JP2800057B2 - Cyclic olefin polymer composition and impact modifier - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to heat resistance, heat aging resistance, chemical resistance, solvent resistance,
The present invention relates to a cyclic olefin polymer composition excellent in dielectric properties, rigidity, appearance, and the like, and also excellent in impact resistance, and an impact modifier comprising the cyclic olefin polymer composition.

[Conventional technology]

The cyclic olefin random copolymer composed of a cyclic olefin component represented by the following general formula [I] and an ethylene component has heat resistance, heat aging, chemical resistance, solvent resistance, dielectric properties, rigidity, appearance, and the like. It is known as an excellent resin (for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-60-115916, etc.).

These cyclic olefin-based random copolymers are resins having particularly excellent heat resistance and rigidity, but further improvement in impact resistance is required.

On the other hand, JP-A-58-127728 discloses 1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (tetracyclo [4.4.0.12 ^{, 5.1 7,10]} -3-opening homopolymer of dodecene hereinafter), or ring-opening copolymer chemical resistance of a comonomer of the cyclic olefin and norbornene type, excellent solvent resistance such as a resin Further, JP-A-60-26024 discloses that a hydrogenated ring-opened polymer obtained by hydrogenating the ring-opened polymer has heat resistance,
Although it has been proposed as a resin with improved heat aging resistance,
In any case, improvement in impact resistance is desired.

[Problems to be solved by the invention]

An object of the present invention is to provide a cyclic olefin random copolymer comprising at least one cyclic olefin component selected from cyclic olefins represented by the following general formula [I] and an ethylene component, or a general formula [I] described below. A ring-opened polymer comprising at least one cyclic olefin component selected from the cyclic olefins represented by the formula or a hydrogenated product thereof as a resin component, a cyclic olefin-based polymer composition having an excellent balance between rigidity and impact resistance; To provide.

Another object of the present invention is to provide an impact modifier comprising the above-mentioned cyclic olefin polymer composition.

[Means for solving the problem]

The present invention relates to the following cyclic olefin polymer composition and an impact modifier comprising the cyclic olefin polymer composition.

(1) [A] It comprises at least one cyclic olefin component selected from the cyclic olefins represented by the following general formula [I] and an ethylene component, and has an intrinsic viscosity [η] of 0.05 to 10 dl measured in decalin at 135 ° C. / g, softening temperature (TMA) 70
A mixture of a cyclic olefin random copolymer having a temperature of at least ℃ and [B] an α-olefin / diene copolymer comprising at least two kinds of α-olefins and at least one kind of non-conjugated diene; A cyclic olefin-based polymerization composition (hereinafter abbreviated as composition I), characterized by comprising a reaction product obtained by contacting the composition.

(Wherein, R ^{1 to} R ¹² are a hydrogen atom, a hydrocarbon group, or a halogen atom, and may be the same or different. Further, R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² are integrated. R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other, n is 0 or a positive integer, and R ⁵ or When R ⁸ is repeated a plurality of times, they may be the same or different.) (2) [C] At least one cyclic olefin component selected from the cyclic olefins represented by the following general formula [I] A ring-opened polymer or a hydrogenated product thereof, having an intrinsic viscosity (η) measured in decalin at 135 ° C. of 0.05 to 10 dl / g,
A cyclic olefin-based ring-opening polymer having a softening temperature (TMA) of 70 ° C. or higher; [B] an α-olefin / diene-based copolymer comprising at least two α-olefins and at least one non-conjugated diene; A cyclic olefin-based polymerization composition (hereinafter abbreviated as composition II) comprising a reaction product obtained by contacting a mixture of the above with a cationic polymerization initiator.

(Wherein, R ^{1 to} R ¹² are a hydrogen atom, a hydrocarbon group, or a halogen atom, and may be the same or different. Further, R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² are integrated. R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other, n is 0 or a positive integer, and R ⁵ or When R ⁸ is repeated a plurality of times, these may be the same or different.) (3) An impact modifier comprising the cyclic olefin polymer composition described in the above (1) (hereinafter referred to as “resistance modifier”). Abbreviated as impact modifier I).

(4) An impact modifier comprising the cyclic olefin polymer composition according to the above (2) (hereinafter abbreviated as impact modifier II).

The cyclic olefin as a component of the cyclic olefin random copolymer [A] used in the present invention is at least one type of cyclic olefin selected from the group consisting of unsaturated monomers represented by the general formula [I]. is there.

In the cyclic olefin random copolymer [A], the cyclic olefin represented by the general formula [I] is
It mainly forms a repeating unit having a structure represented by the following general formula [Ia].

(In the formula, n and R ^{1 to} R ¹² are the same as those in the general formula [I].) In the general formula [I], R ^{1 to} R ⁸ are, for example, a hydrogen atom; fluorine, chlorine, bromine and the like. Halogen atom; lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group, etc., which may be different from each other, may be partially different, and all are the same. You may.

R ^{9 to} R ¹² in the general formula [I] include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, Alkyl group such as stearyl group; cycloalkyl group such as cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon group such as phenyl group, tolyl group, ethylphenyl group, isopropylphenyl group, naphthyl group and anthryl group; An aralkyl group such as a phenethyl group can be exemplified. Also R ⁹ and
R ¹⁰ , or R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group, or R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other.

Examples of the divalent hydrocarbon group formed by integrating R ⁹ and R ¹⁰ or R ¹¹ and R ¹² include an alkylidene group such as an ethylidene group, a propylidene group and an isopropylidene group.

The ring formed from R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may be a single ring or a condensed polycyclic ring, may be a cross-linked polycyclic ring, and may be a ring having an unsaturated bond, Or a ring composed of a combination of these rings. Specifically as such a ring, for example, And so on. These rings may have a substituent such as a methyl group. In the above chemical formula, the carbon atom with 1 or 2 represents the carbon atom to which R ^{9 to} R ¹² are bonded in the general formula [I].

The cyclic olefin represented by the general formula [I] can be easily produced by condensing a cyclopentadiene and a corresponding olefin or cyclic olefin by a Diels-Alder reaction.

The cyclic olefin represented by the general formula (I), for example, bicyclo [2.2.1] hept-2-ene or derivatives thereof, tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-
Dozeten or a derivative thereof, hexacyclo (6.6.1.
1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene or derivatives thereof, octacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^11,18 .1
^13,16 .0 ^3,8 .0 ^12,17] -5-docosene or derivatives thereof, pentacyclo [6.6.1.1 ^3,6 .0 ^2,7 .0 ^9,14] -4-hexadecene or derivatives thereof, pentacyclo (6.5.1.
^3,6 .0 ^2,7 .0 ^9,13] -4-pentadecene or derivatives thereof, heptacyclo ^{[8.7.0.1 2,9 .1 4,7 .0 11,17 .0 3,8} .0
^12,16] -5-eicosene or derivatives thereof, heptacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .0 3,8} .0 12,17 ] -5-heneicosene or derivatives thereof, tricyclo (4.3.0.1
^2,5 ] -3-decene or a derivative thereof, tricyclo [4.
4.0.1 ^2,5] -3-undecene or derivatives thereof, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] 4,10 penta decadiene or a derivative thereof, pentacyclo [4.7. 0.1 ^2,5 .0
^8,13 .1 ^9,12] -3-pentadecene or derivatives thereof, heptacyclo ^{[7.8.0.1 3,6 .0 2,7 .1 10,7 .0 11,16} .1 12,15 ]
-4-eicosene or a derivative thereof, nonacyclo [9.1
0.1.1 ^4,7 .0 ^3,8 .0 ^2,10 .0 ^{12, 21} .1 ^{13, 20} .0 ^{14 and 19} .1 ^{15, 18]}
And -5-pentacosene or a derivative thereof.

Further, examples of the cyclic olefin represented by the general formula [I] include compounds represented by the following general formula [II].

(Where p is an integer of 0 or 1 or more, q and r are 0,
1 or 2, R ^{1 to} R ⁴ and R ^{10 to} R ¹² are represented by the general formula [I]
And R ^{13 to} R ²¹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ¹¹ ( Or R ¹² ) and R ¹⁵ (or R ¹³ ) may be bonded via an alkylene group having 1 to 3 carbon atoms to form a ring, or may be directly bonded without any group to form a ring. May be formed. R ^{13 to} R ²¹ in the general formula [II] include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a hexyl group. , Stearyl group and other aliphatic hydrocarbon groups; cyclohexyl and other cycloalkyl groups; substituted or unsubstituted aromatic hydrocarbon groups such as phenyl, tolyl, ethylphenyl, isopropylphenyl, naphthyl and anthryl groups Aralkyl groups such as benzyl group and phenethyl group; and alkoxy groups such as methoxy group, ethoxy group and propoxy group.

As the compound represented by the general formula [II], those having p of 0 to 3 are preferable.

Specific examples of the compound represented by the general formula [I] include those described in Table 1.

The cyclic olefin-based random copolymer [A] contains the above-mentioned cyclic olefin component and ethylene component as essential components, but may be any other component that does not impair the object of the present invention in addition to these two essential components. If necessary, other copolymerizable unsaturated monomer components may be contained. Examples of the unsaturated monomer that may be optionally copolymerized include α-olefins having 3 to 20 carbon atoms, and hydrocarbon monomers containing two or more carbon-carbon double bonds in one molecule. And so on. As the α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 4-
Methyl-1-pentene, 3-methyl-1-pentene, 1
-Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Hexadecene, 1-octadecene, 1-eicosene and the like. Specific examples of the hydrocarbon monomer containing two or more carbon-carbon double bonds in one molecule include 1,4-hexadiene, 1,6-octadiene, and 2-methyl-1,1.5. -Hexadiene, 4-methyl-1,5-hexadiene, 5-methyl-1,5-hexadiene, 6-methyl-
Linear non-conjugated dienes such as 1,5-heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene, 4,9,5,8-dimethano-3a, 4,4a, 5,8 Cyclic unconjugated dienes such as, 8a, 9,9a-octahydro-1H-benzoindene; 2,3-diisopropylidene-5-norbornene; 2-ethylidene-3-isopropylidene-5-norbornene; 2-propenyl-2 , 2-norbornadiene and the like. Of these, 1,4-hexadiene, 1,6-octadiene, and cyclic non-conjugated dienes, especially dicyclopentadiene,
-Ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 1,4-
Hexadiene and 1,6-octadiene are preferred.

In the cyclic olefin-based random copolymer [A],
The structural unit derived from the ethylene component is in the range of 40 to 85 mol%, preferably 50 to 75 mol%, and the structural unit derived from the cyclic olefin component is 15 to 60 mol%, preferably 25 to 50 mol%.
The structural unit derived from the ethylene component and the structural unit derived from the cyclic olefin component form a substantially linear cyclic olefin-based random copolymer randomly arranged. The fact that the cyclic olefin-based random copolymer [A] is substantially linear and has no gel-like crosslinked product can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

The intrinsic viscosity [η] of the cyclic olefin random copolymer [A] measured in decalin at 135 ° C. is 0.05 to 10 dl / g,
It is preferably 0.08 to 5 dl / g, and the softening temperature (TMA) measured by a thermal mechanical analyzer is 70 ° C. or more, preferably 90 to 250 ° C., and more preferably 100 to 200 ° C.

Further, as the cyclic olefin-based random copolymer [A], the iodine family (g-iodine / 100 g copolymer) is 30 or less, preferably 25 or less, and the glass transition temperature (Tg) is usually 50 or less.
The crystallinity measured by X-ray diffraction at 0 to 230 ° C, preferably 70 to 210 ° C, is in the range of 0 to 10%, preferably 0 to 7%, and particularly preferably 0 to 5%.

As the cyclic olefin-based random copolymer [A],
Although a copolymer consisting only of those having the physical properties in the above range may be used, a copolymer having physical properties outside the above range may be partially contained, and in this case, the entire physical property value falls in the above range. It only has to be included.

The cyclic olefin-based random copolymer [A] is obtained by polymerizing an ethylene component, a cyclic olefin component represented by the above general formula [I], and optionally other copolymerized monomer components in the presence of a well-known Ziegler-based catalyst. Can be manufactured.

Examples of the Ziegler-based catalyst include (A) a catalyst comprising a complex containing at least magnesium, titanium and halogen and an organoaluminum compound;
A catalyst comprising a vanadium compound and an organoaluminum compound can be used. Among these, the latter (a) catalyst is preferred, and a catalyst composed of a soluble vanadium compound and an organoaluminum compound is particularly preferred.

Specific production methods for the cyclic olefin random copolymer [A] are described in JP-A-60-168708 and JP-A-61-1208.
No. 16, JP-A-61-115912, JP-A-61-115916
And Japanese Patent Application Laid-Open Nos. Sho 61-271308, 61-272216, 62-252406, and 62-252407.

As the α-olefin / diene copolymer (B),
A copolymer consisting of at least two α-olefins and at least one non-conjugated diene is used.
Ethylene / α-olefin / diene copolymers and (a) propylene / α-olefin / diene copolymers are preferably used.

(A) As the α-olefin constituting the ethylene / α-olefin / diene copolymer, usually an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene,
Examples thereof include 1-octene, 1-decene, and mixtures thereof. Of these, propylene and 1-butene are particularly preferred.

On the other hand, (a) the α-olefin constituting the propylene / α-olefin / diene copolymer is usually an α-olefin having 4 to 20 carbon atoms, for example, 1-butene, 1-pentene, 1-hexene, Methyl-1-pentene, 1-
Octene, 1-decene or a mixture thereof can be exemplified. Of these, 1-butene is particularly preferred.

The diene components in (a) the ethylene / α-olefin / diene copolymer and (a) the propylene / α-olefin / diene copolymer include 1,4-hexadiene and 1,6-
Octadiene, 2-methyl-1,5-hexadiene, 6-
Chain non-conjugated dienes such as methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5
Cyclic non-cyclic compounds such as -vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene; Conjugated dienes; 2,3-diisopropylidene-5-norbornene; 2-ethylidene-3-isopropylidene-5-norbornene; 2-propenyl-2,2-norbornadiene. Of these, 1,4 hexadiene, 1,6-octadiene and cyclic non-conjugated dienes, especially dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, and 5-methylene-2-norbornene are preferred. .

(A) In the ethylene / α-olefin / diene copolymer, the molar ratio between ethylene and α-olefin (ethylene / α-olefin) varies depending on the type of α-olefin, but is usually 50/50 to 95/50. 5 is preferred. The molar ratio is 50/50 when the α-olefin is propylene.
It is preferably from 90 to 90/10. When the α-olefin has 4 or more carbon atoms, it is preferably from 80/20 to 95/5.

The content of the diene component in the (a) ethylene / α-olefin / diene copolymer is 0.5 to 10 mol%, preferably 0.5 to 5 mol%.

(A) In the propylene / α-olefin / diene copolymer union, the molar ratio of propylene to α-olefin (propylene / α-olefin) varies depending on the type of α-olefin, but is usually 50/50 to 95. / 5 is preferred. The molar ratio is preferably 50/50 to 90/10 when the α-olefin is 1-butene, and 80/20 to 95 when the α-olefin has 5 or more carbon atoms. / 5 is preferred.

Further, (a) the content of the diene component in the propylene / α-olefin / diene copolymer is 0.5 to 10 mol%,
Preferably, it is 0.5 to 5 mol%.

The α-olefin-diene copolymer [B] has a crystallinity of 0 to 10%, preferably 0 to 10%, as measured by X-ray diffraction.
Desirably, it is about 5%.

Further, 135 of the α-olefin / diene copolymer [B]
The intrinsic viscosity [η] measured in decalin at 0.1 ° C. is 0.1 to 10 dl /
g, preferably 1 to 5 dl / g, iodine value is 1 to 30, preferably 5 to 25, density is 0.32 to 1.00 g / cm ³ , preferably 0.85 to
0.90 g / cm ³ is desirable.

The composition I of the present invention comprises a cyclic olefin random copolymer [A] and an α-olefin / diene copolymer [B].
And a reaction product obtained by contacting the mixture with a cationic polymerization initiator, wherein the component (A) and the component (B)
The proportion of the component (B) is preferably 5 to 900 parts by weight based on 100 parts by weight of the component (A).

The composition I of the present invention tends not to lower the softening temperature (TMA) even when about 45 parts by weight of the component [B] is blended with respect to 100 parts by weight of the component [A]. Further, the composition I of the present invention comprises:
As the blending amount of the component (B) decreases, the rigidity increases, but the impact resistance tends to decrease. Conversely, [B]
Increasing the amount of components improves impact resistance,
Rigidity tends to decrease. Therefore, the mixing ratio of the component (A) and the component (B) needs to be selected according to the intended use of the composition I of the present invention.

That is, when the composition I of the present invention is used as a composition having an excellent balance between rigidity and impact resistance, 5 to 100 parts by weight of the component (B) to 100 parts by weight of the component (A), preferably It is blended in an amount of 7 to 80 parts by weight, particularly preferably 10 to 70 parts by weight. When formulated in such a ratio, the composition I of the present invention usually has a softening temperature (TMA) of 80 to 250 ° C. measured by a thermal mechanical analyzer and an iodine surface of
It is in the range of 0.3-50.

On the other hand, when the composition I of the present invention is used as an impact modifier, the component (B) 4
0 to 900 parts by weight, preferably 50 to 500 parts by weight, particularly preferably 60 to 200 parts by weight.

The impact modifier I comprising the composition I of the present invention is a conventional polymer mainly composed of a cyclic olefin, for example, a cyclic olefin-based polymer mainly composed of the cyclic olefin represented by the general formula [I]. It can be used as an impact resistance improver.

By adding the impact modifier I comprising the composition I of the present invention to the cyclic olefin polymer, the rigidity is slightly reduced, but the impact resistance is improved, and the rigidity and impact resistance as a whole are excellent. A balanced composition is obtained.

The amount of the impact modifier I used depends on the type of the cyclic olefin polymer to be added, but is usually 5 to 45% by weight.

The cyclic olefin-based ring-opening polymer [C] is a ring-opening polymer composed of the cyclic olefin component represented by the general formula [I] or a hydrogenated product thereof.

The cyclic olefin constituting the cyclic olefin-based ring-opening polymer [C] is at least one type of cyclic olefin selected from the group consisting of the unsaturated monomers represented by the general formula [I].

In the ring-opened polymer before hydrogenation of the hydrogenated product of the cyclic olefin-based ring polymer, the above-mentioned general formula [I]
The cyclic olefin component represented by the following general formula [I-
b) are mainly formed, and in the ring-opened polymer after hydrogenation, the repeating units having the structure represented by the following general formula [Ic] are mainly formed.

(In the formula, n and R ^{1 to} R ¹² are the same as those in the general formula [I].) The cyclic olefin-based ring-opened polymer [C] contains the above-mentioned cyclic olefin as an essential component. As long as the object of the invention is not impaired, other copolymerizable unsaturated monomer components may be contained as necessary. Examples of the unsaturated monomer which may be optionally copolymerized include, for example, a cyclic olefin represented by the following general formula [III].

(Wherein, R ²² and R ²³ are a hydrogen atom, a hydrocarbon group, or a halogen atom, and may be the same or different. M is an integer of 2 or more, and R ²² and R ²³ are plural times. When repeated, these may be the same or different.) Examples of the monomer component represented by the general formula [III] include cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cyclodecene.
Methylcyclopentene, methylcycloheptene, methylcyclooctene, methylcyclononene, methylcyclodecene, ethylcyclopentene, ethylcycloptene, ethylcyclooctene, dimethylcyclopentene, dimethylcycloheptene, dimethylcyclooctene, trimethylcyclodecene, etc. .

The intrinsic viscosity [η] of the cyclic olefin-based ring-opened polymer [C] measured in decalin at 135 ° C. is 0.05 to 10 dl / g, preferably 0.08 to 5 dl / g, and the softening temperature (TMA) is 70 ° C. or more, preferably Is 90-200 ° C.

Further, the cyclic olefin ring-opened polymer [C] preferably has an iodine value of 0 to 200, preferably 0 to 60.

As the cyclic olefin-based ring-opening polymer (C), a polymer consisting of only those having the physical properties in the above range may be used, but a polymer having physical properties outside the above range may be partially contained. In this case, it is sufficient that the entire physical property value is included in the above range.

To produce a ring-opened polymer of the cyclic olefin component represented by the general formula [I], a monomer component selected from the general formula [I] is used as a raw material, and ring-opening is performed by a normal cyclic olefin ring-opening polymerization method. It can be polymerized. In this case, as the polymerization catalyst, for example, ruthenium, rhodium,
A system comprising a halide such as palladium, osmium, iridium, platinum, molybdenum and tungsten, a nitrate or acetylacetone compound and an organic tin compound, a reducing agent such as an alcohol, or a halide such as titanium, vanadium, zirconium, tungsten and molybdenum or acetylacetone A system composed of a compound and an organic aluminum or the like can be used.

The molecular weight of the ring-opened polymer to be produced can be adjusted by adding an olefin or the like at the time of the ring-opening polymerization.

When hydrogenating the ring-opened polymer obtained above,
Conventional hydrogenation methods can be used. As the hydrogenation catalyst, those used for hydrogenation of olefin compounds can be generally used. Specifically, examples of the heterogeneous catalyst include nickel, palladium, platinum, and the like, and solid catalysts in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. , Nickel / diatomaceous earth, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like. As a homogeneous catalyst, there is a catalyst based on a metal of Group VIII of the periodic table, for example, nickel naphthenate /
Ni and Co compounds such as triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum, and Periodic Tables I to II
Examples thereof include those composed of an organometallic compound of a Group I metal, and Rh compounds.

The hydrogenation of the ring-opened polymer is carried out in a homogeneous or heterogeneous system under a hydrogen pressure of 1 to 150 atm and at a temperature of 0 to 180 ° C, preferably 20 to 100 ° C, depending on the type of catalyst. Will be The hydrogenation rate can be adjusted by hydrogen pressure, reaction temperature, reaction time, catalyst concentration, and the like.

The composition II of the present invention comprises a reaction product obtained by contacting a mixture of a cyclic olefin-based cyclic polymer [C] and an α-olefin / diene-based copolymer [B] with a cationic polymerization initiator. A composition, wherein the mixing ratio of the component (C) and the component (B) is 100 parts by weight of the component (C) and the component (B)
Preferred is from 5 to 900 parts by weight of the components.

The composition II of the present invention tends not to lower the softening temperature (TMA) even when about 45 parts by weight of the component [B] is blended with respect to 100 parts by weight of the component [C]. Further, the composition II of the present invention comprises
As the blending amount of the component (B) decreases, the rigidity increases, but the impact resistance tends to decrease. Conversely, [B]
Increasing the amount of components improves impact resistance,
Rigidity tends to decrease. Therefore, it is necessary to select the mixing ratio of the component (C) and the component (B) according to the intended use of the composition II of the present invention.

That is, when the composition II of the present invention is used as a composition having an excellent balance between rigidity and impact resistance, the iodine value of the component (C) is preferably low, specifically 100 or less. Regarding the compounding ratio of the component (C) and the component (A), 5 to 100 parts by weight of the component (C) and 100 parts by weight of the component (B)
Parts by weight, preferably 7 to 80 parts by weight, particularly preferably 10 to 80 parts by weight.
It is blended in a ratio of 70 parts by weight.

On the other hand, when the composition II of the present invention is used as an impact modifier, the component (B) 4
0 to 900 parts by weight, preferably 50 to 500 parts by weight, particularly preferably 60 to 200 parts by weight.

In the present invention, the impact modifier II composed of the composition II is a conventional cyclic olefin-based polymer, for example, a cyclic olefin-based polymer represented by the general formula [I]. It can be used as an impact resistance improver.

By adding the impact modifier II composed of the composition II of the present invention to the cyclic olefin polymer, the rigidity is slightly reduced, but the impact resistance is improved, and the rigidity and impact resistance as a whole are excellent. A balanced composition is obtained.

The use amount of the impact modifier II depends on the type of the cyclic olefin polymer to be added, but is usually 5 to 45% by weight.

The composition I of the present invention comprises a cyclic olefin random copolymer [A] and an α-olefin / diene copolymer [B].
By contacting the mixture with a cationic polymerization initiator.

Examples of the above-mentioned cationic polymerization initiator include “Toshinobu Higashimura, Lecture Polymerization Reaction, Vol. 3,“ Cation Polymerization ”, Kagaku Dojin, 1974
The initiators listed in Chapter 2 of the year include protonic acids, metal oxides, halogens, metal halides, organometallic compounds, and stable cations, among which protonic acids and metal halides are preferred. . As the protonic acid, specifically, H ₃ PO ₃ , H ₂ SO ₄ , HClO ₄ , HCl, HBr, C
Cl ₃ CO ₂ H, CHCl ₂ CO ₂ H, CF ₃ CO ₂ H, H (CF ₂ ) ₆ CO ₂ H, ClSO ₃
H, FSO ₃ H, p- toluenesulfonic _{acid, CF 3 SO 3 H, CH} 3 COCl
O ₄ (acetyl perchlorate) and the like can be exemplified.
Also, as the metal halide, Be, Mg, Zn, Cd, Hg,
B, Al, Ga, Ti, Zr, Sn, P, Sb, Nb, Bi, Ta, U, R
Examples include halides of metals such as e and Fe, and among these, halides of B, Al, Ti, Sn, and Fe are particularly preferable. Specifically, boron trifluoride (BF ₃ ), boron trifluoride / diethyl ether complex (BF ₃ O (C ₂ H ₅ ) ₂ ), boron trifluoride / phenol complex (BF ₃ · HOC ₆ H ₅ ), General formula R
An organoaluminum compound represented by nAlX _3-n (X is any one of chlorine, bromine, iodine and fluorine, and n is 0 ≦ n <3
, R represents an alkyl group), titanium tetrachloride (TiCl ₄ ), tin tetrachloride (SnCl ₄ ), iron trichloride (FeCl ₃ )
And so on. Examples of the organoaluminum compounds represented by R _n AlX _3-n, such as diethyl aluminum chloride, diethyl aluminum pro bromide, ethylaluminum sesquichloride, ethylaluminum sesquichloride pro bromide, ethyl aluminum dichloride, ethyl aluminum dipropionate bromide and the like. As long as the composition is R _n AlX _3-n, it may be a mixture of various organic aluminum compounds.

To produce the composition I of the present invention, a cyclic olefin random copolymer [A] and an α-olefin / diene copolymer [B] are heated and melted using an extruder, a Brabender, a kneader or the like. After mixing, a method of reacting by adding a cationic polymerization initiator, a method of mixing the components (A) and (B) in a solution using a solvent, and then reacting by adding a cationic polymerization initiator. Although the latter method can be adopted, the latter method is particularly preferable. In the latter case, any solvent may be used as long as it does not inhibit the cationic polymerization of carbon-carbon double bonds. Specific examples of preferred solvents include aromatic compounds such as benzene, chlorobenzene, dichlorobenzene, trichlorobenzene and nitrobenzene; saturated aliphatic hydrocarbons having 5 to 18 carbon atoms such as n-hexane; cyclohexane, methylcyclohexane,
Saturated alicyclic hydrocarbons such as ethylcyclohexane, dimethylcyclohexane, trimethylcyclohexane and methylethylcyclohexane; and their halides such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and the like. Of course, the solvent that can be used in the present invention is not limited to the above compounds. Note that two or more solvents can be used in combination. Further, the reaction rate, the reaction rate and the like change depending on the type of the solvent. For example, when a polar solvent such as a halide solvent is used, the reaction tends to proceed relatively quickly.

When a metal halide is used as the cationic polymerization initiator, it is preferable to add a compound having active hydrogen or an organic halogen compound as a co-initiator (co-catalyst) to the reaction system. Examples of the compound having active hydrogen include water, alcohols, phenols, organic and inorganic acids, and the like. As the alcohols, aliphatic, alicyclic and aromatic alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, cyclohexanol and benzyl alcohol are used. Phenols such as phenol and cresol are used. Further, carboxylic acids such as acetic acid, trichloroacetic acid, propionic acid, fumaric acid, and benzoic acid are used as organic acids; sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid; and sulfuric acid, phosphoric acid, and hydrochloric acid are used as inorganic acids. . As the organic halogen compounds, aliphatic,
Alicyclic, aromatic organic halogen compounds, for example, isopropyl chloride, sec-butyl chloride, cyclohexyl chloride, cyclohexyl bromide, second halogen compounds such as 1-phenylchloroethane; t-butyl chloride, t-amyl chloride, Tertiary halogen compounds such as triphenylchloromethane; acid chlorides such as acetyl chloride, acetyl bromide and benzoyl chloride are preferably used. Among these co-initiators, the use of water or an organic halogen compound is most preferable in consideration of the reaction rate, the ease of post-treatment, the corrosion of the apparatus, the economic efficiency, and the like.

Regarding the reaction temperature, when the reaction is carried out in a heated and molten state, the temperature is from the temperature at which the components are melted to 350 ° C. or less, and when the reaction is carried out in the solution state, the temperature is from room temperature to 200 ° C.
The following is preferred.

The amount of the cationic polymerization initiator to be used varies depending on the content of the carbon-carbon double bond (ie, iodine value) of the copolymer to be used, the reaction temperature, the solvent to be used, the reaction time, and the like, but is usually subjected to the reaction. The amount is 0.01 to 300 mmol, preferably 0.1 to 200 mmol, based on 100 g of the copolymer composition.

After completion of the reaction, the reaction product is first washed with alkaline water, water, methanol or the like to remove the used cationic polymerization initiator, and then dried under reduced pressure to obtain the desired composition I. The ratio of each component in the obtained composition I is as follows:
It is the same as the ratio of the charged amount of the raw material copolymer used for the reaction.

The composition I thus produced comprises the component (A) and the component (B)
By contacting the components with a cationic polymerization initiator,
The double bonds in the component (B) are cross-linked, and the cross-linked component (B) is intricately entangled with the molecular chain of the component (A) to form a simple mixture of the component (A) and the component (B). Is presumed to have a different three-dimensional structure. When the non-conjugated diene component is contained in the component (A), the components (A), (B), and (A) and (B) are crosslinked, and these components are complicated. Intertwined,
It is presumed that the simple mixture of the component [A] and the component [B] has a different steric structure.

The composition II of the present invention can be produced by bringing a mixture of the cyclic olefin-based ring-opening polymer [C] and the α-olefin / diene-based copolymer [B] into contact with a cationic polymerization initiator. .

As the cationic polymerization initiator, the same one as used in producing the composition I can be used.

The composition II of the present invention can be produced by the same method as that for producing the composition I.

The composition II thus produced comprises the component (C) and the component (B)
By contacting the components with a cationic polymerization initiator,
[C] non-hydrogenated double bonds in the component,
The double bonds in the component (B), and the component (C) and the component (B) are crosslinked, and these are intertwined in a complicated manner to form a simple mixture of the component (C) and the component (B). Is presumed to have a different three-dimensional structure.

The composition I and the composition II are the component (A) or the component (C)
It is presumed that the reason for having the property of improved impact resistance while maintaining the property of the component is due to the three-dimensional structure as described above.

The cyclic olefin polymer composition (composition I and composition II) of the present invention is used in the same applications as the conventional cyclic olefin polymer composition and as an impact modifier for the conventional cyclic olefin polymer. it can. When used as an impact modifier, the cyclic olefin polymer composition is a polymer such as the component (A), the component (B), the component (C),
An appropriate amount can be blended with another thermoplastic resin or the like. In addition, heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes,
Pigments, natural oils, synthetic oils, waxes and the like can be blended, and the blending ratio is an appropriate amount. For example, as a stabilizer blended 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'-oxamidobis [ethyl-
Phenolic antioxidants such as 3 (3,5-di-t-butyl-4-biloxyphenyl) propineate; fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; glycerin monostearate; Examples thereof include polyhydric alcohol fatty acid esters such as glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be used alone or in combination. For example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate and glycerin A combination with monostearate and the like can be exemplified.

Specific applications of the cyclic olefin polymer composition of the present invention include, for example, microwave appliances, printed boards, high-frequency circuit boards, electric fields such as conductive sheets and films, camera bodies, housings for various instruments and devices. It can be used in various fields such as films, seats, helmets and interior materials for automobiles.

〔The invention's effect〕

The composition obtained by contacting a mixture of a specific cyclic olefin polymer and a specific α-olefin / diene copolymer with a cationic polymerization initiator and reacting the mixture has excellent rigidity and excellent impact resistance. And have an excellent balance. Furthermore, the appearance, particularly the gloss, is excellent. This composition can also be used as an impact modifier.

〔Example〕

Next, the present invention will be described specifically with reference to Examples.
The present invention is not limited to these examples.

 The methods for measuring and evaluating various physical properties are shown below.

(1) Flexural modulus; measured at a temperature of 23 ° C. by the method of ASTM-D790.

(2) Flexural strength: measured at a temperature of 23 ° C. according to the method of ASTM-D790.

(3) Izod impact strength (with notch); temperature 23 ° C,-
Measured at 30 ° C. according to the method of ASTM-D256.

(4) Heat deformation temperature (HDT): Measured by the method of ASTM-D648 under the condition of 18.6 kg / cm ² load.

(5) Melt flow index (MFR); at 260 ° C., ASTM-D78
Measure by the method of 5.

(6) Gloss (surface gloss); at room temperature, ASTM-D523
It measures by the method of.

Polymerization Example 1 (Synthesis of Cyclic Olefin Random Copolymer) Using a glass polymerization vessel having a volume of 2 equipped with a stirring blade,
Continuously ethylene and tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10]
-3-dodecene (structural formula: Hereinafter, abbreviated as TCD-3) and 5-ethylidene-2-norbornene (structural formula: (Hereinafter abbreviated as ENB)) was carried out by the following method.

From the top of the polymerization vessel, a cyclohexane solution containing two kinds of monomers, TCD-3 and ENB, was added to the polymerization vessel at a TCD-3 concentration of 6%.
0g /, ENB concentration to 6g /, and V as catalyst
O a (OC ₂ H ₅₎ of Cl ₂ cyclohex solution, the vanadium concentration in the polymerization vessel is 0.6 mmol /, a cyclohexane solution of ethyl aluminum sesquichloride _{[Al (C 2 H 5) 1} · 5 Cl 1 · 5 ] , The aluminum concentration in the polymerization vessel is 4.8
The amount of the polymerization solution in the polymerization reactor was continuously supplied from the lower portion of the polymerization reactor.
And continuously withdrawn so that the average residence time was 0.5 hour. From the top of the polymerization vessel, ethylene is fed at 30
, Hydrogen was supplied at a rate of 0.5 per hour and nitrogen was supplied at a rate of 10 per hour. The copolymerization reaction was performed at 10 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.

A copolymerization reaction was carried out under the above reaction conditions to obtain a polymerization reaction mixture containing an ethylene / TCD-3 / ENB random copolymer. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid extracted from the lower part of the polymerization vessel. Next, the polymerization liquid was introduced into a domestic mixer containing about 3 cups of acetone with respect to the polymerization liquid while rotating the mixer to precipitate a produced copolymer, and the precipitated copolymer was filtered. The polymer was dispersed in acetone so that the polymer concentration became about 50 g /, and the copolymer was treated at the boiling point of acetone for about 2 hours. After the treatment, the copolymer was collected by filtration and dried under reduced pressure at 120 ° C. for 24 hours.

The ethylene / TCD-3 / ENB random copolymer obtained as described above had a composition ratio of ethylene / TCD-3 / ENB of 60/34 by molar ratio in the copolymer measured by ¹³ C-NMR analysis. / 6,135
Intrinsic viscosity [η] measured in decalin at 0.65 dl / g,
The softening temperature (TMA) was 150 ° C. and the iodine value was 20.3.

Polymerization Examples 2 to 6 Various cyclic olefin-based random copolymers were synthesized in the same manner as in Polymerization Example 1 except that the monomers and hydrogen supply amounts shown in Table 2 were used.

Table 2 shows the physical properties of the cyclic olefin-based random copolymers obtained in Polymerization Examples 1 to 6. However, the structural formula Is represented by 8M-TCD-3 or dicyclopentadiene (structural formula: ) Is abbreviated as DCPD.

Polymerization Example 7 (preparation of the cyclic olefin ring-opening polymer) tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene (TCD-3) and the following conditions ring opening copolymerization reaction between cyclopentene I went in.

Toluene 200 in a 500 ml glass polymerization vessel equipped with stirring blades
ml, TCD-3 100 ml, cyclopentene 20 ml, 1-hexene
1 ml, 0.4 g of tungsten hexachloride and 0.43 g of tetraphenyltin were added, and polymerization was carried out at 40 ° C. for 1 hour. The obtained reaction solution was washed with aqueous hydrochloric acid, and then precipitated in 6 times the volume of methanol. The precipitate was collected and dried under reduced pressure for 24 hours. The resulting ring-opened polymer had an intrinsic viscosity [η] in toluene at 30 ° C. of 0.48 g / dl, a TCD-3 content of 95 mol% as determined by ¹³ C-NMR analysis, and an iodine value of 165.

(Hydrogenation reaction) Next, the hydrogenation reaction of the above-mentioned obtained ring copolymer was performed under the following conditions.

100 ml of a tetrahydrofuran solution of 10 g of a ring-opening copolymer and 1 g of a hydrogenation catalyst in which 1.8% by weight of Pd is supported on silica
Into a stainless steel autoclave, hydrogen pressure 50 kg / cm ²
The reaction was performed at G at 50 ° C. for 20 hours.

After distilling off the solvent from the obtained reaction solution, it is dissolved in cyclohexane, reprecipitated in a large amount of methanol, and
Dry for 24 hours. The product thus obtained had an iodine value of 5.0, an intrinsic viscosity [η] of 0.40 dl / g and a TMA of 155 ° C. measured in decalin at 135 ° C. (hereinafter abbreviated as polymer 7). ).

Production Example 1 96 g of the copolymer (polymer 1) obtained in Polymerization Example 1 and an ethylene / propylene / 5-ethylidene-2-norbornene copolymer (ethylene / propylene / diene = 68/30 /
2 (molar ratio)) 224 g and cyclohexane 10 (polymer concentration 30 g /) were charged into a glass reaction vessel and dissolved at about 60 ° C. with sufficient stirring under a nitrogen atmosphere. Thereafter, the temperature of the reaction system was lowered to 23 ° C, and the H ₂ O (co-initiator) concentration in the system was lowered.
H ₂ O was added at 9.0 mmol /. Next, a cyclohexane solution of ethylaluminum dichloride (cationic polymerization initiator) was added dropwise over 145 minutes such that the concentration of ethylaluminum dichloride in the system became 4.8 mmol /, and a post-reaction was performed for 30 minutes. The reaction was stopped by adding 100 ml of methanol to the system.

The obtained reaction product was poured into a large excess of methanol, and the polymer was deposited while being finely cut in a mixer, washed with acetone, and dried at 100 ° C. under reduced pressure.

 Table 3 shows the plant values of the obtained reaction products.

Production Examples 2 to 9 Production was performed in the same manner as in Production Example 1 using the polymers shown in Table 3 and the α-olefin / diene-based copolymer.

 Table 3 shows the vegetable properties of the obtained reaction products.

Production Example 10 A reaction was performed in the same manner as in Production Example 1 except that ethyl aluminum dichloride and H ₂ O were not used, using the polymers shown in Table 3 and the α-olefin / diene copolymer. Was. Table 3 shows the results.

As can be seen from Table 3, the reaction product obtained in Production Example 10 has almost no change in iodine value and MFR, indicating that no reaction has occurred.

Example 1 After sufficiently mixing the pellets of the composition obtained in Production Example 6, the mixture was melt-blended at a cylinder temperature of 250 ° C by a twin-screw extruder (PCM-45 manufactured by Ikegai Iron Works Co., Ltd.) and pelletized by a pelletizer. did.

The obtained pellets were subjected to injection molding to evaluate physical properties. Table 4 shows the results.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the composition obtained in Production Example 10 was used. Table 4 shows the results.

Hereinafter, examples in which the composition of the present invention is used as an impact modifier to be added to a cyclic olefin copolymer will be described.

(Synthesis for base polymer) Copolymerization reaction of ethylene and TCD-3 was continuously performed by the following method using two glass polymerization reactors equipped with stirring blades.

From the top of the polymerization vessel, a cyclohexane solution of TCD-3 was added
The TCD-3 concentration in the polymerization vessel is 45g /, and VO (OC ₂
H ₅₎ cyclohexane solution of Cl _2, concentration of vanadium in the polymerization vessel is 0.6 mmol /, a cyclohexane solution of ethyl aluminum sesquichloride _{[Al (C 2 H 5) 1} · 5 Cl 1 · 5 ], the polymerization vessel Were continuously fed into the polymerization reactor such that the aluminum concentration in the polymerization reactor was 4.8 mmol /, while the polymerization liquid in the polymerization reactor was 1 from the bottom of the polymerization reactor.
And continuously withdrawn so that the average residence time was 0.5 hour. From the top of the polymerization vessel, ethylene was fed at 35
, Hydrogen was supplied at a rate of 0.5 per hour, and nitrogen was supplied at a rate of 10 per hour. The copolymerization reaction was performed at 10 ° C. by circulating a refrigerant through a jacket attached outside the polymerization vessel.

A copolymerization reaction was carried out under the above reaction conditions to obtain a polymerization reaction mixture containing an ethylene / TCD-3 random copolymer. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid extracted from the lower part of the polymerization vessel. Next, the polymerization liquid was introduced into a household mixer containing about three times the amount of acetone with respect to the polymerization liquid while rotating the mixer to precipitate a produced copolymer. The precipitated copolymer was collected by filtration, dispersed in acetone so that the polymer concentration became about 50 g /, and the copolymer was treated at the boiling point of acetone for about 2 hours. After the treatment, the copolymer was collected by filtration and dried under reduced pressure at 120 ° C. for 24 hours.

The ethylene content of the ethylene / TCD-3 random copolymer obtained as described above was determined by ¹³ C-NMR analysis to be 70 mol%, and the intrinsic viscosity measured in decalin at 135 ° C. [ η] was 0.60 dl / g, and the softening temperature (TMA) was 111 ° C. This copolymer is referred to as a base polymer A.

(Synthesis of base polymer B) Except that the TCD-3 concentration is 60 g / and the ethylene supply rate is 30 / hr, the same method as the synthesis method of base polymer A is used.
Base polymer O was synthesized. The base polymer B had an ethylene content of 63 mol%, an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.49 dl / g, and a softening temperature (TMA) of 147 ° C. This copolymer is referred to as Base Polymer B.

Example 2 After sufficiently mixing 5.5 kg of the base polymer A pellets and 1.5 kg of the composition pellets obtained in Production Example 1, the cylinder temperature was 250 ° C. using a twin-screw extruder (PCM-45 manufactured by Ikegai Iron Works Co., Ltd.). And then pelletized with a pelletizer.

The obtained pellets were subjected to injection molding to evaluate physical properties. Table 4 shows the results.

Example 3 Example 2 was repeated, except that the base polymer B was used in place of the base polymer A used in Example 2 and the cylinder temperature was set to 290 ° C. Table 4 shows the results.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yozo Yamamoto 61-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industries, Ltd. (72) Inventor Shin Shin Waki, Waka-machi, Kuga-gun, Yamaguchi Prefecture No. 6 1-2 Ki, Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-1-204924 (JP, A) JP-A-53-108143 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 23/00-23/36 C08L 45/00 C08L 65/00

Claims (4)

(57) [Claims] (A) An ethylene component comprising at least one cyclic olefin component selected from cyclic olefins represented by the following general formula (I) and an intrinsic component having an intrinsic viscosity [η] of 0.05 measured at 135 ° C. in decalin: ~ 10dl / g, softening temperature (TM
A) a mixture of a cyclic olefin-based random copolymer having a temperature of 70 ° C. or higher and [B] an α-olefin-diene-based copolymer comprising at least two α-olefins and at least one non-conjugated diene. A cyclic olefin polymer composition comprising a reaction product obtained by contacting with a cationic polymerization initiator. (Wherein, R ^{1 to} R ¹² are a hydrogen atom, a hydrocarbon group, or a halogen atom, and may be the same or different. Further, R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² are integrated. R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other, and n is 0 or a positive integer, and R ⁵ to When R ⁸ is repeated a plurality of times, they may be the same or different.) 2. [C] a ring-opened polymer comprising at least one cyclic olefin component selected from the cyclic olefins represented by the following general formula [I] or a hydrogenated product thereof,
The limit viscosity [η] measured in decalin at 5 ° C is 0.05 to 10 d
l / g, a cyclic olefin-based ring-opening polymer having a softening temperature (TMA) of 70 ° C. or higher; A cyclic olefin-based polymer composition comprising a reaction product obtained by contacting a mixture with a copolymer with a cationic polymerization initiator. (Wherein, R ^{1 to} R ¹² are a hydrogen atom, a hydrocarbon group, or a halogen atom, and may be the same or different. Further, R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² are integrated. R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other, n is 0 or a positive integer, and R ⁵ or When R ⁸ is repeated a plurality of times, they may be the same or different.) 3. An impact modifier comprising the cyclic olefin polymer composition according to claim 1. 4. An impact modifier comprising the cyclic olefin polymer composition according to claim 2.