JPH08231652A - Cyclic olefin copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain cyclic olefinic copolymer compositions excellent in impact resistance, transparency and heat resistance by copolymerizing a cyclic olefin in the presence of a specific copolymer to form a polymer having specific properties.

SOLUTION: A desired cyclic olefin copolymer composition can be obtained by copolymerizing, in the presence of (A) an aromatic ring-containing vinyl hydrocarbon/conjugated diene copolymer having an intrinsic viscosity (in decalin at 135°C) of 0.5-5.0 dl/g, at least one glass transition temperature by DSC of lower than 15°C and containing a polymerizable C-C double bond with a content of the double bond by iodine value of 2-150 (g iodine/100 g polymer) and having a refractive index (25°C) of 1.50-1.65 or a hydrogenated copolymer thereof, (B) a ≥2C α-olefin with (C) a cyclic olefin represented by formula I or formula II, and the composition has a content of component (A) of 1-40 wt.% and a difference in refractive index between component A and a copolymer to be obtained by copolymerizing component (B) with component (C) in the absence of component (A) being not greater than 0.015.

COPYRIGHT: (C)1996,JPO

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 more excellent in impact resistance than a cyclic olefin random copolymer, but further improvement in impact resistance is desired. Further, the applicant of the present application discloses in Japanese Patent Application No. 4-133822 that a cyclic olefin-based compound obtained by copolymerizing an α-olefin and a cyclic olefin in the presence of a hydrocarbon-based elastomer having a polymerizable double bond. A copolymer is proposed.

Although such a cyclic olefin-based copolymer is excellent in impact resistance, further improvement in transparency has been required. The inventors of the present invention have made extensive studies to solve the above-mentioned problems in the prior art, and as a result, a specific aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer having a polymerizable double bond or hydrogen thereof. A compound component [A] is prepared and obtained by copolymerizing an α-olefin having 2 or more carbon atoms such as ethylene with a cyclic olefin in the presence of the component [A], and the component [A] is specified. The difference between the refractive index n _D (A) of the component [A] and the refractive index n _D (B) of the copolymer obtained by the above copolymerization in the absence of the component [A] is specified. It was found that a cyclic olefin-based copolymer composition within the range of 1) has particularly excellent transparency and impact resistance, and thus completed the present invention.

[0006]

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.

[0007]

SUMMARY OF THE INVENTION The cyclic olefin copolymer composition according to the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.5 to 5.0 dl / g, and DSC.
At least one glass transition temperature (Tg) obtained by the measurement is less than 15 ° C., it has a polymerizable carbon-carbon double bond, and the content of the double bond is 2 to an iodine value.
150 (g-iodine / 100 g-polymer), 25
In the presence of an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer having a refractive index n _D (A) measured in ° C of 1.50 to 1.65 or a hydride component [A] thereof,
A cycloolefin copolymer composition [C obtained by copolymerizing (a) an α-olefin having 2 or more carbon atoms and (b) a cycloolefin represented by the following general formula [I] or [II] ] In the copolymer composition [C], the component [A] is present in an amount of 1 to 40% by weight, and the refractive index n _D (A) of the component [A] and Difference from the refractive index n _D (B) shown by Δn _D (= | n _D (A) −n
_The feature is that _D (B) |) is 0.015 or less. The refractive index n _D (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 absence of the above component [A]. It is the refractive index of the cyclic olefin-based copolymer component [B] obtained by copolymerizing with a cyclic olefin.

[0008]

Embedded image

(In the formula [I], n is 0 or 1, and m is
Is 0 or a positive integer, r 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. );

[0010]

[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. ).

In a preferred embodiment of the present invention, the content of polymerizable carbon-carbon double bond in the aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or its hydride is 2 to iodine value. It is preferably 50 (g-iodine / 100 g-polymer).

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.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The cyclic olefin copolymer composition [C] according to the present invention will be specifically described below.

First, the aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer having a polymerizable carbon / carbon double bond or the hydride component [A] thereof of the present invention will be described. Aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or hydride component thereof [A] Aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or hydride component thereof (thermoplastic elastomer) used in the present invention [ A] has an intrinsic viscosity [η] measured at 135 ° C. in decalin of 0.5 to 5.0 dl / g, preferably 1.0 to 4.5 dl / g, and is at least obtained by DSC measurement. One glass transition temperature (Tg) is less than 15 ° C., preferably less than 0 ° C., it has a polymerizable carbon-carbon double bond, and the content of the double bond is 2-150 (g in iodine value). -Iodine / 100g-polymer),
Preferably 2 to 50 (g-iodine / 100 g-polymer)
Is. When the iodine value exceeds 150, the fluidity of the polymerization reaction system is deteriorated.

The refractive index n _D (A) measured at 25 ° C. is
It is in the range of 1.50 to 1.65, preferably 1.51 to 1.55. Such a component [A] ASTM D12
Melt flow rate (MF
R: measured at 230 ° C. and a load of 2,16 kg) is usually 0.
01-200g / 10 minutes, preferably 0.1-100g
/ 10 minutes, more preferably 0.5 to 50 g / 1
0 minutes.

Such aromatic ring-containing vinyl hydrocarbons
Specific examples of the conjugated diene copolymer or its hydride component [A] include SBS [polystyrene (PS) -polybutadiene-PS] and SBR (styrene-butadiene block copolymer) which are styrene / conjugated diene-based block copolymers. ), Styrene-isoprene block copolymer, S
In addition to IS (PS-polyisoprene-PS), SBS hydride and SIS hydride styrene (ethylene / butylene) / styrene block copolymer (SEB)
S), styrene (ethylene / propylene) / styrene block copolymer (SEPS) and the like.

More specifically, the styrene / conjugated diene-based block copolymer is more specifically described in "Kraton (Kraton)".
ton) "(manufactured by Shell Chemical Co., Ltd.)," Cariflex TR "(manufactured by Shell Chemical Co., Ltd.)," Sorprene "(manufactured by Philippe Petroleum Co., Ltd.)," Europrene SO "
"LT" (manufactured by Anich), "Toughprene" (manufactured by Asahi Kasei Co., Ltd.), "Sorprene-T" (manufactured by Nippon Elastomer Co., Ltd.), "JSRTR" (manufactured by Nippon Synthetic Rubber Co., Ltd.)
TR "(manufactured by Denki Kagaku)," Quintac "(manufactured by Zeon Corporation)," Clayton G "(manufactured by Shell Chemical Co., Ltd.),
Examples include "Tough Tech" (manufactured by Asahi Kasei Co., Ltd.).

As the hydride of the styrene / conjugated diene block copolymer, more specifically, "Kraton G1650," which is one of the above SEBS,
"G1652, G1657, G1701" (manufactured by Shell Chemical Co., Ltd.), "Tuftec" (manufactured by Asahi Kasei Co., Ltd.), and the like.

SEBS [styrene ・ (ethylene /
Butylene) / styrene block copolymer] is a thermoplastic elastomer composed of polystyrene block units and polyethylene / polybutylene rubber block units.

This styrene (ethylene / butylene)
In the styrene block copolymer, the polystyrene block unit which is a hard segment exists as a bridging point of the rubber block unit to form a physical crosslink (domain), and the rubber block unit existing between the polystyrene block units is soft. It is a segment and has rubber elasticity.

SEBS is, for example, Japanese Patent Publication No. 60-573.
It can be obtained by a known method described in Japanese Patent Publication No. 63-63. In the present invention, two or more kinds of aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or hydride thereof may be used in combination.

In the present invention, SEBS, SEPS, SBR and SBS are preferably used among the above-mentioned styrene / conjugated diene block copolymers and hydrogenated products thereof.

Next, the cycloolefin copolymer composition [C] of the present invention will be described. Cyclic Olefin Copolymer Composition [C] The cyclic olefin copolymer composition [C] is an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer containing a polymerizable double bond as described above. Alternatively, in the presence of the hydride component [A], (a) an α-olefin having 2 or more carbon atoms and (b) a cyclic olefin represented by the following general formula [I] or [II] are copolymerized: The resulting cyclic olefin copolymer component.

Α-olefin (a) having 2 or more carbon atoms
May be a linear α-olefin or a branched α-olefin. Such carbon number 2
As the above α-olefin, 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 Examples include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and other α-olefins having 2 to 20 carbon atoms. 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), a cyclic olefin represented by the following formula [I] and / or [II] is used.

[0027]

Embedded image

In the formula [I], n is 0 or 1, m is 0 or a positive integer, and r is 0 or 1. In addition, when r is 1, a 6-membered ring is formed, and when r is 0, respective bonds bond to each other to form a 5-membered ring.

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.

[0033]

[Chemical 6]

In the above exemplification, 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.

[0036]

[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 a methoxy group, an ethoxy group and a 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.

[0043]

Embedded image

In the above example, q has the same meaning as q in the formula [II]. The above formula [I] or [I
Specific examples of the cyclic olefin represented by the formula [I] are shown below.

[0045]

[Chemical 9]

The bicyclo [2.2.1] -2-heptene (= norbornene) represented by (in the above general formula, the numbers 1 to 7 represent the carbon position numbers) and the hydrocarbon group in the compound. Substituted derivatives are mentioned.

As the hydrocarbon group, 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5 -Phenyl, 5
-Benzyl, 5-tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthracenyl), 5 An example is 6,6-diphenyl.

As other derivatives, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-
Tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a
-Bicyclo [2.2.1] such as hexahydroanthracene-
A 2-heptene derivative can be illustrated.

In addition, tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, 5
- tricyclo [4.3.0.1 ^2,5] -3- decene derivatives such as methyl tricyclo [4.3.0.1 ^2,5] -3- decene, tricyclo [4.4.0.1 ^2,5] -3- undecene, 10-methyl Tricyclo [4.4.0.1 ^2,5 ] -3-Tricyclo [4.4.
0.1 ^2,5 ] -3-Undecene derivative,

[0050]

[Chemical 10]

Tetracyclo [4.4.0.1 ^2,5 .1 represented by the [0051]
^7,10 ] -3-dodecene and derivatives in which a hydrocarbon group is substituted are included. As the hydrocarbon group, 8-methyl,
8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10-dimethyl, 8,9-dimethyl, 8-ethyl- 9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl
-9-ethyl, 9-isobutyl-2,7-dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,1
2-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8
-Ethylidene-9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-
n-propylidene, 8-n-propylidene-9-methyl, 8-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8 -Isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 8-
Isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-
Fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl,
Examples thereof include 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (anthracenyl) and 5,6-diphenyl.

Further, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene derivative such as an adduct of (cyclopentadiene-acenaphthylene adduct) and cyclopentadiene, pentacyclo [6.5.1.1 ^{3, 6.0 2,7} .0 ^9,13] -4-pentadecene and its derivatives, pentacyclo [7.4.0.1 ^2,5 .1
^9,12 .0 ^8,13] -3-pentadecene and its derivatives, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene and derivatives thereof, pentacyclo [6.6.1.1 ^{3 , 6} .0 ^2,7 .0
^9,14] -4-hexadecene and derivatives thereof, hexacyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] -4- heptadecene and its derivatives, heptacyclo [8.7.0.1 ^{2 , 9} .1 ^4,7 .1
^11,17 .0 ^3,8 .0 ^12,16] -5-eicosene and its derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0
^11,16] -4-eicosene and its derivatives, heptacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .0} 3,8 .0 12,17] -5- heneicosene and its derivatives, octacyclo [8.8.0.1 ^2,9 .1
^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17] -5-docosene and its derivatives, Nonashikuro [10.9.1.1 ^4,7 .1 ^{13, 20} .1 ^{15 and 18} .0
^2,10 .0 ^3,8 .0 ^12,21 .0 ^14,19] such as 5-pentacosene and derivatives thereof.

Specific examples of the cyclic olefin represented by the above formula [I] or formula [II] which can be used in the present invention are as described above. The present invention is disclosed in paragraph Nos. [0032] to [0054] of Japanese Patent Application Laid-Open No. 7-145213 (Japanese Patent Application No. 5-196475), which is also an example of the present invention. What is mentioned can be used as a cyclic olefin of this invention.

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

These cyclic olefins may be used alone or in combination of two or more. Specific examples of the above-mentioned cyclic olefin-based copolymer (α-olefin / cyclic olefin-based copolymer) are given. Specific examples of such α-olefin / cyclic olefin-based copolymers include ethylene / norbornene copolymer, ethylene / 5-methyl-2-norbornene copolymer, and 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 Polymer, 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-
Examples thereof include a decene / 5-phenyl-2-norbornene copolymer and an ethylene / 1-decene / tetracyclododecene copolymer.

The cyclic olefin copolymer composition [C] of the present invention comprises an α-olefin (a) having 2 or more carbon atoms.
And a cyclic olefin (b) represented by the above formula [I] or formula [II], the aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer having the above-mentioned substantially polymerizable double bond. Alternatively, it is a copolymer obtained by copolymerization in the presence of the hydride component [A].

In the above-mentioned cyclic olefin copolymer composition [C], in addition to the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b), as long as the properties of the copolymer component are not impaired. It is also possible to copolymerize a cyclic olefin (other cyclic olefin) other than the cyclic olefin represented by the above formula [I] or [II].

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.

In the cycloolefin copolymer composition [C] according to the present invention, the component [A] is present in an amount of 1 to 40% by weight, preferably 2 to 30% by weight. In the cyclic olefin copolymer composition [C] according to the present invention,
Refractive index n of the aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or its hydride component [A]
_D and (A), the difference △ n _D = the refractive index of the cycloolefin copolymer component as follows _{[B] n D (B)} | n D (A)
-N _D (B) | is 0.015 or less. Here, the cyclic olefin copolymer component [B] is (a) an α-olefin having 2 or more carbon atoms in the absence of the above component [A],
(B) A cyclic olefin-based copolymer component obtained by copolymerizing the cyclic olefin represented by the general formula [I] or [II].

In the present invention, the refractive index of the aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or its hydride component [A] and the refractive index of the cyclic olefin copolymer component [B] are Abbe Refractometer (D line 589n
The value measured using m) is adopted.

In the cyclic olefin copolymer composition [C] according to the present invention, the cyclic olefin copolymer component formed from the α-olefin (a) and the cyclic olefin (b) as described above. And an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or its hydride component [A]
Is considered to be chemically bonded at least in part. This means that the cyclic olefin-based copolymer composition [C] according to the present invention is an α-olefin having 2 or more carbon atoms in the absence of the above-mentioned polymerizable double bond-containing component [A]. Cyclic olefin random copolymer component [B] obtained by copolymerizing (a) and cyclic olefin (b)
And the cyclic olefin-based copolymer composition obtained by simply blending the above-mentioned component [A].

In the cycloolefin copolymer composition [C] according to the present invention, as described above, the refractive index n _D of the aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or its hydride component [A]. A cyclic olefin-based copolymer component [B] obtained by copolymerizing (A) with an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b) in the absence of the above component [A]. Difference from the refractive index n _D (B) of Δn _D (= |
n _D (A) -n _D (B) |) is 0.015 or less, preferably 0.010 or less, and more preferably 0.
It is 005 or less.

In the cyclic olefin copolymer composition [C], a part of the above cyclic olefin copolymer component is chemically bonded to the component [A], so the composition [C] Only the above cyclic olefin-based copolymer component cannot be extracted from the inside.

For these reasons, in the present specification, the refractive index n _D (B) is such that the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b) are present in the absence of the component [A]. The value of the refractive index n _D (B) of the cyclic olefin random copolymer [B] consisting of

When the component [A] (aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or its hydride component) as described above is produced, and in the presence of the component [A], α
-When copolymerizing an olefin and a cyclic olefin to produce a cyclic olefin-based copolymer composition [C],
A transition metal catalyst is used.

Specific examples of such a transition metal catalyst include (i) a catalyst formed from a soluble vanadium compound and an organoaluminum compound, or (ii) a transition selected from Group IVB or lanthanide of the periodic table. A catalyst formed from a metallocene compound of a metal, an organoaluminum oxy compound and, if necessary, an organoaluminum compound is used.

The soluble vanadium compound forming the catalyst (i) is specifically represented by the following general formula. Examples are VO (OR) aXb or V (OR) cXd.

In the formula, R is a hydrocarbon group, and a,
b, c and d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3 and 2 ≦ a, respectively.
+ B ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4 are satisfied.

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 expressed by equation (b).

(A) General formula R ¹ _m Al (OR ² ) _n H _p X _q (where 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. ).

[0072] (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.

(Ii) Periodic Table IV used in the present invention
A metallocene compound of a transition metal selected from Group B or lanthanides, an organoaluminum oxy compound, and, if necessary, a catalyst formed from an 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

MLx ... [a] In the above general formula [a], M is a transition metal selected from Group IVB and lanthanides of the periodic table, 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.

Next, the organoaluminum oxy compound used when 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 conventionally known aluminoxane is specifically represented by the following general formula.

[0078]

[Chemical 11]

(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.) 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,
Alternatively, it can be obtained by a method of bringing the above organoaluminum compound into contact with water.

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.

Further, 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. ) A soluble vanadium compound, an organoaluminum compound, a metallocene compound of a transition metal, an organoaluminum oxy compound, which constitutes the above-mentioned transition metal catalysts (i) and (ii) that can be used in the present invention, and is used as necessary. For more specific examples of the organoaluminum compound, see Japanese Patent Application Laid-Open No. 6-4136 filed by the applicant of the present application.
Paragraph numbers [0100] to [015] in the specification of Japanese Patent Publication No. 4
3] can be exemplified, and in the present invention, a catalyst composed of these compounds can be used in the reaction of the present invention.

In the present invention, the catalyst (i) or (ii) as described above is used to produce a carbon atom in the presence of an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or its hydride component [A]. The α-olefin of 2 or more and the cyclic olefin represented by the above formula [I] or [II] are 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 cycloaliphatic 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 may be 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 amount of 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 ° C., preferably −30 ° C. to 150 ° C., more preferably −20 ° C. to 100 ° C., pressure exceeding 0 and 50 kg /
It is carried out under the conditions of not more than cm ² , preferably more than 0 and not more than 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-containing 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, in the presence of the aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or its hydride component [A], α- having 2 or more carbon atoms
By copolymerizing the olefin (a) and the cyclic olefin (b) represented by the general formula [I] or [II], a solution containing the cyclic olefin-based copolymer composition [C] is obtained. In such a solution, the cyclic olefin copolymer composition [C] is usually contained at a concentration of 10 to 500 g / liter, preferably 10 to 300 g / liter. This solution is treated by a conventional method to obtain the cyclic olefin-based copolymer composition [C].

To produce the cyclic olefin copolymer composition [C] according to the present invention, more specifically, the aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer already produced or its hydrogen is produced. Compound [A], for example, elastomer pellets may be dissolved in a hydrocarbon solvent and the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b) may be copolymerized in this solution. Such an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or a hydride component [A] thereof is produced, and an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin (b) are contained in the polymerization solution. May be copolymerized.

The cyclic olefin copolymer composition according to the present invention is molded and processed by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, practicator, mixer, planetary screw extruder,
It is extrusion-molded, injection-molded, blow-molded or rotational-molded by a gear type extruder, a screwless extruder or the like.

Further, the cyclic olefin copolymer composition [C] of the present invention further improves the impact strength of the 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, a stabilizer to be added as an optional component is 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.

[0097]

The cyclic olefin copolymer composition [C] obtained in the present invention is an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer containing a polymerizable carbon / carbon double bond or a copolymer thereof. In the presence of the hydride component [A], the α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b).
And a cyclic olefin random copolymer component obtained by copolymerizing an α-olefin (a) having 2 or more carbon atoms and a cyclic olefin. At least a part of the component [A] is chemically bonded. Moreover, the refractive index of the component [A] and a cyclic olefin-based random copolymer component [[alpha] -olefin (a) and a cyclic olefin (b) which are randomly copolymerized in the absence of the above component [A] are used. The difference from the refractive index of B] is 0.015 or less. Therefore, in this cyclic olefin copolymer composition [C], transparency and impact resistance are particularly improved.

[0098]

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

The methods for measuring and evaluating various physical properties in the present invention are shown below. (1) Intrinsic viscosity ([η]) was measured at 135 ° C. in a decalin solution (1 g / liter) using an Ubbelohde viscometer. (2) Glass transition point (Tg) manufactured by Seiko Instruments Inc., DS
Using C-220C under N ₂ (nitrogen) atmosphere, 10 ° C /
It was measured at a temperature rising rate of minutes. (3) Refractive index: Abbe's refractometer (D line, 589 nm) was used to measure at 25 ° C. (4) Iodine number Measured by the iodine monochloride method according to JIS K3331. (5) Preparation of test piece Toshiba Machine Co., Ltd. injection molding machine IS50EP
Using N and a predetermined test piece mold, molding was performed under the following molding conditions. After molding, the test piece was left for 48 hours at room temperature and then subjected to measurement.

Molding conditions: cylinder temperature 260 ° C., mold temperature 60 ° C., injection pressure: primary / secondary = 1000/800
(Kg / cm ² ) (6) Measured with a Haze Haze meter (sheet thickness 2 mm). (7) Izod impact strength Measured according to ASTM D256.

Test piece shape: 5/2 × 1/8 × 1/2 ^t inch (with notch) Test temperature: 23 ° C.

[0102]

Example 1 80 mg of isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride was taken in a 100 ml glass container which had been dried and purged with nitrogen, and 70 ml of methylalumoxane (MAO) was collected. Toluene solution (Witco,
The aluminum concentration was 1.50 mmol / l) and the mixture was irradiated with ultrasonic waves for 15 minutes to completely dissolve the metallocene.

[Ethylene in the Presence of Component [A] (Rubber)
-Norbornene copolymer] Aromatic-containing vinylated hydrocarbon / conjugated diene copolymer (aromatic ring-containing vinyl-based hydrocarbon
As a conjugated diene copolymer), a partially hydrogenated SBS (styrene / butadiene / styrene block copolymer, styrene content (St content) 45 wt%, hydrogenation rate 56%, refractive index 1.533, shown in Table 1 a), Iodine value 100.3) 2
00 g was taken and dissolved in 5 liters of cyclohexane. Then, this was precipitated in a 4-fold amount of a mixed solution of methanol / acetone (volume ratio 7/1) under vigorous stirring, the solid part was recovered by filtration, washed well with methanol, and then at 50 ° C. under a nitrogen stream. It was dried under reduced pressure for 12 hours.

This was dissolved in dry cyclohexane to give 1.
After making it 5 liters and performing nitrogen bubbling for 1 hour, 1.2 liters of the mixture was charged into a 5 liter stainless steel autoclave which was dried under reduced pressure and purged with nitrogen.

Norbornene (hereinafter referred to as N
(Abbreviated as B) (887 g) and cyclohexane 731 m
1, triisobutylaluminum (TIBA) in 1 mmol / l of cyclohexane solution, 24 ml was added so that the concentration in the system was 8 mmol / l,
The mixture was stirred for 5 minutes. Then 6 with ethylene while stirring
After pressurizing to kg / cm ² G, depressurization was repeated 3 times to create an ethylene atmosphere in the system.

The internal temperature of the autoclave was maintained at 70 ° C. and pressurized with ethylene so that the internal pressure became 6 kg / cm ² . After stirring for 10 minutes, 50 ml of a toluene solution containing isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and methylalumoxane prepared in advance was added to the system to obtain ethylene and NB. The copolymerization reaction was started. The catalyst concentration at this time was 0.05 mmol / liter for isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and 25 mmol / liter for methylalumoxane, based on the total system. During the polymerization, the internal pressure was increased to 6 kg by continuously supplying ethylene to the system.
/ Cm ² was maintained. After 60 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 in which 15 ml of concentrated hydrochloric acid was added to 3 liters of water with a homomixer at a ratio of 1: 1 under strong stirring to transfer the catalyst residue to the aqueous phase. After the catalyst mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed with distilled water twice to purify and separate the polymerization liquid phase.

Then, the purified and separated polymerization liquid is contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer, and then a solid part (copolymer) is collected by filtration, and acetone is sufficiently added. Washed. Further, in order to extract unreacted NB existing in the polymer, this solid part was put into acetone at 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction process, the solid part was collected by filtration, and under a nitrogen flow at 130 ° C and 350 mmHg.
And dried for 12 hours.

The ethylene / norbornene copolymer composition thus obtained has an intrinsic viscosity [η] of 0.7.
It had a glass transition temperature Tg of 141 ° C. and a component [A] (rubber) content of 17.8 wt%. The iodine value of the obtained composition was 19.2, the Izod impact strength of the molded product was 8.0 kg · cm / cm,
Haze was 44%.

The results are shown in Tables 2 and 3.

[0110]

Example 2 In Example 1, as an aromatic-containing vinylated hydrocarbon / conjugated diene copolymer, SBS and SE shown in a and b of Table 1 were used to adjust the refractive index.
Polymerization was carried out in the same manner as in Example 1 except that PS was mixed and used.

The results are shown in Tables 2 and 3.

[0112]

Example 3 In Example 2, as an aromatic-containing vinylated hydrocarbon / conjugated diene copolymer, SBS and SE shown in a and b of Table 1 were used to adjust the refractive index.
Example 2 except that PS was mixed and used in different ratios
Polymerization was carried out in the same manner as in.

The results are shown in Tables 2 and 3.

[0114]

Comparative Example 1 As in Example 1, except that the aromatic-containing vinylated hydrocarbon / conjugated diene copolymer was not supplied and the catalyst concentration was changed as shown in Tables 2 to 3. Synthesis was performed in the same manner.

The results are shown in Tables 2 and 3.

[0116]

Comparative Example 2 In Example 1, as the aromatic-containing vinylated hydrocarbon / conjugated diene copolymer, SEPS shown in b and c of Table 1 were mixed and used in order to adjust the refractive index. Polymerization was performed in the same manner as in Example 1 except for the above.

The results are shown in Tables 2 and 3.

[0118]

Comparative Example 3 As in Example 1, except that the partially hydrogenated product of SIS shown in d of Table 1 was used as the aromatic-containing vinylated hydrocarbon / conjugated diene copolymer. Polymerization was performed in the same manner.

The results are shown in Tables 2 and 3.

[0120]

Comparative Example 4 Ethylene synthesized under the same conditions as in Comparative Example 1
Using a twin-screw extruder (BT-30 manufactured by Institute of Plastics Engineering), the norbornene copolymer was allowed to reach a maximum cylinder temperature of 2
Pelletization was carried out under the conditions of 60 ° C. and a residence time of 1 minute. The pellets were blended with the partially hydrogenated SBS shown in a of Table 1 using the above extruder.

Table 4 shows the evaluation results of the injection-molded products.

[0122]

Comparative Example 5 Ethylene synthesized under the same conditions as in Comparative Example 1
Using a twin-screw extruder (BT-30 manufactured by Institute of Plastics Engineering), the norbornene copolymer was allowed to reach a maximum cylinder temperature of 2
Pelletization was carried out under the conditions of 60 ° C. and a residence time of 1 minute. This pellet and the partially hydrogenated S shown in a and b of Table 1
Blending of BS and SEPS was performed using the above extruder.

Table 4 shows the evaluation results of the injection-molded products.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

[Table 3]

[Note] Copolymerization conditions : 3 liter scale in a 5 liter autoclave, 70 ° C., 60 minutes, N
B: 887 g / 3 liter in cyclohexane. Metallocene: isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride.

As can be seen from the examples and comparative examples in Tables 2 to 3, cyclic olefin-based copolymers obtained by copolymerizing ethylene and norbornene in the presence of the rubber of the component [A] shown in Table 1 Regarding the physical properties of the combined composition [C], when the iodine value of the component [A] is 2 or less, the Izod value is small and the impact resistance is poor. Further, in the cycloolefin copolymer component [B] shown in Comparative Example 1 obtained by copolymerization in the absence of the component [A], the Haze value is small and the transparency is good, but the impact resistance may be poor. Recognize.

[0129]

[Table 4]

[Note] As the component (A), a copolymer synthesized under the same conditions as in Example 1 was used. As shown in Comparative Examples 4 and 5, an ethylene / norbornene copolymer, which is a cyclic olefin copolymer component [B], and an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer (an aromatic-containing vinyl A blend of a partially hydrogenated SBS that is a partially hydride component [A] of a modified hydrocarbon / conjugated diene copolymer) has a small Izod value and poor impact resistance, and also has a large Haze value for transparency. Inferior.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 45/00 LKB C08L 45/00 LKB

Claims (2)

[Claims] 1. The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 5.0 dl / g, and DSC
At least one glass transition temperature (Tg) obtained by the measurement is less than 15 ° C., it has a polymerizable carbon-carbon double bond, and the content of the double bond is 2 to an iodine value.
150 (g-iodine / 100 g-polymer), 25
In the presence of an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer having a refractive index n _D (A) measured in ° C of 1.50 to 1.65 or a hydride component [A] thereof,
A cycloolefin copolymer composition [C obtained by copolymerizing (a) an α-olefin having 2 or more carbon atoms and (b) a cycloolefin represented by the following general formula [I] or [II] ] In the copolymer composition [C], the above component [A] is 1 to
Is present in an amount of 40% by weight and has a refractive index n _D of the above component [A]
Difference between (A) and refractive index n _D (B) shown by: Δn
_{D (= | n D (A} ) -n D (B) |) is a cyclic olefin copolymer composition characterized in that 0.015 or less [refractive index n _D (B) is the component [ A cyclic olefin system obtained by copolymerizing (a) an α-olefin having 2 or more carbon atoms with (b) a cyclic olefin represented by the following general formula [I] or [II] in the absence of A] It is the refractive index of the copolymer component [B]]; (In the formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently, It is a hydrogen atom, a halogen atom or a hydrocarbon group, and R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle has a double bond. R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group.); (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 R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, or an aliphatic carbon atom. A hydrogen atom, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ⁹ (or R ¹⁰ ) is bonded and the carbon atom to which R ¹³ or R ¹¹ is bonded; May be bonded 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 to form a monocycle or It may form a polycyclic aromatic ring.). 2. Polymerizable carbon in the aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or hydride thereof
The composition according to claim 1, wherein the content of carbon double bonds is 2 to 50 (g-iodine / 100g-polymer) in iodine value.