JP3315729B2 - Cyclic olefin copolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cyclic olefin copolymer composition having excellent properties such as oil resistance, solvent resistance and heat resistance.

[0002]

BACKGROUND OF THE INVENTION Cyclic olefin copolymers (cyclic olefin random copolymers), which are copolymers of cyclic olefins such as tetracyclododecene and α-olefins such as ethylene, are transparent. It is a synthetic resin with excellent balance of heat resistance, heat aging resistance, dielectric properties and rigidity properties. Therefore, this cyclic olefin copolymer is highly useful as a material for forming optical materials such as optical memory disks and optical fibers, and has already been used (for example, JP-A-60-168,708 and JP-A-61-9).
No. 8,780, No. 61-115,912, No. 61-115,916, No. 61-120,
Nos. 816 and 62-252,407).

However, these cyclic olefin-based copolymers are resins having particularly excellent transparency, heat resistance and rigidity as described above, but have insufficient properties such as oil resistance and solvent resistance.

[0004] Therefore, the oil resistance, without impairing the excellent properties inherent in the cyclic olefin copolymer,
It is required to improve the solvent resistance. As a method for improving the oil resistance and solvent resistance of a cyclic olefin-based copolymer, a method in which a crystalline polymer such as nylon is mixed has conventionally been adopted, and the oil resistance is improved by mixing the crystalline polymer. Improves.

However, transparency is sacrificed due to the mixing of the crystalline polymer, and excellent characteristics such as low water absorption and good dimensional stability inherent to the cyclic olefin copolymer tend to be reduced. However, there was no sufficient improvement effect.

The present inventors have made intensive studies to solve the problems in the prior art as described above, and found that α-olefin was polymerized at a specific ratio between a cyclic olefin and an α-olefin in the presence of a vanadium-based catalyst. It has been surprisingly found that the olefin / cyclic olefin copolymer has improved oil resistance and solvent resistance while maintaining properties such as conventional mechanical properties and transparency. The inventors have found that a composition obtained by blending the α-olefin / cyclic olefin copolymer with a conventionally known cyclic olefin copolymer exhibits excellent oil resistance and solvent resistance, and completed the present invention. I came to.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems in the prior art as described above, and without impairing the excellent properties of the cyclic olefin-based random copolymer, in particular, the oil resistance and the oil resistance. It is an object of the present invention to provide a cyclic olefin copolymer composition having improved solvent properties.

[0008]

SUMMARY OF THE INVENTION The cyclic olefin copolymer composition of the present invention comprises a sparingly soluble cyclic olefin copolymer [a] and an easily soluble cyclic olefin copolymer [b], and comprises a boiling cyclohexane-insoluble component. Is 4% by weight or more.

Here, the sparingly soluble cyclic olefin copolymer
(A) is (a) a soluble vanadium compound, and (ii) copolymerized in the presence of an organoaluminum compound, (a) at least one α-olefin having 2 or more carbon atoms, and (b) A) a copolymer of at least one kind of cyclic olefin represented by the following formula [I] or [II], wherein a cyclic unit and a cyclic unit derived from α-olefin (a) in the copolymer are The molar ratio with the repeating unit derived from the olefin (b) is in the range of 47/53 to 60/40, and the content of the repeating unit derived from the cyclic olefin (b) in the copolymer. X (mol%) and 10
The difference Y between the temperature at which the DSC curve starts to fall (T ₁ ) and the temperature at which the DSC curve flattens again (T ₂ ) when the glass transition temperature is measured by the DSC curve under the condition of a temperature rise rate of ° C./min. (T ₂ −T ₁ = ΔT), when X is 40 ≦ X <45, Y ≧ −X + 50... [A] When X is 45 ≦ X <51, Y ≧ 5. X has a relationship of Y ≧ X−46... [C] when 51 ≦ X ≦ 53, and the boiling cyclohexane insoluble content is 2
0% by weight or more of a cyclic olefin copolymer.

Here, the value of ΔT is a measure of the magnitude of the composition distribution of the copolymer. Further, the easily soluble cyclic olefin-based copolymer [b] comprises (a) at least one kind of α-olefin having 2 or more carbon atoms, and (b) the following formula [I] or [I
A copolymer of at least one kind of cyclic olefin represented by the formula (I), wherein the repeating unit derived from α-olefin (a) in the copolymer and a cyclic olefin;
The molar ratio with the repeating unit derived from (b) is 40 /
The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 5.0 dl / g, and the glass transition temperature (Tg) measured by DSC is in the range of 60 to 95/5. But-
50 to 280 ° C, and boiling cyclohexane insoluble matter is 1
It is a cyclic olefin-based copolymer in an amount of not more than% by weight.

[0011]

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[I] In the above formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, R ^{1 to} R ^18, R ^a and R ^b independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic group. And the monocyclic or polycyclic group may have a double bond;
¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.

[0013]

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... [II] In the above 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, an aliphatic hydrocarbon group, alicyclic hydrocarbon group, an atom or group selected from the group consisting of aromatic hydrocarbon group and an alkoxy group, R ⁹ is bonded And the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹⁰ is bonded to R ¹¹
Is directly or a carbon atom having 1 to 3 carbon atoms.
May be bonded via an alkylene group of
When = 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.

Since the cyclic olefin polymer composition of the present invention comprises a sparingly soluble cyclic olefin copolymer [A] and an easily soluble cyclic olefin copolymer [B], it has oil resistance and solvent resistance. It is excellent in transparency, rigidity and heat resistance.

[0016]

Next, the cyclic olefin copolymer composition of the present invention will be described in detail. The cyclic olefin-based copolymer composition of the present invention comprises a sparingly soluble cyclic olefin-based copolymer [A] and a readily soluble cyclic olefin-based copolymer [B]. First, the hardly soluble cyclic olefin copolymer [A] will be described.

The sparingly soluble cyclic olefin copolymer [A] used in the present invention has a carbon number of 2 which is copolymerized in the presence of a soluble vanadium compound and an organoaluminum compound.
A copolymer of the above α-olefin and a specific cyclic olefin.

As the α-olefin having 2 or more carbon atoms (a), specifically, ethylene, propylene, 1-butene,
1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4, 4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene,
3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. These can be used alone or in combination.

Of these, ethylene or propylene is preferred, and ethylene is particularly preferred. As the cyclic olefin (b), a cyclic olefin represented by the formula [I] or [II] is used.

Here, the cyclic olefin (b) can be represented by the following formula [I] or [II].

[0021]

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

Further, R ^{1 to} R ¹⁸ and R ^a and R
^b is each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In addition, examples of the hydrocarbon group independently include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the cycloalkyl group include a cyclohexyl group.

Further, in the above formula [I], R ¹⁵ and R
¹⁶ and includes a R ¹⁷ and R ¹⁸ may further have a R ^{1 5} and R ^17, R ¹⁶
And R ¹⁸ may be combined with R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ (together with each other) to form a monocyclic or polycyclic structure, The monocyclic or polycyclic structure thus formed may have a double bond.

Here, examples of monocyclic or polycyclic structures are shown below.

[0026]

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In the above exemplified structure, the carbon atoms numbered 1 and 2 are represented by the following formulas [I]:
It represents a carbon atom of an alicyclic structure to which groups represented by R ¹⁵ (R ¹⁶ ) and R ¹⁷ (R ¹⁸ ) are bonded.

Further, 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,
Propylidene and isopropylidene.

Next, the cyclic olefin represented by the formula [II] will be described.

[0030]

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... [II] In the above formula [II], p is 0 or a positive integer, preferably 0 to 3. In the above formula [II], m and n are 0, 1 or 2. further,
q is 0 or a positive integer, preferably 0 or 1.

R ^{1 to} R ¹⁹ are each independently
It is a hydrogen atom, a halogen atom or a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Also,
Examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms, and a 6 to 1 carbon atom.
And 2 aromatic groups. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, an n-amyl group, a neopentyl group, an n-hexyl group,
Examples include an n-octyl group, an n-decyl group and a 2-ethylhexyl group. Specific examples of the cycloalkyl group include a cyclohexyl group, a methylcyclohexyl group, and an ethylcyclohexyl group. Further, specific examples of the aromatic group include an aryl group and an aralkyl group, and specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, a phenylethyl group, a biphenyl group, and the like. These groups may have a lower alkyl group.

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. Furthermore, the above formula [II], R ⁹ and the carbon atom to which R ¹⁰ is bonded R ^{1 3} is bonded to that carbon atom or R ¹¹
Is a carbon atom to which is directly or
And 3 may be bonded via an alkylene group. That is, when the two carbon atoms are bonded via an alkylene group, R ⁹ and R ¹³ or R ¹⁰ and R ¹¹ together form a methylene group (—CH ₂ —) , An ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH ₂ CH ₂ —).

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Preferred examples in this case include the following groups in which R ¹⁵ and R ¹² further form an aromatic ring when n = m = 0.

[0035]

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In the above formula, q has the same meaning as in formula [II]. The cyclic olefin represented by the formula [I] or [II] can be produced by condensing cyclopentadiene with a corresponding olefin or a corresponding cyclic olefin by utilizing a Diels-Alder reaction. .

Specific examples of the cyclic olefin represented by the above formula [I] or [II] used in the present invention include the following compounds and derivatives thereof.

A bicyclo [2.2.1] hept-2-ene derivative,
Tricyclo [4.3.0.1 ^2,5] -3- decene derivatives, tricyclo [4.3.0.1 ^2,5] -3- undecene derivatives, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives, pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivative,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- hexadecene derivative, pentacyclo ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3
- pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3-
Pentadecene derivatives, hexacyclo [6.6.1.1 ^3,6 .1
^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] - 4-eicosene derivatives, heptacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1
^12,17 .0 ^2,7 .0 ^11,16] -5-eicosene derivatives, heptacyclo ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8 .0 12,17] - 5-heneicosene derivatives, heptacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1
^11,18 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8.
0 ^12,17 ] -5-docosene derivative, nonacyclo [10.9.1.
1 ^4,7 .1 ^13,20 .1 ^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, Nonashikuro [10.10.1.1 ^5,8. 1 ^14,21 .
1 ^16,19 .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives.

1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative, cyclopentadiene-acenaphthylene adduct .

The formulas [I] and [I
Examples of specific compounds of the cyclic olefin represented by I] include the compounds described below.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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The sparingly soluble cyclic olefin-based copolymer [A] used in the present invention comprises a mixture of the above-mentioned α-olefin and cyclic olefin with a soluble vanadium compound described later.
(i) and a copolymer copolymerized in the presence of an organoaluminum compound (ii), wherein the copolymer is derived from a cyclic olefin (b) and a repeating unit derived from the α-olefin (a). 47/53 to 6
0/40, preferably from 48/52 to 58/42, particularly preferably from 49/51 to 55/45. By having a repeating unit derived from the component (a) and the component (b) in such a molar ratio, oil resistance and solvent resistance, which are not found in other cyclic olefin copolymers, are improved. That is, a cyclic olefin resin having a repeating unit derived from a conventionally known cyclic olefin (b) and having a content less than the above range, and a cyclic olefin resin having a content significantly exceeding the above range, have a resistance to an oil agent and a solvent. low, the polymer composition is within the range (a) and (b) exhibits a very high oil resistance and solvent resistance.

Further, the temperature rise rate of this copolymer was 10
When the glass transition temperature was measured by a DSC curve under the conditions of ° C./min, as shown in FIG. 1, a temperature T _{1 at} which the endotherm began and the curve began to fall, and the curve was flattened again after the end of the endothermic curve. and temperature T ₂ to return to is observed. Where T ₁
On-set (Onset) temperature, the T ₂ that the Final (Final) temperature. The final temperature T ₂ and the onset temperature T ₁
The magnitude of ΔT is a measure of the breadth of the composition distribution of the copolymer. FIG. 2 shows the ΔT on the Y axis and the content X (mol%) of the repeating unit derived from the cyclic olefin (b) in the poorly soluble cyclic olefin copolymer [A] on the X axis. As described above, the poorly soluble cyclic olefin-based copolymer [A] used in the present invention is a cyclic olefin.
When the content X of the repeating unit derived from (b) is in the range of 40 ≦ X <45, Y ≧ −X + 50... [A] Similarly, when the content of X is in the range of 45 ≦ X <51, Y .Gtoreq.5... [B] Similarly, X is in a region represented by Y.gtoreq.X-46... [C] in the range of 51.ltoreq.X.ltoreq.53. That is, the sparingly soluble cyclic olefin-based copolymer [a] is in the region shown by hatching in FIG.

The glass transition temperature, ie, the onset temperature (T ₁ ) of the sparingly soluble cyclic olefin copolymer [A].
Varies depending on the type of cyclic olefin used as described below, but is usually in the range of -50 to 280C.

The glass transition temperature of the hardly soluble cyclic olefin-based copolymer [A] is completely different depending on the type of the cyclic olefin being copolymerized, so that the preferable range of the copolymer cannot be shown at once. Hereinafter, the glass transition temperature of the main copolymer is shown for each type of cyclic olefin as a raw material.

Preferred Tg ranges for different cyclic olefins are exemplified. Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene Tg
150-200 ° C Bicyclo [2.2.1] hept-2-ene Tg
100-140 ° C 5-phenylbicyclo [2.2.1] hept-2-ene Tg
130-170 ° C 5-methylbicyclo [2.2.1] hept-2-ene Tg
90-130 ° C 5-ethylcyclo [2.2.1] hept-2-ene Tg
80-120 ° C 5-n-decylbicyclo [2.2.1] hept-2-ene Tg
-40 to 30 ° C. In FIG. 2, the hardly soluble cyclic olefin-based copolymer [A] in the shaded region shows excellent oil resistance and solvent resistance. That is, the boiling cyclohexane insoluble content of the copolymer of the present invention is usually 20% by weight or more, preferably 40% by weight or more, and more preferably 45% by weight or more. The content of this boiling cyclohexane insoluble matter is
One gram of this copolymer can be measured by placing it in a 300 mesh stainless steel mesh and performing Soxhlet extraction with hot cyclohexane for 4 hours.

The test piece formed from this copolymer also has excellent solvent resistance to toluene. For example, when a 0.1 × 15 × 35 mm (weight: about 0.12 g) press film is immersed in toluene at room temperature for 96 hours, there is little change in the appearance. Few. For example, the film is immersed in toluene under the above conditions, and then dried in a nitrogen stream for 1 hour. The film usually has a weight change rate of -30 to + 20% by weight, and often -20 to + 10% by weight. It is in.

When the intrinsic viscosity of this hardly soluble cyclic olefin copolymer [A] can be measured in decalin at 135 ° C., it is usually 0.1 to 5.0 dl / g, preferably 0.1 dl / g.
It is in the range of 2 to 2.0 dl / g, particularly preferably 0.3 to 1.5 dl / g. The poorly soluble cyclic olefin-based copolymer [a] in such a range is excellent in moldability. In addition,
Since the poorly soluble cyclic olefin copolymer [A] has low solubility in a solvent as described above, the intrinsic viscosity at 135 ° C. using decalin may not be measured in some cases.

Further, the softening temperature (TMA) of this hardly soluble cyclic olefin copolymer [A] is usually -50 to 3
It is in the range of 00 ° C. In addition, since the softening temperature of the hardly-soluble cyclic olefin-based copolymer [a] is completely different depending on the type of the cyclic olefin being copolymerized, the hardly-soluble cyclic olefin-based copolymer [a] is completely different. Although the preferred range cannot be shown collectively, the softening temperature of the main copolymer is shown below for each type of cyclic olefin as a raw material.

Preferred ranges of TMA according to the cyclic olefin are exemplified. Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene TMA
160-210 ° C Bicyclo [2.2.1] hept-2-ene TMA
110-150 ° C 5-phenylbicyclo [2.2.1] hept-2-ene TMA
140-180 ° C 5-methylbicyclo [2.2.1] hept-2-ene TMA
100-140 ° C 5-ethylcyclo [2.2.1] hept-2-ene TMA
90-130 ° C and the like.

The haze of this hardly soluble cyclic olefin copolymer [A] measured according to ASTM-D1003-52 is usually 1 to 20%, preferably 1 to 20%.
-15%, which is excellent in transparency.

The hardly soluble cyclic olefin copolymer [A] used in the present invention comprises a repeating unit derived from α-olefin (a) and a repeating unit derived from cyclic olefin (b) substantially. Are linearly arranged, and these repeating units are randomly arranged.

The repeating unit derived from the cyclic olefin represented by the formula [I] is considered to form a structure represented by the following formula [IA].

[0075]

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[IA] In the above formula [IA], n, m, r and R ¹
To R ¹⁸ and R ^a and R ^b have the same meaning as [I].

The repeating unit derived from the cyclic olefin represented by the formula [II] is considered to form a structure represented by the following formula [II-A].

[0078]

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... [II-A] In the above formula [II-A], n, m, p, q and R ^{1 to} R ¹⁹ have the same meaning as [II].

[0080] repeating units derived from a cyclic olefin (a) has a structure represented by the above formula [IA] or [II-A] were determined for this copolymer ¹³
It can be confirmed from the result of the C-NMR spectrum.

The poorly soluble cyclic olefin-based copolymer [I] can be prepared in the liquid phase in the presence of (i) a soluble vanadium compound and (ii) an organoaluminum compound.
It can be produced by copolymerizing (a) an α-olefin having 2 or more carbon atoms and (b) a cyclic olefin represented by the above formula [I] or [II].

The soluble vanadium compound used here is specifically represented by the following formula. Formula VO (OR) _a
X _b or the formula V (OR) _c X _d .

In the above formula, R is a hydrocarbon group, X is a halogen atom, and a, b, c and d are respectively 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b
≤3, 0≤c≤4, 0≤d≤4, and 3≤c + d≤4.

Examples of these vanadium compounds include:
VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ )
₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (On-C ₄
H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ ,
_{VOCl 2, VO (O-n} -C 4 H 9) 3 and VCl ₃ · 2
(OC ₈ H ₁₇ OH) and the like. These vanadium compounds can be used alone or in combination.

Further, the soluble vanadium compound (i)
As represented by the following formula, a vanadium compound having a tertiary alkoxy group may be used. ^{_{VO (OCR 1 3) a X}} b or ^{_{V (OCR 2 3) c X}} d proviso, R ^1, R ² in the above formula is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, X is It is a chlorine atom or a bromine atom. A, b, c, and d are 0.5 ≦
a ≦ 3, 0 ≦ b ≦ 2.5, 2 ≦ a + b ≦ 3, 0.5 ≦ c ≦
4. Satisfies 0 ≦ d ≦ 3.5 and 3 ≦ c + d ≦ 4.

Specific examples of the soluble vanadium compound having a tertiary alkoxy group represented by the above formula as a ligand include the compounds described below. VO (tert-butyloxy) Cl ₂ , VO (tert-butyloxy) ₂ Cl, VO (tert-butyloxy) ³ , VO
(2,3-dimethyl-2-butyloxy) Cl ₂ , VO (2,3-dimethyl-2-butyloxy) ₂ Cl, VO (2,3-dimethyl-2)
-Butyloxy) ₃ , VO (2-methyl-2-pentyloxy) Cl ₂ , VO (2-methyl-2-pentyloxy) ₂ C
1, VO (2-methyl-2-pentyloxy) ₃ , VO (3-methyl-3-pentyloxy) Cl ₂ , VO (3-methyl-3-pentyloxy) ₂ Cl, VO (3-methyl-3 -Pentyloxy) ₃ , VO (2,3-dimethyl-3-pentyloxy) C
l ₂ , VO (2,3-dimethyl-3-pentyloxy) ₂ Cl,
VO (2,3-dimethyl-3-pentyloxy) ₃ , VO (3-ethyl-3-pentyloxy) Cl ₂ , VO (3-ethyl-3-pentyloxy) ₂ Cl, VO (3-ethyl-3) -Pentyloxy) ₃ , VO (2-methyl-2-hexyloxy) Cl ₂ , V
O (2-methyl-2-hexyloxy) ₂ Cl, VO (2-methyl-2-hexyloxy) _{3 and the} like.

V (tert-butyloxy) Cl ₃ , V (tert-butyloxy) ₂ Cl ₂ V (tert-butyloxy) ₃ Cl V (2,3-dimethyl-2-butyloxy) Cl ₃ V (2,3-dimethyl -2-butyloxy) ₂ Cl ₂ V (2,3-dimethyl-2-butyloxy) ₃ Cl and the like.

V (tert-butyloxy) Cl ₃ V (tert-butyloxy) ₂ Cl ₂ V (tert-butyloxy) ₃ Cl and the like.

Among these vanadium compounds having a tertiary alkoxy group, VO (alkoxy group) Cl ₂ is preferable. Further, the soluble vanadium compound (i) may be a vanadium compound having β-diketone as a ligand as represented by the following formula.

[0090] VO (acac) _e Y _f or V (mmh) _g Y _h, however, is acac in the above formula represents an acetylacetonato group represented by the following formula, mmh 2-methyl-1,3-butanedionate Represents a group. Y is an alkyl group, an alkoxy group, or a halogen atom, and e, f, g, and h are 1 ≦
e ≦ 2, 0 ≦ f ≦ 1, 2 ≦ e + f ≦ 3, 1 ≦ g ≦ 3, 0
Satisfies ≦ h ≦ 3, 3 ≦ g + h ≦ 4.

[0091]

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Specific examples of the soluble vanadium compound having the β-diketone represented by the above formula as a ligand include the compounds described below. In the following formula, X represents Cl, F, Br, I, an alkyl group,
It represents any of a primary alkoxy group and a secondary alkoxy group, and is preferably Cl.

VO (acac) ₂ , VO (mmh) ₂ , VO (aca
c) X ₂ , VO (acac) X, VO (mmh) X ₂ , VO (mm
h) X etc. V (acac) ₃ , V (mmh) ₃ , V (acac)
Such as _{2 X 2, V (acac)} 2 X, V (mmh) 2 X 2, V (mmh) 2 X.

In the soluble vanadium compounds having these β-diketones as ligands, VO (acac) ₂ and VO (m
mh) ₂ , V (acac) ₃ and V (mmh) ₃ are preferred. Further, the vanadium compound may be an adduct obtained by adding an electron donor to the vanadium compound represented by the above formula.

Here, examples of the electron donor forming an adduct with the above-mentioned vanadium compound include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acids and the like. Anhydrides, and oxygen-containing electron donors such as alkoxysilanes,
And nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

Examples of specific compounds used as such electron donors include methanol, ethanol,
Having 1 to 18 carbon atoms such as propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol; Alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol
Halogen-containing alcohols; phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol (these phenols may have a lower alkyl group) ); Acetone, methyl ethyl ketone, methyl isobutyl ketone,
C3-C15 ketones such as acetophenone, benzophenone and benzoquinone; acetaldehyde,
C2-15 aldehydes such as propylaldehyde, octylaldehyde, benzaldehyde, trialdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, Methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, ethyl methacrylate, ethyl crotonate,
Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl C2-C2, such as ethyl benzoate, methyl alis, ethyl alis, ethyl ethoxy benzoate, γ-butyl lactone, δ-valerolactone, coumarin, phthalide and ethyl carbonate
30 organic acid esters; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and alis acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole And 2 to 2 carbon atoms such as diphenyl ether
Ethers such as acetic anhydride, phthalic anhydride and benzoic anhydride; alkoxysilanes such as ethyl silicate and diphenylmethoxysilane; acetic acid N, N-
Acid amides such as dimethylamide, benzoic acid N, N-dimethylamide and toluic acid N, N-dimethylamide; trimethylamine, triethylamine, tributylamine,
Amines such as tribenzylamine and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile; and pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine. These electron donors can be used alone or in combination.

The organoaluminum compound (ii) used together with the vanadium compound is a compound having at least one Al-carbon bond in the molecule. Examples of the organoaluminum compound include compounds represented by the following formulas (a) and (b).

(A) An organoaluminum compound represented by the formula R ¹ _m Al (OR ² ) _n H _p X _q . Here, R ¹ and R ² are each a hydrocarbon group having usually 1 to 15, preferably 1 to 4 carbon atoms, which may be the same or different. X is a halogen, m is 0 ≦ m ≦ 3, n is 0 ≦ n <
3, p is a number satisfying 0 ≦ n <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q = 3.

[0099] (ii) alkylated complex of Group I metal and aluminum represented by the formula M ¹ AlR ¹ _4. Where M
¹ is Li, Na or K, and R ¹ has the same meaning as described above.

Specific examples of the organoaluminum compound represented by the above formula (A) include the following compounds. A compound represented by the formula: R ¹ _m Al (OR ² ) _3-m (1); wherein R ¹ and R ² have the same meaning as described above, and m is preferably 1.5 ≦ m <3. Is a number.

A compound represented by the formula R ¹ _m AlX _3-m (2); wherein R ¹ has the same meaning as described above, X is a halogen atom, and m is preferably 0 <m <3. .

A compound represented by the formula R ¹ _m AlH _3-m (3); wherein R ¹ has the same meaning as described above, and m preferably satisfies 2 ≦ m <3.

A compound represented by the formula: R ¹ _m Al (OR ² ) _n X _q (4); wherein R ¹ and R ² have the same meanings as described above, X represents a halogen atom, and 0 <m ≦ 3, 0 ≦ n <
3, 0 ≦ q <3, and m + n + q = 3.

Specific examples of the organoaluminum compound represented by the above formula (1) include trialkylaluminum such as triethylamylminium and tributylaluminum; trialkenylaluminum such as triisopropenylaluminum; diethylaluminum ethoxide and dialkylaluminum alkoxides such as dibutyl aluminum butoxide; ethylaluminum sesquichloride ethyl chloride, butyl aluminum sesqui butoxide and formula _{^{R 1 2.5 Al (oR 2)}} 0.5 and the like (R ^1,
R ² is an alkyl group) and a partially alkoxylated alkyl aluminum having an average composition represented by the formula:

Specific examples of the organoaluminum compound represented by the above formula (2) include dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; ethylamylnium sesquichloride, butylaluminum sesquichloride And alkylaluminum sesquihalides, such as ethylaluminum sesquibromide; and partially halogenated alkylaluminums, such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide.

Specific examples of the organoaluminum compound represented by the above formula (3) include dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; and compounds such as ethylaluminum dihydride and propylaluminum dihydride. Partially hydrogenated alkylaluminum is mentioned.

Specific examples of the organoaluminum compound represented by the above formula (4) include partially alkoxylated and halogenated alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide. Aluminum.

Further, the organoaluminum compound may be a compound similar to the compound represented by the formula (A), such as an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. .

Specific examples of such compounds include:
(C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ Al
OAl (C ₄ H _{9) 2} and _{(C 2 H 5) 2 AlN} (C 6 H 5)
Al (C ₂ H ₅ ) ₂ .

Examples of the organoaluminum compound represented by the above formula ( _II ) include LiAl (C ₂ H ₅ ) ₄
And LiAl (C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use an alkyl aluminum halide, an alkyl aluminum dihalide or a mixture thereof.

Further, as the organic aluminum compound, an organic aluminum oxy compound (aluminoxane) can be used. The aluminoxane may be a conventionally known aluminoxane or a benzene-insoluble aluminoxane.

The conventionally known aluminoxane is specifically represented by the following formula.

[0113]

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In the above formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is 2 or more, preferably Is an integer of 5 to 40.

Here, this aluminoxane is represented by the formula (O)
It may be formed from a mixed alkyloxyaluminum unit composed of an alkyloxyaluminum unit represented by Al (R ^a )) and an alkyloxyaluminum unit represented by the formula (OAl (R ^b )). Here, R ^a and R ^b are the same hydrocarbon groups as R in the above formula, and are different from each other.

The conventionally known aluminoxane as described above is usually obtained as an aromatic hydrocarbon solution, for example, by the method described below. (1) Compounds containing water of adsorption or salts containing water of crystallization (eg, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, primary chloride
A method in which an organoaluminum compound such as trialkylaluminum is added to an aromatic hydrocarbon solvent in which cerium hydrate is suspended and reacted to obtain an aluminoxane-containing aromatic solvent.

(2) Water (water, ice or steam) is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to produce an aromatic compound containing aluminoxane. A method for obtaining a solvent.

Of these, the method described in the above (1) is preferable. Examples of the organoaluminum compound used in producing the above aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butyl. Trialkylaluminums such as aluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum and tricyclooctylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide Aluminum halides such as and diisobutylaluminum chloride Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutyl aluminum hydride dialkylaluminum arylene Loki Sid such as diethylaluminum phenoxide and the like. Of these, trialkylaluminum is particularly preferred.

As the organoaluminum compound, isoprenylaluminum represented by the following formula can also be used. _{(I-C 4 H 9)} x Al y (C 5 H 10) in _z above formula, x, y and z are positive numbers each independently a z ≧ 2x.

The organoaluminum compound as described above is
Used alone or in combination. The above-mentioned conventional aluminoxane is soluble in benzene, but in the present invention, in addition to such a conventional aluminoxane soluble in benzene, a benzene-insoluble organic aluminum oxy compound (aluminoxane) Can be used. This organoaluminum oxy compound is insoluble in benzene, and is different from conventional benzene-soluble aluminoxane.

Such a benzene-insoluble organoaluminum compound can be prepared, for example, by contacting an aluminoxane solution with water or an active hydrogen-containing compound, or by contacting the above-mentioned organoaluminum compound with water. It can be manufactured by a method or the like.

The benzene-insoluble organic aluminum oxide
Infrared spectroscopy (IR) measured for xy compounds
1220cm^-1Absorbance near (D₁₂₂₀) And 12
60cm ^-1Absorbance near (D₁₂₆₀) And D
₁₂₆₀/ D₁₂₂₀When calculating the ratio, this ratio is usually 0.0
9 or less, preferably 0.08 or less, particularly preferably 0.0
It is in the range of 4-0.07.

The above-mentioned benzene-insoluble organoaluminum compound is presumed to have an alkyloxyaluminum unit represented by the following formula.

[0124]

Embedded image

In the above formula, R ³ is a hydrocarbon group having 1 to 12 carbon atoms. Examples of such a hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl and cyclooctyl. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable. Also,
In the above formula, R ³ may be single or may have different types of R ³ .

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

[0127]

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In the above formula, R ⁴ is an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group,
It is a halogen atom or a hydrogen atom. Further, R ⁴ in this formula and R ³ in the above formula represent different groups.

When the benzene-insoluble organic aluminum oxy compound has the oxyaluminum unit represented by the above formula, the alkyloxy aluminum unit in the benzene-insoluble organic aluminum oxy compound is
Usually, it is contained in an amount of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more.

The organoaluminum oxy compound (ii) used in the present invention may be used in an amount which does not impair its properties.
An organic compound component having a metal other than aluminum may be contained.

In the present invention, the soluble vanadium compound (i) and the organoaluminum compound (ii) described above can be used as they are, or can be used by being supported on a carrier. Here, as the carrier compound, Si
O ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, T
Use inorganic carrier compounds such as iO ₂ , ZnO, ZnO ₂ , SnO, BaO, and ThO, and resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-vinylbenzene copolymer. be able to. These carrier compounds can be used alone or in combination.

The sparingly soluble cyclic olefin-based copolymer [A] used in the present invention is a compound of the above-mentioned vanadium compound (i)
The α-olefin (a) having 2 or more carbon atoms and the cyclic olefin (b) are copolymerized in the liquid phase in the presence of the organic aluminum compound (ii). However, other monomers may be copolymerized within a range that does not impair the properties of the hardly soluble cyclic olefin copolymer [A] used in the present invention.
Examples of other olefin compounds used herein include:
Cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene and 3a, 5,6,7a-tetrahydro-
Cycloolefins such as 4,7-methano-1H-indene; 1,4-
Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-
1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-
Non-conjugated dienes such as 2-norbornene; norbornene-2,
5-methylnorbornene-2,5-ethylnorbornene-2,5-
Isopropyl norbornene-2,5-n-butyl norbornene
Norbornenes such as -2,5-i-butylnorbornene-2,5,6-dimethylnorbornene-2, 5-chloronorbornene-2, 2-fluoronorbornene-2 and 5,6-dichloronorbornene-2. .

The copolymerization reaction between the α-olefin (a) having 2 or more carbon atoms and the above-mentioned specific cyclic olefin (b) is usually carried out in a liquid phase. In this reaction, a hydrocarbon solvent is usually used.

Examples of the hydrocarbon solvent used herein include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof; cyclohexane, methylcyclopentane and methylcyclohexane. Alicyclic hydrocarbons and their halogen derivatives; aromatic hydrocarbons such as benzene, toluene and xylene and halogen derivatives such as chlorobenzene. In addition, in the copolymerization reaction, among the α-olefin and the cyclic olefin used as the reaction raw materials, a liquid α-olefin or a cyclic olefin under the reaction conditions can be used as a reaction solvent. These solvents may be used as a mixture.

The reaction can be carried out in either a batch system or a continuous system, but it is efficient to carry out the reaction in a continuous system. Vanadium compounds soluble in such polymerization solvents
(i) is usually 0.01 to 50 per liter of the polymerization solution.
Mmol, preferably 0.05 to 3 mmol, and the organoaluminum compound (ii) has a ratio of aluminum atoms to vanadium atoms (Al / V) in the polymerization solution,
Usually, it is supplied in an amount of 2 or more, preferably 2 to 50, more preferably 3 to 20.

The soluble vanadium compound (i) and the organoaluminum compound (ii) are usually diluted with a reaction solvent and supplied to the polymerization solution. At this time, the soluble vanadium compound (i) is usually 10 times or less, preferably 1 to 10 times the concentration of the soluble vanadium compound (i) in the polymerization solution.
It is supplied after being diluted to a concentration of 7 times, more preferably 1 to 5 times. The organoaluminum compound (ii) is usually supplied after being diluted to a concentration of 50 times or less the concentration in the polymerization solution.

In the present invention, the above-mentioned cyclic olefin (b) and α-olefin (a) are added to the polymerization solution supplied with the soluble vanadium compound (i) and the organoaluminum compound (ii) in the above amounts. The molar ratio [(b) / (a)] is 5.0 or more, preferably the concentration ratio is 5.5 to 500,
Particularly preferably, the supply amount of the cyclic olefin (b) and / or the supply amount of the α-olefin (a) are adjusted so as to be 6.0 to 400.

The method for determining the supply concentration ratio [(b) / (a)] between the cyclic olefin (b) and the α-olefin (a) is as follows: the supply liquid is actually analyzed to determine the concentration of each component. However, in general, if the amount of (b) to be supplied is known, the concentration of (b) can be calculated, and if the amount of (a) to be supplied is known, the concentration of (a) can be calculated. Can be calculated. If (a) is a gas,
If the partial pressure of (a) is known, it can be obtained by Henry's law.

Further, in the present invention, it is preferable that the α-olefin (a) and the cyclic olefin (b) are copolymerized while supplying hydrogen to the polymerization solution. Hydrogen has a molar ratio of hydrogen / α-olefin (a) to be supplied to the polymerization solution of 0.1.
It is adjusted so as to be 025 or less, preferably 0.020 or less, particularly preferably 0.015 or less, and supplied to the polymerization liquid.

The concentration ratio of hydrogen / α-olefin to be supplied can be calculated by actually analyzing the supply liquid and determining the concentration of each component. If you know the hydrogen concentration, you can calculate the hydrogen concentration by Henry's law.If the α-olefin to be supplied is gas, then if you know the partial pressure of the supplied α-olefin, the α-olefin concentration can be calculated by Henry's law. Even if the α-olefin is liquid, it can be calculated if the amount of α-olefin to be supplied and the total volume are known.

As described above, the feed concentration ratio between the cyclic olefin (b) and the α-olefin (a), and the hydrogen / α-olefin
By adjusting both the supply concentration ratios of (a) and supplying as described above, a sparingly soluble cyclic olefin-based copolymer [a] excellent in oil resistance, solvent resistance and the like can be produced.

The soluble vanadium compound (i) as described above
And α-olefin (a) and cyclic olefin (b) at a reaction temperature of usually −50 to 100 ° C., preferably −30 to 80 ° C., and more preferably −20. ~ 60 ° C, pressure usually above 0 and 50
Kg / cm ² or less, is preferably set to less than 20 Kg / cm ² than 0 reaction. The reaction time under these conditions varies depending on the reaction conditions such as the type of the monomer, the catalyst concentration, the polymerization temperature and the like, but is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours. In addition, this reaction time means the average residence time of a polymerization liquid when copolymerizing by a continuous system.

By reacting under the above conditions, a solution or a slurry containing the sparingly soluble cyclic olefin copolymer [A] is obtained. In this polymerization solution, the hardly soluble cyclic olefin-based copolymer [i] is usually 1 to 500 g /
Liters, preferably at a concentration of 5-300 g / liter
Included . By treating this polymerization solution according to a conventional method, a sparingly soluble cyclic olefin-based copolymer [a] is obtained.

For example, after reacting an α-olefin (a) with a cyclic olefin (b), cyclohexane / cyclohexane /
The reaction was stopped by adding a mixed solvent such as a methanol mixed solution (volume mixing ratio = 1: 1), and then the mixed solution and an acidic aqueous solution were brought into contact with vigorous stirring to transfer the catalyst residue to the aqueous phase. And removing the aqueous phase to separate the catalyst from the copolymer. Further, if necessary, the polymerization solution is repeatedly washed with water for purification. Next, this polymerization solution is poured into a poor solvent such as acetone in a large excess (for example, 3 times or more) under vigorous stirring to precipitate a poorly soluble cyclic olefin-based copolymer [a]. The precipitated copolymer is separated by filtration, washed with a poor solvent for the copolymer such as acetone, to remove unreacted cyclic olefin, and then dried.

Hardly soluble cyclic olefin copolymer [A]
Is an α-olefin (a) and a cyclic olefin as described above.
(b) can be produced by copolymerizing under specific conditions, and the copolymer produced as described above is further subjected to an extraction treatment with a solvent such as boiling cyclohexane so as to be soluble in boiling cyclohexane. It can be used after removing the minute. By performing the solvent treatment in this manner, the solvent resistance is further improved, and with the improvement in the solvent resistance, the oil resistance is also significantly improved.

The cyclic olefin copolymer composition of the present invention comprises the above sparingly soluble cyclic olefin copolymer [A] and the easily soluble cyclic olefin copolymer [B]. The easily soluble cyclic olefin copolymer [b]
(c) a copolymer of at least one α-olefin having 2 or more carbon atoms and (d) at least one cyclic olefin represented by the above formula [I] or [II]. And a cyclic olefin copolymer other than the hardly soluble cyclic olefin copolymer [A].

Here, an α-olefin (c) having 2 or more carbon atoms, which forms the easily soluble cyclic olefin copolymer [II],
And, as an example of one kind of the cyclic olefin (d) represented by the formula [I] or [II], the α-olefin (c) mentioned in the description of the sparingly soluble cyclic olefin copolymer [A] And cyclic olefin (d) compounds. In addition, in the easily soluble cyclic olefin-based copolymer [b], monomers other than the α-olefin (c) and the cyclic olefin (d) are used as long as the properties of the copolymer are not impaired. Examples of the other monomer which may be copolymerized and which can be copolymerized include the compounds listed in the description of the hardly soluble cyclic olefin copolymer [A].

The molar ratio of the repeating unit derived from α-olefin (c) to the repeating unit derived from cyclic olefin (d) in this easily soluble cyclic olefin-based copolymer [b] is 40/60. ９５95/5, preferably 60/40 to 90/10.

The intrinsic viscosity [η] of this easily soluble cyclic olefin copolymer [b] measured in decalin at 135 ° C. must be within the range of 0.1 to 5.0 dl / g. And preferably in the range of 0.2 to 2.0 dl / g, particularly preferably in the range of 0.3 to 1.5 dl / g.

Further, the glass transition temperature (Tg) of this easily soluble cyclic olefin copolymer [b] measured by DSC must be in the range of -50 to 280 ° C.
Further, the temperature is preferably in the range of −40 to 250 ° C. Further, this easily soluble cyclic olefin copolymer [b]
ΔT measured in the same manner as in the above-mentioned copolymer [A] is usually represented by the following formulas [D], [E], [F],
It has a relationship represented by [G] and [H].

That is, when the content X of the repeating unit derived from the cyclic olefin (d) is in the range of 5 ≦ X <40, Y ≦ 40 (D), preferably Y ≦ 30 (D) [D-1] Similarly, within the range of 40 ≦ X <45, Y <X + 50... [E] Similarly, within the range of 45 ≦ X <51, Y <5. Within a range of ≦ X <53, Y <X−46... [G] Similarly, within a range of 53 ≦ X <60, there is a relationship represented by Y <40.

This easily soluble cyclic olefin copolymer [b] has a boiling cyclohexane insoluble content of 1% by weight or less. Further, the softening temperature (TMA) of this easily soluble cyclic olefin-based copolymer [b] is usually -30 to
It is in the range of 300C, preferably -20 to 270C.

This readily soluble cyclic olefin copolymer [b] is dissolved in toluene. The easily soluble cyclic olefin-based copolymer [b] having the above-mentioned properties can be obtained by converting an α-olefin having 3 or more carbon atoms and a cyclic olefin represented by the above formula [I] or [II] into a conventionally known method. To produce a copolymer. For example, it is produced by copolymerizing the α-olefin and the cyclic olefin in a liquid phase in the presence of a vanadium compound, a zirconium compound, a titanium compound, and the like, an organic aluminum compound, and further, if necessary, an electron donor. Can be.

For example, in the easily soluble cyclic olefin-based copolymer obtained as described above, a repeating unit derived from α-olefin (c) and a repeating unit derived from cyclic olefin (d) include: They are arranged substantially linearly, and furthermore, these repeating units are arranged randomly.

Further, the repeating unit derived from the cyclic olefin represented by the formula [I] or [II] may form a structure represented by the above formula [IA] or [II-A], respectively. Conceivable.

The cyclic olefin-based copolymer composition of the present invention comprises the sparingly soluble cyclic olefin-based copolymer [A] and the easily soluble cyclic olefin-based copolymer [B] and has a boiling point. The cyclohexane insoluble content is at least 4% by weight, preferably at least 5% by weight, particularly preferably at least 10% by weight.

The cyclic olefin copolymer composition of the present invention comprises the above-mentioned poorly soluble cyclic olefin copolymer [A] and the easily soluble cyclic olefin copolymer [B] ([A]). / [B]), usually in a weight ratio of 1/99 to 80/20.

That is, this cyclic olefin copolymer composition shows excellent solvent resistance. For example, a molded article formed from this composition does not completely dissolve even when immersed in toluene. The residual weight of the molded body after immersion for 96 hours is usually 20% by weight or more, preferably 50% by weight.
% By weight or more.

The cyclic olefin copolymer composition of the present invention is also excellent in heat resistance and transparency, and the softening temperature (TMA) of this composition is usually from -30 to 300.
° C, preferably in the range of -20 to 270 ° C, and the haze is usually in the range of 5 to 20%, preferably 7 to 18%.

The cyclic olefin copolymer composition of the present invention is prepared by separately producing a sparingly soluble cyclic olefin copolymer [A] and an easily soluble cycloolefin copolymer [B], and then blending them. It can be prepared by producing a readily soluble cyclic olefin-based copolymer [b] by a multistage polymerization method and then polymerizing the sparingly soluble cyclic olefin-based copolymer [a]. it can.
Also, after producing and once taking out the easily soluble cyclic olefin-based copolymer [b], the easily soluble cyclic olefin-based copolymer [b] is dissolved again in the solution, and the hardly soluble cyclic olefin-based copolymer is dissolved in the solution. It can be prepared by polymerizing the polymer [A].

Further, [A] and [B] can be simultaneously synthesized using a catalyst having two kinds of active sites. In order to mix the sparingly soluble cyclic olefin-based copolymer [A] and the easily soluble cyclic olefin-based copolymer [B], methods such as melt blending and solution blending can be used.

The cyclic olefin copolymer composition of the present invention can be used by mixing with another polymer compound. There is no particular limitation on the polymer compound that can be blended in the cyclic olefin copolymer composition of the present invention, and a thermoplastic resin, a reaction curable resin, or a rubber-like substance can be used.

Examples of the polymer compound used here are shown below. Polyolefins (eg, low-density polyethylene to high-density polyethylene, polyethylene such as LLDPE, VLDPE, modified polyethylene, polypropylene, poly-4-methylpentene-1, polybutene-1
); Polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-vinylidene chloride copolymer, Vinyl chloride-butadiene copolymer, vinyl chloride-acrylate copolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer,
(Co) polymers of unsaturated alcohols such as polyvinylidene chloride, polytetrafluoroethylene, polytrifluorochloroethylene and polyvinylidene fluoride; unsaturated alcohols such as polyvinyl alcohol and polyallyl alcohol; unsaturated ethers such as polyvinyl ether and polyallyl ether (Co) polymers of unsaturated carboxylic acids such as acrylic acid and methacrylic acid; polyvinyl esters such as polyvinyl acetate; polyallyl esters such as polyphthalic acid; polyacrylates and polymethacrylic acid Esters, and (co) polymers of maleic acid esters or fumaric acid esters; (co) polymers of acrylonitrile or methacrylonitrile; (co) polymers of malononitrile or fumaronitrile; poly (vinylidene cyanide); Styrene, poly α- methyl styrene,
Poly-p-methylstyrene, styrene-α-methylstyrene copolymer, styrene-p-methylstyrene copolymer, polyvinylbenzene and polyhalogenated styrene; polyvinylpyridine, polyN-vinylpyrrolidine and polyN-vinylpyrrolidone; polycarbonate Nylon 6, nylon 6.6, polyparaphenylene terephthalamide; (co) polymers of acid anhydrides such as maleic anhydride and fumaric anhydride, and (co) polymers of compounds obtained by imidating these acid anhydrides Polymer; polyamide imide, polyether imide, polyimide, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyether sulfone and polyarylate; unsaturated polyester resin,
Epoxy resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin and silicon resin; polybutadiene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, ethylene-propylene copolymer rubber and isoprene-isobutylene copolymer Polymer rubber; a polymer having a carbazole skeleton such as polyvinyl carbazole; celluloses such as ethyl cellulose and regenerated cellulose.

For example, by blending an elastomer with the composition of the present invention, the impact resistance of a molded article is improved. Further, a low molecular weight wax or the like can be blended to improve the fluidity of the composition of the present invention.

These high molecular compounds and the cyclic olefin copolymer composition of the present invention can be kneaded using a usual kneading apparatus. The cyclic olefin-based copolymer composition of the present invention can be molded and processed by a known method, similarly to a normal thermoplastic resin. For example, a single-screw extruder, a vented extruder, a twin-screw extruder, a conical twin-screw extruder, a co-kneader, a plasticizer, a mixer, a twin-screw conical screw extruder, a planetary screw extruder, and a gear-type extruder Extrusion, injection molding, blow molding, rotational molding or the like is performed using a molding machine or a molding machine such as a screwless extruder to obtain a molded article having a desired shape.

At the time of molding, if necessary, antioxidants, heat stabilizers, weather stabilizers, light stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural Oil, synthetic oil, and the like can be blended, and the blending ratio can be appropriately set.

As stabilizers to be blended as optional components, phenol stabilizers, phosphorus stabilizers, sulfur stabilizers, fatty acid metal salt stabilizers, fatty acid ester stabilizers and the like can be used.

For example, specific examples of the phenolic oxidation stabilizer include tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β-
(3,5-di-t-butyl-4-hydroxyphenyl) alkyl propionate and 2,2′-oxamidobis [ethyl
-3 (3,5-di -t- butyl-4-hydroxyphenyl)] propionate and the like be mentioned up.

Specific examples of the fatty acid metal salt include zinc stearate, calcium stearate and calcium 12-hydroxystearate. Specific examples of fatty acid esters of polyhydric alcohols include glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin fatty acid esters such as glycerin distearate and glycerin dilaurate; pentaerythritol monoester Stearate, pentaerythritol monolaurate, pentaerythritol dilaurate,
Fatty acid esters of pentaerythritol such as pentaerythritol distearate and pentaerythritol tristearate.

In the present invention, it is particularly preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol, and the fatty acid ester of the polyhydric alcohol is one of alcoholic hydroxyl groups of a trihydric or higher polyhydric alcohol. It is preferable that the polyhydric alcohol fatty acid ester is partly esterified. Examples of the combination include a combination of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane with zinc stearate and glycerin monostearate.

Such a phenolic antioxidant is usually 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 copolymer. Used in amounts. The fatty acid ester of the polyhydric alcohol is a cyclic olefin copolymer 100.
0 to 10 parts by weight, preferably 0 to 10 parts by weight,
Used in amounts of up to 5 parts by weight.

Further, in the present invention, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, hydroxide, etc. may be added to the cyclic olefin copolymer within a range not to impair the object of the present invention. Aluminum, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads,
Calcium silicate, montmorillonite, bentonite,
Graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, α-olefin fiber with 2 or more carbon atoms, polypropylene fiber, polyester fiber,
A filler such as polyamide fiber may be blended.

[0173]

As described above, the cyclic olefin copolymer composition of the present invention contains a sparingly soluble cyclic olefin copolymer [A] and an easily soluble cyclic olefin copolymer [B] as described above. It has excellent oil resistance, transparency, rigidity,
Excellent heat resistance.

The cyclic olefin copolymer composition of the present invention can be used in a wide range of applications, such as functional materials such as optical materials in which conventional cyclic olefin copolymers are usually used, structural materials utilizing heat resistance, and the like. In addition, it can be used in fields where chemical resistance and oil resistance are required.

[0175]

Next, the present invention will be described in more detail with reference to examples and comparative examples of the present invention, but the present invention is not limited to these examples.

The measuring methods and evaluation results of various physical properties in the present invention are shown below. [Evaluation method] (1) Intrinsic viscosity [η] It was measured at 135 ° C in a decalin solution (1 g / liter) using an Ubbelohde viscometer.

(2) Glass transition point (Tg) Using DSC-220C manufactured by Seiko Electronics Co., Ltd.
The temperature was measured at a rate of temperature rise in minutes. As shown in FIG. 1, the temperature at which the DSC curve descends and the endotherm is disclosed is the onset temperature (T
₁ ) The temperature at which the endotherm was completed and the curve became flat again was defined as the final temperature (T ₂ ). Also, for DSC measurement,
A sample that was a copolymer obtained by a copolymerization reaction and that had undergone a thermal history of once reaching a molten state after the completion of the reaction was used.

(3) Softening Temperature (TMA) The softening temperature was measured by the thermal deformation behavior of a sheet having a thickness of 1 mm using a Thermo Mechanical Analyzer manufactured by DuPont. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, the temperature was increased at a rate of 5 ° C./min, and the temperature when the quartz needle penetrated 0.635 mm into the sheet was defined as TMA.

(4) Haze Transparency (Haze) was measured according to ASTM-D1003-
The measurement was performed on a 1 mm-thick press sheet using a haze meter conforming to No. 52.

(5) Oil resistance 1. Solubility in boiling cyclohexane 1.0 g of the copolymer powder was wrapped in a 300-mesh stainless steel wire gauze, and subjected to Soxhlet extraction for 4 hours. The mixture was separated into an insoluble portion and a soluble portion, and the weight was determined.

2. Solubility in Toluene A press film of 0.1 × 15 × 35 mm was prepared using about 0.12 g of the copolymer. This was immersed in toluene at room temperature for 96 hours, and the change in appearance was observed. The film taken out was dried under reduced pressure at room temperature for 1 hour under a nitrogen stream, and the change in weight was measured.

[0182]

EXAMPLE 1 Using a 1 liter glass polymerization vessel equipped with a synthetic stirring blade insoluble cyclic olefin copolymer [i], ethylene and tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10 Copolymerization with] -3-dodecene (hereinafter abbreviated as TCD-3) was continuously performed by the following method.

A cyclohexane solution of TCD-3 was supplied from the upper part of the polymerization vessel, and the concentration of TCD-3 supplied into the polymerization vessel was 120 g.
/ Liter was continuously supplied at a rate of 0.4 liter / hour.

Further, from the upper part of the polymerization vessel, VO as a catalyst was
A cyclohexane solution of (O-Et) Cl ₂ was continuously supplied at a rate of 0.5 liter / hour so that the vanadium concentration in the polymerization vessel was 0.5 mmol / liter.
The supply vanadium concentration at this time is 2.86 times the vanadium concentration in the polymerization vessel. A cyclohexane solution of ethyl aluminum sesquichloride (AlEt _1.5 Cl _1.5 ) was continuously supplied at a rate of 0.4 liter / hour so that the aluminum concentration in the polymerization vessel was 4.0 mmol / liter. . The supplied aluminum concentration at this time is five times the aluminum concentration in the polymerization vessel. Further, cyclohexane was continuously fed into the polymerization vessel at a rate of 0.7 liter / hour.

Further, 18.0 liter / hour of ethylene, 52.6 liter / hour of nitrogen, and 1.4 liter / hour of hydrogen were supplied to the polymerization solution using a bubbling tube.
A copolymerization reaction was carried out while circulating a refrigerant through a jacket attached to the outside of the polymerization vessel and maintaining the polymerization liquid at 10 ° C. Ethylene / TCD generated by the above copolymerization reaction
-3 from the top of the polymerization vessel the polymerization liquid containing the random copolymer,
The polymerization liquid inside the polymerization vessel was continuously withdrawn so that the polymerization liquid was always 1 liter (that is, the average residence time was 0.5 hours).

The polymerization reaction was terminated by adding a cyclohexane / methanol mixture (1: 1) to the withdrawn polymerization liquid. Thereafter, an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymer solution withdrawn are brought into contact with each other with vigorous stirring using a homomixer at a volume ratio of 1: 1 to transfer the catalyst residue to the aqueous phase. I let it.

After the contact mixture was allowed to stand, the aqueous phase was separated and removed, and then washed twice with distilled water to purify and separate the polymerization liquid phase. Subsequently, the polymer solution purified and separated was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a solid, and then a solid portion was collected by filtration and washed sufficiently with acetone. Further, in order to extract TCD-3 present in the polymer, the separated and washed solid portion was poured into acetone so as to have a concentration of 40 g / liter, and the extraction operation was performed at 60 ° C. for 2 hours. . After the extraction treatment, the solid portion was collected by filtration, and dried at 130 ° C. and 350 mmHg for 24 hours under a nitrogen flow.

As described above, an ethylene / TCD-3 copolymer was obtained in an amount of 20.4 g / hour (that is, 10.2 g / liter). When the obtained copolymer was measured by ¹³ C-NMR analysis, the ethylene content was 56.6 mol%. The intrinsic viscosity [η] of this copolymer measured at 135 ° C. in decalin was 0.51 dl / g. When the glass transition temperature (Tg) was measured at a heating rate of 10 ° C./min by the DSC method, the onset temperature (T ₁ ) was 170.2 ° C. and the final temperature (T ₂ ) was 18
3.1 ° C.

The ethylene / TCD-3 copolymer is referred to as a polymer (a-1). The production conditions and properties of the polymer (a-1) are shown in Tables 1 and 2. Synthesis of easily soluble cyclic olefin copolymer [b] In the synthesis of the hardly soluble cyclic olefin copolymer [b], TCD-3 was supplied such that the TCD-3 concentration in the polymerization vessel became 60 g / l. The ethylene / TCD-3 copolymer was adjusted by adjusting the supply amount of ethylene to 36.0 liters / hour, the supply amount of hydrogen to 3.0 liters / hour, and the supply amount of nitrogen to 33.0 liters / hour. Was synthesized.

The obtained copolymer was measured by ¹³ C-NMR analysis to find that the ethylene content was 62.7 mol%. The intrinsic viscosity [η] of this copolymer measured at 135 ° C. in decalin was 0.59 dl / g.
When the glass transition temperature (Tg) was measured at a heating rate of 10 ° C./min by the DSC method, the onset temperature (T ₁ ) was 137.8 ° C. and the final temperature (T ₂ ) was 149.4 ° C. .

This ethylene / TCD-3 copolymer is referred to as polymer (b-1). The production conditions and properties of this polymer (b-1) are shown in Tables 1 and 2. Production of cyclic olefin copolymer composition The polymer (a-1) and polymer (b-
Was mixed with a solution blend (solvent: decalin) to obtain a cyclic olefin-based copolymer composition.

A test piece was prepared from this composition and its properties were measured. Table 3 shows the obtained results.

[0193]

Examples 2 to 5, 8 to 11 and Comparative Example 1 The obtained polymers of Table 1 were combined and solution-blended at 135 ° C. in decalin to produce a cyclic olefin copolymer composition.

Table 3 shows the properties of the obtained composition.

[0195]

Examples 6, 7, and 12 The obtained polymers shown in Table 1 were combined, and used in combination with Toyo Seiki Seisakusho's Labo Plastomill 20R20.
Using 0, Examples 6 and 7 were kneaded at a cylinder temperature of 220 ° C., and Example 12 was a cylinder temperature of 280 ° C. and kneaded at a rotation speed of 200 rpm for 5 minutes under a N ₂ gas flow to produce a cyclic olefin copolymer composition. did.

Table 3 shows the properties of the obtained composition.

[0197]

[Table 1]

[0198]

[Table 2]

[0199]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a diagram illustrating an example of a relationship between an onset temperature (T ₁ ) and a final temperature (T ₂ ) in a DSC curve.

FIG. 2 is a view showing the relationship between ΔT and the composition of a copolymer component in a sparingly soluble cyclic olefin-based copolymer [A] used in the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-161407 (JP, A) JP-A-1-163241 (JP, A) JP-A-4-161408 (JP, A) JP-A-63-163 273655 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 232/00-232/08 C08F 4/68-4/685 C08F 210/00-210/14

Claims (3)

(57) [Claims] 1. A cyclic olefin copolymer comprising a sparingly soluble cyclic olefin copolymer [a] and an easily soluble cyclic olefin copolymer [b] and having a boiling cyclohexane insoluble content of 4% by weight or more. A poorly soluble cyclic olefin copolymer [A], which is obtained by copolymerizing in the presence of (i) a soluble vanadium compound and (ii) an organoaluminum compound; (B) a copolymer of at least one kind of α-olefin and (b) at least one kind of cyclic olefin represented by the following formula [I] or [II], wherein α in the copolymer is The molar ratio of the repeating unit derived from the olefin (a) to the repeating unit derived from the cyclic olefin (b) is in the range of 47/53 to 60/40, and the cyclic unit in the copolymer is Olefin
Content X (mol%) of repeating unit derived from (b)
When the glass transition temperature is measured by a DSC curve under the condition of a heating rate of 10 ° C./min, a temperature (T ₁ ) at which the DSC curve starts to fall and a temperature (T ₁ ) at which the DSC curve flattens again
₂ ) and the difference Y (T ₂ −T ₁ = ΔT) is as follows: when X is 40 ≦ X <45, Y ≧ −X + 50... [A] When X is 45 ≦ X <51, Y ≧ 5 [B] X has a relationship of Y ≧ X−46 [C] when 51 ≦ X ≦ 53, and the boiling cyclohexane-insoluble content is 2
0% by weight or more of a cyclic olefin-based copolymer, wherein the easily soluble cyclic olefin-based copolymer [b] comprises (c) at least one α-olefin having 2 or more carbon atoms, and (d) A copolymer of at least one kind of cyclic olefin represented by the following formula [I] or [II], wherein a repeating unit derived from α-olefin (c) in the copolymer and a cyclic olefin The molar ratio with the repeating unit derived from (d) is in the range of 40/60 to 95/5 and the intrinsic viscosity [η] measured in decalin at 135 ° C.
Is in the range of 0.1 to 5.0 dl / g, the glass transition temperature (Tg) measured by DSC is -50 to 280 ° C., and the boiling cyclohexane-insoluble content is 1% by weight or less. Cyclic olef characterized by being united
In-based copolymer composition ; [In the formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently:
Represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group; The ring or polycyclic group may have a double bond, and 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, an aliphatic hydrocarbon group, alicyclic hydrocarbon group, an atom or a group selected from the group consisting of aromatic hydrocarbon group and an alkoxy group, R ⁹ is a bond And the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹⁰ is bonded to R
^The carbon atom to which ¹¹ is bonded is either directly or
3 may be bonded via an alkylene group;
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]. 2. The cyclic olefin copolymer composition according to claim 1, wherein the α-olefin having 2 or more carbon atoms is ethylene. 3. The compounding weight ratio of the sparingly soluble cyclic olefin-based copolymer [a] and the sparingly soluble cyclic olefin-based copolymer [b] is in the range of 1/99 to 80/20. The cyclic olefin copolymer composition according to claim 1, wherein