Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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SPECIFICATION
TITLE OF THE INVENTION
Molding resin composition
BACKGROUND.OF TIIE INVENTION
This invention relates to a molding thermoplas-tic,
elastomeric resin compositi.on having superior charac-
teristics.
In recent years, thermoplastic elastomers having
rubber elasticity even when uncured and also having
thermoplasticity have been noted in the ields o~ par-ts
for automobiles, domestic appliances and -their parts,
wire coating materials, footwears, materials for
asphalt pavement, etc.
As such thermoplastic elastomers, polyolefin
elastomers, polystyrene elastomers, etc. have so far
been known.
Polystyrene elastomers, particularly styrene-
butadiene block copolymer (SBS) and styrene-isoprene
block copolymer (SIS) have a superior flexibility and
a good rubber elasticity, but since they contain double
bonds therein, their heat stability (heat deterioration
and thermal-oxidative de-terioration) and weather
resistance are insufficient.
Thus, in order to improve such insuffici,ent charac-
teristics of the polystyrene elastomers, there have beenemployed or proposed ~ a process of hydrogenating
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the double bonds inside the molecules of styrene-conjugated
diene block copolymers, ~ a process of reacting the double
bonds within ~he molecules with each other by adding a free-
radical generator or a crosslinking agent to form a reticular
structure inside the molecules, and the like processes.
In any of these processes, it is intended to reduce the
quantity of the double bonds inside the block copolymers or make
it zero.
However, the thermoplastic elastomers obtained
aeeording to the process ~ are superior in heat stability and
molding and processing properties, but since the hydrogenation
process relies on a solution process, the operation is
eomplicated and the hydrogenation cannot be easily effected.
Moreover, the hydrogenated thermoplastie elastomers are not
regarded as exhibiting a good rubber elasticity as compared with
unhydrogenated thermoplastic elastomers.
On the other hand, the thermoplastic elastomers
obtained aceording to the process ~ have drawbacks in that
notable reduction in the flowability and inferior appearance of
the resulting molded products, such as silver streaks, occur.
Further, as to the polyolefin thermoplastic elastomers,
it has been known that when a hydrogenated derivative of
styrene-butadiene-styrene block copolymers
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is blended with a propylene polymer, a composition having a good
flexibility and also high mechanical strengths is obtained.
~ owever, when a hydrocarbon oil used as a softening
agent is further added to the above-mentioned composition in
order to improve its flowability, the composition is reduced in
mechanical strength.
Further, if propylene homopolymer is blended with the
above-mentioned composition, good rubber-elasticity is hindered
~nd high-impact properties at low temperatures are insufficient.
~0 In the case of the composition of a propylene-ethylene
block copolymer with a hydrogenated derivative of a styrene-
conjugated diene copolymer, as the quantity of the hydrogenated
derivative of a styrene-conjugated diene block copolymer blended
increases, flow marks appear on the surface of the resulting
molded product to yieid a molded product having an inferior
appearance.
On the other hand, in the case of a polyolefin
elastomer obtained by blending a propylene polymer with a non-
crystalline ethylene-propylene random copolymer, the elastomer
~0 has a good rubber elasticity, but its mold-release
characteristics during the molding process are inferior, and in
the case of those containing a large quantity of the non-
crystalline
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ethylene-propylene random copolymer, thexe of ten occurs
no mold release.
SU~lM~RY O~ T~IE INVENTION
The present invention has been made based on the
above-mentioned situations.
'l`he ob ject o~ the present invention is to provide
a molding thermoplastic, elas-tolneric resin composition
having a good flexibility and superior high-impact
properties, mechanical ch~racteristics, moldability,
lO etc.
The preserlt invention in a first aspect resides in
1~ molding elastonleric resin composition having the
components (a), (b), (c) ,and (d) in which the quantity oE each
component is based on the total weight of components (a), (b),
and (c) comprising:
(a) 1 to 50 ~O by weight oE a block copolyrner expressed by
the f ormula (I)
B-~-B' (I)
wherein 1~ represents a conjugated diene polymer block and B
20 and B' each represent an aromatic vinyl compound polymer bloc~
having a number-average molecular weight of 5, 000 to 125, 000, B
and B are the same or diffrent and the total weight of B and
B present in the copolymer is in an amount of 5 to 50 % by
weight;
(b) no more than 50 96 of a non-crystalline ethylene-a-olefin
random copolymer wherein the carbon number o~ the a-olefin is
3 or more;
(c) ~0 to 90 ~ by weight of at least one of a propylene-
ethylene block copolymer and a crys-talline propylene-ethylene
30 rar1dom copolymer; and
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~d) 0.01 to 5 parts by weight of a phenolic antioxidant
expressed by the formula (II)
OH o-C-CH=CH2
(C~13)3(~ C(~13)3
R2 Rl . . . ( u
wherein R' and R2 each represent a lower alkyl group of 1 to 4
carbon atoms.
Tlle presellt invent ion in a second aspect resides in
~ molding elastomeric composition having the components
comprising 10 to 50 % by weight oE a hydrogenated derivative
oE a block copolymer expressed by the formula (III)
B-~-B' (III)
.1~ wherein ~ represents a conjugated diene polymer block and B
and ~' each represent an aromatic vinyl compound polymer
block, and having a solution viscosity oE ~00 cps or less as
measured in a 20 ~ by weight toluene solution at 25~C,and
50 to 70 -O by weight of a crystalline propylene-ethylene
random copolymer having a flexural modulus oE 3,000 to 9,000
kg E/cm2,a~d the total oE the percentages by weight.of said
hydrogenated derivative oE a,block copolymer expressed by the
Eormula (III) and said crystalline propylene-ethylene random
copolymer in said molding elastomeric composition is 100 -O by
20 weight.
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DETAIL~D DESCRIPTION OF PREFERRED EMBODIMENTS
The block copolymer having a structure of B-A-B'
of the formula ~I) (a first component) generally has
a two-phase structure consisting of the conjugated
diene polymer block A and the polymer blocks B and B',
and since the conjugated diene polymer block A is
incompatible with the respective pol~mer blocks s and B',
a structure is formed wherein the polymer blocks s and B'
are respectively dispersed between the phases of the
conjugated diene polymer A. Further, in this first
component, since the polymer blocks B and B' each have
a stiffness, these consti-tute physical crosslinks to
develop a rubbery structure.
Thus, as the conjugated diene polymer block A,
those having a structure obtained by polymerizing one
or two kinds of butadiene, isoprene, neoprene, etc.,
are herein enumerated. In the present invention, as
the conjugated diene polymer block A, polybutadiene
block is preferred.
Further, the polymer blocks B and B' each have
a structure obtained by polymerizing an aromatic vinyl
compound, and polystyrene structure is preferred.
Further, in this first component, the polymer
block B and B' each have a number-average molecular
weight ~ 5,000 to 1l5, 00, particularly 8,000 to 50,OoO.
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If the number-average molecular weight is less
than 5,000, the rubber elasticity cannot be developed,
while if it exceeds 125,000, the resulting block
copolymer is too stiff.
Further, in the present invention, it is important
that the block copolymer having the structure of B-A-B'
con-tains the polymer blocks s and s' in a proportion
of 5 to 50~ by weigh-t, preferably 20 to 40% by weight
therein.
If the content of the.polymer bloc]cs B and B' is
lower than 5% by weight, physical crosslinks of this
block copolymer are not realized; hence development of
rubber elasticity is inferior. If the content is higher
than 50~ by weight, the resulting molding resin compo-
`15 sition-is too stiff.
The blending proportion of the first component in
the total weight of the first, second and third compo-
nents is in the range of usually 1 to 50% by weight,
particularly preferably 10 to 40% by welght.
If the blending proportion is less than 1% by
weight, the resul-ting composition often cannot exhibit
a sufficient flexibility, while if it exceeds 50% by
weight, the resulting composition is often reduced in
mechanical strenqth particularly the tensile
strength, and inferior in hiah-temperature stiffness.
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Next, the non-crystalline ethylene-~-olefin random
copolymer as the second componen-t imparts flexibilit~
and high-impact properties to the molding resin compo-
si-tion.
The ~-olefin constitu-ting the second component is
those having 3 or more carbon atoms, particularly 3 to
18 carbon atoms, and concrete examples thereof are
propylene, l-butene, l-pentene, l-hexene, 4-methyl-1-
pentene, l-heptene, l-octene, l-nonene, l-decene, etc.
Further, the ~-olefin in the second component may
be alone or in admixture of two or more kinds.
The second component is preferred to be non-
crystalline ethylene-propylene random copolymer.
When the second component is non-crystalline
ethylene-propylene random copolymer, the ethylene
content is in the range of 25 to 75% by weight, partic-
ularly preferably 25 to 50% by weight.
The blending proportion of the second component in
the total of the first, second and third components is
50~ by weight or less. If the blending proportion
exceeds 50% by weight, the mechanical strengths and
high-temperature stiffness ~of the resulting composition
may often be reduced.
The above third component is considered to function
as a hard segment in the molding resin composition, and
it adjusts the hardness of the molding resin composition
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and at the same time improves its mechanical strength.
~ s the third component, propylene-e-thylene block
copolymer, crystal]ine propylene-ethylene random
copolymer or the mixture thereof is used, and in any
of these, the densi-ty is preferred -to be in the range
of 0.885 to 0.910 g/cm3.
Further, the third component is preferred -to have
a melt flow rate (MFR) [JIS K 6758, 230C] expressing
its molecular weight, of 0.5 to 100 g/10 min.,prefer-
ably 1 to 60 g/10 min.
In the case of propylene-ethylene block copolymer,
the ethylene content therein is usually in the range of
5 to 20% by weight, preferably 5 to 15% by weight, more
preferably 7 to 13~ by weight, while in the case of
crystalline propylene-ethylene random copolymer, the
ethylene content is in the range of 1 to 10% by weight,
preferably 3 to 8% by weight, more preferably 4 to 8%
by weight. .Further, this crystalline propylene-
ethylene random copolymer also includes a crystalline
propylene-ethylene-butene random terpolymer having
a butene content of 1 to 5% by weight and an ethylene
content o 1 to 5~ by weight.
The blending proportion of the third component in
the total of the first, second and third components is
usually in the range of 40 to 90% by weight, particularly
preferably 50 to 70~ by weight.
If the blendlng proportion is less than 40% by weiyht,
the mechanical strength, particularly tensile strength, oE the
resulting resin composition may often be reduced, while if it
exceeds 90% by weight, the hardness of the resulting composition
may often be too high.
In the formula (II) expressing the above phenolic
antioxidant, R1 and R2 each concretely represent any one of
methyl group, ethyl group, propyl group, isopropyl group and
butyl group, and R1 and R2 may be the same or different group.
Among the above phenolic antioxidants, those wherein
R1 and R2 each are methyl group or ethyl group are preferred,
and as such, e.g. "Sumilizer G~" (trade-mark of product made by
Sumitomo Chemical Company, Limited) as a commercially available
product may be used.
The phenolic antioxidant has functions of improving the
heat ~tability of the resulting molding resin composition and
besides, retaining the good elastomeric properties of the
composition.
Thus, in order for such properties to be sufficiently
~0 exhibited, the blending proportion of the phenolic antioxidant
is preferred to be usually in the range of 0.01 to 5 parts by
weight, particularly 0.05 to 1 part by weight, based on 100
parts by weight of the total of the first, second and third
components.
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In addition, in the present invention, other
antioxidants may be, if necessary, used together with the
phenolic antioxidant expressed by the formula (II).
As such other antioxidant, an antioxidant expressed by
the formula (IVj
(R3-s-cH2cH2coocH2)4c ... (IV)
wherein R3 represents an alkyl group of 4 to 20 carbon atoms,
is preferred. When this antioxidant is used together with the
above phenolic antioxidant, it is possible to obtain a superior
heat stability as a synergistic effect, over the sum of the heat
stabilities of the respective compositions obtained when these
stabilizers are singly blended, respectively.
Further, the above-mentioned hydrogenated derivative
as the fourth component is a product obtained by hydrogenating
the unsaturated bonds contained in the conjugated diene polymer
block A and the aromatic vinyl compound polymer blocks B and B'
in the above-mentioned formula (III).
The process for hydrogenating the block copolymer
expressed by the above formula (III) can be suitably carried out
according to a known process e.g. described in Japanese Patent
Publication No. Sho 42-8704/1967 or Japanese Patent Publication
No. Sho 43-6636/1968; thus its detailed description is omitted
herein.
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As the conjugated diene polymer block A in the above
formula (III), a block having a structure as obtained by
polymerizing one or two kinds o~ conjugated dienes such as
butadiene, isoprene, neoprene, etc. is illustrated. In the
present invention, polybutadiene block is preferred as the
conjugated diene polymer block ~.
Further, the above-mentioned polymer block B and B'
have a structure as obtained by polymerizing an aromatic vinyl
compound, and a polystyrene structure is preferred.
~0 In the block copolymer of formula III, at least 90%
by weight of the polymer block A is a hydrogenated
polybutadiene block or polyisoprene block and no more than lO~
by weight of the total of polymer blocks B and B' is a
hydrogenated polystyrene block.
Further, the hydrogenated derivative of the block
copolymer has a solution viscosity of 800 cps or less,
preEerably 600 cps or less, as measured in a 20% by weight
toluene solution at 25C. If a hydrogenated derlvative having
a solution viscosity exceeding 800 cps is blended, the
compatibility thereof with the crystalline propylene-ethylene
random copolymer as the fifth component lS inferior so that
flow marks appear on the surface of the resulting molded
product or the flowability of the composition when melted
lowers.
The blending proportion of the hydrogenated derivative
in the mold1ng elastomerlc composition is usually in the range
of lO to 50% by weight, preferably l5 to 45% by weight.
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If the blending proportion is less than 10% by weight,
the resulting composition .is often inferior
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in the moldability such as mold-release characteristics, while
if it exceeds 50% by weight, flow marks often appear on the
surface of the molded product obtained from the composition.
The crystalline propylene-ethylene random copolymer as
the fifth component is considered to function as a hard segment
in the molding elastomeric composition.
The crystalline propylene-ethylene random copolymer as
the fifth component has a melt flow rate (MFR) [according to JIS
1~ 6758] expressing its molecular weight, of usually 1 to 100
g/10 min., preferably 10 to 60 g/10 mi.n., more preferably 20 to
g/10 min. If a crystalline propylene-ethylene random
copolymer having a MFR less than 1 g/10 min. is blended, the
flowability of the molten composition may be inferior so that
molding of a large size molded product such as a bumper is
difficult, while if the MFR exceeds 100 g/10 min., the high-
impact properties of the resulting molded product are reduced.
The crystalline propylene-ethylene random copolymer as
the fifth component is preferred to have as its characteristics,
a ~lexural modulus of 3,000 to 9,000 Kg f/cm2, particularly
~0 5,000 to 8,000 Kg f/cm2. Similarly, the crystalline propylene-
ethylene random copolymer of the present invention may be a
crystalline propylene-ethylene-butene random terpolymer having
a flexural modulus of 3,000 to 9,000 Xg f/cm2.
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In the case where a crystalline propylene-ethylene
random copolymer having a flexural modulus exceeding 9,000 Kg
f cm2 is blended, if the blending proportion of the hydrogenated
derivative of the block copolymer expressed by the formula
(III), as the fourth component, is in the range of 50% by weight
or less, an elastomeric composition having a good flexibility
is often not obtained; in addition, in order to prepare an
elastomeric composition having a good flexibility, if the
hydrogenated derivative of the block copolymer is blended in a
blending proportion exceeding 50% by weight, the mold-release
characteristics are often inferior and flow marks appear on the
surface of the resulting molded product. Further, if a
crystalline propylene-ethylene random copolymer having a
~lexural modulus less than 3,000 Kg f/cm2 is blended as the
~fifth component, the mechanical strength of the resulting molded
product is reduced and the mold-release characterlstics at the
time of molding are inferior.
The blending proportion of the crystalline propylene-
ethylene random copolymer as the fifth component in the molding
~0 elastomeric composition is in the range of usually~50 to 70% by
weight, preferably 55 to 65% by weight.
If the blending proportion is less than 50% by weight,
the appearance of the molded product is often
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inferior, while it exceeds 70% by weiyht, high-impact properties
at low temperatures of the molded product using the composition
is reduced.
As to the molding elastomeric composition of the
present invention, when 10 to 50% by weight of the hydrogenated
derivative to the block copolymer is blended with 50 to 90% by
weight of the crystalline propylene-ethylene random copolymer,
the resulting elastomeric composition exhibits good mechanical
characteristics, and when a non-crystalline ethylene-~-olefin
l~ random copolymer is further ~blended with the above two
components, it is possible to improve the tear strength of the
molding elastomeric composition.
The ~-olefin contained in such a non-crystalline
ethylene-~-olefin random copolymer includes ~-olefins of 3
carbon atoms or more, particularly 3 to 18 carbon atoms.
Concrete examples thereof are propylene, 1-butene, 1-pentene,
l-hexene, 4-methyl-1-pentene, 1-heptene, l-octenej l-nonene, 1-
decene, etc.
Further, the ~-olefin in the non-crystalline ethylene-
olefin random copolymer may be a ~ingl~e ~-olefin or a mixture
o~ t~o or more kinds of ~-olefins.
Further, the non-crystalline ethylene-~-olefin random
copolymer may contain a sligbt quanti~y of a diene component.
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A preferred non-crystalline ethylene-~-olefin random
copolymer is a non-crystalline ethylene-propylene random
copolymer.
The ethylene content in the non-crystalline ethylene-
propylene random copolymer is in the range of usually 25 to 75%
by weight, preferably 25 to 50% by weight.
The blending proportion of the non-crystalline
ethylene-~-olefin random copolymer in the molding elastomeric
composition is 30% by weight or less. If the blending
proportion exceeds 30~ by weight, the moldability, particularly
the mold-release characteristics of the resulting composition
are often inferior.
Further,-in the present invention, it i5 possible, if
necessary, to adequately add and blend various additives such
an antioxidant, antistatic agent, coloring agent, flame
retardant, flame-retardant adjunct, UV ray absorber,
plasticizer, inorganic filler, softening agent~for non-aromatic
rubber, etc. as far as their addition does not hinder the
.
effectiveness of the present invention.
Examples of the antioxidant~ nre alkylphenols,2~6-di-
t-butyl-p-cresol, bisphenol A, amines, quinons, etc.~ Examples
of the antistatlc agent are various~kinds of surfactants.
Examples of the coloring agent are difficultly water-soluble azo
dyes, red coloring
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agent,~cadmium yellow, cream yellow, titanium white,
etc. Examples of the flame retardant are organic
halogen-containing flame retardants such as deca-
bromodiphenyl o~ide, decachlorododecahydrodimethano-
5 dibenzocyclooctene, etc. Examples of the flame
retardant adjunct are antimony oxide, antimony sulfide,
zirconium oxide, etc. Examples of the plasticizer are
phthalic acid dies-ters, adipic acid diesters, phos-
phoric acid diesters, etc. Examples of the inorganic
10 filler are calcium carbonate, gypsum, talc, mica,
barium sulfate, glass fibers, wollastonite, magnesium
hydroxide, aluminium hydroxide, etc. Examples of the
softening agent for non-aromatic rubber are extender
for EPDM, mineral softening agent for rubber called
15 process oil, etc.
r The molding resin composition of the present
invention can be produced by blending the above-
mentioned fi~rst, second and third components~and
a phenolic antioxidant expressed by the ormula (II)
20 and if desired, further the above-mentioned various
additives.
The blending process has no particular limitation;
for example, the total components may be blended all
at once, or a phenolic antioxidant~expressed~by the
25 formula (II) may be blended with the third component
to prepare a master batch, followed by blending this
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master batch with the first and second components.
Further, the molding elastomeric composition o~ the
present invention can be produced by blending the above-
mentioned hydrogenated derivative of a block copolymer as the
fourth component with the above-mentioned cyrstalline propylene-
ethylene random copolymer as the fifth component and if
re~uired, further with the above-mentioned non-crystalline
ethylene-~-olefin random copolymer and the above-mentioned
additives.
In any case, the blending may be carried out by means
of e.g. ribbon blender, tumbler mixer, Henschel mixer
(trademark), super mixer, open rolls, Banbury mixer, single
screw extruder, twin-screw extruder, single reciprocating screw
kneader, etc.
The thus obtained molding resin composition and molding
elastomeric composition are molded into various molded products
according to various molding processes such as injection
molding, vacuum molding, compression molding, extrusion moldlng,
etc.
The molding resin composition and molding elastomerlc
composition can be suitably used for molding e.g. automobile
parts such as bumper, OA apparatus such as housing, domestic
appliance, wire coating material, footwear~such as shoe soles,
etc. - ~ ~
Since the molding resin compositi~on of the~ present
invention is obtained by blending a specified block
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copolymer having a two-phase s-tructure consisting of
plastic phase and rubber phase, a specified non-
crystalline random copolymer, a propylene-ethylene
block copolymer and/or a crystalline propylene-
S ethylene random copolymer and a specified phenolicantioxidant, the composition is moldable into a molded
product having a good flexibility, superior high-impact
properties, mechanical s-trength and molding process-
ability and a good appearance.
Further, since the molding composition of the
present invention is also obtained by blending
a specified hydrogenated derivative of a block copolymer
having a two-phase structure consisting of plastic
phase and rubber phase with a crystalline propylene-
ethylene random copolymer in a speclfied proportion,
the composition is also moldable into a molded product
having a good flexlbility, superlor high-impact proper-
ties,mechanical strength and molding processability
:
and a good appearance.
The present invention will be described in more
:
detail by way of Examples~and;Comparatlve~examples.
In additio~, the present invention should not be
construed to be limited thereto, but it can be, of~
course, optlonally carried out within the scope of
the present;invention.-
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Examples 1 ~ 8 and Comparative examples 1 _ 6
The first, second and third components of kinds
and quantities indicated in Table 1 and phenolic
antioxidants of kinds and quantities indicated in
Table 1 were stirred by means of Henschel mixer
(trademark) for 3 minutes, followed by extruding
the resulting mixture by means of a single screw
extruder (manufactured by Thermoplastic Company)
at 200C into pellets. Wikh the pellet`s, measurement
of melk flow rake (MFR) shown below was carried out,
and further, various test pieces were prepared there-
from and subjected to various tests.
Further, in CoMparative examples 1 ~6, the respec-
tive components of kinds and~quantities indicated in
Table 1 were stlrred in the same manner as in Examples
1 ~8 to obtain pellets. With ~he pellets, varlous
tests of melt flow rate and others were carried out.
The results of the respective Examples and Comparative
.
examples are shown in Table 1.
:
In addition, the respective components us~ed in
the respective Examples and~Comparative examples and
the testing;methodsemployed thereln wlll be~described
below.
With regard to blending components~
The first component ~
* SBS copolymer ("TUFPRENE~-A" a trademark of
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a product manufac-tured by Asahi Chemical Industry
Co., Ltd.; styrene-bu-tadiene ratio = 40 :60,
MI (ASTM-D-1238, E condition) = 2.6 g/10 min.).
The second component
* Non-crystalline ethylene-propylene random
copolymer ("EPO2P", tradename of a product
manufactured by Japan Synthetic Rubber Co., Ltd.;
MFR (JIS-K-6758) = 3.6 g/10 min., Mooney
viscosity = 24).
The third component
* Propylene-ethylene block copolymer (ethylene
content 12.5% by weight, MFR 45 g/10 min.)
* Crystalline propylene-ethylene random
copolymer (crystalline propylene-ethylene-butene
terpolymer: ethylene content 4.5% by weight,
butene content 4.5% by weight~, MFR 50 g/10 min.)
Antioxidant
* Phenolic antioxidant ("Sumilizer GM" and
"Sumilizer TP-D", both trademarks of products
manufactured by Sumitomo Chemical Company, Ltd.) ;
Free-radical generator
* 1,3-bis~t-butylperoxypropyl)benzene ~ ~
Inorganic filler ;
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* Calcium carbonate
With regard to testing method~
MFR [g/10 min.] ~
according to JIS-K-6758; load 2.16 Xg, 2~30C ~ ;
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Flexural modulus ~Kq f/cm2]
according to JIS-K-7203
Dupont high-impact strength (Chisso process)
Employing a dupont high-impact tester
(manufactured by Toyo Seiki Company) (a tip end of
center of impact of 1/4 inch R and a pad for the center
of impact, of 3/2 inch R), a load of 3.8 Kg was dropped
from the height of 1 m to observe the prèsence or
absence of ductile failure. The measurement
temperature at that time was -40~C.
Appearance
Injection molding was carried out employing
NEOMAT N 350/120 type injection molding machine
(trademark of product manufactured by SUMITOMO HEAVY
INDUSTRIES, LTD.) and under conditions of
Mold: flat plate~of:~l50~x~150 x~3~ mm ~ :
Injection temperature: 250C
Mold temperature: ~ 50C.
The appearance~of:;the resulting fLat plate was::
judged by the~naked~ eye, ;and~ when~silver streaks or~
flow marks were~not~:observed,~the appearance of the :~
molded~product~was regarded good~
Luster (%)
according to JIS-Z-7841
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- 24 -
Examples 9 ~ 13 and Comparative examples 7 ~ ll
~ hydrogenated derivative of a block copolymer as
the fourth component of kind and quantity indicated in
Table 2, a crystalline propylene-ethylene random
copolymer as the fifth component of quantity indicated
in Table 2 and a non-crystalline ethylene-propylene
random copolymer of quantity indicated in Table 2
(Examples 11 to 13) were stirred by means of Henschel
mixer (trademark) for 3 minutes, followed by extruding
the mixture by means of a single screw extruder
(manufactured by Therrnoplastic Company) at 200C into
pellets. With the pellets, the melt flow rate (MFR)
indicated below was measured, and test pieces prepared
therefrom were subjected to various tes-ts.
lS Further, in the case of Comparative examples 7.~11,
the respective components of klnd and quantity indicated
in Table 2 were stirred in the same manner as ln Examples
9 ~13 to obtain pellets. With the pellets, the melt flow
rate was measured and various tests were carried out.
The results of the respective Examples and Comparative
examples are shown in Table 2.
.:
In addition, the respective components used in
the Examples and Comparative examples and the testing
methods employed therein will be described below.
:
~286~42
- 25 -
With regard to the blendiny components: -
Hydrogenated derivative of block copolymer
(the fourth component)
Hydrogenated product of SBS copolymer ("Kraton
G-1652", trademark of a product manufactured by
Shell Chemical Company; solution viscosity,
550 cps as measured in 20% by weight toluene
solution at 25C) and ("Kraton G-1650", trade-
mark of a product manufactured by the same
company; solution viscoslty, 1,100 cps as measured
in 20% by weight toluene solution at 25C)
Crystalline propylene-ethylene random copolymer
(the fifth component)
a crystalline propylene-'ethylene-butene~random
terpolymer (ethylene content 4.5% by;weight,
butene content;4.5% by weight) (MFR = 42 g/10 min.,
flexural~modulus = 6,000~ Kg f/c~m2).
Non-crystalline ethylene-propylene random c~opolymer
"EPO2P" (tradename of a p~roduct manufactured~by
Japan Synthetic Rubber Co., Ltd.) ~(Mooney
visaosity M104 = 24).
Propylene-ethylene block~ copolymer
(Ethylene content 12.5% by weight)~
~(MFR = 45 g/lO g)~
:, ~ '',` . ~,;: . , '' '
- ,. ; ' ~,: , ' ' :.
, . ::: , , : ,
~28~
26
With regard to testing methods:
MFR ~g~l0 min.)
according to JIS-K-6758 (load 2.16 Kg, 230C).
Flexural modulus tKg f/cm2)
according to JIS-K-7203 (23C)
Dupont impact strenqth (Chisso ~rocess~
This measurement method is the same as described
above.
Tear strenqth (Kg f/cm2)
according to JIS-K-6301 (23~C)
Appearance
Injection molding was carried out employing
IS200B type injection molding machine (tradename of
product manufactured by TOSHIBA MACHINE CO., LTD.), and
under conditions of
Mold: îlat plate of 400 x 80 x 3 mm
In~ection temperature: 230C
Mold temperature: 30C.
The appearance of the resulting flat plate was
judged by the naked eye, and when silver streaks or
flow marks were not observed, the~ appearance of the
molded product was regarded good. ~ ~
Moldability (mold-release characteristics)
Injection Imolding was carried out employing
IS200B type injection molding machine~ and under the
conditions of
~J ~
:. ', ~. ' ' -
, ' ~ ';' ,, ' :
- 27 -
Molding temperature: 230C
Injection pressure: 600 Kg f/cm
Pressure keeping and cooling~times:
20 sec.-20 sec.
Mold temperature: 30C
Mold: cage mold,
and the mold-release characteristlcs a~ the time
of injection molding was judged by naked eyes.
i: .
~28~
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