JP2017110179A - Antistatic agent and production method of the same - Google Patents
Antistatic agent and production method of the same Download PDFInfo
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- JP2017110179A JP2017110179A JP2016136909A JP2016136909A JP2017110179A JP 2017110179 A JP2017110179 A JP 2017110179A JP 2016136909 A JP2016136909 A JP 2016136909A JP 2016136909 A JP2016136909 A JP 2016136909A JP 2017110179 A JP2017110179 A JP 2017110179A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
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- 229920005989 resin Polymers 0.000 claims abstract description 88
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- 229920001400 block copolymer Polymers 0.000 claims abstract description 80
- 229920000570 polyether Polymers 0.000 claims abstract description 79
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 77
- 238000004898 kneading Methods 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000002542 deteriorative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
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- 244000043261 Hevea brasiliensis Species 0.000 description 2
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- 235000021355 Stearic acid Nutrition 0.000 description 2
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- 230000005856 abnormality Effects 0.000 description 2
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- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
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- 239000008117 stearic acid Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
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- 239000011787 zinc oxide Substances 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006147 copolyamide elastomer Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- -1 ethylene, propylene, butene Chemical class 0.000 description 1
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- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Abstract
Description
本発明は、架橋可能なゴム成分およびポリエーテルを含むブロック共重合体樹脂を含有する帯電防止剤およびその製造方法に関する。 The present invention relates to an antistatic agent containing a block copolymer resin containing a crosslinkable rubber component and a polyether, and a method for producing the same.
ポリエーテルを含むブロック共重合体樹脂は、樹脂や熱可塑性エラストマーの永久帯電防止剤として知られている。ポリエーテルを含むブロック共重合体樹脂は高分子型帯電防止剤であるため、樹脂や熱可塑性エラストマーの表面にブルームやブリードが発生せず、効果の持続性に優れること、湿度依存性が小さいことなどから、帯電防止性能が要求される多くの樹脂製品および熱可塑性エラストマー製品に使用されている（例えば、特許文献１）。 Block copolymer resins containing polyethers are known as permanent antistatic agents for resins and thermoplastic elastomers. Since block copolymer resin containing polyether is a polymer antistatic agent, it does not generate bloom or bleed on the surface of the resin or thermoplastic elastomer, has excellent sustainability, and has low humidity dependence Therefore, it is used in many resin products and thermoplastic elastomer products that require antistatic performance (for example, Patent Document 1).
このように、ポリエーテルを含むブロック共重合体樹脂は、樹脂製品および熱可塑性エラストマー製品に用いる帯電防止剤として優れている。しかし、ポリエーテルを含むブロック共重合体樹脂の融点は高温であり、一般的なゴム組成物の混練温度より高いため、ポリエーテルを含むブロック共重合体樹脂をゴム製品に用いる場合は、該ブロック共重合体樹脂が十分に分散せず、塊となって残り、ゴム組成物の外観不良や物性低下といった問題が発生する。また、該ブロック共重合体樹脂を融解させるために、混練温度を高温にすると、ゴム成分や他の配合剤が熱で劣化する、混練時間が長くなるなどの問題が発生する恐れがある。 Thus, the block copolymer resin containing a polyether is excellent as an antistatic agent used in resin products and thermoplastic elastomer products. However, since the melting point of the block copolymer resin containing a polyether is high and higher than the kneading temperature of a general rubber composition, when the block copolymer resin containing a polyether is used for a rubber product, The copolymer resin is not sufficiently dispersed and remains as a lump, causing problems such as poor appearance of the rubber composition and deterioration of physical properties. Further, if the kneading temperature is increased to melt the block copolymer resin, problems such as deterioration of the rubber component and other compounding agents due to heat and longer kneading time may occur.
本発明は、ゴム組成物に配合し、一般的なゴム組成物の混練温度で混練りしても、ゴム組成物中に良好に分散し、ゴム組成物の物性を低下させることなく優れた帯電防止性能を発揮する帯電防止剤および該帯電防止剤の製造方法を提供することを目的とする。 The present invention can be blended in a rubber composition, and even when kneaded at a kneading temperature of a general rubber composition, it can be dispersed well in the rubber composition and has excellent charging without deteriorating the physical properties of the rubber composition. It is an object of the present invention to provide an antistatic agent that exhibits antistatic performance and a method for producing the antistatic agent.
本発明者らは、鋭意検討の結果、ポリエーテルを含むブロック共重合体樹脂を、架橋可能なゴム成分と所定の含有比で含有した帯電防止剤とすることで、一般的なゴム組成物の混練温度で混練りしても、ゴム組成物中に良好に分散できる帯電防止剤が得られることを見出し、さらに検討を重ねて本発明を完成させた。 As a result of intensive studies, the inventors of the present invention have made a block copolymer resin containing a polyether into an antistatic agent containing a crosslinkable rubber component and a predetermined content ratio. The inventors have found that an antistatic agent that can be well dispersed in a rubber composition can be obtained even when kneaded at a kneading temperature, and have further studied to complete the present invention.
すなわち、本発明は、架橋可能なゴム成分、およびポリエーテルを含むブロック共重合体樹脂を含有する帯電防止剤であり、架橋可能なゴム成分とポリエーテルを含むブロック共重合体樹脂との質量含有比（ゴム成分／ポリエーテルを含むブロック共重合体樹脂）が９５／５〜４０／６０である帯電防止剤に関する。 That is, the present invention is an antistatic agent containing a crosslinkable rubber component and a block copolymer resin containing a polyether, and contains a mass of the crosslinkable rubber component and the block copolymer resin containing a polyether. The present invention relates to an antistatic agent having a ratio (rubber component / block copolymer resin containing polyether) of 95/5 to 40/60.
また、本発明は、架橋可能なゴム成分、およびポリエーテルを含むブロック共重合体樹脂を、ポリエーテルを含むブロック共重合体樹脂の融点以上の混練温度で混練する工程を含む本発明の帯電防止剤の製造方法に関する。 The present invention also includes a step of kneading a block copolymer resin containing a crosslinkable rubber component and a polyether at a kneading temperature equal to or higher than the melting point of the block copolymer resin containing the polyether. The present invention relates to a method for producing an agent.
本発明によれば、ゴム組成物に配合し、一般的なゴム組成物の混練温度で混練りしても、ゴム組成物中に良好に分散し、ゴム組成物の物性を低下させることなく優れた帯電防止性能を発揮する帯電防止剤およびその帯電防止剤の製造方法を提供することができる。 According to the present invention, even when blended in a rubber composition and kneaded at a kneading temperature of a general rubber composition, it is well dispersed in the rubber composition and is excellent without deteriorating the physical properties of the rubber composition. An antistatic agent that exhibits high antistatic performance and a method for producing the antistatic agent can be provided.
本発明の帯電防止剤は、架橋可能なゴム成分およびポリエーテルを含むブロック共重合体樹脂を含有する帯電防止剤であり、架橋可能なゴム成分とポリエーテルを含むブロック共重合体樹脂との質量含有比（ゴム成分／ポリエーテルを含むブロック共重合体樹脂）が９５／５〜４０／６０であることを特徴とする。本発明の帯電防止剤中にはポリエーテルを含むブロック共重合体樹脂が良好に分散しており、ポリエーテルを含むブロック共重合体樹脂の塊が目視できない。このような本発明の帯電防止剤をゴム組成物に配合すれば、一般的なゴム組成物の混練温度で混練りしても、帯電防止剤がゴム組成物中に良好に分散して塊となって残らず、ゴム組成物の物性を低下させることなく優れた帯電防止性能を発揮させることができる。 The antistatic agent of the present invention is an antistatic agent containing a block copolymer resin containing a crosslinkable rubber component and a polyether, and the mass of the crosslinkable rubber component and the block copolymer resin containing a polyether. The content ratio (rubber component / block copolymer resin containing polyether) is 95/5 to 40/60. In the antistatic agent of the present invention, the block copolymer resin containing the polyether is well dispersed, and the block copolymer resin containing the polyether cannot be visually observed. When such an antistatic agent of the present invention is blended in a rubber composition, the antistatic agent is well dispersed in the rubber composition even when kneaded at a kneading temperature of a general rubber composition. Therefore, excellent antistatic performance can be exhibited without deteriorating the physical properties of the rubber composition.
架橋可能なゴム成分としては、ゴム工業で一般的に用いられるゴム成分を用いることができ、例えば、クロロプレンゴム（ＣＲ）、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、イソプレンゴム（ＩＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、水素化ニトリルゴム（ＨＮＢＲ）、エチレンプロピレンジエンゴム（ＥＰＤＭ）、ブチルゴム（ＩＩＲ）、エチレンプロピレンゴム、ポリノルボルネンゴム、シリコーンゴム、塩化ポリエチレンゴム、フッ素ゴム（ＦＫＭ）、アクリルゴム（ＡＣＭ）、ヒドリンゴムなどが挙げられる。これらの架橋可能なゴム成分は、単独で用いてもよく、２種以上を併用してもよいが、帯電防止剤のゴム組成物中への分散性の観点から、本発明の帯電防止剤を配合するゴム組成物の主ゴム成分とすることが好ましい。耐オゾン性、耐候性、耐熱老化性、耐寒性、低温特性などに優れるという理由からは、ＥＰＤＭを用いることが好ましい。 As the crosslinkable rubber component, rubber components generally used in the rubber industry can be used. For example, chloroprene rubber (CR), natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR) , Isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), hydrogenated nitrile rubber (HNBR), ethylene propylene diene rubber (EPDM), butyl rubber (IIR), ethylene propylene rubber, polynorbornene rubber, silicone rubber, chlorinated polyethylene rubber , Fluoro rubber (FKM), acrylic rubber (ACM), hydrin rubber and the like. These crosslinkable rubber components may be used alone or in combination of two or more. From the viewpoint of dispersibility of the antistatic agent in the rubber composition, the antistatic agent of the present invention is used. The main rubber component of the rubber composition to be blended is preferable. EPDM is preferably used because it is excellent in ozone resistance, weather resistance, heat aging resistance, cold resistance, low temperature characteristics, and the like.
ＥＰＤＭとしては、エチレンとプロピレンに少量の第３成分（ジエン分）を加えることで主鎖中に二重結合を導入した種々のＥＰＤＭがいずれも使用可能である。かかるＥＰＤＭとしては、例えば第３成分の種類や量の違いによる様々な製品が提供されている。代表的な第３成分としては、例えばエチリデンノルボルネン（ＥＮＢ）、１，４−ヘキサジエン（１，４−ＨＤ）、ジシクロペンタジエン（ＤＣＰ）などが挙げられる。またＥＰＤＭとしては、伸展油を加えて柔軟性を調整した油展タイプのものと加えない非油展タイプのものとがあるが、本発明ではいずれのタイプのＥＰＤＭを用いてもよい。これらＥＰＤＭは、単独で用いてもよく、２種以上を併用してもよい。 As the EPDM, any of various EPDMs in which a double bond is introduced into the main chain by adding a small amount of a third component (diene component) to ethylene and propylene can be used. As such EPDM, for example, various products are provided depending on the type and amount of the third component. Representative examples of the third component include ethylidene norbornene (ENB), 1,4-hexadiene (1,4-HD), dicyclopentadiene (DCP), and the like. The EPDM includes an oil-extended type in which flexibility is adjusted by adding an extending oil and a non-oil-extended type in which flexibility is not added, but any type of EPDM may be used in the present invention. These EPDM may be used independently and may use 2 or more types together.
ポリエーテルを含むブロック共重合体樹脂としては、特に限定はなく、従来樹脂製品、熱可塑性エラストマー製品などに使用されているものを用いることができ、例えば、ポリエーテル／ポリオレフィンブロック共重合体樹脂、ポリエーテルエステルアミド樹脂の変性物、ポリエーテル／ポリアミドブロック共重合体樹脂などが挙げられる。これらのポリエーテルを含むブロック共重合体樹脂は、単独で用いてもよく、２種以上を併用してもよい。帯電防止性能およびＥＰＤＭとの相溶性に優れ、比較的融点が低いという理由からは、ポリエーテル／ポリオレフィンブロック共重合体樹脂を用いることが好ましい。 The block copolymer resin containing polyether is not particularly limited, and those conventionally used for resin products, thermoplastic elastomer products, etc. can be used. For example, polyether / polyolefin block copolymer resins, Examples thereof include a modified product of a polyether ester amide resin and a polyether / polyamide block copolymer resin. The block copolymer resin containing these polyethers may be used independently and may use 2 or more types together. A polyether / polyolefin block copolymer resin is preferably used because it has excellent antistatic performance and compatibility with EPDM and has a relatively low melting point.
ポリエーテル／ポリオレフィンブロック共重合体樹脂を構成するポリエーテルの単量体としては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシドなどのアルキレンオキシドが挙げられる。また、ポリエーテル／ポリオレフィンブロック共重合体樹脂を構成するポリオレフィンの単量体としては、例えば、エチレン、プロピレン、ブテン、ペンテン、ヘキセンなどのオレフィンが挙げられる。前記ポリエーテルとポリオレフィンとの化学結合は、特に限定されず、例えば、エステル結合、アミド結合、エーテル結合などが挙げられる。 Examples of the polyether monomer constituting the polyether / polyolefin block copolymer resin include alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples of the polyolefin monomer that constitutes the polyether / polyolefin block copolymer resin include olefins such as ethylene, propylene, butene, pentene, and hexene. The chemical bond between the polyether and the polyolefin is not particularly limited, and examples thereof include an ester bond, an amide bond, and an ether bond.
ポリエーテル／ポリオレフィンブロック共重合体樹脂としては、例えば、三洋化成工業株式会社製のペレスタット（登録商標）、ペレクトロン（登録商標）などの市販品を用いることができる。 As the polyether / polyolefin block copolymer resin, for example, commercially available products such as Pelestat (registered trademark) and Peletron (registered trademark) manufactured by Sanyo Chemical Industries, Ltd. can be used.
前記のような従来帯電防止剤として用いられているポリエーテルを含むブロック共重合体樹脂としては、例えば、１２０〜２００℃の融点のものが挙げられる。本発明の帯電防止剤に配合するポリエーテルを含むブロック共重合体樹脂の融点は、帯電防止剤作製時にゴム成分が熱で劣化することを抑制できるという理由から、低い方が好ましく、具体的には、２００℃以下が好ましく、１５０℃以下がより好ましい。 Examples of the block copolymer resin containing a polyether conventionally used as an antistatic agent include those having a melting point of 120 to 200 ° C. The melting point of the block copolymer resin containing the polyether to be blended with the antistatic agent of the present invention is preferably low because it can suppress the rubber component from being deteriorated by heat during the preparation of the antistatic agent. Is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
架橋可能なゴム成分とポリエーテルを含むブロック共重合体樹脂との質量含有比（ゴム成分／ポリエーテルを含むブロック共重合体樹脂）は、４０／６０以上であり、４５／５５以上が好ましく、５０／５０以上がより好ましく、６０／４０以上がさらに好ましい。該質量含有比が４０／６０未満である場合、ポリエーテルを含むブロック共重合体樹脂が帯電防止剤中に十分に分散せず塊となって残る恐れがある。そして、ポリエーテルを含むブロック共重合体樹脂が十分に分散していない帯電防止剤をゴム組成物に配合し、一般的なゴム組成物の混練条件で混練した場合、ゴム組成物中に帯電防止剤が十分に分散せず、本発明の効果を十分に発揮できない傾向がある。また、該質量含有比は、９５／５以下であり、９０／１０以下が好ましく、８０／２０以下がより好ましい。該質量含有比が９５／５を超える場合は、帯電防止効果が十分に得られない恐れがある。 The mass content ratio between the crosslinkable rubber component and the block copolymer resin containing polyether (rubber component / block copolymer resin containing polyether) is 40/60 or more, preferably 45/55 or more, 50/50 or more is more preferable, and 60/40 or more is more preferable. When the mass content ratio is less than 40/60, the block copolymer resin containing the polyether may not be sufficiently dispersed in the antistatic agent and may remain as a lump. When an antistatic agent in which the block copolymer resin containing the polyether is not sufficiently dispersed is blended in the rubber composition and kneaded under the general rubber composition kneading conditions, the antistatic agent is added to the rubber composition. There is a tendency that the agent is not sufficiently dispersed and the effects of the present invention cannot be sufficiently exhibited. The mass content ratio is 95/5 or less, preferably 90/10 or less, and more preferably 80/20 or less. When the mass content ratio exceeds 95/5, the antistatic effect may not be sufficiently obtained.
本発明の帯電防止剤には、前記成分以外にも、カーボンブラックなどの導電性充填剤、老化防止剤、顔料、加工助剤、架橋剤など、一般的に樹脂やゴム組成物に配合される添加剤を適宜配合することができる。但し、帯電防止剤が架橋されることを防ぐため、硫黄や有機過酸化物などの架橋剤は含有しないことが好ましい。 In addition to the above components, the antistatic agent of the present invention is generally blended into a resin or rubber composition such as a conductive filler such as carbon black, an anti-aging agent, a pigment, a processing aid, and a crosslinking agent. Additives can be blended as appropriate. However, in order to prevent the antistatic agent from being crosslinked, it is preferable not to contain a crosslinking agent such as sulfur or an organic peroxide.
本発明の帯電防止剤の製造方法は特に限定されないが、ポリエーテルを含むブロック共重合体樹脂が良好に分散して塊が目視できない帯電防止剤となり、本発明の効果がより好適に得られるという理由から、架橋可能なゴム成分およびポリエーテルを含むブロック共重合体樹脂を、ポリエーテルを含むブロック共重合体樹脂の融点以上の混練温度で混練する工程（混練工程Ａ）を含む製造方法により製造することが好ましい。 The production method of the antistatic agent of the present invention is not particularly limited, but the block copolymer resin containing a polyether is well dispersed and becomes an antistatic agent in which no lumps can be visually observed, and the effects of the present invention are more suitably obtained. For this reason, a block copolymer resin containing a crosslinkable rubber component and a polyether is produced by a production method including a step of kneading at a kneading temperature equal to or higher than the melting point of the block copolymer resin containing a polyether (kneading step A). It is preferable to do.
前記混練工程Ａには、例えば、バンバリーミキサーやニーダー、オープンロール、二軸押出機などの装置を用いることができる。 For the kneading step A, for example, a Banbury mixer, a kneader, an open roll, a twin screw extruder, or the like can be used.
二軸押出機は、主に、材料の供給口であるホッパー、二本のスクリューを備え材料を混練りしながら一方向に押出すシリンダ、シリンダの排出側先端部に位置するヘッド、混練物を連続的に一定形状に成形するためのダイ（金型）、ヘッドとダイをつなぐアダプタにより構成される。二本の螺旋状のスクリューがシリンダ内で回転しながら、ホッパーから供給される材料を圧縮し発熱させて溶融混合、混練りし、混練物をヘッドに送り出し、ダイを通して押出成形する。また、二軸押出機の各部には、供給物の溶融を促進するために、熱媒体または鋳込み電気ヒーターによる加熱手段が設けられている。 The twin-screw extruder mainly includes a hopper that is a material supply port, a cylinder that is equipped with two screws and extrudes in one direction while kneading the material, a head that is located at the discharge end of the cylinder, and a kneaded product. Consists of a die (mold) for continuously forming a fixed shape and an adapter that connects the head and the die. While the two spiral screws rotate in the cylinder, the material supplied from the hopper is compressed and heated to melt and mix and knead, and the kneaded product is sent to the head and extruded through a die. Each part of the twin-screw extruder is provided with heating means using a heat medium or a cast electric heater in order to promote melting of the feed.
前記混練工程Ａにおける混練温度は、ポリエーテルを含むブロック共重合体樹脂が良好に分散して塊が目視できない帯電防止剤となり、本発明の効果がより好適に得られるという理由から、ポリエーテルを含むブロック共重合体樹脂の融点以上であることが好ましく、ポリエーテルを含むブロック共重合体樹脂の融点の＋１０℃以上であることがより好ましい。また、混練工程Ａにおける混練温度は、ゴム成分の熱劣化を抑制するという理由から、ポリエーテルを含むブロック共重合体樹脂の融点の＋１００℃以下が好ましく、＋５０℃以下がより好ましい。なお、本願明細書中における混練温度とは、混練中の最高温度であり、例えば、混練機として二軸押出機を用いる場合の混練温度とは、二軸押出機の最高設定温度を示す。 The kneading temperature in the kneading step A is an antistatic agent in which the block copolymer resin containing the polyether is well dispersed and the lumps cannot be visually observed, and the polyether is used because the effects of the present invention can be obtained more suitably. It is preferably higher than the melting point of the block copolymer resin containing, more preferably + 10 ° C. or higher of the melting point of the block copolymer resin containing polyether. Further, the kneading temperature in the kneading step A is preferably + 100 ° C. or less, more preferably + 50 ° C. or less of the melting point of the block copolymer resin containing polyether, for the reason of suppressing the thermal deterioration of the rubber component. The kneading temperature in the present specification is the highest temperature during kneading. For example, the kneading temperature when using a twin screw extruder as the kneader indicates the highest set temperature of the twin screw extruder.
本発明の帯電防止剤の製造方法には、前記混練工程Ａの他に、混練工程Ａで得られた混練物とゴム成分およびポリエーテルを含むブロック共重合体樹脂以外の配合剤とを混練する工程（混練工程Ｂ）、得られた混練物を成形する工程（成形工程）などを含むことができる。 In the method for producing an antistatic agent of the present invention, in addition to the kneading step A, the kneaded product obtained in the kneading step A and a compounding agent other than the block copolymer resin containing a rubber component and a polyether are kneaded. The process (kneading | mixing process B), the process (molding process) etc. which shape | mold the obtained kneaded material can be included.
前記成形工程は、混練工程で得られた混練物を成形する工程である。成形方法や形状などは、特に限定されず、本発明の帯電防止剤を配合する物により適宜選択することができ、例えば、ひも状に押出成形し、水槽などで冷却した後、長さ２〜５ｍｍ程度にカットしてペレット状とすることができる。 The forming step is a step of forming the kneaded product obtained in the kneading step. The molding method and shape are not particularly limited, and can be appropriately selected depending on the compound containing the antistatic agent of the present invention. For example, after extrusion in a string shape and cooling in a water tank or the like, a length of 2 It can be cut to about 5 mm to form a pellet.
本発明の帯電防止剤は、ポリエーテルを含むブロック共重合体樹脂が良好に分散しているため、該帯電防止剤をゴム組成物に配合し、一般的なゴム組成物の混練温度で混練りしても、ゴム組成物中に良好に分散する。そのため、ゴム組成物の混練温度を高くしたり、混練時間を長くしたりする必要が無いため、ゴム組成物の物性を低下させずに、帯電防止性能に優れたゴム組成物を製造することができる。 In the antistatic agent of the present invention, since the block copolymer resin containing the polyether is well dispersed, the antistatic agent is blended in a rubber composition and kneaded at a kneading temperature of a general rubber composition. Even so, it is well dispersed in the rubber composition. Therefore, since it is not necessary to increase the kneading temperature of the rubber composition or lengthen the kneading time, it is possible to produce a rubber composition having excellent antistatic performance without deteriorating the physical properties of the rubber composition. it can.
本発明の帯電防止剤を含有するゴム組成物は、帯電防止性能に優れることから、帯電防止性能が求められるゴム製品に用いることができ、例えば、紙送りローラのゴム材料、電子部品製造装置のゴム部材などが挙げられる。なかでも、ゴム組成物表面にブルームやブリードが発生する心配が無く、顔料を添加することで任意の色に着色できることから、紙送りローラのゴム材料として好適に用いることができる。 Since the rubber composition containing the antistatic agent of the present invention is excellent in antistatic performance, it can be used for rubber products that require antistatic performance. For example, rubber materials for paper feed rollers, electronic component manufacturing equipment Examples thereof include a rubber member. In particular, there is no concern that bloom or bleed is generated on the surface of the rubber composition, and since it can be colored in an arbitrary color by adding a pigment, it can be suitably used as a rubber material for a paper feed roller.
本発明を実施例に基づいて説明するが、本発明は、実施例にのみ限定されるものではない。 The present invention will be described based on examples, but the present invention is not limited to the examples.
以下、実施例および比較例において用いた各種薬品をまとめて示す。
ＥＰＤＭ１：住友化学（株）製のエスプレン５０５Ａ（非油展、第３成分（ジエン分）：ＥＮＢ）
ＥＰＤＭ２：住友化学（株）製のエスプレン６０７Ｆ（ゴム固形分１００質量部に対してオイルを１００質量部含有）
ＮＢＲ：日本ゼオン（株）のＮｉｐｏｌ ＤＮ３３５０
ＳＢＲ：日本ゼオン（株）のＮｉｐｏｌ １５０２
ブロック共重合体樹脂：三洋化成工業（株）製のペレクトロンＨＳ（ポリエーテル／ポリオレフィンブロック共重合体樹脂、融点：約１３５℃）
老化防止剤：ＢＡＳＦ社製のＩＲＧＡＮＯＸ１０１０
酸化亜鉛：三井金属鉱業（株）製の酸化亜鉛２種
ステアリン酸：日本油脂（株）製のステアリン酸 椿
カーボンブラック：三菱化学（株）製のダイアブラックＨ（ＨＡＦ級）
炭酸カルシウム：白石カルシウム（株）製のホワイトンＢＦ−２００
クレー：サウスイースタン・クレー社製のハードクラウンクレー
有機過酸化物：日油（株）製のパークミルＤ（ジクミルパーオキサイド）
硫黄：鶴見化学（株）製のＳｕｌｆａｘ ＰＳ
加硫促進剤ＤＭ：大内新興化学工業（株）製のノクセラーＤＭ（ジ−２−ベンゾチアジルジスルフィド）
加硫促進剤ＴＥＴ：大内新興化学工業（株）製のノクセラーＴＥＴ（テトラエチルチウラムジスルフィド）
Hereinafter, various chemicals used in Examples and Comparative Examples are shown together.
EPDM1: Esprene 505A manufactured by Sumitomo Chemical Co., Ltd. (Non-oil extended, third component (diene component): ENB)
EPDM2: Esprene 607F manufactured by Sumitomo Chemical Co., Ltd. (containing 100 parts by mass of oil with respect to 100 parts by mass of rubber solid content)
NBR: Nipol DN3350 from Nippon Zeon Co., Ltd.
SBR: Nipol 1502 from Nippon Zeon Co., Ltd.
Block copolymer resin: Peletron HS (polyether / polyolefin block copolymer resin, melting point: about 135 ° C.) manufactured by Sanyo Chemical Industries
Anti-aging agent: IRGANOX1010 manufactured by BASF
Zinc oxide: 2 types of zinc oxide manufactured by Mitsui Mining & Smelting Co., Ltd. Stearic acid: Stearic acid manufactured by Nippon Oil & Fats Co., Ltd. 椿 Carbon Black: Dia Black H (HAF grade) manufactured by Mitsubishi Chemical Corporation
Calcium carbonate: Whiten BF-200 manufactured by Shiraishi Calcium Co., Ltd.
Clay: Hard crown clay manufactured by Southeastern Clay Organic peroxide: Parkmill D (dicumyl peroxide) manufactured by NOF Corporation
Sulfur: Sulfax PS manufactured by Tsurumi Chemical Co., Ltd.
Vulcanization accelerator DM: Noxeller DM (di-2-benzothiazyl disulfide) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator TET: Noxeller TET (tetraethylthiuram disulfide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
帯電防止剤の調製
実施例１〜５および比較例２については、表２の「帯電防止剤」に示す配合処方に従い、表１の条件とした二軸押出機を用いて混練りし（混練温度：１５０℃）、直径２〜５ｍｍのひも状に押出した後、水槽で冷却し、長さ２〜５ｍｍにカットしてペレット状帯電防止剤を調製した。
Preparation of Antistatic Agents Examples 1 to 5 and Comparative Example 2 were kneaded using a twin screw extruder having the conditions shown in Table 1 according to the formulation shown in “Antistatic Agent” in Table 2 (kneading temperature). : 150 ° C.), extruded into a string having a diameter of 2 to 5 mm, cooled in a water tank, and cut to a length of 2 to 5 mm to prepare a pellet-shaped antistatic agent.
ゴム組成物の作製
表２および３に示す配合内容に従い、各種薬品を、３Ｌニーダーおよびオープンロールにて、混練物の温度が１００℃を超えないように混練りし、未架橋ゴム組成物を得た。得られた未架橋ゴム組成物を１７０℃の条件下で２０分間プレス架橋し、２００×２００ｍｍ、厚さ２ｍｍの架橋ゴムシートを得た。得られた未架橋ゴム組成物および架橋ゴムシートについて下記評価を行った。結果を表２に示す。なお、比較例１および３〜６は本発明の帯電防止剤を使用していないゴム組成物であり、比較例１、４および５はポリエーテルを含むブロック共重合体樹脂を含有していないゴム組成物、比較例３および６はポリエーテルを含むブロック共重合体樹脂を本発明の帯電防止剤とせず、そのまま添加したゴム組成物である。
Preparation of rubber composition According to the blending contents shown in Tables 2 and 3, various chemicals were kneaded with a 3 L kneader and an open roll so that the temperature of the kneaded material did not exceed 100 ° C. to obtain an uncrosslinked rubber composition. It was. The obtained uncrosslinked rubber composition was press-crosslinked for 20 minutes at 170 ° C. to obtain a crosslinked rubber sheet having a size of 200 × 200 mm and a thickness of 2 mm. The following evaluation was performed about the obtained uncrosslinked rubber composition and crosslinked rubber sheet. The results are shown in Table 2. Comparative Examples 1 and 3 to 6 are rubber compositions not using the antistatic agent of the present invention, and Comparative Examples 1, 4 and 5 are rubbers not containing a block copolymer resin containing a polyether. The compositions, Comparative Examples 3 and 6, are rubber compositions in which a block copolymer resin containing a polyether was added as it was without using the antistatic agent of the present invention.
＜外観 未架橋ゴム組成物＞
ポリエーテルを含むブロック共重合体樹脂を含有する実施例および比較例について、各未架橋ゴム組成物の表面および断面におけるポリエーテルを含むブロック共重合体樹脂または帯電防止剤の塊の有無を目視にて観察し、下記の基準で評価した。
○：ポリエーテルを含むブロック共重合体樹脂または帯電防止剤の塊が全く確認できないもの
×：ポリエーテルを含むブロック共重合体樹脂または帯電防止剤の塊が少しでも確認できるもの
<Appearance Uncrosslinked rubber composition>
For Examples and Comparative Examples containing a block copolymer resin containing a polyether, the presence or absence of a block copolymer resin or an antistatic agent block in the surface and cross section of each uncrosslinked rubber composition was visually observed. And evaluated according to the following criteria.
○: Block copolymer resin containing polyether or antistatic agent mass cannot be confirmed at all ×: Block copolymer resin containing polyether or antistatic agent mass can be confirmed even a little
前記未架橋ゴム組成物の外観評価が○であったものについて、以下の評価を行った。ポリエーテルを含むブロック共重合体樹脂を含有していない比較例１、４および５については、体積固有抵抗率測定、ゴム硬度測定、および引張り試験のみを行った。 The following evaluation was performed about the thing whose external appearance evaluation of the said uncrosslinked rubber composition was (circle). For Comparative Examples 1, 4 and 5 that did not contain a block copolymer resin containing a polyether, only volume resistivity measurement, rubber hardness measurement, and tensile test were performed.
＜外観 架橋ゴムシート＞
各架橋ゴムシートの表面および断面におけるポリエーテルを含むブロック共重合体樹脂または帯電防止剤の塊の有無を目視にて観察し、下記の基準で評価した。
○：ポリエーテルを含むブロック共重合体樹脂または帯電防止剤の塊が全く確認できないもの
×：ポリエーテルを含むブロック共重合体樹脂または帯電防止剤の塊が少しでも確認できるもの
<Appearance cross-linked rubber sheet>
The presence or absence of block copolymer resin or antistatic agent lumps containing polyether on the surface and cross section of each crosslinked rubber sheet was visually observed and evaluated according to the following criteria.
○: Block copolymer resin containing polyether or antistatic agent mass cannot be confirmed at all ×: Block copolymer resin containing polyether or antistatic agent mass can be confirmed even a little
＜体積固有抵抗率＞
各架橋ゴムシートの体積固有抵抗率を、ＪＩＳ Ｋ６２７１に準じて、２３℃、湿度５５％の雰囲気下において１ｋＶの電圧で測定した。体積固有抵抗率の値が小さいほど、帯電防止性能に優れることを示す。なお、体積固有抵抗率は１．０×１０11Ω・ｃｍ未満を性能目標値とする。
<Volume specific resistivity>
The volume resistivity of each crosslinked rubber sheet was measured at a voltage of 1 kV in an atmosphere of 23 ° C. and 55% humidity according to JIS K6271. It shows that it is excellent in antistatic performance, so that the value of volume resistivity is small. The volume resistivity is set to a performance target value of less than 1.0 × 10 11 Ω · cm.
＜ゴム硬度測定＞
各架橋ゴムシートのタイプＡデュロメータ硬さをＪＩＳ Ｋ６２５３に準じて、２３℃の雰囲気下で測定した。なお、試験片は、厚さ２ｍｍの架橋ゴムシートを３枚重ねたものを使用し、測定時間は３秒とした。
<Rubber hardness measurement>
The type A durometer hardness of each crosslinked rubber sheet was measured in an atmosphere of 23 ° C. according to JIS K6253. In addition, the test piece used what laminated | stacked 3 sheets of 2 mm thick crosslinked rubber sheets, and the measurement time was 3 second.
＜引張り試験＞
前記架橋ゴムシートとは別に作成した各架橋ゴム組成物からなる３号ダンベル型試験片を用いて、ＪＩＳ Ｋ６２５１に準じて引張り試験を実施し、引張強さ（ＭＰａ）および破断時伸び（％）を測定した。
<Tensile test>
A tensile test (MPa) and elongation at break (%) were conducted using a No. 3 dumbbell-shaped test piece made of each crosslinked rubber composition prepared separately from the crosslinked rubber sheet, in accordance with JIS K6251. Was measured.
架橋可能なゴム成分およびポリエーテルを含むブロック共重合体樹脂を含有する帯電防止剤であり、架橋可能なゴム成分とポリエーテルを含むブロック共重合体樹脂との質量含有比（ゴム成分／ポリエーテルを含むブロック共重合体樹脂）が９５／５〜４０／６０である実施例１〜３は、未架橋ゴム組成物の表面および断面が均一に仕上がっており、ポリエーテルを含むブロック共重合体樹脂の分散は良好であった。これに対して、架橋可能なゴム成分とポリエーテルを含むブロック共重合体樹脂との質量含有比が所定の範囲を外れる帯電防止剤を用いた比較例２、およびゴム成分と混練した帯電防止剤とせずポリエーテルを含むブロック共重合体樹脂をそのまま添加した比較例３は、未架橋ゴム組成物に帯電防止剤やポリエーテルを含むブロック共重合体樹脂の塊が明らかに残っており、実施例１〜３のような均一な未架橋ゴム組成物は得られなかった。 Antistatic agent containing a block copolymer resin containing a crosslinkable rubber component and a polyether, and a mass content ratio of the crosslinkable rubber component and the block copolymer resin containing a polyether (rubber component / polyether) Examples 1 to 3 in which the block copolymer resin containing 95/5 to 40/60 has a uniform surface and cross-section of the uncrosslinked rubber composition, and the block copolymer resin containing polyether The dispersion of was good. On the other hand, Comparative Example 2 using an antistatic agent in which the mass content ratio between the crosslinkable rubber component and the block copolymer resin containing the polyether deviates from a predetermined range, and the antistatic agent kneaded with the rubber component In Comparative Example 3 in which the block copolymer resin containing the polyether was added as it was, the block copolymer resin mass containing the antistatic agent and the polyether was clearly left in the uncrosslinked rubber composition. A uniform uncrosslinked rubber composition such as 1 to 3 was not obtained.
比較例２および３は未架橋ゴム組成物に帯電防止剤やポリエーテルを含むブロック共重合体樹脂の塊が残っており、明らかに分散不良であったため、架橋ゴムシートを用いた評価は行わなかった。実施例１〜３およびポリエーテルを含むブロック共重合体樹脂を配合していない比較例１の架橋ゴムシートの表面および断面は均一に仕上がっており、異常は見られなかった。特に、ポリエーテルを含むブロック共重合体樹脂をゴム成分と混練した帯電防止剤として配合した実施例１〜３の体積固有抵抗率は、１０9台であり、帯電防止用のゴム組成物として有用な体積固有抵抗率であった。ポリエーテルを含むブロック共重合体樹脂を配合していない比較例１の体積固有抵抗率は１０14台であり、いわゆる絶縁ゴム組成物であった。 In Comparative Examples 2 and 3, the block copolymer resin block containing the antistatic agent and the polyether remained in the uncrosslinked rubber composition, and the dispersion using the crosslinked rubber sheet was not evaluated because it was clearly poorly dispersed. It was. The surface and cross section of the crosslinked rubber sheet of Examples 1 to 3 and Comparative Example 1 in which no block copolymer resin containing polyether was blended were uniformly finished, and no abnormality was observed. In particular, the volume resistivity of Examples 1 to 3 in which a block copolymer resin containing a polyether was blended as an antistatic agent kneaded with a rubber component is 10 9 units, and is useful as an antistatic rubber composition. Volume resistivity. The specific volume resistivity of Comparative Example 1 in which no block copolymer resin containing polyether was blended was 10 14 units, which was a so-called insulating rubber composition.
架橋可能なゴム成分およびポリエーテルを含むブロック共重合体樹脂を含有する帯電防止剤であり、架橋可能なゴム成分とポリエーテルを含むブロック共重合体樹脂との質量含有比（ゴム成分／ポリエーテルを含むブロック共重合体樹脂）が９５／５〜４０／６０である実施例４および５は、未架橋ゴム組成物の表面および断面が均一に仕上がっており、ポリエーテルを含むブロック共重合体樹脂の分散は良好であった（図１参照）。これに対して、ゴム成分と混練した帯電防止剤とせずポリエーテルを含むブロック共重合体樹脂をそのまま添加した比較例６は、未架橋ゴム組成物に帯電防止剤やポリエーテルを含むブロック共重合体樹脂の塊が明らかに残っており、実施例４および５のような均一な未架橋ゴム組成物は得られなかった（図２参照）。 Antistatic agent containing a block copolymer resin containing a crosslinkable rubber component and a polyether, and a mass content ratio of the crosslinkable rubber component and the block copolymer resin containing a polyether (rubber component / polyether) Examples 4 and 5 in which the block copolymer resin containing 95) to 95/40/60 has a uniform finish on the surface and cross section of the uncrosslinked rubber composition, and the block copolymer resin containing polyether The dispersion of was good (see FIG. 1). On the other hand, Comparative Example 6 in which the block copolymer resin containing the polyether without adding the antistatic agent kneaded with the rubber component was added as it is is the block copolymer containing the antistatic agent and the polyether in the uncrosslinked rubber composition. A lump of coalesced resin remained clearly, and a uniform uncrosslinked rubber composition as in Examples 4 and 5 was not obtained (see FIG. 2).
比較例６は未架橋ゴム組成物に帯電防止剤やポリエーテルを含むブロック共重合体樹脂の塊が残っており、明らかに分散不良であったため、架橋ゴムシートを用いた評価は行わなかった。実施例４および５ならびにポリエーテルを含むブロック共重合体樹脂を配合していない比較例４および５の架橋ゴムシートの表面および断面は均一に仕上がっており、異常は見られなかった。しかし、実施例４および５の体積固有抵抗率は、１０9〜１０10台であり、帯電防止用のゴム組成物として有用な体積固有抵抗率であった。ポリエーテルを含むブロック共重合体樹脂を配合していない比較例４および５の体積固有抵抗率は、それぞれ１０11台および１０14台であり、いわゆる絶縁ゴム組成物であった。 In Comparative Example 6, a block copolymer resin mass containing an antistatic agent and a polyether remained in the uncrosslinked rubber composition, which was clearly poorly dispersed. Therefore, evaluation using a crosslinked rubber sheet was not performed. The surfaces and cross sections of the crosslinked rubber sheets of Examples 4 and 5 and Comparative Examples 4 and 5 not blended with the block copolymer resin containing polyether were finished uniformly, and no abnormality was observed. However, the volume resistivity of Examples 4 and 5 was 10 9 to 10 10 , which was useful as a rubber composition for antistatic. The volume specific resistivities of Comparative Examples 4 and 5 in which no block copolymer resin containing polyether was blended were 10 11 units and 10 14 units, respectively, which were so-called insulating rubber compositions.
Claims (2)
ポリエーテルを含むブロック共重合体樹脂を含有する帯電防止剤であり、
架橋可能なゴム成分とポリエーテルを含むブロック共重合体樹脂との質量含有比（ゴム成分／ポリエーテルを含むブロック共重合体樹脂）が９５／５〜４０／６０である帯電防止剤。 An antistatic agent comprising a crosslinkable rubber component and a block copolymer resin comprising a polyether;
Antistatic agent whose mass content ratio (rubber component / block copolymer resin containing polyether) of the crosslinkable rubber component and the block copolymer resin containing polyether is 95/5 to 40/60.
ポリエーテルを含むブロック共重合体樹脂の融点以上の混練温度で混練する工程を含む請求項１記載の帯電防止剤の製造方法。 A block copolymer resin containing a crosslinkable rubber component and a polyether,
The method for producing an antistatic agent according to claim 1, comprising a step of kneading at a kneading temperature equal to or higher than the melting point of the block copolymer resin containing a polyether.
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| CN109251420A (en) * | 2017-07-12 | 2019-01-22 | 住友橡胶工业株式会社 | Antistatic rubber composition and paper feed roller |
| CN112480390A (en) * | 2020-11-30 | 2021-03-12 | 广东聚航新材料研究院有限公司 | Antistatic agent for dicyclopentadiene resin and preparation method thereof |
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| JP2004189884A (en) * | 2002-12-11 | 2004-07-08 | Sumitomo Rubber Ind Ltd | Semiconductive thermoplastic elastomer composition and antistatic paper feed roller using the same composition |
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| JPH07228785A (en) * | 1993-12-24 | 1995-08-29 | Marubishi Yuka Kogyo Kk | Modifier for resin and rubber |
| JP2003048990A (en) * | 2001-05-28 | 2003-02-21 | Sanyo Chem Ind Ltd | Block polymer having branched skeleton and antistatic agent made of the same |
| JP2004189884A (en) * | 2002-12-11 | 2004-07-08 | Sumitomo Rubber Ind Ltd | Semiconductive thermoplastic elastomer composition and antistatic paper feed roller using the same composition |
| JP2006137790A (en) * | 2004-11-10 | 2006-06-01 | Sanko Kagaku Kogyo Kk | Antistatic composition, method for producing the same and molded product, coating and antistatic coated material using the same |
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| CN109251420A (en) * | 2017-07-12 | 2019-01-22 | 住友橡胶工业株式会社 | Antistatic rubber composition and paper feed roller |
| CN112480390A (en) * | 2020-11-30 | 2021-03-12 | 广东聚航新材料研究院有限公司 | Antistatic agent for dicyclopentadiene resin and preparation method thereof |
| CN112480390B (en) * | 2020-11-30 | 2023-05-09 | 广东聚航新材料研究院有限公司 | Antistatic agent for dicyclopentadiene resin and preparation method thereof |
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