Background

[001] Petroleum-based polymeric materials are used extensively in fabricating automobile interiors, furniture, enclosures for electronics, and many other uses. There is a desire to replace petroleum-based polymers with renewable materials for cost and environmental reasons, as well as a preference by some consumers to use natural materials. Natural materials usually retain some texture, which typically has the beneficial effect of hiding minor abrasions, scratches, and other irregularities.

[002] Petroleum-based polymers, however, often have high gloss and require texturing steps to reduce their gloss and produce a texture that hides blemishes and appears natural. Another disadvantage of petroleum are periodic tight supplies and high cost. Further, polymeric materials in automobiles and other consumer goods often are not recovered for reuse, which increases the desire to use renewable or organic materials that will ultimately recycle or decompose at end of vehicle life.

[003] Renewable organic materials, however, often degrade by the action of moisture, UV light or microbes. Renewable organic materials are often hygroscopic and have porosity that enhances uptake and retention of water, oil and other contaminates. Therefore, renewable organic substrates need to be protected to make them viable replacements for traditional petroleum-based polymers.

[004] A thin layer of impervious material (e.g., paints, varnishes, etc.) can protect renewable substrates. However, impervious material such as paints and varnishes, often have variable penetration into the substrate, which may result in non-uniform substrate color or appearance. Protective films can be laminated onto substrates to protect them, but many films become smooth and glossy when laminated. Summary

[005] In one aspect, the present disclosure provides a composite sheet material (optionally in roll form) comprising:

a first layer (e.g., having a top or exposed surface) comprising at least 30 (including at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, or even 100) percent by weight aliphatic polyurethane (in some embodiments, for example, a polyurethane-acrylate copolymer layer or a polyurethane-acrylate blend layer), based on the total weight of the layer, and having first and second generally opposed major surfaces; and

a hot melt adhesive layer having first and second, generally opposed major surfaces, wherein the first major surface of the hot melt adhesive layer is bonded or otherwise attached to the first major surface of the aliphatic polyurethane layer, and the first layer has a higher melting point than the hot melt adhesive layer, the first layer is only slightly cross-linked, or both. Optionally, the composite sheet further comprises a release liner contacting the second major surface of the hot melt adhesive. The second major surface of the first layer can be a top or exposed surface.

[006] Composite sheets described herein can be useful, for example, in making a variety of articles. Therefore, in another aspect, the present invention provides a composite article comprising:

a first layer comprising at least 30 (including at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, or even 100) percent by weight aliphatic polyurethane (in some embodiments, for example, a polyurethane-acrylate copolymer layer or a polyurethane- acrylate blend layer), based on the total weight of the layer, and having first and second, generally opposed major surfaces;

an organic fibrous layer comprising organic binder having first and second, generally opposed major surfaces; and

a hot melt adhesive penetrated into the organic fibrous layer and bonding the first major surface of the organic fibrous layer and the first major surface of the first layer together, wherein the first layer has a higher melting point than the hot melt adhesive layer, the first layer is only slightly cross-linked, or both. The first layer at least does not melt, and preferably does not flow or even soften at the temperature and pressure needed to cause the hot melt adhesive layer to flow and penetrate into the organic fibrous layer. Embodiments of the latter articles include those having uncured and/or cured organic binder. Exemplary embodiments of composite articles described herein can include door panels (e.g., vehicle door panels), trim components (including vehicle trim components), and insulation panels.

[007] In an additional aspect, the present disclosure provides a method of making a composite article, with the method comprising:

providing a composite sheet comprising:

a first layer comprising at least 30 (including at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, or even 100) percent by weight aliphatic polyurethane (in some embodiments, for example, a polyurethane- acrylate copolymer layer or a polyurethane-acrylate blend layer), based on the total weight of the layer, and having first and second, generally opposed major surfaces; and

a hot melt adhesive layer having first and second, generally opposed major surfaces, wherein the first major surface of the hot melt adhesive layer is attached to the first major surface of the first layer, and the first layer has a higher melting point than the hot melt adhesive layer, the first layer is only slightly cross-linked, or both;

providing an organic fibrous layer comprising organic binder and having first and second generally opposed major surfaces; and

compression molding the organic fibrous layer and composite sheet together with sufficient heat and pressure to cause the hot melt adhesive layer to flow and penetrate into the organic fibrous layer and to provide a composite article (e.g., like that described herein), wherein the first layer has a higher melting point than the hot melt adhesive layer and/or the first layer is only cross-linked enough so as not to soften, flow, or at least not to melt, at the temperature and pressure needed to cause the hot melt adhesive layer to flow and penetrate into the organic fibrous layer. Brief Description Of The Drawings

[008] FIG. 1 is a cross-sectional view of an exemplary composite sheet article, prior to being heated and formed, that comprises an exemplary composite sheet material described herein.

[009] FIG. 2 is a perspective view of an exemplary composite article made by heating and forming an exemplary composite sheet article, like that shown in FIG. 1.

Detailed Description

[0010] Referring to FIG. 1 , exemplary composite sheet article 9 comprises composite sheet material described herein 10 and organic fibrous layer 14. Composite sheet article 9 is shown before being heated and formed (e.g., by a thermoforming operation). Composite sheet material 10 comprises first or aliphatic polyurethane layer 11 and hot melt adhesive layer 12. Organic fibrous layer 14 comprises organic fibers 15 and organic binder 17.

[0011] Referring to FIG. 2, exemplary composite sheet article 9, described herein that had been formed and heated, comprises first or aliphatic polyurethane layer 11 , hot melt adhesive layer 12, and organic fibrous layer 14.

[0012] Optionally, the aliphatic polyurethane comprises a polyol. Suitable polyols are known in the art and may comprise at least one of polyester polyol, caprolactone polyol, castor oil-based polyol, or polycarbonate polyol, and possibly a polyether polyol.

[0013] The composite sheet comprising the aliphatic polyurethane layer and the hot melt adhesive layer can be provided, for example, by coating the aliphatic polyurethane onto a controlled gloss release liner such that after the aliphatic polyurethane cures it replicates the low gloss surface from the low gloss release liner. The release coat on the low gloss liner can be, for example, a silicone, acrylic, melamine, or acrylic-melamine that comprises flattening agent particles (e.g., silicas, urea-formaldehyde, and ceramic microspheres).

Useful silica flattening agents include those available, for example, from Evonik-Degussa, Parsippany, NJ, under the trade designation "AEROSIL"; PPG Industries, Inc, Pittsburgh, PA, under the trade designation "LO-VEL"; and Cabot Corp., Tuscola, IL, under the trade designation "CAB-O-SIL". Useful urea- formaldehyde flattening agents include those available, for example, from Albemarle Corp, Baton Rouge, LA, under the trade designation "PERGOPAK". Useful ceramic microspheres include those available, for example, from 3M Company, Maplewood, MN, under the trade designation "ZEEOSPHERES". The gloss level can be controlled by the weight percent and the particle size of the flattening agent added to the release coat. For typical automotive trim applications, a preferred 60 degree gloss reading is less than 15, more preferably, less than 8.

[0014] The aliphatic polyurethane layer can be coated or extruded, for example, from a solvent-based or water-based polyurethane or solvent-free formulation. The polyurethane can be made, for example, from polyether polyol, polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, castor oil-based polyol, or combinations thereof. It is desirable, but not required, that the aliphatic polyurethane layer used in the first layer to be at least a slightly crosslinked but not a heavily crosslinked or thermoset. A slightly crosslinked polyurethane is one that can exhibit some extensibility when heated to a thermoform or compression form temperature, and a thermoset polyurethane is one that is so heavily crosslinked that it does not exhibit any appreciable elongation at room temperature or at compression molded temperature or thermoformed temperature. In contrast to the slightly crosslinked polyurethane, a thermoset polyurethane is more prone to crack when

compression molded or thermoformed into a trim parts. The elongation of the polyurethane is desirable to have at least 25% elongation and preferable to have elongation greater than 50% when tested at room temperature (i.e., 23.9°C (75°F)).

[0015] The water-based polyurethane can be a reaction product of constituents comprising at least one diisocyanate or a mixture of diisocyanate and polyisocyanate. Preferably, a mixture of at least one diisocyanate and at least one polyisocyanates is used. Useful water-based polyurethanes for low gloss clear coat include those available, for example, from Neoresins, Inc, DSM, Wilmington, MA, under the trade designation "NEOREZ" (e.g., "NEOREZ- 9679", "NEOREZ-R960", and "NEOREZ-9603"); Alberdingk Boely, Greensboro, NC, under the trade designation "ALBERDINGK" (e.g., "ALBERDINGK U933",

"ALBERDINGK U915", "ALBERDINGK U91 1", "ALBERDINGK U615",

"ALBERDINGK CUR99", and "ALBERDINGK CUR69"); Bayer Chemical, Pittsburgh, PA, under the trade designation "BAYHYDROL" (e.g., "B AYHYDROL- 121 ," "BAYHYDROL- 122", and "BAYHYDROL-123"; and Lubrizol, Cleveland, OH, under the trade designation "SANCURE" (e.g., "SANCURE 898", "SANCURE 853", and "SANCURE 843". Other usable water-based polyurethanes include those available, for example, from Cytec Industries, Woodland Park, J, under the trade designation "CYDROTHANE" (e.g., CYDROTHANE HP-5035 and CYDROTHANE HP-6000), and Chemtura, Tarrytown, NY, under the trade designation "WITCOBOND" (e.g., "WITCOBOND W213", "WITCOBOND 232",

"WITCOBOND 234", and "WITCOBOND 290H").

[0016] In some cases the aliphatic polyurethane layer can be a copolymer of acrylic and polyurethane or a blend of acrylic and polyurethane. Useful water-based acrylic-urethane hybrid polymers are available, for example, Neoresins, Inc, DSM, Wilmington, MA, under the trade designation "NEOPAC"(e.g., "Neopac-9699" and "Neopac-9000"); Alberdingk Boely, under the trade designation "ALBERDINGK APU 1014" and "ALBERDINGK MAC34"; Air Products and Chemicals, Allentown, PA, under the trade designation

"HYBRIDUR" (e.g., "HYBRIDUR 560", "HYBRIDUR 570", "HYBRIDUR 580",

HYBRIDUR 870", and "HYBRIDUR 878"); and Chemtura, Tarrytown, NY, under the trade designation "WITCOBOND" (e.g., "WITCOBOND A100").

[0017] The water-based polyurethane can be crosslinked by a crosslinking agent (e.g., polyaziridines) available, for example, from DSM, Wilmington, MA, under the trade designation "NEOCRYL" (e.g.," NEOCRYL CX-100"); or Bayer Corp, Pittsburgh, PA, under the trade designation "XAMA" (e.g., "XAMA-2" and "XAMA-7"). Other useful crosslinkers include carbodiimides and epoxy. The carbodiimide crosslinkers are available, for example, from Dow Chemicals, Piscataway, NJ, under the trade designation

"UCARLINK" (e.g., "UCARLINK" XL-29SE"); and from Neoresins DSM, Wilmington, MA, under the trade designation "NEOCRYL" (e.g., "NEOCRYL CX300"). The epoxy crosslinker is available, for example, from Chemtura, Tarrytown, NY, under the trade designation "WITCOBOND" (e.g., "WITCOBOND XW"); and Alberdingk Boely,

Greensboro, NC, under the trade designation "ALBERDINGK" (e.g., "ALBERDINGK CUR21" and "ALBERDINGK U2101").

[0018] Optionally, the aliphatic polyurethane layer has an average thickness in a range from 5 micrometers to 150 micrometers. [0019] Optionally, the second major surface of the aliphatic polyurethane layer has matte or glossy finish. Optionally, the second major surface of the aliphatic polyurethane layer has a patterned surface (e.g., a leather-like appearance). The pattern may be random, repeating, or include portions of each.

[0020] Optionally, the second major surface of the aliphatic polyurethane layer is at least one of moisture resistant, oil resistant, stain resistant (as determined by the "Staining Test: in the Example section, below), or UV resistant (as determined by the "Accelerated UV Exposure Test" in the Example section, below).

[0021] "Hot Melt Adhesive" as used herein refers to a meltable material (e.g., thermoplastic polymeric material), applied in molten state (typically, although not limited to, at 65°C to 180°C) that after solidifying or cooling, forms a bond between joined materials or substrates. While a hot melt adhesive may be a thermoplastic polymeric material, not all thermoplastic polymeric materials are hot melt adhesives. Hot-melt adhesives, as the term is used herein, exhibit a number of differences in their properties compared to thermoplastic polymeric materials that are not hot melt adhesives, especially the properties that enable the polymeric material to bond to an organic fibrous substrate and, in particular, to a coarse surface of an organic fibrous substrate. For example, hot melt adhesives typically exhibit at least one, a combination or all of the following properties, compared to thermoplastic polymeric materials that are not hot melt adhesives: (1) a higher melt flow index, (2) a lower heat activation temperature, and (3) a lower Shore A hardness. The heat activation temperature is the temperature that is sufficient to activate the wetting of the polymeric material to a substrate.

[0022] As used herein, it can be desirable for a hot melt adhesive (e.g., polyester polyol- based, caprolactone polyol-based, or polycarbonate polyol-based polyurethane hot melt adhesives) to have a melt flow index between 15 and 35 when measured at 190 °C with a piston force of 2160 grams, according to ASTM test method D1238. Thermoplastic polyurethanes (TPUs) based on the same polyols, however, will typically have a melt flow index below 10 based on the same measurement. The value of the melt flow index is inversely proportional to the molecular weight of the base polymer. It can also be desirable for the hot melt adhesive of the present invention to have a heat activation temperature below 250 °F (121 °C) to exhibit the adhesive melting and surface wetting needed to obtain good bond formation. TPUs typically require much higher temperatures to soften and usually do not exhibit acceptable wet out on the rough surface of an organic fibrous substrate. In addition, it can be desirable for a hot melt adhesive of the present invention to exhibit a Shore A hardness below 70. Most TPUs that are not hot melt adhesive, however, exhibit a Shore A hardness of greater than 75. Most such TPUs in commercial use today exhibit a Shore A hardness in the range of from 85 to 90.

[0023] Optionally, the hot melt adhesive can comprise at least one aliphatic polyurethane, blends thereof with polyacrylate or aliphatic polyester, and combinations thereof. Useful hot melt adhesives may also include acrylic polymers, ethylene -vinyl acetate copolymers, ethylene -vinyl acetate -vinyl alcohol terpolymers, polyesters, polyolefins, polyamides or a mixture of them. The hot melt adhesive can be coated from water-based or solvent-based solution or can be extrusion coated. Useful hot melt adhesives include polyurethanes, and blends thereof with one or more acrylic polymers.

[0024] The polyurethane (hot-melt) adhesives can be coated from water-based chemistry. Useful water-based polyurethane hot melt adhesive are available, for example, from

Neoresins DSM, Wilmington, MA, under the trade designation "NEOREZ" (e.g., "NEOREZ 551", "NEOREZ 563", NEOREZ 9330", NEOREZ 9621", and "NEOREZ 974"); Chemtura, Tarrytown, NY, under the trade designation "WITCOBOND" (e.g., "WITCOBOND 253"); Lubrizol, Cleveland, OH, under the trade designation "SANCURE" (e.g., "SANCURE 2019," "SANCURE 2026," "SANCURE 2255", and "SANCURE 1601"); Alberdingk Boely, Greensboro, NC, under the trade designation "ALBERDINGK" (e.g., "ALBERDINGK CUR21" and "ALBERDINGK U2101"). Acrylic adhesives can also be from water-based or extrusion coated. Useful water-based acrylic adhesives are available, for example, from Neoresins DSM, Wilmington, MA, under the trade designation "NEOCRYL" (e.g.,

"NEOCRYL A45", "NEOCRYL Al 120", and "NEOCRYL A2092").

[0025] Useful extrusion coated hot melt adhesives include, for example, ethylene -vinyl acetate polymers available, for example, from Dupont, Wilmington, DE, under the trade designation "EL VAX" (e.g., "ELVAX 350", "EL VAX 410", "EL VAX 760", and "EL VAX 4310"), Henkel Loctite, Madison Heights, MI, under the trade designation "LOCTITE HYSOL" (e.g., "LOCTITE HYSOL 1942", "LOCTITE HYSOL 232", and "LOCTITE HYSOL IX"). The polyamide hot melt adhesives are available, for example, from Henkel Loctite, Madison Heights, MI, under the trade designation "LOCTITE HYSOL" (e.g., "LOCTITE HYSOL 7802", "LOCTITE HYSOL 7804", and "LOCTITE HYSOL 7809"). The useful polyolefin hot melt adhesives include those available, for example, from Dow Chemicals, Midland MI, under the trade designation "AFFINITY" (e.g., "AFFINITY

EG8100G", "AFFINITY 1900", "AFFINITY 1950", and "AFFINITY 1140G"). Useful hot melt adhesives based on different chemistries such as polyester, polyurethane, polyamide, polyolefins are available, for example, from Bostik, Wauwatosa, WI, and H. B. Fuller Company, St. Paul, MN. Optionally, the hot melt adhesive has an average thickness in a range from 20 micrometers to 100 micrometers.

[0026] Optionally, the aliphatic polyurethane layer includes one, a combination or all of a UV light absorber, free radical scavengers, and/or at least one colorant (e.g., dyes and pigments). The aliphatic polyurethane layer and/or hot melt adhesive can further comprise colorants. The colorants can be pigments or dyes and can be in concentrations that make the layer opaque (e.g., when the composite sheet of the present invention is used for decorative purposes such as, for example, a paint replacement film). Pigments are commercially available, for example, as pigment dispersions from, for example, Penn Color, Doylestown, PA (e.g., 36R85 trans red oxide, 36G16 green, 36B17 black pigment dispersion); Reitch Corp, Reading, PA, under the trade designation "REISPERSE" (e.g., "REISPERSE R1015 292 RED IRON OXIDE", "REISPERSE R122R330 QUINACRIDONE MAGENTA", and "REISPERSE G7R158 PHTHLO GREEN"); AQUIS Plus Heucotech Ltd., Fairless Hills, PA, under the trade designation "AQUIS".

[0027] Useful dyes are available, for example, from BASF, Florham Park, NJ, under the trade designation "ZAPON" (e.g., "ZAPON ORANGE", "ZAPON BROWN", and "ZAPON RED").

[0028] UV light stabilizers can comprise a combination of UV light absorber and free radical scavengers to prevent discoloration of the film and the organic fibrous under layer. The organic fibrous under layer could be made using plastic fibers, cellulose fibers, lignocellulose fibers, or a combination thereof. Free radical scavengers can include hindered amines and antioxidants.

[0029] The aliphatic polyurethane layer and hot melt adhesive layer can each independently comprise at least 1.5% by weight UV light stabilizer, based on the total weight of each respective layer. If the under layer is a lignocellulose-based sheet, it is preferred, but not required, that each layer comprises at least 2.5% UV light stabilizer. Sometimes a

combination of two different types of UV light stabilizers is used to protect a wider range wavelength of UV light to achieve maximum protection of the organic fibrous layer. In the case of the latter, the amount of free radical scavenger in each layer is typically greater than 1.5% by weight, and if the under layer is a lignocellulose. It is preferred that each layer comprises at least 2.5% free radical scavenger, based on the total weight of each respective layer.

[0030] Useful UV light absorbers include the benzotriazole type, cyanoacrylate type, benzophenone type, hydroxytriazine type, and oxalanilide type.

[0031] Useful benzotriazole type UV light absorbers include those available, for example, from Ciba Specialty Chemical, Tarrytown, NY, under the trade designation "TINUVIN" (e.g., "TINUVIN- 1130", "TINUVIN-571", "TINUVIN-384", and "TINUVIN-928"); BASF, Florham Park, NJ, under the trade designation "UVINUL" (e.g., "UVINUL 3026",

"UVINUL 3027", and "UVINUL 3029"); Clariant, Charlotte, NC, under the trade

designation "SANDUVOR" (e.g., "SANDUVOR 3310" and "SANDUVOR 3326"); and Cytec Industries, Woodland Park, NJ, under the trade designation "CYSORB" (e.g.,

"CYSORB 5411").

[0032] Useful cyanoacrylate type UV light absorbers include those available, for example, from BASF, Florham Park, NJ, under the trade designation "UVINUL" (e.g., "UVINUL 3035" and "UVINUL 3039").

[0033] Useful benzophenone type UV light absorbers include those available, for example, from BASF, Florham Park, NJ, under the trade designation "UVINUL" (e.g., "UVINUL 3008"); Cytec Industries, Woodland Park, NJ, under the trade designation "CYSORB" (e.g., "CYSORB UV-9", "CYSORB UV-24", "CYSORB UV-531", and CYSORB UV-2126"); Ciba Specialty Chemicals, Tarrytown, NY, under the trade designation "CHIMASSOB" (e.g., "CHIMASSOB 81"); and Clariant, Charlotte, NC, under the trade designation "SANDUVOR" (e.g., "SANDUVOR 3035").

[0034] Useful hydroxytriazine type UV light absorbers include those available, for example, from Ciba Specialty Chemical, Tarrytown, NY, under the trade designation "TINUVIN" (e.g., "TINUVIN-400", "TINUVIN-405", "TINUVIN-477DW", and "TINUVIN-479"); Clariant, Charlotte, NC, under the trade designation "SANDUVOR" (e.g., "SANDUVOR TB-01"); and Cytec Industries, Woodland Park, NNJ, under the trade designation "CYSORB" (e.g., "CYSORB 1164" and "CYSORB 1164L").

[0035] Useful oxalanilide type includes those available, for example, Clariant, Charlotte, NC, under the trade designation "SANDUVOR" (e.g., "SANDUVOR VSU" and "SANDUVOR 3206").

[0036] The free radical scavengers include the group of hindered amine light stabilizers (HALS) and the group of antioxidants. Useful hindered amine light stabilizers are available, for example, from Ciba Specialty Chemicals, Tarrytown, NY, under the trade designation "TINUVIN" (e.g., "TINUVIN- 123", "TINUVIN-292", and "TINUVIN-765"), BASF, Florham Park, NJ, under the trade designation "UVINUL" (e.g., "UVINUL 4050H",

"UVINUL 4077H", "UVINUL 4092H", and "UVINUL 5050H"; Clariant, Charlotte, NC, under the trade designation "SANDUVOR" (e.g., "SANDUVOR 3050", "SANDUVOR 3051", "SANDUVOR 3055"), and the trade name Cysorb from Cytec Industries, Woodland Park, NJ, under the trade designation "CYANOX" (e.g., "CYSORB 3346", "CYSORB 3529", and "CYSORB 3853").

[0037] The antioxidants include sterically hindered phenolic antioxidants and phosphite type antioxidant. Useful sterically hindered phenolic antioxidants included those available, for example, from Ciba Specialty Chemicals, Tarrytown, NY, under the trade designation "IRGANOX" (e.g., "IRGANOX 1010", "IRGANOX 1035", "IRGANOX 1135", and

"IRGANOX 245"); and Cytec Industries, Woodland Park, NJ, under the trade designation "CYANOX" ("CYANOX 425", "CYANOX 1790", "CYANOX 2246", "CYANOX 2777", and "CYANOX XS4"). [0038] Useful phosphate type antioxidant includes those available, for example, from Ciba Specialty Chemicals, Tarrytown, NY, under the trade designation "IRGAFOS" (e.g.,

"IRGAFOS 38", "IRGAFOS 126", and "IRGAFOS 168".

[0039] Optionally, the composite sheet material described herein can , for example, be perforated to allow for the passage of water vapor therethrough. Such water vapor may be released from, for example, the organic fibrous layer during the processing (e.g., during the bonding of the hot melt adhesive layer to the fibrous layer). Numerous perforation methods known in the art may be useful, including cold or hot needle punching, passing the materials through a pair of nip rolls having raised projections, pulsed high velocity water or air, ultrasonics using a patterned anvil roll, electrostatic or electric arc, infrared and microwave heating, and/or laser perforation. C0 ₂ lasers may be particularly useful.

[0040] Optionally, the organic fibrous layer comprises at least one of plastic fibers, cellulose fibers and lignocellulose fibers. Optionally, the organic fibrous layer comprises wood.

Optionally, the organic fibrous layer comprises at least one of coconut fibers, vegetable fibers, cotton fibers, jute fibers, flax fibers, ramie fibers, agave fibers, sisal fiber, soy bean fibers, bamboo fibers, hemp fibers, kenaf fibers, coir fibers, or leather fibers.

[0041] Techniques for providing the organic fibrous materials are known in the art. Some embodiments of such materials are sometimes referred to in the art as "bio-fibre reinforced polymer composites" (see, e.g., "Cars From BioFibres," Bledzik et al., Marcomol. Mater. Eng., 291 (2006), pp. 449-457, the disclosure of which is incorporated herein by reference. Optionally, the organic fibrous layer is needle tacked.

[0042] Suitable binders include at least one of acrylic resin, polyurethane resin, epoxy resin, or polypropylene. Optionally, at least a portion of the binder is fibrous.

[0043] Optionally, the organic fibrous layer has an average thickness in a range from 0.25 mm to 50 mm (or 0.25 mm to 25 mm, or even from 0.5 mm to 10 mm).

[0044] Articles described herein can be made, for example, by a method comprising:

providing a composite sheet comprising:

a first layer comprising at least 30 (including at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, or even 100) percent by weight aliphatic polyurethane (in some embodiments, for example, a polyurethane - acrylate copolymer layer or a polyurethane-acrylate blend layer), based on the total weight of the layer, and having first and second generally opposed major surfaces; and

a hot melt adhesive layer having first and second, generally opposed major surfaces, wherein the first major surface of the hot melt adhesive layer is attached to the first major surface of the first layer, and the first layer has a higher melting point than the hot melt adhesive layer and/or the first layer is only slightly cross-linked;

providing an organic fibrous layer comprising organic binder having first and second, generally opposed major surfaces; and

compression molding the organic fibrous layer and composite sheet together with sufficient heat and pressure to cause the hot melt adhesive layer to flow and penetrate into the organic fibrous layer and to provide the composite article, wherein the first layer has a higher melting point than the hot melt adhesive layer and/or the first layer is only cross-linked enough so as not to soften, flow, or at least not to melt, at the temperature and pressure needed to cause the hot melt adhesive layer to flow and penetrate into the organic fibrous layer. The heat and pressure for a particular construction may depend, for example, on the materials and sizes making up the construction, as well as, for example, the desired shape and properties of the resulting article.

[0045] Optionally, the aliphatic polyurethane layer and hot melt adhesive layer (e.g., a composite sheet of the aliphatic polyurethane layer and hot melt adhesive layer) can be laminated to the organic fibrous layer, for example, prior to compression molding. It may be desirable to use heat to pre -bond the hot melt adhesive layer to the organic fibrous layer prior to lamination, wherein the heat (e.g., from a heated platen or iron) is applied to the major surface most opposite from the hot melt adhesive (e.g., the top exposed surface of the polyurethane layer). Optionally, lamination further comprises applying a vacuum to a major surface of the organic fibrous layer opposite of perforated aliphatic polyurethane and hot melt adhesive. [0046] In compression molding, for example, a mold release may be applied to at least one of the mold or material(s) being molded. Suitable mold release materials should be apparent to one skilled in the art after reviewing the present disclosure.

[0047] In some embodiments, and typically, the hot melt adhesive penetrates into the organic fibrous layer.

[0048] Uses of composite sheet materials described herein include being a low gloss protective film for injection molded parts. For example, the film can be inserted into the mold with the polyurethane layer side in contact with the metal surface of the mold, and the hot melt adhesive layer side open to the resin (e.g., acrylonitrile butadiene styrene) injected into the mold. Typically the injected resin bonds well to the adhesive side of the film and the resin cools immediately in the mold, which is at a lower temperature than the resin itself.

[0049] The composite sheet material can be subjected to a thermo forming operation before being used in an insert molding process. For example, the composite sheet can be first softened with heat (e.g., by infra-red, induction or some other form of heating), and then positioned over a mold under pressure and/or vacuum to form the composite sheet into an initial shape that is then inserted into the die cavity of the injection molding equipment. The thermoformed composite sheet can bond well to the molded part, and serve as a protective layer. The composite sheet material can also be used in thermoforming equipment where the mold tool is an already injection molded part. For example, the composite sheet can be first softened with heat (e.g., by infra-red, induction or some other form of heating), and then draped over the previously molded part under pressure and/or vacuum. The hot melt adhesive layer of the heated composite sheet can bond well to the molded part, and serve as a protective layer. Exemplary embodiments of composite articles according to the present invention can include door panels (e.g., vehicle door panels), trim components (including vehicle trim components), and insulation panels.

[0050] Advantages and embodiments of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All parts and percentages are by weight unless otherwise indicated. Tensile Elongation Test

[0051] The elongation at break of the sample being tested was conducted according to ASTM D882-09, the disclosure of which is incorporated herein by reference. The test speed was at 15.25 cm (6 inch) per minute and the jaw gap was at 5 cm (2 inch). The thickness of the 2-Layer sample being tested was about 58 micrometers; the width was 2.5 cm (1 inch). 2-Layer film was tested at room temperature (23.9°C (75°F), 93.3°C (200°F), and 143.3°C (290°F)) individually.

Staining Test

[0052] The amount of discoloration of the sample being tested when exposed to different colored materials was conducted as follows. The film layers were compression molded on an organic fibrous layer. Staining materials (i.e., ketchup (obtained from H.J. Heinz Company, Pittsburgh, PA, under the trade designation "HEINZ TOMATO KETCHUP"), honey mustard (obtained from Frenchs' Food Service, A Unit of Reckitt Benckiser, Inc., Parsippany, NJ, under the trade designation "FRENCHS' HONEY MUSTARD"), strawberry jam

(obtained from J. M. Smucker Company, Orrville, OH, under the trade designation

"SMUCKER'S STRAWBERRY), red chilly sauce (obtained from Huy Fong Foods, Inc, Rosemead, CA, under the trade designation "SRIRACHA CHILI SAUCE"), and coffee (obtained from McDonald's Restaurant) were placed on the film and aged for 1 hour. The film was cleaned with water and examined visually for discoloration for each of the fluids. Passed indicates no discoloration was visually observed and failed indicates that

discoloration was observed.

Heat Age Test

[0053] This test evaluates the discoloration of the laminated, compressed composite sheet over an organic fibrous layer when heat aged 500 hours at 100°C, 90°C, and 80°C, respectively. Color change was measured using equipment obtained under the trade designation "DATACOLOR SPECFLASH" (Model SF600) from Datacolor International, Lawrence, NJ. The color change is reported in delta E (total color change), delta L, delta a, and delta b. Delta L is a measurement of white to black. Delta a is a measurement of red to green. Delta b is a measurement of yellow to blue.

Accelerated UV Exposure Test

[0054] Sample sheets were tested according to the standard SAE J1885 accelerated UV exposure test for automotive interior trim, the disclosure of which is incorporated herein by reference using a controlled irradiance water cooled Xenon Arc apparatus. Samples were exposed to the irradiance energy from Xenon Arc which delivered 0.55 watts per square meter at 340 nanometers. The total time exposed was about 790 hours, which was equivalent to total 1240 kilojoules of energy. The discoloration was measured and reported in delta E, delta L, delta a, and delta b.

Example 1

[0055] Into a glass container was added 89.7 grams of water-based polyurethane dispersion (obtained under the trade designation "ALBERDINGK U933" from Alberdingk Boely, Greensboro, NC), 0.35 gram of UV light absorber (obtained under the trade designation "TINUVIN-123" from Ciba Specialty Chemicals, Tarrytown, NY), 0.05 gram of neutralizer (obtained under the trade designation "AMP-95" from Dow Chemical, Midland, MI), 0.2 gram of surfactant (obtained under the trade designation "TRITON GR-7M" from Dow Chemical), 8.5 grams of butyl carbitol solvent (obtained from Eastman Chemical Company, Kingsport, TN), 1.2 gram of UV light absorber (obtained under the trade designation

"UVINUL N3039"from BASF, Florham Park, NJ) and de-ionized water to keep the viscosity in between 70 cps and 200 cps measured at 25°C with a viscometer (obtained under the trade designation "BROOKFIELD VISCOMETER" from Brookfield Engineering Laboratory, Middleboro, MA) having a Number 2 spindle at 50 rpm. The clear coating solution was added 1.8 gram of crosslinker (obtained under the trade designation "NEOCRYL CX-100" from Neoresins, Inc, Wilmington, MA) and 4 grams of UV light absorber (obtained under the trade designation "TINUVIN 477DW" from Ciba Specialty Chemicals) prior to coating. The solution mixture was agitated for 5 minutes. The clear coat solution was coated 80 micrometers wet thickness on a polyester carrier web on which the web has a controlled low gloss reading and release coat. The controlled gloss web has 60 degrees gloss reading of about 6. The clear coat was then cured in jet air ovens (i.e., 1 minute in 65.6°C (150°F), 1 minute in 118.3°C (245°F) and 1 minute in 140.6°C (285°F) ovens). The dry thickness of the resulting cured clear coat was 20 micrometers. The 60° gloss reading was about 6.4.

[0056] Into a glass container was added 87.8 grams of water-based polyurethane adhesive dispersion (obtained under the trade designation "NEOREZ-9330"from Neoresins-DSM), 0.03 gram of neutralizer (obtained under the trade designation "AMP-95" from Dow

Chemical, Midland, MI), 2.2 grams of UV light stabilzer (obtained under the trade designation "TINUVIN B75" from Ciba Specialty Chemicals, Tarrytown, NY), 0.2 gram of surfactant (obtained under the trade designation "TRITON GR-7M" from Dow Chemical), 5.8 grams of butyl cellosolve solvent (obtained from Eastman Chemical Company), 4 gram of UV light absorber (obtained under the trade designation "TINUVIN 477DW" from Ciba Specialty Chemicals) and de-ionized water to keep the viscosity in between 70 cps and 150 cps measured at 25°C with a viscometer ("BROOKFIELD VISCOMETER") having a Number 2 spindle at 50 rpm. The adhesive solution mixture was agitated for 5 minutes. It was coated 100 micrometers wet thickness on the above cured clear coat. The adhesive was then cured in jet air ovens (i.e., 1 minute in 65.6°C (150°F), 1 minute in 1 18.3°C (245°F) and 1 minute in 140.6°C (285°F) the ovens). The dry thickness of the resulting cured clear coat was 38 micrometers.

[0057] The Tensile Elongation Test was conducted on the 2-layer film at room temperature (23.9°C (75°F)), 93.3°C (200°F), and 143.3°C (290°F) individually. The results are reported in Table 4, below.

[0058] The 2-layer film was compression molded to a 7-9.5 mm lignocellulosic layer (organic fibrous layer) (2226 g/m ² ; obtained from JCI, Holland, MI) with top platen at 162.8°C (325°F) directly in contact with the low gloss clear coat and the bottom platen at 176.7°C (350°F) directly in contact with the lignocellulosic layer. It was compressed at 4535 kilogram (5 tons) of pressure for 15 seconds and 8165 kilogram (9 tons) of pressure for 15 seconds. The hot platens were then opened for a few seconds to release moisture and then closed for 30 seconds at 8165 kilogram (9 tons) of pressure. The final thickness of compressed composite sheet was about 2-2.7 mm. The composite sheet was heat aged 500 hours in 80°C, 90°C, and 100°C individually. It was exposed to SAE J1885 accelerated UV exposure up to 1240 kilojoules. The staining test was also conducted. The test results of measured color shift delta E, L, a, and b are reported in Tables 1-3, below. A three- dimensional composite part can be made using a three-dimensional, shaped mold, instead of the flat top and bottom platens used above.

Table 1

Table 2

Table 3

Table 4

Example 2

[0059] Example 2 was prepared as described for Example 1, UV light absorber (obtained under the trade designation "TINUVIN 477DW" from Ciba Specialty Chemicals) added in the clear coat was 8 grams rather than 4 grams, and the controlled gloss liner was at a gloss level of about 3. After the clear coat was cured, the 60 degrees gloss reading was about 3. The 2-layer film was compression molded to a sheet as described in Example 1. The composite sheets were subjected to the same tests as in Example 1. The test results of measured color shift delta E, L, a, and b are reported in Tables 1-3, above.

[0060] The Tensile Elongation Test was conducted on the 2-layer film at room temperature ((23.9°C (75°F)), (93.3°C (200°F), and (143.3°C (290°F) individually. The results are reported in Table 4, above.

Example 3

[0061] The lignocellolosic layer was compressed as described in Example 1.

[0062] The resulting sheet was evaluated using the Heat Age Test and the UV Exposure Test. The results are reported in Tables 1-3, above.

Example 4

[0063] A 2-layer film for Example 4 was prepared as described for Example 2. The 2-layer film was laser perforated with holes size at 200 micrometers and holes spacing at 15 mm using an X-Y laser. The laser perforated 2-layer film was then compression molded to lignocellulosic layer as described for Example 1.

[0064] The resulting composite sheet was subjected to the Staining Test. The test results are reported in Table 1 , above.

Example 5

[0065] A 2-layer film for Example 5 was prepared as described for Example 2. The 2-layer film was mechanically perforated with holes size at 200-250 micrometers and holes spacing at 3 mm. The perforation was done at 3 meters (10 feet) per minute with the aliphatic polyurethane side facing the pins at 176.7°C (350°F). The perforated 2-layer film was then compression molded to lignocellulosic layer as described for Example 1 Λ

[0066] The resulting composite sheet was subjected to the Staining Test. The test results are reported in Table 1 , above.

Example 6

[0067] Example 6 was prepared as described for Example 1 , except the clear coat formulation had 1 gram of a green pigment dispersion added (obtained from Penn Color, Doylestown, PA, as "36G16 green pigment dispersion"). The resulting composite sheet had a green color shade.

Example 7

[0068] Example 7 was prepared as described for Example 1, except the hot melt adhesive formulation had 0.4 gram of an orange dye added (obtained from BASF, Florham Park, NJ, under the trade designation "ZAPON ORANGE DYE"). The resulting composite sheet showed slight orange color shade. Example 8

[0069] A laminate was prepared using the 2-layer polyurethane/hot melt adhesive film and anorganic fibrous layer as described in Example 1 , except a roll of 76 cm (30 inches) wide, 58 micrometers (0.0023 inch) thick of the 2-layer polyurethane/hot melt adhesive film was unrolled and laminated onto a 66 cm. (26 inch) wide web of organic fibrous layer (2226 g/m ² ; obtained from JCI, Holland, MI) over a vacuum table having eight 1.3 cm (0.5 inch) wide slots placed 2.5 cm (1 inch) apart. A stainless steel carrier web was used to transport the film and organic fibrous layer over the vacuum box. An infrared radiant lamp (Model Number P1560AX019, Watlow, St. Louis, MO) was used to heat the film and laminate the film and organic fibrous layer together. The lamp temperature set point was 143°C (290°F). The lamp was centered over the vacuum slots at a distance of 14 cm (5.5 inch) from the web. The line speed was 4.6 meters per minute (15 feet per minute), with a vacuum draw sufficient to pull the film in intimate contact with the organic fibrous layer surface and yield a bond between the organic fibrous layer surface and film greater than the cohesive strength of the organic fibrous mat after exposure to the lamp and cooling to room temperature.

[0070] A molded part (including three-dimensional part) can be made as described in Example 1.

Example 9

[0071] A laminate was prepared as in Example 8 except the 2-layer polyurethane/hot melt adhesive film was perforated prior to lamination using a 100 watt, pulsed C0 ₂ laser (obtained under the trade designation "M-800" from Eurolaser GmbH, Seevetal, Germany) operated at 3 watts with a frequency of 2 kilohertz. The holes were spaced 10 mm apart and were about 150 micrometers by about 250 micrometers. The line speed was 3 meters per minute (10 feet per minute). The lamp was centered over the vacuum slots at a distance of 14 cm (5.5 inch) from the web.

[0072] A molded part (including three-dimensional part) can be made as described in Example 1. Example 10

[0073] A laminate was prepared as in Example 9, except the holes were spaced 15 mm apart.

[0074] A molded part (including three-dimensional part) can be made as described in Example 1.

[0075] Foreseeable modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention. This invention should not be restricted to the embodiments that are set forth in this application for illustrative purposes.