U.S. patent application number 09/904977 was filed with the patent office on 2002-03-07 for thermoplastic resin composition.
Invention is credited to Tasaka, Michihisa, Yamanaka, Toshimi.
Application Number | 20020028882 09/904977 |
Document ID | / |
Family ID | 18717179 |
Filed Date | 2002-03-07 |
United States Patent
Application |
20020028882 |
Kind Code |
A1 |
Tasaka, Michihisa ; et
al. |
March 7, 2002 |
Thermoplastic resin composition
Abstract
A thermoplastic resin composition comprising 40 to 95 parts by
weight of (a) a saponified ethylene-vinyl acetate copolymer resin
and 60 to 5 parts by weight of (b) at least one selected from the
group consisting of copolymers of a vinyl aromatic compound with a
conjugated diene compound, and hydrogenated derivatives thereof,
characterized in that the saponified ethylene-vinyl acetate
copolymer resin (a) has an ethylene content of 40 to 95 wt % based
on a weight of the saponified ethylene-vinyl acetate copolymer
resin and a degree of saponification of the vinyl acetate of at
least 80 wt % and (b)at least one selected from the group
consisting of copolymers of a vinyl aromatic compound with a
conjugated diene compound is selected from the group consisting of
(b-1) block copolymers of a vinyl aromatic compound with a
conjugated diene compound, and hydrogenated derivatives thereof and
(b-2) hydrogenated random copolymers of a vinyl aromatic compound
with a conjugated diene compound, the copolymers having a vinyl
aromatic compound content of at most 50 wt %, a number average
molecular weight(Mn) of from 5,000 to 1,000,000, a
polydispersity(Mw/Mn) of at most 10, and a content of vinyl bonds
derived from the conjugated diene compound of at least 10% based on
bonds derived from the conjugated diene compound.
Inventors: |
Tasaka, Michihisa; (Tokyo,
JP) ; Yamanaka, Toshimi; (Tokyo, JP) |
Correspondence
Address: |
Gerald Levy, Esq.
PITNEY, HARDIN, KIPP & SZUCH LLP
711 Third Avenue
New York
NY
10017-4059
US
|
Family ID: |
18717179 |
Appl. No.: |
09/904977 |
Filed: |
July 13, 2001 |
Current U.S.
Class: |
525/192 |
Current CPC
Class: |
C08L 23/08 20130101;
C08L 53/025 20130101; C08L 25/10 20130101; C08L 53/02 20130101;
C08L 53/02 20130101; C08L 29/04 20130101; C08L 53/02 20130101; C08L
75/04 20130101; C08L 53/02 20130101; C08L 53/025 20130101; C08L
33/066 20130101; C08L 15/00 20130101; C08L 25/10 20130101; C08L
53/025 20130101; C08L 29/04 20130101; C08L 23/26 20130101; C08L
23/08 20130101; C08L 23/26 20130101; C08L 53/025 20130101; C08L
23/0861 20130101; C08L 29/04 20130101; C08L 2666/06 20130101; C08L
2666/02 20130101; C08L 2666/04 20130101; C08L 2666/02 20130101;
C08L 2666/04 20130101; C08L 2666/14 20130101; C08L 2666/04
20130101; C08L 2666/14 20130101; C08L 25/00 20130101; C08L 2666/04
20130101; C08L 2666/24 20130101; C08L 2666/24 20130101; C08L 29/00
20130101; C08L 2666/02 20130101; C08L 2666/24 20130101; C08L 75/04
20130101; C08L 29/04 20130101; C08L 15/00 20130101; C08L 75/04
20130101 |
Class at
Publication: |
525/192 |
International
Class: |
C08F 008/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 24, 2000 |
JP |
2000-223021 |
Claims
1. A thermoplastic resin composition comprising 40 to 95 parts by
weight of (a) a saponified ethylene-vinyl acetate copolymer resin
and 60 to 5 parts by weight of (b) at least one selected from the
group consisting of copolymers of a vinyl aromatic compound with a
conjugated diene compound, and hydrogenated derivatives thereof,
characterized in that the saponified ethylene-vinyl acetate
copolymer resin (a) has an ethylene content of 40 to 95 wt % based
on a weight of the saponified ethylene-vinyl acetate copolymer
resin and a degree of saponification of the vinyl acetate of at
least 80 wt % and (b)at least one selected from the group
consisting of copolymers of a vinyl aromatic compound with a
conjugated diene compound and hydrogenated derivatives thereof is
selected from the group consisting of (b-1) block copolymers of a
vinyl aromatic compound with a conjugated diene compound, and
hydrogenated derivatives thereof and (b-2) hydrogenated random
copolymers of a vinyl aromatic compound with a conjugated diene
compound, the copolymers having a vinyl aromatic compound content
of at most 50 wt %, a number average molecular weight (Mn) of from
5,000to 1,000,000, a polydispersity(Mw/Mn) of at most 10, and a
content of vinyl bonds derived from the conjugated diene compound
of at least 10% based on bonds derived from the conjugated diene
compound.
2. The thermoplastic resin composition according to claim 1,
wherein component (b) is a hydrogenated styrene-isoprene-styrene
block copolymer having a weight average molecular weight of from
5,000 to 1,500,000, wherein 70 to 100 wt % of the isoprene is in
1,4-micro structure and at least 90% of aliphatic double bonds
derived from the isoprene are hydrogenated.
3. The thermoplastic resin composition according to claim 1,
wherein component (b) is a hydrogenated styrene-butadiene random
copolymer wherein at least 70% of olefinic unsaturated bonds are
hydrogenated.
4. The thermoplastic resin composition according to any one of
claims 1 to 3, wherein the composition further comprises 0.01 to 3
parts by weight of (c) an organic peroxide and 0.01 to 5.5 parts by
weight of (d) a cross-linking aid, based on 100 parts by weight of
component (a) and component (b) in total.
5. The thermoplastic resin composition according to any one of
claims 1 to 4, wherein the composition further comprises 1 to 20
parts by weight of (e) (poly)hydroxyalkyl (meth)acrylate, based on
100 parts by weight of component (a) and component (b) in
total.
6. The thermoplastic resin composition according to any one of
claims 1 to 5, wherein the composition further comprises at least
one component selected from the group consisting of 5 to 150 parts
by weight of (f)a thermoplastic polyurethane resin, 0.1 to 20 parts
by weight of (g) a liquid polybutadiene, 0.05 to 5 parts by weight
of (h) an unsaturated carboxylic acid or a derivative thereof, 0.05
to 30 parts by weight of (i) a peroxide-decomposing polyolefin
resin, and 0.05 to 30 parts by weight of (j) a
peroxide-crosslinking polyolefin resin, wherein a total amount of
component (a) and component (b) is 100 parts by weight.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a thermoplastic resin
composition. More specifically, the present invention relates to a
thermoplastic resin composition comprising a specific saponified
ethylene-vinyl acetate copolymer resin, a vinyl aromatic-conjugated
diene copolymer and/or a hydrogenated derivative thereof. The
composition has a good moldability and is suitably used for toys
and automobile interior parts.
Description of the Prior Art
[0002] A rotational powder molding method is suitable for molding
articles of complicated shapes. The method gives a high production
yield and a uniform thickness of a molded article with ease. Thus,
the method is widely used to produce toys and automobile interior
parts. In the rotational powder molding, raw material powder which
has not stuck to a mold is recovered and reused in a subsequent
molding operation. The recovered powder tends to agglomerate after
it is heated in the precedent molding to partly melt on the
surface. The granules of agglomerated powder tend to cause pinholes
in molded articles. Pinholes also take place in an unmelted part of
a material where a molding temperature is lower than the melting.
Moreover, when a gas evolves from the material, conformity of a
shape of a molded article to a mold is deteriorated. Therefore, it
is desired to use a raw material that meets product requirements
and, moreover, does not show the aforesaid problems in molding.
[0003] As raw material resins for rotational powder molding, use is
made of polyvinyl chloride resins, polyolefinic elastomers, and
thermoplastic polyurethane elastomers. The polyvinyl chloride resin
contains a large quantity of a low molecular weight plasticizer
and, therefore, a molded article therefrom tends to lose a
soft-to-touch property at a temperature lower than the solidifying
point of the plasticizer. In a long term use, there arises a
problem that a matting effect and a soft-to-touch property are lost
due to migration of the plasticizer to the molded articles surface.
The polyolefinic elastomer is cheaper and has good weatherability,
but is poor in moldability and scratch resistance. Some
compositions were examined which had improved scratch resistance
through compositional designs and modification of surfaces, e.g.,
by coating. However, they are costly and, therefore, not practical.
The thermoplastic polyurethane elastomer has a longer molding cycle
time and tends to be stringy or to agglomerate in molding. In
addition, a molded article therefrom does not have a smooth
backside. When a foaming resin is shaped on the backside, an
evolved gas leaks from the uneven backside surface. Further, it is
expensive and inferior in weatherability and resistance to
flame.
[0004] An ethylene-vinyl acetate copolymer(EVA) or a saponified
derivative thereof, an ethylene-ethyl acrylate copolymer(EEA) can
be molded at a lower temperature than the aforesaid resins. A
composition is described in Japanese Patent Publication
No.H2-60687/1990, which comprises a saponified derivative of an
ethylene-vinyl acetate copolymer and a copolymer of a vinyl
aromatic compound with a conjugated diene compound or a
hydrogenated derivative thereof. However, the present inventors
have found that the composition is not suitable for the rotational
powder molding.
[0005] A composition containing a thermoplastic polyurethane
elastomer can be molded at a temperature similar to that for the
saponified derivative of an ethylene-vinyl acetate copolymer.
However, as described above, molded articles therefrom are inferior
in weatherability and backside smoothness.
SUMMARY OF THE INVENTION
[0006] An object of the present invention is to provide a
thermoplastic elastomeric composition which solves the aforesaid
problems in rotational powder molding, i.e., to provide a
composition which does not generate gas, pinholes, or agglomeration
and which provides molded articles having superior weatherability,
resistance to flame and smooth backside.
[0007] The present inventors have found that the above problems can
be solved by using a saponified ethylene-vinyl acetate copolymer
having a specific ethylene content and a degree of saponification
and a copolymer of a vinyl aromatic compound and a conjugated diene
compound. Thus the present invention is (1)a thermoplastic resin
composition comprising
[0008] 40 to 95 parts by weight of (a) a saponified ethylene-vinyl
acetate copolymer resin and
[0009] 60 to 5 parts by weight of (b) at least one selected from
the group consisting of copolymers of a vinyl aromatic compound
with a conjugated diene compound, and hydrogenated derivatives
thereof, characterized in that
[0010] the saponified ethylene-vinyl acetate copolymer resin (a)
has an ethylene content of 40 to 95 wt % based on a weight of the
saponified ethylene-vinyl acetate copolymer resin and a degree of
saponification of the vinyl acetate of at least 80 wt % and
[0011] (b)at least one selected from the group consisting of
copolymers of a vinyl aromatic compound with a conjugated diene
compound ,and hydrogenated derivatives there of is selected from
the group consisting of
[0012] (b-1) block copolymers of a vinyl aromatic compound with a
conjugated diene compound, and hydrogenated derivatives thereof
and
[0013] (b-2) hydrogenated random copolymers of a vinyl aromatic
compound with a conjugated diene compound, the copolymers having a
vinyl aromatic compound content of at most 50 wt %, a number
average molecular weight (Mn) of from 5,000 to 1,000,000, a
polydispersity(Mw/Mn) of at most 10, and a content of vinyl bonds
derived from the conjugated diene compound of at least 10% based on
bonds derived from the conjugated diene compound. Preferred
embodiments of the above invention are as follows.
[0014] (2)The thermoplastic resin composition described (1) above,
wherein component (b) is a hydrogenated styrene-isoprene-styrene
block copolymer having a weight average molecular weight of from
5,000 to 1,500,000, wherein 70 to 100 wt % of the isoprene is in
1,4-micro structure and at least 90% of aliphatic double bonds
derived from the isoprene are hydrogenated.
[0015] (3) The thermoplastic resin composition described (1) above,
wherein component (b) is a hydrogenated styrene-butadiene random
copolymer wherein at least 70% of olefinic unsaturated bonds are
hydrogenated.
[0016] (4)The thermoplastic resin composition described in any one
of (1) to (3) above, wherein the composition further comprises 0.01
to 3 parts by weight of (c) an organic peroxide and 0.01 to 5.5
parts by weight of (d) a cross-linking aid, based on 100 parts by
weight of component (a) and component (b) in total.
[0017] (5) The thermoplastic resin composition described in any one
of (1) to (4) above, wherein the composition further comprises 1 to
20 parts by weight of (e) (poly)hydroxyalkyl (meth)acrylate, based
on 100 parts by weight of component (a) and component (b) in
total.
[0018] (6)The thermoplastic resin composition described in any one
of (1) to (5) above, wherein the composition further comprises at
least one component selected from the group consisting of 5 to 150
parts by weight of (f)a thermoplastic polyurethane resin,
[0019] 0.1 to 20 parts by weight of (g) a liquid polybutadiene,
[0020] 0.05 to 5 parts by weight of (h) an unsaturated carboxylic
acid or a derivative thereof,
[0021] 0.05 to 30 parts by weight of (i) a peroxide-decomposing
polyolefin resin, and
[0022] 0.05 to 30 parts by weight of (j) a peroxide-crosslinking
polyolefin resin,
[0023] wherein a total amount of component (a) and component (b) is
100 parts by weight.
PREFERRED EMBODIMENTS OF THE INVENTION
[0024] The components constituting the present composition will be
explained below.
[0025] Component (a) Saponified Ethylene-Vinyl Acetate
Copolymer
[0026] The present composition is characterized in that it contains
a saponified ethylene-vinyl acetate copolymer resin, hereinafter
referred to as "EVOH." The EVOH in the composition improves
weatherability of the composition and makes the backside of a
molded article have smoother.
[0027] The EVOH has an ethylene content of from 40 to 95 wt %,
preferably from 60 to 90 wt %, and a degree of saponification of
the vinyl acetate component of at least 80 wt %, preferably at
least 90 wt %. If the ethylene content is lower than 40 wt %, the
composition has worse heat resistance. Meanwhile, softness of the
composition is deteriorated, if the ethylene content is higher than
95 wt %. If the degree of saponification is smaller than 80%, the
composition has worse heat resistance.
[0028] The EVOH has a melt flow rate (MFR), determined according to
the Japanese Industrial Standards (JIS) K6924-2 at 190.degree. C.
under a load of 21.18N, of from 10 to 400 g/10 min., preferably
from 20 to 250 g/10 min. If the MFR is less than 10 g/10 min., the
composition has worse flowability. If MFR exceeds 400, mechanical
strength and heat resistance are deteriorated.
[0029] (b)Vinyl Aromatic Compound-Conjugated Diene Compound
Copolymer and/or Hydrogenated Derivative Thereof
[0030] The present component (b) is at least one selected from the
group consisting of (b-1) block copolymers of a vinyl aromatic
compound with a conjugated diene compound and hydrogenated
derivative thereof, and (b-2) hydrogenated random copolymers of a
vinyl aromatic compound with a conjugated diene compound. The vinyl
aromatic compound in the component (b) may be one or more selected
from, for instance, styrene, tert.-butylstyrene,
.alpha.-methylstyrene, p-methylstyrene, divinylbenzene,
1,1-diphenylstyrene, N,N-diethyl-p-aminoethylstyrene, vinyl-
toluene and p-tert. -butylstyrene, with styrene being
preferred.
[0031] The conjugated diene compound maybe one or more selected
from, for instance, butadiene, isoprene, 1,3-pentadiene, and
2,3-dimethyl-1,3-butadiene, with butadiene and/or isoprene being
preferred.
[0032] The block copolymer and/or the hydrogenated derivative
thereof (b-1), hereinafter collectively referred to as
"(hydrogenated) block copolymer", consists of at least one
polymeric block (A) composed mainly of a vinyl aromatic compound
and at least one polymeric block (B) composed mainly of a
conjugated diene compound, and has a structure, for example, A-B,
A-B-A, B-A-B-A or A-B-A-B-A. When two or more of each polymeric
block (A) and polymeric block (B) are present, they may be same
with or different from each other in structure. Component(b-1)
contains 5 to 60% by weight, preferably 20 to 50% by weight, of the
vinyl aromatic compound. The polymeric block (A) composed mainly of
a vinyl aromatic compound consists solely of a vinyl aromatic
compound or is a copolymeric block comprising more than 50% by
weight, preferably at least 70% by weight, of a vinyl aromatic
compound with a conjugated diene compound and/or a hydrogenated
conjugated diene compound (hereinafter referred to as
(hydrogenated) conjugated diene compound).
[0033] Preferably, the polymeric block (B) composed mainly of a
(hydrogenated) conjugated diene compound is composed solely of a
(hydrogenated) conjugated diene compound or is a copolymeric block
comprising more than 50% by weight, preferably at least 70% by
weight, of a (hydrogenated) conjugated diene compound with a vinyl
aromatic compound. In the polymeric block (A) composed mainly of a
vinyl aromatic compound or the polymeric block B composed mainly of
a (hydrogenated) conjugated diene compound, the vinyl aromatic
compound or the (hydrogenated) conjugated diene compound may be
distributed at random, in a tapered manner (i.e., a monomer content
increases or decreases along a molecular chain), in a form of a
partial block or in mixture thereof.
[0034] Any microstructure may be selected in the polymeric block B
composed mainly of the conjugated diene compound. It is preferred
that the block derived from butadiene has 20 to 50%, more
preferably 25 to 45%, of 1,2-microstructure. In the block derived
from isoprene, it is preferred that 70 to 100% by weight of
isoprene is in 1,4-microstructure and at lest 90% of the aliphatic
double bonds derived from isoprene is hydrogenated. The block
derived from a mixture of butadiene and isoprene preferably has
less than 50%, more preferably less than 25%, most preferably less
than 15% of 1,2-microstructure. Many methods were proposed for the
preparation of such block copolymers. As described, for instance,
in JP Publication 40-23798/1965, block polymerization may be
carried out using a lithium catalyst or a Ziegler catalyst in an
inert solvent. The hydrogenated block copolymer may be obtained by
hydrogenating the block copolymer thus obtained in the presence of
a hydrogenation catalyst in an inert solvent.
[0035] Examples of the (hydrogenated) block copolymer include SBS,
SIS, SEBS, SEPS and SEEPS. A particularly preferred (hydrogenated)
block copolymer in the invention is a hydrogenated block copolymer
with a weight average molecular weight of from 5,000 to 1,500,000,
preferably from 10,000 to 550,000, more preferably from 10,000 to
150,000 which is composed of polymeric block A composed mainly of
styrene and polymeric block B which is composed mainly of isoprene
and in which 70 to 100% by weight of isoprene has
1,4-microstructure and 90% of the aliphatic double bonds derived
from isoprene is hydrogenated. More preferably, 90 to 100% by
weight of isoprene has 1,4-microstructure in the aforesaid
hydrogenated block copolymer. Preferably, a polydispersity (Mw/Mn),
i.e., a ratio of the weight average molecular weight (Mw) to the
number average molecular weight(Mn), is preferably at most 10, more
preferably at most 5, and most preferably at most 2. The
(hydrogenated) block copolymer may have a molecular structure of
straight, branched, or radiant chain or a mixture thereof. More
preferably, 90 to 100% by weight of isoprene has 1,4-microstructure
in the aforesaid hydrogenated block copolymer.
[0036] The hydrogenated random copolymer (b-2) is a random
copolymer of at most 50 wt % of a vinyl aromatic compound with a
conjugated diene compound and has a number average molecular weight
of from 5,000 to 1,000,000, a polydispersity(Mw/Mn) of at most 10,
and a vinyl bond content in its conjugated diene moieties, such as
vinyl 1,2-bond and vinyl 3,4-bond, of at least 10%, preferably from
20 to 90%, particularly from 40 to 90%. If the content is less than
10%, a molded article obtained therefrom is hard to touch, which
does not fit the present object. A content of the vinyl aromatic
compound constituting component (b-2) is at most 50 wt %,
preferably 5 to 35 wt %. If the content is higher than 50%, a
molded article obtained therefrom is hard to touch, which does not
fit the present object.
[0037] Any vinyl aromatic compound described for component (b-1)
may be used as the vinyl aromatic compound of component (b-2) . The
vinyl aromatic compounds are bonded randomly and a content of the
vinyl aromatic compound bonded to make a block, determined
according to the Kolthoff's method(I. M. Kolthoff, J.Polymer Sci.,
Vol.1,429(1946)), is at most 10 wt %, preferably at most 5 wt %,
based on a total weight of the bonded vinyl aromatic compound.
[0038] As the conjugated diene compound of component(b-2), any
compound described for component (b-1), for example, butadiene,
isoprene, 2,3-dimethylbutadiene, or pentadiene, may be used.
Moreover, it is preferred that at least 90% of the aliphatic double
bonds derived from the conjugated diene compound is hydrolyzed.
[0039] A weight ratio of component (a) to component (b) is in the
range of from 40:60 to 95:5, preferably from 50:50 to 90:10, more
preferably from 60:40 to 80:20.
[0040] (c) Organic Peroxide
[0041] Through dynamic cross-linking treatment using an organic
peroxide, the composition is improved in heat resistance and
abrasion resistance. Examples of the organic peroxide include
dicumyl peroxide, di-tert.-butyl peroxide,
2,5-dimethyl-2,5-di(tert.-butylperoxy) hexane,
2,5-dimethyl-2,5-di(tert.-butylperoxy) hexine-3,
1,3-bis(tert.-butylperox- yisopropyl) benzene,
1,1-bis(tert.-butylperoxy)-3,3,5-trimethylcyclohexane- ,
n-butyl-4,4,-bis(tert.-butylperoxy) valerate, benzoylperoxide,
p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide,
tert.-butylperoxy benzoate, tert.-butylperoxyisopropyl carbonate,
diacetyl peroxide, lauroyl peroxide, and tert.-butylcumyl
peroxide.
[0042] Among those, 2,5-dimethyl-2,5-di (tert.-butylperoxy)hexane,
2,5-dimethyl-2,5-di(tert.-butylperoxy) hexine-3 and
1,3-bis(tert.-butylperoxyisopropyl)benzene are most preferred in
terms of smell, coloring and scorch stability.
[0043] The amount of the peroxide to be added is at least 0.01 part
by weight, preferably at least 0.05 part by weight , and at most 3
parts by weight, preferably at most 2 parts by weight, per 100
parts by weight of components (a) and (b) in total. If the amount
is less than the aforesaid lower limit, required crosslinking may
not be obtained. Meanwhile, if the amount exceeds the aforesaid
upper limit, the crosslinking proceeds so much as to decrease
flowability of the composition and result in poor moldability of
the composition.
[0044] (d) Crosslinking Aid
[0045] In the present invention, a crosslinking aid is used to
increase a crosslinking efficiency of component(c) Examples of the
crosslinking aid include polyvalent vinyl monomers such as
divinylbenzene, triallylcyanurate; polyvalnet methacrylate monomers
such as ethyleneglycol dimethacrylate, diethyleneglycol
dimethacrylate, triethylenglycol dimethacrylate, polyethylenglycol
dimethacrylate, trimethylolpropane trimethacrylate; 1,9-nonanediol
dimethacrylate and and 2-methyl-1,8-ocutanediol dimethacrylate.
[0046] Particularly, in the present invention, triethylenglycol
dimethacrylate is most preferred, because it is easy to handle and
it solubilizes the organic peroxide to serve as a dispersion aid
for the organic peroxide and, as a result, homogeneous crosslinking
is efficiently attained by heat treatment, which gives a
crosslinked thermoplastic elastomer balanced hardness and rubber
elasticity.
[0047] The amount of the crosslinking aid to be added is at least
0.01 part by weight, preferably at least 0.05 part by weight, and
at most 5.5 parts by weight, preferably at most 4 parts by weight,
per 100 parts by weight of components (a) and (b) in total. If the
amount is less than the aforesaid lower limit, the improvement in
crosslinking may not be sufficient. Meanwhile, if it exceeds the
aforesaid upper limit, the crosslinking proceeds so much that
dispersion of the each component is hindered, resulting in bad
moldability. It is preferred that the crosslinking aid is added in
an amount of about 1.0 to 3.0 times as large as the amount of the
peroxide added.
[0048] (e)Poly(Hydroxyalkyl(Meth)Acrylate)
[0049] Component (e),poly(hydroxyalkyl(meth)acrylate), improves
compatibility of component (a) with (b). Examples of component(e)
include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropylacrylate, 2-hydroxypropyl methacrylate,
3-chloro-2-hydroxypropyl methacrylate, 3-hydroxybutylacrylate,
ethyl-2-hydroxyethyl fumarate, 2-hydroxybutyl acrvlate,
4-hydroxybutyl acrylate, polymers thereof, copolymers thereof, and
copolymers of one or more of the aforesaid (meth)acrylate with an
other kind of monomer. Examples of the other monomer coplymerizable
with the above (meth)acrylate include ethylene, propylene, styrene,
vinyl acetate, and vinyl chloride. Preferably,
2-hydroxymethacrylate is used.
[0050] The amount of component(e) to be added is at least 1 part by
weight, preferably at least 1.3 parts by weight, and at most 20
parts by weight, preferably at most 10 parts by weight, per 100
parts by weight of components (a) and (b) in total. If the amount
is less than the aforesaid lower limit, compatibility is not
sufficiently improved. If the amount exceeds the aforesaid higher
limit, a larger amount of gas generates in molding.
[0051] (f)Thermoplastic Polyurethane Elastomer
[0052] In the present invention, the thermoplastic polyurethane
elastomer improves abrasion resistance and heat resistance of the
composition.
[0053] Generally, the thermoplastic polyurethane elastomer is
produced from a polyol, a diisocyanate, and a chain extender.
Examples of the polyol include polyesterpolyol,
polyesteretherpolyol, polycarbonatepolyol and polyetherpolyol.
[0054] Examples of the polyesterpolyol include those prepared by
dehydration condensation reaction of aliphatic dicarboxylic acid
such as succinic acid, adipic acid, sebacic acid, and azelaic acid;
aromatic dicarboxylic acid such as phthalic acid, terephthalic
acid, isophthalic acid, and naphthalene dicarboxylic acid; or
alicyclic dicarboxylic acid such as hexahydrophthalic acid,
hexahydroterephthalic acid and hexahydroisophthalic acid, esters
thereof, or acid anhydrides thereof, with ethylene glycol,
1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol,
1,9-nonanediol, or a mixture thereof; and polylactonediol prepared
by ring-opening copolymerization of a lactone monomer such as
.di-elect cons.- caprolactone.
[0055] Examples of the polycarbonatepolyol include those prepared
by reacting at least one polyhydric alcohol such as ethylene
glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
3-methyl-1,5-pentanediol- , neopentyl glycol, 1,8-octanediol,
1,9-nonanediol, and diethylene glycol, with diethylene carbonate,
dimethyl carbonate, diethyl carbonate.
[0056] Examples of the polyesteretherpolyol include those prepared
by dehydration condensation reaction of aliphatic dicarboxylic acid
such as succinic acid, adipic acid, sebacic acid, and azelaic acid;
aromatic dicarboxylic acid such as phthalic acid, terephthalic
acid, isophthalic acid, and naphthalene dicarboxylic acid; or
alicyclic dicarboxylic acid such as hexahydrophthalic acid,
hexahydroterephthalic acid and hexahydroisophthalic acid, esters
thereof, or acid anhydrides thereof, with glycol such as dietylene
glycol and propylene oxide adducts or a mixture thereof.
[0057] Examples of the polyetherpolyol include polyethylene glycol,
polypropylene glycol, polytetramethylene ether glycol prepared by
polymerising ethylene oxide, propylene oxide, tetrahydrofuran,
respectively, and copolyethers thereof.
[0058] Among the polyols mentioned above, polyetherpolyols are
preferred because they are more resistant to hydrolysis.
[0059] Examples of the isocyanates to be reacted with the
above-mentioned polyols include tolylene diisocyanate,
4,4'-diphenylmethane diisocyanate(MDI), 1,5-naphthylene
diisocyanate, tolidine diisocyanate, 1,6-hexamethylene
diisocyanate, isophorone diisocyanate, xylilene diisocyanate(XDI),
hydrogenated XDI, triisocyanate, tetramethylxylene
diisocyanate(TMXDI), 1,6,11-undecane triisocyanate, 1,8-
diisocyanatemethyloctane, lysine ester triisocyanate,
1,3,6-hexamethylene triisocyanate, and bicycloheptane
triisocyanate. Among those, 4,4'-diphenylmethane diisocyanate(MDI)
is preferred.
[0060] As the chain extender, a low molecular weight polyol may be
used, of which examples include aliphatic polyols such as ethylene
glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
3-methyl-1,5-pentanediol- , neopentyl glycol, 1,8-octanediol,
1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol, and
glycerol; and aromatic glycols such as 1,4-dumethyrolbenzene,
bisphenol A, and addicts of ethylene oxide or propylene oxide to
bisphenol A.
[0061] Component(f) is incorporated in an amount of at least 5
parts by weight, preferably 8 parts by weight, and at most 150
parts by weight, preferably at most 100 parts by weight, more
preferably 80 parts by weight, per 100 parts by weight of component
(a) and (b) in total. If the amount is less than the aforesaid
lower limit, improvements in abrasion resistance and heat
resistance are not sufficient. If it exceeds the aforesaid higher
limit, a molded article obtained has worse weatherability. Also a
backside of the molded article is so rough that a gas which is
generated in shaping of a foaming resin on the backside of the
article in a later process may leak through the rough parts in the
backside.
[0062] If the present composition containing the polyurethane
elastomer is used for a skin layer of an automobile interior part
comprising an olefin core and a middle layer made of urethane foam,
the automobile part can be crushed altogether and recycled.
[0063] (g) Liquid Polybutadiene
[0064] By incorporating liquid polybutadiene in the composition,
heat resistance and abrasion resistance of the composition are
improved.
[0065] Liquid polybutadiene is a transparent liquid polymer at room
temperature in which microstructure of a main chain is composed of
vinyl 1,2-bond, trans 1,4-bond and cis 1,4-bond. Preferably, the
amount of the vinyl 1,2-bond is 30% by weight or less. If the vinyl
1,2-bond exceeds 30% by weight, low-temperature properties of the
composition obtained tend to deteriorate, which is not
preferable.
[0066] A number average molecular weight of the liquid
polybutadiene is preferably at most 5,000, more preferably at most
4,000, and preferably at least 1,000, more preferably at least
2,000. If the number average molecular weight is below the lower
limit, heat deformation resistance of the composition obtained
tends to be worse. Meanwhile, if it exceeds the upper limit, the
compatibility in the composition obtained tends to become
worse.
[0067] The liquid polybutadiene is preferably a copolymerizable
compound having one or more groups selected from epoxy, hydroxyl,
isocyanate and carboxyl groups. Among these, one having a hydroxyl
group and a copolymerizable unsaturated double bond is particularly
preferred, for example, R-45HT, trade mark, ex Idemitsu
Petrochemical Co.
[0068] Component (g) is incorporated in an amount of at most 20
parts by weight, preferably at most 10 parts by weight, and at
least 0.1 part by weight, preferably at least 1 part by weight, per
100 parts by weight of component (a) and (b) in total. If the
amount is below the lower limit, improvements in heat resistance
and scratch resistance are not sufficient. Meanwhile, bleed-out may
occur, if the amount exceeds the aforesaid upper limit.
[0069] (h) Unsaturated Carboxylic Acid or Derivative Thereof
[0070] By incorporating the unsaturated carboxylic acid or
derivative thereof, compatibility of component(b) with component
(f) is improved. Preferred examples of the unsaturated carboxylic
acid or derivative thereof include acrylic acid, methacrylic acid,
maleic acid, dicarboxylic acid or derivatives thereof such as
acids, halides, amides, imides, anhydrides or esters. Particularly,
maleic anhydride (MAH) is preferably used. Preferably,
polypropylene is modified by the unsaturated carboxylic acid or
derivative thereof. That is, it is believed that a soft segment in
component (b-1), hydrogenated block copolymer, or hydrogenated
conjugated diene moiety in component (b-2), hydrogenated random
copolymer, and component(i), peroxide-decomposing type olefinic
resin, are modified.
[0071] Component (h) is incorporated in an amount of at most 5
parts by weight, preferably at most 1 part by weight, and at least
0.05 part by weight, and preferably at least 0.1 part by weight,
per 100 parts by weight of components (a) and (b) in total. If the
amount is less than the aforesaid lower limit, the compatibility is
not sufficiently improved. If the amount exceeds the aforesaid
upper limit, a larger amount of gas evolves in a molding process,
causing fogging and more pinholes in a molded article.
[0072] (i) Peroxide-Decomposing Type Olefinic Resin
[0073] Component(i) in the present invention improves dispersion of
component (b) in the composition, appearance and heat resistance of
a molded article.
[0074] Component(i) is incorporated in an amount of at least 0.05
part by weight, preferably at least 1 part by weight, and at most
30 parts by weight, preferably at most 10 parts by weight, per 100
parts by weight of components (a) and (b) in total. If the amount
is less than the aforesaid lower limit, improvement in heat
resistance is not sufficient; if the amount is more than the
aforesaid upper limit, the composition is harder, which results in
worse moldability.
[0075] A peroxide-decomposing type olefinic resin suitable for
component (i) of the invention has at least 20% of rrrr/1-mmmm in a
pentad ratio measured by a .sup.13C- nuclear magnetic resonance
method, a fusion peak temperature (Tm) of at least 150.degree. C.,
and a fusion enthalpy (.DELTA.Hm) of at most 100 J/g as determined
by differential scanning calorimetry (DSC). Preferably, Tm is in
the range of from 150 to 167.degree. C. and .DELTA.Hm is in the
range of from 25 to 83 mJ/mg. Crystallinity may be estimated from
Tm and .DELTA.Hm. If Tm and .DELTA.Hm are out of the aforesaid
ranges, rubber elasticity at 100.degree. C. or higher of the
composition obtained is not improved.
[0076] Preferred peroxide-decomposing type polyolefin resin are
high molecular weight propylene homopolymers such as isotactic
polypropylenes, or copolymers of propylene with a smaller amount of
other .alpha.-olefin such as ethylene, 1-butene, 1-hexene or
4-methyl-1-pentene. These resins preferably have an MFR (ASTM
D-1238, Condition L, 230.degree. C.) of 0.1 to 10 g/10 min., more
preferably 3 to 8 g/10 min.
[0077] If the MFR of the peroxide-decomposing type olefinic resin
is less than 0.1 g/10 min., moldability of the composition obtained
is worse. If it exceeds 10 g/10 min., rubber elasticity of a
composition obtained is worse.
[0078] In addition to the peroxide-decomposing type olefinic resin
described above, use may be made of a peroxide-decomposing type
olefinic resin composed of boiling heptane-soluble polypropylene
having a number average molecular weight (Mn) of at least 25,000
and a ratio of Mw to Mn, Mw/Mn, of at most 7 and boiling
heptane-insoluble polypropylene having a melt index of 0.1 to 4
g/10 min. and/or a peroxide-decomposing type olefinic resin
composed of boiling heptane-soluble polypropylene having an
intrinsic viscosity [.eta.] of at least 1.2 dl/g and boiling
heptane-insoluble polypropylene having an intrinsic viscosity
[.eta.] of 0.5 to 9.0 dl/g.
[0079] (J) Peroxide-Crosslinking Type Olefinic Resin
[0080] By incorporating the peroxide-crosslinking type olefinic
resin, a tensile strength of the composition is improved.
[0081] As the peroxide-crosslinking type olefinic resin, use is
made of one or more selected from polyethylene such as high density
polyethylene (polyethylene prepared in a low pressure method), low
density polyethylene (polyethylene prepared in a high pressure
method), linear low density polyethylene (copolymers of ethylene
with a smaller amount, preferably 1 to 10 mole %, of .alpha.-olefin
such as butene-1, hexene-1 or octene-1); ethylene-propylene
copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylate
copolymer.
[0082] Particularly preferred is ethylene-octene copolymer having a
density of at most 0.90 g/cm.sup.3 or ethylene-hexene copolymer
having a density of at least 0.90 g/cm.sup.3 which are prepared
using a metallocene catalyst (single site catalyst) . When Tm of
these copolymer is not higher than 100.degree. C., it is necessary
to add them and let them crosslink by the time of dynamic
cross-linking treatment at the latest. By the crosslinking, Tm
disappears and fusion of octene or hexene does not occur. If they
are added after the dynamic cross-linking treatment , fusion of
octene or hexene at 30 to 60.degree. C. takes place and,
consequently, heat resistance is decreased.
[0083] One example of component (j) an olefinic polymer which is
prepared using a catalyst for olefine polymerization which is
prepared in accordance with the method described in Japanese Patent
Application Laid-Open No. S61-296008 and which is composed of a
carrier and a reaction product of metallocene having at least one
metal selected from the 4b group, 5b group and 6b group in the
periodic table with alumoxane, the reaction product being formed in
the presence of the carrier.
[0084] Another example of component (j) is an olefinic polymer
prepared using a metal coordinated complex described in Japanese
Patent Application Laid-Open No. H3-163008, which metal coordinated
complex contains a metal selected from the group 3 (except
scandium), groups 4 to 10 and the lanthanoid group and a
delocalized .pi.-bond part replaced with a constrained inducing
part, and is characterized in that said complex has a constrained
geometrical form around said metal atom, and a metal angle between
a center of the delocalized substituted .pi.-bond part and a center
of at least one remaining substituted part is smaller than that in
a comparative complex which is different the complex only in that a
constrained inducing substituted part is replaced with a hydrogen,
and wherein in each complex having further at least one delocalized
substituted .pi.-bond part, only one, per metal atom, of the
delocalized substituted .pi.-bond parts is cyclic.
[0085] If desired, a modified product of the aforesaid polyolefin
may be used. Examples of such include (co)polymers modified with,
for example, maleic anhydride, methyl methacrylate, glycidyl
methacrylate, allylglycidylether, oxazolyl methacrylate,
allyloxazolylether, carboxylmethacrylate and allylcarboxylether.
Among these, ethylene-glycidyl methacrylate copolymer, and
polyethylene modified with glycidyl methacrylate or with maleic
anhydride are preferred. Preferably, component(j) has an MFR,
determined at 190.degree. C. under a load of 2.16 kg, of from 0.1
to 300 g/10 min., more preferably from 0.3 to 200 g/10 min.
Component(j) is incorporated in an amount of at most 30 parts by
weight, preferably at most 20 parts by weight, and at least 0.05
part by weight, preferably at least 1 part by weight, per 100 parts
by weight of components (a) and (b) in total. If the amount is less
than the aforesaid lower limit, improvement in mechanical
properties is not sufficient. If the amount is more than the
aforesaid upper limit, the composition is harder to have worse
moldability.
[0086] Other Components
[0087] In addition to the above-described components, the present
compositions may contain mold release agents such as stearic acid,
silicone oils, lubricants such as polyethylene wax, pigments,
inorganic fillers such as alumina, anti-oxidant agents, inorganic
or organic blowing agents, flame-retardants such as hydrated metal
compounds, red phosphorus, ammonium polyphosphate, antimony, and
silicones, in concentrations which do not adversely affect the
present invention.
[0088] The present thermoplastic resin composition may be prepared
by melt-kneading the aforesaid components in an arbitrary order or
simultaneously. Preferably, all of the components except
component(a), EVOH, are melt kneaded in a first step, and component
(a) is added and melt kneaded in a second step, wherein parts of
component(c), organic peroxide, and component(d), cross-linking
aid, are added in the first step and the rest are added in the
second step.
[0089] Any known means for melt-kneading can be used, for example,
single screw extruders, twin screws extruders, rolls, Banbury
mixers, and various kneaders. When a twin screws extruder is used,
the melt-kneading is performed at a screw rotation speed of 100 rpm
and at a temperature of from 180 to 240.degree. C., preferably from
200 to 220.degree. C.
EXAMPLES
[0090] The present invention will be further elucidated with
reference to the following Examples and Comparative Examples, but
shall not be limited to them.
[0091] Evaluation Methods
[0092] 1.Pinholes in a molded article
[0093] Surface of a molded article obtained by rotational powder
molding was observed through a magnifying glass at 5.times.
magnification and rated according to the following criteria;
[0094] .largecircle.:no pinhole,
[0095] .DELTA.:pinholes in parts of the surface, and
[0096] X:pinholes throughout the surface.
[0097] 2.Smoothness of a backside of a molded article
[0098] A backside of a molded article was illuminated with light at
an incident angle of 60.degree. and a gloss value of the reflected
light from the backside was measured with a glossmeter, GMX-202, ex
Murakami Shikisai Kenkyu-sho. Evaluation criteria are as
follows;
[0099] .circleincircle.:gloss value of 50 or larger,
[0100] .largecircle.:gloss value of 10 or larger, and
[0101] X: gloss value of smaller than 10.
[0102] 3. Agglomeration
[0103] Powder recovered in a powder box after a rotational powder
molding was examined to see whether it agglomerated by heating or
not. Evaluation criteria are as follows;
[0104] .largecircle.:no agglomeration,
[0105] .DELTA.:a little agglomeration, and
[0106] X:severe agglomeration.
[0107] 4.Heat resistance
[0108] A resin composition was molded into a No.3 dumbbell test
piece. The test piece was placed in a gear oven kept at 110.degree.
C. for 168 hours and then a degree of deformation of the test piece
was measured. Evaluation criteria are as follows;
[0109] .circleincircle.:deformation of 0%,
[0110] .largecircle.:deformation of less than 5%, and
[0111] X:deformation of 5% or more.
[0112] 5.Taber abrasion resistance
[0113] Determined in accordance with JIS K 7204 on a 2 mm-thick
pressed sheet. Weight loss(mg) by abrasion was determined after
1,000 turns with a truck wheel, H-22.
[0114] 6.Hardness(HDD)
[0115] Measured according to JIS K 7215 on a 6.3 mm-thick sheet
prepared by pressing pellets made by melt-kneading, at 240.degree.
C.
[0116] 7.Tensile strength(TS)
[0117] Determined according to JIS K7161 with a tension speed of
500 mm/min on a No.3 dumbbell test piece prepared from a press
sheet of 1 mm thickness.
[0118] 8. Modulus at 100% elongation(100% M)
[0119] Determined according to JIS K7161 with a tension speed of
500 mm/min on a No.3 dumbbell test piece prepared from a press
sheet of 1 mm thickness.
[0120] 9.Elongation(EL)
[0121] Determined according to JIS K7161 with a tension speed of
500 mm/min on a No.3 dumbbell test piece prepared from a press
sheet of 1 mm thickness.
[0122] 10. Tear strength
[0123] Determined according to JIS K6252 with a tear speed of 500
mm/min on a No.3 dumbbell test piece prepared from a press sheet of
2 mm thickness.
[0124] Materials Used
[0125] Component(a):EVOH
[0126] (1) Melthene -H H6922X(trade name), ex Tosoh Co.,
[0127] Ethylene content 72 wt %, and
[0128] Degree of saponification: 90 wt %.
[0129] (2) Melthene -H H6920(trade name), ex Tosoh Co.,
[0130] Ethylene content : 72 wt %, and
[0131] Degree of saponification: 90 wt %.
[0132] Component(b):vinyl aromatic compound-conjugated diene
compound copolymer and/or a hydrogenated derivative thereof
[0133] (b-1) Septon 2002,ex Kuraray Co.,
[0134] styrene content:30% by weight,
[0135] isoprene content:70% by weight,
[0136] number average molecular weight(Mn) :55,000,
[0137] weight average molecular weight(Mw) : 60,000,
[0138] polydispersity (Mw/Mn): 1.09, and
[0139] hydrogenation degree : at least 90%.
[0140] (b-2) Dynalon 1320P(trade name), hydrogenated random
copolymer(SBR), ex JSR Co.,
[0141] styrene content:10% by weight,
[0142] Mn : 300,000,
[0143] Mw/Mn :1, and
[0144] hydrogenation degree : at least 90%.
[0145] Component(c):organic peroxide, Perhexa 25B (
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, ex Nippon Oils &
Fats Co.
[0146] Component(d):crosslinking aid NK Ester 3G (triethylene
glycol dimethacrylate), ex Shin-Nakamura Kagaku Co.
[0147] Component(e):(poly)hydroxy (meth)acrylate Rightester
HO(trade name), 2-hydroxyethyl methacrylate(HEMA), ex Kyoeishya
Kagaku Co.
[0148] Component(f): thermoplastic polyurethane resin Pandex T-8180
(trade mark) , ex Dainippon Ink Co.
[0149] Component(g): liquid polybutadiene R-45HT (trade mark) , ex
Idemitsu Petrochemical Industries Inc.
[0150] Component(h): unsaturated carboxylic acid or a derivative
thereof maleic anhydride, ex Kanto Kagaku Co.
[0151] Component(i): peroxide-decomposing type olefinic resin
BC03C(trade mark), polypropylene, ex Mitsubishi Chemical Industries
Inc.
[0152] Component(j): peroxide-crosslinking type olefinic resin
FS370 (trade name), linear low density polyethylene, ex Sumitomo
Chemical Co.
[0153] Other Components:
[0154] heavy calcium carbonate, NS400(trade name), ex
[0155] Shiraishi Calcium Co.,
[0156] silicone oil, SH-200 1000CS(trade name),ex Toray Dow Corning
Co.
[0157] Materials used in Comparative Examples:
[0158] ethylene-vinyl acetate copolymer, Ultrathene 680(trade
name), Tosoh Co.,
[0159] ethylene content:80 wt %, and
[0160] MFR:160g/10 min.
[0161] ethylene-vinyl acetate copolymer, Ultrathene 760(trade
name), Tosoh Co.,
[0162] ethylene content:58 wt %, and
[0163] MFR:70g/10 min.
[0164] EVOH, Melthene-H H6251(trade name), ex Tosoh co.,
[0165] ethylene content:72 wt %,
[0166] degree of saponification: 21.4 wt %, and
[0167] MFR:5g/10 min.
[0168] Preparation of the Compositions
[0169] The components except component (a), EVOH, were first
kneaded in the weight ratios shown in Tables 1 and 2 in a
twin-screw extruder. Then, parts of the peroxide (c) and the
cross-linking aid(d) , if used, were added and dynamic
cross-linking treatment was carried out at a kneading temperature
of 210.degree. C., a screw rotation of 350 rpm, and an extruder
throughput of 20kg/hr. Then, component(a) was side-fed and the
remaining parts of peroxide(c) and cross-linking aid(d), if any,
were added and kneaded at 210.degree. C. The compositions obtained
were evaluated.
1 TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example
6 Example 7 Example 8 Example 9 component(a)(1) 30 30 30 30 30 30
30 30 30 component(a)(2) 40 40 40 40 40 40 40 40 40 component(b-1)
30 0 30 30 30 30 30 30 30 component(b-2) 0 30 0 0 0 0 0 0 0
component(c) 0 0 0.18 0.18 0.18 0 0.18 0.18 0.18 component(d) 1 1
0.34 0.34 0.34 0 0.34 0.34 0.34 component(e) 0 0 1.5 1.5 0 1.5 1.5
1.5 component(f) 0 0 0 0 0 0 0 10 0 component(g) 0 0 0 0 0 0 0 0 3
component(h) 0 0 0 0 0 0 0 0.3 0 component(i) 0 0 0 0 3 3 0 0 0
component(j) 0 0 0 0 0 0 3 0 0 Calcium carbonate 5 5 5 5 5 5 5 5 5
Silicone oil 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 total (parts by
weight) 105.5 105.5 106.02 107.52 110.52 108.5 110.52 117.82 110.52
Pinholes .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .smallcircle. .smallcircle. .smallcircle.
.circleincircle. .circleincircle. Backside smoothness
.circleincircle. .circleincircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .smallcircle. .smallcircle.
.smallcircle. Agglomeration .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .circleincircle. .circleincircle.
.smallcircle. .circleincircle. Heat resistance .smallcircle.
.smallcircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
Taber abrasion .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .smallcircle. .smallcircle.
.circleincircle. .smallcircle. Hardness(HDD) 44 33 44 44 45 45 38
40 40 TS 9.5 7.5 9.5 9.4 8.8 8.9 10.5 10 9.5 100% M 8.2 7 9.3 9.2 9
8.4 9.1 9.5 9.3 EL 200 400 150 200 150 200 200 170 200 Tear
strength 45 50 54 55 48 50 45 51 45
[0170]
2TABLE 2 (Comparative Examples) Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3
Comp. Ex. 4 Comp. Ex. 5 Comp. Ex. 6 Comp. Ex. 7 Comp. Ex. 8
component(a)(1) 20 40 30 30 0 0 0 30 component(a)(2) 10 57 40 40 0
0 0 40 Melthene-H H6251 0 0 0 0 0 0 70 0 Ultrathene 680 0 0 0 0 70
0 0 0 Ultrathene 760 0 0 0 0 0 70 0 0 component(b-1) 70 3 30 30 30
30 30 30 component(b-2) 0 0 0 0 0 0 0 0 component(c) 0 0 10 0.18 0
0 0 0 component(d) 0 0 10 0.34 0 0 0 0 component(e) 0 0 1.5 1.5 0 0
0 0 component(f) 0 0 0 0 0 0 0 200 component(g) 0 0 0 0 0 0 0 0
component(h) 0 0 0 0 0 0 0 0 component(i) 0 0 0 35 0 0 0 0
component(j) 0 0 0 0 0 0 0 0 Calcium carbonate 5 5 5 5 5 5 5 5
Silicone oil 0.5 0.5 0.5 0.5 0.5 0.5 total (parts by weight) 105.5
105.5 127 142.52 105.5 105.5 105 205 Pinholes .DELTA.
.circleincircle. X X .circleincircle. .circleincircle.
.circleincircle. .smallcircle. Backside smoothness X
.circleincircle. X X .circleincircle. .circleincircle.
.circleincircle. X Agglomeration .circleincircle. X
.circleincircle. .circleincircle. X X X .circleincircle. Heat
resistance .smallcircle. .DELTA. .circleincircle. .circleincircle.
X X X .circleincircle. Taber abrasion A A 0 0 .DELTA. X X 0
Hardness(HDD) 80A 55 44 50 80A 44 84A 92A TS 9.5 18 8 8.7 4.2 10 8
10 100% M 5 15 79 8.3 3.7 8 4.5 5 EL 600 300 100 150 600 400 600
500 Tear strength 45 100 37 55 52 46 42 60
[0171] Comparing Table 1 with Table 2, it is seen that the present
resin composition causes no agglomeration and no pinholes, and a
molded article therefrom has a smooth backside. The article also
has superior resistance to heat and abrasion.
* * * * *