JPH01318054A - Random cycloolefin copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in heat resistance, chemical resistance, solvent resistance, dielectric properties, rigidity and impact resistance by mixing a specified random cycloolefin copolymer with a specified alpha-olefin copolymer and a specified copolymer. CONSTITUTION:100 pts.wt. random cycloolefin copolymer (A) of an intrinsic viscosity (at 135 deg.C in decalin) of 0.05-10dl/g and a softening temperature of 70-210 deg.C, comprising 40-85mol% ethylene component (A) and 60-15mol% cycloolefin component of formula I or II (wherein n and m are each 0 or a positive integer, l>=3, and R<1-10> are each H, a halogen atom or a hydrocarbon group) is mixed with 5-100 pts.wt. mixture (B) of 95-5wt.% crystalline or amorphous alpha-olefin copolymer (a) of at least two alpha-olefins (e.g., an ethylene/propylene copolymer or a propylene-1-butene copolymer) and having a crystallinity of 0-50% and an intrinsic viscosity of 0.2-10dl/g with 5-95wt.% amorphous or lowly crystalline styrene copolymer (b) containing styrene (derivative) as a monomer component and having glass transition temperature at least one of which is below 0 deg.C (e.g., styrene/butadiene copolymer).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a cyclic olefin-based random copolymer that has excellent heat resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, etc., and also has excellent impact resistance. The present invention relates to polymer compositions.

[Conventional technology]

As a synthetic resin with an excellent balance of rigidity and impact strength,
Polycarbonate, ABS (acrylonitrile-butadiene-styrene copolymer), and the like are known. For example, polycarbonate is a resin that has excellent heat resistance and impact resistance as well as rigidity.

However, there are problems in that it is easily attacked by strong alkalis, has poor chemical resistance, and has a high water absorption rate. Also A
Although BS has excellent mechanical properties, it has a problem in that it is inferior in chemical resistance and heat resistance.

On the other hand, crystalline general-purpose polyolefins such as polyethylene and polypropylene have excellent chemical resistance and solvent resistance, but many of them have poor heat resistance, and furthermore, their crystallinity is not high enough, resulting in poor rigidity.

Therefore, in order to improve the rigidity and heat resistance of polyolefins, it is common to add nucleating agents to accelerate crystal growth.
Alternatively, a method has been adopted in which slow cooling is performed to promote crystal growth, but it is difficult to say that the effect is sufficient. On the contrary, adding a third component such as a nucleating agent may impair the excellent properties originally possessed by the polyolefin, and the slow cooling method has problems such as poor production efficiency.

In addition, a cyclic olefin random copolymer consisting of ethylene and a specific bulky cyclic olefin has heat resistance,
Moreover, it has been proposed as a synthetic resin with chemical resistance, solvent resistance, dielectric properties, and rigidity (Japanese Patent Application Laid-Open No. 60-168708
No. 61-115912, Japanese Patent Application Laid-Open No. 1983-115912
-115916, JP-A-62-120816, etc.).

However, although these cyclic olefin-based random copolymers are olefin-based polymers, they have excellent heat resistance and rigidity, but they have the problem of insufficient impact resistance depending on the application. Ta.

[Problem to be solved by the invention]

The purpose of the present invention is to solve these problems by creating a cyclic olefin random copolymer composition that has excellent heat resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, etc., and also has excellent impact resistance. It is about providing something.

[Means to solve the problem]

The present invention comprises [A] an ethylene component and the following general formula (1).
Or, it consists of a cyclic olefin component represented by [H], and has an intrinsic viscosity [η] of 0 when measured in decalin at 135°C.
．． 05 to 1 odl/g, a cyclic olefin random copolymer having a softening temperature (TMA) of 70°C or higher, [B] an amorphous or low crystalline α-olefin formed from at least two types of α-olefins and [C] an amorphous or low-crystalline styrenic copolymer that has styrene or a derivative thereof as one of the monomer components and has at least one glass transition temperature of 0°C or lower. , for 100 parts by weight of component [A], [B
The total amount of component [B] and component [C] is 5 to 100 parts by weight, and the ratio of component [B] to component [C] is 95 parts by weight.
:5 to 5:95.

In the general formula C, both n and m are O or a positive integer, Q is an integer of 3 or more, and R1 to Rto each represent a hydrogen atom, a halogen atom, or a hydrocarbon group. ] The cyclic olefin random copolymer [A] constituting the cyclic olefin random copolymer composition of the present invention is a cyclic olefin random copolymer composed of an ethylene component and a specific cyclic olefin component. The above cyclic olefin component is represented by the general formula (1) or the general formula [1
1], and in the cyclic olefin random copolymer [A] of the present invention, it forms a repeating unit with a structure represented by the following general formula (III) or general formula (IVI). .

[In the formula, n, m, Q and R1 to Rto are the same as above. ] The cyclic olefin as a component of the cyclic olefin random copolymer [A] constituting the cyclic olefin random copolymer composition of the present invention has the general formula (1) and the general formula [
(2) At least one cyclic olefin selected from the group consisting of unsaturated monomers represented by [2]. General formula CI)
The cyclic olefin represented by can be easily produced by condensing cyclopentadiene and the corresponding olefin by Diels-Alder reaction. Similarly, the cyclic olefin represented by the general formula (II) can be easily produced by condensing a cyclopentadiene and a corresponding cyclic olefin by a Diels-Alder reaction.

Specific examples of the cyclic olefin represented by the general formula (1) include the compounds listed in Table 1, or 1.

4.5.8-dimethano-1,2,3,4,4a,5,8
, 8a-octahydronaphthalene, as well as 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,5
, 8.8a-octahydronaphthalene, 2-ethyl-1
,4,5,8-dimethano-1,2,3,4,4a,5,
8.8a-octahydronaphthalene, 2-propyl-1
,4,5,8-dimethano-1,2,3,4,4a,5,
8,8a-octahydronaphthalene, 2-hexyl-1
,4,5,8-dimethano-1,2,3,4°4a,5,
8.8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-
3-ethyl-1,4,5,8-dimethano-1,2,3,
4,4a,5,8.8a-octahydronaphthalene, 2
-chloro-1,4,5,8-dimethano-1,2,3,4
, 4a.

5.8,8a-octahydronaphthalene, 2-bromo-
1,4゜5.8-dimethano-1,2,3,4,4a,5
, 8,8a-octahydronaphthalene, 2-fluoro-
1,4,5,8-dimethano-1,2゜3 + 4 e
4 a , 5 + 8 + 88-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-
1,2,3,4,4a,5,8.8a-octahydronaphthalene, 2-cyclohexyl-1,4,5°8-dimethano-1,2,3,4,4a,5,8. 8a-octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,3°4.4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4, 5,8-
octahydronaphthalenes such as dimethanol-1,2,3,4,4a,5,8,8a-octahydronaphthalene;
Examples include the compounds listed in Table 2.

Further, specific examples of the cyclic olefin represented by the general formula (II) include the compounds shown in Table 3 and Table 4.

The cyclic olefin random copolymer [A] constituting the composition of the present invention has an ethylene component and the above-mentioned cyclic olefin component as essential components, but in addition to these two essential components, the object of the present invention If necessary, other copolymerizable unsaturated monomer components may be contained within a range that does not impair the properties. Specifically, the optionally copolymerized unsaturated monomers include, for example, propylene, 1-butene, and 4-methyl-1 in an amount less than equimolar to the ethylene component unit in the random copolymer to be produced. -Pentene, 1-hexene, ■-octene, 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene,
Examples include α-olefins having 3 to 20 carbon atoms such as 1-eicosene.

In the cyclic olefin random copolymer [A] constituting the composition of the present invention, the repeating unit (a) derived from the ethylene component is 40 to 85 mol%, preferably 50 to 7
The repeating unit (b) derived from the cyclic olefin component is in the range of 5 mol%, 15 to 60 mol%, preferably 25 to 5 mol%.
A range of 0 mol% is suitable, and the repeating unit (a) derived from the ethylene component and the repeating unit (b) derived from the cyclic olefin component form a substantially linear cyclic olefin-based random copolymer arranged randomly. are doing.

The fact that the cyclic olefin random copolymer is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving the copolymer in decalin at 135°C.

The intrinsic viscosity [η] of the cyclic olefin random copolymer [A] constituting the composition of the present invention measured in decalin at 135°C is 0.05 to 10 So/g, preferably 0.08
~5 min/g.

The cyclic olefin random copolymer [A] constituting the composition of the present invention has a softening temperature (TMA) of 70°C or higher, preferably 90 to 250°C, more preferably 100°C or higher, as measured by a thermomechanical analyzer. ~20
0°C range, cyclic olefin random copolymer [A]
The glass transition temperature (Tg) of is usually 50 to 230°C, preferably 70 to 210°C. Further, the crystallinity of the cyclic olefin random copolymer [A] measured by X-ray diffraction method is 0 to 10%, preferably 0 to 7%,
Particularly preferred is a range of 0 to 5%.

As the cyclic olefin random copolymer [A] constituting the composition of the present invention, a copolymer consisting only of those having physical properties within the above range may be used, but a copolymer having physical properties outside the above range may be used. Some coalescence may be included, and in this case, it is sufficient that the physical property values of the whole are within the above range.

The cyclic olefin random copolymer [A] constituting the composition of the present invention is disclosed in JP-A-60-168708, JP-A-61-1.20816, and JP-A-61-115.
Publication No. 912.

JP-A-61-115916, JP-A-61-271
308, JP 61-272216, JP 62-252406, JP 62-25240
It can be produced by appropriately selecting conditions according to the method proposed by the applicant in Publication No. 7 and the like.

The α-olefin copolymer [B] constituting the cyclic olefin random copolymer composition according to the present invention is an amorphous or low-crystalline copolymer formed from at least two types of α-olefins. Specifically, (i) ethylene/α-olefin copolymer, (■) propylene/α-
Olefin copolymers are used.

(i) Constitutes an ethylene/α-olefin copolymer
Examples of α-olefins include α-olefins usually having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, ■-hexene, 4-methyl-1-petene, 1-octene, 1-decene, or these. Examples include mixtures of the following. Especially propylene or 1
-Butene is preferred.

(■) The α-olefin constituting the propylene/α-olefin copolymer is usually an α-olefin having 4 to 20 carbon atoms, such as 1-butene, 1-petene,
Examples include 1-hexene, 4-methyl-1-pentene, 1-octene, -decene, and mixtures thereof. Among these, 1-butene is particularly preferred.

In the above (i) ethylene/α-olefin copolymer, the molar ratio of ethylene to α-olefin (
Ethylene/α-olefin) is generally preferably from 50150 to 9515, although it varies depending on the type of α-olefin. The above molar ratio is preferably 50,150 to 90/10 when the α-olefin is propylene, and preferably 60/40 to 9,515 when the α-olefin has 4 or more carbon atoms. .

In the above (it) propylene/α-olefin copolymer, the molar ratio of propylene to α-olefin (propylene/α-olefin) varies depending on the type of α-olefin, but is generally 50150 to 95.
It is preferable that it is 15.

It is desirable that the α-olefin copolymer [B] has a crystallinity of 0 to 50%, preferably 0 to 25%, as measured by X-ray diffraction.

In addition, the intrinsic viscosity [η] of the α-olefin copolymer [B] measured in decalin at 135°C is 0.2 to 10 dl/
g.

Preferably it is 1 to 7 dl/g.

The styrenic copolymer [C] constituting the cyclic olefin random copolymer composition according to the present invention has styrene or its derivative as one of the monomer constituents, and at least one of the glass transition temperatures is 0°C. The following are amorphous or low crystalline copolymers, specifically random copolymers and block copolymers of styrene or α-methylstyrene and butadiene or isoprene, and hydrogenated products thereof. can give.

The cyclic olefin random copolymer composition according to the present invention comprises a cyclic olefin random copolymer [A1100 parts by weight, an α-olefin copolymer [B], a styrene copolymer [C] The total amount of is 5 to 100 parts by weight,
Preferably 7 to 80 parts by weight, particularly preferably 10 to 70 parts by weight
It is present in an amount of parts by weight.

For 100 parts by weight of component [A], component [8] and [C
] If the total amount of the components is less than 5 parts by weight, although the rigidity is excellent, the impact resistance is poor, so it is not preferable;
If it exceeds 0.00 parts by weight, although the impact resistance is excellent,
It is unfavorable because its rigidity is low and the balance between rigidity and impact strength is poor. [B] component and [C] acid component ratio is 9 in terms of polymerization ratio.
5:5-5:95, preferably 90:10-10:
The range is 90. If each proportion is less than 5% by weight, the effect of improving impact resistance becomes small, which is not preferable.

The composition of the present invention includes, in addition to the above acid components [A] to [C], a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, and a natural oil. , synthetic oil, wax, etc. can be blended, and the blending ratio is appropriate.

For example, as a stabilizer that may be added as an optional component, tetrakis[methylene-3 (3,5-di-t-
Butyl-4-hydroxyphenyl)propionate comethane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate alkyl ester, 2.27-
Phenolic antioxidants such as oxamide bis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate, fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate, glycerin mono stearate,
Examples include polyhydric alcohol fatty acid esters such as glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination; for example, tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane and zinc stearate and Examples include combinations with glycerin monostearate.

As a method for producing the cyclic olefin random copolymer composition according to the present invention, known methods can be applied. A method of mechanically blending the polymer [C] and other components added as necessary using an extruder, kneader, etc., or a method of blending each component with a suitable good solvent such as hexane, heptane, decane, cyclohexane, benzene, Examples include a method of simultaneously dissolving in a hydrocarbon solvent such as toluene and xylene, or dissolving each separately and then mixing to remove the solvent, and a method of combining these two methods.

The cyclic olefin random copolymer composition obtained in the above manner has the heat resistance and chemical resistance of the cyclic olefin random copolymer [A] because it contains the [B] and [C] acid components in the [A] component. , impact resistance can be improved without impairing excellent properties such as solvent resistance and dielectric properties. In this case, by using the α-olefin copolymer [B], the styrene copolymer, and [C] in combination, the performance is dramatically improved compared to a composition in which these are used alone.

The cyclic olefin random copolymer composition of the present invention is
Due to the above characteristics, it can be used in the same applications as polycarbonate, ABS, etc., such as automobile interior materials.

〔Effect of the invention〕

The cyclic olefin random copolymer composition of the present invention is
Cyclic olefin random copolymer [A], α-olefin copolymer [B], and styrene copolymer [C]
Therefore, it has excellent heat resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, etc., as well as excellent #t'fA@ properties.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

In addition, the measuring method and evaluation method of various physical property values in this invention are shown next.

(1) Melt flow index (MRFzso℃) ASTM 01
Measurement was conducted at a temperature of 260° C. and a load of 2.16 kg according to 238.

(2) Preparation of test piece Using injection molding fiIs-35 manufactured by Toshiba Machinery Co., Ltd. and a predetermined test piece mold, molding was performed under the following molding conditions. After molding, the test piece was left at room temperature for 48 hours and then subjected to measurement.

Molding conditions Nijilinda temperature 220℃, mold temperature 60℃, injection pressure primary/secondary = 1000/800kg/cA
, injection speed (-order) 30 mm/see, screw rotation speed 1.5 Orpm, cycle ([injection + holding pressure]/cooling)
=7/15eC (3) Bending test Conducted according to ASTM 0790.

Test piece shape: 5X1/2X1/8t inches, distance between spans 511Ilal Test speed: 20mm/! ll1n Test temperature = 23°C (4) Izot impact test It was conducted according to ASTM D256.

Test piece shape: 2 x 1/2 x 1/8 t inch (notched) Test temperature: 23°C (5) Heat distortion temperature (HDT) Tested according to ASTM 064g.

Test piece shape: 5X1/4Xl/2t inch Load:
264ρ5i (6) Glass transition temperature (Tg) Measured using DSC-20 manufactured by SEIKO Electronics Co., Ltd. at a temperature increase rate of 10° C./min.

Example 1 ``Ethylene content measured by 3C-NMR ft52mol1
%, MFRzso-c35g/10+sin, 135
Intrinsic viscosity [η] measured in decalin at °C 0.47 S/g
, 4 kg of random copolymer pellets (abbreviated as 20 MON) with a softening temperature (TMA) of 148°C, 4 kg of ethylene-propylene random copolymer (ethylene content 80 mo1%, T
g-54℃, NFR0.7g/Lowin, 230℃ [η)2.2dl/g) pellets, 1kg of styrene.
Butadiene-styrene block copolymer (Califlex TR-1101, trademark, manufactured by Shell Chemical Co., Ltd., Tg-8
After thoroughly mixing 1 kg of pellets at temperatures of 0° C. and 95° C., they were melt-blended using a twin-screw extruder (PCM 45 manufactured by Ikegai Tekko Co., Ltd.) at a cylinder temperature of 220° C., and pelletized using a pelletizer. Using the obtained pellets, test pieces were prepared by the method described above, and the physical properties were measured.

The results are shown in Table 5.

Example 2.3 The same procedure as in Example 1 was conducted except that the amounts of the ethylene/propylene random copolymer and the styrene/butadiene/styrene block copolymer used in Example 1 were changed.

The results are shown in Table 5.

Examples 4 to 8 The same procedure as in Example 1 was conducted except that various styrene copolymers were used in place of the styrene-butadiene-styrene block copolymer used in Example 1. The results are shown in Table 6.

Example 9 In place of the ethylene/DMON random copolymer used in Example 1, ethylene content 71 mo1%, MFRz6
o℃20g/10+ni,n,(η)0.60dll/
g, TMA The same procedure as in Example 1 was carried out except that the 115°C ethylene/DHON random copolymer was used. MFR260'C-Izod impact strength of the resulting composition,
Flexural modulus, bending strength, )IDT are each 6.7 g/
10m1n, 29kg-cm/c++18000kg/
ci, 690 kg/cd, and 93°C.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the styrene-butadiene-styrene block copolymer was not used and the amount of the ethylene-propylene random copolymer used was changed to 2 kg.

The results are shown in Table 7.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the ethylene/propylene random copolymer was not used and the amount of the styrene/butadiene/styrene block copolymer used was changed to 2 kg.

The results are shown in Table 7.

Agent: Patent attorney Sei Yanagi Hara

Claims (1)

[Claims] (1) [A] Consists of an ethylene component and a cyclic olefin component represented by the following general formula [I] or [II],
The intrinsic viscosity [η] measured in decalin at 135°C is 0.
05 to 10 dl/g, a cyclic olefin random copolymer with a softening temperature (TMA) of 70°C or higher, [B] an amorphous to low crystalline α-olefin formed from at least two types of α-olefins and [C] styrene or a derivative thereof as one of the monomer constituents, consisting of an amorphous or low crystalline styrenic copolymer having at least one glass transition temperature of 0 ° C. or lower, For 100 parts by weight of the above [A] component, [B]
The total amount of component [B] and component [C] is 5 to 100 parts by weight, and the ratio of component [B] to component [C] is 95:
A cyclic olefin random copolymer composition characterized in that the ratio is 5 to 5:95. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, n and m are both 0 or a positive integer, and l is 3 or more is an integer between R^1 and R^1^0
each represents a hydrogen atom, a halogen atom, or a hydrocarbon group. ]