JPH0232139A - Cyclic olefin-based random copolymer composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent rigidity and impact resistance by blending a specific cyclic olefin-based random copolymer with an aromatic vinyl hydrocarbon/conjugated diene block copolymer and an inorganic filler and/or organic filler. CONSTITUTION:(A) 100 pts.wt. cyclic olefin-based random copolymer which comprises an ethylene component and a cyclic olefin component shown by formula I or formula II (n and m are 0 or positive integer; l is >=3 integer; R<1>-R<10> are H, halogen or hydrocarbon group) and has 0.05-10dl/g, preferably 0.08-5dl/g intrinsic viscosity (135 deg.C, in decalin) and >=70 deg.C, preferably 90-250 deg.C softening temperature is blended with (B) 1-100 pts.wt. aromatic vinyl hydrocarbon/conjugated diene copolymer (hydrogenated substance), such as styrene/butadiene copolymer rubber and (C) 1-100 pts.wt. organic and/or inorganic filler.

Description

[Detailed description of the invention] 11a Kuzu beans 1 The present invention has heat resistance, heat aging resistance, chemical resistance, solvent resistance,
The present invention relates to a cyclic olefin polymer composition that has excellent dielectric properties, rigidity, and IIT impact properties.

As a synthetic resin with an excellent balance of stiffness and impact strength,
Polycarbonate, ABS (acrylonitrile-butadiene-styrene composition), etc. are known. For example, polycarbonate is a resin that has excellent heat resistance, heat aging resistance, and impact resistance as well as rigidity. However, there are problems in that it is easily attacked by strong alkalis, has poor chemical resistance, and has a high water absorption rate. Furthermore, although ABS has excellent mechanical properties, it has poor chemical resistance, and because it contains double bonds in its system, it has poor weather resistance, and furthermore, it has poor heat resistance.

On the other hand, polyolefins that are widely used as general-purpose resins have excellent chemical and solvent resistance, but many have poor heat resistance, and furthermore, their crystallinity is not perfect and their homogeneity is poor. Therefore, in order to improve the rigidity and heat resistance of polyolefins, methods are generally used to accelerate crystal growth by adding a nucleating agent or slow cooling, but these methods are not sufficiently effective. In fact, adding a third component such as a nucleating agent may impair the excellent properties originally possessed by polyolefin, and the slow cooling method not only has low production efficiency but also There is a risk that the impact strength will decrease due to the decrease.

For copolymers of ethylene and bulky comonomers,
For example, U.S. Pat. No. 2,883,372 discloses copolymers of ethylene and 2,3-dihydroxydicyclopentadiene. Although this copolymer has an excellent balance between rigidity and transparency, it has a problem in that its glass transition temperature is about 100° C. and its heat resistance is poor. Further, copolymers of ethylene and 5-ethylidene-2-norbornene also have similar problems.

In addition, in Japanese Patent Publication No. 46-14910, 1.4, 5
．． 8-dimethano-1,2,3,4,4a,5,8.8a
, -octahydronaphthalene homopolymers have been proposed, but these polymers have poor heat resistance and heat aging resistance. Furthermore, JP-A No. 58-127728 includes 1, 4, 5.
8-dimethano-1,2,3,4,4a,5,8,8a-
Although a homopolymer of octahydronaphthalene or a copolymer of the cyclic olefin and a norbornene type comonomer has been proposed, it is clear from the description in the above publication that these polymers are ring-opening polymers. be.

Since such ring-opened polymers have unsaturated bonds in the polymer main chain, they have a problem of poor heat resistance and heat aging resistance.

In addition, the applicant has previously discovered that a cyclic olefin-based random copolymer consisting of ethylene and a specific noble cyclic olefin has heat resistance, tends to have heat aging resistance, chemical resistance, solvent resistance, and dielectric properties. , it was discovered that it is a synthetic resin with rigidity, and has already been published in Japanese Patent Application Laid-open No. 168708 (1983) and Japanese Patent Application No. 1687-
220550, Japanese Patent Application No. 59-236828, Japanese Patent Application No. 59-236829, Japanese Patent Application No. 59-242336,
This was proposed in Japanese Patent Application Laid-open No. 61-95906. Although these cyclic olefin-based random copolymers are olefin-based polymers, they are resins with excellent heat resistance and rigidity, but have the problem of being brittle and having poor impact resistance.

The present inventors have developed a method for achieving rigidity, impact resistance, etc. without impairing the excellent properties of the above-mentioned cyclic olefin random copolymer, such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, and dielectric properties. As a result of intensive studies to improve properties, we have developed a composition consisting of a cyclic olefin random copolymer having a specific softening temperature (TMA) and an aromatic vinyl hydrocarbon/conjugated diene block copolymer or its hydride. The present inventors have discovered that a cyclic olefin random copolymer having excellent properties can be obtained by blending an inorganic filler, an organic filler, or both of them with a cycloolefin filler, and have completed the present invention.

1. The present invention aims to solve the problems associated with the conventional technology as described above, and has excellent heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, etc. ,rigidity,
Resistance [rl! The purpose of the present invention is to provide a cyclic olefin random copolymer composition with excellent properties.

I skin blood I! The cyclic olefin random copolymer composition according to the present invention comprises (^) an ethylene component and the following general formula [I] or [Ir
consisting of a cyclic olefin component represented by l, 135
Intrinsic viscosity [η] measured in decalin at °C is 0.05~
10 dl/, with a softening temperature (TMA) of 70
℃ or higher, (B) an aromatic vinyl hydrocarbon/conjugated diene copolymer or its hydride, and (C) an inorganic filler or an organic filler, and the above ( A) For 100 parts by weight of component,
Component (B) is 1 to 100 parts by weight, component (C) is 1 to 10 parts by weight.
It is characterized in that it is present in an amount of 0 parts by weight.

General formula (where n and m are both 0 or a positive integer, o is an integer of 3 or more, and R1 to R10 each represent a hydrogen atom, a halogen atom, or a hydrocarbon group)
.

The cyclic olefin random copolymer composition according to the present invention is formed from the above component (^), (B) component, and (C) component, and (B) per 10 parts by weight of the above (^) component.
Because the component (C) is present in an amount of 1 to 100 parts by weight, and component (C) is present in an amount of 1 to 100 parts by weight, it has excellent heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, etc., and has excellent rigidity. , has excellent impact resistance.

Quick turn! ``U Kugi Kaiku Tomo The cyclic olefin random copolymer composition according to the present invention will be specifically explained below.

According to the present invention, (A) an ethylene component and the following general formula [I] or [II]
], consisting of a cyclic olefin component represented by 135
Intrinsic viscosity [η] measured in decalin at °C is 0.05~
106j/, with a softening temperature (TMA) of 70
℃ or higher, CB) an aromatic vinyl hydrocarbon/conjugated diene copolymer or its hydride, and (C) an inorganic filler or an organic filler; ) per 100 parts by weight of the component,
Component (B) is 1 to 100 parts by weight, component (C) is 1 to 10 parts by weight.
A random cyclic olefin copolymer composition is provided, wherein the random copolymer composition is present in an amount of 0 parts by weight.

General formula (where n and m are both 0 or a positive integer, 1 is an integer of 3 or more, and R1 to R10 each represent a hydrogen atom, a halogen atom, or a hydrocarbon group)
.

Cyclic olefin-based random copolymer [A] constituting the cyclic olefin-based random copolymer composition according to the present invention
is a cyclic olefin 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 [II or general formula [1], and in the cyclic olefin random copolymer of the present invention,
The cyclic olefin component forms a structure represented by general formula [II [] or general formula (■)].

general formula R10 is a hydrogen atom, (indicates a hydrogen group).

Halogen atom or carbon (in the formula, n and m are both O or a positive integer, 1 is an integer of 3 or more, R1 or in the formula, n,
m, j and R to R10 are the same as above. ) The cyclic olefins as the constituent components of the cyclic olefin random copolymer constituting the cyclic olefin random copolymer composition according to the present invention have the general formula [II and the general formula [I
At least 61 selected from the group consisting of unsaturated monomers represented by N] l! It is a cyclic °olefin. The cyclic olefin represented by II in the general formula can be easily produced by condensing a cyclopentadiene and a corresponding olefin in a Diels-Alder reaction. Similarly, the cyclic olefin represented by the general formula [II] can be easily produced by condensing a cyclopentadiene and a corresponding cyclic olefin by a Diels-Alder reaction.

Specifically, the cyclic olefins represented by the general formula [II include the compounds listed in Table 1, or 1, 4, 5.
8-dimethano-1,2,3,4,4a,5,8.8a-
In addition to 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,5,8.8
a-octahydronaphthalene, 2-propyl-1,4,
5,8-dimethano-1,2,3,4,4a,5,8.8
a-octahydronaphthalene, 2-hexyl-1,4,
5,8-dimethano-1,2,3,4,4a,5,8.8
a-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-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a
, 5,8,8a-octahydronaphthalene, 2-promo 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-dimethano-1,2,3
,4,4a,5,8,8a-octahydronaphthalene,
2-isobutyl-1,4,5,8-dimethano-1,2,
Octahydronaphthalenes such as 3,4,4a, 5,8,8a-octahydronaphthalene, and the compounds listed in Table 2 can be exemplified.

Table 1 Further, specific examples of the cyclic olefin represented by the general formula [II] include the compounds shown in Table 3 and Table 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 cyclic olefin component as essential components as described above. In addition to the two essential components, it may contain other copolymerizable unsaturated monomer components as necessary, and may be optionally copolymerized, as long as the object of the present invention is not impaired. Specifically, the unsaturated monomer includes, for example, propylene in an amount less than equimolar to the ethylene component unit in the random copolymer to be produced, 1
-butene, 4-methyl-1-pentene, 1-hexene,
Examples include α-olefins having 3 to 20 carbon atoms, such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-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 40 to 85 mol%, preferably 50 to 85 mol%. The repeating unit (b) derived from the cyclic olefin is present in the range of 75 mol%, and the repeating unit (b) derived from the cyclic olefin is present in the range of 15 to 60 mol%, preferably 25 mol%.
The repeating units (a) derived from the ethylene component and the repeating units b) derived from the cyclic olefin component are present in a range of ˜50 mol %, and are arranged randomly and substantially linearly. The fact that this cyclic olefin random copolymer [A] is substantially linear and does not have gel-like crosslinking can be confirmed by completely dissolving the copolymer in decalin at 135°C. .

The intrinsic viscosity [η] of such a cyclic olefin random copolymer [A] measured in decalin at 135°C is 0.
．． 05-10dl/g, preferably 0.08-5dl/
in the range of g.

In addition, the softening temperature (T
MA) is in the range of 70°C or higher, preferably 90 to 250°C, more preferably 100 to 200°C. Also,
The glass transition temperature (TQ) of the cyclic olefin random copolymer [A] is usually 50 to 230°C, preferably 7
It is in the range of 0 to 210°C.

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

The aromatic vinyl hydrocarbon-conjugated diene copolymer or its hydride [B] constituting the cyclic olefin-based random copolymer composition according to the present invention includes (i) styrene-butadiene copolymer rubber, ( ii) Styrene-butadiene-styrene block copolymer rubber, (i) Styrene-isoprene block copolymer rubber, (+V) Styrene-isoprene-styrene block copolymer rubber, (
V) Hydrogenated styrene/butadiene/styrene block copolymer comb, (vl) Hydrogenated styrene/isoprene/styrene block copolymer comb, etc. are used.

<i) In styrene-butadiene copolymer rubber,
The molar ratio of styrene and butadiene (styrene/butadiene) is generally preferably from O/100 to 60/40.

(i) In the styrene-butadiene-styrene block copolymer rubber, the molar ratio of styrene and butadiene (
Styrene/butadiene) is preferably 0/100 to 60/40, and the degree of polymerization of each block is about 0 to 5000 for styrene, and 10 to 2 for butadiene.
It is preferable that it is about 0000.

(i) In styrene/isoprene block copolymer rubber, the molar ratio of styrene to isoprene (styrene/isoprene
isoprene) preferably has -fi of O/100 to 60/40.

(1v) In the styrene/isoprene/styrene block copolymer rubber, the molar ratio of styrene and isoprene (styrene/isoprene) is 0/100 to 60/40.
The degree of polymerization of each block is preferably about 0 to 5,000 for styrene, and about 10 to 5,000 for isoprene.
It is preferable that it is about 20,000.

(V) Hydrogenated styrene/butadiene/styrene block copolymer rubber is the styrene/butadiene/styrene block copolymer rubber mentioned above.
A copolymer rubber in which double bonds remaining in the styrene block copolymer rubber are partially hydrogenated, and the weight ratio of styrene to the rubber part (styrene/rubber part) is O/100 to 5.
0150 is preferable.

(vl) Hydrogenated styrene/isoprene/styrene block copolymer rubber is a copolymer rubber in which the double bonds remaining in the styrene/isoprene/styrene block copolymer described above are partially hydrogenated. Therefore, the weight ratio of styrene and rubber part (styrene/rubber part) is O/100 to 50.
Preferably, it is 150.

GPC (gel permeation chromatography, ortho-dichlorobenzene) of such an aromatic vinyl hydrocarbon/conjugated diene copolymer.

The weight average molecular weight Mw measured at 140°C is 500
~2000000 preferably toooo~100000
It is desirable that the iodine value is 0, and the iodine value is 0 to 2.
It is desirable that it be 50.

Further, it is desirable that the density is 0.80 to 1.10 r/-, preferably 0.88 to 0.96 g/cj.

The cyclic olefin random copolymer composition according to the present invention includes the above-mentioned cyclic olefin random copolymer [A
] and the aromatic vinyl hydrocarbon/conjugated diene copolymer or its hydride [B], an inorganic filler or an organic filler [C] is included.

Specifically, inorganic fillers include silica, silica-alumina, alumina, glass powder, glass beads, glass fiber, glass fiber cloth, glass fiber mat, asbestos, graphite, carbon fiber, carbon fiber cloth, and carbon fiber mat. , titanium oxide, molybdenum disulfide, magnesium hydroxide, talc, celite, metal powder,
Metal fiber etc. are used.

Specific examples of the organic filler include polyterephthaloyl-p-phenylenediamine, polyterephthaloyl isophthaloyl-p-phenylenediamine, polyisophthaloyl-p-phenylenediamine, and polyisophthaloyl-p-phenylenediamine. Fibers of fully aromatic polyamide such as diamine, or nylon 66, nylon 6, nylon 10
A fibrous material such as polyamide is used.

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

These inorganic or organic fillers may be used alone or in combination.

The inorganic filler or organic filler [C] is blended into the cyclic olefin random copolymer composition according to the present invention for various purposes, such as improving the heat resistance or flammability of the composition. In order to color the composition, improve its properties, and suppress mold shrinkage, it is used in an amount depending on the purpose.

In the cyclic olefin random copolymer composition according to the present invention, a cyclic olefin random copolymer [A1100
Based on the weight part, the aromatic vinyl hydrocarbon/conjugated diene copolymer or its hydride [B] is 1 to 100 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 5 to 100 parts by weight.
The inorganic filler or organic filler [C] is present in an amount of 1 to 100 parts by weight, preferably 5 to 100 parts by weight, relative to 1100 parts by weight of the cyclic olefin random copolymer [A1]. It is present in an amount of 5 to 50 parts by weight, particularly preferably from 5 to 50 parts by weight. The aromatic vinyl hydrocarbon/conjugated diene copolymer or its hydride [B] based on 1100 parts by weight of the cyclic olefin random copolymer [A]
If it is less than 1 part by weight, it is undesirable because it lowers the impact strength, while if it exceeds 100 parts by weight, it is not preferable because the durability is lowered.

In addition, the cyclic olefin random copolymer [A]i0
Inorganic filler or organic filler [C] per 0 parts by weight
If it exceeds 100 parts by weight, moldability deteriorates, which is not preferable.

As mentioned above, cyclic olefin random copolymer [A]
When an aromatic vinyl hydrocarbon/conjugated diethylene copolymer or its hydride [B] is blended in an amount of about 40% by weight, the impact resistance of the cyclic olefin random copolymer composition is significantly improved. At the same time, heat resistance does not decrease.

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-61-12.
0816, JP 61-115912, JP 61-115916, JP 61-9590
No. 5, Japanese Patent Application No. 61-95906, Japanese Patent Application No. 61-271
It can be produced by appropriately selecting conditions according to the method proposed by the present applicant in JP-A No. 308, JP-A-61-272216, and the like.

As a method for producing the cyclic olefin random copolymer composition according to the present invention, known methods can be applied. Hydride [B] and inorganic filler or organic filler [C] are produced separately, [
A method of blending A], [B] and [C] in an extruder, or a method of blending [A], [B] and [C] with a suitable solvent, such as heptane, hexane, decane, cyclohexane, etc. A solution blending method carried out by sufficiently dissolving a saturated hydrocarbon, an aromatic hydrocarbon such as toluene, benzene, or xylene, or a polymer obtained by synthesizing [A] and [B] in separate polymerization vessels, and [C] A method for producing the cyclic olefin random copolymer composition according to the present invention by blending them in a separate container can be mentioned.
The intrinsic viscosity [η] of the cyclic olefin random copolymer composition according to the present invention measured in decalin at 135°C is:
0.05-10dl/g, preferably 0.08-5dJ
/g, and the softening temperature (TMA) measured by a thermal mechanical analyzer is 80-250
C5, preferably in the range of 100-200C, and the glass transition temperature ('I'!I+) is in the range of 70-230'C5, preferably 90-210C.

The cyclic olefin random copolymer composition according to the present invention comprises the cyclic olefin random copolymer [A],
Aromatic vinyl hydrocarbon/conjugated diene copolymer or its hydride [B] and inorganic filler or organic filler [
C] is an essential ingredient, but it also contains heat stabilizers, weather stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, and waxes. etc., and the blending ratio is appropriate. For example, as a stabilizer that may be added as an optional component, specifically, tetrakis[methylene-3
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate comethane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2,2-oxamidobisethyl-3(3,5
- Phenolic antioxidants such as di-t-butyl-4-biloxyphenyl) propionate, fatty acid metal salts such as zinc stearate, calcium stearate, calcium 12-droxystearate, glycerin monostearate, glycerin monolaurate, etc. Examples include polyhydric alcohol fatty acid esters such as ester, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination; for example, tetrakis[methylene-3 (3,5-di-t-butyl-4
Examples include a combination of comethane (droxyphenyl)propionate, zinc stearate, and glycerin monostearate.

The cyclic olefin random copolymer composition according to the present invention comprises a cyclic olefin random copolymer composition as described above [
A], an aromatic vinyl hydrocarbon/conjugated diene copolymer or its hydride [B], and an inorganic filler or an organic filler [C]; Since the coalesce [B] is present in an amount of 1 to 100 parts by weight, and the inorganic filler or organic filler [C] is present in an amount of 1 to 100 parts by weight, it has good heat resistance, heat aging resistance, chemical resistance, and solvent resistance. Excellent in properties, dielectric properties, cohesiveness, and impact resistance.

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

(1) Heat distortion temperature (TMA): Seiko Electronics TM
A 10 (Thermonechanical^n
The thermal deformation behavior of the IIfi+ thickness sheet was measured using the Alyser).

That is, a quartz needle was placed on the sheet, a load of 50 g was applied, the temperature was raised at a rate of 5° C./min, and the temperature at which the needle penetrated 0.1 m was defined as TMA.

(2) WI impact strength: Using Toyo Seiki's Izotsu WI impact tester, a length of 63.8 was measured from a 2rm thick press sheet.
A test piece with a width of 12.7 m and a width of 12.7 m was punched out, a notch of 0-25 m + R was inserted, and measurements were taken at 23°C.

(3) Rigidity modulus (flexural modulus): Using an Instron tensile tester, a length of 63.8r was measured from a 2-bit thick press sheet.
Ma, punched a test piece with a width of 12.7 am, compression speed 5
Measurements were carried out at m/min, support pressure M32 ml, and 23°C.

The IZ impact test and bending test were conducted 3 days after press molding.

As the filler [C], (1) Asahi Fiberglass Glass Long Chop Strand GR-3-3A (GF) or (2) Fujimi White Alumina #4000 (WA) was used.

Heavy Gome 11 (Synthesis of copolymer (^) with a softening temperature of 70°C or higher) Using a 2J glass polymerization vessel equipped with a stirring blade, ethylene and 1,4,5,8-dimethane were continuously synthesized. -1,2,3゜4,
4a, 5.8.8a-octahydronaphthalene (structural formula: The reaction was carried out. That is, from the top of the polymerization vessel, DMO
A cyclohexane solution of N was used as a catalyst with a DMON concentration of 30 t/1 in the polymerization vessel -(VO(OCH)CI2
A cyclohexane solution of Continuously feed each into the polymerization vessel so that it becomes 7.2 mmol/j,
On the other hand, the polymer solution in the polymerization vessel is continuously drawn out from the lower part of the polymerization vessel so that the volume of polymerization liquid in the polymerization vessel becomes 11. In addition, from the top of the polymerization vessel, 85J/hour of ethylene, 0.21J/hour of hydrogen, and 45J/hour of nitrogen
supply at a speed of j. The copolymerization reaction is carried out by circulating a refrigerant through a jacket attached to the outside of the polymerization.
It was carried out at 0°C.

When 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 solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction. After this, the polymerization solution was poured into a household mixer containing about three times the amount of acetone as the polymerization solution while rotating the mixer.
The resulting copolymer was precipitated. The precipitated copolymer was collected by filtration, dispersed in acetone to a polymer concentration of about 50 t/Jl, and 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 in the copolymer measured by 13C-NMR analysis of the ethylene/DMON random copolymer (A) obtained as described above was 67 mol%, and the intrinsic viscosity measured in decalin at 135°C was [ η] was 0.60 dJ/, and the softening temperature (TMA) was 111°C.

Copolymer (A) obtained in Polymerization Example 1 and styrene-butadiene-styrene block copolymer (Cariflex TR1102 manufactured by Shell Chemical Co., Ltd., density 0.94 g/ff1)
) and (B) in a weight ratio of 80/10, and tetrakis[methylene-3(
3,5-di-tert-butyl-4-hydroxyphenyl)propionate comethane and di-lauryl-thio-di-
Propionate was blended at 0.5% and 0.3%, respectively, based on the total amount of resins (A) and (B), and after kneading at 220°C using a 30 m + φ twin screw extruder, GF was added to the total amount of resins A and B. Tri-blend 10% by weight with respect to 30IflIφ2
After kneading at 220°C using a screw extruder, compression molding was carried out at 240°C to obtain pressed sheets of 1 inch and 2 fi thickness. A test piece was cut out from this sheet and subjected to an impact test, a bending test, and an 'I'MA measurement.

The notched Izo impact strength of this composition is 8kgcx
r/C16, initial bending modulus is 31000kg/c
d, TMA was 115°C. Rigidity, heat resistance, 1FN
A composition that collapsed under 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 with a thickness of 1- and 2 m. A test piece was cut out from this sheet and subjected to an impact test, a bending test, and a T
MA measurement was performed.

The notched Izo impact strength of this test piece is 2kg c
sa/aa, initial bending modulus is 28900kg/
cd and TMA were 111°C, and compared to the blend obtained in Example 1, the blend was inferior in impact strength, initial bending modulus, and heat resistance.

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

Copolymers (A), (B) and filler (C
) were blended at the blend ratio shown in Table 5, and the same evaluation as in Example 1 was performed. The results are shown in Table 5, stiffness, heat resistance,! A composition with excellent I impact strength was obtained.

The same evaluation as in Comparative Example 1 was conducted using the copolymer (A) shown in Table 5. The results are summarized in Table 5. Compared to the compositions obtained in Examples 4 to 6, the compositions were inferior in rigidity, heat resistance, and impact strength.

Claims (2)

[Claims] (1) (A) Consists of an ethylene component and a cyclic olefin component represented by the following general formula [I] or [II],
The intrinsic viscosity [η] measured in decalin at 135°C is 0.
The softening temperature (TMA) is in the range of 05 to 10 dl/g.
is formed from a cyclic olefin random copolymer having a temperature of 70° C. or higher, (B) an aromatic vinyl hydrocarbon/conjugated diene copolymer or a hydride thereof, and (C) an inorganic filler or an organic filler, For 100 parts by weight of component (A) above,
Component (B) is 1 to 100 parts by weight, component (C) is 1 to 10 parts by weight.
Cyclic olefin random copolymer composition characterized by being present in an amount of 0 parts by weight: General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...[I] ▲ Numerical formulas, chemical formulas, tables, etc. ▼...[II] (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^1^0
each represents a hydrogen atom, a halogen atom, or a hydrocarbon group). (2) The aromatic vinyl hydrocarbon/conjugated diene copolymer or its hydride is styrene/butadiene copolymer rubber, styrene/butadiene/styrene block copolymer rubber, styrene/isoprene block copolymer rubber, styrene・Isoprene/styrene block copolymer rubber,
The composition according to claim 1, which is a hydrogenated styrene/butadiene/styrene block copolymer rubber or a hydrogenated styrene/isoprene/styrene block copolymer rubber.