WO2013070502A1 - Structure polymère multicouches - Google Patents

Structure polymère multicouches Download PDF

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Publication number
WO2013070502A1
WO2013070502A1 PCT/US2012/063164 US2012063164W WO2013070502A1 WO 2013070502 A1 WO2013070502 A1 WO 2013070502A1 US 2012063164 W US2012063164 W US 2012063164W WO 2013070502 A1 WO2013070502 A1 WO 2013070502A1
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WO
WIPO (PCT)
Prior art keywords
layer
acrylate
copolymers
olefin
ethylene
Prior art date
Application number
PCT/US2012/063164
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English (en)
Inventor
Charles C. Crabb
Thomas H. Richards
Florence Mehlmann
Original Assignee
Arkema France
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Publication date
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Publication of WO2013070502A1 publication Critical patent/WO2013070502A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • the invention relates to multilayer polymer structures having at least three layers. These layers include a polar capstock layer, an olefinic substrate layer, and a tie layer containing a heterogeneous olefin-acrylate copolymer.
  • the heterogeneous olefin-acrylate copolymer is found to have increased adhesion when compared to a relatively homogeneous olefin-acrylate of the same monomer composition.
  • Multi-layered polymeric structures are used to take advantage of the properties of two or more different polymers.
  • the multi-layer polymeric structures (or sheets) are found in parts used in many applications, including the automotive industry;
  • communications such as telephones, radio, TV, cassettes, etc.; power tools;
  • the layers of the structures must adhere securely to each other for good performance. If the layers of the structure do not adhere well to each other, a special adhesive, or in other cases a tie layer, may be used to join the layers of the multilayer structure together.
  • the multilayer structures of the invention may be produced by any methods available in the art, such as by co-extrusion techniques, lamination techniques, thermoforming, injection molding, blow molding or any combination thereof.
  • Co- extrusion is a process in which two or more molten polymeric compositions are simultaneously extruded through a feedblock die or, alternatively, through a multi- manifold die, to form a laminar structure with different functional properties in each layer.
  • a feedblock die can be used to feed a multi-manifold die in a single process, to provide excellent flexibility in the manufacture of the multilayer structures.
  • Lamination is the process of bonding together prefabricated sheet or film layers, or prefabricated and extruded sheet or film layers, by the use of adhesives, or by a combination of heat and pressure.
  • hot melt lamination or thermal lamination brings two or more molten polymer layers together outside the extrusion die, usually at a nip roll or at the top roll of a roll stack.
  • Multilayer structures formed by blends of different polymer compositions are known. Examples of such multilayer structures include those disclosed in U.S. Pat. Nos. 5,264,280, 5,374,680 and 5,385,781. Generally speaking, these patent references disclose multilayer structures having olefinic core layers and capstock layers containing polymers of vinyl aromatic compounds such as polystyrene.
  • Polyolefin substrate layers and especially thermoplastic polyolefin (TPO)
  • TPO thermoplastic polyolefin
  • acrylic capstock layer provide an excellent combination of the strength and low-cost value of a TPO, with the weatherable and appealing appearance of an acrylic capstock layer.
  • non-polar TPO and polar acrylics do not adhere well to each other, and a tie layer must be found that can adhere these layers together.
  • US 6,455,171, US 6,420,050, and US 2008/0220274 disclose multilayer structures which provide the physical properties of an olefinic core layer and the scratch and chemical resistive properties of an acrylic capstock layer.
  • the tie layers disclosed are either an olefinic acrylate copolymer, or a block copolymer of vinyl aromatic monomer with aliphatic conjugated diene, partially hydrogenated diene, or olefin monomer. These references are silent on the means by which the olefin- acrylic copolymer is synthesized, or any mention of monomer distribution within the copolymer, only broad over-all monomer levels. Examples use olefin-acrylics from Eastman and elfAtochem. Each of these manufacturers use an autoclave polymerization process.
  • a paper by Chou, et al. (“High Flexibility EMA made from High Pressure Tubular Process", 2002 ANTEC) describes differences in monomer distributions between ethylene/methyl acrylates (EMA) made by autoclave reactors and those made in tubular reactors where monomers and initiator are added at multiple locations along the reactor.
  • the autoclave reactor benefitting from a uniform mixture of monomers, produces a relatively homogeneous distribution of comonomer in the polymer chains.
  • the tubular reactor lacks back-mixing of the monomers, and has a long polymerization time, leading to a broader comonomer distribution among the polymer chains.
  • the more homogeneous autoclave-produced polymer has a melting point that decreases essentially linearly with monomer content, while the more heterogeneous tubular reactor polymer has a higher melting point despite a high MA content.
  • Heterogeneous olefin-acrylate copolymers have been found to have good adhesion to polyesters (US 5,532,066 and US 2004/0001960) There is a need to develop tie layer compositions with improved adhesion of a polar capstock layer to an olefinic polymer substrate.
  • tie layers containing heterogeneous olefin- acrylic copolymer provide much better adhesion than homogeneous olefin- acrylic copolymers for adhering a variety of polar capstock films to an olefinic substrate.
  • the invention relates to a multi-layer thermoformable structure comprising: a) at least one polyolefin-based layer,
  • tie layer comprising a heterogeneous olefin-acrylate copolymer, wherein said tie layer(s) is directly adjacent to, and in between the polyolefin- based layer and the capstock layer.
  • the invention relates to a multilayer polymer structure containing at least a capstock layer, a tie layer, and a substrate layer.
  • the multilayer structure of this invention contains at least one polar capstock layer.
  • Polar capstock layer polymers include, but are not limited to styrenic-based polymers, acrylic -based polymers, polyesters, polycarbonate and thermoplactic polyurethane (TPU).
  • Preferred capstock layer polymers are styrenic and/or acrylic- based.
  • the acrylic -based layer comprises either an acrylic polymer, or a vinyl cyanide- containing compound,- for example an acrylonitrile-butadiene-styrene (ABS) copolymer, an acrylonitrile-styrene-acrylate (ASA) copolymer, or styrene acrylonitrile (SAN) copolymer.
  • ABS acrylonitrile-butadiene-styrene
  • ASA acrylonitrile-styrene-acrylate
  • SAN styrene acrylonitrile
  • Alkyl methacrylate monomer is preferably methyl methacrylate, which may make up from 50 to 100 percent of the monomer mixture. 0 to 50 percent of other acrylate and methacrylate monomers or other ethylenically unsaturated monomers, included but not limited to, styrene, alpha methyl styrene, acrylonitrile, and crosslinkers at low levels may also be present in the monomer mixture.
  • Suitable acrylate and methacrylate comonomers include, but are not limited to, methyl acrylate, ethyl acrylate and ethyl methacrylate, butyl acrylate and butyl methacrylate, iso-octyl methacrylate and acrylate, lauryl acrylate and lauryl methacrylate, stearyl acrylate and stearyl methacrylate, isobornyl acrylate and methacrylate, methoxy ethyl acrylate and methacrylate, 2-ethoxy ethyl acrylate and methacrylate, dimethylamino ethyl acrylate and methacrylate monomers.
  • Alkyl (meth) acrylic acids such as methacrylic acid and acrylic acid can be useful for the monomer mixture.
  • the acrylic polymer is a copolymer having 70 - 99.5 weight percent of methyl methacrylate units and from 0.5 to 30 weight percent of one or more Ci-g straight or branched alkyl acrylate units.
  • Styrenic-based polymers include, but are not limited to, polystyrene, high- impact polystyrene (HIPS), acrylonitrile-butadiene- styrene (ABS) copolymers, acrylonitrile-styrene-acrylate (ASA) copolymers, styrene acrylonitrile (SAN) copolymers, methacrylate-butadiene- styrene (MBS) copolymers, styrene -butadiene- styrene block (SBS) copolymers and their partially or fully hydrogenenated derivatives, styrene-isoprene- styrene (SIS) block copolymers and their partially or fully hydrogenenated derivatives, and styrene-methyl methacrylate copolymers (S/MMA).
  • HIPS high- impact polystyrene
  • ABS acrylonitrile-styrene
  • a preferred styrenic polymer is ASA.
  • the styrenic polymers of the invention can be manufactured by means known in the art, including emulsion polymerization, solution polymerization, and suspension polymerization.
  • Styrenic copolymers of the invention have a styrene content of at least 10 percent by weight, preferably at least 25 percent by weight.
  • the capstock layer polymer has a weight average molecular weight of between 50,000 and 500,000 g/mol, and preferably from 75,000 and 150,000 g/mol, as measured by gel permeation chromatography (GPC).
  • the molecular weight distribution of the acrylic polymer is monomodal or multimodal and the polydispersity index is higher than 1.5.
  • the acrylic-based layer is a blend of an acrylic polymer and 5 to 80 wt%, preferably 10 to 40 wt%, of a polyvinylidene fluoride polymer or copolymer thereof.
  • the multilayer structure of the invention contains two or more polar capstock layers, and two or more tie layers, such as a five- layer structure of polar capstock/tie layer/polyolefin-based polymer/tie layer/polar capstock layer.
  • the structure could have an acrylic layer on one side, and a styrenic layer on the other side.
  • the acrylic or styrenic layers and tie layers can be of the same of different compositions, though in a preferred embodiment the multiple acrylic or styrenic layers and tie layers are the same.
  • the polar capstock layers may be composed of two or more acrylic layers or two or more styrenic layers directly in contact with each other.
  • the tie- layer may be composed of two or more tie layers directly in contact with each other.
  • the capstock layer of the invention has a thickness of from 0.025 to 3 mm, and preferably from 0.075 to 0.5 mm.
  • the polyolefin-based layer herein also referred to as a substrate layer, is thicker than the acrylic based layer(s) and tie layer(s) combined. It could contain one or more different polyolefin layers, and a polyolefin layer could be a blend of two or more different polyolefins.
  • the polyolefins employed in the semicrystalline or crystallizable olefin polymers can be homopolymers, copolymers, terpolymers, or mixtures thereof, etc., containing one or more olefin monomeric units.
  • the polyolefins are generally present in an amount from 30 to 100% by weight, preferably at least 55%, and more preferably at least 60% by weight.
  • the polyolefin of this invention excludes cyclic olefin copolymer (COCs). It is common for one or more of the polyolefin layers to contain rework - material that has already been processed into an article, such as a film or sheet. The rework polyolefin is then granulated and blended with virgin polyolefin prior to re-extrusion. The rework may contain non-polyolefin components.
  • alpha-olefins or 1 -olefins are preferred in the present invention, and these alpha-olefins may contain from 2 to about 20 carbon atoms. Alpha-olefins containing 2 to about 6 carbon atoms are preferred.
  • the olefin polymers may be derived from olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-l- pentene, 1-octene, 1-decene, 4-ethyl-l-hexene, etc.
  • polyolefins include polypropylene, polyethylene, and ethylene propylene copolymers.
  • the polyolefins include polypropylene and ethylene- propylene polymers and copolymers.
  • Propylene polymers may be semi-crystalline or crystalline in structure.
  • the number average molecular weight of the propylene polymers is preferably above about 10,000 and more preferably above about 50,000.
  • the apparent crystalline melting point be above about 75°C. and preferably between about 75° C. and about 250° C.
  • the propylene polymers useful in the present invention are well-known to those skilled in the art and many are available commercially.
  • Polypropylene are the preferred propylene polymers.
  • Thermoplastic polyolefins (TPO) are an especially preferred substrate layer.
  • the multilayer structure of the invention contains two or more substrate layers.
  • the tie layer or layers used between the polar capstock layer(s) and the olefinic substrate layer(s) contains a heterogeneous olefinic-acrylic copolymer. In the case of more than one tie layer, at least one must contain a heterogeneous olefinic- acrylic copolymer.
  • heterogeneous olefinic-acrylic copolymer is meant a copolymer having a broad comonomer distribution within polymer chains, for a given overall monomer ratio - some chains containing a higher level of olefin monomer units than others, and some containing a higher level of acrylate monomer units - while the average monomer ratio over all of the changes is the same as a homogeneous polymer.
  • a heterogeneous olefinic-acrylate copolymer could have long runs of olefin monomer units.
  • the mechanical beta relaxation region as measured by dynamic mechanical spectroscopy (DMS) also known as dynamic mechanical analysis (DMA) may show two distinct peaks, indicating two distinct compositions. More commonly, the peak is broadened, or a shoulder is present indicating a more continuous heterogeneous composition.
  • an ethylene- alkyl acrylate copolymer having an alkyl acrylate content of X weight percent, X being equal to or greater than 15 and being based on the total weight of ethylene and alkyl acrylate in the copolymer, having an average melting point temperature in degrees Celsius (°C), as measured by differential scanning calorimetry, of greater than the value obtained from the expression: 114.44 - 1.2X.
  • the heterogeneous copolymer would have an average melting point temperature in degrees Celsius (°C), as described in EP
  • 0605643 measured by differential scanning calorimetry, of greater than the value obtained from the expression: 120 - 1.61Y.
  • the olefin-acrylate copolymers generally contain 40 - 95 weight percent and preferable 60 - 85 weight percent of one or more olefin monomer(s), and 5-60 weight percent and preferably 15-40 weight percent of one or more acrylate monomer(s).
  • Useful olefin comonomers include, but are not limited to, alpha-olefins containing 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-l- pentene, 1-octene, 1-decene, 4-ethyl-l-hexene, etc.
  • Examples of polyolefins include polypropylene, polyethylene, and ethylene propylene copolymers. Poly ethylene is especially preferred.
  • Useful acrylates include, but are not limited to the acrylates listed for the acrylic capstock layer.
  • the C 1-6 acrylates are preferred, especially methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, and hexyl acrylate. Methyl acrylate and ethyl acrylate are especially preferred.
  • olefin acrylate copolymers examples include, but are not limited to ethylene methyl acrylate copolymers (EMA), ethylene butyl acrylate copolymers (EBA), ethylene-n-butyl acrylate-maleic anhydride, ethylene-ethylacrylate- maleic anhydride, ethylene- glycidyl methacrylate, ethylene-ethyl acrylate, ethylene-methyl acrylate-glycidyl methacrylate.
  • Ethylene vinyl acetate based copolymers and olefin/(meth)acrylic acid copolymers are also useful for the tie layer.
  • Heterogeneous olefin acrylates can be made by means known in the art, including, but not limited to a continuous tubular reactor, and an autoclave reactor with multiple feeds, and described in US 2004001960 and US 5,532,066 respectively.
  • the heterogeneous olefin acrylate is made in a tubular reactor in which monomer and initiator are added at multiple locations along the reactor.
  • heterogeneous olefin acrylate polymer could be blended with a homogeneous olefin acrylate copolymer of the same or different composition.
  • at least 10 percent by weight, preferably 25 percent, more preferably 50 percent and even more preferably at least 70 percent of the blend is heterogeneous olefin acrylate copolymer
  • the olefin acrylate is blended with one or more polymers or oligomers selected from the groups of polydienes, polyolefins, polyesters (such as polylactic acid), acrylics, and styrenics, which can contain functional moieties such as epoxide, carboxylic acid, carboxylate, amine, amide, siloxane, silicone, urethane, anhydride.
  • oligomer as used herein, is meant to include organic molecules with a weight average molecular weight of 200 g/mol to 20,000 g/mol, as measured by gel permeation chromatrography.
  • Polymer as used herein, is meant to include organic molecules with a weight average molecular weight higher than 20,000 g/mol, preferably higher than 50,000 g/mol, as measured by gel permeation
  • the acrylic polymer is as defined above, and can be the same or different from the acrylic polymer capstock layer or the acrylate in the olefin- acrylate copolymer of the tie layer. In one embodiment this acrylic polymer has a weight average molecular weight of less than 200,000 g/mol, and preferably less than 100,000 g/mol, and more preferably less than 80,000 g/mol. In another embodiment, the added polymer is an acrylic polymer comprising at least 20% of butyl
  • the polymeric or oligomeric material contains covalently bonded functional moieties.
  • Functional moieties include, but are not limited to, epoxide, carboxylic acid, carboxylates, anhydride, amide, amine, siloxane, silicone, urethane, and amino groups.
  • the average weight molecular weight of this material is preferably lower than 20,000 g/mol, more preferably lower than 10,000 g/mol.
  • the added component is an oligomer of (meth) acrylate and / or styrene, copolymerized with a glycidyl (meth)acrylate or a (meth)acrylic acid monomer (e.g. JONCRYL from BASF).
  • the functionalized oligomers are intended to be materials that improve adhesion without being too volatile.
  • Functional oligomers includes, for example, an epoxidized C 18 olefin.
  • the ratio of the olefin- acrylate copolymer to the added polymer or oligomer of the tie layer blend is from 20 - 99 weight percent of the olefin- acrylate copolymer, preferably 80-95 weight percent, to respectively 1 - 80 weight percent of the added polymer or oligomer, and preferably 5 to 20 wt percent.
  • the components of the blend can be combined by means known in the art, including but not limited to dry blending, solvent blending, and melt blending in an extruder.
  • the tie layer of the invention has a thickness of from 0.025 to 2 mm, and preferably from 0.075 to 0.5 mm.
  • the polar capstock layer(s), polyolefin-based substrate layer(s) and tie layers may contain one or more impact modifiers, fillers or fibers, or other additives of the type used in the polymer art.
  • impact modifiers include, but are not limited to, core-shell particles and block or graft copolymers.
  • additives include, for example, UV light inhibitors or stabilizers, lubricant agents, heat stabilizers, flame retardants, synergists, pigments and other coloring agents.
  • fillers employed in a typical compounded polymer blend according to the present invention include talc, calcium carbonate, mica, matting agents, wollastonite, dolomite, glass fibers, boron fibers, carbon fibers, carbon blacks, pigments such as titanium dioxide, or mixtures thereof.
  • the acrylic polymer is blended with a polyvinylidene fluoride polymer or copolymer, or with an aliphatic polyester - such as polylactic acid.
  • matting agents include, but are not limited to, cross-linked polymer particles of various geometries.
  • the amount of filler and additives included in the polymer compositions of each layer may vary from about 0.01 to about 70% of the combined weight of polymer, additives and filler. Generally amounts from about 5% to about 45%, from about 10% to about 40%, are included.
  • the fillers may be treated with coupling agents to improve the bond between the fillers to the resin.
  • the fillers can be treated with materials such as fatty acids (e.g., stearic acid), silanes, maleated polypropylene, etc.
  • the amount of coupling agent used is an amount effective to improve the bond between the fillers with the resin.
  • the multi-layer structure of the invention can contain three or more layers, and can be made by any method known to the art. This includes separate formation of the layers, followed by lamination, coextrusion of all layers - which is preferred, or a combination of coextrusion and lamination.
  • the multilayer structure can have any given geometry, including but not limited to, a flat sheet, a rod, or a profile.
  • the multilayer structure exhibits excellent structural integrity, excellent surface appearance, high impact strength, high scratch resistance, and excellent resistance to UV rays. It has been found that a homogeneous tie layer (autoclave reactor-produced) has much less adhesion than a heterogeneous tie layer (tubular reactor-produced) as measured by a 90° peel test, e.g. ASTM D6862, for the same overall monomer content.
  • the heterogeneous tie layer provides increased adhesion to the polar capstock layer, olefinic substrate, and preferably both.
  • Example 1 Comparing adhesive strength of coextruded sheet made with homogeneous vs. heterogeneous tie layer
  • Basell E3400 Basell E3400
  • an acrylic capstock SOLARKOTE-H300 from Arkema
  • three different ethylene- methyl acrylate copolymers each containing 24% methyl acrylate.
  • MI melt flow rate per ASTM 1228 measured at 190°C and 2.16Kg weight
  • M.P. is the melting point as measured by differential scanning calorimetry.
  • Samples A and B were made via an autoclave process giving a homogeneous product.
  • Sample C having the same average composition, was made via a tubular reactor and has a heterogeneous composition.
  • Adhesion of the capstock was measured using a 90° peel test per ASTM

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne des structures polymères multicouches comprenant au moins trois couches. Ces couches comprennent une couche de protection polaire, une couche de substrat oléfinique et une couche d'accroche contenant un copolymère d'oléfine-acrylate hétérogène. Il s'est avéré que le copolymère d'oléfine-acrylate hétérogène a une adhérence améliorée par comparaison à un copolymère d'oléfine-acrylate relativement homogène ayant la même composition de monomère. La structure thermoformable multicouches comprend au moins une couche à base de polyoléfine, au moins une couche de protection polaire contenant un polymère et au moins une couche d'accroche comprenant un copolymère d'oléfine-acrylate hétérogène, la ou lesdites couches d'accroche étant directement adjacentes à la couche à base de polyoléfine et à la couche de protection, et situées entre celle-ci.
PCT/US2012/063164 2011-11-07 2012-11-02 Structure polymère multicouches WO2013070502A1 (fr)

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US201161556465P 2011-11-07 2011-11-07
US61/556,465 2011-11-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013154877A3 (fr) * 2012-04-13 2015-06-18 Arkema France Structure polymère multicouche

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4959271A (en) * 1988-07-06 1990-09-25 The Dow Chemical Company Multilayer sheet
US5385781A (en) * 1992-09-21 1995-01-31 Ferro Corporation Multilayer thermoformable structure
US20020001730A1 (en) * 2000-02-03 2002-01-03 Scheibelhoffe Anthony S. Multilayer structure with acrylic cap layer, polyolefin core layer, and intermediate tie layer
USRE37699E1 (en) * 1994-05-25 2002-05-14 Cryovac, Inc. Film containing alpha-olefin/vinyl aromatic copolymer
US20040048086A1 (en) * 1994-06-06 2004-03-11 Kennedy Thomas Duane Films having enhanced sealing characteristics and packages containing same
US20080220274A1 (en) * 2005-09-23 2008-09-11 Arkema France Acrylic/Thermoplastic Olefin Composite
US20080254308A1 (en) * 2007-04-11 2008-10-16 Tara Thomasson Multilayered polymeric structure and methods

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4959271A (en) * 1988-07-06 1990-09-25 The Dow Chemical Company Multilayer sheet
US5385781A (en) * 1992-09-21 1995-01-31 Ferro Corporation Multilayer thermoformable structure
USRE37699E1 (en) * 1994-05-25 2002-05-14 Cryovac, Inc. Film containing alpha-olefin/vinyl aromatic copolymer
US20040048086A1 (en) * 1994-06-06 2004-03-11 Kennedy Thomas Duane Films having enhanced sealing characteristics and packages containing same
US20020001730A1 (en) * 2000-02-03 2002-01-03 Scheibelhoffe Anthony S. Multilayer structure with acrylic cap layer, polyolefin core layer, and intermediate tie layer
US20080220274A1 (en) * 2005-09-23 2008-09-11 Arkema France Acrylic/Thermoplastic Olefin Composite
US20080254308A1 (en) * 2007-04-11 2008-10-16 Tara Thomasson Multilayered polymeric structure and methods

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013154877A3 (fr) * 2012-04-13 2015-06-18 Arkema France Structure polymère multicouche
EP2836362A4 (fr) * 2012-04-13 2016-04-27 Arkema France Structure polymère multicouche
US11607869B2 (en) 2012-04-13 2023-03-21 Trinseo Europe Gmbh Multilayer polymeric structure

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