Polyurethane resin type composition for slush molding

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...

Reexamination Certificate

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C524S306000, C524S311000, C524S314000, C524S378000, C524S590000, C525S424000, C525S455000

Reexamination Certificate

active

06235830

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a composition for slush molding, more particularly to a slush molding composition capable of producing molded articles suitable for automotive trims such as instrument panels.
BACKGROUND OF THE INVENTION
Slush molding process has been widely practiced for molding various articles as interior component parts of motor vehicles. In this molding, there have been proposed modifications of PVC with flexible thermoplastic polyurethane resin as materials to provide soft touch without a low molecular weight plasticizer, as disclosed in Examined Japanese Patent Publication Nos. S53-29705, S59-39464 and S60-30688.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a molded article of improved compatibility of plasticizer and soft feel even at low temperature. It is another object of the present invention to provide a molded article of little or reduced fogging problem (formation of oil film of evaporated plasticizer on the automotive front windshield) and suitable for automotive instrument panels. It is a further object of the present invention to provide a molded article having improved pigment dispersibility without causing uneven color even in light color. It is still another object of the present invention to provide a molded article having improved durability and resistance to ultraviolet, high temperature and chemicals. It is yet another object of the present invention to provide a slush molding composition and a process, capable of producing a molded article as above.
Briefly, these and other objects of this invention as hereinafter will become more readily apparent have been attained broadly by a slush molding composition, comprising a thermoplastic polyurethane elastomer (A), a plasticizer (B) and a radical polymerizable group-containing compound (C). The thermoplastic polyurethane elastomer (A) usually has a number average molecular weight (measured by GPC, hereinafter referred to as Mn) of about 10,000 to about 50,000, a glass transition temperature of not higher than −35° C., and a heat softening initiation temperature of about 120° C. to about 200° C.
DETAILED DESCRIPTION OF THE INVENTION
Suitable thermoplastic urethane elastomers (A) according to the present invention include, for example, those desclosed in U.S. Pat. No. 5,906,704. Illustrative of (A) are ones obtainable by reacting an NCO-terminated urethane prepolymer (a) with a non-aromatic diamine (b1) and an aliphatic monoamine (b2). Said prepolymer (a) is derived from an excess non-aromatic diisocyanate (a1) and a high-molecular diol (a2) having a number average molecular weight of 500 to 10,000 with, optionally, a low-molecular diol (a3).
Suitable non-aromatic diisocyanates (a1) include, for example, {circle around (1+L )} aliphatic diisocyanates with 2 to 18 carbon atoms (except the carbon atoms in the NCO groups, similarly hereinafter), e.g., ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter referred to as HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanato ethyl)carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and the like; {circle around (2+L )} alicyclic diisocyanates with 4 to 15 carbon atoms, e.g., isophorone diisocyanate (hereinafter referred to as IPDI), dicyclohexylmethane-4,4′-diisocyanate (hereinafter referred to as hydrogenated MDI), cyclohexylene diisocyanate, methyl cyclohexylene diisocyanate (hereinafter referred to as hydrogenated TDI), bis(2-isocyanato ethyl)-4-cyclohexene, and the like; {circle around (3+L )} araliphatic isocyanate with 8 to 15 carbon atoms, e.g., m- and/or p-xylylene diisocyanate (hereinafter a referred to as XDI), &agr;, &agr;, &agr;′, &agr;′-tetramethyl xylylene diisocyanate (hereinafter referred to as TMXDI), and the like; {circle around (4+L )} modified diisocyanates from these, e.g., diisocyanates having a carbodiimide group, an urethodione group, an urethoimine group or an urea group; and {circle around (5+L )} mixtures of two or more of those compounds.
Among these compounds, preferred are alicyclic diisocyanates, particularly IPDI and hydrogenated MDI.
Suitable high molecular weight diols (a2) include polyester diols, polyether diols and mixtures of two or more of those compounds.
As the aforesaid polyester diol can be cited: {circle around (1+L )} polycondensates of a low molecular weight diol and/or a polyether diol with a dicarboxylic acid or its ester-forming derivative (acid anhydride, lower alkyl ester containing one to 4 carbon atoms, acid halide, and the like); {circle around (2+L )} ring opening polymerizates of a lactone monomer with a low molecular weight diol and/or a polyehter diol as initiator; and mixtures of two or more of those compounds.
The aforesaid low molecular weight diol usually has a molecular weight of 62-about 500. Examples of such diol include: aliphatic diols [linear ones such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and the like, branched ones such as propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanedio 1,1,2-butanediol, 1,3-butanediol, and 2,3-butanediol]; and diols that contain cyclic group [ones described in exemplified Japanese Patent Publication No. S45-1474, alicyclic diols such as 1,4-bis(hydroxymethyl)cyclohexane and hydrogenated bisphenol A, aromatic ring-containing diols such as m-xylylene glycol, p-xylylene glycol, alkylene oxide adduct of bisphenol A, alkylene oxide adduct of bisphenol S, alkylene oxide adduct of bisphenol F, alkylene oxide adduct of dihydroxynaphthalene and bis(2-hydroxyethyl)terephthalate]. Suitable polyether diols include the same ones as described below. Mixtures of two or more of these diols may also be used.
Of these compounds preferable are aliphatic diols (particularly neopentyl glycol) and alicyclic diols (particularly hydrogenated bisphenol A).
Examples of the dicarboxylic acid or its ester-forming derivative in aforesaid {circle around (1)} include aliphatic dicarboxylic acids with 4 to 15 carbon atoms such as succinic, adipic, sebacic, glutaric, azelaic, maleic and fumaric acids; aromatic dicarboxylic acids with 8 to 12 carbon atoms such as terephthalic and isophthalic acids; their ester-forming derivatives such as acid anhydrides, lower alkyl esters (e.g., dimethyl ester, diethyl ester), acid halides (e.g., acid chloride); and mixtures of two or more of these compounds. Among these, preferred are adipic acid and isophthalic acid.
Examples of the lactone monomer in aforesaid {circle around (2+L )} include &ggr;-butyrolactone, &egr;-caprolactone, &ggr;-valerolactone and mixtures of two or more of these compounds.
As the aforesaid polyether diol can be cited alkylene oxide adducts of dihydroxyl compound such as the aforesaid low molecular weight diols and dihydric phenols.
Among the dihydric phenols are bisphenols, e.g., bisphenol A bisphenol F and bisphenol S, and monocyclic phenols e.g., catechol and hydroquinone.
Suitable alkylene oxides include ones containing 2-8 carbon atoms, for example, ethylene oxide (hereafter, referred to as “EO”), propylene oxide (hereafter, referred to as “PO”), 1,2-butylene oxide, 1,3-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, styrene oxide, a-olefin oxide with 5 to 10 or more carbon atoms, epichlorohydrin, and combinations of two or more of these compounds, which may be added blockwise and/ or randomwise.
Of those polyether diols, preferable are alkylene oxide adducts of dihydric phenols, particularly EO adducts of dihydric phenols (especially bisphenol A).
Of those high molecular weight diols (a2), preferable are polyester diols, and more preferable polycondensates between a low molecular weight diol and a dicarboxylic acid, in view of providing excellent soft touch.
(a2) generally has an Mn of 500 to 10,000, preferably 800 to 5,000, more prefer

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