JPH06228243A - Cyclic olefin copolymer composition - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in impact resistance and transparency, useful as an optical material, etc., comprising each specific cyclic olefin elastomer component and cyclic olefin copolymer component at specified proportion with the refractive index difference between the components A and B specified. CONSTITUTION:The objective composition comprising (A) 8-40wt.% of a cyclic olefin elastomer component obtained by copolymerization between (1) a >=2C alpha-olefin and (2) a cyclic olefin of formula I or II, with the content of the component 2 at >=3mol%, having the following characteristics: (a) intrinsic viscosity [eta]: 0.5-5.0dl/g; (b) Tg: <15 deg.C; (c) free from C=C bond; and (d) refractive index nD: 1.500-1.650 and (B) a cyclic olefin copolymer component obtained by copolymerization between the components 1 and 2 in the presence of the component A. The difference between the refractive index of the component A: nD (A) and that of the component B: nD (B), namely, DELTAnD is <=0.015.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclic olefin-based copolymer composition, more specifically, impact resistance, transparency,
The present invention relates to a cyclic olefin copolymer composition having excellent heat resistance.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION A cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene is excellent in transparency, and further has heat resistance, heat aging resistance and chemical resistance. , Solvent resistance, dielectric properties,
It is known that it is a synthetic resin with well-balanced rigidity and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers (for example, JP-A-60-168,708). Japanese Patent Laid-Open No. 61-9
8,780, JP 61-115,912, JP 61-115,916, JP 61-
120,816, and JP-A-62-252407 (1987).

These cyclic olefin-based random copolymers are resins having particularly excellent heat resistance and rigidity, but further improvement in impact resistance is required. By the way, in the specification of Japanese Patent Application No. 2-52,971, the applicant of the present application discloses a cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene, and a soft polymer. A resin composition composed of (rubber) is proposed.

Such a resin composition is superior in impact resistance to the cyclic olefin random copolymer, but further improvement in impact resistance is desired, and the obtained resin composition is It was sometimes inferior in transparency.

Further, the applicant of the present invention is the Japanese Patent Application No. 4-1338.
No. 22 proposes a cyclic olefin copolymer obtained by copolymerizing an α-olefin and a cyclic olefin in the presence of a hydrocarbon elastomer having a polymerizable double bond.

Although such a cyclic olefin-based copolymer has excellent impact resistance, further improvement in transparency has been required. The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems in the prior art. As a result, a specific cyclic olefin elastomer component [A] having substantially no polymerizable double bond and the elastomer component In the presence of [A], α- having 2 or more carbon atoms such as ethylene
It is composed of a cyclic olefin elastomer component [B] obtained by copolymerizing an olefin and a cyclic olefin, contains the above component [A] in a specific amount, and has a refractive index n _D (A) of the component [A]. The cyclic olefin-based copolymer composition having a difference from the refractive index n _D (B) of the component [B] within a specific range has particularly excellent transparency and impact resistance. The present invention has been completed and the present invention has been completed.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems in the prior art, and has the excellent properties of a cyclic olefin random copolymer, as well as impact resistance and transparency. It is an object of the present invention to provide a cyclic olefin-based copolymer composition having improved properties.

[0008]

SUMMARY OF THE INVENTION Cyclic Olefin Copolymer According to the Invention
Is (a) an α-olefin having 2 or more carbon atoms, and (b) below
Cyclic olefin represented by the general formula [I] or [II]
And, and the resulting copolymer has a cyclic
The olefin unit is contained in an amount of 3 mol% or more,
Intrinsic viscosity [η] measured at 135 ° C in Karin is 0.5
To 5.0 dl / g and has a glass transition temperature (T
g) is less than 15 ° C. and is substantially polymerizable carbon / carbon
Refractive index n containing no double bond and measured at 25 ° C.
_D(A) is a ring o in the range of 1.500 to 1.650
Reffin-based elastomer component [A] and the elastomer
In the presence of the component [A], (a) α-ole having 2 or more carbon atoms
Fin, and (b) represented by the following general formula [I] or [II]
Cyclic olefin obtained by copolymerization with cyclic olefin
A cyclic olefin containing a fin-based copolymer component [B]
A copolymer composition [C], which comprises:
The component [A] is present in the product [C] in an amount of 8 to 40% by weight.
The refractive index n of the above component [A]_D(A) and the above components
Refractive index n of [B]_DDifference from (B): △ n_D(= | N
_D(A) -n_D(B) |) is 0.015 or less
It has a feature.

The above cyclic olefin elastomer component [A] is preferably a copolymer of cyclic olefins represented by the following formula [II], and the cyclic olefin copolymer component [B]. Is preferably a copolymer of a cyclic olefin represented by the following formula [I].

[0010]

[Chemical 3]

(In the formula [I], n is 0 or 1, and m is
Is 0 or a positive integer, q is 0 or 1, and R
^{1 to} R ¹⁸ and R ^a and R ^b are each independently
A hydrogen atom, a halogen atom or a hydrocarbon group, R ¹⁵
To R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. );

[0012]

[Chemical 4]

(In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2,
R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom,
It is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ¹³ (or R ¹⁰ ) is bonded to the carbon atom to which R ¹³ or R ¹¹ is bonded. It may be bonded to the carbon atom directly or via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other. It may form a monocyclic or polycyclic aromatic ring. ).

The cyclic olefin-based copolymer composition according to the present invention has the excellent properties of the cyclic olefin-based random copolymer and has particularly improved impact resistance and transparency.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The cycloolefin copolymer composition according to the present invention will be specifically described below.

The cyclic olefin-based copolymer composition [C] according to the present invention comprises a cyclic olefin-based elastomer component [A] and a cyclic olefin-based copolymer component [B]. The combined component [B] is represented by (a) an α-olefin having 2 or more carbon atoms and (b) the following general formula [I] or [II] in the presence of the cyclic olefin elastomer component [A]. It is obtained by copolymerizing with a cyclic olefin. In such a cycloolefin copolymer composition [C] according to the present invention, the cycloolefin elastomer component [A] and the cycloolefin copolymer component [B] have excellent compatibility. Conceivable.

First, the cycloolefin elastomer having no polymerizable carbon-carbon double bond of the present invention will be described. Cyclic Olefin Elastomer Component [A] The cyclic olefin elastomer component [A] used in the present invention is an elastomer having substantially no polymerizable carbon / carbon double bond in the elastomer, and specifically, A copolymer of (a) an α-olefin having 2 or more carbon atoms and (b) a cyclic olefin represented by the following general formula [I] or [II] can be given.

Examples of the α-olefin (a) having 2 or more carbon atoms include ethylene, propylene, 1-butene, 1-
C2-C20 alpha such as pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene Mention may be made of olefins.
Of these, ethylene or propylene is preferable.

As the cyclic olefin (b), a cyclic olefin represented by the following formula [I] and / or [II] is used.

[0020]

[Chemical 5]

In the formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. In addition, when q is 1, R ^a and R ^b each independently represent the following atom or hydrocarbon group, and when q is 0, each bond is bonded to form a 5-membered ring. Form.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom,
Examples thereof include chlorine atom, bromine atom and iodine atom.

The hydrocarbon group is usually, independently of each other, an alkyl group having 1 to 20 carbon atoms and 3 to 1 carbon atoms.
And the cycloalkyl group of 5. More specifically,
Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, and examples of the cycloalkyl group include a cyclohexyl group.

These groups may be substituted with a halogen atom. Further, in the above formula [I], R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ^{15 16} and R ¹⁷ may be bonded to each other (cooperate with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed has a double bond. May be.

The monocycle or polycycle formed here is exemplified below.

[0026]

[Chemical 6]

In the above example, the carbon atom numbered 1 or 2 is represented by R ¹⁵ (R ¹⁶ ) in the formula [I].
Alternatively, it is a carbon atom forming an alicyclic structure to which R ¹⁷ (R ¹⁸ ) is bonded.

R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸
And may form an alkylidene group. Such an alkylidene group usually includes an alkylidene group having 2 to 20 carbon atoms, and specific examples thereof include an ethylidene group, a propylidene group and an isopropylidene group.

[0029]

[Chemical 7]

In the formula [II], p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group.

In the formula [II], the halogen atom is the same as the halogen atom in the above formula [I]. Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group and octadecyl group.

The alicyclic hydrocarbon group has 3 carbon atoms.
The alicyclic hydrocarbon group of 15 to 15 are mentioned, and a cyclohexyl group is specifically mentioned. Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, a phenylethyl group, and the like, and these groups are lower alkyl groups. May have.

Examples of the alkoxy group include methoxy group, ethoxy group and propoxy group. These groups may be substituted with a halogen atom.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or have 1 to 3 carbon atoms.
May be bonded via the alkylene group of. That is, when the above two carbon atoms are bonded via an alkylene group, R ⁹ and R ¹³ or R ¹⁰ and R ¹¹ cooperate with each other to form a methylene group (—CH ₂ —) , An ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH ₂ CH ₂ —) to form an alkylene group.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. In this case, examples of the monocyclic or polycyclic aromatic ring include R ¹⁵ and R when n = m = 0.
Mention may be made of the groups described below in which ¹² further forms an aromatic ring.

[0036]

[Chemical 8]

In the above example, q has the same meaning as q in the formula [II]. The above formula [I] or [I
As the cyclic olefin represented by [I], specifically,
Bicyclo [2.2.1] hept-2-ene derivative, tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, tricyclo [4.4.
0.1 ^2,5 ] -3-Undecene derivative, tetracyclo [4.4.0.
1 ^2,5 .1 ^7,10 ] -3-Dodecene derivative, pentacyclo [6.6.
1.1 ^3,6 .0 ^2,7 .0 ^9,14 ] -4-Hexadecene derivative, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] -4-Pentadecene derivative, pentacyclo [7.4. 0.1 ^2,5 .1 ^9,12 .0 ^8,13] -3-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] -3 hexadecene derivative, hexacyclo [6.6.1.1 ^3,6 .1 ^10,13 .0
^2,7 .0 ^9,14] -4-heptadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] -4- eicosene derivatives, heptacyclo [8.7.0.1 ^2,9 .1 ^4,7 .1 ^11,17 .0
^{3,8 12,16} ] -5-Eicosene derivative, heptacyclo [8.
8.0.1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, heptacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^{11, 18.0
3,8} .0 ^12,17] -5-heneicosene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8 .0 12,17] - Five-
Docosenoic derivatives, Nonashikuro [10.9.1.1 ^4,7 .1 ^13,20 .1
^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, Nonashikuro [10.10.1.1 ^5,8 .1 ^14,21 .1 ^16,19.
0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^{15, 20]} -6-hexacosenoic derivatives,
1.4-methano-1.4.4a.9a-tetrahydrofluorene derivative, 1.4-methano-1.4.4a.5.10.10a-hexahydroanthracene derivative, cyclopentadiene-acenaphthylene adduct and the like can be mentioned.

The details will be described below.

[0039]

[Chemical 9]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

[0055]

[Chemical 25]

[0056]

[Chemical formula 26]

[0057]

[Chemical 27]

[0058]

[Chemical 28]

[0059]

[Chemical 29]

The cyclic olefin (b) represented by the above general formula [I] or [II] is produced by subjecting cyclopentadiene and olefins having a corresponding structure to a Diels-Alder reaction. You can

These cyclic olefins (b) can be used alone or in combination of two or more. The cyclic olefin elastomer component [A] that does not have a carbon / carbon double bond that is substantially polymerizable as described above will be specifically exemplified.

Specific examples of such α-olefin / cycloolefin copolymers include ethylene / norbornene copolymers, ethylene / 5-methyl-2-norbornene copolymers, ethylene / 5-ethyl- 2-norbornene copolymer, ethylene / 5-propyl-2-norbornene copolymer,
Ethylene-5-butyl-2-norbornene copolymer, ethylene-5-pentyl-2-norbornene copolymer, ethylene / 5
-Hexyl-2-norbornene copolymer, ethylene / 5-heptyl-2-norbornene copolymer, ethylene / 5-octyl-
2-norbornene copolymer, ethylene-5-nonyl-2-norbornene copolymer, ethylene-5-decyl-2-norbornene copolymer, ethylene-5-undecyl-2-norbornene copolymer, ethylene-5- Dodecyl-2-norbornene copolymer, ethylene / 5-phenyl-2-norbornene copolymer, ethylene / 1,4-methano-1,4,4a, 9a-tetrahydrofluorene copolymer, ethylene / tetracyclododecene Copolymer, ethylene / propylene / norbornene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 5-methyl-2-norbornene copolymer, ethylene / propylene / 5-ethyl
-2-norbornene copolymer, ethylene / propylene / 5-
Propyl-2-norbornene copolymer, ethylene / propylene / 5-butyl-2-norbornene copolymer, ethylene /
Propylene / 5-pentyl-2-norbornene copolymer, ethylene / propylene / 5-hexyl-2-norbornene copolymer, ethylene / propylene / 5-heptyl-2-norbornene copolymer, ethylene / propylene / 5-octyl -2-
Norbornene copolymer, ethylene / propylene / 5-nonyl-2-norbornene copolymer, ethylene / propylene / 5
-Decyl-2-norbornene copolymer, ethylene / propylene / 5-undecyl-2-norbornene copolymer, ethylene / propylene / 5-dodecyl-2-norbornene copolymer,
Ethylene / propylene / 5-phenyl-2-norbornene copolymer, ethylene / propylene / tetracyclododecene copolymer, ethylene / 1-butene / norbornene copolymer, ethylene / 1-butene / 5-ethylidene-2- Norbornene copolymer, ethylene / 1-butene / 5-methyl-2-norbornene copolymer, ethylene / 1-butene / 5-ethyl-2-norbornene copolymer, ethylene / 1-butene-5-propyl
-2-norbornene copolymer, ethylene / 1-butene-5-butyl-2-norbornene copolymer, ethylene / 1-butene / 5
-Pentyl-2-norbornene copolymer, ethylene / 1-butene-5-hexyl-2-norbornene copolymer, ethylene / 1
-Butene-5-heptyl-2-norbornene copolymer, ethylene / 1-butene-5-octyl-2-norbornene copolymer,
Ethylene / 1-butene / 5-nonyl-2-norbornene copolymer, ethylene / 1-butene / 5-decyl-2-norbornene copolymer, ethylene / 1-butene-5-undecyl-2-norbornene copolymer , Ethylene-1-butene-5-dodecyl-2-
Norbornene copolymer, ethylene / 1-butene / 5-phenyl-2-norbornene copolymer, ethylene / 1-butene / tetracyclododecene copolymer, ethylene / 1-hexene
Norbornene copolymer, ethylene / 1-hexene / 5-methyl-2-norbornene copolymer, ethylene / 1-hexene / 5
-Ethyl-2-norbornene copolymer, ethylene / 1-hexene / 5-propyl-2-norbornene copolymer, ethylene / 1
-Hexene-5-butyl-2-norbornene copolymer, ethylene / 1-hexene / 5-pentyl-2-norbornene copolymer, ethylene / 1-hexene / 5-hexyl-2-norbornene copolymer, ethylene 1-hexene-5-heptyl-2-norbornene copolymer, ethylene / 1-hexene-5-octyl-2-norbornene copolymer, ethylene / 1-hexene-5
-Nonyl-2-norbornene copolymer, ethylene / 1-hexene / 5-decyl-2-norbornene copolymer, ethylene / 1-
Hexene-5-undecyl-2-norbornene copolymer, ethylene / 1-hexene / 5-dodecyl-2-norbornene copolymer, ethylene / 1-hexene-5-phenyl-2-norbornene copolymer, ethylene / 1 -Hexene / tetracyclododecene copolymer, ethylene / 1-octene / norbornene copolymer, ethylene / 1-octene / 5-methyl-2-norbornene copolymer, ethylene / 1-octene / 5-ethyl-2 -
Norbornene copolymer, ethylene / 1-octene / 5-propyl-2-norbornene copolymer, ethylene / 1-octene / 5-butyl-2-norbornene copolymer, ethylene / 1-octene-5-pentyl-2 -Norbornene copolymer, ethylene / 1-octene / 5-hexyl-2-norbornene copolymer, ethylene / 1-octene / 5-heptyl-2-norbornene copolymer, ethylene / 1-octene-5-octyl- 2-norbornene copolymer, ethylene / 1-octene / 5-nonyl
-2-norbornene copolymer, ethylene / 1-octene / 5-
Decyl-2-norbornene copolymer, ethylene / 1-octene / 5-undecyl-2-norbornene copolymer, ethylene / 1-octene-5-dodecyl-2-norbornene copolymer,
Ethylene / 1-octene / 5-phenyl-2-norbornene copolymer, ethylene / 1-octene / tetracyclododecene copolymer, ethylene / 1-decene / norbornene copolymer, ethylene / 1-decene-5- Methyl-2-norbornene copolymer, ethylene / 1-decene / 5-ethyl-2-norbornene copolymer, ethylene / 1-decene-5-propyl-2-norbornene copolymer, ethylene / 1-decene-5 -Butyl-2-
Norbornene copolymer, ethylene / 1-decene-5-pentyl-2-norbornene copolymer, ethylene / 1-decene-5-
Hexyl-2-norbornene copolymer, ethylene / 1-decene-5-heptyl-2-norbornene copolymer, ethylene / 1
-Decene-5-octyl-2-norbornene copolymer, ethylene / 1-decene-5-nonyl-2-norbornene copolymer, ethylene / 1-decene-5-decyl-2-norbornene copolymer, ethylene 1-decene-5-undecyl-2-norbornene copolymer, ethylene / 1-decene-5-dodecyl-2-norbornene copolymer, ethylene / 1-decene-5-phenyl-2
-Norbornene copolymer and ethylene / 1-decene / tetracyclododecene copolymer can be mentioned.

The intrinsic viscosity [η] of these cyclic olefin elastomer components [A] measured in decalin at 135 ° C. is 0.5 to 5.0 dl / g, preferably 0.7.
~ 4.0 dl / g.

Further, the cyclic olefin elastomer component [A] desirably contains the cyclic olefin unit in an amount of 3 mol% or more, preferably 5 mol% or more, and has a glass transition temperature (Tg). , Less than 15 ° C, preferably less than 12 ° C.

Further, a cyclic olefin elastomer component
Refractive index n of [A] measured at 25 ° C. _D(A) is 1.5
00 to 1.650, preferably 1.510 to 1.600
Is in the range.

Next, the cycloolefin copolymer component [B] of the present invention will be described. Cyclic olefin copolymer component [B] The cyclic olefin copolymer component [B] according to the present invention is
Copolymerization of α-olefin (a) having 2 or more carbon atoms and cyclic olefin (b) in the presence of a cyclic olefin elastomer component [A] that does not contain a polymerizable double bond as described above. Can be obtained.

The α-olefin (a) having 2 or more carbon atoms is
It may be a linear α-olefin or a branched α-olefin. As such α-olefins, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-
Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. Of these, ethylene or propylene is preferable, and ethylene is particularly preferable. These α-olefins can be used alone or in combination of two or more.

As the cyclic olefin (b), specifically, the above-mentioned general formulas [I] and / or [II]
The cyclic olefin represented by is used. These cyclic olefins (b) can be used alone or in combination of two or more kinds.

The cyclic olefin copolymer component [B] according to the present invention comprises an α-olefin (a) having 2 or more carbon atoms,
In the presence of the above-mentioned cyclic olefin (b) represented by the formula [I] or the formula [II] in the presence of the above-mentioned substantially polymerizable double bond-free cycloolefin elastomer component [A], It is an addition polymer obtained by polymerization.

The above cyclic olefin copolymer component [B]
In addition to the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b) within a range that does not impair the properties of the copolymer component, the cyclic ring represented by the above formula [I] or [II] Cyclic olefins other than olefins (other cyclic olefins) can also be subjected to addition polymerization.

The "other cyclic olefin" used herein is represented by a broad concept including unsaturated polycyclic hydrocarbon compounds other than the cyclic olefins represented by the formulas [I] and [II]. .

More specifically, examples of other cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, styrene, Examples thereof include α-methylstyrene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene.

Cyclic Olefin Copolymer Composition [C] Cyclic Olefin Copolymer Composition [C]
Comprises a cyclic olefin-based elastomer component [A] and a cyclic olefin-based polymer component [B] as described above. The cyclic olefin-based elastomer component [A]
Is present in an amount of 8-40% by weight, preferably 10-35% by weight.

In the cycloolefin copolymer composition [C] according to the present invention, the refractive index n _D (A) of the cycloolefin elastomer component [A] as described above and the cycloolefin as described above are Refractive Index n of Copolymer Component [B]
The difference between _{D (B) △ n D =} | n D (A) -n D (B) | 0.
It is preferably 015 or less, and the cyclic olefin elastomer component [A] is preferably a copolymer of the cyclic olefin represented by the above formula [II], and the cyclic olefin copolymer component [B] is It is preferably a cyclic olefin copolymer represented by the formula [I].

In the present invention, the refractive index of the cycloolefin elastomer component [A] and the refractive index of the cycloolefin copolymer component [B] are measured using an Abbe refractometer (D line 589 nm). The adopted value is adopted.

Such a cyclic olefin copolymer composition [C] according to the present invention comprises a cyclic olefin elastomer component [A] having substantially no polymerizable carbon-carbon double bond, and the cyclic olefin. System elastomer component [A]
And a cyclic olefin-based copolymer component [B] obtained by copolymerizing an α-olefin (a) having 2 or more carbon atoms with a cyclic olefin (b) in the presence of the composition [C ], The dispersibility of the cyclic olefin-based copolymer component [B] formed from the α-olefin (a) and the cyclic olefin (b) and the cyclic olefin-based elastomer component [A] is extremely good. This means that the cyclic olefin-based copolymer composition [C] according to the present invention has a carbon number of 2 or more in the presence of the above-mentioned cyclic olefin-based elastomer [A] which does not substantially contain a polymerizable double bond. A cyclic olefin random copolymer composition obtained by copolymerizing an α-olefin (a) and a cyclic olefin (b) comprises an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b). Superior in transparency and impact resistance to a cyclic olefin copolymer composition obtained by simply blending a cyclic olefin random copolymer obtained by polymerization and the above cyclic olefin elastomer component [A]. It is also shown from that.

In the cycloolefin copolymer composition [C] according to the present invention, as described above, the refractive index n _D (A) of the cycloolefin elastomer component [A] and the α-olefin having 2 or more carbon atoms are used. Difference between refractive index n _D (B) of cyclic olefin random copolymer component [B] obtained by copolymerizing (a) and cyclic olefin (b) Δn _D (= | n
_D (A) -n _D (B) |) is 0.015 or less,
It is preferably 0.012 or less, more preferably 0.01
It is 0 or less.

Here, the cyclic olefin copolymer component [B] is the cyclic olefin copolymer composition [C] produced in the presence of the cyclic olefin elastomer [A].
In the above, the component other than the component [A] is meant, but actually, the compatibility between the component [B] and the elastomer component [A] is good in the cycloolefin copolymer composition [C] of the present invention. Therefore, only the cyclic olefin-based copolymer component [B] cannot be taken out from the composition [C].

Therefore, in the present specification, the refractive index n _D (B) of the component [B] is the same as the production example of the component [B] except that the cyclic olefin elastomer component [A] is not present. Of a cyclic olefin random copolymer [B] composed of an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b) produced under the conditions of
The value of _D (B) is used.

In producing the cyclic olefin elastomer component [A] as described above, and in the presence of the cyclic olefin elastomer component [A], the α-olefin and the cyclic olefin are copolymerized to give a cyclic olefin copolymer weight. A transition metal-based catalyst is used in the production of the combined component [B]. Specifically, (i) a catalyst formed from a soluble vanadium compound and an organoaluminum compound, or (ii) Periodic Table IVB. It can be carried out in the presence of a catalyst formed from a metallocene compound of a transition metal selected from the group or lanthanides, an organoaluminumoxy compound, and optionally an organoaluminum compound.

The soluble vanadium compound forming such catalyst (i) is specifically represented by the following general formula. VO (OR) _a X _b or V (OR) _c X _d where R is a hydrocarbon group and a, b, c, d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦, respectively. a + b ≦ 3,0
≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4 are satisfied. More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO
(OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , V
_{O (O-n-C 4} H 9) Cl 2, VO (OC 2 H 5) 3, VOB
r ₂ , VCl ₄ , VOCl ₂ , VO (O-n-C ₄ H ₉ ) ₃ , V
A vanadium compound such as OCl ₃ .2OC ₈ H ₁₇ OH is used.

These compounds can be used alone or in combination of two or more kinds. The soluble vanadium compound can also be used as an electron donor adduct obtained by contacting an electron donor as shown below.

Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, ethers, diethers and acid amides. , Acid anhydrides, oxygen-containing electron donors such as alkoxysilane, and nitrogen-containing electron donors such as ammonia, amines, nitriles, pyridines, and isocyanates. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl. C1-C18 alcohols such as alcohol, C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol, and trichlorohexanol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol , C6-20 phenols which may have a lower alkyl group such as naphthol, acetone, methyl ethyl ketone Emissions, methyl isobutyl ketone,
C2-C15 ketones such as acetophenone, benzophenone and benzoquinone, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and other carbon atoms 2
~ 15 aldehydes, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate,
Ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoate Phenyl acid,
Benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate and other organic acid esters having 2 to 18 carbon atoms, acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and the like having 2 to 1 carbon atoms
5, acid halides, methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether, acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic acid, and alkoxy such as ethyl silicate and diphenyldimethoxysilane. Acid amides such as silane, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide, amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine Examples thereof include nitriles such as acetonitrile, benzonitrile and trinitrile, and pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine.

In preparing the electron donor adduct of the soluble vanadium compound, these electron donors can be used alone or in combination of two or more kinds. In the present invention, the organoaluminum compound used together with the soluble vanadium compound in forming the catalyst (i) has at least one Al-C bond in the molecule, and for example, the following (a) and (b ) Is represented by the formula.

(A) General formula R ¹ _m Al (OR ² ) _n H _p X _q (wherein R ¹ and R ² are usually 1 to 15 carbon atoms,
It is preferably 1 to 4 hydrocarbon groups, which may be the same or different. X is a halogen atom, m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <
3 and q are numbers 0 ≦ q <3, and m + n + p +
q = 3. ).

[0086] (b) the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, K, R ¹ is as defined above) alkylated complex of Group 1 metal and aluminum represented by.

Specific examples of the organoaluminum compound represented by the above (a) include the following compounds. (1) General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.
5 ≦ m <3). (2) General formula R ¹ _m AlX _3-m (wherein R ¹ is the same as described above, X is halogen, and m is preferably a number of 0 <m <3). (3) General formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above. M is preferably a number of 2 ≦ m <3). (4) General formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as above. X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3. ).

More specific examples of the organoaluminum compound represented by the above (a) include the following compounds. Examples of the organoaluminum compound represented by (1) include trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisopropenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide; Mention may be made of sesquiethoxide, butylaluminum sesquibutoxide, and partially alkoxylated alkylaluminums having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 .

Examples of the organoaluminum compound represented by (2) include dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride.
Alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide; partially halogenated alkyl aluminums such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide.

Examples of the organoaluminum compound represented by (3) include dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; partially hydrogenated alkylaluminums such as ethylaluminum dihydride and propylaluminum dihydride. Can be mentioned.

Examples of the organoaluminum compound represented by (4) include partially aluminum-alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

Further, it may be a compound similar to the compound represented by the above general formula (a), for example, an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. As such a compound, specifically,

[0093]

[Chemical 30]

Examples thereof include: The compound belonging to (b) above includes LiAl (C ₂ H ₅ ) ₄ ,
LiAl (C ₇ H ₁₅₎ and the like can be exemplified _4.

Of these, alkylaluminum halides, alkylaluminum dihalides and mixtures thereof are particularly preferable. It is then used in the present invention (ii)
A metallocene compound of a transition metal selected from Group IVB of the periodic table or a lanthanide, an organoaluminum oxy compound, and, if necessary, a catalyst formed from the organoaluminum compound will be described.

Such a metallocene compound of a transition metal selected from Group IVB or lanthanides of the periodic table (hereinafter sometimes referred to as "component [a]") is represented by the following general formula [a]. Examples of the compound include

ML _x ... [a] In the above general formula [a], M is a transition metal selected from Group IVB of the Periodic Table and lanthanides, and specifically, zirconium, titanium, hafnium, neodymium,
Samarium or ytterbium, L is a ligand that coordinates to a transition metal, and at least one ligand L among these L is a ligand having a cyclopentadienyl skeleton, and cyclopentadienyl The ligand L other than the ligand having a dienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, SO ₃ R (where R is halogen, etc. Is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent) or a hydrogen atom, and x is the valence of the transition metal.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, propylcyclopentadienyl group, butylcyclopentadienyl group. Group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, methylethylcyclopenta group Dienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, ethylbutylcyclopentadienyl group, ethylhexylcyclopenta group Enyl, alkyl or cycloalkyl substituted cyclopentadienyl groups such as methylcyclohexyl cyclopentadienyl group, further indenyl group, tetrahydroindenyl group and a fluorenyl group.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. The ligand L other than the ligand having a cyclopentadienyl skeleton has a carbon number of 1
~ 12 hydrocarbon groups, alkoxy groups, aryloxy groups,
Sulfonic acid-containing group (-SO ₃ R ^a:. Wherein, R ^a is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group substituted with an aryl group or a halogen atom or an alkyl group), a halogen atom Or a hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, and more specifically, a methyl group, an ethyl group, n-propyl group. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group, cyclopentyl group, cyclohexyl group, etc. Examples thereof include an aryl group such as an alkyl group, a phenyl group and a tolyl group, and an aralkyl group such as a benzyl group and a neofil group.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group and an octoxy group.

Examples of the aryloxy group include a phenoxy group and the like. Examples of the sulfonic acid-containing group (—SO ₃ ^Ra ) include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, and a p-chlorobenzenesulfonato group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. When the valence of the transition metal is 4, the compound represented by the above general formula [a] is more specifically represented by the following general formula [a '].

R ¹ _a R ² _b R ³ _c R ⁴ _d M ... [a ′] (In the general formula [a ′], M is zirconium, titanium, hafnium, neodymium, samarium or ytterbium, and R ^{1 a} Is a group having a cyclopentadienyl skeleton, and R ² , R ³ and R ⁴ are groups having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen. Atom, trialkylsilyl group,
SO ₃ R or a hydrogen atom, a is an integer of 1 or more, and a + b + c + d = 4. In the present invention, a transition metal compound in which one of R ² , R ³ and R ^{4 in} the above general formula [a ′] is a group having a cyclopentadienyl skeleton, for example, R ¹ and R ² are cyclopentadienyl A transition metal compound which is a group having a skeleton is preferably used.
Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, alkylidene groups such as isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene groups or dimethylsilylene, diphenylsilylene, substituted methylphenylsilylene groups and the like. It may be bound via a silylene group or the like. R ³ and R ⁴ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, SO ₃ R or a hydrogen atom. Is.

Specific examples of the transition metal metallocene compound in which M is zirconium are shown below.
Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) Zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) ) Zirconium bis (methane sulfonate), ethylene bis (indenyl) zirconium bis (p-toluene sulfonate), ethylene bis (indenyl) zirco Umbis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopenta) Dienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclo) Pentadienyl) zirconium dichloride, dimethylsilylene bis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene Bis (indenyl) zirconium dichloride, dimethylsilylene bis (indenyl) zirconium bis (trifluoromethanesulfonato), dimethylsilylene bis (4,
5,6,7-Tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (cyclopentadiene) (Enyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride Chloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride , Bis (cyclopentadienyl)
Methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclo Pentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl)
Zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (dimethylcyclopentadienyl) dimethylzirconium, bis (ethylcyclopentadienyl) zirconium dichloride, bis (Methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadiene) ) Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopenta) Dienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium Dichloride.

In the above examples of the transition metal compound, the disubstituted cyclopentadienyl ring is 1,2- and 1,2-
3-substitutes are included, and tri-substitutes include 1,2,3- and 1,2,4-substitutes. In addition, alkyl groups such as propyl and butyl are
It includes isomers such as n-, i-, sec-, and tert-. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, neodymium metal, samarium metal or ytterbium metal in the metallocene compound as described above can also be used.

These compounds may be used alone or
You may use it in combination of 2 or more type. Further, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.
In the present invention, the metallocene compound is preferably diluted with a hydrocarbon solvent before use.

The metallocene compound as described above can also be used together with the carrier compound by bringing it into contact with the particulate carrier compound. Carrier compounds include SiO ₂ , Al ₂
O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, TiO ₂ , Z
Inorganic carrier compounds such as nO, SnO ₂ , BaO and ThO, polyethylene, polypropylene, poly-1-butene, poly 4-
Resins such as methyl-1-pentene and styrene-divinylbenzene copolymer can be used. These carrier compounds may be used as a mixture of two or more kinds.

In the present invention, as the metallocene compound, a zirconocene compound having a central metal atom of zirconium and having a ligand containing at least two cyclopentadienyl skeletons is preferably used.

Next, the organoaluminum oxy compound used for forming the catalyst (ii) in the present invention will be explained. The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound.

Such a conventionally known aluminoxane is specifically represented by the following general formula.

[0112]

[Chemical 31]

(In the above general formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is 2 or more. , Preferably an integer of 5 to 40.) Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹ )) and an alkyloxyaluminum represented by the formula (OAl (R ² )). Even if it is formed of a mixed alkyloxyaluminum unit consisting of a unit [wherein R ¹ and R ² can represent the same hydrocarbon group as R, and R ¹ and R ² represent different groups] Good.

The conventionally known aluminoxane is produced, for example, by the following method and is usually recovered as a solution of an aromatic hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to an aromatic hydrocarbon solvent in which is suspended and reacted to recover a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice, or steam) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a solution of an aromatic hydrocarbon solvent.

Among these methods, it is preferable to adopt the method (1). The organoaluminum compound used in producing the solution of aluminoxane specifically includes trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec- Butyl aluminum, tri
tert-Butylaluminium, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, trialkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminium chloride, diethylaluminium chloride, diethylaluminum bromide, diisobutylaluminum chloride. Dialkyl aluminum hydrides such as dialkyl aluminum hydride, diethyl aluminum hydride, diisobutyl aluminum hydride, etc., dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, etc.
Examples thereof include dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum is particularly preferable. Further, as the organoaluminum compound, isoprenylaluminum represented by the following general formula can also be used.

[0117] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) The organic aluminum such as The compounds may be used alone or in combination.

The benzene-insoluble organoaluminum oxy compound used in the present invention is, for example, a method of bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound, or the above-mentioned organoaluminum compound and water. It can be obtained by a method of contacting.

[0119] In benzene-insoluble organoaluminum oxy-compound used in the present invention, the compound was analyzed by infrared spectroscopy (IR), the absorbance at around 1220 cm ^-1 and (D _1220), the absorbance at around 1260 cm ^-1 (D ₁₂₆₀₎ and the ratio of (D _{12 60} / D ₁₂₂₀₎ is 0.09
Or less, preferably 0.08 or less, particularly preferably 0.04
It is preferably in the range of to 0.07.

The above benzene-insoluble organoaluminum oxy compound is presumed to have an alkyloxy aluminum unit represented by the following formula.

[0121]

[Chemical 32]

In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n- group.
Examples thereof include a butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group and cyclooctyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The benzene-insoluble organoaluminum oxy compound may contain an oxyaluminum unit represented by the following formula in addition to the alkyloxyaluminum unit represented by the above formula.

[0124]

[Chemical 33]

In the formula, R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a halogen or a hydrogen atom. Further, R ⁸ and R ⁷ in the above formula represent different groups.

When containing an oxyaluminum unit, an organoaluminum oxy having an alkyloxyaluminum unit containing an alkyloxyaluminum unit in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more Compounds are desirable.

The organoaluminum oxy compound used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum. The organoaluminum oxy compound can also be used by supporting it on the above-mentioned carrier compound.

Examples of the organoaluminum compound used in the present invention as needed include the organoaluminum compounds represented by the following general formula [b].

R ⁵ _n AlX _3-n ... [b] (In the general formula [b], R ⁵ has 1 to 1 carbon atoms.
2 is a hydrocarbon group, X is a halogen atom or a hydrogen atom, and n is 1 to 3. In the above general formula [b], R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group,
Examples thereof include n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

As such an organic aluminum compound, the following compounds are specifically used. Trialkylaluminums such as trimethylaluminum, totriethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum;
Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, and dimethyl aluminum bromide; methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, etc. Alkyl aluminum dihalides such as alkyl aluminum sesquihalide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; alkyl aluminum aluminum such as diethyl aluminum hydride and diisobutyl aluminum hydride Such as beam hydride.

As the organoaluminum compound, a compound represented by the following general formula [b '] can also be used. ^{_{R 5 n AlY 3-n ···}} [b '] ( provided that the general formula [b' in], R ⁵ are as defined above, Y is -OR ⁶ group, -OSiR ⁷ ₃ group, -OAlR ⁸
₂ group, -NR ⁹ ₂ group, -SiR ¹⁰ ₃ group or -N (R ¹¹⁾ A
1 is a R ¹² ₂ group, n is 1 to 2, and R ⁶ , R ⁷ , R ⁸ and R ¹² are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, a trimethylsilyl group, etc. , R ⁹ is a hydrogen atom, a methyl group, an ethyl group, an isopropylyl group, a phenyl group, a trimethylsilyl group or the like, and R ¹⁰ and R ¹¹ are a methyl group, an ethyl group or the like. ) As such an organoaluminum compound, the following compounds are specifically used. (I) a compound represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide; and (ii) R ⁵ _n Al (OSiR ⁷ ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂
Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt
₃ ) and the like, (iii) a compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu)
₂ AlOAl (iso-Bu) ₂ etc., (iv) R ⁵ _n Al (NR
⁹ ₂ ) _3-n represented by a compound such as Me ₂ AlNEt ₂ ,
Et ₂ AlNHMe, Me ₂ AlNHEt, Et ₂ AlN
(SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) ₂
Such as (v) a compound represented by R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe ₃ .

[0132]

[Chemical 34]

Among the organoaluminum compounds represented by the above general formulas [b] and [b ′], the general formula R ⁵ ₃ Al,
Preferred examples include organic aluminum compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n and R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , wherein R ⁵ is an isoalkyl group and n = 2 is particularly preferable. Two or more kinds of these organoaluminum compounds can be mixed and used.

In the present invention, using the catalyst (i) or (ii) as described above, in the presence of the cyclic olefin elastomer component [A], an α-olefin having 2 or more carbon atoms,
The cyclic olefin represented by the above formula [I] or [II] is copolymerized in a liquid phase, preferably in a hydrocarbon solvent.

Examples of such a hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof, and alicyclic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane. Hydrogen and its halogen derivatives, aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives such as chlorobenzene are used. The above-mentioned copolymerization reaction can also be carried out by using α-olefin or cyclic olefin itself as a hydrocarbon solvent. These solvents may be mixed and used.

In the present invention, the copolymerization is preferably carried out in the coexistence of the above hydrocarbon solvent, and among these, cyclohexane-hexane, cyclohexane-heptane, cyclohexane-pentane, toluene-hexane, toluene-heptane, It is preferably carried out in the coexistence of a mixed solvent such as toluene-pentane.

The copolymerization is carried out by either a batch method or a continuous method, but the continuous method is preferred. The concentration of the catalyst used at this time is as follows. When the catalyst (i) is used, the soluble vanadium compound in the polymerization system is usually used in an amount of 0.01 to 5 mmol, preferably 0.05 to 3 mmol, per liter of the polymerization volume, and an organic solvent. The aluminum compound is supplied in an amount of 2 or more, preferably 2 to 50, more preferably 3 to 20 in terms of a ratio of aluminum atoms to vanadium atoms in the polymerization system (Al / V). The soluble vanadium compound is 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound (when the copolymerization is carried out by a continuous method) present in the polymerization system. It is desirable to be supplied at a concentration of.

The soluble vanadium compound and the organoaluminum compound are usually liquid monomers and / or
Alternatively, it is diluted with the above hydrocarbon solvent and supplied to the polymerization system. At this time, the soluble vanadium compound is preferably diluted to the above-mentioned concentration, but the organoaluminum compound should be prepared at an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization system and supplied to the polymerization system. Is desirable.

When the catalyst (ii) is used, the metallocene compound in the polymerization system is usually about 0.00005 to 1.0 mmol, preferably about 0.0001 to 0.3 mmol, per liter of the polymerization volume. The amount of the organoaluminum oxy compound is such that the aluminum atom in the organoaluminum oxy compound is usually about 1 to 10000 mol, preferably 10 to 5000 mol with respect to 1 mol of the transition metal atom in the metallocene compound. Used in quantity.

The copolymerization reaction carried out in the presence of the catalyst (i) or (ii) as described above is usually carried out at a temperature of -50 ° C to 2 ° C.
00 ℃, preferably -30 ℃ ~ 150 ℃, more preferably -20 ℃ ~ 100 ℃, the pressure exceeds 0 ~ 50Kg
/ Cm ^2, preferably more than 0 carried out under conditions of to 20 kg / cm ^2. The reaction time (average residence time when the copolymerization is carried out by a continuous method) is usually 5 minutes to 5 hours, though it varies depending on conditions such as the type of monomer used, the catalyst concentration and the polymerization temperature. , Preferably 10 minutes to 3 hours.

In the above copolymerization reaction, α- having 2 or more carbon atoms is used.
The olefin (a) and the cyclic olefin (b) represented by the above formula [I] or [II] have a (a) / (b) molar ratio of 10/90 to 90/10, preferably 10/90. ~ 5
It is fed to the polymerization system in an amount such that it is 0/50.

Further, in the case of copolymerization, a molecular weight modifier such as hydrogen can be used. As described above, the cyclic olefin-based elastomer component [A], in the presence of the elastomer component [A], the α-olefin (a) having 2 or more carbon atoms and the general formula [I] or [II] A solution containing a cyclic olefin-based copolymer composition [C] comprising a cyclic olefin-based copolymer component [B] obtained by copolymerizing the cyclic olefin (b) is obtained. In such a solution, the cyclic olefin-based copolymer composition [C]
Is usually 10 to 500 g / liter, preferably 10
Included at a concentration of ~ 300 g / l. This solution is treated by a conventional method to obtain the cyclic olefin-based copolymer composition [C].

In order to produce the cycloolefin copolymer composition [C] according to the present invention, more specifically, the cycloolefin elastomer component [A] which has already been produced, such as elastomer pellets or veils, is converted into hydrocarbon. It may be dissolved in a solvent and the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b) may be copolymerized in this solution. Further, the cyclic olefin elastomer component [A] as described above is first prepared. It may be produced and copolymerized with a C 2 or more α-olefin (a) and a cyclic olefin (b) in the polymerization solution.

The cyclic olefin copolymer composition according to the present invention is molded by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plastifier, mixer, twin-screw conical screw extruder, planetary screw extruder, gear-type extruder. Machine, screwless extruder, etc., extrusion molding, injection molding, blow molding, rotational molding.

Further, the cyclic olefin copolymer composition [C] of the present invention further improves the impact strength of the above cyclic olefin copolymer composition [C] within a range not impairing the object of the present invention. Or a heat resistant stabilizer, weather resistant stabilizer, antistatic agent, slip agent, antiblocking agent, antifog agent, lubricant, dye, pigment, natural oil, synthetic oil, wax, etc. be able to.

For example, as a stabilizer to be added as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamide bis [ethyl-3 (3,5- Di-t-butyl-4-hydroxyphenyl)] propionate and other phenolic antioxidants, zinc stearate, calcium stearate, fatty acid metal salts such as 12-hydroxy calcium stearate, glycerin monostearate, glycerin monolaurate, glycerin Examples thereof include fatty acid esters of polyhydric alcohols such as distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate and Examples thereof include a combination with glycerin monostearate.

In the present invention, it is particularly preferable to use a phenolic antioxidant and a polyhydric alcohol fatty acid ester in combination, and the polyhydric alcohol fatty acid ester is one of the alcoholic hydroxyl groups of the trihydric or higher polyhydric alcohol. The part is preferably a polyhydric alcohol fatty acid ester esterified. As such fatty acid ester of polyhydric alcohol, specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin fatty acid ester such as glycerin dilaurate, Pentaerythritol monostearate, pentaerythritol monolaurate,
Fatty acid esters of pentaerythritol such as pentaerythritol dilaurate, pentaerythritol distearate and pentaerythritol tristearate are used. Such a phenolic antioxidant is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, more preferably 0 to 2 parts by weight, based on 100 parts by weight of the cyclic olefin resin, and a polyhydric alcohol. The fatty acid ester is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the cyclic olefin resin.

In the present invention, the cyclic olefin random copolymer composition is added to silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, water to the extent that the object of the present invention is not impaired. Aluminum oxide, magnesium hydroxide, basic magnesium carbonate,
Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber Fillers such as silicon carbide fibers, α-olefin fibers having 2 or more polycarbons, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

[0149]

The cyclic olefin copolymer composition [C] obtained in the present invention comprises a cyclic olefin elastomer component [A] which does not substantially contain a polymerizable carbon-carbon double bond, and the elastomer component. It comprises a cyclic olefin-based copolymer component [B] obtained by copolymerizing an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b) in the presence of [A]. The cyclic olefin random copolymer component [B] obtained by copolymerizing two or more α-olefins (a) and a cyclic olefin and the cyclic olefin elastomer component [A] have excellent compatibility.
Moreover, the difference between the refractive index of the cyclic olefin elastomer component [A] and the refractive index of the cyclic olefin random copolymer component [B] is 0.015 or less. Therefore, in this cyclic olefin-based copolymer composition [C], the cyclic olefin-based random copolymer phase and the elastomer phase are well dispersed, and particularly the transparency and impact resistance are improved.

[0150]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The measuring methods and evaluation results of various physical properties in the present invention are shown below. (1) Intrinsic viscosity [η] It was measured at 135 ° C in a decalin solution using an Ubbelohde viscometer. (2) Glass transition point (Tg) The glass transition point was measured using a DSC-220C manufactured by Seiko Instruments Inc. in a nitrogen atmosphere at a temperature rising rate of 10 ° C / min. (3) According to MFR ASTM D1238, it was measured at 260 ° C. under a load of 2.16 kg. (4) Preparation of test piece Using an injection molding machine IS50EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece mold, molding was performed under the following molding conditions. After molding, the test piece was allowed to stand at room temperature for 48 hours and then measured. (5) Izod impact test Measured according to ASTM D256.

Test piece shape: 5/2 × 1/8 × 1 / 2t inch (notched) Test temperature: 23 ° C. (6) Refractive index measurement: Abbe refractometer (D line, 589)
nm). (7) Light transmittance The light transmittance was defined as the transmittance at a wavelength of 780 nm in the visible spectrum measured using a Shimadzu spectrophotometer MPS-2000 as a sample with a press sheet having a thickness of 2 mm. (Production Example of Cyclic Olefin Elastomer Component [A])
Using a 1 liter glass polymerization vessel equipped with a stirring blade,
The cyclic olefin-based elastomer was synthesized as follows.

Glass with an internal volume of 1 liter equipped with a stirrer
To the polymerization vessel made of stainless steel, insert 5-phenyl-bicyclo from the top of the polymerization vessel.
[2.2.1] Hept-2-ene (hereinafter abbreviated as PhBH) sikh
The rhohexane solution was added to the PhBH concentration of 10.
0.4 liter / hour, or 6 g / liter
VO (OC₂H_Five) Cl₂Cyclohexane
The solution has a vanadium concentration of 0.5 mmol in the polymerization vessel.
0.7 liters / hour (at this time
The supplied vanadium concentration is 2. of the vanadium concentration in the polymerization vessel.
86 times), isobutyl aluminum sesquichlori
De (Al (C_FourH₉) _1.5Cl_1.5) Cyclohexane solution
Aluminum concentration in the polymerization vessel is 4.0 mmol / liter
At 0.4 liters / hour torr and then sikh
Rohexane at 0.5 liter / hour in each polymerization vessel
Was continuously fed to. A bubbling tube is used for the polymerization system.
20.0 l / h of ethylene and 10.0 of nitrogen
L / h, hydrogen at 0.5 l / h
I paid.

A cooling medium was circulated in a jacket attached to the outside of the polymerization vessel to carry out a copolymerization reaction while maintaining the polymerization system at 10 ° C. The polymerization solution of the ethylene / PhBH copolymer produced by the above-mentioned copolymerization reaction should be constantly adjusted to 1 liter from the upper part of the polymerization vessel (that is, the average residence time should be 0.5 hours). To) continuously extracted. A small amount of methyl alcohol was added to the extracted polymerization liquid to stop the polymerization reaction. Then, the aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymerization solution were brought into contact with each other under strong stirring using a homomixer, and the catalyst residue was transferred to a water tank. After the contact mixed solution was allowed to stand still, the aqueous phase was separated and removed, and then washed twice with distilled water to purify and separate the polymerization liquid phase. After contacting the polymerization solution with 3 volumes of acetone under strong stirring,
The solid part was collected by filtration, washed thoroughly with acetone, and
It was dried at 30 ° C. and 350 mmHg for 12 hours.

As described above, an ethylene / PhBH copolymer was obtained in an amount of 40.0 g / hour, that is, 20.0 g / liter. The ethylene and PhBH contents in the obtained copolymer were 87.8 mol /% and 12.2 mol%, respectively, and the intrinsic viscosity [η] was 1.91 dl / g and DS.
The glass transition temperature Tg of the C method was 2.4 ° C. Again 2
The refractive index n _D (A) measured at 5 ° C. was 1.5416. Separately, 10 g of anhydrous magnesium sulfate was added to 1 liter of the polymerization solution to the polymerization solution obtained in the main polymerization reaction, and the mixture was shaken to remove water contained in the polymerization solution. I served.

[0156]

Example 1 Using a 1-liter glass-made polymerization vessel equipped with a stirring blade, in the presence of a cyclic olefin-based elastomer component [A] substantially free of a polymerizable double bond,
Ethylene and tetracyclo [4.4.0.1 ^2,5 . Copolymerization with 1 ^7,10 ] -3-dodecene (hereinafter abbreviated as TCD) was continuously carried out by the following method.

An ethylene / PhBH copolymer ([η] = 1.91 dl / g, iodine value 0.2, Tg 2.
The cyclohexane solution (4 ° C.) was continuously fed in an amount of 0.5 liter / hour so that the ethylene / PhBH copolymer concentration in the polymerization vessel was 6.9 g / liter. Further, a cyclohexane solution of TCD was continuously supplied in an amount of 0.4 liter / hour so that the TCD concentration in the polymerization vessel was 60.0 g / liter. Further, a cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ was used as a catalyst from the upper part of the polymerization vessel at 0.7 liter / hour (at this time, so that the vanadium concentration in the polymerization vessel was 0.5 mmol / liter). The supplied vanadium concentration is 2.86 times the vanadium concentration in the polymerization vessel), and isobutylaluminum sesquichloride (Al (C ₄ H ₉ ) _1.5 Cl _1.5 )
The cyclohexane solution of 1 was continuously fed into the polymerization vessel in an amount of 0.4 liter / hour so that the aluminum concentration in the polymerization vessel was 4.0 mmol / liter. In addition, ethylene was added to the polymerization system by using a bubbling tube.
0.6 liter / hour, nitrogen 40.6 liter / hour, and hydrogen 0.85 liter / hour were supplied.

Copolymerization reaction was carried out while maintaining the polymerization system at 10 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel. Ethylene / TCD containing ethylene / PhBH copolymer produced by the above copolymerization reaction
The polymerization solution of the copolymer composition was continuously withdrawn from the upper part of the polymerization vessel so that the polymerization solution in the polymerization vessel was always 1 liter (that is, the average residence time was 0.5 hours). A small amount of methanol was added to the extracted polymerization liquid to stop the polymerization reaction. Then, the aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymerization solution were brought into contact with each other under strong stirring using a homomixer, and the catalyst residue was transferred to a water tank. After allowing this contact mixture to stand,
After the aqueous phase was separated and removed, it was further washed twice with distilled water to purify and separate the polymerization liquid phase.

Then, the purified and separated polymerization liquid was contacted with 3-fold amount of acetone under strong stirring, and then the solid portion was collected by filtration and sufficiently washed with acetone. In addition, the solid portion washed to extract the TCD present in the polymer is 40
After charging into acetone so that the concentration would be g / liter, 6
The extraction operation was performed under the conditions of 0 ° C. for 2 hours. After the extraction treatment, the solid part was collected by filtration, and under a nitrogen stream, 130
It was dried at 350 ° C. and 350 mmHg for 12 hours.

As described above, the cyclic olefin copolymer composition comprising the ethylene / PhBH copolymer and the ethylene / TCD copolymer was added at an amount of 53.4 g / hour, that is, 26.7 g / liter. Obtained. The ratio of the component [A] contained in the produced copolymer was 25.8% by weight. The copolymer obtained had an MFR of 2.9 g / 10 minutes measured at 260 ° C. under a load of 2.16 kg. The Tg of the component [B] was 142 ° C.

The results obtained are shown in Table 1.

[0162]

Example 2 A cyclic olefin copolymer composition comprising an ethylene / PhBH copolymer and an ethylene / TCD copolymer was prepared in the same manner as in Example 1 except that the conditions were changed as shown in Table 1. Manufactured. The results are shown in Table 1.

[0163]

Example 3 7.8 g of ethylene / PhBH copolymer obtained in the synthesis example of toluene 239 ml and the above elastomer component [A] ([η] = 2.02 dl / g, Tg-6.
To a 1 liter-stainless steel autoclave containing 0 ° C., norbornene (hereinafter abbreviated as NB) (134 g) was added at room temperature under a nitrogen stream, and the mixture was stirred for 5 minutes. Subsequently, ethylene was circulated at normal pressure while stirring to create an ethylene atmosphere in the system. Keep the internal temperature of the autoclave at 70 ℃,
It was pressurized with ethylene so that the internal pressure was 4 kg / cm 2. After stirring for 10 minutes, 5.2 ml of a toluene solution containing ethylenebis (indenyl) zirconium dichloride and methylalumoxane prepared above was added to the system to initiate a copolymerization reaction of ethylene and NB. At this time, the catalyst concentration was 0.1% of ethylenebis (indenyl) zirconium dichloride with respect to the whole system.
0 mmol / liter and 2 methylalumoxane
It is 0 mmol / liter. During the polymerization, the internal pressure was 4 kg / cm ² by continuously supplying ethylene into the system.
Held in. After 20 minutes, the polymerization reaction was stopped by adding isopropyl alcohol. After depressurization, the polymer solution was taken out and brought into contact with an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water with a homomixer at a ratio of 1: 1 under vigorous stirring to transfer the catalyst residue to the aqueous phase. After the contact mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water to purify and separate the polymerization liquid phase.

Then, the purified and separated polymerization liquid was contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer composition, and then a solid portion (copolymer) was collected by filtration and washed with acetone. Washed thoroughly. Further, in order to extract unreacted NB existing in the polymer, after pouring this solid part into acetone so as to be 40 g / liter, the mixture was heated at 60 ° C. for 2 hours.
The extraction operation was performed under the conditions of time. After the extraction process, the solid part was collected by filtration, under nitrogen flow, 130 ° C, 350 mm
It was dried with Hg for 12 hours.

As described above, a cyclic olefin-based copolymer composition comprising an ethylene / PhBH copolymer and an ethylene / NB copolymer was obtained. The ratio of the component [A] contained in the produced copolymer composition was 25.7% by weight. The obtained copolymer composition had a temperature of 260 ° C. and 2.16.
The MFR measured under a load of kg was 2.6 g / 10 minutes. The Tg of the component [B] was 135 ° C.

The results are shown in Table 1.

[0167]

Comparative Examples 1 to 3 Cyclic olefin copolymer compositions were produced in the same manner as in Example 1 except that the conditions were changed as shown in Table 1.

The results are shown in Table 1. Further, as shown in Comparative Example 2, the intrinsic viscosity [η] of the elastomer component [A] is
It can be seen that the impact strength decreases at 0.5 dl / g or less. Further, as shown in Comparative Example 3, when the glass transition temperature (Tg) of the elastomer component [A] is 15 ° C. or higher,
It can be seen that the impact resistance strength decreases.

[0169]

[Table 1]

Claims (2)

[Claims] 1. An α-olefin having 2 or more carbon atoms,
(B) A cyclic o represented by the following general formula [I] or [II]
Copolymerized with reffin, and in the resulting copolymer
Contains cyclic olefin units in an amount of 3 mol% or more
And intrinsic viscosity [η] measured at 135 ° C in decalin
Is in the range of 0.5 to 5.0 dl / g, and the glass transition temperature is
And a temperature (Tg) of less than 15 ° C. that is substantially polymerizable.
-Refractive index n containing no carbon double bond and measured at 25 ° C
_D(A) is a ring o in the range of 1.500 to 1.650
In the presence of the reffin-based elastomer component [A] and the elastomer component [A], (a) the number of carbon atoms is 2
The above α-olefin, and (b) the following general formula [I]
Is obtained by copolymerizing with a cyclic olefin represented by [II]
A cyclic olefin-based copolymer component [B], which is
Then, the component [A] in the copolymer composition [C] is 8 to 40
Is present in an amount of% by weight, and the refractive index n of the above component [A]_D(A) and the refractive index n of the above component [B]_DDifference from (B): △ n_D(= |
n_D(A) -n_D(B) |) is 0.015 or less
A cyclic olefin-based copolymer composition characterized by:(In the formula [I], n is 0 or 1, and m is 0 or positive.
Is an integer, q is 0 or 1, and R¹ ~ R¹⁸Nara
Bini R^a And R^b Are each independently a hydrogen atom,
Rogen atom or hydrocarbon group, R¹⁵~ R¹⁸Are each other
And may form a monocyclic ring or a polycyclic ring, and
The monocycle or polycycle may have a double bond, and
R¹⁵And R¹⁶Or with or R¹⁷And R¹⁸And alkylidene group
May be formed. );(In the formula [II], p and q are 0 or an integer of 1 or more.
, M and n are 0, 1 or 2, and R¹ ~ R¹⁹Is
Independently hydrogen atom, halogen atom, aliphatic hydrocarbon
Elementary groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or
R is a Coxy group⁹ (Or R^Ten) Is attached to the charcoal
Elementary atom and R¹³Or R¹¹Is the carbon atom to which is bound
Bonded directly or through an alkylene group having 1 to 3 carbon atoms
R, when n = m = 0, R¹⁵And R¹²Well
Or R¹⁵And R¹⁹And are linked to each other to form a monocyclic or polycyclic
It may form an aromatic ring. ). 2. (a) an α-olefin having 2 or more carbon atoms,
(B) a cyclic olefin represented by the above general formula [II],
The copolymer obtained by copolymerizing
The fin unit is contained in an amount of 3 mol% or more.
Intrinsic viscosity [η] measured at 135 ° C
In the range of 5.0 dl / g, glass transition temperature (Tg)
Is less than 15 ° C. and is substantially polymerizable carbon / carbon double
Refractive index n containing no bond and measured at 25 ° C. _D(A) is
Cyclic olefin system in the range of 1.500 to 1.650
An elastomer component [A] and (a) a carbon number of 2 in the presence of the elastomer component [A].
The above α-olefin, and (b) represented by the above general formula [I]
Cyclic olefins obtained by copolymerizing
A cyclic olefin-based copolymer composition [C] comprising a reffin-based copolymer component [B]
Then, the component [A] in the copolymer composition [C] is 8 to 40
Is present in an amount of% by weight, and the refractive index n of the above component [A]_D(A) and the refractive index n of the above component [B]_DDifference from (B): △ n_D(= |
n_D(A) -n_D(B) |) is 0.015 or less
A cyclic olefin-based copolymer composition comprising: