COATED CONTAINER DEVICE

专利摘要:
Device for preparing a coated container summary device, coated closure container device and method for coating, method for preparing a coated closure device The present invention provides a coated container device, and method for its manufacture. The coated container device according to the present invention comprises: (1) a metal substrate; and (2) one or more crosslinked coating layers associated with the metal substrate, wherein one or more crosslinked coating layers are derived by applying one or more aqueous dispersions to at least one surface of the metal substrate and one or more aqueous dispersions comprise: (a) one or more of a base polymer; (b) one or more of a stabilizing agent; (c) optionally one or more neutralizing agents; (d) one or more crosslinking agents; and (e) water.
公开号:BR112012000906B1
申请号:R112012000906-0
申请日:2010-07-23
公开日:2019-12-03
发明作者:Bernhard Kainz；Richard Lundgard；David Malotky；Jodi Mecca；Charles Diehl；Ray Drumright
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

"COATED CONTAINER DEVICE" Field of the invention [001] The present invention relates to a coated container device and method for its manufacture.
History of the invention [002] The application of various treatment and pretreatment solutions on metals to slow or inhibit corrosion is well established. This is particularly true in the area of metal food and beverage cans, as well as metal containers used for purposes other than food. Coatings are applied to the inside of such containers to prevent their contents from coming into contact with the metal in the container. The contact between the metal and the food or drink, as well as with non-food substances can lead 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 products or beverages are highly acidic in nature and / or have a high salt content, such as rhubarb-based products or isotonic drinks. The strongly alkaline content of non-food substances, such as hair dye, can react with metals, such as aluminum. Coatings applied, for example, inside food and beverage containers can also help prevent corrosion in the top 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 to provide protection from the external environment or to provide a decorative layer, including fillers and / or pigments. In addition to corrosion protection, coatings for food and beverage cans must be non-toxic and inert, and, if applied to the inner surface, should not adversely affect taste or appearance, such as the color of the food or drink in the can, or contribute to the contamination of the can contents. Popping resistance, whitening of the coating ("blushing") and / or blistering ("blistering") is also desired. Certain coatings are particularly applicable to spiral metal material, such as the spiral metal material from which the can ends, "can end material" and valve buttons, such as the upper ends of aerosol cans, are made. Since coatings designed for use on can end material are applied before the ends are cut and stamped out of the spiral metal material, they are also typically flexible and / or stretchable. For example, the can end material is typically coated on both sides. Then, the coated metal material is perforated and can be chamfered or bent. It can also be grooved for the "pop-top" opening and the "pop-top" ring is then connected with a separately manufactured pin. The end is then connected to the can body by an edge winding process. Consequently, the coating applied to the can end material typically has a certain degree of toughness and flexibility, so that it can withstand long manufacturing processes, in addition to all or part of the other desirable characteristics discussed above. Various coatings, such as those based on epoxy and polyvinyl chloride, for example organosol type coatings, have been used in the past to coat the inside of metal cans to prevent corrosion. However, there remains a need for coatings for food and beverage cans, as well as coatings for non-food containers, having, for example, 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, and method for its manufacture.
[004] In one embodiment, the present invention provides a coated container device comprising: (1) a metallic substrate; and (2) one or more layers of cross-linked coating, associated with the metallic substrate, where one or more layers of cross-linked coating are derived from the application of one or more aqueous dispersions to at least one surface of the metallic substrate, and where to a or more aqueous dispersions comprise: (a) one or more base polymers; (b) one or more stabilizing agents; (c) optionally one or more neutralizing agents, (d) one or more crosslinking agents; and (e) water.
[005] In an alternative embodiment, the present invention further provides a method for preparing a coated container device comprising the steps of: (1) selecting a metallic substrate; (2) selecting one or more aqueous dispersions comprising: (a) one or more base polymers; (b) one or more stabilizing agents; (c) optionally one or more stabilizing agents, (d) one or more cross-linking agents; and (e) water; (3) applying one or more aqueous dispersions to at least one surface of said metallic substrate; (4) removing at least a portion of the water from one or more aqueous dispersions; (5) thus forming one or more layers of crosslinked coating associated with at least one surface of the metallic substrate; and (6) forming the coated metal substrate in a coated container device.
[006] In another alternative embodiment, the present invention also provides a method for making a coated container device comprising the steps of: (1) selecting a metallic substrate; (2) forming the metal in 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, (d) one or more crosslinking agents; and (e) water; and (4) applying one or more aqueous dispersions to at least one surface of the container device; (5) removing at least a portion of the water from one or more aqueous dispersions; (6) thus forming one or more layers of cross-linked coating, associated with at least one surface of the container device; and (7) thus forming the coated container device.
[007] 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.
[008] 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 one or more base polymers comprises one or more polyolefins.
[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 one or more base polymers comprises one or more selected polyolefins of the group consisting of an ethylene-based polymer, and a propylene-based polymer.
[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 one or more base polymers comprises one or more polyolefins having a crystalline melting point greater than 60oC.
[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 one or more base polymers comprises one or more polyolefins having a crystalline melting point greater than 90oC.
[012] 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 one or more base polymers comprises one or more polyolefins having a crystalline melting point greater than 100oC.
[013] 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 one or more base polymers comprises one or more polyolefins having a crystalline melting point greater than 120oC.
[014] 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 one or more base polymers comprises one or more polyolefins having a crystalline melting point greater than 130oC.
Detailed description of the invention [015] The present invention provides a coated container device and method for its manufacture.
[016] The coated container device according to the present invention comprises: (1) a metallic substrate; and (2) one or more crosslinked layers associated with the metallic substrate, where one or more crosslinked coating layers are derived from the application of one or more aqueous dispersions to at least one surface of the metallic substrate, and where to one or more dispersions aqueous solutions comprise: (a) one or more base polymer; (b) one or more stabilizing agents; (c) optionally one or more neutralizing agents; (d) one or more crosslinking agents; and (e) water.
[017] The metallic substrate comprises one or more metals, including, but not restricted to aluminum and aluminum alloys, cold rolled low carbon sweet steel coated with electrolytic tinplate ("ETP"), steel cold rolled cold carbon coated with chromium / electrolytic chromium oxide (ECCS), and any other pretreated 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 metal substrate may comprise a sheet, strip or spiral. The metallic substrate can comprise one or more layers, and each layer can have a thickness in the range of 0.01 μm to 2mm; for example, from 0.0 µm to 1.5 mm; or alternatively, from 0.0 µm to 1mm; or alternatively, from 0.0 µm to 0.5 mm; or alternatively, from 0.0 µm to 0.2 mm; or alternatively, from 0.0 μm to 0.1 mm or alternatively, from 0.0 μm to 100 μm; or alternatively, from 0.0 μm to 50 μm; or alternatively, from 0. ^ m to 50 μm; or alternatively, from ^ m to 15μm. The substrate can be pre-coated with one or more pre-coating compositions. Such pre-coating compositions can optionally include, but are not restricted to one or more resin binders, one or more resin crosslinkers, one or more solvents, one or more additives, and one or more pigments. Representative resin binders include, but are not limited to, epoxy, polyester, polyvinyl chloride containing organosols / vinyls, phenolic, alkyd, oleoresin, acrylic resin, and the like. Representative 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, block 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. Representative solvents and thinners include, but are not limited to, glycol ethers, alcohols, aromatics, such as aromatic hydrocarbons, turpentine, branched ketones and esters. Representative 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, anti-caking agents, stabilizers UV, adhesion promoters. Pigments include, but are not limited to, titanium dioxide, zinc oxide, aluminum oxide, zinc and aluminum. The substrate can also be pre-coated with one or more pre-coated laminate compositions. Such compositions can, for example, include compositions of polyethylene, polypropylene, or polyester, and can be applied as a film via a film lamination process, or melt extrusion coating processes on the metal surface.
[018] The one or more layers of coating are derived from the application of one or more aqueous dispersions to at least one surface of the metallic substrate. The one or more aqueous dispersions comprise the mixture product by melting one or more base polymers and one or more stabilizing agents, and one or more crosslinking agents in the presence of water and optionally one or more neutralizing agents under pressure conditions and temperature controlled. Alternatively, the one or more aqueous dispersions comprise the mixture product by melting one or more base polymers and one or more stabilizing agents, in the presence of water and optionally one or more neutralizing agents under controlled pressure and temperature conditions, and the post-addition of one or more crosslinking agents.
Base Polymer [019] The aqueous dispersion comprises from 1 to 99 weight percent of one or more base polymers, based on the total weight of the solids content of the aqueous dispersion. All individual values and sub-ranges from 1 to 99 weight percent are included in the present invention and described herein; for example, the weight percentage can be from a minimum limit of 1, 5, 8, 10, 15, 20, 25 weight percent up to a maximum limit of 40, 50, 60, 70, 80, 90, 95 or 99 percent by weight. For example, the aqueous dispersion can 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 the solids content of the aqueous dispersion. The aqueous dispersion comprises at least one or more base polymers.
[020] The base polymer can, for example, be selected from the group consisting of a thermoplastic material, and a thermoset material. The one or more base polymers can comprise one or more olefin-based polymers, one or more acrylic-based polymers, one or more polyester-based polymers, one or more epoxy-based polymers, one or more polyurethane polymers thermoplastic, one or more polymers on a styrenic basis, one or more copolymers based on vinyl, one or more polyamides, or combinations thereof.
[021] In one embodiment, the one or more base polymers comprise one or more polyolefins. The one or more base polymers comprising one or more polyolefins may further include one or more non-polyolefinic thermoplastic materials, and / or one or more non-polyolefinic thermoset materials. Such additional non-polyolefin based polymers include, but are not restricted to one or more acrylic based polymers, one or more polyester based polymers, one or more epoxy based polymers, one or more thermoplastic polyurethane polymers, one or more styrenic-based polymer, one or more vinyl-based copolymers, one or more polyamides, or combinations thereof.
[022] 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-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-1-butene copolymers, and propylene-1-butene copolymer; copolymers (including elastomers) of an alpha-olefin, with a conjugated or unconjugated diene, as typically represented by ethylene-butadiene copolymer and ethylene-ethylidene norbornene copolymer, and polyolefins (including elastomers), such as copolymers of two or more alpha-olegines, with a conjugated or unconjugated diene, as typically represented by ethylene-propylene-butadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-1,5-hexadiene copolymer, and ethylene-propylene copolymer norbornene ethylidene; copolymers of ethylene-vinyl compound, such as ethylene-vinyl acetate copolymer, vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, ethylene acrylic or ethylene-acid (meth) acrylic copolymers, and ethylene-acrylic copolymer (met) acrylate.
[023] In certain embodiments, one or more polyolefin-based polymers can be functionalized polyolefins, such as polypropylene or polyethylene homopolymer or copolymer in which the polymer has been modified with hydroxyl, amine, aldehyde, epoxide, ethoxylated, carboxylic acid, ester , or anhydride group. Such functionalized olefins, such as polypropylene or polyethylene homopolymers or copolymers, are provided, for example, by Baker Petrolite, a subsidiary of Baker Hughes, Inc.
[024] Representative polyolefins include, but are not restricted to one or more thermoplastic polyolefin 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 1-dodecene, 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 representative polyolefins can 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. [025] In one embodiment, one or more polyolefins have a crystalline melting point greater than 60oC; for example, greater than 95oC; or alternatively, greater than 100oC; or alternatively, greater than 120oC; or alternatively, greater than 130oC.
[026] In one embodiment, at least one or more of the base polymers comprises a thermoplastic polar polyolefin polymer, having a polar group as a grafted comonomer or monomer. Representative polar polyolefins include, but are not restricted to polyethylene homopolymer or copolymer grafted with maleic anhydride, polypropylene homopolymer or copolymer grafted with maleic anhydride, ethylene-acrylic acid (EAA) and ethylene-methacrylic acid copolymers, such as those available under the PRIMACORTM brands, marketed by The Dow Chemical Company, NUCRELTM, marketed by EIDuPont de Nemours, and ESCORTM, marketed by ExxonMobil Chemical Company and described in U.S. Pat. 4,599,392, 4,988,781 and 5,938,437, each of which is incorporated by reference in so far as it describes such polar polyolefins. Other representative polar polyolefins include, but are not limited to, ethylene ethyl acrylate (EAA) copolymer, ethylene methyl methacrylate (EMMA), and ethylene butyl acrylate (EBA).
[027] In one embodiment, the polar polyolefinic polymer is a copolymer of ethylene-acrylic acid (EAA) or ethylene-methacrylic acid, which can be neutralized with one or more neutralizing agents, such as a base such as an alkaline metal hydroxide , ammonia, or an organic amine, in the dispersion process.
[028] The thermoplastic material can comprise non-polyolefinic thermoplastic materials. Such non-polyolefinic thermoplastic materials include polymers, such as polystyrene, styrenic copolymers (including elastomers), ABS, acrylonitrile-styrene copolymer, a-methylstyrene-styrene copolymer, styrene vinyl alcohol, styrene acrylates, such as styrene styrene butyl acrylate, styrene butyl methacrylate, and styrene butadienes, and cross-linked styrene polymers; and styrene block copolymers (including elastomers), such as styrene-butadiene copolymer and its hydrate, and styrene-isoprene-styrene triblock copolymer; polyvinyl compounds such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, vinyl chloride copolymers with vinyl acetate, vinyl alcohol, maleic acid anhydride, hydroxyalkyl acrylate, glycidyl methacrylate and the like, acrylate polymethyl, 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, polyhydroxyaminoethers and polyhydroxy esters and the like, for example, polyhydroxyethers, such as the reaction product of diglycidyl bisphenol-A ether with bisphenol A or the like, for example, polyhydroxyaminoethers, as the diglycidylether reaction product bisphenol A with ethanolamine and polyhydroxyester, such as the reaction product of diglycidyl ether bisphenol A with isophthalic acid or terephthalic acid and the like; polycarbonate, polyphenylene oxide, and the like; and glassy hydrocarbon resins, including polymers of poly-dicyclopentadiene and related polymers (copolymers, terpolymers); esters of saturated acids with mono-olefinic 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, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, glycidyl methacrylate, dodecyl acrylate, n-octyl acrylate , phenyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate, and the like; acrylonitrile, methacrylonitrile, acrylamide, mixtures thereof; resins produced by ring opening via metathesis, and polymerization via cross metathesis and the like. These resins can be used alone or in combination of two or more.
[029] Representative (Met) acrylates, as base polymers, include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and acrylate isooctyl, n-decyl acrylate, isodecyl acrylate, tert-butyl acrylate, methyl methacrylate, butyl methacrylate, hexyl methacrylate, isobutyl methacrylate, isopropyl methacrylate as well as 2-hydroxyethyl acrylate, methacrylate hydroxyethyl, 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, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylamide. Other suitable (meth) acrylates that can be polymerized from monomers include lower alkyl acrylates and methacrylates, including acrylic and methacrylic ester monomers: methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, acrylate 2-ethylhexyl, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, methacrylate methacrylate, cyclohexyl methacrylate isodecyl, isobornyl methacrylate, t-butylaminoethyl methacrylate, stearyl methacrylate, glycidyl methacrylate, dicyclopentenyl methacrylate, phenyl methacrylate.
[030] 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 block-olefin copolymers. In particular, in some embodiments, the base polymer can comprise one or more non-polar polyolefins.
[031] In certain specific embodiments, polyolefins such as polypropylene, polyethylene, their copolymers and mixtures, as well as ethylene-propylene-diene terpolymers, can be used. In some embodiments, representative olefinic polymers include homogeneous polymers, such as those described in U.S. Patent No. 3,645,992; high density polyethylene (HDPE), such as that described in U.S. Patent No. 4,076,698; heterogeneously branched linear low density polyethylene (LLDPE); heterogeneously branched linear ultra low density polyethylene (ULDPE); homogeneously branched linear ethylene / alpha-olefin copolymers; substantially linear, homogeneously branched ethylene / alpha-olefin polymers, which can be prepared, for example, by processes described in U.S. Pat. 5,272,236 and 5,278,272, the descriptions of which have been incorporated herein by reference; as well as polymers and copolymers of ethylene polymerized via free radical under high pressure, such as low density polyethylene (LDPE) or polymers of ethylene vinyl acetate (EVA).
[032] In other specific embodiments, the base polymer can, for example, be polymers based on ethylene vinyl acetate (EVA). In other embodiments, the base polymer can, for example, be polymers based on ethylene-methyl acrylate (EMA). In other specific embodiments, the ethylene-alpha olefin copolymer can, for example, be ethylene-butene, ethylene-hexene or ethylene-octene copolymers or interpolymers. In other specific embodiments, the propylene-alpha olefin copolymer can, for example, be a propylene-ethylene or propylene-ethylene-butene copolymer or interpolymer.
[033] In a specific embodiment, the base polymer can be a propylene / alpha-olefin copolymer, characterized by having substantially isotactic propylene sequences. "Substantially isotactic propylene sequences" means that the sequences have an isotactic triad (mm) measured by 13C NMR greater than about 0.85; alternatively, greater than about 0.90; alternatively, greater than about 0.92; and as another alternative, greater than about 0.93. Isotactic triads are well known in the state of the art and are described, for example, in U.S. Patent No. 5,504,172 and in international publication No. WO 00/01745, which refer to the isotactic sequence in terms of a triadic unit in the chain molecular weight of the copolymer determined through 13C NMR spectra.
[034] The propylene / alpha-olefin copolymer can have a crystallinity in the range of at least 1 weight percent (a melting heat of at least 2 Joules / gram) to 30 weight percent (a lower melting heat) at 50 Joules / gram). All values and individual sub-ranges from 1 weight percent (a heat of fusion of at least 2 Joules / gram) to 30 weight percent (a heat of fusion less than 50 Joules / gram) are included and described herein; for example, the crystallinity can be from a minimum limit of 1 weight percent (a heat of fusion of at least 2 Joules / gram), 2.5 percent (a heat of melting of at least 4 Joules / gram), or 3 percent (a heat of fusion of at least 5 Joules / gram) up to a maximum value of 30 percent by weight (a heat of fusion less than 50 Joules / gram), 24 percent by weight (a heat of fusion less than 40 Joules / gram), 15 weight percent (a melting heat less than 24.8 Joules / gram) or 7 weight percent (a melting heat less than 11 Joules / gram). For example, the propylene / alpha-olefin copolymer can 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 lower melting heat at 40 Joules / gram); or alternatively, the propylene / alpha-olefin copolymer can 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 melting heat 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 melting heat of at least 2 Joules / gram) to 7 weight percent (a melting heat less than 11 Joules / gram); or alternatively, the propylene / alpha-olefin copolymer can have a crystallinity in the range of at least 1 weight percent (a melting heat of at least 2 Joules / gram) to 5 weight percent (a melting heat less than 8.3 Joules / gram). Crystallinity is measured using the differential scanning calorimetry (DSC) method. The propylene / alpha-olefin copolymer comprises units derived from propylene and polymer units derived from one or more alpha-olefin comonomers. Representative comonomers used in the preparation of propylene / alpha-olefin copolymer are alpha-olefins C2 and C4 to C10; 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 alpha-olefin comonomers. All values and individual sub-ranges from 1 to 40 weight percent are included and described here; for example, the weight percentage of units derived from one or more alpha-olefin comonomers can be from a minimum limit of 1, 3, 4, 5, 7 or 9 weight percent up to a maximum limit of 40, 35, 30, 27, 20, 15, 12 or 9 weight percent. For example, the propylene / alpha-olefin copolymer comprises from 1 to 35 weight percent of 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 comprises from 3 to 20 weight percent 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.
[035] The propylene / alpha-olefin copolymer has a molecular weight distribution (MWD), defined as the average molecular weight by weight divided by the numerical average molecular weight (Mw / Mn) of 3.5 or less; alternatively, 3.0 or less; or as another alternative, from 1.8 to 3.0.
[036] Such propylene / alpha-olefin copolymers are also described in detail in U.S. Patent Nos. 6,960,635 and 6,525,157, incorporated herein by reference. Such propylene / alpha-olefin copolymers are marketed by The Dow Chemical Company, under the brand VERSIFYTM, or by ExxonMobil Chemical Company, under the brand name VISTAMAXXTM.
[037] In one embodiment, propylene / alpha-olefin copolymers are also characterized as 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 of ethylene, and / or a C4-10 α-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 herein, refers to a chain extension with at least one (1) carbon more than a short chain branch, and short chain branch, as used herein, refers to a chain extension with two (2) carbons to less than the number of carbons in the comonomer. For example, a propylene / 1-octene interpolymer has main chains with long chain branches with at least seven (7) extension carbons, although these main chains also have short chain branches with only six (6) extension carbons. The maximum number of long chain branches typically does not exceed 3 long chain branches / 1000 total carbons. Such propylene / alpha-olefin copolymers are also described in detail in provisional U.S. patent application No. 60 / 988,999 and international patent application No. PCT / US08 / 082599, each of which is incorporated herein by reference.
[038] In other selected embodiments, block olefin copolymers, for example, the multiblock ethylene copolymer, such as those described in international publication No. WO2005 / 090427 and American patent application publication No. US 2006/0199930, incorporated herein by reference in so far as they describe such block olefin copolymers, can be used as the base polymer. Such a block olefin copolymer can be an ethylene / a-olefin interpolymer: (a) having an Mw / Mn of about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius , and a density, d, in grams / cubic centimeter, with the numerical values of Tm and d corresponding to the relationship: Tm> -2002.9 + 4538.5 (d) - 2422.2 (d) 2; or (b) having an Mw / Mn of about 1.7 to about 3.5, and being characterized by a heat of fusion, DH in J / g and a delta amount, DT, in degrees Celsius defined as the difference in temperature between the highest DSC peak and the highest CRYSTAF peak, with the numerical values of DT and DH having the following relationships: DT> -0.1299 (DH) + 62.81 for DH greater than zero and up to 130 J / g, DT> 48oC for Dh greater than 130 J / g, with the CRYSTAF peak being determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature will be 30oC; or (c) being characterized by an elastic recovery, Re, in percentage at 300 percent deformation and 1 cycle measured with a compression molded film of the ethylene / a-olefin interpolymer, and having a density, d, in grams / cubic centimeter, where the numerical values of Re ed satisfy the following relationship when the ethylene / α-olefin interpolymer is substantially free of a crosslinked phase: Re> 1481 - 1629 (d); or (d) having a molecular fraction that elutes between 40oC and 130oC when fractionated using TREF, characterized by the fact that the fraction has a molar comonomer content at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, with said comparable random ethylene interpolymer having the same comonomer (s) and a melting index, density and molar comonomer content (based on the total polymer) in the range of 10 percent in relation to that of the ethylene / a-olefin interpolymer; or (e) having a storage module at 25oC, G '(25oC), and a storage module at 100oC, G' (100oC), where the ratio of G '(25oC) to G' (100oC) is at range from about 1: 1 to about 9: 1. Such a block olefin copolymer, for example, the ethylene / a-olefin interpolymer can also: (b) have a molecular fraction that elutes between 40oC and 130oC when fractionated using TREF, characterized by the fact that the fraction has a block index at least 0.5 and about up to 1 and a molecular weight distribution, Mw / Mn, greater than about 1.3; or (c) have an average block index greater than zero and about up to 1.0 and a molecular weight distribution, Mw / Mn, greater than about 1.3.
[039] In certain embodiments, the base polymer, for example, comprises a polar polymer, having a polar group as a comonomer or grafted monomer. In representative embodiments, the base polymer may, for example, comprise one or more polar polyolefins, having a polar group as a comonomer or grafted monomer. Representative polar polyolefins include, but are not limited to, ethylene-acrylic acid (EAA) and ethylene-methacrylic acid copolymers, such as those available under the PRIMACORTM brands, marketed by The Dow Chemical Company, NUCRELTM, marketed by EI, DuPont de Nemours, and ESCORTM, marketed by ExxonMobil Chemical Company and described in U.S. Patent Nos. 4,599,392, 4,988,781 and 5,938,437, each of which is incorporated herein by reference in its entirety. Other representative base polymers include, but are not limited to, ethylene ethyl acrylate (EEA) copolymer, ethylene methyl methacrylate (EMMA) and ethylene butyl acrylate (EBA).
[040] Another ethylene-carboxylic acid copolymer can also be used. The one or more base polymers could also be derived through chemical modification of the functional acid group in one or more polar polymers to form hydroxyl ester groups, or an amide and the like. Those skilled in the art recognize that several other useful polymers can also be used. Another base polymer could include copolymers, such as ethylene vinyl alcohol and ethylene vinyl acetate and the like.
[041] In one embodiment, the base polymer can, for example, comprise a polar polyolefin selected from the group consisting of ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer, and combinations thereof, and the stabilizing agent can, for example, comprising a polar polyolefin selected from the group consisting of ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer, and combinations thereof; provided, however, that the base polymer may, for example, have an acid number, measured according to ASTM D-974, less than that of the stabilizing agent.
[042] In certain embodiments, the base polymer can, for example, comprise a polyester resin. Polyester resin refers to thermoplastic or thermoset resins that can include polymers containing at least one ester bond. They may have hydroxyl functionality or carboxyl functionality. The polyester can, for example, be prepared via the conventional esterification process using a molar excess of an aliphatic diol or glycol with respect to a polycarboxylic acid or its anhydride. Triols or polyols can be used to provide branched polyesters. Examples of glycols, triols and polyols that can be employed to prepare 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 polypropylene glycols, 1, 3-propanediol, 1,4-butanediol and other butanedioles, 1,5-pentanediol and other pentanedioles, hexanedioles, decanedioles, and dodecanedioles, glycerol, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, a polyethylene glycol, a polyethylene glycol, a polyethylene glycol and a polyethylene glycol. 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.
[043] Illustrative examples of polycarboxylic acids or anhydrides, which can be used in the preparation of polyesters include, but are not limited to maleic acid, maleic anhydride, malonic acid, fumaric acid, succinic acid, succinic anhydride, glutaric acid, adipic acid , 2-methyl-1,6-hexanoic acid, pyelic acid, submeric acid, dodecanedioic acids, phthalic acid, phthalic anhydride, 5-ter-butyl isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, endomethylenetetrahydrate sebacic acid, tetrachloro-phthalic anhydride, chloric acid, isophthalic acid, trimellitic anhydride, terephthalic acid, naphthalene dicarboxylic acid, cyclohexane-dicarboxylic acid, and mixtures thereof. In some embodiments, alkanedioic acids can contain from 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 in the preparation of the polyester.
[044] Other embodiments of the present invention use polyester resins containing aliphatic diols, such as UNOXOLTM (a mixture of cis and trans 1,3- and 1,4-cyclohexanedimethanol) supplied by The Dow Chemical Company (Midland, MI).
[045] In certain embodiments, the base polymer can, for example, comprise a thermoset material comprising an epoxy resin. The epoxy resin refers to a composition that has one or more vicinal epoxy groups per molecule, that is, at least one 1,2-epoxy group per molecule. In general, such a compound is a saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic compound that has at least one 1,2-epoxy group. Such a compound can be substituted, if desired, with one or more non-interfering substituents, such as halogen atoms, hydroxy groups, ether radicals, lower alkyls and the like. One or more epoxy-containing substances can be combined to prepare the desired epoxy resin.
[046] Illustrative epoxies are described in the Handbook of Epoxy Resins by H.E.Lee and K.Neville published in 1967 by McGraw-Hill, New York and U.S. Patent No. 4,066,628, incorporated herein by reference.
[047] Particularly useful compounds that can be used in the practice of the present invention are epoxy resins with the following formula: where n has an average value of 0 or more.
[048] Epoxy resins useful in the present invention can include, for example, glycidyl polyethers of polyhydric phenols and polyhydric alcohols. As an illustration of the present invention, examples of known epoxy resins that can 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-hydroxyphenyl) ) -1-phenylethane), bisphenol F, bisphenol K, bisphenol S, tetrabromobisphenol A, phenol-formaldehyde novolac resins, alkyl-substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentene resins -phenol, phenol resins substituted with dicyclopentadiene, tetramethylbiphenol, tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol, tetrachlorobisphenol A and any combination thereof.
[049] Examples of diepoxides particularly useful in the present invention include 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether (commonly referred to as bisphenol A) and 2,2-bis (3,5-dibromo-4 diglycidyl ether) -hydroxyphenyl) propane (generally referred to as tetrabromobisphenol A). Mixtures of any two or more polyepoxides can also be used in the practice of the present invention.
[050] Other representative diepoxides include diglycidyl ethers of dihydric phenols, such as those described in U.S. Patent Nos. 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 ethers of dicarboxylic acids such as those described in Other bisphenol-based epoxy resin epoxy resins (marketed 300 and 600 series, Midland, Michigan).
[051] The practical epoxy resins of the present invention prepared or via dihydric phenols with dihydric phenols with and "adherent resins (" taffy "[052] Epoxy resins rep the diglycidyl ethers of which R is an hydrocarbon group optionally comprising one or more heteroatoms (such as, without limitation, Cl, Br and S) or an atom or group of atoms forming a stable bond with carbon (such as, without limitation, Si, P and B), where n is one equal to or greater than 1.
[055] Cycloaliphatic epoxide can be a monopoxide, a diepoxide, a polyepoxide or a mixture thereof. For example, any cycloaliphatic epoxide described in U.S. Patent No. 3,686,359, incorporated herein by reference, can be used in the present invention. As an illustration, cycloaliphatic epoxides that can be used in the present invention include, for example, (3,4-epoxycyclohexyl-methyl) -3,4-epoxy-cyclohexane, bis- (3,4-epoxycyclohexyl) adipate, monoxide vinylcyclohexene and mixtures thereof.
[056] In certain embodiments, the base polymer may, for example, comprise a thermoset material comprising a modified epoxy resin that has been generated by reacting one of the aforementioned epoxy resins with a dioic acid, such as, although not restricted to adipic acid , 2-methyl-1,6-hexanoic acid, pyelic acid, submeric acid, dodecanedioic acids, phthalic acid, 5-ter-butyl isophthalic acid, hexahydrophthalic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid , cyclohexane-dicarboxylic acid, and mixtures thereof.
[057] In certain embodiments, the base polymer can, for example, comprise a thermoset material comprising a modified epoxy resin. The modifications could be caused by reacting the terminal epoxy groups of the epoxy resin with a substance containing nucleophilic group, 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 with a phenolic compound, such as bisphenol-A. It may also be the reaction product of the aforementioned epoxy group with an acid functional polyester resin.
[058] In certain embodiments, the base polymer can, for example, comprise a thermoplastic or thermoset polyurethane polymer. Such polyurethane polymers are generally known, and are also described, for example, in international publication No. 2008/057878, incorporated herein by reference in so far as it describes a thermoplastic polyurethane polymer.
[059] Those skilled in the art will recognize that the above listing of representative base polymers is non-comprehensive. It will be appreciated that the scope of the present invention is restricted only by the claims.
[060] 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 12 and the like.
Stabilizing Agent [061] The aqueous dispersion may further comprise at least one or more stabilizing agents to promote the formation of a stable dispersion. The stabilizing agent can preferably be an external stabilizing agent. The dispersion of the present invention comprises from 1 to 50 weight percent of one or more stabilizing agents, based on the total weight of the dispersion solids content. All values and individual sub-ranges from 1 to 45 weight percent are included and described here; for example, the weight percentage may vary from a minimum limit of 1.3.5.10 percent by weight to a maximum limit of 15, 25.35.45 or 50 percent by weight. For example, the dispersion can comprise from 1 to 25; or alternatively, from 1 to 35; or alternatively, from 1 to 40; or alternatively, from 1 to 45 weight percent of one or more stabilizing agents, based on the total weight of the dispersion solids content. In selected embodiments, the stabilizing agent can be a surfactant, a polymer or mixtures thereof. In certain embodiments, the stabilizing agent can be a polar polymer, having a polar group as a comonomer or grafted monomer. In representative embodiments, the stabilizing agent comprises one or more polar polyolefins, having a polar group as a comonomer or as a grafted monomer. Representative polymeric stabilizing agents include, but are not limited to ethylene-acrylic acid (EAA) and ethylene-methacrylic acid copolymers, such as those provided under the PRIMACORTM trademarks by The Dow Chemical Company, NUCRELTM, marketed by EIDuPont de Nemours , and ESCORTM, marketed by ExxonMobil Chemical Company and described in U.S. Patent Nos. 4,599,392, 4,988,781 and 5,938,437, each of which is incorporated herein by reference in its entirety. Other representative polymeric stabilizing agents include, but are not limited to, ethylene ethyl acrylate (EEA) copolymer, ethylene methyl methacrylate (EMMA) and ethylene butyl acrylate (EBA). Another ethylene-carboxylic acid copolymer can also be used. Those skilled in the art will recognize that several other useful polymers can also be used.
[062] In certain embodiments, the stabilizing agent may be a functionalized polyolefin, such as polypropylene or polyethylene homopolymer or copolymer, in which the polymer has been modified with hydroxyl, amine, aldehyde, epoxide, ethoxylated, carboxylic acid, ester or anhydride. These functionalized polyolefins, such as polypropylene or polyethylene homopolymers and copolymers, are provided, for example, by Clariant Corporation under the trade names LICOCENE 4351 and LICOCENE 6452, and by Baker Petrolite, a subsidiary of Baker Highes, Inc.
[063] Other stabilizing agents that can be used include, but are not limited to, long-chain fatty acids, fatty acid salts, or fatty acid alkyl 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.
[064] 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 nonionic surfactants. Examples of anionic surfactants include, but are not limited to, sulfonates, carboxylates, and phosphates. Examples of cationic surfactants include, although they are not restricted to quaternary amines. Examples of nonionic 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 can be external surfactants or internal surfactants. External surfactants are surfactants that do not react chemically in the base polymer during the preparation of dispersion. Examples of external surfactants useful in the present invention include, but are not limited to dodecyl benzene sulfonic acid salts, and lauryl sulfonic acid salt. Internal surfactants are surfactants that actually react chemically on the base polymer during dispersion preparation. An example of an internal surfactant useful in the present invention includes 2,2-dimethylol propionic acid and its salts. Additional surfactants that may be useful in the practice of the present invention include cationic surfactants, anionic surfactants, nonionic surfactants, or combinations thereof. Various commercially available surfactants can be used in embodiments described here, including: OP-100 (a sodium stearate), OPK-1000 (a potassium stearate), and OPK-181 (a potassium oleate), supplied by RTD Hallstar ; UNICID 350, by Baker Petrolite; DISPONIL FES 77-1S and DISPONIL TA-430, supplied by Cognis; RHODAPEX CO-436, SOPROPHOR 4D384, 3D-33, and 796 / P, RHODACAL BX-78 and LDS-22, RHODAFAC RE-610 and RM-710 and SUPRAGIL MNS / 90, supplied by 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 BG-10 and TRITON CG -110, provided by The Dow Chemical Company, Midland, Michigan.
[065] Additional stabilizing agents that can be used are polymers in suspension and solution, 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.
[066] Representative polymeric stabilizing agents include, although not restricted to amphiphilic copolymer compositions, the copolymer comprising the reaction product of (i) from 5 to 95% by weight of one or more hydrophilic monomers and (ii) from 5 to 95% by weight of one or more ethylenically unsaturated copolymerizable hydrophobic monomers. These materials are soluble or emulsifiable in water, especially by neutralization and can act as colloidal stabilizers. Representative stabilizing agents, for example, include, but are not limited to, butyl acrylate and lauryl methacrylate.
[067] Non-ionic water-soluble monomers, suitable for the production of amphiphilic copolymer compositions include, but are not restricted to acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide , N-vinylmethylacetamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, t-butylacrylamide, N-methylolacrylamide, alkyl (methyl) acrylates, such as (methyl) acrylates , butyl acrylate and ethyl acrylate, vinyl monomers such as ethylene, styrene, divinylbenzene, diisobutylethylene, vinyl acetate and N-vinyl pyrrolidone, and allyl monomers such as allyl (meth) acrylate.
[068] Representative and suitable water-soluble cationic monomers for the production of amphiphilic copolymer compositions include, but are not restricted to, quaternary ammonium salts of amine functionalized monomers, such as acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylmethylacetamide, N-vinyl pyrrolidone, t-butylacrylamide, N-methylolacrylamide, ethyl (meth) tributylammonium acrylate TBAEMA, DMAEMA, DMAPMYLAMIDE, chloride, DMAPMAM, chloride, DMAPMAM, chloride methylacrylamidopropyltrimethylammonium (MAPTAC), acrylamidopropyltrimethylammonium chloride (APTAC), N-vinyl pyrrolidone, vinylimidazole, polycarbonate-11 and polycarbonate-4.
[069] "Anionic" and "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, vinylphosphonic acid and vinyl sulfonic acid.
[070] In an alternative embodiment, one or more stabilizing agents can be based on resins, such as polyester, epoxy resins, polyamide resins, which can be reacted with acrylic resins or acrylic monomers to form polyester acrylates, polyamide acrylates and acrylates of epoxy resin.
[071] Polyester resins suitable for producing stabilizing agents can be obtained according to conventional procedures known in the art by reacting, for example, a polybasic acid that contains at least two carboxyl groups per molecule of polybasic acid (eg, an acid polycarboxylic at least dibasic) with a polyhydric alcohol containing at least two hydroxyl groups in the polyhydric alcohol (eg at least dihydric alcohol) in the presence of a conventional esterification catalyst at an elevated temperature with or without the presence of solvent. 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 can be included in the polyester, using a polybasic acid that contains polymerizable double bonds and / or polyhydric alcohol that contains polymerizable double bonds.
[072] Polyester acrylates as stabilizing agents can be formed via in-situ polymerization of ethylenically unsaturated copolymerizable 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 the absence or presence of a reaction fluid. Polyester acrylates in solvents can be dried according to appropriate methods known in the art.
[073] Epoxy resins suitable for producing stabilizing agents can be obtained according to conventional procedures well known in the art, by reacting a polyepoxide with an appropriate polynucleophile. Suitable epoxides include, but are not limited to, glycidyl ethers, and other molecules containing epoxy group.
Suitable polynucleophils include, but are not restricted to polyhydric phenols and polyphenols, polythioles, aliphatic polyalcohols or polybasic acids or polyamines. Suitable representative epoxies include, for example, although not restricted to glycidyl ether that contains at least two glycidyl ether groups per polyglycidyl ether molecule (eg one at least diglidicyl ether) with a polyhydric phenol that contains at least two hydroxyl groups in the polyhydric polyphenol (eg at least dihydric phenol or diphenol) in the presence of a conventional catalyst at an elevated temperature with or without solvent. Another class of epoxy resins can be obtained according to conventional procedures known in the art, by reacting, for example, a polyglycidyl ether containing at least two glycidyl ether groups per polyglycidyl ether molecule (eg, at least one diglycidyl ether ) with a polybasic acid containing at least two carboxyl groups per molecule of polybasic acid (eg a polycarboxylic acid at least dibasic) in the presence of a conventional catalyst at an elevated temperature in the absence or presence of solvent.
[074] Epoxy acrylates to produce stabilizing agents can be formed via in-situ polymerization of ethylenically copolymerizable unsaturated monomers in the presence of epoxy resins. Examples include, but are not restricted to ethylenically unsaturated mono or polyfunctional acids, ethylenically unsaturated mono or polyfunctional acid esters, amides, nitriles, as well as vinyl monomers and vinyl ester with epoxy resins in the presence or absence of a reaction fluid. Alternatively, an acid-functional acrylic resin can be reacted with an epoxy resin in the presence of an appropriate catalyst to form epoxy acrylate. Epoxy acrylates in solvents can be dried according to appropriate methods known to those skilled in the art.
Neutralizing Agent [075] The stabilizing agent can be totally or partially neutralized with a neutralizing agent. In certain embodiments, neutralization of the stabilizing agent, such as a long-chain fatty acid or EAA, can be 25 to 200 percent on a molar basis; or alternatively, it can be 50 to 150 percent on a molar basis; or alternatively, it can be 50 to 120 percent on a molar basis; or alternatively, it can be 50 to 110 percent on a molar basis. For example, for EAA, the neutralizing agent can be a base, such as ammonium hydroxide or potassium hydroxide, for example. Other neutralizing agents can include lithium hydroxide or sodium hydroxide, for example. As another alternative, the neutralizing agent can be, for example, a carbonate. As another alternative, the neutralizing agent can be, for example, any amine such as monoethanolamine, or 2-amino-2-methyl-1-propanol (AMP). Amines useful in embodiments described in the present invention can include diethanolamine, triethanolamine, and TRIS AMINOTM (provided by Angus). NEUTROLTMTE (from BASF), as well as triisopropanolamine, diisopropanolamine and N, N-dimethylethanolamine (provided by The Dow Chemical Company, Midland, MI). Other useful amines can include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-n-propylamine, butylamine, dibutylamine, tributylamine, dimethyl benzyl amine, dimethyl n-propylamine, N-methanolamine, N-aminoethylethanolamine, N- methyldiethanolamine, monoisopropanolamine, N, N-dimethyl propanolamine, 2-amino-2-methyl-1-propanol, 1,2-diaminopropane, tris (hydroxymethyl) -aminomethane, ethylenediamine, Ν, Ν, Ν'Ν'-tetracis (2 hydroxypropyl) ethylenediamine, N, N, N ', N'-tetramethylpropanediamine, 3-methoxypropylamine, imino bis-propyl amine, and the like. In some embodiments, mixtures of amines or mixtures of amines and surfactants can be used. In one embodiment, the neutralizing agent can be a polymeric amine, such as for example diethylene triamine. Those skilled in the art will appreciate that the selection of an appropriate neutralizing agent will depend on the specific composition formulated, and that such a choice is part of knowledge of the state of the art. In one embodiment, amines with boiling points below 250 ° C can be used as neutralizing agents.
Fluid Medium [076] The aqueous dispersion further comprises a fluid medium. The fluid medium can be any medium; for example, the fluid medium can be water. The dispersion of the present invention comprises from 15 to 99 volume percent of water, or alternatively, a mixture of water and one or more organic solvents, for example, one or more water miscible solvents, one or more solvents immiscible in water, or their combinations, based on the total volume of the dispersion. In specific embodiments, the water content can be in the range of 30 to 75, or alternatively, from 35 to 65, or alternatively, from 40 to 60 volume percent, based on the total volume of the dispersion. The water content of the dispersion can preferably be controlled in such a way that the solids content (one or more base polymers plus stabilizing agent) is between about 1 percent to about 99 volume percent. In specific embodiments, the range of solids can be between about 15 percent and about 25 percent. In other specific embodiments, the range of solids can be between 25 percent to about 70 percent by volume. In other specific embodiments, the range of solids is between about 35 percent to about 65 percent by volume. In certain other embodiments, the range of solids is between about 40 percent to about 60 percent by volume.
Additional Components [077] The aqueous dispersion of the present invention can optionally be mixed with one or more binder compositions, such as acrylic latex, acrylic vinyl latex, styrene acrylic 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, additives to mask sulfur stains, pigment wetting / dispersing agents, anti-caking agents, UV stabilizers, adhesion promoters; optionally one or more lubricants, such as fatty acid ester wax, silicon based wax, fluorine based wax, polyethylene wax or any other similar polyolefinic wax, carnauba wax, lanolin wax or the like; optionally one or more corrosion inhibitors, such as aluminum and zinc; optionally one or more pigments, for example, titanium dioxide, barium sulfate, mica, calcium carbonate, silica, zinc oxide, ground glass, aluminum trihydrate, talc, antimony trioxide, fly ash, and clay or the like; optionally one or more cosolvents, for example, glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alcohols, mineral essences, aromatic solvents and benzoate esters or the like; optionally, one or more dispersants, for example, amino alcohols, and polycarboxylates; optionally one or more surfactants; optionally one or more preservatives, for example, biocides, mildiocides, fungicides, algaecides, and combinations thereof; optionally one or more thickeners, for example, cellulosic based thickeners, such as hydroxyethyl cellulose, hydrophobically modified soluble alkali emulsions (HASE thickeners such as UCAR POLYPHOBE TR-116) and hydrophobically modified ethoxylated urethane thickeners (HEUR); or optionally one or more additional neutralizing agents, for example, hydroxides, amines, ammonia, and carbonates; optionally one or more solvents or coalescing agents. [078] In addition, the aqueous dispersion can be mixed with one or more dispersions, emulsions, suspensions, colloidal suspensions, and the like.
Cross-linking Agent [079] The aqueous dispersion may further comprise at least one or more cross-linking agents to promote cross-linking. The aqueous dispersion of the present invention comprises from 1 to 50 weight percent of one or more crosslinking agents, based on the total weight of the dispersion solids content. All values and individual sub-ranges from 1 to 50 weight percent are included and described here; for example, the weight percentage can vary from a minimum value of 1,3,5,10,15,20 weight percent to a maximum limit of 10,12,15,18,20,25,30,35, 40.45 or 50 weight percent. For example, the dispersion can comprise from 1 to 18; or alternatively, from 1 to 15; or alternatively, from 1 to 12; or alternatively, from 1 to 10; or alternatively, from 1 to 20; or alternatively, from 1 to 30; or alternatively, from 1 to 40; or alternatively, from 1 to 45; or alternatively, from 1 to 50 weight percent of one or more crosslinking agents, based on the total weight of the dispersion solids content. In selected embodiments, the crosslinking agent can be, although not restricted to phenol-formaldehyde resins, amino-formaldehyde resins, including, although not restricted to urea-formaldehyde resins, melamine-formaldehyde resins, benzoguanamine-formaldehyde resins , anhydride resins, epoxy group containing resins, including, although not restricted to epoxy resins, polyester or acrylic resins containing epoxy group, and block isocyanate resins, and combinations of two or more thereof, provided that the combinations of such crosslinkers is compatible.
[080] The crosslinking agent can be a compound that reacts with a reactive functional group contained in the dispersion formulation, thus facilitating its crosslinking. Such functional groups can be present in both the base polymer and the stabilizing agent.
[081] For example, reactive functional groups include, although they are not restricted to acid groups such as carboxylic acid groups, in free or neutralized form, or any functional groups containing another active hydrogen through another component such as alcohol groups, amino groups, epoxy groups, or the like.
[082] Cross-linkable functional groups in the cross-linking agent are groups capable of reacting with the reactive functional group of the base polymer or stabilizer. For example, a carbodiimide group, an oxazoline group, an isocyanate group, an epoxy group, a methylol group, an aldehyde group, an acid anhydride group, a hydroxy group, an aziridinyl group, or a silane group can be used in a crosslinker.
[083] Another possibility to cross-link groups with acid functionality is through the use of multivalent metal ions by reacting the acid groups previously mentioned, with a substance containing multivalent metal ions, such as zinc oxide.
[084] Carboxylic acids can also be cross-linked in reactions with multifunctional unsaturated olefinic substances under strong acid catalysis. Multifunctional carbonates can also react with carboxylic acids to give ester bonds with carbon dioxide release.
[085] Alternatively, polyolefinic materials can be cross-linked through cross-linking via free radicals, initiated by the addition of peroxides or via radiation, such as an electron beam.
[086] With respect to crosslinkable functional groups, one or more may be present in a crosslinking agent. Alternatively, two or more cross-linkable functional groups can be present in a single molecule.
[087] The crosslinking agent containing the crosslinkable functional group described above can be a substance dispersed in water or dispersible in water or soluble in water. In one embodiment, representative crosslinking agents include, but are not restricted to, an aqueous monomeric or polymeric substance, which contains two or more oxazoline groups, carbodiimide groups, epoxy groups, isocyanate groups, methylol groups, etc., or several of these per molecule.
[088] A representative oxazoline crosslinking agent is an aqueous polymer having two or more oxazoline groups in its molecules, the substances of which can be obtained by polymerizing a monomer containing an oxazoline group, and, as necessary, an unsaturated ethylene monomer. Alternatively, an oxazoline crosslinking agent can also be obtained by reaction between a nitrile group and an aminoethanol group, dehydration of a hydroxylalkylamide group and the like.
[089] Crosslinking agents having two or more carbodiimide groups can be produced from diisocyanate compounds through a condensation reaction accompanied by a decarboxylation reaction of a diisocyanate compound. Examples of the diisocyanate compound include, but are not limited to, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2, diisocyanate 4-tolylene, 2,6-tolylene diisocyanate, hexanomethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexanehexane diisocyanate, and diocyanate similar. These compounds can also be used as mixtures.
[090] Monofunctional isocyanates can be included to control the molecular chain length of the resin, such as phenyl isocyanate, tolyl isocyanate, cyclohexylisocyanate, dimethylphenyl isocyanate, butylisocyanate, and naphthyl isocyanate are useful.
[091] Diisocyanate substances can be partially reacted with aliphatic compounds, alicyclic compounds, or aromatic compounds having a hydroxyl group, an imino group, an amino group, a carboxyl group, a mercapto group, an epoxy group and the like.
[092] In the condensation reaction accompanied by decarboxylation of a diisocyanate compound, a carbodiimidization catalyst can be used. Useful as a catalyst are, for example, phosphene oxides, such as 1-phenyl-2-phosphene-1-oxide, 3-methyl-2-phosphene-1-oxide, 1-ethyl-2-phosphene-1-oxide, and 3-phosphene isomers thereof.
[093] To convert a polymer containing carbodiimide group to an aqueous polymer, a hydrophilic segment is provided in the molecular structure of the polymer containing carbodiimide group. For example, an aqueous polymer containing a carbodiimide group can be obtained by providing a hydrophilic segment containing a functional group that is reactive with an isocyanate group. Useful as the hydrophilic segment are: quaternary ammonium salts, dialkylamino alkylamine salts (eg, 2-dimethylaminoethanol quaternary ammonium salts); quaternary salts of dialkylamino alkylamine (ex: 3-dimethylamino-n-propylamine); alkyl sulfonic acid having at least one reactive hydroxyl group (eg, sodium hydroxypropanesulfonate); a mixture of polyethylene oxide or polyethylene oxide whose end is capped with an alkoxy group, and a polypropylene oxide (eg polyethylene oxide whose end position is capped with a methoxy group or an ethoxy group).
[094] As an aqueous crosslinking agent containing an epoxy group, exemplified are polyglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether trimethylolpropane, triglycidyl ether, poly (ethylene glycol) diglycidyl ether, poly (propylene glycol) diglycidyl glycol) ether, and lauryl alcohol ethylene glycidyl ether or the like. In addition to the above, examples are mentioned such as: a water-soluble epoxy resin obtained by reacting a carboxy compound, which is obtained by reacting a polyoxyethylene polyol compound and an acid anhydride compound, and an epoxy resin having two or more epoxy groups in their molecules; and a self-emulsifiable epoxy resin composition obtained by mixing the water-soluble epoxy resin and the epoxy resin having two or more epoxy groups in their molecules. Such resins can be obtained, for example, under the trade names XZ 92533.00, XZ 92598.00 and XZ 92446.00 from The Dow Chemical Company, Midland, MI. Examples of the anhydride compound include, although they are not particularly restricted to aromatic anhydrides, such as phthalic anhydride, trimellitic anhydride and pyromelitic anhydride; and cyclic aliphatic anhydrides, such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl naic anhydride, succinic alkenyl anhydride, hexahydrophthalic anhydride, and hexahydrophthalic methyl anhydride. There is no limitation in relation to the epoxy resin with two or more epoxy groups in its molecules, and all known epoxy resins with an epoxy functionality equal to or greater than two can be used. Examples are polyglycidyl ether obtained from epichlorohydrin and a polyhydric compound such as phenol novolac, cresol novolac, bisphenol A, bisphenol F, bisphenol S, resorcinol, hydroquinone or catechin; bisphenol A added with alkylene oxide; polyalcohols such as polypropylene glycol, 1,6-hexanediol, trimethylolpropane, glycerin, cyclohexanedimethanol; and polyglycidyl ether and polyglycidyl amine of polycarboxylic acids such as adipic acid, phthalic acid, dimeric acid and the like.
[095] Aqueous crosslinking agent containing an isocyanate group are, for example: polyisocyanate mainly containing at least one member selected from the group consisting of a polyisocyanate containing isocyanurate group, a polyisocyanate containing uretodione group, a polyisocyanate containing uretodione group / isocyanurate group, a polyisocyanate containing urethane group, a polyisocyanate containing allophanate group, a polyisocyanate containing biuret group, a polyisocyanate containing carbodiimide group, and a polyisocyanate containing uretodione group, each containing 1,6-hexamethylene diisocyanate and / or isophorone diisocyanate as raw material; and a self-emulsifying polyisocyanate obtained by reacting a hydrophilic surfactant having at least one active hydrogen group that can react with an isocyanate group or polyethylene alcohol ether containing at least three units of polyethylene oxide with fatty acid ester in which the sum of the number of fatty acid carbons and a compound containing hydroxyl as a raw material is 8 or more and has at least one active hydrogen group that can react with an isocyanate group. In addition to the above, a polyisocyanate containing urethane group obtained by reaction between 1,6-hexamethylene diisocyanate and / or an isophorone diisocyanate and a compound containing active hydrogen group or polyisocyanate obtained by an allophanatization reaction, carbodiimidization reaction, reaction of uretodionization, and biuretization reaction of these diisocyanate compounds can be mentioned.
[096] Examples of suitable crosslinking agents containing an aldehyde are phenol-formaldehyde resins, amino-formaldehyde resins or combinations thereof dispersed in water or dispersible in water or soluble in water.
[097] Phenol-formaldehyde crosslinking agents include, but are not limited to, reaction products of aldehydes with phenols. Preferred, but not exclusive, aldehydes are formaldehyde and acetaldehyde. A wide variety of phenols can be used, such as, but not restricted to phenol, cresol, p-phenylphenol, p-ter-butylphenol, p-ter-amylphenol, cyclopentylphenol, cresylic acid, bisphenol A, bisphenol F, and the like, and their combinations. Acid-functional phenols can also be used in the preparation of phenol-formaldehyde resins. Crosslinkers can be non-etherified or etherified with alcohols or polyols. These phenol-formaldehyde resins can be soluble or self-emulsifiable in water or can be stabilized by the use of colloidal stabilizers, such as polyvinyl alcohol.
[098] Amino-formaldehyde crosslinking agents include, but are not restricted to reaction products of aldehydes with molecules containing amino group or starch. Representative aldehydes include, but are not limited to, formaldehyde and acetaldehyde. A wide variety of molecules containing an amino group or starch can be used, such as, but not limited to, urea, melamine, benzoguanamine, acetoguanamine, glycoluryl, and the like. Suitable amino crosslinking resins include melamine-formaldehyde, urea-formaldehyde, benzoguanamine-formaldehyde, acetoguanamine-formaldehyde, glycoluryl-formaldehyde resins. Also, the methylol groups of an amino formaldehyde resin can be partially or totally etherified with at least one of the monohydric aliphatic alcohol groups, such as methanol and / or n-butanol. These amino formaldehyde resins can be soluble or self-emulsifiable in water or can be stabilized using colloidal stabilizers, such as polyvinyl alcohol, and can be used to stabilize dispersions of amino formaldehyde.
[099] Commercially available amino-formaldehyde resins that are water-soluble or water-dispersible and useful for the purpose of the present invention include CymelTM 301, CymelTM 303, CymelTM 370 and CymelTM 373 (all products from Cytec Surface Specialties, Brussels, Belgium). Other aldehydes used to react with the amino compound to form the resinous material are crotonic aldehyde, acrolein, or compounds that generate aldehydes, such as hexamethylene-tetramine, paraldehyde and the like.
[100] Another class of crosslinking agents for carboxylic acid groups are water soluble hydroxyalkylamide crosslinkers, such as Bis (N, N'-dihydroxyethyl) adipamide and the like. Such compounds are available on the market under the trade name of EMS-PRIMID crosslinker resins from Switzerland, for example, PRIMIDTM XL-522, PRIMIDTM SF-4510 and PRIMIDTM QM-1260.
[101] The one or more crosslinking agents can be added to the aqueous dispersion as part of the aqueous dispersion formulation process; or alternatively, the one or more crosslinking agents can be added to the aqueous dispersion after the dispersion formulation process.
[102] Depending on the type of food or drink that must be contained in a coated container, and the coating properties required, it may be beneficial to combine several crosslinkers or some crosslinkers may be more appropriate than others. Some crosslinkers may not be suitable for all applications. Some crosslinkers may require the addition of catalysts for proper curing.
[103] Crosslinkers help to build thermosetting crosshairs, which is indicated by higher Double Friction values with methyl ethyl ketone compared to an identical formulation not containing the crosslinker.
Dispersion Formation [104] The aqueous dispersion can be formed by any number of methods recognized by those skilled in the art. Dispersion equipment can be operated in batch, semi-stacked or continuous mode. Examples of mixers include rotor-stator, microfluidizer, high pressure homogenizer, ultrasonic jet, CowlesTM blade, planetary mixers, and melting kneading devices such as extruders.
[105] In one embodiment, one or more base polymers, one or more stabilizing agents are mixed by melting together with water and optionally with 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 combined, and then kneaded by melting in an extruder in the presence of water and optionally with one or more neutralizing agents to form a dispersion. In some embodiments, the dispersion is first diluted to contain about 1 to about 20%, for example, 1 to 5%, or 1 to 3%, by weight of water and then subsequently diluted to understand more than about 25% by weight of water. In one embodiment, further dilution can be performed using a solvent.
[106] Any melting kneading medium known in the art can be used. In some embodiments, a kneader / mixer, a BANBURY mixer, single screw extruder, or multiple screw extruder, for example, a double screw extruder, is used. A process for producing the dispersions according to the present invention is not particularly restricted. For example, an extruder, in certain embodiments, for example, a twin screw extruder is coupled to a back pressure regulator, fusion pump, or gear pump. Representative embodiments also provide a base reservoir and an initial water reservoir, each including 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, although in some embodiments, for example, a pump that can provide a flow of around 150cc / min at a pressure of 240 bar is used to provide the base and the starting water for the extruder. In other embodiments, a liquid injection pump provides a flow of 300cc / min at 200 bar or 600 cc / min at 133 bar. In some embodiments, the base and initial water are preheated in a preheater.
[107] One or more base polymers, in the form of pellets, powder or scales, are fed from the feeder to an extruder inlet where the resin is melted or mixed. One or more additional components can optionally be fed simultaneously with one or more base polymers in the extruder via the feeder; or alternatively, one or more additional components can be mixed into one or more base polymers and then fed into the extruder via the feeder. Alternatively, one or more additional components can optionally be measured through an inlet before the emulsification zone in the molten compound comprising one or more base polymers. In some embodiments, the dispersing agent is added to one or more base polymers through and together with the resin and in other embodiments, the dispersing agent is supplied 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 are added through an inlet. In some embodiments, the dispersing agent can be added additionally or exclusively to the water stream. In some embodiments, additional dilution water can be added via the water inlet of 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. In addition, the diluted mixture can be diluted any number of times until the desired dilution level is reached. In some embodiments, the dispersion is also cooled after leaving the extruder using an appropriate 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 formation of vapor pressure in the extruder is eliminated and the dispersion is formed in a secondary mixing device, such as rotor stator mixer.
[108] In another embodiment, the aqueous dispersion can be formed in a continuous high-shear mixer without the use of a melt mix extruder. In this embodiment, the first stream comprising one or more liquid or molten base polymers is supplied to a continuous high shear mixer from a suitable liquid pump, for example, a syringe pump, gear pump, or progressive cavity pump. The first stream is drained through a first conduit and continuously connected to a second stream containing a continuous aqueous phase which is drained through a second conduit. The first and second streams are joined in a disperser in the presence of a stabilizing agent with an optional neutralizing agent. The agents can be added to the first or second streams, or as a separate stream. A third stream comprising water can be added downstream of the disperser. The flow rates of the streams are adjusted to obtain a dispersion that has the desired amount of polymer phase and percentage solids. The disperser can be any one of several continuous in-line mixers, such as, for example, IKA high shear mixer, Oakes rotor mixer mixer, Ross mixer, Silverson mixer, or centrifugal pump. The dispersion rpm setting 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 polymeric and neutralizing components at a viscosity suitable for pumping. Steam formation is reduced by controlling the pressure using a back pressure regulator, gear pump, dosing pump, or other device near the process outlet. In some embodiments, the dispersion is also cooled after leaving the disperser using an appropriate heat exchanger.
[109] In another embodiment, the aqueous dispersion can be formed in a high shear batch or semi-batch mixer, where the mixer can, for example, be arranged inside a pressurized tank to, for example, reduce the formation of steam. All or at least a portion of the dispersion is removed from the tank during processing and, optionally, cooled using an appropriate heat exchanger.
[110] 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 stain masking additives, pigment wetting / dispersing agents, anti-caking agents, UV stabilizers, promoters adherence; optionally one or more lubricants, such as fatty acid ester wax, silicon based wax, fluorine based wax, polyethylene wax or any other similar polyolefin wax, carnauba wax, lanolin wax, or the like; optionally one or more corrosion inhibitors, such as aluminum and zinc; optionally one or more pigments, for example, titanium dioxide, mica, calcium carbonate, barium sulfate, silica, zinc oxide, ground glass, aluminum trihydrate, talc, antimony trioxide, fly ash, and clay and the like; optionally one or more pigments; optionally one or more cosolvents, for example, glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alcohols, mineral essences, and benzoate esters or the like; optionally, one or more dispersants, for example, amino alcohols, and polycarboxylates; optionally one or more surfactants; optionally one or more defoamers; optionally one or more preservatives, for example, biocides, mildiocides, fungicides, algaecides, and combinations thereof; optionally one or more thickeners, for example, cellulosic based thickeners, such as hydroxyethylcellulose, hydrophobically modified soluble alkali emulsions (HASE thickeners such as UCAR POLYPHOBE TR-116) and hydrophobically modified ethoxylated urethane thickeners (HEUR); or optionally one or more additional neutralizing agents, for example, hydroxides, amines, ammonia, and carbonates can be added to the aqueous dispersion formulation; or alternatively, they can be added to the dispersion after the dispersion formulation process.
[111] During the preparation of the aqueous dispersion, one or more stabilizing agents can also be added to the aqueous dispersion formulation; or alternatively, they can be added to the dispersion after the dispersion formulation process.
[112] Optionally, during the dispersion of one or more base polymers, another polymer dispersion or emulsion can be used as a portion of the aqueous phase of the dispersion. Examples include, but are not limited to dispersions, emulsions, suspensions, colloidal suspensions containing acrylic, epoxy, polyester, polyurethane, polyolefin, polyamide and the like.
Coating Applications and Formation of Containers and Coated Closing Devices [113] The aqueous dispersion can be used, for example, in containers, for example, can, coating application or coating application in closing device. Such coated container devices include, but are not restricted to cans, such as beverage cans, food cans; aerosol containers, such as those for non-food products, such as hair spray, hair dye or colored spray lacquers; drums; barrels; buckets; decorative cans; open trays; tubes, flasks / bottles, monoblocks, and the like. Coated closing devices include, but are not limited to, covers, lids, such as thin aluminum foil lids for yogurt and butter containers, or bottle stoppers; closures for plastic jars and flasks / bottles, such as threaded closures ("roll-on"), vacuum closures, tamper-resistant closures, easy-open lids for can closures, as well as easy-open or conventional can ends. The cans can be cans in two or three pieces. Beverage cans include, but are not restricted to beer cans, carbonated soft drink cans, energy drink cans, isotonic drink cans, water cans, juice cans, tea cans, coffee cans, milk cans, and similar. Food cans include, but are not limited to, vegetable cans, fruit cans, meat cans, soup cans, ready-made food cans, fish cans, edible oil cans, sauce cans and the like. Such cans can have any shape; for example, such a can can have a cylindrical, cubic, spherical, semi-spherical shape, bottle-shaped, elongated cubic shape, low or high 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 can be formed by stamping, drawing, restoring, mechanical ironing / drawing method ("wall ironing"), folding, chamfering, embossing, engraving, flanging, edge placement ("necking" "), stretch, blow stretch and any other appropriate conventional method. Such methods are generally known in the art. The aqueous dispersion can, for example, be applied to a metallic substrate, for example, a metal sheet or sheet, and then the coated substrate can be formed in a coated container device or coated closure device. Alternatively, the metal substrate can be formed in a container device or a closure device, and then the container device or closure device is coated with one or more dispersions to form the coated container device or the coated closure device. The coating can be applied by any method; for example, through roller coating, spray coating, powder coating, dip coating, electroplating coating, stamping, semi-transparent thin coating (wash coating), flow coating, curtain coating.
[114] One or more dispersions applied to at least one surface of the metal substrate can be dried using any conventional drying method. Such conventional drying methods include, but are not limited to, air drying, convection drying, hot air drying and / or infrared drying. During the drying process, crosslinking of one or more base polymers, stabilizing agents, or combinations thereof, may occur, involving one or more crosslinking agents. Additional curing can take place through radiation curing, for example, electron beam curing. One or more aqueous dispersions applied to at least one surface of the metal substrate can be dried at any temperature; for example, it can be dried at a temperature in the range equal to or greater than the melting point temperature of the base polymer; or alternatively, it can be dried at a temperature in the range below the melting point of the base polymer. One or more dispersions applied to at least one surface of the metal substrate can be dried at a temperature in the range of the base polymer; or alternatively, it can be dried at a temperature in the range below the melting point of the base polymer. One or more aqueous dispersions applied to at least one surface of the metal substrate can be dried at a temperature in the range of about 60oC (15.5oC) to about 700oC (371oC) 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 minutes, or less than 20 seconds. All individual values and sub-ranges from about 60oF (15.5oC) to about 700oC (371oC) are included and described here; for example, one or more aqueous dispersions applied to at least one surface of the metal substrate can be dried at a temperature in the range of about 60oC (15.5oC) to about 500oF (260oC) for less than 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, or alternatively, to one or more dispersions applied to at least one surface of the metal substrate can be dried at a temperature in the range of about 60oF (15.5oC) to about 450oC (232.2oC) 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 dispersions applied to at least one surface of the metal substrate can 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 and individual sub-bands of less than about 40 minutes are included and described here; for example, the temperature of one or more dispersions applied to at least one surface of the metal substrate can 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 20 minutes, or alternatively, the temperature of one or more dispersions applied to at least one surface of the metallic substrate can 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 5 minutes, or as another alternative, the temperature of one or more dispersions applied to at least one surface of the metal substrate can 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 one or more dispersions applied to at least one surface of the metallic substrate can be raised to a temperature in the range below the melting point temperature of the base polymer for a period of less than 40 minutes. All values and individual sub-bands under 40 minutes are included and described here; for example, the temperature of one or more dispersions applied to at least one surface of the metallic substrate can be raised to a temperature in the range below the melting point temperature of the base polymer for a period of less than 20 minutes, or alternatively, at The temperature of one or more dispersions applied to at least one surface of the metal substrate can be raised to a temperature in the range below the melting point temperature of the base polymer for a period of less than about 5 minutes, or alternatively, the temperature One or more aqueous dispersions applied to at least one surface of the metal substrate can be raised to a temperature in the range below the melting point temperature of the base polymer, for a period in the range of about 0.5 to 300 seconds.
[115] The coated metal substrate can also be coated with one or more coating compositions, or it can be laminated to one or more layers. Such conventional coating compositions are generally known in the art, and may include, but are not limited to epoxy resin coating compositions, acrylate-based coating compositions, and polyester-based coating compositions. The lamination process is generally known, and representative lamination layers may include, but are not limited to polyester laminates, polyolefin-based laminates, such as polypropylene laminates.
[116] One or more dispersions applied to at least one surface of a metallic substrate, for example, a pre-coated substrate, such as one or more layers of cross-linked coating may have a cross-section adhesion index of at least 3B; for example, 5B, measured according to ASTM-D 3359-08. The one or more dispersions applied to at least one surface of a metallic substrate such as one or more layers of crosslinked coating may be a double friction index in methyl ethyl ketone (MEK) of at least 10. To one or more dispersions applied to at least at least one surface of a metallic substrate such as one or more layers of crosslinked coating may have a wedge-bend approval rating of at least 90 percent, measured via the Gardner "COVERALL" IG 1125 Bend Tester.
Examples [117] The following examples illustrate the present invention, although they are not intended to limit the scope of the invention. The examples of the present invention demonstrate that one or more dispersions applied to at least one surface of a metallic substrate provide improved coating layer flexibility, as well as coating layer adhesion to the metallic substrate.
Preparation of the Aqueous Dispersion A of the Invention [118] Aqueous dispersion A was prepared according to the following procedures, based on the formulation components listed in Table 1. PRIMACORTM 1410 (CAS No. 9010-77-9), which is the ethylene-acrylic acid copolymer with an acrylic acid content of approximately 9 to 10 weight percent and a melting index of approximately 1.3 to 1.6 g / 10 minutes (ASTM D 1238, 190oC / 2.16 kg), marketed by The Dow Chemical Company, as the base polymer, and PRIMACORTM5980i (CAS No. 9010-77-9), an ethylene-acrylic acid copolymer with an acrylic acid content in the range of approximately 19.5 at 21.5 weight percent and a melt index of approximately 300g / 10 minutes (ASTM D 1238, 190oC / 2.16 kg), marketed by The Dow Chemical Company, as the stabilizing agent were fed into a twin screw extruder 25mm in diameter using a speed controlled feeder, where were transferred and merged. The temperature profile of the extruder was increased to approximately 160oC before the addition of the initial water and AMP-95, amino-2-methyl-1-propanol (95%) (CAS No. 124-68-5), as a neutralizing agent and later, it was cooled to a temperature below 100oC at the end of the extruder, after the dilution water was added. The speed of the extruder was approximately 450 rpm. The amine base and water were mixed together and fed into the extruder at the point of initial water introduction. The dilution water was fed via a second pump, and 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 adequate pressure inside the extruder barrel, to reduce the formation of steam at the operating temperature. The resulting dispersions were cooled and filtered through a 200 micron filter.
Preparation of the Aqueous Dispersion B of the Invention [119] Aqueous dispersion B was prepared according to the following procedures, based on the formulation components listed in Table 1. PRIMACORTM 1321 (CAS No. 9010-77-9), which is the ethylene-acrylic acid copolymer with an acrylic acid content of approximately 6 to 7 weight percent and a melting index of approximately 2.2 to 2.8 g / 10 minutes, marketed by The Dow Chemical Company , as the base polymer, and HDPE 30460M (CAS No. 26211-73-8), a high density polyethylene with a density in the range of approximately 0.958 to 0.962 g / cm3 and a melt index of approximately 24 to 36g / 1 minute, marketed by The Dow Chemical Company, as the additional base polymer and PRIMACORTM5980i (CAS No. 9010-77-9), ethylene-acrylic acid copolymer with an acrylic acid content in the range of approximately 19.5 to 21.5 weight percent and a melt index of approximately 30 0g / 10 minutes (ASTM D 1238, 190oC / 2.16 kg), marketed by The Dow Chemical Company, as the stabilizing agent were fed into a 25mm diameter twin screw extruder through a controlled speed feeder, where transferred and merged. The temperature profile of the extruder was increased to approximately 160oC before the addition of the initial water and AMP-95, amino-2-methyl-1-propanol (95%) (CAS No. 124-68-5), as a neutralizing agent and later, it was cooled to a temperature below 100oC at the end of the extruder, after the dilution water was added. The speed of the extruder was approximately 450 rpm. The amine base and water were mixed together and fed into the extruder at the point of initial water introduction. The dilution water was fed via a second pump, and 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 adequate pressure inside the extruder barrel, to reduce the formation of steam at the operating temperature. The resulting dispersions were cooled and filtered through a 200 micron filter.
Preparation of the Aqueous Dispersion C of the Invention [120] Aqueous dispersion C was prepared according to the following procedures, based on the formulation components listed in Table 1. PRIMACORTM 1321 (CAS No. 9010-77-9), which is the ethylene-acrylic acid copolymer with an acrylic acid content of approximately 6 to 7 weight percent and a melting index of approximately 2.2 to 2.8 g / 10 minutes (ASTM D 1238, 190oC / 2 , 16 kg), marketed by The Dow Chemical Company, as the base polymer, and PRIMACORTM5980i (CAS No. 9010-77-9), an ethylene-acrylic acid copolymer with an acrylic acid content in the range of approximately 19.5 to 21.5 weight percent and a melt index of approximately 300g / 10 minutes (ASTM D 1238, 190oC / 2.16 kg), marketed by The Dow Chemical Company, as the stabilizing agent were fed into a twin screw extruder. 25mm in diameter through a speed controlled feeder, where were transferred and merged. The temperature profile of the extruder was increased to approximately 160oC before the addition of the initial water and DMEA, 2-dimethylamino ethanol (100%) (CAS No. 108-010), as a neutralizing agent and was subsequently cooled to a temperature below 100oC at the end of the extruder, after the dilution water is added. The speed of the extruder was approximately 450 rpm. The amine base and water were mixed together and fed into the extruder at the point of initial water introduction. The dilution water was fed via a second pump, and 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 adequate pressure inside the extruder barrel, to reduce the formation of steam at the operating temperature. The resulting dispersions were cooled and filtered through a 200 micron filter.
Preparation of the Aqueous Dispersion D of the Invention [121] Dispersion D was prepared similarly to dispersion A, but with the formulation components listed in Table 1.
Preparation of Complementary S1-28 Aqueous Dispersions [122] Complementary S1-28 Aqueous Dispersions of the invention were prepared similarly to dispersion A, but with the formulation components listed in Table 1.
Coatings Preparations Based on Formulations with Melamine Formaldehyde Crosslinker [123] The AD dispersions were mixed with CymelTM327 (CAS No. 9003-08-1), melamine formaldehyde resin, from Cytec Surface Specialties, Brussels, Belgium, as a crosslinker in a beaker using an IKA RW 16 electric mixer mixer at level 5 with an R-1302 mixer at room temperature, approximately 25oC, for about 1 minute to give the finished formulation. The mixture is allowed to settle until the bubbles dissipate. The details of the coating formulations based on the combinations of aqueous dispersions A-D and CymelTM327, a crosslinking agent, as shown in Table II.
Preparation of Coatings Based on Formulations with Phenolic Crosslinker Example 5 of Formulation of the Invention [124] Step 1 - Preparation of the dispersion of the phenolic crosslinker mixture: [125] 20g of experimental epoxy curing agent XZ 95320.02, 20g of PhenodurTM PR401 and phenolic resin 0.75g of dimethylethanolamine was mixed under agitation with an IKA RE-166 electric mixer mixer and a propeller blade mixer at about 2000 rpm. Then 18.0 g of water was added slowly with stirring until a phase inversion occurred. The resulting emulsion had a solids content of 41.1%.
[126] The experimental epoxy curing agent XZ 95320.02 is available from The Dow Chemical Company, Midland Michigan. PhenodurTMPR 401 phenolic resin is supplied by Cytec Surface Specialties, Brussels, Belgium.
[127] Step 2 - Preparation of the Final Formulation [128] 25.46g of the dispersion D of the invention are mixed with 4.44g of the above phenolic crosslinker dispersion in a beaker using an IKA RW 16 electric stirrer mixer on level 5 with an R stirrer -1302 at room temperature, approximately 25oC, for about one minute to give the final formulation.
[129] Step 3: A tinplate panel supplied by Rasselstein, with a standard finish type TS 245, 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 tinplate panel via a 30 micron spiral stretch bar, thereby coating a surface of the tinplate panel. Subsequently, the panel was placed in a convection oven to be cured at 200oC for 3 minutes. The coating showed slightly opaque. The details of the coating formulation are listed in Table III.
Invention Formulation Example 6 Preparation of coatings with acrylic resin composition [130] Step 1: Dimethylamino ethanol was mixed with water to form a 50% aqueous solution [131] Step 2: 2.14g of the dimethylamino ethanol aqueous solution ( 50%) from step 1 were slowly added to 4.65g of PRIMALTME 3203 acrylic emulsion in a beaker using an IKA RW 16 electric mixer stirrer on level 5 with an R-1302 stirrer at room temperature, approximately 25oC, for about one minute . A high viscosity dispersion was obtained.
[132] Step 3: The PRIMIDTM XL552 crosslinker was dissolved in water to form a 50% aqueous solution.
[133] Step 4: 6.72g of the mixture resulting from step 2 was mixed with 24.48g of dispersion D in beaker using an IKA RW electric mixer stirrer at level 5 with an R-1302 stirrer at room temperature, approximately 25oC, for about a minute. Then 2g of the PRIMIDTM XL-552 solution (50%) from step 3 was added using an IKA RW 16 electric mixer mixer at level 5 with an R-1302 mixer at room temperature, approximately 25oC, for about one minute.
[134] PRIMALTM E-3203 is provided by The Dow Chemical Company, Midland, MI; PRIMIDTM XL 552, is provided by EMS Chemie, Donat; Switzerland.
[135] A tinplate panel supplied by Rasselstein, with a standard finish type TS-245, approximately 10cm to 20cm in size, was cleaned with acetone, and then dried. About 3 grams of the coating formulation was applied to the tinplate panel via a 30 micron spiral stretch bar, thereby coating a surface of the tinplate panel. Subsequently, the panel was placed in a convection oven to be cured at 200oC for 3 and 6 minutes. The details of the coating results are listed in Table IV.
Invention Formulation Example 7 [136] 1.74g of experimental novolac epoxy emulsion XZ 92546.00 at 57.5% nv were mixed with 31.47g of dispersion D of the invention in a beaker using an electric mixer stirrer on level 5 with an R stirrer -1302 at room temperature, approximately 25oC, for about a minute to give the finished formulation.
[137] A tinplate panel supplied by Rasselstein, with a standard finish type TS-245, approximately 10cm to 20cm in size, was cleaned with acetone, and then dried. About 3 grams of the coating formulation was applied to the tinplate panel via a 30 micron spiral stretch bar, thereby coating a surface of the tinplate panel. Subsequently, the panel was placed in a convection oven to be cured at 200oC for 3 minutes. The details of the coating results are listed in Table V.
[138] Preparation of a tinplate panel coated with a polyester resin formulation [139] 23.28g of DynapolTM 952 polyester and 3.98g of SFC 112/65 from the SI group were mixed with 43.23g of a mixture of 52 parts by weight of SolvessoTM100 aromatic solvent and 48 parts by weight of DowanolTM glycol ether in a sealed glass bottle that was spinning in a row of rotating bars at room temperature for 72 hours. Then 0.181g of phosphoric acid (25% in glycol ether DowanolTM) was added and the flask was rotated for another 24 hours. Dynapol is a registered trademark of Evonik. Solvesso is a registered trademark of ExxonMobil, Dowanol is a registered trademark of The Dow Chemical Company.
[140] A tinplate panel supplied by Rasselstein, with a standard finish type TS-245, approximately 10cm to 20cm in size, was cleaned with acetone, and then dried. About 3 grams of the coating formulation was applied to the tinplate panel via a 30 micron spiral stretch bar, thereby coating a surface of the tinplate panel. Subsequently, the panel was placed in a convection oven to be cured at 200oC for 10 minutes. The coating had a thickness of 3.9 microns and 15 double rubs with methyl ethyl ketone (MEK DR).
Coating application on a pre-coated panel [141] The tinplate panel with polyester-based formulas was used with additional external cleaning. About 3 grams of the coating formulation 4 of the invention was applied to the polyester coating through a 30 micron spiral stretch bar. Subsequently, the panel was placed in a convection oven to be cured for 3 minutes at 200oC.
[142] The coated tinplate panels were tested for coating thickness, wedge bending, MEK DR cross-section adhesion (double friction with methyl ethyl ketone) before sterilization, and cross-section adhesion and whitening of the coating after sterilization in water, according to the procedures described below. The results are shown in Table VI.
Coating application on uncoated panels [143] A tinplate panel supplied by Rasselstein, with a standard finish type TS-245, with a size of approximately 10cm to 20cm, was cleaned with acetone, and then dried. About 3 grams of the coating formulations of the invention were applied to the tinplate panel via a 30 micron spiral stretch bar, thereby coating a surface of the tinplate panel.
Subsequently, the panel was placed in a convection oven to be cured. Curing conditions are reported in Table VII.
[144] Coated tinplate panels were tested for coating thickness, wedge bending, MEK DR cross-section adhesion (double friction with methyl ethyl ketone) before sterilization, and cross-section adhesion and whitening of the ink film after sterilization, according to the procedures described below. The results are shown in Table VII.
Comparative Experiment [145] A tinplate panel supplied by Rasselstein, with a standard finish type TS-245, with an approximate size of 10cm to 20cm, was cleaned with acetone, and then dried. About 3 grams of a dispersion of the invention listed in Table IV were applied to the tinplate panel via a 30 micron spiral stretch bar, thereby coating a surface of the tinplate panel. Subsequently, the panel was placed in a convection oven to be cured. Curing conditions and test results are reported in Table VIII.
[146] Coated tinplate panels were tested for coating thickness, wedge bending, MEK DR cross-section adhesion (double friction with methyl ethyl ketone) before sterilization, and cross-section adhesion and whitening of the ink film after sterilization in water, according to the procedures described below. Test Methods The test methods include the following: Cross-sectional adhesion [147] Cross-sectional adhesion is measured according to ASTM-D 3359-08, Measurement of adhesion through the adhesive tape test, Method B, using a cross-sectional tester Erichsen EPT 675R. This method provides the procedure for evaluating the adhesion of the coating films to metallic substrates by applying and removing an adhesive tape (type: transparent TESA 4124) on the cuts made in the film. Place the central part of a piece of adhesive tape over the grid and smooth the area of the grid with your finger. To ensure satisfactory contact with the tape, rub the tape firmly. After 90 ± 30 seconds of application, remove the adhesive tape by holding the free end and pulling quickly (without jolting) as close as possible to an angle of 180 degrees. Examine the checkered area for the removal of coating from the substrate or a previous coating, using a lighted magnifying glass. Rate membership according to the scale below.
Sterilization in Water [148] The coated panels were immersed in water in a pressurized metal container and placed in an Automat V Sterilizer where they were twisted at 129oC for 30 minutes. Subsequently, the pressurized container was placed in a containment container with ice water, and the temperature of the pressurized container was lowered to a temperature in the range below 50oC before opening. The panels were removed and dried. The whitish appearance of the paint film ("blushing") was then classified. "Blushing" means a whitish appearance of the coating. If the coating does not show whitening, then the classification will be zero whitening; on the other hand, it will be classified as very light whitening, light whitening, whitening, strong whitening.
Lactic Acid Sterilization [149] The coated panels were immersed in a 2% lactic acid solution in a pressurized metal container, and placed in an Automat V Sterilizer where they were twisted at 121oC for 30 minutes. Subsequently, the pressurized container was placed in a containment container with ice water, and the temperature of the pressurized container was lowered to a temperature in the range below 50oC before opening. The panels were removed and dried. The whitish appearance of the paint film ("blushing") was then classified. "Blushing" means a whitish appearance of the coating. If the coating does not show whitening, then the classification will be zero whitening; on the other hand, it will be classified as very light whitening, light whitening, whitening, strong whitening.
Double Friction with Methyl Ethyl Ketone [150] The flat end of a hemispherical hammer weighing 1230 ± 10g was used. A "VILEDA 3168" fabric was tied around the end of the hammer which was impregnated with methyl ethyl ketone (MEK). The hammer was placed in contact with the liner and moved back and forth over the entire liner, with each forward and backward movement of the entire liner being considered a double friction. No additional pressure was applied to the hammer. After every 10 double rubs, the fabric was again impregnated. The double friction step was repeated until the coating was removed by friction, that is, when at least a portion of the metallic substrate was exposed. If the double friction step reached 100 double frictions, the test was completed, and 100 double frictions were reported as the final result.
Wedge Bending [151] The wedge bend was measured using the Gardner "COVERALL" IG 1125 Bending Test Apparatus. The apparatus used for this test consisted of two parts to convert it into a bending apparatus. A steel rod (mandrel) is mounted on the front of the base. The 100mm wide coated test panel was flexed over the 3mm mandrel; thus, the coating appears on the outside of the fold. The flexed panel was inserted into the wedge rail. The impactor, that is, a metal weight, was lifted up to 7 inches high, and then lowered. The impactor is restored in its first jump and fixed. The cylindrical fold in the panel has been compressed into a conical shape. The edge of the coated panel was rubbed with a solution of copper sulfate (mixture of 10 grams of copper sulfate, 90 grams of water and 3 grams of sulfuric acid). Somewhere the liner was cracked; dark spots appeared, indicating failure. The extent of the intact area along the length of the 100mm wedge-fold was measured in millimeters and expressed as percentage approval.
Coating Thickness [152] The coating thickness was measured according to ASTM-D 1186-01, Non-destructive measurement of the dry film thickness of non-magnetic coatings applied to a ferrous base, using a PERMASCOPE D- coating thickness gauge 211D. The standard uncoated panel was used for calibration. The coating thickness of the coated panels was the average of 10 measurements, in which each measurement of the coating thickness of the coated panels was made using a probe for ferrous materials in relation to the thickness of the standard panel coating, that is, zero. The measured thickness was reported in microns.
Degree of Neutralization [153] The percentage of neutralization was the calculated amount of acrylic acid groups in the resin melt neutralized by the base.
Particle Size Measurement [154] Particle size was measured by a particle size analyzer (Beckman Coulter Corporation).
Measurement of Percent Solids [155] The percent solid was measured using a microwave solid analyzer.
[156] The present invention can be incorporated in other forms, without departing from its essential spirit and attributes and, consequently, reference is made to the appended claims, rather than to the report, as indicating the scope of the invention.

权利要求:
Claims (2)
[1]
1. Coated container device, characterized by the fact that it comprises: - a metallic substrate; and - one or more layers of cross-linked coating, associated with said metal substrate, said one or more layers of cross-linked coating are derived from the application of one or more aqueous dispersions to at least one surface of said metal substrate, and said being one or more aqueous dispersions comprise: - one or more base polymers; - one or more stabilizing agents; - one or more crosslinking agents; and water.
[2]
2. Device according to claim 1, characterized in that said metallic substrate is a pre-coated metallic substrate.

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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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2019-07-16| B09A| Decision: intention to grant|

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2019-10-08| 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 |

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2019-11-19| B16B| Notification of grant cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 16.1 NA RPI NO 2544 DE 08/10/2019 POR TER SIDO INDEVIDA. |

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2019-11-26| B09W| Decision of grant: rectification|Free format text: REFERENTE A RPI 2532 DE 16/07/2019. |

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2019-12-03| 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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US22836609P| true| 2009-07-24|2009-07-24|

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US61/228,366|2009-07-24|

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PCT/US2010/043086|WO2011011707A2|2009-07-24|2010-07-23|Coated container device, method of making the same|

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