JPH06263938A - 4-methyl-1-pentene polymer composition - Google Patents

Abstract

PURPOSE:To obtain a 4-methyl-1-pentene polymer composition having excellent heat-resistance and impact resistance, free from change of strength and dimension by water-absorption and suitable for various structural materials. CONSTITUTION:This 4-methyl-1-pentene polymer composition contains (A) 60-95 pts.wt. of a 4-methyl-1-pentene polymer, (B) 40-5 pts.wt. of a polyphenylene sulfide and (C) 0.5-20 pts.wt. (based on 100 pts.wt. of A+B) of a styrene- ethylene.butylene-styrene block copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 4-methyl-1-pentene polymer composition, and in particular, it has excellent heat resistance and impact resistance, has no strength change or dimensional change due to water absorption, and has various structures. The present invention relates to a 4-methyl-1-pentene polymer composition suitable as a material.

[0002]

2. Description of the Related Art A 4-methyl-1-pentene polymer is
It has excellent transparency, a melting point of 220 to 240, and a high heat deflection temperature, and is therefore widely used for various purposes. But,
Because of its low mechanical strength, impact resistance, or low temperature rigidity, it has limited applications as a structural material. Therefore, in order to improve the rigidity of the 4-methyl-1-pentene-based polymer at high temperature, a composition containing a 4-methyl-1-pentene-based polymer and polyphenylene sulfide as main components has been proposed. (Kaihei 2-67349, JP-A-3-33140). This composition has high rigidity at high temperatures, low water absorption, and excellent hydrolysis resistance, so that there is no dimensional change or mechanical strength reduction due to water absorption,
Suitable for structural materials.

[0003]

However, 4-methyl-
Since the 1-pentene polymer and polyphenylene sulfide have poor compatibility, a simple blend of these two components results in large dispersed particles of polyphenylene sulfide, and the resulting composition has low impact resistance and is brittle. Low industrial value. Therefore, there is a strong demand for materials that have high impact resistance, high rigidity at high temperature, and high mechanical strength, and that do not suffer from mechanical strength reduction or dimensional change due to water absorption.

Therefore, an object of the present invention is to maintain the rigidity at high temperature, to have excellent heat resistance and impact resistance, and to have no strength change or dimensional change due to water absorption, which is suitable for various structural materials. It is to provide a 1-pentene polymer composition.

[0005]

The present inventors have improved the impact resistance of a composition containing a 4-methyl-1-pentene polymer and polyphenylene sulfide while maintaining the rigidity at high temperature. As a result of various studies aimed at that,
It was found that a composition containing a 4-methyl-1-pentene polymer and polyphenylene sulfide, and further containing a styrene-ethylene / butylene-styrene block copolymer in a specific ratio can solve the above-mentioned problems, and the present invention is achieved. It came to completion.

That is, the present invention provides (A) 4-methyl-
60 to 95 parts by weight of 1-pentene polymer, 40 to 5 parts by weight of (B) polyphenylene sulfide, and (A)
+ (B) 100 parts by weight of (C) styrene-ethylene / butylene-styrene block copolymer 0.5 to 20
The present invention provides a 4-methyl-1-pentene-based polymer composition containing 1 part by weight.

The 4-methyl-1-pentene polymer composition of the present invention (hereinafter referred to as "the composition of the present invention") will be described in detail below.

The 4-methyl-1-pentene polymer, which is the component (A) of the composition of the present invention, is a polymer containing 4-methyl-1-pentene as a main component, and is 4-methyl-1-pentene. It is a homopolymer of pentene or a random copolymer of 4-methyl-1-pentene and other α-olefin.
Other α-olefins include, for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1
-Α-olefins having 2 to 20 carbon atoms such as decene, 1-dodecane, 1-tetradecene, 1-hexadecane, 1-octadecene, 1-eicosene, etc., and these include one kind alone or a combination of two or more kinds. It may be. Among these other α-olefins, 1-decene, 1-dodecane, 1-tetradecane, 1-hexadecane, 1-octadecane and 1-eicosene are preferable.

The content of 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (A) is
The melting point of the 4-methyl-1-pentene-based polymer (A) is in an appropriate range, and a composition excellent in rigidity at high temperature and suitable for a structural material can be obtained, and thus is usually 80% by weight or more, preferably 90 to It is 99% by weight.

The 4-methyl-1-pentene polymer (A) has a load of 5.0 k according to ASTM D1238.
g, temperature: melt flow rate (MFR) measured under the conditions of 260 ° C. is 0.1 to 200 g / 10 minutes, particularly preferably 1 to 1 from the viewpoint that a composition having excellent impact resistance can be obtained.
It is at 00 g / 10 minutes.

The polyphenylene sulfide which is the component (B) of the composition of the present invention has the following formula (b-1):

[0012]

[Chemical 1]

[In the formula, n is an integer of 10 to 500]
The main component is a repeating structural unit represented by and a small amount of another copolymerizable component unit may be contained.

Other copolymerizable component units include, for example, the following formula:

[0015]

[Chemical 2]

The repeating structural unit represented by:

In the polyphenylene sulfide (B) used in the present invention, the content of the other copolymerizable component unit is preferably 0.1 to 20% by weight, particularly 0.5 to 10% by weight. Some are preferred.

This polyphenylene sulfide (B)
Is preferably one having a melt viscosity of 100 to 50,000 poise under the conditions of 300 ° C. and a shear rate γ = 100 sec ⁻¹ , particularly preferably 200 to 40,000 poise.

Specific examples of the polyphenylene sulfide (B) include crosslinked K-3 and K manufactured by Topren Co., Ltd.
-4, semi-linear type T-1, T-2, T-3, T-4,
T-4AG, T-7, and linear type LN-1, LN
-2, LCX-4, LCX-7, etc., or cross-linked M2900 manufactured by Toray Phillips Petroleum Co., Ltd.,
M2100, Linear type M2888, M2588, E24
80, E1880 and the like, and products equivalent thereto.

In the composition of the present invention, 4-methyl-
The compounding ratio of the 1-pentene-based polymer (A) and the polyphenylene sulfide (B) is 40 to 5 parts by weight of the polyphenylene sulfide (B) with respect to 60 to 95 parts by weight of the 4-methyl-1-pentene-based polymer (A). The ratio is parts by weight.

The styrene-ethylene / butylene-styrene block copolymer, which is the component (C) of the composition of the present invention, comprises a block polymer unit derived from styrene and a block copolymer unit derived from ethylene / butylene. It is a copolymer having both.

The content ratio of styrene / rubber (ethylene / butylene) in the styrene / ethylene / butylene / styrene block copolymer (C) is such that the compatibilizing agent of the styrene / ethylene / butylene / styrene block copolymer (C) is used. Also, from the viewpoint that the composition exerts a role as rubber and is excellent in impact resistance, it is preferably 10/90 to
60/40, particularly preferably 15 / 85-50 /
It is a ratio of 50.

In the composition of the present invention, the styrene-ethylene / butylene-styrene block copolymer (C) has a load of 2.1 according to ASTM D1238.
Melt flow rate (MFR) measured at 6 kg and temperature: 230 ° C. is preferably 0.01 to 200 g / 10.
Min, particularly preferably 0.1 to 50 g / 10 min.

Further, the styrene-ethylene / butylene-styrene block copolymer (C) may be graft-modified with various monomers without changing its basic characteristics. Examples of the monomer used for the graft modification include maleic anhydride, maleic acid, glycidyl methacrylate and the like. When the styrene-ethylene / butylene-styrene block copolymer (C) is graft-modified, the graft amount is usually about 0.1 to 10% by weight, preferably 0.2.
It is about 5% by weight.

Specific examples of the styrene-ethylene / butylene-styrene block copolymer (C) include Kraton G1650 and Kraton 165 manufactured by Shell Chemical Co., Ltd.
2, Clayton 1657X, Clayton 1726X and Clayton FG1901X, and Tuftec H1052, H1041, H1051, M manufactured by Asahi Kasei Corporation.
1913 and M1943 or the like, or an equivalent product thereof. Among these, Clayton G1
726 and Tuftec H1051 are preferred.

In the composition of the present invention, the roles of the styrene-ethylene / butylene-styrene block copolymer (C) as a compatibilizer and a rubber component are sufficiently exhibited,
In addition, the increase in the dispersed particle size of polyphenylene sulfide is suppressed, the impact resistance is sufficiently improved, and the rigidity at high temperature is good, so that styrene-ethylene-butylene-
The mixing ratio of the styrene block copolymer (C) is 0.5 with respect to 100 parts by weight of the total of the 4-methyl-1-pentene polymer (A) and the polyphenylene sulfide (B).
The proportion is from 20 to 20 parts by weight, and particularly preferably from 1 to 10 parts by weight.

The composition of the present invention comprises, in addition to the (A) 4-methyl-1-pentene polymer and (B) polyphenylene sulfide, if necessary, a silane coupling agent, a weather resistance stabilizer, a heat resistance stabilizer. Various additives commonly used for polyolefins such as slip agents, nucleating agents, pigments and dyes may be added within a range that does not impair the object of the present invention.

The composition of the present invention can be produced by the method described in (A) 4-
Methyl-1-pentene polymer, (B) polyphenylene sulfide, (C) styrene-ethylene / butylene-
The styrene block copolymer and, if necessary, various other compounding ingredients may be dry-blended or mixed, melt-kneaded, and further granulated or pulverized. Examples of the mixing method include various known methods such as a V-type blender, a ribbon blender, a Henschel mixer, and a tumbler blender. Examples of the melt kneading method include a single-screw extruder and a multi-screw extruder. A method using a machine, a kneader, a Banbury mixer or the like can be used.

When (A) 4-methyl-1-pentene polymer and (B) low density polyethylene are melt-blended in the composition of the present invention, the MFR of the composition obtained by melt-blending is According to ASTM D1238, load: 5.0K, in that a composition having high fluidity, easy production of a desired molded article, and excellent impact resistance can be obtained.
g, temperature: MFR measured under the condition of 260 ° C is 0.1
It is preferably 200 g / 10 minutes, particularly 1 to 10
It is preferably 0 g / 10 minutes.

[0030]

In the composition of the present invention, the styrene-ethylene / butylene-styrene block copolymer (C) is used not only as a rubber component but also as a 4-methyl-1-pentene polymer (A) and polyphenylene sulfide (C). It acts as a compatibilizer for B). Therefore, it is considered that in the composition of the present invention, the dispersed particle size of the polyphenylene sulfide (B) becomes fine, and the impact resistance and the mechanical strength can be improved without lowering the rigidity at high temperature. Further, the composition of the present invention has a low water absorption, a high hydrolysis resistance, no strength reduction or dimensional change due to water absorption,
It is suitable for use in various structural materials.

[0031]

EXAMPLES Examples and comparative examples of the present invention will be given below.
The present invention will be specifically described, but the present invention is not limited to these examples unless it exceeds the gist.

The physical properties in the following examples and comparative examples were measured according to the following methods.

(1) Molding of test piece A test piece was molded by injection molding under the following conditions. Molding conditions Injection molding machine Miki Co., Ltd., M100 Cylinder temperature C1 / C2 / C3 / Nozzle 270/290/300/300 ° C Mold temperature 60 ° C

(2) Evaluation of physical properties Each physical property was measured or evaluated according to the following methods. According to MFR ASTM D1238, it was measured at a load of 5 kg and a temperature of 260 ° C. Izod impact strength Measured according to ASTM D256. Tensile test ASTM-type IV test pieces were prepared and ASTM D
It measured based on 638. Heat distortion temperature (HDT) Measured at a load of 66 psi according to JIS 7206. Dispersion particle size of polyphenylene sulfide (average) A square plate having a size of 110 mm × 120 mm × 2 mm was prepared, the central part thereof was cut, and the cut surface was observed by an electron microscope for measurement.

Example 1 4-Methyl-1-pentene
80 parts by weight of 1-hexadecene copolymer powder (1-hexadecene content: 4.0% by weight, MFR: 0.5 g / 10 minutes), polyphenylene sulfide (Toprene Co., Ltd.)
(Trade name: LN-1) 20 parts by weight and styrene-ethylene / butylene-styrene block copolymer (manufactured by Asahi Kasei Co., Ltd., trade name: H1051) 5 parts by weight, and 3,9-bis [as a stabilizer. 2- (3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] 2,4,8,10
-Tetraoxaspiro [5,5] undecane (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA80) 0.10 parts by weight, penta (erythrityl-tetra-β-mercaptolauryl) propionate (Cypro Kasei Co., Ltd., Trade name: Seanox 412S) 0.30 parts by weight and zinc stearate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: SZ-200)
0) 0.03 parts by weight was blended and mixed at a high speed for 1 minute using a Henschel mixer. The obtained mixture was melt-kneaded with a twin-screw extruder at 310 ° C. to prepare pellets of the composition. This pellet was subjected to MFR measurement.

The pellets thus obtained were subjected to injection molding to prepare test pieces, and the physical properties thereof were measured or evaluated. The results are shown in Table 1.

Example 2 4-Methyl-1-pentene
80 parts by weight of 1-hexadecene copolymer powder (1-hexadecene content: 4.0% by weight, MFR: 0.5 g / 10 minutes), polyphenylene sulfide (Toprene Co., Ltd.)
Made, trade name: LN-2) 20 parts by weight, and styrene-
5 parts by weight of an ethylene / butylene-styrene block copolymer (manufactured by Asahi Kasei Corporation, trade name: M1913) was added to 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy) as a stabilizer. -5-Methylphenyl) propionyloxy) -1,1-dimethylethyl] 2,4,8,1
0-Tetraoxaspiro [5,5] undecane (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA80) 0.10
Parts by weight, penta (erythrityl-tetra-β-mercaptolauryl) propionate (manufactured by Cypro Kasei Co., Ltd., trade name: Seanox 412S) 0.30 parts by weight, and zinc stearate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: SZ-20
00) 0.03 parts by weight, and mixed for 1 minute at high speed using a Henschel mixer. The obtained mixture was melt-kneaded with a twin-screw extruder at 310 ° C. to prepare pellets of the composition. This pellet was subjected to MFR measurement.

The obtained pellet was subjected to injection molding to prepare a test piece, and its physical properties were measured or evaluated. The results are shown in Table 1.

Example 3 4-Methyl-1-pentene
80 parts by weight of 1-hexadecene copolymer powder (1-hexadecene content: 4.0% by weight, MFR: 0.5 g / 10 minutes), polyphenylene sulfide (Toprene Co., Ltd.)
(Trade name: T-4), 20 parts by weight, and 5 parts by weight of styrene-ethylene / butylene-styrene block copolymer (trade name: H1052, manufactured by Asahi Kasei Co., Ltd.) and 3,9-bis as a stabilizer. [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] 2,4,8,10
-Tetraoxaspiro [5,5] undecane (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA80) 0.10 parts by weight, penta (erythrityl-tetra-β-mercaptolauryl) propionate (Cypro Kasei Co., Ltd., Trade name: Seanox 412S) 0.30 parts by weight and zinc stearate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: SZ-200)
0) 0.03 parts by weight was blended and mixed at a high speed for 1 minute using a Henschel mixer. The obtained mixture was melt-kneaded with a twin-screw extruder at 310 ° C. to prepare pellets of the composition. This pellet was subjected to MFR measurement.

The obtained pellet was subjected to injection molding to prepare a test piece, and its physical properties were measured or evaluated. The results are shown in Table 1.

(Comparative Example 1) 4-methyl-1-pentene
80 parts by weight of 1-hexadecene copolymer powder (1-hexadecene content: 4.0% by weight, MFR: 0.5 g / 10 minutes), polyphenylene sulfide (Toprene Co., Ltd.)
Manufactured by Trade Name: T-4), and 3,9-bis [2- (3- (3-tert-butyl-4) as a stabilizer.
-Hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA80) 0.10 parts by weight, penta (erythrityl-tetra-β-mercaptolauryl) propionate (manufactured by Cypro Kasei Co., Ltd., trade name: Synox 412S) 0.30 parts by weight and zinc stearate (manufactured by Sakai Chemical Co., Ltd.) Product name: SZ-200
0) 0.03 parts by weight was blended and mixed at a high speed for 1 minute using a Henschel mixer. The obtained mixture was melt-kneaded with a twin-screw extruder at 310 ° C. to prepare pellets of the composition. This pellet was subjected to MFR measurement.

The obtained pellet was subjected to injection molding to prepare a test piece, and its physical properties were measured or evaluated. The results are shown in Table 1.

[0043]

[0044]

The 4-methyl-1-pentene polymer composition of the present invention is excellent in impact resistance, rigidity at high temperature, mechanical strength, low water absorption and high hydrolysis resistance. ,
It is suitable as a material for various structural materials because it has a small strength reduction and dimensional change due to water absorption.

Therefore, the composition of the present invention is suitable as a material for molding various structural materials by the injection molding method. Further, by the extrusion molding method, it is possible to obtain a film which is excellent in impact resistance, rigidity at high temperature, mechanical strength, has low water absorption, and has high hydrolysis resistance, so that strength reduction and dimensional change due to water absorption are small. . This film is
For example, it can be used as a release film or the like when molding a printed circuit board.

Claims (4)

[Claims] (1) 60-95 parts by weight of (A) 4-methyl-1-pentene polymer, 40-5 parts by weight of (B) polyphenylene sulfide, and 100 parts by weight of (A) + (B). (C) Styrene-ethylene / butylene-styrene block copolymer 0.5 to 20 parts by weight, and a 4-methyl-1-pentene polymer composition. 2. The (A) 4-methyl-1-pentene polymer is a random copolymer containing an α-olefin having 2 to 20 carbon atoms and 4-methyl-1-pentene.
The 4-methyl-1-pentene polymer composition according to claim 1, wherein the content of -methyl-1-pentene is 80% by weight or more. 3. The (A) 4-methyl-1-pentene polymer is at least one selected from 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene, and 4-methyl. The 4-methyl-1-pentene polymer composition according to claim 1, which is a random copolymer of -1-pentene. 4. The styrene-ethylene / butylene-styrene block copolymer (C) has a styrene / rubber weight ratio of 10/90 to 60/40.
The 4-methyl-1-pentene polymer composition described.