Ionomer laminates and articles formed from ionomer laminates

Abstract

The present invention includes a laminate and formation of a laminate having at least one layer of an ionomer and at least one layer of an acid polymer or blend of acid polymer and a thermoplastic polyolefin that can be thermoformed to form a shaped laminate. The shaped laminate can then be contacted with a plastic substrate such as a thermoplastic polyolefin to form a composite article by such means as, for example, injection molding. The laminate can be pigmented to eliminate the need to paint the surface of the plastic substrate. Impact and scratch resistant articles can be formed from the laminated substrate such as automotive parts, appliance body parts and sporting equipment.

We claim:  
     
         1 . A laminate comprising a tie-layer having a first side and a second side, wherein the first side is contacted to an ionomer layer, and wherein the tie-layer comprises one or more layers of material selected from acid polymers, soft ionomers, thermoplastics, or blends thereof.  
     
     
         2 . The laminate of  claim 1 , wherein the ionomer layer has a peak melt temperature of at greater than 70° C.  
     
     
         3 . The laminate of  claim 1 , wherein the ionomer layer comprises a first ionomer layer and a second ionomer layer.  
     
     
         4 . The laminate of  claim 3 , wherein the first ionomer layer or the second ionomer layer is pigmented.  
     
     
         5 . The laminate of  claim 3 , wherein the tie-layer comprises a material selected from the group consisting of acid terpolymers, polypropylene, polyethylene, and blends thereof.  
     
     
         6 . The laminate of  claim 1 , wherein the melt indexes of adjacent laminate layers are within less than 4 dg/min of one another.  
     
     
         7 . The laminate of  claim 1 , wherein the thermoplastic is a polyolefin selected from polyethylene polymers, polyethylene copolymers, polypropylene polymers, polypropylene copolymers, polypropylene impact copolymer and a blend of polypropylene impact copolymer and ethylene plastomer, and mixtures thereof.  
     
     
         8 . The laminate of  claim 1 , wherein the thermoplastic is present in the tie-layer from 30 wt % to 70 wt %.  
     
     
         9 . The laminate of  claim 1 , wherein the thermoplastic is present in the tie-layer from 40 wt % to 60 wt %.  
     
     
         10 . The laminate of  claim 1 , wherein the one or more layers of material comprises a blend of an acid terpolymer and a polypropylene.  
     
     
         11 . The laminate of  claim 1 , wherein the one or more layers of material comprises a blend of acid terpolymer and a polyethylene.  
     
     
         12 . The laminate of  claim 1 , wherein the one or more layers of material comprises a blend of acid terpolymer, linear low density polyethylene, and high density polyethylene.  
     
     
         13 . The laminate of  claim 1 , wherein the laminate is formed into an article selected from the group consisting of a bumper, dashboard interior trim, fuel tank body panel, boat hull, airbag door, and automotive door panels.  
     
     
         14 . A composite comprising a tie-layer having a first side and a second side, wherein the first side is contacted to an ionomer layer, and the second side is secured to a substrate comprising at least one thermoplastic; and wherein the tie-layer comprises one or more layers of material selected from acid polymers, soft ionomers, thermoplastics, or blends thereof.  
     
     
         15 . The composite of  claim 14 , wherein the ionomer layer has a peak melt temperature of at greater than 70° C.  
     
     
         16 . The composite of  claim 14 , wherein the ionomer layer comprises a first ionomer layer and a second ionomer layer.  
     
     
         17 . The composite of  claim 16 , wherein the first ionomer layer or second ionomer layer is pigmented.  
     
     
         18 . The composite of  claim 14 , wherein the melt indexes of adjacent laminate layers are within less than 4 dg/min of one another.  
     
     
         19 . The composite of  claim 14 , wherein the thermoplastic is selected from the group consisting of a polyolefin selected from polyethylene polymers, polyethylene copolymers, polypropylene polymers, polypropylene copolymers, polypropylene impact copolymer and a blend of polypropylene impact copolymer and ethylene plastomer, and mixtures thereof.  
     
     
         20 . The composite of  claim 14 , wherein the thermoplastic is present in the at least one tie-layer from 30 wt % to 70 wt %.  
     
     
         21 . The composite of  claim 14 , wherein the thermoplastic is present in the at least one tie-layer from 40 wt % to 60 wt %.  
     
     
         22 . The composite of  claim 14 , wherein the one or more layers of material comprises a blend of an acid terpolymer and a polypropylene.  
     
     
         23 . The composite of  claim 14 , wherein the one or more layers of material comprises a blend of acid terpolymer and a polyethylene.  
     
     
         24 . The composite of  claim 14 , wherein the one or more layers of material comprises a blend of acid terpolymer, linear low density polyethylene, and high density polyethylene.  
     
     
         25 . The composite of  claim 14 , wherein the tie-layer comprises at least two layers of material secured to one another, wherein one layer is secured to the ionomer layer.  
     
     
         26 . The composite of  claim 25 , further comprising a backing layer comprising a blend of at least two layers of material secured to the substrate.  
     
     
         27 . A composite article comprising: 
 a) an ionomer layer,    b) a tie-layer;    c) a backing layer; and    d) a substrate;    wherein the ionomer layer and tie-layer contact one another;    wherein the backing layer is secured to the substrate; and    wherein the backing layer comprises a blend of at least one acid polymer and at least one substrate material.    
     
     
         28 . The composite article of Clam 27, wherein the ionomer layer comprises a first ionomer layer and a second ionomer layer.  
     
     
         29 . The composite article of  claim 28 , wherein the first ionomer layer comprises an external layer.  
     
     
         30 . The composite article of  claim 28 , wherein the second ionomer layer comprises a pigment.  
     
     
         31 . The composite article of  claim 27 , wherein the substrate material is selected from EPDM (ethylene-propylene-diene monomer), EP (ethylene-propylene rubber), acrylonitrile-butadiene-styrene terpolymer, acetal polymer, acrylic polymers, cellulosics, fluoroplastics, nylon and other polyamides, polyamide-imide, polycarbonate, polyester, polyetheretherketone, polyetherimide, polyethylene, polyimide, polyphenylene, polyphenylene sulfide, plastomer, polypropylene, polypropylene impact copolymers, polystyrene, polysulfone, polyurethane, polyvinyl chloride, and foams of such materials, as well as blends of these materials.  
     
     
         32 . The composite article of  claim 27 , wherein the substrate material is present in the backing layer from 10 wt % to 80 wt % of the backing layer.  
     
     
         33 . The composite article of  claim 27 , wherein the acid polymer is a terpolymer of ethylene derived units, alkyl acrylate derived units, and acrylic acid derived units.  
     
     
         34 . The composite article of  claim 33 , wherein the alkyl acrylate derived unit is selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and combinations thereof.  
     
     
         35 . The composite article of  claim 27 , wherein the thickness of the composite article is from 200 μm to 6000 μm.  
     
     
         36 . The composite article of  claim 27 , wherein the melt indexes of adjacent laminate layers are within less than 5 dg/min of one another.  
     
     
         37 . The composite article of  claim 27 , wherein the ionomer layer is a blend of two or more ionomers.  
     
     
         38 . The composite article of  claim 27 , wherein the blend comprises a zinc-neutralized ionomer and a sodium-neutralized ionomer.  
     
     
         39 . The composite article of  claim 27 , wherein the ionomer layer has a melt index of from 0.2 dg/min to 8 dg/min.  
     
     
         40 . The composite article of  claim 27 , wherein the blend has an melt index of from 1 to 30 dg/min.  
     
     
         41 . The composite article of  claim 27 , wherein the composite article is an external automotive body part.  
     
     
         42 . The composite article of  claim 27 , wherein the composite article is an appliance body part.  
     
     
         43 . A method of forming a composite article comprising: 
 (a) forming a laminate;    (b) forming the laminate into a shape, the laminate comprising an ionomer layer contacted to a tie-layer; and    (c) securing a substrate to the tie-layer of the laminate to form the composite article, wherein the substrate has a 1% secant flexural modulus of greater than 100 MPa.    
     
     
         44 . The method of  claim 43 , wherein the ionomer layer comprises a first ionomer layer and a second ionomer layer.  
     
     
         45 . The method of  claim 44 , wherein the first ionomer layer or second ionomer layer is pigmented.  
     
     
         46 . The method of  claim 43 , wherein the tie-layer comprises an acid polymer, soft ionomer, polyolefin, and blends thereof.  
     
     
         47 . The method of  claim 46 , wherein the polyolefin is selected from polyethylene polymers, polyethylene copolymers, polypropylene polymers, polypropylene copolymers, polypropylene impact copolymer and a blend of polypropylene impact copolymer and ethylene plastomer, and mixtures thereof.  
     
     
         48 . The method of  claim 43 , wherein the substrate is a polyolefin selected from polyethylene polymers, polyethylene copolymers, polypropylene polymers, polypropylene copolymers, polypropylene impact copolymer and a blend of polypropylene impact copolymer and ethylene plastomer, and mixtures thereof.  
     
     
         49 . The method of  claim 43 , wherein the laminate is thermoformed.  
     
     
         50 . The method of  claim 43 , wherein the tie-layer comprises a blend of ethylene acrylic acid terpolymer and a polypropylene.  
     
     
         51 . The method of  claim 43 , wherein the tie-layer comprises a blend of ethylene acrylic acid terpolymer, linear low density polyethylene, and high density polyethylene.  
     
     
         52 . A method of forming a composite article comprising: 
 (a) co-extruding at least two materials to form a laminate;    (b) thermoforming the laminate into a shape, the laminate comprising an ionomer layer contacted to a tie-layer, the tie-layer comprising an acid polymer; and    (c) injection molding a substrate layer to the tie-layer of the laminate to form the composite article.    
     
     
         53 . The method of  claim 52 , wherein the ionomer layer comprises a first ionomer layer and a second ionomer layer.  
     
     
         54 . The method of  claim 52 , wherein the tie-layer further comprises at least one layer of material selected from an additional acid polymer, a soft ionomer, a polyolefin, or blends thereof.  
     
     
         55 . The method of  claim 54 , wherein the polyolefin is selected from polyethylene polymers, polyethylene copolymer, polypropylene polymers, polypropylene copolymers, polypropylene impact copolymer and a blend of polypropylene impact copolymer and ethylene plastomer, and mixtures thereof.  
     
     
         56 . The method of  claim 52 , wherein the tie-layer comprises a blend of an acid terpolymer and a polyolefin, the polyolefin present in the blend from 30 wt % to 70 wt % of the blend.  
     
     
         57 . The method of  claim 52 , wherein the ionomer layer is extruded at a material melt temperature of greater than 200° C.  
     
     
         58 . The method of  claim 52 , wherein the melt indexes of adjacent laminate layers are within less than 1 to 4 dg/min of one another.  
     
     
         59 . The method of  claim 52 , wherein the substrate is a polyolefin selected from polyethylene polymers, polyethylene copolymers, polypropylene polymers, polypropylene copolymers, polypropylene impact copolymer and a blend of polypropylene impact copolymer and ethylene plastomer, and mixtures thereof.  
     
     
         60 . The method of  claim 52 , wherein the tie-layer comprises a blend of ethylene acrylic acid terpolymer and a polypropylene.  
     
     
         61 . The method of  claim 52 , wherein the tie-layer comprises a blend of ethylene acrylic acid terpolymer, linear low density polyethylene, and high density polyethylene.  
     
     
         62 . The method of  claim 53 , wherein the first ionomer layer and the second ionomer layer are co-extruded at a temperature of from 180° C. to 230° C.  
     
     
         63 . The method of  claim 62 , wherein the final melt temperate of the co-extruded ionomer layer is from 200° C. to 220° C.  
     
     
         64 . A composite article formed by the method comprising: 
 (a) forming a laminate comprising an ionomer layer and a tie-layer, wherein the ionomer layer and the tie-layer contact one another;    (b) coextruding the ionomer layer and the tie-layer with a backing layer;    (c) forming a shape from the laminate, resulting in a shaped laminate; and    (d) securing a substrate material to the shaped laminate such that the substrate material is secured to the backing layer.    
     
     
         65 . The composite article of  claim 64 , wherein the laminate is thermoformed.  
     
     
         66 . The composite article of  claim 64 , wherein the ionomer layer comprises a first ionomer layer and a second ionomer layer.  
     
     
         67 . The composite article of  claim 66 , wherein the first ionomer layer or the second ionomer layer composes a pigment.  
     
     
         68 . The composite article of  claim 66 , wherein the first ionomer layer comprises an external clear layer.  
     
     
         69 . The composite article of  claim 68 , wherein the second layer includes a pigment.  
     
     
         70 . The composite article of  claim 64 , wherein the backing layer is a blend of an acid polymer and a substrate material, the substrate material present in the backing layer from 10 wt % to 80 wt % of the backing layer.  
     
     
         71 . The composite article of  claim 64 , wherein the substrate material is selected from EPDM (ethylene-propylene-diene monomer), EP (ethylene-propylene rubber), acrylonitrile-butadiene-styrene terpolymer, acetal polymer, acrylic polymers, cellulosics, fluoroplastics, nylon and other polyamides, polyamide-imide, polycarbonate, polyester, polyetheretherketone, polyetherimide, polyethylene, polyimide, polyphenylene, polyphenylene sulfide, plastomer, polypropylene, polypropylene impact copolymers, polystyrene, polysulfone, polyurethane, polyvinyl chloride, and foams of such materials, as well as blends of these materials.  
     
     
         72 . The composite article of  claim 64 , wherein the tie-layer includes an acid polymer, the acid polymer being a terpolymer of ethylene derived units, alkyl acrylate derived units, and acrylic acid derived units.  
     
     
         73 . The composite article of  claim 72 , wherein the all acrylate derived unit is selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and combinations thereof.  
     
     
         74 . The composite article of  claim 64 , wherein the thickness of the laminate is from 200 μm to 6000 μm.  
     
     
         75 . The composite article of  claim 64 , wherein the melt indexes of adjacent laminate layers are within less than 5 dg/min of one another.  
     
     
         76 . The composite article of  claim 64 , wherein the melt indexes of adjacent laminate layers are within less than 4 dg/min of one another.  
     
     
         77 . The composite article of  claim 64 , wherein the ionomer layer comprises a blend of two or more ionomers.  
     
     
         78 . The composite article of  claim 77 , wherein the blend comprises a zinc-neutralized ionomer and a sodium-neutralized ionomer.  
     
     
         79 . The composite article of  claim 64 , wherein the ionomer layer has a melt index of from 0.2 dg/min to 8 dg/min.  
     
     
         80 . The composite article of  claim 77 , wherein the blend has an melt index of from 1 to 30 dg/min.  
     
     
         81 . The composite article of  claim 64 , wherein the ionomer layer is a copolymer of ethylene derived units and acrylic acid derived units neutralized with sodium and zinc ions to from 10% to 50%.