CA1329437C - Cycloolefin type random copolymer compositions - Google Patents

Abstract

ABSTRACT
In accordance with the present invention, there are provided cycloolefin type random copolymer compositions excellent in heat resistance, chemical resistance, rigidity, impact resistance, etc., which comprise (A) a cycloolefin type random copolymer containing 40-85 mol%
of an ethylene component and 60-15 mol% of a cycloolefin component represented by the following general formula [I] or [II] and having an intrinsic viscosity [?] of 0.05-10 dl/g as measured at 135°C in decalin and a softening temperature (TMA) of not lower than 70°C, and (B) one or more non-rigid copolymers selected from the group consisting of:
(i) a cycloolefin type random copolymer containing an ethylene component, at least one other .alpha.-olefin component and a cycloolefin component and having an intrinsic viscosity [?] of 0.01-10 dl/g as measured at 135°C in decalin and a softening temperature (TMA) of below 70°C, (ii) a non-crystalline to low crystalline .alpha.-olefin type elastomeric copolymer formed from at least two .alpha.-olefins having a crystallinity index as measured by X-ray diffractometry of 0-50%, (iii) an .alpha.-olefin-diene type elastomeric copolymer formed from at least two .alpha.-olefins and at least one non-conjugated diene, and (iv) an aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof, and optionally (C) an inorganic filler or organic filler:

General formula [I]

[II]

wherein n and m are each 0 or a positive integer, ? is an integer of at least 3, and R1 to R10 each represents hydrogen atom, halogen atom or hydrocarbon group.

Description

132~437 TITLE
CYCLOOLEFIN TYPE RANDOM COPOLYMER COMPOSITIONS

FI~LD OF TH~ INV~NTION
This invention relates to cycloolefin type random copolymer compositions which are excellent in heat resistance, heat ageing characteristics, chemical resistance, solvent resistance, dielectric characteristics and rigidity as well as in impact resistance.

BACKGROUND OF THE INVENTION
Known as synthetic resins having well-balanced properties between rigidity and impact strength are polycarbonate~, ABS (acrylonitrile-butadiene-styrene compositions), etc. For instance, polycarbonates are resins which are excellent in rigidity as well as in heat resistance, heat ageing characteristics and impact strength. However, polycarbonates involve such a problem that they are poor in chemical resistance as they are easily attacked by strong alkali. Further, they have high water absorption. Though ABS are excellent in mechanical properties, they have such problems that they are poor in chemical resistance and further, because of double bonds in their molecular structure they are poor in weather resistance and heat resistance.

." ,- , ~ , " ~ , --~ r On one hand, polyolefins which are widely used as general-purpose resins are excellent in chemical resistance and solvent resistance. However, many of polyolefins are poor in heat resistance, insufficient in crystallizability and poor in rigidity. In general, to improve polyolefins in rigidity and heat resistance, there is employed a procedure in whlch nucleating agents are incorporated into polyolefins to expedite the growth of crystal, or a procedure in which polyolefins are gradually cooled to accelerate the growth of crystal. However, it is hard to say that the alleged effects obtained by these procedures are sufficient. The procedure of incorporating into polyolefins a third component such as nucleating agents rather involves the risk of marring various excellent properties inherent in polyolefins, and the gradually cooling procedure is low in production efficiency and involves the risk of lo~ering impact strength as the non-crystalline part of polyolefins decreases.
A copolymer of ethylene and 2,3-dihydroxy-dicyclopentadiene has been disclosed as an example of copoly~ers of ethylene and bulky comonomers, for example, in U.S. Patent No. 2,883,372. However, this copolymer is poor in heat resistance as it has a glass transition temperature in the vicinity of 100C, though said ., , ~ . .

copolymer is well balanced between rigidity and transparency. Similar drawback is also observed in copolymers of ethylene and 5-ethylidene-2-norbornene.
Japanese Patent Publn. No. 14910/19~1 proposes a homopolymer of 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene. The proposed poly~er, however, is poor in heat resistance and heat ageing characteristics.
Japanese Patent L-O-P Publn. No. 12~728/19B3 further proposes a homopolymer of 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene or copolymers of said cycloolefin and norbornene type comonomers, which are apparently those obtained by ring opening polymerization (ring opening polymers) in light of the disclosure in said publication. These ring opening polymers which have unsaturated bonds in the polymer main chains, however, have such a drawback that they are poor in heat resistance and heat agelng characteristics.
In the course of these researches, we found that cycloolefin type random copolymers of ethylene and bulky cycloolefins are synthetic resins which are excellent in heat resistance as well as in heat ageing characteristics, chemical resistance, solvent resistance, dielectric characteristics and rigidity. On the basis of the above findings, we have already made various technical proposals as disclosed in Japanese Patent L-O-P Publn. No.

.: : - ~: . . - . . .:

, , . - ~ : . . ; ~

~329~37 168708~1985 and Japanese Patent Appln. Nos. 220550/1984, ~36828/1984, 236829/~984, 242336/1984 and 95906/lg86. In spite of their being olefin type polymers, the cycloolefin type random copolymers as proposed are excellent in heat resistance and rigidity. However, they involve such problems that they are brittle and poor in impact resistance.
We have made studies to improve the rigidity and impact resistance of cycloolefin type random copolymers without detriment to their excellent heat resistance, heat ageing characteristics, chemical resistance, solvent resistance and dielectric characteristics. As a result, we have found that compositions consisting of a cycloolefin type random copolymer having a specific softening temperature (TMA) and at least one specific non-rigid copolymer or compositions obtained by blending inorganic filler and/or organic filler with said composition consisting of said random copolymer and said non-rigid copolymer have the above-described excellent characteristics. This invention has been performed on the basis of the ab~ve findings.

OBJBCT OF THE INVBNTION
The present invention is intended to solve such problems associated with the prior art as mentioned above - . : .......... . , ~: . , -:.:; , , .- : : :

: : . . : : . : . . : ~ : . .:

1 3 2 9 ~ 3 rl and an object of the invention is to provide cycloolefin type random copolymer compositions which are excellent in heat resistance, heat ageing characteristics, solvent resistance and dielectric characteristics as well as in rigidity and impact resistance.

DISCLOS~RE OF TH~ INVENTION
The first cycloolefin type random copolymer compositions of the present invention are characterized by comprising ~A~ a cycloolefin type random copolymer containing an ethylene component and a cycloolefin component represented by the following general formula ~I~ or [II] and having an intrinsic viscosity ~ of 0.05-10 dl/g as measured at 135 C in decalin and a softening temperature (TMA) of not lower than 70C, and (B) one or more non-rigid copolymers selected from the group consisting of:
(i) a cycloolefin type random copolymer containing an ethylene component, at least one otherG~-olefin component and a cycloolefin component represented by the following general formula ~I~ or [II] and having an intrinsic viscosity [~] of 0.01-10 dl/g as measured at 135C in decalin and a softening temperature ~TMA) of below 70 C, 132~4~7 (ii) a non-crystalline to low crystalline ~-olefin type elastomeric copolymer formed from at least two ~-olefins, (iii) anO~-olefin-diene type elastomeric copolymer formed from at least two ~~olefins and at least one non-conjugated diene, and (iv) an aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof, the total amount of said (B) component being 5 to 100 parts by wei~ht based on 100 parts by weight of said (A~
component.
The second cycloolefin type random copolymer compositions are characterized by comprising (A) a cycloolefin type random copolymer containing an ethylene component and a cycloolefin component represented by the following general formula [I] or [II] and having an intrinsic viscosity ~ of 0.05-10 dl/g as measured at 135 C in decalin and a softenin~ temperature tTMA~ of not lower than 70C, (B) one or more non-rigid copolymers selected from the group consisting of:
(i) a cycloolefin type random copolymer containing an ethylene component, at least one otherC~-olefin component and a cycloolefin component represented by the follo~ing general formula ~I] or tII~ and :: , having an intrinsic viscosity ~] of 0.01-10 dl/g as measured at 135C in decalin and a soft~ning temperature (TMA) of below 70 C, (ii) a non-crystalline to low crystalline ~-olefin type elastomeric copolymer formed from at least two ~-olefins, (iii) an ~-olefin-diene type elastomeric copolymer formed from at least two ~-olefins and at least one non-conjugated diene, and (iv) an aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof, and (C) an inorganic filler component or an organic filler component, the total amount of said (B) component beiny 1 to 100 parts by weight based on 100 parts by weight of said (A) component and the amount of said (C) component being 1 to 100 parts by weight based on 100 parts by weight of said (A) component.

.. . ........ . ...... . . . .

. . . .

1329~37 General formula R ~
R~ R9 n ~C-R~ ~ Q

R' R8 m wherein n and m are each O or a positive integer, ~ is an integer of at least 3, and R to R each represent hydrogen atom, halogen atom or hydrocarbon group.
The first cycloolefin type random copolymer compositions of the present invention comprise said (A) component and said (B) component in a proportion o~ 5-100 parts by weight of said (B) component per 100 parts by weight of said ~A) component so that they are excellent in heat resistance, heat ageing characteristics, chemical ~-- , , ,:

~. ~

~329437 resistance, solvent resistance, dielectric characteristics and rigidity as well as in impact resistance.
The second cycloolefin type random copolymer compositions of the present invention comprise said (A) co~ponent, said (B) component and said (C) component in proportions of 1-100 parts by weight of said (B) component and 1-100 parts by weight of said (C) component per 100 parts by weight of said (A) composition so that they are excellent in heat resistance, heat ageing characteristics, chemical resistance, solvent resistance and dielectric characteristics as well as in impact resistance.

BRIEF D~SCRIPTION OF TH~ DR~WINGS
Figure 1 is a graph showing the relationship between the amount of the cycloolefin type random copolymer [B~(i) to be blended in the cycloolefin type random copolymer composition of the invention and the impact strength (IZ strength) of said composition.
Figure 2 is a graph showing the relationship between the amount of the cycloolefin random copolymer ~B](i) blended in the cycloolefin type random copolymer composition of the invention and the softening temperature ~TMA) of said composition.
Figure 3 $s a graph showing the relationship between the amount of the ~-olefin type random copolymer _ g _ : , ~B](ii) blended in the cycloolefin type random copolymer composition of the invention and the impact strength (IZ
strength) of said composition.
Figure 4 i5 a graph showing the relationship between the amount of theO~-olefin type random copolymer [B](ii) blended in the cycloolefin type random copolymer composition of the invention and the softening temperature (TMA) of said composition.
Figure 5 is a graph showing the relationship between the amount of theG~-olefin-diene type random copolymer ~B](iii~ blended in the cycloolefin type random copolymer composition of the invention and the lmpact strength (IZ strength) of said composition.
Figure 6 is a graph showing the relationship between the amount of the ~-olefin-diene type random copolymer tB](iii) blended in the cycloolefin type random copolymer composition and the softening temperature (TMA) of said composition.
Figure 7 i~ a graph showing the relationship between the amount of the aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof blended in the cycloolefin type random copolymer composition of the invention and the impact strength (IZ
strength) of said composition.
Figure 8 is a graph showing the relationship .. ~ . ...................... ..

~' . ' '' ~ ' : :: .'~ ' " , between the amount of the aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof blended in the cycloolefin type random copolymer composition of the invention and the softening temperature (TMA) of said composition.
Figure 9 is a graph showing the relationship between the total amount of two or more non-rigid copolymers (B) blended in the cycloolefin type random copolymer composition of the invention and the impact strength (IZ strength) of said composition.
Figure 10 is a graph showing the relationship between the total amount of the non-rigid copolymer (B) blended in the cycloolefin type random copolymer composition of the invention and the softening temperature of said composition.

D~TAILED D~SCRIPTION OF TH~ INV~NTION
The cycloolefin type random copolymer compositions of the present invention are illustrated below in detail.
In accordance with the present invention, there are provided cycloolefin type random copolymer compositions characterized by comprising (A) a cycloolefin type random copolymer containing an ethylene component and a cycloolefin component represented by the following general formula [I] or tII] and having an . . , ~ ~ , .

1329~37 intrinsic viscosity [~] of 0.01-10 dl/g as measured at 135 C in decalin and a softening temperature (TMA) of not lower than ~0C, and (B) one or more non-rigid copolymers selected from the group consisting of:
(i~ a cycloolefin type random copolymer containing an ethylene component, at least one other ~-olefin component and a cycloolefin component represented by the following general formula ~I] or ~II] and having an intrinsic viscosity ~] of 0.01-10 dl/g as measured at 135C in decalin and a softening temperature (TM~) of below ~0 C, (ii) a non-crystalline to low crystalline ~-olefin type elastomeric copolymer formed from at least two ~-olefin~, (iii) an~-olefin-diene type elasto~eric copolymer formed from at least twoC~-olefins and at least one non-conjugated diene, and ~iv) an aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof, the total amount of said (B) component being 5 to 100 ~:
parts by weight based on 100 parts by weight of said (A) component.

. : . . . . . ., ., . . .~ ... . . .

:.,: ,... , . . ~ , . . ,: . . .. . .. . .

1329~37 General formula !I]

R~ R~ n ~C R'~ )Q III]

R~ Rd m wherein n and m are each O or a positive integer, Q is an integer of at least 3, and R1 to R10 each represent hydrogen atom, halogen atom or hydrocarbon group.
The cycloolefin type random copolymer ~A] and ~B](i~ whicb constitute the cycloolefin type random copolymer compositions of the present invention are cycloolefin type random copolymers containing an ethylene component and a specific cycloolefin component. The said cycloolefin component is a cycloolefin component . :: . - : . . . . . . .

.

represented by the following general fo~mula [I] or [II], and in the cycl~olefin type random copolymers, said cycloolefin component forms a structure represented by the general formula [III] or [IV].
General formula R' R7 [ I

R' R8 n R' R' R' 1?.8 m wherein n and m are each O or a positive integer, ~ is an integer of at least 3, and R to R10 each represent hydrogen atom, halogen atom or hydrocarbon group.

~ 14 -U3 ~ R7 ~
[III]

R~ R8 n [IV]

R4 m wherein n, m, ~ and R1 to R10 are as defined above.
The cycloolefin, i.e. a constituent component of the cycloolefin type random copolymer as one component in the cycloolefin type copolymer composition of the present invention is at least one cycloolefin selected from the group consisting of unsaturated monomers represented by the general formulas tI] and ~II]. The cycloolefins represented by the genral formula tI] can be easily prepared by condensation of cyclopentadienes with r, : ' ': :, ': ~.: ., -', . ' '' ,, , ' ' ' ' , : , : : , i3~9~37 appropriate olefins by Diels-Alder reaction. Similarly, the cycloolefins represented by the general formula [II]
can be easily prepaxed by condensation of cyclopentadienes with appropriate cycloolefins by Diels-Alder reaction.
The cycloolefins represented by the general formula [I] in the concrete are such compounds as exemplified in Table 1, or in addition to lt4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, such octahydronaphthalenes as 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-di-methano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-propyl- . .
1,4,5,8-dimethano-1,2,3,4,4a,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-di~ethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene/ 2-cyclohexyl-1,4,5,8,dimethano-1,2,3,4,4a,5,8,8a~octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2- :
isobutyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-:,: .

1329~37 octahydronaphthalene, etc. and such compour~ds as exemplified in T~ble 2.

: ~ .. : . , ~ .

Taole 1 1329437 Chemical formula Compound name ~ Bicyclot2,2,l]hept-2-ene C~3 6-Methy1bicyc10~2,2,1~hept-2-e~e CX3 5,6-Dimethylbicyclo~2,2,l]hept-- CX3 2-ene CH
l-Methylbicyclo~2,2,l]hept-2-ene 2X5 6-~thylbicyclo~2,2,l]hept-2-ene / 4 9 6-n-Butylbicyclo~2,2,1]hept-2 ene iC4H9 6-Isobutylbicyclo~2,2,l~hept-2-ene ~/ ' ' ~ CH3 ~-~e~hy1bicyclc[2,2,1]hept-2-ene --./~' ' ' Ta~le 2 1329~37 Chemical for~ula Com~ound name 5,10-Dimethyltetracyclo-2.5 17.10] 3 dodecene C~3 C\~3 2,10-Dimethyltetracyclo-~4,4,0,1 ,1 ]-3-dodecene 11,12-Dimethyltetracyclo-[4l4lo~l2-5l17-lO]-3-dodecene ~3 CH3 2,7,9-Trimethyltetracyclo-. ~4 4 0 12.5 17.10] 3 dod~cene 2HS ~-3thyl-2,7-dimethyltetracyclo-~4 4 0 12.5 17 13] 3 dodecene c~3 2 3 3-Isobutyl-2,7-dimethyltetracyclo ~4,4,o,l2.5,17.10~_3_dodeCene c~3 _/q .- .

.,., , . . - . .
.. . . .

, . . .

Table 2 (continued) 13~437 `- `

/ 3 9,11,12-tri~ethyltetracyclo-3 ~ 3 [4,4,o,12 5,17 ~]-3-dodecene C~ 9-Ethyl-11,12-di~ethyltetracyclo-~4.4,0,12 5,1~ 1]-3-dodece~e CH CH(CH ) 3 ~ ~3 9-Isobutyl-11,12-dimethyltetra-cyclo~4,4,0,1 ,1 ]-3-dodecene 5,8,9,10-Itramethyltetracyclo ~4,4,0,1 ,1 ]-3-dodecene ~ 2 ~ 12 Hexacyclo~6t6~l~l3-6 110.13 5 ~ W o2.~ 09 14~-4-heptadecene 3 12-Methylhexacyclot6,6,1,13 6, 10.13 o2-7 o9~14~-4-heptadecene H~2-3thylhexacyclot6,6,1,13 3 o2-~ o9~l4]-~-heptadecene " ~ " ~ -Iqo~ utylhexacyclot6,6,1,13 , 10.13 o 2-7 o9 14~-4-heptadesene --?c : ~ . , ., , . - -, .

' ::: ~ ~ : : :

Table 2 (cor~tinued) 1 3 2 9 4 3 7 c~.~3 1,6,10-Trimethyl-12-isoDutyl-hexacycloC6,6,1 13-6 110-13 o2-7 CH3 CH3 0 ]-4-hep~adecene tacyclo[8~8~o~ 9~l4 7 13.16 o38 ol217]--~--docosene 3 lS-Methyloctacyclot8,8,0,12 14.~ 111.18 113.16 o3~8~ol2 5-docosene ~2H5 15-Ethyloctacyclota,8,0,12'g,14'2, 11.18 113.16 o3~8 ol2.17]_5_ docosene , . . . .

The cycloolefins represented by the general formula tII] in the concrete are such compounds a~
exemplified in Tables 3 and 4.

Table 3 1329437 Chemical formula Compound name CH~ CH3 1,3-Dimethylpentacyclo~6,6,1, 1,6-Dimethylpentacyclo~6,6,1,13 ~J o2 7~09 14]-4-hexadecene o~3 15,16-Dimethylpentacyclo~6,6,1, ~ W 13'6, o2 ~ ~ o9 14]-4-hexadecene 4 ~ 12 Pentacyclo~6,5,1,1 ,0 ,0 ~-. ~ ~ 11 4-pentadecene C~ CH
1,3-Dimethylpentacyclo[6,5,1,13 2.7 09-l3]-4-pentadecene 1,6-Dimethylpentacyclo~6,5,1, 13-6 o2-~ 09 13]-~-pentadecene 14,15-Dimethylpentacyclo~6,5,1, 1 5, 02 7, 09 - 13 ] -4-pentadecene -- Z3 -- :

: . - . . . . . ~ . . -- .

: Table 3 (continued~ 1329437 3 Pentacyclo~6,6,1,13 6,02 ~,09 14]-7 ~ 9 ~ 11 4-hexadecene ~ 3 ~ 1 ~ 6 15 Heptacyclo~8r7lo~l2-~ 14-7 111.17 6 ~ 14 03 8,o1 ]-5-eicosene 5 ~ 15 ~eptacyclo~8~8~o~l2-9~l4-~ .l8r I¦ >I >I )I Io3.8 ol2 17~-5-heneicosene 6 ~ 14 .

Table 4 1329437 Chemical formula Compound name 1 _ 9 Tricyclot4,3,0,12' ]-3-decene 4 ~J~8 2-Methyl-tricyclo[4,3,0,1 ~-3-decene ~ ~ 5-Methyl--tricycloC4,3,0,12'5~-;~ ~ 3-decene c~3 3l ~ Tricyclo[4,4,0,12 5]-3-undecene 10-Methyl-tricyclot4,4,0,12 5]-3-undecene --2~

.~ . . ... - ~, ... ` . ,. -, . . .

132g437 The cycloolefin type random copolymer ~A] as one component in the cycloolefin type random copolymer composition of the present invention contains as essential components an ethylene component and the aforementioned cycloolefin component as described above. In addition to said two essential components, however, the cycloolefin type random copolymer [A] may optionally contain other copolymerizable unsaturated monomer components in such a range that they do not hinder the object of the present invention. Such unsaturated monomers which ~ay optionally be copolymerized in the concrete areD~-olefinQ of 3 to 20 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.
in the range of less than an equimolar amount of the ethylene component in the resulting random copolymer.
In the cycloolefin type random copolymer ~A~, repeating units (a) derived from ethylene are present in the range of 40 to 85 mol %, preferably 50 to 75 mol %, and repeating units (b) derived from the cycloolefin or cycloolefin are present i~ in the range o~ 15 to 60 mol ~, preferably 25 to 50 mol %. The repeating units (a~ are arranged substantially linear by and at random. That the cycloolefin type random copolymers ~A~ are substantially linear a~d do not contain a gel-forming cross-linked :- . . . ;: . : ., ~ , . , ~ .. . . ..

132g~37 structure can be conf irmed by the fact that said copolymers perfectly dissolve in decalin kept at 135C.
An intrinsic viscosity ~] as measured at 135 C in decalin of the cycloolefin type random copolymer [A] is in the range of 0.05-10 dl/g, preferably 0.08-5 dl/g.
A softening temperature (TMA) as measured with a thermal mechanical analyzer of the cycloolefin type random copolymer ~A] is not lower than ~0C, preferably in the range of 90-250C, more preferably 100-200C.
Furthermore, a glass transition temperature (Tg) of said cycloolefin type random copolymer ~A] is usually in the range of 50-230C, preferably 70-210C.
A crystallinity index as measured by X-ray diffractometry of the cycloolefin type random copolymer ~A] is in the range of 0-10%, preferably 0-7%, more preferably 0-5%.
The cycloolefin type random copolymer ~B](i~, which can be one component in the cycloolefin type random copolymer compositions of the present invention, contains as essential components an ethylene co~ponent and the aforementioned cycloolefin component and further must contain in addition to said two essential components at least one other copolymerizable unsaturated monomer component as an ess~ntial component. Such at least one unsaturated monomer which must be copolymerized in the . : ~ ~ , ,, ~ .
; ~ : : .: :

concrete includes ~-olefins of 3 to 20 carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosane, etc. in the range of less than an e~uimolar amount of the ethylene component unit in the resulting random copolymer.
In the cycloolefin type random copolymer [B]~
there are present repeating units (a) derived from ethylene in the range of 40 to 99 mol %, preferably 75 to 98 mol %, repeating units (b) derived from the cycloolefin(s~ in the range of 1 to 40 mol %, preferably 1 to 15 mol %, and repeating unîts (c) derived from at least one ~-olefin other than ethylene in the range of 1 to 45 mol %, preferably 1 to 35 mol %, and the repeating unit (a), (b) and (c) are arranged substantially line alloy and at random. That the cycloolefin type random copolymers ~B]~i) are substantially linear and do not contain a gel-forming cross-linked structure can be confirmed by the fact that said copolymers perfectly dissolve in decalin kept at 13~5C.
The ~-olefin elastomeric copolymers tB](ii) as one component in the cycloolefin type random copolymers of the present invention are non-crystalline to low crystalline copolymers formed from at least two d-olefins. There are used in the concrete (i) ethylene- ~-olefin copolymer ': ~ . , ..

1329~

rubber and (ii) pr~pylene ~-olefin copolymer rubber as said component [B](ii). Examples of theC~-olefins which constitute said ~i) ethylene ~ -olefin copolymer rubber are usually ~ olefins of 3 to 20 carbons, such as propylene, 1-butene, 1-pentene, 1 hexene, 4-methyl-1-pentene, 1-octene, 1-decene or mixtures thereof. Among them, propylene or 1-butene is particularly preferred.
Examples of the ~-olefins which constitute said (ii) propylene~-olefin copolyme~ rubber are usually ~-olefins of 4 to 20 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or ~ixtures thereof. Among them, 1-butene is particularly preferred.
The molar ratio of ethylene to ~-olefin in the (i) ethylene- ~-olefin copolymer rubber varies depending on the types of the ~-olefins, but is generally in Lhe range of from 30/70 to 95/5, preferably from 50/50 to 95/5.
When the ~-olefin is propylenel said molar ratio is preferably in the range of from 50/50 to 90/10, while when the ~ -olefins are those of four or more carbon ato~s, said molar ratio i5 preferably in the range of from 80/20 to 95/5.
The molar ratio of propylene to ~ olefin in the (ii) propylene ~-olefin copolymers rubber varies depending on the types of theC~-olefins, but is preferably in the -- 2g -- , " ~ .. , .. , . ~................. . -.
.

;: . : .

1329~37 range o~ ~irom 50f50 to 95/s. When the ~-olefin is 1-butene, said molar ratio is preferably in the range ofi from 50/50 to 90/10, while when the ~-olefins are those of five or more carbon atoms, said molar ratio i~ preferably in the range of from 80/20 to 95/5.
A crystallinity index as measured by X~ray diffractometry of the ~-olefin type elastomeric copolymer [B](ii) is preferably in the range of 0-50%, more preferably 0-25~.
An intrinsic viscosity ~ as measured at 135 C in decalin of the ~-olefin type elastomeric copolymer ~B](ii) is in the range of 0.2-10 dl/g, preferably 1-5 dl/g as measured at 135C in decalin. The density thereof is preferably in the range of 0.82-0.96 g/cm3, more preferably O.B4-0.92 g/cm .
Thed~-olefin type elastomeric copolymers ~B~(ii) which are used in the present invention may be graft-modified copolymers which are modified with 0.01 to 5~ by .
weight, preferably 0.1 to 4% by weight of graft monomers selected from unsaturated carboxylic acids or derivatives thereof.
~ xamples of the unsaturated carboxylic acids andderivatives thereof which are used for the modification of the ~-olefin type elastomeric copolymers [B](ii) in the present invention include such unsaturated carboxylic ; .: . . ,, . ., . . . . -1329~37 acids as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic aci ~ (endocis-bicyc~o[2,2,1]hept-5-ene-2,3-dicarboxylic acid), etc. and derivatives thereof such as acid halides, amides, imides, anhydrides, esters, etc. Concrete examples of said derivatives include malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, etc. Among them, unsaturated dicarboxylic acids or acid anhydrides thereof are preferred and maleic acid, nadic aci ~ and anhydrides thereof are particularly preferred.
The modified ~-olefin type elastomeric copolymers can be produced by graft-copolymerizing a graft monomer selected from said unsaturated carboxylic acids and said -~
derivatives onto the ~-olefin type elastomeric copolymer ~B~(ii) by any of various conventional methods. For example, the modified ~-olefin type elastomeric copolymers can be produced by a method wherein said O~-olefin type elastomeric copolymer is molten, a graft monomer is added thereto and a graft polymerization reaction is carried out, or a method wherein said ~-olefin type elastomeric copolymer is dissolved in a solvent, a graft monomer is added thereto and a graft copolymerization reaction is carried out. In either case, it is preferred to carry out - 31 ~

~3~9437 the graft reaction in the presence of a radical initiator to graft-copolymerize efficiently the graft monomer. The graft reaction is usually carried out at a temperature of 60 to 350C. The amount of the radical initiator to be used is generally in the range of 0.001 to 1 part by weight based on 100 parts by weight of the ethylene~ -olefin random copolymer.
~ amples of the radical initiator include organic peroxides and organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl~2,5-di(peroxide benzoate)hexine-3, 1,4-bis(tert-butyl peroxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylpersxy)hexine-2, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert~butyl perphenylacetate, tert~butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethylacetate; and azo compounds such as azobisisobutyronitrile, dimethyl azoisobutyrate, etc.
Among them, dialkyl peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexine-3, 2,5-dimethyl 2,5-di(tert-butylperoxy)hexane, 1,4-bis(tert-butylperoxyisopropyl)benzene, etc. are preferred.
Amon~ said ~-olefin type elastomeric copolymers [Bl(ii), graft-modified copolymers obtained by modifying . , ~ , ~ , . - ~

- . ~ ,, . "

1329~37 ethylene-propylene random copolymers or ethylene-0~-olefin random copolymers having an ethylene content of 35 to 50 mol% and a crystallinity index of not higher than 5% with a graft monomers selected from said unsaturated carboxylic acids and derivatives thereof are the most preferred, because they exhibit the best effect of improving impact resistance.
The ~-olefin-diene type elastomeric copolymers ~B](iii) as one component in the cycloolefin type copolymers compositions of the present invention are copolymers of at least two olefins and at least one non-conjugated diene. There are concretely used (i) ethylene-~-olefin-diene copolymer rubber and (ii) propylene ~ -olefin-diene copolymer rubber as said component tB~(iii)-The ~-olefins which constitute the (i) ethylene ~-olefin-diene copolymer rubber are usually those of 3 to 20 carbo~ atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or mixtures -~
thereof. Among them, propylene or 1-butene is preferred.
The ~-olefins which constitute the (ii) propylene-~-olefin-diene copolymer rubber are usually those of 4 to 20 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or mixtures thereof.
Among them, 1-butene i5 particularly preferred.
Examples of the diene components for the (i) : .: , , . : . . , .. . , . .: : . .

~ 32~37 ethylene-~-olefin-diene copolymer rubber or the (ii) propylene-~-olefin-diene copolymer rubber include linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, etc.; cyclic non-conjugated dienes such as cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropyldiene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropyldiene~5-norbornene, 2-propenyl-2,2-norbornadiene, etc. Among them, 1,4-hexadiene and cyclic non-conjugated dienes, particularly, dicyclopentadiene or 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 1,4-hexadiene and 1,4-octadiene are preferred.
The ~olar ratio of ethylene to ~-olefin in the (i) ethylene-~-olefin-diene copolymer rubber varies depending on the types of the ~-olefins, but is preferably in the range of from 50/50 to 95/5. When the ~-olefin is propylene, said ~olar ratio is preferably in the range of fro~ 50/50 to 90/10, while when the ~-olefins are those of four or more carbon ato~s, said molar ratio is preferably in the ran~e of from 80/20 to 95/5.
The content of the diene component in the ' . . ' '.' .

copolymer rubber is in the range of 0.5 to 10 mol%, preferably 0.5 to 5 mol%.
The molar ratio of propylene to ~-olefin in the (ii) propylene-~-olefin-diene copolymer rubber varies depending on the types of the ~-olefins, but is preferably in the range of from 50/50 to 95/5. When the ~-olefin is 1-butene, said molar ratio is preferably in the range of from 50/50 to 90/10, while when the ~-olefins are those of five or more carbon atoms, said molar ratio is preferably in the range of from eO/20 to 95/5.
The content of the diene component in the copolymer rubber is ln the range of O.S to 10 mol%, preferably 0.6 to S mol%.
A crystallinity index as measured by X-ray diffractometry of the ~-olefin-diene type elastomeric copolymer ~B~(iii) is preferably in the range of 0-10%, more preferably 0-5%.
An intrinsic viscosity t~ as measured at 135C in decalin of the ~-olefin-diene type elastomeric copolymers ~B~iii) is in the range of 0.1-10 dl/g, preferably 1-5 dl/g. The iodine value thereof is in the range of 1-30, preferably 5-25, and the density thereof is in the range of 0.82-1.00 g/cm3, preferably 0.85-0.90 g/cm3.
The aromatic vinyl type hydrocarbon-conjugated diene copolymers or hydrog~nated products thereof tB~(iV) ...
.

. ~, . . . - .. ..
.
.

as one component in the cycloolefin type random copolymer compositions of the present invention are concretely (a) styrene-butadiene copolymer rubbers, (b) styrene-butadiene-styrene copolymer r~bbers, (c) styrene-isoprene block copolymer rubbers, (d~ styrene-isoprene-styrene block copolymer rubbers~ ~e) hydrogenated styrene-butadiene-styrene block copolymer rubbers, (f) hydrogenated styrene-isoprene-styrene block copolymer rubbers, etc. The molar ratio of styrene to butadiene in the (a) styrene-butadiene copolymer rubbers is preferably in the range of from 0/100 to 60/40. The molar ratio of styrene to butadiene in the (b) styrene-butadiene-styrene block copolymer rubbers is preferably in the range of from 0/100 to 60/40 and a degree of polymerization of styrene in each block is preferably in the range of about 0 to 5000 and a degree of polymerization of butadiene in each block is preferably in the range of about 10 to 20000. The molar ratio of styrene to isoprene in the lc) styrene-isoprene block copolymer rubbers is preferably in the range of from 0/100 to 60/40. The molar ratio of styrene to isoprene in the (d3 styrene-isoprene-styrene block copolymer rubbers is preferably in the range of from 0/100 to 60/40 and a degree of polymerization of styrene in each block is preferably in the range of about 0 to 5000 and a degree of polymerization of isoprene in each block is preferably in ,. . : ::.: : : ::: -: .

. .

1329~37 the range of about lO to 20000. The (e) hydrogenated styrene-butadiene-styrene block copolymer rubbers are copolymer rubbers wherein double bonds left in said styrene-butadiene-styrene block copolymer rubbers are partially hydrogenated and the weight ratio of styrene to rubber moiety is preferably in the range of from 0/100 to ~ :
50/50. The tf) hydrogenated styrene-isoprene-styrene block copolymer rubbers are copolymer rubbers wherein double bonds left in said styrene-isoprene-styrene block copolymers are partially hydrogenated and the weight ratio of styrene to rubber moiety is preferably in the range of from 0/lO0 to 50/50.
A weight-average molecular weight Mw as measured with GPC (gel permeation chromatography, solvent: o-dichlorobenzene, 140C~ of the aromatic vinyl type hydrocarbon-conjugated diene block copolymer is in the range of 500 to 2000000, preferably lO000 to lO00000, and the density thereof i~ in the range of 0.80-l.lO g/cm3, preferably 0.88-O.g6 g/cn3.
In the present invention, the aforementioned non-rigid copolymers ~i3 to (iv) are used either alone or in combination of two or more of them and incorporated into the cycloolefin type random copolymer compositions. When said non-rigid copolymers are used in combination, any of the combinations of the non-rigid copolymers (i) to (iv~

, can be used.
In the cycloolefin type random copolymercompositions of the present invention, the total amount of the non-rigid copolymer (B) used is in the range of 5 to 100 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 10 to 70 parts by weight based on 100 parts by weight of the cycloolefin type random copolymer [A~. When the total amount of the non-rigid copolymer tB] is less than 5 parts by weight based on 100 parts by weight of the cycloolefin type random copolymer tA]. the compositions are poor in impact resistance, though they are excellent in rigidity, while when the total amount of the non-rigid copolymer [B] is more than 100 parts by weight, the rigidity of the compositions is low and the balance between rigidity and impact strength becomes poor.
Figure 1 is a graph showing the relationship between the amount of the cycloolefin type random copolymer [B] blended in the cycloolefin type random copolymer composition of the present invention and the impact strength (IZ strength) of said composition.
It is apparent from Fig. 1 that when the cycloolefin type random copolymer tB] is blended with the cycloolefin type random copolymer tA], the impact resistance of the resulting cycloolefin type random copolymer composition is remarkably improved.
Figure 2 is a graph showing the relationshipbetween the amount of the cycloolefin type random copolymer [B] blended in the cycloolefin type random copolymer composition of the present invention and the softening temperature (TMA) of said composition.
It is apparent from Fig. 2 that even when up to 30 wt.% of the cycloolefin type random copolymer [B~ is blended with the cycloolefin type random copolymer tA], it is surprisingly found that the softening temperature (TMA) of the cycloolefin type random copolymer composition is not lowered at all.
The impact resistance of the cycloolefin type copolymer composition is greatly improved and heat re~istance is nDt lowered, when up to about 30 wt.% of the cycloolefin type random copolymer [B] i~ blended with the cycloolef~n type random copolymer [A].
In Figs. 1 and 2, the mark o represents values for Examples 1 to 3 and Comparative Example 1, the mark represents values for Example 4 and Comparative ~xample 2, the mark~ represents values for Examples 5 to 7 and Comparative Example 3, the mark 0 represents values for ~xamples 8 and 9 and Comparative Example 4, the mark represent~ values for ~xamples 10 and 11 and Comparative Example 5, the mark ~ represents values for Example3 12 .", ,~ ~ .

`~

and 13, and the mark V represents values for Examples 14and 15 and Comparative Example 6.
Figure 3 is a graph showing the relationship between the amount of the ~-olefin type elastomeric composition [B] blended in the cycloolefin type random copolymer composition and the impact strength (IZ
strength) of said composition.
It is apparent from Fig. 3 that the impact strength of the cycloolefin type random copolymer composition is remarkably improved, when the ~-olefin type elastomeric copolymer [B] is blended with the cycloolefin type random copoly~er [A].
Figure 4 is a graph showing the relationship between the amount of the ~-olefin type elastomeric copolymer tB] blended in the cycloolef in type random copolymer composition and the softening temperature (TMA) of said composition.
It is apparent from Fig. 4 that it is surprisingly found that the softening temperature (TMA) of the cycloolefin type random copolymer composition is scarcely lowered, when up to 30 wt.% of the ~-olefir. type elastomeric copolymer tB] is blended with the cycloolefin type random copolymer tA~.
The impact resistance of the cycloolefin type random copolymer composition is greatly improved and heat ; :: ~ :: ' : : : : ~: : , - ,-. . ..

~329437 resistance is not lowered, when up to about 30 wt.% of the ~-olefin type elastomeric copolymer CB] is blended with the cyclolefin type random copolymers ~A].
In Figs. 3 and 4, the mark o repre~ents values for ~xamples 16 to 20 and Comparative Example 7, the mark n represents values for ~xamples 21 to 23 and Comparative ~xample 8, the mark o represents values for Examples 26 and 27 and Comparative Example 10, and the mark A
represents values for ~xamples 28 and 29 and Comparative ~xample 11.
Figure 5 is a graph showing the relationship between the amount of the ~-olefin-diene type elastomeric copolymer ~B~ blended in the cycloolefin type random copolymer composition of the present invention and the impact strength (IZ strength) of said composition.
It is apparent from Fig. 5 that the impact resistance of the resulting cycloolefin type random `~
copolymer composition is remarkably improved, when the olefin-diene type elastomeric copolymer tBJ is blended with the cycloolefin type random copolymer [A].
Figure 6 is a graph showing the relatiohship between the amount of the ~-olefin-diene type elastomeric copolymer [B~ blended in the cycloolefin type random copolymer composition of the present invention and the softening temperature (TMA) of said composition.

; . , ., , . ~ , - ~, , . , ~ . . .

1329~37 It is apparent from Fig. 6 that the softening temperature (TMA) of the cycloolefin type rand~m copolymer composition i5 surprisinsly not lowered at all, even when up to about 30 wt.~ of the.~-olefin-diene type elastomeric copolymer ~B] is blended with the cyclsolefin type random copolymer ~A~.
As stat~d above, the impact resistance of the cycloolefin type random copolymer composition is remarkably improved and heat resistance is not lowered, when up to about 30 wt.% of the ~ -olefin-diene type elastomeric copolymer [B] is blended with the cycloolefin type random copolymer tA~.
In Figs. 5 and 6, the mark o repre~ents values for Examples 35 to 41 and Comparative ~xample 13, the mark O
represents values for Example~ 42 to 44 and Comparative ~xample 14, the mark repre~ents values for ~xample3 45 and 46 and Comparative ~xample 15, the mark ~ represents : -values for ~xamples 47 and 48 and Comparative ~xample 16, and the mark ~ represent values for ~xamples 49 and 50 and Comparative Example 17.
Figure ~ is a graph showing the relationship between the amount of the aromatic vinyl type hydrocarbon- :
conjugated copolymer or hydrogenated product thereof ~B]
blended in the cycloolefin type random copolymer composition of the present invention and the impact ... . .
- . ., .: . ~ , . . , , :

. . :: ~ ~ ::: ~ :: : : : :

1~29437 strength (IZ strength) of said composition.
It is apparent from Fig. ~ that the impact resistance of the resulting cycloolefin type random copoly~er composition is remarkably improved, when the aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof tB] is blended with the cycloolefin type random copolymer ~A].
Figure 8 i5 a graph showing the relationship between the amount of the aromatic vinyl type hydrocarbon-conjugated diene copolymer or hydrogenated product thereof ~B~ blended in the cycloolefin type random copolymer composition of the present invention and the softsning te~perature (TMA) of said composition.
It is apparent from Fig. 8 that the softening te~perature (TMA) of the cycloolefin type random copolymer composition is surprisingly not lowered at all, even when up to about 30 wt.X of the aromatic vinyl type hydrocarbon-conjugated diene copolymer or hydrogenated product thereof [B] is blended with the cycloolefin type random copolymer ~A].
As stated above, the i~pact resistance of the cyloolefin type random copolymer composition is remarkably improved and heat resistance is not lowered, when up to about 30 wt.% of the aromatic vinyl type hydrocarbon-conjugated diene copolymer or hydrogenated product thereof , .. ... . .... .

:, - ~ , . . - . . ,:
, . . . .
, . . .
, . . : . . .

1329~37 [B] is blended with the cycloolefin type random copolymer [A]-In Figs. 7 and 8, the mark o represents values forExamples 51 to 57 and Comparative Example 18, the mark a represents values for Examples 58 to 60, the mark o represents values for ~xamples 61 and 62 and Comparative Example 20, the mark ~ represents values for Examples 65 and 66 and Comparative Example 21, and the mark A
represents values for Examples 65 and 66 and Comparative Example 22.
Figure 9 is a graph showing the relationship between the amount of the non-rigid copolymers [B] blended in the cycloolefin type random copolymer composition of the present invention and the impact strength (IZ
strength) of said composition.
It is apparent from Fig. 9 that the impact resistance of the cycloolefin type random copolymer composition is remarkably improved, when the non-rigid copolymers [B~ are blended with the cycloolefin type random copolymer ~A].
Figure 10 is a graph showing the relationship between the amount of the non-rigid copolymers [B] blended in the cycloolefin type random copolymer composition and the softening temperature (TMA) of said composition.
It is apparent from Fig. 10 that the softening -: :~ : - ~ : : . - . . . ~: : .: : . . . .

132~37 temperature (TMA) of the cycloolefin type random copolymer composition is surprisingly not lowered at all, even when up to about 30 wt.% of the non-rigid copolymer [~ is blended ~ith the cycloolefin type random copolymer [~].
As stated above, the impact resistance of the cycloolePin type random copolymer composition is remarkably improved and heat resistance i5 not lowered, when up to about 30 wt.% of the non-rigid copolymer ~B~ is blended with the cycloolefin type random copolymer ~A].
In Figs. 9 and 10, the mark o represents values for Examples 67 to ~2 and Comparative Example 23, the mark represents values for ~xamples ~3 to 7~ and Comparative ~xample 24, the mark ~ represents values for ~xamples 78 to 80 and Comparative Example 25, the mark ~ represents values for Bxamples 81 and 82 and Comparative ~xample 26, and the mark ~ represents values for ~xamples 83 and 84 and Comparative ~xample 27.
The second cycloolefin type copolymer compositions of the present invention contain an inorganic or organic filler-component (C~ in addition to said cycloolefin type random copolymer (A) and ~aid non-rigid copolymer (B).
Concrete examples of the inorganic fillers include silica, silica-alumina, alumina, glass powder, glass bead, glass fiber, glass fiber cloth, glass fiber mat, asbestos, graphite, carbon fiber, carbon fiber cloth, carbon fiber ., . . " . , , . . . , . - . ~ ., ~

. . ' .. ,. ' , ' . ~ ' ' " ' , . . ' ' ' .
. .

mat, titanium oxide, molybdenum disulfide, magnesium hydroxide, talc, sellaite, metallic powder, metallic fiber, etc.
Concrete examples of the organic fillers include fibrous materials of wholly aromatic polyamides such as polyterephthaloyl-p-phenylenediamine, polyterephthaloylisophthaloyl-p-phenylenediamine, polyisophthaloyl-p-phenylenediamine, polyisophthaloyl-m-phenylenediamine, etc. or fibrous materials of polyamides such as nylon 66, nylon 6, nylon 10, etc.
The fibrous materials may be in any form of single fiber, strand, cloth, mat, etc.
These inorganic or organic fillers may be used either alone or in combination of two or more of them.
The inorganic or organic fillers are incorporated into the cycloolefin type random copolymer compositions for various purposes. For example, they are used for purposes of improving the heat resistance or flame retardance of the compositions, coloring said compositions, i~proving their rigidity, or inhibiting mold shrinkage factor. They are used in an appropriate amount which meets requirements according to the intended uses of the compositions.
In the second cycloolefin type random copolymer compositions of the present invention, the total amount of .. .. ,..... :- . .~ . : . . ~ .

.. . . . . .

132943~

the non-rigid copolymer (B) is in the range of 1 to 100 parts by weight, preferably 5 to 100 parts by weight, ~ore preferably 5 to 50 parts by weight based on 100 parts by weight of the cycloolefin type rando~ copolymer (A) and the amount of the inorganic or organic filler (C) is in the range of 1 to 100 parts by weight, preferably S to 100 parts by weight~ more prefeably 5 to 50 parts by weight based on 100 parts by weight o~ the cycloolefin type random copolymer (A). Impact resistance :Ls lowered, when the total amount of the non-rigid copolymer (B) is less than one part by weight based on 100 parts by weight of the cycloolefin type random copolymer (A), while rigidity is lowered, when the total amount of the non-rigid copolymer 5B~ is more than 100 parts by weight.
The moldability of the compositions is deteriorated, when the amount of the inorganic or organic filler (C) is more than 100 parts by weight based on 100 parts by weight of the cycloolefin type copolymer (A).
The cycloolefin type random copolymers (A) and (B1~i) which constitute the cycloolefin type random copolymer co~positions of the present invention may both be prepared by suitably selecting the conditions under which they are prepared in accordance with the processes as proposed by the present applicant in Japanese Patent L-0-P Publns. Nos. 168708/1985, 120816/1986, 115912/1986, . 4~ -- - , . .................. . . .: . . ~ -. . . . .

13294~7 115916/1986, 95905/1986, 95gO6~1986, 271308/1986 and 272216~1g~6.
In preparing the cyloolefin type random copolymer compositions of the present invention, there are applicable various known processes which include, fGr example, a proces~ wherein the cycloolefin type random copolymers ~A) and the non-rigid copolymers (B) are prepared separately, and the copolymers (A) and (B) thus prepared are blended by meanQ of an extruder to obtain a desired compo~ition, a solution blending process wherein the copolymers (A) and (B) are thoroughly dis~olved separately in suitable solvent~, for example, saturated hydrocarbons such as heptane, hexane, decane, cyclohexane, etc., or aromatic hydrocarbons such as toluene, benzene, xylene, etc., and the respective solutions are sub~ected to solution blending to obtain a desired composition, or a process wherein the copolymers (A) and (B) are prepared individually by means of separate polymerization reactors, and the resulting polymers are blended with a third vessel to obtain a desired composition.
An intrin ic viscosity ~ a~ measured at 135 C in decalin of the cycloolefin type random copolymer compo~itions of the present invention is in the range of 0.05-10 dl/~, preferably 0O2-3 dl/g, and a softening temperature (TMA) as measured with a thermal mechanical - . . ~'; ~ . ' :
. . .
, , , ~` ~

1~29437 analyzer of said compositions is in the range of 80-250 c, preferably 100-200~C t and a glass transition temperature (Tg~ of said compositions is in the range of 70-230C, preferably 90-210C.
The cycloolefin type random copolymer compositions contain the aforesaid cycloolefin type copolymer (A~ and the aforesaid non-rigid copolymer (B), and optionally said inorganic or organic filler. In addition to the above-mentioned components, however, the present compositions may be incorporated with heat stabilizers, weathering stabilizers, antistatic a~ents, slip agents, anti-blocking agents, anti-fogging agents, lubricants, dyes, pigments, natural oil, synthetic oil, wax, etc., and amounts of these additives may be suitably decided. For instance, the stabilizers which may be optionally incorporated include concretely phenolic antioxidants such as tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
methane, ~-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2,2'-oxamidobis~ethyl-3-(3,5-di~t-butyl-4-hydroxyphenyl)] propionate, etc., metallic salts of fatty acid such as zinc stearate, calcium stearate, calcium 12-hydroxystearate, etc., and fatty esters of polyhydric alcohol su~h as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol distearate, pentaerythri*ol tristearate, etc. These ~ ' ' , , ' '. . .. ,, ' . . .'. . .: , . ' ; ' " ' " "" ' . ' ' . ~' ' ' , ' ,. ' ' ' :' ; , : ' ~ ' `

compounds may be incorporated into the presentcompositions either singly or in combination. For instance, there may be used such a combination of tetrakis [methylene-3-(3,5-di-t-butyl-4-h~droxyphenyl)propionateJ
methane with zinc stearate or glycerin monostearate, and the like combinations.

. : . : .~ . ~ : .: : :. .

~FFECT OF THE INV~NTION
The cycloolefin type random copolymer composition~
of the present invention comprise the cycloolefin type random copolymer (A), the cycloolefin type random copolymer (B) and optionally, the inorganic or organic filler ~C), in whlch ~aid copolymer (B) and ~aid inorganic or organlc filler (C) are pre~ent in ~pecific on the basis of 100 parts by weight of ~aid copolymer (A), are excellent in heat re~istance, heat ageing characteristics, chemical re~i~tance, ~olvent resi3tance, dielectric characteristic3 and rigidity a~ well as in impact re~i~tance.

~MBODIM~NT OF TH~ INVENTION
The present invention is illu~trated be~ow in more detail with reference to exampleq. Variou~ phy~ical properties indicated in the examples were mea~ured or evaluated according to the following procedure~.
(1) Softening temperature tTMA): U3ing Thermomechanical Analyser TMA 10 (~anufactured by Seiko Denshi K.K.), the softening temperature wa~ measured in terms of heat deformation behavior of a test ~heet of a 1 mm thick. That ~5, to a quartz needle placed vertically on the te~t sheet wa~ applied a load of 50 g, while elevating the temperature at a rate of ~C/min of the te3t sheet, and an elevated temperature at which the needlepenetrated O.1 mm into the test sheet was taken as the softening temperature (TMA).
(2) Impact strength: Using Izod impact tester (manufactured by Toyo Seiki KK), a test piece (length:
63.8 mm, width: 12.7 mm) punched out of a 2 mm thick pressed sheet and notched (0.25 mm~ was tasted at 23C.
(3) Modulu~ of rigidity (flexural modulus): Using Instron tensile tester, a test piece (length: 63.8 mm, widtA: 12.7 mm) punched out of a 2 mm thick pressed sheet was tasted under conditions including a compression rate of 5 mm/min, a distance between supports of 32 mm and a temperature of 23C.
The IZ impact test and the flexural test were conducted after 3 days from pressing.
Polymerization ~xample la Preparation of copolymer (A) having a softening temperature of at least ~O C
With a 2-litre glass polymerization reactor equipped with a stirring blade, there was carried out ~:
continuously a copolymerization reaction between ethylene and 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene (structural formula~
hereinafter abbreviated to DMON~. That is, into the polymerization reactor were continuously charged a - i52 -:: . - , . , -,; . . . , ., ~ . ............. .. .. - . .
.. ... - . - . . : . : . . ~ . ...

~329~37 solution of DMON in cyclohexane so that the DMON
concentration in the polymerization reactor became 60 g/l, a solution of VO(OC2H5)C12 as a catalyst in cyclohexane so that the vanadium concentration in the polymerization reactor became 0.9 mmol/l, and a solution of ethylaluminum sesquichloride IAl(C2H5)1 5C11 5) in cyclohexane so that the aluminum concentration in the polymerization reactor became 7.2 mmol/l, while continuously withdrawing from the bottom of the polymerization reactor the polymerization liquid so that the volume of the polymerization liquid in the polymerization reactor was constantly 1 litre.
Simultaneously, into the polymerization reactor from the top of the polymerization reactor ethylene was fed at a rate of 85 l/hr, hydrogen was fed at a rate of 6 l/hr and nitrogen was fed at a rate of 45 l/hr. The copolymerization reaction was carried out at 10 C by circulating a refri~erant through a ~acket fitted externally to the polymerization reactor.
The copolymerization was carried out under the conditions as illustrated above, whereupon a polymerization reaction mixture containing an ethylene DMON random copolymer was obtained. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid withdrawn from the bottom of the reactor. Thereafter, the polymerization .: . : : ~ ~ , .. , : .. ,: , .: .: .:

liquid was poured into a household mixer containingacetone of about three times the volume of the polymerization liquid, while rotating the mixer, thereby depositing the resulting copolymer. The deposited copolymer was collected by filtration, dispersed in acetone so that the polymer concentration became about 50 g/l, and the copolymer was treated at the boiling point of acetone for 2 hours. After the treatment as above, the copolymer was collected by filtration and dried at 120C
overnight (12 hours) under reduced pressure. :~
The thus obtained ethylene DMON-random copolymer (A) had an ethylene unit of 59 mol% as measured by 13C-NMR
analysis, an intrinsic viscosity t~] of 0.42 dl/g as measured at 135C in decalin, and a softening temperature tTMA) of 154C.
Polymerization ~xam~le lb Preparation of copolymer (A) having a softening temperature of at lea~t 70C
In Example lb, a copolymerization reaction wa~
continuously carried out in the same manner as in Example la. After the completion of the copolymerization reaction, the resulting copolymer was precipitated out, recovered and dried at 120 C overnight under reduced pressure.
The thus obtained ethylene DMON copolymer (A) had an ethylene unit of 59 mol% as measured by 13C-NMR
analysis, an intrinsic viscosity [~ of 0.60 dl/g as measured at 135C in decalin and a softening temperature ~TMA) of 111 (:;.
Polymerization Example 2 Preparation of copolymer (A) having an intrinsic vi~cosity ~] different from that of the copolymer (A) of Polymerization Example la The same copolymerization reaction as in Polymerization Example la was continuously carried out except that the concentrations of DMON, VO(OC2H5)Cl2 and ethylal~minum sesquichloride in the polymerization reactor and the feed rates of ethylene, hydrogen and nitrogen were those given in Table 5. After the completion of the copolymerizaticn, the resulting copolymer was deposited, recovered and dried at 120C under reduced pressure for 12 hours a~ in polymerization ~xample la. The thus obtained ethylene DMON copolymer (A) had an ethylene unit of 58 mol% as measured by C-NMR analysis, an intrinsic vi~cosity ~ of 0.94 dl/g as measured at 135C in decalin and softening temperature of 1~0C.
Polymerization ~xample 3 Preparation of copolymer (A) having an intrinsic viscosity ~ difPerent from that of the copolymer (A) of Polymerization Example la . . - . ... . : : . .: :: :.

The same copolymerization reaction as in Polymerization Example la was continuously carried out except that the concentrations of DMON, VO(OC2H5)Cl2 and ethylaluminum sesquichloride in the polymerization reactor and the feed rates of ethylene, hydrogen and nitrogen were those given in Table 5. After the completion of the copolymerization, the resulting copolymer was deposited, recovered and dried at 120C overnight (12 hours) under reduced pressure as in polymerization ~xample la. The thus obtained ethylene DMON copolymer (A) had an ethylene unit of 67 mol% as measured by 13C-NMR analysis, an intrin~ic viscosity ~] of 0.60 dl/g as measured at 135C -~
in decalin and a softening temperature (TMA) of 111C.

. . ..
- . .- ~ : . . - ., ;. . .-, 132~437 Table 5 ¦ Polymn. Polymn.
~x. 2 ~. 3 Vo(DC2H5)C12 (mmol/l) 0.9 0.9 Ethylaluminum sesquichloride7.2 7.2 (mmol/l) DMON ~g/l) 60 30 Ethylene (l/hr~ 100 85 Hydrogen (l/hr) 0.2 0.2 Nitrogen [l/hr) 45 45 Polymerizat on ~xample 4 Preparatlon of copolymer (B) having a softening temperature of below 70C
The ~ame copolymerization reaction as in Polymerization ~xample la waC carried out except that DMON, VO(OC2H:5)Cl~ and ethylaluminum sesquichloride were ' '' ; ' ' ' ' ' ' : ' ' :
., :

~ ^ .~

1 329~37 fed into the polymerization reactor so that theconcentrations of DMON, vO~OC2H5)Cl2 and ethylaluminum sesquichloride in the polymerization reactor became 15 g/l, 0.5 mmol/l and 4 mmol/l, respectively, and that ethylene, propylene, hydrogen and nitrogen were fed into the polymerization reactor at rates of 45 l/hr, 15 l/hr, 0.2 l/hr and 25 l/hr, respectively, and the polymerization temperature was 10C. After the completion of the copoly~erization, the resulting copolymer was deposited, collected and dried at 120C under reduced pressure for 12 hours as in polymerization Example la.
The thu~-obtained ethylene propylene DMON
copolymer (B) had an ethylene unit of 76 mol~ and a propylene unit of 17 mol% as measured by 13C-NMR analysis, an intrinsic viscosity ~ of 0.89 dl/g as measured at 135 C in decalin and a softening temperature (TM~) of -10C.
Polymerization Example 5 Preparation of copolymer (B) having an intrinsic visc05ity ~] different from that of the copolymer (B) of Polymerization Example 4 The same copolymerization reaction as in Example 4 was carried out except that the concentrations of DMON, VO(OC2H5)Cl2 and ethylaluminum sesquichloride in the polymerization reactor and the feed rates of ethylene, . .~- ' ~ '; . : ' , ~329437 propylene, hydrogen and nitrogen were those given in Table 6. After the completion of the copolymerization, the resulting copolymer was deposited, collected and dried at 120C under reduced pressure for 12 hours as in Polymerization Example la.
The thus obtained ethylene propylene DMON
copolymer (B) had an ethylene unit of 69 mol~ and a propylene unit of 21 mol% as measured by 13C-NMR analysis, an intrinsic viscosity [~ of 1.44 dl/g as measured at 135 C, in decalin and a softening temperature (TMA) of -4C.
Polymerization ~xample 6 Preparation of copolymer (B) having an intrinsic viscosity ~7, different from that of the copolymer (B) of Polymerization ~xample 4 The same copolymerization reaction as in Polymerization Example 4 was carried out except that the ~oncentrations of DMON, VO~OC2H5)C12 and ethylaluminum sesquichloride in the polymerization reactor and the feed rate~ of ethylene, propylene, hydrogen and nitrogen were those given in Table 6. After the completion of the copolymerization, the resulting copoly~er was deposited, collected and dried at 120C under reduced pressure for 12 hours as in Polymerization ~xample la.

The thus obtained ethyle~e propylene DMON
- 5g -copolymer (B) had an ethylene unit of 76 mol% and a propylene unit of 16 mol% as measured by C-NMR analysis, an intrinsic viscosity ~] of 0.98 dl/g as measured at 135 C in decalin and a softening temperature ~TMA) of -8 C.

Table 6 Polymn. Polymn.
Ex. 5 ~. 6 :

VO(DC2H5)C12 (mmol/l) 0.5 0.5 ~thylaluminum sesquichloride 4 4 ~mmol/l) DMON (g/l) 20 15 ~thylene (l/hr) 45 45 Propylene (l/hr) 30 15 Hydrogen (l/hr) 0.1 0.1 Nitrogen ~l/hr) 25 25 ' ~ ' .... . I - , .: - , : ~

. ' ~ . ; ~ , ! . . .

~xample 1 In 2 litres of cyclohexane were poured 85 g of the copolymer (A) obtained in Polym~rizati~n Example 3 and 15 g of the copolymer ~s) obtained in Polymerization Example 5 (weight ratio: ~A)/(B) - 85/15), and dissolved at about 70C while thoroughly stirring to obtain a homogeneous solution. The thus obtained homogeneous solution was poured in 2 litres of acetone to deposit an (A)/(B) blend.
The thus obtained blend was dried at 120C under reduced pressure overnight.
The (A)/~B) blend thus obtained was incorporated with 0.5%, based on the total weight of the resins [A] and ~B], of tetrakis [methylene-3-(3,5~di-t-butyl-4-hydroxyphenyl) propionate~ methane as stabilizer. The re~ulting blend ~as knead0d at 190C by using 8rabender Plastograph and compression molded at 240C to obtain a pressed sheet of 2 mm in thickness. Test pieces were punched out of the sheet, and impact test, flexural test and TMA measurement were carried out. It was found that the blerld had an Izod impact strength of 40.0 kg.cm/cm, ~lexural modulus of 22100 kg/cm2, stress at flexural yield point of 830 kg/cm2 and a TMA of 108C. There could be obtained a blend excellent in rigidity and heat resistance as well a3 in impact strength.
ComParative Bxample 1 , . ~ , :~,, 1~29437 The copolymer (A~ prepared in Polymerization Example 3 was compression-molded at 240C to obtain a pressed sheet of 2 mm in thickness. Test pieces punched out of the sheet were subjected to impact test, flexural test and TMA measurement in the same manner as in ~xample 1. The sample was found to have an Izod impact strength of 2.0 kg.cm/cm, a flexural modulus of 28900 kg/cm2, stress at flexural yield point of 810 kg/cm and a TMA of 110C. Therefore, the sample was low in impact resistance and brittle, though it was excellent in rigidity and heat resistance.
Examples 2 to 4 The copolymers (A) prepared in Polymerization ~xamples la and 3 were blended with the copolymers (B) prepared in Poly~erization ~xamples 4 and 5 as in ~xample 1 in weight ratios indicated in Table 7 and evaluated in the same manner as in ~xample 1. The results are shown in Table ~.
Comparative ~xamPles 2 and 3 The copolymers (A) prepared in Polymerization Examples la and 2 were evaluated in the same manner as in Comparative ~xample 1. The results are shown in Table 7.
The samples were low in impact resistance and brittle, though the samples were excellent in rigidity and heat resistance.

13294~7 ~xample 5 A blend composed of B0 ~ of the copolymer (A) prepared in Polymerization Example 2 and 20 g of the ~opoly~er (B) prepared in Polymerization Example 6 (weight ratio: (A)/(B) = 80/20) was incorporated with 0.5%, based on the tot~l we$ght of the resins (A~ and (B), of tetrakis-~methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
methane as stabilizer. The blend was kneaded at 190C by using Brabender Plastograph and evaluated in the same manner as in Example 1. The results are shown in Table 7.
There could be obtained a composition excellent in ri~idity and heat resistance as well as in impact resistance.
_xample~ 6 and ~ :
The copolymer (A) prepared in Polymerization Example 2 was blended with the copolymer (B) prepared in Polymerization ~xample 6 in the manner as in ~xample 5 in weight ratios indicated in Table 7, and evaluated in the manner as in ~xample 5. The results are shown in Table ~.
xam~les 8 to 15 Copolymers (A) indicated in Table 8 which had been prepared substantially following the procedure of Poly~erization ~xample la were blended with copolymers (B) indicated in Table 8 which had been prepared substantially follow~ng the procedure of Polymerization Example 4 in the - 63 ~

,; ~. ., - . . : ~

. ' . . ' . ' ~ ' ' ' ' . ' ; '; ' ,. ".', ' . ~ . . , "' ' " ' ' ' :

t 329437 following the procedure of Polymerization Example 4 in the manner as in Bxample 5 in weight ratios indicated in Table 8, and evaluated in the manner as in Example 5.
Comparative Bxamples 4 to 6 Copolymers (A) indicated in Table 9 which had been prepared substantially following the procedure of Polymerization Example la were tested as in Co~parative Bxample 1. The results are shown in Table 9. The samples were low in impact resistance and brittle, though they were excellent in rigidity and heat resistance.

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1329~37 Example 16 9o g of the copolymer (A) prepared in Polymerization Example 3 and 10 g of an ethylene-propylene random copolymer (B) (ethylene/propylene - 80/20 mol%) (weight ratio: (A)/(B) = 90/10) were poured in two litres of cyclohexane and dissolved at about 70 C while thoroughly stirring. The resulting homogeneous solution was poured in two litre~ of acetone to deposit an (A)/(B) blend. The thus obtained blend was dried at 120C under reduced pressure overnight.
The (A)/(B) blend was incorporated with 0.5%, based on the total weight of the resins (A) and (B), of tetrakis tmethYlene-3-~3,5-di-t-b~tyl-4-hYdroxYPhenYl) propionate] methane as stabilizer. The blend was kneaded at 1~0C by using Brabender Plastograph and compression-molded at 240C to obtain a pressed sheet of 2 mm in thicknes3. Te t pieces were punched out of the sheet and sub~ected to impact te~t, flexural test and TMA
measurement. The blend was found to have an Izod impact strength of 9.4 k~.cm/cm, a ~lexural modulas of 23000 kg/cm2, a stress at flexural yield point of 840 kg/cm2 and a TMA of 110C. There was obtained a blend excellent in rigidity and heat resistance as well as in impact strength.
_omparative Example 7 , .: . . . -... , . - ..... , ........... : ~-: :.: :.: . .. .... . :
: :: :,. .: .- : . . : : : : : . . : .. -~329~37 The copolymer (A) prepared in Polymerization Example 3 was compression-molded at 240C to obtain a pre~sed sheet of 2 mm in thicknes~. Test pieces punched out of the sheet were tested in the same manner as in Example 16. The test piece~ were found to have an Izod impact ~trength of 2.0 kg.cm/cm, a flexural modulus of 28900 kg/cm2, stre~s at flexural yield point of 8?0 kg/cm2 and a TMA of 110 C. Hence, the sample was low im impact strength and brittle, though lt wa~ excellent in rigidity and heat resistance.
xamples 1~ and 18 The copolymer (A) prepared in Polymerization ~xample 3 and the ethylene propylene copolymer (B) were processed and evaluated as in Bxample 16 except that the copolymers were blended in weight ratio~ indicated in Tabel 10. The result~ are shown in Table 10. There could be obtained compo~itions excellent in rigid~ty and heat resi~tance as well aQ in i~pact resi3tance.
~xample 19 The polymer (A) prepared in Polymerization ~xa~ple 3 and an ethylene-1-butene copolymer ~B) indicated in Table 10 were blended together in a weight ratio given in Table 10, processed and evaluatsd in the ~ame manner as in ~xample 16. The reQult~ are shown in Table 10. There could be obtained a compo~ition excellent in rigidity and - ~4 -132~37 heat resi tance as well as high in impact re~i~tance.~xample 20 A blend of 80 g of the copolymer (B) prepared in Polymerization ~xample 3 and 20 g of an ethylene-1-butene copolymer (B) indicated in Table 10 (weight ratio: (A)/(B) = 80/20) was incorporated with 0.5%, ba~ed on the total weight of the resins (A) and (B), of tetrakis ~methylene-3-(3,5-di t-butyl-4-hydroxyphenyl) propionate~ methane as ~abillzer. The blend was kneaded at 190C by using Brabender Plastograph and evaluated in the -Qame manner as in Rxa~ple 16. The result~ are shown in Table 10. There could be obtained a compo~ition excellent in rigidity and heat re~i~tance as well as in impact re~istance.
Comarative ~xamPle 8 The copoly~er (A) prepared in Polymerization ~xample 2 was co~pre~sion-molded at 240C to obtain a pre~ed ~heet of 2 mm in thickness. The evaluation thereof wa~ made in the ~ame manner as in ~xample 16. The results are ~hown in Table 10. The te~t ~ample was found to be low in impact resistance and to be brittle, though it wa~ excellent in rigidity and heat re~i tance.
Exa~ 1 e s 2 1 and 23 Blends of the copolymer (A) prepared in poly~erization Exa~ple 2 and an ethylene propylene copolymer (B) indicated in Table 10 in weight ratios given - , . ; ., ... . .... ~, .. .... . . .

1329~37 in Table 10 were processed and evaluated in the same manner a~ in ~xample 16. The results are shown in Table 10. There could be obtained compositions excellent in rigidity and heat resistance as well as high in impact resistance.
~xa~s 24 to 29 Copolymers (A) indicated in Table 11 which had been prepared substantially following the procedure of Polymerization Example 2 and ~-olefin type random copolymers indicated in Table 11 were blended in the manner as in Example 20 in weight rations indicated in Table 11, and evaluated in the manner a-~ in ~xampole 2~.
Com~arative ~xamples 9 to 11 Copolymers indicated in Table 12 which had been prepared substantially following the procedure of Polymerization ~xampole 2 were tested as in Comparative ~xample 7. The results are shown in Table 12. Samples were ~ound to be low in impact strength and to be brittle, though they were excellent in rigidity and heat re~istance.

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132~37 Example 30 90% by weight of the ethylene polycyclic olefin copolymer obtained in Polymerization ~xample la was mixed with lOX by weight of an ethylene propylene random copolymer (hereinafter abbreviated to EPC-I) having a crystallinity index of 5% as measured by X-rays, an ethylene content of 80 mol~, an MFR of 4.6 g/10 ~in and a density of 0.865 g/cm in Henshel mixer. The mixture was melt-kneaded and extruded by means of a 40 mm~ single screw extruder (preset temperature: 230C), and pelletized. The pellets were injection-molded (cylinder temperature: 240C, mold te~perature: 70C) to obtain test pieces for use in the evaluation of physical properties.
The thus obtained test pieces were subjected to a flexural test (ASTM D ~90) and an Izod impact teqt (ASTM D
256, not notched). The results are shown in Table 13.
xample 31 The procedure of Example 30 was repeated except that 70% by weight of the ethylene polycyclic olefin copolymer and 30~ by weight of ~PC-I were used. In the sa~e way as in Example 30, test pieces for the evaluation of the physical properties were obtained and the ~lexural test and the Izod i~pact test were conducted. The results are shown in Table 1~.
~xample 32 ... . . . . . .. .

. : - .:

. ~

1329~37 The procedure of Example 30 was repeated except that an ethylene 1-butene random copolymer having a crystallinity index of 25% as measured by X-rays, an ethylene content of 92 mol%, an MFR of 18 g/10 min and a density of 0. 895 g/cm was used in place of EPC-I. In the same way as in ~xample 30 test pieces for the evaluation of physical properties were prepared and the flexural test and the Izod impact test were conducted. The results are shown in Table 13.
Example 33 The procedure of Example 30 was repeated except that an ethylene propylene random copolymer having a crystallinity index of 1~ as measured by X~rays, an ethylene content of 40 mol%, an MFR of 1.0 g/10 min and a density of 0.8S8 g/cm was used in place of ~PC-I. In the same way as in Example 30 test pieces for the evaluation of physical properties were prepared and the flexural test and the Izod impact test were conducted. The results are shown in Table 13. :
~xample 34 The procedure of Example 30 was repeated excep~
that a modified ethylene 1-butene random copolymer (cry~tallinity index as measured by X-rays; 15%, MFR: 5 g/10 min) obtained by graft-copolymerizing O.S parts by weight of maleic anhydride onto 100 parts by weight of an . ~ , .,. , . .. ' . -, , , ', ' ', , . ' ' ! . . . .

ethylene 1-butene random copolymer having a crystallinity index of 17% as measured by X-rays, an ethylene content of 89 mol%, an MFR of 4.0 g/10 min and a density of 0.885 g/cm3 was used in place of BPC-I. In the same way as in Bxample 30 test pieces for the evaluation of physical properties were prepared and the flexural test and the Izod impact test were condùcted. The results are shown in Table 13.
Comparative Bxample 12 The procedure of Example 30 was repeated except that only the ethylene polycyclic olef~n copolymer was used in place of the composition of Bxample 30 and injection-molded to prepare test pieces. The flexural test and the Izod impact test were conducted. The results are shown in Table 13.

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1329~37 ~xample 35 80 g of the copolymer (A~ obtained in polymerization Example 3 and 20 g of an ethylene propylene 2-ethylidene-2-norbornene random copolymer tB) (ethylene/propylene/diene = 66/31/3 mol%) (weight ratio:
(A)/(B) = 80/20) were poured in 2 litreQ of cyclohexane and di~olved at about 70C while thoroughly ~tirring.
The resulting homogeneous 301ution was poured in 2 litres of acetone to deposit an (A)/(B~ blend. The blend was dried at 120~C under reduced pre~ure overnight.
The thu~ obtained (A)/(B) blend wa~ incorporated with 0.5%, based on the total weight of the resin~ ~A) and ~B), o~ tetrakis ~methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl~ propionate~ methane as ~tabilizer. The blend wa~ then kneaded at 190C by using Brabend~r Pla~tograph and compres~ion-molded at 240C to obtain a pres~ed ~heet of 2 ~m in thickness. Test piece~ were punched out of the ~heet and impact te~t, f lexural test and TMA measurement were conducted. The blend was found to have an Izod impact 3trength of 53.4 kg.cm/cm, a f lexural modulu~ o~ 16000 kg/cm2, ~tre~s at flexural yield point of 590 kg/c~2 and a TMA of 110C. Hence, there could be obtained a blend excellent in rigidity and heat resi~tance a~ well as in impact strength.

Comparative Example 13 _ ~9 _ .

13294~7 The copolymer (A) prepared in Polymerization ~xample 3 wa compression-molded at 240C to obtain a pre~sed ~heet of 2 m~ in thicknesQ. In the s~me way as in ~xample 35, test pieces were punched out of the ~heet and te~ts were conducted. The test pieces were found to have an Izod impact strength of 2.0 kg.cm/cm, a flexural modulus of 28900 kg/cm2, stress at flexural yield point of 870 kg/cm and a TMA of 111 C. Hence, the sample was found to be low in impact resiQtance and to be brittle, though it was excellent in rigidity and heat resistance.
~xample~ 36 and 37 Blends of the copolymer (A) prepared 1n Polymerization ~xample 3 and the ethylene propylene 5-ethylidene-2-norbornene random copolymer (B~ (ethylene/
propylene/ diene = 66/31/3 mol% ) in weight ratio~ given ln Table 14 were proceQ3ed and evaluated in the same manner as in ~xample 35. The re~ult~ are ~hown in Table 14. There could be obtained compo~ition~ excellent in rigidity and heat re~i~tance a~ well a~ in impact re~i~tance.
Bxample3 38 to 39 Blend~ of the copolymer (A) obtained in Polymerization Example 3 and an ethylene propylene 5-ethylidene-2-norbornene random copolymer (B) (ethylene/
propylene/ diene = 6~/31/2 mol~ ) in weight ratio ~iven -- 90 -- :

- : . , ~ : .

1329~37 in Table 14 were processed and evaluated in the sa~e manner a~ in ~xample 35. The results are shown in Table 14. There could be obtained compo itions excellent in rigidlty and heat resistance a~ well as high in impact re3istance.
ExampleQ 40 and 41 Blends of the copoly~er (A) prepared in Poly~erization Example 3 and an ethylene propylene dicyclopentadiene random copolymer (B) (ethylene/
propylene/ diene = 67/32/1 mol%), in weight rations indicated in Table 14 were processed and evaluated in the sa~e manner as in ~xample 35. The results are shown in Table 14.
~xample 42 A blend of 80 g of the copolymer (A) prepared in Polymerlzation ~xample 2 and 20 ~ of the ethylene propylene 5-ethylidene-2-norbornene random copolymer (B) (ethylene/propylene/diene - 66/31/3 mol%) (weight ratio :
(A)/~B) = 80/20) was incorporated with 0.5%, ba~ed on the total weight o~ the resins (A) and (B~, of tetrakis tmethylene-3-(3~5-di-t-butyl-4-hydroxyphenyl)propionate~
methane a3 stabilfzer. The blend wa~ kneaded at 190C by using Brabender Plastograph and evaluated in the same 1329~37 manne~ as in Example 35. The results are shown in Table 14. There could be obtained a composition excellent in rigidity and heat resistance as well as in impact resistance.
Comparative Example 14 The copolymer (A) prepared in polymerization Example 2 was conpression-molded at 240C to obtain a pressed sheet of 2 mm in thickness. In the same way as in Example 35, test pieces were prepared, evaluated and found to be low in impact strength and to be brittle, though they were excellent in rigidity and heat resistance.
Examples 43 and 44 The copolymer (A) prepared in Polymerizati~n ~xample 2 was blended withG~-olefin diene copolymers (B) given in Table 14 in the same manner as in ~xample 42.
The evaluation of the ~lends was made. The results are shown in Table 14.
~xamples 45 to 50 Blends of copolymers ~) indicated in Table 15 and ~-olefin-diene elastomers ~B~ indicated in Table 15 were processed and evaluated in the same way as in ~xample 42. The results are shown in Table 15. There could be obtained compositions excellent in rigidity and heat resistance as well as in impact resistance.
Comparative Examples 15 to 17 -- 9~2 --... ,, . , ,. , , ., .,,, " , ,,.. . ,. , ,. ., ." ,.,, "., ., . ,,, ~ ., ,., .. . ",.. . . ..... .. .. .

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Copolymers (A~ indicated i~ Table 16 were processed and evaluated in the same way as in Comparati~e Example 14. The results are shown in Table 16.

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xample 51 A dry blend of 90 g of the copolymer (A) obtained in Polymerization Example 3 and 10 g of a ~tyrene-butadiene-styrene block copolymer (B) (density: 0.94 g/cm , Cariflex TR1102, a product of Shell Kagaku KK) (wei~ht ratio: (A)/(B) = 90/10) wa~ incorporated with 0.5%
and 0.3%, ba~ed on the total weight of the re~ins (A) and (B3, of tetraki~ ~methylene-3-(3,5-di-t-butyl-4-hydroxyphen~l)propionate] methane and dilauryl thiodipropionate as ~tabilizer~, re~pectively. The re~ulting blend was kneaded at 190C by uqing Brabender Plastograph and compres~ion-molded at 240C to prepare pressed sheet~ of 1 mm in thickne~s and a pre~sed sheet of 2 mm in thickne~s, respectively. Te~t pieces were punched out of these QheetQ and impact test, flexural te~t and TMA
measurement were conducted.
The blend wa~ found to have an Izod impact strength of 5.0 kg.cm/cm, a flexural modulus of 23000 kgJcm2 and a TMA of 111C. Nence, there could be obtained a blend excellent in rigidity and heat re~istance a~ well as in impact strength.
Com~arative ~xample 18 The copolymer (A) prepared in Polymerization ~xa~ple 3 wa~ compre~sion-molded at 240C to prepare pre~sed ~heet~ of 1 mm and 2 mm in thickne~s. Te~t~ were ''" ' ' ' ' :" .''""' ,. ' . ' ' '''' " ' ' ;

13~9437 conducted in the same way as in ~xample 51. The sample wa~ found to have an Izod impact ~trength of 2.0 kg.cm/cm, a flexural modulu of 28900 kg/cm2, a stress at flexural yield point of 870 kg/cm and a TMA of 111C. Therefore, it was found that the sample was low in impact reRistance and brlttle, though it was excellent in rigidity and heat resistance.
~xampleQ 52 and 53 The evaluation of blends of the copolymer (A) obtained in Polymerization ~xample 3 and the ~tyrene-butadiene-~tyrene bloc~ polyuer (B) (density: 0.94 g/cm3, Cariflex TR1102, a product of Shell Kagaku KK) in weight ratio~ of (A) / ~B) given in Table 17 was made in the same manner as in ~xample 51. The results are ~hown in Table 1~. There could be obtained compositions excellent in rigidity and heat resi~tance as well as high in impact resistance.
~xam~le 54 The evaluation of a blend o~ the copolymer (~) obtained in Polymerization ~xample 3 and a hydrogenated styrene-butadiene-styrene block copolymer (B) (density:
0.90 g/cm , Clayton G1657, a product of Shell Kagaku KK) (weight ratio of (A)/(B] being given in Table 17) wa~ made in the same manner a~ in ~xample 51. The result3 are shown in Table 17. There could be obtained a compo~ition l329~37 excellent in rigidity and heat re~istance a~ well as in impact resistance.
~xample 55 The evaluation of a blend of the copolymer (A) prepared in Polymerization ~xample 3 and a styrene-isoprene-styrene block copolymer (B3 (density6: 0.92 g/cm3, Cariflex T~1107, a product of Shell Kagaku KK) (weight ratio of (A)/(B) being given in Table 17) wa~ made in the same manner as in Exa~ple 51. The results are shown in Table 17. There could be obtained a composition excellent in rigidity and heat re~istance as well as hlgh in impact resistance.
Examples 56 and 57 ~ he evaluation of blends of the copolymer (A) obtained in Polymerization ~xample 3 and a styrene-butadiene copolymer (B) (den~ity: 0.94 g/cm3, Nipol 1502, a product of Nippon Geon Co., Ltd.) in weight ratios of (A)/(B) given in Table 1~ was made in the same manner as in E~ample 51. The results are shown in Table 1~. There could be obtained compositions excellent in rigidity ~nd heat resistance as well as ln impact resis~ance.
~xam~le 58 The evaluation of a blend of the copolymer (A) prepared in Polymerization ~xample 2 and a styrene-butadiene-styrene block copolymer (B) ~density: 0.94 . : . . , ., . "

g/cm , Cariflex 1102, a product of Shell Kagaku KK)(weight ratio of ~A)/~B) being given in Table 17) wa~
conducted in the same ~anner as in Example 51. The results are shown in Table 1~. There could be obtained a composition excellent in rigidity and heat resistance as well as in impact resistance.
Comparative Example 19 The copolymer (A) prepared in Polymerization Example 2 was compression-molded at 240 C to prepare pressed sheets of 1 mm and 2 mm in thickness. Test pieces obtained from the sheets were tested. The results are shown in Table 1~. The sheets were found to be low in impact resistance and to be brittle, though they were excellent in rigidity and heat resistance.
~xamples 5g and 60 The evaluation of blends of the copolymer (A) prepared in Polymerization Example 2 and a hydrogenated styrene-butadiene-styrene block copolymer (B) (density:
0.90 g/cm , Clayton G 1657, a product of Shell Kagaku KK) in weight ratios of (A)/(B) given in Table 17 was conducted in the same manner as in ~xample 51. The results are shown in Table 17. There could be obtained compositions excellent in rigidity and heat resistance as well as in impact resistance.
~xamples 61 to 66 . - , - , : . - . . ~ . .
~:;., ., . : . . . ~ : : , . : :: . -. . .

1329~37 The evaluation of blends of a copolymer (A~ -(composition being given in Table 17) prepared substantially following the procedure of Polymerization Example lb and a styrene-conjugated diene block copolymer (B) given in Table 17 (weight ratio of (A)/(B) being given in Table 17) was conducted in the same way as in ~xamiple 51. The results are shown in Table 17. There could be obtained compositions excellent in rigidity and heat resistance as well as high in impact resistance.
Comparative ~xamples 20 to 22 The evaluation of copolymers (A) (compositi~n being given in Table 17~ prepared isubstantially following the procedure of polymerization ~xample lb was conducted in the same way as in Comparative Rxample 19. The resu7.ts are shown in Table 17.

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~32g437 Example 67 A dry blend of 40 g of the copolymer (A~ obtained in Polymerization Example lb, 5 g of the cycloolefin type random copolymer prepared in Polymerization Example 5 (hereinafter abbreviated to T3R) (B1~ and 5 g of ethylene-propylene random copolymer (hereinafter abbreviated to EPR~ (B2) containing 80 mol% of ethylene units and having a crystallinity index of 15%, a denslty of 0.88 g/cm3 and an intrinsic viscosity [7, of 2.2 dl/g (weight ratio =
80/10/10) was incorporated with 0.5% and 0.3%, based on the total weight of the resins (A) and (P), of tetrakis~methylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate]methane and dilauryl thiodipropionate, respectively. The blend was kneaded at 150C by using Brabender Plastograph and compression-molded at 240 C to prepare pressed sheets of 1 mm and 2 mm in thickness.
Test pieces were punched out of these sheets and impact test, flexural test and TMA measurement w~re conducted.
The blend was found to have an Izod impact strength of 40.2 kg.cm/cm, a flexural modulus cf 19000 kg/cm and a TMA of 110 C. There could be obtained a blend excellent in rigidity and heat resistance as well as in impact strength.
Comparative Example 23 The copolymer (A) prepared in Polymerization ~xample 3 was compre~sion-molded at 2400C to prepare pressed sheets of 1 mm and 2 mm in thickne~. The sheets were tested in the qame manner a in Example 67.
The sample wa~ found to have an IZ impact strength of 2.0 kg.cm/cm, a flexural modulu~ o~ 28900 kg/cm2, stre~s at ~lexural yield point of 870 kg/cm2 and a TMA of 110C. The sample was found to be low in impact re~istance and to be brittle, though it was excellent in rigidity and heat re~istance.
_xa~ple 68 The evaluation of a blend of the copolymer (A) obtained in Polymerization ~xample 3, TDR ~B1) and a styrene-butadiene-styrene block copolymer (hereinafter abbreviated to SBS) (B2) (density: 0.94 g/cm2, Cariflex TRllOZ, a product of Shell Kagaku RK~ (weight ratio being given in Table 18) wa~ conducted in the ~ame manner a~ in ~xample 67. The re~ult~ are ~how~ in Table 18. There could be obtained a compo~ition excellent ~n rigidity and heat resistance as well a~ high in impact res~stance.
Example 69 The evaluation of a blend of the copoly~er (A) prepared in Polymerization 2xample 3, an ethylene-propylene-diene copolymer (hereinafter abbreviated to ZPDM) (B2) (ethylene/propylene/5-ethylidene-2-norbornene =
66/31/3 mol%, [7, ~ 2.1 dl/g, iodine value : 22, den~ity :

. .
, : : :
:': :, ' .. :
.

0.87 g/cm2) was conducted ln the ~ame manner as in Example67, the weight ratio of (A)/tB1)/(B2) being given in Table 18. The re~ults are shown in Table 18. The results are shown in Table 18. There could be obtained a composition excellent in rigidity and heat re~i~tance as well as ln impact resistance.
Rxample~ ~0 to 72 The evaluation of blend~ of the copolymer (~) prepared in Polymerization ~xample 3, ~PR (B1) and SBS
(B2) in weight ratio~ given in Table 18 was conducted in the same manner a~ in ~xample 67. There could be obtained compo~itions excellent in rigidity and heat resistance as well a~ in impact strength.
Exam~les 73 to The evaluation of blends of the copolymer (A) prepared in Polymerization Example 2, ~PDM (B1) and SBS
~B2) in weight ratio~ given in Table 18 wa~ conducted in the same manner as in Rxample 67. The re~ults are shown in Table 18. There were obtained co~positions excellent in rigidity and heat resi~tance a~ well a~ in impact ~trength. . -Com~arative ~xample 24 -~
The evaluation of the copolymer (A) prepared in Polymerization ~xample 2 wa3 made in the ~ame manner a~ in ~ .
Comparative ~xample 23. The results are shown in Table ,,, . ~ ~ ~- - -1329~137 18. The sample was found to be low in impact resistance and to be brittle, though it was excellent in rigidity and heat resistance.
~xamples 78 to 80 The evaluation of blends of a copolymer (A) indicated in Table 18 which had been prepared substantially following the procedure of Polymerization Example lb, EPR (B1) and ~PDM (B2) in weight ratios given in Table 18 was conducted in the same manner as in Example 67. The results are shown in Table 18. There were obtained compositions excellent in rigidity and heat resistance as well as high in impact resistance.
xamples 81 and 82 The evaluation of blends of a copolymer (A) indicated in Table 18 which had been prepared substantially following the procedure of Polymerization ~xample lb, ~PDM (B1) and SBS (B2) in weight ratios given in Table lg was conducted in the same way as in ~xample 67. The results are shown in Table 18. There were obtained compositions excellent in rigidity and heat resistance as well as high in impact resistance.
~xample_ 83 and 84 The evaluation of blends of a copolymer (A) indicated in Table 18 which had been prepared substantially following the procedure of Polymerization 1 3~437 Example lb, TDR (B1) and SBS (B2) in weight ratios given in Table 18 was conducted in the same way as in Example 67. The results are shown in Table 18. There were obtained compositions excellent in rigidity and heat resistance as well as high in impact resistance.
Comparative_~xamples 25 to 27 The evaluation of copolymers (A) indicated in Table 18 which had been prepared substantially following the procedure of Polymerization 2xample lb was conducted in the same manner as in Comparative ~xample 23. The results are shown in Table 18. They were found to be low in impact strength and to be brittle, though they were excellent in rigidity and heat resistance.

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~3294~7 In the following examples, ~1) Asahi Fiber Glass glass roving chopped strand GR-S-3A (GF) or (2) Fujimi white alumina #4000 (WA) was used as the filler (Cj.
Example 85 The copolymer (A) prepared in Polymerization Example 3 was dry-blended with a copolymer (B) given in Table 19, prepared substantially following the procedure of Polymerization Example 3 in a weight xatio of 80/10.
The dry blend was incorporated with 0.5% and 0.3%, based on the total weight of the resins (A) and (B), of tetrakis ~methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane and dilauryl thiodipropionate as stabilizers, respectively. The dry blend was kneaded at 220C in a 30 mm~ twin-screw extruder and dry-blended with 10% by weight, ba~ed on the total amount of the resins (A) and (B), of GF. The resulting blend was kneaded at 220C in a 30 mm~ twin-screw extruder and compression-molded at 240C to prepare pressed sheets of 1 mm and 2 mm in thickness. Test piece~ were punched out of these sheets and subjected to impact test, flexural test and TMA measurement.
The blend was found to have a notched Izod impact strength of 6 kg.cm/cm, an initial flexural modulus of 31000 kg/cm2 and a TMA of 113C. There was obtained a blend excellent in rigidity, heat resistance and impact .~: . : , . . .

strength.
Comparative Example 2 a The copolymer (A) obtained in Polymeri~ationExample 3 was compression-molded at 240C to prepare pressed sheets of 1 mm and 2 mm in thickness. Test pieces were prepared from these sheets and subjected to impact test, flexural test and TMA measurement.
The test pieces were found to have a notched Izod impact strength of 2 kg.cm/cm, an initial flexural modulus of 28900 kg/cm2 and a TMA of 111C. Therefore, the sample was inferior in impact strength, initial flexural modulus and heat resistance as compared with the blend of Example 85.
~xamPles 86 and 87 The evaluation o~ blend~ of copolymers (A) and (B) and filler(C) given in Table 19 in blending ratios given in Table 19 was conducted in the same manner as in Example 85. The results are shown in Table 19. There were obtained compositions excellent in rigidity, heat resistance and impact strength.
~xamples 88 to 90 .

The evaluation of blend~ of copolymers (A~ and (B) and filler~C) given in Table 19 in blending ratios given in Table 19 was conducted in the same manner as in Example 85. The results are shown in Table 19. There were l32~37 obtained compositions excellent in rigidity, heat resistance and impact strength.
Comparative Example 2g The evaluation of the copolymer (A) given in Table 19 was conducted in the same manner as in Comparative Example 28. The results are shown in Table 19. The sample was inferior to the blends of ~xamples 88 to 90 in rigidity, heat resistance and impact strength.
Examples 91 to_93 The evaluation of blends of copolymers (A) and (B) and filler (C) given in Table 19 in blending ratios given in Table 19 was conducted in the same manner as in Example 85. The results are shown in Table 19. There were obtained compositions excellent in rigidity, heat re~istance and impact strength.
Com~arative ~xample 30 The evaluation of the copolymer (A) given in Table 19 was conducted in the same manner as in Comparative ~xample 28. The results are shown in Table 19. The s~mple was inferior to the compositions of ~xamples 91 to 93 in rigidity, heat resistance and impact strength.

b 1 3 2 9 4 3 7 0 ~
.~

~ 0~ .r = I u~ = I ~ = I
_ , _~ ~ d' ~ N == ~ ~
_ O O
~ X h a~ ~ ~ ~ , = : I a) _ _ ~ Oa N
a E~ ~
a ~ Ul ~ ~ ~ a) = I ~
O t~ P3 ~ :

~ ~ .
a ~ I a ~ a ~n ~ ~ O
~JO a ~

U~ ~o o ~, = O = ~ : = = ~
~ _ ~
O O ID
= = = U~ = = ~: = =
~ ~o o O O

~ X h . ~.
~ ~ 1 0 0 = = . _ = =
_ a ~ ~ O
~ o ...
0 ~ ~ : ~
~ O~ ~ ~: ' R ~ 1~ = = = O = = = ~o :

a I = = ~ = = = a fl ~ 8 = 8 ~= :
~o It) - ~ 10 01 0 0 I N C') . O
l~i O ~
7'1~ :

. ` . . . . . .. .
. :" . ~ ` ', ;' ' . . '` ,; . " " ' 1329~37 î~
o ~ ~ o ,~ ~ 0 .~
~ , U ooo oooooooo o U) ~ ~ ~ ~ U~ ~ ~ o C~l ~ ~~ U~ o~ ~
X ~ ~ ~ ~ u~ co ~ ~ ~n~n ~ ~ ~ a-o ~
U~ R

U~ ,, C`~
~ ~ h ~ C~ o o o o o o o o oo o o .,, .,1_I~ ooo oooo oooo o X ~ ~ o a~
~rl 0 ~ ~ ~~ r~ o H ~1 13 ~1 ~
E~ ~ ~ t) O _l O ~ t~
N ~ .~6 H J) --O
O
~rl /11t~ OOO OOOOOOOO O
~ ^ o o o o o o o o u~ u) ~ o ~ m ~ _, ,, _l ,, ,, _, o o o o o o o ~ U)U> O
0 P' ~D O ~ ~ ~ 0 0~ ~ O
., _. ,, m U) lD C~ n o ~ ~ ~ o X o X X o X X o _ l _ - . ~ - ~ : . : . . ..

- . . .: . .. ,~ . - ~ . . . . .
. . . , . . - , ... ~ . -, . , 1 ~ .

1329~37 Example 94 The copolymer ~A) obtained in Polymerization Example 3 was dry-blended with an ethylene propylene random copolymer tB) (ethylene/propylene = 30/20 mol%) in a weight ratio of 80/10. The dry blend was incorporated with 0.5% and 0.3%, based on the total weight of the resins (A) and (B), of tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] methane and dilauryl thiodipropionate as stabilizers, respectively. The resulting blend was kneaded at 220C in a 30 mm~ twin-screw extruder and dry-blended with 10% by weight, based on the total amount of the resins (A) and ~B), of GF. The resulting blend was kneaded at 240C in a 30 mm~ twin-screw extruder and compression-molded at 240C to prepare pressed sheets of 1 mm and 2 mm in thickness. Test pieces were prepared from these sheets and subjected to impact test, flexural test and TMA measurement.
The blend was found to have a notched Izod impact strength of 7 kg.cmJcm, an initial flexural modulus of 30600 kgJcm2 and a TMA oP 114C. There was obtained a blend excellent in rigidity, heat resistance and impact strength.
Co~parative Example 31 The copolymer (A) prepared in Polymerization Example 3 was compression-molded at 240C to prepare ' : . , . . ~ '. : ', .

' ' .:

1329~37 pressed sheets of 1 mm and 2 mm in thickness. Test pieces were cut out of the~e sheets and ~ubjected to impact test, flexural test and TMA measurement.
The test pieces were found to have a notched Izod impact strength of 2 ~g.cm/cm, an initial flexural modulus of 28900 kg/cm and a TMA of 110 C. The sample was inferior to the blend of ~xample 94 in impact strength, initial flexural modulus and heat resistance.
Examples 95 and 96 The evaluation of blends of copolymers (A) and (B) and filler (C) given in Table 20 in blending ratios given in Table 20 was conducted in the same manner as in ~xample 94. The results are shown in Table 20. There were obtained compositions excellent in rigidity, heat resistance and impact strength.
Examples g7 to 99 The evaluation of blends of copolymerq (A) and (B) and filler (C) given in Table 20 blending ratios given in Table 20 wa~ conducted in the same manner as in Example 94. The results are shown in Table 20. There were obtained compositions excellent in rigidity, heat resistance and impact strength.
Comparative ~xam~le 32 The evaluation of copolymer (A) given in Table 20 was conducted in the same manner as in Comparative ~xample 1329~37 31. The results are shown in Table 20. The sample wasinferior to the blends of Examples g7 to 99 in rigidity, heat resistance and impact strength.
Examples 100 to 102 The evaluation of blends of copolymers (A) and (~) and filler (C) given in Table 20 in blending ratios given in Table 20 was conducted in the same ~anner as in Example 94. The results are shown in Table 20. There were obtained compositions excellent in rigidity, heat resistance and impact strength.
Comparative Example 33 The evaluation of copolymer (A) given in Table 20 was conducted in the same manner as in Comparative ~xample 31. The results are shown in Table 20. The sample was inferior to the blends of ~xamples 100 to 102 in rigidity, heat resistance and impact strength.

.. . : , . , , , , .~ ., ~ , . . .

.. . .

132~37 ~- = , ¢ , ,4, ~!1 3 ~
.1 _ >~ c"_ 0 o~ :0 O 0 : : I 0 = : I 0 ~) O o o 1~ --111 ~.
Y ~ X _ U) : : I o : _ I o : : I
~ a _ ~
m ~ ,, ~ , ~ , '' = I
----' 'a N ~I N
h ~
~ ~ I - ~ I O = = I o:: I ' O:~
ô m _ 8 ~ N l l O
~ h O O.

t~ _~ O : = I O
O ~q 0 0 ~ o ,- : : u~ : : : ~r : : :
E~ --~ O O
_. ~ : : , = N
~ O O ~

_ O 'a 13 0 N
¢ 13 ~ 1: _ : o =: : ~

~ O _l ~ : : - O : : : .~ _ = :

O ~ ~
~ C~ ~
~ a~ ~
~ ~ ~ ~ .
~ O
~ ~ m ,~, ~
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.r u~ 0~I O ~ N
0 ~ 0 C~) 0 0 0 ~ C'7 0 0 0 ~ X X

:. . ' -, ' ': ' :, .' , ': ' .

1329~37 ~ O ~ ~ a~

U~t, ooo oooooooo o X ~ ~ r~ ~D ~ a~ ~ r . ~ :n ~ ~ lO a-,1 o _ ~a~
ooo oooooooo o .~.~ oooC~ooo oooo o X ~ ~ ID ~ ~ tS~ J) ~ ~ N It) ~ a-~ QJ ~ ~ O ~ r~ 3 ~ O ~1 ~ ~ ~ O
o ~ -- ~ c~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
-o a~
h P.. C t~
_I
O ~ 0 a~
O ~ ~
N ~ .~C
H U~ --O
O
~rl ooo oooo oooo o h -- o o o o o o o o o o o o 1 ~ ~ ~ o co r~ ID O ~ O
.
_I--3 m O _, ~ o o o c~
,~ o X ~ ~o X

. - . . . . :
- ~ - . - . ~ - .

Example 103 The copolymer (A) obtained in Polymerization Example 3 was dry-blended with an ethylene propylene 5-ethylidene-2-norbornene random cspolymer (B) (e~hylene/
propylene/diene = 66/31/3 mol%) in a weight ratio of 80/10. The dry blend was incorporated with 0.5% and 0.3%, based on the total weight of the resins (A) and (B), o~
tetrakis ~methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and dilauryl thiodipropionate as stabilizers, respectively. The resulting blend was dry-blended with 10% by weight, based on the total amount of the resins (A) and ~B), of GF. The thus-formed dry blend was kneaded at 220C in a 30 mm~ twin-screw extruder and compression molded at 240C to prepare pressed sheets of 1 mm and 2 mm in thickness. Test pieces were cUt out from these sheets and subjected to impact test, flexural test and TMA measurement.
The blend was found to have a notched Izod impact strength of 8 kg.cm/cm, an initial flexural modulus of 31100 kg/cm2 and a TMA of 114C. There was obtained a hlend excellent in rigidity, heat resistanoe and impact strength.
Com~arative Example 34 The copolymer (A~ obtained in Polymerization Example 3 was compres~ion-molded at 240C to prepare 1329~37 pressed sheets of 1 mm and 2 mm in thickness. Test pieceswere prepared from these sheets and subjected to impact test, flexural test and TMA measurement.
The sample was found to have a notched Izod impact strength of 2 kg.cm/cm, an initial flexural modulus of 28900 kg/cm2 and a TMA of 111C. The sample was in~erior to the blend of Bxample 103 in rigidity, initial flexural modulus and heat resistance.
Bxamples 104 and 105 The evaluation of blends of copolymers (A) and (B) and filler (C) given in Table 21 in weight ratios given in Table 21 was conducted in the same manner as in Example 103. The results are shown in Table 21. There were obtalned compo~tions excellent in rigidity, heat resistance and impact strength.
~xamples 106 to 108 The evaluation of blends of copolymers (A) and (B) and filler (C) given in Table 21 in weight ratios given in Table 21 was conducted in the same manner as in ~xample 103. The results are shown in Table 21. There were obtained compositions excellent in rigidity, heat resistance and impact strength.
Comparative ~xamPle 35 The evaluation of the copolymer (A) given in Table 21 was conducted in the same manner as in Comparative - 12~ -.: - , , . : : . ~:, , , - .

~xample 34. The results are shown in Table 21. The sample was inferior to the compositions of Examples 106 to lQ8 in rigidity, heat resistance and impact strength.
~xamples 109 to 111 The evaluation of blends of copolymers (A) and (B) and fille~ (C) given in Table 21 in blending ratios given in Table 21 was made in the same manner as in Example 103.
The results are shown in Table 21. There were obtained compositions exc~llent in rigidity, heat resistance and impact strength.
Comparative Bxample 36 The evaluation of the copolymer (A) given in Table 21 was conducted in the same manner as in Comparative Example 34. The result~ are shown in Table 21. The sample was inferior to the compositions of Examples 109 to 111 in rigidity, heat resistance and impact strength.

r. r~
V~ ~ ~ : - I ~ = = I OD = = I
C: ~ o o o ~, .
X o = , , o = , o h ~
a a~
~ r-1 N = _ I O = _ I C') = : I
_ O ~

~ ~ .~ ~1 b ~ ,_~ N
._ X ~
~ ~ ~ : : I ~ : : I ,~ : : I

. a o ~ ~o = I ~O = = I ~ = = I
U r ~ t~
E~ - ~1 = = : Y):: : ~:: :

~ o o U~
o o o X ~ ~ a~
~C~ ,,o ' ' ' o = ,, = = , ~ ~ a~
. ~
, o , ~ = = = o = = = ,~ = = =
~ ~ ID
o o ~
t, ~, P~
n~ ~ ~
h O ~ O
.c o I I I I ~ = r~ ~
E~ 11 ~tl ~ a~
o~
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O O O ~ ~ O O O ~ ~ O r~
~
~27--. .`: - - ` ` ` , : ~ -1329~37 ¢ O~ ~ O

o) .,, ~, ~
m s. v o o oo o o ~ o o o o o V~ ~ ~ ~ ~ ~ ~r~ 0 a~ ~ ~D O ~ --I
X ~ ~ ~ u~ ~CD ~ ~ ~ C ~ ~ ~ O~
,, o _ , C~l o o oo o o o o o o o o a~ ~ . ~ ~ o o o o o o o o o o o o co 10 ~ ~ ~ O ~ u~a~ o ~n ; ~ ~ ~ ~0 ~ D O ~ I O
0 -- 0 ~ l 0 C~) er ~C') C~ ~ C~) t, , ~, _ '~ R..C C) , E~ ~ V a: ~ ~ ~ ~P ~ ~_I u) ~ ~ .1 .
O
H O _ ~.' o ~rlO
_~rl O OO O O O O O O O G O
-- ~ OO O O O O O O O O O
~ m 1~ ~ ~ ,, ,, ~ ,, ,, _, ,, o OO O O OO ~ O O O
1 ~ r~ ~ o co ~ ~ 0 0 ~ ~ O
,1--3 m ~ _ _~ U
_I _ ~ ~C
."

~ ~U~ ~ ~ 0 ~O
O OO ~ OO O 0 0 X o ~ X o X X o X
U P~

. . ~... . ~ -.
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' 132~437 Example 112 The copolymer tA) obtained in Polymerization Example 3 was dry-blended with a styrene butadiene styrene copolymer (B) (density: 0.94 g/~m , Cariflex TR1102, a product of Shell Bagaku KK) in a weight ratio of 80/10.
The dry blend was incorporated with 0.5% and 0.3%, based on the total weight of the resins (A) and (B), of tetrakis ~methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate]
methane and dilauryl thiodipropionate as stabilizers, respectively. The resulting blend was kneaded at 220C in a 30 mm~ twin-screw extruder and dry-blended with 10~ by weight, based on the total amount of the resins (A) and (B), of GF. The thus formed dry blend was then kneaded at 220C in a 30 mm~ twin-screw extruder and compression-molded at 240 C to prepare pressed sheets of 1 mm and 2 mm in thic~ness. Test pieces were cut out from these sheets and subjected to impact test, flexural test and TMA
measurement.
The composition was found to have a notched Izod impact strength of 8 kg.cm/cm, an initial flexural modulus of 31000 kg/cm2 and a TMA of 115 C. There was obtained a composition excellent in rigidity, heat resistance and impact strength.
Comparative Example 37 The copolymer (A~ obtained in Polymerization - ~: . "~

: .: ~ : -:; : : ;
. .. .. .. ~, . . .

1~29437 Example 3 was compression-molded at 240 C to prepare pressed sheets of 1 mm and 2 mm in thickness. Test pieces were cut out of these shee.s and subjected to impact test, flexural test and TMA measurement.
The test pieces were found to have a notched Izod impact strength of 2 kg.cm/cm, an initial flexural modulus of 28900 kg/cm and a TMA of 111 C. The sample was inferior to the blend of Example 112 in impact strength, initial flexural modulus and heat resistance.
Examples 113 and 114 The evaluation of blends of copolymers (A) and (B) and the filler (C) given in Table 22 in blending ratios given in Table 22 was conducted in the same manner as in ~xample 112. The result~ are shown in Table 22. There were obtained compositions excellent in rigidity, heat resistance and impact strength.
~xam~les 115 to 117 The evaluation of blends of copolymers (A) and (B) and the filler (C) given in Table 22 in blending ratios gi~en in Table 22 was conducted in the same manner as in ~xample 112. The results are shown in Table 22. There were obtained compositions excellent in rigidity, heat re~i~tance and impact strength.
ComFIarative ExamRle 38 The evaluation of the copolymer (A) given in Table - 13~ -:. -: ~ , . . : . , . :, -- : : .. . , - ..... .... . .. ...

~329437 22 was conducted in the same manner as in Comparative Example 37. The results are shown in Table 22. The sample was inferior to the compositions of ~xamples 115 to 117 in rigidity, heat resistance and impact strength.

¢ o~ ~ 0 1 3 2 9 4 ~ 7 a O O O O O O O O
X ~ ~ ~ ~ 0 0 rl O ~ ~ (D ~ 0 ~, ~, ~ U~ C`l O
X ~ ~ o ~ 0 ~ m ~ ~ o~
rl O .Y ~ 0 O CO t~ N ~ O

~ C~
~ `
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H ~rl U) ~

^O
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0 ~1 0 0 E~ ~ o ~, o t~ ~ ~ ~p ~0~
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-I
a ,P, ~4 :
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_I ~1 A u7 _( ~ O A
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~ 8 ~ N ~ ~
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~329437 Example 118 A dry blend of the copolymer (A~ obtained in Polymerization Example 3, the cycloolefin type random copolymer (B1) obtained in Polymerization Example 5 (hereinafter abbreviated to T~R) and an ethylene-propylene random copolymer (B2~ (hereinafter abbreviated to ~PR) containing an ethylene unit of 80 mol% and having a crystallinity index of 5%, a density of 0.88 g/cm3 and an intrinsic viscosity ~] of 2.2 dl/g (weight ratio =
80/5/5), was incorporated with 0.5% and 0.3%, based on the total weight of the resins (A), (B1) and (B2), of tetrakis ~methylene-3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate]methane and dilauryl thiodipropionate as stabilizers, respectively. The dry blend was dry-blended with 10% by weight, based on the total amount of the resins (A), (B1) and ~B2), of GF. The resulting blend was kneaded at 220C in a 30 mm~ twin-screw extruder and compression-molded at 240C to prepare pressed sheets of 1 mm and 2 mm in thickness. Test pieces were cut out from these sheets and subjected to impact test, flexural test and TMA measurement.
The composition was found to have a notched Izod i~pact strength of 6 kg.cm/cm, an initial flexural modulus of 30900 kg/cm2 and a TMA of 114C. There was ohtained a composition excellent in rigidity, heat resistance and impact resistance.
Comparative ~xample 3~
The evaluation of the copolymer (A) obtained inPolymerization Example 3 was compression molded at 240C
to prepare pressed sheets of 1 ~m and 2 mm in thickness.
Test pieces were punched out of these sheets and subjected to impact test, flexural test and TMA measurement~
The sample was found to have a notched Izod impact strength of 2kg.cm/cm, an initial f lexural modulus of 28900 k~/cm a~d a TMA of 111C. The sam,ple was inferior to the blend of Example 118 in impact strength, initial flexural modulus and heat resistance.
~xample 119 A blend of the copolymer (A) obtained in Polym,erization ~xample 3 and given in Table 23, TDR (B1), a styrene~butadiene-styrene block copolymer (hereinafter -abbreviated SBS) (B2) (density: 0.94 g/cm , Cariflex TR1102, a product of Shell Kagaku KK) and GF in a ratio given in Table 23 was processed and evaluated in the same manner as in ~xample 118. The results are shown in Table 23. There was obtained a composition excellent in rigidity, heat resistance and impact resistance.
Example 120 A blend of the copolymer (A) obtained in Polymerization ~xample 3, an ethylene-propylene-diene - ' .:

~329437 copolymer (hereinafter abbreviated to EPDM) (B1) ~ethylene/propylene/5-ethylidene-2-norbornene = 66/31/3 mol% t7] - 2.1 dl/g, iodine value: 22, density: 0.8~
g/cm3), SBS (B2) and GF in a blending ratio given in Table 23 was processed and evaluated in th~ same manner as in ~xample 118. The results are shown ln Table 23. There was obtained a composition excellent in rigidity, heat resistance and impact resistance.
~xamples 121 to 123 Blends of a copolymer (A) given in Table 23, which had been prepared substantially following the procedure of Polymerization ~xample 3, copolymers ~Bl) and (B2) given in Table 23 and filler (C) in blending ratios given in Table 23 were processed and evaluated in the same manner as in Example 118. The results are shown in Table 23.
There were obtained compositions excellent in rigidity, heat resistance and impact resistance.
Com~arative ~xample 40 The evaluation of the copolymer (A) given in Table 23 was conducted in the same manner as in Co~parative Example 39. The results are shown in Table 23. The sample wa~ inferior to the compositions of Examples 121 to 123 in rigidity, heat resistance and impact strength.

,: . . . ~ . . ~ - : . .: :

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Claims (10)

1. A cycloolefin type random copolymer composition characterized by comprising (A) a cycloolefin type random copolymer containing 40-85 mol% of an ethylene component and 60-15 mol% of a cycloolefin component represented by the following general formula [I] or [II] and having an intrinsic viscosity of [?] of 0.05-10 dl/g as measured at 135°C in decalin and a softening temperature (TMA) of not lower than 70°C, and (B) one or more non-rigid copolymers selected from the group consisting of:
(i) a cycloolefin type random copolymer containing an ethylene component, at least one other .alpha.-olefin component, and a cycloolefin component represented by the following general formula [I] or [II] and having an intrinsic viscosity [?] of 0.01-10 dl/g as measured at 135°C in decalin, and a softening temperature (TMA) of below 70°C, (ii) a non-crystalline to low crystalline .alpha.-olefin type elastomeric copolymer formed from at least two .alpha.-olefins having a crystallinity index as measured by X-ray diffractometry of 0-50%, (iii) an .alpha.-olefin-diene type elastomer copolymer formed from at least two .alpha.-olefins and at least one non-conjugated diene, and (iv) an aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof, in such a proportion that the total amount of the component (B) is 5 to 100 parts by weight based on 100 parts by weight of the component (A):

General formula [I]

[II]

wherein n and m are each 0 or a positive integer, ? is an integer of at least 3, and R1 to R10 each represents hydrogen atom, halogen atom or hydrocarbon group.

2. The composition as claimed in claim 1, wherein the cycloolefin type random copolymer containing an ethylene component, at least one other .alpha.-olefin component and a cycloolefin component represented by the following formula [I] or [II] is a cycloolefin type random copolymer containing an ethylene component, a propylene component and a cycloolefin component represented by the following general formula [I] or [II], or a cycloolefin type random copolymer containing an ethylene component, a butene component and a cycloolefin component represented by the following general formula [I] or [II]:

General formula [I]

[II]

3. The composition as claimed in claim 1, wherein the .alpha.-olefin type elastomeric copolymer is ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber or propylene-butene copolymer rubber.

4. The compositions as claimed in claim 1, wherein the .alpha.-olefin-diene type elastomeric copolymer is an ethylene-propylene-diene type elastomeric copolymer.

5. The composition as claimed in claim 1, wherein the aromatic vinyl type hydrocarbon-conjuated diene copolymer or a hydrogenated product thereof is styrene-butadiene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, hydrogenated styrene-butadiene-styrene block copolymer rubber or hydrogenated styrene-isoprene-styrene block copolymer rubber.

6. A cycloolefin type random copolymer composition characterized by comprising (A) a cycloolefin type random copolymer containing 40-85 mol% of an ethylene component and 60-15 mol% of a cycloolefin component represented by the following general formula [I] or [II] and having an intrinsic viscosity [?] of 0.05-10 dl/g as measured at 135°C in decalin and a softening temperature (TMA) of not lower than 70°C, (B) at least two non-rigid copolymers selected from the group consisting of:
(i) a cycloolefin type random copolymer containing an ethylene component, at least one other .alpha.-olefin component, and a cycloolefin component represented by the following general formula [I] or [II] and having an intrinsic viscosity [?] of 0.01-10 dl/g as measured at 135°C in decalin and a softening temperature (TMA) of below 70°C, (ii) a non-crystalline to low crystalline .alpha.-olefin type elastomeric copolymer formed from at least two .alpha.-olefins having a crystallinity index as measured by X-ray diffractometry of 0-50%, (iii) an .alpha.-olefin-diene type elastomeric copolymer formed from at least two .alpha.-olefins and at least one non-conjugated diene, and (iv) an aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof, and (C) an inorganic filler or organic filler, in such a proportion that the total amount of the component (B) is 1 to 100 parts by weight based on 100 parts by weight of the component (A) and the amount of the component (C) is 1 to 100 parts by weight based on 100 parts by weight of the component (A):

General formula [I]

[II]

wherein n and m are each 0 or a positive integer, ? is an integer of at least 3, and R1 to R10 each represents hydrogen atom, halogen atom or hydrocarbon group.

7. The composition as claimed in claim 6, wherein the cycloolefin type random copolymer containing an ethylene component, at least one other .alpha.-olefin component and a cycloolefin component represented by the following general formula [I] or [II] is a cycloolefin type random copolymer containing an ethylene component, a propylene component and a cycloolefin component represented by the following general formula [I] or [II], or a cycloolefin type random copolymer containing an ethylene component, a butene component and a cycloolefin component represented by the following general formula [I] or [II]:

General formula [I]

[II]

8. The composition as claimed in claim 6, wherein the .alpha.-olefin type elastomeric copolymer is ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber or propylene-butene copolymer rubber.

9. The composition as claimed in claim 6, wherein the .alpha.-olefin-diene type elastomeric copolymer is an ethylene-propylene-diene type elastomeric copolymer.

10. The composition as claimed in claim 6, wherein the aromatic vinyl type hydrocarbon-conjugated diene copolymer or a hydrogenated product thereof is styrene-butadiene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene block copolymer rubber, styrene-isoprene-styrene block copolymer rubber, hydrogenated styrene-butadiene-styrene block copolymer rubber or hydrogenated styrene-isoprene-styrene block copolymer rubber.