The interior (floor. inside roof. door and side paneling, rear window shelf. columns, etc.) and the luggage compartment (rear partitions. rear load floor, side paneling. tailgate. etc.) in a vehicle are covered with carpets of various classes and qualities, which by means of molding (pressing the carpet pattern) can be exactly adjusted to fit the shell body of the respective vehicle model.

Carpets are usually fitted into vehicles, particularly cars. to improve comfort by reducing noise levels. increasing thermal insulation and resilience underfoot and adding to the decor.

The floor covering of small and middle-class vehicles is usually of pile. In upper classes as well as in the comfort and luxury classes high-grade velvet-pile carpeting is used with few exceptions.

Vehicles from the upper class to the luxury class are fitted with high-grade velvet-pile molded carpet, which is padded with a polyurethane soft foam backing.

Besides an upper fibrous layer and a flexible polyurethane foam laver. all the carpets also comprise a thermoplastic resin interlayer.

There are at least two general processes for the manufacture of automotive carpets.

In one of them the upper fibrous layer is sprinkled on the reverse side with polyethylene powder (about 200-400 glm-) The powder is melted into a film by means of radiant heat treatment. A thermoplastic protective laminate is bonded under pressure to the polyethylene film and then a heavy layer (fleece, non-woven fabric or felt) is laminated onto the surface of the protective laminate. Sometimes the heavy layer is fixed without using the polyethylene powder.

Rolled goods are then divided into carpet pieces. The individual pieces are placed in the feeder of the molding machine xvhere they undergo radiant heat treatment in particular areas and strengthened with additional, fitted heay material.

Finall ! the pieces pieces conveyed conveyed to forming station, heated to approximately 140 °C and shaped with the appropriate plug.

The shaped sections are hung on a conveyor be) t and transported one by one into the foam-padding chamber. In these closed chambers. whose inside shape on the reverse side of the carpet corresponds exactly to the shape of the vehicle floor it will be applied to. the hollow on the back of the molded carpet is filled under pressure with poiyurethane soft foam.

\S'hen the element has cooled. a robot cuts it exactly to fit usina a water jet.

The function of the protective laminate in molded carpet manufacturing is to tighth protect the shaped carpet from the high-pressure injected polvurethane foam. The foam mus be prevented from penetrating the underside of the carpet and soiling the surface.

Typically protective laminates 40 to 60 pm thick. comprising a core polyamide laver and outer polyethylene layers are employed in this process.

In the other process. the upper fibrous layer is sprinkled on the reverse side with polyethylene powder (about 400 to 600 g/m2) in a laminating machine. Then a heavy layer is fixed upon it and a protective thermoplastic laminate is put onto the heavy layer.

The outer layer of the protective laminate bonded to the heavy layer will typically be of polyethylene while the other outer laver bill be of polyamide. Since pol-urethane soft foam adheres directly to polyamide. this outer layer is foam coated on the back.

This latter process appears to be the most advanced one but still presents some disadvantages: i) since the protective laminate lies on the outside of the molded carpet to be padded with foam polvurethane. the essential polyamide laver bill be more readily damaged and a thicker laminate, with respect to that required by the former process. is needed: ii) if all free surfaces are not covered during the radiant heat treatment. the laminate will burn through on the unprotected areas.

Protective laminates with a different structure have been proposed to overcome these drawbacks.

Japanese Kokai 201940/85 (Derwent Accession Number 85-293325) describes for instance the use of a thermoplastic elastomer layer. typically formed from partially cross- linked ethylene-α-olefin copolymer rubber, laminated to a polyurethane foam layer by means of an adhesive based on a-high vinyl acetate EVA copolymer.

Japanese Kokai 147172/93 (Derwent Accession Number 93-223931) teaches the use of an elastomer composition of ethylene-propylene diene copolymer and EVA.

Still however the mechanical properties provided by the polyamide are missing and the adhesion of the polyurethane foam to said intermediate laminate is insufficient.

Object of the present invention is a thermoplastic laminate, particularly suitable for use as protective laminate in the manufacture of a polyurethane padded carpet for the automotive industn-. that is characterized by good mechanical properties at low thickness and by a suitable adhesive strength to the polyurethane foam without the need of an additional adhesive in-between.

The protective thermoplastic laminate according to the present invention comprises at least three layers and is characterized by the presence of a first outer layer comprising an ethylene homo-or copolymer. a core layer comprising a polyamide and a second outer layer comprising a thermoplastic polsmrethane If necessarv or advisable to improve the bond between the outer layer and the core layer. suitable tie lavers mas also be present in the laminate.

DEFINITIONS As used herein. the phrases"inner layer"and"internal layer"refer to any film layer having both of its principal surfaces directly adhered to another layer of the film.

As used herein. the phrase"outer layer"refers to any film layer having only one of it principal surfaces directly adhered to another layer of the film.

As used herein. the term"core", and the phrase"core layer"refer to any internal film layer that has a priman function other than serina as an adhesive or compatibilizer for adhering two layers to one another.

As used herein. the phrase"bulk layer"refers to any layer that is present for the purpose of improving the abuse-resistance. toughness. moulus. etc.. of the film. Bulk layers generally comprise polymers which are inexpensive relative to other polymers in the film which provide some specific purpose unrelated to abuse-resistance. moulus. etc.

As used herein. the phrase"tie layer"refers to anv internal layer having the primary purpose of adhering two layers to one another.

As used herein the terms"polyethylene"and"ethylene homopolymer"identify polymers consisting essentially of an ethylene repeating unit. Depending on the polymerization process employed, polymers with a different dearee of branching and a different density can be obtained. Those characterized bv a low degree of branching and shoping a densiy higher than 0.940 g/cm'are called HDPE while those with a higher level of branching and a density up to 0.940 g/cm. are called LDPE.

As used herein the term"ethylene copolymer"refers to the copolymers of ethylene with one or more other olefins and/or with a non-olefinic comonomer copolymerizable-ith ethylene. such as vinyl monomers, modified polymers thereof. and the like. Specific examples <BR> <BR> <BR> <BR> <BR> copolymers,ethylene/vinylacetatecopolymers,ethylene/ethylinc ludeethylene/α-olefin acrylate copolymers, copolymers,ethylenemethylacrylateacrylate acidcopolymers,ethylene/methacrylicacidcopolymers,copolymers ,ethylene/acrylic ionomer acrylate/maleicanhydrideter-polymers,etc.,ethylene/alkyl As used herein. the phrase"heterogeneous polymer'refers to polymerization reaction products of relatively wide variation in molecular weight and relatively wide variation in composition distribution, i. e.. polymers made. for example, usina conventional Ziegler-Natta catalvsts. Such polymers typically contain a relative wide variez ouf chain lengths and comonomer percentages.

As used herein, the phrase"homogeneous polymer"refers to polymerization rection products of relatively narrow molecular weight distribution and relatively narrow composition distribution. Homogeneous polymers exhibit a relatively even sequencing of comonomers

within a chain. the mirroring of sequence distribution in all chains, and the similariy of length of all chains. and are typically prepared using metallocene. or other single-site type catalysis.

More particularly, homogeneous ethylene/a-olefin copolymers may be characterized by one or more methods known to those of skill in the art. such as molecular weight distribution (Mw/Mn), composition distribution breadth index (CDBI). and narrow melting point range and single melt point behavior.

As used herein. the term"ethylene/a-olefincopolymer"refersto such heterogeneous materials as linear low density polyethylene (LLDPE) linear medium density polyethylene (LMDPE) and very low and ultra low densitn polyethylene (VLDPE and ULDPE): and homogeneous polymers such as metallocene catalyzed polymers such as EXACT@@ materials supplied by Exxon. AFFINITYTM and ENGAGETM materials supplied by Dow. LUFLXENTM materials supplied by BASF and TAFMERTM materials supplied @y Mitsui Petrochemical Corporation. These materials generally include copolymers of ethylene with one or more comonomers selected from C4 to C, p a-olefins such as butene-1. hexene-l. octene-1. etc..

As used herein the term "ethylene-acrylic acid and ethylene-methacryilic acid copolymers@ refers to copolymers of ethylene with a copolymerisable ethylenicaliy unsaturated carboxylic acidic monomer selected from acrylic acid and methacn-lic acid. The copolymer typically contains from about 4 to about 18% by weight of acrylic or methacrylic acid units. Said copolymer can also contain. copoiymerised therein an alkyi (meth)acrylate. such as n-buts l acn, late or methacrylate or isobut are latte or methacrylate. Said copol me. can be in the free acid form as well as in the ionized or partiale%. ionized form wherein the neutralizing cation can be any suitable metal ion. e. cr. an alkali metal ion. a zinc ion or other multivalent metal ions: in this latter case the copolymer is also termed"ionomer".

As used herein the term "ethylene-vinyl acetate copolymer" or "EVA" is intended to refer to a copolymer formed from ethylene and viny ! acetate monomers wherein the ethylene derived units in the copolymer are present in major amounts, preferably between about 60° e

and 98% by weight and the vinyl acetate derived units in the copolymer are present in minor amounts, preferably between about 2% and about 40% by weight, As used herein the term "ethylene-alkyl (meth) acrylate copolymers" refers to ethylene,withalkyl(meth)acrylates,e.g.methyl(meth)acrylate,b utylcopolymersof (meth) acrylate. and iso-butyl (meth) acrylate wherein the ethylene derived units in the copolymer are present in major amounts and the alkyl (meth)acrylate derived units in the copotymer are present in minor amounts. preferably between about 2% and about 28% bv weight.

As used herein. the term polyamide is intended to refer to both polyamides and co- polyamides. This term specificallv includes those aliphatic polyamides or copolyamides commoniy referred to as e. polyamide 6 (homopolymer based on s-caprolactam) polyamide 66 (homopolycondensate based on hexamethylenediamine and adipic acid). polyamide 69 (homopolycondensate based on hexamethylenediamine and azelaic acid). polyamide 610 (homopolvcondensate based on hexamethylenediamine and sebacic acid). polyamide 612 (homopolycondensate based on hexamethylenediamine and dodecandioic 11(homopolymerbasedon11-aminoundecanoicacid).polyamide12acid ),polyamide (homopolymer based on o-aminododecanoic acid or on laurolactam), polyamide 6@2 <BR> <BR> basedon#-caprolactamandlaurolactam),polyamide6@66(polyamide( polyamidecopolymer copolymer based on hexamethylenediamine and adipic acid and E-caprolactam). polyamide 66/610 (poiyamide copotymers based on hexamethylenediamine, adipic acid and sebacic acid), terpolyamides. modifications thereof and blends thereof. Said term also inclues crystalline or partially crystalline, aromatic or partially aromatic, poiyamides.

As used herein the term"modified polyolefin"is inclusive of modified polymer prepared by copolymerizins the homopolymer of the olefin or copolymer thereof with an unsaturated carboxylic acid. e. g., maleic acid, fumaric acid or the like. or a derivative thereof such as the anhydride. ester or metal salt or the like : as welt as of modified polymer obtained by incorporating, into the olefin homopolvmer or copolymer, an unsaturated carboxylic acid.

e. g. maleic acid. fumaric acid. or the like, or a derivative thereof such as the anhydride, ester or metal salt or the like. Examples of said modified polvolefins are graft copolymers of maleic acid or anhydride onto ethylene/α-olefin copolymers, graft copolymers of fused ring carboxylic anhydrides onto polyethylene, resin mixtures of these and mixtures with polyethylene or ethyleneia-olefin copolymers.

DETAILED DESCRIPTION OF THE INVENTION The protective laminate according to the present invention comprises at least three layers: a first outer layer a core layer and a second outer layer The first outer layer comprises an ethylene homo-or co-polvmer as defined above. In a preferred embodiment of the present invention said first outer layer comprises an ethylene homo-or copolymer selected from the group consisting of ethylene homo-polymers and ethylene-α-olefin copolymers, In a more preferred embodiment said first outer layer comprises an ethn lene homo-or co-polymer selected from the group consisting of polyethylene of low. medium or high density, and homogeneous or heterogeneous ethylene-a- olefin copolymers of low or medium density (LLDPE or LMDPE).

Said first outer layer may also comprise in addition to the ethylene homo-or co-polymer a modified polyolefin preferably a modified ethvlene homo-or co-polymer, to possibiy avoid the use of a serrate tie laver to improve the bond between said first outer layer and the core polyamide tayer. In such a case the amount of modified polyolefin may be as low as 5-10 % bv weight of the overall weight of the first outer layer and still provide for the desired improved adhesion.

The core laver comprises a polyamide as defined above, In a preferred embodiment of the present invention the polyamides suitable for use in said core laver have a melting temperature below 220 °C. In a more preferred embodiment said core layer comprises a polvamide with a melting temperature below 210 °C. Certain copolyamides asPA6/12CR-8andCR-9byEMS),certaincopolyamides6/66(such (such as Cniamid CF 815 b%, Caffaro). certain copolyamides of polyamide 6 and a partially

aromatic polyamide (such as Durethan# CI31 F and C131FKS by Bayer) or certain terpolyamides such as those based on polyamide 6. polyamide 11. and polyamide 66 I such as those sold by Baver under the trade name Durethan KU 2-2153 or KU 2-2153F). are examples of suitable polyamides.

The second outer layer in the protective laminate of the present invention comprises a thermoplastic polyurethane, or a blend of thermoplastic polyurethanes.

The thermoplastic polyurethane of the second outer layer may be of the ether or of the ester type. In case a blend of polyurethanes is employez, each polyurethane component ma- independenlty be of the ether or ester type.

These polymers tend to be sticky and are suitable blended with anti blocking agents. They can be used in blends in order to adjust the polymer flow viscosity and surface tackiness as desired.

In a preferred embodiment of the present invention said second outer layer will essentially consist of said thermoplastic polyurethane or blend of thermoplastic poluyrethanes optionally containing up to 10 %, preferably up to 7 %. and more preferably up to 5 % of a masterbatch of the desired additives in a thermoplastic compatible resin, such as the same or another polyurethane resin or any other resin compatible therewith.

The overall thickness of the protective laminate according to the present invention is typically comprised between about 25 and about 80 um. preferablv between about 30 and about 70 um and even more preferably between about and about 60 um.

Tne thickness of the first outer layer is generally at least 5 um. preferably at least 7 um and es-en more preferably at least 9 fut As this poiymer is the least expensive one. when the bulk of the laminate has to be increased this is the layer that is generally increased in thickness.

The second outer layer has a thickness that is generally comprised between about 5 and about 20 µm, preferably between about 7 and about I 5 um and even more preferably between about 8 and about 14 um.

Thin polyamide core layers are generally sufficient to provide the laminate with the desired mechanical properties. Typical thicknesses are between about 5 im and about 25 µm. preferably between about 10 and about 18 um.

If present. tie layers will have a thickness of few microns, e.g., from about 2 to about 10 µm, preferably from about 3 to about 8 pm and even more preferably from about 4 to about 6 um.

The thermoplastic protective laminate according to the present invention is obtained bv coextrusion, The film is not stretched or oriented. at least intentionally. A slight orientation. so-called accidental orientation. may be present depending on the production method employed.

A preferred method of manufacture thereof is the hot blown method.

Alternativelv it is possible also to use the cast extrusion method. either throuoh a round or preferably through a flat die.

The new protective laminate according to the present invention is then suitable emplo ! ed in the manufacture of a molded carpet as known in the area.

Fic 1, 2, and 3 represent a schematic cross-sectional view of alternative molded carpets that can be manufactured usine-té protective laminate according to the present invention In particular. with reference to Figure 1. the tufted carpet. made up by the combination of (1). (2), and (3) wherein (I) represents a layer of carpet pile or of fleece. (2) is a layer of fleece or cotton have. and (3) is a layer of latex or hot melt or polyethylene bond, is charged from the roll onto a feeder machine and sprinkled on the reverse side with polyethylene powder (200-400 g'nr). The powder is melted into a film by a heat treatment forcing layer (4) and a heaw layer (7) is laminated thereto. Then. the protective laminate of the invention is fixed with the polyethylene side to the heay layer. After shaping in an extra operational step. poivurethane foam is applied under pressure to the free polyurethane side. Instead of a heavy laver. thai is a non-moyen material obtained from several resins, often recycle materials. fleece or a textile molding compound can be used as layer (7).

Alternatively. as illustrated in Figure 2. the molded carpet does not contain a heavy layer (7) and the protective laminate (5) is directly adhered with the polyethylene outer layer to the sintered (4).layer Still alternatively. as-illustrated in Figure 3. the protective laminate (5) of the present invention is directly adhered with the polyethylene outer layer to the latex or hot melt layer (3) without the intermediate sintered polyethylene layer (4).

The avantages of this overall method are man: elasticityofthenewthermoplasticaminate,influencedbythe---the improvespunctureresistanceandthemoldingcapacityofthepolyuret hanelayer, carpet structure: -compare to the conventional polyethylene/polyamide laminates on the market. appreciable reductions in thickness are possible with the protective laminate of the invention : -the use of the new laminate eliminates the problems caused by the curling of the polyethylene polyamide conventional structures around the swell and the connecting part that does not lie flat Another object of the present invention is therefore a process for the preparation of a carpet comprising an upper fibrous rayer. an intermediate thermoplastic protective iaminate and a polyurethane foam layer wherein the poiyurethane foam layer is formed on the surface of the protective laminate which is hot bonded to the upper fibrous layer characterized in that said protective laminate comprises a first outer layer which is fascina the upper fibrous layer. comprising an eth ! lene homo-or copolymer. a core layer comprising a polyamide and a second outer layer comprising a thermoplastic polyurethane.

The invention is further illustrated by the following examples that are provided for the purpose of representation and are not to be construed as limitine thé scopie of the invention L'nless indicated otherwise. all percentages are by weight.

EXAMPLES Five layer films having the following general structure have been coextruded on a hot <BR> <BR> blown line :<BR> <BR> LDPE/tie/PA/tie/TPU, General resin descriptions are shown in Table 1.

TABLE 1<BR> RESIN TRADE NAME SUPPLIER DENSITY (g/cm@) Tm(°C)<BR> # LDPE Quantum NA345-013 Quantum(@hem. 0,922 12.5<BR> # tie Tymor 1203 Norton lot. 0,91 1.30<BR> (anhydride<BR> grußed LLDPE)<BR> #PA Cniamid CF 81.5 Caffaro 1.12 195<BR> Nylon 6/66<BR> # TPU@ Elastollan 806-10 BASF 1.12 @120<BR> (ether type)<BR> # TPU@ Elastollan 883-50 BASF 1.19 @120<BR> (ester type)<BR> # TPU@ Elastllan 1154-D10 BASF 1.17 @120<BR> (ether type)<BR> #TPU4<BR> TPU3 plus 5% of antiblock Elastollan Konz, 978 cncentrate by BASF<BR> # TPU@<BR> TPU2 plus 9% of antiblock Elastollan Konz 978 (BASF).

The temperature profiles for the TPU were established so that to keep the polymer melt below the critical temperature of 230°C.

Both TPU and PA resins were pre-dried for at least 4 hours at 85-90°C in a convection oven prior to extrusion. The coextrusion system was also equipped with an enclosed feeder and a dry/inert gas purge to prevent moisture absorbtion by the TPU from the atmosphere.

The film lavers were added starting with LDPE at the bottom of the die and ending with the TPU on the outside of the bubble at the top of the die.

Layer target thickness was 15 5 µm/5 µm/15 µm/5 µm/10 um for the LDPE tie PA tie TPL- layers respectively.

The obtained films were cooled with a standard air ring. slit on both edges and separated to provide two singie p) y films that were wound with the TPU layer on the outside of the roll.