JPH0768419B2 - Cyclic olefin random copolymer composition - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to heat resistance, heat aging resistance, chemical resistance, solvent resistance,
The present invention relates to a cyclic olefin-based random copolymer composition having excellent dielectric properties and rigidity as well as excellent impact resistance.

Technical background of the invention and its problems As a synthetic resin excellent in balance of rigidity and impact strength,
Polycarbonate, ABS (acrylonitrile, butadiene-styrene block copolymer composition) and the like are known. For example, polycarbonate is a resin that is excellent not only in rigidity but also in heat resistance, heat aging resistance, and impact resistance. However, polycarbonate has the problems that it is easily corroded by strong alkalis, has poor chemical resistance, and has a high water absorption. Further, although ABS has excellent mechanical properties, it has poor chemical resistance, and since it contains a double bond in the system, it has poor weather resistance and further has poor heat resistance.

On the other hand, polyolefins, which are widely used as general-purpose resins, have excellent chemical resistance and solvent resistance, but often have poor heat resistance, and their crystallinity is not perfect and their rigidity is poor. Therefore, generally, in order to improve the rigidity and heat resistance of the polyolefin, a method of adding a nucleating agent to accelerate the growth of crystals or performing slow cooling to promote the growth of crystals is used. Is hard to say. Rather, adding a third component such as a nucleating agent may impair the excellent properties that polyolefin originally has,
In addition, the slow cooling method has poor production efficiency, and the impact strength may decrease as the amorphous portion decreases.

Regarding a copolymer of ethylene and a bulky comonomer, for example, US Pat. No. 2,883,372 discloses a copolymer of ethylene and 2,3-dihydroxydicyclopentadiene. This copolymer has an excellent balance of rigidity and transparency, but has a glass transition temperature of 100.
There is a problem in that the heat resistance is inferior because the temperature is about ° C. Further, a copolymer of ethylene and 5-ethylidene-2-norbornene has the same problem.

Further, Japanese Patent Publication No. 46-14910 proposes a homopolymer of 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. However, the polymer is inferior in heat resistance and heat aging resistance. Furthermore, in Tokkai Sho 58-127728,
Homopolymer of 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene or a copolymer of the cyclic olefin and a nobornene type comonomer is proposed. However, it is clear from the description in the above-mentioned publication that all the polymers are ring-opening polymers. Since such a ring-opening polymer has an unsaturated bond in the polymer main chain, it has a problem of poor heat resistance and heat aging resistance.

Furthermore, the present applicant has previously found that a cyclic olefin random copolymer composed of ethylene and a specific bulky cyclic olefin has heat resistance, and further has heat aging resistance, chemical resistance,
It has been found that it is a synthetic resin having solvent resistance, dielectric properties and rigidity, and it has already been disclosed in JP-A-60-168708 and Japanese Patent Application No. 59-22.
No. 0550, Japanese Patent Application No. 59-236828, Japanese Patent Application No. 59-236829, Japanese Patent Application No. 59-242336. Although these cyclic olefin random copolymers are olefin polymers, they are resins excellent in heat resistance and rigidity, but have a problem that they are brittle and inferior in impact resistance.

The present inventors have obtained impact resistance without impairing excellent properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, and dielectric properties of the cyclic olefin random copolymer as described above. As a result of extensive studies to improve the composition, a composition comprising a cyclic olefin random copolymer having a specific softening temperature (TMA) and a specific α-olefin / diene elastic copolymer has excellent properties as described above. The present invention has been completed and the present invention has been completed.

OBJECT OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, rigidity and the like. ,
It is an object of the present invention to provide a cyclic olefin-based random copolymer composition having excellent impact resistance.

SUMMARY OF THE INVENTION The cyclic olefin random copolymer composition according to the present invention comprises (A) an ethylene component and the following general formula [I] or [II].
A cyclic olefin-based random copolymer having an intrinsic viscosity [η] measured in decalin of 135 ° C in the range of 0.05 to 10 dl / g and a softening temperature (TMA) of 70 ° C or higher. A polymer and (B) an α-olefin formed from at least two α-olefins and at least one non-conjugated diene
It is characterized in that it is formed from a diene-based elastic copolymer, and that the component (B) is present in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of the component (A).

General formula (In the formula, n and m are both 0 or a positive integer, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group).

The cyclic olefin-based random copolymer composition according to the present invention is formed from the components (A) and (B), and the component (B) is contained in an amount of 5 to 100 parts by weight per 100 parts by weight of the component (A). Since it is present in the amount of, it is excellent in heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and the like, as well as in impact resistance.

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

According to the present invention, (A) an ethylene component and the following general formula [I] or [II]
A cyclic olefin-based random copolymer having an intrinsic viscosity [η] measured in decalin of 135 ° C in the range of 0.05 to 10 dl / g and a softening temperature (TMA) of 70 ° C or higher. A polymer and (B) an α-olefin formed from at least two α-olefins and at least one non-conjugated diene
A cyclic olefin-based random copolymer, characterized in that the diene-based elastic copolymer is present, and the component (B) is present in an amount of 5 to 100 parts by weight relative to 100 parts by weight of the component (A). A coalescing composition is provided.

General formula (In the formula, n and m are both 0 or a positive integer, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom, or a hydrocarbon group) Cycloolefin Random Copolymer Constituting Cycloolefin Random Copolymer Composition [A]
Is a cyclic olefin-based random copolymer composed of an ethylene component and a specific cyclic olefin component.
The cyclic olefin component is a cyclic olefin component represented by the following general formula [I] or general formula [II], and in the cyclic olefin random copolymer of the present invention,
The cyclic olefin component has the general formula [III] or the general formula [I
V] is formed.

General formula (In the formula, n and m are both 0 or a positive integer, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group).

General formula (In the formula, n, m, l and R ¹ to R ¹⁰ are the same as above.) Of the constituent components of the cyclic olefin random copolymer constituting the cyclic olefin random copolymer composition of the present invention, The cyclic olefin has the general formula [I] and the general formula [I
[I] is at least one cyclic olefin selected from the group consisting of unsaturated monomers. The cyclic olefin represented by [I] in the general formula can be easily produced by condensing cyclopentadiene and the corresponding olefin by the Diels-Alder reaction. Further, the cyclic olefin represented by the general formula [II] is
Similarly, it can be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by the Diels-Alder reaction.

Specific examples of the cyclic olefin represented by the general formula [I] are compounds shown in Table 1, or 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a. -Octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,
4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,
4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-
3-Ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene,
2-Bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5, 8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-n-butyl- 1,4,5,8-Dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Examples include octahydronaphthalene such as octahydronaphthalene, and the compounds described in Table 2.

Specific examples of the cyclic olefin represented by the general formula [II] include compounds shown in Tables 3 and 4.

Cycloolefin-based random copolymer [A] constituting the cycloolefin-based random copolymer composition according to the present invention
Is an essential component of the ethylene component and the cyclic olefin component as described above, but other copolymerizable other than the essential two components, if necessary, within a range not impairing the object of the present invention. Such unsaturated monomer component may be contained. As the unsaturated monomer which may be optionally copolymerized, specifically, for example, propylene in the range of less than equimolar to the ethylene component unit in the random copolymer to be produced,
1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
Examples thereof include α-olefins having 3 to 20 carbon atoms such as eicosene.

In the cyclic olefin random copolymer [A] constituting the cyclic olefin random copolymer composition according to the present invention, the repeating unit (a) derived from the ethylene component
Is present in the range of 40 to 85 mol%, preferably 50 to 75 mol%, and the repeating unit (b) derived from the olefin is in the range of 15 to 60 mol%, preferably 25 to 50 mol%. The repeating unit (a) derived from the ethylene component and the repeating unit (b) derived from the cyclic olefin component are randomly arranged substantially linearly. The fact that this cyclic olefin-based random copolymer [A] is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving the copolymer in decalin at 135 ° C. .

Of such a cyclic olefin random copolymer [A]
The intrinsic viscosity [η] measured in decalin at 135 ℃ is 0.05
It is in the range of -10 dl / g, preferably 0.08-5 dl / g.

In addition, the softening temperature (TM) of the cyclic olefin random copolymer [A] measured by a thermal mechanical analyzer
A) is in the range of 70 ° C or higher, preferably 90 to 250 ° C, more preferably 100 to 200 ° C. The glass transition temperature (Tg) of the cyclic olefin random copolymer [A] is
It is usually in the range of 50 to 230 ° C, preferably 70 to 210 ° C.

The crystallinity of the cyclic olefin random copolymer [A] measured by the X-ray diffraction method is in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

The α-olefin / diene-based elastic copolymer [B] constituting the cyclic olefin-based random copolymer composition according to the present invention includes (i) ethylene / α-olefin / diene copolymer rubber, (ii) A propylene / α-olefin / diene copolymer rubber is used.

(I) The α-olefin constituting the ethylene / α-olefin / diene copolymer rubber usually has 3 carbon atoms.
.About.20 .alpha.-olefins such as propylene, 1-butene, 1-pentene, 1-hexane, 4-methyl-1-pentene, 1-octene, 1-decene or a mixture thereof can be exemplified. Of these, propylene or 1-butene is particularly preferable.

The (ii) α-olefin constituting the propylene / α-olefin / diene copolymer rubber is usually an α-olefin having 4 to 20 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 4- Methyl-1-pentene, 1
Examples thereof include octene, 1-decene, and mixtures thereof. Of these, 1-butene is particularly preferable.

The diene component in (i) ethylene / α-olefin / diene copolymer rubber or (ii) propylene / α-olefin / diene copolymer rubber includes 1,4-hexadiene, 1,6-octadiene, and 2 Chain non-conjugated dienes such as -methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5- Vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-
Cyclic non-conjugated dienes such as chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2, 2-norbornadiene can be exemplified. Of these, 1,
4-hexadiene and cyclic non-conjugated dienes, especially dicyclopentadiene or 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 1,4-hexadiene, 1,4-octadiene preferable.

In the above-mentioned (i) ethylene / α-olefin / diene copolymer rubber, the molar ratio of ethylene and α-olefin (ethylene / α-olefin) varies depending on the type of α-olefin, but is generally It is preferably 50/50 to 95/5. When the α-olefin is propylene, the above molar ratio is preferably 50/50 to 90/10, and when the α-olefin has 4 or more carbon atoms.
It is preferably 80/20 to 95/5.

The content of the diene component in this copolymer rubber is
0.5 to 10 mol%, preferably 0.5 to 5 mol% is desirable.

In the above (ii) propylene / α-olefin / diene copolymer rubber, the molar ratio of propylene and α-olefin (propylene / α-olefin) is α-
Generally 50 / 50-9, depending on the type of olefin
It is preferably 5/5. The above 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. It is preferably 5.

The content of the diene component in this copolymer rubber is
0.5 to 10 mol%, preferably 0.5 to 5 mol% is desirable.

Such an α-olefin / diene-based elastic copolymer [B] has a crystallinity of 0 to 10 as measured by an X-ray diffraction method.
%, Preferably 0 to 5%.

Further, the α-olefin / diene-based elastic copolymer [B]
The intrinsic viscosity [η] measured in decalin at 135 ° C is 0.1-
10 dl / g, preferably 1 to 5 dl / g. Further, it is desirable that its iodine value is 1 to 30, preferably 5 to 25. Furthermore, the density of 0.82~1.00g / cm ³
It is preferably 0.85 to 0.90 g / cm ³ .

In the cyclic olefin-based random copolymer composition according to the present invention, the α-olefin / diene-based elastic copolymer [B] is 5 to 100 parts by weight with respect to 100 parts by weight of the cyclic olefin-based random copolymer [A]. Parts by weight, preferably 7-80 parts by weight,
Particularly preferably it is present in an amount of 10 to 70 parts by weight. The α-olefin / diene elastic copolymer [B] is added to 100 parts by weight of the cyclic olefin random copolymer [A].
If it is less than 5 parts by weight, it is excellent in rigidity but inferior in impact resistance, and if it exceeds 100 parts by weight, it is excellent in impact resistance but inferior in rigidity and the balance between rigidity and impact strength is poor. Therefore, it is not preferable.

FIG. 1 shows the blending amount of the α-olefin / diene elastic copolymer [B] in the cyclic olefin random copolymer composition according to the present invention and the impact strength (IZ strength) of the composition. Show the relationship.

From FIG. 1, when the cyclic olefin random copolymer [A] is blended with the α-olefin / diene elastic copolymer [B], the resulting cyclic olefin random copolymer composition has impact resistance. It can be seen that is significantly improved.

Further, FIG. 2 shows the blending amount of the α-olefin / diene elastic copolymer [B] in the cycloolefin random copolymer composition according to the present invention, and the softening temperature (TM) of the composition.
The relationship with A) is shown.

From FIG. 2, it is surprising that even if the cyclic olefin random copolymer [A] is blended up to about 30% by weight of the α-olefin / diene elastic copolymer [B], the cyclic It can be seen that the softening temperature (TMA) of the olefin-based random copolymer composition does not decrease at all.

As described above, the cyclic olefin random copolymer [A]
30% of the α-olefin / diene-based elastic copolymer [B]
When blended in an amount of about wt%, the impact resistance of the cyclic olefin random copolymer composition is remarkably improved and the heat resistance is not lowered.

The cyclic olefin random copolymer [A] constituting the cyclic olefin random copolymer composition according to the present invention is disclosed in JP-A-60-168708 and JP-A-61-10816.
JP-A-61-115912, JP-A-61-115916, JP-A-61-95905, JP-A-61-95906, JP-A-61-95906
It can be produced by appropriately selecting the conditions according to the method proposed by the present applicant in JP-A-61-271308, JP-A-61-272216 and the like.

As a method for producing the cycloolefin random copolymer composition according to the present invention, a known method can be applied, and the cycloolefin random copolymer [A] and the olefin random copolymer [B] are separately produced. , [A] and [B] are blended with an extruder or the like, and [A] and [B] are mixed with a suitable solvent, for example, saturated hydrocarbon such as heptane, hexane, decane and cyclohexane, toluene, Examples thereof include a solution blending method performed by sufficiently dissolving it in an aromatic hydrocarbon such as benzene and xylene, and a method of kneading a solution blended product of [A] and [B] with an extruder or the like. .

The intrinsic viscosity [η] of the cyclic olefin random copolymer composition according to the present invention measured in decalin at 135 ° C. is 0.0
It is in the range of 5 to 10 dl / g, preferably 0.08 to 5 dl / g, and the softening temperature (TMA) measured by a thermal mechanical analyzer is in the range of 80 to 250 ° C, preferably 100 to 200 ° C.

The cyclic olefin random copolymer composition according to the present invention contains the cyclic olefin random copolymer [A] and the α-olefin / diene elastic copolymer [B] as essential components. In addition, heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifog agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. can be added, and their mixing ratios. Is an appropriate amount. For example, as a stabilizer to be added as an optional component, specifically, tetrakis [methylene-3 (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,
Phenolic antioxidants such as 2'-oxamide bis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate, fatty acid metal salts such as zinc stearate, calcium stearate and 12-hydroxy calcium stearate , Glycerin monostearate, glycerin monolaurate, glycerin distearate,
Examples thereof include polyhydric alcohol fatty acid esters such as pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone,
They may be combined in combination, and examples thereof include a combination of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane with zinc stearate and glycerin monostearate. be able to.

Advantageous Effects of Invention The cycloolefin random copolymer composition according to the present invention comprises the above-mentioned cyclic olefin random copolymer [A] and α-olefin / diene elastic copolymer [B], Since the copolymer [B] is present in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of the copolymer [A], heat resistance, heat aging resistance, chemical resistance, solvent resistance and dielectric It has excellent characteristics and rigidity, as well as impact resistance.

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition,
The methods for measuring and evaluating various physical property values in the present invention are shown below.

(1) Heat distortion temperature (TMA): TMA10 (Th
ermo mechanical analyzer) was used to measure the thermal deformation behavior of a 1 mm thick sheet. That is, a quartz needle was placed on the sheet, a load of 50 g was applied, the temperature was raised at 5 ° C./min, and the temperature at which the needle penetrated 0.1 mm was taken as TMA.

(2) Impact strength: Using an Izod impact tester manufactured by Toyo Seiki, from a press sheet having a thickness of 2 mm, a length of 63.8 mm and a width of 12.
A 7 mm sample was punched out and a notch of 0.25 mm R was inserted, and measurement was performed at 23 ° C.

(3) Rigidity (raised elastic modulus): Using an Instron tensile tester, from a 2 mm thick press sheet, length 63.8 mm, width 1
2.7mm sample was punched out, compression speed 5mm / min, support distance 3
The measurement was performed at 2 mm and 23 ° C.

IZ impact test, bending test, 3 days after press molding,
I did.

Polymerization Example 1 (Synthesis of Copolymer (A) with Softening Temperature of 70 ° C. or Higher) Continuously using a 2 l glass polymerization vessel equipped with a stirring blade,
Ethylene and 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (structural formula: (Hereinafter abbreviated as DMON)). That is, from the top of the polymerization vessel, a cyclohexane solution of DMON was added, and the concentration of DMON in the polymerization vessel was 60 g / VO (OC ₂ H ₅ ) Cl ₂
Of cyclohexane solution of vanadium in the polymerization vessel is 0.9 mmol /, and the concentration of ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) in cyclohexane solution is 7.2 mmol / of aluminum in the polymerization vessel. Thus, each is continuously fed into the polymerization vessel, while continuously being withdrawn from the lower portion of the polymerization vessel so that the polymerization liquid in the polymerization vessel becomes 1. Also, from the top of the polymerization vessel, ethylene
, Hydrogen at a rate of 0.2 and nitrogen at a rate of 45 per hour. The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant through a jacket attached outside the polymerization.

When the copolymerization is carried out under the above reaction conditions, a polymerization reaction mixture containing an ethylene / DMON random copolymer is obtained. A small amount of isopropyl alcohol was added to the polymerization liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction. Then, the mixture was put into the polymerization liquid while rotating the mixer in a household mixer in which about 3 times the amount of acetone was added to the polymerization liquid to precipitate the produced copolymer. The precipitated copolymer was collected by filtration, dispersed in acetone so that the polymer concentration became about 50 g /, and treated with the boiling point of acetone for about 2 hours. After the treatment described above, the copolymer was collected by filtration and dried under reduced pressure at 120 ° C. for a whole day and night.

The ethylene composition of the ethylene / DMON random copolymer (A) thus obtained was measured by ¹³ C-NMR analysis to find that the ethylene composition was 59 mol% and the intrinsic viscosity [η was measured in 135 ° C. decalin. ] Was 0.42 dl / g and the softening temperature (TMA) was 154 ° C.

Polymerization Example 2 (Synthesis of Copolymer (A) Having [η] Different from Polymerization Example 1) In Polymerization Example 1, the concentration of DMON in the polymerization vessel was 60 g /, and the blowing rates of ethylene and hydrogen were 100 / hour, respectively. 0.2 per hour
Polymerization was continuously carried out in the same manner except that After completion of the polymerization, the produced copolymer was precipitated in the same manner as in Polymerization Example 1,
The precipitated copolymer was collected and dried at 120 ° C. under reduced pressure for 12 hours.

The ethylene composition of the obtained ethylene / DMON copolymer (A) measured by ¹³ C-NMR analysis was 58 mol%,
The intrinsic viscosity [η] measured in decalin at ℃ was 0.94 dl / g, and the softening temperature was 170 ℃.

Example 1 Copolymer (A) obtained in Polymerization Example 1 and ethylene / propylene / 5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 66/31/3 mol%) (B) 80 g and 20 g (80/20 in weight ratio) of cyclohexane and 2 of cyclohexane were added and dissolved at about 70 ° C. with sufficient stirring. The resulting homogeneous solution was poured into acetone 2,
The (A) / (B) blend was deposited. The resulting blend was dried overnight at 120 ° C. under reduced pressure.

The resulting blend of (A) / (B) was treated with tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane as a stabilizer to prepare resins (A) and (B). 0.5% was added to the total amount, and the mixture was kneaded at 190 ° C. using a Brabender Plastograph and then compression molded at 240 ° C. to obtain a press sheet having a thickness of 2 mm.
Test pieces were punched out from this sheet, and impact strength, bending test and TMA measurement were performed. The Izod impact strength of this blend is 53.4 kg.cm/cm, the flexural modulus is 16000 kg / cm ² ,
The bending yield stress was 590 kg / cm ² , and TMA was 110 ° C. A blend having excellent rigidity and heat resistance and excellent impact strength was obtained.

Comparative Example 1 The same measurement as in Example 1 was carried out using a 2 mm thick press sheet obtained by compression molding the copolymer (A) synthesized in Polymerization Example at 240 ° C.

IZ impact strength is 2.0 kg.cm/cm, flexural modulus is 28900 kg / cm ² ,
The bending yield point stress was 870 kg / cm ² , TMA was 110 ° C, and the sample was excellent in rigidity and heat resistance, but had low impact resistance and was brittle.

Examples 2 to 3 Copolymer (A) obtained in Polymerization Example 1 and ethylene / propylene / 5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 66/31/3 mol%) ( B) was evaluated in the same manner as in Example 1 with the polymerization ratios shown in Table 5. The results are shown in Table 5. A composition having excellent rigidity and heat resistance and high impact resistance was obtained.

Examples 4 to 5 Copolymer (A) obtained in Polymerization Example 1 and ethylene / propylene / 5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 67/31/2 mol%) ( B) was evaluated in the same manner as in Example 1 with the polymerization ratios shown in Table 5. The results are shown in Table 5. A composition having excellent rigidity and heat resistance and high impact resistance was obtained.

Examples 6 to 7 Copolymer (A) obtained in Polymerization Example 1 and ethylene / propylene / dicyclopentadiene random copolymer (ethylene / propylene / diene = 67/32/1 mol%) (B)
Was evaluated in the same manner as in Example 1 with the polymerization ratios shown in Table 5. The results are shown in Table 5.

Example 8 The copolymer (A) synthesized in Polymerization Example 2 and an ethylene / propylene / 5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 66/31/3 mol%) (B) were used. 80g and 20g respectively (weight ratio (A) / (B)
= 80/20) tetrakis [methylene-3 (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] methane as a stabilizer relative to the total amount of resins (A) and (B).
Blended with 0.5%, using Brabender Plastograph, 1
After kneading at 90 ° C., evaluation was performed in the same manner as in Example 1. The results are shown in Table 5. A composition excellent in rigidity, heat resistance and impact resistance was obtained.

Comparative Example 2 The same measurement as in Example 1 was carried out using a 2 mm thick press sheet obtained by compression molding the copolymer (A) synthesized in Polymerization Example 2 at 240 ° C. The results are shown in Table 5. The sample was excellent in rigidity and heat resistance, but had low impact resistance and was brittle.

Examples 9 to 10 The copolymer (A) obtained in Polymerization Example 2 and the α-olefin / diene-based copolymer (B) shown in Table 5 were used in Example 8
Blending was carried out in the same manner as above and evaluation was performed. The results are shown in Table 5.

Examples 11 to 16 Evaluations were performed in the same manner as in Example 8 using the copolymer (A) synthesized by the same method as in Polymerization Example 1 and the α-olefin / diene elastomer. The results are shown in Table 6. A composition having excellent rigidity and heat resistance and excellent impact resistance was obtained.

Comparative Examples 3 to 5 Using the copolymer (A) synthesized by the same method as in Polymerization Example 1, the same evaluation as in Comparative Example 2 was performed. The results are shown in Table 7.

[Brief description of drawings]

FIG. 1 shows the blending amount of the α-olefin / diene random copolymer [B] in the cyclic olefin random copolymer composition according to the present invention, and the impact strength (IZ
FIG. 2 is a graph showing the relationship between the composition of α-olefin / diene random copolymer [B] in the cyclic olefin random copolymer composition of the present invention, and the composition thereof. Softening temperature (TM
It is a figure which shows the relationship with A). Symbols in the figure indicate Examples 1 to 7, Comparative Example 1 ... (○) Examples 8 to 10, Comparative Example 2 ... (□) Examples 11 to 12, Comparative Example 3 ... (●) Example 13 ~ 14, Comparative Example 4 ... (■) Examples 15 to 16, Comparative Example 5 ... (△).

Claims (2)

[Claims] 1. An ethylene component (A) and the following general formula [I]:
Alternatively, it consists of a cyclic olefin component represented by [II] and has an intrinsic viscosity [η] of 0.0 measured in decalin at 135 ° C.
A cyclic olefin-based random copolymer having a softening temperature (TMA) of 70 ° C. or higher in the range of 5 to 10 dl / g, and (B) at least two α-olefins and at least one non-conjugated diene Α-olefin formed from
A cyclic olefin-based random copolymer, characterized in that the diene-based elastic copolymer is present, and the component (B) is present in an amount of 5 to 100 parts by weight relative to 100 parts by weight of the component (A). Combined composition. General formula (In the formula, n and m are both 0 or a positive integer, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group) 2. The composition according to claim 1, wherein the α-olefin / diene-based elastic copolymer is an ethylene / propylene-diene-based elastic copolymer.