Note: Descriptions are shown in the official language in which they were submitted.
`~ 13~7~2
THERMOPJ.~STIC ELASTOMER COMPOSITIONS
BACKG~OUND OF I'HE INVENTION
The presen-t invention relates to a thermoplas-tic
elastomer composition and more particularly to a thermo-
plastic elastomer composition superior in fluidity,permanent set and ex-ternal appearance of molded articles
obtained therefrom.
As thermoplastic polyoleEin elastomers there are
known compos.itions comprising crystalline polyolefins such
as polyethylene and polypropylene as hard segments and
amorphous copolymer rubbers such as e~hylene/propylene
copolymer rubber (EPR) and ethylene/propylene/non-conju-
gated diene copolymer rubber (EPDM) as soft segments, as
well as compositions obtained :by partially crosslinking
the above compositions. It is also known to prepare hard
and soft segments according to a multi-stage polymeriza-
tion process r And by changing the proportions of those
segments there are ob-tained various grades of products
ranging from one superior in ~lexibility up to one having
rigidity.
Products of the flexibile grade are attracting great
attention because they can be applied as rubbery materials
widely to such uses as automobile parts, hoses, electric
wire coating and packing.
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` .. ' '
,~
'~ . ' . ` ' ~
~ 3 ~ 2
In preparing such flexible grade of products i-t is
necessary to increase the proportion of a soft segmen-t
(e.g. EPR or EPDM) and decrease that of a hard segment
~e.g. polyethylene or polypropylene) in order -to impart
rub~ery flexibility thereto.
However, such soft segments as EPR and EPDM are poor
in tensile strength and inferior in resistance to heat
and oil and also inferior in fluidity. Consequently,
flexi~le, thermoplastic elastomer compositions con-taining
large amounts of such soft segemnts also have the above-
mentioned drawback and cannot be applied to a wide variety
of uses. Increasing the hard segment proportion to remedy
these problems will result in loss of flexibility, deteri-
oration of physical propertles such as permanent set and
consequent impairmen-t of the function as a flexible,
thermoplastic elastomer.
More, in preparing a product of the flexible grade,
it is necessary to carry out polymeriza-tions separately
for hard and so~t segments, thus resulting in that not only
the polymerization apparatus becomes very complicated in
structure but also it is very difficult to control the
properties and proportion of each segment in each polymer-
ization stage and a de~ective product sometimes occurs at
the time of changeover from one to another grade.
1 3 ~ 2
Further, the recover of the resulting polymer is also
very difficult because a large amoun-t of a rubbery
component is contained therein.
The present inventors proposed a novel thermoplastic
elastomer composition to remedy the above problems.
It is, however, not so greatly improved in permanen-t
set and flexibility.
SUMMARY OF THE INVENTION
It is an object of the present invention is to over-
come the above mentioned problems.
It is another ob~ect of the present invention is to
provide a thermoplastic elastomer composition superior in
fluidity, permanent set, external appearance of molded
articles obtained therefrom, flexibility and heat resist-
ance and of which various physical properties are well-
balanced.
The present invention resides in a thermoplastic
elastomer composition obtained b~ crosslinking a composi-
tion comprising the following components (A1, (B) and (C)
using a phenolic curing agent:
(A) 30-70 parts by weight of an ethylene/~-olefin
copolymer prepared by copolymerizi`ng ethylene and an
~-olefin having 3 to 12 carbon a-toms in the presence of a
catalyst comprising a solid component and an organoaluminum
A
` : .
.: ` . . ;
~3~7~2
compound which solid component contains a-t least magne-
sium and titanium, said ethylene~-olefin copolymer having
-the following properties (I) to (IV):
(I) Melt index 0.01-lOOg/10 min
(II) Density 0.860-0.910 g/cm3
(III) Maximum peak
temperature as measured
according to a differen-
` tial scanning not lower than 100~C
calorimetry (DSC)
(IV) Insolubles in boiling
n-hexane not less than 10 wt.%
(B) 70-30 parts by weigh-t of a propylene polymer, and
(C) 70-150 parts by weight rbased on 100 parts by weight
of the components (A) and (B)~ of an ethylene/~- olefin/
non-conjugated diene copolymer rubber.
DETAILED DESCRIPTION OE~ THE PREFERRED EMBODIMENTS
(1) Ethylenek~-Olefin Copolymer (A)
In the ethylene/~-ole-Ein copolymer (A) used in the
present invention, the ~--olefin to be copolymerized with
ethylene is one having 3 to 12 carbon atoms. Examples
are propylene, butene-1, 4-methylpentene-1, hexene-1,
octene-1, decene 1 and dodecene-1. Particularly pre-
ferred are propylene, butene-1, 4-methylpentene-1 and
~3~7~2
hexene-1 which have 3 to 6 carbon atoms. It is prefer~
able that the ~-ole~in conten-t in the ethylene/~-olefin
copolymer be in the range to 5 to 40 mol~.
The ~ollowing ~escription is provided about how to
prepare -the ethylene/~-olefin copolymer ~A~ used in the
present invention.
The catalyst sys-tem used comprises a solid component
and an organoaluminum compound, the solid component
containing at least magnesium and titanium. For example~
the solid component is obtained by supporting a titanium
compound on an inorganic solid compound containing mag-
nesium by a known method. Examples of magnesium-containing
inorganic solid compounds include, in addition to metal
magnesium, magnesium hydroxide, ma~nesium carbonate,
magnesium oxide, magnesium chloride, as well as double
sal-ts, double oxides, carbonates, chlorides and hydrox-
ides, which contain magnesium atom and a metal selected
from silicon, aluminum and calcium Eurther, these inorganic
solid compounds after treatmen-t or reaction with oxygen-
con-taining compounds, sulfur-containing compounds,
aromatic hydrocarbons or halogen-containing substances
As examples of the above oxygen-containing compounds
are mentioned water and organic oxygen-containing
compounds such as alcohols, phenols, ketones, aldehydes,
carboxylic acids, esters, polysiloxanes and acid amides,
-- 5 --
'
. ~. ' . ' ~ ~. ' ' .
- . :
~3~7~2
as well as inorganic oxygen-containing compounds such
as metal alkoxides and metal oxychlorides. As examples
of -the above sul~ur-containing compounds are mentioned
organic sulfur-containing compounds such as thiols,
thio-ethers and the like, and inorganic sulfur-con-taining
compounds such as sulfur dioxide, sulfur trioxide,
sulfuric acid and the like. As examples of -the above
aromatic hydrocarbons are mentioned mono- and polycyclic
aromatic hydrocarhons such as benzene, toluene, xylene,
anthracene and phenanthrene. As examples of the above
halogen-con-taining compounds are mentioned chlorine,
hydro,gen chloride, metal chlorides and organic halides.
To illus-trate the titanium compound, mention may be
made of halides, alkoxyhalides, alkoxides and halogenated
oxides, of titanium. Tetravalent and trivalent titanium
compounds are pre~erred. As tetravalent titanium com-
pounds are preferred those represented by the general
formual Ti(OR)nX4 n wherein R is an alkyl, aryl or aralkyl
group having 1 to 20 carbon atoms, X is a halogen atom
and n is 0 ~ n ~ 4, such as, ~or example, titanium tetra-
chloride, ti-tanium tetrabromidel titanium tetraioxide,
monomethoxytrichlorotitanium, dimethoxydichloroti-tanium,
trimethoxymonochlorititanium, tetramethoxytitanium,
monoethoxytrichlorotitanium, diethoxydichlorotitanium,
triethoxymonochloro-titanium, tetraethoxytitanium,
-- 6 --
,,. .. , :
13~7~2
monoisopropoxytrichloro-titanium, diisopropoxydichloro-
titatium, triisopropoxymonochlorotitaniu~, tetra
isopropoxytitanium, monobutoxytrichlorotitanium,
dibutoxydichlorotitanium, monopentoxytrichloro-titanium,
monophenoxytrichlorotitanium, diphenoxydichlorotitanium,
triphenoxymonochlorotitanium and tetraphenoxytitanium.
As examples of trivalen-t titanium compounds are mentioned
titanium trihalides such as titanium tetrachloride and
ti-tanium tetrabromide reduced with hydrogen, aluminum,
titanium or an organometallic compound of a Group I-III
metal in the Periodic Table, as well as trivalent
titanium compounds obtained by reducing tetravalent
alkoxytitanium halides o~ the general formula
Ti~OR)mX4 m with an organometallic compound o~ a Group
I-III metal in -the Periodic Table in which ~ormula R is
an alkyl, aryl or aralkyl group having 1 to 20 carbon
atoms, X is a halogen a-tom and m is 0~ m c4.
Tetravalent titanium compounds are particularly preferred.
As pre~erred examples o~ catalyst systems are
mentioned combinations o~ organoaluminum compounds with
such solid components as MgO-RX-TiCl4 (Japanese Patent
Publication No. 3514-1976), Mg-SiCl4-ROH-TiCl4 (Japanese
Patent Publication No. 23864/1975), MgCl2-Al(OR)3-TiCl4
(Japanese Patent Publication Nos. 152/1976 and 15111/1977),
MgCl2-SiCl4-ROH-TiCl4 ~Japanese Patent Laid Open No.
-- 7 --
- ~317~52
1065~1/1974), Mg(OOCR)2-~l(OR)3-TiC14 (Japanese Patent
Publication No. 11710/1977, Mg-POC13-TiC14 (~apanese
Patent Publication No. 153/1976), MgCl2-AlOCl~TiCl4
(Japanese Patent Publica-tion No. 15316/1979) and
MgCl~~~l(R)cX3_n-SitORI)mX4_m-TiC14 (Japanese Patent
Laid Open No. 95909/1981), in which formulae R and R'
are each an organic radical and X is a halogen atom.
As other examples of catalyst systems are mentioned
combinations of organoaluminum compounds wi-th reaction
products as solid components obtained by the reaction of
organomagnesium compounds such as so-called Grignard
compounds with titanium compounds. Examples of organo-
magnesium compounds are those of the general formulae
RMgX, R2Mg and RMg(OR) wherein R is an organic radical
having 1 to 20 carbon atoms and X is a halogen atom, and
ether complexes thereof, as well as modified compounds
obtained by modifying these organomagnesium compounds with
other organometallic compounds such as, for example,
organosodium, organolithium, organopotassium, organoboron,
organocalcium~and organozinc.
More concrete examples of such catalyst systems are
combinations of organoaluminum compounds with such solid
components as RMgX-TiC14 (Japanese Patent Publication
No. 39470/1975), RMgX-phenol-TiC14 (Japanese Patent
Publication No. 12953/1979), RMgX-halogenated phenol-
`:
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```` 13~7~2
TiCl4 (Japanese Patent Publication No. 12954/1979) and
RMgX-CO2-TiCl4 (Japanese Patent Laid Open No. 73009/1982).
As still other examples of catalyst systems are
mentioned combinations oE organoaluminum compounds with
solid products obtained by contacting such inorganic
oxides as SiO2 and Al2O3 with the solid component
containing at least magnesium and titanium. In addition
to SiO2 and Al2O3 there also may be mentioned CaO, B2O3
and SnO2 as examples of inorganic oxides. Double oxides
thereof are also employable without any trouble. For
contacting these inorganic oxides with the solid compo-
nent containing magnesium and titanium, there may be
adopted a known method. For example, both may be reacted
at a temperature of 20 -to 400C, preferably 50 to 300C,
usually for 5 minutes to 20 hours, in the presence or
absence of an inert solvent, or both may be subjected to a
co-pulverization treatment, or there may be adopted a
suitable combination of these methods.
As more concrete examples of such ca~alyst systems r
mention may be made of combination of organoaluminum
compounds with SiO2-ROH-MgCl2-TiCl4 (Japanese Patent Laid
Open No. 47407/1981), SiO2-R-O-R'-MgO-AlCl3-TiCl4
~Japanese Patent Laid Open No. 187305/198~ and SiO2-
MgCl2-Al(OR)3-TiCl4-Si(OR')4 (Japanese Patent Laid Open
No. 21405/1983) in which formulae R and R' are each a
hydrocarbon radical.
_ g _
..... . . . . . .
-"` 131~2
In these catalyst systems -the titanium compounds
may be used as adduc-ts with organocarboxylic acid esters,
and the magnesium-containing inorganic solid compounds
may be used after contact treatment wiht organic
carboxylic acid esters. Moreover, the organoaluminum
compounds may be used as adducts with organocarboxylic
acid esters. Further, the catalyst systems may be pre-
pared in the presence of organic carboxylic acid esters.
As organic carboxylic acid esters there may be used
various aliphatic, alicyclic and aromatic carboxylic acid
esters, preferably aromatic carboxylic acid esters having
7 to 12 carbon atoms. Examples are alkyl esters such as
methyl and ethyl of benzoic, anisic and toluic acids.
As preferred examples of the organoaluminum compound
to be combined with the solid component are mentioned those
represented by the general formulae R3Al, R2AlX, RAlX2 r
R2AlOR, RAltOR~X and R3Al~X3 wherein Rs, which may the
same or different, are each an alkyl, aryl or aralkyl
group having 1 to 20 carbon atoms, such as triethylalumi-
num, triisobutylaluminum, trlhexylaluminum, trioctyl-
aluminum, diethylaluminum chloride, diethylaluminum
ethoxide, ethylaluminum sesquichloride, and mixtures
thereof.
The amount o~ the organoaluminum compound used is
not specially limited, but usually it is in the range of
0.1 to 1,000 mols per mol of the titanium compound.
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. ~
3~7~2
The catalyst sys-tem exemplified above may be
contacted with an ~-olefin before it is used in the
polymerization reaction. By so doing, a stabler oper-
ation is ensured as compared with the case where it ls
not so treated.
The polymerization reac-tion is carried out in the
same manner as in the conventional olefin polymerization
reaction using a Ziegler type catalyst. More particularly,
the reaction is performed in a substantially oxygen~ and
water-free condition in vapor phase or in the presence of
an inert solvent or using monomer per se as solvent.
Olefin polymerizing conditions involve temperatures in the
range oE 20 to 300C, preferably 40 to 200Cr and
pressure in the range from normal pressure to 70 kg/cm2~G,
preferably 2 kg/cm2~G or 60 kg/cm2~G. The molecular
weigh-t can be adjusted to some extent by changing poly-
merization conditions such as polymerization temperature
and catalyst mol ratio, but the addition o~ hydrogen into
the polymerization system is more effective for this
purpose. Of course, two or more multi-stage polymerization
reactions involving different polymerization conditions
such as different hydro~en concentrations and different
polymerization temperatures can be carried out withou-t
any trouble.
.. . . . .
`
~3~L7~52
~he melt flow rate MFR, according to JIS K 7210, test
condition No. 4 (190C, 2.16 kgf) of the ethylene/-olefin
copolymer (A) thus prepared is in the range o~ 0.01 to
100 g/10 min, preferably 0.1 to 50 g/10 min. Its density
(accordin~ to JIS K 7112) is in the range of 0.860 to
0.910 g/cm3, preferably 0.870 to 0.905 g/cm3 and more
preferably 0.~70 to 0.900 g/cm3. Its maximum peak temper-
ature (Tm) measured according to a differential scanning
calorimetry (DSC) is not lower than 100C, preferably
not lower than 110C. Its insolubles in boiling n-hexane
are not less than 10 wt.%, preferably 20-~5 wt~ and more
preferably 20-90 wt.%.
If MFR of the ethylene/~-olefin copolymer (A) is
less than 0.01 g/10 min, MFR of the thermoplastic elas~
tomer composition will become too low, resulting in
deterioration of its Eluidity. And i~ it exceeds lO0 g/lO
min, the tensile strength will be ruduced. A density
thereof lower than 0.~60 g/cm3 would result in lowering
of tensile strength,surface stickiness of the composition
and impairmen-t o~ the appearance. A density of the
copolymer exceeding 0.910 g/cm3 is not desirable, because
it would cause deterioration of ~lexibility and trans-
parency. A maximum pea~ temperature thereof as measured
according to DSC of lower than 100C is no-t desirable,
either, because it would result in lowering of tensile
strength, surface stickiness of the composition and
reduced resistance to heat.
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~ 3 ~ 2
If the proportion of insolubles in boiling n-hexane is
smaller than 10 w~.%, the resulting composition will be
reduced in tensile strength and become sticky on i-ts
surface, and thus such a proportion is undesirable.
(2) Propylene Polymer (B)
As examples of -the propylene polymer (B) used in
the present invention there are mentioned not only a
homopolymer of propylene but also block and random
copolymers of propylene and other comonomers. Preferred
as the comonomers are ~-olefins having 2 to 8 carbon
atoms such as, Eor example, ethylene, butane-l, hexene-l,
4-met~ylpentene-1, and octene-l. Preferably, these
comonomers are present in proportions not larger than
30 mol% in the copolymers.
The melt flow rate (MFR, according to JIS K 7210,
test condition Mo. 14 ) of the pxopylene polymer may be
in the range of 0.1 to 100 g/10 min, preferably 0.1 to
50 9/10 min, more preferably 0.5 to 20 g/10 min. If MFR
is smaller than 0.1 g/10 min, it will be impossible to
obtain a resin composition having good fluidity, and i~
MFR exceeds 100 g/10 min, it will result in reduced tensile
strength and impact strength.
- 13 -
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`` 13~70~
(3) Ethylenek~-Olefin/Non-Conjugated Diene Copolymer
Rubber (C)
In the ethylene/~-olefin/non-conjugated diene
copolymer rubber (C), examples of -the ~-olefin are
propylene, butene-1, pentene-1, 4-methylpentene-1,
hexene-1 and octene-1, with propylene being particularly
preferred.
Examples of the non-conjugated diene are 1,4-
hexadiene, 1,6-octadiene, dicyclopentadiene, vinyl
norbornene and ethylidene norbornene, with 1,4-
hexadiene and ethylidene norbornene being preferred.
The ethylenek~-olefin/non-conjugated diene copolymer
rubber used in the invention has a Mooney viscosity
!ML1~4, 100C) of 10 to 95. A Mooney viscosity thereof
lower than 10 is not desirable because it would result in
reduced tensile strength or stlcky surface of the thermo-
plastic elastomer composition. A Mooney viscosity of the
copolymer rubber exceeding 95 is also undesirable because
it will lead to deterioration in the flow property of the
thermoplastic elastomer composition.
:: The iodine value lthe degree of unsaturation) of the
ethylene/~-olefin/non-conjugated diene copolymer is
preferably in the range of S to 30. If the iodine value
is smaller than 5, it would cause reduction of physical
properties of the thermoplastic:elastomer composition.
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~3~70~
If it exceeds 30, i-t would cause reduction of resistance
to heat aging property.
(4) Composition Ra-tio (Mixing Ratio)
The composition ratios of the ethy]ene/~-olefin
copolymer (A) rhereinaf-ter referred to as component (A)J
the propylene polymer (B) [hereinafter referred to as
componen-t (B)~ and the e-thylene/~-olefin/non-conjugated
diene copolymer rubber (C) Lhereinafter referred to as
component (C)~ in the thermoplastic elastomer composition
of the present invention are 30-70 parts, preferably
40-60 parts, by weight of component (A), 70-30 parts,
preferably 60-40 parts, by weigh-t of component (B), and
70-150 parts, preferably 80-120 parts, by weiyht based on
100 parts by weight of components (A) and (B), of compo-
nent (C).
If the proportion of component (A) exceeds 70 partsby weight, -the heat resistance and fluidity will be
reducedl and if it is smaller t:han 30 parts by weight,
the flexlbillty and permanent elongation will be reduced.
If the proportion of component IB) exceeding 70% by
weight, the flexibility and permanent elongation will
be reduced, and if it is smaller than 30 parts by weight,
the heat resistance and fluidity will be reduced.
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, . . ..
~317~
Further, if the proportion of componen-t (C) is
smaller than 70 parts by weight based on 100 parts by
weight of eomponents (A) and (B), the ~lexibility and
permanent elongation will be exceeds 150 parts by weight,
reduced, and if it -the heat resistance strength will be
reduced.
(S) Preparation o~ the Thermoplastic Elastomer
Composition
E~or preparing the thermoplastic elas-tomer composi-
tion of the present invention~ the components (A), (B~ and
~C) may be mixed together in predetermined proportionsfollowed by crosslinking by using a phenolic curing agent.
The mixing and crosslinking may be e~fected by any
known method. A typical example is a mechanical melt-
kneading me-thod which is carried out under the addition
of a phenolic curing agent to the above mixture. According
to this known method, the crosslinkiny can be e~fected
using any of uni- and biaxial extruders, Bambury's mixer,
various kneaders and rolls. The melt-kneading temperature
is usually in the range o~ 100 to 250C.
As the phenomic curing agent there may be used resol
type phenolic resins which have been conventionally used
for curing rubbers such as bu-tyl rubber. As preferred
examples are mentioned oligomers (e.g. dimer, trimer,
tetramér) of alkyl methylol phenols such as tertiary-
- 16 -
~ 13~7~
butyl methylol phenol, ~,~,~ tetramethylbutyl methylol
phenol, dodecyl methylol phenol, eicosyl methylol phenol
and -the like. The crosslinking may be perormed more
efficiently by using a crosslinking accelera-tor together
with the phenolic curing agent. Preferred example of
the crosslinking accelerator are metal oxides such as
zinc oxide, titanium oxide and magnesium oxide, metal
chlorides such as stannous chloride and ferric chloride.
The amount o the phenolic curing agent used differs
according to the performance required for the thermo-
plastic elastomer composition, but is usually in the
range of 0.5 -to 10 parts by weight, preferably 1 to 5
parts by weight.
If a conventional organic ~eroxide is used instead
o the phenolic curing agent. The objects o the present
invention are not attained.
The percent insolubles in boiling xylene ~gel per-
centage) which is determined after extracting the thermo-
plas-tic elastomer composition of the present invention
thus obtained by crosslinking using the phenolic curing
agent, with boiling xylene fox 5 hours, is in the range
o 3 to 60 wt.~, preferably 10 to 50 wt.~. If the gel
percentage is smaller than 3 wt.~, the heat resistance
and the oil resistance will become poor, and a gel per-
centage exceeding 60 wt.~ will result in reducedfluidity and elongation.
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.. .. .
.. ~ .~ .
1 3 ~
Be~ore or after crosslinking, or during crosslinkiny
(particularly during melt-kneading), there may be added,
if necessary, fillers such as carbon black, clay, talc,
calcium carbonate, silica, metallic fibers and carbon
fibers, as well as additives such as antioxidant, flame
retardant and coloring agent, and parafEinic, naphthenic
or aromatic mineral oils for assisting the despersion o~
the fillers and enhancing flexibility and elasticity.
Further, various kinds of resins and rubbers may
be added, i~ necessary, in amoun-ts not causing a change
in performance of the thermoplastic elastomer composition
of the present invention; for example, crystalline
polyolefins such as high and low density polyethylenes
and linear low density polyethylenes, natural and synthetic
rubbers, and styrene-based thermoplastic elastomers.
The thermoplastic elastomer composition of the
present invention has the Eollowing characteristics.
(a) Superlor in 1uidity, so easy to mold, giving
molded produc-ts having good appearance.
(b) Superior in heat and oil resistance.
tc) Small permanent elon~ation makes deformation
dif~icult.
(d) Superior in flexibility.
(e) Low dnesity and very light weight.
Since the thermoplastic elastomer composition o~ the
present invention has such excellent characteristics, its
- 18 -
~17~!~2
application range is extremely wide. The following are
applica-tion examples thereof:
(a) au-tomobile interior sheet, mud guard, lace and
cover
(b) electric wire coating material
(c) components of various electric appliances
(d) hose
(e) various packing
(f) window frame sealing material
(g) sound insulating material
(h) modifier for various polymers
~The ~ollowing examples are given to further illus-
trate the present invention, but the invention is notlimited thereto. In the following working examples and
comparative examples, physical proper-ties were measured
in the Eollowing manner.
LMeasuremerl-t by DSC~
A hot-pressed 100 ~m thick film as a specimen is
hea-ted to 170C and held at this temperature for 15
minutes, followed by cooling to 0C at a rate of 2~5C/
min. Then, from this state the temperature is raised to
l70C at a rate oE 10C/min and.measurement is made. The
vertex positlon of the maximum peak of peaks appearing
during the hea~-up period from 0 to 170C is regarded as
the maximum peak temperature (Tm).
~ .
- 19 -
~ ~ 3~7~
~How to Determine Insolubles in Boiling n-Hexane~
A 200 ,um thick sheet is formed using a hot press
from which are then cut out three sheets each 20 mm long
by 30 mm wide. Using these sheets, extraction is made in
boiling n-hexane for 5 hours by means of a double-tube
type Soxhlet extractor. n-Hexane insolubles are taken
out and vacuum-dried (50C, 7 hours), then the percen-tage
insolubles (C6 insoluble) in boiling n-hexane is calcu-
lated in accordance with the following equa-tion:
Insolubles in
- 10 boiling n-hexane = Weight of extracted sheet
(wt.~) Weight of unextracted sheet
x 100 (wt.~)
rPreparing Test SheetJ
Each resin composition obtained is placed in a
mold 2 mm thick, 150 mm long and 150 mm wide, preheated
a-t 210C for 5 minutés, then pressure-molded for 5
minutes at the same temperature and at 150 kgjcm2, and
thereafter cooled Eor 10 mlnutes a-t 30C under the
pressure of 150 kg/cm2, followed ~y annealing at 50C for
20 hours and allowing to stand at room temperature for 24
hours. Thereafter, physical properties are measured.
CMelt Flow Rate~
~ IS K 7210 test condition No. 14 (230C, 2.16 kgf)
is used.
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.
::
:
~ . ' '
~3~7~
Moreover, another condition (230C and 21.6 kgf) which is
closer to the shear rate in a molding operation is used.
The latter reflec-ts fluidi-ty in practical point of
view more preferably.
~ensile Test~
Test piece is prepared using No. 3 dumbbell in
accordance with JIS K 6301 and it is measured Eor tensile
strength at a pulling rate of 50 mm/min.
fPermanen-t Elongatio~
Test piece is prepared using No. 3 dumbbell in
accordance with JIS K 6301. It is held at 100% elongated
state for 10 minutes, then contrac-ted suddenly and allowed
to stand or 10 minutes to check a percen-tage elongation,
from which is determined a permanent elongation.
[Vicat Sof-tening Point~
A 3mm thick specimen is prepared in accordance with
the test sheet preparing method and it is used ~or
measurement. A heat -transfer medium is heated at a rate
of 50C/min while applying a load of 250 g through a
needle-like indenter placed perpendicularly to the speci-
men in a heating ba-th, and the temperature of the heat
transfer medium at the time when the needle-like indenter
permeated 1 mm is regarded as a Vicat softening point.
7~2
rHardness.~
Test piece is prepared in accordance with JIS K
6301 and measured for hardness using type A tes-t machine.
[Gel Percentage~
A 200 ~lm thick sheet is prepared using a hot press
(at 200C for 5 minutes), from which three 40mm x 20mm
shee-ts are cut out. The three shee-ts are each placed
in a 120-mesh wire gauz~ bag and extrac-ted in boiling
xylene for 5 hours using a double-tube type Soxhlet
extractor. Boiling xylene insolubles are taken out and
vacuum-dried (80C, 7 hours) to determine the boiling
xylene insolubles as a gel percentage.
~xternal Appearance oE Extruded Article~
When MFR is measured at 230C and at 21.6 kgf, the
surface condition of an extruded product is observed
visually.
~ : very good
O : good
~ : slightly bad
X : bad
Components lA) to (C) used in the following Examples
and Comparative Examples are as follows:
~Preparing of Component (A~
An ethylene/butene~1 copolymer (A-1) was prepared by
copolymerizing ehtylene and butene-1 in the presence of
a catalyst comprising a solid ca-talyst component and
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-trie-thylaluminum, the solid catalyst component having
been obtained from a substantially anhydrous magnesium
chloride, 1,2-dichloroethane and titanium te-trachloride.
The ethylene/bu-tene-1 copolymer (A-1) thus ob-tained
was found to have an ethylene con-tent of 88.3 mol%, MER
of 0.9 g/10 min, a density of 0.896 g/cm3, Tm of 119.8C
and a C6 insolubles content of 82 wk.%.
rPreparation of Component (A-2)J
An ethylene/bu-tene-1 copolymer (A-2) was prepared
by copolymerizing ethylene and butene-1 in the presence
of a catalyst comprising a solid catalyst component and
triethylaluminum, the solid catalyst component having been
obtained froma substan-tially anhydrous magnesium chloride,
anthracene and titanium -tetrachloride.
The ethylene/butene-1 copo:Lymer (A-2) thus obtained
was found to have an ethylene content of 85.3 mol%, MFR
of 1.0 g/10 min, a density of 0.890 g/cm3, Tm of 121.6C
and a C6 insolubles content of 58 w-t.%.
~Component (B)~
The characteristics of -two polypropylenes
~Components (B-1) and (B-2)¦ used are as follows:
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EthyTene _
Component Polymerization Content MFR
. . (Mol%) 9/10 min
(B - 1) Random copolymeri- 5.9 7
ration with ethylene
(B 2) Block copolymeri- 3.3 8
~ation with ethylene
. _
~Component (C)]
The characteristics of two ethylene/~-olefin/non-
conjugated diene copolymer rubbers ~EP 57P and EP 27P
(both are products of Japan Synthetic Rubber Co., Ltd.
and re~erred to as (C - 1) and ~C - 2), respectively~
used are as follows.
Mooney Propylene .
10 Component ViscosityContent Iodlne
ML1~4,100C(wt%) a ue
(C - 1) 88 28 15
(C - 2) 47 43~ 15
(C - 31 24 26 0
Examples 1 to 5
Componen-ts (A), (B) and (C) in the proportion, stated
: ~ in Table l were blended and thereafter a predetermined
amount o~ a phenolic curing agent was added and dry-
blended.
.
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Then the resultant mixture was introduced into a Banbury's
mixer prehea-ted to 200C, in which kneading was performed
for 20 minutes at 40 rpm t.o obtain a thermoplastic
elastomer composition.
The physical properties thereof were measured and
are shown in Table 1.
Comparative ~xample 1
The procedure of Example 1 was repeated except that
the phenolic curing agent was replaced by 0.5 part by
weight of di(tertiary-butyl peroxy)diisopropylbenzene.
Physical properties of the resultant composition
was measured, the results of which are as shown in Table 2.
Comparative Example 2
The procedure of ~xample 1 was repeated except that
the phenolic curing agent was not added. The results
are as shown in Table 2.
Comparative Examples 3 and 4
- Components ~A), (B) and IC) in the proportions stated
in Table 2 were blended and thereafter a predetermined
amount of a phenolic curing agent was added and dry-
blended. Then the resultant mixture was introduced into
a Banbury's mixer preheated to 200C, in which kneading
wa~ perEormed for 20 minutes a-t 40 rpm to obtain a
thermoplastic elastomer composition.
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The results are as shown in Table 2.
Examples 6 to 8 and Comparative Example 5
Composi-tions (A), (B~ and (C) and a phenolic curing
agent in the proportions stated in Tables 1 and 2 were
dry-blended and then introduced into a Banbury's mixer
preheated to 200C, in which kneading was per~ormed ~or
S minutes at 40 rpm. Then 5 parts by weight of titanium
oxide and 1.5 parts by weight of stannous chloride(bo-th
are crosslinking accelerators1 were added and kneading
was per~ormed again for 10 minutes to obtain a thermo-
plastic elastomer. The results are as shown in Tables
1 and 2~.
Examples 9 and 10
Compositions (~), (B) and ~C) and phenolic curing
agent in the proportions stated in Table 1 were blended
and th~n 20 parts by weight o~ cIay was added and dry-
blended. Then the resultant mixture was introduced into
a Banbury's mixer preheated to 200C, in which kneading
was performed at 40 rpm for 15 minu-tes while gradually
adding 60 parts by weight of a processin~ oil ("KOMOREX
300", a product of Nippon Oil Co., Ltd.) to obtain a
thermoplastic elastomer composition. The resul-ts are
as shown in Table 1.
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