range of 0.055 to 0.095; and after pasteurization or retort, a continuity of less than 20 mA.
The following preferred embodiments are summarized:
1. A method of coating a food or beverage can, the method comprises:
forming a composition comprising an emulsion polymerized latex polymer and which is substantially free of bound bisphenol A and aromatic glycidyl ether compounds comprising:
forming a salt of an acid- or anhydride-functional polymer and an amine on a carrier comprising water to form an aqueous dispersion;
combining an ethylenically unsaturated monomer component with the aqueous dispersion; and polymerizing the ethylenically unsaturated monomer component in the presence of the aqueous dispersion to form an emulsion polymerized latex polymer; and applying the composition comprising the emulsion polymerized latex polymer to a metal substrate before or after forming the metal substrate in a food or beverage can or part thereof.
2. The method of item 1, wherein applying the composition to a metal substrate comprises applying the composition to the metal substrate in the form of a coil or flat sheet, hardening the emulsion polymerized latex polymer, and forming the substrate into a can of food or drink or part of it.
3. The method of item 2, wherein forming the substrate into a can or part thereof comprises forming the substrate into a can lid or a can body.
Four. The method of item 2, wherein the can is a 2-piece sausage food can, 3-piece food can, a food can lid, a deep-drawn and ironed can, a beverage can lid, and the like.
5. The method of item 1, wherein the metal substrate comprises steel or aluminum.
6. The method of item 1, wherein applying the composition to a metal substrate comprises applying the composition to the metal substrate after the metal substrate is formed into a can or part thereof.
7. The method of item 1, wherein combining an ethylenically unsaturated monomer component with the aqueous dispersion comprises adding the ethylenically unsaturated monomer component to the aqueous dispersion.
8. The method of item 7, wherein the ethylenically unsaturated monomer component is progressively added to the aqueous dispersion.
9. The method of item I, wherein the ethylenically unsaturated monomer component comprises a mixture of monomers comprising at least one monomer containing an oxirane functional group.
10. The method of item 9, wherein the monomer mixture comprises at least one alpha, betaethylenically unsaturated monomer containing an oxirane functional group.
ES 2 367 516 T3
eleven. The method of item 9, wherein the monomer containing an oxirane functional group is present in the ethylenically unsaturated monomer component in an amount of at least 0.1% by weight, based on the weight of the monomer mixture.
12. The method of item 9, wherein the monomer containing an oxirane functional group is present in the ethylenically unsaturated monomer component in an amount of not more than 30% by weight, based on the weight of the monomer mixture.
13. The method of item 1 further comprising combining the emulsion polymerized latex polymer with one or more crosslinking agents, fillers, catalysts, dyes, pigments, developers, extenders, lubricants, anti-corrosion agents, flow control agents, thixotropic agents, agents dispersants, antioxidants, adhesion promoters, light stabilizers, organic solvents, surfactants, or combinations thereof in the coating composition.
14. The method of item i, wherein the acid-functional polymer has an average molecular weight value of 1500 to 50,000.
fifteen. The method of item 1, wherein the composition is substantially free of mobile BPA and aromatic glycidyl ether compounds.
16. The method of item 1, wherein the acid- or anhydride-functional polymer comprises an acid- or anhydride-functional acrylic polymer, acid- or anhydride-functional alkyd resin, acid- or anhydride-functional polyester resin, acid- or anhydride polyurethane -functional, or combinations thereof.
17. The method of item 16, wherein the acid- or anhydride-functional polymer comprises an acid-functional acrylic polymer.
18. The method of item 16, wherein the acid- or anhydride-functional polymer comprises a polyester polymer.
19. The method of item 18, wherein the polyester polymer comprises one or more segments of Formula I:
-O-Ar-Rn-C (O) -OR<sup>1</sup>-OC (O) -Rn-Ar-O in which:
each Ar is independently a divalent aryl group or heteroarylene group;
each R is independently a divalent organic group;
R<sup>1</sup> it is a divalent organic group; and each n is 0 or 1.
twenty. The method of item 1, wherein the amine is a tertiary amine.
twenty-one. The method of item 20, wherein the tertiary amine is selected from the group consisting of trimethyl amine, dimethyl ethanol amine, methyldiethanolamine, triethanolamine, ethyl methyl ethanol amine, dimethyl ethyl amine, dimethyl propyl amine, dimethyl 3-hydroxy 1-propyl amine, dimethylbenzyl amine, dimethyl 2-hydroxy-1-propyl amine, diethyl methyl amine, dimethyl
1-hydroxy-2-propyl amine, triethyl amine, tributyl amine, N-methyl morpholine, and mixtures thereof.
22. The method of item 1, in which the acid- or anhydride-functional polymer is neutralized at least 25% with the amine in water.
2. 3. The method of item 1, wherein the ethylenically unsaturated monomer component is polymerized in the presence of the aqueous dispersion with a water soluble free radical initiator at a temperature of 0 ° C to 100 ° C.
24. The method of item 23, wherein the free radical initiator comprises a peroxide initiator.
25. The method of item 24, wherein the free radical initiator comprises hydrogen peroxide and benzoin.
26. The method of item 23, wherein the free radical initiator comprises a redox initiator system.
27. The method of item 1, wherein the aqueous dispersion additionally comprises an organic solvent.
28. The method of item 27 further comprising the removal of at least a part of the organic solvent.
29. A method of coating a food or beverage can, the method comprises:
ES 2 367 516 T3 form a composition comprising an emulsion polymerized latex polymer, comprising:
forming a salt of an acid- or anhydride-functional polymer and a tertiary amine on a carrier comprising water to form an aqueous dispersion;
combining an ethylenically unsaturated monomer component comprising 0.1% by weight to 30% by weight of an alpha, beta-ethylenically unsaturated oxirane-functional monomer with the aqueous dispersion, based on the weight of the monomer component; and polymerizing the ethylenically unsaturated monomer component in the presence of the aqueous dispersion to form an emulsion polymerized latex polymer; and applying the composition comprising the emulsion polymerized latex polymer to a metal substrate before or after forming the metal substrate in a food or beverage can or part thereof.
30. A can of food or drink prepared using the method in point 1.
31. A can of food or drink prepared using the method in point 29.
32. A can of food or drink comprising:
a body part or an end part comprising a metal substrate; and a coating composition disposed thereon, wherein the coating composition comprises an emulsion polymerized latex polymer and is substantially free of bound bisphenol A and aromatic glycidyl ether compounds, wherein the emulsion polymerized latex polymer It is prepared from a salt of an acid- or anhydride-functional polymer and an amine, an ethylenically unsaturated monomer component, and water.
33. The can of item 32, wherein the ethylenically unsaturated monomer component comprises a monomer mixture comprising at least one functional oxirane-containing monomer.
3. 4. The can of item 33, wherein the monomer mixture comprises at least one alpha, betaethylenically unsaturated monomer containing an oxirane functional group.
35. The can of item 33, wherein the monomer containing an oxirane functional group is present in the ethylenically unsaturated monomer component in an amount of 0.1% by weight to 30% by weight, based on the weight of the mixture of monomer.
36. The can of item 31, wherein the acid- or anhydride-functional polymer comprises an acid- or anhydride-functional acrylic polymer, acid- or anhydride-functional alkyd resin, acid- or anhydride-functional polyester resin, acidic polyurethane or anhydride-functional, or combinations thereof.
37. The can of item 36, wherein the acid- or anhydride-functional polymer comprises an acid-functional acrylic polymer.
38. The can of item 31, wherein the amine is a tertiary amine.
39. A composition for use in coating a food or beverage can, the composition comprising an emulsion polymerized latex polymer, wherein the emulsion polymerized latex polymer is prepared from a salt of an acidic polymer. or functional anhydride and a tertiary amine, an ethylenically unsaturated monomer component that includes a mixture of monomers that includes at least one alpha monomer, beta-ethylenically unsaturated containing an oxirane functional group in an amount of at least 0.1% by weight and not more than 30% by weight, based on the weight of the monomer mixture, and water.
Examples
The following examples are offered to aid in understanding the present invention and are not to be construed as limiting the scope thereof. Unless otherwise indicated, all parts and percentages are by weight.
Curing Conditions
For in-beverage spray oven drying, curing conditions involve maintaining the measured can dome temperature at 188 ° C to 199 ° C for 30 seconds.
For beverage lid coil oven drying, the curing conditions involve the use of a temperature sufficient to provide a peak metal temperature within the specified time (e.g.
For example, 10 seconds at 204 ° C means 10 seconds, in the furnace, for example, and a metal temperature peak reached of 204 ° C).
The cited constructions were evaluated by tests as follows:
Initial Metal Exhibition
This test method determines the amount of the inner surface of the can that has not been effectively coated by spray coating. This determination is made through the use of an electrically conductive solution (1% NaCl in deionized water). The coated can is charged with this conductive solution, and an electrical probe is attached in contact with the outside of the can (uncoated, electrically conductive). A second probe is dipped into the salt solution in the central part of the inside of the can. If any uncoated metal is present inside the can, a current is passed between these two probes and records a value on an LED display. The LED displays the carried currents in milliamps (mA). The current that is passed through is directly proportional to the amount of metal that has not been effectively covered with coating. The goal is to achieve 100% coating coverage on the inside of the can, which would result in a 0.0 mA LED reading. Preferred coatings provided metal exposure values of less than 3 mA, more preferred values of less than 2 mA, and even more preferred values of less than 1 mA. Acceptable metal exposure values in the market are typically less than 2.0 mA on average.
Metal Exposure After Fall Damage
Drop Damage Resistance measures the ability of the coated reservoir to resist cracking after the drop conditions of a loaded can are simulated. The presence of cracks is measured by passing an electrical current through an electrolyte solution, as described above in the Metal Exposure section. A coated reservoir is charged with the electrolyte solution and the initial metal exposure is recorded. The can is then loaded with water and dropped through a tube from a specified height onto an inclined plane, generating a dent in the bell area. The can is then rotated 180 degrees, and the process is repeated. The water is then removed from the can and the metal exposure is measured again as described above. If there is no damage, no change in current (mA) will be observed. Typically, an average of 6 or 12 depot runs are recorded. Both the results of the metal exposures before and after the fall are expressed. The lower the milliamp value, the better the coating's resistance to drop damage. Preferred coatings provide metal exposure values after drop damage of less than 3.5 mA, more preferred values of less than 2.5 mA, and even more preferred values of less than 1.5 mA.
Solvent Resistance
The extent of cure or crosslinking of a coating is measured as a resistance to solvents, such as methyl ethyl ketone (MEK, available from Exxon, Newark, NJ) or isopropyl alcohol (IPA). This test is performed as described in ASTM D 5402-93. The number of double-rubbing (ie, a back-and-forth movement) is indicated.
Global Extractions
The global extraction test is designed to estimate the total amount of mobile material that can potentially migrate out of a coating and into food packaged in a coated can. Typically, the coated substrate is subjected to mixtures of water or solvent under a variety of conditions to simulate a proportionate end use. Acceptable extraction conditions and means can be found in 21CFR 175,300 paragraphs (d) and (e). The global allowable extraction limit as defined by FDA regulation is 50 parts per million (ppm).
The extraction procedure used in the present invention is described in 21CFR 175,300 paragraph (e) (4) (xv) with the following modifications to ensure the worst case operating scenario: 1) the alcohol content was increased to 10 wt% and 2) the charged reservoirs were held for a 10 day equilibrium period at 37.78 ° C (100 ° F). These conditions are per the FDA Guidelines for Industry publication for the preparation of Food Contact Notifications. The coated beverage can was charged with 10 weight percent aqueous ethanol and subjected to pasteurization conditions 65.56 ° C (150 ° F) for 2 hours, followed by an equilibrium period of 10 days at 37.78 ° C (100 ° F). The determination of the amount of extractives was determined as described in 21 CFR 175.300 paragraph (e) (5), and the ppm values were calculated based on the surface area of the 44 square inch can (not cap) with a volume of 355 ml. Preferred coatings provide overall extraction results of less than 50 ppm, more preferred results of less than 10 ppm, even more preferred results of less than 1 ppm. Most preferably, the overall extraction results are optimally undetectable.
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Accession
The adhesion test is performed to evaluate whether the coating adheres to the coated substrate. The adhesion test was performed in accordance with ASTM D 3359 - Test Method B, using SCOTCH 610 tape, available from the 3M Company of Saint Paul, Minnesota. Adhesion is generally rated on a 010 scale where a category of 10 indicates no bond failure , a category of 9 indicates that 90% of the coating remains adhered, a category of 8 indicates that 80% of the coating remains adhered, and so on. Adhesion categories of 10 are typically desired for commercially viable coatings.
Resistance to surface color alteration
Resistance to surface color fading measures the ability of a coating to resist attack by various solutions. Typically, surface color change is measured by the amount of water absorbed into a coated film. When the film absorbs water, it generally turns cloudy or appears white. Surface discoloration is generally measured visually using a 0-10 scale in which a category of 10 indicates no surface discoloration and a category of 0 indicates complete whitening of the film. Surface color alteration categories of at least 7 are typically desired for commercially viable coatings and optimally 9 or higher.
Process or Retort Resistance
This is a measure of the integrity of the coating on the coated substrate after exposure to heat and pressure with a liquid such as water. The retort procedure is not necessarily required for all food and beverage coatings, but is desirable for some types of product that are packaged in retort conditions. The procedure is similar to the Sterilization or Pasteurization test. The test is achieved by subjecting the substrate to heat ranging from 105-130 ° C and a pressure ranging from 0.7 to 1.05 kg / cm<sup>2 </sup>for a period of 15 to 90 minutes. For the present evaluation, the coated substrate was immersed in deionized water and subjected to a heat of 121 ° C (250 ° F) and pressure of 1.05 kg / cm<sup>2</sup> for a period of 90 minutes. The coated substrate was then tested for adhesion and surface discoloration as described above. In food or beverage applications that require retorting, adhesion categories of 10 and surface color alteration categories of at least 7 are typically desired for commercially viable coatings.
Cracking - Reverse Impact Resistance
Reverse impact measures the ability of the coated substrate to withstand the deformation encountered when impacted by a steel punch with a hemispherical head. For the present evaluation, the coated substrate was subjected to 1.36 N m (12 in-lbs) of force using a coverall BYK-Gardner Impactometer and Resistometer and was visually evaluated for micro-cracks or micro-fracturing - commonly termed as cracking. The test pieces were impacted on the uncoated or reverse side. A category of 10 indicates no cracking and suggests sufficient flexibility and cure. A category of 0 indicates complete failure. Commercially viable coatings preferably show slight cracking or no cracking in a reverse impact test.
Impact on Dome
Dome impact was evaluated by subjecting the dome apex of a 340.19 g (12 oz.) Beverage can to reverse impact as described in the previous section. Cracking was evaluated after impact. A category of 10 indicates no cracking and suggests sufficient flexibility and cure. A category of 0 indicates complete failure. Beverage can interior liners preferably show no cracking (category 10) in a dome impact.
Joy Detergent Trial
A solution of JOY Detergent 1% (available from Procter & Gamble) in deionized water is prepared and heated to 82 ° C (180 ° F). The coated panels are soaked in the heated solution for 10 minutes and then removed, rinsed, and dried. The samples are then evaluated for adhesion and surface discoloration, as described above. Commercially viable beverage undercoats preferably provide adhesion categories of 10 and surface color alteration categories of at least 7, optimally at least 9, in the detergent test.
Beveled
Chamfering is a term used to describe the loss of adhesion of a coating on the flange of a beverage can lid. When a beverage can is opened, a piece of free film may be present across the
ES 2 367 516 T3 opening of the can if the coating loses adhesion on the flange. This is beveled.
To test for beveling, a flange is scored on the back of a coated panel, with the coated side of the panel facing downward. The test piece is then pasteurized as described in the Pasteurization section below.
After pasteurization, pliers are used to bend the cut flange at a 90 degree angle away from the coated side of the substrate. The test piece is then placed on a flat surface, coated side down. The cut flange is grasped using pliers and the flange is pulled from the test panel at a 180 degree angle until it is completely withdrawn. After removing the flange, any coating that extends into the opening in the test panel is measured. The distance of the greatest penetration (bevel) is expressed in inches. The coatings for the beverage lids preferably show bevels below 0.508 cm (0.2 inches), more preferably below 0.254 cm (0.1 inches), most preferably below 0.127 cm (0.05 inches). , and optimally below 0.051 cm (0.02 inch).
Dowfax Detergent Trial
The Dowfax test is designed to measure the resistance of a coating to a boiling detergent solution. This is a general test embodiment for beverage cap coatings and is primarily used to evaluate adhesion. Historically, this test was used to indicate problems with the interaction of a coating to a substrate pretreatment. The solution is prepared by mixing 5 ml of Dowfax 2A1 (product of Dow Chemical) in 3000 ml of deionized water. Typically, the coated substrate strips are immersed in the boiling Dowfax solution for 15 minutes. The strips are then rinsed and cooled in deionized water, dried, and then tested and graded for surface discoloration and adhesion as described above. Preferred beverage cap coatings provide adhesion ratings of 10 and surface color disclosure ratings of at least 4, more preferably 6 or above in the Dowfax detergent test.
Sterilization or Pasteurization
The sterilization or pasteurization test determines how a coating withstands the processing conditions for different types of food products packaged in a tank. Typically, a coated substrate is immersed in a water bath and heated for 5-60 minutes at temperatures ranging from 65 ° C to 100 ° C. For the present evaluation, the coated substrate was immersed in a deionized water bath for 45 minutes at 85 ° C. The coated substrate was removed after the water bath and tested for adhesion and surface discoloration of the coating as described above. The viable coatings on the market preferably provide adequate pasteurization resistance with perfect adhesion (category 10) and surface color disclosure categories of at least 5, optimally at least 9.
Coefficient of friction
Coefficient of Friction (COF) is a measure of the lubricity of a coating and is used to provide an indication of how a cured coating will perform on commercial manufacturing equipment and presses. Typically, lubricants are added to coatings that require aggressive application manufacturing to provide proper lubricity.
For the present evaluation, an Altek Model 9505AE Mobility / Lubricity Tester with a time logger was used to measure the COF of cure beverage cap coatings on aluminum substrates. The instrument works by dragging a drag paddle with steel bearings attached to a load bar across the surface of the coated substrate, and the COF is tentatively plotted as resistance on a 010 graph paper scale. Each unit corresponds to 0.25 COF units. The coatings of the present invention are formulated to provide a preferred COF range of 0.055 to 0.095.
Manufacture or Continuity of the Lid
This test measures the ability of a coated substrate to retain its integrity as it undergoes the forming process necessary to produce a beverage can lid. It is a measure of the presence or absence of cracks or fractures in the formed cap. The cap is typically placed on a cup filled with an electrolyte solution. The cup is inverted to expose the surface of the cap to the electrolyte solution. The amount of electrical current that passes through the cap is then measured. If the coating remains intact (no cracks or fractures) after fabrication, minimal current will pass through the cap.
For the present evaluation, 202 fully converted conventional opening drink lids were exposed for a period of 4 seconds to an electrolyte solution comprised of 1% by weight NaCl in deionized water. Metal exposure was measured using a WACO Enamel Rater II, available from WilkensAnderson Company, Chicago, IL, with an output voltage of 6.3 volts. The measured electrical current, in
ES 2 367 516 T3 milliamps, is expressed. Typically, the continuities of the cap are tested initially and then the caps are pasteurized or retorted.
The preferred coatings of the present invention initially pass less than 10 milliamps (mA) when tested as described above, more preferably less than 5 mA, most preferably less than 2 mA, and optimally less than 1 mA . After pasteurization or retort, preferred coatings provide continuities of less than 20 mA, more preferably less than 10 mA, even more preferably less than 5 mA, and even more preferably less than 2 mA.
List of Raw Materials and Ingredients
The following table lists some of the raw materials and ingredients used in the following examples. Alternative materials or suppliers can be substituted as appreciated by one of ordinary skill in the art.
<td>Chemical name</td><td>Tradename</td><td>Supplier</td><td>Location</td>
<td>Glacial Methacrylic Acid</td><td></td><td>Rohm & Haas</td><td>Philadelphia, PA</td>
<td>Butyl Acrylate</td><td></td><td>Rohm & Haas</td><td>Philadelphia, PA</td>
<td>Styrene</td><td></td><td>Rohm & Haas</td><td>Philadelphia, PA</td>
<td>Benzoyl peroxide</td><td></td><td>Norac Company</td><td>Helena, AR</td>
<td>Butanol</td><td></td><td>Dow</td><td>Midland, MI</td>
<td>Ethylene Glycol Butyl Ether</td><td>Butyl Cellosolve / Dowanol EB</td><td>Dow</td><td>Midland, MI</td>
<td>Butyl Methacrylate</td><td></td><td>Rohm & Haas</td><td>Philadelphia, PA</td>
<td>I-Butyl Peroctoate</td><td></td><td>Arkema</td><td>Philadelphia, PA</td>
<td>Ethyl acrylate</td><td></td><td>Rohm & Haas</td><td>Philadelphia, PA</td>
<td>Acrylic acid</td><td></td><td>Rohm & Haas</td><td>Philadelphia, PA</td>
<td>Hydroxypropylmethacrylate</td><td>ROCRYL 410</td><td>Rohm & Haas</td><td>Philadelphia, PA</td>
<td>Hydroxyethyl methacrylate</td><td>ROCRYL 400</td><td>Rohm & Haas</td><td>Philadelphia, PA</td>
<td>Dimethylethanol amine</td><td></td><td>Huntsman Chemical</td><td>Dallas, TX</td>
<td>Glycidyl methacrylate</td><td>SR 379</td><td>Sartomer, Inc</td><td>Warrington, PA</td>
<td>Hydrogen peroxide</td><td></td><td>Ashland Chemical</td><td>Pittsburgh, PA</td>
<td>Benzoin</td><td></td><td>Estron</td><td>Calvert City, KY</td>
<td>N- Isobutoxymethacrylamide</td><td>CYLINK IBMA Monomer</td><td>Cytec Ind.</td><td>West Patterson, NJ</td>
<td>Amyl alcohol</td><td></td><td>Dow</td><td>Midland, MI</td>
<td>Propylene Glycol Butyl Ether</td><td>DOWANOL PNB</td><td>Dow</td><td>Midland, MI</td>
<td>Secondary ethoxylated alcohol</td><td>TERGITOL 15-S-7</td><td>Dow</td><td>Midland, MI</td>
<td>sec-butanol</td><td></td><td>Dow</td><td>Midland, MI</td>
<td>Polyethylene Wax</td><td>Slipayd 404</td><td>Elementis</td><td>Staines, UK</td>
<td>Phenolic based on Thermostable Phenol</td><td>SD-912B</td><td>Valspar</td><td>Minneapolis, MN</td>
<td>Carnuba wax emulsion</td><td>Michemlube 160 PFE</td><td>Michelman</td><td>Cincinnati, OH</td>
<td>Isooctyl alcohol</td><td></td><td>Aldrich Chemical</td><td>Milwaukee, WI</td>
<td>Polyethylene Wax</td><td>Lanco Glidd 5118</td><td>Lubrizol</td><td>Wickliffe, OH</td>
<td>Dipropylene glycol</td><td></td><td>Aldrich Chemical</td><td>Milwaukee, WI</td>
<td>Isophthalic Acid</td><td></td><td>BP Amoco</td><td>Chicago, IL</td>
<td>Dibutyl tin oxide</td><td>Fastcat 4201</td><td>Arkema</td><td>Philadelphia, PA</td>
<td>Xylene</td><td></td><td>Exxon</td><td>Newark, NJ</td>
<td>Trimellitic Anhydride</td><td></td><td>BP Amoco</td><td>Chicago, IL</td>
<td>Iron Complex</td><td>Hamp-OL 4.5% Iron</td><td>Traylor Chemical</td><td>Orlando, FL</td>
<td>Erythorbic acid</td><td></td><td>Aldrich Chemical</td><td>Milwaukee, WI</td>
<td>T-Butylhydoperoxide</td><td>Trigonox A-W70</td><td>Akzo</td><td>Philadelphia, PA</td>
<td>Ethylene glycol</td><td></td><td>Ashland Chemical</td><td>Pittsburgh, PA</td>
<td>Sebacic acid</td><td></td><td>Ivanhoe Indutries</td><td>Tampa FL</td>
<td>1,4-cyclohexane dimethanol 90% in water</td><td>CHDM-90</td><td>Eastman</td><td>Kingsport, TN</td>
<td>Buti Stanoic Acid</td><td>Fastcat 4100</td><td>Arkema</td><td>Philadelphia, PA</td>
<td>4-Hydroxybenzoic Acid</td><td></td><td>Acros Organics through Fisher Scientific</td><td>Houston, TX</td>
<td>Diglycidyl ether of 1,4-cyclohexane dimethanol</td><td>Erisys GE-22</td><td>CVC Specialty Chemicals</td><td>Maple Shade, NJ</td>
ES 2 367 516 T3
<td>Chemical name</td><td>Tradename</td><td>Supplier</td><td>Location</td>
<td>Ethyl triphenyl phosphonium iodide</td><td>Catalyst 1201</td><td>Deepwater chemicals</td><td>Woodward, OK</td>
<td>Succinic anhydride</td><td></td><td>JLM Marketing</td><td>Tampa, FL</td>
<td>Bisphenol A</td><td></td><td>Dow</td><td>Midland, MI</td>
<td>Diglycidyl Ether of Bispenol A</td><td>Epon 828</td><td>Resolution Performance Products</td><td>Houston, TX</td>
<td>Methyl isobutyl ketone</td><td></td><td>Dow</td><td>Midland, MI</td>
<td>Dibasic ester</td><td></td><td>Dupont</td><td>Wilminton, DE</td>
<td>Propylene Glycol Methyl Ether</td><td>Dowanol PM</td><td>Dow</td><td>Midland, MI</td>
Example 1: Embodiment 1. Preparation of Acid-Functional Acrylic
A premix of 512.6 parts of glacial methacrylic acid (MAA), 512.6 parts of butyl acrylate (BA), 114.0 parts of styrene, and 73.2 parts of benzoyl peroxide (70% moisture) was prepared in a separate container. A 3-liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. Ten percent of the premix was added to the flask along with 405.9 parts of butanol and 30.6 parts of deionized water. To the remaining premix 496.1 parts of butanol and 38.3 parts of deionized water were added. With the protective nitrogen atmosphere flowing into the flask, the contents were heated to 93 ° C. At 93 ° C, external heating was stopped and the material was allowed to rise in temperature for fifteen minutes. After fifteen minutes, the batch was at 97 ° C, and the remaining premix was added uniformly over two hours maintaining 97 ° C to 100 ° C. When the premix addition was complete, the premix container was rinsed with 5 parts of butanol. The batch was kept at temperature for two and a half hours. Heating was discontinuous and 317.7 parts of butyl cellosolve were added. The resulting acrylic prepolymer had 44.3% solids (NV), with an acid number of 313 and a Brookfield viscosity (as determined by ASTM D-2196) of 4,990 centipoise (cps).
Example 1: Embodiment 2. Preparation of Acid-Functional Acrylic
A premix of 677.7 parts of glacial methacrylic acid, 677.7 parts of butyl methacrylate (BMA), 150.8 parts of styrene, and 96.9 parts of benzoyl peroxide (70% moisture) was prepared in a separate container. A 5 liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. Ten percent of the premix was added to the flask along with 536.9 parts of butanol and 40.7 parts of deionized water. To the remaining premix, 758.1 parts of butanol and 50.6 parts of deionized water were added. With the protective nitrogen atmosphere flowing into the flask, the contents were heated to 93 ° C. At 93 ° C, external heating was stopped and the material was allowed to rise in temperature for ten minutes. After ten minutes, the batch was at 98 ° C, and the remaining premix was added uniformly over two hours maintaining 97 ° C to 100 ° C. The batch was kept at temperature for three hours. Heating was discontinuous and the batch was cooled. The resulting acrylic prepolymer had 49.9% NV, with an acid number of 304 and a Brookfield viscosity of 101,000 centipoise.
Example 1: Embodiment 3. Preparation of Acid-Functional Acrylic
A premix of 802.6 parts of glacial methacrylic acid, 807 parts of butyl methacrylate, 178.5 parts of styrene, 80.3 parts of t-butyl peroctoate, 838.5 parts of butanol and 59.9 parts of water deionized was prepared in a separate container. A 5 liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 635.8 parts of butanol and 48.1 parts of deionized water were added to the 5-liter flask. The flask was heated to 94 ° C. At 94 ° C, 12.5 parts of t-butyl peroctoate were added. The batch was held for five minutes after which the premix was added for two and a half hours. A second premix was prepared containing 59.2 parts of butanol and 16.1 parts of t-butyl peroctoate. When the addition of the first premix was complete the second premix was added over 30 minutes. Once completed, the batch was held for 30 minutes. A 3.4 part extraction of t-butyl peroctoate was added and the batch was held for two hours. After holding for two hours, the heat was discontinuous and the batch was cooled. The resulting acrylic prepolymer had 50.1% NV, with an acid number of 292 and a Brookfield viscosity of 150,000 centipoise.
Example 1: Embodiment 4. Preparation of Acid-Functional Acrylic
A premix of 802.6 parts of glacial methacrylic acid, 445.9 parts of ethyl acrylate, 535.1 parts of styrene, and 108.6 parts of t-butyl peroctoate, 838.5 parts of butanol and 59.9 parts of deionized water was prepared in a separate container. A 5 liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 635.8 parts of butanol and 48.1 parts of deionized water were added to the 5-liter flask. The flask was heated to 94 ° C. At 94 ° C, 16.6 parts of t-butyl peroctoate were added. The batch was held for five minutes after which the premix was added for two and a half hours. A second premix was prepared containing 59.2 parts of butanol and 21.2 parts
ES 2 367 516 T3 of t-butyl peroctoate. When the addition of the first premix was complete the second premix was added over 30 minutes. Once completed, the batch was held for 30 minutes. A 4.6 part extraction of t-butyl peroctoate was added and the batch was held for two hours. After holding for two hours the heat was discontinuous and the batch was cooled. The resulting acrylic prepolymer had 49.8% NV, with an acid number of 303 and a Brookfield viscosity of 21,650 centipoise.
Example 1: Embodiments 5-11
Using techniques from Example 1: Embodiment 4, the systems shown in Table 1 were prepared.
Table 1: Acid-Functional Acrylics
<td>Ex. 1</td><td>Realization 4</td><td>Realization 5</td><td>Realization 6</td><td>Realization 7</td><td>Realization 8</td><td>Realization 9</td><td>Realization 10</td><td>Realization eleven</td>
<td>MAA</td><td> 45</td><td> 30</td><td> 45</td><td> 0</td><td> 30</td><td> 45</td><td> 25</td><td> 45</td>
<td>EA</td><td> 25</td><td> 50</td><td> 45</td><td> 23</td><td> 0</td><td> 15</td><td> 30</td><td> 0</td>
<td>Styrene</td><td> 30</td><td> 5</td><td> 10</td><td> 10</td><td> 25</td><td> 0</td><td> 25</td><td> 10</td>
<td>BMA</td><td> 0</td><td> 15</td><td> 0</td><td> 31</td><td> 0</td><td> 40</td><td> 0</td><td> 45</td>
<td>AA '</td><td> 0</td><td> 0</td><td> 0</td><td> 36</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>
<td>BA</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 45</td><td> 0</td><td> 0</td><td> 0</td>
<td>HPMA<sup>2</sup></td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 20</td><td> 0</td>
<td>Solid</td><td> 49,8%</td><td> 62,8%</td><td> 49,4%</td><td> 51,4%</td><td> 55,4%</td><td> 49,6%</td><td> 50,5%</td><td> 49,7%</td>
<td>Acidity index</td><td> 303</td><td> 198</td><td> 295</td><td> 246</td><td> 192</td><td> 293</td><td> 155</td><td> 292</td>
<td>Visc. Brookfield (cps)</td><td> 21.650</td><td> 50.000</td><td> 8.730</td><td> 1.100</td><td> 6.660</td><td> 27.800</td><td> 3.532</td><td> 106.000</td>
<td colspan="9">Glacial acrylic acid<sup>2</sup> Hydroxypropyl methacrylate</td>
Example 1: Embodiment 12. Preparation of Acid-Functional Acrylic
A premix of 803.4 parts of glacial methacrylic acid, 446.3 parts of ethyl acrylate (EA), 535.5 parts of styrene, 153 parts of benzoyl peroxide (70% moisture), 839.2 parts of butanol , and 60 parts of deionized water was prepared in a separate container. A 5 liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. To the flask, 636.3 parts of butanol were added and 48.2 parts of deionized water were added and heated from 97 ° C to 100 ° C with a nitrogen blanket flowing into the flask. The premix was added uniformly over two and a half hours maintaining 97 to 100 ° C. When the premix was in the flask it was rinsed with 59.2 parts of butanol and added to the flask. The batch was kept at temperature for two hours. Heating was discontinuous and the batch was cooled. The resulting acrylic prepolymer had 50.2% NV, with an acid number of 301 and a Brookfield viscosity of 25,400 centipoise.
Example 1: Embodiments 13-15
Using techniques from Example 1: Embodiment 12 the systems shown in Table 2 were prepared.
Table 2: Acid-Functional Acrylics
<td>Example N ° 1:</td><td>Embodiment 12</td><td>Embodiment 13</td><td>Embodiment 14</td><td>Embodiment 15</td>
<td>MAA</td><td> 45</td><td> 25</td><td> 35</td><td> 25</td>
<td>EA</td><td> 25</td><td> 25</td><td> 25</td><td> 33</td>
<td>Styrene</td><td> 30</td><td> 30</td><td> 30</td><td> 22</td>
<td>HPMA</td><td> 0</td><td> 20</td><td> 10</td><td> 20</td>
<td>Solid</td><td> 51,2%</td><td> 50,2%</td><td> 50,0%</td><td> 50,3%</td>
<td>Acidity index</td><td> 301</td><td> 171</td><td> 234</td><td> 169</td>
<td>Brookfield Viscosity (cps)</td><td> 25.400</td><td> 2.820</td><td> 6.020</td><td> 2.220</td>
Example 2: Embodiment 1. Preparation of Acid-Functional Acrylic Salt
A 3 liter flask was equipped with a stirrer, reflux condenser, Dean Stark tube, thermocouple, heating mantle, and a nitrogen blanket. 711.5 parts of the acrylic from Example 1: Embodiment 1, 762.9 parts of deionized water, and 56.9 parts of dimethyl ethanolamine (DMEA) were added to the flask. The contents were heated to reflux and 553 parts were distilled from the flask. After the distillation was completed, 598 parts of deionized water was added. The batch was cooled to provide an acrylic solution at 20.3% solids and an acid number of 307.
Example 2: Embodiment 2. Preparation of Acid-Functional Acrylic Salt
ES 2 367 516 T3
A 5 liter flask was equipped with a stirrer, reflux condenser, Dean Stark tube, thermocouple, heating mantle, and a nitrogen blanket. 1853 parts of the acrylic from Example 1: Embodiment 2, 2220.4 parts of deionized water, and 163.3 parts of dimethyl ethanol amine were added to the flask. The contents were heated to reflux and 1587 parts were distilled from the flask. After the distillation was completed, 1718 parts of deionized water was added. The batch was cooled to provide a 22.2% solids acrylic solution, acid number 294, pH 6.0, and a viscosity of 13 seconds (Ford cup viscosity Number 4 as determined by ASTM D- 1200).
Example 2: Embodiment 3. Preparation of Acid-Functional Acrylic Salt
A 5 liter flask was equipped with a stirrer, reflux condenser, Dean Stark tube, thermocouple, heating mantle, and a nitrogen blanket. 1852.3 parts of the acrylic from Example 1: Embodiment 3, 2219 parts of deionized water, and 163 parts of dimethyl ethanol amine were added to the flask. The contents were heated to reflux and 1463 parts were distilled from the flask. After the distillation was completed, 1581 parts of deionized water was added. The batch was cooled to provide a 21.6% solids acrylic solution, acid number 284, pH 6.23, and a viscosity of 13 seconds (Ford cup Number 4).
Example 2: Embodiment 4. Preparation of Functional Acid Acrylic Salt
A 5 liter flask was equipped with a stirrer, reflux condenser, Dean Stark tube, thermocouple, heating mantle, and a nitrogen blanket. 1799.2 parts of the acrylic from Example 1: Embodiment 4, 2155.9 parts of deionized water, and 158.6 parts of dimethyl ethanol amine were added to the flask. The contents were heated to reflux and 1541 parts were distilled from the flask. After the distillation was completed, 1615 parts of deionized water was added. The batch was cooled to provide a 22.1% solids acrylic solution, acid number 302, pH 6.55, and a Brookfield viscosity of 2060 centipoise.
Example 2: Embodiments 5-15
Using techniques from Example 2: Embodiment 4, the systems shown in Table 3 were prepared. Each embodiment of Example 2 used the corresponding numbered embodiment from Example 1. That is, Example 2: Embodiment 5 used the acrylic prepolymer a starting from Example 1: Embodiment 5, etc.
Table 3: Acid-Functional Acrylic Salts
<td>Ex. 2:</td><td>Realization 4</td><td>Realization 5</td><td>Realization 6</td><td>Realization 7</td><td>Realization 8</td><td>Realization 9</td>
<td>Solid</td><td> 22,1 %</td><td> 21,4%</td><td> 21,6%</td><td> 22,0%</td><td> 21,7%</td><td> 21,3%</td>
<td>Acidity index</td><td> 302</td><td> 198</td><td> 291</td><td> 248</td><td> 193</td><td> 291</td>
<td>PH</td><td> 6,55</td><td> 6,49</td><td> 5,96</td><td> 5,95</td><td> 7,30</td><td> 6,26</td>
<td>Viscosity'</td><td>2,060 cps</td><td>1,050 cps</td><td>1,770 cps</td><td> —</td><td> —</td><td>20 s</td>
<td>Ex. 2:</td><td>Realization 10</td><td>Realization eleven</td><td>Realization 12</td><td>Realization 13</td><td>Embodiment 14</td><td>Realization fifteen</td>
<td>Solid</td><td> 21,7%</td><td> 21,7%</td><td> 22,0%</td><td> 21,3%</td><td> 21,7%</td><td> 22,2%</td>
<td>Acidity index</td><td> 153</td><td> 300</td><td> 291</td><td> 169</td><td> 231</td><td> 271</td>
<td>pH</td><td> 7,29</td><td> 6,54</td><td> 6,37</td><td> 6,72</td><td> —</td><td> 6,67</td>
<td>Viscosity<sup>1</sup></td><td>881 cps</td><td>15 s</td><td>167 cps</td><td>304 cps</td><td>248 cps</td><td>1900 cps</td>
<td colspan="7"><sup>1</sup> Brookfield viscosity values in cps and Ford Cup Number 4 viscosity values in s.</td>
Example 3: Embodiment 1. Emulsion
A 1 liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 313.9 parts of salt from Example 2: Embodiment 3 and 267.3 parts of deionized water were added to the flask. The contents of the flask were heated to 75 ° C at 280 revolutions per minute (RPM). In a separate container, a premix of 71.4 parts of styrene, 116.3 parts of butyl methacrylate, and 16.3 parts of glycidyl methacrylate (GMA) was prepared. Once the flask was at 75 ° C, 10% of the premix was added followed by 2.04 parts of benzoin and 20 parts of deionized water. The flask was further heated to 79 ° C. At 79 ° C, 2.04 parts of 35% hydrogen peroxide were added and held for five minutes. After five minutes the temperature control was adjusted to 81 ° C and the remaining premix was added over a period of one hour. When the addition was complete, 20 parts of deionized water was used
ES 2 367 516 T3 to clear the residual premix in the flask. The batch was held for ten minutes and then 0.35 part of benzoin, 20 parts of deionized water, and 0.35 part of 35% hydrogen peroxide were added. After two hours the heat was removed and the batch was cooled. This provided a 31.9% solids emulsion, acid number 63.3, pH 6.48, and a Brookfield viscosity of 203 centipoise.
Example 3: Embodiment 2. Emulsion
A 0.5 liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 155.6 parts of salt from Example 2: Embodiment 4 and 120.6 parts of deionized water were added to the flask. The contents of the flask were heated to 75 ° C at 240 RPM. In a separate container, a premix of 66.3 parts of styrene, 19.6 parts of ethyl acrylate, and 7.5 parts of glycidyl methacrylate was prepared. Once the flask was at 75 ° C, 10% of the premix was added followed by 0.91 parts of benzoin and 9.4 parts of deionized water. The flask was further heated to 79 ° C. At 79 ° C, 0.91 parts of 35% hydrogen peroxide was added and held for five minutes. After five minutes the temperature control was adjusted to 81 ° C and the remaining premix was added over one hour. When the addition was complete, 9.4 parts of deionized water was used to clear the residual premix in the flask. The batch was held for ten minutes and then 0.16 parts of benzoin, 9.4 parts of deionized water and 0.16 parts of 35% hydrogen peroxide were added. After two hours the heat was removed and the batch was cooled. This gave a 30.9% solids emulsion, acid number of 83.8, pH of 6.70, and a viscosity of 40 seconds (Ford cup Number 4).
Example 3: Embodiment 3. Emulsion
A 1-liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 311.2 parts of salt from Example 2: Embodiment 4 and 241.2 parts of deionized water were added to the flask. The contents of the flask were heated to 75 ° C at 270 RPM. In a separate container, a premix of 112.1 parts of styrene, 59.8 parts of ethyl acrylate, and 14.9 parts of glycidyl methacrylate was prepared. Once the flask was at 75 ° C, 10% of the premix was added followed by 1.87 parts of benzoin and 18.8 parts of deionized water. The flask was further heated to 79 ° C. At 79 ° C, 1.87 parts of 35% hydrogen peroxide were added and held for five minutes. After five minutes, the temperature control was adjusted to 81 ° C and the remaining premix was added over one hour. When the addition was complete, 18.8 parts of deionized water was used to clear the residual premix in the flask. The batch was held for ten minutes and then 0.32 parts of benzoin, 18.8 parts of deionized water and 0.32 parts of 35% hydrogen peroxide were added. After two hours, the heat was removed and the batch was cooled. This gave a 31.8% solids emulsion, acid number of 76.7, pH of 6.67, and a viscosity of 28 seconds (Ford cup Number 4).
Example 3: Embodiment 4. Emulsion
A 5 liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 1525.0 parts of salt from Example 2: Embodiment 4 and 1219.1 parts of deionized water were added to the flask. The contents of the flask were heated to 70 ° C at 250 RPM. In a separate container, a premix of 380.4 parts of styrene, 278.3 parts of butyl acrylate, 194.9 parts of butyl methacrylate and 74.2 parts of glycidyl methacrylate was prepared. Once the flask was at 70 ° C, 10% of the premix was added followed by 9.29 parts of benzoin and 92.9 parts of deionized water. The flask was further heated to 79 ° C. At 79 ° C, 9.29 parts of 35% hydrogen peroxide were added and held for five minutes. After five minutes the temperature control was adjusted to 81 ° C and the remaining premix was added over one hour. When the addition was complete, 92.9 parts of deionized water was used to clear the residual premix in the flask. The batch was held for ten minutes and then 1.59 parts of benzoin, 92.9 parts of deionized water, and 1.59 parts of 35% hydrogen peroxide were added. The batch was held for 45 minutes and then 0.52 parts of benzoin and 0.52 parts of 35% hydrogen peroxide were added. After two hours, the heat was removed and the batch was cooled. This gave an emulsion at 31.4% solids, acid number 64.1, pH 6.95, and a viscosity of 22 seconds (Ford cup Number 4).
Example 3: Embodiment 5. Emulsion
A 12 liter flask was fitted with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 3886.5 parts of salt from Example 2: Embodiment 4 and 3022.5 parts of deionized water were added to the flask. The contents of the flask were heated to 70 ° C at 235 RPM. In a separate container, a premix of 771.25 parts of styrene, 933.75 parts of butyl acrylate, 537.5 parts of butyl methacrylate and 93.75 parts of glycidyl methacrylate was prepared. Once the flask was at 70 ° C, 23.38 parts of benzoin and 116.25 parts of deionized water were added followed by 10% of the premix. The flask was further heated to 79 ° C. At 79 ° C, 23.38 parts of 35% hydrogen peroxide and 116.25 parts of deionized water were added and held for five minutes. After five minutes the temperature control was adjusted to 81 ° C and the remaining premix was added over one hour. When the addition was complete, 232.5 parts of deionized water was used to clear the residual premix in the flask. The lot was kept
ES 2 367 516 T3 for ten minutes and then 4.0 parts of benzoin, 232.5 parts of deionized water and 4.0 parts of 35% hydrogen peroxide were added. The batch was held for 45 minutes and then 1.25 parts of benzoin and 1.25 parts of 35% hydrogen peroxide were added. After two hours the heat was removed and the batch was cooled. This gave a 31.4% solids emulsion, acid number of 72.4, pH of 7.05, and a viscosity of 32 seconds (Ford cup Number 4).
Example 3: Embodiments 6-10
Using the process indicated in Example 3: Embodiment 4, the Emulsions shown in Table 4 were prepared.
Table 4: Emulsions
<td>Example 3:</td><td>Embodiment 4</td><td>Embodiment 6</td><td>Embodiment 7</td><td>Embodiment 8</td><td>Embodiment 9</td><td>Realization10</td>
<td>Acrylic Salt</td><td>Ex. 2: Embodiment 4</td><td>Ex. 2: Embodiment 4</td><td>Ex. 2: Embodiment 4</td><td>Ex. 2: Embodiment 4</td><td>Ex. 2: Embodiment 4</td><td>Ex. 2: Embodiment 4</td>
<td>Monomers</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Styrene</td><td> 41,0</td><td> 39,0</td><td> 42,0</td><td> 43,5</td><td> 43,5</td><td> 45,0</td>
<td>BA</td><td> 30,0</td><td> 53,0</td><td> 54,0</td><td> 54,5</td><td> 54,5</td><td> 55,0</td>
<td>BMA</td><td> 21,0</td><td> 0,0</td><td> 0,0</td><td> 0,0</td><td> 0,0</td><td> 0,0</td>
<td>GMA</td><td> 8,0</td><td> 8,0</td><td> 4,0</td><td> 2,0</td><td> 2,0</td><td> 0,0</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Emulsion Reviews</td><td>Good Appearance</td><td>Good Appearance</td><td>Good Appearance</td><td>White-High Viscosity</td><td>White-Low Conversion</td><td>Separated Emulsion</td>
<td>Solid</td><td> 31,4%</td><td> 31,3%</td><td> 31,5%</td><td> 31,7%</td><td> 28,6%</td><td> 31,2%</td>
<td>Viscosity (Ford Cup No. 4)</td><td>22 s</td><td>51 s</td><td>103 s</td><td></td><td>22 s</td><td></td>
<td>Brookfield Viscosity</td><td> ---</td><td>230 cps</td><td>610 cps</td><td>25,000cps</td><td> ----</td><td> ----</td>
<td> _</td><td> 6,95</td><td> 7,05</td><td> 6,88</td><td> ---</td><td> 6,65</td><td> —</td>
These resin series showed that as the GMA level decreases, acceptable emulsions become more difficult to produce.
Example 3: Embodiments 11-18
A design experiment using Example 2: Embodiment 9 as the acid functional acrylic salt and the process outlined above was set up and described in Table 5.
Table 5: Emulsion Design Experiment
<td>Example 3:</td><td>Realization eleven</td><td>Realization 12</td><td>Realization 13</td><td>Realization 14</td><td>Realization fifteen</td><td>Realization 16</td><td>Realization 17</td><td>Realization 18</td>
<td>Acrylic / Monomer Ratio</td><td colspan="4"> 73/27</td><td colspan="4"> 65/35</td>
<td></td><td colspan="2">Composition of Monomer 1</td><td colspan="2">Composition of Monomer 2</td><td colspan="2">Composition of Monomer 1</td><td colspan="2">Composition of Monomer 2</td>
<td>GMA level</td><td>Under</td><td>Tall</td><td>Under</td><td>Tall</td><td>Under</td><td>Tall</td><td>Under</td><td>Tall</td>
<td>Monomers</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Styrene</td><td> 42</td><td> 39</td><td> 33</td><td> 33</td><td> 43</td><td> 41</td><td> 33</td><td> 33</td>
<td>BA</td><td> 54</td><td> 53</td><td> 40</td><td> 41</td><td> 54</td><td> 53</td><td> 40</td><td> 40</td>
<td>BMA</td><td> 0</td><td> 0</td><td> 23</td><td> 18</td><td> 0</td><td> 0</td><td> 24</td><td> 21</td>
<td>GMA</td><td> 4</td><td> 8</td><td> 4</td><td> 8</td><td> 3</td><td> 6</td><td> 3</td><td> 6</td>
<td></td><td>32.0% l</td><td> 31,3%</td><td> 31,6%</td><td> 31,9%</td><td> 31,6%</td><td> 32,0%</td><td> 31,7%</td><td> 32,0%</td>
<td>Viscosity (Ford Cup No. 4)</td><td></td><td>63 s</td><td></td><td></td><td>35 s</td><td>210 s</td><td>42 s</td><td></td>
<td>Brookfield Viscosity (cps)</td><td> 10.000</td><td></td><td> 10.000</td><td> 695</td><td></td><td></td><td></td><td> 1.384</td>
<td>Acidity index</td><td> 74,7</td><td> 72,9</td><td> 74,9</td><td> 70,2</td><td> 101</td><td> 96,1</td><td> 101</td><td> 96,5</td>
The lattice structures from Table 5 were tested without further formulation or modification, and the results are shown in Table 6. Each composition was dropped onto Alcoa ALX aluminum at a film weight of 1.1-1, 25 milligrams per square centimeter (mg / cm<sup>2</sup>) (7-8 milligrams per square inch (msi)) and cured for 10 seconds to achieve a metal temperature peak of 215 ° C (420 ° F) in a gas-fired coil furnace.
ES 2 367 516 T3
Table 6: Performance of Beverage Lid Film
<td></td><td>Water based control<sup>1</sup></td><td>Ex. 3: Realization eleven</td><td>Ex. 3: Realization 12</td><td>Ex. 3: Realization 13</td><td>Ex. 3: Embodiment 14</td><td>Ex. 3: Realization 15</td><td>Ex. 3: Realization 16</td><td>Ex. 3: Realization 17</td><td>Ex. 3: Realization 18</td>
<td>Cracking</td><td>Neither</td><td>Neither</td><td>Neither</td><td>Neither</td><td>Neither</td><td>Neither</td><td>Mild</td><td>Neither</td><td>Neither</td>
<td>MEK resistance</td><td> 19</td><td> 5</td><td> 6</td><td> 3</td><td> 7</td><td> 5</td><td> 6</td><td> 4</td><td> 8</td>
<td>Beveled<sup>4</sup></td><td> 0,343</td><td> 0,013</td><td> 0,020</td><td> 0,071</td><td> 0,003</td><td> 0,020</td><td> 0,013</td><td> 0,030</td><td> 0,013</td>
<td>Retort of Water<sup>2</sup></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Superficial color alteration</td><td> 9,5</td><td> 10</td><td> 9,5</td><td> 9,5</td><td> 9,5</td><td> 9</td><td> 10</td><td> 8</td><td> 10</td>
<td>Accession</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>
<td>Pasteurization<sup>3</sup></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Superficial color alteration</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>
<td>Accession</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>
<td>Cover Continuity</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Initial</td><td> 0</td><td> 0,22</td><td> 25,3</td><td> 11,5</td><td> 57,8</td><td> 17,7</td><td> 133,5</td><td> 27,5</td><td> 132,2</td>
<td>After Retort<sup>2</sup></td><td> 8,4</td><td> 31,8</td><td>Not Tested</td><td> 31,7</td><td>Not Tested</td><td>Not Tested</td><td>Not Tested</td><td> 34,3</td><td>Not Tested</td>
<td colspan="10">'' Commercially available beverage cap liner from Valspar code 13Q80AG.<sup>2</sup> 90 minutes at 121 ° C (250 ° F).<sup>3</sup> 30 minutes at 85 ° C (185 ° F).<sup>4</sup> Performed after a 45 minute pasteurization at 85 ° C (185 ° F). Measured in centimeters.</td>
Example 3: Embodiments 5b and 19-25
A design experiment using Example 2: Embodiment 4 as the acid-functional acrylic salt and the process indicated above was prepared and described in Table 7. Example 3: Embodiment 5b was included as one of the variables and it was a repeat of Embodiment 5.
Table 7: Emulsion Design Experiment
<td>Example 3:</td><td>Realization 19</td><td>Realization twenty</td><td>Embodiment 5b</td><td>Realization twenty-one</td><td>Realization 22</td><td>Realization 2. 3</td><td>Realization 24</td><td>Realization 25</td>
<td>Acrylic / Monomer Ratio</td><td colspan="4"> 73/27</td><td colspan="4"> 65/35</td>
<td></td><td colspan="2">Composition of Monomer 1</td><td colspan="2">Composition of Monomer 2</td><td colspan="2">Composition of Monomer 1</td><td colspan="2">Composition of Monomer 2</td>
<td>GMA level</td><td>Under</td><td>Tall</td><td>Under</td><td>Tall</td><td>Under</td><td>Tall</td><td>Under</td><td>Tall</td>
<td>Monomers</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Styrene</td><td> 42</td><td> 39</td><td> 33</td><td> 33</td><td> 43</td><td> 41</td><td> 33</td><td> 33</td>
<td>BA</td><td> 54</td><td> 53</td><td> 40</td><td> 41</td><td> 54</td><td> 53</td><td> 40</td><td> 40</td>
<td>BMA</td><td> 0</td><td> 0</td><td> 23</td><td> 18</td><td> 0</td><td> 0</td><td> 24</td><td> 21</td>
<td>GMA</td><td> 4</td><td> 8</td><td> 4</td><td> 8</td><td> 3</td><td> 6</td><td> 3</td><td> 6</td>
<td>Solid</td><td> 31,5%</td><td> 31,6%</td><td> 31,6%</td><td> 31,4%</td><td> 31,3%</td><td> 31,6%</td><td> 31,5%</td><td> 31,7%</td>
<td>Viscosity (Ford Cup No. 4)</td><td>55 s</td><td>60 s</td><td>50 s</td><td>56 s</td><td>106 s</td><td> —</td><td>70 s</td><td> —</td>
<td>Brookfield Viscosity (cps)</td><td> —</td><td> —</td><td> —</td><td> —</td><td> —</td><td> 2.624</td><td> —</td><td> 3.000</td>
<td>Acidity index</td><td> 71,9</td><td> 73,0</td><td> 69,0</td><td> 68,3</td><td> 95,4</td><td> 92,5</td><td> 94,7</td><td> 98,0</td>
The lattice structures from Table 7 were tested without further modification or formulation, and the results are shown in Table 8. Each composition was dropped onto Alcoa ALX aluminum at a weight of
ES 2 367 516 T3 1.1-1.25 mg / cm foil<sup>2</sup> (7-8 msi) and cured for 10 seconds to achieve a metal temperature peak of 215 ° C (420 ° F) in a gas fired coil furnace.
Table 8. Performance of Beverage Lid Film
<td></td><td>Water based control<sup>1</sup></td><td>Ex. 3: Realization 19</td><td>Ex. 3: Realization 20</td><td>Ex. 3: Embodiment 5b</td><td>Ex. 3: Realization 21</td><td>Ex. 3: Realization 22</td><td>Ex. 3: Realization 23</td><td>Ex. 3: Realization 24</td><td>Ex. 3: Embodiment 25</td>
<td>Cracking</td><td>Neither</td><td>Neither</td><td>Neither</td><td>Neither</td><td>Neither</td><td>Neither</td><td>Mild</td><td>Neither</td><td>Yes</td>
<td>MEK</td><td> 19</td><td> 4</td><td> 7</td><td> 4</td><td> 10</td><td> 6</td><td> 11</td><td> 4</td><td> 6</td>
<td>Beveled<sup>4</sup></td><td> 0,343</td><td> 0,064</td><td> 0,051</td><td> 0,038</td><td> 0,033</td><td> 0,056</td><td> 0,013</td><td> 0,046</td><td> 0,013</td>
<td>Retort of Water<sup>2</sup></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Superficial color alteration</td><td> 9,5</td><td> 9,5</td><td> 9,5</td><td> 10</td><td> 10</td><td> 9,5</td><td> 10</td><td> 7</td><td> 9,5</td>
<td>Accession</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>
<td>Pasteurization<sup>3</sup></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Superficial color alteration</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>
<td>Accession</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10 -</td><td> 10</td><td> 10</td><td> 10</td>
<td>Cover Continuity</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Initial</td><td> 0</td><td> 5,5</td><td> 2,6</td><td> 6,0</td><td> 12,3</td><td> 20,2</td><td> 61,2</td><td> 1,9</td><td> 93,6</td>
<td>After Retort<sup>2</sup></td><td> 8,4</td><td> 23,5</td><td> 143</td><td> 23,4</td><td> 134,0</td><td> 78,8</td><td>Not Tested</td><td> 52,5</td><td>Not Tested</td>
<td colspan="10"><sup>1</sup> Commercially available beverage cap liner from Valspar code 13Q80AG.<sup>2</sup> 90 minutes at 121 ° C (250 ° F).<sup>3</sup> 30 minutes at 85 ° C (185 ° F).<sup>4</sup> Performed after a 45 minute pasteurization at 85 ° C (185 ° F). Measured in centimeters.</td>
Example 3: Embodiments 26-33
A design experiment using Example 2: Embodiment 11 as the acid functional acrylic salt and the process outlined above was set up and described in Table 9.
Table 9: Design Experiment. Emulsion
<td>Example 3:</td><td>Realization 26</td><td>Realization 27</td><td>Realization 28</td><td>Realization 29</td><td>Realization 30</td><td>Realization 31</td><td>Realization 32</td><td>Realization 33</td>
<td>Acrylic / Monomer Ratio</td><td colspan="4"> 73/27</td><td colspan="4"> 65/35</td>
<td></td><td colspan="2">Composition of Monomer 1</td><td colspan="2">Composition of Monomer 2</td><td colspan="2">Composition of Monomer 1</td><td colspan="2">Composition of Monomer 2</td>
<td>GMA level</td><td>Under</td><td>Tall</td><td>Under</td><td>Tall</td><td>Under</td><td>Tall</td><td>Under</td><td>Tall</td>
<td>Monomers</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Styrene</td><td> 42</td><td> 39</td><td> 33</td><td> 33</td><td> 43</td><td> 41</td><td> 33</td><td> 33</td>
<td>BA</td><td> 54</td><td> 53</td><td> 40</td><td> 41</td><td> 54</td><td> 53</td><td> 40</td><td> 40</td>
<td>BMA</td><td> 0</td><td> 0</td><td> 23</td><td> 18</td><td> 0</td><td> 0</td><td> 24</td><td> 21</td>
<td>GMA</td><td> 4</td><td> 8</td><td> 4</td><td> 8</td><td> 3</td><td> 6</td><td> 3</td><td> 6</td>
<td>Solid</td><td> 31,0%</td><td> 31,8%</td><td> 31,5%</td><td> 31,4%</td><td> 30,9%</td><td> 31,3%</td><td> 31,4%</td><td> 31,6%</td>
<td>Viscosity (Ford Cup No. 4)</td><td>40 s</td><td>48 s</td><td> —</td><td>17 s</td><td>14 s</td><td>16 s</td><td>14 s</td><td>16 s</td>
<td>Brookfield Viscosity (cps)</td><td> —</td><td> —</td><td> 17.000</td><td> —</td><td> —</td><td> —</td><td> —</td><td> —</td>
<td>Acidity index</td><td> 73,5</td><td> 68,7</td><td> 71,2</td><td> 68,6</td><td> 97,0</td><td> 93,9</td><td> 99,3</td><td> 93,9</td>
The lattice structures from Table 9 were tested without further modification or formulation, and the results are shown in Table 10. Each composition was dropped onto Alcoa ALX aluminum in a film weight of 1.1-1 , 25 mg / cm<sup>2</sup> (7-8 msi) and cured for 10 seconds to achieve a metal temperature peak of 215 ° C (420 ° F) in a gas fired coil furnace.
ES 2 367 516 T3
<td rowspan="6">DOE C Emulsion Drink Lid Film</td><td>Ex. 3: Realization 33</td><td>ω</td><td>rjZi</td><td> 0,013</td><td></td><td> 9,5</td><td>OR</td><td></td><td>OR</td><td>OR</td><td></td><td>cn I co co</td><td>Do not Tested</td><td rowspan="10"><sup>1</sup> Beverage end coating available commercially from Valspar code 13Q80AG.<sup>2</sup> 90 minutes at 121 C (250 ° F).<sup>3</sup> 30 minutes at 85 ° C (185 ° F). * Performed after a 45 minute pasteurization at 85 ° C (1 85 ° F). Measured in centimeters.</td>
<td>c or • 'or -. CO UJ 7c m LL</td><td>ω</td><td>r--</td><td> 0,020</td><td></td><td>CO</td><td>or</td><td></td><td>or</td><td>or</td><td></td><td><sup>lj</sup>L IT</td><td>Do not Tested</td>
<td>Ex. 3: Realization 31</td><td>ω</td><td>lj-.i</td><td> 0,013</td><td></td><td>or</td><td>or</td><td></td><td>OR</td><td>or</td><td></td><td> 315,9</td><td>Do not Tested</td>
<td>C or .. □ ° g <sub>or</sub>-. .L! co LU ® > 1 ' LL</td><td>ω</td><td>co</td><td> 0,013</td><td></td><td> 04</td><td>or</td><td></td><td>OR</td><td>or</td><td></td><td> 178,9</td><td>Do not Tested</td>
<td>Ex. 3: Realization 29</td><td>ω</td><td>C-4</td><td> 0,025</td><td></td><td>OR</td><td>or</td><td></td><td>or</td><td>or</td><td></td><td> 215,6</td><td>Not Tested</td>
<td>Ex. 3: Realization 28</td><td>Neither</td><td>co</td><td> 0,013</td><td></td><td>S'6</td><td>or</td><td></td><td>or</td><td>or</td><td></td><td> 12,2</td><td>Not Tested</td>
<td rowspan="2">la 10: Performance of I</td><td>Ex. 3: Realization 27</td><td>Neither</td><td>co</td><td> 0,043</td><td></td><td> 10,0</td><td>or</td><td></td><td>or</td><td>or</td><td></td><td> 107,4</td><td>Not Tested</td>
<td>Ex. 3: Realization 26</td><td>Mild</td><td>r--</td><td> 0,046</td><td></td><td>S'6</td><td>or</td><td></td><td>or</td><td>or</td><td></td><td> 82,4</td><td>Not Tested</td>
<td rowspan="2">_Ci Item· I—</td><td>Water based control<sup>1</sup></td><td>Neither</td><td>CD</td><td> 0,343</td><td></td><td> 9,5</td><td>or</td><td></td><td>or</td><td>or</td><td></td><td>OR</td><td> 8.4</td>
<td></td><td>Cracking</td><td>LU</td><td>Beveled*</td><td>(D 73 > T3 -ι-i O δ ® tj π LL · = 1.</td><td>Superficial alteration of the Colour</td><td>Accession</td><td>c or 03 N 'k— Z5 (D k '13 LL</td><td>Superficial alteration of the Colour</td><td>Accession</td><td>m 73 73 03 lu</td><td>Initial</td><td>After Retort<sup>2</sup></td>
ES 2 367 516 T3
The following are some of the conclusions drawn from the DOEs emulsion results shown in Tables 5 to 10. The styrene-free acrylic stabilizer polymer from Example 2: Embodiment 9 produced higher viscosity emulsions, which are less desired for some end uses. The composition from Example 2: Embodiment 4 provided better overall film performance. In general, a higher polymer / acrylic monomer ratio tended to provide poorer film integrity (continuities). Higher GMA levels in the emulsion monomer mixture tended to provide higher emulsion viscosities and greater increases in mAs film continuity after retort. A small difference was noted between the various comonomer compositions, so there is latitude to vary the overall emulsion monomer composition.
Example 3: Embodiments 34-35
A series of emulsions, shown in Table 11 were prepared using an acid functional monomer to acrylic ratio of 73/27 solids / solids. These systems were prepared using the process outlined in Example 3: Embodiment 5 using Example 2: Embodiment 4 as the acid functional acrylic salt.
Table 11: Study of the Emulsion GMA Level
<td>Example 3:</td><td>Embodiment 5b</td><td>Embodiment 34</td><td>Embodiment 35</td>
<td>GMA level</td><td> 4%</td><td> 12%</td><td> 20%</td>
<td>Monomers</td><td></td><td></td><td></td>
<td>Styrene</td><td> 33</td><td> 33</td><td> 33</td>
<td>BA</td><td> 40</td><td> 42</td><td> 44</td>
<td>BMA</td><td> 23</td><td> 13</td><td> 3</td>
<td>GMA</td><td> 4</td><td> 12</td><td> 20</td>
<td>Solid</td><td> 31,6%</td><td> 31,8%</td><td> 32,0%</td>
<td>Viscosity (Ford cup No. 4)</td><td>50 s</td><td> —</td><td> —</td>
<td>Visc. Brookfield (cps)</td><td> —</td><td> 1.070</td><td> 33.950</td>
<td>Acidity index</td><td> 69,0</td><td> 59,5</td><td> 44,9</td>
It can be seen that as the level of glycidyl methacrylate was increased, the resulting acid number decreased, indicating that the GMA consumed some of the acid groups in the acrylic polymer stabilizer.
Example 3: Embodiments 36-42
A series of emulsions, shown in Table 12, were prepared using an acid functional monomer to acrylic ratio of 73/27 solids / solids. These systems were prepared using the process outlined in Example 3: Embodiment 5b using Example 2: Embodiment 10 as the acid functional acrylic salt. This acrylic contains hydroxyl functionality that can theoretically co-react with IBMA during cure.
Table 12: Effect of IBMA on Emulsions
<td>Example 3:</td><td>Realization 36</td><td>Realization 37</td><td>Realization 38</td><td>Realization 39</td><td>Realization 40</td><td>Realization 41</td><td>Realization 42</td>
<td>IBMA level</td><td> 0%</td><td> 4%</td><td> 5%</td><td> 6%</td><td> 7%</td><td> 8%</td><td> 42%</td>
<td>Monomers</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Styrene</td><td> 33</td><td> 26</td><td> 26</td><td> 26</td><td> 26</td><td> 26</td><td> 26</td>
<td>BA</td><td> 40</td><td> 45</td><td> 46</td><td> 46</td><td> 46</td><td> 47</td><td> 48</td>
<td>BMA</td><td> 23</td><td> 21</td><td> 19</td><td> 18</td><td> 17</td><td> 15</td><td> 10</td>
<td>GMA</td><td> 4</td><td> 4</td><td> 4</td><td> 4</td><td> 4</td><td> 4</td><td> 4</td>
<td>IBMA<sup>1</sup></td><td> 0</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 12</td>
<td>Solid%</td><td> 31,4%</td><td> 31,6%</td><td> 30,9%</td><td> 30,4%</td><td> 30,4%</td><td> 30,0%</td><td> 29,8%</td>
<td>Viscosity (Ford cup No. 4)</td><td>22 s</td><td>17 s</td><td>18 s</td><td>16 s</td><td>16 s</td><td>16 s</td><td>17 s</td>
<td>Acidity index</td><td> 38,1</td><td> 40,1</td><td> 40,9</td><td> 39,5</td><td> 40,5</td><td> 41,0</td><td> 40,4</td>
<td colspan="8"><sup>1</sup> N-Isobutoxymethyl acrylamide</td>
The lattice structures from Table 12 were tested without further formulation or modification, and the results are shown in Table 13. Each composition was dropped onto Alcoa ALX aluminum at a film weight of 1.1-1, 25 mg / cm<sup>2</sup> (7-8 msi) and cured for 10 seconds to achieve a metal temperature peak of 215 ° C (420 ° F) in a gas fired coil furnace.
ES 2 367 516 T3
Table 13: Beverage Cap Continuities (IBMA Level)
<td>Example 3:</td><td>Realization 36</td><td>Realization 37</td><td>Realization 38</td><td>Realization 39</td><td>Realization 40</td><td>Realization 41</td><td>Realization 42</td>
<td>IBMA level</td><td> 0%</td><td> 4%</td><td> 5%</td><td> 6%</td><td> 7%</td><td> 8%</td><td> 12%</td>
<td>Cover Continuity</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Initial</td><td> 3</td><td> 1,5</td><td> 1,1</td><td> 1,0</td><td> 0,4</td><td> 0,9</td><td> 0,7</td>
<td>After Retort<sup>1</sup></td><td> 19</td><td> 12</td><td> 4,3</td><td> 6,5</td><td> 6,6</td><td> 9,3</td><td> 31</td>
<td colspan="8"><sup>1</sup> 90 minutes at 121 ° C (250 ° F).</td>
The results from Table 13 indicate the optimal level of IBMA in the emulsion monomer composition to be around 5%, when used in conjunction with hydroxyl functionality in the acrylic polymer stabilizer.
Example 4: Embodiments 1-2. Spray Application
The water-based emulsion of Example 3: Embodiment 4 was successfully formulated into a spray-applied coating for the interior of aluminum beer / beverage cans. The product was formulated with or without additional surfactant, as described in Table 14.
Table 14: Spray Coating Compositions Inside Beverage
<td>Example 4:</td><td>Embodiment 1</td><td>Embodiment 2</td>
<td>Composition (parts)</td><td></td><td></td>
<td>Example 3: Embodiment 4</td><td> 62</td><td> 65</td>
<td>Butanol</td><td> 6</td><td> 5</td>
<td>Butyl Cellosolve</td><td> 3</td><td> 0</td>
<td>Amyl alcohol</td><td> 1</td><td> 0</td>
<td>Dowanol GNP '</td><td> 0</td><td> 5</td>
<td>TERGITOL 15-S-7<sup>2</sup></td><td> 0</td><td> 1</td>
<td>Deionized water</td><td> 28</td><td> 24</td>
<td></td><td></td><td></td>
<td>Formulation Solids,%</td><td> 20</td><td> 21</td>
<td>Viscosity, Ford cup # 4</td><td>20 s</td><td>30 s</td>
<td>VOC, kg / 1 - H2O</td><td> 0,358</td><td> 0,358</td>
<td colspan="3"><sup>1</sup> Commercially available from Dow Chemical.<sup>2</sup> Commercially available surfactant from Dow Chemical.</td>
These formulations were sprayed under typical laboratory conditions at a coating weight of 120 milligrams per can (mg / can) to 130 mg / can for the application of beverage interior coatings, and cured at 188 ° C to 199 ° C ( measured at the can dome) for 30 seconds via a gas oven conveyor in typical thermal programs for this application. The film properties shown in Table were achieved.
15.
Table 15: Interior Spray Film Properties
<td>Example 4:</td><td>Embodiment 1</td><td>Embodiment 2</td>
<td>Metal Exhibitions</td><td></td><td></td>
<td>Initial</td><td>2 mA</td><td>3 BA</td>
<td>After fall damage</td><td>2 mA</td><td>7 mA</td>
<td>MEK resistance</td><td> < 2</td><td> < 2</td>
<td>Water Retort<sup>1</sup></td><td></td><td></td>
<td>Superficial color alteration</td><td>None</td><td>None</td>
<td>Accession</td><td>Excellent</td><td>Excellent</td>
<td>Global Extraction<sup>2</sup></td><td>0.25 ppm</td><td>3.8 ppm</td>
<td colspan="3"><sup>1</sup> 90 minutes at 121 ° C (250 ° F).<sup>2</sup> 2 hours at 65.56 ° C (150 ° F) in 90% aqueous ethanol.</td>
ES 2 367 516 T3
The cured films showed excellent strength properties and low overall pull-outs despite the fact that their solvent resistance as determined by MEK rubs is low. The highest overall extraction result for Example 4: Run 2 was determined because the surfactant was present.
Example 4: Embodiments 3-4. Spray Application
The water-based emulsion of Example 3: Embodiment 4 and Example 3: Embodiment 7 were successfully formulated into spray applied coatings for the interior of aluminum beer / beverage cans. The coating compositions are shown in Table 16.
Table 16: Interior Spray Coating Compositions
<td>Example 4</td><td>Embodiment 3</td><td>Embodiment 4</td>
<td>Compositions (parts)</td><td></td><td></td>
<td>Example 3 Embodiment 4</td><td> 62,8</td><td> 0</td>
<td>Example 3 Embodiment 7</td><td> 0</td><td> 62,8</td>
<td>Deionized water</td><td> 22,1</td><td> 22,1</td>
<td>Butanol</td><td> 5,9</td><td> 5,3</td>
<td>Butyl Cellosolve</td><td> 2,9</td><td> 2,9</td>
<td>Amyl alcohol</td><td> 1,3</td><td> 1,3</td>
<td>Secondary butanol</td><td> 0</td><td> 0,5</td>
<td>Deionized water</td><td> 5,0</td><td> 5,1</td>
<td>Dimethyl ethanolamine</td><td>As necessary</td><td>As necessary</td>
<td>Formulation solids</td><td> 20,7%</td><td> 20,4%</td>
<td>Viscosity (Ford cup No. 4)</td><td>20 s</td><td>16 s</td>
These formulations were sprayed under typical laboratory conditions at a coating weight of 120 mg / can to 130 mg / can (340.19 g (12-ounces)) for the application of interior beverage coatings, and cured at 188 ° C to 199 ° C (measured at the can dome) for 30 seconds via a gas oven conveyor on typical thermal programs for this application. The film properties shown in Table 17 were achieved, using a commercial epoxy acrylate coating as a control.
Table 17: Interior Spray Film Properties
<td></td><td>Water based control<sup>1</sup></td><td>Example 4: Embodiment 3</td><td>Example 4: Embodiment 4</td>
<td>Coating weight, mg / can</td><td> 124</td><td> 123</td><td> 121</td>
<td>Metal Exhibitions</td><td></td><td></td><td></td>
<td>Initial</td><td>0.9 mA</td><td>2.2 mA</td><td>0.5 mA</td>
<td>After fall damage</td><td>1.3 mA</td><td>2.9 mA</td><td>1.2 mA</td>
<td>MEK resistance</td><td> 20 -50</td><td> 2 -5</td><td> < 1</td>
<td>Impact on Dome</td><td> 10</td><td> 10</td><td> 10</td>
<td>Isopropanol resistance</td><td> >100</td><td> >100</td><td> 5 - 10</td>
<td>Water Retort<sup>2</sup></td><td></td><td></td><td></td>
<td>Superficial color alteration</td><td> 7</td><td> 10</td><td> 10</td>
<td>Accession</td><td> 10</td><td> 10</td><td> 10</td>
<td>Joy Detergent Trial</td><td></td><td></td><td></td>
<td>Superficial color alteration</td><td> 7</td><td> 10</td><td> 10</td>
<td>Accession</td><td> 10</td><td> 10</td><td> 10</td>
<td>Global withdrawals<sup>3</sup></td><td><0.1 ppm<sup>4</sup></td><td><0.1 ppm<sup>4</sup></td><td><0.1 ppm<sup>4</sup></td>
<td colspan="4">'Commercially available inner beverage can liner from Valspar code 10Q45AF.<sup>2</sup> 90 minutes at 121 ° C (250 ° F).<sup>3</sup> 2 hours at 65.56 ° C (150 ° F) in 90% aqueous ethanol.<sup>4</sup> Below current detection limit.</td>
As can be seen from Table 17, the coatings of the present invention compare favorably to the commercial epoxy acrylate coating, and there is a substantial benefit for retort resistance.
Example 5: Embodiment 1. Beverage Cap Coil Coating
In a jar with a stirrer, 483.25 parts of the emulsion from Example 3: Embodiment 5 was stirred with 16.75 parts
ES 2 367 516 T3 of SLIPAYD 404 wax. The mixture was stirred for 10 minutes to make it uniform. Then the mixture was filtered. The mixture had approximately 31% solids. The mixture was applied at 7-8 milligrams per square inch (msi) (1.1-1.25 mg / cm<sup>2</sup>) on Alcoa ALX aluminum and oven dried for 10 second (s) to achieve a metal temperature peak of 204 ° C (400 ° F) in a coil oven. It was also applied at 7-8 msi (1.1-1.25 5 mg / cm<sup>2</sup>) on Alcoa ALX aluminum and oven dried for 10 seconds to achieve a peak metal temperature of 224 ° C (435 ° F) in a coil oven. Film properties are shown in Table 18.
Table 18: Beverage Cap Film Properties
<td></td><td colspan="4">Water based controls<sup>1</sup></td><td colspan="4">Example 5 Embodiment 1</td>
<td>Oven dried</td><td colspan="2">10 s to get 204 ° C (400 ° F)</td><td colspan="2">10 s to get 224 ° C (435 ° F)</td><td colspan="2">10 s to get 204 ° C (400 ° F)</td><td colspan="2">10 s to get 224 ° C (435 ° F)</td>
<td></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Res. MEK</td><td colspan="2"> 23</td><td colspan="2"> 35</td><td colspan="2"> 4</td><td colspan="2"> 4</td>
<td>Beveled<sup>2</sup></td><td colspan="2"> 0,500</td><td colspan="2"> 0,193</td><td colspan="2"> 0,018</td><td colspan="2"> 0,010</td>
<td>Dowfax<sup>3</sup></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Superficial color alteration</td><td colspan="2"> 4</td><td colspan="2"> 9</td><td colspan="2"> 4</td><td colspan="2"> 9</td>
<td>Accession</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td>
<td>Pasteurization <sup>4</sup></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Superficial color alteration</td><td colspan="2"> 6</td><td colspan="2"> 9</td><td colspan="2"> 5</td><td colspan="2"> 10</td>
<td>Accession</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td>
<td>Water Retort<sup>5</sup></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Superficial color alteration</td><td colspan="2"> 6,5</td><td colspan="2"> 10</td><td colspan="2"> 5,5</td><td colspan="2"> 10</td>
<td>Accession</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td>
<td>Continuities of Top</td><td>Initial</td><td>After</td><td>Initial</td><td>After</td><td>Initial</td><td>After</td><td>Initial</td><td>After</td>
<td>Pasteurization<sup>4</sup></td><td> 0,13</td><td> 0,33</td><td> 0,06</td><td> 0,28</td><td> 2,76</td><td> 21,35</td><td> 1,5</td><td> 17,9</td>
<td>Water Retort<sup>5</sup></td><td> 0,016</td><td> 2,22</td><td> 0,06</td><td> 0,52</td><td> 4,16</td><td> 22,9</td><td> 1,4</td><td> 17,55</td>
<td colspan="9">'' Commercially available beverage cap liner from Valspar code 13Q80AG.<sup>2</sup> Performed after a 45 minute pasteurization at 85 ° C (185 ° F). Measured in centimeters.<sup>3</sup> 15 minutes at 100 ° C (212 ° F).<sup>4</sup> 30 minutes at 85 ° C (185 ° F).<sup>5</sup> 90 minutes at 121 ° C (250 ° F).</td>
Example 5: Embodiments 2-4 Beverage Cap Liners
Using the process of Example 5: Embodiment 1, the formulations shown in Table 19 were prepared to investigate the effect of GMA level on cap continuities. Each formula was applied at 7-8 milligrams per square inch (msi) (1.1-1.25 mg / cm<sup>2</sup>) on Alcoa ALX aluminum and oven dried for 10 seconds to achieve a metal temperature peak of 215 ° C (420 ° F) in a coil oven. Cap continuities are shown in Table 20.
Table 19: Effect of GMA Level
<td>Example 5:</td><td>Embodiment 2</td><td>Embodiment 3</td><td>Embodiment 4</td>
<td>Example 3 Embodiment 5</td><td> 95,7</td><td> 0</td><td> 0</td>
<td>Example 3 Embodiment 34</td><td> 0</td><td> 95,7</td><td> 0</td>
<td>Example 3 Embodiment 35</td><td> 0</td><td> 0</td><td> 95,7</td>
<td>Phenolic <sup>1</sup></td><td> 2,3</td><td> 2,3</td><td> 2,3</td>
<td>SLIPAYD 404</td><td> 1,5</td><td> 1,5</td><td> 1,5</td>
<td>Michem Lube 160 PFE <sup>2</sup></td><td> 0,5</td><td> 0,5</td><td> 0,5</td>
<td>Water / Solvent<sup>3</sup></td><td>Up to 23% Solids</td><td>Up to 23% Solids</td><td> --</td>
<td>Deionized water</td><td> --</td><td> --</td><td>Up to 23% Solids</td>
<td colspan="4"><sup>1</sup> A 50% phenolic phenol-formaldehyde in water, prepared by reacting 2.3 moles of formaldehyde with 1 mole of phenol.<sup>2</sup> Lubricant commercially available from Michelman Inc.<sup>3</sup> 1: 1 mix of deionized water and isopropyl alcohol.</td>
ES 2 367 516 T3
Table 20: Effect of GMA Level on Beverage Cap Performance
<td>Example 5:</td><td>Embodiment 2</td><td>Embodiment 3</td><td>Embodiment 4</td>
<td>GMA level</td><td> 4%</td><td> 12%</td><td> 20%</td>
<td>Cover Continuities</td><td></td><td></td><td></td>
<td>Initial</td><td> 2</td><td> 49</td><td> 149</td>
<td>After Retorta<sup>1</sup></td><td> 21</td><td> 193</td><td> 304</td>
<td colspan="4"><sup>1</sup> 90 minutes at 121 ° C (250 ° F).</td>
As can be seen from the data in Table 20, the lower GMA levels appear to provide better film integrity on manufactured caps, especially after retorting.
Example 5: Embodiment 5 Beverage Cap Coating
Using the process of Example 5: Embodiment 1, the formulation shown in Table 21 was prepared. The formula was applied at 7-8 milligrams per square inch (msi) (1.1-1.25 mg / cm<sup>2</sup>) on Alcoa ALX aluminum and oven dried for 10 seconds to achieve peak metal temperatures of 204 ° C (400 ° F) and 215 ° C (420 ° F) in a coil oven. Film and cap performance properties are shown in Table 22. This material contains 4% GMA and 5% IBMA in the emulsion monomer blend and a hydroxyl functional acrylic composition.
___________________ Table 21: Drink Cap Formulation___________________
<td></td><td>Example 5 Embodiment 5</td>
<td>Composition</td><td></td>
<td>Example 3, Embodiment 38</td><td> 90,80</td>
<td>Dowanol PNP <sup>1</sup></td><td> 2,425</td>
<td>Dowanol DPNB <sup>1</sup></td><td> 2,425</td>
<td>Isooctyl Alcohol</td><td> 1,54</td>
<td>Michem Lube 160 PFE</td><td> 0,57</td>
<td>Lanco Glidd 5118 2</td><td> 2,24</td>
<td>Solids (%)</td><td> 27,5 -29,5</td>
<td>Viscosity (Ford Cup No. 4)</td><td>20 s- 30 s</td>
<td colspan="2">1 Commercially available from Dow Chemical</td>
<td colspan="2">2 Lubricant commercially available from Lubrizol Corp.</td>
Table 22: Film Yield of Beverage Cap Formulation
<td></td><td colspan="4">Water Based Control<sup>1</sup></td><td colspan="4">Example 5 Embodiment 5</td>
<td>Oven dried</td><td colspan="2">10 s to get 204 ° C (400 ° F)</td><td colspan="2">10 s to get 215 ° C (420 ° F)</td><td colspan="2">10 s to get 204 ° C (400 ° F)</td><td colspan="2">10 s to get 215 ° C (420 ° F)</td>
<td>Res. MEK</td><td colspan="2"> 34</td><td colspan="2"> 40</td><td colspan="2"> 10</td><td colspan="2"> 8</td>
<td>Beveled<sup>4</sup></td><td colspan="2"> 0,178</td><td colspan="2"> 0,094</td><td colspan="2"> 0,074</td><td colspan="2"> 0,038</td>
<td>Pencil Hardness</td><td colspan="2">3H - 4H</td><td colspan="2">3H</td><td colspan="2">HB</td><td colspan="2">HB</td>
<td>COF</td><td colspan="2"> 0,068</td><td colspan="2"> 0,076</td><td colspan="2"> 0,068</td><td colspan="2"> 0,075</td>
<td>Pasteurization<sup>2</sup></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Superficial color alteration</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 9</td><td colspan="2"> 10</td>
<td>Accession</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td>
<td>Water Retort<sup>3</sup></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Superficial color alteration</td><td colspan="2"> 9</td><td colspan="2"> 10</td><td colspan="2"> 8</td><td colspan="2"> 9</td>
<td>Accession</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td>
<td>Continuities of<sup>Ta</sup>p<sup>to</sup></td><td>Initial</td><td>After</td><td>Initial</td><td>After</td><td>Initial</td><td>After</td><td>Initial</td><td>After</td>
<td>Pasteurization<sup>2</sup></td><td> 0,0</td><td> 0,1</td><td> 1,1</td><td> 17,6</td><td> 0,5</td><td> 0,7</td><td> 0,5</td><td> 4,3</td>
<td>Water Retort<sup>3</sup></td><td> 0,05</td><td> 0,15</td><td> 1,4</td><td> 11,2</td><td> 0,15</td><td> 0,35</td><td> 0,78</td><td> 10,5</td>
<td colspan="9"><sup>1</sup> Commercially available beverage cap liner from Valspar code 13Q80AG.<sup>2</sup> 30 minutes at 85 ° C (185 ° F).<sup>3</sup> 90 minutes at 121 ° C (250 ° F).<sup>4</sup> Performed after a 45 minute pasteurization at 85 ° C (185 ° F). Measured in centimeters.</td>
ES 2 367 516 T3
The results from Table 22 show that a beverage cap formulation of the present invention can provide similar performance to a commercial epoxy-based aqueous beverage cap coating even with lower solvent resistance as measured by double rubs. MEK. There is also an added benefit of improved chamfer resistance.
Example 6: Latex with Polyester Stabilizer
Example 6 is designed to illustrate the use of a different acid-functional polymer salt as a stabilizer for an emulsion of the present invention.
Stage a
A 2 liter flask was equipped with a stirrer, packed column, Dean Stark trap, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 700.1 parts of dipropylene glycol and 700.1 parts of isophthalic acid were added to the flask. In a protective nitrogen atmosphere, the contents were heated to 125 ° C. At 125 ° C, 1.05 parts of FASCAT 4201 were added. The temperature was increased to remove water. At 210 ° C, the water began to collect. After an acid number of 5.2 was obtained, 37 parts of xylene were added to aid in the removal of water. An acid number of 0.9 was obtained, and a part of the product was used in Stage B.
Stage B
Material from Step A (599.8 parts) was placed in a 2 liter flask. The temperature was adjusted to 112 ° C and 82 parts of trimellitic anhydride were added. The material was heated to 232 ° C, and the water was removed. After an acid number of 48.4 was obtained, a part of the material was used in Step C.
Stage C
The material from Step B (198.8 parts) was added to a 2 liter flask, and 40 parts of DOWANOL PNP was added. The material was adjusted to 74 ° C, and the slow addition of deionized water (200 parts) was started. After about 30 parts of water were added, 7.6 parts of dimethyl ethanolamine were introduced. When there were about 150 parts of the deionized water, the heating was stopped (the temperature was 80 ° C) and 2.4 parts of dimethyl ethanolamine were added. After the full charge of deionized water was completed, the viscosity was visually high and an additional 200 parts of deionized water was added. The material was allowed to cool slowly while more dimethyl ethanolamine was added gradually to increase the pH to 6.6. The resulting product had 29.7% solids with an acid number of 53.9.
Stage D
A 500 milliliter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 93.2 parts of the material from Step C and 179 parts of deionized water were added to the flask. While the contents of the flask were heated to 50 ° C at 240 RPM, 2 drops of HAMP-OL 4.5% Iron and 1.11 parts of erythorbic acid were added. In a separate container a premix of 28.8 parts of styrene, 50.9 of BA, 21.0 parts of BMA, 5.6 parts of BMA, 4.5 parts of GMA and 1.11 parts of TRIgOnOX A-W70 were premixed. Once the flask was at 52 ° C, 10% of the premix was added and held for five minutes. After five minutes, the temperature control was adjusted to 50 ° C and the remaining premix was added over one hour. When the addition was complete, 15.0 parts of deionized water was used to clear the residual premix in the flask. The batch was then held for two hours at temperature, and the batch was cooled. This gave a 34.0% solids emulsion, acid number of 14.5, pH of 5.45, and a viscosity of 11.5 s (Ford Cup Number 4).
Stage E
To 50 parts of the emulsion from Step D, 3.125 parts of a 50/50 mixture of ethylene glycol and butyl cellosolve were added. This material was applied to chrome treated aluminum panels and oven dried for 10 seconds to achieve a peak metal temperature of 217 ° C (420 ° F). Results from the beverage cap test of this example against a commercial control formula are shown in Table 23.
ES 2 367 516 T3
Table 23:
<td></td><td>Water based control<sup>1</sup></td><td>Example 6</td>
<td>MEK resistance</td><td> 22</td><td> 11</td>
<td>Beveled<sup>4</sup></td><td> 0,102</td><td> 0,013</td>
<td>Pasteurization<sup>2</sup></td><td></td><td></td>
<td>Superficial color alteration</td><td> 10</td><td> 9,5</td>
<td>Accession</td><td> 10</td><td> 10</td>
<td>Water Retort<sup>3</sup></td><td></td><td></td>
<td>Superficial color alteration</td><td> 10</td><td> 10</td>
<td>Accession</td><td> 10</td><td> 10</td>
<td>Cover Continuity</td><td></td><td></td>
<td>Initial</td><td> 1,35</td><td> 0,25</td>
<td>Pasteurization2</td><td> 2,38</td><td> 1,35</td>
<td colspan="3"><sup>1</sup> Commercially available beverage cap liner from Valspar code 13Q80AG.<sup>2</sup> 30 minutes at 85 ° C (185 ° F).<sup>3</sup> 90 minutes at 121 ° C (250 ° F).<sup>4</sup> Performed after pasteurization at 85 ° C (185 ° F). Measured in centimeters.</td>
Example 7: Emulsion for Interior Spray
A 3 liter flask was equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. In the flask 392.2 parts of the Functional Acid Acrylic of Example 1: Embodiment 4, 86.4 parts of deionized water, 34.6 parts of DMEA, and 1120.8 parts of deionized water were added. The contents of the flask were heated to 70 ° C. A premix of 215.8 parts of styrene, 302.7 parts of butyl acrylate, and 42.0 parts of glycidyl methacrylate was prepared in a separate container. Once the flask was at 70 ° C, 5.5 parts of benzoin and 27.8 parts of deionized water were added, followed by 10% of the premix. The flask was further heated to 79 ° C and when this temperature was reached 5.5 parts of 35% hydrogen peroxide and 27.8 parts of deionized water were added and held for five minutes. The flask was shaken at 210 rpm. After five minutes the temperature control was adjusted to 81 ° C and the remaining premix was added over one hour. When the addition was complete, 55.9 parts of deionized water was used to clear the residual premix in the flask. The batch was held for ten minutes and then 0.96 parts of benzoin, 55.9 parts of deionized water, and 0.95 parts of 35% hydrogen peroxide were added. The batch was held for 45 minutes and then 0.31 part of benzoin and 0.31 part of 35% hydrogen peroxide were added. After two hours the batch was cooled to 45 ° C. Once at 45 ° C, 0.46 parts of HAMP-OL 4.5% Iron were added 2.98 parts of TRIGONOX A-W70, and a premix of 2.1 parts of erythorbic acid, 0.91 parts of DMEA , and 18.0 parts of deionized water. The batch was kept at 45 ° C for one hour. The material was then cooled to provide a 31.6% solids emulsion, acid number of 67.7, pH of 7.04, and a viscosity of 84 seconds (Ford cup # 4).
Example 8: Spray Application
The water-based emulsion of Example 7 was successfully formulated into a spray-applied coating for the interior of aluminum beer / beverage cans. The product was formulated as described in Table 24.
<td colspan="2">Table 24</td>
<td>Coating Composition p</td><td>> or Spraying Inside Beverage</td>
<td>Composition (parts)</td><td>Example 8</td>
<td>Material of Example 7</td><td> 62,8</td>
<td>Deionized water</td><td> 25,3</td>
<td>Butyl Cellosolve</td><td> 5,1</td>
<td>Amyl alcohol</td><td> 3,1</td>
<td>Butanol</td><td> 0,7</td>
<td>Deionized water</td><td> 3,0</td>
<td></td><td></td>
<td colspan="2">Additional Deionized Water to 18.5% Solids</td>
<td>Formulation Solids,%</td><td> 18,5%</td>
<td>Viscosity, Ford cup # 4</td><td>46 second</td>
ES 2 367 516 T3
This formulation was sprayed under typical laboratory conditions at a coating weight of 120 milligrams per can (mg / can) to 130 mg / can for the application of interior beverage coatings, and cured at 188 ° C to 199 ° C ( measured at the can dome) for 30 seconds via a gas oven conveyor on typical thermal programs for this application. The film properties shown in Table 25 were achieved.
<td colspan="3">Table 25</td>
<td colspan="2">Spraying Film Properties</td><td>> n Interior</td>
<td></td><td>Water based control<sup>1</sup></td><td>Example 8</td>
<td>Metal Exhibitions</td><td></td><td></td>
<td>Initial</td><td>2 mA</td><td>1 mA</td>
<td>After fall damage</td><td>2 mA</td><td>5 mA</td>
<td>Water Retort<sup>2</sup></td><td></td><td></td>
<td>Superficial color alteration</td><td>None</td><td>None</td>
<td>Accession</td><td>Excellent</td><td>Excellent</td>
<td colspan="3"><sup>1</sup> Inner beverage can liner commercially available from Valspar code 10Q45AF.<sup>2</sup> 90 minutes at 121 ° C (250 ° F).</td>
As can be seen from Table 25, the coatings of the present invention compare favorably to the commercial epoxy-acrylate coating.
Example 9: Latex with Polyester-Polyether Stabilizer
Example 9 illustrates the use of a different acid-functional polymer salt as a stabilizer for an emulsion of the present invention.
Stage a
A flask was equipped with a stirrer, packed column, Dean Stark trap, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. To the flask, 809.8 parts of sebacic acid and 1283.0 parts of CHDM-90 (90% 1,4-cyclohexane dimethanol in water) were added. In a protective nitrogen atmosphere, the contents were heated to distill the water from the CHDM-90. While the contents were heated to 165 ° C, 1.96 parts of FASCAT 4100 were added. The temperature was increased to 220 ° C to remove water. A sample from the batch was tested and found to have an acid number of 0.5. The remainder of the batch was weighed, and 1711.7 parts of this material were added 1040.2 parts of para-hydroxy benzoic acid. The batch was heated to 230 ° C to remove water. To aid in the removal of water, xylene was gradually added. After two days of water removal, 1.04 parts of FASCAT 4100 was added to aid reaction. The reaction was held for an additional 5 hours and then considered complete. A part of the product was used in Stage B.
Stage B
The material from Step A (1915.2 parts) was placed in a flask along with 823.8 parts of ERISYS GE-22 (diglycidyl ether of cyclohexanedimethanol, 84.8 parts of methyl isobutyl ketone (and 2.63 parts of Catalyst 1201 (Ethyl triphenyl phosphonium iodide). The temperature was adjusted to 170 ° C and the contents were heated. After three hours at temperature, the epoxy value of the material was 0.003. The batch was adjusted to have 2684, 2 parts of this material in the flask. 145.0 parts of methyl isobutyl ketone and 294.7 parts of succinic anhydride were added to the flask. The temperature was kept at 120-135 ° C for two hours. After holding for two hours, 124.8 parts of deionized water and a premix of 214.2 parts of DMEA with 265.8 parts of deionized water were added. Then 6325.8 parts of deionized water were added. The material was cooled resulting in a product with 26.4% solids, an acid number of 71.9, a pH of 7.7, and a Ford Number 4 viscosity of 15 seconds. This material was used in Stage C.
Stage C
A 5-liter flask is equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. 1183.4 parts of the material from Step B and 779.6 parts of deionized water were added to the flask. A premix of 7.25 parts of erythorbic acid, 6.5 parts of DMEA, and 76.7 parts of deionized water was prepared. This initial premix and 0.18 part of HAMP-OL 4.5% Iron were added to the flask. The contents of the flask were heated to 30 ° C. A monomer premix of 249.0 parts of styrene, 113.8 of BA, 106.7 parts of BMA, 177.8 parts of Hydroxy Ethyl Methacrylate (HEMA), 35.6 parts of IBMA, was prepared in a separate container. and 28.5 parts of GMA. A third premix of 7.25 parts of
ES 2 367 516 T3
TRIGONOX A-W70 and 82.2 parts of deionized water. After all of the premixes were made and the flask was at 30 ° C, the shaker was set at 240 rpm and all of the monomer premix was added. The monomer premix vessel was rinsed with 81.6 parts deionized water, which was also added to the flask. The contents of the flask were stirred for 10 minutes, after which 10% of the third premix was added within one minute. Once 10% of the third premix was in, the temperature was increased to 37 ° C and the batch was held for five minutes. After five minutes, the remaining amount of the third premix was added over 45 minutes. The temperature was allowed to rise with no external heat applied. During the addition the maximum temperature was 57 ° C. After the addition was complete the temperature was 51 ° C. Temperature control was set at 52 ° C. The third premix was rinsed with 108.4 parts deionized water and added to the batch. The batch was held for 1.5 hours and then cooled. This provided a 33.1% solids emulsion, acid number of 27.1, pH of 7.9, and a viscosity of 12 s (Ford Cup Number 4).
Stage D
To 1473.75 parts of the emulsion from Step C, 26.25 parts of DMEOA were added to increase the pH to 8.6. Using 1330.18 parts of this increased pH material, 89.51 parts of ethylene glycol, 16.65 parts of dibasic ester, 16.67 parts of DOWANOL PM, 5.17 parts of xylene, 17.5 parts of a 50% solids solution of a phenolic phenol-formaldehyde, and 24.57 parts of MICHEM 160 PFE. This formulation was determined to have 30.1% solids, Ford Number 4 viscosity of 12 seconds, and 8.75 pounds per gallon (1.05 kg / L).
The Stage D composition was applied to chrome-free aluminum panels and oven dried for 10 seconds to achieve a metal temperature peak of 215 ° C (420 ° F). A second set was oven dried for 10 seconds to achieve a peak metal temperature of 227 ° C (440 ° F). Results from testing the beverage cap of this example against commercial water-based and solvent-based control formulas are shown in Tables 26 and 27.
<td colspan="7">Table 26</td>
<td colspan="7">Comparative Cure Test of Example 9 Stage D at 215 ° C (420 ° F)</td>
<td></td><td colspan="2">Water based control<sup>1</sup></td><td colspan="2">Solvent based control<sup>2</sup></td><td colspan="2">Example 9 Stage D</td>
<td>MEK</td><td colspan="2"> 44</td><td colspan="2"> 34</td><td colspan="2"> 38</td>
<td>Beveled<sup>3</sup></td><td colspan="2"> 0,0457</td><td colspan="2"> 0,0457</td><td colspan="2"> 0,000</td>
<td>COF</td><td colspan="2"> 0,061</td><td colspan="2"> 0,066</td><td colspan="2"> 0,063</td>
<td>Pasteurization<sup>4</sup></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Superficial color alteration</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2">8 to 9<sup>6</sup></td>
<td>Accession</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td>
<td>Water Retort<sup>5</sup></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Superficial color alteration</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2">4 to 10<sup>6</sup></td>
<td>Accession</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"></td>
<td>Cover Continuity</td><td>Initial</td><td>After</td><td>Initial</td><td>After</td><td>Initial</td><td>After</td>
<td>Pasteurization</td><td> 0,08</td><td> 0,12</td><td> 0,0</td><td> 0,30</td><td> 0,0</td><td> 0,5</td>
<td>Retort of Water</td><td> 0,10</td><td> 0,4</td><td> 0,02</td><td> 0,72</td><td> 0,27</td><td> 1,2</td>
<td colspan="7"><sup>1</sup> Commercially available beverage cap liner from Valspar code 13Q80AG.<sup>2</sup> Commercially available beverage cap liner from Valspar code 92X205S.<sup>3</sup> Performed after a 45 minute pasteurization at 85 ° C (185 ° F). Measured in centimeters (cm).<sup>4</sup> 30 minutes at 85 ° C (185 ° F).<sup>5</sup> 90 minutes at 121 ° C (250 ° F).<sup>6</sup> Superficial alteration of initial color observed improving within 5 minutes.</td>
ES 2 367 516 T3
<td colspan="7">Table 27</td>
<td colspan="3">Comparative E Cure Test</td><td colspan="4">Example 9 Stage D at 227 ° C (440 ° F)</td>
<td></td><td colspan="2">Water based control<sup>1</sup></td><td colspan="2">Solvent based control<sup>2</sup></td><td colspan="2">Example 9 Stage D</td>
<td>MEK</td><td colspan="2"> 52</td><td colspan="2"> 37</td><td colspan="2"> 40</td>
<td>Beveled<sup>3</sup></td><td colspan="2"> 0,0559</td><td colspan="2"> 0,0356</td><td colspan="2"> 0,000</td>
<td>COF</td><td colspan="2"> 0,059</td><td colspan="2"> 0,065</td><td colspan="2"> 0,063</td>
<td>Pasteurization<sup>4</sup></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Superficial color alteration</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2">8 to 10<sup>6</sup></td>
<td>Accession</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"> 10</td>
<td>Water Retort<sup>5</sup></td><td colspan="2"></td><td colspan="2"></td><td colspan="2"></td>
<td>Superficial color alteration</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2">6 to 10<sup>6</sup></td>
<td>Accession</td><td colspan="2"> 10</td><td colspan="2"> 10</td><td colspan="2"></td>
<td>Cover Continuity</td><td>Initial</td><td>After</td><td>Initial</td><td>After</td><td>Initial</td><td>After</td>
<td>Pasteurization</td><td> 0,0</td><td> 0,48</td><td> 0,07</td><td> 0,23</td><td> 0,1</td><td> 0,8</td>
<td>Water Retort</td><td> 0,05</td><td> 0,4</td><td> 0,25</td><td> 1,5</td><td> 0,35</td><td> 0,8</td>
<td colspan="7"><sup>1</sup> Commercially available beverage cap liner from Valspar code 13Q80AG.<sup>2</sup> Commercially available beverage cap liner from Valspar code 92X205S.<sup>3</sup> Performed after a 45 minute pasteurization at 85 ° C (185 ° F). Measured in cm.<sup>4</sup> 30 minutes at 85 ° C (185 ° F).<sup>5</sup> 90 minutes at 121 ° C (250 ° F).<sup>6</sup> Superficial alteration of initial color observed improving within 5 minutes.</td>
Example 10
Example 10 illustrates the use of a different acid-functional polymer salt as a stabilizer for an emulsion of the present invention.
Stage 1
Approximately 1055 parts of BPA are placed in a flask along with approximately 1684 parts of liquid epoxy resin (EPON 828), 85 parts of methyl isobutyl ketone, and 2 to 3 parts of Catalyst 1201. The temperature is adjusted to 160 ° C and the contents are then heated for about three hours to achieve a material epoxy value of about 0.003. The batch is then adjusted to have 2684.2 parts of this material in the flask. Added to the flask are 145.0 parts of methyl isobutyl ketone and 294.7 parts of succinic anhydride. The temperature is kept at 120-135 ° C for two hours. After holding for two hours, 124.8 parts of deionized water and a premix of 214.2 parts of DMEA with 265.8 parts of deionized water are added. Then 6325.8 parts of deionized water are added. The material cools, and should result in a product with target solids values of 26% to 27%, an acid number of approximately 72, a pH of approximately 7 to 9, and a Ford Number 4 viscosity of 15 Seconds. This material is used in Stage 2.
Stage 2
A 5-liter flask is equipped with a stirrer, reflux condenser, thermocouple, heating mantle, and a nitrogen blanket. About 1183 parts of the Step 1 material and 780 parts of deionized water are added to the flask. A premix of 7.25 parts of erythorbic acid, 6.5 parts of DMEA, and 77 parts of deionized water is prepared. This initial premix and 0.18 part of HAMP-OL 4.5% Iron are added to the flask. The contents of the flask are heated to 30 ° C. In a separate container a monomer premix of 249 parts of styrene, 114 of BA, 107 parts of BMA, 178 parts of HEMA, 36 parts of IBMA, and 28 parts of GMA is prepared. A third premix of 7.25 parts of tRiGONOX A-W70 and 82.2 parts of deionized water is prepared. Once all of the premixes are prepared and the flask is at 30 ° C, the shaker is set to 240 rpm and all of the monomer premix is added. The monomer premix container is rinsed with 82 parts deionized water, which is also added to the flask. The contents of the flask are stirred for 10 minutes, after which 10% of the third premix is added within one minute. Once there is 10% the temperature is increased to 37 ° C. The batch is kept for five minutes. After five minutes, the remaining amount of the third premix is added over 45 minutes. The temperature is allowed to rise without external heat applied. During the addition the maximum temperature is 57 ° C. After the addition is complete the temperature is adjusted to 52 ° C. The third premix is rinsed with 109 parts deionized water and added to the batch. The batch is kept for 1.5 hours and cooled. This process should provide an emulsion with a goal of
ES 2 367 516 T3 approximately 33% solids, acid number of 27, pH of 8 and a viscosity of 12 s (Ford Cup Number 4).
Stage 3
To 1474 parts of the emulsion from Step 2, 26.25 parts of DMEOA are added to increase the pH to 8.6. Using 1330.18 parts of this increased pH material, add 89.51 parts of ethylene glycol, 16.65 parts of dibasic ester, 16.67 parts of Dowanol PM, 5.17 parts of xylene, 17.5 parts of a 50% solids solution of a phenolic phenol-formaldehyde, and 24.57 parts of Michem 160 PFE. This formulation should provide a composition that is approximately 30% solids.
The Stage 3 composition can be applied to chrome-free aluminum panels and oven dried for 10 seconds to achieve a peak metal temperature of 217 ° C.
Contents21
67 members in 14 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 620639P | United States of America | – | |
| 62063904 | United States of America | P | |
| 62063904 | United States of America | P | |
| US20040620639P | – | – | – |
Members67
| Document | Office | Kind | |
|---|---|---|---|
| US798230A | United States of America | A | |
| US956818A | United States of America | A | |
| AU2005295228A1 | Australia | A1 | |
| CA2579232A1 | Canada | A1 | |
| WO2006045017A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2006100366A1 | United States of America | A1 | |
| MX2007004463A | Mexico | A | |
| NO20071422L | Norway | L | |
| KR20070065879A | Republic of Korea | A | |
| EP1819789A1 | European Patent Office (EPO) | A1 | |
| CN101040016A | China | A | |
| JP2008516769A | Japan | A | |
| BRPI0517414A | Brazil | A | |
| US7592047B2 | United States of America | B2 | |
| US2010075084A1 | United States of America | A1 | |
| US2010178442A1 | United States of America | A1 | |
| US2010183835A1 | United States of America | A1 | |
| WO2011009024A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP1819789B1 | European Patent Office (EPO) | B1 | |
| AT513025T | Austria | T | |
| ATE513025T1 | Austria | T1 | |
| CN101040016B | China | B | |
| ES2367516T3This record | Spain | T3 | |
| PL1819789T3 | Poland | T3 | |
| US8092876B2 | United States of America | B2 | |
| AU2005295228B2 | Australia | B2 | |
| EP2420541A1 | European Patent Office (EPO) | A1 | |
| EP2420542A1 | European Patent Office (EPO) | A1 | |
| US8142868B2 | United States of America | B2 | |
| CN102390590A | China | A | |
| US8173265B2 | United States of America | B2 | |
| AU2012202815A1 | Australia | A1 | |
| JP5027666B2 | Japan | B2 | |
| KR20130003024A | Republic of Korea | A | |
| US2013064938A1 | United States of America | A1 | |
| KR101260526B1 | Republic of Korea | B1 | |
| US2013196037A1 | United States of America | A1 | |
| US8617663B2 | United States of America | B2 | |
| EP2420542B1 | European Patent Office (EPO) | B1 | |
| ES2488391T3 | Spain | T3 | |
| US8835012B2 | United States of America | B2 | |
| AU2012202815B2 | Australia | B2 | |
| US2015030770A1 | United States of America | A1 | |
| CA2579232C | Canada | C | |
| EP2420541B1 | European Patent Office (EPO) | B1 | |
| US9242763B2 | United States of America | B2 | |
| CN102390590B | China | B | |
| ES2565502T3 | Spain | T3 | |
| US2016137348A1 | United States of America | A1 | |
| EP3037488A1 | European Patent Office (EPO) | A1 | |
| US9415900B2 | United States of America | B2 | |
| BRPI0517414B1 | Brazil | B1 | |
| US2017029652A1 | United States of America | A1 | |
| US9862854B2 | United States of America | B2 | |
| US2018258309A1 | United States of America | A1 | |
| EP2420542B2 | European Patent Office (EPO) | B2 | |
| BR122016007793B1 | Brazil | B1 | |
| ES2488391T5 | Spain | T5 | |
| US10336909B2 | United States of America | B2 | |
| US2020032096A1 | United States of America | A1 | |
| EP3733798A1 | European Patent Office (EPO) | A1 | |
| EP3778809A1 | European Patent Office (EPO) | A1 | |
| EP3733798B1 | European Patent Office (EPO) | B1 | |
| EP3037488B1 | European Patent Office (EPO) | B1 | |
| PL3037488T3 | Poland | T3 | |
| EP4119626A1 | European Patent Office (EPO) | A1 | |
| EP3778809B1 | European Patent Office (EPO) | B1 |
Numbers
- Publication
- 2367516
- Publication, DOCDB
- 2367516
- Publication, EPODOC
- ES2367516T
- Application
- 5825629
- Application, DOCDB
- 05825629
- Application, EPODOC
- ES20050825629T
Titles2
- Spanish
- COMPOSICIONES DE RECUBRIMIENTO PARA LATAS Y METODOS DE RECUBRIMIENTO.
- English
- COATING COMPOSITIONS FOR CANS AND COATING METHODS.
Classification
- CPC, 50
- B65D17/00
- C09D123/04
- B65D25/14
- C08F2/22
- C08F265/00
- C08F265/02
- C08F265/04
- C08F265/06
- C08F265/10
- C08F283/006
- C08F283/02
- C08F291/00
- C09D4/06
- C09D151/003
- C09D151/08
- Y10T428/1386
- Y10T428/1393
- Y10T428/139
- Y10T428/1352
- Y10T428/1355
- Y10T428/31678
- Y10T428/31855
- Y10T428/31551
- Y10T428/31681
- Y10T428/31688
- Y10T428/31696
- Y10T428/31699
- Y10T428/31692
- Y10S525/93
- Y10S525/922
- C09D123/00
- B05D1/02
- B05D3/007
- B05D2202/25
- B05D2202/00
- B05D2202/20
- B05D2254/00
- B05D2254/04
- B05D2259/00
- B05D2520/05
- B05D2401/21
- B32B15/04
- B32B15/20
- B32B27/00
- B32B15/06
- C09D133/14
- C23C4/12
- C09D133/068
- B05D7/227
- C08F220/16
- IPC, 3
- C09D151 08
- B65D17 00
- B32B1 00