Patent Application
20140147644
The invention relates to a multi-layer polymer structure having a polyolefin-based layer, an acrylic-based or other polar polymer layer, and a tie-layer between and adjacent to the polyolefin and polar polymer-based layers. Each layer could contain multiple sub-layers. The invention specifically relates to the composition of the tie-layer used to bond the polyolefin- and the polar polymer layers together. The multilayer structure can contain more than three layers, with polar polymer layers on each side of the polyolefin-based layer, and can be made by any method known to the art. The multilayer structure exhibits excellent structural integrity, excellent surface appearance, high impact strength, high scratch resistance, and excellent resistance to UV rays.
Multi-layered polymeric structures are useful to take advantage of the properties of the different polymers. The multi-layer structures (or sheets) are found in parts used in many industries, including the automotive industry; communications such as telephones, radio, TV, cassettes, etc.; power tools; appliances; business machines; toys; furniture; medical devices, building and construction, etc. When preparing multilayer structures, the layers of the structures must adhere securely to each other. If the layers of the structure do not adhere 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. Alternatively, 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 in the prior art. 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 comprising olefinic core layers and cap layers comprising polymers of vinyl aromatic compounds such as polystyrene.
Polyolefin substrate layers, and especially thermoplastic polyolefin (TPO), capped with an acrylic layer provide an excellent combination of the strength and low-cost value of a TPO with the weatherable and appealing appearance of an acrylic cap layer. Unfortunately, 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. U.S. Pat. No. 6,455,171, U.S. Pat. No. 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 cap 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. U.S. Pat. No. 7,740,951 discloses a similar olefin-based substrate, an acrylic cap layer, and a tie layer using a blend of a styrenic block copolymer with a vinyl cyanide-containing compound.
Unfortunately, for many applications, none of the described tie-layers, by themselves, result in sufficient adhesion to both olefin and acrylic-based layers, while affording high quality sheet surface. Efforts to optimize such compositions can improve adhesion to one layer, but simultaneously reduce the adhesion to the other layer. Only specific epoxy-functionalized polyolefin-acrylate copolymers have shown satisfactory adhesion to both layers, (U.S. Pat. No. 6,455,171, U.S. Pat. No. 6,420,050, and US 2008/0220274), however the presence of gels in these types of materials resulted in a structure with unacceptable surface appearance.
In most cases, the tie-layer compositions of the art provide high adhesion to the polyolefin layer, but a weak adhesion to the acrylic layer. Surprisingly, it has now been found that the addition of selected polymers or oligomers to such tie-layer compositions improves the adhesion to the acrylic or other polar polymer layer, without significantly weakening the adhesion to the polyolefin. Useful polymers or oligomers for use in the tie layer are selected from polydienes, polyolefins, polyesters, acrylics, and styrenics; and these polymers or oligomers can contain functional moieties such as epoxy, carboxylic acid, carboxylate, amine, amide, siloxane, silicone, urethane, and anhydride. The result of using the novel tie layer with the polyolefin and polar polymer layers is a multilayer structure which displays enhanced structural integrity, as well as excellent surface appearance. In addition, a tie layer having a high impact polystyrene, or a copolymer of an olefin with (meth)acrylic acid which can be partially or fully in the salt form can be used as the tie layer of the invention, with or without the addition of the selected polymer or oligomers.
The invention relates to a multi-layer thermoformable structure comprising:
a) at least one polyolefin-based layer,
b) at least one acrylic, or other polar polymer-based layer, and
c) at least one tie layer comprising a blend of A) one or more polymers selected from the groups of olefinic acrylate copolymers, olefinic (co)polymers grafted with anhydride moities, copolymers of olefin and (meth)acrylic acid which can be partially or fully in the salt form, a high impact polystyrene, vinyl cyanide-containing compounds, and block copolymers of vinyl aromatic monomer with aliphatic conjugated diene which can be partially or fully hydrogenated diene and where the dienes can be functionalized and B) one or more polymer or oligomers selected from the groups of polydienes, polyolefins, olefin acrylate copolymers, polyesters, acrylics, and styrenics, which can contain functional moieties such as epoxy, carboxylic acid, carboxylate, amine, amide, siloxane, silicone, urethane, anhydride,
wherein said tie layer is directly adjacent to, and in between the polyolefin-based layer and the polar polymer-based layer.
The invention excludes tie-layer composed only of a blend of (A) an olefin acrylate copolymer that is functionalized with anhydride or unsaturated epoxide functions, and (B) an acrylic polymer or oligomer. The invention also excludes tie-layers composed only of a blend of (A) vinyl cyanide-containing compounds, and (B) block copolymers of vinyl aromatic monomer with aliphatic conjugated diene, fully or partially hydrogenated diene, or olefin monomer.
The invention further relates to a multi-layer thermoformable structure comprising:
a) at least one polyolefin-based layer,
b) at least one acrylic- or other polar polymer-based layer, and
c) at least one tie layer comprising at least a high impact polystyrene, and/or at least one olefinic (co)polymer grafted with anhydride moities, and/or at least one copolymer of olefin and (meth)acrylic acid partially or fully in the salt form,
wherein said tie layer is directly adjacent to, and in between the polyolefin-based layer and the polar polymer-based layer.
The invention relates to a multi-layer polymer structure having a polyolefin-based layer, an acrylic or other polar polymer-based layer, and a tie-layer. The multilayer structure can contain three or more layers, and can be made by any method known to the art. 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.
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, though preferably is a single layer. 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. In a polyolefin-based layer, 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).
Polymers of 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. Thus, the olefin polymers may be derived from olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 4-ethyl-1-hexene, etc. Examples of polyolefins include polypropylene, polyethylene, and ethylene propylene copolymers.
In one embodiment, the polyolefins include polypropylene and ethylene-propylene polymers. 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 as measured by gel permeation chromatography. In addition, it is preferred in one embodiment that 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.
In one embodiment, the multilayer structure of the invention contains two or more substrate layers.
The multilayer structure of this invention contains at least one polar polymer layer. Polar capstock layer polymers include, but are not limited to acrylic-based polymers, styrenic-based polymers, polyesters, polycarbonate, polyvinylidene fluoride, and thermoplastic polyurethane (TPU), or compatible mixtures thereof. Preferred capstock layer polymers are styrenic-based, and acrylic-based polymers.
The acrylic-based layer comprises an acrylic polymer. “Acrylic polymer” as used herein is meant to include polymers, copolymers and terpolymers formed from alkyl methacrylate and alkyl acrylate monomers, and mixtures thereof. The 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. Most preferably 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 C1-8 straight or branched alkyl acrylate units.
In one embodiment, the acrylic polymer has a weight average molecular weight of between 50,000 and 500,000 g/mol, and preferably from 75,000 and 150,000, as measured by gel permeation chromatography. The molecular weight distribution of the acrylic polymer may be monomodal, or multimodal with a polydispersity index greater than 1.5.
In one embodiment, the acrylic polymer contains at least 20% of butyl methacrylate comonomer. In another embodiment, 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.
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 copolymers, styrene-butadiene-styrene block (SBS) copolymers and their partially or fully hydrogenated derivatives, styrene-isoprene copolymers, styrene-isoprene-styrene (SIS) block copolymers and their partially or fully hydrogenated derivatives, and styrene-(meth)acrylate copolymers such as styrene-methyl methacrylate copolymers (S/MMA). 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.
In one embodiment, 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 may be monomodal, or multimodal with a polydispersity index greater than 1.5.
In one embodiment, the multilayer structure of the invention contains two or more polar polymer layers, and two or more tie layers, such as a five-layer structure of polar polymer/tie layer/polyolefin-based polymer/tie layer/polar polymer. In a structure in which multiple polar polymer layers and/or multiple tie layers are used in layers non-adjacent to each other, each of the polar polymer-based layers and tie layers can be of the same of different compositions, though in a preferred embodiment the multiple polar polymer and tie layers are the same. In another embodiment, the polar polymer layer may be composed of two or more polar polymer layers directly in contact with each other. In another embodiment, the tie-layer may be composed of two or more tie layers directly in contact with each other.
“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 chromatography. “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 chromatography. “High impact polystyrene” or “HIPS” as used herein, is meant to include polystyrene compounds that contain polybutadiene rubber.
Tie layers useful in the present invention are composed of a blend of A) one or more polymers selected from the groups of olefinic acrylate copolymers, olefinic (co)polymers grafted with anhydride moities, copolymers of olefin and (meth)acrylic acid which can be partially or fully in the salt form, a high impact polystyrene, vinyl cyanide-containing compounds, and block copolymers of vinyl aromatic monomer with aliphatic conjugated diene which can be partially or fully hydrogenated diene and where the dienes can be functionalized, with B) one or more polymers or oligomers, selected from polyolefins, olefin acrylate copolymers, polydienes, polyesters, acrylics, and styrenics, which can contain functional moieties such as epoxy, carboxylic acid, carboxylate, amine, siloxane, silicone, urethane, amide, anhydride.
Tie layers composed of a high impact polystyrene and/or a copolymer of olefin and methacrylic acid which can be partially or fully in a salt form can be used with or without an added polymer or oligomer. Preferably the salt cation is selected from the group of, sodium, potassium, calcium, zinc, lithium. magnesium and barium.
This invention excludes tie-layer composed only of a blend of vinyl cyanide-containing compounds and block copolymers of vinyl aromatic monomer with aliphatic conjugated diene which can be fully or partially hydrogenated and where the dienes can be functionalized, or olefin monomer.
The invention also excludes tie-layer composed only of a blend of (A) an olefin acrylate copolymer that is functionalized with anhydride or unsaturated epoxide functions, and (B) an acrylic polymer or oligomer.
The acrylic or styrenic polymer of B) can be the same or different from the acrylic or styrenic polymer in one of the polar polymer-based layers. Preferably the weight average molecular weight of the polar polymer composition in the tie layer will be equal to or less than the molecular weight of the acrylic in the acrylic-based layer.
The olefin acrylate copolymer of A) can be made by any method known in the art, including but not limited to high pressure autoclaves and tubular reactors, and can have a homogeneous or heterogeneous distribution of compositions and molecular weights.
In one embodiment, B) is an aliphatic polyester, such as polylactic acid.
In another embodiment, B) is an acrylic polymer, preferably an acrylic polymer with a weight average molecular weight lower than 200,000 g/mol, more preferably lower than 100,000 g/mol, and most preferably lower than 80,000 g/mol.
In another embodiment, B) is an acrylic polymer comprising at least 20% of butyl methacrylate as a comonomer.
In another embodiment, B) is a polymeric or oligomeric material than contains covalently bonded functional moieties. Functional moieties include, but are not limited to, epoxy, carboxylic acid, carboxylates, anhydride, amide, 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.
In another embodiment, B) 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 C18 olefin.
The ratio of A) to B) in the blend is from 20-95 weight percent of A), and preferably 50-85 weight percent, to respectively 5-80 weight percent B) and preferably 15 to 50 wt percent.
The above polar polymer-based layers, polyolefin-based layers and tie layers may contain one or more impact modifiers, fillers or fibers, or other additives of the type used in the polymer art. Examples of impact modifiers include, but are not limited to, core-shell particles and block or graft copolymers. Examples of additives include, for example, UV light inhibitors or stabilizers, lubricant agents, heat stabilizers, flame retardants, synergists, pigments and other coloring agents. Examples of 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. Other polymer additives could include polycarbonates, polyurethanes, polysulfones, polyamides, polyolefin including copolymers and terpolymers based on these polymers, and including linear, branched, block, and grafted polymer structures. Examples of 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. For example, 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 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. Components A, B, and optionally C can be blended separately with one of the other components, then blended with the other component(s), or all components can be blended together in the same process.
In the multi-layer structure of the invention, the tie layer and polar polymer layers range in thickness from 0.025 to 2.5 mm, and preferably from 0.05 to 1 mm in thickness.
The multi-layer structure of the invention can contain three or more layers, with the choice of the number and composition of the layers being adjusted to meet the needs of the end-use application. The structure 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 planar multilayered polymeric structure of the present invention may be further shaped into a three-dimensional part by any suitable method. Thermoforming, for example, is the process of heating a plastic material in film or sheet form to its particular processing temperature and forming the hot and flexible material against the contours of a mold by mechanical or pneumatic means.
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.
Comparing adhesive strength of coextruded sheet made with tie-layer “A” versus tie-layer “A+B”. Three-layer coextrusion was performed using a TPO substrate (Lyondell-Basell E3400), an acrylic capstock (Arkema SOLARKOTE A200) and two different tie-layer materials:
Comparing adhesive strength and surface appearance of coextruded sheet made with tie-layer “B” versus tie-layer “A+B”. Three-layer coextrusion was performed using a TPO substrate (Mytex METAFORM7200), an acrylic capstock (Arkema SOLARKOTE H300) and two different tie-layer materials:
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US12/50835 | 8/15/2012 | WO | 00 | 1/30/2014 |
| Number | Date | Country | |
|---|---|---|---|
| 61524473 | Aug 2011 | US | |
| 61623767 | Apr 2012 | US |
