JP4834966B2 - Tetrafluoroethylene copolymer - Google Patents
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Description
本発明は、テトラフルオロエチレン共重合体に関する。 The present invention relates to a tetrafluoroethylene copolymer.
テトラフルオロエチレン／ペルフルオロ（プロピルビニルエーテル）共重合体（以下、ＰＦＡという。）は、耐薬品性、耐熱性、表面非粘着性に優れ、化学産業、半導体産業、ＯＡ機器産業等のさまざまな分野で使用されている。 Tetrafluoroethylene / perfluoro (propyl vinyl ether) copolymer (hereinafter referred to as PFA) is excellent in chemical resistance, heat resistance, and surface non-adhesiveness, and is used in various fields such as the chemical industry, semiconductor industry, and OA equipment industry. in use.
ＰＦＡは、耐薬品性に優れる特徴を活かして、半導体産業分野において、シリコンウェハー用薬液及び洗浄薬液に接する容器、チューブ、継ぎ手等の成形品として用いられる。しかし、従来のＰＦＡは、薬液やガスのバリア性が低いため、薬液等がＰＦＡに浸透して外部に染み出し、周辺機器を腐食させる等の影響があり、薬液やガスのバリア性の向上が要望される。 PFA is used as a molded product for containers, tubes, joints, etc. in contact with a chemical solution for silicon wafers and a cleaning chemical solution in the field of semiconductor industry, taking advantage of its excellent chemical resistance. However, since conventional PFA has low barrier properties against chemicals and gases, chemicals and the like penetrate into the PFA and seep outside, corrode peripheral equipment, and improve the barrier properties of chemicals and gases. Requested.
これまで、ＰＦＡの薬液やガスのバリア性を向上させるために、種々の検討が実施されてきた。例えば、以下の方法が知れれている。ＰＦＡに特定のポリテトラフルオロエチレン（ＰＴＦＥ）を添加する方法（特許文献１を参照。）。ペルフルオロ（アルキルビニルエーテル）として、長鎖と短鎖の２種類のペルフルオロアルキル基を有数するペルフルオロ（アルキルビニルエーテル）を混合して、テトラフルオロエチレン（以下、ＴＦＥいう。）と共重合する方法（特許文献２を参照。）。ＴＦＥ／ペルフルオロ（エチルビニルエーテル）とＰＦＡとを溶融混合する方法（特許文献３を参照。）。 So far, various studies have been carried out in order to improve the barrier properties of PFA chemicals and gases. For example, the following method is known. A method of adding specific polytetrafluoroethylene (PTFE) to PFA (see Patent Document 1). As perfluoro (alkyl vinyl ether), a method of mixing perfluoro (alkyl vinyl ether) having two kinds of long-chain and short-chain perfluoroalkyl groups and copolymerizing with tetrafluoroethylene (hereinafter referred to as TFE) (Patent Document) 2). A method of melt-mixing TFE / perfluoro (ethyl vinyl ether) and PFA (see Patent Document 3).
本発明は、薬液やガスのバリア性に優れるＴＦＥ共重合体の提供を目的とする。 An object of this invention is to provide the TFE copolymer excellent in the barrier property of a chemical | medical solution or gas.
本発明は、ＴＦＥに基づく繰り返し単位（ａ）と、ペルフルオロ（シクロヘキシルメチルビニルエーテル）、ペルフルオロ（シクロヘキシルエチルビニルエーテル）、およびペルフルオロ（シクロヘキシルプロピルビニルエーテル）からなる群から選ばれるフルオロモノマーに基づく繰り返し単位（ｂ）とを含有し、（ａ）／（ｂ）＝９０／１０〜９９．８／０．２（モル比）であり、３８０℃における容量流速が０．１〜１０００ｍｍ３／秒であることを特徴とするＴＦＥ共重合体を提供する。 The present invention relates to a repeating unit (a) based on TFE and a repeating unit (b) based on a fluoromonomer selected from the group consisting of perfluoro (cyclohexyl methyl vinyl ether), perfluoro (cyclohexyl ethyl vinyl ether), and perfluoro (cyclohexylpropyl vinyl ether ). containing the door, a (a) / (b) = 90 / 10~99.8 / 0.2 ( molar ratio), characterized in that volume flow rate at 380 ° C. is 0.1~1000mm 3 / sec A TFE copolymer is provided.
本発明のＴＦＥ共重合体は、薬液やガスのバリア性に優れる。また、高い融点、高い降伏強度を示し、耐熱性、機械的特性に優れる。 The TFE copolymer of the present invention is excellent in chemical and gas barrier properties. In addition, it has a high melting point and high yield strength, and is excellent in heat resistance and mechanical properties.
本発明のＴＦＥ共重合体は、ＴＦＥに基づく繰り返し単位（ａ）と、ペルフルオロ（シクロヘキシルメチルビニルエーテル）、ペルフルオロ（シクロヘキシルエチルビニルエーテル）、およびペルフルオロ（シクロヘキシルプロピルビニルエーテル）からなる群から選ばれるフルオロモノマーに基づく繰り返し単位（ｂ）とを含有し、（ａ）／（ｂ）＝９０／１０〜９９．８／０．２（モル比）である。好ましくは（ａ）／（ｂ）＝９３／７〜９９．５／０．５（モル比）であり、より好ましくは９５／５〜９９／１（モル比）である。（ｂ）の含有量が少なすぎるとＴＦＥ共重合体は耐屈曲疲労性が低く、多すぎると融点や弾性率が低い。（ａ）／（ｂ）がこの範囲にあると、ＴＦＥ共重合体は、薬液やガスのバリア性に優れ、また、融点及び弾性率が高く、耐屈曲疲労性に優れる。 The TFE copolymer of the present invention is based on a TFE-based repeating unit (a) and a fluoromonomer selected from the group consisting of perfluoro (cyclohexyl methyl vinyl ether), perfluoro (cyclohexyl ethyl vinyl ether), and perfluoro (cyclohexylpropyl vinyl ether). The repeating unit (b) is contained, and (a) / (b) = 90/10 to 99.8 / 0.2 (molar ratio). Preferably (a) / (b) = 93/7 to 99.5 / 0.5 (molar ratio), more preferably 95/5 to 99/1 (molar ratio). When the content of (b) is too small, the TFE copolymer has low bending fatigue resistance, and when too large, the melting point and elastic modulus are low. When (a) / (b) is within this range, the TFE copolymer is excellent in chemical and gas barrier properties, has a high melting point and elastic modulus, and is excellent in bending fatigue resistance.
本発明のＴＦＥ共重合体としては、（ａ）及び（ｂ）からなるＴＦＥ共重合体が好ましい。また、本発明のＴＦＥ共重合体は、（ａ）及び（ｂ）に加えて、その他のモノマーに基づく繰り返し単位（ｃ）を含有することも好ましい。その他のモノマーは特に限定されないが、具体例としては、ペルフルオロ（プロピルビニルエーテル）（以下、ＰＰＶＥという。）等のペルフルオロシクロヘキシル基又はシクロヘキサン骨格を含まないペルフルオロ（アルキルビニルエーテル）、エチレン等の炭化水素系オレフィン、フッ化ビニル、フッ化ビニリデン、ＣＨ２＝ＣＸ（ＣＦ２）ｎＹ（ここで、Ｘ及びＹは、それぞれ独立に水素又はフッ素原子、ｎは２〜８の整数である。）等の不飽和基に水素原子を有するフルオロオレフィン、ヘキサフルオロプロピレン（以下、ＨＦＰという。）等の不飽和基に水素原子を有しないフルオロオレフィン（ただし、ＴＦＥを除く。）等が挙げられる。その他のモノマーとしては、ＰＰＶＥ及びＨＦＰが好ましい。 As a TFE copolymer of this invention, the TFE copolymer which consists of (a) and (b) is preferable. Moreover, it is preferable that the TFE copolymer of this invention contains the repeating unit (c) based on another monomer in addition to (a) and (b). Other monomers are not particularly limited, but specific examples include perfluorocyclohexyl groups such as perfluoro (propyl vinyl ether) (hereinafter referred to as PPVE) or perfluoro (alkyl vinyl ethers) not containing a cyclohexane skeleton, and hydrocarbon olefins such as ethylene. , Vinyl fluoride, vinylidene fluoride, CH 2 ═CX (CF 2 ) n Y (where X and Y are each independently hydrogen or a fluorine atom, and n is an integer of 2 to 8). Examples include fluoroolefins having a hydrogen atom in a saturated group, fluoroolefins having no hydrogen atom in an unsaturated group such as hexafluoropropylene (hereinafter referred to as HFP) (excluding TFE), and the like. As other monomers, PPVE and HFP are preferable.
その他のモノマーに基づく繰り返し単位を含有すると、ＴＦＥ共重合体は、耐熱性、耐薬品性に優れる。その他のモノマーに基づく繰り返し単位（ｃ）を含有する場合には、その含有量は、（ｃ）／（（ａ）＋（ｂ）＋（ｃ））＝０．１／１００〜１０／１００（モル比）が好ましく、０．２／１００〜８／１００（モル比）がより好ましい。 When a repeating unit based on another monomer is contained, the TFE copolymer is excellent in heat resistance and chemical resistance. When the repeating unit (c) based on another monomer is contained, the content is (c) / ((a) + (b) + (c)) = 0.1 / 100 to 10/100 ( Molar ratio) is preferable, and 0.2 / 100 to 8/100 (molar ratio) is more preferable.
本発明のＴＦＥ共重合体の３８０℃における容量流速は０．１〜１０００ｍｍ３／秒である。容量流速は、ＴＦＥ共重合体の溶融流動性を表す指標であり、分子量の目安となる。容量流速が大きいと分子量が低く、小さいと分子量が高いことを示す。容量流速が小さすぎると溶融流動性が不充分で、成形品の表面が均一でなく、平滑でない。容量流速が大きすぎるとＴＦＥ共重合体の耐屈曲疲労性が低下する。３８０℃における容量流速がこの範囲にあると溶融成形性に優れる。好ましくは１０〜５００ｍｍ３／秒、より好ましくは２０〜２００ｍｍ３／秒である。 The capacity flow rate at 380 ° C. of the TFE copolymer of the present invention is 0.1 to 1000 mm 3 / sec. The volume flow rate is an index representing the melt fluidity of the TFE copolymer and is a measure of the molecular weight. A large volumetric flow rate indicates a low molecular weight and a small volume flow rate indicates a high molecular weight. If the volume flow rate is too small, the melt fluidity is insufficient, and the surface of the molded product is not uniform and smooth. When the capacity flow rate is too large, the bending fatigue resistance of the TFE copolymer is lowered. When the capacity flow rate at 380 ° C. is in this range, the melt moldability is excellent. Preferably it is 10-500 mm < 3 > / sec, More preferably, it is 20-200 mm < 3 > / sec.
本発明のＴＦＥ共重合体のガスのバリア性は、ＡＳＴＭ Ｄ１４３４−７５（Ｍ法）に準じて、厚さ１００μｍの試料を用いて測定される酸素透過係数が、４．５×１０−１３（ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１）以下が好ましく、４．０×１０−１３ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１）以下がより好ましい。また、窒素透過係数は、１．５×１０−１３（ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１）以下が好ましく、１．３×１０−１３（ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１）以下がより好ましい。酸素及び窒素透過係数が小さいと、ガスや薬液のバリア性に優れる傾向にある。 The gas barrier property of the TFE copolymer of the present invention is such that the oxygen permeability coefficient measured using a sample having a thickness of 100 μm is 4.5 × 10 −13 (according to ASTM D1434-75 (M method)). cm 3 (STP) · cm · cm −2 · s −1 · Pa −1 ) or less is preferable, and 4.0 × 10 −13 cm 3 (STP) · cm · cm −2 · s −1 · Pa −1 The following is more preferable. Further, the nitrogen permeability coefficient is preferably 1.5 × 10 −13 (cm 3 (STP) · cm · cm −2 · s −1 · Pa −1 ) or less, and preferably 1.3 × 10 −13 (cm 3 ( STP) · cm · cm −2 · s −1 · Pa −1 ) or less is more preferable. When the oxygen and nitrogen permeability coefficients are small, the barrier properties of gas and chemical solution tend to be excellent.
本発明のＴＦＥ共重合体の融点は、２００〜３２０℃が好ましく、２５０〜３１０℃がより好ましい。この範囲にあると耐熱性が高く、溶融成形性に優れる。 200-320 degreeC is preferable and, as for melting | fusing point of the TFE copolymer of this invention, 250-310 degreeC is more preferable. Within this range, the heat resistance is high and the melt moldability is excellent.
本発明のＴＦＥ共重合体は、ＡＳＴＭ Ｄ２１７６に準じて測定されるＭＩＴ折り曲げ寿命が、１０万回以上が好ましく、１５万回以上がより好ましく、２５万回以上が最も好ましい。ＭＩＴ折り曲げ寿命が多いほど耐屈曲疲労性に優れることを示し、この範囲にあると耐屈曲疲労性に著しく優れる。 In the TFE copolymer of the present invention, the MIT bending life measured according to ASTM D2176 is preferably 100,000 times or more, more preferably 150,000 times or more, and most preferably 250,000 times or more. The longer the MIT bending life, the better the bending fatigue resistance.
本発明のＴＦＥ共重合体の製造方法は特に制限はなく、ラジカル重合開始剤を用いる重合方法が用いられる。重合方法としては、塊状重合、フッ化炭化水素、塩化炭化水素、フッ化塩化炭化水素、アルコール、炭化水素等の有機溶媒を使用する溶液重合、水性媒体及び必要に応じて適当な有機溶剤を使用する懸濁重合、水性媒体及び乳化剤を使用する乳化重合が挙げられ、特に溶液重合が好ましい。 The method for producing the TFE copolymer of the present invention is not particularly limited, and a polymerization method using a radical polymerization initiator is used. Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons, aqueous media, and appropriate organic solvents as required. Suspension polymerization, emulsion polymerization using an aqueous medium and an emulsifier, and solution polymerization is particularly preferable.
ラジカル重合開始剤としては、半減期１０時間である温度が０℃〜１００℃であることが好ましく、２０〜９０℃であることがより好ましい。具体例としては、アゾビスイソブチロニトリル等のアゾ化合物、イソブチリルペルオキシド、オクタノイルペルオキシド、ベンゾイルペルオキシド、ラウロイルペルオキシド等のジアシルペルオキシド、ジイソプロピルペルオキシジカ−ボネート等のペルオキシジカーボネート、ｔｅｒｔ−ブチルペルオキシピバレート、ｔｅｒｔ−ブチルペルオキシイソブチレート、ｔｅｒｔ−ブチルペルオキシアセテート等のペルオキシエステル、（Ｚ（ＣＦ２）ｐＣＯＯ）２（ここで、Ｚは水素原子、フッ素原子又は塩素原子であり、ｐは１〜１０の整数である。）で表される化合物等の含フッ素ジアシルペルオキシド、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の無機過酸化物等が挙げられる。特に、ＴＦＥ共重合体が耐熱性及び耐薬品性に優れることから、含フッ素ジアシルペルオキシドが好ましい。 As a radical polymerization initiator, the temperature which has a half-life of 10 hours is preferably 0 ° C to 100 ° C, more preferably 20 to 90 ° C. Specific examples include azo compounds such as azobisisobutyronitrile, diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide and lauroyl peroxide, peroxydicarbonates such as diisopropylperoxydicarbonate, and tert-butylperoxy. Peroxyesters such as pivalate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate, (Z (CF 2 ) p COO) 2 (where Z is a hydrogen atom, a fluorine atom or a chlorine atom, p is Inorganic peroxides such as fluorine-containing diacyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, and the like. In particular, the fluorine-containing diacyl peroxide is preferable because the TFE copolymer is excellent in heat resistance and chemical resistance.
本発明において、ＴＦＥ共重合体の容量流速を制御するために、連鎖移動剤を使用することも好ましい。連鎖移動剤としては、メタノール、エタノール等のアルコール、１，３−ジクロロ−１，１，２，２，３−ペンタフルオロプロパン、１，１−ジクロロ−１−フルオロエタン等のクロロフルオロハイドロカーボン、ペンタン、ヘキサン、シクロヘキサン等のハイドロカーボン等が挙げられる。 In the present invention, it is also preferable to use a chain transfer agent in order to control the volume flow rate of the TFE copolymer. Chain transfer agents include alcohols such as methanol and ethanol, chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, Examples thereof include hydrocarbons such as pentane, hexane, and cyclohexane.
本発明において重合条件は特に限定されず、重合温度は０〜１００℃が好ましく、２０〜９０℃がより好ましい。重合圧力は０．１〜１０ＭＰａが好ましく、０．５〜３ＭＰａがより好ましい。重合時間は１〜３０時間が好ましい。 In the present invention, the polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.
本発明のＴＦＥ共重合体は、−ＣＯＯＨ、−ＣＯＦ、−ＣＨ２ＯＨ等の不安定末端基の含有量が炭素原子数百万個当り１０個以下であることが好ましい。不安定末端基量がこの範囲にあるとＴＦＥ共重合体は耐薬品性及び耐久性に特に優れる。不安定末端基含有量の低減方法としては、ＴＦＥ共重合体を、粉末、粒、ペレット等の形状で、フッ素ガスによりフッ素化処理することが好ましい。該フッ素化処理により、不安定末端基は−ＣＦ３基等の安定末端基に変換されると考えられる。 In the TFE copolymer of the present invention, the content of unstable terminal groups such as —COOH, —COF, and —CH 2 OH is preferably 10 or less per several million carbon atoms. When the amount of unstable terminal groups is within this range, the TFE copolymer is particularly excellent in chemical resistance and durability. As a method for reducing the content of unstable terminal groups, it is preferable that the TFE copolymer is fluorinated with fluorine gas in the form of powder, granules, pellets or the like. It is considered that the unstable terminal group is converted into a stable terminal group such as —CF 3 group by the fluorination treatment.
以下の実施例及び比較例により本発明を具体的に説明するが、本発明はこれらに限定されない。ＴＦＥ共重合体の特性は以下の方法を用いて側定した。
［ＴＦＥ共重合の共重合組成］旭硝子研究報告１９９０、４０（１）、７５の記載に準じて、ＴＦＥ共重合体を熱溶融状態で１９Ｆ−ＮＭＲ測定する方法によって求めた。
［容量流速（ｍｍ３／秒）］ＴＦＥ共重合体の容量流速は、島津製作所製フローテスタを用いて、温度３８０℃において、荷重７ｋｇ下に直径２．１ｍｍ、長さ８ｍｍのオリフィス中にＴＦＥ共重合体を押出すときの押出し速度である。
The present invention will be specifically described by the following examples and comparative examples, but the present invention is not limited thereto. The properties of the TFE copolymer were determined using the following method.
[Copolymerization composition of TFE copolymer] According to the description of Asahi Glass Research Report 1990, 40 (1), 75, the TFE copolymer was determined by 19 F-NMR measurement in a hot melt state.
[Capacity flow rate (mm 3 / sec)] The volume flow rate of the TFE copolymer was measured using a flow tester manufactured by Shimadzu Corporation at a temperature of 380 ° C. in an orifice having a diameter of 2.1 mm and a length of 8 mm under a load of 7 kg. It is the extrusion speed when extruding the copolymer.
［ガス透過係数（ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１）］ＴＦＥ共重合体を３４０℃で圧縮成形して得た、厚さ１００μｍの試料を用いた。ＡＳＴＭ Ｄ１４３４−７５（Ｍ法）に準じて、酸素透過係数及び窒素透過係数を測定した。酸素及び窒素透過係数が小さいほど、ガスバリア性及び薬液バリア性に優れることを示す。
［融点（℃）］セイコー電子社製ＴＧ−ＤＴＡを用いて、試料１０ｍｇを窒素雰囲気下に１０℃／分の速度で昇温し、溶融ピークの温度を融点とした。
[Gas Permeability Coefficient (cm 3 (STP) · cm · cm −2 · s −1 · Pa −1 )] A sample having a thickness of 100 μm obtained by compression molding a TFE copolymer at 340 ° C. was used. The oxygen permeability coefficient and the nitrogen permeability coefficient were measured according to ASTM D1434-75 (M method). It shows that it is excellent in gas barrier property and chemical | medical solution barrier property, so that oxygen and nitrogen permeability coefficient are small.
[Melting Point (° C.)] Using TG-DTA manufactured by Seiko Electronics Co., Ltd., 10 mg of the sample was heated at a rate of 10 ° C./min in a nitrogen atmosphere, and the temperature of the melting peak was taken as the melting point.
［ＭＩＴ折り曲げ寿命］３４０℃でＴＦＥ共重合体を圧縮成形して得た、厚さ０．２２０〜０．２３６のフィルムを、幅１２．５ｍｍの短冊状に打ち抜いて試料とした。ＡＳＴＭ Ｄ２１７６に準じて、荷重１．２５ｋｇ、折り曲げ角度±１３５度、室温で東洋精機製作所製折り曲げ試験機ＭＩＴ−Ｄを用いて試料の折り曲げ試験を行った。破断するまでの折り曲げ回数がＭＩＴ折り曲げ寿命である。この値が高いほど耐屈曲疲労性に優れる。 [MIT Bending Life] A film having a thickness of 0.220 to 0.236 obtained by compression-molding a TFE copolymer at 340 ° C. was punched into a strip having a width of 12.5 mm to prepare a sample. In accordance with ASTM D2176, the sample was subjected to a bending test using a bending tester MIT-D manufactured by Toyo Seiki Seisakusho at a load of 1.25 kg, a bending angle of ± 135 degrees, and room temperature. The number of folds until rupture is the MIT fold life. The higher this value, the better the bending fatigue resistance.
［機械特性］ＴＦＥ共重合を、３４０℃で圧縮成形して得た、厚さ１．５ｍｍのシートを用いて、ＪＩＳ Ｄ３３０７に準じて、室温で、引張強度（ＭＰａ）、伸度（％）、降伏強度（ＭＰａ）を測定した。 [Mechanical Properties] Tensile strength (MPa) and elongation (%) at room temperature according to JIS D3307 using a 1.5 mm thick sheet obtained by compression molding TFE copolymerization at 340 ° C. The yield strength (MPa) was measured.
［実施例１］
１．３Ｌの撹拌機付き重合槽を脱気し、ペルフルオロ（シクロヘキシルメチルビニルエーテル）（以下、ＰＣＨＭＶＥという。）の６８．１ｇ、１，３−ジクロロ−１，１，２，２，３−ペンタフルオロプロパン（以下、ＨＣＦＣ２２５ｃｂという。）の３５３ｇ、イオン交換水５９０ｇ、メタノールの１８．９ｇ、ＴＦＥの９７ｇを仕込んだ。重合槽内を５０℃に保って、（ＣＦ3ＣＦ3ＣＦ２ＣＯＯ）２の０．０２５％ＨＣＦＣ２２５ｃｂ溶液の８ｃｍ３を仕込んで重合を開始させた。重合が進行するにしたがい圧力が低下するので、圧力が一定になるようにＴＦＥを追加仕込みした。重合を継続させるために（ＣＦ3ＣＦ3ＣＦ２ＣＯＯ）２の０．０２５％ＨＣＦＣ２２５ｃｂ溶液を断続的に追加仕込みし、合計２９ｃｍ３仕込んだ。ＴＦＥの追加仕込み量が１４５ｇとなった時点で重合槽を室温まで冷却し、未反応ＴＦＥをパージした。得られたＴＦＥ共重合体１のスラリーを乾燥し、白色のＴＦＥ共重合体１の１５５ｇが得られた。ＴＦＥ共重合体１の共重合組成は、ＴＦＥに基づく繰り返し単位／ＰＣＨＭＶＥに基づく繰り返し単位＝９８．０／２．０（モル比）であった。ＴＦＥ共重合体１の容量流速は２．４ｍｍ３／秒、融点は３１１℃、ＭＩＴ折り曲げ寿命は６９００００回であった。酸素透過係数は３．５８×１０−１３ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１、窒素透過係数は１．１８×１０−１３ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１であった。引張強度は２３．５ＭＰａ、伸度は２２４％、降伏強度は１４．６ＭＰａであった。
[Example 1]
A 1.3 L polymerization tank equipped with a stirrer was degassed, and 68.1 g of 1,3-dichloro-1,1,2,2,3-pentafluoro perfluoro (cyclohexylmethyl vinyl ether) (hereinafter referred to as PCHMVE) was obtained. 353 g of propane (hereinafter referred to as HCFC225cb), 590 g of ion-exchanged water, 18.9 g of methanol, and 97 g of TFE were charged. While maintaining the inside of the polymerization tank at 50 ° C., 8 cm 3 of a 0.025% HCFC225cb solution of (CF 3 CF 3 CF 2 COO) 2 was charged to initiate polymerization. As the polymerization progressed, the pressure decreased, so TFE was additionally charged so that the pressure became constant. In order to continue the polymerization, a 0.025% HCFC225cb solution of (CF 3 CF 3 CF 2 COO) 2 was intermittently added in a total of 29 cm 3 . When the added amount of TFE reached 145 g, the polymerization tank was cooled to room temperature, and unreacted TFE was purged. The obtained slurry of TFE copolymer 1 was dried, and 155 g of white TFE copolymer 1 was obtained. The copolymer composition of TFE copolymer 1 was a repeating unit based on TFE / a repeating unit based on PCHMVE = 98.0 / 2.0 (molar ratio). The capacity flow rate of TFE copolymer 1 was 2.4 mm 3 / sec, the melting point was 311 ° C., and the MIT bending life was 690000 times. The oxygen permeability coefficient is 3.58 × 10 −13 cm 3 (STP) · cm · cm −2 · s −1 · Pa −1 , and the nitrogen permeability coefficient is 1.18 × 10 −13 cm 3 (STP) · cm · It was cm −2 · s −1 · Pa −1 . The tensile strength was 23.5 MPa, the elongation was 224%, and the yield strength was 14.6 MPa.
［実施例２］
メタノールの３２ｇを仕込んだ以外は実施例１と同様にして、ＴＦＥ共重合体２の１５９ｇを得た。ＴＦＥ共重合体２の共重合組成は、ＴＦＥに基づく繰り返し単位／ＰＣＨＭＶＥに基づく繰り返し単位＝９８．０／２．０（モル比）であった。ＴＦＥ共重合体２の容量流速は４．６ｍｍ３／秒、融点は３１０℃、ＭＩＴ折り曲げ寿命は２１００００回であった。酸素透過係数は３．７７×１０−１３ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１、窒素透過係数は１．２７×１０−１３ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１であった。引張強度は３２．６ＭＰａ、伸度は３３３％、降伏強度１５．０ＭＰａであった。
[Example 2]
159 g of TFE copolymer 2 was obtained in the same manner as in Example 1 except that 32 g of methanol was charged. The copolymer composition of TFE copolymer 2 was a repeating unit based on TFE / a repeating unit based on PCHMVE = 98.0 / 2.0 (molar ratio). The capacity flow rate of TFE copolymer 2 was 4.6 mm 3 / sec, the melting point was 310 ° C., and the MIT bending life was 210,000 times. The oxygen permeability coefficient is 3.77 × 10 −13 cm 3 (STP) · cm · cm −2 · s −1 · Pa −1 , and the nitrogen permeability coefficient is 1.27 × 10 −13 cm 3 (STP) · cm · It was cm −2 · s −1 · Pa −1 . The tensile strength was 32.6 MPa, the elongation was 333%, and the yield strength was 15.0 MPa.
［比較例１］
ＰＣＨＭＶＥのかわりにＰＰＶＥの４２．４ｇを仕込んだ以外は実施例１と同様にして、ＴＦＥ共重合体３の１５８ｇを得た。ＴＦＥ共重合体３の共重合組成は、ＴＦＥに基づく繰り返し単位／ＰＰＶＥに基づく繰り返し単位＝９８．５／１．５（モル比）であった。ＴＦＥ共重合体３の容量流速は２．３ｍｍ３／秒、融点は３０５℃、ＭＩＴ折り曲げ寿命は７６００００回であった。酸素透過係数は４．７７×１０−１３ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１、窒素透過係数は１．６１×１０−１３ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１であった。引張強度は３２．４ＭＰａ、伸度は３４０％、降伏強度が１３．０ＭＰａであった。
[Comparative Example 1]
158 g of TFE copolymer 3 was obtained in the same manner as in Example 1 except that 42.4 g of PPVE was charged instead of PCHMVE. The copolymer composition of the TFE copolymer 3 was a repeating unit based on TFE / a repeating unit based on PPVE = 98.5 / 1.5 (molar ratio). The capacity flow rate of TFE copolymer 3 was 2.3 mm 3 / sec, the melting point was 305 ° C., and the MIT bending life was 760000 times. The oxygen permeability coefficient is 4.77 × 10 −13 cm 3 (STP) · cm · cm −2 · s −1 · Pa −1 , and the nitrogen permeability coefficient is 1.61 × 10 −13 cm 3 (STP) · cm ·. It was cm −2 · s −1 · Pa −1 . The tensile strength was 32.4 MPa, the elongation was 340%, and the yield strength was 13.0 MPa.
［比較例２］
ＰＣＨＭＶＥのかわりにＰＰＶＥの４２．４ｇを、メタノールの３２ｇを仕込んだ以外は実施例１と同様にして、ＴＦＥ共重合体４の１５５ｇを得た。ＴＦＥ共重合体４の共重合組成は、ＴＦＥに基づく繰り返し単位／ＰＰＶＥに基づく繰り返し単位＝９８．５／１．５（モル比）であった。ＴＦＥ共重合体４の容量流速は５．８ｍｍ３／秒、融点は３０７℃、ＭＩＴ折り曲げ寿命は９６００００回であった。酸素の透過係数は４．９４×１０−１３ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１、窒素の透過係数は１．６２×１０−１３ｃｍ３（ＳＴＰ）・ｃｍ・ｃｍ−２・ｓ−１・Ｐａ−１であった。引張強度は３２．４ＭＰａ、伸度は３４０％、降伏強度は１３．０ＭＰａであった。
[Comparative Example 2]
155 g of TFE copolymer 4 was obtained in the same manner as in Example 1, except that 42.4 g of PPVE and 32 g of methanol were charged instead of PCHMVE. The copolymer composition of TFE copolymer 4 was a repeating unit based on TFE / a repeating unit based on PPVE = 98.5 / 1.5 (molar ratio). The capacity flow rate of TFE copolymer 4 was 5.8 mm 3 / sec, the melting point was 307 ° C., and the MIT bending life was 960000 times. The permeability coefficient of oxygen is 4.94 × 10 −13 cm 3 (STP) · cm · cm −2 · s −1 · Pa −1 , and the permeability coefficient of nitrogen is 1.62 × 10 −13 cm 3 (STP) · It was cm · cm −2 · s −1 · Pa −1 . The tensile strength was 32.4 MPa, the elongation was 340%, and the yield strength was 13.0 MPa.
本発明のＴＦＥ共重合体は、薬液及びガスのバリア性に優れるので、半導体製造プロセス用の薬液容器、継ぎ手、チューブ等に適する。また、電線被覆材料、ＯＡ機器、コピー機、携帯電話等の精密部品等の用途に適する。
Since the TFE copolymer of the present invention is excellent in chemical and gas barrier properties, it is suitable for chemical containers, joints, tubes and the like for semiconductor manufacturing processes. In addition, it is suitable for applications such as precision parts such as wire coating materials, OA equipment, copiers and mobile phones.
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