JPH11302394A - Molding product of crosslinked fluorine-containing polymer and its production - Google Patents
Molding product of crosslinked fluorine-containing polymer and its productionInfo
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- JPH11302394A JPH11302394A JP10106694A JP10669498A JPH11302394A JP H11302394 A JPH11302394 A JP H11302394A JP 10106694 A JP10106694 A JP 10106694A JP 10669498 A JP10669498 A JP 10669498A JP H11302394 A JPH11302394 A JP H11302394A
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- fluorine
- mol
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は架橋含フッ素重合体
の成形体及びその製造方法に関する。The present invention relates to a molded article of a crosslinked fluoropolymer and a method for producing the same.
【０００２】[0002]
【従来の技術】フッ素樹脂はその優れた耐熱性、耐薬品
性、表面特性により、様々な分野で利用されているが、
その欠点として弾性率の低いことが挙げられる。またポ
リテトラフルオロエチレン（以下、ＰＴＦＥという）以
外のフッ素樹脂は融点以上の温度に加熱すると流動して
形が保てないことも欠点として挙げられる。ＰＴＦＥは
融点以上の温度に加熱しても流動しないが、逆に溶融成
形できない欠点がある。そのため、弾性率が高く、溶融
成形ができて、しかも融点以上の温度に加熱しても流動
しないフッ素樹脂の開発が望まれていた。2. Description of the Related Art Fluororesins are used in various fields due to their excellent heat resistance, chemical resistance and surface properties.
The disadvantage is that the elastic modulus is low. Another drawback is that a fluororesin other than polytetrafluoroethylene (hereinafter, referred to as PTFE) flows and cannot maintain its shape when heated to a temperature higher than its melting point. Although PTFE does not flow even when heated to a temperature higher than the melting point, it has a disadvantage that it cannot be melt-molded. Therefore, development of a fluororesin which has a high elastic modulus, can be melt-molded, and does not flow even when heated to a temperature higher than the melting point has been desired.
【０００３】フッ素樹脂を成形後、成形体を架橋するこ
とによりこれらの要求物性を満たすことが考えられ、い
ままでに様々な架橋方法が提案されている。例えば、特
開昭６１−１５５４１０ではフッ素樹脂にトリアリルシ
アヌレートなどの架橋剤を添加して電子線架橋を行って
いる。しかしこの方法で得られた樹脂は架橋剤の存在に
より耐薬品性、耐熱性が劣る。また特開昭６３−６８６
０４やＵＳＰ４２０４９２７ではフッ素樹脂に光反応基
を付加し光架橋を行っている。しかしこれらの方法でも
得られた樹脂は耐薬品性、耐熱性に劣る。[0003] It is considered that these required physical properties are satisfied by cross-linking a molded article after molding a fluororesin, and various cross-linking methods have been proposed so far. For example, in JP-A-61-155410, electron beam crosslinking is performed by adding a crosslinking agent such as triallyl cyanurate to a fluororesin. However, the resin obtained by this method is inferior in chemical resistance and heat resistance due to the presence of the crosslinking agent. Also, Japanese Patent Application Laid-Open
No. 04 and US Pat. No. 4,204,927 perform photocrosslinking by adding a photoreactive group to a fluororesin. However, the resins obtained by these methods are inferior in chemical resistance and heat resistance.
【０００４】これらの問題を解決すべく、特開平３−２
３４７５３では、式（１）−（ＣＦ2 −ＣＦＸ）−［た
だしＸはフッ素原子又は塩素原子である］で表される単
位が７０〜９９．９モル％、式（２）−（ＣＦ2 −ＣＦ
ＯＲf Ｙ）−［ただしＲf は２価のフッ素置換有機基、
Ｙはカルボン酸基又はカルボン酸誘導体基である］で表
される単位が０．１〜２０モル％、及び式（３）−（Ｃ
Ｆ2 −ＣＦＺ）−［ただしＺは１価のフッ素置換有機基
である］で表される単位［ただし、式（２）で表される
単位を除く］が０又は１０モル％以下の割合である含フ
ッ素重合体を成形し、それを２００℃以上含フッ素重合
体の融点以下の温度で熱処理する方法が開示されてい
る。しかしこの熱処理架橋では処理時間が長い欠点があ
る。To solve these problems, Japanese Patent Laid-Open No.
In 34753, the unit represented by the formula (1)-(CF 2 -CFX)-[where X is a fluorine atom or a chlorine atom] is 70 to 99.9 mol%, and the formula (2)-(CF 2- CF
OR f Y)-[where R f is a divalent fluorine-substituted organic group,
Y is a carboxylic acid group or a carboxylic acid derivative group] in an amount of 0.1 to 20 mol%, and a compound represented by the formula (3)-(C
F 2 —CFZ) — [where Z is a monovalent fluorine-substituted organic group] (but excluding the unit represented by the formula (2)) in a proportion of 0 or 10 mol% or less. A method is disclosed in which a certain fluorinated polymer is molded and heat-treated at a temperature of 200 ° C. or higher and a melting point of the fluorinated polymer or lower. However, this heat treatment crosslinking has a disadvantage that the treatment time is long.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、弾性率が高
く、溶融成形ができて、しかも融点以上の温度に加熱し
ても流動しない架橋含フッ素重合体の成形体及びその製
造方法を提供する。SUMMARY OF THE INVENTION The present invention provides a molded article of a crosslinked fluorine-containing polymer which has a high elastic modulus, can be melt-molded, and does not flow even when heated to a temperature higher than the melting point, and a method for producing the same. I do.
【０００６】[0006]
【課題を解決するための手段】本発明は前述の問題を解
決すべくなされたものであり、式（１）−（ＣＦ2 −Ｃ
ＦＸ）−［ただしＸはフッ素原子又は塩素原子である］
で表される単位が７０〜９９．９モル％、式（２）−
（ＣＦ2 −ＣＦＯＲf Ｙ）−［ただしＲf は２価のフッ
素置換有機基、Ｙはカルボン酸基又はカルボン酸誘導体
基である］で表される単位が０．１〜２０モル％、及び
式（３）−（ＣＦ2 −ＣＦＺ）−［ただしＺは１価のフ
ッ素置換有機基である］で表される単位［ただし、式
（２）で表される単位を除く］が０又は１０モル％以下
の割合である含フッ素重合体を成形し、その成形体に紫
外線を照射して得られる架橋含フッ素重合体の成形体を
提供する。また、上記の架橋含フッ素重合体の成形体の
製造方法を提供する。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and has the following formula (1)-(CF 2 -C
FX)-[where X is a fluorine atom or a chlorine atom]
The unit represented by the formula is 70 to 99.9 mol%, and the formula (2)-
0.1 to 20 mol% of a unit represented by (CF 2 -CFOR f Y)-[where R f is a divalent fluorine-substituted organic group, and Y is a carboxylic acid group or a carboxylic acid derivative group], and A unit represented by the formula (3)-(CF 2 -CFZ) -where Z is a monovalent fluorine-substituted organic group [however, excluding the unit represented by the formula (2)] is 0 or 10; A molded article of a crosslinked fluoropolymer obtained by molding a fluoropolymer having a ratio of not more than mol% and irradiating the molded article with ultraviolet rays. Further, the present invention provides a method for producing the above-mentioned molded article of the crosslinked fluoropolymer.
【０００７】本発明において用いる含フッ素共重合体
は、式（１）−（ＣＦ2 −ＣＦＸ）−［ただしＸはフッ
素原子又は塩素原子である］で表される単位が７０〜９
９．９モル％、式（２）−（ＣＦ2 −ＣＦＯＲf Ｙ）−
［ただしＲf は２価のフッ素置換有機基、Ｙはカルボン
酸基又はカルボン酸誘導体基である］で表される単位が
０．１〜２０モル％、式（３）−（ＣＦ2 −ＣＦＺ）−
［ただしＺは１価のフッ素置換有機基である］で表され
る単位［ただし、式（２）で表される単位を除く］が０
又は１０モル％以下である含フッ素重合体である。The fluorine-containing copolymer used in the present invention has a unit represented by the formula (1)-(CF 2 -CFX)-wherein X is a fluorine atom or a chlorine atom.
9.9 mol%, formula (2)-(CF 2 -CFOR f Y)-
Wherein R f is a divalent fluorine-substituted organic group, Y is a carboxylic acid group or a carboxylic acid derivative group, and 0.1 to 20 mol% of the unit represented by the formula (3)-(CF 2 -CFZ )-
[Where Z is a monovalent fluorine-substituted organic group], except for the unit represented by the formula (2).
Or it is a fluorine-containing polymer of 10 mol% or less.
【０００８】この含フッ素重合体において、式（１）の
Ｘはフッ素原子であるものの方が耐熱性、耐薬品性など
の面からより好ましい。含フッ素重合体中に式（１）で
表される単位が１種含まれていてもよく、２種含まれて
いてもよい。In this fluoropolymer, X in the formula (1) is more preferably a fluorine atom from the viewpoint of heat resistance and chemical resistance. The fluorine-containing polymer may contain one kind of the unit represented by the formula (1), or may contain two kinds of the unit.
【０００９】式（２）におけるＲf は２価のフッ素置換
有機基であり、置換フッ素原子の数が１個以上であれば
よく、完全フッ素化された２価のフッ素置換有機基がよ
り好ましい。また、Ｒf は炭素原子のみにより、又は炭
素原子と酸素原子により鎖が形成された２価のフッ素置
換有機基が好ましい。R f in the formula (2) is a divalent fluorine-substituted organic group, provided that the number of substituted fluorine atoms is at least one, and a fully fluorinated divalent fluorine-substituted organic group is more preferable. . R f is preferably a divalent fluorine-substituted organic group in which a chain is formed by only a carbon atom or by a carbon atom and an oxygen atom.
【００１０】その具体例としては、パーフルオロアルキ
レン基又はエーテル結合を含むパーフルオロアルキレン
基が挙げられる。Ｒf の鎖を構成する炭素数は、１〜１
５、特に１〜１０の範囲が好ましい。Ｒf は、直鎖の構
造が好ましいが、分岐の構造であってもよい。分岐の構
造である場合には、分岐部分の炭素数が１〜３程度の短
鎖であるものが好ましい。Specific examples thereof include a perfluoroalkylene group or a perfluoroalkylene group containing an ether bond. The number of carbon atoms constituting the chain of R f is 1 to 1
5, particularly preferably in the range of 1 to 10. R f preferably has a linear structure, but may have a branched structure. In the case of a branched structure, a branched portion having a short chain having about 1 to 3 carbon atoms is preferable.
【００１１】Ｒf の具体例としては、例えば、−（ＣＦ
2 ）2 −、−（ＣＦ2 ）3 −、−（ＣＦ2 ）4 −、−
（ＣＦ2 ）5 −、−（ＣＦ2 ）6 −、−ＣＦ2 ＣＦ（Ｃ
Ｆ3 ）Ｏ（ＣＦ2 ）3 −、ＣＦ2 ＣＦ（ＣＦ3 ）ＯＣＦ
2 ＣＦ（ＣＦ3 ）Ｏ（ＣＦ2 ）2 −、−（ＣＦ2 ＣＦ2
Ｏ）2 −（ＣＦ2 ）3 −、−ＣＦ2 ＣＦ（ＣＦ3 ）ＣＦ
2 ＣＦ2 ＣＦ（ＣＦ3 ）ＣＦ2 −などが挙げられる。式
（２）で表される単位は、１種のみ含まれていてもよ
く、２種以上含まれていてもよい。A specific example of R f is, for example,-(CF
2 ) 2 -,-(CF 2 ) 3 -,-(CF 2 ) 4 -,-
(CF 2 ) 5 -,-(CF 2 ) 6- , -CF 2 CF (C
F 3 ) O (CF 2 ) 3 —, CF 2 CF (CF 3 ) OCF
2 CF (CF 3 ) O (CF 2 ) 2 -,-(CF 2 CF 2
O) 2- (CF 2 ) 3- , -CF 2 CF (CF 3 ) CF
2 CF 2 CF (CF 3 ) CF 2 — and the like. The unit represented by the formula (2) may include only one type, or may include two or more types.
【００１２】式（２）におけるＹは、カルボン酸基又は
カルボン酸誘導体基である。具体的には−ＣＯＯＡ（Ａ
は水素原子、炭素数１〜３のアルキル基、炭素数１〜３
のフルオロアルキル基、アルカリ金属、アンモニウム、
又は置換アンモニウム）又は−ＣＯＢ（Ｂはフッ素原子
又は塩素原子）が例示される。Ｙとして好ましいもの
は、−ＣＯＯＣＨ3 である。本発明では、含フッ素重合
体が上記Ｙで表される基を有するため、後述の方法によ
り架橋含フッ素重合体を製造できる。Y in the formula (2) is a carboxylic acid group or a carboxylic acid derivative group. Specifically, -COOA (A
Is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms,
A fluoroalkyl group, an alkali metal, ammonium,
Or substituted ammonium) or -COB (B is a fluorine atom or a chlorine atom). Preferred as Y is -COOCH 3. In the present invention, since the fluoropolymer has the group represented by Y, a crosslinked fluoropolymer can be produced by the method described below.
【００１３】本発明の方法における含フッ素重合体は式
（１）で表される単位７０〜９９．９モル％、式（２）
で表される単位を０．１〜２０モル％の割合で含有す
る。式（２）で表される単位が少なすぎると後述の方法
により処理しても架橋含フッ素重合体を得にくい。ま
た、多すぎると含フッ素重合体の融点が低下し、高温で
の機械特性が劣る、などの欠点が生じる。The fluorine-containing polymer in the method of the present invention comprises 70 to 99.9 mol% of a unit represented by the formula (1),
Is contained at a ratio of 0.1 to 20 mol%. If the amount of the unit represented by the formula (2) is too small, it is difficult to obtain a crosslinked fluorinated polymer even when treated by the method described below. On the other hand, if the amount is too large, the melting point of the fluoropolymer is lowered, resulting in poor mechanical properties at high temperatures.
【００１４】また、本発明の方法における含フッ素重合
体は、上述の式（１）で表される単位及び式（２）で表
される単位のみから構成されるものであってもよいし、
式（３）−（ＣＦ2 −ＣＦＺ）−［ただしＺは１価のフ
ッ素置換有機基である］で表される単位であってかつ式
（２）で表される単位以外の単位（以下、単に「式
（３）で表される単位」という）を含むものであっても
よい。Further, the fluoropolymer in the method of the present invention may be composed of only the unit represented by the above formula (1) and the unit represented by the formula (2),
A unit represented by the formula (3)-(CF 2 -CFZ)-[where Z is a monovalent fluorine-substituted organic group] and a unit other than the unit represented by the formula (2) (hereinafter, referred to as “ Simply referred to as “unit represented by formula (3)”.
【００１５】式（３）で表される単位は、溶融成形性の
向上、紫外線照射後の架橋含フッ素重合体の耐衝撃性、
強靭性などの物性向上などに寄与する。ただし、式
（３）で表される単位を過剰に含むと弾性率が低くな
る。したがって、この物性付与のために式（３）で表さ
れる単位を存在させる場合は、好ましくは０．１〜１０
モル％、特に好ましくは０．１〜５モル％存在させる。
この場合、式（３）で表される単位を、１種のみ存在さ
せてもよく、２種以上存在させてもよい。The unit represented by the formula (3) is used to improve the melt moldability, the impact resistance of the crosslinked fluoropolymer after irradiation with ultraviolet light,
It contributes to improvement of physical properties such as toughness. However, when the unit represented by the formula (3) is excessively contained, the elastic modulus becomes low. Therefore, when the unit represented by the formula (3) is present for imparting the physical properties, it is preferably 0.1 to 10
Mol%, particularly preferably 0.1 to 5 mol%.
In this case, only one unit represented by the formula (3) may be present, or two or more units may be present.
【００１６】なお、含フッ素重合体が式（１）で表され
る単位と式（２）で表される単位とのみから構成される
ものである場合には、含フッ素重合体は式（１）で表さ
れる単位を８０〜９９．９モル％、式（２）で表される
単位を０．１〜２０モル％の割合で含有するものが好ま
しい。When the fluoropolymer is composed of only the unit represented by the formula (1) and the unit represented by the formula (2), the fluoropolymer is represented by the formula (1) )) And 80 to 99.9 mol% of the unit represented by the formula (2), and 0.1 to 20 mol% of the unit represented by the formula (2).
【００１７】式（３）におけるＺは、パーフルオロアル
キル基又はパーフルオロアルコキシ基であることが耐熱
性、耐薬品性などの面で好ましい。特に、含フッ素重合
体及び架橋含フッ素重合体の物性の点から、Ｚは炭素数
１〜１０のものが好ましい。In the formula (3), Z is preferably a perfluoroalkyl group or a perfluoroalkoxy group in terms of heat resistance and chemical resistance. Particularly, from the viewpoint of the physical properties of the fluoropolymer and the crosslinked fluoropolymer, Z preferably has 1 to 10 carbon atoms.
【００１８】また、この含フッ素重合体は、式（１’）
ＣＦ2 ＝ＣＦＸ［Ｘは前述と同じ］で表される単量体
（以下、単量体（１’）という）、式（２’）ＣＦ2 ＝
ＣＦＯＲf Ｙ［Ｒf 、Ｙは前述と同じ］で表される単量
体（以下、単量体（２’）という）及び必要により式
（３’）ＣＦ2 ＝ＣＦＺ［Ｚは前述と同じ］で表される
単量体であって単量体（２’）以外の単量体（以下、単
量体（３’）という）を重合開始源の存在下に共重合す
ることによって得られる。重合開始源としては、電離性
放射線や、有機パーオキシド系重合開始剤、酸化還元系
重合開始剤などの重合開始剤などが採用される。The fluorine-containing polymer has the formula (1 ′)
CF 2 = CFX [X are as defined above] monomer represented by (hereinafter, the monomer ( 'hereinafter), the formula (2 1)') CF 2 =
A monomer represented by CFOR f Y [R f , Y is the same as described above] (hereinafter referred to as monomer (2 ′)) and, if necessary, a formula (3 ′) CF 2 = CFZ [Z is the same as that described above; Obtained by copolymerizing a monomer other than the monomer (2 ′) (hereinafter, referred to as monomer (3 ′)) in the presence of a polymerization initiation source . As the polymerization initiation source, ionizing radiation, a polymerization initiator such as an organic peroxide-based polymerization initiator, a redox-based polymerization initiator, or the like is employed.
【００１９】ここで重合開始剤としてはラジカル重合開
始剤が好ましく、例えばビス（フルオロアシル）パーオ
キシド類、ビス（クロロフルオロアシル）パーオキシド
類、ジアルキルパーオキシジカーボネート類、ジアシル
パーオキシド類、パーオキシエステル類、過硫酸塩類な
どが挙げられる。The polymerization initiator is preferably a radical polymerization initiator, for example, bis (fluoroacyl) peroxides, bis (chlorofluoroacyl) peroxides, dialkylperoxydicarbonates, diacyl peroxides, peroxyesters And persulfates.
【００２０】重合媒体としては、溶液重合では、ヒドロ
クロロフルオロカーボン類、ヒドロフルオロカーボン
類、パーフルオロカーボン類、ｔ−ブタノール、などが
挙げられ、懸濁重合、乳化重合では水又は水と溶媒との
混合媒体が用いられる。重合温度は０〜１００℃、重合
圧力は０．５〜３０ｋｇ／ｃｍ2 Ｇの範囲から選択でき
る。Examples of the polymerization medium include hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, and t-butanol in solution polymerization, and water or a mixed medium of water and a solvent in suspension polymerization and emulsion polymerization. Is used. The polymerization temperature can be selected from 0 to 100 ° C, and the polymerization pressure can be selected from the range of 0.5 to 30 kg / cm 2 G.
【００２１】重合反応は、例えば撹拌機付きオートクレ
ーブに重合媒体と単量体（２’）、及び必要により単量
体（３’）、分子量調節剤をまず仕込み、必要量の単量
体（１’）を圧入し、重合開始剤を加えて重合を開始す
る。重合の進行とともに圧力が低下するので、圧力の低
下を補うように単量体（１’）を追加圧入し、目的量の
重合体が生成するまで重合を続ける。重合終了後は未反
応モノマーを放出後、重合体を洗浄、乾燥する。In the polymerization reaction, for example, a polymerization medium, a monomer (2 ′), and if necessary, a monomer (3 ′) and a molecular weight regulator are first charged into an autoclave equipped with a stirrer, and a required amount of the monomer (1) is added. ') And start polymerization by adding a polymerization initiator. Since the pressure decreases with the progress of the polymerization, the monomer (1 ′) is additionally injected so as to compensate for the decrease in the pressure, and the polymerization is continued until a desired amount of the polymer is produced. After the completion of the polymerization, the unreacted monomer is released, and the polymer is washed and dried.
【００２２】得られた重合体は、重合体の融点以上の温
度に加熱することにより溶融成形できる。なお、含フッ
素重合体の融点は約３００℃である。含フッ素重合体を
成形し、続いて成形体に紫外線を照射することにより架
橋剤の添加なしに重合体を架橋でき、弾性率が高く、融
点以上でも流動しない架橋含フッ素重合体の成形体が得
られる。成形における含フッ素重合体の溶融成形温度
は、３４０〜４００℃の範囲が選定される。被覆基材に
架橋前の粉末状の重合体を粉体塗装した後、塗装面に紫
外線を照射する方法なども可能である。The obtained polymer can be melt-molded by heating to a temperature higher than the melting point of the polymer. The melting point of the fluoropolymer is about 300 ° C. By molding the fluorinated polymer and subsequently irradiating the molded body with ultraviolet rays, the polymer can be crosslinked without the addition of a crosslinking agent, the elastic modulus is high, and the molded article of the crosslinked fluorinated polymer which does not flow even at the melting point or higher is obtained can get. The melt molding temperature of the fluoropolymer in the molding is selected from the range of 340 to 400 ° C. It is also possible to apply a method such as applying a powdery polymer before crosslinking to the coated substrate and then irradiating the coated surface with ultraviolet rays.
【００２３】本発明において、架橋前の含フッ素重合体
はメルトフローレートが０．０１〜１００のものが好ま
しい。メルトフローレートとは含フッ素重合体の融点以
上の温度で測定される押出速度（ｇ／分）である。メル
トフローレートが極めて小さい、すなわち超高分子量の
ものは成形性が極めて低下し、成形材料として適さなく
なり、また、メルトフローレートが極めて大きい、すな
わち、低分子量のものは機械的強度が著しく低下し好ま
しくない。In the present invention, the fluoropolymer before crosslinking preferably has a melt flow rate of 0.01 to 100. The melt flow rate is an extrusion rate (g / min) measured at a temperature equal to or higher than the melting point of the fluoropolymer. An extremely low melt flow rate, that is, an ultra-high molecular weight one has extremely low moldability and is not suitable as a molding material, and an extremely high melt flow rate, that is, a low molecular weight one, has a significantly reduced mechanical strength. Not preferred.
【００２４】含フッ素重合体の融点はセイコー電子製分
析機（ＤＳＣ）を用いて測定した。含フッ素重合体の融
点は約３００℃であり、紫外線照射によって融点はわず
かに数℃上昇するだけである。The melting point of the fluorinated polymer was measured using a Seiko Electronics analyzer (DSC). The melting point of the fluorinated polymer is about 300 ° C., and the melting point rises only a few degrees by UV irradiation.
【００２５】本発明は、上述の含フッ素重合体に紫外線
を照射することが重要である。紫外線照射処理を行うこ
とにより架橋含フッ素重合体が得られる。紫外線照射は
所望の形状に成形した後に行う。In the present invention, it is important that the above-mentioned fluoropolymer is irradiated with ultraviolet rays. By performing the ultraviolet irradiation treatment, a crosslinked fluoropolymer is obtained. Irradiation with ultraviolet light is performed after molding into a desired shape.
【００２６】紫外線の波長は２００〜４５０ｎｍである
ことが好ましいが、この範囲以外の波長を含んでもよ
い。短波長すぎると含フッ素重合体の低分子量化が激し
くなる。より好ましくは３００ｎｍ以上である。また、
波長が長波長すぎると架橋反応は遅くなり、また含フッ
素重合体の発熱が激しく、成形体の形状を保つことが困
難である。The wavelength of the ultraviolet light is preferably from 200 to 450 nm, but may include a wavelength outside this range. If the wavelength is too short, the reduction of the molecular weight of the fluoropolymer becomes severe. It is more preferably at least 300 nm. Also,
If the wavelength is too long, the cross-linking reaction will be slow, and the fluoropolymer will generate too much heat, making it difficult to maintain the shape of the molded article.
【００２７】紫外線照射時における含フッ素重合体の温
度は、室温から含フッ素重合体の融点までの範囲であ
る。温度が低いと架橋反応が遅いため、１００℃以上か
つ含フッ素重合体の融点以下で行うことが好ましい。融
点以上では成形体の形状維持が困難になる。紫外線照射
に要する時間は成形体の形状（特に厚さ）や照射時の温
度などに大きく左右されるが１〜６０分間が好ましく、
例えば１００μｍ厚のフィルムを２００℃で処理する場
合には、約５分間である。また、紫外線照射は窒素ガス
などの不活性ガス中で行ってもよいし、空気中で行って
もよい。作業性の面から空気中で行うことが好ましい。The temperature of the fluoropolymer at the time of ultraviolet irradiation is in the range from room temperature to the melting point of the fluoropolymer. If the temperature is low, the crosslinking reaction is slow, so it is preferable to carry out the reaction at a temperature of 100 ° C. or higher and the melting point of the fluoropolymer or lower. Above the melting point, it is difficult to maintain the shape of the compact. The time required for irradiation with ultraviolet rays largely depends on the shape (particularly the thickness) of the molded body and the temperature at the time of irradiation, but is preferably 1 to 60 minutes,
For example, when a film having a thickness of 100 μm is processed at 200 ° C., it takes about 5 minutes. The ultraviolet irradiation may be performed in an inert gas such as a nitrogen gas, or may be performed in the air. It is preferable to perform in air from the viewpoint of workability.
【００２８】[0028]
【実施例】含フッ素重合体のメルトフローレート、融
点、組成を以下の方法により測定した。 ［メルトフローレート］メルトインデクサーを用い、含
フッ素重合体を内径９．５ｍｍのシリンダに入れ、３８
０℃で５分間保持した後、その温度で５ｋｇのピストン
荷重下に内径２．１ｍｍ、長さ８．０ｍｍのオリフィス
を通して押出し、このときの押出速度（ｇ／分）をメル
トフローレートとした。 ［融点］セイコー電子製分析機（ＤＳＣ）を用い、試料
１０ｍｇをアルミニウムパンに入れ、室温より毎分１０
℃で昇温し、融解吸熱ピーク温度を融点とした。EXAMPLES The melt flow rate, melting point and composition of the fluoropolymer were measured by the following methods. [Melt flow rate] Using a melt indexer, put the fluoropolymer into a cylinder having an inner diameter of 9.5 mm,
After holding at 0 ° C. for 5 minutes, the material was extruded at that temperature under a 5 kg piston load through an orifice having an inner diameter of 2.1 mm and a length of 8.0 mm, and the extrusion speed (g / min) at this time was defined as a melt flow rate. [Melting point] Using a Seiko Analyzer (DSC), 10 mg of a sample was placed in an aluminum pan, and the temperature was 10 min / min from room temperature.
C. and the melting endothermic peak temperature was taken as the melting point.
【００２９】［組成］含フッ素重合体の約３０μｍ厚の
成形フィルムの赤外吸収スペクトルを測定し以下のよう
に求めた。（ＣＦ2 ＝ＣＦＯ（ＣＦ2 ）3 ＣＯＯＣＨ3
に基づく重合単位）／（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）は２３７０ｃｍ
-1における吸収量の値に対する１８００ｃｍ-1における
吸収量に１．２８を掛けた値との比（重量比）をモル比
に換算し、（パーフルオロ（プロピルビニルエーテル）
に基づく重合単位）／（ＴＦＥに基づく重合単位）につ
いては２３７０ｃｍ-1における吸収量の値に対する９８
５ｃｍ-1における吸収量に０．９５を掛けた値との比
（重量比）をモル比に換算して求めた。[Composition] An infrared absorption spectrum of a molded film of a fluoropolymer having a thickness of about 30 μm was measured and determined as follows. (CF 2 ＣＦCFO (CF 2 ) 3 COOCH 3
Polymerized unit based on styrene / (polymerized unit based on tetrafluoroethylene (hereinafter referred to as TFE)) is 2370 cm
The ratio (weight ratio) of the value of the absorption at 1800 cm -1 to the value of the absorption at -1 multiplied by 1.28 (weight ratio) was converted into a molar ratio, and the ratio was calculated as (perfluoro (propyl vinyl ether)).
(Polymerized units based on TFE) / (polymerized units based on TFE) is 98% of the value of the absorption amount at 2370 cm −1 .
The ratio (weight ratio) to the value obtained by multiplying the absorption amount at 5 cm -1 by 0.95 was determined by converting it to a molar ratio.
【００３０】［例１（実施例）］１リットルの重合槽に
水を４７０ｇ、パーフルオロヘキサンを２９０ｇ、メタ
ノールを１９ｇ、ＣＦ2 ＝ＣＦＯ（ＣＦ2 ）3 ＣＯＯＣ
Ｈ3 を１０．５ｇ、パーフルオロ（プロピルビニルエー
テル）を２３ｇ仕込み、槽内の温度を５０℃とした後に
ＴＦＥを仕込んで槽内の圧力を１３ｋｇ／ｃｍ2 Ｇとし
た。重合開始剤としてビス（パーフルオロブチリル）パ
ーオキシドの０．２５％パーフルオロヘキサン溶液を添
加して重合を開始させた。圧力が一定になるようにＴＦ
Ｅを仕込んだ。重合開始剤溶液は、重合速度が重合中ほ
ぼ一定になるように連続的に仕込み、合計６．５ｃｃ仕
込んだ。重合開始５時間後、後仕込みのＴＦＥの合計が
１２０ｇになった時点で重合を終了した後、得られたス
ラリーを分離、乾燥し１２３ｇの白色の重合体を得た。Example 1 (Example) 470 g of water, 290 g of perfluorohexane, 19 g of methanol, CF 2 ＣＦCFO (CF 2 ) 3 COOC in a 1 liter polymerization tank
10.5 g of H 3 and 23 g of perfluoro (propyl vinyl ether) were charged, the temperature in the tank was set to 50 ° C., and then TFE was charged to adjust the pressure in the tank to 13 kg / cm 2 G. As a polymerization initiator, a 0.25% perfluorohexane solution of bis (perfluorobutyryl) peroxide was added to initiate polymerization. TF so that the pressure is constant
E was charged. The polymerization initiator solution was continuously charged so that the polymerization rate was substantially constant during the polymerization, and a total of 6.5 cc was charged. Five hours after the start of the polymerization, the polymerization was terminated when the total amount of the TFE charged later reached 120 g, and the obtained slurry was separated and dried to obtain 123 g of a white polymer.
【００３１】得られた重合体は、（ＣＦ2 ＝ＣＦＯ（Ｃ
Ｆ2 ）3 ＣＯＯＣＨ3 に基づく重合単位）／（パーフル
オロ（プロピルビニルエーテル）に基づく重合単位）／
（ＴＦＥに基づく重合単位）＝０．４／１．１／９８．
５（モル％）の割合の組成で、メルトフローレートは
２．５ｇ／分で、融点は３００℃であった。The obtained polymer is represented by (CF 2 ＣＦCFO (C
F 2 ) 3 Polymerized units based on COOCH 3 / (polymerized units based on perfluoro (propyl vinyl ether)) /
(Polymerized unit based on TFE) = 0.4 / 1.1 / 98.
With a composition of 5 (mol%), the melt flow rate was 2.5 g / min, and the melting point was 300 ° C.
【００３２】この重合体を３４０℃に加熱した圧縮プレ
スで１００μｍ厚のフィルムに成形した。フィルムの２
００℃における弾性率は０．５×１０9 ｄｙｎ／ｃｍ2
であった。次に、このフィルムに波長が２３０〜４５０
ｎｍの紫外線を２００℃の雰囲気下で５分間照射した。
照射後の２００℃における弾性率は１．１×１０9 ｄｙ
ｎ／ｃｍ2 であり、紫外線照射後のメルトフローレート
は０ｇ／分であった。なお、照射後のフィルムの融点は
３１０℃以下であった。This polymer was formed into a film having a thickness of 100 μm by a compression press heated to 340 ° C. Film 2
The elastic modulus at 00 ° C. is 0.5 × 10 9 dyn / cm 2
Met. Next, a wavelength of 230 to 450 is applied to this film.
Irradiation was performed for 5 minutes in an atmosphere of 200 ° C. with an ultraviolet ray of nm.
The elastic modulus at 200 ° C. after irradiation is 1.1 × 10 9 dy
n / cm 2 , and the melt flow rate after ultraviolet irradiation was 0 g / min. In addition, the melting point of the film after irradiation was 310 ° C. or less.
【００３３】［例２（比較例）］ＣＦ2 ＝ＣＦＯ（ＣＦ
2 ）3 ＣＯＯＣＨ3 を用いず、パーフルオロ（プロピル
ビニルエーテル）を３５ｇ仕込んだ以外は例１と同様に
して重合を行った。得られた重合体は、（パーフルオロ
（プロピルビニルエーテル）に基づく重合単位）／（Ｔ
ＦＥに基づく重合単位）＝１．３／９８．７（モル％）
の割合の組成で、メルトフローレートは２．１ｇ／分で
あり、１００μｍ厚のフィルムの２００℃における弾性
率は０．７×１０9 ｄｙｎ／ｃｍ2 であり、融点は３０
９℃であった。例１と同様に紫外線を照射したが、メル
トフローレート、弾性率、融点に変化はなかった。Example 2 (Comparative Example) CF 2 ＣＦCFO (CF
2 ) Polymerization was carried out in the same manner as in Example 1 except that 35 g of perfluoro (propyl vinyl ether) was used without using 3 COOCH 3 . The polymer obtained was (polymerized units based on perfluoro (propyl vinyl ether)) / (T
(Polymerized unit based on FE) = 1.3 / 98.7 (mol%)
The melt flow rate is 2.1 g / min, the elasticity at 200 ° C. of a 100 μm thick film is 0.7 × 10 9 dyn / cm 2 , and the melting point is 30.
9 ° C. Irradiation with ultraviolet light was carried out in the same manner as in Example 1, but there was no change in the melt flow rate, elastic modulus or melting point.
【００３４】[0034]
【発明の効果】本発明の方法により、弾性率が高く、融
点以上の温度に加熱しても流動しない架橋された含フッ
素共重合体の成形体を簡便に得ることができる。According to the method of the present invention, it is possible to easily obtain a molded article of a crosslinked fluorine-containing copolymer which has a high elastic modulus and does not flow even when heated to a temperature higher than the melting point.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ (Ｃ０８Ｆ 214/26 216:14） ──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. 6 Identification code FI (C08F 214/26 216: 14)
Claims (6)
Ｘはフッ素原子又は塩素原子である］で表される単位が
７０〜９９．９モル％、式（２）−（ＣＦ2 −ＣＦＯＲ
f Ｙ）−［ただしＲf は２価のフッ素置換有機基、Ｙは
カルボン酸基又はカルボン酸誘導体基である］で表され
る単位が０．１〜２０モル％、及び式（３）−（ＣＦ2
−ＣＦＺ）−［ただしＺは１価のフッ素置換有機基であ
る］で表される単位［ただし、式（２）で表される単位
を除く］が０又は１０モル％以下の割合である含フッ素
重合体を成形し、その成形体に紫外線を照射して得られ
る架橋含フッ素重合体の成形体。A unit represented by the formula (1)-(CF 2 -CFX)-[where X is a fluorine atom or a chlorine atom] is 70 to 99.9 mol%, and the formula (2)-(CF 2- CFOR
f Y)-wherein R f is a divalent fluorine-substituted organic group, Y is a carboxylic acid group or a carboxylic acid derivative group, and 0.1 to 20 mol% of a unit represented by the formula (3)- (CF 2
—CFZ) — [where Z is a monovalent fluorine-substituted organic group] (provided that the unit represented by the formula (2) is excluded) is 0 or 10 mol% or less. A molded article of a crosslinked fluoropolymer obtained by molding a fluoropolymer and irradiating the molded article with ultraviolet rays.
下の温度で、１〜６０分間紫外線を照射して得られる請
求項１記載の架橋含フッ素重合体の成形体。2. The cross-linked fluoropolymer molded article according to claim 1, which is obtained by irradiating ultraviolet rays at a temperature of 100 ° C. or higher and a melting point of the fluoropolymer for 1 to 60 minutes.
して得られる請求項１又は２記載の架橋含フッ素重合体
の成形体。3. The crosslinked fluoropolymer molded article according to claim 1, which is obtained by irradiating an ultraviolet ray having a wavelength of 200 to 450 nm.
Ｘはフッ素原子又は塩素原子である］で表される単位が
７０〜９９．９モル％、式（２）−（ＣＦ2 −ＣＦＯＲ
f Ｙ）−［ただしＲf は２価のフッ素置換有機基、Ｙは
カルボン酸基又はカルボン酸誘導体基である］で表され
る単位が０．１〜２０モル％、及び式（３）−（ＣＦ2
−ＣＦＺ）−［ただしＺは１価のフッ素置換有機基であ
る］で表される単位［ただし、式（２）で表される単位
を除く］が０又は１０モル％以下の割合である含フッ素
重合体を成形し、その成形体に紫外線を照射することを
特徴とする架橋含フッ素重合体の成形体の製造方法。4. A unit represented by the formula (1)-(CF 2 -CFX)-[where X is a fluorine atom or a chlorine atom] is 70 to 99.9 mol%, and the formula (2)-(CF 2- CFOR
f Y)-wherein R f is a divalent fluorine-substituted organic group, Y is a carboxylic acid group or a carboxylic acid derivative group, and 0.1 to 20 mol% of a unit represented by the formula (3)- (CF 2
—CFZ) — [where Z is a monovalent fluorine-substituted organic group] (provided that the unit represented by the formula (2) is excluded) is 0 or 10 mol% or less. A method for producing a molded article of a crosslinked fluoropolymer, comprising molding a fluoropolymer and irradiating the molded article with ultraviolet rays.
下の温度で、１〜６０分間紫外線を照射する請求項４記
載の製造方法。5. The method according to claim 4, wherein the ultraviolet ray is irradiated for 1 to 60 minutes at a temperature of 100 ° C. or higher and lower than the melting point of the fluoropolymer.
する請求項４又は５記載の製造方法。6. The method according to claim 4, wherein ultraviolet light having a wavelength of 200 to 450 nm is irradiated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10106694A JPH11302394A (en) | 1998-04-16 | 1998-04-16 | Molding product of crosslinked fluorine-containing polymer and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10106694A JPH11302394A (en) | 1998-04-16 | 1998-04-16 | Molding product of crosslinked fluorine-containing polymer and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11302394A true JPH11302394A (en) | 1999-11-02 |
Family
ID=14440151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10106694A Pending JPH11302394A (en) | 1998-04-16 | 1998-04-16 | Molding product of crosslinked fluorine-containing polymer and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11302394A (en) |
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| JPWO2015098773A1 (en) * | 2013-12-26 | 2017-03-23 | 旭硝子株式会社 | Method for producing fluorine-containing crosslinked product and use thereof |
| US10214619B2 (en) | 2013-12-26 | 2019-02-26 | AGC Inc. | Process for producing fluorinated crosslinked product and use thereof |
| WO2018159307A1 (en) * | 2017-03-01 | 2018-09-07 | Ａｇｃ株式会社 | Fluoropolymer, method for producing cured product thereof, and light-emitting device |
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| CN110382615B (en) * | 2017-03-06 | 2021-12-03 | Ａｇｃ株式会社 | Curable composition, coating material, electric wire, and resin article |
| US11248117B2 (en) | 2017-07-20 | 2022-02-15 | 3M Innovative Properties Company | Fluorinated elastomers cured by actinic radiation and methods thereof |
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