JP2598097B2 - Cyclic olefin random copolymer composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a cyclic olefin polymer composition having excellent heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, and excellent impact resistance. About things.

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION Polycarbonate, ABS (acrylonitrile-butadiene-styrene composition) and the like are known as synthetic resins having an excellent balance between rigidity and impact strength. For example, polycarbonate is a resin having excellent rigidity, heat resistance, heat aging resistance and impact resistance. However, it has a problem that it is easily attacked by strong alkalis, has poor chemical resistance, and has a high water absorption. In addition, ABS is excellent in mechanical properties, but is poor in chemical resistance, and has a problem that it has a double bond in the system, so that it is poor in weather resistance and heat resistance.

On the other hand, polyolefins widely used as general resins are excellent in chemical resistance and solvent resistance, but many of them have poor heat resistance, and further have poor crystallinity and poor rigidity. Therefore, in order to improve the rigidity and heat resistance of 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 generally used, but the effect is not sufficient. Is hard to say. Rather, adding a third component such as a nucleating agent may impair the excellent properties inherent to polyolefins,
In addition, the slow cooling method has poor production efficiency, and may have a reduced impact strength as the amorphous portion is reduced.

As for a copolymer of ethylene and a bulky comonomer, a copolymer of ethylene and 2,3-dihydroxydicyclopentadiene is disclosed, for example, in U.S. Pat. No. 2,883,372. This copolymer has an excellent balance between rigidity and transparency, but has a glass transition temperature of 10
There is a problem that the heat resistance is inferior at about 0 ° C. Further, a copolymer of ethylene and 5-ethylidene-2-norbornene has the same problem.

JP-B-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. Further, JP-A-58-127728 discloses 1,
A homopolymer of 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene or a copolymer of the cyclic olefin and a norbornene-type comonomer has been proposed. However, it is clear from the description in the above publication that all of the polymers are ring-opening polymers. Since such a ring-opened polymer has an unsaturated bond in the polymer main chain, there is a problem that heat resistance and heat aging resistance are poor.

In addition, the applicant has previously described that a cyclic olefin random copolymer composed of ethylene and a specific bulky cyclic olefin has heat resistance, and furthermore, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, It has been found that the resin is a synthetic resin having rigidity, which has already been disclosed in JP-A-60-168708 and Japanese Patent Application No. 59-220550.
No., Japanese Patent Application No. 59-236828, Japanese Patent Application No. 59-236829, Japanese Patent Application No.
59-242336 and Japanese Patent Application No. 61-95906. Although these cyclic olefin-based random copolymers are resins having excellent heat resistance and rigidity despite being olefin-based polymers, they have a problem that they are brittle and have poor impact resistance.

The present inventors have the heat resistance of the cyclic olefin-based random copolymer as described above, heat aging resistance, chemical resistance, solvent resistance, without impairing excellent properties such as dielectric properties,
As a result of intensive studies to improve rigidity and impact resistance, a composition consisting of a cyclic olefin random copolymer having a specific softening temperature (TMA) and a specific α-olefin / diene elastic copolymer has been developed. It has been found that a cyclic olefin-based random copolymer having the above-mentioned excellent properties can be obtained by blending an inorganic filler and / or an organic filler, and the present invention has been completed.

Object of the Invention The present invention is 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, etc. 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-based random copolymer composition according to the present invention comprises (A) an ethylene component and the following general formula [I] or [II]
A cyclic olefin random copolymer having an intrinsic viscosity [η] of 0.05 to 10 dl / g measured in decalin at 135 ° C and a softening temperature (TMA) of 70 ° C or higher. A polymer; (B) an α-olefin formed from at least two α-olefins and at least one non-conjugated diene;
A diene-based elastic copolymer, and (C) an inorganic filler or an organic filler, and based on 100 parts by weight of the component (A),
It is characterized in that the component (B) is present in an amount of 1 to 100 parts by weight and the component (C) is present in an amount of 1 to 100 parts by weight.

General formula (Where n and m are each 0 or a positive integer, 1 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), (B) and (C), and (B) is added to 100 parts by weight of the component (A).
Since the component is present in an amount of 1 to 100 parts by weight and the component (C) in an amount of 1 to 100 parts by weight, heat resistance, heat aging resistance, chemical resistance,
It has excellent solvent resistance and dielectric properties, as well as excellent rigidity and impact resistance.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the cyclic olefin-based random copolymer composition according to the present invention will be specifically described.

According to the present invention, (A) an ethylene component and the following general formula [I] or [II]
A cyclic olefin random copolymer having an intrinsic viscosity [η] of 0.05 to 10 dl / g measured in decalin at 135 ° C and a softening temperature (TMA) of 70 ° C or higher. A polymer; (B) an α-olefin formed from at least two α-olefins and at least one non-conjugated diene;
A diene-based elastic copolymer, and (C) an inorganic filler or an organic filler, and based on 100 parts by weight of the component (A),
A cyclic olefin-based random copolymer composition is provided, wherein the component (B) is present in an amount of 1 to 100 parts by weight and the component (C) is present in an amount of 1 to 100 parts by weight.

General formula (Where n and m are each 0 or a positive integer, 1 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 random copolymer [A] constituting the cyclic olefin random copolymer composition according to the present invention.
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].

General formula (Where n and m are each 0 or a positive integer, 1 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 described above.) The components of the cyclic olefin random copolymer constituting the cyclic olefin random copolymer composition according to the present invention are described below. The cyclic olefin is at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the general formulas [I] and [II]. The cyclic olefin represented by [I] in the general formula can be easily produced by condensing cyclopentadiene and a corresponding olefin by a Diels-Alder reaction. Similarly, the cyclic olefin represented by the general formula [II] can be easily produced by similarly condensing a cyclopentadiene and a corresponding cyclic olefin by a Diels-Alder reaction.

As the cyclic olefin represented by the general formula [I], specifically, the compounds described in Table 1 or 1,4,5,8-
In addition to dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,
4,4a, 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,
3,4,4a, 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-1,2,3,4,4
a, 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-dimetano-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 octahydronaphthalenes such as octahydronaphthalene and the compounds described in Table 2.

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

The cyclic olefin random copolymer [A] constituting the cyclic olefin random copolymer composition according to the present invention.
Has an ethylene component and the above-mentioned cyclic olefin component as essential components as described above, but other copolymerizable components can be used as necessary within a range not to impair the object of the present invention in addition to the essential two components. Or unsaturated unsaturated monomer components. As the unsaturated monomer that may be optionally copolymerized, specifically, for example, propylene in a range of less than equimolar to the ethylene component unit in the produced random copolymer,
1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
Α-olefins having 3 to 20 carbon atoms such as eicosene.

The cyclic olefin random copolymer [A] constituting the cyclic olefin random copolymer composition according to the present invention.
Wherein the repeating unit (a) derived from an 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 cyclic olefin has 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 and substantially linearly arranged.
The fact that the cyclic olefin-based random copolymer [A] is substantially linear and does not have a gel-like cross-linked structure can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

Such a cyclic olefin-based random copolymer [A]
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.0
It is in the range of 5-10 dl / g, preferably 0.08-5 dl / g.

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

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

The α-olefin / diene-based elastic copolymer [B] constituting the cyclic olefin-based random copolymer composition according to the present invention includes (i) an ethylene / α-olefin / diene copolymer rubber, and (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.
And α-20-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Of these, propylene or 1-butene is particularly preferred.

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 and 1-butene.
Pentene, 1-hexene, 4-methyl-1-pentene,
Examples thereof include 1-octene, 1-decene, and mixtures thereof. Of these, 1-butene is particularly preferred.

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, Linear 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. this house,
1,4-hexadiene and cyclic non-conjugated dienes, especially dialkylcopentadiene or 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 1,4-hexadiene, 1,4- Octadiene is preferred.

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

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

In the above (ii) propylene / α-olefin / diene copolymer rubber, the molar ratio of propylene to α-olefin (propylene / α-olefin) is α
-Depends on the type of olefin, but generally 50/50
Preferably it is ~ 95/5. The molar ratio is preferably 50/50 to 90/10 when the α-olefin is 1-butene, and 80/20 to 95/50 when the α-olefin has 5 or more carbon atoms. It is preferably 5.

The content of the diene component in the copolymer rubber is preferably 0.5 to 10 mol%, more preferably 0.5 to 5 mol%. Such an α-olefin / diene-based elastic copolymer [B] preferably has a crystallinity of 0 to 10%, preferably 0 to 5%, as measured by an X-ray diffraction method.

Further, an α-olefin / diene-based elastic copolymer [B]
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1
1010 dl / g, preferably 1 to 5 dl / g.
Further, the iodine value is desirably 1 to 30, preferably 5 to 25. Furthermore, its density is 0.82-1.00g / cm
^{3 It is} preferably 0.85 to 0.90 g / cm ³ .

In addition to the cyclic olefin random copolymer [A] and the α-olefin / diene elastic copolymer [B], the cyclic olefin random copolymer composition according to the present invention includes an inorganic filler or Organic filler [C] is included.

As the inorganic filler, specifically, silica, silica-
Alumina, alumina, glass powder, glass beads, glass fiber, glass fiber cloth, glass fiber mat, asbestos, graphite, carbon fiber, carbon fiber cloth, carbon fiber mat, titanium oxide, molybdenum disulfide, magnesium hydroxide, talc, celite , Metal powder, metal fiber, and the like.

As the organic filler, specifically, polyterephthaloyl-p-phenylenediamine, polyterephthaloylisophthaloyl-p-phenylenediamine, polyisophthaloyl-p-phenylenediamine, polyisophthaloyl-
fibrous material of wholly aromatic polyamide such as m-phenylenediamine, or nylon 66, nylon 6, nylon 10
A fibrous material such as polyamide is used.

These fibrous materials can be in the form of a single fiber, a strand, a cloth, a mat, or the like.

These inorganic or organic fillers are used alone or in combination.

The inorganic filler or the organic filler [C] is blended in the cyclic olefin-based random copolymer composition according to the present invention for various purposes, for example, to improve the heat resistance or flame retardancy of the composition. In order to color the composition, improve the rigidity, or suppress the molding shrinkage, the composition is used in an amount according to the purpose.

In the cyclic olefin random copolymer composition according to the present invention, the cyclic olefin random copolymer [A] 100
The α-olefin / diene-based elastic copolymer [B] is present in an amount of 1 to 100 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 5 to 50 parts by weight with respect to parts by weight. ,
Further, the inorganic filler or the organic filler [C] is 1 to 100 parts by weight of the cyclic olefin random copolymer [A].
It is present in an amount of 100 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 5 to 50 parts by weight. If the α-olefin / diene-based elastic copolymer [B] is less than 1 part by weight per 100 parts by weight of the cyclic olefin-based random copolymer [A], the impact strength decreases, which is not preferable. Ten
Exceeding 0 parts by weight is not preferred because the rigidity is reduced.

Further, the cyclic olefin-based random copolymer [A] 10
0 parts by weight, inorganic filler or organic filler [C]
If it exceeds 100 parts by weight, the moldability deteriorates, which is not preferred.

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-61-120816.
JP-A-61-115912, JP-A-61-115916, Japanese Patent Application No. 61-95905, Japanese Patent Application No. 61-95906,
It can be produced by appropriately selecting conditions according to the method proposed by the present applicant in JP-A-61-271308 and JP-A-61-272216.

As the method for producing the cyclic olefin random copolymer composition according to the present invention, a known method can be applied, and the cyclic olefin random copolymer [A] and the α-olefin.
A method in which a diene-based elastic copolymer [B] and an inorganic filler or an organic filler [C] are separately manufactured, and [A], [B], and [C] are blended by an extruder, or [A], [B] and the filler [C] are sufficiently dissolved in a suitable solvent, for example, a saturated hydrocarbon such as heptane, hexane, decane and cyclohexane, and an aromatic hydrocarbon such as toluene, benzene and xylene. The cyclic olefin-based random copolymer composition according to the present invention, wherein a polymer obtained by synthesizing [A] and [B] in a separate polymerization vessel and [C] are blended in a separate container. A method of manufacturing a product can be given.

The intrinsic viscosity [η] of the cyclic olefin-based random copolymer composition according to the present invention measured in decalin at 135 ° C. is
0.05 to 10 dl / g, preferably in the range of 0.08 to 5 dl / g,
The softening temperature (TMA) measured by a thermal mechanical analyzer is in the range of 80 to 250C, preferably 100 to 200C, and the glass transition temperature (Tg) is in the range of 70 to 230C, preferably 90 to 210C. It is in.

The cyclic olefin random copolymer composition according to the present invention includes the cyclic olefin random copolymer [A],
An α-olefin / diene-based elastic copolymer [B] and an inorganic or organic filler [C] are essential components. In addition, a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a slip agent , An antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, and the like, and the mixing ratio is an appropriate amount. For example, as a stabilizer blended as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane,
β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis [ethyl-3 (3,5-di-tert-butyl-4-viroxyphenyl) Phenolic antioxidants such as propionate, zinc stearate, calcium stearate,
Fatty acid metal salts such as calcium 12-hydroxystearate, polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate And the like. These may be blended alone or in combination, for example, tetrakis [methylene-3 (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] methane with zinc stearate and glycerin monostearate.

Effect of the Invention The cyclic olefin-based random copolymer composition according to the present invention includes the cyclic olefin-based random copolymer [A] and the α-olefin / diene-based elastic copolymer [B] as described above.
And the inorganic filler or the organic filler [C], and the copolymer [B] is 1 to 100 parts by weight based on 100 parts by weight of the copolymer [A], and the inorganic filler or the organic filler [ C] is present in an amount of 1 to 100 parts by weight, and thus has excellent heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, and impact resistance.

Examples Next, the present invention will be described specifically with reference to Examples.
The present invention is not limited to these examples. The methods for measuring and evaluating various physical properties in the present invention are shown below.

(1) Thermal deformation temperature (TMA): TMA10 (Th
It was measured by the thermal deformation behavior of a 1 mm thick sheet using an thermomechanical analyzer. 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 defined as TMA.

(2) Impact strength: Using a Toyo Seiki Izod impact tester, a 63.8 mm long and 12.7 m wide sheet from a 2 mm thick pressed sheet
The test piece of m was punched out, a notch of 0.25 mmR was inserted, and the measurement was performed at 23 ° C.

(3) Rigidity (flexural modulus): Using an Instron tensile tester, press a sheet with a thickness of 2 mm to a length of 63.8 mm and a width of 12.
Punched 7mm test piece, compression speed 5mm / min, distance between supports 3
The measurement was performed at 2 mm and 23 ° C.

The IZ impact test and bending test were performed three days after press molding.

As the filler [C], (1) Asahi fiber glass glass Ron chop strand GR-S-3A (GF) or (2) Fujimi white alumina # 4000 (WA) was used.

Polymerization Example 1 (Synthesis of copolymer (A) having a softening temperature of 70 ° C. or higher) Ethylene and 1,4,5,8-dimethanol were continuously used in a two-glass polymerization vessel equipped with stirring blades. 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 to VO (OC ₂ H ₅ ) Cl ₂ with a DMON concentration of 30 g / catalyst in the polymerization vessel.
The cyclohexane solution of the above, the vanadium concentration in the polymerization vessel was 0.9 mmol /, the cyclohexane solution of ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) was changed to the aluminum concentration in the polymerization vessel of 7.2 mmol /. The polymerization solution is continuously supplied into the polymerization vessel so that the polymerization liquid in the polymerization vessel becomes 1 from the lower portion of the polymerization vessel. Also, from the top of the polymerization vessel, ethylene
85, supply hydrogen at a rate of 0.2 per hour and nitrogen at a rate of 45 per hour. The copolymerization reaction was performed at 10 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization.

When copolymerization is performed 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. Thereafter, the polymerization liquid was introduced into a household mixer containing about three times the amount of acetone with respect to the polymerization liquid while rotating the mixer, to precipitate a produced copolymer. The precipitated copolymer was collected by filtration, dispersed in acetone so that the polymer concentration became about 50 g /, and the copolymer was treated at the boiling point of acetone for about 2 hours. After the treatment described above, the copolymer was collected by filtration and dried under reduced pressure at 120 ° C. overnight.

The ethylene composition of the ethylene / DMON random copolymer (A) obtained as described above was determined by ¹³ C-NMR analysis to be 67 mol%, and the intrinsic viscosity [η] measured in decalin at 135 ° C. ] Was 0.60 dl / g, and softening temperature (TMA) was 111 ° C.

Example 1 The copolymer (A) obtained in Polymerization Example 1 and ethylene-
Propylene-5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 66/31/3
Mol%) and (B) were dry blended at a weight ratio of 80/10, and tetrakis [methylene-3] was added thereto as a stabilizer.
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate] methane and di-lauryl-thio-di-
Propionate was blended at 0.5% and 0.3% with respect to the total amount of the resins (A) and (B), respectively, and was mixed with a 30 mmφ twin-screw extruder to obtain 220%.
After kneading at ℃, GF was dry blended at 10% by weight based on the total amount of resins A and B, kneaded at 220 ℃ using a 30 mm φ twin screw extruder, and compression molded at 240 ℃ to press 1mm and 2mm thick I got a sheet. A test piece was cut out from this sheet and subjected to an impact test, a bending test, and a TMA measurement.

Notched Izod impact strength of 8kg
cm / cm, the initial flexural modulus was 31100 kg / cm ² , and the TMA was 114 ° C. Thus, a blend having excellent rigidity, heat resistance and impact strength was obtained.

Comparative Example 1 The copolymer (A) obtained in Polymerization Example 1 was compression-molded at 240 ° C. to obtain press sheets having a thickness of 1 mm and 2 mm. A test piece was cut out from this sheet, and an impact test, bending test, TMA
A measurement was made.

The notched Izod impact strength of this test piece is 2 kg cm / c
m, the initial flexural modulus was 28900 kg / cm ² , and the TMA was 111 ° C., which was inferior to the blend obtained in Example 1 in impact strength, initial flexural modulus, and heat resistance.

Examples 2-3 The copolymers (A) and (B) and the filler (C) shown in Table 5 were blended at the blend ratio shown in Table 5, and the same evaluation as in Example 1 was performed. Table 5 shows the results. rigidity,
A composition having excellent heat resistance and impact strength was obtained.

Examples 4 to 6 The copolymers (A) and (B) and the filler (C) shown in Table 5 were blended at the blend ratio shown in Table 5, and the same evaluation as in Example 1 was performed. Table 5 shows the results. rigidity,
A composition having excellent heat resistance and impact strength was obtained.

Comparative Example 2 The same evaluation as in Comparative Example 1 was performed using the copolymer (A) shown in Table 5. Table 5 shows the results. The rigidity, heat resistance, and impact strength were inferior to those of the compositions obtained in Examples 4 to 6.

Examples 7 to 9 The copolymers (A) and (B) and the filler (C) shown in Table 5 were blended at the blend ratio shown in Table 5, and the same evaluation as in Example 1 was performed. Table 5 shows the results. rigidity,
A composition having excellent heat resistance and impact strength was obtained.

Comparative Example 3 The same evaluation as in Comparative Example 1 was performed using the copolymer (A) shown in Table 5. Table 5 shows the results. The rigidity, heat resistance, and impact strength were inferior to those of the compositions obtained in Examples 7 to 9.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 45/00 LKB C08L 45/00 LKB (72) Inventor Yozo Yamamoto Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture 6-1-2 1-2 Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP 7-68419 (JP, B2)

Claims (2)

(57) [Claims] (1) An ethylene component (A) having the following general formula [I]
Or the cyclic olefin component represented by [II], and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.0
A cyclic olefin random copolymer having a softening temperature (TMA) of 70 ° C. or more in the range of 5 to 10 dl / g, and (B) at least two α-olefins and at least one non-conjugated diene. Α-olefins formed
A diene-based elastic copolymer, and (C) an inorganic filler or an organic filler, and based on 100 parts by weight of the component (A),
The cyclic olefin random copolymer composition, wherein the component (B) is present in an amount of 1 to 100 parts by weight and the component (C) is present in an amount of 1 to 100 parts by weight: General formula: (Where n and m are each 0 or a positive integer, 1 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.