Note: Descriptions are shown in the official language in which they were submitted.
1339967
SPECIFICATION
POT.YMF.R COMPO.~ITION
Technic~l F;el~ of the Invent;on
The present invenlion relates to an ionomer composition
which is excellent in scratch resistance, adhesion to
metals, resistance to heat deformation, flexibility,
antibleeding property of mineral oil softener contained and
low surface gloss.
1 0
R~ckgrolln~ of the ;nvent;on
:Because ionomer resins are :Lightweight and rigid, and
are excellent in adhes:ion to metal, gloss, and scratch
resistance, ionomer re,ins draw attention of the art as
attra-tive resins for use in automotive exteriors.
Depen~1ing upon intended uses, however, ionomer resins which
are flexible and deluslered are desired, while retaining
their excellent adhesion to metals or scratch resistance.
In applications where scratch resistance is of
paramount importance, :it is necessary to use such ionomer
resin.s that they conta:in increased amounts of metallic ions.
The h.igher the metallic ion content becomes, however,
ionomer resins tend to become more rigid and more lustrous.
While it is desired to make flexible and delusterd ionomer
resins which contain a large amount of metallic ions to
become rigid and lustrous, it is not necessarily easy to do
so .
1339967
For example, Japanese Patent: Laid-open Publication No.
57-190034 discloses a low lustrous ionomer composition
comprising about from "0 to 80 % by weight of an ionomer and
S about from 20 to 60 % by weight of an ethylene/propylene
copolymer rubber. With the ionomer composition of this
publil_ation, if scratch resistance is sought, it is
difficult to obtain a :Low lustrous composition, whereas low
luster can only be ach:Leved at the costs of scratch
resistance or heat deformation resistance. In other words
it has been difficult to provide an ionomer composition
having a combination o~E the scrat:ch resistance and the low
luster.
'~ur Japanese Patent Laid-open Publication No. 61-36347
discloses a polymer composition having excellent scratch
resis-tance and heat de:Eormation resistance comprising an
ionomer and a thermopl(~stic elastomer derived from olefins.
With this polymer composition, again, it has been difficult
to realize a combination of scratch resistance and low
luster.
Further, the polymer compos:Ltion of Japanese Patent
Laid-open Publication No. 61-36347 involves such problems
that ~ mineral oil soflening agent contained in the
thermoplastic elastome:r derived from olefins, if any, bleeds
up to surfaces of shaped article-, made of the polymer
3 1339967
comp~sition, renderin~ the surfaces sticky or of poor
appe.~rance.
In view of these state of t:he art, an object of the
invention is to provide an ionomer compostion which is
excellent in scratch resistance, adhesion to metals,
resistance to heat de:Eormation,
flexibility, antibleeding property of mineral oil softener
cont~ined and low sur:Eace gloss.
D;sclosure of the Invention
According to the invention there is provided a polymer
composition which comprises from 50 to 85 parts by weight of
an ethylene-type ionomer resin comprising ethylene and an
unsaturated carboxylic acid in which the carboxyl groups are
partially neutralized., from 10 to 39 parts by weight of a
partially crosslinked. olefin-type thermoplastic elastomer
comprising a partiall.y crosslinlked ethylene/alpha-olefin
copolymer rubber and a polyolefin resin, and from 1 to 15
parts by weight of an ethylene/alpha-olefin copolymer rubber.
Rest Mo~e for C~rry~n(J out the Invent~on
The polymer composition according to the invention will
now be described in detail.
The ethylene-type ionomer resins which can be used
herein are prepared by neutralizing a part, normally from 5
to 9~ %, of carboxyl qroups of ethylene/alpha, beta-
unsaturated carboxylic acid copolymers (1) or
ethylene/alpha, beta-unsaturated acid/alpha, beta-
unsa-turated acid ester copolymers (2~ with metallic ions.
r ~ ., j,
4 1339~67
Preferred ethylenle/alpha, beta-unsaturated carboxylic
acid copolymers (1) and ethylene/alpha, beta-unsaturated
acid/alpha, beta-unsat-urated acid ester copolymers (2)
comprise normally from 75 to 99.l5 mol % preferably from 88
to 98 mol % of ethylen~e units; normally from 0.5 to 15 mol %
preferably from 1 to 6 mol% of alpha, beta-unsaturated
carboxylic acid units; and normally from
0 to 10 mol%, preferably from 0 lto 6 mol % of alpha, beta-
unsaturated carboxylic acid este:r units. In case where the
copolymers (1) or ~2) contains the ethylene, alpha, beta-
unsaturated carboxylic acid and alpha, beta-unsaturated
carboxylic acid ester units in the above-mentioned
proportions, polymer compositions according to the invention
are particularly excellent in adhesion to metals and in heat
resistance.
The ethylene-type ionomer resins which can be used
herein are prepared by neutraliz:ing a part, normally from 5
to 90 % of carboxyl groups of the copolymers (1) or (2) with
metallic ions. This percentage will be referred to herein
as a neutralization deqree. A preferred neutralization
degree of the ionomer :resins is from 15 to 90 % in
parti-ular from 40 to '30 %.
~ uitable alpha, beta-unsaturated carboxylic acids which
constitute the copolymers (1) or (2) are those having from 3
to 8 carbon atoms including, for example, acrylic acid,
1~39967
s
metha-rylic acid, male:ic acid, fumaric acid and maleic
anhydride. Of these, <icrylic ac-Ld and methacrylic acid are
particularly preferred. Suitable alpha, beta-unsaturated
carboxylic acid esters which con-,titute the copolymers (2
are those having from 4 to 12 caxbon atoms including, for
example, methyl acrylate, methyl methacrylate, ethyl
acrylate, ethyl methacrylate, isobutyl acrylate, butyl
methacrylate and dimethyl fumarale. Of these, acrylate and
methacrylate are particularly preferred.
1 0
Metallic ions suitable for use in the neutralization of
the carboxyl groups of the copolymers (1) or (2) are those
having a valency of form 1 to 3, in particular such ions of
metals of the Groups I, II, III, IVA and VIII of the
Periodic Table. Specifically, Na +, K +, Li +, Cs +,
Ag +, Hg +, Cu +, Be + t, Mg ++, Ca ++, Sr ++, Ba ++,
Cu ++, Cd ++, Hg ++, S;n ++, Pb +-t, Fe ++, Co ++, Ni ++,
Zn ++, Sc ++ Al +++, Fe +++ and ~ +++ can be used alone or
in combination. Further, a comb:ination of metallic ions and
ammonium ion may also be used. Of the metallic ions,
Zn ++ and Na + are par-ticularly preferred.
The ethylene-type ionomer resins used herein have a
melt flow rate of normilly from 0.1 to 1000 g/10 min.,
preferably from 0.1 to 30 g/10 m:in., and more preferably
from 0.1 to 10 g/10 min, as measured in accordance with ASTM
D 1238 at a temperature of 190 ~C.
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The partially crosslinked olefin-type thermoplastic
elastomer ~B) which can be used herein preferably comprises
as essential components, a partially cross-linked
ethyl~_ne/alpha-olefin ~_opolymer rubber and a polyolefin
resin. This thermoplastic elastomer ~B) preferably prepares
by partially crosslink:ing a rubbery composition comprising
an ethylene/alpha-olef:in copolymer rubber and a polyolefin
resin.
This partially crosslinked olefin-type thermoplastic
elastomer ~B) further contains a polyolefin resin in
addition to the partia:lly crossl:Lnked olefin-type
thermoplastic elastome:r.
Preferably the thermoplastic elastomer ~B) contains
from 5 to 80 parts by weight, preferably from 20 to 70 parts
by weight of the polyo:Lefin reSirl and from 20 to 95 parts by
weight, preferably frorn 30 to 80 parts by weight of the
parti~lly crosslinked ethylene/alpha-olefin copolymer rubber
with the proviso that lhe sum of both the components is 100
parts by weight.
l~hen partial crosslinking the above-mentioned rubbery
compo3ition, peroxide-noncrosslinkable hydrocarbon rubbers
and/or mineral oil softeners may be added to the rubbery
composition. These cornponents are preferably be used in an
amounl of up to 50 ~ by weight, in particular from 5 to 40
by weight, based on the total weight of the rubbery
composltlon.
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Preferred partially crosslinked olefin-type
thermoplastic elastomers (B) which can be used herein
comprise:
[I] from lO0 to 30 parts by weight of a partially
S cross-linked rubber compositior1 obtained by dynamic heat
treatment of a mixture comprising:
(a) from 20 to '35 parts by weight of an ethylene/alpha-
olefin copolymer rubber,
(b) from 5 to 80 parts by weight of a polyolefin resin,
the total weight of the (a) + (b) being lO0 parts by weight,
and
from 5 to 80 parts by weight of components selected
from
(c) peroxide-noncrosslinkable hydrocarbon rubbers and
(d) mineral oil softeners
in the presence of a cross-link:ing agent, and
[II] from 0 to 70 parts by weight of a polyolefin
resin,
the lotal weight of (b) and [II] in the elastomer (B) being
from 5 to 80 parts by weight based on lO0 parts by weight of
the elastomer (B).
By the term "dynamic heat treatment of a mixture" used
herein is meant kneading the mixture in molten condition.
The kneading is preferably carried out using a closed
apparatus under an atmosphere of an inert gas such as
nitrogen and carbon dioxide. The kneading temperature is
normally from 150 to 230~C., preferably from 170 to 240 ~C.,
1~39967
and the kneading time is normally from 1 to 20 minutes,
preferably from 1 to 10 minutes.
As the ethylene/alpha-olefin copolymer rubber (a) for
preparing the partially crosslinked olefin-type
thermoplastic elastomer (B), use can be made of
substantially amorphous or low crystalline elastomers having
a crystallinity index of not higher than 20 %, preferably
not higher than 10 %, derived from ethylene and alpha-olefin
having from 3 to 14 carbon atoms, such as ethylene/propylene
copolymer rubbers, ethylene/propylene/ nonconjugated diene
terpolymer or quaternary polymer rubbers,
ethylene/propylene/1-butene terpolymer rubbers. ethylene/1-
butene copolymer rubbers and ethylene/1-butene/nonconjugated
diene terpolymer or quaternary polymer rubbers. Of these,
ethylene/ propylene copolymer rubbers and
ethylene/propylene/nonconjugated diene terpolymer rubbers
are particularly preferred. Examples of the nonconjugated
dienes include, for example, dicyclopentadienes, 1,4-
2 0 hexadiene, cyclooctadi~ene, methylenenorbornenes and 5-
ethylidene-2-norbornen~e. Of these, dicyclopentadienes and 5-
ethylidene-2-norbornene are preferred.
The ethylene/alph~-olefin copolymer rubbers ~a),
including terpolymer and quaternary polymer rubbers, which
can be used herein, have a Mooney viscosity [ML1+~
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. 9
(100 ~C.)] of normally from 10 to 180, preferably from 40 to
140, and preferably have an iodine value (degree of
unsaturation) of not more than 16.
The ethylene/alpha-olefin copolymer rubbers (a) used
herein preferably cont~in units derived from ethylene and
alpha-olefin in such a molar rat:io that ethylene
units/alpha-olefin uni-ts is from 50/50 to 90~10, and more
preferably from 60/40 to 84/16. When the copolymer rubbers
(a) contain units derived from one or more nonconjugated
dienes, in addition to units der:ived from ethylene and
alpha-olefin, a molar ratio of UllitS derived from l-olefin
(ethylene + alpha-olefin) to unils derived from one or more
nonconjugated dienes is normally 98/2 to 90/10, and
preferably from 97/3 to 94/6.
As the polyolefin resin (b) which is dynamically heat
treated with the ethylene/alpha-olefin copolymer (a), use
can be made of homopolymers of l--olefins such as ethylene,
propylene, butene-l, hexene-l an~ 4-methyl-pentene-1,
copolymers of at least two l-olefins and copolymers of 1-
olefins and up to 15% by mole of at least one other
copolymerizable monome:r, such as ethylene/vinyl acetate
copolymers, ethylene/a~_rylic acid copolymers,
ethylene/methyl acrylale copolymers, ethylene/ethyl acrylate
copolymers, ethylene/methacrylic acid copolymers and
ethylene/methyl methacrylate copolymers. Of these,
polyolefin resins having a melt ilow rate of from 0.1 to 50
g/10 min., in particular from 5 t:o 20 g/10 min., as measured
1339967
1 o
in accordance with ASTM-D-1238-65T and having a
crystallinity index of at least 40 ~, as measured by X-ray
diffractometry, are preferred.
As the polyolefin resin (b), particularly preferred are
peroxide-decomposable polyolefin resins having the above-
specified melt flow rate and crystallinity. The term
"peroxide-decomposable polyolefin resins" means that the
polyolefin resins undergo cleavage of polymer chains to some
extent to reduce molecular weight thereof and to increase in
melt flow rate, when kneaded together with a peroxide under
heat. Examples of such peroxide-decomposable polyolefin
resins include, for example, isotactic polypropylene and
copolymers of propylene with up to 15 mol % of other alpha-
olefins such as propylene/ethyle;ne copolymers, propylene/1-
butene copolymers, propylene/1-hexene copolymers and
propylene/4-methyl-1-pentene copolymers.
Blends of such peroxide-decomposable polyolefin resins
2'0 with peroxide crosslinkable resins such as low, medium and
high density polyethylenes having a density of from 0.810 to
0.940 g/cm3 may also be used as t:he polyolefin resin (b) in
the practice of the invention. The term"peroxide
crosslinkable polyolefin resins" means that the polyolefin
resins undergo crosslinking of polymer chains to some extent
and decrease in melt flow rate when kneaded together with a
peroxide under heat.
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1 1
Examples of the peroxide-noncrosslinkable hydrocarbon
rubbers (c), which can be used herein, include, for example,
polyisobutylene rubbers, butyl rubbers, propylene/ethylene
copolymer rubbers havi:ng a propy:lene content of at least 70
% by mole, propylene/1-butene copolymer rubbers having a
propylene content of at least 70 % by mole and atactic
polypropylenes. Of these, polyisobutylene and propylene/l-
butene copolymer rubbers are pre:ferred. By the term
"peroxide-noncrosslinkable hydrocarbon rubbers" is meant
that the hydrocarbon rubbers do not undergo crosslinking of
polymer chain and do not decrease in melt flow rate even
when they are kneaded in the presence of a peroxide under
heat.
As the mineral oils (d), use can be made of paraffinic,
naphthenic and aromatic high boi.ling petroleum fractions
normally employed in rubber industry for a purpose of
weakening intermolecular action of rubbers thereby
facilitating roll processing the:reof and promoting
2'0 dispersion of carbon black or wh.ite carbon thereinto, or for
a purpose of reducing :hardness of vulcanized rubbers thereby
enhancing flexibility or elastic.ity thereof.
Upon preparation of the partially cross-linked olefinic
thermoplastic elastomer (B), the peroxide-noncross-linkable
hydrocarbon rubbers (c) and/or m:ineral oil softeners (d) are
not necessarily be used. Howeve:r, for a purpose of further
improving flow properties and mo:ldability of the polymer
1339967
12
composition according to the invention, it is generally
advantageous to incorporate (c) and/or ~d) to a mixture of
the ethylene/alpha-olefin copolymer rubber ~a) and the
polyolefin resin (b) in an amount of up to 100 parts by
S weight, preferably up to 80 part;s by weight, in particular
from 5 to 80 parts by weight based on 100 parts by weight of
the combined (a) and (:b), and to subject the resulting blend
to the dynamic heat treatment to provide the partially
crosslinked rubber composition [I].
l O
A preferred partially crosslinked olefin-type
thermoplastic elastomer (B) which can be used herein
comprises from 100 to 30 parts by weight of the partially
crosslinked rubber composition [:I] prepared in the manner as
described above and from 0 to 70 parts by weight of a
polyolefin resin [II], the total weight of (b) and [II] in
the elastomer (B) being from 5 to 80 parts by weight based
on 100 parts by weight of the elastomer (B). As the
polyolefin resin [II], which is optionally added to the
2 0 partially crosslinked rubber composition [I] after the
dynamic heat treatment, use can be made of those
hereinbefore described with respect to the polyolefin resin
(b), that is, homopolymers of 1-olefins such as ethylene,
propylene, butene-1, hexene-1 and 4-methyl-pentene-1,
copolymers of at least two 1-olefins and copolymers of 1-
olefins and up to 15% by mole of at least one other
copolymerizable monome:r, such as ethylene/vinyl acetate
copolymers, ethylene/acrylic acid copolymers,
1339967
13
ethylene/methyl acrylate copolymers, ethylene/ethyl acrylate
copolymers, ethylene/m.ethacrylic acid copolymers and
ethylene/methyl methacrylate copolymers. Of these,
polyolefin resins having a melt flow rate of from 5 to 100
g/10 min., in particular from 10 to 50 g/10 min., as
measured in accordance with ASTM-D-1238-65T ~at 190 ~C., or
at 2-,0 ~C. in the case of polyme:rs of propylene), are
prefe!rred.
0 To prepare the partially crosslinked rubber composition
[I], a mixture comprising from 95 to 20 parts by weight of
the e!thylene/alpha-olefin copolymer rubber (a), from 5 to 80
parts by weight of the polyolefin resin ~b) and optionally
from 5 to 80 parts by weight of the peroxide-
noncrosslinkable hydrocarbon rubber ~c) and/or the mineral
oil softener ~d), is dynamically heat treated in the
presence of from about 0.05 to 2 parts by weight, preferably
from 0.1 to 0.5 part by weight of a crosslinking agent so as
to pa.rtially crosslink the ethylene/alpha-olefin copolymer
rubbe!r ~a).
The crosslinking agents, which can be used herein,
inclu.de organic peroxides, sulfur, phenolic vulcanizing
agents, oximes and polyamines. Of these, organic peroxides
and phenolic vulcanizing agents are preferred in view of
properties of the resulting partially crosslinked products.
13399~7
14
Examples of the phenolic vulcanizing agents include,
for example, alkylphenol-formaldehyde resins, triazine-
forma.ldehyde resins and melamine-formaldehyde resins.
S Examples of organic peroxides include, for example,
dicumyl peroxide, di-tert.-butyl peroxide, 2,5-dimethyl-2,5-
bis(tert.-butylperoxy)hexane, 2,3-dimethyl-2,5-bis(tert.-
butyl.peroxy)hexyne-3, 1,3-bis(tert.-
butyl.peroxyisopropyl)benzene, 1,1-bis(tert.-butylperoxy)-
]L 0 3,3,~-trimethylcyclohexane, n-butyl-4,4-bis(tert.-
butyl.peroxy)valerate, dibenzoyl peroxide and tert.-
butylperoxy benzoate. Of course, bisperoxide compounds, in
parti.cular, 1,3-bis(tert.-butylperoxyisopropyl)benzene, is
preferred in view of their less ill-smelling and scorch
]L 5 resistant properties.
Upon dynamic heat treatment of the above-mentioned
mixture, incorporation to the mixture of crosslinking
promcters such as p-quinonedioxime and p,p'-
dibenzoylquinonedioxime or polyfunctional vinyl monomerssuch as divinylbenzene (DVB), diethyleneglycol methacrylate,
polyethylenediglycol methacrylate and the like is preferred.
By doing so more uniform and moderate crosslinking reaction
can be realized. Particularly p:referred is divinylbenzene
2 5 (DVB), since it provides uniform crosslinking effects to
obtain thermoplastic elastomers having balanced flow and
mechanical properties.
1339967
The partially crosslinked thermoplastic elastomer (B)
used herein may optionally contain additives, including
fillers such as carbon black, clay, talc, calcium carbonate,
calcium bicarbonate, diatomaceous earth, silica, alumina,
asbestos, graphite and glass fibers, antioxidant such as
phenyl-alpha-naphthylamine, 2,6-di-tert.-butylphenol and
tetrakis[methylene(3,5-di-tert.-butyl-4-hydroxyphenyl)
propionate], and other additives. These additives may be
added during or after the preparation of the partially
crosslinked thermoplastic elastomer (B).
By the term "partially crosslinked" used herein is
meant that the product is crosslinked to such an extent that
it still retain thermoplastic and elastomeric properties.
As the ethylene/alpha-olefin copolymer rubber (C), use
can be made of those hereinbefore described with respect to
the ethylene/alpha-olefin copolymer rubber (a) used in the
preparation of the partially crosslinked thermoplastic
elastomer (B). In a particular polymer composition
according to the invention, the rubbers (a) and (C) may be
the same or different.
The polymer composition according to he invention
comprises from 50 to 85 parts by weight, preferably from 50
to 75 parts by weight of the ethylene-type ionomer resin
(A), from 10 to 39 parts by weight, preferably from 20 to 35
parts by weight of the partially crosslinked olefin-type
1339967
16
thermoplastic elastomer (B) and from 1 to 15 parts by
weight, preferably from 5 to 15 parts by weight of the
ethylene/alpha-olefin copolymer rubber (C). If the content
of (A) is excessively high, it is difficult to appreciably
5 reduce surface gloss, and flexibility tends to become poor,
whereas if the content of (A) is unduly low, scratch
resistance and adhesion to metals tend to decrease. If the
content of (B) is excessively high, it is difficult to
appreciable reduce in surface gloss and scratch resistance
tends to become poor, whereas if the content of (B) is
unduly low, appreciable improvement in flexibility and
reduction of surface gloss is not realized. If the content
of (C) exceeds the above-prescribed range, resistance to
heat deformation and scratch resistance tend to decrease,
whereas if the content of (C) is unduly low, a mineral oil
softener, if any, tends to bleed out and surface gloss is
not appreciably reduced.
The polymer composition according to the invention
preferably has a melt flow rate (MFR) of from 0.1 to 50 g/10
min., in particular from 0.1 to 10 g/10 min., as measured at
a temperature of 190 ~C. and under a load of 2160 g.
The polymer composition according to the invention is
prepared by dry or melt blending simultaneously or
sequentially suitable amounts of the ethylen-type ionomer
resin (A), partially crosslinked olefin-type thermoplastic
elastomer (B) and ethylene/alpha-olefin copolymer rubber
1339967
17
(C). The dry blending may be carried out using various
blenders such as a Henschel*mixer, tumbling mixer and ribbon
blender, while the melt blending may be carried out using
various mixers such as a single screw extruder, twin-screw
extruder and Bumbury's mixer, a roll mill, and various
kneaders. The order of the components to be blended is not
particularly limited.
To the polymer composition according to the invention
there may be added various fillers such as carbon black,
clay, talc, calcium carbonate, calcium bicarbonate, kaolin,
diatomaceous earth, silica, alumina, asbestos, graphite,
wisker, metal powder, glass beads, glass fibers and carbon
fibers, coloring agents such as titanium oxide, zinc flower,
red iron oxide, ultramarine, prussian blue, azo pigments,
lake pigments and phthalocyanine pigments, and other
additives, or example, antioxidants, plasticizers, heat
stabilizers, weathering stabilizers, antistatic agents,
lubricants such as metal soaps and waxes, and flame
retardants, in such amounts that the additives may not
adversely affect desired properties of the composition.
As already stated, the fillers, coloring agent and
other additives may be added during the stage of preparing
the partially crosslinked olefin-type thermoplastic
elastomer (B), or during the stage of blending to prepare
the polymer composition according to the invention.
Further, a foaming agent may be added to the composition
:: * trade-marks
1339967
18
according to the invention for a purpose of producing foamed
shaped articles.
F.ffect of the Invent-on
The polymer composition according to the invention has
excellent moldability and is capable of being molded into
shaped articles which are excellent in scratch resistance,
adhesion to metals, resistance to heat deformation and
flexibility, antibleeding property of mineral oil softener
contained and low surface gloss. Accordingly, the polymer
compositions according to the invention are particularly
useful in molding various articles including automotive
parts such as bumper moldings, materials for interior finish
of ceiling and doors, and instrument panels; bicycle parts,
sports goods, construction materials, electric parts,
housings and daily necessaries such as bags; and
decorations. These articles can be prepared by various
molding processes, including injection, extrusion, blow and
compression molding processes.
Examples
The invention will now be further described by the
following examples.
Component materials used in the examples are as
follows.
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1 9
Ionomer ~ comprising 96 mol % of ethylene, 1 mol %
of methacrylic acid and 3 mol % of zinc methacrylate, and
having MFR of 1 g/10 min., as measured at 190 ~C. and under
a load of 2160 g.
Ionomer (2) : comprising 95 mol % of ethylene, 3 mol %
of methacrylic acid and 2 mol % of zinc methacrylate, and
having MFR of 1.5 g/10 min., as measured at 190 ~C. under a
load of 2160 g.
1 0
Ionomer (3) : comprising 96 mol % of ethylene, 3 mol %
of methacrylic acid and 1 mol % of zinc methacrylate, and
having MFR of 5 g/10 min., as measured at 190 ~C. and under
a load of 2160 g.
1 5
Iono~er (4) : comprising 96 mol % of ethylene, 2 mol %
of methacrylic acid and 2 mol % of sodium methacrylate, and
having MFR of 1.0 g/10 min., as measured at 190 ~C. and
under a load of 2160 g.
Thermoplastic elastomer (5) : "Milastomer" ~ 8030B, a
partially crosslinked olefin-type thermoplastic elastomer,
supplied by MITSUI Petrochemical Industries Ltd., having MFR
of 10 g/10 min., as measured at 230 ~C. and under a load of
10 kg, and a Shore hardness of (A)85.
Thermoplastic elastomer (6) : "Milastomer" ~ 8032B, a
partially crosslinked olefin-type thermoplastic elastomer,
133gg67
supplied by MITSUI Petrochemical Industries Ltd., having MFR
of 15 g/10 min., as measured at 230 ~C. and under a load of
10 kg, and a Shore hardness of (A)80.
Copolymer rl]hher ~7) : EPT 3092P, an
ethylene/propylene/ ethylidenenorbornene terpolymer rubber,
supplied by MITSUI Petrochemical Industries Ltd.
Copolymer rllhher (8~ : an ethylene/l-butene copolymer
rubber having an ethylene content of 85 mol %, MFR of 4 g/10
min., as measured at 190 ~C., under a load of 2180 g, and a
crystallinity index of 17 %.
F.x~m~l es 1 to 4 ~n~ Co~p~r~tive F.x~m~l es 1 to 4
A mixture of the ionomer (1), partially crosslinked
thermoplastic elastomer (5) and ethylene/alpha-olefin
copolymer rubber (7) in amounts indicated in Table 1 was
supplied to a single screw extruder having a diameter of 40
mm, where the mixture was melt blended under conditions of a
die temperature of 200 ~C. and a screw rotation of 40 rpm,
and pelletized. Properties of the pellets were evaluated in
the manner as noted below.
The results are shown in Table 1.
Gloss
Using a single screw extruder having a diameter of 30
mm, the pellets were extruded to a ribbon having a width of
1339967
21
15 mm and a thickness of 0,55 mm. Surface gloss of the
ribbon was visually examined. Low, intermediate and high
gloss surfaces were rated as A. B and C, respectively.
T~er ~hr~s;on in~ex
The pellets were heat pressed at a temperature of 160
~C., to a sheet having a thickness of 3 mm. The sheet was
tested for Taper abrasion index in accordance with ASTM D
1175 (in mg /1000 rotations using a CS-17 abrasion ring).
1 0
Ren~; ng ~o~n 1 US
The pellets were heat pressed at a temperature of 160
~C., to a sheet having a thickness of 3 mm. The sheet was
tested for bending modulus in accordance with ASTM D 747.
Gr~v;ty ~rAw~own
The pellets were heat pressed at a temperature of 160
~C., to a sheet having a length of 100 mm, a width of 200 mm
and a thickness of 3 mm. The sheet was horizontally held
along one 20 mm side with the other sides free. The
assembly so constructed was placed in an oven maintained at
a temperature of 90 ~C., for a period 3 hours. At the end
of the period a drawdown of the other 20 mm side of the
sheet in mm was measured. The gravity drawdown (mm) can be
a measure of heat resistance.
Bleed resistance
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22
The pellets were heat pressed at a temperature of 160
~C., to a sheet having a thickness of 3 mm. The sheet was
placed in an oven at a temperature of 50 ~C., for a period
of 2 weeks. At the end of the period, the surface of the
sheet was visually observed as to yes or no of bleedout of a
mineral oil softener. Ratings A, C and B were given to
surface where no bleedout was observed, surface where
bleedout was observed and surface that was intermediate.
1 0 F.~C;3TI~1 e 5
Example 1 was repeated except that the ionomer (2) was
used instead of the ionomer (1).
The results are shown in Table 1.
F.x;~tr~l e 6
Example 1 was repeated except that the ionomer (3) was
used instead of the ionomer (1).
The results are shown in Table 1.
Example 7
Example 1 was repeated except that the ionomer (4) was
used instead of the ionomer (1).
The results are shown in Table 1.
F.x;~rr~l e 8
1339967
23
Example 1 was repeated except that the partially
crosslinked thermoplastic elastomer (6) was used instead of
the partially crosslinked thermoplastic elastomer ~5).
The results are shown in Table 1.
F.~c~rr~l e 9
Example 1 was repeated except that the ethylene/alpha-
olefin copolymer rubber ~8) was used instead of the
ethylene/alpha-olefin copolymer rubber ~7).
The results are shown in Table 1.
2~ 1339967
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