KR910008771B1 - Random cycloolefin copolymer composition - Google Patents

Abstract

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Description

[Name of invention]

Cyclic Olefin Random Copolymer Composition

[Brief Description of Drawings]

1 is a diagram showing the relationship between the blending amount of the cyclic olefin random copolymer (B) (iii) in the cyclic olefin random copolymer composition according to the present invention and the impact resistance (IZ strength) of the composition.

2 is a diagram showing the relationship between the blending amount of the cyclic olefinic random copolymer (B) (iii) and the softening temperature (TMA) of the composition in the cyclic olefin random copolymer composition according to the present invention.

3 is a diagram showing the relationship between the blending amount of the α-olefin random copolymer (B) (ii) in the cyclic olefin random copolymer composition according to the present invention and the impact resistance (IZ strength) of the composition.

4 is a diagram showing the relationship between the blending amount of the α-olefin random copolymer (B) (ii) and the softening temperature (TMA) of the composition in the cyclic olefin random copolymer composition according to the present invention.

5 is a graph showing the relationship between the blending amount of α-olefin and diene random copolymer (B) (i) in the cyclic olefin random copolymer composition according to the present invention and the impact resistance (IZ strength) of the composition. .

FIG. 6 is a diagram showing the relationship between the blending amount of α-olefin and diene random copolymer (B) (iii) and the softening temperature (TMA) of the composition in the cyclic olefin random copolymer composition according to the present invention.

7 shows the relationship between the compounding amount of the aromatic vinyl hydrocarbon, conjugated diene copolymer or its hydride (B) in the cyclic olefin random copolymer composition according to the present invention and the impact strength (IZ impact strength) of the composition. Drawing.

8 is a diagram showing the relationship between the blending amount of an aromatic vinyl hydrocarbon, conjugated diene copolymer or its hydride (B) in the cyclic olefin random copolymer composition according to the present invention and the softening temperature (TMA) of the composition. .

FIG. 9 is a graph showing the relationship between the total amount of two or more types of soft copolymers (B) in the cyclic olefin random copolymer composition according to the present invention and the impact resistance (IZ strength) of the composition.

10 is a diagram showing the relationship between the blending amount of the soft copolymer (B) and the softening temperature (TMA) of the composition in the cyclic olefin random copolymer composition according to the present invention.

Detailed description of the invention

[Technical Field]

The present invention relates to a converted olefin polymer composition having excellent heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, rigidity and excellent impact resistance.

[Background]

As a synthetic resin having excellent balance of rigidity and impact strength, polycarbonate, ABS (acrylonitrile-butadiene-styrene composition) and the like are known.

For example, polycarbonate is a resin having excellent heat resistance, heat aging resistance, and impact resistance.

However, there is a problem that strong alkali is easily eroded, so that the chemical resistance falls and the absorption rate is large.

In addition, ABS has excellent mechanical properties, but has poor chemical resistance, and includes a double bond in the system, which results in poor weather resistance and poor heat resistance.

On the other hand, polyolefins widely used as general-purpose resins are excellent in chemical resistance and solvent resistance, but lack heat resistance, and cannot be said to be perfect in crystallinity, but also have low rigidity.

For this reason, in order to improve rigidity and heat resistance with polyolefin generally, the method of adding a nucleating agent to accelerate crystal growth or slow cooling to promote crystal growth is used, but the effect is hardly said to be sufficient.

On the contrary, the addition of a third component such as a nucleating agent may damage the excellent properties of the polyolefin inherently, and the slow cooling method may not only produce poor production efficiency but also reduce the impact strength according to the decrease in non- government.

Copolymers of ethylene and sublimated cononomers are disclosed, for example, in US Pat. No. 2,883,372, which discloses copolymers of ethylene and 2,3-dihydroxy dicyclopentadiene.

This copolymer has a good balance between rigidity and transparency, but has a problem in that heat resistance is poor because the glass transition temperature is about 100 ° C.

In addition, a copolymer of ethylene and 5-ethylidene-2-norbornene has the same problem.

Also, Japanese Unexamined Patent Publication No. 46-14910 proposes homopolymers of 1, 4, 5, 8-dimethano-1, 2, 3, 4, 4a, 5, 8, and 8a-octahydronaphthalene. Is inferior in heat resistance and heat aging resistance, and Japanese Patent Application Laid-Open No. 58-127728 discloses 1, 4, 5, 8-dimethano-1, 2, 3, 4, 4a, 5, 8, and 8a-octahydronaphthalene alone. Polymers or copolymers of these cyclic olefins and norbornene-type comonomers have been proposed, but it is evident from the description of this publication that all of these polymers are ring-opening polymers.

Since the ring-opening polymer has an unsaturated bond in the polymer backbone, there is a problem in that heat resistance and heat aging resistance are poor.

In addition, the present applicant has already found that a random copolymer of ethylene and a sublime cyclic olefin having characteristics is a synthetic resin having heat resistance and heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity. The proposals were made in the number of the special elements 59-220550, the special number 59-236828, the special number 59-236829, the special number 59-242336, and the special number 61-95906.

Although these cyclic olefin random copolymers are resins excellent in heat resistance and rigidity, although they are an olefin copolymer, they have the problem that they are fragile and their impact resistance is inferior.

The present inventors have diligently studied to improve rigidity and impact resistance without impairing excellent properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, and dielectric properties of the cyclic olefin random copolymer as described above. The composition obtained by blending a cyclic olefin random copolymer having a softening temperature (TMA) with at least one or more soft copolymers, or an inorganic filler or an organic filler or a combination thereof, has the same characteristics as described above. Discovering the superiority to complete the present invention.

[Purpose of invention]

The present invention is to solve the problems according to the prior art as described above to provide a cyclic olefin-based random copolymer composition excellent in heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, etc. The purpose.

[Initiation of invention]

The first cyclic olefin random copolymer composition according to the present invention comprises (A) an ethylene component and a cyclic olefin component represented by the following general formula [I] or [II], and an intrinsic viscosity measured in decalin at 135 ° C. [ (eta)] is the range of 0.05-10 dl / g, and cyclic olefin random copolymer whose softening temperature (TMA) is less than 70 degreeC, (B) (i) at least 1 type of alpha olefin component different from an ethylene component, and the following general formula Cyclic olefin system which consists of cyclic olefin component represented by [I] or [II], the intrinsic viscosity [eta] measured in decalin at 135 degreeC is 0.01-10 dl / g, and softening temperature (TMA) is 70 degreeC or more. A random copolymer, (ii) an amorphous to low crystalline random copolymer of at least two α-olefins, and (iii) at least two α-olefins and at least one nonconjugated diene. α-olefins, diene elastomers, and (iii) aromatic vinyl hydrocarbons, copolymers Formed from one or two or more soft copolymers selected from the group consisting of an inverse diene copolymer or a hydride thereof, and the total amount of the component (B) is present in an amount of 5 to 100 parts by weight based on 100 parts by weight of the component (A). Characterized in that.

Moreover, the 2nd cyclic olefin random copolymer composition which concerns on this invention becomes the cyclic olefin component represented by (A) ethylene component and the following general time [I] or [II], and the intrinsic viscosity measured in 135 degreeC decalin a cyclic olefin random copolymer having a [η] in the range of 0.05 to 10 dl / g and a softening temperature (TMA) of 70 ° C. or higher, (B) (iii) at least one α-olefin component different from the ethylene component and the following general Cyclic olefin random having a cyclic olefin component represented by the formula [I] or [II] and having an intrinsic viscosity [η] of 0.01-10 dl / g and a softening temperature (TMA) of less than 70 ° C measured in decalin at 135 ° C. Copolymer, (ii) an amorphous to low crystalline α-olefin-based elastomeric copolymer formed of at least two α-olefins, and (iii) α formed of at least two α-olefins and at least one nonconjugated diene -Olefins, diene elastomers, and (iv) aromatic vinyl hydrocarbons, conjugated It is formed of one or two or more soft copolymers selected from the group consisting of an en copolymer or a hydride thereof, and (C) an inorganic filler or an organic filler, and the total amount of the component (B) is based on 100 parts by weight of the component (A). 1 to 100 parts by weight and (C) component are present in an amount of 1 to 100 parts by weight.

[General Formula]

(Wherein n and m are both o or positive integers, l is an integer of 3 or more and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group)

The first cyclic olefin random copolymer composition according to the present invention is formed of the component (A) and (B), and the component (B) is present in an amount of 5 to 100 parts by weight based on 100 parts by weight of the component (A). It is excellent in heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, and impact resistance.

The 2nd cyclic olefin random copolymer composition which concerns on this invention is formed from the said (A) component, (B) component, and (C) component, and the total amount of (B) component with respect to 100 weight part of said (A) component Since 1 to 100 parts by weight and (C) component are present in an amount of 1 to 100 parts by weight, they are excellent in heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, etc., and also excellent in rigidity and impact resistance.

[Detailed Description of the Invention]

Hereinafter, the cyclic olefin random copolymer composition according to the present invention will be described in detail.

According to this invention, it becomes (A) ethylene component and cyclic olefin component represented by the following general formula [I] or [II], and the intrinsic viscosity [eta] measured in decalin at 135 degreeC is the range of 0.05-10 dl / g. Cyclic olefin random copolymer having a softening temperature (TMA) of 70 ° C. or higher, and (B) (iii) at least one α-olefin component different from the ethylenic component and represented by the following general formula [I] or [II] At least two cyclic olefin random copolymers (ii) having an intrinsic viscosity [η] in the range of 0.01 to 10 dl / g and a softening temperature (TMA) of less than 70 ° C., measured in decalin at 135 ° C. amorphous to low crystalline α-olefin-based elastomeric copolymers formed of α-olefins, (iii) α-olefins, diene-based elastomeric copolymers formed of at least two α-olefins and at least one nonconjugated diene, and ( I) aromatic vinyl hydrocarbons, conjugated diene copolymers or hydrides thereof; Provided is a cyclic olefin random copolymer composition formed of one or two or more soft copolymers selected from the group, wherein the total amount of component (B) is present in an amount of 5 to 100 parts by weight based on 100 parts by weight of the component (A). do.

[General Formula]

(Wherein n and m are both o or positive integers, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group)

Cyclic olefin random copolymer constituting the cyclic olefin random copolymer composition according to the present invention

(A) and (B) (iii) are both cyclic olefin random copolymers composed of an ethylene component and a specific cyclic olefin component. This cyclic olefin component is a cyclic olefin component represented by the following general formula [I] or general formula [II], and in this cyclic olefin random copolymer of this invention, this cyclic olefin component is a general formula [III] or a general formula [ [IV] is formed.

[General Formula]

(Wherein n and m are both o or positive integers, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group)

[General Formula]

Wherein n, m, L and R ¹ to R ¹⁰ are the same as above.

The cyclic olefin which is a component of the cyclic olefin random copolymer as one component of the cyclic olefin random copolymer composition according to the present invention is a group consisting of unsaturated monomers represented by the general formulas [I] and [II] as described above. At least one cyclic olefin selected from.

The cyclic olefin represented by [I] in general formula can be manufactured easily by condensing cyclopentadiene and the olefins corresponding to it by a Diels-Alder reaction.

In addition, the cyclic olefin represented by general formula [II] can be manufactured easily by condensing cyclotentadiene and cyclic olefins corresponding to it by a D. Alder reaction.

Specifically as a cyclic olefin represented by general formula [I], the compound of Table 1 or 1, 4, 5, 8- dimethano-1,2,3,4,4a, 5,8,8a-octa 2-methyl-1,2,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8 in addition to hydronaphthalene 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, 5,8,8, a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene , 2-furoto-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, 5,8,8 a-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, Octahydronaphthalenes, such as 2,3,4,4a, 5,8,8a-octahydronaphthalene, and the compound of Table 2 can be illustrated.

TABLE 1

TABLE 2

Moreover, the cyclic olefin represented by general formula [II] can specifically mention the compound etc. which were shown in Table 3 and Table 4, for example.

TABLE 3

Although the cyclic olefin random copolymer (A) as one component of the cyclic olefin random copolymer composition according to the present invention contains an ethylene component and the cyclic olefin component as essential components as described above, in addition to the essential two components, You may contain the other copolymerizable unsaturated monomer component as needed in the range which does not impair the objective.

Unsaturated monomers which may be optionally copolymerized specifically include, for example, poropylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene in the range of less than equimolar to the ethylene component unit in the resulting random copolymer. And α-olefins having 3 to 20 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In such a cyclic olefin random copolymer (A), the repeating unit (a) derived from an ethylene component exists in 40 to 85 mol%, Preferably it is 50 to 75 mol%, and is derived from this cyclic olefin The repeating unit (b) is present in the range of 15 to 60 mol%, preferably 25 to 50 mol%, and the repeating unit (a) derived from the ethylene component and the repeating unit (b) derived from this cyclic olefin component are substantially It is arranged on the line.

It can be confirmed that this cyclic olefin random copolymer (A) is substantially linear and does not have a gel crosslinked structure by dissolving this copolymer completely in 135 degreeC decalin.

Intrinsic viscosity [η] measured in 135 degreeC decalin of such cyclic olefin random copolymer (A) is 0.05-10 dl / g, Preferably it is the range of 0.08-5 dl / g.

Moreover, the swallowing temperature (TMA) measured by the thermal mechanical analyzer of the cyclic olefin random copolymer (A) is 70 degreeC or more, Preferably it is 90-250 degreeC, More preferably, it is the range of 100-200 degreeC.

Moreover, the glass transition temperature (Tg) of this cyclic olefin random copolymer (A) is 50-230 degreeC normally, Preferably it is the range of 70-210 degreeC.

Moreover, the crystallinity degree measured by the X-ray diffraction method of this cyclic olefin random copolymer (A) is 0 to 10%, Preferably it is 0 to 7%, Especially preferably, it is the range of 0 to 5%.

Although the cyclic olefin random copolymer (B) (VII) as one component of the cyclic olefin random copolymer composition which concerns on this invention has an ethylene component and the said cyclic olefin component as an essential component, at least 1 type other than this essential two component The other copolymerizable unsaturated monomer component mentioned above is an essential component.

At least one of these unsaturated monomers is specifically propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, for example, in the range less than equimolar with the ethylene component units in the resulting random copolymer, Α-olefins having 3 to 20 carbon atoms, such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene, may be exemplified.

In such a cyclic olefin random copolymer (B) (iii), the repeating unit (a) derived from an ethylene component exists in 40-99 mol%, Preferably it is 75-98 mol%, and this cyclic olefin The repeating unit (b) derived from is present in the range of 1 to 40 mol%, preferably 1 to 15 mol%, and the repeating unit (c) derived from at least one α-olefin component other than the ethylene component is 1-45 mol%, Preferably it exists in the range of 1-35 mol%, The repeating unit (a) derived from an ethylene component, At least 1 type other than the repeating unit (b) derived from this cyclic olefin component, and an ethylene component The repeating units (c) derived from the α-olefin component of are randomly arranged in a substantially linear shape.

It is confirmed that this cyclic olefin random copolymer (B) (iii) is substantially linear and does not have a gel crosslinked structure by dissolving this copolymer completely in 135 degreeC decalin.

The α-olefin elastomer copolymer (B) (ii) as one component of the cyclic olefin random copolymer composition according to the present invention is an amorphous to low crystalline copolymer formed of at least two kinds of α-olefins. (Iii) ethylene. α-olefin copolymer rubber (ii) propylene. α-olefin copolymer rubber is used.

(Iii) ethylene. As an alpha olefin which comprises an alpha olefin copolymer rubber, it is a C3-C20 alpha olefin, for example, propylene. 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or mixtures thereof and the like can be exemplified.

Among these, propylene or 1-butene is particularly preferable.

And (ii) propylene. As the α-olefin constituting the α-olefin copolymer rubber, an α-olefin having 4 to 20 carbon atoms, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1 -Decene or mixtures thereof and the like can be exemplified.

Among these, 1-butene is particularly preferable.

Ethylene as above. In the α-olefin copolymer rubber, the molar ratio (ethylene / α-olefin) of ethylene and α-olefin varies depending on the type of α-olefin, but is generally 30 / 70-95 / 5, preferably 50 / 50-95 / It is preferable that it is five.

The molar ratio is preferably 80 / 20-95 / 5 when the α-olefin has 4 or more carbon atoms.

(Ii) propylene as above. In the α-olefin copolymer rubber, the molar ratio (propylene / α-olefin) of propylene and α-olefin varies depending on the type of α-olefin, but is generally preferably 50 / 50-95 / 5.

The molar ratio is preferably 50 / 50-95 / 10 when the α-olefin is 1-butene and 80 / 20-95 / 5 when the α-olefin has 5 or more carbon atoms.

Such α-olefin-based elastomeric copolymer (B) (ii) is desired to have a crystallinity of 0-5%, preferably 0-25%, as measured by the X-ray diffraction method.

The intrinsic viscosity [η] measured at 135 ° C and decalin of the α-olefin elastomeric copolymer (B) (ii) is preferably 0.2 dl / g, preferably 1-5 dl / g. do.

In addition, the density is desired to be 0.82-0.96 g / cm 3, preferably 0.84-0.92 g / cm 3.

In addition, the α-olefin elastomer copolymer (B) (ii) used in the present invention is a graft monomer selected from unsaturated carbonic acid or derivatives thereof, and is graft-modified to 0.01 to 5% by weight, preferably 0.1 to 4% by weight. A copolymer may be sufficient.

(엔도시스-비시클로[2,2,1]헵트-5-엔-2,3-디카본산)등의 불포화카본산 또는 그 유도체, 예를 들면 산할라이드, 아미드, 이미드, 무술물, 에스테르 등을 들을 수 있다.The unsaturated carbonic acid or derivative thereof used to modify the α-olefin-based elastomeric copolymer (B) (ii) in the present invention may be acrylic acid, maleic acid, pmaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid or crotonic acid. , Isocrotonic acid, nadic acid

Unsaturated carboxylic acids or derivatives thereof such as (endocys-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), for example, acid halides, amides, imides, martial arts, esters Etc. can be heard.

Specifically, maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like are used.

, 또는 이들의 산무수물이 바람직하다.In these, unsaturated dicarboxylic acid or its acid anhydride is preferable, and maleic acid and nadic acid are especially preferable.

Or acid anhydrides thereof are preferable.

Graft copolymerization of a graft monomer selected from such an unsaturated carboxylic acid or a derivative thereof into an α-olefin-based elastomeric copolymer (B) (ii) to produce a modified α-olefin-based elastomeric copolymer is known in various ways. Can be adopted.

For example, there is a method of melting the α-olefin-based elastomeric copolymer to add a graft monomer to graft polymerization, or a method of dissolving in a solvent to add a graft monomer to graft copolymerization.

In any case, in order to graft copolymerize the graft monomer efficiently, it is preferable to carry out the reaction in the presence of a radical initiator.

The graft reaction is usually carried out at a temperature of 60-350 ° C.

The ratio of radical initiator used is ethylene. It is the range of 0.001-1 weight part normally with respect to 100 weight part of alpha-olefin random copolymers.

As a radical initiator, organic peroxide, organic per ether, for example, benzoyl peroxide, dichloro benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (per Oxidebenzo edit) hexyne-3, 1,4-bis (t-butylperoxyisopropyl) benzene, lauroylperoxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-butyl Peroxide) hexyn-3, 2,5-dimethyl-2,5-di (t-butylperoxyisopropyl) hexane, t-butylperbenzoate, t-butylperphenyl acetate, t-butyl perisobutylate , Cumylphenpivaletart and t-butylperdiethyl acetate, and other azo compounds such as azobisisobutylonitrile, dimethylazoisobutyrate.

Among them, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (t- Dialkyl peroxides, such as butyl peroxy) hexane and 1, 4-bis (t-butyl peroxy isopropyl) benzene, are used preferably.

Among the α-olefin-based elastomeric copolymers (B) and (ii), unsaturated carboxylic acids of ethylene, propylene random copolymers or ethylene and α-olefin random copolymers having an ethylene content of 35-50 mol% and a crystallinity of 5% or less, or Copolymers graft-modified with graft monomers selected from the derivatives are preferred because they have the best effect of improving impact strength.

(Alpha) -olefin as one component of the cyclic olefin random copolymer composition which concerns on this invention. The diene elastic copolymer (B) (iii) is a copolymer of at least 2 types of alpha-olefins, and at least 1 type of nonconjugated diene. Specifically, (iii) ethylene. Alpha -olefin.diene copolymer rubber and (ii) propylene. Alpha -olefin.diene copolymer rubber are used.

(Iii) Ethylene. Α-olefin. As the α-olefin constituting the diene copolymer rubber, an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1 -Decene or mixtures thereof and the like can be exemplified.

Among these, propylene or 1-butene is particularly preferable.

And (ii) propylene. Alpha -olefin. As the α-olefin constituting the diene copolymer rubber, an α-olefin having 4 to 20 carbon atoms, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene Or mixtures thereof.

Among these, 1-butene is particularly preferable.

And (iii) ethylene. Alpha -olefin. Diene copolymer rubber or (ii) propylene. α-olefins. As diene components in the diene copolymer rubber, 1,4-hexadiene, 1,6-octaene, 2-methyl-1.5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1, 6- Chain nonconjugated dienes such as octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydrointene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene Cyclic nonconjugated dienes such as nene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene Den, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornidene.

Among these, 1,4-hexadiene and cyclic nonconjugated dienes, in particular dicyclopentadiene or 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 1,4-hexadiene and 1,4-octadiene are preferable.

In the above ethylene, α-olefin and diene copolymer rubber, the molar ratio (ethylene / α-olefin) between ethylene and α-olefin varies depending on the type of α-olefin, but is generally 50 / 50-95. It is preferable that it is / 5.

The molar ratio is preferably 50 / 50-90 / 10 when the α-olefin is propylene, and 80 / 20-95 / 5 when the α-olefin has 4 or more carbon atoms.

In addition, the content of the diene component in the polymer rubber is preferably 0.5-10 mol%, preferably 0.5-5 mol%.

In the above-mentioned (ii) propylene, alpha -olefin and diene copolymer rubber, the molar ratio (propylene / alpha -olefin) of propylene and alpha -olefin is different depending on the type of alpha -olefin, but is generally 50 / 50- 95/5 is preferable.

The molar ratio is preferably 50 / 50-90 / 10 when the α-olefin is 1-butene and 80 / 20-95 / 5 when the α-olefin has 5 or more carbon atoms.

Moreover, content of the diene component in this copolymer rubber is 0.5-10 mol%, Preferably it is desirable that it is 0.5-5 mol%.

Such α-olefin.diene-based elastomeric copolymer (B) (ii) is desired to have a crystallinity of 0-10%, preferably 0-5%, as measured by X-ray diffraction.

And α-olefins. It is desired that the intrinsic viscosity [η] measured in the diene-based elastomer (B) (ii) at 135 ° C. and decalin is 0.1-10 dl / g, preferably 1-5 dl / g.

In addition, the oxo value is preferably 1-30, preferably 5-25.

The density is preferably 0.82-1.00 g / cm 3 and preferably 0.85-0.90 g / cm 3.

Aromatic secret type hydrocarbon water as one component of the cyclic olefin random copolymer composition which concerns on this invention. Specifically as a conjugated diene copolymer or its hydride (B) (i), (a) Styrene. Butadiene copolymer rubber, (B) Styrene. Butadiene. Styrene copolymer rubber, (C) Styrene. Isoprene block copolymer rubber. (D) styrene.isoprene.styrene block copolymer rubber; (e) hydrogenated styrene.butadiene. Styrene block copolymer rubber, (bar) hydrogenated styrene, isoprene, styrene block copolymer rubber, and the like.

(A) In the styrene-butadiene copolymer rubber, the molar ratio (styrene / butadiene) between styrene and butadiene is generally preferably 0/100 / -60 / 40.

(B) For styrene, butadiene and styrene block copolymer rubber, the molar ratio of styrene and butadiene (styrene / butadiene) is preferably 0 / 100-60 / 40, and the degree of polymerization of each block is about 0-5000 in styrene and in butadiene It is preferable that it is about 10-20000.

(C) Styrene. In the isoprene block copolymer rubber, the molar ratio (styrene / isoprene) between styrene and isoprene is generally preferably 0 / 100-60 / 40.

(D) In the styrene, isoprene and styrene block copolymer rubber, the molar ratio (styrene / isoprene) between styrene and isoprene is preferably 0 / 100-60 / 40, and the degree of polymerization of each block is about 0-5000 in styrene and isoprene. In about 10-20000 is preferable.

(E) Hydrogenated styrene, butadiene and styrene block copolymer rubbers are copolymer rubbers partially hydrogenated of the remaining double bonds in the above styrene, butadiene and styrene block copolymer rubbers, and the weight ratio of styrene and rubber parts (styrene / rubber) Part) is preferably 0 / 100-50 / 50.

(F) Hydrogenated styrene, isoprene and styrene block copolymer rubber is a copolymer rubber obtained by partially hydrogenating the double bond remaining in the styrene, isoprene and styrene block copolymer as described above, and the weight ratio of styrene and rubber part (styrene / rubber part). ) Is preferably 0 / 100-50 / 50.

Such aromatic vinyl hydrocarbons. The weight average molecular weight MW measured by GPC (gel permeation chromatography. Solvent sodichlorobenzene, 140 degreeC) of a conjugated diene block copolymer is 500-2000000, It is desirable that it is 10000-1000000 preferably.

The density is preferably 0.80-1.10 g / cm 3 and preferably 0.88-0.96 g / cm 3.

In the present invention, the above-described soft copolymer (VII)-(VII) is used in one or two or more kinds thereof in a cyclic olefin random copolymer composition.

In the case of using such a soft copolymer in combination, the soft copolymer (i)-(i) can be used in any combination.

In the cyclic olefin random copolymer composition according to the present invention, the total amount of the soft copolymer (B) is 5-100 parts by weight, preferably 7-80 parts by weight, based on 100 parts by weight of the cyclic olefin random copolymer (A), Especially preferably, it is present in the amount of 10-70 weight part.

When the total amount of the soft copolymer (B) is less than 5 parts by weight based on 100 parts by weight of the cyclic olefin random copolymer (A), the rigidity is excellent, but the impact resistance is bad, and it is not preferable. However, it is not preferable because of the low rigidity and the poor balance between the stiffness and the impact strength.

In FIG. 1, the relationship between the compounding quantity of the cyclic olefin random copolymer (B) in the cyclic olefin random copolymer composition by this invention, and the impact resistance (IZ strength) of this composition was shown.

It can be seen that the impact resistance of the cyclic olefin random copolymer composition obtained by blending the cyclic olefin random copolymer (A) with the cyclic olefin random copolymer (B) in FIG. 1 is remarkably improved.

2, the relationship of the compounding quantity of the cyclic olefin random copolymer (B) in the cyclic olefin random copolymer composition by this invention, and the softening temperature (TMA) of this composition was shown.

In FIG. 2, even if the cyclic olefin random copolymer (A) is mixed with the cyclic olefin random copolymer (B) in an amount of about 30% by weight, the softening temperature (TMA) of the cyclic olefin random copolymer composition is surprisingly low. It can be seen that it does not lose.

As described above, when the cyclic olefin random copolymer (A) is mixed with the cyclic olefin random copolymer (B) in an amount of about 30% by weight, the impact resistance of the cyclic olefin random copolymer composition is remarkably improved and heat resistance is not lowered. Do not.

In FIG. 1 and FIG. 2, the symbol ○ is a value relating to Examples 1-3 and Comparative Example 1, the symbol is a value relating to Example 4 and Comparative Example 2, and the symbol is shown in Examples 5-7 and Comparative Example. A value relating to 3 is a value relating to Example 8-9 and Comparative Example 4, a Δ mark is a value related to Example 10-11 and Comparative Example 5, a ▲ mark is a value related to Example 12-13, ? Is a value relating to Example 14-15 and Comparative Example 6.

3 shows the relationship between the blending amount of the α-olefin elastomeric copolymer (B) in the cyclic olefin random copolymer composition according to the present invention and the impact resistance (IZ strength) of the composition.

In FIG. 3, when the α-olefin copolymer is blended with the cyclic olefin random copolymer (A), the impact resistance of the cyclic olefin random copolymer composition is remarkably improved.

4, the relationship between the compounding quantity of the (alpha) -olefin elastomeric copolymer (B) in the cyclic olefin random copolymer composition by this invention, and the softening temperature (TMA) of this composition was shown.

4, the softening temperature (TMA) of the cyclic olefin random copolymer composition is almost as high as the amount of the α-olefin elastomer copolymer (B) to the amount of about 40% by weight to the cyclic olefin random copolymer (A). It can be seen that it is not lowered.

As described above, when the α-olefin elastic copolymer (B) is added to the cyclic olefin random copolymer (A) in an amount of about 30% by weight, the impact resistance of the cyclic olefin random copolymer composition is significantly improved, but the heat resistance is not lowered. .

In FIG. 3 and FIG. 4, ○ mark is a value for Example 16-20 and Comparative Example 7, and □ mark is a value for Example 21-23 and Comparative Example 8, and ● mark is Example 24-25. And a value relating to Comparative Example 9, and a mark denotes a value relating to Examples 26-27 and Comparative Example 10, and a Δ mark denotes a value relating to Examples 28-29 and Comparative Example 11.

5 shows the relationship between the blending amount of the α-olefin-based diene-based elastomeric copolymer (B) and the impact resistance (IZ strength) of the composition in the cyclic olefin random copolymer composition according to the present invention.

In FIG. 5, it can be seen that the impact resistance of the cyclic olefin random copolymer composition obtained by blending the? -Olefin diene elastomer copolymer (B) with the cyclic olefin random copolymer (A) is remarkably improved.

6 shows the relationship between the amount of the α-olefin.diene-based elastic copolymer (B) in the cyclic olefin random copolymer composition according to the present invention and the softening temperature (TMA) of the composition.

6, the softening temperature (TMA) of the cyclic olefin random copolymer composition is surprisingly compounded to the cyclic olefin random copolymer (A) up to about 30% by weight of the α-olefin.diene-based elastomeric copolymer (B). It can be seen that is not lowered at all.

When the α-olefin.diene-based elastomeric copolymer (B) is added to an amount of about 30% by weight to the cyclic olefin random copolymer (A) as described above, the impact resistance of the cyclic olefin random copolymer composition is significantly improved, but the heat resistance Not lower.

In FIG. 5 and FIG. 6, ○ mark is a value for Example 35-41 and Comparative Example 13, and □ mark is a value for Example 42-44 and Comparative Example 14, and ● mark is Example 45-46 and A value relating to Comparative Example 15 is indicated by Example 47-48 and a value relating to Comparative Example 16, and a Δ mark is a value related to Example 49-50 and Comparative Example 17.

Fig. 7 shows the relationship between the aromatic vinyl hydrocarbon and the conjugated diene copolymer or its hydride (B) compounding amount in the cyclic olefin random copolymer composition according to the present invention and the impact resistance (IZ strength) of the composition. .

7 shows that the impact resistance of the cyclic olefin random copolymer composition obtained by blending the aromatic vinyl hydrocarbon.conjugated diene copolymer or its hydride (B) to the cyclic olefin random copolymer (A) is remarkably improved. have.

Moreover, the aromatic vinyl hydrocarbon in the cyclic olefin random copolymer composition which concerns on FIG. 8 in this invention. The relationship between the compounding quantity of a conjugated diene copolymer or its hydride (B), and the softening temperature (TMA) of this composition was shown.

The aromatic vinyl hydrocarbon to the cyclic olefin random copolymer (A) in FIG. Even if the conjugated diene copolymer or its hydride (B) is blended in an amount of about 30% by weight, it is surprisingly found that the softening temperature (TMA) of the cyclic olefin random copolymer composition is not lowered at all.

As described above, the aromatic vinyl hydrocarbon is a cyclic olefin random copolymer (A). When the conjugated diene copolymer or its hydride (B) is blended in an amount of about 30% by weight, the heat resistance is not lowered even though the impact resistance of the cyclic olefin random copolymer composition is significantly improved.

In Figs. 7 and 8, the symbol ○ is a value relating to Examples 51-57 and Comparative Example 18, and the symbol □ is a value relating to Examples 58-60 and Comparative Example 19, and the symbol is shown in Examples 61-62 and FIG. The value relating to Comparative Example 20 is indicated by Example 63-64 and the value related to Comparative Example 21, and the value Δ indicates values related to Example 65-66 and Comparative Example 22.

9 shows the relationship between the blending amount of the soft copolymer (B) in the cyclic olefin random copolymer composition according to the present invention and the impact resistance (IZ strength) of the composition.

In FIG. 9, it can be seen that the impact resistance of the cyclic olefin random copolymer composition is remarkably improved when the soft copolymer is added to the cyclic olefin random copolymer (A).

10 shows the relationship between the blending amount of the soft copolymer (B) and the softening temperature (TMA) of the composition in the cyclic olefin random copolymer composition according to the present invention.

10 shows that even when the soft copolymer (B) is added to the cyclic olefin random copolymer (A) in an amount of about 40% by weight, the softening temperature (TMA) of the cyclic olefin random copolymer composition is not lowered at all. Can be.

When the soft copolymer (B) is added in an amount of about 40% by weight to the cyclic olefin random copolymer (A) as described above, the impact resistance of the cyclic olefin random copolymer composition is significantly improved, but the heat resistance is not lowered.

In Figs. 9 and 10, the symbol ○ is a value relating to Examples 67-72 and Comparative Example 23, and the symbol □ is a value relating to Examples 73-77 and Comparative Example 24, and the indication is Example 78-80. And a value relating to Comparative Example 25, and a mark denotes a value relating to Examples 81-82 and Comparative Example 26, and a Δ mark denotes a value relating to Examples 83-84 and Comparative Example 27.

The second cyclic olefin random copolymer composition according to the present invention contains an inorganic filler or an organic filler (C) in addition to the cyclic olefin random copolymer (A) and the soft copolymer (B).

Specific examples of the 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, carbon fiber mat, titanium oxide, 2 Molybdenum sulfide, magnesium hydroxide, talc, celite, metal powder, metal fibers and the like are used.

Specific examples of the organic fillers include polyterephthaloyl-p-phenylenediamine, polyterephthaloylisophthaloyl-p-phenylenediamine, polyisophthaloyl-p-phenylenediamine, and polyisophthaloyl-m-. Fibrous objects, such as polyamides, such as a wholly aromatic polyamide, such as phenylenediamine, or nylon 66, nylon 6, nylon 10, are used.

These fibrous materials can take the form of short fibers, strands, crosses, mats and the like.

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

Inorganic fillers or organic fillers (C) are formulated for various purposes in the cyclic olefin random copolymer composition according to the present invention, for example, to improve the heat resistance or flame retardancy of the composition, to color the composition or to improve the rigidity. It is used in an amount according to the purpose to suppress the shrinkage rate.

In the second cyclic olefin random copolymer composition according to the present invention, the total amount of the soft copolymer (B) is 1-100 parts by weight, preferably 5-100 parts by weight, based on 100 parts by weight of the cyclic olefin random copolymer (A). Parts, particularly preferably in an amount of 5-50 parts by weight, and with respect to 100 parts by weight of the cyclic olefin random copolymer (A), 1-100 parts by weight of the inorganic filler or the organic filler (C), preferably 5- 100 parts by weight, particularly preferably 5-50 parts by weight.

If the total amount of the soft copolymer (B) is less than 1 part by weight relative to 100 parts by weight of the cyclic olefin random copolymer (A), it is not preferable because the impact strength is low, whereas if it exceeds 100 parts by weight, the rigidity is not preferable. not.

Moreover, when an inorganic filler or an organic filler (C) exceeds 100 weight part with respect to 100 weight part of this cyclic olefin random copolymers (A), since moldability deteriorates, it is unpreferable.

Moreover, the cyclic olefin random copolymers (A) and (B) (iii) which comprise the cyclic olefin random copolymer composition by this invention are Unexamined-Japanese-Patent No. 60-168708, Unexamined-Japanese-Patent No. 61-120816, The hostile conditions in accordance with the method proposed by the applicant in 61-115912, 61-115916, 61-95905, 61-95906, 61-71906, 61-272216, etc. It can manufacture by selecting.

As the manufacturing method of 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 soft copolymer (B) are separately prepared, and (A) and (B) are prepared. Process by blending with an extruder or a solution by (A) and (B) by sufficiently dissolving in a suitable solvent such as saturated hydrocarbons such as heptane, hexane, decane, cyclohexane, aromatic hydrocarbons such as toluene, benzene, xylene The blending method and the method of manufacturing a polymer by blending the polymer obtained by synthesize | combining (A) and (B) in a separate polymerization machine in a separate container are mentioned.

The intrinsic viscosity [η] measured in decalin at 135 ° C. of the cyclic olefin random copolymer composition according to the present invention is in the range of 0.05-10 dl / g, preferably 0.08-5 dl / g, and is determined by thermal mechanical analyzer. The measured softening temperature (TMA) is in the range of 80-250 ° C, preferably 100-200 ° C and the glass transition temperature (Tg) is in the range of 70-230 ° C, preferably 90-120 ° C.

The cyclic olefin random copolymer composition according to the present invention includes the cyclic olefin random copolymer (A), the soft copolymer (B) and, if necessary, an inorganic filler or an organic filler, in addition, heat stabilizer and weather stabilizer. , Antistatic agents, slip agents, antiblocking agents, antifog agents, lubricants, dye pigments, natural oils, synthetic oils, waxes and the like can be blended.

For example, as a stabilizer to mix as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di -t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamide bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, etc. Fatty acid metal salts such as phenolic antioxidants, zinc stearate, zinc stearate, calcium stearate, calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, penta Polyhydric alcohol fatty acid ester, such as erythritol tristearate, etc. are mentioned.

These may be blended alone or in combination, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate and glycerin monostearate May be exemplified.

[Effects of the Invention]

The cyclic olefin random copolymer composition according to the present invention comprises the above cyclic olefin random copolymer (A), the cyclic olefin random copolymer (B) and, if necessary, an inorganic filler or an organic filler (C). Since the copolymer (B) and the inorganic filler or the organic filler (C) are present in a specific amount with respect to 100 parts by weight of the copolymer (A), they are excellent in heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity. At the same time, the impact resistance is excellent.

EXAMPLE

Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Moreover, the measuring rice method and evaluation method of the various physical property values by this invention are as follows.

(1) Heat Deflection Temperature (TMA): TMA 10 (Thermomechanical Analyser) manufactured by Seigo Electronics Co., Ltd. was used to measure the thermal deformation behavior of 1 mm thick sheets.

In other words, a quartz needle was placed on the sheet, and a 50g load was applied to increase the temperature to 5 ° C / min, and the temperature at which the needle penetrated by 0.1 mm was TMA.

(2) Impact strength: A test tube of 63.8 mm in length and 12.7 mm in width was punched out from a 2 mm thick press sheet by using an Iojo impact tester manufactured by Toyo Chemical Co., Ltd., ^and a notch of 0.25 mm ^{and placed} therein was measured at 23 ° C.

(3) Stiffness (bending elastic modulus): Using an Instron tensile tester, a test piece of 63.8 mm in length and 12.7 mm in length was punched out of a 2 mm thick press sheet, and the compression speed was 5 mm / min, the support distance was 32 mm, and 23 ° C. Measured.

The IZ impact test and the bending test were performed after 3 days had elapsed after the press molding.

Polymerization example la

(Synthesis of Copolymer (A) with Softening Temperature of 70 ° C or higher)

이하 DMON로 약기함)의 공중합 반응을 행하였다.Continuously using ethylene and 1,4,5,8-dimethano-1,2,3,4,4, a, 5,8,8a-octahydronaphthalene using a 2 L glass polymerizer with stirring blades ( constitutional formula:

(Hereinafter abbreviated as DMON)).

In other words, the concentration of DMON cyclohexane in the polymerization vessel was 60 g / l in the polymerization vessel, and the concentration of VO (OC ₂ H ₅ ) CI ₂ cyclohexane in the polymerization vessel was 0.9 mmol in the polymerization vessel. / l, a cyclohexane solution of ethyl aluminum sesquichloride (AL (C ₂ H ₅ ) _1.5 CI _1.5 ) was continuously fed into the polymerization reactor so that the aluminum concentration in the polymerization reactor was 7.2 mmol / l while At the bottom, the polymerization liquid in the polymerization reactor is continuously drawn out to 1 l.

At the top of the polymerizer, ethylene is fed at an hourly rate of 85 l, hydrogen at 6 l hourly, and nitrogen at 45 l hourly.

The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant in a jacket attached to the outside of the polymerization reactor.

When copolymerization is carried out under the above reaction conditions, a polymerization reaction mixture containing an ethylene-DMON random copolymer is obtained.

The polymerization liquid extracted from the lower part of the polymerization reactor stopped the polymerization reaction by adding a small amount of isopropyl alcohol.

Thereafter, the polymerization solution was added while rotating the mixer in a domestic mixer containing about three times the amount of acetone relative to the polymerization solution to precipitate the resulting copolymer.

The precipitated copolymer was collected by filtration, dispersed in acetone so that the polymer concentration was about 50 g / l, and the copolymer was treated for about 2 hours at the boiling point of acetone.

After the treatment of the substrate, the copolymer was collected by filtration and dried under reduced pressure at 120 ° C. overnight (12 hours).

Ethylene composition in the copolymer measured by ¹³ C-NMR analysis of the ethylene / DMON random copolymer (A) obtained as described above was 59 mol% and the ultimate viscosity [η] measured in 135 ° C decalin was 0.42 dl / g. , Softening temperature (TMA) was 154 ° C.

Polymerization Example 1b

(Synthesis of Copolymer (A) with Softening Temperature of 70 ° C or higher)

In the polymerization example 1b, it carried out similarly to the polymerization example 1a, and superposed | polymerized continuously.

After the completion of the polymerization, the resultant copolymer was precipitated as in the polymerization example 1a, and the precipitated copolymer was collected and dried overnight at 120 ° C. under reduced pressure.

The ethylene composition in the copolymer measured by ¹³ C-NMR analysis of the ethylene-DMON copolymer (A) obtained as described above was 59 mol%, and the intrinsic viscosity [η] measured in 135 ° C decalin was 0.60 dl / g, Softening temperature (TMA) was 111 ° C.

Polymerization Example 2

(Synthesis of Copolymer (A) with [η] Different from Polymerization Example 1a)

In Polymerization Example 2, the concentrations of DMON.VO (OC ₂ H ₅ ) CI ₂ and ethylaluminum sesquichloride in 1a and the intake amounts of ethylene, hydrogen, and nitrogen in 1a were continuously performed in the same manner as in Table 5 except that The polymerization was carried out.

After the completion of the polymerization, the resulting copolymer was precipitated as in the polymerization example 1a, and the precipitated copolymer was collected and dried at 120 ° C. under reduced pressure for 12 hours.

As described above, the ethylene composition in the copolymer measured by ¹³ C-NMR analysis of the ethylene-DMON copolymer (A) obtained in Polymerization Example 2 was 58 mol% and the intrinsic viscosity [η] measured in 135 ° C decalin was 0.94. dl / g and softening temperature (TMA) were 170 degreeC.

Polymerization Example 3

(Synthesis of Copolymer (A) with [η] Different from Polymerization Example 1a)

In polymerization example 3, the concentrations of DMON, VO (OC ₂ H ₅ ) CI ₂ , and ethylaluminum sesquichloride in the polymerization reactor and the intake amounts of ethylene, hydrogen, and nitrogen in polymerization example 1a were continuously performed in the same manner as in Table 5 except that The polymerization was carried out by.

After the completion of the polymerization, the resultant copolymer was precipitated as in the polymerization example 1a, and the precipitated copolymer was collected and dried overnight at 120 ° C. under reduced pressure.

As described above, the ethylene composition in the copolymer measured by ¹³ C-NMR analysis of the ethylene-DMON copolymer (A) obtained in Polymerization Example 3 was 67 mol% and the intrinsic viscosity [η] measured in 135 ° C decalin was 0.60. dl / g and softening temperature (TMA) were 111 degreeC.

TABLE 5

Polymerization Example 4

(Synthesis of Copolymer (B) with Softening Temperature of Below 70 ° C)

In the polymerization example 1a, the concentrations of DMON.VO (OC ₂ H ₅ ) CI ₂ and ethyl aluminum sesquichloride in the polymerization reactor were continuously supplied to be 15 g / l, 0.5 mmol / l and 4 mmol / l, respectively, 45 liters of ethylene, 15 liters of propylene, 0.2 liters of hydrogen and 25 liters of nitrogen were supplied each hour, and polymerization was carried out continuously except that the polymerization temperature was set at 10 占 폚.

After completion of the polymerization, the resulting copolymer was precipitated in the same manner as in the polymerization example 1a, and the precipitated copolymer was collected and dried at 120 ° C. under reduced pressure for 12 hours.

Intrinsic viscosity measured in 76 mol% of ethylene composition, 17 mol% of propylene composition, and 135 degreeC decalin in the copolymer measured by ¹³ C-NMR analysis of the ethylene propylene-DMON copolymer (B) obtained as mentioned above. [] was 0.89 dl / g and the softening temperature (TMA) was -10 ° C.

Polymerization Example 5

(Synthesis of Copolymer (B) with [η] Different from Polymerization Example 4)

In Polymerization Example 5, the concentrations of DMON.VO (OC ₂ H ₅ ) CI ₂ and ethyl aluminum sesquichloride in Polymerization Example 4 and the intake amounts of ethylene, propylene, hydrogen, and nitrogen in Polymerization Example 4 were the same as those shown in Table 6. It carried out similarly and superposed | polymerized continuously.

After completion of the polymerization, the resultant copolymer was precipitated as in the polymerization example 1a, and the precipitated copolymer was collected and dried at 120 ° C under pressure for 12 hours.

The ethylene composition in the copolymer measured by ¹³ C-NMR analysis of the ethylene propylene-DMON copolymer (B) obtained in the polymerization example 5 as described above in 69 mol%, the propylene composition in 21 mol%, 135 degreeC decalin The measured intrinsic viscosity [η] was 1.44 dl / g and the softening temperature (TMA) was -4 ° C.

Polymerization Example 6

(Synthesis of Copolymer (B) with [η] Different from Polymerization Example 4)

In Polymerization Example 6, the concentrations of DMON.VO (OC ₂ H ₅ ) CI ₂ and ethylaluminum sesquichloride in the polymerization reactor and the intake amounts of ethylene, propylene, hydrogen, and nitrogen in Polymerization Example 4 were the same as those shown in Table 6. The polymerization was carried out in succession.

After the completion of the polymerization, the produced polymer was precipitated as in the polymerization example 1a, and the precipitated copolymer was taken out and dried at 120 ° C. under reduced pressure for 12 hours.

As mentioned above, the ethylene composition of the copolymer measured by ¹³ C-NMR analysis of the ethylene propylene-DMON copolymer (B) obtained by the polymerization example 6 in 76 mol%, the propylene composition in 16 mol%, and 135 degreeC decalin was measured. One-intrinsic viscosity [eta] was 0.98 dl / g, and the softening temperature (TMA) was -8 degreeC.

TABLE 6

85 g and 15 g (weight ratio (A) / (B) = 85/15) of the copolymer (A) obtained in Synthesis Example 3 and the copolymer (B) obtained in Polymerization Example 5 were respectively added to 2 l of cyclohexane and sufficiently stirred. It was dissolved at about 70 ° C.

The obtained homogeneous solution was poured into 2 L of acetone, and the (A) / (B) blend was precipitated.

The resulting blend was dried overnight at 120 ° C. under reduced pressure.

Tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane as a stabilizer in the obtained (A) / (B) blend was used as a stabilizer (A), (B) 0.5% of the total amount was added and kneaded at 190 ° C. using a Brabender-Plastgraph, followed by compression molding at 240 ° C. to obtain a press sheet having a thickness of 2 mm.

The test piece was punched out of this sheet, and the impact strength, the bending test, and the TMA measurement were performed.

The Izot impact strength of this blend was 40.0 kg cm / cm, the flexural modulus was 22100 kg / cm 2, the bending yield point stress was 830 kg / cm 2, and the TMA was 108 ° C. Blends excellent in rigidity, heat resistance and excellent impact strength were obtained.

Comparative Example 1

The same measurement as in Example 1 was carried out using a 2 mm thick press sheet obtained by compression molding the copolymer (A) synthesized in Polymerization Example 3 at 240 ° C.

IZ impact strength was 2.0㎏㎝ / ㎝, flexural modulus was 28900㎏ / ㎠, bending yield point stress was 870㎏ / ㎠ and TMA was 110 ° C. It was a weak sample with excellent stiffness and heat resistance but low impact resistance.

Example 2-4

The copolymer (A) obtained by the polymerization examples 1a and 3 and the copolymer (B) obtained by the polymerization examples 4 and 5 were evaluated by the method similar to Example 1 by the weight ratio shown in Table 7. The results are shown in Table 7.

Comparative Example 2-3

It evaluated by the method similar to the comparative example 1 using the copolymer (A) synthesize | combined in superposition | polymerization example 1a and 2.

The results are shown in Table 7.

It was a vulnerable sample having good rigidity and heat resistance but low impact resistance.

Example 5

To 80 g and 20 g (weight ratio (A) / (B) = 80/20) of the copolymer (A) synthesized in Polymerization Example 2 and the copolymer (B) synthesized in Polymerization Example 6, respectively, tetrakis [methylene-3 ( 3,5-di-t-butyl-4-hydroxyphenyl) proionate] methane as a stabilizer was blended 0.5% of the total amount of the resins (A) and (B) and 190 ° C using a Brabender plastgraph. After kneading in, evaluation was conducted in the same manner as in Example 1.

The results are shown in Table 7.

The composition which was excellent in rigidity, heat resistance, and also excellent in impact resistance was obtained.

Example 6-7

The copolymer (A) synthesize | combined by the polymer 2 and the copolymer (B) synthesize | combined in the polymerization example 6 were evaluated by the method similar to Example 5 by the weight ratio shown in Table 7.

The results are shown in Table 7.

Example 8-15

Evaluation was carried out in the same manner as in Example 5 using the copolymer (A) synthesized in the same manner as in Polymerization Example 1a and the copolymer (B) synthesized in the same manner as in Polymerization Example 4.

The results are shown in Table 8.

A composition excellent in rigidity, heat resistance and excellent impact strength was obtained.

[Comparative Example 4-6]

It evaluated by the method similar to the comparative example 1 using the copolymer (A) synthesize | combined by the method similar to the polymerization example 1a.

The results are shown in Table 9. It was a vulnerable sample having excellent rigidity and heat resistance but low impact resistance.

TABLE 7

TABLE 8

Example 16

90 g and 10 g (weight ratio (A) (B) = 90/10) of the copolymer (A) and the ethylene-propylene random copolymer (ethylene / propylene = 80/20 mol%) (B) obtained in the polymerization example 2 were respectively 2 liters of cyclohexane was added and dissolved at about 70 ° C. with sufficient stirring.

The obtained homogeneous solution was poured into 2 L of acetone, and the (A) / (B) blend was precipitated.

The resulting blend was dried overnight at 120 ° C. under reduced pressure.

Tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane was used as a stabilizer in the obtained (A) / (B) blend. Resin (A), (B) 0.5% of the total amount of the mixture was kneaded at 190 ° C using a Brabender-Plastgraph, followed by compression molding at 240 ° C to obtain a press sheet having a thickness of 2 mm.

The impact strength, the bending test, and the TMA measurement were performed on the test piece obtained by punching out the test piece from this sheet.

The Izot impact strength of this blend was 9.4 kg cm / cm, the bending elastic modulus was 23000 kg / cm 2, the bending yield point stress was 840 kg / cm 2, and the TMA was 110 ° C.

Blends excellent in rigidity, heat resistance and excellent impact strength were obtained.

Comparative Example 7

The measurement similar to Example 16 was performed using the 2 mm-thick press sheet obtained by compression molding the copolymer (A) synthesize | combined by the polymerization example 2 at 240 degreeC.

The specimen obtained had a IZ impact strength of 2.0 kgcm / cm, a bending elastic modulus of 28900 kg / cm 2, a bending yield point stress of 870 kg / cm 2, and a TMA of 110 ° C., which were excellent in stiffness and heat resistance but low in impact resistance.

Example 17-18

The copolymer (A) and the ethylene-propylene copolymer (B) obtained in the polymerization example 2 were evaluated similarly to Example 16 by the weight ratio shown in Table 10.

The results are shown in Table 10.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 19

The copolymer (A) and the ethylene-1-butene copolymer (B) obtained from the polymer 2 were evaluated in the same manner as in Example 16 by the weight ratios shown in Table 10. The results are shown in Table 10. The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 20

80 g and 20 g (weight ratio (A) / (B) = 80/20) of the copolymer (A) and the ethylene-propylene copolymer (B) synthesized in the polymerization example 3, respectively, were tetrakis [methylene-3 (3,5) -Di-t-butyl-4-hydroxyphenyl) propionate] methane as a stabilizer 0.5% of the total amount of resins (A), (B) and kneaded at 190 ° C using a Brapender-Plastgraph After the evaluation, evaluation was performed in the same manner as in Example 16.

The results are shown in Table 10.

The composition which was excellent in rigidity, heat resistance, and also excellent in impact resistance was obtained.

Comparative Example 8

Evaluation similar to Example 16 was performed using the 2 mm-thick press sheet obtained by compression molding the copolymer (A) synthesize | combined in the polymerization example 3 at 240 degreeC.

The results are shown in Table 10.

It was a vulnerable sample having excellent rigidity and heat resistance but low impact resistance.

Example 21-22

The copolymer (A) and the ethylene-propylene copolymer (B) synthesize | combined by the polymerization example 3 were evaluated similarly to Example 16 by the weight ratio shown in Table 10.

The results are shown in Table 10.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 24-29

The copolymer (A) synthesized in the same manner as in General Example 2 and the α-olefin random copolymer (B) shown in Table 11 were evaluated in the same manner as in Example 20.

The results are shown in Table 11.

The composition which was excellent in rigidity, heat resistance, and high impact strength was obtained.

[Comparative Example 9-11]

The copolymer (A) synthesized in the same manner as in Polymerization Example 2 was evaluated in the same manner as in Comparative Example 7.

The results are shown in Table 12.

It was a weak sample with excellent stiffness and heat resistance but low impact strength.

TABLE 10

TABLE 11

TABLE 12

Example 30

90% by weight of the ethylene polycyclic olefin copolymer obtained in Polymerization Example 1a, 5% crystallinity by X-ray, 80 mol% of ethylene content, 4.6 g / 10min of MFR and 0.865 g / cm3 of density (hereinafter EPC) 10 wt% of the mixture was mixed with a Henschel mixer and melt-kneaded in a 40-mm single-screw extruder (set temperature: 230 ° C) to obtain a composition.

Subsequently, this composition was injection molded (cylinder temperature: 240 degreeC, mold temperature: 70 degreeC), and the test piece for physical property evaluation was obtained.

Thus, the bending test (ASTM D 790) and the eye impact test (no ASTM D 256 notch) were performed about the test piece for physical property evaluation obtained.

The results are shown in Table 13.

Example 31

In Example 30, a test piece for evaluation of physical properties was obtained in the same manner as in Example 30 except that 70% by weight of the ethylene polycyclic olefin copolymer and 30% by weight of EPC-I were used to obtain a test piece for physical property evaluation.

The results are shown in Table 13.

Example 32

Example 30 was used in place of EPC-I except that the crystallinity was 25% by X-ray, 92 mol% of ethylene, MER 18g / 10min, and 0.895 g / cm3 ethylene / 1-butene random copolymer. In the same manner as described above, a test piece for evaluation of physical properties was obtained, and a bending test and an eye impact test were performed.

The results are shown in Table 13.

Example 33

Example 30 was carried out in the same manner as in Example 30 except that, instead of EPC-I, an ethylene-propylene random copolymer having a crystallinity of 1%, an ethylene content of 40 mol%, a MER of 1.0 / 10 min, and a density of 0.858 g / cm 3 was used. A test piece for evaluation of physical properties was obtained, and a bending test and an eye shock test were performed. The results are shown in Table 13.

Example 34

In Example 30 maleic anhydride in 100 parts by weight of ethylene-butene random copolymer having a crystallinity of 17% by X-ray, 89 mol% of ethylene, MFR 4.0 g / 10min, and density 0.885 g / cm ³ instead of EPC-I. Was carried out in the same manner as in Example 30 except that a modified ethylene-butene random copolymer (0.5% by weight of X-rays crystallization, MFR 2.5g / 10min) obtained by graft copolymerization was subjected to graft copolymerization. And an Izot impact test.

The results are shown in Table 13.

Comparative Example 12

In Example 30, except that only the ethylene polycyclic olefin copolymer was used for injection molding instead of the composition of Example 30, the test piece for evaluation of physical properties was obtained in the same manner as in Example 30, and a bending test and an eye test were performed.

The results are shown in Table 13.

TABLE 13

Example 35

80 g of the copolymer (A) and the ethylene propylene 5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 66/31/3 mol%) (B) obtained in the polymerization example 1a, respectively, 20 g (weight ratio 80/20) and 2 liters of cyclohexane were added, and it melt | dissolved at about 70 degreeC, fully stirring.

The obtained homogeneous solution was added to 2 L of acetone to precipitate (A) / (B) blend.

The resulting blend was dried overnight at 120 ° C. under reduced pressure.

To the obtained (A) / (B) blend, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methanol stabilizer of resin (A), (B) 0.5% of the total amount was mixed and kneaded at 190 ° C. using a Brabender Plastgraph, followed by compression molding at 240 ° C. to obtain a press sheet having a thickness of 2 mm.

In this sheet, the test piece was punched out, the impact strength, the bending test, and the TMA measurement were performed.

The Izot impact strength of this blend was 53.4 kg.cm/cm, the bending elastic modulus was 16000 kg / cm <2>, the bending yield point stress was 590 kg / cm <2>, and TMA was 110 degreeC.

Blends excellent in rigidity, heat resistance and excellent impact strength were obtained.

Comparative Example 13

The same measurement as in Example 35 was carried out using a 2 mm thick press sheet obtained by compression molding the copolymer (A) synthesized in the polymerization example 1a at 240 ° C.

The IZ impact strength was 2.0 kg.cm/cm, the flexural modulus was 28900kg / cm 2, and the bending yield stress was 870kg / cm 2 TMA at 110 ° C. The specimen was excellent in stiffness and heat resistance but low in impact resistance.

Example 36-37

The copolymer (A) and ethylene propylene 5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 66/31/3 mol%) (B) which were obtained by the polymerization example 1a are shown in Table 14 Evaluation similar to Example 35 was performed with the weight ratio shown.

The results are shown in Table 14.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

[Example 38-39]

The copolymer (A) and the ethylene propylene 5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 67/31 / 2mol%) (B) which were obtained by the polymerization example 1a are shown in Table 14. Evaluation similar to Example 35 was performed with the weight ratio shown.

The results are shown in Table 14.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 40-41

The copolymer (A) and the ethylene propylene dicyclopentadiene random copolymer (ethylene / propylene / diene = 67/32/1 mol%) (B) which were obtained by the polymerization example 1a are shown by the weight ratio shown in Table 14. Evaluation similar to 35 was performed.

The results are shown in Table 14.

Example 42

80 g of each of the copolymer (A) synthesized in the polymerization example 2 and the ethylene propylene 5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 66/31/3 mol%) (B) , Stabilizer of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane in 20 g (weight ratio (A) / (B) = 80/20) 0.5% of the total amount of (A) and (B) was mixed and kneaded at 190 ° C. using a Brandender prestgraph, and evaluated in the same manner as in Example 35.

The results are shown in Table 14.

The composition which was excellent in rigidity, heat resistance, and also excellent in impact resistance was obtained.

Comparative Example 14

Evaluation similar to Example 35 was performed using the 2 mm thick press sheet obtained by compression molding the copolymer (A) synthesize | combined by the polymerization example 2 at 240 degreeC.

The results are shown in Table 14.

It was a vulnerable sample having excellent rigidity and heat resistance but low impact resistance.

Example 43-44

The copolymer (A) synthesized in Polymerization Example 2 and the α-olefin-diene copolymer (B) shown in Table 14 were blended and evaluated in the same manner as in Example 42.

The results are shown in Table 14.

Example 45-50

It evaluated like Example 42 using the copolymer (A) synthesize | combined by the method similar to the polymerization example 1a, and the (alpha)-olefin diene type elastic body.

The results are shown in Table 15.

A composition excellent in rigidity, heat resistance and excellent impact resistance was obtained.

[Comparative Example 15-17]

Evaluation similar to the comparative example 14 was performed using the copolymer (A) synthesize | combined by the method similar to polymerization example 1a.

The results are shown in Table 16.

TABLE 14

TABLE 15

TABLE 16

Example 51

90 g and 10 g (weight ratio 90/10) of each of the copolymer (A) and the styrene-butadiene-styrene block copolymer (Kariprex TR 1102 manufactured by Shell Chemicals, Density 0.94 g / cm 3) (B) obtained in the polymerization example 1b were respectively obtained. Tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and di-lauryl-thio-di-propionate were used as stabilizers. 0.5% and 0.3% of the total amount of (B) and (B), respectively, were kneaded at 190 ° C. using a Brabender-Plastgraph, and compression molded at 240 ° C. to obtain press sheets having a thickness of 1 mm and 2 mm.

The test piece was punched out of this sheet, and the impact strength, the bending test, and the TMA measurement were performed.

The Izot impact strength of this blend was 5.0 kg cm / cm, the bending elastic modulus was 23000 kg / cm <2>, and TMA was 111 degreeC.

Blends with excellent stiffness, heat resistance and excellent impact strength were obtained.

[Comparative Example 18]

The same measurement as in Example 51 was carried out using a 1 mm and 2 mm thick press sheet obtained by compression molding the copolymer (A) synthesized in 1b at the polymerization.

IZ impact strength was 2.0㎏㎝ / ㎝, flexural modulus was 28900㎏ / ㎠, bending yield point stress was 870㎏ / ㎠ and TMA was 111 ℃. It was a weak sample with excellent stiffness and heat resistance but low impact resistance.

Example 52-53

The copolymer (A) and the styrene-butadiene-styrene block copolymer (Cariprex TR 1102, manufactured by Shell Chemicals, density 0.94 g / cm 3) (B) obtained in the polymerization example 1b were the same as in Example 51 by the weight ratio shown in Table 17. Evaluation was performed.

The results are shown in Table 17.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 54

The copolymer (A) and the hydrogenated styrene-butadiene-styrene block copolymer (Crayton G 1657, manufactured by Shell Chemical Company, Density 0.90 g / cm 3) (B) obtained in the polymerization example 1b were prepared in accordance with Example 51 by the weight ratio shown in Table 17. The same evaluation was performed.

The results are shown in Table 17.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 55

The copolymer (A) and the styrene-isoprene-styrene block copolymer (polymer manufactured by Shell Chemical Co., Calif. TR 1107, density 0.92 g / cm 3) (B) obtained in Polymerization Example 1b were used in Example 51 by the weight ratio shown in Table 17. The same evaluation was performed.

The results are shown in Table 17.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 56-57

The copolymer (A) and styrene-butadiene copolymer (Nipol 1502 by Nippon Zeon, density 0.94 g / cm <3>) (B) obtained by the polymerization example 1b were evaluated similarly to Example 51 by the weight ratio shown in Table 17.

The results are shown in Table 17.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 58

The copolymer (A) synthesized in the polymerization example 2 and the styrene-butadiene styrene block copolymer (Kariprex TR 1102 manufactured by Shell Chemical Co., Ltd., density 0.94 g / cm 3) (B) were the same as those in Example 51 by the weight ratio shown in Table 17. Evaluation was performed.

The results are shown in Table 17.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Comparative Example 19

The measurement similar to Example 51 was performed using the 1 mm and 2 mm thickness press sheets obtained by compression-molding the copolymer (A) synthesize | combined by the polymerization example 2 at 240 degreeC.

The results are shown in Table 17.

It was a weak sample having excellent rigidity and heat resistance but low impact resistance.

Example 59-60

The copolymer (A) synthesized in the polymerization example 2 and the hydrogenated styrene-butadiene-sterine block copolymer (Creton G 1657, manufactured by Shell Chemicals, Density 0.90 g / cm 3) (B) were obtained by the weight ratio shown in Table 17. Evaluation similar to 51 was performed.

The results are shown in Table 17.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 61-66

The copolymer (A) synthesized in the same manner as in Polymerization Example 1b (the composition is shown in Table 17) and the styrene-conjugated diene block copolymer shown in Table 17 were evaluated in the same manner as in Example 51 by the weight ratio shown in Table 17. It was.

The results are shown in Table 17.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

[Comparative Example 20-22]

Evaluation similar to the comparative example 19 was performed using the copolymer (A) (composition shown in Table 17) synthesize | combined by the method similar to the polymerization example 1b.

The results are shown in Table 17.

TABLE 17

Example 67

Copolymer (A) obtained in Polymerization Example 1b and cyclic olefin random copolymer (hereinafter abbreviated as TDR) (B1) obtained in Polymerization Example 5 and ethylene composition 80 mol%, crystallinity 15%, density 0.88 g / cm 3, [ 40 g, 5 g, and 5 g (weight ratio 80/10/10) of ethylene.propylene random copolymer (hereinafter abbreviated as EPR) (B2) having a η] = 2.2 dl / g and dry blended tetrakis [methylene as a safety agent -3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and di-lauryl-thio-di-propionate to the total amount of resins (A), (B) And 0.5% and 0.3% respectively, and kneaded at 190 ° C. using a Brabender-melt mixer, followed by compression molding at 240 ° C. to obtain press sheets having a thickness of 1 mm and 2 mm.

The test piece was punched out of this sheet, and the impact strength, the bending test, and the TMA measurement were performed.

The Izot impact strength of this blend was 40.2 kgcm / cm, the flexural modulus was 19000 kg / cm <2>, and TMA was 110 degreeC.

Blends excellent in rigidity, heat resistance and excellent impact strength were obtained.

Comparative Example 23

The same measurement as in Example 67 was carried out using a 1 mm and 2 mm thick press sheet obtained by compression molding the copolymer (A) synthesized in the polymerization example 1b at 240 ° C.

IZ impact strength was 2.0㎏㎝ / ㎝, flexural modulus was 28900㎏ / ㎠, flexural yield stress was 870㎏ / ㎠, TMA was 110 ℃, and it was a weak sample with excellent stiffness and heat resistance but low impact resistance.

Example 68

The copolymer (A) and TDR (B1) obtained from the polymerization example 1b, and the styrene-butadiene-styrene block copolymer by Shell Chemicals Co., Carreprex TR 1102, density 0.94 g / cm <3> (hereinafter abbreviated as SBS) (B2) are shown in the table. Evaluation similar to Example 67 was performed with the weight ratio shown in 18.

The results are shown in Table 18.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 69

66/31/3 mol% of the copolymer (A) obtained by the polymerization example 1b, and ethylene / propylene / 5-ethylidene- 2-norbornene, [(eta)] = 2.1dl, 22 oxo, 0.87 g of density Ethylene-propylene-diene copolymer (hereinafter abbreviated as EPDM). (B1) and SBS (B2) were evaluated in the same manner as in Example 67 by the weight ratios shown in Table 18.

The results are shown in Table 18.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 70-72

The copolymer (A) and EPR (B1) and SBS (B2) obtained in the polymerization example 1b were evaluated similarly to Example 67 by the weight ratio shown in Table 18.

The results are shown in Table 18.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 73-77

The copolymer (A) synthesize | combined in the polymerization example 2, EPDM (B1), and SBS (B2) were evaluated similarly to Example 67 by the weight ratio shown in Table 18.

The results are shown in Table 18.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Comparative Example 24

Evaluation similar to the comparative example 23 was performed using the copolymer (A) synthesize | combined in the polymerization example 2.

The results are shown in Table 18.

It was a vulnerable sample having excellent rigidity and heat resistance but low impact resistance.

Example 78-80

The copolymer (A) and the EPR (B1) and the EPDM (B2) synthesized in the same manner as in the polymerization example 1b were evaluated in the same manner as in Example 67 by the weight ratios shown in Table 18.

The results are shown in Table 18.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 81-82

The copolymer (A), EPDM (B1), and SBS (B2) which were synthesize | combined and carried out similarly to Polymerization Example 1b, were evaluated similarly to Example 67 by the weight ratio shown in Table 18.

The results are shown in Table 18.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

Example 83-84

The copolymer (A) and TDR (B1) and SBS (B2) which were synthesize | combined and carried out similarly to Polymerization Example 1b, were evaluated similarly to Example 67 by the weight ratio shown in Table 18.

The results are shown in Table 18.

The composition which was excellent in rigidity, heat resistance, and high impact resistance was obtained.

[Comparative Example 25-27]

The copolymer (A) synthesized in the same manner as in Polymerization Example 1b was evaluated in the same manner as in Comparative Example 23.

The results are shown in Table 18.

It was a weak sample with excellent stiffness and heat resistance but low impact strength.

In the following examples, *** original defect *** (1) Asahi Fiber Glass Glass Ron Hox strand GR-S-3A (GF) or (2) Fumi White Alumina # 4000 (WA) was used.

Example 85

The copolymer (A) obtained in the polymerization example 3 and the copolymer (B) shown in Table 19 superposed | polymerized by the same method are dry blended at a ratio of 80/10, and this is tetrakis [methylene-3 (3,5-, 3) as a stabilizer. Di-t-butyl-4-hydroxyphenyl) propionate] methane and di-lauryl-thio-di-propionate are 0.5% and 0.3% of the total amount of the resins (A) and (B), respectively. After kneading at 220 ° C using a 30mmø twin screw extruder, GF was dry blended by 10% by weight with respect to the total amount of resins A and B and kneaded at 220 ° C using a 30mmø twin screw extruder at 240 ° C. Compression molding was performed to obtain press sheets of 1 mm and 2 mm thickness.

The test piece was cut out from this sheet, and the impact test, the bending test, and the TMA measurement were performed.

The notched portion impact strength of the blend was 6 kgcm / cm, bending initial modulus of 31000kg / cm 2, and TMA of 113 ° C.

Blends excellent in stiffness, heat resistance and impact strength were obtained.

Comparative Example 28

The copolymer (A) obtained in the polymerization example 3 was compression molded at 240 ° C. to obtain press sheets having a thickness of 1 mm and 2 mm.

The test piece was cut out from this sheet, and the impact test, the bending test, and the TMA measurement were performed.

The notched portion of the specimen had an impact strength of 2 kgcm / cm, an initial bending elastic modulus of 28900 kg / cm2, and a TMA of 111 ° C. The impact strength, initial bending elastic modulus, and heat resistance were inferior to those of the blend obtained in Example 85. .

Example 86-87

The copolymers (A), (B) and fillers (C) shown in Table 19 were blended with the blend ratios shown in Table 19, and the same evaluations as in Example 85 were performed.

The results are shown in Table 19.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Example 88-90

The copolymers (A), (B) and fillers (C) shown in Table 19 were blended with the blend ratios shown in Table 19, and the same evaluations as in Example 85 were performed.

The results are shown in Table 19.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Comparative Example 29

Evaluation similar to the comparative example 28 was performed using the copolymer (A) shown in Table 19.

The results are shown in Table 19.

Compared with the composition obtained in Examples 88-90, the stiffness, heat resistance and impact strength were inferior.

Example 91-93

The copolymers (A), (B) and filler (C) shown in Table 19 were blended with the blend ratios shown in Table 19, and the same evaluation as in Example 85 was performed.

The results are shown in Table 19.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Comparative Example 30

Evaluation similar to the comparative example 28 was performed using the copolymer (A) shown in Table 19.

The results are shown in Table 19.

The stiffness, heat resistance, and impact strength were inferior to the composition obtained in Examples 91-93.

TABLE 19

Example 94

The copolymer (A) and the ethylene-propylene random copolymer (ethylene / propylene = 80/20 mol%) (B) obtained in the polymerization example 3 were respectively dry-blended at a ratio of 80/10 by weight, and tetrakis [ Methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and di-lauryl-thio-di-propionate to the total amount of resins (A) and (B) 0.5% and 0.3%, respectively, and kneaded at 220 ° C using a 30mm ø twin-screw extruder, followed by dry blending of GF by 10% by weight, based on the total amount of resins A and B, After kneading, compression molding was performed at 240 ° C. to obtain press sheets having a thickness of 1 mm and 2 mm.

The test piece was cut out from this sheet, and the impact test, the bending test, and the TMA measurement were performed.

The notched portion impact strength of the blend was 7 kgcm / cm, initial bending modulus of 30600 kg / cm 2, and TMA of 114 ° C.

Blends excellent in stiffness, heat resistance and impact strength were obtained.

Comparative Example 31

The copolymer (A) obtained in the polymerization example 3 was compression-molded at 240 degreeC, the press sheet of thickness 1mm and 2mm was manufactured, the test piece was cut out from this sheet, and the impact test, the bending test, and the TMA measurement were performed.

The notched portion of the specimen had an impact strength of 2 kgcm / cm, an initial bending modulus of 28900 kg / cm2, and a TMA of 111 ° C. The impact strength, initial bending modulus of elasticity, and heat resistance were inferior to those of the blend obtained in Example 1. .

Example 95-96

The copolymers (A), (B) and filler (C) shown in Table 20 were blended with the blend ratios shown in Table 20, and the same evaluation as in Example 94 was performed.

The results are shown in Table 20.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Comparative Example 32

Evaluation similar to the comparative example 31 was performed using the copolymer (A) shown in Table 20.

The results are shown in Table 20.

The stiffness, heat resistance, and impact strength were inferior to the composition obtained in Examples 97-99.

Example 100-102

The copolymers (A), (B) and filler (C) shown in Table 20 were blended with the blend ratios shown in Table 20, and the same evaluation as in Example 94 was performed.

The results are shown in Table 20.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Comparative Example 33

Evaluation similar to Example 31 was performed using the copolymer (A) shown in Table 20.

The results are shown in Table 20.

The stiffness, heat resistance, and impact strength were inferior to those of the composition obtained in Examples 100-102.

TABLE 20

The copolymer (A) and the ethylene-propylene-5-ethylidene-2-norbornene random copolymer (ethylene / propylene / diene = 66/31/3 mol%) (B) obtained in the polymerization example 3 were each weight ratio 80 Dry blended at a ratio of / 10 and to this as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and di-lauryl-thio-di- Propionate was blended 0.5% and 0.3% with respect to the total amounts of resins (A) and (B), respectively, and kneaded at 220 ° C. using a 30 mm ø twin screw extruder. After weight blending and kneading at 220 ° C. using a 30 mm 2 twin screw extruder, compression molding was performed at 240 ° C. to obtain press sheets of 1 mm and 2 mm thickness.

The test piece was cut out from this sheet, and the impact test, the bending test, and the TMA measurement were performed.

The notched portion of the blend had an impact strength of 8 kgcm / cm, a bending initial modulus of 31100 kg / cm 2, and a TMA of 114 ° C., and a blend having excellent stiffness, heat resistance, and impact strength was obtained.

Comparative Example 34

The copolymer (A) obtained in the polymerization example 3 was compression molded at 240 ° C. to obtain press sheets having a thickness of 1 mm and 2 mm.

The test piece was cut out from this sheet, and the impact test, the bending test, and the TMA measurement were performed.

The notched portion of the specimen had an impact strength of 2 kgcm / cm, an initial bending modulus of 28900 kg / cm2, and a TMA of 111 ° C. The impact strength, initial bending modulus of elasticity and heat resistance were inferior to those of the blend obtained in Example 103. lost.

Example 104-105

The copolymers (A), (B) and fillers (C) shown in Table 21 were blended with the blend ratios shown in Table 21, and the same evaluations as in Example 103 were performed.

The results are shown in Table 21.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Example 106-108

The copolymers (A), (B) and fillers (C) shown in Table 21 were blended with the blend ratios shown in Table 21, and the same evaluations as in Example 103 were performed.

The results are shown in Table 21.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Comparative Example 35

Evaluation similar to the comparative example 34 was performed using the copolymer (A) shown in Table 21.

The results are shown in Table 21.

Stiffness, heat resistance, and impact strength were inferior to the compositions obtained in Examples 106-108.

Example 109-111

The copolymers (A), (B) and fillers (C) shown in Table 21 were blended with the blend ratios shown in Table 21, and the same evaluations as in Example 103 were performed.

The results are shown in Table 21.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Comparative Example 36

It evaluated like the comparative example 34 using the copolymer (A) shown in Table 21.

The results are shown in Table 21.

The stiffness, heat resistance, and impact strength were inferior to the composition obtained in Examples 109-111.

TABLE 21

Example 112

The copolymer (A) and the styrene-butadiene-styrene block copolymer (Cariprex TR 1102 manufactured by Shell Chemical Co., Ltd., density 0.94 g / cm 3) (B) obtained in Polymerization Example 3 were each dry blended at a ratio of 80/10 by weight. Tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and di-lauryl-thio-di-propionate as stabilizers to the resin (A), 0.5% and 0.3% of the total amount of (B) were respectively mixed and kneaded at 220 ° C. using a 30 mm ø twin screw extruder, followed by dry blending of GF by 10% by weight based on the total amount of resins A and B, followed by 30 mm ø 2. After kneading at 220 ° C. using an axial extruder, compression molding was performed at 240 ° C. to obtain press sheets having a thickness of 1 mm and 2 mm.

The test piece was cut out from this sheet, and the impact test, the bending test, and the TMA measurement were performed.

The notched portion of the composition had an impact strength of 8 kgcm / cm, a bending initial modulus of 31000 kg / cm 2, and a TMA of 115 ° C.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Comparative Example 37

The copolymer (A) obtained in the polymerization example 3 was compression molded at 240 ° C. to obtain press sheets having a thickness of 1 mm and 2 mm.

The test piece was cut out from this sheet, and impact strength, bending test, and TMA measurement were performed.

The notched portion of the specimen had an impact strength of 2 kgcm / cm, an initial bending modulus of 28900 kg / cm2, and a TMA of 111 ° C. The impact strength, initial bending modulus of elasticity, and heat resistance were inferior to those of the blend obtained in Example 112. .

Example 113-114

The co-interbody (A), (B) and filler (C) shown in Table 22 were blended with the blend ratios shown in Table 22, and the same evaluation as in Example 112 was performed.

The results are shown in Table 22.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

Example 115-117

The copolymers (A), (B) and fillers (C) shown in Table 22 were blended with the blend ratios shown in Table 22, and the same evaluations as in Example 112 were performed.

The results are shown in Table 22.

The composition excellent in rigidity, heat resistance, and impact strength was obtained.

[Comparative Example 38]

Evaluation similar to the comparative example 37 was performed using the copolymer (A) shown in Table 22.

The results are shown in Table 22.

The stiffness, heat resistance, and impact strength were inferior to the compositions obtained in Examples 115-117.

Table 22

Copolymer (A) obtained in Polymerization Example 3 and cyclic olefin random copolymer (hereinafter abbreviated as TDR) (B1) obtained in Polymerization Example 5 and ethylene composition 80 mol%, crystallinity 5%, density 0.88 g / cm 3, [ Ethylene-propylene random copolymer (hereinafter abbreviated as EPR) (B2) having η] = 2.2 dl was dry blended at a ratio of 80/5/5 by weight, and tetrakis [methylene-3 (3,5-, 3) as a stabilizer. Di-t-butyl-4-hydroxyphenyl) propionate] methane and di-lauryl-thio-di-propionate 0.5% each with respect to the total amount of resins (A), (B1) and (B2) , 0.3% blended and kneaded at 220 ° C. using a 30 mmø twin screw extruder, followed by 10% by weight dry blending of GF to the total amount of resins (A), (B1) and (B2) After kneading at 220 ° C. using an extruder, compression molding was performed at 240 ° C. to obtain press sheets having a thickness of 1 mm and 2 mm.

The test piece was cut out from this sheet, and the impact test, the bending test, and the TMA measurement were performed.

The notched portion of the composition had an impact strength of 6 kgcm / cm, a bending initial modulus of 30900 kg / cm 2, and a TMA of 114 ° C.

The composition excellent in rigidity, heat resistance, and impact resistance was obtained.

Comparative Example 39

The copolymer (A) obtained in Polymerization Example 3 was compression molded at 240 ° C. to obtain press sheets of 1 mm and 2 mm thickness.

The test piece was cut out from this sheet, and the impact test, the bending test, and the TMA measurement were performed.

The notched portion of the specimen had an impact strength of 2 kgcm / cm, an initial bending modulus of 28900 kg / cm2, and a TMA of 111 ° C. The impact strength, initial bending modulus of elasticity, and heat resistance were inferior to those of the blend obtained in Example 118. .

Example 119

Copolymer (A) and TDR (B1) shown in Table 23 obtained in Polymerization Example 3, and styrene-butadiene-styrene block copolymer Kaliprex TR 1102 manufactured by Shell Chemical Co., Ltd., density 0.94 g / cm 2 (hereinafter abbreviated as SBS) (B2) ) And GF were evaluated in the same manner as in Example 118 at the weight ratios shown in Table 23.

The results are shown in Table 23.

The composition excellent in rigidity, heat resistance, and impact resistance was obtained.

Example 120

The copolymer (A) obtained in the polymerization example 3 and the composition of ethylene / propylene / 5-ethylidene-2-norbornene were 66/31/3 mol%, [η] = 2.1 dl, oxo was 22, and density was 0.87. Evaluation similar to Example 118 was performed at the weight ratio shown in Table 23 using the ethylene-propylene-diene copolymer (hereinafter abbreviated as EPDM) (B1) and SBS (B2) and GF which are g / cm <3>.

The results are shown in Table 23.

The composition excellent in rigidity, heat resistance, and impact resistance was obtained.

Example 121-123

Example 118, using the copolymer (A) shown in Table 23 obtained in the same manner as in Polymerization Example 3 and the copolymers (B1), (B2) and filler (C) shown in Table 23, and blended in the blend ratios shown in Table 23. The evaluation was performed as follows.

The results are shown in Table 23.

The composition excellent in rigidity, heat resistance, and impact resistance was obtained.

[Comparative Example 40]

Evaluation similar to the comparative example 39 was performed using the copolymer (A) shown in Table 23.

The results are shown in Table 23.

The stiffness, heat resistance and impact strength were inferior to the compositions obtained in Examples 121-123.

TABLE 23

Claims (10)

(A) The ethylene component and the cyclic olefin component represented by the following general formula [I] or [II], the intrinsic viscosity [η] measured in decalin at 135 degreeC are the range of 0.05-10 dl / g, and softening temperature ( A cyclic olefin random copolymer having a TMA of 70 ° C. or more, and at least one α-olefin component different from the (B) ethylene component and a cyclic olefin component represented by the following general formula [I] or [II] A cyclic olefin random copolymer having an intrinsic viscosity [η] in the range of 0.01 to 10 dl / g and a softening temperature (TMA) of less than 70 ° C. measured in decalin at 135 ° C. (ii) A secret formed of at least two α-olefins. Qualitative to low crystalline α-olefin elastomers (i) α-olefin-diene elastomers and (v) aromatic vinyl hydrocarbons formed of at least two α-olefins and at least one nonconjugated diene One or more selected from the group consisting of conjugated diene copolymers or hydrides thereof A cyclic olefin random copolymer composition formed from two or more soft copolymers, wherein the total amount of the component (B) is present in an amount of 5 to 100 parts by weight based on 100 parts by weight of the component (A).

(Wherein n and m are both o or a positive integer, l is an integer of 3 or more and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group.) The cyclic olefin random copolymer according to claim 1, wherein the cyclic olefin random copolymer comprising at least one α-olefin component different from the ethylene component and the cyclic olefin component represented by the following general formula [I] or [II] is selected from the ethylene component and the propylene component. A cyclic olefin random copolymer comprising a cyclic olefin component represented by the following general formula [I] or [II], or an ethylene component and a butene component and a cyclic olefin component represented by the following general formula [I] or [II] A composition comprising a cyclic olefin random copolymer. [General Formula]

The composition according to claim 1, wherein the α-olefin elastomer is an ethylene propylene copolymer rubber, an ethylene butene copolymer rubber, or a propylene butene copolymer rubber. The composition according to claim 1, wherein the α-olefin-diene-based elastomer is an ethylene-propylene-diene-based copolymer. The aromatic vinyl hydrocarbon conjugated diene copolymer or a hydride thereof is styrene butadiene copolymer rubber, styrene butadiene styrene block copolymer rubber, styrene isoprene block copolymer rubber, styrene isoprene styrene. A composition which is a block copolymer rubber, hydrogenated styrene butadiene styrene block copolymer rubber, or hydrogenated styrene isoprene styrene block copolymer rubber. (A) 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 in the range of 0.05 to 10 dl / g, and a softening temperature (TMA Cyclic olefin random copolymer (B) (iii) having an ethylene component of 70 ° C. or more and at least one α-olefin component different from the cyclic olefin component represented by the following general formula [I] or [II] and 135 ° C. Cyclic olefin random copolymers having an intrinsic viscosity [η] in the range of 0.01 to 10 dl / g and a softening temperature (TMA) of less than 70 ° C. (ii) from amorphous to at least two α-olefins. Low-crystalline α-olefin elastomer (i) α-olefin-diene-based elastomer and (iii) aromatic vinyl hydrocarbon-conjugated diene formed of at least two α-olefins and at least one non-conjugated diene At least two selected from the group consisting of copolymers or hydrides thereof It is formed of the above-mentioned stretched copolymer and (C) inorganic filler or organic filler, and the total amount of (B) component is 1-100 weight part and (C) component is 1-100 weight part with respect to 100 weight part of said (A) component. Cyclic olefin random copolymer composition, characterized in that present in:

(Wherein n and m are both o or positive integers, l is an integer of 3 or more and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group) The cyclic olefin random copolymer according to claim 6, wherein the cyclic olefin random copolymer comprising at least one α-olefin component different from the ethylene component and the cyclic olefin component represented by the following general formula [I] or [II] is selected from the ethylene component and the propylene component. A cyclic olefin random copolymer composed of cyclic olefin components represented by the following general formula [I] or [II], or an ethylene component and a butene component and a cyclic olefin component represented by the following general formula [I] or [II] The composition is characterized in that the olefin random copolymer.

The composition according to claim 6, wherein the α-olefin-based elastic copolymer is ethylene.propylene copolymer rubber, ethylene.butene copolymer rubber, propylene.butene copolymer rubber. The composition according to claim 6, wherein the α-olefin-diene-based elastomer is an ethylene-propylene-diene-based elastomeric copolymer. 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. A composition which is a block copolymer rubber, hydrogenated styrene butadiene styrene block copolymer rubber, or hydrogenated styrene isoprene styrene block copolymer rubber.

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