Thermoformed article having low gloss and a composition for its preparation

A thermoplastic composition comprising a resinous blend of a polyether-polyol based thermoplastic polyurethane having a Shore A hardness no greater than 90, and a grafted polybutadiene rubber is disclosed. In the inventive composition, the relative amount in the blend of polyurethane predominates the amount of grafted polybutadiene rubber. The composition is especially suitable for the preparation, by thermoforming, of articles having low gloss which are additionally characterized by their "soft-touch". Also disclosed is a method for reducing the 60 degree gloss of a thermoformed article prepared from a thermoplastic composition containing a blend of thermoplastic polyurethane and grafted polybutadiene rubber.

FIELD OF THE INVENTION 
The invention concerns thermoplastic molding compositions and more 
particularly compositions suitable for thermoforming articles having low 
60 degree gloss value. 
SUMMARY OF THE INVENTION 
A thermoplastic composition comprising a resinous blend of a 
polyether-polyol based thermoplastic polyurethane having a Shore A 
hardness no greater than 90, and a grafted polybutadiene rubber is 
disclosed. In the inventive composition, the relative amount in the blend 
of polyurethane predominates the amount of grafted polybutadiene rubber. 
The composition is especially suitable for the preparation, by 
thermoforming, of articles having low gloss which are additionally 
characterized by their "soft-touch". Also disclosed is a method for 
reducing the 60 degree gloss of a thermoformed article prepared from a 
thermoplastic composition containing a blend of thermoplastic polyurethane 
and grafted polybutadiene rubber. 
BACKGROUND OF THE INVENTION 
Molding compositions containing thermoplastic polyurethane (herein "TPU") 
and graft polymers of olefinically unsaturated monomers are known. 
Compositions of this type and having good mechanical properties, most 
notably tear resistance, were disclosed in U.S. Pat. No. 3,049,505. Also 
noted is U.S. Pat. No. 4,317,890 which disclosed relevant compositions 
which contain a predominant amount of TPU. In this patent there is no 
distinction made between polyether-polyol based TPU's and their 
polyester-polyol based counterparts. Compositions containing 
polyether-polyol derived TPU, ABS and an acrylic polymer processing aid 
additive have been disclosed in U.S. Pat. No. 4,179,479. Nothing is 
disclosed in this document relative to gloss values or to thermoformed 
articles prepared from the compositions. Injection molded compositions 
said to exhibit improved strength, expansion coefficient, wear, gasoline 
and hydrolysis resistance were disclosed in German DOS 3,931,419. Nothing 
relative to thermoforming or the attainment of low gloss has thus been 
disclosed. U.S. Pat. Nos. 4,317,890 and 4,342,847 both disclosed 
compositions containing TPU and ABS, yet neither evidenced a recognition 
in this context of the critical difference between polyether polyol-based 
TPU and its polyester polyol based counterparts. 
Also relevant is U.S. Pat. No. 5,491,194 which disclosed a composition 
containing a thermally processable, high modulus polyurethane and 
mass-polymerized ABS, the composition said to exhibit improved solvent 
resistance and greater impact strength and stiffness than the comparable 
composition which is based on emulsion-ABS. The polyurethane component of 
the disclosed composition is characterized in that its tensile modulus is 
at least 150,000 psi. Further relevant is U.S. Pat. No. 5,055,525 which 
disclosed a composition containing relevant rubber, including ABS, and a 
polyester polyol-based TPU. The composition is said to exhibit low 
temperature impact strength. In fact, the disclosure, in column 6 line 34, 
et seq., teaches away from using polyether polyol-based TPU (wherein 50 
percent or more of the of the soft segment content is composed of 
ether-linked repeating units) in the context of that invention. 
The present invention is directed to a thermoplastic composition especially 
suitable for the preparation of thermoformed articles having low gloss and 
"soft-touch". These articles have in recent years found applicability in 
the preparation of interior automotive parts. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention is based on the finding that the inventive 
composition which comprises polyether-polyol based thermoplastic 
polyurethane is suitable for preparing thermoformed articles having a low 
60 degree gloss value. The gloss value was found to be lower than the 
value measured on a identically prepared article made of a corresponding 
composition wherein polyurethane is one based on polyester-polyol. The 
thermoplastic composition of the present invention comprises a resinous 
blend of (i) about 51 to 85% by weight of a polyether-polyol based 
thermoplastic polyurethane having a Shore A hardness no greater than 90, 
preferably about 65 to 87, and (ii) about 15 to 49% by weight of grafted 
polybutadiene rubber having a grafted phase containing a copolymer of a 
monovinylidene aromatic monomer and at least one member selected from the 
group consisting of (a) an ethylenically unsaturated nitrile and (b) an 
ethylenically unsaturated ester. The percents are relative to the weight 
of the blend. Importantly, the composition is characterized in that it 
contains no additional acrylic polymer components. In a preferred 
embodiment, the blend contains 55 to 85%,more preferably 60 to 80% of 
thermoplastic polyurethane. 
An additional embodiment of the invention is directed to a thermoplastic 
composition which is characterized in that thermoformed articles made 
therefrom have low gloss values. The composition contains a resinous blend 
of (i) about 51 to 85%, preferably 55 to 85%, most preferably 60 to 80%, 
by weight of a polyether-polyol based thermoplastic polyurethane having a 
Shore A hardness no greater than 90 preferably about 65 to 87, and (ii) 
about 15 to 49%, preferably 15 to 45%, most preferably 20 to 40% by weight 
of grafted polybutadiene rubber having a grafted phase containing a 
copolymer of a monovinylidene aromatic monomer and at least one member 
selected from the group consisting of (a) an ethylenically unsaturated 
nitrile and (b) an ethylenically unsaturated ester. Importantly, the 
composition is characterized in that it contains no additional acrylic 
polymer components. The percents are relative to the weight of the blend. 
The lower gloss is in comparison to a corresponding article prepared from 
a composition wherein polyurethane is based on polyester-polyol. 
An additional embodiment of the invention is directed to a thermoformed 
article having a low 60 degree gloss value. The article is prepared from a 
thermoplastic composition comprising a resinous blend of (i) about 51 to 
85%, preferably 55 to 85%, most preferably 60 to 80%, by weight of a 
polyether-polyol based thermoplastic polyurethane having a Shore A 
hardness no greater than 90 preferably about 65 to 87, and (ii) about 15 
to 49%, preferably 15 to 45%, most preferably 20 to 40% by weight of 
grafted polybutadiene rubber having a grafted phase containing a copolymer 
of a monovinylidene aromatic monomer and at least one member selected from 
the group consisting of (a) an ethylenically unsaturated nitrile and (b) 
an ethylenically unsaturated ester. The percents being relative to the 
weight of the blend. The low gloss is in comparison to a corresponding 
article prepared from a composition wherein polyurethane is based on 
polyester-polyol. 
A yet additional embodiment of the invention is directed to a method to 
reduce the 60 degree gloss of a thermoformed article prepared from a 
thermoplastic composition containing a blend of (i) about 51 to 85% by 
weight of a thermoplastic polyurethane based on polyester-polyol having a 
Shore A hardness no greater than 90 preferably about 65 to 87 and (ii) 
about 15 to 49% by weight of grafted polybutadiene rubber having a grafted 
phase containing a copolymer of a monovinylidene aromatic monomer and at 
least one member selected from the group consisting of (a) an 
ethylenically unsaturated nitrile and (b) an ethylenically unsaturated 
ester. The inventive method comprises replacing at least a portion of the 
polyester-polyol based polyurethane by a corresponding polyether-polyol 
based thermoplastic polyurethane. The percents being relative to the 
weight of the blend. 
Articles made of the inventive composition, most notably thermoformed 
articles, are noted for their low gloss and soft-touch quality. The 
soft-touch property is believed to be a consequence of the low hardness of 
the resinous components. 
Thermoplastic polyurethane resin suitable in the context of the present 
invention (herein "TPU-PE") are substantially linear thermoplasts prepared 
from a diisocyanate, a hydroxyether polyol and a chain extender. These are 
characterized in that they contain structural units derived from a 
hydroxyether polyol and by their hardness, measured as Shore A, which is 
equal to or lower than 90. This hardness is also reflected by the low 
tensile modulus of TPU-PE which is below 50,000 psi and in their urethane 
density which is typically equal to or smaller than 3.0 moles per kilogram 
of TPU-PE. In the preparation of TPU-PE, the relative amounts of the A 
component (diisocyanate) and the B component (long chain polyether polyol 
and chain extender) are selected so that the equivalent ratio of 
isocyanate to isocyanate-reactive compounds is about 0.95 to 1.05. The 
hardness of the TPU-PE are known to be also controlled by the quantity and 
type of the chain extender employed in its preparation. Smaller amounts of 
chain extender generally yield greater softness. TPU-PE resins are known 
and are readily available in commerce. Among the commercial resins, 
mention may be made of Texin 985 thermoplastic polyurethane, a product of 
Bayer Corporation. In the present context, the polyester-polyol based 
thermoplastic polyurethane, herein sometimes referred to as "TPU-PS", is a 
resin which is in all respect, save one, identical to TPU-PE; the 
difference being that its structure contains a predominance of units 
derived from a polyester-polyol. The synthesis of TPU-PE (and of TPU-PS) 
resins is known and has been disclosed, e.g., in U.S. Pat. No. 3,214,411, 
the specification of which is incorporated herein by reference. 
The hydroxyether polyols is preferably at least one member selected from 
the group consisting of ethylene oxide, propylene oxide and 
tetrahydrofuran having a number average molecular weight of about 600 to 
3000. Suitable polyols are disclosed, for instance, in U.S. Pat. Nos. 
3,963,697; 3,984,607; and 4,035,213, the specification of which are 
incorporated herein by reference. 
Suitable organic diisocyanate for use in accordance with the invention 
include the known aliphatic, cycloaliphatic and aromatic diisocyanates. 
While the diphenylmethane diisocyanate isomers, particularly 
4,4'-diisocyanatodiphenylmethane, are the most preferred organic 
diisocyanates, other preferred diisocyanates include 
napthylene-1,5-diisocyanate, 3,3'-dimethyl-4,4'-diisocyanato-biphenyl, 
1,4-diisocyanatobenzene and the corresponding hydrogenated product, 
toluene diisocyanate, ethylene diisocyanate, ethylidene diisocyanate, 
propylene diisocyanate, butylene diisocyanate, 
cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, 
azobenzene-4-4'-diisocyanate, diphenylsulphone4,4'-diisocyanate, 
dichlorohexamethylene diisocyanate, tetramethylene diisocyanate, 
pentamethylene diisocyanate, hexamethylene diisocyanate, 
1-chlorobenzene-1,4-diisocyanate, furfurylidene diisocyanate and the like. 
The polyol, the organic polyisocyanate and the chain extender may be 
individually heated preferably to a temperature of from about 60.degree. 
C. to about 135.degree. C., and then the polyol and chain extender may be 
substantially simultaneously mixed with the polyisocyanate. Preferably, 
the chain extender and the polyol, each of which has been previously 
heated, are first mixed and the resulting mixture is mixed with the heated 
polyisocyanate. This method is preferred for the reason that the extender 
and the polyol will not react prior to the introduction of polyisocyanate 
and rapid mixing with the polyisocyanate is thus facilitated. 
Advantageously, the rate of reaction may be increased by adding any 
suitable catalyst to the reaction mixture such as tertiary amines and the 
like set forth in U.S. Pat. Nos. 2,620,516; 2,621,166 and 2,729,618 all 
incorporated herein by reference. 
Other techniques for the production of thermoplastic polyurethanes useful 
in the context of the present invention are disclosed in the text of 
"Polyurethanes: Chemistry and Technology" Vol. 2, pp-299-452 by J. H. 
Saunders and K. C. Frisch, Interscience Publishers, New York (1964) 
incorporated herein by reference. 
The above and other thermoplastic polyurethanes such as are disclosed in 
U.S. Pat. Nos. 2,621,166; 2,729,618; 3,214,411; 2,778,810 and 4,376,834, 
Canadian Patents 754,233; 733,577 and 842,325 all incorporated herein by 
reference, which are suitable in the context of the presently described 
invention, may be used to prepare the thermoplastic polyblends. 
The grafted polybutadiene rubber suitable in the context of the invention 
is known in the art and such grafted rubbers are readily available in 
commerce. Such suitable grafted rubbers are available in commerce, notably 
from Bayer Corporation as ABS under the trademark Lustran. 
Rubber modified mass, solution, mass/suspension or mass/solution 
polymerized monovinylidene aromatic/ethylenically unsaturated nitrile 
graft copolymers (herein collectively referred to as "graft polybutadiene 
rubber") suitable for use herein have discrete rubbery polymer particles 
dispersed therein, which particles serve as substrates having grafted 
thereto a portion of the monovinylidene aromatic copolymer as a grafted 
superstrate and the remainder of said monovinylidene aromatic copolymer 
constitutes a continuous matrix phase in which the indicated grafted 
rubbery particles are dispersed. The matrix phase of such copolymers 
typically constitutes from about 40 to about 95 (preferably from about 60 
to about 80) % of the overall weight of the indicated rubber-modified 
compositions and the grafted copolymer constituents constitute the 
remainder thereof. Typically the grafted copolymer constituent will have a 
grafted superstrate to graftable rubber substrate ratio (i.e., a graft to 
rubber or "G/R" ratio) of from about 0.1:1 to about 2:1 (preferably from 
about 0.25:1 to about 0.8:1). The dispersed rubbery polymer particles 
within such copolymer will typically have an overall volume average 
particle size of from about 0.08 to about 10 (preferably from about 0.05 
to about 5) microns. 
Monovinylidene aromatic monomers suitable for use in the aforementioned 
rubber-modified monovinylidene aromatic/ethylenically unsaturated nitrile 
copolymers include styrene, alkyl substituted styrenes such as 
.alpha.-alkyl-styrene (e.g., .alpha.-methylenestyrene, 
.alpha.-ethylstyrene, etc.), various ring-substituted styrenes such as 
ortho or para-methylstyrene, ortho-ethylstyrene, 2,4-dimethylstyrene, 
etc., ring-substituted halo-styrenes such as chloro-styrenes, 
2,4-chloro-styrene, etc. and the like. Such monovinylidene aromatic 
monomers (especially styrene) typically constitutes from about 55 to about 
99 weight percent of said monovinylidene aromatic copolymer and preferably 
constitute from about 60 to 95 (more preferably from about 65 to about 90) 
weight percent thereof. Such monovinylidene aromatic copolymers are 
typically normally solid, hard (i.e., non-elastomeric) materials having a 
glass transition temperature in excess of 25.degree. C. 
Suitable ethylenically unsaturated nitrile monomer ingredients for use, 
typically as a minor constituent in (i.e., constituting from about 1 to 
about 45, preferably from 5 to 40 and more preferably from 10 to 35, 
weight percent of) the indicated monovinylidene aromatic copolymers 
include acrylonitrile, methacrylonitrile, ethylacrylonitrile, 
furmaronitrile, etc. 
The indicated rubber modified monovinylidene aromatic copolymers can also 
optionally contain additional monomer ingredients, typically in relatively 
minor proportions such as, for example, from about 1 to about 25 
(preferably from about 2 to about 15) weight percent on a rubber modified 
monovinylidene aromatic copolymer weight basis. Examples of such suitable 
optional monomer ingredients include ethylenically unsaturated anhydrides 
such as maleic anhydride; ethylenically unsaturated amides such as 
acrylamide, methacrylamide, etc.; esters (especially lower, e.g., C.sub.1 
-C.sub.6 alkyl esters) of ethylenically unsaturated carboxylic acids such 
as methyl methacrylate, 2-ethylhexylacrylate, etc.; ethylenically 
unsaturated dicarboxylic acid imides such as N-alkyl or N-aryl maleimides 
such as N-phenyl maleimide, etc.; and the like. 
Preferably, the matrix phase portion of the above-described mass 
polymerized monovinylidene aromatic copolymer has a solubility parameter 
of from about 9.0 to about 10.2 (preferably from about 9.2 to 10.0) as 
calculated pursuant to the method described in Polymer Blends, Academic 
Press, pp 45-48, 1978, edited by D. R. Paul and S. Newman. 
Suitable rubbery polymer materials for use as the dispersed rubbery 
particles, both within the mass polymerized rubber modified monovinylidene 
aromatic copolymer constituent hereof and within the emulsion polymerized 
grafted rubber concentrate ingredient hereof, include homopolymers of 
1,3-conjugated alkadiene monomers; copolymers of from about 60 to about 99 
weight percent of said 1,3-conjugated alkadienes with from about 1 to 
about 40 percent of one or more monoethylenically unsaturated monomers 
such as, for example, monovinyldiene aromatic monomers (e.g., styrene, 
etc.), and ethylenically unsaturated nitrites such as acrylonitrile, 
methacrylonitrile, etc., alkyl acrylate or methacrylate monomers such as 
methyl methacrylate and the like; ethylene/propylene copolymer rubbers and 
rubbery ethylene/propylene/non-conjugated diene copolymers; and the like. 
Especially preferred rubbery copolymers for use herein include polymers 
composed of from about 60 to 100 weight percent of 1,3-butadiene and from 
0 to 40 weight percent of styrene or acrylonitrile. Typically, the 
indicated rubbery polymer materials are of a sort which have a glass 
transition temperature of -20.degree. C. or lower and, preferably, said 
materials have a glass transition temperature of -30.degree. C. or lower. 
While not being particularly critical for the purposes of the present 
invention, it can nonetheless be noted that the mass polymerized rubber 
modified monovinylidene aromatic copolymers employed herein will typically 
comprise from about 1 to 35 (preferably from about 5 to 25) weight percent 
of the above-discussed dispersed rubbery polymer particles. The emulsion 
polymerized grafted rubber concentrate ingredient hereof will typically 
have a dispersed rubber polymer content of from about 35 to about 85 
(preferably from about 40 to about 85 and most preferably from about 45 to 
about 80) weight percent on a grafted rubber concentrate weight basis. 
The aforementioned mass polymerized monovinylidene aromatic graft copolymer 
hereof can be suitable by being prepared by way of any convenient 
conventional mass, solution, mass/suspension or mass/solution graft 
polymerization process conducted in the presence of the desired rubbery 
polymer material. 
Suitable grafted rubber concentrate ingredients for use herein include 
relatively high rubber content emulsion polymerized graft copolymer 
ingredients wherein the grafted superstrate polymer thereof is a 
monovinylidene aromatic/ethylenically unsaturated nitrile copolymer of the 
sort which has hereinbefore been more fully discussed and described in 
connection with the mass polymerized graft copolymer ingredient hereof. 
Also suitable for use as the grafted rubber concentrate ingredient herein 
are those wherein the grafted superstrate polymer is different from the 
above discussed monovinylidene aromatic/unsaturated nitrile copolymer and 
thus include those rubber concentrate ingredients wherein the grafted 
superstrate polymer is an acrylate or methacrylate polymer such as 
polymethyl methacrylate, the various methyl methacrylate copolymers and 
the like. Such grafted rubber concentrate compositions can be conveniently 
prepared in accordance with the various well known emulsion graft 
polymerization methods and techniques and are also available commercially, 
for example, from Rohm and Haas as Paraloid.RTM. EXL-3607 which is a 
polymethylmethacrylate grafted butadiene rubber material. 
While not being particularly critical, it is generally desirable to employ 
a predominant proportion (e.g., from about 50 to about 95, preferably from 
about 60 to about 90, weight percent) of the indicated mass polymerized 
rubber modified monovinylidene aromatic copolymer ingredient in 
combination with a minor proportion (e.g., from about 5 to 50, preferably 
from about 10 to 40, weight percent) of the indicated relatively high 
rubber content emulsion polymerized rubber modified graft copolymer 
ingredient, said weight percentages being based only upon the combined 
weight of the two different types of rubber-modified graft copolymer 
ingredients. The dispersed rubbery particles associated with the emulsion 
polymerized graft copolymer ingredient will typically have an overall 
weight average particle size of from about 0.08 to about 0.8 micron and 
will constitute from about 10 to about 90 (preferably about 20 to 80) 
weight percent of the total dispersed rubbery polymer particle content 
within the rubber modified monovinylidene aromatic copolymer in question. 
The particle size distribution of said emulsion polymerized graft 
copolymer particles can be mono-modal or can, if desired in a particular 
instance, be of a bimodal or multi-modal character. The dispersed rubbery 
polymer particles of the mass polymerized component will typically have a 
weight average particle size of from about 0.5 to about 10 (preferably 
from about 0.8 to about 7) microns; will generally constitute from about 
10 to about 90 (preferably from about 20 to about 80) weight percent of 
the total dispersed rubbery polymer particle content therein; and can also 
be of a monomodal, bimodal or multimodal particle size distribution. 
As has been noted above, the above-described mass polymerized 
monovinylidene aromatic graft copolymer ingredient typically constitutes 
from about 19 to about 64 weight percent of the subject polymer blend 
compositions. In preferred instances, however, said ingredient constitutes 
from about 20 to about 60 (more preferably from about 35 to about 55) 
weight percent of such compositions. The emulsion polymerized grafted 
rubber concentrate typically constitutes from 1 to about 30 weight percent 
of the subject polymer blends and preferably constitutes from about 5 to 
about 20 or 24 weight percent thereof. 
Particle size of the rubber component was measured using a Horiba Particle 
Size Analyzer model Capa 700, and the measurements were conducted at about 
25 centigrade using a gradient mode. 
The preparation of the inventive blends is carried out in an extruder, 
preferably a twin screw extruder, conventionally following procedures and 
using equipment which are well known in the art. 
Shore A hardness, a critical characteristic of the suitable thermoplastic 
polyurethane is a material property well recognized in the art, measured 
in accordance with ASTM D-2240.

EXPERIMENTAL 
Compositions representative of the invention have been prepared and used in 
extruding strips. The strips were thermoformed and their presently 
relevant properties determined. The resinous components used in the 
preparing the compositions are detailed below: 
"TPU-PE" refers to Texin 985 polyurethane which is a thermoplastic resin 
based on polyether polyol having a shore A Hardness of 86 and about 61% of 
soft segments. 
"TPU-PS" refers to Texin 285 polyurethane which is a thermoplastic resin 
based on polyester polyol having a shore A Hardness of 86 and about 66% of 
soft segments. 
"ABS-1" refers to mass process polymerized ABS, having butadiene content of 
about 14% by weight, and an S/AN ratio of about 70/30 and that its volume 
average particle size is about 5 microns. 
"ABS-2" refers to suspension process polymerized-ABS, having butadiene 
content of about 13% by weight, and a S/AN ratio of about 75/25 and that 
its volume average particle size is about 1 microns. 
"ABS-3" refers to mass process polymerized-ABS, having butadiene content of 
about 13% by weight, and an S/AN ratio of about 75/25 and that its volume 
average particle size is about 0.8 microns. 
"ABS-4" refers to mass process polymerized ABS having a polybutadiene 
content 15% and an S/AN ratio of about 70/30 and a volume average particle 
size of about 5 microns. 
"ABS-5" refers to suspension polymerized ABS having a polybutadiene content 
13% and an S/AN ratio of about 75/25 and a volume average particle size of 
about 5 microns. 
"ABS-6" refers to emulsion polymerized-ABS having a polybutadiene content 
38% and an S/AN ratio of about 70/30 and a volume average particle size of 
about 0.2 microns. 
Strips measuring about 12 by 5 inches by 0.065 inch were prepared by 
extrusion following conventional procedures. The strips were then 
thermoformed at draw ratios of 1.3, 1.8 and 2.3. The gloss values of the 
thermoformed articles were determined in accordance with ASTM D 2457 and 
the shore A hardness values were determined in accordance with ASTM D 
2240. The table below summarizes the results of the evaluation. The gloss 
(60 degree) data presented in Table 1 refer to thermoformed articles made 
of compositions containing 60% TPU and 40% ABS, at the indicated draw 
ratios. 
TABLE 1 
______________________________________ 
Draw Ratio 
No draw 1.3 1.8 2.3 *H 
______________________________________ 
TPU-PE/ABS-1 
37.4 26.5 21.9 4.9 92-93 
TPU-PS-ABS-1 
55.2 41.8 35.4 
8.6 94-95 
TPU-PE/ABS-2 
26.2 18.7 12.9 
4.3 94-96 
TPU-PS/ABS-2 
65.8 41.8 28.3 
10.5 
91-92 
TPU-PE/ABS-3 
7.1 12.7 6.5 
3 95-97 
TPU-PS/ABS-3 
49.6 37 43.9 
11.8 
97 
TPU-PE/ABS-4 
25.8 17.7 13.7 
4 92-93 
TPU-PS/ABS-4 
51.1 41.7 34.5 
9.2 95 
TPU-PE/ABS-5 
49.1 34.4 20.1 
6.3 93 
TPU-PS/ABS-5 
46.8 35.3 35.4 
10.6 
93-94 
______________________________________ 
*H Shore A hardness. 
In a second set of experiments, compositions representative of the 
invention were prepared and extruded to form, strips. The strips were 
thermoformed as stated above. The gloss (60 deg) of thermoformed articles 
made of the compositions are set below (Table 2) in comparison to 
corresponding, similar compositions containing polyester-polyol based TPU 
(TPU-PS) which are outside the scope of the present invention. The 
indicated ratio is the weight percent ratio between the resinous 
components (TPU to ABS) in the compositions. The strips were then 
thermoformed to different draw ratios of 1.3, 1.8 and 2.3. The 60 degree 
gloss values are reported in Table 2 below. 
TABLE 2 
______________________________________ 
Draw Ratio 1.3 1.8 2.3 *H 
______________________________________ 
TPU-PE/ABS-6 
60/40 13.8 11.3 5.3 95 
TPU-PS/ABS-6 
60/40 
67.6 69.1 61.0 
95 
TPU-PE/ABS-6 
80/20 
40.7 35.9 11.2 
91 
TPU-PS/ABS-6 
80/20 
83.5 82.5 69.8 
91 
TPU-PE/ABS-4 
51/49 
18.7 12.2 4.0 
95 
TPU-PS/ABS-4 
51/49 
23.1 17.0 5.6 
95 
TPU-PE/ABS-4 
69/31 
35.7 32.4 9.1 
92 
TPU-PS/ABS-4 
69/31 
53.3 40.4 13.8 
92 
TPU-PE/ABS-4 
80/20 
59.3 52.4 17.7 
91 
TPU-PS/ABS-4 
80/20 
71.5 70.7 34.4 
91 
TPU-PE/ABS-4 
69/31 
57.5 51.6 20.8 
93 
TPU-PS/ABS-4 
69/31 
80.0 70.7 37.4 
93 
______________________________________ 
*H Shore A hardness. 
The results clearly show the criticality of TPU-PE in the context of the 
invention. The gloss values characterizing the thermoformed articles made 
of compositions containing TPU-PE are considerably lower than the 
corresponding articles containing TPU-PS. 
Although the invention has been described in detail in the foregoing for 
the purpose of illustration, it is to be understood that such detail is 
solely for that purpose and that variations can be made therein by those 
skilled in the art without departing from the spirit and scope of the 
invention except as it may be limited by the claims.