JP2022505773A - フッ素系共重合体組成物 - Google Patents
フッ素系共重合体組成物 Download PDFInfo
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- JP2022505773A JP2022505773A JP2021522432A JP2021522432A JP2022505773A JP 2022505773 A JP2022505773 A JP 2022505773A JP 2021522432 A JP2021522432 A JP 2021522432A JP 2021522432 A JP2021522432 A JP 2021522432A JP 2022505773 A JP2022505773 A JP 2022505773A
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- thermoplastic resin
- fluorine
- fluoroelastomer
- copolymer composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 98
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- 239000011737 fluorine Substances 0.000 title claims abstract description 70
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 70
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 120
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- 239000000806 elastomer Substances 0.000 claims abstract description 37
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 85
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- 229920002313 fluoropolymer Polymers 0.000 claims description 33
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Abstract
Description
本出願は、2016年4月28日に出願された日本特許出願第2016-91886号及び72016年9月2日に出願された日本特許出願第2016-172023号に基づき、当該出願の優先権の利益を主張する2017年4月25日に出願されたPCT出願第PCT/JP2017/016436号の継続出願である2018年10月24日に出願された米国特許出願第16/169,247号の優先権を主張する。これらの各出願の内容は、その全体が参照により本明細書に組み込まれる。
以下の開示は、フッ素系共重合体組成物に関する。
本開示は、熱可塑性樹脂Aと、熱可塑性樹脂A内に分散されたフッ素系エラストマーBとを含むフッ素系共重合体組成物を提供する。熱可塑性樹脂Aは、ASTM D3835による、キャピラリーレオメーターを用いて、せん断速度243/秒、温度360℃で測定したときのせん断応力(τA)が0.11MPa以上である。熱可塑性樹脂A内に分散されたフッ素系エラストマーBは、平均分散粒径が50μm以下である。
CR1/2-B/CR1/2-A<0
を満たす。CR1/2-Bは、窒素雰囲気中、315℃の等温制御下でのフッ素系エラストマーBの結晶化に由来する発熱ピークの最大値に達するまでの時間(分)である。また、CR1/2-Aは、熱可塑性樹脂Aの結晶化に由来する発熱ピークが315℃の窒素雰囲気下で等温制御されて最大になるまでの時間(分)である。
熱可塑性樹脂Aは、ポリアリレート、ポリエーテルスルホン、ポリアリルスルホン、芳香族ポリアミド、芳香族ポリエーテルアミド、芳香族ポリエーテルイミド、ポリフェニレンスルファイド、ポリアリルエーテルケトン、ポリアミドイミド及び液晶ポリエステルからなる群から選択される少なくとも1の溶融成形可能な耐熱性熱可塑性樹脂である。
フッ素系エラストマーBは、テトラフルオロエチレン(TFE)、ヘキサフルオロプロピレン(HFP)、フッ化ビニリデン(VdF)及びクロロトリフルオロエチレン(CTFE)からなる群から選択される少なくとも1の単量体(以下、「単量体(MB1)」ともいう)に由来する単位を含むフッ素系弾性共重合体である。「単量体に由来する単位」とは、単量体の重合によって形成される単位を意味する。単量体由来の単位は、単量体の重合反応によって直接形成された単位であってよく、又はポリマーや単位の処理によって他の構造に変換された単位であってよい。
CF2=CF(ORF) (I)
(式中、RFは、C1~8の直鎖状又は分岐状のパーフルオロアルキル基である)
で表される化合物であり、具体的には、パーフルオロ(メチルビニルエーテル)(PMVE)、パーフルオロ(エチルビニルエーテル)(PEVE)、パーフルオロ(プロピルビニルエーテル)(PPVE)、又はパーフルオロ(ブチルビニルエーテル)(PBVE)を用いることができる。
フッ素系エラストマーBは、少なくとも1の単量体(MB1)と、場合によっては単量体(MB2)及び単量体(MB3)の片方又は両方とを共重合させることにより製造することができる。
(その他の成分)
フッ素系共重合体組成物は、熱可塑性樹脂A及びフッ素系エラストマーB及びいかなる他の成分を含んでよい。
本開示はまた、フッ素系共重合体組成物を製造する方法を提供する。
この方法としては、熱可塑性樹脂Aとフッ素系エラストマーBとを溶融混練する工程(以下、「溶融混練工程」という)があげられる。
あるいは、そのような他の成分を熱可塑性樹脂A及びフッ素系エラストマーBとは別に装置に供給してよい。さらに、上記のように、熱可塑性樹脂A及びフッ素系エラストマーBを溶融混練した後に、当該他の成分を添加してよい。
本開示の成形品は、フッ素系共重合体組成物を含む成形材料を成形して得られる成形品である。
チューブ、ホース、タンク、シールまたはワイヤとしては、特許文献1に記載のものを用いうる。さらに、チューブやホースは、石油、天然ガス、シェールオイル等のエネルギー資源を掘削するチューブであってよい。電線、ケーブル等の電線被覆材は、通常、ハイブリッド車(HEV)や電気自動車(EV)の駆動モータに用いられる電線やモータコイル用の平角銅線の絶縁被覆として用いられ、その場合、絶縁被覆は、通常、フィルムによってなされる。また、石油、天然ガス、シェールオイル等のエネルギー資源を掘削するダウンホールケーブルへの応用も考えられる。さらに、スピーカーの振動板、外傷や骨折用の板、モータの絶縁紙等の各種電気絶縁性粘着テープの絶縁紙、石油や天然ガスの配管に用いられるシールテープ等の用途がある。
本開示のプリプレグは、マトリクス樹脂及び補強用繊維を含む。特に、これは、補強用繊維に含浸されたマトリクス樹脂を備えるシート状材料であり、当該マトリクス樹脂(すなわち、フッ素系重合体組成物)に埋め込まれた補強用繊維を備えるシート状材料といってよい。
補強用繊維としては、当該繊維補強化成形品の機械的特性の観点から、長さが少なくとも10mmの連続長繊維が一般的に用いられる。補強用繊維シートの縦方向の全長にわたって、又は幅方向の全幅方向にわたって補強用繊維を連続させなくてよく、中央で分割してよい。
本開示の繊維補強化成形品は、本開示のプリプレグを用いる。
質量比、粘度比、せん断応力、平均分散粒子サイズ、及びせん断応力の比は、全て、上記で広範囲にわたり記載したように計算されることが理解されるべきである。Izod衝撃強度は、ASTM D 256-10試験方法Aにより、70°±5°F、50%±10% R.H.で、以下の条件:A40+時間、70°±5°f、50%±10% R.H.、端半径が0.010”の45°の角度であるノッチを用いて測定された。テストバーの成形方法は、射出成形温度プロファイル(F)、NOZ=707-734、バレル680-716、及びツール390を用いた。蒸気浸漬は、蒸気を用いて260℃で21日間行った。ディーゼル燃料の浸漬は、CAS No.68476-34-6に規定される質量比100%のディーゼル燃料No.2を用いて、150℃で21日間行った。
Claims (19)
- 以下の:
ASTM D3835により、キャピラリーレオメーターを用いて、せん断速度243/秒、温度360℃で測定した場合のせん断応力(τA)が、0.11MPaより大きい熱可塑性樹脂A;及び
熱可塑性樹脂A内に分散された、平均分散粒径が50μm未満であるフッ素系エラストマーB;
を含む、フッ素系共重合体組成物。 - 前記熱可塑性樹脂Aは、ポリアリレート、ポリエーテルスルホン、ポリアリルスルホン、芳香族ポリアミド、芳香族ポリエーテルアミド、芳香族ポリエーテルイミド、ポリフェニレンスルファイド、ポリアリルエーテルケトン、ポリアミドイミド及び液晶ポリエステルからなる群から選択される少なくとも1の溶融成形可能な耐熱性熱可塑性樹脂である、請求項1に記載のフッ素系共重合体組成物。
- 前記フッ素系エラストマーBは、テトラフルオロエチレン、ヘキサフルオロプロピレン、フッ化ビニリデン及びクロロトリフルオロエチレンからなる群から選択される少なくとも1の単量体に由来する単位を含む、請求項1又は2に記載のフッ素系共重合体組成物。
- 曲げ弾性率が1,000~3,700MPaである、請求項1~3のいずれか一項に記載のフッ素系共重合体組成物。
- ASTM D3835により、せん断速度12.1/秒、360℃の条件でキャピラリーレオメーターを用いて粘度を測定する場合の熱可塑性樹脂Aとフッ素系エラストマーBの粘度の比が、0.35より大きい、請求項1~4のいずれか1項に記載のフッ素系共重合体組成物。
- ASTM D3835により、せん断速度12.1/秒、360℃のキャピラリーレオメーターで測定した場合のフッ素系エラストマーBの粘度は、2,000Pa・s以上である、請求項1~5のいずれか一項に記載のフッ素系共重合体組成物。
- 前記フッ素系エラストマーBは、テトラフルオロエチレンとプロピレンから誘導される単位を有する共重合体、ヘキサフルオロプロピレンとフッ化ビニリデンから誘導される単位を有する共重合体、及びテトラフルオロエチレンとパーフルオロ(アルキルビニルエーテル)から誘導される単位を有する共重合体からなる群から選択され、前記パーフルオロ(アルキルビニルエーテル)は、下記式(I):
CF2=CF(ORF) (I)
(式中、RFは、C1~8の直鎖状又は分岐状のパーフルオロアルキル基である)
で表される、請求項1~6のいずれか一項に記載のフッ素系共重合体組成物。 - 前記フッ素系エラストマーBは、テトラフルオロエチレンとプロピレンに由来する単位を有する共重合体である、請求項1~7のいずれか一項に記載のフッ素系共重合体組成物。
- 前記熱可塑性樹脂Aは、ポリアリルエーテルケトン、ポリエーテルスルホン、ポリエーテルエーテルケトン、芳香族ポリエーテルアミド及びポリアリルスルホンからなる群から選択される、請求項1~8のいずれか一項に記載のフッ素系共重合体組成物。
- 前記熱可塑性樹脂Aは、ポリアリルエーテルケトン又はポリエーテルエーテルケトンである、請求項1~9のいずれか一項に記載のフッ素系共重合体組成物。
- 前記熱可塑性樹脂Aの質量%とフッ素系エラストマーBの質量%との比は、99/1~55/45である、請求項1~10のいずれか一項に記載のフッ素系共重合体組成物。
- ASTM D638-14により200℃で測定した場合に引張伸びが120%以上である、請求項1~11のいずれか一項に記載のフッ素系共重合体組成物。
- 前記熱可塑性樹脂Aのせん断応力(τA)が、0.2MPaより高く、ASTM D3835によるせん断速度12.1/秒、360℃でキャピラリーレオメーターを用いて粘度を測定した場合の、熱可塑性樹脂Aとフッ素系エラストマーBの粘度の比は、1.1以上1.3未満である、請求項1~12のいずれか一項に記載のフッ素系共重合体組成物。
- 前記熱可塑性樹脂A内に分散されたフッ素系エラストマーBの平均分散粒径は、15μm未満である、請求項1~13のいずれか一項に記載のフッ素系共重合体組成物。
- 前記熱可塑性樹脂Aは、ポリアリルエーテルケトン、ポリエーテルエーテルケトン又はそれらの組み合わせであり、前記フッ素系エラストマーBは、テトラフルオロエチレン及びプロピレンから誘導される単位を有する共重合体である、請求項14に記載のフッ素系共重合体組成物。
- 請求項1~15のいずれか一項に記載のフッ素系共重合体組成物を含む成形材料を射出成形して得られる成形品。
- 請求項1~15のいずれか一項に記載のフッ素系共重合体組成物を押出成形して得られる押出成形品。
- 以下の:
(i)熱可塑性樹脂Aに(ii)フッ素系エラストマーBを溶融混練して、フッ素系エラストマーBが熱可塑性樹脂A内に50μm以下の平均分散粒径で分散するように、フッ素系共重合体組成物を形成する工程;
を含むフッ素系共重合体組成物を形成する方法であって、ここで、
ASTM D3835により、キャピラリーレオメーターを用いてせん断速度243/秒、温度360℃で測定した場合の前記熱可塑性樹脂Aのせん断応力(τA)は0.11MPaより大きい、
方法。 - ASTM D3835によりせん断速度12.1/秒、360℃のキャピラリーレオメーターで測定した場合の前記熱可塑性樹脂Aの粘度と前記フッ素系エラストマーBの粘度の比は、0.35より大きい、請求項18に記載の方法。
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