JP2011032359A - Fluororesin composition - Google Patents
Fluororesin composition Download PDFInfo
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- JP2011032359A JP2011032359A JP2009179398A JP2009179398A JP2011032359A JP 2011032359 A JP2011032359 A JP 2011032359A JP 2009179398 A JP2009179398 A JP 2009179398A JP 2009179398 A JP2009179398 A JP 2009179398A JP 2011032359 A JP2011032359 A JP 2011032359A
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- vinylidene fluoride
- fluororesin
- copolymer
- fluororesin composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920001971 elastomer Polymers 0.000 claims abstract description 37
- 239000000806 elastomer Substances 0.000 claims abstract description 37
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 7
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 claims abstract description 5
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 13
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 12
- 229920001897 terpolymer Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 229920006027 ternary co-polymer Polymers 0.000 abstract 2
- 238000002156 mixing Methods 0.000 description 13
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 8
- FRZPYEHDSAQGAS-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]=1C=CN(C)C=1 FRZPYEHDSAQGAS-UHFFFAOYSA-M 0.000 description 6
- INDFXCHYORWHLQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-3-methylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F INDFXCHYORWHLQ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 fluoroalkyl sulfonate Chemical compound 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229920001780 ECTFE Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920007478 Kynar® 740 Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- FEDFHMISXKDOJI-UHFFFAOYSA-M lithium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FEDFHMISXKDOJI-UHFFFAOYSA-M 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Abstract
Description
本発明は、帯電性が小さなフッ素樹脂組成物に関し、熱可塑性のフッ素樹脂組成物、およびそれを用いたフッ素樹脂成形品に関する。 The present invention relates to a fluororesin composition having low chargeability, a thermoplastic fluororesin composition, and a fluororesin molded product using the same.
フッ素樹脂は、表面抵抗、及び静電気の帯電性が大きな物質である。フッ素樹脂組成物のフィルムを袋状の包装用部材とした場合には、摩擦帯電によってフィルムが付着して包装用部材相互あるいは包装される部材との間での引きはがしが困難となることが起こる。
また、複写機、プリンターの熱定着部用ロールにロールカバーとしてフッ素樹脂組成物の薄肉チューブを使用すると、紙との摩擦帯電によって紙がロールから離れなくなるという問題があった。
あるいは、フッ素樹脂組成物製の部材によって半導体装置を収容した場合には、帯電した電位によって半導体装置が破壊されるという問題があった。
フッ素樹脂製組成物の帯電特性を改善するめに、フッ素樹脂組成物中にカーボンブラック等の導電性粒子を配合することが提案されている。
導電性粒子として、カーボンブラック等を配合した場合には、フッ素樹脂組成物が着色するために、内容物が見えなくなるという問題があった。また、使用中のフッ素樹脂組成物からの抜け落ちの問題を解決するためにカーボンナノチューブを配合することが提案されている（例えば、特許文献１参照）。
A fluororesin is a substance having a large surface resistance and electrostatic chargeability. When a film of a fluororesin composition is used as a bag-like packaging member, the film adheres due to triboelectric charging, and it may be difficult to peel it off between the packaging members or between the members to be packaged. .
Further, when a thin tube of a fluororesin composition is used as a roll cover for a roll for a heat fixing part of a copying machine or a printer, there is a problem that the paper cannot be separated from the roll due to frictional charging with the paper.
Alternatively, when a semiconductor device is accommodated by a member made of a fluororesin composition, there is a problem that the semiconductor device is destroyed by a charged potential.
In order to improve the charging characteristics of the fluororesin composition, it has been proposed to blend conductive particles such as carbon black in the fluororesin composition.
When carbon black or the like is blended as the conductive particles, the fluororesin composition is colored, and there is a problem that the contents cannot be seen. In addition, in order to solve the problem of falling off from the fluororesin composition in use, it has been proposed to blend carbon nanotubes (see, for example, Patent Document 1).
本発明は、フッ素樹脂が備えた透明性を維持し、帯電性が小さなフッ素樹脂組成物、およびフッ素樹脂組成物からなる帯電性が小さなフッ素樹脂成形体を提供することを課題とするものである。 An object of the present invention is to provide a fluororesin composition having a low chargeability while maintaining the transparency possessed by the fluororesin, and a fluororesin molded product having a low chargeability comprising the fluororesin composition. .
本発明は、熱可塑性フッ素樹脂組成物中に、フッ化ビニリデン構造を有するエラストマーを配合したフッ素樹脂組成物である。
また、フッ化ビニリデン構造を有するエラストマーがビニリデンフロライド／ヘキサフルオロプロピレン／テトラフルオロエチレン三元共重合体、ビニリデンフロライド／パーフルオロメチルビニルエーテル／テトラフルオロエチレン三元共重合体、ビニリデンフロライド／ヘキサフルオロプロピレン二元共重合体、あるいはビニリデンフロライドとクロロトリフルオロエチレンとの共重合体である前記のフッ素樹脂組成物である。
また、電解質を含有する前記のフッ素樹脂組成物である。
フッ素樹脂が、テトラフルオロエチレン−フルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）から選ばれる少なくとも一種の樹脂である前記のフッ素樹脂組成物である。
また、熱可塑性フッ素樹脂組成物中に、フッ化ビニリデン構造を有する前記のエラストマーを配合したフッ素樹脂組成物を用いた成形品である。
The present invention is a fluororesin composition in which an elastomer having a vinylidene fluoride structure is blended in a thermoplastic fluororesin composition.
Further, the elastomer having a vinylidene fluoride structure is vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene terpolymer, vinylidene fluoride / perfluoromethyl vinyl ether / tetrafluoroethylene terpolymer, vinylidene fluoride / hexa. The fluororesin composition is a fluoropropylene binary copolymer or a copolymer of vinylidene fluoride and chlorotrifluoroethylene.
Moreover, it is the said fluororesin composition containing electrolyte.
The fluororesin is at least one resin selected from tetrafluoroethylene-fluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and ethylene-tetrafluoroethylene copolymer (ETFE). It is the said fluororesin composition which is.
Moreover, it is a molded article using the fluororesin composition which mix | blended the said elastomer which has a vinylidene fluoride structure in a thermoplastic fluororesin composition.
本発明のフッ素樹脂組成物は、熱可塑性フッ素樹脂中に、フッ化ビニリデン構造を有するエラストマーを配合したことによって、導電性粒子等を配合することなくフッ素樹脂組成物の帯電性を小さくすることが可能となるので、帯電性が小さな部材が求められる用途において利用可能であって耐食性が大きく、透明性が大きなフッ素樹脂組成物、およびそれを用いて作製したフッ素樹脂製の部材を提供することができる。 The fluororesin composition of the present invention can reduce the chargeability of the fluororesin composition without blending conductive particles or the like by blending an elastomer having a vinylidene fluoride structure in the thermoplastic fluororesin. Therefore, it is possible to provide a fluororesin composition that can be used in applications where a member with low chargeability is required, has high corrosion resistance, and has high transparency, and a member made of the fluororesin using the fluororesin composition. it can.
本発明は、熱可塑性フッ素樹脂組成物中に、フッ化ビニリデン構造を有するエラストマーを配合することによって帯電性を減少させたフッ素樹脂の組成物を得ることが可能であることを見いだしたものである。
すなわち、本発明のフッ素樹脂組成物は、テトラフルオロエチレン−フルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）等のフッ素樹脂組成物中に、フッ化ビニリデン構造を有するエラストマーを配合したことを特徴とし、この組成物を用いた成形体は、コロナ放電によって帯電させた場合には、帯電の減衰の半減期が短くなる。
The present invention has found that it is possible to obtain a fluororesin composition with reduced chargeability by blending an elastomer having a vinylidene fluoride structure in a thermoplastic fluororesin composition. .
That is, the fluororesin composition of the present invention comprises a tetrafluoroethylene-fluoroalkyl vinyl ether copolymer (PFA), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and an ethylene-tetrafluoroethylene copolymer (ETFE). And the like, and a molded product using this composition, when charged by corona discharge, has a half-life of charge decay when blended with an elastomer having a vinylidene fluoride structure. Becomes shorter.
フッ化ビニリデン構造を有するエラストマーを配合したフッ素樹脂組成物は、帯電後の半減期が短く、除電性が良好なものが得られる理由は定かではないが、エラストマー中のフッ化ビニリデン構造を有する柔軟な材料によって、電場が加えられた場合にフッ素樹脂組成物中に電子が流れる通路が形成されるものと考えられる。また、ポリフッ化ビニリデンは、強誘電性物質として知られているが、フッ化ビニリデン構造を有するエラストマーによって帯電後の除電性が大きな物質が得られることは、全く予期し得ないことである。
その結果、フッ素樹脂にカーボンブラック等の導電性粒子を添加した時のようにフッ素樹脂を着色したり、あるいは光透過性を阻害することなく摩擦帯電性を減少することが可能となる。
The reason why a fluororesin composition containing an elastomer having a vinylidene fluoride structure has a short half-life after charging and a good charge-removing property is not clear, but it is flexible with a vinylidene fluoride structure in the elastomer. It is considered that a path through which electrons flow is formed in the fluororesin composition when an electric field is applied depending on the material. Polyvinylidene fluoride is known as a ferroelectric substance, but it is completely unexpected that a substance having a high charge-removing property after charging can be obtained by an elastomer having a vinylidene fluoride structure.
As a result, it becomes possible to color the fluororesin as in the case of adding conductive particles such as carbon black to the fluororesin, or to reduce the triboelectric chargeability without impairing the light transmittance.
フッ素樹脂は、耐薬品性等が他の合成樹脂に比べて優れた樹脂であり、耐薬品性が要求される分野、あるいはプラスチックからの溶出物による液体の汚染等がないことが要求される分野において広く利用されている。
本発明のフッ素樹脂組成物は、フッ素樹脂組成物中にフッ化ビニリデン構造を有するエラストマーを含有するものの導電性粒子を含まないので、電気絶縁性が良好でありながら帯電性が小さいフッ素樹脂組成物を提供することができる。
特に、コロナ放電によって帯電した場合に速やかに除電するフッ素樹脂組成物を提供することができる。
Fluororesin is a resin with superior chemical resistance compared to other synthetic resins, and is a field that requires chemical resistance or a field that requires no liquid contamination due to eluate from plastic. Widely used.
Since the fluororesin composition of the present invention contains an elastomer having a vinylidene fluoride structure in the fluororesin composition but does not contain conductive particles, the fluororesin composition has good electrical insulation but low chargeability Can be provided.
In particular, it is possible to provide a fluororesin composition that quickly removes charge when charged by corona discharge.
本発明に使用することが可能がフッ化ビニリデン構造を有するエラストマーとしては、ビニリデンフロライド／ヘキサフルオロプロピレン／テトラフルオロエチレン三元共重合体、例えば、−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＣＦ3））m（ＣＦ2ＣＦ2）n −, ビニリデンフロライド／パーフルオロメチルビニルエーテル／テトラフルオロエチレン三元共重合体、例えば、−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＯＣＦ3））m（ＣＦ2ＣＦ2）n −を挙げることができる。
また、ビニリデンフロライド／ヘキサフルオロプロピレン二元共重合体、例えば、−（ＣＨ2ＣＦ2）n−（ＣＦ2ＣＦ（ＣＦ3））m −を挙げることができる。
また、ビニリデンフロライドとクロロトリフルオロエチレンとの共重合体を挙げることができる。
Examples of elastomers having a vinylidene fluoride structure that can be used in the present invention include vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene terpolymers such as — (CH 2 CF 2 ) 1 — (CF 2 CF (CF 3 )) m (CF 2 CF 2 ) n −, vinylidene fluoride / perfluoromethyl vinyl ether / tetrafluoroethylene terpolymer, for example, — (CH 2 CF 2 ) 1 — (CF 2 CF ( OCF 3)) m (CF 2 CF 2) n - can be exemplified.
Further, a vinylidene fluoride / hexafluoropropylene binary copolymer, for example, — (CH 2 CF 2 ) n — (CF 2 CF (CF 3 )) m — may be mentioned.
Moreover, the copolymer of vinylidene fluoride and chlorotrifluoroethylene can be mentioned.
具体的には、ビニリデンフロライド／ヘキサフロロプロピレン／テトラフロロエチレン三元共重合体としては、ダイニオンＴＨＶ２２０Ａ（住友スリーエム製）：−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＣＦ3））m−（ＣＦ2ＣＦ2）n −：ｌ／ｍ／ｎ＝４０／２０／４０（モル比）、ダイニオンＴＨＶ５００Ｇ：−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＣＦ3））m−（ＣＦ2ＣＦ2）n −：ｌ／ｍ／ｎ＝２５／２０／５５（モル比）、ダイエルＧ９０２（ダイキン）：−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＣＦ3））m−（ＣＦ2ＣＦ2）n −を挙げることができる。
ビニリデンフロライド／パーフルオロメチルビニルエーテル／テトラフロロエチレン三元共重合体としては、バイトンＧＬＴ（デュポンエラストマー製）：−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＯＣＦ3））m−（ＣＦ2ＣＦ2）n −を挙げることができる。
また、ビニリデンフロライド／ヘキサフロロプロピレン二元共重合体としては、バイトンＡ−２００：−（ＣＨ2ＣＦ2）m−（ＣＦ2ＣＦ（ＣＦ3））n −、あるいは、粘度が高いバイトンＡ−７００を挙げることができる。
Specifically, as vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene terpolymer, Dionion THV220A (manufactured by Sumitomo 3M): — (CH 2 CF 2 ) 1 — (CF 2 CF (CF 3 )) m - (CF 2 CF 2) n -: l / m / n = 40/20/40 ( molar ratio), Dyneon THV500G :-( CH 2 CF 2) l - (CF 2 CF (CF 3)) m - (CF 2 CF 2 ) n −: 1 / m / n = 25/20/55 (molar ratio), Daiel G902 (Daikin): — (CH 2 CF 2 ) 1 — (CF 2 CF (CF 3 )) m - (CF 2 CF 2) n - can be exemplified.
As vinylidene fluoride / perfluoromethyl vinyl ether / tetrafluoroethylene terpolymer, Viton GLT (manufactured by DuPont elastomer): — (CH 2 CF 2 ) 1 — (CF 2 CF (OCF 3 )) m — (CF 2 CF 2 ) n- .
As the vinylidene fluoride / hexafluoropropylene binary copolymer, Viton A-200 :-( CH 2 CF 2 ) m - (CF 2 CF (CF 3)) n -, or high viscosity Viton A -700.
また、ビニリデンフロライドとクロロトリフルオロエチレンとの共重合体としては、セフラルソフトＧ１５０Ｆ２００（セントラル硝子製）を挙げることができる。
これらのフッ化ビニリデン構造を有するエラストマーの添加量は、フッ素樹脂１００質量部に対して、０．０１質量部以上であることが好ましく、より好ましくは０．１質量部以上、２０質量部以下であり、０．５質量部以上、１０質量部以下とすることがより好ましい。添加量が０．０１質量部よりも少ないと帯電性が小さなものが得られず、また２０質量部よりも多いとフッ素樹脂組成物が有する特性、例えば、他の合成樹脂に比べて優れた耐薬品性あるいは溶出物による液体の汚染等がないという特性が低下する。
An example of a copolymer of vinylidene fluoride and chlorotrifluoroethylene is Cefalsoft G150F200 (manufactured by Central Glass).
The addition amount of the elastomer having a vinylidene fluoride structure is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the fluororesin. Yes, and more preferably 0.5 parts by mass or more and 10 parts by mass or less. If the amount added is less than 0.01 parts by weight, a product having a small chargeability cannot be obtained. If the amount added is more than 20 parts by weight, the characteristics of the fluororesin composition, for example, superior resistance to other synthetic resins. The characteristic that there is no contamination of the liquid due to chemicals or eluate is reduced.
また、本発明のフッ素樹脂組成物には、より帯電性を小さくするために、電解質を配合することができる。電解質としては、無機塩、有機塩を用いることができるが、例えば、フルオロアルキルスルホン酸塩、トリフルオロメチルスルホニルイミド化合物、あるいはイオン液体を挙げることができる。フルオロアルキルスルホン酸塩としては、トリフルオロメタンスルホン酸リチウム、パーフルオロブタンスルホン酸リチウム、パーフルオロブタンスルホン酸カリウムからなる群から選ばれる少なくとも一種のフルオロアルキルスルホン酸塩を挙げることができる。また、スルホニルイミドとしては、リチウムビス（トリフルオロメタンスルホニル）イミドを挙げることができる。
また、イオン液体としては、１−ブチル−３−メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＢＭＩＴＦＳＩ）、１−ブチル−３−メチルイミダゾリウムトリフルオロメタンスルホネート（ＢＭＩＴＦＳ）を挙げることができる。
これらの電解質の添加量は、フッ素樹脂１００質量部に対して、０．００１質量部以上であることが好ましく、より好ましくは０．００３質量部以上、５質量部以下であり、０．００５質量部以上、２質量部以下とすることがより好ましい。
添加量が０．００１質量部よりも少ないと帯電性が小さくならず、また５質量部よりも多いとフッ素樹脂組成物の加工性が低下する。
In addition, an electrolyte can be blended with the fluororesin composition of the present invention in order to further reduce the chargeability. As the electrolyte, an inorganic salt or an organic salt can be used, and examples thereof include a fluoroalkyl sulfonate, a trifluoromethylsulfonylimide compound, and an ionic liquid. Examples of the fluoroalkyl sulfonate include at least one fluoroalkyl sulfonate selected from the group consisting of lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, and potassium perfluorobutanesulfonate. Examples of the sulfonylimide include lithium bis (trifluoromethanesulfonyl) imide.
Examples of the ionic liquid include 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (BMITSI) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMITFS).
The addition amount of these electrolytes is preferably 0.001 part by mass or more, more preferably 0.003 part by mass or more and 5 parts by mass or less, and 0.005 part by mass with respect to 100 parts by mass of the fluororesin. More preferably, it is at least 2 parts by mass.
When the addition amount is less than 0.001 part by mass, the chargeability is not reduced, and when it is more than 5 parts by mass, the processability of the fluororesin composition is lowered.
本発明のフッ素樹脂組成物として使用可能なフッ素樹脂としては、テトラフルオロエチレン−フルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、エチレン−クロロトリフルオロエチレンコポリマー（ＥＣＴＦＥ）の少なくともいずれか一種を選ぶことができる。これらのなかでもテトラフルオロエチレン−フルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）を挙げることができる。
またフッ素樹脂としては、重合によって得られたフッ素樹脂をフッ素化剤によって末端基のフッ素化処理を行った末端基安定化処理フッ素樹脂、あるいは末端基安定化処理フッ素樹脂とともに末端基安定化処理をしていないフッ素樹脂の両者を配合することができる。
Examples of the fluororesin usable as the fluororesin composition of the present invention include tetrafluoroethylene-fluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and ethylene-tetrafluoroethylene copolymer. At least one of a polymer (ETFE), polychlorotrifluoroethylene (PCTFE), and ethylene-chlorotrifluoroethylene copolymer (ECTFE) can be selected. Among these, a tetrafluoroethylene-fluoroalkyl vinyl ether copolymer (PFA), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and an ethylene-tetrafluoroethylene copolymer (ETFE) can be exemplified.
In addition, as the fluororesin, the end group stabilization treatment fluororesin obtained by subjecting the fluororesin obtained by polymerization to the end group fluorination treatment with a fluorinating agent, or the end group stabilization treatment fluororesin, and the end group stabilization treatment Both fluororesins that are not used can be blended.
本発明のフッ素樹脂組成物は、フッ素樹脂とフッ化ビニリデン構造を有するエラストマーとを所定の割合で混合した後に、押出成形法、ロール成形法、射出成形法等の方法によって所望の形状に成形することができる。
以下に実施例、比較例を示し本発明を説明する。
The fluororesin composition of the present invention is molded into a desired shape by a method such as an extrusion molding method, a roll molding method or an injection molding method after mixing the fluororesin and an elastomer having a vinylidene fluoride structure at a predetermined ratio. be able to.
Hereinafter, the present invention will be described with reference to examples and comparative examples.
実施例１
フッ素樹脂：テトラフルオロエチレン−フルオロアルキルビニルエーテル共重合体（ＰＦＡ：三井デュポンフロロケミカル製ＰＦＡ４５１ＨＰ−Ｊ）１００質量部に対して、ダイニオンＴＨＶ２２０Ａ（住友スリーエム製）：−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＣＦ3））m−（ＣＦ2ＣＦ2）n −：ｌ／ｍ／ｎ＝４０／２０／４０（モル比）の配合量をそれぞれ、０．０５，０．１、０．５、１，２，４，８質量部に変更したフッ素樹脂組成物１−１〜１−７を調製し、ローラミキサ型混練装置（東洋精機製作所製 ラボプラストミルモデル３０Ｃ１５０）に投入し、ローラ回転数２０ｒｐｍ、３４０℃２０分間で混合した後、混練装置から取り出し、３４０℃の熱プレスで厚さ０．１ｍｍ、縦横各４０ｍｍの試料１−１から１−７を作製した。
Example 1
Fluororesin: Tetrafluoroethylene-fluoroalkyl vinyl ether copolymer (PFA: PFA451HP-J manufactured by Mitsui DuPont Fluorochemicals), 100 parts by weight of Dionion THV220A (manufactured by Sumitomo 3M):-(CH 2 CF 2 ) l- ( CF 2 CF (CF 3 )) m − (CF 2 CF 2 ) n −: 1 / m / n = 40/20/40 (molar ratio), respectively, in amounts of 0.05, 0.1, and. The fluororesin compositions 1-1 to 1-7, which were changed to 5, 1, 2, 4, and 8 parts by mass, were prepared and charged into a roller mixer type kneader (labor plast mill model 30C150, manufactured by Toyo Seiki Seisakusho Co., Ltd.). After mixing at several 20 rpm and 340 ° C. for 20 minutes, the sample is taken out from the kneading apparatus, and samples 1-1 to 1-7 having a thickness of 0.1 mm and length and width of 40 mm are prepared by a hot press at 340 ° C. Made.
帯電電圧の減衰の測定
作製した試料１−１から試料１−７を、半減期測定機（シシド静電気製 スタティックオネストメーター）を使用して、−１０ｋＶの電圧で帯電した後に、ＪＩＳ Ｌ１０９４に規定する方法によって飽和電圧と、帯電後の電圧の半減期を測定して、その結果を表１に示す。
Measurement of decay of charging voltage Samples 1-1 to 1-7 were charged with a voltage of −10 kV using a half-life measuring device (Static Honest Meter manufactured by SHICIDO static electricity) and then specified in JIS L1094. The saturation voltage and the half-life of the voltage after charging were measured by the method, and the results are shown in Table 1.
実施例２
フッ化ビニリデン構造を有するエラストマーとして、ダイニオンＴＨＶ２２０Ａ（住友スリーエム製）を、また、電解質として、トリフルオロメタンスルホン酸リチウム（ＣＦ3ＳＯ3Ｌｉ）、リチウムビス（トリフルオロメタンスルホニルイミド）（Ｌｉ（ＣＦ3ＳＯ2）2Ｎ）、１−ブチル−３−メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＢＭＩＴＦＳＩ）、１−ブチル−３−メチルイミダゾリウムトリフルオロメタンスルホネート（ＢＭＩＴＦＳ）を、それぞれ表１に記載の配合量で配合した点を除き実施例１と同様にして調製した組成物を用いて試料２−１から２−７を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 2
Dyneon THV220A (manufactured by Sumitomo 3M) is used as an elastomer having a vinylidene fluoride structure, and lithium trifluoromethanesulfonate (CF 3 SO 3 Li), lithium bis (trifluoromethanesulfonylimide) (Li (CF 3 SO) is used as an electrolyte. formulation according 2) 2 N), 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (BMITFSI), 1- butyl-3-methylimidazolium trifluoromethanesulfonate (BMITFS), in table 1, respectively Samples 2-1 to 2-7 were prepared using the composition prepared in the same manner as in Example 1 except that they were blended in amounts, and the saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例３
実施例２で使用した電解質の２種類ずつを表１に記載の配合量で配合した点を除き実施例２と同様にして調製した組成物を用いて、試料３−１から３−３を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 3
Samples 3-1 to 3-3 were prepared using a composition prepared in the same manner as in Example 2 except that each of the two electrolytes used in Example 2 was blended in the blending amounts shown in Table 1. Then, the saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1, and the results are shown in Table 1.
実施例４
実施例１のフッ化ビニリデン構造を有するエラストマーに代えて、ダイニオンＴＨＶ５００Ｇ（住友スリーエム製）−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＣＦ3））m−（ＣＦ2ＣＦ2）n −：ｌ／ｍ／ｎ＝２５／２０／５５（モル比）を４質量部配合した点を除き実施例１と同様にして調製した組成物を用いて試料４−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 4
Instead of the elastomer having the vinylidene fluoride structure of Example 1, DIONION THV500G (manufactured by Sumitomo 3M) — (CH 2 CF 2 ) 1 — (CF 2 CF (CF 3 )) m — (CF 2 CF 2 ) n — Sample 4-1 was prepared using the composition prepared in the same manner as in Example 1 except that 4 parts by mass of 1 / m / n = 25/20/55 (molar ratio) was blended. In the same manner as above, the saturation voltage and the half-life of the voltage were measured, and the results are shown in Table 1.
実施例５
実施例１で使用したフッ化ビニリデン構造を有するエラストマーに代えて、ダイエルＧ９０２（ダイキン工業）：−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＣＦ3））m−（ＣＦ2ＣＦ2）n −を４質量部配合した点を除き実施例１と同様にして調製した組成物を用いて試料５−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 5
In place of the elastomer having the vinylidene fluoride structure used in Example 1, Daiel G902 (Daikin Industries): — (CH 2 CF 2 ) 1 — (CF 2 CF (CF 3 )) m — (CF 2 CF 2 ) Sample 5-1 was prepared using the composition prepared in the same manner as in Example 1 except that 4 parts by mass of n − was blended, and the saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例６
実施例５で使用したフッ化ビニリデン構造を有するエラストマーに加えて、更に電解質として、トリフルオロメタンスルホン酸リチウムを配合した試料６−１と、リチウムビス（トリフルオロメタン）スルホニルイミド（Ｌｉ（ＣＦ3ＳＯ2）2Ｎ）を配合して調製した組成物を用いて試料６−２を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 6
In addition to the elastomer having the vinylidene fluoride structure used in Example 5, a sample 6-1 containing lithium trifluoromethanesulfonate as an electrolyte and lithium bis (trifluoromethane) sulfonylimide (Li (CF 3 SO 2) ) Sample 6-2 was prepared using the composition prepared by blending 2 N), and the saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1. The results are shown in Table 1. .
実施例７
実施例１のフッ化ビニリデン構造を有するエラストマーに代えて、バイトンＧＬＴ（デュポンエラストマー製）：−（ＣＨ2ＣＦ2）l−（ＣＦ2ＣＦ（ＯＣＦ3））m−（ＣＦ2ＣＦ2）n −を４質量部配合した点を除き実施例１と同様にして調製した組成物を用いて試料７−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 7
Instead of the elastomer having the vinylidene fluoride structure of Example 1, Viton GLT (made by DuPont elastomer): — (CH 2 CF 2 ) 1 — (CF 2 CF (OCF 3 )) m — (CF 2 CF 2 ) n Sample 7-1 was prepared using the composition prepared in the same manner as in Example 1 except that 4 parts by mass of-was blended, and the saturation voltage and the voltage half-life were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例８
実施例７で使用したフッ化ビニリデン構造を有するエラストマーに加えて、更に電解質として、トリフルオロメタンスルホン酸リチウムを配合して調製した組成物を用いて試料８−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 8
Sample 8-1 was prepared using the composition prepared by blending lithium trifluoromethanesulfonate as the electrolyte in addition to the elastomer having the vinylidene fluoride structure used in Example 7, and the same as in Example 1. The saturation voltage and the half-life of the voltage were measured, and the results are shown in Table 1.
実施例９
実施例１のフッ化ビニリデン構造を有するエラストマーに代えて、バイトンＡ−２００（デュポンエラストマー製）：−（ＣＨ2ＣＦ2）m−（ＣＦ2ＣＦ（ＣＦ3））n −を４質量部配合した点を除き実施例１と同様にして調製した組成物を用いて試料９−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 9
In place of the elastomer having the vinylidene fluoride structure of Example 1, 4 parts by mass of Viton A-200 (made of DuPont elastomer): — (CH 2 CF 2 ) m — (CF 2 CF (CF 3 )) n — A sample 9-1 was prepared using the composition prepared in the same manner as in Example 1 except for the points described above, and the saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1. It is shown in 1.
実施例１０
実施例９で使用したフッ化ビニリデン構造を有するエラストマーに加えて、更に電解質として、トリフルオロメタンスルホン酸リチウム（ＣＦ3ＳＯ3Ｌｉ）、１−ブチル−３−メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＢＭＩＴＦＳＩ）、１−ブチル−３−メチルイミダゾリウムトリフルオロメタンスルホネート（ＢＭＩＴＦＳ）を、それぞれ表１に記載の配合量で配合した点を除き実施例１と同様にして調製した組成物を用いて試料１０−１から１０−３を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 10
In addition to the elastomer having a vinylidene fluoride structure used in Example 9, as electrolyte, lithium trifluoromethanesulfonate (CF 3 SO 3 Li), 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (BMITFSI), 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMITFS), each sample using a composition prepared in the same manner as in Example 1 except that it was blended in the blending amounts shown in Table 1. 10-1 to 10-3 were prepared and the saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例１１
実施例６のフッ化ビニリデン構造を有するエラストマーであるバイトンＡ−２００に代えて、高粘度のバイトンＡ−７００（デュポンエラストマー製）を４質量部配合した点を除き実施例１と同様にして調製した組成物を用いて試料１１−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 11
Prepared in the same manner as in Example 1 except that 4 parts by mass of high-viscosity Viton A-700 (made of DuPont elastomer) was blended instead of Viton A-200, which is an elastomer having a vinylidene fluoride structure in Example 6. Sample 11-1 was prepared using the composition, and the saturation voltage and the voltage half-life were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例１２
実施例７で使用したフッ化ビニリデン構造を有するエラストマーに加えて、更に電解質として、トリフルオロメタンスルホン酸リチウムを配合した試料１２−１を調製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 12
In addition to the elastomer having the vinylidene fluoride structure used in Example 7, a sample 12-1 containing lithium trifluoromethanesulfonate as an electrolyte was prepared, and the saturation voltage and the voltage were adjusted in the same manner as in Example 1. The half-life was measured and the results are shown in Table 1.
実施例１３
実施例１のフッ化ビニリデン構造を有するエラストマーに代えて、セフラルソフトＧ１５０Ｆ２００（セントラル硝子製）を４質量部配合した点を除き実施例１と同様にして調製した組成物を用いて試料１３−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 13
Instead of the elastomer having the vinylidene fluoride structure of Example 1, Sample 13-1 was prepared using a composition prepared in the same manner as in Example 1 except that 4 parts by mass of Cephralsoft G150F200 (manufactured by Central Glass) was blended. The saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1 and the results are shown in Table 1.
実施例１４
実施例１のフッ素樹脂に代えて、フッ素樹脂をテトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（三井デュポンフロロケミカル製ＦＥＰ１００Ｊ）を用い、フッ化ビニリデン構造を有するエラストマーとして、ダイニオンＴＨＶ２２０Ａ（住友スリーエム製）を４質量部配合して調製した組成物を用いて試料１４−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 14
Instead of the fluororesin of Example 1, a tetrafluoroethylene-hexafluoropropylene copolymer (FEP100J manufactured by Mitsui Dupont Fluorochemical) was used as the fluororesin, and Dyneon THV220A (manufactured by Sumitomo 3M) was used as the elastomer having a vinylidene fluoride structure. Sample 14-1 was prepared using a composition prepared by blending 4 parts by mass of the sample, and the saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例１５
実施例１４で使用したフッ化ビニリデン構造を有するエラストマーに加えて、更に電解質として、トリフルオロメタンスルホン酸リチウム（ＣＦ3ＳＯ3Ｌｉ）を表１に記載の配合量で配合した点を除き実施例１４と同様にして調製した組成物を用いて試料１５−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 15
In addition to the elastomer having the vinylidene fluoride structure used in Example 14, lithium trifluoromethanesulfonate (CF 3 SO 3 Li) was further blended in the blending amount shown in Table 1 as an electrolyte. Sample 15-1 was prepared using the composition prepared in the same manner as in Example 1, and the saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例１６
実施例１のフッ素樹脂に代えて、フッ素樹脂をエチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ：旭硝子製Ｃ−８８ＡＸ）１００質量部を用い、フッ化ビニリデン構造を有するエラストマーとして、ダイニオンＴＨＶ２２０Ａ（住友スリーエム製）を４質量部配合して調製した組成物を用いて試料１６−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 16
Instead of the fluororesin of Example 1, 100 parts by mass of an ethylene-tetrafluoroethylene copolymer (ETFE: C-88AX manufactured by Asahi Glass) is used as the fluororesin, and Dyneon THV220A (Sumitomo 3M) is used as an elastomer having a vinylidene fluoride structure. Sample 16-1 was prepared using a composition prepared by blending 4 parts by mass of the product, and the saturation voltage and the half-life of the voltage were measured in the same manner as in Example 1. The results are shown in Table 1. Show.
実施例１７
実施例１６で使用したフッ化ビニリデン構造を有するエラストマーに加えて、更に電解質として、トリフルオロメタンスルホン酸リチウム（ＣＦ3ＳＯ3Ｌｉ）を表１に記載の配合量で配合した点を除き実施例１６と同様にして調製した組成物を用いて試料１７−１を作製して実施例１と同様にして飽和電圧と、電圧の半減期を測定して、その結果を表１に示す。
Example 17
In addition to the elastomer having a vinylidene fluoride structure used in Example 16, lithium trifluoromethanesulfonate (CF 3 SO 3 Li) was further blended in the blending amount shown in Table 1 as an electrolyte. Sample 17-1 was prepared using the composition prepared in the same manner as in Example 1, and the saturation voltage and the voltage half-life were measured in the same manner as in Example 1. The results are shown in Table 1.
比較例１
フッ化ビニリデン構造を有するエラストマーを配合しない点を除き、実施例１と同様にして作製した比較試料１を調製し、実施例１と同様にして帯電後の電圧の半減期を測定しようとしたが、半減期を測定することはできなかった。その結果を表１に示す。
Comparative Example 1
A comparative sample 1 prepared in the same manner as in Example 1 was prepared except that an elastomer having a vinylidene fluoride structure was not blended, and the half-life of the voltage after charging was measured in the same manner as in Example 1. The half-life could not be measured. The results are shown in Table 1.
比較例２
フッ化ビニリデン構造を有するエラストマーに代えて、フッ化ビニリデンのホモポリマーであるポリフッ化ビニリデン（アルケマ製ＫＹＮＡＲ７４０）４質量部を添加した点を除き実施例１と同様にして調製した組成物を用いて比較試料２を作製し、実施例１と同様にして帯電後の電圧の半減期を測定しようとしたが、半減期を測定することはできなかった。その結果を表１に示す。
Comparative Example 2
Instead of the elastomer having a vinylidene fluoride structure, a composition prepared in the same manner as in Example 1 except that 4 parts by mass of polyvinylidene fluoride (KYNAR740 manufactured by Arkema), which is a homopolymer of vinylidene fluoride, was added. Comparative sample 2 was prepared, and an attempt was made to measure the half-life of the voltage after charging in the same manner as in Example 1. However, the half-life could not be measured. The results are shown in Table 1.
本発明のフッ素樹脂組成物は、コロナ放電によって帯電させた場合に、帯電電圧の半減時間が短く、除電性が大きなフッ素樹脂が求められる様々な分野においての使用が期待できる。 When the fluororesin composition of the present invention is charged by corona discharge, it can be expected to be used in various fields in which a fluororesin having a short half-life of charging voltage and a large charge removal property is required.
Claims (5)
ッ素樹脂組成物。 Elastomers having a vinylidene fluoride structure are vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene terpolymer, vinylidene fluoride / perfluoromethyl vinyl ether / tetrafluoroethylene terpolymer, vinylidene fluoride / hexafluoropropylene 2. The fluororesin composition according to claim 1, which is a binary copolymer or a copolymer of vinylidene fluoride and chlorotrifluoroethylene.
A nitrogen resin composition.
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| WO2012141025A1 (en) * | 2011-04-15 | 2012-10-18 | ユニマテック株式会社 | Rubber/metal laminate |
| WO2013161708A1 (en) | 2012-04-25 | 2013-10-31 | 株式会社潤工社 | Fluororesin composition |
| US9440044B2 (en) | 2014-06-06 | 2016-09-13 | Zeus Industrial Products, Inc. | Peelable heat-shrink tubing |
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| WO2012141025A1 (en) * | 2011-04-15 | 2012-10-18 | ユニマテック株式会社 | Rubber/metal laminate |
| JP2012223888A (en) * | 2011-04-15 | 2012-11-15 | Unimatec Co Ltd | Rubber/metal laminate |
| US10213987B2 (en) | 2011-04-15 | 2019-02-26 | Unimatec Co., Ltd. | Rubber metal laminate |
| EP2842997A4 (en) * | 2012-04-25 | 2015-11-11 | Junkosha Inc | Fluororesin composition |
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| KR20140145169A (en) | 2012-04-25 | 2014-12-22 | 가부시키가이샤 쥰코샤 | Fluororesin composition |
| KR101615952B1 (en) | 2012-04-25 | 2016-04-27 | 가부시키가이샤 쥰코샤 | Fluororesin composition |
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| WO2013161708A1 (en) | 2012-04-25 | 2013-10-31 | 株式会社潤工社 | Fluororesin composition |
| US9440044B2 (en) | 2014-06-06 | 2016-09-13 | Zeus Industrial Products, Inc. | Peelable heat-shrink tubing |
| US9901661B2 (en) | 2014-06-06 | 2018-02-27 | Zeus Industrial Products, Inc. | Peelable heat-shrink tubing |
| US10434222B2 (en) | 2014-06-06 | 2019-10-08 | Zeus Industrial Products, Inc. | Peelable heat-shrink tubing |
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