coated container device and method for making a coated container device

专利摘要:
Coated container device and method for making a coated container device The present invention provides a coated container device, and method for making it. The coated container device according to the present invention comprises (1) a metal substrate; and (2) one or more coating layers associated with the metal substrate, one or more coating layers being derived by applying one or more aqueous dispersions to at least one surface of the metal substrate, and wherein the one or more aqueous dispersion (s) comprises: (a) one or more base polymers; (b) one or more stabilizing agents; (c) optionally one or more neutralizing agents, and (d) water.
公开号:BR112012000451B1
申请号:R112012000451
申请日:2010-07-23
公开日:2019-09-03
发明作者:Kainz Bernhard；Diehl Charles；Malotky David；Mecca Jodi；Drumright Ray；Lundgard Richard
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

COATED CONTAINER DEVICE AND METHOD FOR MAKING A COATED CONTAINER DEVICE
Field of the invention [001] The present invention relates to a coated container device, and a method for doing so.
Background of the invention [002] The application of various pre-treatment and treatment solutions to metals to retard or inhibit corrosion is well established. This is particularly true in the area of metal cans for food and drinks as well as for non-food metal containers. Coatings are applied to the interior of such containers to prevent the contents from contacting the metal in the container. The contact between the metal and the food or drink as well as non-food substances leads to corrosion of the metal container, which can then contaminate the food or drink or the non-food content of such metal containers. Corrosion is particularly problematic when food and beverage products are highly acidic in nature and / or have a high salt content, such as rhubarb-based products or isotonic drinks. Also, high alkaline levels of non-food substances such as hair dyes may react with metal such as aluminum. The coating applied, for example, to the inside of food and beverage cans also helps to prevent corrosion in the upper free space of the cans, which is the area between the food product filling line and the can lid. Coatings can be applied to the outside of metal containers in order to provide protection against the external environment or to provide a decorative layer including fillers and / or
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2/68 pigments. In addition to corrosion protection, coatings for food and beverage cans must be non-toxic and inert, and, if applied to the internal surface, should not adversely affect the taste or appearance, the color of the food or drink in the can or contribute to contamination of the contents of the can. Resistance to popcorn, whitening and / or blistering is also desired
Certain coatings are particularly applicable for application on coiled metal material, such as coiled metal material from which the ends of the cans can be made, “can end material, valve cups, eg upper ends of aerosol cans.
Since coatings designed for use on can end materials are applied to the end material before the ends are cut and stamped from the coiled metal material, they are also typically flexible and / or extensible. For example, the extreme can material is typically coated on both sides. Then, the coated metal material is punctured and may be edged or folded. It can also be scratched for the pop-top opening and the pop-top ring is then connected with a pin that is manufactured separately. The end is then connected to the can body by an edge pressing process. Consequently, the coating applied to the can end material typically has a degree of toughness and flexibility, such that it can withstand extensive manufacturing processes, in addition to some or all of the other desirable features discussed above. Various coatings, such as epoxy-based and
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3/68 poly (vinyl chloride), eg, organosol type, have been used in the past to coat the inside of metal cans to prevent corrosion. However, there is a need for linings for food and beverage cans as well as a liner for non-food containers that provides improved properties such as having resistance to degradation in corrosive media as well as an appropriate level of flexibility.
Summary of the invention [003] The present invention provides a coated container device comprising: (1) a metallic substrate; and (2) one or more coating layers associated with the metallic substrate, one or more coating layers being derived from the application of one or more aqueous dispersions to at least one surface of the metallic substrate, and the (s) one or more aqueous dispersion (s) comprises: (a) one or more base polymers; (b) one or more stabilizing agents;
(c) optionally one or more neutralizing agents, and (d) water.
In an alternative embodiment, the present invention additionally provides a method for making a coated container device comprising the steps of:
(1) select a metallic substrate; and (2) shaping the metal as a container device; (3) selecting one or more aqueous dispersions comprising: (a) one or more base polymers; (b) one or more stabilizing agents; (c) optionally one or more neutralizing agents, and (d) water;
(4) applying one or more aqueous dispersion (s) to at least one surface of the container device; (5) remove at least a portion of the water from the at least one or more
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4/68 aqueous dispersion (s);
(6) thus forming one or more layers of coating associated with at least one surface of the container device;
and (7) thus forming the coated container device.
[005]
In an alternative embodiment, the present invention provides a coated container device, a method for making a coated container device, according to any of the preceding embodiments, except that the metallic substrate is a pre-coated metallic substrate.
In an alternative embodiment, the present invention provides a coated container device, a method for making a coated container device, according to any of the preceding embodiments, except that the at least one or more polymer (s) comprises (m ) one or more polyolefin (s). In an alternative embodiment, the present invention provides a coated container device, a method for making a coated container device, according to any of the preceding embodiments, except that the at least one or more polymer (s) comprises (m ) one or more polyolefin (s) selected from the group consisting of an ethylene-based polymer and a propylene-based polymer.
In an alternative embodiment, the present invention provides a coated container device, a method for making a coated container device, according to any of the preceding embodiments, except that the at least one or more polymer (s) comprises (s) one or more having a crystalline melting point greater than
60 ° C.
In an alternative embodiment, the present
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The invention provides a coated container device, a method for making a coated container device, according to any of the preceding embodiments, except that the at least one or more polymer (s) comprises one or more polyolefin (s) having a crystalline melting point greater than 90 ° C.
[009] In an alternative embodiment, the present invention provides a coated container device, a method for making a coated container device, according to any of the preceding embodiments, except that the at least one or more polymer (s) comprises (m) one or more polyolefin (s) having a crystalline melting point greater than 100 ° C.
[010] In an alternative embodiment, the present invention provides a coated container device, a method for making a coated container device, according to any of the preceding embodiments, except that the at least one or more polymer (s) comprises (m) one or more polyolefin (s) having a crystalline melting point greater than 120 ° C.
[011] In an alternative embodiment, the present invention provides a coated container device, a method for making a coated container device, according to any of the preceding embodiments, except that the at least one or more polymer (s) comprises (one) one or more polyolefin (s) having a crystalline melting point greater than 130 ° C.
Detailed description of the invention [012] The present invention provides a coated container device, and a method for doing so.
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6/68
The coated container device according to the present invention comprises: (1) a metallic substrate;
(2) one or more coating layers associated with metallic substrate, one or more coating layers being derived from the application of one or more aqueous dispersions to at least one surface of the metallic substrate, and the one or more more aqueous dispersion (s) comprises: (a) one or more base polymers; (b) one or more stabilizing agents;
optionally one or more neutralizing agents, and (d) water.
The metallic substrate comprises one or more metals including, but not limited to, aluminum and aluminum alloys, electrolytically tinned cold rolled low carbon (ETP) mild steel, electrolytically coated cold rolled low carbon sweet steel chromium / chromium oxide (ECCS), and any other pre-treated steel.
Pretreatment may include, but is not limited to, treatment with phosphoric acid, zirconium phosphate, chromium phosphate, and the like, as well as silanes for reasons such as primary corrosion protection and improved adhesion.
The metallic substrate may comprise one or more layers, and each layer may have a thickness in the range of 0.01 mm to 2 mm; for example, from
0.01 mm to 1.5 mm;
or alternatively, from 0.01 mm to 1 mm; or alternatively, 0.01
mm to 1.5 mm; or alternatively, in 0, 01 mm to 100 mm; or on alternatively, from 0.01 mm to 50 mm; or at alternative, in 1 mm to 50 mm; or in the alternative, 1 mm The 15 mm. The substrate may be pre coated with one or more compositions of pre-
coating. Such pre-coating compositions may optionally additionally include, but are not
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7/68 limited to, one or more resin binders, one or more resin crosslinkers, one or more solvents, one or more additives, and one or more pigments. Exemplary resin binders include, but are not limited to, epoxy resin, polyester, organosols containing poly (vinyl chloride) / vinyls, alkyds, oleoresins, acrylic resin, and the like. Exemplary crosslinkers include, but are not limited to, phenol-formaldehyde resins; amino-formaldehyde resins including, but not limited to urea-formaldehyde, melamine-formaldehyde, benzoguanamine formaldehyde, anhydride resins, blocked isocyanate resins, and resins containing epoxy groups, including, but not limited to, epoxy resins, polyesters containing epoxy groups, acrylic resins, vinyl resins, or the like. Exemplary solvents and tiners include, but are not limited to, glycol ethers, alcohols, aromatics, e.g., aromatic hydrocarbons, turpentine, branched ketones, and esters. Exemplary additives include, but are not limited to, catalysts, lubricants, wetting agents, defoamers, flow agents, release agents, glidants, anti-blocking agents, sulfur stain masking additives, pigment wetting / dispersing agents, agents anti-deposition, UV stabilizers, adhesion promoters. Pigments include, but are not limited to, titanium dioxide, zinc oxide, aluminum oxide, zinc oxide and aluminum. The substrate may also be pre-coated with one or more pre-coated laminate compositions. Such compositions may include, for example, compositions of polyethylene, polypropylene, or polyester, and may be applied or as
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8/68 a film by a film lamination process or a coating extrusion melting process on the metal surface.
[015] The one or more coating layer (s) is (are) derived from the application of one or more aqueous dispersions to at least one surface of the metallic substrate. The one or more coating layer (s) comprises the mixture product by melting one or more base polymers in the presence of water and optionally one or more neutralizing agents under controlled pressure and temperature conditions.
Base Polymer [016] The aqueous dispersion comprises from 1 to 99 weight percent of one or more base polymers, based on the total weight of the solid content of the aqueous dispersion. All individual values and sub-ranges from 1 to 99 weight percent are included here and disclosed here; for example, the weight percentage may be from a lower limit of 1, 5, 8, 10, 15, 20, 25 weight percent up to an upper limit of 40, 50, 60, 70, 80, 90, 95 or 99 percent by weight. For example, the aqueous dispersion may comprise 15 to 99, or 15 to 90, or 15 to 80, or 15 to 75, or 30 to 70, or 35 to 65 weight percent of one or more base polymers , based on the total weight of solid content of the aqueous dispersion. The aqueous dispersion comprises at least one or more base polymers.
[017] The base polymer may, for example, be selected from the group consisting of a thermoplastic material, and a thermoset material. The one or more polymer (s) may (s) comprise one or more olefin-based polymers, one or more polymers based on
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9/68 acrylic, one or more polymers based on polyester, one or more polymers based on epoxy, one or more polymers of thermoplastic polyurethane, one or more polymers based on vinyl, one or more polyamides, or combinations thereof.
[018] Examples of polyolefins include, but are not limited to, homopolymers and copolymers (including elastomers) of one or more alpha-olefins such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl- 1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene, and 1-dodecene, as typically represented by polyethylene, polypropylene, poly-1-butene, poly-3-methyl -1butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-1-butene copolymer, and propylene-1-butene copolymer;
copolymers including alpha-olefin (elastomers) with a conjugated or unconjugated diene, as typically represented by ethylene-butadiene copolymer and norbornene ethylene ethylidene copolymer; and polyolefins (including elastomers), such as copolymers of two or more alpha-olefins with a conjugated or unconjugated diene, as typically represented by ethylene-propylene-butadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene copolymer -1,5-hexadiene, and ethylenepropylene-ethylidene norbornene copolymer, copolymers of ethylene-vinyl compound, such as ethylene-vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene vinyl chloride copolymer, ethylene acrylic acid copolymers or ethylene-(meth) acrylic acid, and ethylene- (meth) acrylate copolymer.
[019] In certain embodiments, one or more of the polymers
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10/68 based on polyolefin may be functionalized polyolefins, such as polypropylene or polyethylene homopolymer or copolymer where the polymer has been modified with hydroxyl group, amine, aldehyde, epoxide, ethoxylate, carboxylic acid, ester, or anhydride. These functionalized polyolefins, such as polypropylene or polyethylene homopolymers are commercially available, for example, from Baker Petrolite, a subsidiary of Baker Hughes, Inc.
[020] Exemplary polyolefins include, but are not limited to, one or more homopolymers or copolymers of one or more alpha-olefins such as ethylene, propylene, 1 butene, 3-methyl-1-butene, 4-methyl-1-pentene , 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene, and 1dodecene, as typically represented by polyethylene, polypropylene, poly-1-butene, poly-3-methyl-1-butene, poly-3 methyl-1-pentene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-1-butene copolymer, and propylene-1-butene copolymer. Such exemplary polyolefins may have a molecular weight greater than 800 grams / mol; for example, greater than 5,000 grams / mol; or, alternatively, greater than 50,000 grams / mol.
[021] In one embodiment, the one or more polyolefin (s) has (have) a crystalline melting point greater than 60 ° C; for example, greater than 95 ° C; or, in the alternative, greater than 120 ° C, or, in the alternative, greater than 100 ° C, or, in the alternative, greater than 130 ° C.
[022] In one embodiment, at least one of one or more base polymers comprises a thermoplastic polar polyolefin polymer, having a polar group or as a comonomer or
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11/68 as grafted monomer. Exemplary polar polyolefins include, but are not limited to, polyethylene homopolymer or copolymer grafted with maleic anhydride; polypropylene homopolymer or copolymer grafted with maleic anhydride; copolymers of ethylene-acrylic acid (EAA) and ethylene-methacrylic acid, such as those commercially available under the trade names PRIMACOR ^mr , commercially available from The Dow Chemical Company, NUCREL ^MR , commercially available from EI DuPont de Nemours, and ESCOR ^mr , commercially available from ExxonMobil Chemical Company and described in US patents ^Nos 4,599,392, 4,988,781, and 5,938,937, each of which is incorporated herein by reference to describe where such polar polyolefins. Other exemplary polar polyolefins include, but are not limited to, ethylene ethyl acrylate (EEA) copolymer, ethylene methyl methacrylate (EMMA), and ethylene butyl acrylate (EBA).
[023] In one embodiment, the polar polyolefin polymer is an ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer, which can be neutralized with one or more neutralizing agents, e.g., a base such such as an alkali metal hydroxide, ammonia, or an organic amine, in the dispersion process.
[024] The thermoplastic material may comprise non-polyolefinic thermoplastic materials. Such non-polyolefin thermoplastic materials include polymers such as polystyrene, styrenic copolymers (including elastomers), ABS, acrylonitrile-styrene copolymer, a-methylstyrene-styrene copolymer, styrene alcohol
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12/68 vinyl, styrene acrylates, such as styrene methacrylate, styrene butyl acrylate, styrene butyl methacrylate, and styrene butadiene and cross-linked styrene polymers; and styrene block copolymers (including elastomers) such as styrene-butadiene copolymer and hydrate thereof, and styrene-isoprene-styrene triblock copolymer; polyvinyl compound such as poly (vinyl chloride) poly (vinylidene chloride); copolymer of vinyl chloride, vinylidene chloride, copolymers of vinyl chloride with vinyl acetate, vinyl alcohol, maleic acid anhydride, hydroxyalkyl acrylate, glycidyl methacrylate and the like, polymethyl acrylate and polymethyl methacrylate; polyamides such as nylon 6, nylon 6.6, and nylon 12; thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate and the like; epoxy resins such as polyhydroxy ethers, polyhydroxyamino ethers and polyhydroxy esters and the like, for example polyhydroxyether such as the reaction product of bisphenol A glycidyl ether with bisphenol A or the like, for example, polyhydroxyaminoethers as the digidyl reaction product with isophthalic acid or terephthalic acid and the like; polycarbonate, polyphenylene oxide, and the like; and glassy hydrocarbon-based resins, including polydicyclopentadiene polymers and related polymers (copolymers, terpolymers); esters of acids saturated with monoolefin alcohols such as vinyl acetate, vinyl propionate, vinyl versatate, and vinyl butyrate and the like; vinyl esters, such as esters of unsaturated monocarboxylic acids, including methyl acrylate, ethyl acrylate,
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13/68 n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, glycidyl methacrylate, dodecyl acrylate, n-octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate; acriolonitrile, methacrylonitrile, acrylamide, mixtures thereof; resins produced by polymerization of metathesis and cross metathesis of ring opening and the like. These resins can be used alone or in combinations of two or more.
[025] Exemplary (Met) acrylates, as base polymers, include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, acrylic acrylate
2-ethylhexyl, octyl acrylate isooctyl acrylate, n-decyl acrylate, isodecyl acrylate, tert-butyl acrylate, methyl methacrylate, butyl methacrylate, hexyl methacrylate, isobutyl methacrylate, as well as isopropyl methacrylate as well as isopropylate 2-hydroxyethyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, and acrylamide. Preferred (meth) acrylates include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, methyl methacrylate and butyl methacrylate, butyl methacrylate
2-hydroxyethyl, 2-hydroxypropyl methacrylate, acrylamide. Other suitable (meth) acrylates that may be polymerized from monomers include lower alkyl acrylates and methacrylates including acrylic and methacrylic esters monomers: methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, acrylate of 2Petition 870190008010, of 01/24/2019, p. 18/77
14/68 ethylhexyl, decyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, nbutyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, cyclohexyl methacrylate, sec-butyl methacrylate isodecyl, isobornyl methacrylate, t-butylamonoethyl methacrylate, stearyl methacrylate, glycidyl methacrylate, dicyclopentyl methacrylate, phenyl methacrylate.
In selected embodiments, the base polymer may, for example, comprise one or more polyolefins selected from the group consisting of ethylene alpha olefin copolymers, propylene alpha olefin copolymers, and olefin block copolymers.
In particular, in some embodiments, the base polymer may comprise one or more non-polar polyolefins.
In certain specific embodiments, polyolefins, such as polypropylene, polyethylene, copolymers thereof, mixtures thereof, as well as ethylene-propylene diene terpolymers, may be used. In some embodiments, exemplary olefinic polymers include homogeneous polymers, as described, for example, in the U.S. patent.
No. 3,645,992: high density polyethylene (HDPE), as described, for example, in US Patent
_n the heterogeneously branched linear low density polyethylene (LLDPE);
heterogeneously branched linear ultra low density polyethylene (PEUBD);
substantially linear, homogeneously branched ethylene / alpha-olefin copolymers, which can be prepared, for example, by processes disclosed in U.S. Patent Nos.
5,272,236 and 5,278,272, the disclosures of
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15/68 which are incorporated herein by reference; and homogeneously branched free radical polymerized ethylene polymers and copolymers, such as low density polyethylene (LDPE) or ethylene vinyl acetate (EVA) polymers.
[028] In other particular embodiments, the base polymer may, for example, be polymers based on vinyl acetate (EVA). In other embodiments, the base polymer may, for example, be polymers based on ethylene methylacrylate (EMA). In other particular embodiments, the ethylene alpha-olefin copolymer may, for example, be copolymers or interpolymers of ethylenebutene, ethylene-hexene, ethylene-octene. In other particular embodiments, the propylene / alphaolefin copolymer may, for example, be a propylene-ethylene-butene copolymer or interpolymer.
[029] In a particular embodiment, the base polymer may be a propylene / alpha-olefin copolymer, which is characterized as having substantially isotactic propylene sequences. Substantially isotactic propylene sequences means that the sequences have an isotactic triad (mm) measured by C ¹³ NMR of more than about 0.85; in the alternative, more than about 0.90; in another alternative, more than about 0.92; and alternatively, more than about 0.93. Isotáticas triads are well known in the art and are described, for example, in U.S. Patent No. 5,504,172 and International Publication No. WO 00/01745, which refers to the isotactic sequence in terms of a triad unit in the copolymer molecular chain determined by C ¹³ NMR spectra.
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16/68
The propylene / alpha-olefin copolymer may have a crystallinity in the range of at least 1 weight percent (a melting heat of at least 2 Joules / gram) to weight percent (a melting heat of less than
Joules / gram).
All individual sub-ranges of 1 weight percent (a heat of fusion of at least
Joules / gram) weight percent (a heat of fusion of less than 50
Joules / gram) will be included here disclosed here;
for example, the crystallinity may be from a lower limit of 1 weight percent (a heat of fusion of at least 2 Joules / gram), 2.5 weight percent (a heat of melting of at least 4 Joules / gram ), or 3 weight percent (a heat of fusion of at least 5 Joules / gram) up to an upper limit of 30 weight percent (a heat of fusion of less than 50 Joules / gram), 24 weight percent (a melting heat of less than 40 Joules / gram), 15 percent by weight (a melting heat of less than 24.8 Joules / gram), or 7 percent by weight (a melting heat of less than 11 Joules / gram). For example, the propylene / alphaolefin copolymer may have a crystallinity in the range of at least 1 weight percent (a melting heat of at least 2 Joules / gram) to 24 weight percent (a melting heat of less than 40 Joules / gram); or, alternatively, the propylene / alpha-olefin copolymer may have a crystallinity in the range of at least 1 weight percent (a melting heat of at least 2 Joules / gram) to 15 weight percent (a heat of fusion of less than 24.8 Joules / gram); or, alternatively, the propylene / alpha-olefin copolymer may have a crystallinity in the range of at least 1 weight percent (a heat of fusion of at least 2 Joules / gram) to 7 weight percent.
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17/68 weight (a heat of fusion of less than 11 Joules / gram); or, alternatively, the propylene / alpha-olefin copolymer may have a crystallinity in the range of at least 1 weight percent (a heat of fusion of at least 2 Joules / gram) to 5 weight percent (a heat of less than 8.3 Joules / gram). Crystallinity is measured by the differential scanning calorimetry (DSC) method. The propylene / alpha-olefin copolymer comprises units derived from one or more alpha-olefin comonomers. Exemplary comonomers used to manufacture the propylene / alpha-olefin copolymer are C ₂ and C ₄ to C ₁₀ alpha-olefins; for example, C2, C4, C6 and C8 alpha olefins. The propylene / alpha-olefin copolymer comprises from 1 to 40 weight percent of units derived from one or more alphaolefin comonomers. All values and sub-ranges from 1 to 40 weight percent will be included here and disclosed here; for example, the weight percentage of units derived from one or more alpha-olefin comonomers may be from a lower limit of 1, 3, 4, 5, 7, or 9 weight percent to an upper limit of 40, 353 , 30, 27, 20, 15, 12, or 9 weight percent. For example, the propylene / alphaolefin copolymer comprises from 1 to 35 weight percent units derived from one or more alpha-olefin comonomers; or, alternatively, the propylene / alpha-olefin copolymer comprises from 1 to 30 weight percent units derived from one or more alpha-olefin comonomers; or, alternatively, the propylene / alpha-olefin copolymer comprises from 3 to 27 weight percent units derived from one or more alpha-olefin comonomers; or, alternatively, the propylene / alpha-olefin copolymer
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18/68 comprises 3 to 20 weight percent of units derived from one or more alpha-olefin comonomers; or, alternatively, the propylene / alpha-olefin copolymer comprises from 3 to 15 weight percent units derived from one or more alpha-olefin comonomers.
[031] The ethylene / alpha-olefin copolymer has a molecular weight distribution (MWD), defined as the weight average molecular weight divided by the numerical average molecular weight (Mw / Mn), of 3.5 or less; in the alternative, 3.0 or less; or in another alternative, from 1.8 to 3.0. Such ethylene / alpha-olefin copolymers are further described in details in US Patents ^Nos 6,960,635 and 6,525,157, incorporated herein by reference. Such propylene / alpha-olefin copolymers are commercially available from The Dow Chemical Company, under the trade name VERSIFY ^mr , or from ExxonMobil Chemical Company, under the trade name VISTAMAXX ^mr .
[032] In one embodiment, the propylene / alpha-olefin copolymers are further characterized by comprising (A) between 60 and less than 100, preferably between 80 and 99, and more preferably between 85 and 99, weight percent of units derived from propylene, and (B) between more than zero and 40, preferably between 1 and 20, more preferably between 4 and 16 and even more preferably between 4 and 15, weight percent of units derived from at least one ethylene and / or a C _4-10 a-olefin; and containing an average of at least 0.001, preferably an average of at least 0.005, and more preferably an average of at least 0.01, long chain branches / 1000 total carbons, the term long chain branch as used
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19/68 here, refers to a chain length of at least one (1) carbon more than a short chain branch, and short chain branch, as used here, refers to a chain length of two ( 2) carbons less than the number of carbons in the comonomer. For example, a propylene / 1-octene interpolymer has main chains with long chain branches of at least seven (7) carbons in length, but these main chains also have short chain branches of only six (6) carbons in length. The maximum number of long chain branches typically does not exceed 3 long chain branches / 1000 total carbons. Such propylene / alpha-olefin are also further described in detail in US provisional patent application No. 60 / 988,999 and International Patent Application No. PCT / US08 / 082599, each of which is incorporated herein by reference.
[033] In other selected embodiments, olefin block copolymers, e.g., copolymer of ethylene multi-block, such as those described in International Publication No. WO2005 / 090427 and patent application US Publication No. US 2006 / 0199930, incorporated herein by reference to the extent that they describe such block copolymers, may be used as the base polymer. Such an olefin block copolymer may be an ethylene / aolefin interpolymer. Such an olefin block copolymer may be an ethylene / a-olefin interpolymer:
(a) having an Mw / Mn of about 1.7 to about 3.5, and at least one melting point, Tm, in degrees Celsius, and a density, d, in grams per cubic centimeter, with the numerical values of Tm and d correspond to the relationship:
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20/68
T _m > -2002.9 + 4538.5 (d) - 2422.2 (d) ² or (b) having an M _w / M _n of about 1.7 to about 3.5, and being defined by a heat of fusion, Dh, in J / g, and a delta amount, Dt, in degrees Celsius, defined as the temperature difference between the highest DSC peak and the highest CRYSTAF peak, with the numerical values of ΔΤ and Dh have the following relationships:
DT> -0.1299 (DH) + 62.81 for Dh greater than zero up to 130 J / g,
ΔΤ> 48 ° C for Dh greater than 130 J / g, the peak of CRYSTAF being determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the cumulative polymer has an identifiable peak, then the temperature CRYSTAF is 30 ° C; or (c) being characterized by an elastic recovery, Re, in percentage to 300 percent of elastic deformation and a cycle measured with a film molded by compression of the ethylene / a-olefin interpolymer, and a density d, in grams per centimeter cubic, with the numerical values of Re ed satisfying the following relationship, when the ethylene / α-olefin interpolymer is substantially free of the cross-linked phase:
Re> 1481 - 1269 (d) or (d) having a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, the fraction typically having a comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer eluting between the same temperatures, the comparable random ethylene interpolymer having the same comonomer (s) and melting index, density, and molar comonomer content (based on the entire polymer) within
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21/68 percent of that of the ethylene / a-olefin interpolymer; or (e) having a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° CG' (100 ° C), the ratio of G '(25 ° C) for G '(100 ° C) it is from 1: 1 to 9: 1.
[034] Such an olefin block copolymer, eg ethylene / a-olefin interpolymer may also:
(a) have a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, defined by the fraction having a block index of at least 0.5 and up to about 1 and a molecular weight distribution, Mw / Mn, greater than about 1.3; or (b) have an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw / Mn, greater than about 1.3.
[035] In certain embodiments, the base polymer may, for example, comprise a polar polymer, having a polar group either as a comonomer or as a grafted monomer. Exemplary polar polyolefins include, but are not limited to, ethylene-acrylic acid (EAA) and ethylene-methacrylic acid copolymers, such as those commercially available under the trade name PRIMACOR ^mr , commercially available from The Dow Chemical Company, NUCREL ^mr , commercially available from EI DuPont de Nemours, and ESCOR ^mr, commercially available from ExxonMobil Chemical Company and described in US patents ^Nos 4,599,392, 4,988,781, and 5,938,437, each of which is herein incorporated by reference. Other exemplary base polymers include, but are not limited to, ethylene ethyl acrylate (EEA) copolymer, ethylene
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22/68 methyl methacrylate (EMMA), and ethylene butyl acrylate (EBA).
Another ethylene-carboxylic acid copolymer may also be used. The one or more base polymer (s) could also be derived by chemical modification of the acid functional group in the one or more polar polymer (s) to form hydroxyl ester groups or an amide and the like.
Those of ordinary skill in the art will recognize that a number of other useful polymers can also be used. Another base polymer may include copolymers such as ethylene vinyl alcohol and ethylene vinyl acetate and the like.
[037]
In one embodiment, the base polymer may, for example, comprise a polar polyolefin selected from the group consisting of ethylene acrylic acid copolymer (EAA), ethylene methacrylic acid copolymer, and combinations of these the stabilizing agent may, for example, comprise a polyolefin. polar selected from the group consisting of ethylene acrylic acid copolymer (EAA), ethylene methacrylic acid copolymer, and combinations of these, however, with the proviso that that base polymer may, for example, have a lower acid number, measured according to ASTM
D-974, which the stabilizing agent.
In certain embodiments, the base polymer may, for example, comprise a polyester resin. Polyester resin refers to thermoplastic and thermosetting resins that may include polymers containing at least one ester bond. These may have hydroxyl functionality or carboxyl functionality. For example, polyester can be prepared by a conventional esterification process
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23/68 using a molar excess of diol or aliphatic glycol with respect to a polycarboxylic acid or anhydride thereof. Triols or polyols can also be used to provide branched polyesters. Illustrative of glycols, triols and polyols that may be employed to prepare the polyesters include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, and higher polyethylene glycols, propylene glycol, dipropylene glycol, tripropylene glycol, and higher propylene glycols , 1,3-propanediol, 1,4-butanediol, and other butanedioles, 1,5-pentanediol, and other pentane diols, hexanedioles, decanedioles, and dodecanediol, glycerol, trimethylolpropane, trimethylole-tano, neopentyl glycol, pentaeritritol, cyclohexanime, cyclohexanime a polyethylene or polypropylene glycol having a molecular weight of about
500 or less, isopropylidene bis (p-phenylene-oxypropanol-2), and mixtures thereof. In some embodiments, the aliphatic glycol may contain from 2 to about 8 carbon atoms. [039] Illustrative of polycarboxylic acids or anhydrides that may be used to prepare the polyesters include, but are not limited to, maleic acid, maleic anhydride, malonic acid, fumaric acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, acid 2-methyl1,6-hexanoic acid, pyelic acid, submeric acid, dodecanedioic acid, phthalic acid, phthalic anhydride, 5-ter-butyl isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, endomethylhydrohydric acid, hydrofluorohydride, hydrochloric acid, hydrofluorohydride tetrachlorophthalic, hydrochloric acid, isophthalic acid, trimellitic anhydride, terephthalic acid, naphthalene dicarboxylic acid, acid
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24/68 dicarboxylic cyclohexane, and mixtures thereof. In some embodiments, alkanedioic acids may contain 4 to 12 carbon atoms. It is also understood that an esterifiable derivative of a polycarboxylic acid, such as a dimethyl ester or anhydride of a polycarboxylic acid, can be used to prepare the polyester.
[040] Other embodiments of the present invention use polyester resins containing aliphatic diols such as UNOXOL ^mr (a mixture of cis and trans 1,3- and 1,4cyclohexanedimethanol, commercially available from The Dow Chemical Company (Midland, MI)).
[041] In certain embodiments, the base polymer may, for example, comprise a thermoset material comprising an epoxy resin. Epoxy resin refers to a composition that has one or more vicinal epoxy groups per molecule, i.e., at least one 1,2-epoxy group per molecule. In general, such a compound is an aliphatic, cycloaliphatic, aromatic or heterocyclic saturated or unsaturated compound, which have at least one 1,2-epoxy group. Such a compound may be substituted, if desired, with one or more non-interfering substituents, such as halogen atoms, hydroxy groups, ether radicals, lower alkyl and the like. Also a substance containing one or more epoxies can be combined to make the desired epoxy resin.
[042] Illustrative epoxies are described in the Handbook of Epoxy Resins by Lee and K. Neville HE, published in 1967 by McGraw-Hill, New York, New York and U.S. Patent No. 4,066,628, incorporated herein by reference.
[043] Particularly useful compounds that can be used in the practice of the present invention are epoxy resins
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25/68 using the following formula:
where n has an average value of 0 or more.
[044] Epoxy resins useful in the present invention may include, for example, glycidyl polyethers of polyhydric phenols and polyhydric alcohols. As an illustration of the present invention, examples of known epoxy resins that could be used in the present invention include, for example, the diglycidyl ethers of resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (1,1-bis (4- hydroxylphenyl) -1phenyl ethane), bisphenol F, bisphenol K, Bisphenol S, tetrabromobisphenol A, phenol-formaldehyde resins novolaca, phenol-formaldehyde-substituted alkyl resins, phenol-hydroxybenzaldehyde resins, phenydropentiol-hydroxybenzal resins. , dicyclopentadiene-substituted phenol resins, tetramethylbiphenol, tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol, tetrachlorobisphenol A and any combination thereof.
[045] Examples of diepoxies particularly useful in the present invention include 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether (generally referred to as bisphenol A) and 2,2-bis (3,5-dibromo-4-hydroxyphenyl diglycidyl ether) ) propane (generally referred to as tetrabromobisphenol A). Mixtures of any two or more polyepoxides may also be used in the practice of the present invention.
[046] Other Exemplary diepoxides include the diglycidyl ethers of dihydric phenols, such as those described in ^the patents US No 5,246,751; 5,115,075; 5,089,588; 4,480,082; and 4,438,254, all of which are incorporated herein by reference, or the diglycidyl esters of
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26/68 dicarboxylic acids such as those described in ^the US patent 5.171.8209 n. Other exemplary diepoxides include, for example, epoxy resins based on awdiglycidyloxyisopropylidene-bisphenol (commercially available as DER ^® series epoxy resins
300 and
600, products of The Dow Chemical Company, Midland Michigan).
Epoxy resins that may be used in the practice of the present invention also include epoxy resins prepared either by reacting diglycidyl ethers of dihydric phenols with dihydric phenols or by reacting dihydric phenols with epichlorohydrin (also known as "taffy resins).
Exemplary epoxy resins include, for example, bisphenol A diglycidyl;
4.4'sulfonyldiphenol; 4,4-oxyphenol;
4,4'-dihydroxybenzophenone;
resorcinol;
hydroquinone;
catechol;
hydroxyphenyl) fluorene;
4,4'-dihydroxybiphenyl or 4,4 'dihydroxy-a-methylstilbene and the diglycidyl esters of dicarboxylic acids.
[049] Other useful epoxy compounds include aliphatic epoxides such as diglycidyl polypropylene glycol ether, diglycidyl dipropylene glycol ether, diglycidyl ether of 1,4-butanediol, diglycidyl ether of neopentylglycol, diglycidyl ether of 1,6-hexanediol, diglycidyl ether cyclohexanedimethanol, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether or the like.
[050] Other useful epoxide compounds include cycloaliphatic epoxides. A cycloaliphatic epoxide consists of a saturated carbon ring having an epoxy oxygen attached to two vicinal atoms in the carbon ring as illustrated, for example.
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27/68 example, by the following general formula:
where R is a hydrocarbon group optionally comprising one or more heteroatoms (such as, without limitation to them, Cl, Br, and S), or an atom or group of atoms forming a stable bond with carbon (such as, without limitation to them) , Si, P and B) and where n is greater than or equal to 1.
[051] The cycloaliphatic epoxide may be a monopoxide, a diepoxide, polyepoxide, or a mixture thereof. For example, any of the cycloaliphatic epoxide described in U.S. Patent No. 3,686,359, incorporated herein by reference, may be used in the present invention. As an illustration, cycloaliphatic epoxides that may be used in the present invention include, for example, (3,4-epoxycyclohexyl-methyl) -3,4-epoxy-cyclohexane carboxylate, bis- (3,4-epoxycyclohexyl) adipate, vinylcyclohexene monoxide and mixtures thereof.
[052] In certain embodiments, the base polymer may, for example, comprise a thermoset material comprising a modified epoxy resin that has been generated by co-reacting one or more of the aforementioned epoxy resins with a dioic acid such as, but not limited to , adipic acid, 2methyl-1,6-hexanoic acid, pyelic acid, submeric acid, dodecanoic acids, phthalic acid, 5-ter-butyl isophthalic acid, hexahydrophthalic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, naphthalene acid dicarboxylic acid, cyclohexane-dicarboxylic acid, and mixtures thereof.
[053] In certain embodiments, the base polymer may, for example, comprise a thermoset material comprising a modified epoxy resin. Modifications could be caused by reaction of the terminal epoxy groups of the resin
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28/68 epoxy with a nucleophilic group containing a substance such as a carboxylic group, phenolic hydroxyl, alkyl or glycolic hydroxyl, thiol, amine group or the like. It may also be the reaction product of the aforementioned epoxy group with an acid such as phosphoric acid, hydrogen chloride, hydrogen bromide, or the like. It may also be the reaction product of the aforementioned epoxy group with water or a phenolic compound, such as bisphenol-A. It may also be the reaction product of the epoxy group mentioned above with a polyester resin with acid functionality.
[054] In certain embodiments, the base polymer may, for example, comprise a thermoplastic or thermoset polyurethane polymer. Such polyurethane polymers are generally known and further described, for example, in international publication 2008/057878, incorporated herein by reference to ^the extent that it describes a thermoplastic polyurethane polymer.
[055]
Those of ordinary skill in the art will recognize that the above list is a non-comprehensive listing of exemplary base polymers.
It will be appreciated that the scope of the present invention is restricted to the claims only.
[056]
In certain embodiments, the base polymer comprises a thermoplastic polyamide.
Such polyamide polymers are generally known, for example, nylon 66, nylon 6, nylon 610, and nylon 11, nylon and the like.
Stabilizing Agent [057] The aqueous dispersion may additionally comprise at least one or more stabilizing agents for
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29/68 promote the formation of a stable dispersion.
The dispersion of the present invention comprises 1 to 50 weight percent of one or more stabilizing agents based on the total weight of the solid content of the dispersion. All individual sub-ranges from 1 to 45 weight percent will be included here and disclosed here; for example, weight percentage may be from a lower limit of 1
3,
5, 10 weight percent up to an upper limit of 15,
25,
35,
45, or 50 percent weight. For example, the dispersion may or, in the alternative of a 35;
or, in or, in the alternative of a 45 to comprise percent by weight of alternative,
in 1 to 25; in 1 to 40; one or more
stabilizing agents based on the total weight of the solid content of the dispersion. In selected embodiments, the stabilizing agent may be a surfactant, a polymer, or mixtures thereof. In certain embodiments, the stabilizing agent may be a polar polymer, having a polar group or as a comonomer, or grafted monomer. In exemplary embodiments, the stabilizing agent comprises one or more polar polyolefins, having a polar group or as a comonomer, or grafted monomer. Exemplary polymeric stabilizing agents include, but are not limited to, ethylene-acrylic acid (EAA) and ethylene-methacrylic acid copolymers, such as those available under the PRIMACOR ^MR designations, commercially available from The Dow Chemical Company, NUCREL ^mr , commercially available EI DuPont de Nemours, and ESCOR ^MR, commercially available from ExxonMobil Chemical Company and described in US patents ^Nos 4,599,392,
4,988,781, and 5,938,437, each of which is incorporated herein by reference.
Other agents
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Exemplary polymeric stabilizers include, but are not limited to, ethylene ethyl acetate (EEA) copolymer, ethylene methyl methacrylate (EMMA), and ethylene butyl acrylate (EBA). Other ethylene-carboxylic acid copolymers may also be used. Those of ordinary skill in the art will recognize that a number of other polymers can be used.
[058] In certain embodiments, the stabilizing agent may be a functionalized polyolefin such as a polypropylene or polyethylene homopolymer or copolymer in which the polymer has been modified with hydroxyl group, amine, aldehyde, epoxide, ethoxylate, carboxylic acid, ester, or anhydride. Such functionalized polyolefins such as polyethylene homopolymers and copolymers are commercially available, for example, from Clairant Corporation under the trade names LICOCENE 4351 and LICOCENE 6452, and from Baker Petrolite, a subsidiary of Baker Hughes, Inc.
[059] Other stabilizing agents that may be used include, but are not limited to, long-chain fatty acids, fatty acid salts, or alkyl fatty acid esters having 12 to 60 carbon atoms. In other embodiments, the long-chain fatty acid or fatty acid salt may have 12 to 40 carbon atoms.
[060] Additional stabilizing agents that may be useful in the practice of the present invention include, but are not limited to, cationic surfactants, anionic surfactants, or non-ionic surfactants. Examples of anionic surfactants include, but are not limited to, sulfonates, carboxylates, and phosphates. Examples of cationic surfactants include, but are not limited to,
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31/68 are not limited to, quaternary amines. Examples of non-ionic surfactants include, but are not limited to, block copolymers containing ethylene oxide and silicone surfactants. Stabilizing agents useful in the practice of the present invention may be external surfactants or internal surfactants. External surfactants are surfactants that do not become chemically reacted with the base polymer during the preparation of the dispersion. Examples of external surfactants useful here include, but are not limited to, dodecyl benzene sulfonic acid salts and lauryl sulfonic acid salt. Internal surfactants are surfactants that become chemically reacted with the base polymer during the preparation of the dispersion. An example of an internal surfactant useful here includes 2,2-dimethylol propionic acid and
Additional surfactants that may be useful in your salts.
practices of the present invention include cationic surfactants, anionic surfactants, non-ionic surfactants, or combinations thereof.
Several commercially available surfactants may be used in embodiments disclosed here, including: OP-100 (a sodium stearate), OPK-1000 (a potassium stearate), and OPK-181 (a potassium oleate) all commercially available from
Hallstar RTD; UNICID
350, commercially available from Baker Petrolite; AVAILABLE
FES
77-IS and
AVAILABLE
TA-430, both commercially available from
Cognis;
RHODAPEX
CO436, SOPROPHOR 4D384, and 796 / P, RHODACAL
BX-78
LDS-22,
RHODAFAC RE-610, and RM-710, and SUPRAGIL
MNS / 90 all commercially available from
Rhodia; and TRITON QS-15,
TRITON
W-30,
DOWFAX 2A1, DOWFAX 3B2,
DOWFAX 8390,
DOWFAX C6L,
TRITON
X-200,
TRITON XN-45S, TRITON
H-55, TRITON
GR-5M, TRITON BG10, and
TRITON CG-110, all commercially available from The
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32/68
Dow Chemical Company, Midland, Michigan.
[061] Additional stabilizing agents that could be used are polymers in solution or suspension consisting of ethylenically unsaturated monomers such as acrylic and / or methacrylic acid and its esters or amides (C1-C30);
acrylamide / methacrylamide and its N-substituted derivatives;
acrylonitrile; styrene and substituted styrene derivatives.
[062] Exemplary polymeric stabilizing agents include, but are not limited to, amphiphilic copolymer compositions, copolymer comprising the reaction product of (i) 5
95% w / w of one or more hydrophilic monomers and (ii) 95% w / w of one or more ethylenically unsaturated hydrophobic monomers copolymerizable.
These materials are soluble or emulsifiable in water, especially after neutralization and may act as colloidal stabilizers. Exemplary stabilizing agents include, for example, but are not limited to, butyl acrylate and lauryl methacrylate.
[063] Representative non-ionic water-soluble monomers suitable for the production of amphiphilic copolymer compositions include, but are not limited to acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N diethylacrylamide, N-isopropylacrylamide, N-vinyl -da, N-vinylmethylacetamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, tbutylacrylamide, N-methylolacrylamide, (methyl) acrylates, such as (methyl) acrylates butyl acrylate and ethyl acrylate, vinyl monomers such as ethylene, styrene, divinylbenzene, diisobutylethylene,
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33/68 vinyl acetate and N-vinyl-pyrrolidone, and alkyl monomers such as allyl (meth) acrylate.
[064] Representative cationic water-soluble monomers suitable for the production of amphiphilic copolymer compositions include, but are not limited to, quaternary ammonium salts of amine functionalized monomers such as acrylamide, methacrylamide, N, Ndimethylacrylamide, N, N- diethylacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylmethylacetamide, N-vinyl pyrrolidone, t-butylacrylamide, N-methylolacrylamide, ethyl (methyl) tributylammonium acrylate TBAEMA, DMAEMA, DMAPMAMethylmethyl chloride, dialectic chloride, dialectic chloride) (MAPTAC), acrylamidopropyltrimethylammonium chloride (APTAC), N-vinyl pyrrolidone, vinylimidazole, polyquaternium-11 and polyquaternium-4.
[065] Anionic or "acid-containing monomer suitable for the production of amphiphilic copolymer compositions include, but are not limited to, ethylenically unsaturated monomers containing carboxylic acid, phosphonic acid, phosphonic acid, sulfinic acid and sulfonic acid groups.
Suitable examples include (meth) acrylic acid, maleic acid, succinic acid, itaconic acid, vinyl phosphonic acid, and vinyl sulfonic acid.
In an alternative embodiment, one or more stabilizing agents may be based on more resins such as polyester acrylate, polyamide acrylates, epoxy resin acrylates.
[067] Polyester resins suitable for producing stabilizing agents can be obtained according to conventional procedures well known to those
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34/68 moderately skilled in the subject by reacting, for example, a polybasic acid, containing at least two carboxyl groups per molecule of polybasic acid (eg at least dibasic carboxylic acid) with a polyhydric alcohol containing at least two groups hydroxyl in polyhydric alcohol (eg at least dihydric alcohol) in the presence of a conventional esterification catalyst at an elevated temperature with or without a solvent present. Alternatively, alkyl esters of polycarboxylic acids can be reacted in the presence of a conventional esterification catalyst at an elevated temperature. One or more polymerizable double bonds may be included in the polyester employing a polybasic acid containing double polymerizable bonds and / or polyhydric alcohol containing double polymerizable bonds and / or a polyhydric alcohol containing double polymerizable bonds.
[068] Polyester acrylates as stabilizing agents may be formed by in situ polymerization of copolymerizable ethylenically unsaturated monomers in the presence of polyesters. Examples include ethylenically unsaturated mono- or polyfunctional acids, ethylenically unsaturated mono- or polyfunctional acid esters, amides, nitriles, as well as vinyl and vinyl ester monomers with a polyester in or without the presence of a reaction fluid. Polyester acrylates in solvents may be dried according to suitable methods known to those of ordinary skill in the art.
[069] Epoxy resins suitable for producing stabilizing agents can be obtained according to conventional procedures well known to those
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35/68 moderately understood in the subject by reacting a polyepoxide with a suitable polynucleophile. Suitable epoxides include, but are not limited to, glycidyl ethers, and other molecules containing epoxy groups. Suitable polynucleophils include, but are not limited to, polyhydric phenols, and poly phenols, polythioles, aliphatic polyalcohols or polyasic acids or polyamines. Exemplary suitable epoxies include, for example, but are not limited to, a glycidyl ether that contains at least two glycidyl ether groups per polyglycidyl ether molecule (eg, at least one diglycidyl ether) with a polyhydric phenol that contains at least two hydroxyl groups in the polyhydric polyphenol (eg, at least one dihydric phenol or diphenol) in the presence of a conventional catalyst at an elevated temperature with or without a solvent present. Another class of epoxy resins may be obtained according to conventional procedures well known to those of ordinary skill in the art by reacting, for example, a polyglycidyl ether that contains at least two glycidyl ether groups per polyglycidyl ether molecule (e.g., at least one diglycidyl ether) with a polybasic acid containing at least two carboxyl groups per polybasic acid molecule (eg at least one dibasic polycarboxylic acid) in the presence of a conventional catalyst at an elevated temperature with or without a solvent present.
[070] Epoxy acrylates to produce stabilizing agents may be formed by in situ polymerization of copolymerizable ethylenically unsaturated monomers in the presence of epoxy resins. Examples include, but are not limited to, ethylenically mono- or polyfunctional acids
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36/68 unsaturated, esters of ethylenically unsaturated mono- or polyfunctional acids, amides, nitriles, as well as vinyl monomers and vinyl ester with epoxy resins in or without the presence of a reaction fluid. Alternatively, an acrylic resin with polymeric acid functionality may be reacted with an epoxy resin in the presence of a suitable catalyst to form an epoxy acrylate. Epoxy acrylates in solvents can be dried according to
with methods known those moderately understood at the subject matter. Neutralizing Agent [071] O stabilizing agent may be partially or fully neutralized with one neutralizing agent. In
neutralization of certain agents to
embodiments, stabilizer, such as a long-chain fatty acid or
EAA, may be from 25 to
200 percent on a molar basis;
or, alternatively, it could be 50 to 150 percent on a molar basis;
or, alternatively, it can be 50
120 percent on a molar basis; or, alternatively, it can be 50
110 percent on a molar basis. For example, for
EAA, neutralizing agent can be a base, such as ammonium hydroxide, or potassium hydroxide, for example. Other neutralizing agents may include lithium hydroxide or sodium hydroxide, for example. In another alternative, the neutralizing agent may be a carbonate. In another alternative, the neutralizing agent may, for example, be an amine such as monoethanolamine, or 2-amino-2-methyl-1-propanol (AMP).
Amines useful in embodiments disclosed herein may include diethanolamine, triethanolamine, and TRIS AMINO ^mr all commercially
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37/68 available from Angus), NEUTROL ^mr TE (commercially available from BASF), as well as triisopropanolamine, diisopropanolamine, and N, N-dimethylethanolamine (all commercially available from The Dow Chemical Company, Midland, MI). Other useful amines may include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, dibutylamine propylamine, triethylamine, mono-n-propylamine, butylamine, tributylamine, dimethyl benzyl amine, dimethyl-nN-methanol amine, N-aminoethylethanolamine, N-aminoethylethanolamine, N-aminoethylethanolamine , monoisopropa-nolamine,
N, N-dimethyl propanolamine,
2-amino-2-methyl-1-propanol,
1,2diaminopropane, tris (hydroxymethyl) -aminomethane, ethylenediamine, N, N, N ', N, -tetrakis (2hydroxylpropyl) ethylenediamine, 3-methoxypropyl amine, iminobis-propyl amine and the like. In some embodiments, mixtures of amines or mixtures of amines and surfactants may be used. In one embodiment, the neutralizing agent may be a polymeric amine, e.g., diethylene triamine. Those of ordinary skill in the art will appreciate that the selection of a suitable neutralizing agent depends on the specific composition formulated, and that such a choice is within the knowledge of those of ordinary skill in the art. In one embodiment, amines with boiling points below 250 ° C can be used as neutralizing agents.
Fluid Medium [072] The aqueous dispersion additionally comprises a fluid medium. The fluid medium can be any medium; for example, the fluid medium may be water; or, alternatively, the fluid medium may be a mixture of water and one or more
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38/68 organic solvents, eg, one or more water-miscible solvents or one or more water-immiscible solvents, or combinations thereof. The dispersion of the present invention comprises 15 to 99 volume percent water, based on the total volume of the dispersion. In particular embodiments, the water content may be in the range of 30 to 75, or, alternatively, from 35 to 65, or, in the alternative, from 40 to 60 percent by volume, based on the total volume of the dispersion. The water content of the dispersion may preferably be controlled in such a way that the solids content (one or more base polymers plus stabilizing agent) is from about 1 percent to about 99 volume percent. In particular embodiments, the range of solids content may be from about 25 percent to about 70 percent by volume. In other particular embodiments, the range of solids is from about 35 percent to about 65 percent by volume. In certain other particular embodiments, the range of solids is from about 40 percent to about 60 percent by volume.
Additional Components [073] The aqueous dispersion of the present invention may optionally be mixed with one or more binder compositions such as acrylic latex, acrylic vinyl latex, acrylic styrene latex, ethylene vinyl acetate latex, and combinations thereof; optionally one or more charges; optionally one or more additives, such as catalysts, wetting agents, defoamers, flow agents, release agents, glidants, anti-blocking agents, UV stabilizers, adhesion promoters; optionally one or more lubricants such as fatty acid ester wax,
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39/68 silicone-based wax, fluorine-based wax, polyethylene wax or similar polyolefin, carnauba wax, lanolin wax or the like; optionally one or more corrosion inhibitors such as aluminum, and zinc; optionally one or more pigments, eg, titanium dioxide, barium sulfate, mica, calcium carbonate, silica, zinc oxide, ground glass, aluminum trihydrate, talc, antimony trioxide, fly ash, and clay, or similar; optionally one or more solvents, eg, glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alcohols, turpentine, aromatic solvents, and benzoate esters or the like; optionally one or more dispersants, e.g., aminoalcohols, and polyabroxylates; optionally one or more surfactants; optionally one or more preservatives, eg, biocides, mildicides, fungicides, algaecides, and combinations thereof; optionally one or more thickeners, eg cellulose-based thickeners such as hydroxyethyl cellulose, modified alkali-soluble emulsions (HASE thickeners such as UCAR POLYPHOBE TR116) and modified ethoxylated urethane thickeners (HEUR); or optionally one or more neutralizing agents, e.g., hydroxides, amines, ammonia, and carbonates; optionally one or more solvents or coalescing agents.
[074] Additionally, the aqueous dispersion may be mixed with one or more dispersions, emulsions, suspensions, colloidal suspensions, and the like.
Forming the Dispersion [075] The aqueous dispersion can be formed by any number of methods recognized by those with a moderate understanding of the subject. The dispersion equipment may be
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40/68 operated in batch, semi-batch or continuous mode. Examples of mixers used in the dispersion include rotor-stator mixers, microfluidizers, high pressure homogenizers, ultrasonic, competing jets, Cowles blade, planetary mixers and melt kneading devices, such as extruders. [076] In one embodiment, one or more base polymers, one or more stabilizing agents are kneaded by melting in an extruder together with water and optionally one or more neutralizing agents, such as ammonia, potassium hydroxide, amine, or a combination of two or more, to form a dispersion. In another embodiment, one or more base polymers and one or more stabilizing agents are formulated, and then kneaded by melting in an extruder in the presence of water, and optionally one or more neutralizing agents thus forming a dispersion. In some embodiments, the dispersion is first diluted to contain about 1 to about 20%, e.g., 1 to 5% or 1 to 3%, by weight of water and then subsequently further diluted in a manner to understand more than about 25% by weight of water. In one embodiment, further dilution can be done with a solvent.
[077] Any melting kneading medium known in the art can be used. In some embodiments, a kneader, a BANBURY ^® mixer, single screw extruder, or a multiple screw extruder, eg, a double screw extruder, is used. A process for producing the dispersions according to the present invention is not particularly limited. For example, an extruder, in certain embodiments, for example, a screw extruder
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41/68 double, is coupled to a back pressure regulator, cast pump, or gear pump.
Exemplary embodiments also provide a base reservoir and an initial water reservoir, each of which includes a pump. Desired amounts of base and starting water are provided from the base reservoir and the starting water reservoir, respectively. Any suitable pump can be used, but in some embodiments, for example, a pump that provides a flow of about 150 cm ³ / min at a pressure of 240 bar is used to supply the base and the initial water to the extruder. In other embodiments, a fuel injection pump
liquid provides a flow of 300 cm ³ / min at 200 bar or 600 cm ³ / min at 133 bar. In some embodiments, the base and water initial are preheated in a preheater. [078] One or more base polymers, in the form of pellets, powder,
or flakes, are fed from the feeder to an extruder inlet where the resin is melted or formulated. One or more additional components may optionally be fed simultaneously with one or more base polymers to the extruder through the feeder; or, alternatively, one or more additional components may be formulated with one or more base polymers, and then fed to the extruder through a feeder. Alternatively, one or more additional components may optionally be additionally dosed via an inlet prior to the emulsification zone to the molten compound comprising one or more base polymers. In some embodiments, the dispersing agent is added to one or more base polymers via, and together with, the resin and, in other embodiments, the dispersing agent is added to one or more base polymers via, and
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42/68 together with the resin and, in other embodiments, the dispersing agent is provided separately to the twin screw extruder. The resin melt is then released from the mixing and transport zone to an emulsification zone of the extruder where the initial amount of water and base from the water and base reservoirs is added through an inlet. In some embodiments, the dispersing agent may be added additionally or exclusively to the water stream. In some embodiments, additional dilution water may be added by entering water from the water reservoir into a dilution and cooling zone of the extruder. Typically, the dispersion is diluted to at least 30 weight percent water in the cooling zone.
Additionally, the diluted mixture can be diluted any number of times until the desired level of dilution is reached. In some embodiments, the dispersion is additionally cooled after leaving the extruder using a suitable heat exchanger. In other embodiments, water is not added to the twin screw extruder, but to a stream containing the resin melt after the melt has left the extruder. In this way, the accumulation of water vapor pressure in the extruder is eliminated and the dispersion is formed in a secondary mixing device such as a stator rotor mixture.
[079] In another embodiment, the aqueous dispersion may be formed in a continuous high-shear mixer without the use of a melt extruder. In this embodiment, the first stream comprising one or more liquid or molten base polymers is supplied to a continuous high shear mixture with a suitable pump,
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43/68 for example, a syringe pump, gear pump, or progressive cavity pump. The first stream is drained through a first conduit and fused continuously with a second stream containing a continuous aqueous phase which is drained through a second conduit. The first and second streams are incorporated in a disperser in the presence of a stabilizing agent with additional neutralizing agent. The agents can be added either to the first or the second stream, or as a separate stream. A third stream comprising water may be added downstream of the disperser. The flow rates of the streams are adjusted to achieve a dispersion having the desired amount of polymer phase and percentage of solids. The disperser can have any number of continuous in-line mixers, for example, an IKA high shear mixer, Oakes rotor mixer, Ross mixer, Silverson mixer, or centrifugal pump. The RPM setting of the disperser can be used to help control the particle size of the hydrophobic phase dispersed in the dispersion. The system can be heated to provide the polymer and neutralizing components at a viscosity suitable for pumping. The formation of water vapor is reduced by controlling the pressure by using a back pressure regulator, gear pump, dosing pump, or other suitable device near the process outlet. In some embodiments, the dispersion is additionally cooled after leaving the disperser using a suitable heat exchanger.
[080] In another embodiment, the aqueous dispersion may be formed in a batch or semi-batch process
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44/68 batch using a high shear mixture, where the mixer may, for example, be arranged inside a pressurized tank to, for example, reduce the formation of water vapor. All or at least a portion of the dispersion is removed from the tank during processing, and optionally cooled using a suitable heat exchanger.
[081] During the preparation of the aqueous dispersion, optionally one or more fillers; optionally one or more additives such as catalysts, wetting agents, defoamers, flow agents, release agents, glidants, anti-blocking agents, sulfur-staining additives, pigment wetting / dispersing agents, anti-deposition agents, stabilizers UV, adhesion promoters, optionally one or more lubricants such as fatty acid ester wax, silicone based wax, fluorine based wax, polyethylene wax or other similar polyolefin, carnauba wax, lanolin wax or the like; optionally one or more corrosion inhibitors such as aluminum, and zinc; optionally one or more pigments, eg, titanium dioxide, barium sulfate, mica, calcium carbonate, silica, zinc oxide, ground glass, aluminum trihydrate, talc, antimony trioxide, fly ash, and clay, or similar; optionally one or more solvents, e.g., glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alcohols, turpentine, aromatic solvents, and benzoate esters or the like; optionally one or more dispersants, e.g., aminoalcohols, and polyabroxylates; optionally one or more surfactants; optionally one or more preservatives, eg, biocides, mildicides, fungicides, algaecides, and combinations thereof;
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45/68 optionally one or more thickeners, eg cellulose based thickeners such as hydroxyethyl cellulose, modified alkali-soluble emulsions (HASE thickeners such as UCAR POLYPHOBE TR-116) and modified ethoxylated urethane thickeners, carbonates may be (HEUR); or optionally one or more
e.g., hydroxides, amines, ammonia, and added to the aqueous dispersion formulation; or, alternatively, dispersion may be added after the dispersion formulation process.
During the preparation of the aqueous dispersion, one or more stabilizing agents may also be added to the aqueous dispersion formulation;
or, alternatively, they can be added to the dispersion after the dispersion formulation process.
Optionally, during the dispersion of one or more base polymers, another polymer dispersion or emulsion may be used as a portion of the aqueous phase of the dispersion.
Examples include, but are not limited to, acrylic, epoxy, polyester, polyurethane, polyolefin, polyamide, the like containing dispersions, emulsions, suspensions, colloidal suspensions.
Applications
Coatings and Formation of
Coated Containers or Devices
Closing [085]
The aqueous dispersion can be used, for example, for container applications, or coating applications for closure devices. Such coated container devices include, but are not limited to, cans, such as beverage cans, food cans; aerosol containers such as those non-food products; eg, hairspray, hair dyes, or colored hairsprays
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6/68 in spray; beer kegs; buckets; decorative cans; open trays; tubes, bottles, monoblocks, and the like. Coated closing devices include, but are not limited to, lids, covers such as those based on thin aluminum laminates for yogurt and butter containers, or bottle caps; closures for glass jars, such as “rollon” closures, vacuum closures, theft-proof closures, easy peeling lids for can closings, and easy opening and conventional ends for cans. The cans can be 2-piece cans and 3-piece cans. Beverage cans include, but are not limited to, beer cans, carbonated drink cans, energy drink cans, isotonic beverage cans, water cans, juice cans, tea cans, coffee cans, milk cans, and similar. Foods may include, but are not limited to, cans of vegetables, cans of fruit, cans of meat, cans of soup, cans of ready meals, cans of fish, cans of edible oils, cans of sauces, and the like. Such cans can have many shapes; for example, they may have a cylindrical, cubic, spherical, semi-spherical shape, bottle shape, elongated cubic shape, shallow or tall shape, round or rectangular shape, or any other suitable shape. The coated container devices according to the present invention can be formed by any conventional method. For example, the coated container device may be formed by stamping, extracting, drawing, drawing, body stamping (“wall ironing), folding, edging, embossing, indentation, flanging,
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47/68 drawing, blowing drawing, and any other suitable conventional method. Such methods are generally known to those of ordinary skill in the art. The aqueous dispersion may, for example, be applied to a metallic substrate, e.g., metallic foil or metallic laminate, and then the coated substrate may be formed as a coated container device or a coated closure device. Alternatively, the metal substrate may be formed as a container device or a closure device, and then the container device or closure device is coated with one or more aqueous dispersions to form the coated container device or a coated closure device. The coating can be applied by any method, for example, roller coating, spray coating, powder coating, dip coating, electroplating coating, printing, wash coating, flow coating, curtain coating.
[086]
The one or more aqueous dispersion (s) applied to the at least one surface of the metal substrate may be dried by any conventional drying method.
Such conventional drying methods include, but are not limited to, air drying, convection oven drying, hot air drying, and / or infrared oven drying.
The one or more aqueous dispersion (s) applied to the at least one surface of the metallic substrate may be dried at any temperature; for example, it (s) may be dried at a temperature in the range equal to or greater than the melting point temperature of the base polymer; or, alternatively, it (s) may be
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48/68 dried (s) at a temperature in the range of less than the melting point of the base polymer. The one or more aqueous dispersion (s) applied to at least one surface of the metallic substrate may (s) in the range of about 15.5 ° C during a period of less example, less than 20 minutes less than 5 minutes, or less than minutes, or less than 20 individual and sub-strips can be dried at a temperature (60 ° F) at about 371 ° C (700 ° F) that is about 40 minutes, for, or less than 10 minutes, or 2 minutes, or less than 1 seconds. All values range from 15.5 ° C (60 ° F) to about
371 ° C (700 ° F) will be included here and disclosed here; for example, one or more aqueous dispersion (s) applied to at least one surface of the metal substrate may be dried at a temperature in the range of about 15.5 ° C (60 ° F) to about 260 ° C (500 ° F) for a period of less than about 40 minutes, for example, less than 20 minutes
minutes, or any less that 10 minutes, or less than 5 minutes, or less than 2 minutes, or less than 1 minute or, at alternative,at) an or more dispersion (s) watery ( s) applied (s) The fur any less an substrate surface metallic
it can be dried at a temperature in the range of about 15.5 ° C (60 ° F) to about 232.2 ° C (450 ° F) for less than about 40 minutes , for example, less than 20 minutes, or less than 10 minutes, or less than 5 minutes, or less than 2 minutes, or less than 1 minute. The temperature of one or more aqueous dispersion (s) applied to at least one surface of the metal substrate may be raised to a temperature in the range equal to or greater than the melting point temperature of the base polymer for a period of less than about 40 minutes. All values
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49/68 individual and sub tracks for less than about 40 minutes will be included here and posted here; for example, the temperature of one or more aqueous dispersion (s) applied to at least one surface of the metal substrate may be raised to a temperature in the range of equal to or greater than the temperature of the spot melting time of the base polymer over a period of less than about 20 minutes or, alternatively, the temperature of the one or more aqueous dispersion (s) applied to at least one surface of the metal substrate may be raised to a temperature in the range equal to or greater than the melting point temperature of the base polymer over a period of less than about 5 minutes or, alternatively, the temperature of the one or more dispersion (s) ) aqueous (s) applied to at least one surface of the metallic substrate may be raised to a temperature in the range equal to or greater than the melting point temperature of the base polymer for a period in the range of about 0, 5 to 300 seconds. In another alternative, the temperature of the one or more aqueous dispersion (s) applied to at least one surface of the metal substrate may be raised to a temperature in the range of less than the temperature of the melting of the base polymer over a period of less than about 40 minutes. All individual values and sub-bands of less than about 40 minutes will be included here and disclosed here; for example, the temperature of one or more aqueous dispersion (s) applied to at least one surface of the metal substrate may be raised to a temperature in the range of less than the melting point temperature of the base polymer for a period of less than about 5 minutes or, in another
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50/68 Alternatively, the temperature of one or more aqueous (s) applied to at least one surface of the metal substrate may be raised to a temperature in the range of less than the melting point temperature of the base polymer for a period in the range of 0.5 to
300 seconds.
coated metallic substrate may additionally be coated with one or more conventional compositions, or may additionally be laminated to one or more other layers. Such conventional coating compositions are generally known to those of ordinary skill in the art, and they may include, but are not limited to, epoxy resin coating compositions, acrylate-based coating compositions, and polyester-based compositions. The lamination process is generally known and exemplary lamination layers may include, but are not limited to, polyester laminates, polyolefin based laminates, such as polypropylene laminates.
[088] The one or more aqueous dispersion (s) applied to at least one surface of the metallic substrate may have a cross-section adhesion rating of at least 3B; for example, 5B, measured according to ASTM-D 3359-08. The one or more aqueous dispersion (s) applied to at least one surface of a metallic substrate, for example, a pre-coated metallic substrate, such as one or more layers of coating may have a smear rating double with methyl ethyl ketone (MEK) of at least 10, for example, at least 20. The one or more aqueous dispersion (s) applied to the hair
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51/68 minus one surface of the metal substrate may have a wedge bend pass rating of at least 90 percent, measured with a Gardner Bending Tester “COVERALL Bend Tester IG 1125.
Examples [089] The following examples illustrate the present invention, but are not intended to limit the scope of the invention. The examples of the present invention demonstrate that one or more aqueous dispersions applied to at least one surface of a metallic substrate provide for improved coating layer flexibility as well as coating layer adhesion to the metallic substrate. Preparation of Aqueous Dispersion The inventive [090] The aqueous dispersion was prepared according to the following procedures based on the formulation components listed in Table I. ^Mr PRIMACOR 1410 (CAS No. 901077-9), ethylene-acrylic acid copolymer having an acrylic acid content of approximately 9 to 10 weight percent and a melting index of approximately 1.3 to 1.6 g / 10 min. (ASTM D 1238, 190 ° C / 2.16 kg) commercially available from The Dow Chemical Company as the base polymer, and ^Mr PRIMACOR 5980i (CAS No. 9010-77-9), ethylene-acrylic acid copolymer having an acrylic acid content of approximately in the range of 19.5 to 21.5 weight percent and a melt index of approximately 300 g / 10 min. (ASTM D 1238, 190 ° C / 2.16 kg), commercially available from The Dow Chemical Company, as the stabilizing agent were fed to a 25 mm diameter twin screw extruder through a controlled rate feeder where they were forwarded and merged. The temperature profile
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52/68 of the extruder was increased to about 160 ° C before the addition of initial water and AMP-95 - amino-2-methyl-1-propanol (95%) (CAS No. 124-68-5) as the agent neutralizing and subsequently cooled to a temperature below 100 ° C at the end of the extruder after adding the dilution water. The speed of the extruder was approximately 450 rpm. Amine base and water were mixed together and fed to the extruder at the point of initial water introduction. The dilution water was fed through a second pump, and was introduced into the dilution zone of the extruder. The initial water and dilution water streams were optionally preheated to the temperature of the extruder. At the extruder outlet, a back pressure regulator was used to adjust an appropriate pressure inside the extruder cylinder in order to reduce the formation of water vapor at the operating temperature. The resulting dispersions were cooled and filtered through a 200 micron filter. Preparation of Inventive Aqueous Dispersions BF [091] Dispersions B to F were prepared in a similar manner to dispersion A, but with the formulation components listed in table I.
[092] Preparation of Inventive Aqueous Dispersions
Supplements S1-26 [093] Dispersions S1 to 26 were prepared similarly to dispersion A, but with the formulation components listed in table I.
Preparation of Inventive Aqueous Dispersions Containing Solvent [094] Dispersions G, H, and I were prepared similarly to dispersion A, but with the addition of solvent to the dilution water supply. For dispersion G the
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53/68 water miscible solvent propylene glycol was added to the
extruder with feeding in Water in dilution. For The dispersal H the propylene solvent glycol was added to cylinder gives extruder to zone in Fusion in polymer before gives
introduction of the initial water flow. For dispersion I, the water-immiscible mineral oil was added to the extruder cylinder to the polymer melting zone prior to the introduction of the initial water stream. The formulation components are listed in table II.
Coating application to Uncoated Panels
Coating example I.
Tinned Panel Coating Application [095] A tinned panel provided by Rasselstein, having a TS-245 grade finish pattern, approximately 10 cm to 20 cm in size, was cleaned with acetone, and then dried. About 3 grams of the inventive dispersion A was applied to the tinned panel with a spiral micron applicator bar thus coating a surface of the tinned panel. Subsequently, the panel was placed in a convection oven to be cured. The curing conditions are reported in table III.
[096] The coated tinned panels were tested for coating thickness, wedge bending, MEK DR (double rubbing with methyl ethyl ketone) cross-section adhesion before sterilization, and cross-section adhesion and whitening after sterilization in water according to the procedures described below. The results are reported in table III.
Coating example 2
Aluminum Panel Coating Application
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54/68 [097] An aluminum panel made of clean aluminum can material as can be obtained, eg, from All Foils Inc. with a size of approximately 10 cm to 20 cm was cleaned with methyl ethyl ketone and then dried. About 3 grams of an inventive dispersion listed in table IV were applied to the plate panel with a rod then spiral bar # 10 thereby coating an aluminum panel surface. Subsequently, the panel was placed in a convection oven to be cured under the conditions given in table IV.
[098] The coated aluminum panels were tested for coating thickness, cross-section adhesion before sterilization, and cross-section adhesion and whitening after lactic acid sterilization according to the procedures described below. The results are reported in table IV.
Coating Example 3
Application of Coating to a Pre-Coated Panel Preparation of a tinned panel coated with a polyester resin formulation [099] 23, 28 g of Dynapol ^MR 952 polyester and 3.98 g of EFC
112/65 of the SI group were mixed with 43.23 g of a mixture of 52 parts by weight of aromatic solvent Solvesso ^MR 100 and 48 parts by weight of glycol ether Dowanol ^MR PMA in a sealed bottle, which was spun in an arrangement of rotating bars at room temperature for 72 hours. Then, 0.181 g of phosphoric acid (25% in glycol ether Dowanol ^MR ) was added and the bottle was spun for an additional 24 hours. Dynapol is a registered trademark of Evonik. Solvesso is a registered trademark of ExxonMobil, Dowanol is a
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55/68 registered trademark of The Dow Chemical Company.
[100] A tinned panel, provided by Rasselstein, having a TS-245 grade finish pattern, approximately 10 cm to 20 cm in size, was cleaned with acetone, and then dried. About 3 grams of the coating formulation was applied to the tinned panel with a 30 micron spiral applicator bar thereby coating a tinned panel surface. Subsequently, the panel was placed in a convection oven to be cured at 200 ° C for 10 minutes. The coating had a thickness of 5.1 microns and MEK DR of 15.
Pre-coated panel coating with inventive dispersion [101] The tinned panel above, coated with the polyester-based formula, was used without any additional cleaning. About 3 grams of coating formulation F was applied to the tinned panel with a 30 micron spiral applicator bar over the polyester coating. Subsequently, the panel was placed in a convection oven to be cured for 3 minutes at 200 ° C. The coated tinned panels were tested for coating thickness, wedge bending, MEK DR (double rubbing with methyl ethyl ketone) cross-section adhesion before sterilization, and cross-section adhesion and whitening after sterilization in water according to the procedures described below. The results are reported in table V.
Test Method
The test methods include the following:
Cross-section adhesion [102] Cross-section adhesion is measured according to
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56/68 with ASTM D-3359-08, measure adhesion by n = tape test, Method B, using an Erichsen EPT 675R cross-section tester. This method provides the procedure for evaluating the adhesion of coating films to metallic substrates by applying and removing a tape (grade: TESA 4124 colorless) on the slits made in the film. Locate the center of a piece of tape over the crosshair and in the area of the crosshair and position it by smoothing it with your finger. To ensure good contact with the film, rub the tape vigorously. After 90 + 30 seconds of application, remove the tape by holding the free end by pulling quickly (without jerks) as close as possible to a 180 degree angle as possible. Inspect the area of the reticulum to remove coating from the substrate or a previous coating using a lighted magnifying glass. Classify adherence according to the following scale:
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5B The edges of the cuts are completely smooth; none of the lattice squares came off 4B Small scales of the coating broke off at intersections; less than 5% of the area has been affected 3B Small scales of the coating broke off along the edge and at the intersections of the cuts. The affected area is 5-15% of the reticulate 2B The coating formed scales along the edges and in parts of the squares. The affected area is 15-35% of the lattice 1B The coating formed scales along the edges and in large bands and entire squares came off. The affected area is 35-65% of the lattice 0B Scaling and shedding are worse than in 1B
Sterilization in Water [104] The coated panels were immersed in water in a pressurizable metallic container, and placed in a Steriliser Automat V where they were retorted at 129 ° C for 30 minutes. Subsequently, the pressurized container was placed in a cold water containment vessel, and the temperature of the pressurized container was lowered to a temperature in the range of less than 50 ° C before opening. The panels were removed, and dried. The whitish appearance was then assessed. The whitening is called a whitish appearance of the coating. If the coating does not show any whitening, then the classification is without whitening; otherwise, it will be classified as very slight whitening, slight whitening or strong whitening.
Lactic Acid Sterilization [105] The coated panels were immersed in a 2% lactic acid solution in a glass beaker and placed in a Tuttnauer Brinkman 3850E autoclave where they were treated at 121 ° C for 30 minutes. The panel was cooled in the autoclave
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58/68 to below 60 ° C before being removed, rinsed and dried. The whitish appearance was then classified. The whitening is called a whitish appearance of the coating. If the coating does not show any whitening, then the classification is without whitening; otherwise, it will be classified as very slight whitening, slight whitening or strong whitening.
Double Scrubbing with MEK [106] The flat end of a hemispherical hammer having a weight of 1230 + 10 g was used. A normal VILEDA 3168 tissue was tied around the end of the hammer. It has been soaked with methyl ethyl ketone (MEK). The hammer was placed in contact with the coating and moved back and forth across the entire coating, the back and forth movement across the entire coating being considered a double scrub. No additional pressure was applied to the hammer. After every 10 double rubs, the tissue was soaked. The double scrubbing step was repeated until the coating was removed, i.e., at least a portion of the metallic substrate was exposed. If the double swab reached 100 double swabs, the test was terminated and the 100 double swabs were reported as the final result.
Wedge Bending [107] Wedge bending was measured with a Gardner COVERALL Bend Tester IG 1125 Bending Tester. The apparatus used for this test consists of two parts to convert it into a bending machine. A steel rod
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59/68 (mandrel) is mounted in front of the base. The 100 mm wide coated test panel was flexed over the 3 mm shank chuck; thus, the coating appears on the outside of the fold. The flexed panel was inserted into the wedge chuck. The impactor is recovered in its first jump and retained. The cylindrical fold in the panel was squeezed to a conical shape. The edge of the coated panel was rubbed with a solution of copper sulphate (mixture of 10 grams of copper sulphate, 90 grams of water and 3 grams of sulfuric acid). Anywhere the coating has cracked; dark spots appeared, indicating failure. The length of the intact area along the wedge bend, which is 100 mm, was measured in millimeters and expressed as a percentage pass. Coating Thickness [108] The coating thickness was measured according to ASTM D-1186-01, non-destructive dry film thickness measurement of non-magnetic coatings applied to a ferrous base, using a PERMASCOPE D coating thickness gauge -211D. The standard panel with no coating was used for calibration. The coating thickness of the control panels was the average of 10 measurements, with each measurement of the coating thickness of the coated panels being measured using a ferrous material probe relative to the thickness of the standard panel coating, i.e., zero. The measured thickness was reported in microns. Degree of Neutralization [109] The percentage of neutralization was the calculated amount of acrylic acid groups in the resin melt that were neutralized by the base.
Particle Size Measurement
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60/68 [110] Particle size was measured by a Coulter LS-230 particle size analyzer (Beckman Coulter Corporation).
Percentage of Solids Measurement [111] The percentage of solids was measured using a microwave solid analyzer.
[112] The present invention may be realized in other ways without departing from its spirit and essential attributes and, consequently, reference should be made to the attached claims, instead of the description above, as indicative of the scope of the invention.
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Table I
Aqueous Dispersion PolymerBase(g / min) AgentStabilizer (g / min) Additional Base Polymer (g / min) Neutralizing Agent (mL / min.) Water RateInitial (mL / min.) Dilution Water Rate (mL / min) Size ofMedium Particle (micron) THE PRIMACOR ^mr 1410 (49) PRIMACOR ^mr 5980i (21) none AMP-95 ^MR (12.4) 33 130 0.4 B 109MFR Exp.Polypropylene (52.9) PRIMACOR ^mr 5980i (22.7) none DMEA(7.55) 20, 6 80 2.1 Ç 109MFR Exp.Polypropylene (52.9) PRIMACOR ^mr 5980i (17.0) EPOLENE ^mr E-25 (5.7) DMEA (6.08) 19 80 2.0 D D118.01 polypropylene (47.3) PRIMACOR ^mr 5980I (22.7) epolene ^mr E-25 (5.7) DMEA(7.79) 24, 68 80 8, 85 AND 6D43 polypropylene (52.9) NUCREL ^mr 280 6 (22.7) none 1,2diaminopropane (2.93) 14.88 80 1.37 F PRIMACOR ^mr 1410 (47.6) PRIMACOR ^mr 5980i (20.4) none DMEA(11.2) 33 120- 0.3 S1 PRIMACOR ^mr 1321 (18.8) PRIMACOR ^mr 5980I (25) HDPE 30460M (6.2) AMP-95 ^MR (8.5) 12 160 0.8 S2 PRIMACOR ^mr 1321 (35) PRIMACOR ^mr 5980i (15) none DMEA(7.2) 25 95 1.2 S3 PRIMACOR ^mr 1321 (42) PRIMACOR ^mr 5980i (18) none AMP-95 ^MR (13.5) 30 102 0.7 S4 PRIMACOR ^mr 1321 (25.7) PRIMACOR ^mr 5980I (7.5) HDPE30460M (3.8) DMEA(3.1) 17 50 1.3
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S5 PRIMACOR ^mr 1321 (26, 9) primacor ^MR 5980i (7.5) HDPE 30460M (4.0) dmea(5.8) 17 35 1.7 S6 primacor ^MR 1321 (26, 9) primacor ^MR 5980i (18) none dmea(11.4) 32 94 1.2 S7 primacor ^MR 1410 (45) primacor ^MR 5980i (15) none dmea(15.2) 30 115 0, 9 S8 primacor ^MR 1410 (30) primacor ^MR 5980i (30) none dmea(13) 29 100 0.3 S9 primacor ^MR 1430 (80) primacor ^MR 5980i (20) none dmea(9.8) 50 160 0.3 S10 primacor ^MR 1430 (80) primacor ^MR 5990 (20) none dmea(9.8) 49 173 0.3 S11 primacor ^MR 3150 (29) primacor ^MR 5980i (20) none dmea(6.8) 20 55 1.5 S12 primacor ^MR 3440 (42) primacor ^MR 5980i (18) none AMP-95 ^MR (10.4) 30 114 0.55 S13 primacor ^MR 3460 (48) primacor ^MR 5980i (12) none AMP-95 ^MR (8, 6) 30 102 0.35 S14 HDPE 30460M (35) primacor ^MR 5980i (35) none AMP-95 ^MR (19.4) 20 220 1.0 S15 pead dmda-8965 (30) primacor ^MR 5980i (20) none dmea(10) 17 64 0.8 S16 6D43 polypropylene (79.4) primacor ^MR 5980i (25.5) lycocene ^MR 6452 (8.5) dmea(9.64) 24.7 110 1.0 S17 6D43 polypropylene (52.9) primacor ^MR 5980i (17.0) lycocene ^MR 6452 (5.7) dmea(6.35) 14.31 80 0.84 S18 6D43polypropylene primacor ^MR 5980i (5,7) and lycocene ^MR 6452 (5.7) dmea(4.01) 12, 84 75 2.48
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(61) hemic acid (3.0)S19 6D43 polypropylene(52.9) PRIMACOR ^mr 5980i (11.3) licocene ^mr 6452 (11.3) DMEA(4.99) 13, 02 83 1.45 S20 6D43 polypropylene(52.9) primacor ^mr 5980i (11.3) none AMP-95 ^MR (6.07) 19, 97 85 2.57 S21 6D43 polypropylene(52.9) primacor ^mr 5990 (22.7) none Ammonia 28% (6.07) 16.79 70 3.67 S22 6D43 polypropylene(52.9) primacor ^mr 5980i (22.7) none 1,2diaminopropane (2.72) 14, 93 70 2.29 S23 6D43 polypropylene(52.9) NUCREL ^MR 280 6 (22.7) none DMEA(6.6) 17, 87 90 1.06 S24 6D43 polypropylene(52.9) primacor ^mr 5980i (17.0) epolene ^mr E-25 (5.7) DMEA (6.05) 18, 98 80 1.98 S25 6D43 polypropylene(52.9) primacor ^mr 5980i (17.0) primacor ^mr 3340 (17.0) DMEA(5.3) 14.33 80 2.59 S26 6D43 polypropylene (47.3) primacor ^mr 5980i (22.7) exxelor ^mr PO1020 (5.7) DMEA(7.75) 23.25 80 1, 6
63/68
Petition 870190008010, of 01/24/2019, p. 68/77
4/68 [113] 6D43 polypropylene is a commercially available propylene ethylene copolymer from The Dow Chemical Company with a melt index of 35.
D118.01 polypropylene is a commercially available propylene homopolymer from The Dow Chemical
Company with a melt index of 8.
109MFR Exp. Polypropylene is a commercially available propylene homopolymer from
The
Dow Chemical
Company with a melt index of 109.
Nucrel 2806 is a commercially available acrylic acid ethylene copolymer from DuPont that is
17% acrylic acid with a melt index of 60.
[117] Primacor 1321 is a commercially available ethylene acrylic acid copolymer from Dow Chemical that is 6.5% acrylic acid with a melt flow rate of 2.6 dg / min.
[118] Primacor 1410 is a commercially available ethylene acrylic acid copolymer from Dow Chemical which is 9.7% acrylic acid with a melt flow rate of 1.5 dg / min.
[119] Primacor 1430 is a commercially available ethylene acrylic acid copolymer from Dow Chemical which is 9.7% acrylic acid with a melt flow rate of 5 dg / min.
[120] Primacor 3150 is a commercially available ethylene acrylic acid copolymer from Dow Chemical that is 3% acrylic acid with a melt flow rate of 11 dg / min.
[121] Primacor 3340 is a commercially available ethylene acrylic acid copolymer from Dow Chemical that is 6.5%
Petition 870190008010, of 01/24/2019, p. 69/77
65/68 acrylic acid with a melt flow rate of 9 dg / min.
[122] Primacor 3460 is a commercially available ethylene acrylic acid copolymer from Dow Chemical that is 9.7% acrylic acid with a melt flow rate of 20.0 dg / min.
[123] Primacor 5980i is a commercially available ethylene acrylic acid copolymer from Dow Chemical that is 20.5% acrylic acid with a melt flow rate of 300.
[124] Primacor 5990 is a commercially available ethylene acrylic acid copolymer from Dow Chemical which is 20.5% acrylic acid with a melt flow rate of 1300.
[125] HDPE 30460M is a high density polyethylene from Dow Chemical with a melt flow rate of 30.
[126] HDPE DMDA-8965 is a high density polyethylene from Dow Chemical with a melt flow rate of 66.
[127] Licocene 6452 is a commercially available polypropylene with maleic anhydride functionality from Clairant that has an acid number of 41 mg KOH / g and a melt viscosity of 1100 mPa * sec at 170 ° C.
[128] Epolene E-25 is a commercially available polypropylene with maleic anhydride functionality from Westlake Chemical Corporation that has an acid number of 25 mg KOH / g and a viscosity of 300 mPa * sec at 190 ° C.
[129] Exxelor PO1020 is a commercially available polypropylene with maleic anhydride functionality from ExxonMobil that has 0.5-1.0% maleic anhydride with a melt flow rate of 125.
Petition 870190008010, of 01/24/2019, p. 70/77
66/68 [130] DMEA is dimethylethanolamine.
[131] AMP-95 is 95% 2-amino-2-methyl-1-propanol in water.
Petition 870190008010, of 01/24/2019, p. 71/77
67/68
Table II Dispersion Containing Solvent
Aqueous Dispersion Base Polymer (g / min) AgentStabilizer (g / min) Additive Polymer (g // min.) AgentNeutralizing (mL / min.) Solvent (mL / min.) Rate ofInitial Water (mL / min.) Dilution Water Rate (mL / min) Average Particle Size (micron) G 6D43 polypropylene(52.9) primacor ^mr 5980 (17.0) licocene ^mr 6452 (5.7) DMEA(6.42) Propylene glycol (18.0) 16, 62 65 1.2 H PRIMACOR ^mr 1410 (42.9) primacor ^mr 5980 (18.4) at DMEA(10.72) Propylene glycol (6.8) 30.15 110 0.32 I primacor ^mr 1410 (42.9) primacor ^mr 5980 (18.4) at DMEA(10.73) OilMineral(6.8) 30.15 110 0.31
67/68
Table III
Inventive Dispersion Curing Condition [° C / min. ] Average Coating Thickness (micron) Loss of adhesion in cross-section before sterilization Loss of adhesion in cross section after sterilization water Whitening after sterilization water Wedge bending [% passes] Double scrubbingMEK THE 150/5 5.0 5B 5B didn't whiten 100% 23
Petition 870190008010, of 01/24/2019, p. 72/77
68/68
Table IV
DispersalInventive Curing Condition [° C / min. ] Average Coating Thickness (micron) Loss of adhesion in cross-section before sterilization Loss of adhesion in cross section after sterilization water Whitening after sterilization water Wedge bending [% passes] Double MEK wipes B 204/3 22, 6 5B 5B Whitish. very light 100% 100 Ç 204/3 7, 9 5B 5B Whitish. very light 100% 100 D 204/3 9, 65 3B 5B Whitish. Light 100% 100 AND 204/3 7, 62 4B 5B Whitish. Light 100% 89
Table V
SubstratePre-Coated DispersionInventivThe Condition ofCure[° C / min. ] Average Coating Thickness (micron) Loss of adhesion in cross-section before sterilization Loss of adhesion in cross section after sterilization water Whitish after sterilization water Wedge folding [% passes] Double scrubbing as MEK Polyester coating on tin plate F 200/3 10.1 thick. total ie the coating.has thick. in5 microns 5B 5B withoutwhitishto 100% 40
68/68

权利要求:
Claims (5)
[1]
1. Coated container device, characterized by the fact that it comprises:
- a metallic substrate; and
- one or more coating layers associated with said metallic substrate, and one or more coating layers are derived from the application of one or more aqueous dispersions to at least one surface of the metallic substrate, and the one (s) being one or more aqueous dispersions include:
one or more base polymers;
one or more stabilizing agents;
water, the base polymer comprising a polar polyolefin selected from the group consisting of:
ethylene-acrylic acid (EAA) copolymers ethylene-methacrylic acid copolymer and combinations thereof, and the stabilizing agent comprises a polar polyolefin, selected from the group consisting of ethylene acrylic acid (EAA) copolymer, ethylene-acid copolymer methacrylic, and combinations thereof; with the provision that the base polymer has a lower acid number, measured according to ASTM D974, than that of the stabilizing agent.
[2]
2. Method for making a coated container device, as defined in claim 1, characterized by the fact that it comprises the steps of:
- select a metallic substrate;
- selecting one or more aqueous dispersions comprising: one or more base polymers; one or more stabilizing agents; and water; the base polymer comprising a polyolefin
Petition 870190008010, of 01/24/2019, p. 74/77
2/3 polar selected from the group consisting of ethylene-acrylic acid (EAA) copolymers, ethylene-methacrylic acid copolymer and combinations thereof, and the stabilizing agent comprises a polar polyolefin, selected from the group consisting of copolymer of ethylene acrylic acid (EAA), ethylene-methacrylic acid copolymer, and combinations thereof;
with the provision that the base polymer has a lower acid number, measured according to ASTM D-974, than that of the stabilizing agent;
- applying said one or more aqueous dispersions to at least one surface of said metallic substrate;
- removing at least a portion of the water from said one or more aqueous dispersions, thereby forming one or more layers associated with said metallic substrate; and
- shaping said coated metallic substrate into a coated container device.
[3]
3. Method for making a coated container device, as defined in section 1, characterized by the fact that it comprises the steps of:
- select a metallic substrate;
- shaping said metallic substrate into a coated container device;
- selecting one or more aqueous dispersions comprising: one or more base polymers; one or more stabilizing agents; and water;
the base polymer comprising a polar polyolefin selected from the group consisting of ethylene-acrylic acid copolymers (EAA), ethylene-methacrylic acid copolymer and combinations thereof, and the stabilizing agent comprises a polar polyolefin, selected from of
Petition 870190008010, of 01/24/2019, p. 75/77
3/3 group consisting of ethylene acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer, and combinations thereof; with the provision that the base polymer has a lower acid number, measured according to ASTM D-974, than that of the stabilizing agent;
- applying said one or more aqueous dispersions to at least one surface of said metallic substrate;
- removing at least a portion of the water from said (s) one or more aqueous dispersions, thus forming one or more layers associated with said metallic substrate; and
- thus forming said coated container device.
[4]
Device or method according to any one of claims 1 to 3, characterized in that said metallic substrate is a pre-coated metallic substrate.
[5]
Device or method according to any one of claims 1 to 3, characterized in that said aqueous dispersions additionally comprise one or more solvents.

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法律状态:
2018-11-27| B06T| Formal requirements before examination|

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2019-01-15| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-07-09| B09A| Decision: intention to grant|

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2019-09-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/07/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/07/2010, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

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申请号 | 申请日 | 专利标题

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US22838309P| true| 2009-07-24|2009-07-24|

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PCT/US2010/043081|WO2011011705A2|2009-07-24|2010-07-23|A coated container device, method of making the same|

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