JPH07149992A - Preparation of polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyolefin resin compsn. capable of being easily formed into a molded product excellent in balance among heat resistance, electrical properties, mechanical strength, formability, dimensional stability, etc., according to a processing method which is usually used for a thermoplastic molding material. CONSTITUTION:(a) 100 pts.wt. amorphous polyolefin comprising a hydrogenation product of a copolymer of dicyclopentadiene with ethylene and/or butadiene, (b) 10-100 pts.wt. polypropylene resin having a thermal deflection temp. of at least 90 deg.C, and (c) 0.001-2 pts.wt. org. peroxide catalyst are dynamically heat- treated to effect crosslinking thereof, followed by addn. thereto of 0.01-5 pts.wt. age resister.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is an IC manufactured by injection molding or the like.
The present invention relates to a method for producing a novel thermoplastic resin composition for a molding material that can be used as a tray molded product or the like. More specifically, it is obtained by dynamically heat-treating a specific amorphous polyolefin and a crystalline polyolefin in the presence of an organic peroxide-based catalyst, and has a good balance of physical properties and appearance, moldability, impact resistance, and heat resistance. The present invention relates to a method for producing an excellent novel thermoplastic resin composition for molding materials.

[0002]

Amorphous polyolefins have excellent rigidity, electrical properties, mechanical strength, moldability and dimensional stability at high temperatures, but they are still insufficient in fluidity and impact resistance. However, since there is almost no toughness when heated, a molded article produced by injection molding or the like lacks practically sufficient toughness, and toughness, fluidity, and It is desired to improve impact resistance. In order to improve these drawbacks, there is disclosed a method of forming a composite sheet in which a crystalline polymer and a hydride of a ring-opening polymer of dicyclopentadiene having a high glass transition point are combined.
Although the composite sheet of the present invention is excellent in impact resistance, it is a sheet rich in crystalline resin having a large dimensional change, which is difficult to form as a molding material and has a large dimensional change. It was difficult to use.

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to the production of a novel thermoplastic resin composition for molding materials, which has an excellent balance of physical properties such as heat resistance, electrical properties, mechanical strength, moldability, and dimensional stability. It is intended to provide a method.

[0004]

The present invention relates to an amorphous polyolefin (a) having excellent rigidity, electrical properties, mechanical strength, moldability and dimensional stability at high temperature and toughness at high temperature. , A polypropylene resin (b) having excellent properties of high temperature impact resistance and fluidity, and further subjected to dynamic heat treatment with an organic peroxide catalyst, wholly or partially, to obtain an amorphous polyolefin. Thermoplastic resin for molding materials, which has an excellent balance of physical properties such as heat resistance, electrical properties, mechanical strength, moldability, and dimensional stability by improving the interfacial adhesion between polypropylene and polypropylene resin. It is a manufacturing method of a composition. Generally, when two or more kinds of resins are combined, it is rare that they are compatible with each other, and even when they are compatible, the adhesive strength at the interface is weak,
In most cases, the resulting blends are in most cases inferior in properties to either polymer. In this case, it is general to add a compatibilizer to improve the compatibility and the adhesive strength at the interface. In the case of the present invention, the amorphous polyolefin (a) having good heat rigidity, moldability and dimensional stability is used as the sea component, and the polypropylene resin (b) having good high temperature impact resistance is used as the island component. By thermally treating the polymer with an organic peroxide catalyst, the amorphous polyolefin and polypropylene graft polymer generated in the system act as a compatibilizing agent, significantly improving the compatibility and fine dispersion. It was found that the adhesive strength of the interface was significantly improved, and based on this finding, various researches were carried out and heat resistance, electrical properties, mechanical strength, moldability, dimensional stability, etc. The present invention has been completed regarding a method for producing a novel thermoplastic resin composition for molding materials, which has an excellent balance of physical properties.

That is, the present invention comprises: (a) 100 parts by weight of an amorphous polyolefin composed of a hydrogenated product of a copolymer of dicyclopentadiene and ethylene and / or butadiene. (B) Polypropylene having a heat distortion temperature of 90 ° C. or higher. Resin 10 to 100 parts by weight (c) Organic peroxide catalyst 0.001 to 2 parts by weight The above (a) to (c) are dynamically heat-treated to be crosslinked, and then (d) Antiaging agent Is added in an amount of 0.01 to 5 parts by weight. The amorphous polyolefin (a) used in the present invention is a polymer having a cyclic olefin structure and can be said to be an amorphous polyolefin because of its structure and properties. This ring-opening polymer can be produced by a known ring-opening polymerization method of a cyclic olefin using dicyclopentadiene or its derivative as a monomer and ethylene and / or butadiene as a comonomer.
Further, the hydrogenated product of this ring-opening polymer can also be obtained by utilizing a usual hydrogenation reaction method. In addition, you may use it as a mixture of 2 or more types of amorphous polyolefins.
The amorphous polyolefin (a) has a heat distortion temperature in the range of 70 to 170 ° C., but for applications requiring heat resistance, it is preferable to use one having a heat distortion temperature of 100 ° C. or higher.

The polypropylene resin (b) used in the present invention is added to improve the toughness at high temperature, the fluidity and the impact resistance, which are the drawbacks of the amorphous polyolefin (a). The polypropylene-based resin (b) alone has excellent toughness and impact resistance at high temperatures, but has insufficient rigidity and dimensional stability at high temperatures, and it is necessary to use it in combination with an amorphous polyolefin. The polypropylene-based resin (b) used in the present invention is, for example, isotactic polypropylene or a random or block copolymer of propylene and a small amount of other α-olefin, specifically polypropylene-ethylene copolymer, propylene-1. -Hexene copolymer, propylene-4-methyl-1-pentene copolymer, poly-4-methyl-1-pentene, polybutene-1 and the like can be mentioned. Further, two or more kinds of polyolefin resins may be used in combination. MFR when using isotactic polypropylene or its copolymer as the polypropylene resin (ASTM-D-1238L condition,
230 ° C) is 0.1 to 50 g / 10 minutes, especially 0.5 to 30 g
Those having a range of / 10 minutes can be preferably used. Further, the reason why the heat distortion temperature (JIS K7207 4.6 kgf / cm2) is limited to 90 ° C or higher here is that if it is lower than that, there is no effect in improving the high temperature impact resistance. In this application, the higher the heat distortion temperature of the polyolefin resin, the more excellent the effect of high temperature toughness and high temperature impact resistance. To increase the heat distortion temperature, it is achieved by controlling the stereoregularity of polypropylene molecules and increasing the crystallinity. In recent years, polypropylene with increased crystallinity has been put on the market and is easily available.

In the thermoplastic resin composition for molding materials according to the present invention, the polypropylene resin (b) should be added in an amount of 10 to 100 parts by weight based on 100 parts by weight of the amorphous polyolefin (a). When the content of the component (b) is more than 100 parts by weight, moldability, dimensional stability and rigidity are not sufficient, and when it is less than 10% by weight,
It is not possible to obtain favorable properties in hot toughness and high temperature impact resistance. Furthermore, the organic peroxide catalyst (c) used in the present invention is a commercially available general organic peroxide as an essential component. The organic peroxide may be used alone, or a system in which the organic peroxide is used in combination with a bismaleimide compound as a cocatalyst may be used as a catalyst. Examples of organic peroxides are 2,5-dimethyl 2,5-di (t-butylperoxy) hexane and 2,5-dimethyl 2,5-di (t-butylperoxy) hexyne-3,1, 3-bis (t-butylperoxyisopropyl) benzene, 1,1-di (t-
Butyl peroxy) 3,5,5 trimethylcyclohexane, 2,5 dimethyl 2,5 di (peroxybenzoyl)
Hexin 3 and dicumyl peroxide. Further, examples of the bismaleimide compound as the organic peroxide co-catalyst used in the present invention include N, N'-m-phenylene bismaleimide and toluylene bismaleimide. N, N'-
m-phenylene bismaleimide is commercially available, for example, HVA
-2 (manufactured by DuPont), Sokushinol BM (Sumitomo Chemical
Manufactured) and the like can be used. By using an organic peroxide-based catalyst, a graft polymer of an amorphous polyolefin resin and a polypropylene-based resin is formed at the interface, and by functioning as a compatibilizer, compatibility is improved and extremely fine dispersion is achieved. Is achieved and the adhesive strength at the interface is improved, so that the impact resistance under heat is significantly improved. The organic peroxide-based catalyst (c) must be added in an amount of 0.001 to 2 parts by weight based on 100 parts by weight of the amorphous polyolefin (a). This is because if it is less than 0.001 part by weight, the graft polymer is not formed at a practical rate, and if it is 2 parts by weight or more, undesirable side reactions (decomposition of polypropylene, gelation) occur.

The antiaging agent (d) is an essential component added to improve the heat resistance and light resistance of the polyolefin resin composition of the present invention. As specific antiaging agents, hindered phenol compounds and hindered amine compounds can be preferably used. An example of a hindered phenol compound used as an antioxidant is pentaerythrityl-tetrakis [3- (3,5
-Di-t-butylhydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol,
2,2'-methylenebis (4-methyl-6-tert-butylphenol) and the like can be mentioned. In addition, an example of a hindered amine compound used as an antioxidant is poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl}.
{(2,2,6,6-tetramethyl-4-piperidyl)
Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and the like. Further, an ultraviolet absorber such as a benzotriazole-based compound may be used in combination for further improving the light resistance. Further, the antiaging agent can bring about an excellent antiaging effect by using a combination of two or more kinds of compounds rather than using them alone. The amount of the antioxidant added is 0.01 with respect to 100 parts by weight of the amorphous polyolefin (a).
It can be suitably selected within the range of 5 to 5 parts by weight. If the amount added is less than the lower limit of the above range, there is no effect of addition, and if the amount added exceeds the upper limit of the above range, there is no merit of increasing the amount. The antiaging agent (d) should be added at (a) (b) (c)
It is indispensable to add after completion of the reaction of. This is because the reactions (a), (b) and (c) proceed by a radical reaction, but the antioxidant (d) deactivates the radicals required for the reaction.

Further, if necessary, compatibilizers, additives, such as dyes and pigments, stabilizers, plasticizers, conductive materials (carbon black, carbon fibers, etc.), within a range that does not impair the basic properties,
An antistatic agent, a lubricant, a filler, an elastomer (for example, a styrene block copolymer) that imparts flexibility, a thermoplastic resin (for example, a polyethylene resin), and the like can also be added. As a method for producing the composition of the present invention, all general methods used for producing ordinary resin compositions and rubber compositions can be adopted. Basically, it is a mechanical melt-kneading method, and a single-screw extruder, a twin-screw extruder, a Banbury mixer, various kneaders, brabenders, rolls and the like are used for these. At this time, the addition order of each component is (a),
Using the components (b) and (c), for example, a resin component is premixed in advance with a mixer such as a Henschel mixer or a blender, melt-kneaded with the above kneader, and then the component (d) is added, or (a) ) (B) (c) components are melt-kneaded in advance and dynamically heat-treated to prepare a reaction product masterbatch, and then a predetermined amount of (a), (b) and (d) components are added thereto and melt-kneaded The method can also be adopted. Further, at this time, the temperature for melt-kneading can be suitably selected from 180 ° C to 300 ° C. The thermoplastic resin composition for a molding material according to the present invention can be easily processed into a molded product or the like by a processing method used for ordinary thermoplastic resin molded products, such as injection molding.

[0010]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. The components blended in the examples and comparative examples shown below are as follows. <Component a (1)> Amorphous polyolefin [APO: Apel 150R manufactured by Mitsui Petrochemical Industry Co., Ltd., heat distortion temperature 1
50 ° C. (ASTM D648 18.6 Kg / cm ² )] <Component a (2)> Amorphous polyolefin [APO: Apel APL6011, manufactured by Mitsui Petrochemical Industry Co., Ltd., heat distortion temperature 95 ° C. (ASTM D648 18.6 Kg / cm ^2). )] <Component b (1)> Highly crystalline homotype polypropylene [PP: Chisso HCPPK5016 manufactured by Chisso Corporation, heat distortion temperature 140 ° C (ASTM D648 4.6Kg / c)
m ² )] <Component b (2)> Block type polypropylene [PP
: Asahi Kasei Co., Ltd. Ace Polypro M8800, heat distortion temperature 112 ° C. (ASTM D648 4.6 Kg / cm ² )] <Component b (3)> Random type polypropylene [PP
: Sumikasen W531 manufactured by Sumitomo Chemical Co., Ltd., heat distortion temperature 80 ° C. (ASTM D648 4.6 Kg / cm ² )] <Component c (1)> Organic peroxide [P-OX: NOF CORPORATION]
Park Mill D Co., Ltd. <Component c (2)> Organic peroxide [P-OX: Sumokinol BM manufactured by Sumitomo Chemical Co., Ltd.><Component d (1)> Hindered phenol [HP: Japan Ciba-Gigi (Co., Ltd.) ) Irganox 1076] <Ingredient d (2)> Hindered amine [HA: Chimasorb 944LD manufactured by Nippon Ciba-Gaigi Co., Ltd.]

<< Examples 1 to 12 and Comparative Examples 1 to 18 >>
After sufficiently dry blending the components a, b, and c, melt-kneading and extruding under a condition that the resin temperature is 180 to 300 ° C. using a biaxial kneader, and dynamically heat-treating to obtain a thermoplastic resin composition. It was then pelletized. The component (d) was dry blended with the pellets, melt-kneaded again, and pelletized to obtain the target composition. Injection molding was performed using this target composition, and the following physical properties were evaluated. (1) Izod impact test (J / cm); ASTM-D25
6) (2) 90 ° C bending test: strength (MPa), elastic modulus (MPa), bending fracture energy (mJ); conforming to ASTM D-790 (3) Warpage of molded product; length 150 mm, width 300 mm, thickness A 1 mm flat plate molded product was measured and evaluated with a height master. (4) Heat-resistant exposure test; 500Hr exposure in 90 ° C atmosphere,
A tensile test was performed and the residual rate before exposure was calculated. (5) Light exposure test; 50 at 63 ° C sunshine weather
The sample was exposed to 0 Hr and a tensile test was performed to calculate the residual rate before exposure.

<< Examples 13 to 18 >> One of the materials a, b, and c and any of the materials prepared by the production methods of Examples 1 and 2 (named as compatibilizer and compatibilizer, respectively) are sufficient. After dry-blending, a thermoplastic resin composition was obtained by melt-kneading and extruding under a condition that the resin temperature was 180 to 300 ° C. using a twin-screw kneader and dynamically heat-treating, and pelletizing this. Injection molding was performed using this composition, and the following physical properties were evaluated. Examples are shown in Tables 1, 2 and 3, and Comparative Examples are shown in Table 4,
The results are shown in Table 5 and Table 6. From these results, it was revealed that the thermoplastic resin composition obtained in the present invention provides a molded article which is excellent in impact resistance, heat resistance rigidity, and toughness upon heating and has a small warpage.

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition for a molding material according to the present invention can be easily processed into a molded article by a processing method used for a usual thermoplastic molding material, for example, injection molding and the like. It provides products with excellent balance of physical properties such as mechanical properties, mechanical strength, moldability, and dimensional stability.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08L 23/10 LCL LDD

Claims (1)

[Claims] 1. An amorphous polyolefin 100 parts by weight of (a) a hydrogenated product of a copolymer of dicyclopentadiene and ethylene and / or butadiene. (B) A polypropylene resin 10 having a heat distortion temperature of 90 ° C. or higher. To 100 parts by weight (c) 0.001 to 2 parts by weight of an organic peroxide-based catalyst to dynamically cross-link the above (a) to (c), and then (d) an antioxidant. A method for producing a polyolefin-based resin composition, which comprises adding 0.1 to 5 parts by weight.