JPH01163241A - Cyclic olefin random copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition outstanding in heat and impact resistances, dielectric properties, rigidity, etc., by blending a random copolymer from ethylene and specific cyclic olefin and a second random copolymer from ethylene, other olefin(s) and the cyclic olefin. CONSTITUTION:The objective composition can be obtained by blending (A) a random copolymer with an intrinsic viscosity [eta] determined in the form of decalin solution at 135 deg.C of 0.05-10dl/g and softening temperature of >=70 deg.C constituted of ethylene component and cyclic olefin component of formula I (R<1>-R<10> are each H, halogen or hydrocarbon; n is 0 or positive integer) or formula II (m is 0 or positive integer; l is positive number of >=3) and (B) a second random copolymer with an intrinsic viscosity determined in the form of decalin solution at 135 deg.C of 0.01-10dl/g and softening temperature of <70 deg.C, constituted of ethylene component, at least one kind of other alpha-olefin component and the cyclic olefin component of the formula I or II in such a proportion as to be 5-100 pts.wt. based on 100 pts.wt. of the component A, of the component B.

Description

[Detailed Description of the Invention] The present invention uses polycarbonate, ABS (acrylonitrile, Butadiene
Styrene block copolymer compositions) and the like are known.

For example, polycarbonate is a resin that has excellent heat resistance, heat aging resistance, and impact resistance as well as rigidity. However, polycarbonate has 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 of them have poor heat resistance, and furthermore, they are not completely crystalline and have poor rigidity. For this reason, 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 effective. cannot be said to be sufficient. In fact, 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 low production efficiency, and there is a risk that the impact strength will decrease as the amorphous portion decreases.

Regarding copolymers of ethylene and bulky comonomers, for example, U.S. Patent Publication No. 2,883°372 discloses a copolymer of ethylene and 2,3-dihydroxydicyclopentadiene. . Although this copolymer has an excellent balance of 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.

Furthermore, 1.4,
5.8-dimethano-1,2,3,4,4a,5,8.8
A homopolymer of a,-octahydronaphthalene has been proposed, but this polymer has poor heat resistance and heat aging resistance. Furthermore, in JP-A-58-127728@publication, 1, 4, 5
．． 8-dimethano-1,2,3,4,4a,5,8.8a
- A homopolymer of octahydronaphthalene or a copolymer of the cyclic olefin and a norbornene type comonomer has been proposed, but it is clear from the description in the above publication that both of these polymers are ring-opening polymers. It is.

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.

Furthermore, the present applicant has previously discovered that a cyclic olefin-based random copolymer consisting of ethylene and a specific noble cyclic olefin has heat resistance, heat aging resistance, chemical resistance,
It was discovered that it is a synthetic resin with solvent resistance, dielectric properties, and rigidity, and was published in Japanese Patent Application Laid-Open No. 60-16S Yoa, Japanese Patent Application No. 59-220550, Japanese Patent Application No. 59-236828, and Japanese Patent Application No. 1983. -236829, patent application 1984-2423
I made a proposal for issue 36, etc. Although these cyclic olefin random copolymers are olefin polymers, they are resins with excellent heat resistance and rigidity, but they are brittle and have poor impact resistance.

The present inventors have discovered that the above-mentioned cyclic olefin random copolymers have improved impact resistance without impairing their excellent properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, and dielectric properties. As a result of intensive studies to improve the properties, it was found that a composition consisting of a cyclic olefin random copolymer having a specific softening temperature (TMA) and a specific α-olefin elastic copolymer has the above-mentioned excellent properties. This discovery led to the completion of the present invention.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and has excellent heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, etc. ,
The object of the present invention is to provide a cyclic olefin random copolymer composition with 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 component represented by E, 135
Intrinsic viscosity [η] measured in decalin at °C is 0.05~
It is in the range of 10 dU/y, and the softening temperature (TMA>70
℃ or higher, and (B) an ethylene component, at least one other kind of α-olefin component, and a cyclic olefin component represented by the following general formula [I] or [n], and the temperature is 135°C. The intrinsic viscosity [η] measured in decalin is 0.01 to 10 d,!
1/g and a softening temperature (TMA) of less than 70°C,
It is characterized in that component B) is present in an amount of 5 to 100 parts by weight.

(In the formula, n and m are both O or a positive integer, g 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-mentioned (A) component and (B) component, and the (B) component is 5 to 1 parts by weight based on 100 parts by weight of the above-mentioned (8) component.
Since it is present in an amount of 0.00 parts by weight, it has excellent heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, etc., as well as excellent 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 [n]
It consists of a cyclic olefin component represented by
The intrinsic viscosity [η] measured in decalin is 0.05 to 1.
It is in the range of 0d, Q/y, and the softening temperature (TMA) is 70
℃ or higher, and (B) consists of an ethylene component, at least one other kind of α-olefin component, and a cyclic olefin component represented by the following general formula [I] or [IIE; The intrinsic viscosity [η] measured in decalin is 0.01 to 10 d,
A cyclic olefin random copolymer having a softening temperature (TMA> of less than 70°C), which is in the range of Il/g and has a softening temperature (TMA> of less than 70°C),
It is characterized in that component B) is present in m of 5 to 100 parts by weight.

(In the formula, n and m are both O or a positive integer, g 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 copolymers [A] and [8] constituting the cyclic olefin random copolymer composition according to the present invention are both cyclic olefin random copolymers composed of an ethylene component and a specific cyclic olefin component. Covered with copolymer.

The cyclic olefin component is a cyclic olefin component represented by the following general formula [E] or general formula [■], and in the cyclic olefin random copolymer of the present invention,
The cyclic olefin component forms a structure represented by general formula [I[1] or general formula [IV].

(In the formula, n and m are both O or a positive integer, 9 is an integer of 3 or more, and R1 to R10 each represent a hydrogen atom, a halogen atom, or a hydrocarbon group)
.

(In the formula, n, m, M and R to Rlo are the same as above.) The cyclic olefin as a component of the cyclic olefin random copolymer constituting the cyclic olefin random copolymer composition according to the present invention is , general formula [I] and general formula [I
At least one cyclic olefin selected from the group consisting of unsaturated monomers represented by I]. - The cyclic olefin represented by [E] in the old formula can be easily produced by condensing cyclopentadiene and the corresponding olefin in a Diels-Alder reaction. Similarly, the cyclic olefin represented by the general formula [n] can be easily produced by condensing a cyclopentadiene and a corresponding cyclic olefin by a Diels-Alder reaction.

Specifically, the cyclic olefin represented by the general formula [I] includes 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
, 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
,4,4a, 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,da, 5,8.8a - Octahydronaphthalenes such as 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,da, 5.8.8a-octahydronaphthalene, and those listed in Table 2 Examples of such compounds include:

Further, specific examples of the cyclic olefin represented by the general formula [n] 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 necessarily contains an ethylene component and the cyclic olefin component as essential components, as described above, but In addition to these two essential components, other copolymerizable unsaturated monomer components may be contained as necessary within a range that does not impair the object of the present invention. Specifically, the unsaturated monomer which may be optionally copolymerized 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 from 40 to 85 mol? 6, preferably 50-75 monoυ%
The repeating unit (b) derived from the cyclic olefin is present in an amount of 15-60 mol%, preferably 25-50 mol%, and the repeating unit (b) derived from the ethylene component is present in an amount of 15-60 mol%, preferably 25-50 mol%. The repeats a) and b) derived from the cyclic olefin component are arranged randomly and substantially linearly. The fact that this cyclic olefin 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. .

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

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. Further, 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 2'10°C.

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

The cyclic olefin random copolymer [B] constituting the cyclic olefin random copolymer composition according to the present invention has an ethylene component and the cyclic olefin component as essential components. In addition, at least one unsaturated monomer component that can be copolymerized is essential. Specifically, the at least one unsaturated monomer includes, for example, propylene in an amount less than equimolar to the ethylene component unit in the random copolymer to be produced;
-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 [B] constituting the cyclic olefin random copolymer composition according to the present invention, the repeating unit (a) derived from the ethylene component is 4
The repeating unit (b) derived from the cyclic olefin is present in an amount of 0 to 99 mol%, preferably 75 to 98 mol%, and 1 to 40 mol%, preferably 1 to 15 mol%.
The repeating unit (C) derived from at least one α-olefin component other than the ethylene component is present in an amount of 1 to 45 mol%, preferably 1 to 35 Tnyl%, A repeating unit (a) derived from an ethylene component, a repeating unit (b) derived from the cyclic olefin component, and at least one other than the ethylene component
Repeating unit (C) derived from the α-olefin component of the species
are randomly arranged substantially in a line. This cyclic olefin random copolymer [B] is substantially linear,
The copolymer does not have a gel-like crosslinked structure.
This can be confirmed by complete dissolution in decalin at 35°C.

The intrinsic viscosity [η] of such a cyclic olefin random copolymer [B] measured in decalin at 135°C is 0.
．． 01-5dβ/g, preferably 0.08-314! /
It is in the range of y.

In addition, the softening temperature of the cyclic olefin random copolymer [B] measured with a thermal mechanical analyzer is:
The temperature is less than 70°C, preferably -40 to 60°C, more preferably in the range of -30 to 30°C. Further, the softening temperature of the cyclic olefin random copolymer [B] is 3° higher than the softening temperature of the cyclic olefin random copolymer [A].
It is suitable that the temperature is 0 to 250°C, preferably 50 to 250°C, and preferably 10 to 100 to 240°C lower.

Further, the glass transition temperature (T!; ) of the cyclic olefin random copolymer [B] is in the range of -60 to 40°C, preferably -50 to 10°C. The glass transition humidity of this cyclic olefin random copolymer [8] is 30 to 250°C higher than the glass transition temperature of the cyclic olefin random copolymer [A].

Preferably, it is necessary that the temperature is lower by 100 to 240°C.

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

In the cyclic olefin random copolymer composition according to the present invention, the cyclic olefin random copolymer [A] 100
fii part, the cyclic olefin random copolymer [B] is 5 to 100@ff1 part, preferably 7 to 80 part
1 part by weight, particularly preferably 10 to 70 parts by weight. The cyclic olefin random copolymer [A]
If the amount of the cyclic olefin random copolymer [B] is less than 5 parts per 100 parts by weight, the rigidity is excellent, but the impact resistance is poor, so it is not preferable, whereas if it exceeds 100 parts by weight, Although it has excellent impact resistance,
It is unfavorable because its rigidity is low and the balance between rigidity and impact strength is poor.

Figure 1 shows the blending amount of the cyclic olefin random copolymer [8] in the cyclic olefin random copolymer composition according to the present invention and the impact strength (17 strength) of the composition.
Indicates the relationship between

From this Figure 1, it can be seen that the cyclic olefin random copolymer [
It can be seen that when the cyclic olefin random copolymer [B] is blended with A], the impact resistance of the resulting cyclic olefin random copolymer composition is significantly improved.

Further, FIG. 2 shows a blended layer of the cyclic olefin random copolymer [8] in the cyclic olefin random copolymer composition according to the present invention, and the softening temperature II (TMA) of the composition.
＞Indicates the relationship with

From this Figure 2, it can be seen that the cyclic olefin random copolymer [
A], 3 cyclic olefin random copolymer [B]
Surprisingly, it can be seen that the softening temperature (TMA>) of the cyclic olefin random copolymer composition does not decrease at all even when it is blended up to about 0ffl%.

Cyclic olefin random copolymer [△] as above
When the cyclic olefin random copolymer [B] is added to m to about 30% by weight, the impact resistance of the cyclic olefin random copolymer composition is significantly improved, and the heat resistance is not reduced.

The cyclic olefin random copolymers [A] and [B] constituting the cyclic olefin random copolymer composition according to the present invention are both disclosed in JP-A-60-168708 and JP-A-61-120816. Publication, JP-A-61-1
No. 15912, Japanese Patent Application Laid-open No. 115916/1983,
Japanese Patent Application No. 61-95905, Japanese Patent Application No. 61-95906, Japanese Patent Application Publication No. 61-271308, Japanese Patent Application No. 61-27
It can be produced by appropriately selecting conditions according to the method proposed by the present applicant in Publication No. 2216 and the like.

As a 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 cyclic olefin random copolymer [8] are separately produced. and [A] and [B]
[A] and [B] are mixed in an appropriate solvent such as heptane, hexane,
A solution blending method is carried out by sufficiently dissolving saturated hydrocarbons such as decane and cyclohexane, and aromatic hydrocarbons such as toluene, benzene, and xylene. A method of kneading with a machine etc. 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:
0.05-10d, f)/li, preferably 0.08-5
dβ/3, and the softening temperature (TM△) measured by a thermal mechanical analyzer is 80 to 2.
50°C, preferably in the range of 100 to 200°C.

The cyclic olefin random copolymer composition according to the present invention contains the cyclic olefin random copolymer [A] and the cyclic olefin random copolymer [B] as essential components. Heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. can be blended into the product, and the blending ratios are appropriate. It's the amount. 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
, phenolic antioxidants such as 2-oxamidobis[ethyl-3(3,5-di-butyl-4-biloxyphenyl)propionate, fatty acid metal salts such as zinc stearate, calcium stearate, calcium 12-hydroxystearate, Examples include polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination, for example, Tetrakis [
Examples include a combination of methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propione-1-]methane, zinc stearate, and glycerin monostearate.

Effects of the Invention The cyclic olefin random copolymer composition according to the present invention comprises the above-mentioned cyclic olefin random copolymer [
A] and a cyclic olefin random copolymer [B], and since the copolymer [B] is present in an amount of 5 to 100 parts by weight relative to 1100 parts by weight of the copolymer [A1], it has a high heat resistance. It has excellent properties such as hardness, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity, as well as excellent impact resistance.

EXAMPLES Next, the present invention will be specifically explained by 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 (TM△): HMA manufactured by Seiko Electronics
10(Ding hermo mechanical anal
yser) to measure the thermal deformation behavior of a 1 m thick sheet.

That is, a quartz needle was placed on the sheet, a load of 50 J was applied, and the temperature was raised at 5°C/min until the needle reached 0. The temperature at which one shoe penetrated was defined as TMA.

(2) Impact strength: A cocoon with a length of 63.8 mm and a width of 1 mm was measured using an Izotsu impact tester manufactured by Toyo Seiki Co., Ltd. from a press sheet with a thickness of 2.
A 2.7 M sample was punched, a 0.25 mR notch was inserted, and measurements were performed at 23°C.

(3) Rigidity modulus (flexural modulus): Using an Instron tensile testing machine, a sample with a length of 63.8M and a width of 12.7mm was handled from a 2m thick press sheet at a compression speed of 5m/mi.
The measurement was performed at 23° C. with a distance between supports of 32 #.

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

Polymerization Example 1 (Synthesis of copolymer (A) with a softening temperature of 70°C or higher) Using a 2β 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, the DMON concentration in the polymerization vessel was 60y/, and VO(OC2H5)CI2 was used as a Q catalyst.
A cyclohexane solution with a vanadium concentration of 0.9 mmol/ρ in the polymerization vessel, a cyclohexane solution of ethylaluminum sesquichloride (AI (02H5) 1.5 CI 1.5>) with an aluminum concentration in the polymerization vessel of 7.2 mmol/ρ is continuously supplied into the polymerization vessel, and on the other hand, the polymerization liquid in the polymerization vessel is continuously pumped out from the bottom of the polymerization vessel so that the amount of polymerization liquid in the polymerization vessel is 1tj. From the top of the vessel, 85 g of ethylene per hour, 6 g of hydrogen per hour,
Nitrogen is fed at a rate of 45 g/hour. The copolymerization reaction was carried out at 10° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization.

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 drained from the bottom of the polymerization vessel to stop the polymerization reaction. After this, the polymerization solution was poured into a household mixer containing about 3 times as much acetone as the polymerization solution, while rotating the mixer.
The resulting copolymer was precipitated. The precipitated copolymer was collected by filtration, dispersed in acetone so that the polymer concentration was about 50 s/Q, and treated at the boiling point of acetone for about 2 hours. The copolymer was collected by the above treatment and filtration, and dried under reduced pressure at 120° C. all day and night.

The ethylene composition in the copolymer measured by 130-NMR analysis of the ethylene/DMON random copolymer (A) obtained as described above was 59 mol%, and the intrinsic viscosity measured in decalin at 135°C was [ η] is 0.42dρ/7,
The softening temperature (TMA') was 154°C.

Polymerization Examples 2 and 3 (Synthesis of copolymer (A) having [η] different from that in Polymerization Example 1) In Polymerization Examples 2 and 3, DMON in Polymerization Example 1, ■0
Polymerization was carried out continuously in the same manner except that the concentrations of (OC2H5)C12 and ethylaluminum sesquichloride in the polymerization vessel and the suction amounts of ethylene, hydrogen, and nitrogen were set to the conditions shown in Table 5.

After completing the procedure, precipitate the produced copolymer 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. 130-N of the nyletin-DMON copolymer (8) obtained in Polymerization Examples 2A3 and 3 as described above.
The ethylene composition in the copolymer measured by MR analysis was 58 mol% and 67 mol%, respectively, and the intrinsic viscosity [η] measured in decalin at 135°C was 0.94617 g and 0.60, respectively.
dρ/g and softening temperature (TMA) are 170°C and 11, respectively.
It was necessary at 1℃.

Ta.

Polymerization Example 4 (Synthesis of copolymer (B) with a softening temperature of less than 70°C) In Polymerization Example 1, the concentrations of DMON, VO(OC2H5)C12, and ethylaluminum sesquichloride in the polymerization vessel were 15y, Q, and 0.5, respectively. 4 mmol/g and 4 mmol/g, and ethylene was supplied from the top of the polymerization vessel at a rate of 45 mmol/g/hour. f! , propylene 159
Polymerization was carried out continuously in the same manner except that 0.2 U/hour of hydrogen and 251 U/hour of nitrogen were supplied and the polymerization temperature was 10°C. After the polymerization was completed, the produced copolymer was precipitated in the same manner as in Polymerization Example 1, and the precipitated copolymer was taken and dried at 120° C. under reduced pressure for 12 hours.

Ethylene/propylene/DM obtained as above
The ethylene composition in the copolymer measured by 130-NMR analysis of ON copolymer (I3) was 76 mol%, the propylene composition was 17 mol%, and the intrinsic viscosity [η] measured in decalin at 135°C was , 0.89 dl/7, softening temperature (H
MA) was -10°C.

Polymerization Example 5.6 (Synthesis of copolymer (I3) having [η] different from that in Polymerization Example 4) In Polymerization Examples 5 and 6, DMON in Polymerization Example 4, ■0
Polymerization was carried out continuously in the same manner except that the concentrations of (OC2H5)C12 and ethylaluminum sesquichloride in the polymerization vessel and the suction of ethylene, propylene, hydrogen, and nitrogen were set to the conditions shown in Table 6. After the polymerization was completed, the produced copolymer was precipitated in the same manner as in Polymerization Example 1, and the precipitated copolymer was taken and dried at 120° C. under reduced pressure for 12 hours.

13C-N of the nyletine-propylene-DMON copolymer (B) obtained in Polymerization Examples 5 and 6 as described above.
The ethylene composition in the copolymer measured by MR analysis was 69 mol% and 76 mol%, the propylene composition was 21 mol% and 16 mol%, and the intrinsic viscosity [η] measured in decalin at 135°C was 1. .44 (IQ/!9.0.98 dU
zl and softening temperature (HMA) were measured at -4°C and 1-8°C, respectively.

Example 1 Copolymer (A) obtained in Polymerization Example 3 and 1 in Polymerization Example 5
The elevated copolymer (B) was 85y and 159 (weight ratio <A)/CB) = 85/15) was cyclohexane 2
g, and was dissolved at about 70° C. with thorough stirring.

The obtained homogeneous solution was poured into 2 g of acetone, and (A)/(
B) The blend was precipitated. The resulting blend was dried at 120° C. under reduced pressure for a day and a night.

Tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane] was added to the (A)/(B) blend as a stabilizer and resin (8), (B) 0.5% based on the total amount and kneaded at 190°C using the graph from Alavender Plus 1.
Compression molding was performed at 240°C to obtain a 2# thick press sheet. A test piece was punched out from the center of this sheet and subjected to impact strength, bending test, and TMA measurement.

The Izod impact strength of this blend is 40, OK
gcm/cm, flexural modulus is 2210 Of(g/c
ri, bending yield point stress is 830 K3/cri, TM
A was 108°C. A blend with excellent rigidity, heat resistance, and impact strength was obtained.

Comparative Example 1 The same measurements as in Example 1 were carried out using a press sheet with a thickness of 2M obtained by compression molding the copolymer (^) synthesized in Polymerization Example 3 at 240''C.

IZ impact strength is 2, OKycm/cm, bending modulus is 289003/ci, bending yield point stress is 870Kg
/cm, HMA was 110°C, and although the sample had excellent rigidity and heat resistance, it had low impact resistance and was brittle.

Examples 2 to 4 Copolymers (A) obtained in Polymerization Examples 1 and 3 and Polymerization Example 4
, 5 was evaluated in the same manner as in Example 1 using the polymerization ratios shown in Table 7. The results are shown in Table 7.

Comparative Examples 2 to 3 Evaluations were conducted in the same manner as in Comparative Example 1 using the copolymers (A) synthesized in Polymerization Examples 1 and 2. The results are shown in Table 7.

The sample had excellent rigidity and heat resistance, but had low impact resistance and was brittle.

Example 5 The copolymer (A) synthesized in Polymerization Example 2 and the copolymer (B) synthesized in Polymerization Example 6 were heated to 80 Ij and 20 V (weight ratio (A)/(B) = 80/20), respectively. 1 to Rakis medilene-3 (3,5-di-t-butyl-4-1 nitroxyphenyl) propionate using comethane as a stabilizer and 0.5 to the total set of resins (A) and (B). % and kneaded at 190° C. using a Brabender Plastograph, and then evaluated in the same manner as in Example 1.

The results are shown in Table 7. A composition with excellent rigidity, heat resistance, and impact resistance was obtained.

Examples 6-7 Copolymer (A) a3 synthesized in Polymerization Example 2 and Polymerization Example 6
The copolymer (B) synthesized in Example 5 was evaluated in the same manner as in Example 5 using the weight ratios shown in Table 7.

The results are shown in Table 7.

Examples 8 to 15 Evaluation was conducted in the same manner as in Example 5 using copolymer (8) synthesized in the same manner as in Polymerization Example 1 and copolymer (B) synthesized in the same manner as in Polymerization Example 4. I did it. The results are shown in Table 8. A composition with excellent rigidity, heat resistance, and impact strength was obtained.

Copolymer (A) synthesized in the same manner as in Polymerization Example 1 was evaluated in the same manner as in Comparative Example 1. The results are shown in Table 9. Although the sample had excellent rigidity and heat resistance, it had low impact resistance and was brittle.

[Brief explanation of the drawing]

Figure 1 shows the blending amount of the cyclic olefin random copolymer [B] in the cyclic olefin random copolymer composition according to the present invention and the impact strength (I2 strength) of the composition.
FIG. 2 shows the blending amount of the cyclic olefin random copolymer [B] in the cyclic olefin random copolymer composition according to the present invention and the softening temperature ( , HMA). Symbols in the figure are Examples 1 to 3, Comparative Example 1 (○) Example 4, Comparative Example 2 (・) Examples 5 to 7, Comparative Example 3 (b) Examples 8 to 9, Comparative Example 4 (■) Examples 10-11, Comparative Example 5 (△) Examples 12-13 (M) Examples 14-1
5, Comparative Example 6 (). Agent Patent Attorney Shunichi Meki 1st Figure CB) Ingredients (% by weight) Figure 2 CBI Ingredients (96% by weight) Procedural Amendment December 5, 1988 1, Indication of Case 1988 Patent Application No. 322,609 2, Name of the invention Cyclic olefin random copolymer composition 4, Agent
Person (Postal code 141) 3rd floor, Araku Building, 2-19-2 Nishigotanda, Tokyo Parts Ward [Telephone: Tokyo (491) 3161] 6. Column 7 of "Detailed description of the invention" in the specification to be amended. Contents of amendment (1) Table 6 on page 42 of the specification and Table 8 on page 51 of the specification (
(Continued) shall be corrected as shown in the attached sheet. Table 6

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.
a cyclic olefin-based random copolymer whose temperature is 70°C or higher, and (B) an ethylene component, at least one other α-olefin 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 0.01 to 10 dl.
/g, and a cyclic olefin random copolymer having a softening temperature (TMA) of less than 70°C.
A cyclic olefin random copolymer composition characterized in that component B) is present in an amount of 5 to 100 parts by weight. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [II] (In the formula, n and m are both 0 or a positive integer, and l is An integer greater than or equal to 3, R^1 to R^1^0
each represents a hydrogen atom, a halogen atom, or a hydrocarbon group). (2) Ethylene-α-olefin-the following general formula [I]
Or the cyclic olefin random copolymer represented by [II] is an ethylene-propylene-cyclic olefin random copolymer represented by the following general formula [I] or [II], or ethylene-butene-the following general formula [I]. The composition according to claim 1, which is a cyclic olefin random copolymer represented by ] or [II]. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [II] (In the formula, n and m are both 0 or a positive integer, and l is An integer greater than or equal to 3, R^1 to R^1^0
each represents a hydrogen atom, a halogen atom, or a hydrocarbon group).