JP2000212365A - Fluorine-containing copolymer composition - Google Patents
Fluorine-containing copolymer compositionInfo
- Publication number
- JP2000212365A JP2000212365A JP11020378A JP2037899A JP2000212365A JP 2000212365 A JP2000212365 A JP 2000212365A JP 11020378 A JP11020378 A JP 11020378A JP 2037899 A JP2037899 A JP 2037899A JP 2000212365 A JP2000212365 A JP 2000212365A
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- Prior art keywords
- poise
- polymerization
- copolymer
- melt viscosity
- ethylene
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は成形性を改良した含
フッ素重合体組成物に関し、詳しくは速い速度で成形し
ても良好な外観を得ることのできる含フッ素重合体組成
物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluoropolymer composition having improved moldability, and more particularly to a fluoropolymer composition capable of obtaining a good appearance even when molded at a high speed.
【０００２】[0002]
【従来の技術】エチレン／テトラフルオロエチレン共重
合体（以下、ＥＴＦＥという）は耐熱性、耐薬品性、耐
溶剤性等が優れた高分子材料であることから、その特徴
を生かして種々の用途に用いられている。特に溶融成形
が可能であるため押出成形、射出成形、圧縮成形、粉体
塗装などの種々の成形方法を利用して、チューブ、被覆
電線、フィルム、ポンプケーシング、ライニングなどに
多く用いられている。2. Description of the Related Art Ethylene / tetrafluoroethylene copolymer (hereinafter referred to as ETFE) is a polymer material having excellent heat resistance, chemical resistance, solvent resistance, etc. It is used for In particular, since melt molding is possible, it is widely used for tubes, coated electric wires, films, pump casings, linings and the like by utilizing various molding methods such as extrusion molding, injection molding, compression molding, and powder coating.
【０００３】一般に、溶融成形可能な樹脂を押出成形す
る際、成形速度をある値以上に上げると成形物の表面に
凹凸の肌荒れが生じる。成形速度は、成形時に樹脂にか
かる剪断速度に対応する。すなわち、成形時に肌荒れが
生じる限界の剪断速度（臨界剪断速度）が大きい樹脂ほ
ど成形速度を上げることができ、その樹脂は成形性が優
れる。臨界剪断速度を上げるためには、一般的に重合体
の重合度を下げて溶融粘度を小さくする方法があるが、
重合度を下げると機械強度が低下する欠点がある。Generally, when extruding a resin which can be melt-molded, if the molding speed is increased to a certain value or more, the surface of the molded product becomes rough. The molding speed corresponds to the shear rate applied to the resin during molding. That is, a resin having a higher critical shear rate (critical shear rate) at which skin roughness occurs during molding can be increased in molding speed, and the resin has excellent moldability. In order to increase the critical shear rate, there is generally a method of reducing the degree of polymerization of the polymer to reduce the melt viscosity,
When the degree of polymerization is reduced, there is a disadvantage that the mechanical strength is reduced.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、成形
物の機械強度を低下させることなく優れた加工性を有す
る含フッ素共重合体組成物を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a fluorine-containing copolymer composition having excellent workability without lowering the mechanical strength of a molded product.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、ＥＴＦＥに高
い溶融粘度を有する含フッ素共重合体を含有させること
により、機械強度を低下させることなく優れた成形加工
性を有する含フッ素重合体組成物が得られることを見い
だし、その知見に基づいて本発明を完成させるにいたっ
た。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, by adding ETFE to a fluorine-containing copolymer having a high melt viscosity, the mechanical strength was improved. The present inventors have found that a fluoropolymer composition having excellent moldability can be obtained without lowering it, and the present invention has been completed based on the findings.
【０００６】すなわち、本発明は、２９７℃における溶
融粘度が５×１０3ポアズ以上１×１０5ポアズ未満であ
るエチレン／テトラフルオロエチレン共重合体（Ａ）
と、２９７℃における溶融粘度が１×１０5ポアズ以上
５×１０6ポアズ以下である含フッ素重合体（Ｂ）とを
含み、含フッ素共重合体（Ｂ）の含有量がエチレン／テ
トラフルオロエチレン共重合体（Ａ）に対し０．１〜３
０重量％であることを特徴とする含フッ素重合体組成物
を提供する。本発明は、上記含フッ素重合体組成物にお
いて、含フッ素重合体（Ｂ）がＥＴＦＥである含フッ素
重合体組成物を提供する。That is, the present invention relates to an ethylene / tetrafluoroethylene copolymer (A) having a melt viscosity at 297 ° C. of 5 × 10 3 poise or more and less than 1 × 10 5 poise.
And a fluoropolymer (B) having a melt viscosity at 297 ° C. of 1 × 10 5 poise to 5 × 10 6 poise, wherein the content of the fluorocopolymer (B) is ethylene / tetrafluoroethylene. 0.1 to 3 based on the copolymer (A)
A fluorine-containing polymer composition characterized by being 0% by weight. The present invention provides the above-mentioned fluoropolymer composition, wherein the fluoropolymer (B) is ETFE.
【０００７】[0007]
【発明の実施の形態】ＥＴＦＥ（Ａ）は、エチレンに基
づく重合単位とテトラフルオロエチレンに基づく重合単
位を有するものであり、好適な具体例としては、エチレ
ンに基づく重合単位／テトラフルオロエチレンに基づく
重合単位のモル比が２０／８０〜８０／２０であり、必
要に応じこれらと共重合可能な一つ以上のビニルモノマ
ーに基づく重合単位をエチレンに基づく重合単位とテト
ラフルオロエチレンに基づく重合単位の合計に対して
０．０１〜１０モル％を含む共重合体が挙げられる。DESCRIPTION OF THE PREFERRED EMBODIMENTS ETFE (A) has a polymerized unit based on ethylene and a polymerized unit based on tetrafluoroethylene, and a preferred example is a polymerized unit based on ethylene / based on tetrafluoroethylene. The molar ratio of the polymerized units is from 20/80 to 80/20, and if necessary, a polymerized unit based on one or more vinyl monomers copolymerizable therewith may be a polymerized unit based on ethylene and a polymerized unit based on tetrafluoroethylene. Copolymers containing 0.01 to 10 mol% based on the total are exemplified.
【０００８】かかるビニルモノマーとしてはＣＦ2＝Ｃ
ＦＲf（Ｒfは炭素数が１〜８のポリフルオロアルキル基
であり、好ましくはパーフルオロアルキル基である）、
ＣＦ 2＝ＣＨＲf、ＣＨ2＝ＣＨＲf、ＣＨ2＝ＣＦＲfなど
のフルオロアルキルエチレン類、ＣＦ2＝ＣＦＯＲf、Ｃ
Ｆ2＝ＣＦＯ（ＣＦ2）nＣ（Ｏ）Ｘ（Ｘは水素原子、水
酸基、ハロゲン原子、またはアルコキシル基）などのフ
ルオロアルキルビニルエーテル類などが例示される。[0008] Such vinyl monomers include CFTwo= C
FRf(RfIs a polyfluoroalkyl group having 1 to 8 carbon atoms
And preferably a perfluoroalkyl group),
CF Two= CHRf, CHTwo= CHRf, CHTwo= CFRfSuch
Fluoroalkyl ethylenes, CFTwo= CFORf, C
FTwo= CFO (CFTwo)nC (O) X (X is a hydrogen atom, water
Acid group, halogen atom or alkoxyl group)
Examples include fluoroalkyl vinyl ethers.
【０００９】ＥＴＦＥ（Ａ）の溶融粘度は、２９７℃で
５×１０3ポアズ以上１×１０5ポアズ未満であり、好ま
しくは１×１０4ポアズ以上５×１０4ポアズ未満であ
る。溶融粘度が高すぎるとＥＴＦＥ （Ａ）に含フッ素
共重合体（Ｂ）を添加した組成物の溶融粘度も高くな
り、成形性が悪くなる。また溶融粘度が低すぎるとＥＴ
ＦＥ （Ａ）に含フッ素共重合体（Ｂ）を添加した組成
物の溶融粘度も小さくなり機械強度が低下する。The melt viscosity of ETFE (A) at 297 ° C. is 5 × 10 3 poise or more and less than 1 × 10 5 poise, preferably 1 × 10 4 poise or more and less than 5 × 10 4 poise. If the melt viscosity is too high, the composition obtained by adding the fluorinated copolymer (B) to the ETFE (A) also has a high melt viscosity, resulting in poor moldability. If the melt viscosity is too low, ET
The composition obtained by adding the fluorinated copolymer (B) to the FE (A) also has a low melt viscosity and a low mechanical strength.
【００１０】含フッ素共重合体（Ｂ）は成形性改良のた
めに添加するものであり、その溶融粘度は２９７℃で１
×１０5ポアズ以上５×１０6ポアズ以下であり、好まし
くは５×１０5ポアズ以上２×１０6ポアズ以下である。
粘度が高すぎるとＥＴＦＥ（Ａ）への混合が困難であ
り、粘度が低すぎると成形性改良に効果が少ない。含フ
ッ素共重合体（Ｂ）の好ましい例としては、ＥＴＦＥ、
プロピレン／テトラフルオロエチレン共重合体などが挙
げられる。The fluorinated copolymer (B) is added for improving the moldability, and has a melt viscosity of 1 at 297 ° C.
It is not less than × 10 5 poise and not more than 5 × 10 6 poise, preferably not less than 5 × 10 5 poise and not more than 2 × 10 6 poise.
If the viscosity is too high, mixing with ETFE (A) is difficult, and if the viscosity is too low, there is little effect on improving moldability. Preferred examples of the fluorine-containing copolymer (B) include ETFE,
A propylene / tetrafluoroethylene copolymer is exemplified.
【００１１】含フッ素共重合体（Ｂ）としてのＥＴＦＥ
は、エチレンに基づく重合単位とテトラフルオロエチレ
ンに基づく重合単位を有するものであり、好適な具体例
としては、エチレンに基づく重合単位／テトラフルオロ
エチレンに基づく重合単位のモル比が２０／８０〜８０
／２０であり、必要に応じこれらと共重合可能な一つ以
上のビニルモノマーに基づく重合単位をエチレンに基づ
く重合単位とテトラフルオロエチレンに基づく重合単位
の合計に対して０．０１〜２０モル％を含む共重合体が
挙げられる。ETFE as fluorinated copolymer (B)
Has a polymerization unit based on ethylene and a polymerization unit based on tetrafluoroethylene. As a preferred specific example, the molar ratio of the polymerization unit based on ethylene / the polymerization unit based on tetrafluoroethylene is 20/80 to 80.
/ 20, and if necessary, the polymerization unit based on one or more vinyl monomers copolymerizable therewith is used in an amount of 0.01 to 20 mol% based on the total of the polymerization unit based on ethylene and the polymerization unit based on tetrafluoroethylene. And a copolymer containing
【００１２】含フッ素共重合体（Ｂ）としてのプロピレ
ン／テトラフルオロエチレン共重合体は、プロピレンに
基づく重合単位とテトラフルオロエチレンに基づく重合
単位を有するものであり、好適な具体例としては、プロ
ピレンに基づく重合単位／テトラフルオロエチレンに基
づく重合単位のモル比が２０／８０〜８０／２０であ
り、必要に応じこれらと共重合可能なビニルモノマーに
基づく重合単位をプロピレンに基づく重合単位とテトラ
フルオロエチレンに基づく重合単位の合計に対して０．
０１〜２０モル％を含む共重合体が挙げられる。含フッ
素共重合体（Ｂ）としては、 ＥＴＦＥ（以下、 ＥＴＦ
Ｅ（Ｂ）という）が好ましい。The propylene / tetrafluoroethylene copolymer as the fluorine-containing copolymer (B) has a polymerized unit based on propylene and a polymerized unit based on tetrafluoroethylene. The molar ratio of the polymerization unit based on styrene / the polymerization unit based on tetrafluoroethylene is 20/80 to 80/20. If necessary, the polymerization unit based on a vinyl monomer copolymerizable therewith may be replaced with a polymerization unit based on propylene and a tetrafluoroethylene. 0.1 based on the total of polymerized units based on ethylene.
Copolymers containing from 01 to 20 mol% are exemplified. As the fluorinated copolymer (B), ETFE (hereinafter, ETF)
E (B)) is preferred.
【００１３】上記の共重合可能なビニルモノマーとして
は、フッ化ビニリデン、ヘキサフルオロプロピレン等の
オレフィン類、ＣＦ2＝ＣＦＲf、ＣＦ2＝ＣＨＲf、ＣＨ
2＝ＣＨＲf、ＣＨ2＝ＣＦＲfなどのフルオロアルキルエ
チレン類、ＣＦ2＝ＣＦＯＲ f、ＣＦ2＝ＣＦＯ（ＣＦ2）
nＣ（Ｏ）Ｘ（Ｘは水素原子、水酸基、ハロゲン原子、
またはアルコキル基）などのフルオロアルキルビニルエ
ーテル類、酢酸ビニルなどのカルボン酸ビニルエステル
類、アクリル酸メチル、メタアクリル酸メチルなどのア
クリル酸エステル類やメタクリル酸エステル類、メチル
ビニルエーテルなどのビニルエーテル類などが例示され
る。As the above copolymerizable vinyl monomer,
For vinylidene fluoride, hexafluoropropylene, etc.
Olefins, CFTwo= CFRf, CFTwo= CHRf, CH
Two= CHRf, CHTwo= CFRfSuch as fluoroalkyl
Tylenes, CFTwo= CFOR f, CFTwo= CFO (CFTwo)
nC (O) X (X is a hydrogen atom, a hydroxyl group, a halogen atom,
Or an alkoxy group)
-Carboxylic acid esters such as ethers and vinyl acetate
, Methyl acrylate, methyl methacrylate, etc.
Acrylates, methacrylates, methyl
Examples include vinyl ethers such as vinyl ether.
You.
【００１４】本発明のＥＴＦＥ（Ａ）および含フッ素重
合体（Ｂ）の製造にあたり、重合方法は特に限定され
ず、乳化重合、懸濁重合、溶液重合など種々の方法で行
うことができる。目的とする溶融粘度を有する共重合体
は、重合に用いる連鎖移動剤の濃度を調節することや重
合圧力を調節することにより得られる。連鎖移動剤とし
てはヘキサン、シクロヘキサンなどの炭化水素類、メタ
ノール、エタノールなどのアルコール類、トリクロロフ
ルオロメタン、ジクロロペンタフルオロプロパンなどの
ハロゲン化炭化水素類などが挙げられる。In producing the ETFE (A) and the fluoropolymer (B) of the present invention, the polymerization method is not particularly limited, and various methods such as emulsion polymerization, suspension polymerization and solution polymerization can be used. The copolymer having the desired melt viscosity can be obtained by adjusting the concentration of the chain transfer agent used for the polymerization or by adjusting the polymerization pressure. Examples of the chain transfer agent include hydrocarbons such as hexane and cyclohexane, alcohols such as methanol and ethanol, and halogenated hydrocarbons such as trichlorofluoromethane and dichloropentafluoropropane.
【００１５】本発明の含フッ素重合体組成物は、通常Ｅ
ＴＦＥ（Ａ）と含フッ押出成形素重合体（Ｂ）を混合す
ることにより得られる。その混合方法は特に限定され
ず、ＥＴＦＥ（Ａ）を溶融し、そこに含フッ素重合体
（Ｂ）を撹拌しながら混合していく方法、単軸または２
軸の混練押出機にＥＴＦＥ（Ａ）と含フッ素重合体
（Ｂ）を同時に供給し混練する方法などが挙げられる
が、簡便さから混練押出機により混合する方法が好まし
い。The fluorine-containing polymer composition of the present invention usually comprises
It is obtained by mixing TFE (A) and a fluorine-containing extruded polymer (B). The mixing method is not particularly limited, and is a method in which ETFE (A) is melted, and the fluoropolymer (B) is mixed therein with stirring, uniaxial or biaxial.
A method in which ETFE (A) and the fluorinated polymer (B) are simultaneously supplied and kneaded to a kneading extruder having a shaft may be mentioned, but a method of mixing with a kneading extruder is preferred for simplicity.
【００１６】混合前のＥＴＦＥ（Ａ）および含フッ素重
合体（Ｂ）の形態も特に限定されず、ペレット、ビー
ズ、粉末、クラム等が用いられる。製造の簡便さから、
好ましくは平均粒径１〜３ｍｍのビーズ状のＥＴＦＥ
（Ａ）と好ましくは平均粒径１〜５ｍｍのクラム状の含
フッ素重合体（Ｂ）を混合し、混練押出機に投入し溶融
混練することが好ましい。ビーズは溶液重合で得られる
重合体を造粒して得られる。クラムは乳化重合で得られ
る重合体を凝集、洗浄して得られる。The forms of the ETFE (A) and the fluoropolymer (B) before mixing are not particularly limited, and pellets, beads, powders, crumbs and the like are used. Because of the ease of manufacture,
ETFE in the form of beads, preferably having an average particle size of 1 to 3 mm
(A) and preferably a crumb-shaped fluoropolymer (B) having an average particle size of 1 to 5 mm are mixed, and the mixture is charged into a kneading extruder and melt-kneaded. Beads are obtained by granulating a polymer obtained by solution polymerization. Crumb is obtained by coagulating and washing a polymer obtained by emulsion polymerization.
【００１７】本発明の含フッ素重合体組成物における含
フッ素重合体（Ｂ）の含有量は、ＥＴＦＥ（Ａ）に対し
て０．１〜３０重量％であり、好ましくは１〜２０重量
％である。含有量が少なすぎると成形性を改良する効果
がなく、また多すぎると混合物全体の溶融粘度が上昇し
すぎ、成形性が低下する。The content of the fluoropolymer (B) in the fluoropolymer composition of the present invention is from 0.1 to 30% by weight, preferably from 1 to 20% by weight, based on the ETFE (A). is there. If the content is too small, there is no effect of improving the moldability, and if it is too large, the melt viscosity of the whole mixture will be too high, and the moldability will be reduced.
【００１８】本発明の含フッ素重合体組成物には、その
性能を損なわない範囲において、充填剤、顔料、紫外線
吸収剤、光安定剤、酸化防止剤、その他の用途に応じて
任意の添加剤などの各種添加剤を配合してもよい。充填
剤としては、無機質粉末、ガラス繊維、炭素繊維、金属
酸化物、カーボンなどの種々の充填剤が挙げられる。The fluoropolymer composition of the present invention may contain any additives, depending on the use, such as fillers, pigments, ultraviolet absorbers, light stabilizers, antioxidants, and the like, as long as the performance is not impaired. Various additives such as the above may be blended. Examples of the filler include various fillers such as inorganic powder, glass fiber, carbon fiber, metal oxide, and carbon.
【００１９】本発明の含フッ素重合体組成物は、押出成
形、射出成形、圧縮成形、インフレーション成形、金型
などを用いるトランスファー成形などの種々の成形方法
により成形できる。本発明の含フッ素重合体組成物を使
用して得られる成形物としては、たとえばチューブ、被
覆電線、フィルム、ポンプケーシングなどが挙げられ
る。The fluoropolymer composition of the present invention can be molded by various molding methods such as extrusion molding, injection molding, compression molding, inflation molding, and transfer molding using a mold. Examples of the molded product obtained by using the fluoropolymer composition of the present invention include a tube, a covered electric wire, a film, a pump casing, and the like.
【００２０】[0020]
【実施例】次に、本発明を実施例により具体的に説明す
る。なお、これらの例は本発明を何ら限定するものでな
い。実施例における試験方法は下記の方法により行っ
た。Next, the present invention will be described in detail with reference to examples. Note that these examples do not limit the present invention in any way. The test method in the examples was performed by the following method.
【００２１】[溶融粘度]高化式フローテスター（株式会
社島津製作所製）を用いて、共重合体を２９７℃で５分
保持した後、７ｋｇ荷重で内径２．１ｍｍ、長さ８ｍｍ
のオリフィスを通して押出したときの容量流速Ｑ1（ｍ
ｍ3／ｓ）を測定し、４０５４００／Ｑ1の値を溶融粘度
（ポアズ）とする。[Melt Viscosity] Using a Koka type flow tester (manufactured by Shimadzu Corporation), the copolymer was held at 297 ° C. for 5 minutes, and then loaded with a 7 kg load, having an inner diameter of 2.1 mm and a length of 8 mm.
Flow rate Q 1 (m
m 3 / s), and the value of 405,400 / Q 1 is defined as the melt viscosity (Poise).
【００２２】[臨界剪断速度]高化式フローテスター（株
式会社島津製作所製）を用いて、共重合体を３２５℃で
５分保持した後、種々の荷重で内径２．１ｍｍ、長さ８
ｍｍのオリフィスを通して押出したときの容量流速Ｑ2
（ｍｍ3／ｓ）を測定し、また押出成形物を観察し、肌
荒れの発生しない限界の剪断速度を臨界剪断速度とす
る。剪断速度（１／ｓ）は容量流速Ｑ2（ｍｍ3／ｓ）×
１．１０の値より求められる。[Critical shear rate] Using a Koka type flow tester (manufactured by Shimadzu Corporation), the copolymer was kept at 325 ° C. for 5 minutes, and then loaded with various loads to an inner diameter of 2.1 mm and a length of 8
volume flow rate Q 2 when extruded through an orifice
(Mm 3 / s) is measured, and the extruded product is observed. The critical shear rate at which no roughening occurs is defined as the critical shear rate. The shear rate (1 / s) is the volume flow rate Q 2 (mm 3 / s) ×
It is obtained from the value of 1.10.
【００２３】[成形時の肌荒れ]剪断速度を１５０（１／
ｓ）にて押出成形を行い、得られたストランドの表面を
観察し、肌荒れを評価した。[Surface roughening during molding] A shear rate of 150 (1 /
Extrusion molding was performed in s), the surface of the obtained strand was observed, and the surface roughness was evaluated.
【００２４】［引張強度］ＡＳＴＭ Ｄ３１５９記載の
方法により測定した。厚み１．５ｍｍのシートをプレス
成形して作成し、規定の形状に打ち抜き引張試験用サン
プルを引張速度５０ｍｍ／分で行った。[Tensile strength] Measured according to the method described in ASTM D3159. A sheet having a thickness of 1.5 mm was prepared by press molding, punched into a prescribed shape, and a sample for a tensile test was performed at a tensile speed of 50 mm / min.
【００２５】（重合例１）内容積１．３リットルのステ
ンレス製反応容器を脱気し、１０５０ｇのＣ6Ｆ1 4、３
１４ｇのＣＣｌＦ2ＣＦ2ＣＨＣｌＦ（以下、ＨＣＦＣ２
２５ｃｂという）、５ｇのＣＨ2＝ＣＨ−Ｃ4Ｆ9、１６
０ｇのテトラフルオロエチレン、１４ｇのエチレンを仕
込んだ。温度を６６℃に保持して、重合開始剤としてｔ
−ブチルパーオキシピバレートの１ｗｔ％Ｃ6Ｆ14溶液
を５ｃｃ仕込み、反応を開始させた。反応中、系内のガ
ス組成を一定に保つようにテトラフルオロエチレンとエ
チレンを導入し、反応圧力を１６．０ｋｇ／ｃｍ2 に保
持した。[0025] (Polymerization Example 1) was degassed stainless steel reaction vessel having an inner volume of 1.3 liters, C 6 F 1 4 of 1050 g, 3
14 g of CCLF 2 CF 2 CHClF (hereinafter, HCFC2
25 cb), 5 g CH 2 ＝ CH—C 4 F 9 , 16
0 g of tetrafluoroethylene and 14 g of ethylene were charged. While maintaining the temperature at 66 ° C., t
5 cc of a 1 wt% C 6 F 14 solution of -butyl peroxypivalate was charged to start the reaction. During the reaction, tetrafluoroethylene and ethylene were introduced so as to keep the gas composition in the system constant, and the reaction pressure was maintained at 16.0 kg / cm 2 .
【００２６】テトラフルオロエチレンとエチレンの導入
量が合計１００ｇになった時点で反応を終了させ、生成
した共重合体を造粒して１０６ｇの白色ＥＴＦＥ（ａ
１）のビーズ（平均粒径：２．５ｍｍ）を得た。The reaction was terminated when the total amount of tetrafluoroethylene and ethylene introduced reached 100 g, and the resulting copolymer was granulated to obtain 106 g of white ETFE (a
1) Beads (average particle size: 2.5 mm) were obtained.
【００２７】該共重合体の組成は、テトラフルオロエチ
レンに基づく重合単位５０．５モル％、エチレンに基づ
く重合単位４８．５モル％、ＣＨ2＝ＣＨ−Ｃ4Ｆ9に基
づく重合単位１．０モル％であり、溶融粘度は４．１８
×１０4ポアズ、臨界剪断速度は１４３（１／ｓ）であ
った。The composition of the copolymer is as follows: 50.5 mol% of a polymerization unit based on tetrafluoroethylene, 48.5 mol% of a polymerization unit based on ethylene, and a polymerization unit based on CH 2 ＣＨCH—C 4 F 9 . 0 mol% and a melt viscosity of 4.18.
× 10 4 poise, critical shear rate was 143 (1 / s).
【００２８】（重合例２）Ｃ6Ｆ14を１３１０ｇ、ＨＣ
ＦＣ２２５ｃｂを５５ｇ仕込み、重合開始剤としてｔ−
ブチルパーオキシピバレートの１ｗｔ％ Ｃ6Ｆ14溶液を
１．７ｃｃ仕込む以外は重合例１と同様に重合を行い、
造粒して１１１ｇの白色ＥＴＦＥ（ｂ１）（平均粒径：
２．５ｍｍ）を得た。該共重合体の組成はテトラフルオ
ロエチレンに基づく重合単位５０．４モル％、エチレン
に基づく重合単位４８．６モル％、ＣＨ2＝ＣＨ−Ｃ4Ｆ
9に基づく重合単位１．０モル％であり、溶融粘度は
１．６２×１０6ポアズであった。(Polymerization Example 2) 1310 g of C 6 F 14 and HC
55 g of FC225cb was charged, and t-
Polymerization was carried out in the same manner as in Polymerization Example 1 except that 1.7 cc of a 1 wt% C 6 F 14 solution of butyl peroxypivalate was charged.
After granulation, 111 g of white ETFE (b1) (average particle size:
2.5 mm). The composition of the copolymer was as follows: 50.4 mol% of polymer units based on tetrafluoroethylene, 48.6 mol% of polymer units based on ethylene, and CH 2 ＣＨCH—C 4 F.
Based on No. 9 , the polymerization unit was 1.0 mol%, and the melt viscosity was 1.62 × 10 6 poise.
【００２９】（重合例３）Ｃ6Ｆ14を１０６０ｇ、ＨＣ
ＦＣ２２５ｃｂを３０３ｇ仕込む以外は重合例１と同様
に重合を行い、造粒して１０５ｇの白色ＥＴＦＥ（ａ
２）（平均粒径：２．５ｍｍ）を得た。該共重合体の組
成はテトラフルオロエチレンに基づく重合単位５０．５
モル％、エチレンに基づく重合単位４８．５モル％、Ｃ
Ｈ2＝ＣＨ−Ｃ4Ｆ9に基づく重合単位１．０モル％であ
り、溶融粘度は４．５１×１０4ポアズ、臨界剪断速度
は１４０（１／ｓ）であった。(Polymerization Example 3) 1060 g of C 6 F 14 and HC
Polymerization was carried out in the same manner as in Polymerization Example 1 except that 303 g of FC225cb was charged, and granulated to give 105 g of white ETFE (a
2) (Average particle size: 2.5 mm) was obtained. The composition of the copolymer was 50.5 polymerized units based on tetrafluoroethylene.
Mol%, 48.5 mol% of polymerized units based on ethylene, C
The polymerization unit was 1.0 mol% based on H 2重合 CH—C 4 F 9 , the melt viscosity was 4.51 × 10 4 poise, and the critical shear rate was 140 (1 / s).
【００３０】［例１］ＥＴＦＥ（ａ１）のビーズ（平均
粒径：２．５ｍｍ）とＥＴＦＥ（ｂ１）のビーズ（平均
粒径：２．５ｍｍ）を９５／５（重量比）の割合で押出
機により３００℃で５分溶融混合し、含フッ素重合体組
成物のペレット（長さ約３ｍｍ）を得た。このペレット
を使用して、各特性を測定した。Example 1 Extrusion of ETFE (a1) beads (average particle size: 2.5 mm) and ETFE (b1) beads (average particle size: 2.5 mm) at a ratio of 95/5 (weight ratio). The mixture was melted and mixed at 300 ° C. for 5 minutes by a machine to obtain a fluoropolymer composition pellet (length: about 3 mm). Each characteristic was measured using this pellet.
【００３１】［例２］ＥＴＦＥ（ａ１）のビーズとＥＴ
ＦＥ（ｂ１）のビーズを９０／１０（重量比）の混合割
合とする以外例１と同様にして各特性を測定した。[Example 2] ETFE (a1) beads and ET
Each characteristic was measured in the same manner as in Example 1 except that the mixing ratio of the beads of FE (b1) was 90/10 (weight ratio).
【００３２】［例３（比較例）］重合例１で重合したＥ
ＴＦＥ（ａ１）のビーズのみをを使用して、各特性を測
定した。Example 3 (Comparative Example) E polymerized in Polymerization Example 1
Each property was measured using only TFE (a1) beads.
【００３３】［例４（比較例）］重合例２で重合したＥ
ＴＦＥ（ｂ１）のビーズのみをを使用して、各特性を測
定した。溶融粘度が大きすぎて、臨界剪断速度が測定で
きず、また引張試験用サンプルは成形できなかった。Example 4 (Comparative Example) E polymerized in Polymerization Example 2
Each property was measured using only TFE (b1) beads. The melt viscosity was too large to measure the critical shear rate, and the tensile test sample could not be molded.
【００３４】［例５（比較例）］重合例３で重合したＥ
ＴＦＥ（ａ２）のビーズのみをを使用して、各特性を測
定した。Example 5 (Comparative Example) E polymerized in Polymerization Example 3
Each property was measured using only TFE (a2) beads.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【発明の効果】本発明の含フッ素共重合体組成物は、成
形物の機械特性が低下することなく成形性が改良されて
おり、電線被覆やチューブの成形に適している。Industrial Applicability The fluorocopolymer composition of the present invention has improved moldability without deteriorating the mechanical properties of the molded product, and is suitable for covering electric wires and molding tubes.
Claims (2)
アズ以上１×１０5ポアズ未満であるエチレン／テトラ
フルオロエチレン共重合体（Ａ）と、２９７℃における
溶融粘度が１×１０5ポアズ以上５×１０6ポアズ以下で
ある含フッ素重合体（Ｂ）とを含み、含フッ素共重合体
（Ｂ）の含有量がエチレン／テトラフルオロエチレン共
重合体（Ａ）に対し０．１〜３０重量％であることを特
徴とする含フッ素重合体組成物。1. An ethylene / tetrafluoroethylene copolymer (A) having a melt viscosity at 297 ° C. of 5 × 10 3 poise or more and less than 1 × 10 5 poise, and a melt viscosity at 297 ° C. of 1 × 10 5 poise or more. 5 × 10 6 poise or less of the fluoropolymer (B), and the content of the fluorocopolymer (B) is 0.1 to 30% by weight based on the ethylene / tetrafluoroethylene copolymer (A). % Of the fluorine-containing polymer composition.
フルオロエチレン共重合体である請求項１に記載の含フ
ッ素重合体組成物。2. The fluoropolymer composition according to claim 1, wherein the fluoropolymer (B) is an ethylene / tetrafluoroethylene copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02037899A JP3791223B2 (en) | 1999-01-28 | 1999-01-28 | Ethylene / tetrafluoroethylene copolymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02037899A JP3791223B2 (en) | 1999-01-28 | 1999-01-28 | Ethylene / tetrafluoroethylene copolymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000212365A true JP2000212365A (en) | 2000-08-02 |
| JP3791223B2 JP3791223B2 (en) | 2006-06-28 |
Family
ID=12025394
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02037899A Expired - Lifetime JP3791223B2 (en) | 1999-01-28 | 1999-01-28 | Ethylene / tetrafluoroethylene copolymer composition |
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| Country | Link |
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| JP (1) | JP3791223B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005052015A1 (en) * | 2003-11-26 | 2005-06-09 | Daikin Industries, Ltd. | Fluororesin and coated electric wire |
| JP2007297594A (en) * | 2006-04-03 | 2007-11-15 | Asahi Glass Co Ltd | Ethylene/tetrafluoroethylene copolymer composition |
| US7820774B2 (en) | 2006-04-03 | 2010-10-26 | Asahi Glass Company, Limited | Ethylene/tetrafluoroethylene copolymer composition |
| WO2011129405A1 (en) | 2010-04-16 | 2011-10-20 | 旭硝子株式会社 | Process for producing fluorine-containing copolymer composition and fluorocarbon-resin molded product |
| WO2013015202A1 (en) | 2011-07-26 | 2013-01-31 | 旭硝子株式会社 | Fluorine-containing copolymer composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151754B (en) * | 2014-08-15 | 2016-05-25 | 上海三爱富新材料股份有限公司 | High fluidity ethylene-tetrafluoroethylene copolymer composition and method of making the same |
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1999
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005052015A1 (en) * | 2003-11-26 | 2005-06-09 | Daikin Industries, Ltd. | Fluororesin and coated electric wire |
| KR100769434B1 (en) * | 2003-11-26 | 2007-10-22 | 다이킨 고교 가부시키가이샤 | Fluororesin and Coated Electric Wire |
| JPWO2005052015A1 (en) * | 2003-11-26 | 2007-12-06 | ダイキン工業株式会社 | Fluororesin and coated wire |
| US7638588B2 (en) | 2003-11-26 | 2009-12-29 | Daikin Industries, Ltd. | Fluororesin and coated electric wire |
| JP4591352B2 (en) * | 2003-11-26 | 2010-12-01 | ダイキン工業株式会社 | Fluororesin and coated wire |
| JP2007297594A (en) * | 2006-04-03 | 2007-11-15 | Asahi Glass Co Ltd | Ethylene/tetrafluoroethylene copolymer composition |
| US7820774B2 (en) | 2006-04-03 | 2010-10-26 | Asahi Glass Company, Limited | Ethylene/tetrafluoroethylene copolymer composition |
| WO2011129405A1 (en) | 2010-04-16 | 2011-10-20 | 旭硝子株式会社 | Process for producing fluorine-containing copolymer composition and fluorocarbon-resin molded product |
| EP2559730A1 (en) * | 2010-04-16 | 2013-02-20 | Asahi Glass Company, Limited | Process for producing fluorine-containing copolymer composition and fluorocarbon-resin molded product |
| EP2559730A4 (en) * | 2010-04-16 | 2014-01-15 | Asahi Glass Co Ltd | Process for producing fluorine-containing copolymer composition and fluorocarbon-resin molded product |
| WO2013015202A1 (en) | 2011-07-26 | 2013-01-31 | 旭硝子株式会社 | Fluorine-containing copolymer composition |
| US9328214B2 (en) | 2011-07-26 | 2016-05-03 | Asahi Glass Company, Limited | Fluorinated copolymer composition |
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