1. Field of the Invention
The present invention relates to moldable polymeric compositions that are useful for making instrument panel skins and other trim panel components used in automobile interiors.
2. Background Art
The way automotive interior components feel to the touch is often called the “haptics” or “hand.” Haptics are very important to consumers in automotive interior components. To manufacture items with quality haptics, slush molding is often used since it allows for high quality textures to be produced that are similar in desirability to leather, which is often considered to have a desirable and/or luxurious feel. Different components may have different desired haptics, however, so one composition or process may not be suitable for all parts.
It is also important for components that are part of the air bag systems to have suitable physical and material properties to perform adequately at low temperatures, for example −30° C. In addition to slush molding, vacuum forming and spray urethane are often used to make interior components. However, vacuum forming and spray urethane do not generally perform as well in air bag components at −30° C. and do not typically have as desirable a “hand” as slush molded components.
Accordingly, a slush moldable polymeric composition with desirable haptics that performs well in low temperature air bag tests would be beneficial.
In one aspect of the invention, a moldable polymeric composition is provided. In at least one embodiment, the polymeric composition comprises:
a) from 50 to 99 wt. percent urethane elastomer;
b) from 0.1 to 15 wt. percent propylene copolymer;
c) from 0.1to 25 wt. percent olefin modified thermoplastic, such as SEBS; and
d) from 0.1 to 30 wight percent olefinic block copolymer;
In another aspect of the invention, a vehicle skin is provided. In at least one embodiment, the skin comprises the dried product of
a) from 50 to 99 wt. percent urethane elastomer;
b) from 0.1 to 15 wt. percent propylene-ethylene copolymer;
c) from 0.1 to 25 wt. percent SEBS; and
d) from 0.1 to 30 wt. percent olefinic block copolymer; and
wherein the skin has a thickness from 0.3 to 3.0 mm and a Shore A hardness from 60 to 90.
Reference will now be made in detail to presently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of practicing the invention presently known to the inventors. The Figure is not necessarily to scale. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for the claims and/or as a representative basis for teaching one skilled in the art to variously employ the present invention.
Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary: percent, “parts of”, and ratio values are by weight; the term “polymer” includes “oligomer”, “copolymer”, “terpolymer”, and the like; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; and the first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation.
It is also to be understood that this invention is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present invention and is not intended to be limiting in any way.
It must also be noted that, as used in the specification and the appended claims, the singular form “a,” “an,” and “the” comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.
Throughout this application, where publications are referenced, the disclosures of these publications in their entireties are hereby incorporated by reference into this application to more fully describe the state of the art to which this invention pertains.
A slush moldable polymeric composition that has tunable haptics is hereby provided. Density and Shore A hardness can be used as indicators of the haptics for automotive interior components. By adjusting the amount of individual modifiers (each having a density and Shore A hardness) in the slush moldable polymeric composition, the haptics of the composition can be adjusted to the desired feel for a component.
An automotive interior component including a skin made of the slush moldable polymeric composition is also provided. To provide haptics that are desirable to a consumer and also meet certain application requirements, the skin, in at least one embodiment, is formed by slush molding and has a certain range of physical and material properties. It should be understood, however, that while sluch molding is described as the predominant manufacturing technique in using this composition, that this composition can be used in other manufacturing processes, such as vacuum forming.
In at least one embodiment, the skin may be 0.3 to 3.0 mm thick, in another embodiment 0.5 to 2.0 mm thick, in yet another embodiment 0.75 to 1.5 mm thick, and in still yet another embodiment 1.0 mm thick. The Shore A hardness and the density of the skin play are two characteristics that heavily influence the haptics of the skin. In at least one embodiment, the skin may have a Shore A hardness of 60 to 90 as measured using ASTM D2240 with a 15 second dwell time. In another embodiment the Shore A hardness is 65 to 85, and in yet another embodiment 70 to 80. The density of the skin in at least one embodiment may be from 0.95 to 1.15 g/cm3 as measured using ASTM D792. In yet another embodiment, the density is 1.0 to 1.10 g/cm3, and in another embodiment 1.03 g/cm3.
For skins that will be used in certain components, such as those involved with an air bag, it is desirable for the physical and material properties to meet certain criteria. In at least one embodiment, the tear strength is from 15 to 35 kN/m as measured using ISO 34 Method B ASTM D624. In another embodiment the tear strength is from 20 to 30 kN/m, and in yet another embodiment 25 kN/m. In at least one embodiment, the tensile strength is from 3.0 to 6.0 MPa as measured using ISO 527 Type 1B at 500 mm/min. The tensile strength is from 4.0 to 5.0 MPa in another embodiment, and 4.5 MPa in yet another embodiment. The elongation at break in at least one embodiment is at least 100% as measured using ISO 527 Type 1B at 500 mm/min. In another embodiment the elongation at break is at least 125%, in yet another embodiment at least 200%, in still yet another embodiment at least 250%, and in still further another embodiment at least 300%.
In certain instances, the resistance to marring and porosity are also properties of concern for the skin. In at least one embodiment, the loss of gloss is less than 5% when measured using test method FLTM BN107-01, and in other embodiments, less than 2.5%. The porosity of the skin can have a substantial impact on the feel, look, and performance of the skin. As examined under light microscope at 50× magnification, the porosity of the skin may be from 0% to 2% in at least one embodiment, 0% to 1% in another embodiment, and substantially 0% in yet another embodiment.
With reference to
In a subsequent step b), urethane based resin composition 10 is heated to a sufficient temperature to form layer 14 over at least a portion of mold tool 12. In one refinement, urethane based resin composition 10 is heated to a temperature between about 170° C. and 260° C. In step c), excess powder is poured out from mold tool 12. The mold tool 12 is further heated, if necessary, in step d) so that the remaining powder melts. Finally, instrument panel skin 20 is removed from mold tool 12 is step e).
With reference to
In one embodiment, mold tool 12 may have a textured surface that contacts urethane-based composition 10 to impart a textured surface onto instrument panel skin 20.
In at least one embodiment of the present invention, the urethane-based composition 10 comprises from 50% to 99% urethane elastomer, in another embodiment 55% to 85%, and in yet another embodiment 60% to 73%. Modifiers may comprise from 1% to 50% of the composition, in another embodiment 15% to 45%, and in yet another embodiment 27% to 40%. The above percents, and other composition percents, are wt. percents unless otherwise specified.
In at least one embodiment, the urethane elastomer is thermoplastic and an aliphatic urethane elastomer comprising polyoxypropylene oxide diol. The polyoxypropylene oxide diol may be capped to provide primary hydroxyl end groups. The polyoxypropylene oxide diol may have a molecular weight from 2,000 to 6,000, in another embodiment 3,000 to 5,000, or in yet another embodiment 4,000. Examples of acceptable urethane elastomers are Bayer Texin DP7-3042 and Huntsman L448-205.
In another embodiment, the urethane elastomer may include residues of a composition having a polyol and an organic diisocyanate. In a refinement, the thermoplastic urethane elastomer includes a chain extender. In a further refinement, the urethane base resin further includes a hindered amine light stabilizer and/or a benzotriazole ultraviolet stabilizing agent.
As set forth above, the urethane elastomer may include the residues of a polyol. Suitable polyols are disclosed in U.S. Pat. Nos.5,824,738 and 6,187,859. Specific examples, include, but are not limited to polyether polyols. In a variation, the polyol is formed in a process utilizing an organometallic catalyst that results in a polyol having a low level of terminal unsaturation. In one refinement, the polyol has a level of terminal unsaturation less than about 0.04 meq/g. In another refinement, the polyol has a level of terminal unsaturation less than about 0.02 meq/g. A representative example of such a polyol is Poly L 255-28 (sold by Olin corporation, Stamford, Conn.). Poly L 255-28 is a ethylene oxide capped poly (propylene oxide) polyol with an approximate molecular weight of 4000 and a hydroxyl number of 28. The polyol component can be present in amounts ranging from approximately 40% to 70% of the total weight of the thermoplastic urethane elastomer composition. In a refinement, the polyol is present in an amount between 40% and 60% of the total weight of the thermoplastic urethane elastomer composition. The amount of polyol is adjusted in this range to vary the hardness of the elastomer produced.
In a variation of the present embodiment, the thermoplastic urethane elastomer composition includes a chain extending agent. Suitable chain extending agents include aromatic secondary or aliphatic primary or secondary diamines, ethylene glycol, diethylene glycol, propylene glycol, pentane diol, 3-methylpentane-1,5-diol, hexane diol, HQEE [hydroquinone bis(2-hydroxyethyl)ether], CHDM (1,4-cyclohexanedimethanol), and HBPA (hydrogenated bisphenol A). A particularly useful chain extender is 1,4-butanediol. In a refinement, such chain extenders are present in concentrations varying from 6% to 15% of the total weight of the thermoplastic urethane elastomer composition. In another refinement, the chain extenders are present in an amount from 7% to 13% of the total weight of the thermoplastic urethane elastomer composition.
The thermoplastic urethane elastomer composition used in the present embodiment includes one or more isocyanates. Suitable isocyanates include aliphatic organic diisocyanates, or mixture of diisocyanates. Specific examples of organic isocyanates include, but are not limited to, (TMXDI) meta-tetramethylxylene diisocyanate and paratetramethylxylene diisocyanate, isophorone diisocyanate (IPDI), dibenzyl diisocyanate, xylene diisocyanate (XDI), 3,3′-bis toluene-4,4-diisocyanate, hexamethylene diisocyanate (HDI), hydrogenated MDI, hydrogenated XDI, cyclohexane diisocyanate, paraphenylene diisocyanate, mixtures and derivatives thereof and the like. In a refinement, the organic diisocyanates are present in an amount from 20% to 50% of the total weight of the thermoplastic urethane elastomer composition. In another refinement, the organic diisocyanates are present in an amount from 25% to 40% of the total weight of the thermoplastic urethane elastomer composition.
As set forth above, the thermoplastic urethane elastomer composition may include an ultraviolet stabilizing agent. Suitable ultraviolet stabilizing agents may include a combination of a hindered amine light stabilizers (HALS) and a benzotriazole. Examples of HALS include, but are not limited to, bis(1,2,2,6,6-pentamethyl-1-4-piperidinyl)sebacate (Chemical Abstract Number 41556-26-7, also known as Tinuvin 292 or 765 Ciba-Geigy Corp., Hawthorne, N.Y.). Examples of benxotriazoles include hydroxyphenyl benzotriazoles such as a benzotriazole mixture of poly (oxy-1,2-ethanediyl), alpha-[3-[3- (2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-omega-hydroxy- and poly(oxy-1,2-ethanediyl), alpha-[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl)-omega-[3 -[(2H-benzotriazol-2-yl)-5 -(1,1,-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy)-, Chemical Abstract Number 104810-47-1 and polyethylene glycol with a molecular weight of 300 Chemical Abstract Number 25322-68-3 (also known as Tinuvin 1130 or 213 Ciba-Geigy Corp., Hawthorne, N.Y.) and any other suitable ultraviolet stabilizing agents. In a refinement, the combination of ultraviolet stabilizing agent are present in a ratio in a range of approximately 1:1 to 2:1 by weight. In another variation, the total concentration of ultraviolet stabilizing agents are present in an amount from about 0.5 to 2.0%, of the total weight of the urethane elastomer composition.
In another variation of the present invention, the urethane elastomer composition includes an antioxidant. Virtually any suitable antioxidant, or mixture of antioxidants, may be used in the practice of the present invention. Representative examples include, but are not limited to, Irganox 1010 [tetrakis (methylene(3,5-di-tert-butyl-4-hydroxycinnamate)]methane from Ciba-Geigy; Irganox 1076 [Octodecyl 3,5 di-tert-butyl-4-hydroxyhydrocinnamate] from Ciba-Geigy; Irganox 245 [Ethylenebis (oxyethylene)bis-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamate)] from Ciba-Geigy; and Vanox 830 (a proprietary blend of a phenolic compound, alkylated diphenylamines and trialkyl phosphite from R. T. Vanderbilt). The antioxidants may be present at a total concentration in a range of approximately 0.10% to 1.0% of the total weight of the urethane elastomer composition. In another refinement, the antioxidants may be present at a total concentration in a range of approximately 0.25% to 0.75% of the total weight of the urethane elastomer composition.
In at least one embodiment of the present invention, the modifiers may comprise a propylene copolymer, such as propylene-ethylene copolymer. The preferred propylene copolymer is propylene-ethylene copolymer, and as such, the propylene copolymer will be described hereinafter as propylene-ethylene copolymer. However, it should be understood that the description of the propylene-ethylene copolymer can apply to other propylene copolymers such as propylene-butylene and the like. The propylene-ethylene copolymer may comprise 0.1% to 15% of the urethane-based composition, in another embodiment 2.5% to 10%, and in yet another embodiment 5.0% to 7.5%. The copolymer may have a narrow molecular weight distribution (about 2 to 3) and a broad crystallinity distribution. The copolymer may have a density of 0.7 to 1.0 g/cm3, in another embodiment of 0.75 to 0.95 g/cm3, in yet another embodiment of 0.8 to 0.9 g/cm3, and in still yet another embodiment of 0.85 g/cm3. The copolymer may have a melt flow rate of 1 to 30 dg/min, in another embodiment of 2 to 25 dg/min, in yet another embodiment of 2 to 15 dg/min, in still yet another embodiment of 2 to 10 dg/min, in still yet another further embodiment of 2 to 5 dg/min, and in still yet even another further embodiment of 2 dg/min. The copolymer may have a total crystallinity of 1% to 20%, in another embodiment of 5% to 10%, in yet another embodiment of 6% to 8%, and in still yet another embodiment of 7%.
The propylene-ethylene copolymer may have a Shore A hardness of 50 to 75, in another embodiment of 60 to 70, in yet another embodiment of 65 to 70, and in still yet other embodiment of 68. The copolymer may have a glass transition temperature of −40 to −15° C., in still another embodiment of −35 to −25° C., in yet another embodiment of −35 to −30° C., and in still yet another embodiment of −33° C. The copolymer may have an ultimate tensile strength of 700 to 1,000 psi, in another embodiment of 800 to 900 psi, in yet another embodiment of 825 to 875 psi, and in still yet another embodiment of 860 psi. The copolymer may have a flexural modulus of 1,000 to 40,000 psi, in another embodiment of 2,000 to 35,000 psi, in yet another embodiment of 2,000 to 10,000 psi, in still yet another embodiment of 2,000 to 5,000 psi, and in still yet another further embodiment of 2,000 psi. An example of an acceptable propylene-ethylene copolymer is VERSIFY™ 2400 Elastomer from Dow®.
In at least one embodiment of the present invention, the modifiers may comprise an olefin modified thermoplastic, such as styrene block copolymers, such as a styrene-ethylene-butadiene-styrene (SEBS) block copolymer. The preferred olefin modified thermoplastic is the styrene block copolymer SEBS, and as such, the olefin modified copolymer will be described hereinafter as SEBS. However, it should be understood that the description of the SEBS can apply to other olefin modified thermoplastics, such as styrene-isoprene (SI) copolymer, styrene-butadiene (SB) copolymer, styrene-ethylene-propylene-styrene(SEPS) copolymer and the like. The SEBS copolymer may comprise 0.1% to 25% of the urethane-based composition, in another embodiment of 5% to 22.5%, in yet another embodiment of 7.5% to 15%, and in still yet another embodiment of 10%. The SEBS copolymer may have a Shore A hardness of 45 to 65, in another embodiment of 50 to 60, and in yet another embodiment of 53. The copolymer may have a density of 0.8 to 1.1 g/cm3, in another embodiment of 0.95 to 1.05 g/cm3, in yet another embodiment of 1.0 to 1.05 g/cm3, and in still yet another embodiment of 1.04 g/cm3. The copolymer may have an ultimate tensile strength of 1.0 to 4.5 MPa. The copolymer may have an ultimate elongation of 500% to 700%, and in yet another embodiment of 600%. The SEBS may have a melting temperature of 95° C. to 110° C. An example of an acceptable SEBS block copolymer is Santoprene 8211 55B100.
In at least one embodiment of the present invention, the modifiers may comprise olefinic block copolymers (OBC) having a broader molecular weight distribution and higher melting and crystallization temperatures than traditional SEBS block copolymers. The olefinic block copolymer may have a variable distribution of block lengths, as opposed to traditional block copolymers which typically have nearly the same block lengths throughout. The blocks may also alternate as relatively hard/rigid and soft blocks. The olefinic block copolymer may be present in the urethane-based composition in an amount from 0.1% to 30%, in yet another embodiment of 2.5% to 20%, in another embodiment, and still yet another embodiment of 5.0% to 12.5%.
The olefinic block copolymers may have a melt flow rate of 0.25 to 1.5 dg/min, and in yet another embodiment of 0.5 to 1.0 dg/min. The copolymers may have a density of 0.7 to 1.0 g/cm3, in another embodiment of 0.8 to 0.9 g/cm3, in yet another embodiment of 0.85 to 0.88 g/cm3, and in still yet another embodiment of 0.877 g/cm3. The copolymer may have a Shore A hardness of 60 to 80, in another embodiment of 70 to 80, and in yet another embodiment of 75. The copolymer may have a melting point of at least 100° C., in yet another embodiment at least 110° C., in yet another embodiment at least 115° C., and in still yet another embodiment of 120° C. The copolymer may have an ultimate tensile strength of 2,000 to 3,000 psi, in another embodiment of 2,250 to 2,750 psi, and in yet another embodiment of 2, 500 to 2,650 psi. The copolymer may have an ultimate tensile elongation of 1,000% to 2,000%, in another embodiment 1,250% to 1,750%, in yet another embodiment of 1,400% to 1,700%, and in still yet another embodiment 1,477% to 1,673%. Examples of acceptable olefinic block copolymers are those from the Dow® INFUSE™ line, such as D9000.00, D9000.05, and D9100.05.
Improvements in the physical properties, such as tensile strength, percent elongation, and tear strength of the tunable polymeric composition may be achieved by the addition of surface modified montmorillonite nanoclays, such as Cloisite 93A and Cloisite 30B from Southern Clay Products. The nanoclays may be modified with a quaternary ammonium salt. In at least one embodiment, the nanoclay is present in the composition in the amount of 0% to 3.0%, in another embodiment of 0.5% to 2.5%, in yet another embodiment of 1.0% to 2.0%, and in still yet another embodiment of 1.5%. Addition of nanoclays within these ranges may be advantageous for automotive interior components involved in air bag deployment, particularly at low temperatures (e.g. −30° C.).
In at least one embodiment of the present invention, the tunable polymeric composition comprises at least two of the afore-mentioned modifiers, in another embodiment at least three modifiers, and in yet another embodiment at least four modifiers. For example, the tunable polymeric composition may comprise urethane elastomer, a propylene-ethylene copolymer, a SEBS block copolymer, and an olefinic block copolymer as described previously.
Urethane-based composition 10 may optionally further include one or more pigments. In at least one embodiment, the pigments are present in an amount from 0% to 10% of the urethane-based composition, in another embodiment 0.1% to 8.0%, and in yet another embodiment 2.0% to 7.0%. In at least certain embodiments, pigments based on TPU-based and/or olefinic-based concentrates have been found to be particularly suitable. In at least certain embodiments, the pigment concentrates comprise pigment dispersed in TPU and/or olefinic carriers having let down ratios of 25:1 to 50:1 of pigment to carrier. Examples of suitable olefin-based pigment concentrates include Americhem DX9 50437-HI-106 from Americhem and TPU-based pigment concentrates include Clariant 2N4A from Clariant Master Batches.
The following examples illustrate the various embodiments of the present invention. Those skilled in the art will recognize many variations that are within the spirit of the present invention and scope of the claims.
Table 1 provides suitable ranges of some of the components in the composition.
Table 2 provides the compositions of several test samples that were used to form skin layers via a slush molding process at 260° C. for 10 minutes.
Table 3 provides test data on the physical and material properties for some of the test samples in Table 2.
While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.