JPH0819292B2 - Thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent impact resistance, and more specifically, to an excellent resistance to an ethylene / polycyclic olefin copolymer as a main component. The present invention relates to a thermoplastic resin composition having impact properties.

Technical Background of the Invention and Problems Thereof Conventionally, as an amorphous thermoplastic resin excellent in heat resistance, as disclosed in JP-A-60-168708 and JP-A-61-115916, ethylene is disclosed. -Polycyclic olefin copolymers are known. This ethylene / polycyclic olefin copolymer is not only excellent in heat resistance, but also excellent in moisture absorption resistance, chemical resistance, solvent resistance, etc., so that it is used for communication equipment, OA equipment, audio equipment and optical equipment. Parts of precision instruments such as instruments are suitable as molding materials.

However, when this ethylene / polycyclic olefin copolymer is used alone, there is a problem that the impact resistance is poor.

Therefore, the inventors of the present invention have earnestly studied the improvement of the impact resistance of the ethylene / polycyclic olefin copolymer, and found that the ethylene / polycyclic olefin copolymer has a specific ethylene / α-olefin random copolymer or The inventors have found that a composition prepared by blending a specific propylene / α-olefin copolymer has excellent impact resistance, and completed the present invention.

OBJECT OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has excellent impact resistance,
It is an object of the present invention to provide a thermoplastic resin composition containing an ethylene / polycyclic olefin copolymer as a main component.

SUMMARY OF THE INVENTION The thermoplastic resin composition according to the present invention is a random copolymer of ethylene and a monomer component represented by the following formula [I] having an ethylene content of 40 to 90 mol%. And the monomer component has a structure represented by the following formula [II] a random copolymer 98 to 50% by weight, (In the formula, R ^{1 to} R ¹² are hydrogen, an alkyl group or halogen, and may be the same or different, and further, R ⁹
Alternatively, R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. n is 0 or a positive integer of 1 or more, and when R ^{5 to} R ⁸ are repeated a plurality of times, these R ⁵ to R ⁸
R ⁸ may be the same or different. ) (Wherein R ^{1 to} R ¹² and n are the same as those in the above [I]), and [B] the ethylene content is 35 to 50 mol%, and the crystallinity by X-ray is 5% or less. An ethylene / propylene random copolymer (B-1) or ethylene and an α-olefin having 3 or more carbon atoms, the crystallinity by X-ray is 0 to 50%, and the ethylene content is 30 to A copolymer (B-2) formed by graft-modifying 95 mol% of an ethylene / α-olefin random copolymer with a graft monomer selected from unsaturated carboxylic acids or derivatives thereof (B-2) in an amount of 2 to 50% by weight. It has a feature.

Specific description of the invention Hereinafter, the thermoplastic resin composition according to the present invention will be specifically described.

Random Copolymer [A] The random copolymer [A] used in the present invention is a random copolymer of ethylene and a monomer component represented by the above formula [I], and has an ethylene content of 40. ~
A random copolymer having 90 mol%, preferably 50 to 85 mol%, and a monomer component having a structure represented by the above formula [II] is used.

A random copolymer having an ethylene content of more than 90 mol% has low heat resistance and is not suitable for use in parts of precision equipment.

The random copolymer [A] used in the present invention has an intrinsic viscosity [η] of 0.03 to 1 measured at 135 ° C. in a decalin solvent.
0dl / g, crystallinity by X-ray diffraction is 10% or less, iodine value is 5 or less, and glass transition temperature (Tg)
Is preferably in the range of 50 to 250 ° C. Among them, the intrinsic viscosity is 0.1 to 5 dl / g, the crystallinity is 5% or less, the iodine value is 1 or less, and the glass transition temperature is 60 to
Random copolymers within the range of 200 ° C. are especially preferred.

Specific examples of the monomer component represented by the above formula [I] used as the copolymerization component of the random copolymer [A] of the present invention include the following monomer components.

Of these, n = 1 in formula [I], that is, formula [III], The monomer component represented by is preferable in terms of availability of the monomer or easiness of synthesizing the monomer. Furthermore R ¹
A monomer component in which R ¹² is hydrogen is more preferable from the viewpoint of heat resistance and solvent resistance.

To produce the above-mentioned monomer component, for example, US Pat. No. 3,557,072 (Japanese Patent Publication No. 46-14910) or
No. 154133 can be applied.

The copolymer of the monomer component of the formula [I] and ethylene may be copolymerized with another monomer component of less than equimolar amount with ethylene, for example, as long as the property is not impaired. Specific examples thereof include α-olefins and cyclic olefins. As α-olefins, usually α-olefins having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as propylene, 1-butene and 3-methyl are included. -1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,
1-tetradecene, 1-hexadecene, 1-eicosene and the like are used. Further, as the cyclic olefin, cycloolefins or styrenes having no bridge, for example, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene,
3-Methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, styrene, α-methylstyrene and the like are used, and polyenes such as dicyclopentadiene, ethylidene norbornene and vinyl norbornene can also be used. It is also possible to copolymerize unsaturated carboxylic acids such as (anhydrous) maleic acid.

Such a polymer is produced by polymerizing the monomer components as described above using a well-known Ziegler catalyst, particularly a vanadium-based Ziegler catalyst. More specifically, the prior patent application by the applicant (for example,
60-168708).

The characteristic feature of the polymer of the present invention thus obtained is that the monomer component of the formula [I] mainly has the structure represented by the formula [II] in the polymer. The value is usually 5 or less, and most are 1 or less. Moreover, ¹³ C-NMR confirms that this structure is adopted.

And, by taking such a structure, the resulting polymer is chemically stable, excellent in water resistance and chemical resistance such as alkali and acid, further solvent resistance, heat resistance, weather resistance. Is also excellent. Further, such a polymer is
It has an extremely low water content and has excellent dimensional accuracy.

Ethylene / α-olefin random copolymer [B] The ethylene / α-olefin random copolymer [B] used in the present invention is ethylene and α having 3 or more carbon atoms.
Is an ethylene / α-olefin random copolymer composed of -olefin and has a crystallinity of 0 to 50% by X-ray,
Preferably it is 0-40% and the ethylene content is 30
~ 95 mol%, preferably 35-93 mol%, but with 3 carbon atoms
The above α-olefins are those with 3 to 18 carbon atoms
Olefin is used, and specific examples thereof include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-decene, and the like, and they are used as one kind or a mixture of two or more kinds.

Further, the ethylene / α-olefin random copolymer [B] is usually used as a melt flow rate (MFR: ASTM D 1238,
E) is 0.1 to 50 g / 10 min, preferably 0.2 to 20 g / 10 min, and the density is 0.850 to 0.905 g / cm ³ , preferably 0.855 to 0.900 g / cm ^3.
Is in the range.

This ethylene / α-olefin random copolymer is
Usually, it is a copolymer of an ethylene component and an α-olefin, but depending on the case, a diene component may be contained in a trace amount, for example, 0.5 mol or less.

The ethylene / α-olefin random copolymer [B] is used in an amount of 2 to 50 parts by weight, preferably 5 to 30 parts by weight, based on the composition.

The ethylene / α-olefin random copolymer [B] used in the present invention is a graft monomer selected from unsaturated carboxylic acids or their derivatives in an amount of 0.01 to 5% by weight, preferably 0.1 to 4% by weight. It may be a prepared copolymer.

 In the present invention, the ethylene / α-olefin copolymer [B] is
Unsaturated carboxylic acid used for modification or its
Derivatives include acrylic acid, maleic acid, fumar
Acid, tetrahydrophthalic acid, itaconic acid, citracone
Acid, crotonic acid, isocrotonic acid, nadic acid (En
Docis-bicyclo [2,2,1] hept-5-ene-2,3-dica
Carboxylic acid) or its derivative
Bodies such as acid halides, amides, imides, anhydrides,
Stell, etc.
Reimide, maleic anhydride, citraconic anhydride, male
Monomethyl acid salt, dimethyl maleate, glycidyl male
Ato etc. are used. Among these, unsaturated Zika
Rubonic acid or its acid anhydride is preferred, especially maleic acid.
Acid, nadic acid Alternatively, these acid anhydrides are preferable.

A graft monomer selected from such unsaturated carboxylic acids or derivatives thereof is graft-copolymerized with an ethylene / α-olefin random copolymer to obtain modified ethylene / α-olefin.
For producing the α-olefin random copolymer, various conventionally known methods can be adopted. For example, a method of melting the ethylene / α-olefin random copolymer and adding a graft monomer to perform graft polymerization,
Alternatively, there is a method of dissolving in a solvent and adding a graft monomer to carry out graft copolymerization. In any case, it is preferable to carry out the reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The ratio of radical initiator used is ethylene / α-
Usually 0.0 per 100 parts by weight of olefin random copolymer
It is in the range of 01 to 1 part by weight.

Radical initiators include organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne- 3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate,
2,5-Dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-
Butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, ter
t-butyl perpivalate, cumyl pen pivalate and
There are tert-butyl perdiethyl acetate and other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-
3,2,5-dimethyl-2,5-di (tert-butylperoxy)
Dialkyl peroxides such as hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.

Among the ethylene / α-olefin random copolymers [B], ethylene / propylene random copolymer (B-1) or ethylene / α-olefin having an ethylene content of 35 to 50 mol% and a crystallinity of 5% or less. The copolymer (B-2) graft-modified with a graft monomer selected from unsaturated carboxylic acids or derivatives thereof of the random copolymer [B] is most preferable because it has the best effect of improving impact strength.

The thermoplastic resin composition of the present invention, in addition to the above components,
To the extent that the objects of the present invention are not impaired, for example, glass fibers, potassium titanate fibers, fibrous reinforcing agents such as carbon fibers, heat resistance stabilizers, weather resistance stabilizers, lubricants, nucleating agents, antistatic agents, dyes, pigments, and May contain an inorganic powder filler such as talc, calcium carbonate, wollastonite, mica and silica.

The thermoplastic resin composition of the present invention can be processed into various molded articles by various known molding methods such as injection molding, extrusion molding and compression molding.

Advantageous Effects of Invention The thermoplastic resin composition according to the present invention is an ethylene / polycyclic olefin copolymer [A] random copolymer,
Since it is composed of the above-mentioned [B] ethylene / α-olefin random copolymer, it can be obtained by molding parts of precision equipment such as communication equipment, OA equipment, audio equipment and optical equipment using this composition. The molded article obtained has excellent impact resistance, and this composition is also excellent in heat resistance, moisture absorption resistance, chemical resistance, solvent resistance and the like.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is
It is not limited to these examples.

Reference Example (Synthesis of Ethylene Polycyclic Olefin Copolymer) Using a 2 liter glass polymerization vessel equipped with a stirring blade, ethylene and polycyclic olefin 1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene (Structural formula: , Hereinafter, abbreviated as DMON). That is,
From the top of the polymerization vessel, a cyclohexane solution of DMON with a DMON concentration of 60 g / l in the polymerization vessel and a cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst were added.
0.9 mmol / l, ethyl aluminum sesquichloride (Al (C ₂
A cyclohexane solution of (H ₅ ) _1.5 Cl _1.5 ) was continuously fed into each of the polymerization reactors so that the aluminum concentration in the polymerization reactor was 7.2 mmol / l. The polymerization liquid of 1 is continuously withdrawn so that it is always 1. Further, from the upper part of the polymerization vessel, ethylene is supplied at a rate of 85 l / h, hydrogen is supplied at a rate of 6 l / h, and nitrogen is supplied at a rate of 45 l / h. The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant through a jacket attached outside the polymerization vessel.

When the copolymerization reaction is performed under the above conditions, a polymerization reaction mixture containing an ethylene polycyclic olefin (ethylene / DMON) copolymer is obtained. A small amount of isopropyl alcohol was added to the polymerization liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction. Then, the polymerization solution was charged into a household mixer containing about 3 times the amount of acetone with respect to the polymerization solution while rotating the mixer to precipitate the produced copolymer. The precipitated copolymer was ingested by filtration, and the polymer concentration was about 50 g /
The mixture was dispersed in acetone so as to have a volume of 1 and the copolymer was treated at the boiling point of acetone for about 2 hours. After the treatment described above, the copolymer was ingested by filtration and dried under reduced pressure at 120 ° C. for 24 hours.

¹³ C-N of the ethylene / DMON random copolymer (ethylene polycyclic olefin copolymer) obtained as described above
The ethylene composition in the copolymer measured by MR analysis was 59 mol%, and the intrinsic viscosity [η] measured in 135 ° C decalin was 0.42d.
The l / g and glass transition temperature were 136 ° C.

Comparative Example 1 Ethylene polycyclic olefin copolymer obtained in the above reference example
90% by weight, X-ray crystallinity 5%, ethylene content
After mixing 80 mol%, 10 wt% of ethylene / propylene random copolymer (hereinafter abbreviated as EPC-I) having a MFR of 4.6 g / 10 min and a density of 0.865 g / cm ³ with a Henschel mixer,
A 40 mmφ uniaxial extruder (set temperature: 230 ° C.) was melt-kneaded and granulated to obtain a composition. Then, this composition was injection-molded (cylinder temperature: 240 ° C., mold temperature: 70 ° C.) to obtain a test piece for physical property evaluation.

The bending test (ASTM D 790) and the Izod impact test (ASTM
D 256, without notch).

 Table 1 shows the results.

Comparative Example 2 In Comparative Example 1, except that 70% by weight of the ethylene polycyclic olefin copolymer and 30% by weight of EPC-I were used,
In the same manner as in Comparative Example 1, a test piece for evaluating physical properties was obtained, and a bending test and an Izod impact test were performed.

 Table 1 shows the results.

Comparative Example 3 In Comparative Example 1, instead of EPC-I, crystallinity by X-ray 25%, ethylene content 92 mol%, MFR18g / 10min,
A test piece for physical property evaluation was obtained in the same manner as in Comparative Example 1 except that an ethylene / 1-butene random copolymer having a density of 0.895 g / cm ³ was used, and a bending test and an Izod impact test were performed.

 Table 1 shows the results.

Example 1 In Comparative Example 1, instead of EPC-I, the crystallinity by X-ray was 1%, the ethylene content was 40 mol%, and the MFR was 1.0 g / 10 mi.
A test piece for physical property evaluation was obtained in the same manner as in Comparative Example 1 except that an ethylene / propylene random copolymer having n and a density of 0.858 g / cm ³ was used, and a bending test and an Izod impact test were performed.

 Table 1 shows the results.

Example 2 In Comparative Example 1, instead of EPC-I, the crystallinity by X-ray was 17%, ethylene content was 89 mol%, MFR4.0g / 10mi.
Modified ethylene-1-butene random copolymer obtained by graft-copolymerizing 0.5 part by weight of maleic anhydride with 100 parts by weight of ethylene / 1-butene random copolymer having n and a density of 0.885 g / cm ³ (crystallization by X-ray 15%, MFR 2.5 g / 10 min) was used, and in the same manner as in Comparative Example 1, a test piece for evaluating physical properties was obtained, and a bending test and an Izod impact test were performed.

 Table 1 shows the results.

Comparative Example 4 A test piece for physical property evaluation was obtained in the same manner as in Comparative Example 1 except that only the ethylene polycyclic olefin copolymer was used for injection molding instead of the composition of Comparative Example 1. Then, a bending test and an Izod test were performed.

 Table 1 shows the results.

Claims (1)

[Claims] 1. A random copolymer of [A] ethylene having a content of ethylene of 40 to 90 mol% and a monomer component represented by the following formula [I], wherein the monomer component is represented by the following formula: A random copolymer having a structure represented by [II]: 98 to 50% by weight, (In the formula, R ^{1 to} R ¹² are hydrogen, an alkyl group or halogen and may be the same or different, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. N may be 0 or a positive integer of 1 or more,
When R ^{5 to} R ⁸ are repeated multiple times, R ^{5 to} R ⁸ may be the same or different. ) (Wherein R ^{1 to} R ¹² and n are the same as those in the above [I]), and [B] ethylene content is 35 to 50 mol%, and crystallinity by X-ray is 5% or less. An ethylene / propylene random copolymer (B-1) or ethylene and an α-olefin having 3 or more carbon atoms, the crystallinity by X-ray is 0 to 50%, and the ethylene content is 30 to Copolymer (B-2) obtained by graft-modifying 95 mol% of ethylene / α-olefin random copolymer with a graft monomer selected from unsaturated carboxylic acid or its derivative: 2 to 50% by weight A thermoplastic resin composition comprising: