Thermoplastic polyurethane foam steering wheel cover

Abstract

A foam cover for a steering wheel and a method of forming the foam cover are provided. The foam cover is made from a mixture of a thermoplastic polyurethane material and a chemical blowing agent. The foam mixture may be injection molded in a closed mold or directly molded onto the steering wheel frame. The present invention relates to a vehicle steering wheel that includes a steering wheel frame and a foam cover that partially or completely covers the steering wheel frame. The foam cover comprises a soft injection molded thermoplastic polyurethane foam as described herein.

Description

[Technical field]

[0001] The present invention relates to a foam vehicle steering wheel cover. Summary of the Invention [Means for solving the problem]

[0002] The present invention relates to a vehicle steering wheel comprising a steering wheel frame and a foam cover partially or completely covering the steering wheel frame. The foam cover comprises a flexible injection molded thermoplastic polyurethane foam as described herein. In one embodiment, the flexible injection molded thermoplastic polyurethane foam has (i) a crystallization peak temperature of 25°C to 205°C or 40°C to 150°C as measured by DSC, (ii) a melting peak temperature of 106°C to 206°C as measured by DSC, and (iii) a difference between the melting peak temperature and the crystallization peak temperature of 1 to 137°C, respectively, as measured by DSC. In another embodiment, the flexible injection molded thermoplastic polyurethane foam has (i) a normal rebound resilience of at least 30% as measured by ASTM D2632, (ii) a compression set at room temperature of 25% or less as measured by ASTM D395, (iii) a compression set at 50° C. of 50% or less as measured by ASTM D395, and (iv) an Asker C hardness of 30 to 65 as measured by ASTM D2240.

[0003] The foam steering wheel cover according to the present invention comprises a thermoplastic polyurethane material that is the reaction product of (i) at least one polyol component, (ii) at least one diisocyanate component, and (iii) at least one chain extender component, the combined weight of the at least one diisocyanate component and the at least one chain extender component constituting the hard segment content of the thermoplastic polyurethane material, the thermoplastic polyurethane material having a hard segment content of 20% to 60% by weight, or 20% to 40% by weight, or 25% to 35% by weight. The flexible thermoplastic polyurethane foam is made by combining the thermoplastic polyurethane material with a blowing agent. In some embodiments, the blowing agent is a heat-activated chemical blowing agent that can be exothermic or endothermic.

[0004] The present invention also includes a method of making a handle comprising the steps of (A) providing a handle frame, and (B) forming a foam cover for at least a portion of the handle frame by (1) providing a thermoplastic polyurethane foaming mixture comprising a thermoplastic polyurethane material comprising the reaction product of (i) at least one polyol component, (ii) at least one diisocyanate component, and (iii) at least one chain extender component, and a chemical blowing agent, (2) mixing the thermoplastic polyurethane material with the chemical blowing agent to obtain a foaming mixture, and (3) injection molding the foaming mixture such that the second thermoplastic polyurethane material interacts with the chemical blowing agent surfactant to form a flexible injection molded thermoplastic polyurethane foam. The method may include injection molding the foaming mixture into a closed mold or directly molding the foam cover onto the handle frame.

[0005] Further features of the invention are described in more detail herein. [Brief description of the drawings]

[0006] [Figure 1] 1 shows a schematic diagram of a handle. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The present invention provides a vehicle steering wheel that includes a steering wheel frame that is at least partially or completely covered by a thermoplastic polyurethane foam cover.

[0008] Fig. 1 shows an example of a steering frame structure according to an embodiment of the present invention. In this exemplary embodiment, the steering frame is composed of a steering rim 1, two side spokes 2, one central spoke 3 and a hub base 4. In this exemplary embodiment, the side spokes 2 and the central spoke 3 connect the steering rim 1 to the hub base 4. The hub base 4 has a bottom surface 40 incorporating one or more recesses 41, 42. In one embodiment, one of the recesses, for example recess 42, may serve to receive a steering shaft of the vehicle in which the steering wheel is used.

[0009] In one embodiment, the hub base 4 is molded to allow for additional vehicle components to be inserted into the hub base, such as, for example, an airbag module. Such additional components may be incorporated by any means known or hereafter discovered in the art.

[0010] 1 shows an example of an embodiment of a handle frame that may fall within the scope of the present invention, but it should be understood that the handle frame may have any type of configuration that is currently known in the art or may be developed in the future. In addition, the handle frame may be made from materials that are currently known in the art or may be developed in the future. For example, handle structures are shown in U.S. Patent Application Publication No. 2010 / 0018343, U.S. Patent No. 5,445,048, British Patent No. 2,061,848, International Publication No. 2002006108, and International Publication No. 2008025546, which are incorporated herein by reference.

[0011] Thermoplastic polyurethane ("TPU") compositions useful in making the foam covers of the invention generally comprise the reaction product of a polyisocyanate component, a polyol component, and a chain extender component, embodiments of which are described in more detail below.

[0012] In some embodiments of the present invention, the polyisocyanate component comprises one or more diisocyanates. Useful polyisocyanates can be selected from aromatic or aliphatic polyisocyanates or combinations thereof. Examples of useful polyisocyanates include aromatic diisocyanates such as 4,4'-methylenebis(phenylisocyanate) (MDI), m-xylene diisocyanate (XDI), phenylene-1,4-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), and toluene diisocyanate (TDI), and aliphatic diisocyanates. Polyisocyanates, such as, but not limited to, isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), and dicyclohexylmethane-4,4'-diisocyanate (H12MDI). In some embodiments, a mixture of two or more polyisocyanates may be used.

[0013] The thermoplastic polyurethane compositions used in the present invention are also made using a polyol component. The polyols can include polyether polyols, polyester polyols, polycarbonate polyols, polysiloxane polyols, and combinations thereof. In some embodiments, the polyol or components thereof are derived from biomass resources, while in other embodiments, the components are synthetic or petroleum derived.

[0014] In one embodiment, the polyol component may be a polyester polyol. The polyester polyols useful in the present invention may be produced by (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) a transesterification reaction, i.e., the reaction of one or more glycols with an ester of a dicarboxylic acid. To obtain linear chains with a predominance of terminal hydroxyl groups, a mole ratio of glycol to acid of greater than 1 mole is generally preferred. Suitable polyester intermediates also include various lactones, such as polycaprolactone, which is typically made from ε-caprolactone and a difunctional initiator, e.g., diethylene glycol. The dicarboxylic acids of the desired polyester may be aliphatic, cycloaliphatic, aromatic, or combinations thereof. In some embodiments, the dicarboxylic acids that may be used alone or in mixtures generally have a total of 4 to 15 carbon atoms and include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, and the like. Anhydrides of the above dicarboxylic acids, such as phthalic anhydride, tetrahydrophthalic anhydride, etc., may also be used. The glycols reacted to form the desired polyester intermediate may be aliphatic, aromatic, or combinations thereof, including any of the glycols described in the chain extender section above, having a total of 2 to 20 or 2 to 12 carbon atoms. Suitable examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and mixtures thereof.

[0015] The polyester polyol component may also include one or more polycaprolactone polyester polyols. The polycaprolactone polyester polyols useful in the technology described herein include polyester diols derived from caprolactone monomers. The polycaprolactone polyester polyols are terminated with primary hydroxyl groups. Suitable polycaprolactone polyester polyols can be made from ε-caprolactone and a difunctional initiator, such as diethylene glycol, 1,4-butanediol, or any of the other glycols and / or diols listed herein. In some embodiments, the polycaprolactone polyester polyol is a linear polyester diol derived from caprolactone monomers.

[0016] Useful examples include CAPA™ 2202A, a linear polyester diol having a number average molecular weight (Mn) of 2,000, and CAPA™ 2302A, a linear polyester diol having a Mn of 3,000, both available from Perstorp Polyols Inc. These materials are sometimes described as polymers of 2-oxepanone and 1,4-butanediol.

[0017] The polycaprolactone polyester polyols can be prepared from 2-oxepanone and a diol, which can be 1,4-butanediol, diethylene glycol, monoethylene glycol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, or any combination thereof. In some embodiments, the diol used to prepare the polycaprolactone polyester polyol is linear. In some embodiments, the polycaprolactone polyester polyol is prepared from 1,4-butanediol. In some embodiments, the polycaprolactone polyester polyol has a number average molecular weight of 500 to 10,000, or 500 to 5,000, or 1,000, or even 2,000 to 4,000, or even 3,000.

[0018] In one embodiment, the polyol component may be a polyether polyol. Suitable polyether polyol intermediates include polyether polyols derived from alkyl diols or glycols reacted with diols or polyols having a total of 2 to 15 carbon atoms, in some embodiments, alkylene oxides having 2 to 6 carbon atoms, typically ethers including ethylene oxide or propylene oxide or mixtures thereof. For example, hydroxyl functional polyethers can be produced by first reacting propylene glycol with propylene oxide, followed by reaction with ethylene oxide. Primary hydroxyl groups resulting from ethylene oxide are preferred as they are more reactive than secondary hydroxyl groups. Useful commercially available polyether polyols include poly(ethylene glycol) comprising ethylene oxide reacted with ethylene glycol, poly(propylene glycol) comprising propylene oxide reacted with propylene glycol, and poly(tetramethylene ether glycol) comprising water reacted with tetrahydrofuran (sometimes described as polymerized tetrahydrofuran, commonly referred to as PTMEG). In some embodiments, the polyether intermediate comprises PTMEG. Suitable polyether polyols also include polyamide adducts of alkylene oxides, such as ethylenediamine adducts including the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adducts including the reaction product of diethylenetriamine and propylene oxide, and similar polyamide-type polyether polyols. Copolyethers can also be utilized in the described compositions. Exemplary copolyethers include the reaction products of THF and ethylene oxide or THF and propylene oxide. These are available from BASF as block copolymers, PolyTHF® B, and random copolymers, PolyTHF® R.The various polyether intermediates generally have a number average molecular weight (Mn) as determined by assay of the terminal functional groups that is an average molecular weight greater than about 700, such as from about 700 to about 10,000, from about 1,000 to about 5,000, or from about 1,000 to about 2,500. In some embodiments, the polyether intermediate comprises a blend of two or more different molecular weight polyethers, such as a blend of PTMEG with Mn 2000 and Mn 1000.

[0019] In another embodiment, the polyol component may be a polycarbonate polyol. Suitable polycarbonate polyols include those prepared by reacting a glycol with a carbonate. U.S. Pat. No. 4,131,731 is incorporated herein by reference for its disclosure of hydroxyl-terminated polycarbonates and their preparation. Such polycarbonates are linear and essentially have terminal hydroxyl groups to the exclusion of other end groups. The essential reactants are glycol and carbonate. Suitable glycols are selected from cycloaliphatic and aliphatic diols containing 4 to 40 and / or even 4 to 12 carbon atoms, and from polyoxyalkylene glycols containing 2 to 20 alkoxy groups per molecule, each alkoxy group containing 2 to 4 carbon atoms. Suitable diols include aliphatic diols containing 4 to 12 carbon atoms, such as 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol, 3-methyl-1,5-pentanediol, and alicyclic diols, such as 1,3-cyclohexanediol, 1,4-dimethylolcyclohexane, 1,4-cyclohexanediol-, 1,3-dimethylolcyclohexane-, 1,4-endomethylene-2-hydroxy-5-hydroxymethylcyclohexane, and polyalkylene glycols. The diol used in the reaction can be a single diol or a mixture of diols depending on the properties desired in the final product. Hydroxyl-terminated polycarbonate intermediates are generally known in the art and in the literature. A suitable carbonate is selected from alkylene carbonates composed of a 5- to 7-membered ring.Suitable carbonates for use herein include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-ethylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 2,3-pentylene carbonate, and 2,4-pentylene carbonate. Also suitable herein are dialkyl carbonates, alicyclic carbonates, and diaryl carbonates. The dialkyl carbonates may contain 2 to 5 carbon atoms in each alkyl group, examples of which are diethyl carbonate and dipropyl carbonate. Alicyclic carbonates, especially bicyclic aliphatic carbonates, may contain 4 to 7 carbon atoms in each ring structure, and there may be one or two such structures. When one group is alicyclic, the other may be either alkyl or aryl. On the other hand, when one group is aryl, the other may be alkyl or alicyclic. Examples of suitable diaryl carbonates, which may contain 6 to 20 carbon atoms in each aryl group, are diphenyl carbonate, ditolyl carbonate, and dinaphthyl carbonate.

[0020] In one embodiment, the polyol component may include a polysiloxane polyol. Suitable polysiloxane polyols include α-ω-hydroxyl or amine or carboxylic acid or thiol or epoxy terminated polysiloxanes. Examples include poly(dimethylsiloxanes) terminated with hydroxyl or amine or carboxylic acid or thiol or epoxy groups. In some embodiments, the polysiloxane polyol is a hydroxyl terminated polysiloxane. In some embodiments, the polysiloxane polyol has a number average molecular weight in the range of 300 to 5,000 or 400 to 3,000.

[0021] Polysiloxane polyols can be obtained by introducing alcoholic hydroxy groups into the polysiloxane skeleton through a dehydrogenation reaction between a polysiloxane hydride and an aliphatic polyhydric alcohol or a polyoxyalkylene alcohol.

[0022] In some embodiments, the polysiloxane may be represented by one or more compounds having the following formula:

[0023] [ka]

[0024] wherein each R1 and R2 is independently an alkyl group of 1 to 4 carbon atoms, a benzyl group, or a phenyl group; and each E is OH or NHR 3 (In the formula, R 3 is hydrogen, an alkyl group of 1 to 6 carbon atoms, or a cycloalkyl group of 5 to 8 carbon atoms, a and b are each independently an integer of 2 to 8, and c is an integer of 3 to 50. In the amino-containing polysiloxane, at least one of the E groups is NHR 3 In hydroxyl-containing polysiloxanes, at least one of the E groups is OH. In some embodiments, R 1 and R 2 are both methyl groups.

[0025] Suitable examples include α,ω-hydroxypropyl-terminated poly(dimethylsiloxane) and α,ω-aminopropyl-terminated poly(dimethylsiloxane), both of which are commercially available materials. Further examples include copolymers of poly(dimethylsiloxane) materials with poly(alkylene oxides).

[0026]

[0027] The thermoplastic polyurethane compositions described herein are typically made using a chain extender component. Chain extenders can include diols, diamines, and combinations thereof.

[0028] Suitable chain extenders include relatively small polyhydroxy compounds, such as lower aliphatic or short chain glycols having 2 to 20, or 2 to 12, or 2 to 10 carbon atoms. Suitable examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane (HEPP), hydroquinone bis(2-hydroxyethyl)ether (HQEE), hexamethylenediol, heptanediol, nonanediol, dodecanediol, 3-methyl-1,5-pentanediol, ethylenediamine, butanediamine, hexamethylenediamine, and hydroxyethylresorcinol (HER), and the like, and mixtures thereof.

[0029] Optional additive components may be present during the polymerization reaction and / or incorporated into the TPU compositions described above to improve processing and other properties. These additives include antioxidants, organic phosphites, phosphines, and phosphonites, hindered amines, organic amines, organic sulfur compounds, lactones, and hydroxylamine compounds, biocides, fungicides, antimicrobial agents, compatibilizers, electrically dissipative or antistatic additives, fillers and reinforcing agents (e.g., titanium dioxide, alumina, clay, and carbon black), flame retardants (e.g., phosphates, halogenated materials, and metal salts of alkylbenzene sulfonates), impact modifiers (e.g., methacrylate-butadiene-styrene ("methacrylate-butadiene-styrene, MBS") and methyl methacrylate butyl acrylate ("methyl methacrylate butyl acrylate, MBS"). butylacrylate, MBA)), release agents (e.g., waxes, fats and oils), pigments and colorants, plasticizers, polymers), rheology modifiers (e.g., monoamines, polyamide waxes, silicones, and polysiloxanes), slip additives (e.g., paraffin waxes, hydrocarbon polyolefins, and / or fluorinated polyolefins), and UV stabilizers (which may be of the hindered amine light stabilizer (HALS) and / or UV light absorber (UVA) type). Other additives may be used to improve the performance of the TPU composition or blend product. All of the above additives may be used in the conventional effective amounts of these materials.

[0030] These additional additives can be incorporated into the components of the reaction mixture or into the reaction mixture to prepare the TPU composition or after the TPU composition has been made. In an alternative process, all of the materials can be mixed with the TPU composition and then melted, or all of the materials can be directly incorporated into the melt of the TPU composition.

[0031] In some embodiments, the additive may include a filler or reinforcing agent. Fillers include a wide range of particulate materials including talc, marble, granite, carbon black, graphite, aramid, silica-alumina, zirconia, bentonite, antimony trioxide, coal-based fly ash, clay, feldspar, nepheline, fumed silica, alumina, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, chalk, crushed glass, silica or glass, glass microspheres, glass beads or glass fibers. The glass fibers used may be made of E, A or C glass, preferably provided with a size and coupling agent. Their diameter is generally 6-20 μm. Either continuous filament fibers (rovings) or chopped glass fibers (staples) with a total length of 1-10 mm, preferably 3-6 mm, may be used.

[0032] The filler may also be, for example, a metal hydroxide, such as magnesium hydroxide, potassium hydroxide, and aluminum trihydroxide; a metal carbonate, such as magnesium carbonate and calcium carbonate; a metal sulfide and sulfate, such as molybdenum disulfide and barium sulfate; a metal borate, such as barium borate, barium metaborate, zinc borate, zinc metaborate; a metal anhydride, such as aluminum anhydride; or aluminum trihydrate.

[0033] Boron nitride and various regenerated and reground thermoset polyurethane and / or polyurea polymers may also be used.

[0034] Representative fillers include, but are not limited to, clays such as diatomaceous earth, kaolin, and montmorillonite; huntite; celite; asbestos; ground minerals; and lithopone. These fillers are typically used in conventional manner and in conventional amounts, for example, from 5% or less to 50% or more by weight based on the weight of the composition.

[0035] Reinforcing agents include high aspect ratio materials such as platelets and fibers, which may be glass, aramid, various other polymers, etc. Additional materials that may be used include mineral fibers, whiskers, alumina fibers, mica, powdered quartz, metal fibers, carbon fibers, and wollastonite. Reinforcing agents are typically used in amounts of 5-50% by weight based on the total layer or composition.

[0036] Fillers useful in some formulations include anti-ignition fillers which may include antimony oxide, decabromobiphenyl oxide, alumina trihydrate, magnesium hydroxide, borates, and halogenated compounds.

[0037] Other miscellaneous fillers include wood fiber / flour / chips, rubber dust, cotton, starch, clay, synthetic fibers (eg, polyolefin fibers), and carbon fibers.

[0038] The level of filler depends on the density of the filler; the higher the density of the filler, the more filler can be added to the formulation without appreciably affecting the volume fraction of that filler. Thus, filler levels are discussed herein in terms of the weight percent of the filler based on the total formulation weight. In the formulations disclosed herein, the filler content ranges from about 0.1% to about 80%, preferably from about 5% to about 50% (excluding carbon black, which is typically used at levels of about 0.1% to about 5%), more preferably from about 5% to about 40%, and especially from about 8% to about 30%.

[0039] In another embodiment, the additive may include a flame retardant additive. The flame retardant may be intumescent, but is not necessarily so. Examples include phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl ethylene hydrogen phosphate, phenyl-bis-3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, diphenyl hydrogen phosphate, bis(2-ethyl-hexyl)p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl)-phenyl phosphate, tri(nonylphenyl) phosphate, phenyl methyl hydrogen phosphate, di(dodecyl)p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and diphenyl hydrogen phosphate. Preferred flame retardants are bisphenol-A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), and cresol bis(diphenyl phosphate).

[0040] Further examples of flame retardants include brominated organic compounds, such as brominated diols, which may contain 5 to 20 carbon atoms, in some embodiments 5 to 10, or even 5 carbon atoms, and may contain quaternary carbon atoms. The additive may be present in an amount sufficient to provide the desired flame retardancy, and in other embodiments may be present at 0 to 15 weight percent of the total composition, or even 0 to 10 weight percent, 0.1 to 7 weight percent, or 0.2 to 5 weight percent of the total composition.

[0041] Further examples include brominated organic compounds.Suitable examples include brominated diols, brominated monoalcohols, brominated ethers, brominated esters, brominated phosphates, and combinations thereof.Suitable brominated organic compounds can include tetrabromobisphenol-A, hexabromocyclododecane, poly(pentabromobenzyl acrylate), pentabromobenzyl acrylate, tetrabromobisphenol A-bis(2,3-dibromopropyl ether), tribromophenol, dibromoneopentyl glycol, tribromoneopentyl alcohol, tris(tribromoneopentyl)phosphate, and 4,4'-isopropylidenebis[2-(2,6-dibromophenoxy)ethanol].

[0042] In some embodiments, the flame retardant additive comprises a metal salt of a halogen borate, a metal salt of a halogen phosphate, or a combination thereof. In some embodiments, a combination of retarders is used. Further examples of flame retardant additives include metal salts of organic sulfonates, such as sodium salts of alkylbenzene sulfonates, and in some embodiments, the flame retardant additive comprises a nitrogen-containing compound.

[0043] In some embodiments, the additive may comprise an impact modifier. The impact modifier may be added to the above TPU composition, and is added in an amount effective to improve the impact resistance of polyurethane, especially low temperature toughness. Improved low temperature toughness means that the Izod impact strength at -30°C according to ASTM D256 can be improved. Another improvement is that melt processability is improved, so that the shear viscosity of polyurethane is reduced as a result of the reduced melt processing temperature, and further, this reduction is achieved without forming a non-cohesive skin on the hot molded product.

[0044] In an embodiment, the impact modifier contains both a rubbery component and a grafted hard phase component. A preferred impact modifier is prepared by grafting a (meth)acrylate and / or vinyl aromatic polymer (including its copolymers such as styrene / acrylonitrile) to the selected rubber. In an embodiment, the grafted polymer is a homopolymer or copolymer of methyl methacrylate. The rubber material can be, for example, one or more of the well-known butadiene type, butyl acrylate type, or EPDM type. In various embodiments, the impact modifier contains at least about 40 weight percent of the rubber material, or at least about 45 weight percent, and in another embodiment at least about 60 weight percent of the rubber material. The impact modifier can contain up to 100 weight percent of the rubber (without the hard phase), in an embodiment, less than 95 weight percent of the rubber material, and in another embodiment, less than 90 weight percent of the rubber material, with the remainder being the hard phase polymer, at least a substantial portion of which is grafted and / or crosslinked around or to the rubber material.

[0045] Examples of impact modifiers include, but are not limited to, methacrylate-butadiene-styrene ("MBS") rubbers such as Paraloid EXL 3607 and methyl methacrylate butyl acrylate ("MBA") rubbers such as Paraloid 3300, which generally contain 45 to 90 weight percent elastomer.

[0046] Another impact modifier that can be used contains as a rubber material a base polymer latex or core made by polymerizing a conjugated diene or by copolymerizing a conjugated diene with a monoolefin or a polar vinyl compound, such as styrene, acrylonitrile, or methyl methacrylate. The base rubber is typically composed of about 45 to 100 percent of a conjugated diene and up to about 55 percent of a monoolefin or a polar vinyl compound. A mixture of monomers is then graft polymerized onto the base latex. Various monomers may be used for this grafting purpose, including: vinyl aromatic compounds such as styrene, vinyl toluene, α-methylstyrene, halogenated styrene, naphthalene, etc.; methacrylonitrile or acrylonitrile, including α-halogenated acrylonitrile; or C1 to C8 alkyl (meth)acrylates such as methyl acrylate, ethyl acrylate, hexyl acrylate, methyl methacrylate, ethyl methacrylate, or hexyl methacrylate; acrylic acid or methacrylic acid; or a mixture of two or more of the foregoing. The degree of grafting is sensitive to the substrate latex particle size and the grafting reaction conditions, and the particle size can be influenced by controlled coagulation techniques, among other methods. The rigid phase can be crosslinked during polymerization by incorporating various polyvinyl monomers such as divinylbenzene.

[0047] The impact modifier (from EP 0353673 B1) may be a carbonyl modified polyolefin. More specifically, it is a graft copolymer containing a polyolefin backbone with pendant carbonyl-containing compounds. Based on the total weight of the graft copolymer, the amount of polyolefin is 90-99.9 weight percent, desirably 93-98 weight percent, and preferably 95-98 weight percent. Suitable graft copolymers may have a melt index of 1-20, in another embodiment 1-10, and in yet another embodiment 1-5.

[0048] The polyolefin component of the impact modifier (i.e., graft copolymer) is a homopolymer or copolymer made from one or more monomers having from 2 to 6 carbon atoms, desirably 2 or 3 carbon atoms. Specific examples of suitable polyolefins include homopolymers of ethylene, propylene, or isobutylene, copolymers of propylene and ethylene, and copolymers of ethylene-propylene-diene monomers with dienes having from 4 to 8 carbon atoms. Ethylene polymers suitable for modification include high density polyethylene, low density polyethylene, and linear low density polyethylene. When copolymers are utilized, the amount of ethylene monomer utilized, and therefore the amount of ethylene repeat units in the copolymer, can vary considerably, from 1 percent to 50 percent, in other cases from 3 percent to 25 percent, and in yet another embodiment is about 10 percent.

[0049] In one embodiment, the impact modifier comprises from 0.1 to 10 weight percent, from 0.2 to 7 weight percent in another embodiment, and from 0.2 to 6 weight percent in yet another embodiment of a carbonyl compound selected from fumaric acid, maleic acid, or maleic anhydride.

[0050] Impact modifiers can be used in the range of 1-30 parts by weight, in some embodiments 1-20 parts by weight, and in other embodiments 5-15 parts by weight per 100 parts by weight of polyurethane. The impact modifiers of the present invention are particularly useful when added to polyurethane blends containing toughening agents and / or fillers. In the past, the addition of toughening agents to polyurethanes resulted in poor impact resistance, especially at low or room temperature, as did the melt processability of the resulting composite. Thus, the impact modifiers of the present invention are useful with toughened polyurethanes to improve impact resistance, melt processability, and produce polyurethane composites with improved dimensional stability. By improved dimensional stability is meant an improvement in one or more of the following characteristics: flexural modulus, flexural strength, tensile yield strength, and heat distortion temperature. When used with toughened polyurethanes, the amount of impact modifier can be the same as that used with un-toughened polyurethanes.

[0051] In some embodiments, the additive may include one or more plasticizers. The type of plasticizer used may be any of the known plasticizers for use in TPUs. The most common type of plasticizer used is the phthalate, with butyl benzyl phthalate being the most preferred. Plasticizers used in the present invention include phthalate plasticizers such as di-n-butyl phthalate, di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisodecyl phthalate, diisooctyl phthalate, octyldecyl phthalate, butyl benzyl phthalate, and di-2-ethylhexyl isophthalate phosphate; di-2-ethylhexyl adipate (DOA), di-n-decyl adipate, diisodecyl adipate, dibutyl sebacate, and sebacate; Examples of suitable plasticizers include aliphatic ester plasticizers such as di-2-ethylhexyl basic acid; pyromellitate plasticizers such as trioctyl trimellitate and tridecyl trimellitate; phosphate plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, and tricresyl phosphate; epoxy plasticizers such as epoxy soybean oil; and polyester polymer plasticizers. For toxicologically sensitive applications such as children's toys and contact with food, di-isononyl-cyclohexane-1,2-dicarboxylate (Hexamoll® DINCH® from BASF) may be used as a plasticizer. One type of plasticizer may be used, or a combination of two or more types of plasticizers may be used. The selection of the desired plasticizer depends on the end use of the TPU polymer, as will be well understood by those skilled in the art of TPU compounding.

[0052] The compositions described herein include the TPU materials described above, and also include TPU compositions that include such TPU materials and one or more additional components. These additional components include other polymeric materials that can be blended with the TPUs described herein. These additional components include one or more additives that can be added to the TPU or blends that contain the TPU to affect the properties of the composition.

[0053] The TPUs described herein may also be blended with one or more other polymers.The polymers that the TPUs described herein can be blended with are not overly limited.In some embodiments, the compositions described include two or more of the TPU materials described.In some embodiments, the compositions include at least one of the TPU materials described and at least one other polymer that is not one of the TPU materials described.

[0054] Polymers that can be used in combination with the TPU materials described herein also include more conventional TPU materials, such as non-caprolactone polyester-based TPUs, polyether-based TPUs, or TPUs that contain both non-caprolactone polyester and polyether groups. Other suitable materials that can be blended with the TPU materials described herein include polycarbonates, polyolefins, styrene polymers, acrylic polymers, polyoxymethylene polymers, polyamides, polyphenylene oxides, polyphenylene sulfides, polyvinyl chloride, chlorinated polyvinyl chloride, polylactic acid, or combinations thereof.

[0055] The polymers used in the blends described herein include homopolymers and copolymers. Suitable examples include (i) polyolefins (PO), such as polyethylene (PE), polypropylene (PP), polybutene, ethylene propylene rubber (EPR), polyoxyethylene (POE), cyclic olefin copolymers (COC), or combinations thereof; (ii) polystyrene (PS), acrylonitrile butadiene styrene (ABS), styrene acrylonitrile (SAN), styrene butadiene rubber (SBR or HIPS), poly-α-methylstyrene, styrene maleic anhydride (SMA), styrene-butadiene copolymers (SBC) (e.g., styrene-butadiene copolymers (SBC)). (iii) styrenic such as styrene-styrene copolymer (SBS) and styrene-ethylene / butadiene-styrene copolymer (SEBS), styrene-ethylene / propylene-styrene copolymer (SEPS), styrene butadiene latex (SBL), SAN modified with ethylene propylene diene monomer (EPDM) and / or acrylic elastomer (e.g., PS-SBR copolymer), or combinations thereof; (iv) thermoplastic polyurethanes (TPUs) other than those mentioned above; (v) polyamide 6,6 (PA66), polyamide 1,1 (PA11), polyamide 1,(v) acrylic polymers such as polymethyl acrylate, polymethyl methacrylate, methyl methacrylate styrene (MS) copolymer, or combinations thereof; (vi) polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), or combinations thereof; (vii) polyoxymethylenes such as polyacetals; (viii) polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), copolyesters and / or polyester elastomers (COPE) including polyether-ester block copolymers, e.g., glycol modified polyethylene terephthalate (PETG), polylactic acid (PLA), polyglycolic acid (PGA), copolymers of PLA and PGA, or combinations thereof; (ix) polycarbonate (PC), polyphenylene sulfide (PPS), polyphenylene oxide (PPO), or combinations thereof, or combinations thereof.

[0056] In some embodiments, the TPU composition may include a UV stabilizing additive. Such additives may be particularly useful in applications where transparency is desired or where the part is exposed to sunlight or other sources of ultraviolet light. Suitable UV light stabilizers include hindered amine light stabilizers (HALS) and UV light absorbers (UVA) additives. Blends of HAL and UVA additives are also effective.

[0057] Representative HALS that can be used in the practice of the present invention include, but are not limited to, sterically hindered amines and their N-derivatives (e.g., N-alkyl, N-hydroxy, N-alkoxy, and N-acyl), such as bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis(2,2,6,6 tetramethylpiperidin-4-yl)succinate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate; bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl-4-hydroxybenzylmalonate; condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid; N,N'- Condensation product of bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine;Tris(2,2,6,6-tetramethylpiperidin-4-yl)nitrilotriacetate;Tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate;1,1'-(1,2ethanediyl)bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine bis(3,3,5,5-tetramethylpiperazinone);4-benzoyl-2,2,6,6-tetramethylpiperidine;4-stearyloxy-2,2,6,6-tetramethylpiperidine;bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]Decane-2,4-dione;Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate;Condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine;2-Chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino) Condensation products with ethane;Condensation products of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane;8-Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione;3-Dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione;3-Dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione Pyrrolidine-2,5-dione;3-dodecyl-l-(1,2,2,6,6-pentamethylpiperidin-4yl)pyrrolidine-2,5-dione;Mixture of 4-hexadecyloxy and 4-stearyloxy-2,2,6,6-tetramethylpiperidine;Condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4yl)hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine;1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine, and Condensates of 4-butylamino-2,2,6,6-tetramethylpiperidine, 2-undecyl-7,7,9,9-tetramethylpiperidine-l-oxa-3,8-diaza-4-oxospiro[4.5]decane; oxo-piperandinyl-triazines and similar materials disclosed in U.S. Pat. No. 5,071,981; photobondable HALS and similar materials disclosed in British Patent Publication No. 2,269,819; and 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4-oxospiro[4.5] Reaction products of decane with epichlorohydrin. See generally U.S. Pat. No. 4,619,956, U.S. Pat. No. 5,106,891, British Patent Publication No. 2,269,819(A), European Patent Publication No. 0,309,400(A), European Patent Publication No. 0,309,401(A), European Patent Publication No. 0,309,402(A), and European Patent Publication No. 0,434,608(A). Some commercially available examples of HALS additives are Tinuvin® 123, Tinuvin 123-DW, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622-SF, Tinuvin 770-DF, Tinuvin 5100 (Tinuvin® series additives available from BASF), Chimassorb® 119, Chimassorb 2020 (Chimassorb® series additives available from BASF), Lowilite® 76, Lowilite 62 (Lowilite® series additives available from Addivant), Uvinul® 4050 FF (BASF), LA-52, LA-576, LA-63P, 68, 72, 77Y, 77G, 81, 82, 87, 4042F, 502XP (LA series additives available from Adeka available from Clariant Corporation), Hostavin® N30, Hostavin N845PP, Hostavin 3050, Hostavin 3051, Hostavin 3052, Hostavin 3053, Hostavin 3055, Hostavin 3058, Hostavin 3065, Hostavin PR-31 (Hostavin® series additives available from Clariant), and Nylostab® S-EED® (available from Clariant); further preferred hindered amine light stabilizers are those described in Plastics Additives Handbook 6th Edition, Hans Zweifel, Ralph Maier, Michael Schiller (Hanser Publications, Inc., Cincinnati, Ohio, USA, 2009). When present, the HALS is typically present in an amount of from greater than 0 to 4 wt.%, more typically from 0.2 to 3 wt.%, and even more typically from 0.5 to 2 wt.%, based on the weight of the composition.

[0058] Without being bound by theory, typically, UV stabilizers function by scavenging free radicals and / or hydroperoxides formed by UV photodamage, while UV absorbers function by absorbing and dissipating UV radiation. Suitable UV absorbers include, but are not limited to, triazines, benzoxazinones, benzotriazoles, benzophenones, benzoates, formamidines, cinnamates / propenoates, aromatic propanedione, benzimidazole, alicyclic ketones, formanilides (including oxamides), cyanoacrylates, benzopyranones, salicylates, and mixtures of two or more thereof.

[0059] Suitable benzophenone UV absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone or sulisobenzone, 2-(4-benzoyl-3-hydroxyphenoxy)-2-propenoic acid ethyl ester, homopolymer of 4-(2-acryloyloxyethoxy)-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone or dioxybenzophenone, 2-hydroxy-4-(2-hydroxy-3-decyloxypropoxy)benzophenone and 2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)benzophenone, 2,4,4'-trihydrobenzophenone, 2- ...methoxybenzophenone or dioxybenzophenone, 2-hydroxy-4-methoxybenzophenone or dioxybenzophenone, 2-hydroxy-4-methoxybenzophenone or dioxybenzophenone, 2-hydroxy-4-methoxybenzophenone or dioxybenzophenone, 2-hydroxy-4-methoxybenzophenone or dioxybenzophenone, 2-hydroxy-4-methoxybenzophenone or dioxybenzophenone, 2-hydroxy 2,2'-dihydroxy-4-(2-hydroxyethoxy)benzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-isooctyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone, disodium salt, 2,4-dihydroxybenzophenone or 4-benzoylresorcinol, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4-(2-hydroxyethoxy)benzophenone, 2-hydroxy-4-benzyloxybenzophenone, and mixtures of two or more thereof. MAXGARD® 300, MAXGARD® 400, MAXGARD® 500, MAXGARD® 600, MAXGARD® 700, MAXGARD® 900, MAXGARD® 1000, MAXGARD® 1800 (Maxgard series chemistries available from Syrugis Performance Specialties)

[0060] Suitable benzopyranone UV absorbers include, but are not limited to, 3,3',4',5,7-pentahydroxyflavone or quercetin.

[0061] Suitable benzotriazole UV absorbers include 2-[2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, 2-(2'-hydroxy-5'-(2-hydroxyethyl))benzotriazole, 2-(2'-hydroxy-5'-methacrylyloxyethylphenyl)-2H-benzotriazole, 1,1,1-tris(hydroxyphenyl)ethanebenzotriazole, 5-t-butyl-3-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxybenzene Propanoic acid octyl ester and 3-(5-chloro-2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxybenzenepropanoic acid octyl ester, α-[3-[3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxy-1,2-ethanediyl) and a-[3-[3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]-1-oxopropyl]-w-[3-[3-( 2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]-1-oxopropoxy]poly(oxy-1,2-ethanediyl), 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3'-5'-di-t-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-t-amylphenyl)benzotriazole Azoles, 3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxybenzenepropanoic acid, 2-(2H-benzotriazol-2-yl)-4-methyl-6-dodecylphenol, 3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxy-1,6-hexanediyl ester of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxy-methyl ester of benzenepropanoic acid, 2-[2-hydroxy-3,5-bis-(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxybenzenepropanoic acid, C7-9 branched and linear alkyl esters, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-sec-butyl-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, bis[2-hydroxy-3-(2H-benzotriazol-2-yl)-5-octylphenyl]methane, and mixtures of two or more thereof. Some commercially available examples of suitable benzotriazole UV absorbers include, but are not limited to, TINUVIN® 99, TINUVIN 109, TINUVIN 328, TINUVIN 350, TINUVIN 360, TINUVIN 384-2, TINUVIN 571, TINUVIN 1130, and TINUVIN P (Tinuvin series additives available from BASF).

[0062] Suitable benzoate UV absorbers include, but are not limited to, hexadecyl 3,5-di-t-butyl-4-hydroxybenzoate, 3-hydroxyphenylbenzoate, ethyl-4-[[(ethylphenylamino)methylene]amino]benzoate, phenyl 2-hydroxybenzoate or phenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 4-bis(polyethoxy)amino acid polyethoxyethyl esters, 4-t-butylphenyl 2-hydroxybenzoate, or 4-t-butylphenyl salicylate, and mixtures of two or more thereof. Some commercially available examples of suitable UV absorbers of this type include, but are not limited to, SEESORB 300; SEESORB 201; SEESORB 202 (SEESORB UV absorbers are available from Shipro Kasei Kaisha, Ltd.); TINUVIN 120 (available from BASF); UVINUL® P 25 (available from BASF).

[0063] Suitable benzoxazinone UV absorbers include, but are not limited to, 2,2'-(p-phenylene)di-3,1-benzoxazin-4-one. Commercially available examples of suitable UV absorbers of this type include, but are not limited to, CYASORB 3638 (manufactured by Cytec Industries Inc.).

[0064] Suitable cinnamate or propenoate UV absorbers include, but are not limited to, dimethyl (p-methoxybenzylidene) malonate, and 3-(4-methoxyphenyl)-2-propenoic acid 2-ethylhexyl ester or octyl p-methoxycinnamate.

[0065] Suitable cyanoacrylate UV absorbers include, but are not limited to, ethyl-2-cyano-3,3-diphenylacrylate; 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 1,3-bis-[(2'-cyano-3,3'-diphenylacryloyl)oxy]-2,2-bis-{[(2-cyano-3',3'-diphenylacryloyl)oxy]methyl}propane, and 2-cyano-3-(2-methylindolinyl)methylacrylate.Some commercially available examples of suitable UV absorbers of this type include, but are not limited to, UVINUL® 3030, UVINUL 3035, and UVINUL 3039. Uvinul series additives are available from BASF.

[0066] Suitable alicyclic ketone UV absorbers include, but are not limited to, 3-(4-methylbenzylidene)-D,L-camphor.

[0067] Suitable formamidine UV absorbers include, but are not limited to, ethyl-4-[[(methylphenylamino)methylene]amino]benzoate.

[0068] Suitable formanilide (including oxamide) UV absorbers include, but are not limited to, N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl)oxamide, N-[5-t-butyl-2-ethoxyphenyl)-N'-(2-ethylphenyl)oxamide, N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)oxamide, 2H-benzimidazole-2-carboxylic acid (4-ethoxyphenyl)amide, and mixtures of two or more thereof. Some commercially available examples of these types of additives are Hostavin® 3206 from Clariant and TINUVIN® 312 from BASF.

[0069] Suitable triazine UV absorbers include, but are not limited to, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-[4-((2-hydroxy-3-dodecyloxy-propyl)oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4,6-trianilino-p-(carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine, and mixtures of two or more thereof. TINUVIN® 400; TINUVIN 1577 ED; UVINUL T-150 from BASF.

[0070] Suitable salicylate UV absorbers include, but are not limited to, 3,3,5-trimethylcyclohexyl salicylate or homomethyl salicylate, and menthyl-o-aminobenzoate. Some commercially available examples of these types of additives are NEO HELIOPAN® HMS and NEO HELIOPAN® MA available from Symrise AG.

[0071] When present, UV absorbers are typically present in an amount of from greater than 0 to 4 wt%, more typically from 0.2 to 3 wt%, and even more typically from 0.3 to 2 wt%, based on the weight of the composition.

[0072] In one non-limiting example, the invention includes a steering wheel frame having a foam cover at least partially or even completely covering the frame. In some embodiments, the foam cover comprises a flexible injection molded thermoplastic polyurethane foam formed from a combination of (a) a thermoplastic polyurethane composition having (i) a weight average molecular weight (Mw) of 50,000 to 350,000 Daltons, such as 100,000 to 200,000 Daltons, or even 125,000 to 175,000, where Mw is measured by gel permeation chromatography, and (ii) a polydispersity (Mw / Mn) of 1.2 to 3.5, or even 2 to 2.5, and (b) a chemical blowing agent and / or a cell opening surfactant. In one embodiment, the flexible injection molded thermoplastic polyurethane foam has the following properties: (a) a peak crystallization temperature of 25° C. to 205° C., or even 40° C. to 150° C., as measured by differential scanning chromatography (DSC), (b) a peak melting temperature of 106° C. to 206° C., as measured by DSC, and (c) a difference between the peak melting temperature and the peak crystallization temperature of 1 to 137° C. In another embodiment, the flexible injection molded thermoplastic polyurethane foam alternatively or additionally exhibits the following properties: (a) a normal rebound resilience of at least 30% as measured according to ASTM D2632, (b) a compression set at room temperature of 25% or less as measured according to ASTM D395, (c) a compression set at 50° C. of 50% or less as measured according to ASTM D395, and (d) an Asker C hardness of 30 to 65 as measured according to ASTM D2240. The chemical blowing agent used to make the thermoplastic polyurethane foam useful herein may be selected from exothermic or endothermic blowing agents. An example of an exothermic blowing agent is azodicarbonamide. An example of an endothermic blowing agent is a mixture of sodium bicarbonate and citric acid. A mixture of exothermic and endothermic blowing agents may also be used. Any known or later developed chemical blowing agent that releases gas when heated may be useful in the present invention.In some embodiments, the blowing agent may be added to the thermoplastic polyurethane composition in the form of a masterbatch containing a polymeric carrier, such as polyethylene or a thermoplastic polyurethane material (which may be the same or different from the thermoplastic polyurethane used in the foam), along with a chemical blowing agent. In embodiments using a masterbatch, the masterbatch is added in an amount of 0.5% to 10% by weight, such as 1% to 5% by weight (based on the total weight of the thermoplastic polyurethane composition and the masterbatch). In other embodiments, the thermoplastic polyurethane composition is foamed by the use of a cell-opening surfactant. Examples of cell-opening surfactants include, but are not limited to, silicones, siloxane copolymers, non-siloxane copolymers, non-silicones, or any combination thereof. In addition to the chemical blowing agent, in some embodiments of the present invention, the mixture for forming the foam may further include a physical blowing agent or nucleating agent. Physical blowing agents include, but are not limited to, linear, branched, or cyclic C1-C6 hydrocarbons, linear, branched, or cyclic C1-C6 fluorocarbons; N2, O2, argon, CO2, or any combination thereof. The nucleating agent may be selected from talc or silica. Thermoplastic polyurethane compositions useful in making the foams of the present invention include the reaction product of at least one polyol component, at least one diisocyanate component, and at least one chain extender component. In an exemplary embodiment, the polyol component may be selected from a polyether polyol (such as polytetramethylene ether glycol), a polyester polyol (such as butanediol adipate), or a polycaprolactone polyol. In an embodiment, the chain extender used in the thermoplastic polyurethane composition for the foam may be selected from 1,4-butanediol, benzene glycol, or a combination thereof. In an embodiment, the thermoplastic polyurethane composition used to construct the handle frame has a hard segment content (total weight percent of isocyanate and chain extender components) of 20% to 60% by weight, or even 20% to 40% by weight, or even 25% to 35% by weight.Examples of thermoplastic polyurethane foams that may be useful in the present invention include those disclosed in U.S. Pat. No. 10,973,281 and U.S. Patent Application Publication No. 20170178181, which are incorporated herein by reference.

[0073] The present invention also includes a method of making a foamed thermoplastic polyurethane cover for a steering wheel, the method comprising the steps of (A) providing a steering wheel frame, and (B) (1) a reaction product of (i) at least one polyol component, (ii) at least one diisocyanate component, and (iii) at least one chain extender component, the reaction product having (a) a hard segment content of 20% to 60%, or 20% to 40%, or 25% to 35% by weight, and (b) a weight average molecular weight of 50,000 to 350,000 Daltons or 100,000 to 200,000 Daltons as measured by gel permeation chromatography. and (c) a polydispersity (Mw / Mn) of 1.2-3.5 or 2.0-2.5, and a chemical blowing agent, (2) mixing the thermoplastic polyurethane material with the chemical blowing agent to obtain a foaming mixture, and (3) injection molding the foaming mixture such that the second thermoplastic polyurethane material interacts with the chemical blowing agent surfactant to form a flexible injection molded thermoplastic polyurethane foam. In one embodiment, the step of injection molding the foaming mixture is performed in a closed mold. In another embodiment, the step of injection molding the foaming mixture includes directly molding the foam cover onto the handle frame.

[0074] Each of the documents mentioned above is incorporated herein by reference, including any prior application to which priority is claimed, whether or not specifically listed above. The reference of any document is not an admission that such document qualifies as prior art or constitutes the general knowledge of the skilled artisan in any jurisdiction. Except in the examples, or unless otherwise expressly indicated, all quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, should be understood as being modified by the word "about". It should be understood that the upper and lower limits of amounts, ranges, and ratios described herein can be independently combined. Similarly, the ranges and amounts for each element of the present invention can be used together with ranges or amounts for any of the other elements.

[0075] As used herein, the transitional term "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each occurrence of "comprising" herein, the term is also intended to encompass, as alternative embodiments, the phrases "consisting essentially of" and "consisting of," where "consisting of" excludes any unspecified element or step, and "consisting essentially of" permits the inclusion of additional, unrecited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

[0076] While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention, which in this regard should be limited only by the scope of the claims that follow.

Claims

1. A steering wheel for a vehicle, Handle frame and a foam cover for the handle frame, the foam cover comprising a flexible injection-molded thermoplastic polyurethane foam formed from a combination of: (a) a thermoplastic polyurethane material having a weight average molecular weight of 50,000 to 350,000 Daltons or 100,000 to 200,000 Daltons, as measured by gel permeation chromatography, and a polydispersity index (Mw / Mn) of 1.2 to 3.5 or 2.0 to 2.5; and (b) a chemical blowing agent and / or a cell-opening surfactant, the foam cover at least partially or completely covering the handle frame; A vehicle handle comprising:

2. The flexible injection molded thermoplastic polyurethane foam is (i) a peak crystallization temperature of 25°C to 205°C or 40°C to 150°C as measured by DSC; (ii) a melting peak temperature of 106°C to 206°C as measured by DSC; and (iii) the difference between the peak melting temperature and the peak crystallization temperature, each measured by DSC, from 1 to 137°C; The handle of claim 1 , wherein

3. The flexible injection molded thermoplastic polyurethane foam is (i) a normal rebound resilience of at least 30% as measured by ASTM D2632; (ii) a compression set at room temperature of 25% or less, as measured by ASTM D395; (iii) a compression set at 50°C of 50% or less, as measured by ASTM D395; and (iv) an Asker C hardness of 30 to 65, as measured by ASTM D2240; 3. The handle of claim 1, wherein the handle comprises:

4. The handle of claim 1 , wherein the foaming agent comprises water.

5. The handle of claim 1 , wherein the foaming agent comprises or consists of a chemical foaming agent.

6. 6. The handle of claim 5, wherein the chemical blowing agent comprises or consists of an exothermic blowing agent.

7. 7. The handle of claim 6, wherein the exothermic blowing agent comprises or consists of azodicarbonamide.

8. The handle of claim 1 , wherein the blowing agent comprises or consists of an endothermic blowing agent.

9. 9. The handle of claim 8, wherein the effervescent agent comprises or consists of a mixture of sodium bicarbonate and citric acid.

10. The handle of claim 5 , wherein the chemical blowing agent is delivered by a masterbatch comprising a polymeric carrier and the chemical blowing agent.

11. 10. The handle of claim 9, wherein the flexible thermoplastic polyurethane foam is formed from a combination of 0.5% to 10% or 1% to 5% by weight of the masterbatch and 90% to 99.5% or 95% to 99% by weight of the thermoplastic polyurethane material.

12. The handle of claim 10, wherein the polymeric carrier comprises or consists of a carrier thermoplastic polyurethane composition.

13. The handle of claim 12, wherein the polymeric carrier comprises or consists of polyethylene.

14. The handle of claim 1 , wherein the cell-opening surfactant comprises one or more silicones, siloxane copolymers, non-siloxane copolymers, non-silicones, or any combination thereof.

15. 2. The handle of claim 1, wherein the thermoplastic polyurethane material comprises the reaction product of (i) at least one polyol component, (ii) at least one diisocyanate component, and (iii) at least one chain extender component, the combined weight of the at least one diisocyanate component and the at least one chain extender component comprising a hard segment content of the thermoplastic polyurethane material, and the thermoplastic polyurethane material has a hard segment content of 20% to 60% by weight, or 20% to 40% by weight, or 25% to 35% by weight.

16. 16. The handle of claim 15, wherein the polyol component is a selected polyether polyol, polyester polyol, or combination thereof.

17. 17. The handle of claim 16, wherein the polyol component comprises or consists of polytetramethylene ether glycol.

18. The handle of claim 17, wherein the thermoplastic polyurethane material has a hard segment content of 20% to 60% by weight or 23% to 45% by weight.

19. 20. The handle of claim 18, wherein the polyol component comprises or consists of a polyester polyol derived from adipic acid.

20. 20. The handle of claim 19, wherein the thermoplastic polyurethane material has a hard segment content of up to 50%, or 24% to 50%, or 24% to 30% by weight.

21. 21. The handle of claim 20, wherein the polyol component comprises or consists of a polycaprolactone polyester polyol.

22. 22. The handle of claim 21, wherein the thermoplastic polyurethane material has a hard segment content of 20% to 60% by weight, or 20% to 40% by weight, or 25% to 35% by weight.

23. The handle of claim 15, wherein the chain extender component comprises 1,4-butanediol, benzene glycol, or any combination thereof.

24. 2. The handle of claim 1, wherein the handle frame comprises a handle rim, a hub base, and at least one spoke, the hub base being positioned inside the handle rim and the hub base being connected to the handle rim by the at least one spoke.

25. 1. A method of making a handle, comprising: (A) providing a handle frame; (B) (1) providing a thermoplastic polyurethane foaming mixture comprising: a thermoplastic polyurethane material comprising the reaction product of (i) at least one polyol component, (ii) at least one diisocyanate component, and (iii) at least one chain extender component, the thermoplastic polyurethane material having (a) a hard segment content of 20% to 60% by weight, or 20% to 40% by weight, or 25% to 35% by weight, (b) a weight average molecular weight of 50,000 to 350,000 Daltons or 100,000 to 200,000 Daltons as measured by gel permeation chromatography, and (c) a polydispersity (Mw / Mn) of 1.2 to 3.5 or 2.0 to 2.5; and a chemical blowing agent; (2) mixing the thermoplastic polyurethane material with the chemical blowing agent to obtain a foamed mixture; (3) forming a foam cover for the handle frame by injection molding the foaming mixture such that a second thermoplastic polyurethane material interacts with a chemical blowing agent surfactant to form a flexible injection molded thermoplastic polyurethane foam; A method comprising:

26. The flexible thermoplastic polyurethane foam is (i) a peak crystallization temperature of 25°C to 205°C or 40°C to 150°C as measured by DSC; (ii) a melting peak temperature of 106°C to 206°C as measured by DSC; and (iii) the difference between the peak melting temperature and the peak crystallization temperature, each measured by DSC, from 1 to 137°C; 26. The method of claim 25, comprising:

27. The flexible injection molded thermoplastic polyurethane foam is (i) a normal rebound resilience of at least 30% as measured by ASTM D2632; (ii) a compression set at room temperature of 25% or less, as measured by ASTM D395; (iii) a compression set at 50°C of 50% or less, as measured by ASTM D395; and (iv) an Asker C hardness of 30 to 65, as measured by ASTM D2240; 27. The method of claim 25 or 26, comprising:

28. 26. The method of claim 25, wherein the chemical blowing agent comprises water.

29. 26. The method of claim 25, wherein the chemical blowing agent comprises or consists of an exothermic blowing agent.

30. 30. The method of claim 29, wherein the exothermic blowing agent comprises or consists of azodicarbonamide.

31. 26. The method of claim 25, wherein the blowing agent comprises or consists of an endothermic blowing agent.

32. 32. The method of claim 31 , wherein the effervescent agent comprises or consists of a mixture of sodium bicarbonate and citric acid.

33. 30. The method of claim 29, wherein the chemical blowing agent is delivered by a masterbatch comprising a polymeric carrier and the chemical blowing agent.

34. 34. The method of claim 33, wherein the foaming mixture contains 0.5% to 10% or 1% to 5% by weight of the masterbatch and 90% to 99.5% or 95% to 99% by weight of the thermoplastic polyurethane material.

35. 34. The method of claim 33, wherein the polymeric carrier comprises or consists of a carrier thermoplastic polyurethane composition.

36. 34. The method of claim 33, wherein the polymeric carrier comprises or consists of polyethylene.

37. 26. The method of claim 25, wherein the polyol component is a selected polyether polyol, polyester polyol, or combination thereof.

38. 38. The method of claim 37, wherein the polyol component comprises or consists of polytetramethylene ether glycol.

39. 39. The method of claim 38, wherein the thermoplastic polyurethane material has a hard segment content of 20% to 60% by weight or 23% to 45% by weight.

40. 38. The method of claim 37, wherein the polyol component comprises or consists of a polyester polyol derived from adipic acid.

41. 41. The method of claim 40, wherein the thermoplastic polyurethane material has a hard segment content of up to 50%, or from 24% to 50%, or from 24% to 30% by weight.

42. 38. The method of claim 37, wherein the polyol component comprises or consists of a polycaprolactone polyester polyol.

43. 43. The method of claim 42, wherein the thermoplastic polyurethane material has a hard segment content of 20% to 60% by weight, or 20% to 40% by weight, or 25% to 35% by weight.

44. 26. The method of claim 25, wherein the chain extender component comprises 1,4-butanediol, benzene glycol, or any combination thereof.

45. 26. The method of claim 25, wherein the handle frame comprises a handle rim, a hub base, and at least one spoke, the hub base being positioned inside the handle rim and the hub base being connected to the handle rim by the at least one spoke.

46. 26. The method of claim 25, wherein the step of injection molding the foaming mixture occurs in a closed mold.

47. 26. The method of claim 25, wherein the step of injection molding the foam mixture includes molding the foam cover directly onto the handle frame.

Images