JP2002012626A - Fluorine-containing copolymer and molding - Google Patents
Fluorine-containing copolymer and moldingInfo
- Publication number
- JP2002012626A JP2002012626A JP2000197963A JP2000197963A JP2002012626A JP 2002012626 A JP2002012626 A JP 2002012626A JP 2000197963 A JP2000197963 A JP 2000197963A JP 2000197963 A JP2000197963 A JP 2000197963A JP 2002012626 A JP2002012626 A JP 2002012626A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- fluorinated copolymer
- copolymer
- polymerization
- melt viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、含フッ素共重合
体、特にブロー成形性に優れた含フッ素共重合体に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing copolymer, and more particularly to a fluorine-containing copolymer excellent in blow moldability.
【０００２】[0002]
【従来の技術】テトラフルオロエチレン／パーフルオロ
（プロピルビニルエーテル）共重合体（以下、ＰＦＡと
いう。）や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（以下、ＦＥＰという。）は、溶融成
形可能な含フッ素樹脂であり、チューブ、パイプ、継
手、容器などの成形品、電線被覆、コーティング、ライ
ニングなどの材料として幅広く用いられている。ＰＦＡ
やＦＥＰは、通常の溶融成形性樹脂の成形方法である押
出し成形、射出成形、トランスファー成形、ブロー成形
などの方法で成形できる。特に、有機液体や腐食性液体
の保存や輸送に使用されるボトル、タンク、ドラムなど
の形状の容器が、ＰＦＡやＦＥＰのブロー成形によって
製造されている。2. Description of the Related Art A tetrafluoroethylene / perfluoro (propyl vinyl ether) copolymer (hereinafter, referred to as PFA) and a tetrafluoroethylene / hexafluoropropylene copolymer (hereinafter, referred to as FEP) are melt-moldable. It is a fluororesin, and is widely used as a molded product such as tubes, pipes, joints, and containers, and as a material for wire coating, coating, and lining. PFA
FEP and FEP can be formed by methods such as extrusion molding, injection molding, transfer molding, and blow molding, which are the usual methods for molding a melt-moldable resin. In particular, containers in the form of bottles, tanks, drums and the like used for storing and transporting organic liquids and corrosive liquids are manufactured by blow molding PFA or FEP.
【０００３】しかし、ＰＦＡやＦＥＰの比重が大きいた
め、ブロー成形時に、合わせ金型内で軟化状態にある円
筒形状となった樹脂（以下、パリソンという。）は、自
重で下方向に引っ張られやすい。その結果、上部のパリ
ソンが伸びてその部分の肉厚が薄くなり、成形体の厚み
が不均一になる問題があった。特に、大型の成形体をブ
ロー成形する場合に、パリソン上部の薄肉化が顕著にな
る。However, due to the large specific gravity of PFA and FEP, a cylindrical resin (hereinafter, referred to as a parison) which is in a softened state in a mating mold during blow molding is easily pulled downward by its own weight. . As a result, there is a problem that the parison on the upper portion is elongated, the thickness of the portion is reduced, and the thickness of the molded body becomes uneven. In particular, when blow molding a large molded body, the thickness of the upper part of the parison is significantly reduced.
【０００４】パリソン上部の薄肉化を防止するために
は、パリソンが自重によって伸長することを抑制すれば
よいが、本発明者は、ＰＦＡやＦＥＰの溶融張力を高く
することが効果的であることを見出した。溶融張力を高
くする方法として、使用する含フッ素樹脂の高分子量化
を検討したが、成形時の含フッ素樹脂の溶融粘度が大き
くなる結果、パリソンを押出す時の含フッ素樹脂の成形
性が低下し、生産性が低くなる問題があった。In order to prevent the upper part of the parison from being thinned, it is sufficient to suppress the elongation of the parison by its own weight. However, the present inventor has found that it is effective to increase the melt tension of PFA or FEP. Was found. As a method to increase the melt tension, we investigated the use of a high molecular weight fluoropolymer to be used.However, the melt viscosity of the fluoropolymer during molding increased, resulting in a decrease in the moldability of the fluorocarbon resin when extruding a parison. However, there is a problem that productivity is reduced.
【０００５】一方、溶融張力を高い状態に保持して成形
する方法を検討したが、低温でパリソンを押出す必要が
あり、その結果、パリソンが合わせ金型内で固まりやす
くなり、ブロー成形が困難になる問題があった。また、
低温でパリソンを押出す場合、含フッ素樹脂の溶融粘度
が大きくなり、上記と同様に、生産性が低くなる問題が
あった。On the other hand, a method of molding while maintaining a high melt tension has been studied. However, it is necessary to extrude the parison at a low temperature, and as a result, the parison is easily solidified in a mating die, and blow molding is difficult. There was a problem. Also,
When a parison is extruded at a low temperature, there is a problem that the melt viscosity of the fluorine-containing resin increases and the productivity decreases as described above.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、従来技術の
有する上記問題点を解消し、ブロー成形において、生産
性を低下させることなく、パリソン上部の薄肉化を抑制
できる含フッ素共重合体を提供することを目的とする。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and provides a fluorine-containing copolymer which can suppress the thinning of the upper part of the parison in blow molding without lowering the productivity. The purpose is to provide.
【０００７】[0007]
【課題を解決するための手段】本発明は、（ａ）テトラ
フルオロエチレン（以下、ＴＦＥという。）に基づく重
合単位、（ｂ）２重結合を１個有する含フッ素モノマー
（ただし、ＴＦＥを除く。）に基づく重合単位及び
（ｃ）２重結合を２個以上有するモノマーに基づく重合
単位を必須とする含フッ素共重合体であって、含フッ素
共重合体中の（ａ）／（ｂ）／（ｃ）の比率がモル比で
５０〜９９／０．９９〜４９．９９／０．０１〜１であ
り、３８０℃での溶融粘度が１×１０2〜５×１０4Ｐａ
・ｓであることを特徴とする含フッ素共重合体を提供す
る。The present invention relates to (a) a polymerized unit based on tetrafluoroethylene (hereinafter referred to as TFE), and (b) a fluorine-containing monomer having one double bond (excluding TFE). ) And (c) a fluorinated copolymer essentially comprising a polymerized unit based on a monomer having two or more double bonds, wherein (a) / (b) in the fluorinated copolymer / (C) is 50 to 99 / 0.99 to 49.99 / 0.01 to 1 in molar ratio, and the melt viscosity at 380 ° C. is 1 × 10 2 to 5 × 10 4 Pa.
-Provide a fluorine-containing copolymer characterized by being s.
【０００８】本発明において、（ａ）はＴＦＥに基づく
重合単位である。（ｂ）は、以下に記載のモノマーに基
づく重合単位が好ましい。（ｂ）のモノマーの例として
は、ＴＦＥを除く、クロロトリフルオロエチレン、ビニ
リデンフルオリド、トリフルオロエチレンなどのフルオ
ロエチレン類、ヘキサフルオロプロピレン（以下、ＨＦ
Ｐという。）、ペンタフルオロプロピレンなどのフルオ
ロプロピレン類、ＣＦ3ＣＦ2ＣＦ2ＣＦ2ＣＨ＝ＣＨ2や
ＣＦ3ＣＦ2ＣＦ2ＣＦ2ＣＦ＝ＣＨ2などのパーフルオロ
アルキル基の炭素数が４〜１２の（パーフルオロアルキ
ル）エチレン類、パーフルオロ（アルキルビニルエーテ
ル）などが挙げられる。（ｂ）のモノマーは、単独で用
いてもよく、２種以上組み合わせて用いてもよい。In the present invention, (a) is a polymerized unit based on TFE. (B) is preferably a polymerized unit based on the monomers described below. Examples of the monomer (b) include fluoroethylenes such as chlorotrifluoroethylene, vinylidene fluoride and trifluoroethylene, and hexafluoropropylene (hereinafter HF), excluding TFE.
It is called P. ), Fluoropropylenes such as pentafluoropropylene, perfluoroalkyl groups such as CF 3 CF 2 CF 2 CF 2 CH = CH 2 and CF 3 CF 2 CF 2 CF 2 CF = CH 2 having 4 to 12 carbon atoms. (Perfluoroalkyl) ethylenes, perfluoro (alkyl vinyl ether) and the like. The monomer (b) may be used alone or in combination of two or more.
【０００９】（ｂ）のモノマーのより好ましい例として
は、ＨＦＰ及び／又はパーフルオロ（アルキルビニルエ
ーテル）が挙げられる。（ｂ）のパーフルオロ（アルキ
ルビニルエーテル）の好ましい例としては、式Ｒf3（Ｏ
ＣＦＸＣＦ2）mＯＣＦ＝ＣＦ2（ここで、Ｒf3は炭素数
１〜８のパーフルオロアルキル基、Ｘはフッ素原子又は
トリフルオロメチル基、ｍは０〜５の整数を示す。）で
示されるモノマーが挙げられる。さらに好ましい例は、
前式中のＲf3が炭素数１〜８のパーフルオロアルキル基
で、ｍが０の場合が挙げられ、特にパーフルオロ（プロ
ピルビニルエーテル）（以下、ＰＰＶＥという。）が、
原料入手の容易性の面で最も好ましい。More preferable examples of the monomer (b) include HFP and / or perfluoro (alkyl vinyl ether). Preferred examples of the perfluoro (alkyl vinyl ether) of (b) include a compound represented by the formula R f3 (O
CFXCF 2 ) m OCF ＝ CF 2 (where R f3 is a perfluoroalkyl group having 1 to 8 carbon atoms, X is a fluorine atom or a trifluoromethyl group, and m is an integer of 0 to 5). Monomers. More preferred examples are
In the above formula, R f3 is a perfluoroalkyl group having 1 to 8 carbon atoms and m is 0. In particular, perfluoro (propyl vinyl ether) (hereinafter referred to as PPVE) is used.
It is most preferable in terms of availability of raw materials.
【００１０】本発明において、（ｃ）は、通常は２重結
合を２個又は３個有するモノマーに基づく重合単位であ
る。（ｃ）は、フッ素原子を含有しても含有しなくても
よいが、フッ素原子を含有するものがより好ましい。In the present invention, (c) is a polymerized unit based on a monomer having usually two or three double bonds. (C) may or may not contain a fluorine atom, but more preferably contains a fluorine atom.
【００１１】２重結合を２個有するモノマーとしては、
ＣＦ2＝ＣＦＯ−Ｒf4−ＯＣＦ＝ＣＦ2（ここで、Ｒf4は
炭素数１〜８のフルオロアルキレン基（ただし、フルオ
ロアルキレン基中にエーテル性酸素原子を含んでいても
よい。）を示す。）、ＣＦ 2＝ＣＦＯ−Ｒf5−ＣＦ＝Ｃ
Ｆ2、ＣＦ2＝ＣＦＯ−Ｒf5−ＣＨ＝ＣＨ2、ＣＦ2＝ＣＦ
−Ｒf5−ＣＦ＝ＣＦ2、ＣＦ2＝ＣＦ−Ｒf5−ＣＨ＝ＣＨ
2、ＣＨ2＝ＣＨ−Ｒ f5−ＣＨ＝ＣＨ2（ここで、Ｒf5は
単結合又は炭素数１〜８のフルオロアルキレン基（ただ
し、フルオロアルキレン基中にエーテル性酸素原子を含
んでいてもよい。）を示す。）などが挙げられる。The monomer having two double bonds includes:
CFTwo= CFO-Rf4-OCF = CFTwo(Where Rf4Is
A fluoroalkylene group having 1 to 8 carbon atoms (however,
Even if the alkylene group contains an etheric oxygen atom
Good. ). ), CF Two= CFO-Rf5-CF = C
FTwo, CFTwo= CFO-Rf5-CH = CHTwo, CFTwo= CF
-Rf5-CF = CFTwo, CFTwo= CF-Rf5-CH = CH
Two, CHTwo= CH-R f5-CH = CHTwo(Where Rf5Is
A single bond or a fluoroalkylene group having 1 to 8 carbon atoms (only
Containing an etheric oxygen atom in the fluoroalkylene group.
You may go out. ). ).
【００１２】２重結合を３個有するモノマーとしては、
３つのトリフルオロビニロキシ基や３つのトリフルオロ
ビニル基で３置換された炭素数２〜８のフルオロアルカ
ン（ただし、フルオロアルカン骨格中にエーテル性酸素
原子を含んでいてもよい。）又は３置換された芳香族化
合物などが挙げられる。The monomer having three double bonds includes:
C2-C8 fluoroalkane tri-substituted by three trifluorovinyloxy groups or three trifluorovinyl groups (however, the fluoroalkane skeleton may contain an etheric oxygen atom) or trisubstitution. Aromatic compounds and the like.
【００１３】特に、（ｃ）のモノマーとしては、ＣＦ2
＝ＣＦＯ−Ｒf1−ＯＣＦ＝ＣＦ2及び／又はＣＦ2＝ＣＦ
Ｏ−Ｒf2−ＣＦ＝ＣＦ2（ここで、Ｒf1は炭素数１〜８
のパーフルオロアルキレン基（ただし、パーフルオロア
ルキレン基中にエーテル性酸素原子を含んでいてもよ
い。）を示し、Ｒf2は単結合又は炭素数１〜８のパーフ
ルオロアルキレン基（ただし、パーフルオロアルキレン
基中にエーテル性酸素原子を含んでいてもよい。）を示
す。）で示されるモノマーが、原料入手の容易性の面か
ら好ましい。In particular, as the monomer (c), CF 2
= CFO-R f1 -OCF = CF 2 and / or CF 2 = CF
O-R f2 -CF = CF 2 ( wherein, R f1 is 1 to 8 carbon atoms
Wherein R f2 is a single bond or a perfluoroalkylene group having 1 to 8 carbon atoms (provided that the perfluoroalkylene group may contain an etheric oxygen atom in the perfluoroalkylene group). An alkylene group may contain an etheric oxygen atom). ) Are preferred from the viewpoint of easy availability of raw materials.
【００１４】（ｃ）のモノマーの好ましい具体例として
は、ＣＦ2＝ＣＦＯＣＦ＝ＣＦ2、ＣＦ2＝ＣＦＯＣＦ2Ｏ
ＣＦ＝ＣＦ2、ＣＦ2＝ＣＦＯ（ＣＦ2）2ＯＣＦ＝Ｃ
Ｆ2、ＣＦ2＝ＣＦＯ（ＣＦ2）3ＯＣＦ＝ＣＦ2、ＣＦ2＝
ＣＦＯ（ＣＦ2）4ＯＣＦ＝ＣＦ2、ＣＦ2＝ＣＦＯ（ＣＦ
2）5ＯＣＦ＝ＣＦ2、ＣＦ2＝ＣＦＯ（ＣＦ2）6ＯＣＦ＝
ＣＦ2、ＣＦ2＝ＣＦＯＣＦ2ＯＣＦ（ＣＦ3）ＣＦ2ＯＣ
Ｆ＝ＣＦ2、ＣＦ2＝ＣＦＯ（ＣＦ2）2ＯＣＦ（ＣＦ3）
ＣＦ2ＯＣＦ＝ＣＦ2、ＣＦ2＝ＣＦＯＣＦ2ＣＦ＝Ｃ
Ｆ2、ＣＦ2＝ＣＦＯ（ＣＦ2）2ＣＦ＝ＣＦ2、ＣＦ2＝Ｃ
ＦＯ（ＣＦ2）3ＣＦ＝ＣＦ2などが挙げられる。Preferred specific examples of the monomer (c) include CF 2 ＣＦCFOCF ＝ CF 2 and CF 2 ＣＦCFOCF 2 O
CF = CF 2 , CF 2 = CFO (CF 2 ) 2 OCF = C
F 2 , CF 2 = CFO (CF 2 ) 3 OCF = CF 2 , CF 2 =
CFO (CF 2) 4 OCF = CF 2, CF 2 = CFO (CF
2 ) 5 OCF = CF 2 , CF 2 ＯCFO (CF 2 ) 6 OCF =
CF 2 , CF 2 = CFOCF 2 OCF (CF 3 ) CF 2 OC
F = CF 2 , CF 2 = CFO (CF 2 ) 2 OCF (CF 3 )
CF 2 OCF = CF 2, CF 2 = CFOCF 2 CF = C
F 2, CF 2 = CFO ( CF 2) 2 CF = CF 2, CF 2 = C
FO (CF 2 ) 3 CF = CF 2 and the like.
【００１５】本発明の含フッ素共重合体中の（ａ）／
（ｂ）／（ｃ）の比率は、モル比で５０〜９９／０．９
９〜４９．９９／０．０１〜１である。（ａ）の比率が
５０より少ない場合は、得られる成形体の機械強度、耐
熱性、耐薬品性などが低下する。また、９９を超えると
ブロー成形性が不良となる。（ｂ）の比率が０．９９よ
り少ないとブロー成形性が不良となり、４９．９９を超
えると得られる成形体の機械強度、耐熱性、耐薬品性な
どが低下する。（ｃ）の比率が０．０１より少ないと溶
融張力の改善効果がほとんどなく、１を超えると溶融粘
度が大きくなり成形が困難になる。（ａ）／（ｂ）／
（ｃ）の比率は、モル比で６０〜９９／０．９９〜３
９．９９／０．０１〜１がより好ましく、７０〜９９／
０．９７〜２９．９７／０．０３〜０．７がさらに好ま
しくい。In the fluorine-containing copolymer of the present invention, (a) /
The ratio of (b) / (c) is 50 to 99 / 0.9 in molar ratio.
9-49.99 / 0.01-1. If the ratio of (a) is less than 50, the resulting molded article will have reduced mechanical strength, heat resistance, chemical resistance and the like. On the other hand, if it exceeds 99, blow moldability becomes poor. If the ratio of (b) is less than 0.99, the blow moldability becomes poor, and if it exceeds 49.99, the mechanical strength, heat resistance, chemical resistance, etc. of the obtained molded body are reduced. If the ratio of (c) is less than 0.01, there is almost no effect of improving the melt tension, and if it exceeds 1, the melt viscosity increases and molding becomes difficult. (A) / (b) /
The ratio of (c) is 60-99 / 0.99-3 in molar ratio.
9.99 / 0.01-1 is more preferable, and 70-99 /
0.97 to 29.97 / 0.03 to 0.7 is more preferable.
【００１６】本発明の含フッ素共重合体は、（ａ）、
（ｂ）および（ｃ）以外に、その他のビニル単量体に基
づく重合単位を１０モル％以下の割合で含むものでもよ
い。その他のビニル単量体の例としては、エチレン、プ
ロピレン、ブテンなどのオレフィン類、メチルビニルエ
ーテル、エチルビニルエーテル、プロピルビニルエーテ
ル、ブテニルビニルエーテル、クロロエチルビニルエー
テル、ヒドロキシブチルビニルエーテル、シクロヘキシ
ルビニルエーテル、グリシジルビニルエーテルなどのビ
ニルエーテル類、アリルアルコール、アリルグリシジル
エーテルなどのアリル化合物、酢酸ビニル、ピバリン酸
ビニル、酪酸ビニル、クロロ酢酸ビニルなどのビニルエ
ステル類、アクリル酸、メタクリル酸、アクリル酸メチ
ル、メタクリル酸メチルなどのアクリル酸誘導体又はメ
タクリル酸誘導体が挙げられる。The fluorine-containing copolymer of the present invention comprises (a)
In addition to (b) and (c), a polymer unit containing 10 mol% or less of a polymer unit based on another vinyl monomer may be used. Examples of other vinyl monomers include ethylene, propylene, olefins such as butene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butenyl vinyl ether, chloroethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexyl vinyl ether, and glycidyl vinyl ether. Compounds, allyl compounds such as allyl alcohol and allyl glycidyl ether, vinyl esters such as vinyl acetate, vinyl pivalate, vinyl butyrate and vinyl chloroacetate, and acrylic acid derivatives such as acrylic acid, methacrylic acid, methyl acrylate and methyl methacrylate Or a methacrylic acid derivative is mentioned.
【００１７】本発明の含フッ素共重合体の製造方法は、
特に限定されず、バルク重合、溶液重合、乳化重合、懸
濁重合などの従来公知の方法が採用される。溶液重合の
場合には、重合媒体としてハイドロフルオロカーボン、
クロロフルオロカーボン、ハイドロクロロフルオロカー
ボン、アルコール、ハイドロカーボンなどが用いられ
る。懸濁重合の場合には、ハイドロフルオロカーボン、
クロロフルオロカーボン、ハイドロクロロフルオロカー
ボン、ハイドロカーボンなどの媒体に水を加えたもの重
合媒体として用いられる。乳化重合の場合には、重合媒
体として水が用いられるが、溶液重合で用いられる同様
の重合媒体を併用してもよい。The process for producing the fluorine-containing copolymer of the present invention comprises:
There is no particular limitation, and conventionally known methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization are employed. In the case of solution polymerization, hydrofluorocarbon as a polymerization medium,
Chlorofluorocarbon, hydrochlorofluorocarbon, alcohol, hydrocarbon and the like are used. In the case of suspension polymerization, hydrofluorocarbon,
A medium obtained by adding water to a medium such as chlorofluorocarbon, hydrochlorofluorocarbon or hydrocarbon is used as a polymerization medium. In the case of emulsion polymerization, water is used as a polymerization medium, but a similar polymerization medium used in solution polymerization may be used in combination.
【００１８】重合開始源としては、ラジカル開始剤、レ
ドックス触媒系開始剤、光、熱、電離放射線などが採用
される。好ましいラジカル開始剤の具体例としては、ア
ゾビスイソブチロニトリルのようなアゾ系開始剤、イソ
ブチリルパーオキシド、オクタノイルパーオキシド、ベ
ンゾイルパーオキシド、ラウロイルパーオキシドのよう
なジアシルパーオキシド類、ジイソプロピルパーオキシ
ジカーボネートのようなパーオキシジカーボネート類、
ｔｅｒｔ−ブチルパーオキシピバレート、ｔｅｒｔ−ブ
チルパーオキシイソブチレート、ｔｅｒｔ−ブチルパー
オキシアセテートのようなパーオキシエステル類、（Ｘ
（ＣＦ2）nＣＯＯ）2（ここで、Ｘは水素原子、フッ素
原子又は塩素原子であり、ｎは１〜１０の整数であ
る。）で示される含フッ素ジアシルパーオキシド類など
の有機過酸化物開始剤、過硫酸カリウム、過硫酸ナトリ
ウム、過硫酸アンモニウムのような無機過酸化物開始剤
などが挙げられる。As the polymerization initiation source, a radical initiator, a redox catalyst initiator, light, heat, ionizing radiation and the like are employed. Specific examples of preferred radical initiators include azo initiators such as azobisisobutyronitrile, diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide and lauroyl peroxide, and diisopropyl peroxide. Peroxydicarbonates such as peroxydicarbonate,
Peroxyesters such as tert-butylperoxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate, (X
(CF 2 ) n COO) 2 (where X is a hydrogen atom, a fluorine atom or a chlorine atom, and n is an integer of 1 to 10), such as an organic peroxide such as a fluorinated diacyl peroxide. And inorganic peroxide initiators such as potassium persulfate, sodium persulfate and ammonium persulfate.
【００１９】重合温度は、０℃〜２００℃の範囲が好ま
しく、１０〜１００℃の範囲が特に好ましい。重合圧力
は、０．０１〜１０ＭＰａの範囲が好ましく、０．５〜
３ＭＰａの範囲が特に好ましい。[0019] The polymerization temperature is preferably in the range of 0 ° C to 200 ° C, particularly preferably in the range of 10 ° C to 100 ° C. The polymerization pressure is preferably in the range of 0.01 to 10 MPa, and 0.5 to 10 MPa.
A range of 3 MPa is particularly preferred.
【００２０】本発明の含フッ素共重合体の３８０℃での
溶融粘度は１×１０2〜５×１０4Ｐａ・ｓである。１×
１０2Ｐａ・ｓより小さい場合は、得られる成形体の機
械強度の面で不利であり、５×１０4Ｐａ・ｓより大き
い場合は、溶融成形性の面で不利になる。好ましくは５
×１０2〜２×１０4Ｐａ・ｓであり、最も好ましくは１
×１０3〜１×１０4Ｐａ・ｓである。The melt viscosity at 380 ° C. of the fluorinated copolymer of the present invention is from 1 × 10 2 to 5 × 10 4 Pa · s. 1x
If it is smaller than 10 2 Pa · s, it is disadvantageous in terms of mechanical strength of the obtained molded body, and if it is larger than 5 × 10 4 Pa · s, it is disadvantageous in terms of melt moldability. Preferably 5
X 10 2 to 2 x 10 4 Pa · s, most preferably 1
× 10 3 to 1 × 10 4 Pa · s.
【００２１】本発明においては、特定量の（ｃ）を使用
することにより、溶融粘度の増大を抑えたままで、溶融
張力を高めることができ、ブロー成形性に優れた含フッ
素共重合体が得られる。一方、含フッ素共重合体の溶融
張力を高めるために高分子量化すると、溶融粘度が大き
くなり押出し成形性が低下する。In the present invention, by using a specific amount of (c), it is possible to increase the melt tension while suppressing the increase in melt viscosity, and obtain a fluorine-containing copolymer excellent in blow moldability. Can be On the other hand, if the molecular weight is increased to increase the melt tension of the fluorinated copolymer, the melt viscosity increases and the extrusion moldability decreases.
【００２２】本発明において、上記の効果を達成するう
えで、溶融張力（単位：ｍＮ）／溶融粘度（単位：Ｐａ
・ｓ）の比を０．０７〜０．５の範囲に制御することが
望ましい。０．０７より小さい場合は、ブロー成形にお
いてパリソンの自重による伸張の面で不利になり、０．
５を超える場合は、ブロー成形が困難になる。０．０７
〜０．１５の範囲がより好ましい。In the present invention, in order to achieve the above effects, melt tension (unit: mN) / melt viscosity (unit: Pa)
It is desirable to control the ratio of (s) in the range of 0.07 to 0.5. If it is smaller than 0.07, it becomes disadvantageous in terms of stretching due to the weight of the parison in blow molding, and it is not preferable to use a parison.
If it exceeds 5, blow molding becomes difficult. 0.07
The range of -0.15 is more preferable.
【００２３】本発明において、上記の効果が達成される
理由については、必ずしも明確でないが、（ｃ）を特定
量使用することによる次のような作用機構に基づくと考
えられる。本発明の含フッ素共重合体の合成反応では、
まず、（ｃ）のモノマー中の一つの２重結合が、（ａ）
のモノマーや（ｂ）のモノマーと共重合し、（ｃ）のモ
ノマー中の残りの２重結合を側鎖に有する含フッ素共重
合体が生成する。この側鎖の２重結合に、さらに（ａ）
のモノマーや（ｂ）のモノマーが共重合し、鎖長の長い
側鎖を生成する。この長い側鎖の構造が何らかの作用に
より、溶融粘度の増大を抑えたままで、溶融張力を高め
ていると考えられる。In the present invention, the reason why the above effect is achieved is not necessarily clear, but it is considered to be based on the following action mechanism by using a specific amount of (c). In the synthesis reaction of the fluorine-containing copolymer of the present invention,
First, one double bond in the monomer of (c) is represented by (a)
Is copolymerized with the monomer (b) and the monomer (b) to form a fluorine-containing copolymer having the remaining double bond in the side chain in the monomer (c). In addition to this double bond in the side chain, (a)
And the monomer of (b) are copolymerized to form a long side chain. It is considered that the structure of the long side chain increases the melt tension by some effect while suppressing the increase in the melt viscosity.
【００２４】本発明においては、成形時の発泡や着色の
原因となる含フッ素共重合体中の不安定部位を安定化す
るために、重合で生成した含フッ素共重合体をフッ素化
することも好ましく採用される。フッ素化は、（ｂ）
が、パーフルオロ（アルキルビニルエーテル）やヘキサ
フルオロプロピレンに基づく重合単位の場合に特に好ま
しく採用される。フッ素化は、フッ素ガス／窒素ガスの
混合ガスを用いるのが取り扱い上好ましい。In the present invention, the fluorinated copolymer produced by polymerization may be fluorinated in order to stabilize unstable sites in the fluorinated copolymer which cause foaming or coloring during molding. It is preferably adopted. Fluorination (b)
Is particularly preferably employed in the case of a polymerization unit based on perfluoro (alkyl vinyl ether) or hexafluoropropylene. For the fluorination, it is preferable in terms of handling to use a mixed gas of fluorine gas / nitrogen gas.
【００２５】フッ素化温度は２００〜２８０℃が好まし
い。２００℃より低い場合はフッ素化に長時間を要し、
２８０℃を超える場合は共重合体が溶融して取り扱いが
困難となるおそれがある。より好ましくは、２２０〜２
５０℃の範囲が採用される。フッ素化時間は、フッ素化
温度に依存するが、通常１〜２４時間が好ましく採用さ
れる。高温では短時間で、低温では長時間でフッ素化が
完結する。The fluorination temperature is preferably from 200 to 280 ° C. If the temperature is lower than 200 ° C., it takes a long time for fluorination,
If it exceeds 280 ° C., the copolymer may melt and handling may be difficult. More preferably, 220-2
A range of 50 ° C is employed. The fluorination time depends on the fluorination temperature, but usually 1 to 24 hours is preferably employed. Fluorination is completed in a short time at a high temperature and for a long time at a low temperature.
【００２６】フッ素化により、含フッ素共重合体に含有
される少量の２重結合や−ＣＯＦ、−ＣＦ2ＣＨ2ＯＨ、
−ＣＯＯＨなどの不安定末端基などが−ＣＦ3基などの
安定末端基に変換される結果、含フッ素共重合体の熱安
定性が向上し、成形時に含フッ素共重合体が発泡や着色
しなくなるものと考えられる。本発明の含フッ素共重合
体は、ブロー成形用原料として好ましく使用される。By the fluorination, a small amount of double bonds, --COF, --CF 2 CH 2 OH,
Results such as unstable end groups, such as -COOH is converted into stable end groups, such as a -CF 3 group, and improved thermal stability of the fluorinated copolymer is a fluorinated copolymer is foamed and colored during molding It is thought to be gone. The fluorinated copolymer of the present invention is preferably used as a raw material for blow molding.
【００２７】[0027]
【実施例】以下に、本発明の実施例および比較例を説明
するが、本発明はそれらに限定されない。なお、含フッ
素共重合体の溶融粘度、溶融張力、組成及びブロー成形
の評価は以下の方法にしたがって測定した。 含フッ素共重合体の溶融粘度（単位：Ｐａ・ｓ）：高化
式フローテスター（島津製作所製）を用い、直径２．１
ｍｍ、長さ８ｍｍのダイス、荷重７ｋｇ、３８０℃で押
出したときの見掛溶融粘度の値である。 溶融張力（単位：ｍＮ）：キャピログラフ（東洋精機製
作所製）を用い、直径３ｍｍ、長さ１０ｍｍのダイス、
速度５ｍｍ／ｍｉｎ、３８０℃で押出し、速度１０ｍ／
ｍｉｎで引き落とした時の引き落とし強度の値である。 含フッ素共重合体の組成：19Ｆ−溶融ＮＭＲ法により求
めた。EXAMPLES Examples of the present invention and comparative examples will be described below, but the present invention is not limited thereto. The evaluation of the melt viscosity, melt tension, composition and blow molding of the fluorinated copolymer was measured according to the following methods. Melt viscosity of fluorocopolymer (unit: Pa · s): Diameter 2.1 using Koka type flow tester (manufactured by Shimadzu Corporation).
This is the value of the apparent melt viscosity when extruded at 380 ° C. with a die having a length of 8 mm and a length of 8 mm. Melt tension (unit: mN): Using a Capillograph (manufactured by Toyo Seiki Seisakusho), a die having a diameter of 3 mm and a length of 10 mm,
Extruded at a speed of 5 mm / min at 380 ° C. and a speed of 10 m / min.
It is the value of the withdrawal strength when it is withdrawn in min. Composition of fluorinated copolymer: determined by 19 F-melt NMR method.
【００２８】ブロー成形の評価：次の模擬試験で実施し
た。溶融粘度測定時に押出された含フッ素共重合体のス
トランドにおいて、ストランドが１ｃｍ押出されたとこ
ろのストランド径及び１０ｃｍ押出されたところのスト
ランド径を測定し、１０ｃｍでのストランド径／１ｃｍ
でのストランド径の比（以下、ＤＣ比という。）を求め
る。ＤＣ比が大きいものは溶融時に自重で伸びる程度が
小さく、ブロー成形に適する。Evaluation of blow molding: The following simulation test was performed. In the extruded fluorine-containing copolymer strand at the time of measuring the melt viscosity, the strand diameter when the strand was extruded by 1 cm and the strand diameter when extruded by 10 cm were measured, and the strand diameter at 10 cm / 1 cm
Is determined (hereinafter referred to as DC ratio). Those having a large DC ratio have a small degree of elongation by their own weight during melting and are suitable for blow molding.
【００２９】［例１］撹拌機付きの１Ｌのオートクレー
ブを真空まで脱気し、１，３−ジクロロ−１，１，２，
２，３−ペンタフルオロプロパン（以下、ＡＫ２２５ｃ
ｂという。旭硝子社製）の１０００ｇ、メタノールの
２．５ｇ、ＰＰＶＥの１２０ｇ、ＣＦ2＝ＣＦＯＣＦ2Ｃ
Ｆ2ＣＦ2ＣＦ2ＯＣＦ＝ＣＦ2（以下、ＤＶＢという。）
の５ｇを仕込んだ。オートクレーブの内温を５０℃と
し、０．７ＭＰａまでＴＦＥを仕込んだ。開始剤として
ビス（パーフルオロブチリル）パーオキシドの１％溶液
（溶媒：ＡＫ２２５ｃｂ）を仕込んで重合を開始させ
た。Example 1 A 1 L autoclave equipped with a stirrer was evacuated to a vacuum, and 1,3-dichloro-1,1,2,2
2,3-pentafluoropropane (hereinafter referred to as AK225c
It is called b. 1000 g of Asahi Glass Co., Ltd., 2.5 g of methanol, 120 g of PPVE, CF 2 = CFOCF 2 C
F 2 CF 2 CF 2 OCF = CF 2 (hereinafter referred to as DVB)
Was charged. The internal temperature of the autoclave was set to 50 ° C., and TFE was charged to 0.7 MPa. A 1% solution of bis (perfluorobutyryl) peroxide (solvent: AK225cb) was charged as an initiator to initiate polymerization.
【００３０】重合の進行に伴い降圧したので、ＴＦＥを
仕込んで圧力を０．７ＭＰａに保持した。時間が経過す
るにつれて重合が進まなくなったので、前記開始剤溶液
を１ｍＬずつ逐次仕込んで重合を進行させた。後から仕
込んだＴＦＥ量が１００ｇになった時点で、オートクレ
ーブの内温を１０℃まで冷却すると同時に、未重合ＴＦ
Ｅをパージした。得られたスラリー状態の懸濁液を濾
過、乾燥して、白色の含フッ素共重合体の１０５ｇを得
た。Since the pressure was lowered as the polymerization proceeded, TFE was charged and the pressure was maintained at 0.7 MPa. Since the polymerization did not progress with the passage of time, the polymerization was advanced by sequentially charging the initiator solution in 1 mL portions. When the amount of TFE charged later reaches 100 g, the internal temperature of the autoclave is cooled to 10 ° C.
E was purged. The obtained slurry suspension was filtered and dried to obtain 105 g of a white fluorinated copolymer.
【００３１】含フッ素共重合体の組成は、モル比でＴＦ
Ｅ／ＰＰＶＥ／ＤＶＢ＝９８．４／１．５／０．１であ
った。溶融粘度は２１００Ｐａ・ｓであり、溶融張力は
１５８ｍＮであった。溶融張力／溶融粘度の比は０．０
７５であり、ＤＣ比は０．９であった。The composition of the fluorine-containing copolymer is TF in molar ratio.
E / PPVE / DVB = 98.4 / 1.5 / 0.1. The melt viscosity was 2100 Pa · s, and the melt tension was 158 mN. The melt tension / melt viscosity ratio is 0.0
75 and the DC ratio was 0.9.
【００３２】［例２］ＤＶＢの仕込量を３０ｇとする以
外は、例１と同様に重合して、白色の含フッ素共重合体
の１１０ｇを得た。含フッ素共重合体の組成は、モル比
でＴＦＥ／ＰＰＶＥ／ＤＶＢ＝９８．０／１．５／０．
５であった。溶融粘度は４１００Ｐａ・ｓであり、溶融
張力は３１６ｍＮであった。溶融張力／溶融粘度の比は
０．０７７であり、ＤＣ比は０．９８であった。Example 2 Polymerization was carried out in the same manner as in Example 1 except that the amount of DVB was changed to 30 g to obtain 110 g of a white fluorinated copolymer. The composition of the fluorinated copolymer is TFE / PPVE / DVB = 98.0 / 1.5 / 0.
It was 5. The melt viscosity was 4100 Pa · s, and the melt tension was 316 mN. The ratio of melt tension / melt viscosity was 0.077 and the DC ratio was 0.98.
【００３３】［例３］ＤＶＢの５ｇのかわりにＣＦ2＝
ＣＦＯＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＯＣＦ＝ＣＦ2（以
下、ＤＶＰという。）の５ｇを用いる以外は例１と同様
に重合して、白色の含フッ素共重合体の１０５ｇを得
た。含フッ素共重合体の組成は、モル比でＴＦＥ／ＰＰ
ＶＥ／ＶＤＰ＝９８．４／１．５／０．１であった。溶
融粘度は１９００Ｐａ・ｓであり、溶融張力は１５３ｍ
Ｎであった。溶融張力／溶融粘度の比は０．０８１であ
り、ＤＣ比は０．９０であった。Example 3 Instead of 5 g of DVB, CF 2 =
Polymerization was carried out in the same manner as in Example 1 except that 5 g of CFOCF 2 CF 2 CF 2 CF 2 CF 2 OCF = CF 2 (hereinafter, referred to as DVP) was used to obtain 105 g of a white fluorinated copolymer. The composition of the fluorinated copolymer is TFE / PP in molar ratio.
VE / VDP = 98.4 / 1.5 / 0.1. The melt viscosity is 1900 Pa · s and the melt tension is 153 m
N. The melt tension / melt viscosity ratio was 0.081 and the DC ratio was 0.90.
【００３４】［例４］ＤＶＢの５ｇのかわりにＣＦ2＝
ＣＦＯＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ＝ＣＦ2（以下、ＤＶ
Ｂ2という）の５ｇを用いる以外は例１と同様に重合し
て、白色の含フッ素共重合体の１０５ｇを得た。含フッ
素共重合体の組成は、モル比でＴＦＥ／ＰＰＶＥ／ＤＶ
Ｂ2＝９８．４／１．５／０．１であった。溶融粘度は
１６００Ｐａ・ｓであり、溶融張力は１１２ｍＮであっ
た。溶融張力／溶融粘度の比は０．０７であり、ＤＣ比
は０．８５であった。Example 4 Instead of 5 g of DVB, CF 2 =
CFOCF 2 CF 2 CF 2 CF 2 CF = CF 2 (hereinafter, DV
Except using 5g of that B 2) is polymerized in the same manner as Example 1 to obtain 105g of white fluorine-containing copolymer. The composition of the fluorinated copolymer is TFE / PPVE / DV in molar ratio.
B 2 = 98.4 / 1.5 / 0.1. The melt viscosity was 1600 Pa · s, and the melt tension was 112 mN. The melt tension / melt viscosity ratio was 0.07 and the DC ratio was 0.85.
【００３５】［例５］ＡＫ２２５ｃｂを１０００ｇのか
わりに５００ｇ、メタノールを２．５ｇのかわりに０．
２ｇ、ＰＰＶＥのかわりにＨＦＰの６００ｇを仕込む以
外は例１と同様に重合して、白色の含フッ素共重合体の
１３０ｇを得た。含フッ素共重合体の組成は、モル比で
ＴＦＥ／ＨＦＰ／ＤＶＢ＝９３．４／６．５／０．１で
あった。溶融粘度は２５００Ｐａ・ｓであり、溶融張力
は１８９ｍＮであった。溶融張力／溶融粘度の比は０．
０７６であり、ＤＣ比は０．９５であった。Example 5 500 g of AK225cb instead of 1000 g and 0.1 g of methanol instead of 2.5 g
Polymerization was carried out in the same manner as in Example 1 except that 2 g and 600 g of HFP were used instead of PPVE to obtain 130 g of a white fluorinated copolymer. The composition of the fluorinated copolymer was TFE / HFP / DVB = 93.4 / 6.5 / 0.1 in a molar ratio. The melt viscosity was 2500 Pa · s, and the melt tension was 189 mN. The ratio of melt tension / melt viscosity is 0.
076 and the DC ratio was 0.95.
【００３６】［例６］例１で得た含フッ素共重合体を、
体積比でフッ素ガス／窒素ガス＝２０／８０のフッ素ガ
ス雰囲気下、２４０℃で６時間保持してフッ素化した。
得られたフッ素化された含フッ素共重合体の赤外吸収ス
ペクトルを測定した結果、フッ素化前に検出された−Ｃ
Ｆ＝ＣＦ2に由来する吸収が検出されなかった。溶融粘
度は２１００Ｐａ・ｓで、溶融張力は１５８ｍＮであ
り、フッ素化前と同じ値であった。ＤＣ比は０．９０で
あった。Example 6 The fluorinated copolymer obtained in Example 1 was
Fluorination was carried out at 240 ° C. for 6 hours in a fluorine gas atmosphere of fluorine gas / nitrogen gas = 20/80 in volume ratio.
As a result of measuring an infrared absorption spectrum of the obtained fluorinated fluorinated copolymer, it was found that -C detected before fluorination.
No absorption derived from F = CF 2 was detected. The melt viscosity was 2100 Pa · s, the melt tension was 158 mN, the same value as before fluorination. The DC ratio was 0.90.
【００３７】［例７（比較例）］ＤＶＢを仕込まない以
外は例１と同様に重合して、白色の含フッ素共重合体の
９７ｇを得た。得られた含フッ素共重合体の赤外吸収ス
ペクトルを測定した結果、−ＣＦ＝ＣＦ2に由来する吸
収は検出されなかった。溶融粘度は１８００Ｐａ・ｓ
で、溶融張力は９７ｍＮであり、例１の含フッ素共重合
体に比べて溶融張力は低い値であった。溶融張力／溶融
粘度の比は０．０５４であり、ＤＣ比は０．７であっ
た。Example 7 (Comparative Example) Polymerization was carried out in the same manner as in Example 1 except that no DVB was charged, to obtain 97 g of a white fluorinated copolymer. Results of infrared absorption spectrum of the obtained fluorine-containing copolymer was measured, absorption derived from -CF = CF 2 was detected. Melt viscosity is 1800Pa · s
The melt tension was 97 mN, which was lower than that of the fluorinated copolymer of Example 1. The melt tension / melt viscosity ratio was 0.054 and the DC ratio was 0.7.
【００３８】［例８（比較例）］ＤＶＢを仕込まない以
外は例５と同様に重合して、白色の含フッ素共重合体の
１２０ｇを得た。得られた含フッ素共重合体の赤外吸収
スペクトルを測定した結果、−ＣＦ＝ＣＦ2に由来する
吸収は検出されなかった。溶融粘度は１９００Ｐａ・ｓ
で、溶融張力は７１ｍＮであり、例５の含フッ素共重合
体に比べて溶融張力は低い値であった。溶融張力／溶融
粘度の比は０．０３８であり、ＤＣ比は０．７であっ
た。Example 8 (Comparative Example) Polymerization was carried out in the same manner as in Example 5 except that DVB was not charged, to obtain 120 g of a white fluorinated copolymer. Results of infrared absorption spectrum of the obtained fluorine-containing copolymer was measured, absorption derived from -CF = CF 2 was detected. Melt viscosity is 1900Pa · s
The melt tension was 71 mN, which was lower than that of the fluorine-containing copolymer of Example 5. The melt tension / melt viscosity ratio was 0.038 and the DC ratio was 0.7.
【００３９】［例９（比較例）］ＤＶＢを５ｇのかわり
に１００ｇ仕込む以外は例１と同様に重合して、白色の
含フッ素共重合体の１０５ｇを得た。含フッ素共重合体
の組成は、モル比でＴＦＥ／ＰＰＶＥ／ＤＶＢ＝９８．
４／１．５／１．２であった。溶融粘度は大きすぎて測
定できなかった。Example 9 (Comparative Example) Polymerization was carried out in the same manner as in Example 1 except that 100 g of DVB was used instead of 5 g to obtain 105 g of a white fluorinated copolymer. The composition of the fluorinated copolymer was TFE / PPVE / DVB = 98.
4 / 1.5 / 1.2. The melt viscosity was too large to be measured.
【００４０】[0040]
【発明の効果】本発明の含フッ素共重合体は、溶融張力
が高く、ブロー成形性に優れる。また、この含フッ素共
重合体をフッ素化することにより、含フッ素共重合体の
熱安定性が向上し、成形時に含フッ素共重合体の発泡や
着色を全くなくす効果も発現する。The fluorinated copolymer of the present invention has a high melt tension and is excellent in blow moldability. Further, by fluorinating this fluorinated copolymer, the thermal stability of the fluorinated copolymer is improved, and an effect of completely eliminating foaming and coloring of the fluorinated copolymer during molding is exhibited.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｆ 216:14 Ｃ０８Ｆ 216:14 214:28 214:28 216:12） 216:12） Ｂ２９Ｋ 27:12 Ｂ２９Ｋ 27:12 Ｃ０８Ｌ 27:18 Ｃ０８Ｌ 27:18 Ｆターム(参考） 4F071 AA27 AA27X AA30X AA76 BB01 BC04 4F208 AA16E AG07 AR17 LB01 LG01 4J100 AC22Q AC24Q AC25Q AC26P AC27Q AC31Q AE09Q CA05 FA19 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (Reference) C08F 216: 14 C08F 216: 14 214: 28 214: 28 216: 12) 216: 12) B29K 27:12 B29K 27:12 C08L 27:18 C08L 27:18 F term (reference) 4F071 AA27 AA27X AA30X AA76 BB01 BC04 4F208 AA16E AG07 AR17 LB01 LG01 4J100 AC22Q AC24Q AC25Q AC26P AC27Q AC31Q AE09Q CA05 FA19
Claims (6)
合単位、（ｂ）２重結合を１個有する含フッ素モノマー
（ただし、テトラフルオロエチレンを除く。）に基づく
重合単位及び（ｃ）２重結合を２個以上有するモノマー
に基づく重合単位を必須とする含フッ素共重合体であっ
て、含フッ素共重合体中の（ａ）／（ｂ）／（ｃ）の比
率がモル比で５０〜９９／０．９９〜４９．９９／０．
０１〜１であり、３８０℃での溶融粘度が１×１０2〜
５×１０4Ｐａ・ｓであることを特徴とする含フッ素共
重合体。1. A polymerization unit based on (a) a tetrafluoroethylene-based polymerization unit, (b) a polymerization unit based on a fluorine-containing monomer having one double bond (excluding tetrafluoroethylene), and (c) a double bond. Is a fluorinated copolymer essentially comprising a polymerized unit based on a monomer having two or more monomers, and the molar ratio of (a) / (b) / (c) in the fluorinated copolymer is 50 to 99. /0.99-49.99/0.
01 to 1 and a melt viscosity at 380 ° C. of 1 × 10 2 to
A fluorine-containing copolymer having a pressure of 5 × 10 4 Pa · s.
キルビニルエーテル）及び／又はヘキサフルオロプロピ
レンに基づく重合単位である請求項１記載の含フッ素共
重合体。2. The fluorine-containing copolymer according to claim 1, wherein the polymerized unit (b) is a polymerized unit based on perfluoro (alkyl vinyl ether) and / or hexafluoropropylene.
f1−ＯＣＦ＝ＣＦ2及び／又はＣＦ2＝ＣＦＯ−Ｒf2−Ｃ
Ｆ＝ＣＦ2（ここで、Ｒf1は炭素数１〜８のフルオロア
ルキレン基（ただし、フルオロアルキレン基中にエーテ
ル性酸素原子を含んでいてもよい。）を示し、Ｒf2は単
結合又は炭素数１〜８のフルオロアルキレン基（ただ
し、フルオロアルキレン基中にエーテル性酸素原子を含
んでいてもよい。）を示す。）で示されるモノマーに基
づく重合単位である請求項１又は２記載の含フッ素共重
合体。3. The polymerized unit of (c) is CF 2 ＣＦCFO-R.
f1 -OCF = CF 2 and / or CF 2 = CFO-R f2 -C
F = CF 2 (where R f1 represents a fluoroalkylene group having 1 to 8 carbon atoms (however, the fluoroalkylene group may contain an etheric oxygen atom), and R f2 represents a single bond or carbon atom 3. A polymerized unit based on a monomer represented by the following formula (1): a fluoroalkylene group of 1 to 8 (however, the fluoroalkylene group may contain an etheric oxygen atom). Fluorine copolymer.
位：Ｐａ・ｓ）の比が、０．０７〜０．５である請求項
１、２又は３記載の含フッ素共重合体。4. The fluorine-containing copolymer according to claim 1, wherein the ratio of melt tension (unit: mN) / melt viscosity (unit: Pa · s) is 0.07 to 0.5.
重合体をフッ素化してなる、安定化された含フッ素共重
合体。5. A stabilized fluorinated copolymer obtained by fluorinating the fluorinated copolymer according to claim 1, 2, 3 or 4.
素共重合体をブロー成形した成形体。6. A molded article obtained by blow molding the fluorinated copolymer according to claim 1, 2, 3, 4, or 5.
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