JPH07157601A - Conductive noncrystalline polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in characteristics, such as electrical conductivity, heat resistance, mechanical strength and antistatic properties. CONSTITUTION:100 pts.wt. resin mixture consisting of 20-94wt.% noncrystalline polyolefin, 3-40wt.% polycarbonate and 3-40wt.% rubbery material is mixed with 10-40 pts.wt. carbon black or 8-40 pts.wt. carbon fibers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has good molding processability such as injection molding, heat resistance, impact resistance, and electrical conductivity.
The present invention relates to a conductive amorphous polyolefin resin composition having excellent antistatic properties.

[0002]

Amorphous polyolefin has excellent properties such as transparency, heat resistance, chemical resistance, solvent resistance, electrical properties, mechanical strength, moldability, and dimensional stability. However, molded articles, sheets or films produced by injection molding, extrusion molding, etc., were fragile and had practically insufficient impact resistance.

[0003]

DISCLOSURE OF THE INVENTION The present invention has a heat distortion temperature (4.6 kgf / cm ² ) of 145 ° C. or higher, is excellent in conductivity and impact resistance, and when carbon fibers are blended, carbon black fading occurs. A non-conductive amorphous polyolefin resin composition is provided.

[0004]

The present invention provides a resin comprising 20 to 94% by weight of an amorphous polyolefin (a), 3 to 40% by weight of a polycarbonate (b) and 3 to 40% by weight of a rubber-like substance (c). A conductive amorphous polyolefin resin composition characterized in that 10 to 40 parts by weight of carbon black (d) or 8 to 40 parts by weight of carbon fiber (d) are blended with 100 parts by weight of the mixture. Is.

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 due to its structure and properties. Examples of the amorphous polyolefin include the following. For example, it is an amorphous polymer represented by the following general formula. (However, in the formula, n is a positive integer of 1 or more, m is a positive integer of 1 or more, R ₁ is a hydrogen atom, a halogen atom, CH ₂ CH
₃ groups or C ₆ H ₄ R ₂ groups are represented, and R ₂ represents a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom. X represents an addition reaction product of cyclopentadiene or its derivative with norbornadiene or its derivative or a hydrogenated product thereof, or an addition reaction product of dicyclopentadiene or its derivative with ethylene. )

The hydrogenation product of the addition reaction product of cyclopentadiene or its derivative with norbornadiene or its derivative, or the general formula of the addition reaction product of dicyclopentadiene or its derivative with ethylene is shown below.

[Chemical 1] (In the formula, n is a positive integer of 1 or more, and R _{1 to} R _1
12 independently represent an atom or a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and R _{9 to} R
₁₂ may combine with each other to form a monocycle or polycycle. )

Examples of the hydrogenation product of the addition reaction product of cyclopentadiene or its derivative with norbornadiene or its derivative, or the addition reaction product of dicyclopentadiene or its derivative with ethylene, include, for example, tetracyclo-3-dodecene, 8 -Methyltetracyclo-3
-Dodecene, 8-ethyltetracyclo-3-dodecene,
8-propyltetracyclo-3-dodecene, 8-butyltetracyclo-3-dodecene, 8-isobutyltetracyclo-3-dodecene, 8-hexyltetracyclo-3-
Dodecene, 8-stearyltetracyclo-3-dodecene, 5,10-dimethyltetracyclo-3-dodecene,
2,10-dimethyltetracyclo-3-dodecene, 8,
9-dimethyltetracyclo-3-dodecene, 8-ethyl-9-methyltetracyclo-3-dodecene, 11,12
-Dimethyltetracyclo-3-dodecene, 2,7,9-
Trimethyltetracyclo-3-dodecene, 9-ethyl-
2,7-Dimethyltetracyclo-3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo-3-dodecene, 9,11,12-trimethyltetracyclo-3-dodecene, 9-ethyl-11,12- Dimethyltetracyclo-3-dodecene, 9-isobutyl-11,12-dimethyltetracyclo-3-dodecene, 5,8,9,10-
Tetramethyltetracyclo-3-dodecene, 8-ethylidene tetracyclo-3-dodecene, 8-ethylidene-9
-Methyltetracyclo-3-dodecene, 8-ethylidene-9-ethyltetracyclo-3-dodecene, 8-ethylidene-9-isopropyltetracyclo-3-dodecene,
8-ethylidene-9-butyltetracyclo-3-dodecene, 8-n-propylidenetetracyclo-3-dodecene, 8-n-propylidene-9-methyltetracyclo-
3-dodecene, 8-n-propylidene-9-isopropyltetracyclo-3-dodecene, 8-n-propylidene-9-butyltetracyclo-3-dodecene, 8-isopropylidenetetracyclo-3-dodecene, 8-isopropylidene Ridene-9-methyltetracyclo-3-dodecene, 8
-Isopropylidene-9-ethyltetracyclo-3-dodecene, 8-isopropylidene-9-isopropyltetracyclo-3-dodecene, 8-isopropylidene-9-
Butyltetracyclo-3-dodecene, 8-chlorotetracyclo-3-dodecene, 8-bromotetracyclo-3-
Dodecene, 8-fluorotetracyclo-3-dodecene,
8,9-Dichlorotetracyclo-3-dodecene, hexacyclo-4-heptadecene, 12-methylhexacyclo-4-heptadecene, 12-methylhexacyclo-4-
Heptadecene, 12-ethylhexacyclo-4-heptadecene, 12-isobutylhexacyclo-4-heptadecene, 1,6,10-trimethyl-12-isobutylhexacyclo-4-heptadecene, octacyclo-5-dococene, 15-methylocta Cyclo-5-dococene, 1
5-ethyloctacyclo-5-dococene, pentacyclo-4-hexadecene, 1,3-dimethylpentacyclo-
4-hexadecene, 1,6-dimethylpentacyclo-4
-Hexadecene, 15,16-dimethylpentacyclo-
4-hexadecene, heptacyclo-5-eicosene, heptacyclo-5-heneicosene, pentacyclo-4-
Examples include pentadecene, 1,3-dimethylpentacyclo-4-pentadecene, 1,6-dimethylpentacyclo-4-pentadecene, 14,15-dimethylpentacyclo-4-pentadecene, and pentacyclo-4,10-pentadecadiene. To be

Examples of the styrene derivative include styrene, o-methylstyrene, m-methylstyrene and p.
-Methylstyrene, α-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o
-Ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-methoxystyrene, p-chloroethylstyrene, p-methyl-α-methylstyrene and the like are used. In addition, these can also be used as a mixture of 2 or more types.

The polycarbonate resin which is the component (b) used in the present invention is an aromatic polycarbonate,
Aliphatic polycarbonates, aliphatic-aromatic polycarbonates and the like can be mentioned. Generally, a polymer of bisphenols such as 2,2-bis (4-oxyphenyl) alkane type, bis (4-oxyphenyl) ether type, bis (4-oxyphenyl) sulfone, sulfide or sulfoxide type, or a copolymer. It is a polymer and is a polymer using bisphenols substituted with halogen according to the purpose. As a method for producing polycarbonate, there are a phosgene method in which bisphenol A and phosgene are reacted, and a transesterification method in which bisphenol A and a carbonic acid diester such as diphenyl carbonate are reacted. In the present invention, the polycarbonate obtained by any method may be used. The molecular weight of the polycarbonate used is not particularly limited, but a polycarbonate having a molecular weight of about 10,000 to 100,000 is usually used.
In the present invention, those of 15,000 to 40,000 are particularly desirable.

Next, the rubber-like substance (c) used in the present invention refers to natural and synthetic polymer materials which are elastic bodies at room temperature. Specific examples thereof include natural rubber, butadiene polymer, butadiene-styrene copolymer (including all random copolymers, block copolymers, graft copolymers, etc.), hydrogenated styrene-butadiene copolymer, S
EBS, isoprene polymer, chlorobutadiene polymer,
Butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylic ester copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, thiocol rubber, Polysulfide rubber,
Examples thereof include polyurethane rubber, polyether rubber (for example, polypropylene oxide), epichlorohydrin rubber and the like. Among these rubber-like substances, particularly butadiene-styrene copolymer (including all random copolymers, block copolymers, graft copolymers, etc.) and hydrogenated styrene-butadiene copolymer are injection moldable, It is desirable to obtain a molding material having excellent strength and conductivity. These rubber-like substances may be produced by any production method (eg emulsion polymerization, solution polymerization) and any catalyst (eg peroxide, trialkylaluminum, lithium halide, nickel-based catalyst).

The carbon black and carbon fiber (d) used in the present invention include carbon black, Ketjen black, acetylene black, furnace black, lamp black, thermal black, which are conventionally known.
Examples thereof include channel black, roll black, disc black and the like. Among these carbon blacks, acetylene black and furnace black are particularly desirable for obtaining a molding material excellent in injection moldability, strength and conductivity. As carbon fiber, fiber diameter 5-18μ
Any of conventionally known rayon type, polyacrylonitrile type, lignin-povar type, pitch type, carbon whisker type, etc. having m and a density of 1.5 to 2.16 g / cm 3 can be used. The carbon black (d) is contained in an amount of 10 to 40 parts by weight, preferably 12 to 30 parts by weight, based on 100 parts by weight of the resin mixture comprising the components (a), (b) and (c). If it is less than 10 parts by weight, the volume resistivity required as a conductive material is higher than 10 ⁸ Ω · cm and the conductivity is insufficient, and if it exceeds 40 parts by weight, fluidity and mechanical strength are lowered, and a good molded product is obtained. Hard to get. Further, the conductive carbon fiber (d) is 8 per 100 parts by weight of the resin mixture consisting of the components (a), (b) and (c).
-40 parts by weight are included. If it is less than 8 parts by weight, the volume resistivity required as a conductive material is larger than 10 ⁸ Ω · cm and the conductivity is insufficient, and if it exceeds 40 parts by weight, the fluidity and mechanical strength are deteriorated and a good molded product is obtained. Is difficult to obtain. Thirteen
When it is contained in an amount of up to 25 parts by weight, preferable properties in conductivity, mechanical strength and fluidity can be obtained. And it becomes difficult to obtain a good molded product.

The composition of the present invention can be obtained by, for example, measuring the components, mixing them with a blender, a mixer, etc., and melt-kneading into pellets with an extruder. At this time, other components such as a heat stabilizer, an antioxidant, a weatherproofing agent, a lubricant, a pigment and carbon fiber may be added in an appropriate amount. The pellet-shaped molding material thus obtained is molded into a desired shape by a generally-used thermoplastic resin molding machine, such as an injection molding machine or an injection compression molding machine, and used.

[0013]

EXAMPLES The present invention will be described with reference to the following examples, but these are merely examples and the present invention is not limited thereto. The obtained pellet-shaped molding material is molded into a desired shape by a generally-used widely used thermoplastic resin molding machine such as an injection molding machine or an injection compression molding machine. (Examples 1 to 6) Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) is used as the component (a), and Panlite L1225 (PC1; manufactured by Teijin Chemicals) is used as the component (b).
Hydrogenated styrene-butadiene rubber as the component (c),
DYNARON 1910P (HSBR; made by Japan Synthetic Rubber) was used, and carbon black, Toka Black # 4500 (CB1; made by Tokai Carbon) was used as the component (d).

Examples 7 to 8 Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) was used as the component (a), and Caliber 200 (PC2; manufactured by Sumitomo Dow) was used as the component (b). However, Dynalon 1910P (HSBR; made by Japan Synthetic Rubber) is used as the component (c), and Toka Black # 4 is used as the component (d).
500 (CB1; manufactured by Tokai Carbon) was used. (Example 9) Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) was used as the component (a), and Panlite L1225 (PC1; manufactured by Teijin Chemicals) was used as the component (b).
As the component (c), hydrogenated styrene-ethylene / butene block copolymer modified with maleic anhydride, Tuftec M
Using 1943 (SEBS; Asahi Kasei Corp.),
Toka Black # 4500 (CB1; as component (d))
Tokai Carbon) was used. (Example 10) Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) was used as the component (a), Panlite L1225 (PC1; manufactured by Teijin Kasei) was used as the component (b), and component (c) was used. DYNARON 1910P (HSBR; made by Japan Synthetic Rubber) was used as the component, and carbon black and Denka black (CB2; made by Denka) were used as the component (d).

(Example 11) Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) was used as the component (a), and Panlite L1225 (PC1; manufactured by Teijin Chemicals) was used as the component (b). ,
As the component (c), DYNARON 1910P (HSB
R; manufactured by Japan Synthetic Rubber) and carbon black, Vulcan XC72 (CB3; manufactured by Cabot Corporation, USA) were used as the component (d). Examples 12 to 14 Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) is used as the component (a), and Panlite L1225 (PC1; manufactured by Teijin Chemicals) is used as the component (b).
As the component (c), DYNARON 1910P (HSB
R; made by Japan Synthetic Rubber), and carbon fiber, DIAREAD K223SE (CF1; made by Mitsubishi Kasei) was used as the component (d). (Example 15) Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) was used as the component (a), and Panlite L1225 (PC1; manufactured by Teijin Chemicals) was used as the component (b).
Hydrogenated styrene-butadiene rubber as the component (c),
DYNARON 1910P (HSBR; made by Japan Synthetic Rubber) was used, and carbon fiber, Bethfite HTA-CMF-0060NS (CF2; manufactured by Toho Rayon) was used as the component (d). (Example 16) Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) was used as the component (a), and Panlite L1225 (PC1; manufactured by Teijin Chemicals) was used as the component (b).
Hydrogenated styrene-butadiene rubber as the component (c),
DYNARON 1910P (HSBR; made by Japan Synthetic Rubber) was used, and carbon fiber, Donacarb S-244 (CF3; made by Donac) was used as the component (d).

Comparative Examples 1 and 2 Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) was used as the component (a), and Panlite L1225 (PC1; manufactured by Teijin Chemicals) was used as the component (b). , (D) component carbon black, Toka Black # 4500
(CB1; made by Tokai Carbon) was used. (Comparative Examples 3 to 4) Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) is used as the component (a), and DYNAR is used as the component (c).
ON1910P (HSBR; made by Japan Synthetic Rubber) is used, and Toka Black # 4500 (CB
1; manufactured by Tokai Carbon Co., Ltd.) was used. (Comparative Example 5) Panlite L1225 (PC1; manufactured by Teijin Kasei) is used as the component (b), and DYNARO is used as the component (c).
Using N1910P (HSBR; made by Japan Synthetic Rubber),
Toka Black # 4500 (CB1; as component (d))
Tokai Carbon) was used.

Comparative Examples 6 to 7 Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) was used as the component (a), and Panlite L1225 (PC1; manufactured by Teijin Chemicals) was used as the component (b). , (C) component was DYNARON 1910P (HSBR; made by Nippon Synthetic Rubber), and (d) component was Toka Black # 4500 (CB1; made by Tokai Carbon Co., Ltd.). (Comparative Examples 8 to 9) Apel 150R (APO; manufactured by Mitsui Petrochemical Industry) is used as the component (a), and Panlite L1225 (PC1; manufactured by Teijin Chemicals) is used as the component (b).
As the component (c), DYNARON 1910P (HSB
R; made by Japan Synthetic Rubber), and carbon fiber, DIAREAD K223SE (CF1; made by Mitsubishi Kasei) was used as the component (d). (Comparative Example 10) As the component (b), Panlite L1225 (PC1;
(Manufactured by Teijin Kasei) and DYNARO as the component (c)
Using N1910P (HSBR; made by Japan Synthetic Rubber),
Diamond lead K223SE (CF1;
Mitsubishi Kasei) was used.

Predetermined amounts of the respective components shown in Tables 1 to 4 were blended, melt-kneaded with a biaxial kneader and pelletized. Each test piece was prepared from the obtained molding material by injection molding, and each physical property was measured. Each physical property was measured according to the following test methods and conditions. Comparative Example 1 among the above Comparative Examples,
No. 2 has a low Izod impact value and is brittle. In Comparative Examples 3 and 4, the molded product becomes brittle immediately after molding and there is a problem in strength. In Comparative Examples 5 and 10, the temperature 145 required by the heat distortion temperature
Lower than ℃ and poor heat resistance. Comparative Examples 6 and 8 have a volume resistivity of 10 ⁸ Ω · cm or more and have poor conductivity, and Comparative Examples 7 and 9 have low fluidity and cannot be molded. Izod impact value: ASTM D256 Tensile strength: ASTM D628 Bending strength: ASTM D790 Flexural modulus: ASTM D790 Heat distortion temperature: ASTM D648 Load 4.6kgf / cm
² Volume resistivity: ASTM D257

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

INDUSTRIAL APPLICABILITY According to the present invention, by blending polycarbonate and a rubber-like substance, carbon black or carbon fiber with an amorphous polyolefin resin, an amorphous material excellent in properties such as conductivity, heat resistance and mechanical strength is obtained. A polyolefin resin composition can be provided. Such a resin composition can be used for a conveying jig such as an electronic device or an IC, a packaging material, or the like, which is particularly required to have antistatic properties.

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Claims (5)

[Claims] 1. (a) Amorphous polyolefin resin 20 to
For 100 parts by weight of a resin mixture consisting of 94% by weight, (b) 3 to 40% by weight of a polycarbonate resin, and (c) 3 to 40% by weight of a rubber-like substance, (d) carbon black 1
A conductive amorphous polyolefin resin composition comprising 0 to 40 parts by weight or 8 to 40 parts by weight of carbon fibers. 2. The amorphous polyolefin (a) comprises an addition reaction product of cyclopentadiene or a derivative thereof and norbornadiene or a derivative thereof, and one or more kinds of unsaturated monomers selected from ethylene, butadiene, or a styrene derivative. The conductive amorphous polyolefin resin composition according to claim 1, which is a copolymer with a polymer or a hydrogenated product thereof. 3. The amorphous polyolefin (a) comprises an addition reaction product of dicyclopentadiene or its derivative and ethylene, and one or more unsaturated monomers selected from ethylene, butadiene, or styrene derivatives. The conductive amorphous polyolefin resin composition according to claim 1, which is a copolymer of 4. The polycarbonate is 2,2-bis (4
-Oxyphenyl) alkane-based, bis (4-oxyphenyl) ether-based, bis (4-oxyphenyl) sulfone, sulfide- or sulfoxide-based polymers or copolymers of bisphenols, depending on the purpose. The conductive amorphous polyolefin resin composition according to claim 1, 2 or 3, which is a polymer using halogen-substituted bisphenols. 5. The rubber-like substance is natural rubber, butadiene polymer, butadiene-styrene copolymer, hydrogenated styrene-
A butadiene copolymer, a block copolymer comprising at least two vinyl aromatic-based terminal copolymer blocks A and at least one conjugated diene compound-based intermediate polymer block B is hydrogenated. Hydrogenated block copolymer (hereinafter abbreviated as SEBS), isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, Acrylic ester copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, thiochol rubber, polysulfide rubber, polyurethane rubber,
The electrically conductive amorphous polyolefin resin composition according to claim 1, which is a polyether rubber or an epichlorohydrin rubber.