JP2002201218A - Tetrafluoroethylene polymer for stretching - Google Patents
Tetrafluoroethylene polymer for stretchingInfo
- Publication number
- JP2002201218A JP2002201218A JP2001226179A JP2001226179A JP2002201218A JP 2002201218 A JP2002201218 A JP 2002201218A JP 2001226179 A JP2001226179 A JP 2001226179A JP 2001226179 A JP2001226179 A JP 2001226179A JP 2002201218 A JP2002201218 A JP 2002201218A
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- Prior art keywords
- ptfe
- polymerization
- tetrafluoroethylene polymer
- stretching
- tfe
- 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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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、延伸用テトラフル
オロエチレン重合体（以下、ＰＴＦＥという）に関す
る。詳しくは、ペースト押出成形後の延伸操作に好適に
使用できる延伸用ＰＴＦＥに関する。TECHNICAL FIELD The present invention relates to a tetrafluoroethylene polymer for stretching (hereinafter referred to as PTFE). More specifically, the present invention relates to PTFE for stretching that can be suitably used for a stretching operation after paste extrusion.
【０００２】[0002]
【従来の技術】従来、ＰＴＦＥは、テトラフルオロエチ
レン（以下、ＴＦＥという）を単独で重合することによ
り、または必要に応じて改質モノマーと共に重合するこ
とにより得られ、種々の用途に使用されている。ＰＴＦ
Ｅは、水性分散重合により製造することができ、重合体
粒子が分散した水性分散液の状態で得ることもできる
し、水性分散重合液を凝固、乾燥させてファインパウダ
ーとして得ることもできる。従来のＰＴＦＥファインパ
ウダーは、高い溶融粘度を有しており、溶融温度では容
易に流動しないため、非溶融二次加工性を有する。その
ため、ＰＴＦＥファインパウダーは、一般的には、ＰＴ
ＦＥファインパウダーを潤滑剤とブレンドし、潤滑化Ｐ
ＴＦＥを押出し法により造形し、次いで潤滑剤を除去し
て得られる押出し物を、通常はＰＴＦＥの融点より高い
温度で融合（燒結）させて、最終製品形状にするペース
ト押出し成形が行われている。2. Description of the Related Art Conventionally, PTFE has been obtained by polymerizing tetrafluoroethylene (hereinafter referred to as TFE) alone or, if necessary, with a modifying monomer, and has been used for various purposes. I have. PTF
E can be produced by aqueous dispersion polymerization, can be obtained in the form of an aqueous dispersion in which polymer particles are dispersed, or can be obtained as a fine powder by coagulating and drying the aqueous dispersion polymerization solution. Conventional PTFE fine powder has a high melt viscosity and does not easily flow at the melting temperature, and therefore has non-melt secondary workability. Therefore, PTFE fine powder is generally
Blending FE fine powder with lubricant
Extrusion obtained by shaping TFE by an extrusion method and then removing a lubricant is usually fused (sintered) at a temperature higher than the melting point of PTFE, and paste extrusion molding is performed into a final product shape. .
【０００３】一方、ＰＴＦＥファインパウダーから得ら
れる重要な他の製品としては、衣服、テント、分離膜等
の製品用の通気性布材料が挙げられる。これらの製品
は、ＰＴＦＥファインパウダーをペースト押出し成形し
て得られる押出し物を、未燒結状態において急速に延伸
させ、水蒸気は透過できるが、凝縮水は透過できない性
質を付与することにより得ることができる。米国特許第
４,６５４,４０６号明細書および米国特許４,５７６,８
６９号明細書には、延伸性ＰＴＦＥファインパウダーの
技術を改善し、１７質量％の潤滑剤を添加して得られた
押出し物を、１０％／秒〜１００％／秒の速度で少なく
とも１０００％延伸することにより、少なくとも７５％
の延伸均一性が達成されることが記載されている。しか
しながら、ＰＴＦＥを延伸して得た延伸製品に対する要
求物性は年々高くなっており、この改良ＰＴＦＥから得
た延伸製品でも、強度が充分でないという問題点を有し
ている。On the other hand, other important products obtained from PTFE fine powder include breathable cloth materials for products such as clothes, tents and separation membranes. These products can be obtained by rapidly stretching an extrudate obtained by paste extrusion of PTFE fine powder in an unsintered state, and imparting a property that allows water vapor to pass through but not condensed water. . U.S. Pat. No. 4,654,406 and U.S. Pat. No. 4,576,8
No. 69 describes an improvement in the technology of extensible PTFE fine powder, in which an extrudate obtained by adding 17% by weight of a lubricant is produced at a speed of 10% / sec to 100% / sec at least 1000%. At least 75% by stretching
It is described that stretching uniformity is achieved. However, the required physical properties of a stretched product obtained by stretching PTFE are increasing year by year, and the stretched product obtained from the improved PTFE has a problem that the strength is not sufficient.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、延伸性、フ
ィブリル化性および非溶融二次加工性を有するＰＴＦＥ
であって、ペースト押出成形後の延伸操作に好適に使用
でき、得られた多孔体製品の強度を高くすることができ
るＰＴＦＥを提供することを目的とする。SUMMARY OF THE INVENTION The present invention relates to PTFE having stretchability, fibrillation and non-melt fabrication properties.
It is an object of the present invention to provide PTFE which can be suitably used for a stretching operation after paste extrusion molding and can increase the strength of the obtained porous product.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記従来技術
の状況に鑑みてなされたものであり、延伸製品の強度を
高めることができるＰＴＦＥを鋭意検討した結果、示差
熱分析（以下、ＤＳＣともいう）測定から算出される吸
熱比が特定の範囲であり、標準比重が特定の範囲である
ＰＴＦＥが上記延伸製品の強度を高めることができるこ
とを見出し、本発明を完成するに至った。すなわち、本
発明は、延伸性、フィブリル化性および非溶融二次加工
性を有するテトラフルオロエチレン重合体であって、該
重合体が２．１６０以下の標準比重を有し、示差熱分析
測定から算出される吸熱比が０．１５以下であることを
特徴とするＰＴＦＥを提供する。また、本発明は、上記
ＰＴＦＥにおいて、吸熱比が０．１３以下であるＰＴＦ
Ｅを提供する。また、本発明は、上記ＰＴＦＥにおい
て、吸熱比が０．１０以下であるＰＴＦＥを提供する。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art. As a result of intensive studies on PTFE capable of increasing the strength of a stretched product, a differential thermal analysis (hereinafter, referred to as DSC) has been made. It has been found that the endothermic ratio calculated from the measurement is within a specific range, and that PTFE having a standard specific gravity within a specific range can enhance the strength of the stretched product, thereby completing the present invention. That is, the present invention relates to a tetrafluoroethylene polymer having stretchability, fibrillation property and non-melt secondary workability, wherein the polymer has a standard specific gravity of 2.160 or less, and from differential thermal analysis measurement. PTFE characterized in that the calculated endothermic ratio is 0.15 or less. Further, the present invention relates to the PTFE having an endothermic ratio of 0.13 or less.
Provide E. The present invention also provides the PTFE having an endothermic ratio of 0.10 or less.
【０００６】また、本発明は、上記ＰＴＦＥにおいて、
標準比重が２．１５７以下であるＰＴＦＥを提供する。
ここで、標準比重とは、ＪＩＳ Ｋ６９３５−２に従っ
て測定した値をいう。また、本発明は、上記ＰＴＦＥに
おいて、応力緩和時間が、少なくとも６５０秒であるＰ
ＴＦＥを提供する。また、本発明は、上記ＰＴＦＥにお
いて、ＰＴＦＥがファインパウダーであるＰＴＦＥを提
供する。また、本発明は、上記ＰＴＦＥにおいて、ＰＴ
ＦＥが水性分散液の分散固体成分であるＰＴＦＥを提供
する。さらに、本発明は、上記の特性を有するＰＴＦＥ
からなる多孔体およびその物品を提供する。Further, the present invention relates to the above PTFE,
A PTFE having a standard specific gravity of 2.157 or less is provided.
Here, the standard specific gravity refers to a value measured according to JIS K6935-2. Further, the present invention provides the PTFE, wherein the stress relaxation time is at least 650 seconds.
Provide TFE. Further, the present invention provides the PTFE, wherein the PTFE is a fine powder. Further, the present invention relates to the PTFE,
FE provides PTFE, which is the dispersed solid component of the aqueous dispersion. Further, the present invention provides a PTFE having the above-mentioned properties.
And a porous body comprising the same.
【０００７】[0007]
【発明の実施の形態】本発明のＰＴＦＥは、ＴＦＥの単
独重合体であってもよいし、ＴＦＥ以外のエチレン性不
飽和基を有する含フッ素モノマーなどの改質モノマーと
の共重合体であってもよい。エチレン性不飽和基を有す
る含フッ素モノマーとしては、例えば、ヘキサフルオロ
プロピレン、パーフルオロブテン−１、パーフルオロへ
キセン−１、パーフルオロノネン−１、パーフルオロ
（メチルビニルエーテル）、パーフルオロ（エチルビニ
ルエーテル）、パーフルオロ（プロピルビニルエーテ
ル）、パーフルオロ（ヘプチルビニルエーテル）、（パ
ーフルオロメチル）エチレン、（パーフルオロブチル）
エチレン、クロロトリフルオロエチレン等が挙げられ
る。これらの含フッ素モノマーは単独で用いてもよい
し、２種以上を併用してもよい。改質モノマーは、通常
１質量％以下であることが好ましく、より好ましくは
０．５質量％以下である。本発明のＰＴＦＥは、延伸
性、フィブリル化性、非溶融二次加工性を有する。これ
らの性質は、ペースト押出し成形に通常要求される性質
である。BEST MODE FOR CARRYING OUT THE INVENTION The PTFE of the present invention may be a homopolymer of TFE or a copolymer with a modifying monomer other than TFE, such as a fluorine-containing monomer having an ethylenically unsaturated group. You may. Examples of the fluorine-containing monomer having an ethylenically unsaturated group include hexafluoropropylene, perfluorobutene-1, perfluorohexene-1, perfluorononene-1, perfluoro (methyl vinyl ether), and perfluoro (ethyl vinyl ether) ), Perfluoro (propyl vinyl ether), perfluoro (heptyl vinyl ether), (perfluoromethyl) ethylene, (perfluorobutyl)
Examples include ethylene and chlorotrifluoroethylene. These fluorinated monomers may be used alone or in combination of two or more. The content of the modifying monomer is usually preferably 1% by mass or less, more preferably 0.5% by mass or less. The PTFE of the present invention has stretchability, fibrillation, and non-melt secondary workability. These properties are those normally required for paste extrusion.
【０００８】また、本発明のＰＴＦＥは、標準比重、吸
熱比が特定の範囲にあるものであり、これにより特徴付
けられる。本発明のＰＴＦＥの標準比重（以下、ＳＳＧ
という）は、２．１６０以下であり、好ましくは２．１
５７以下である。このＳＳＧ値は、低い値であるといえ
る。ＳＳＧは、平均分子量の増大に伴い、減少する傾向
がある。すなわち、本発明のＰＴＦＥは、ＳＳＧ値が小
さいので、その平均分子量がかなり高いものであること
が予測できる。ＳＳＧ値が２．１６０以下のＰＴＦＥ
は、押出し物の延伸倍率が３０００％を超え、延伸均一
性にも優れる。本発明のＰＴＦＥの吸熱比は、０．１５
以下であり、０．１３以下がより好ましく、０．１０以
下が特に好ましい。この吸熱比は、後述する吸熱比の測
定において定義されるものである。一般にＰＴＦＥの示
差熱分析による結晶融解挙動は複数のピークが観察され
る。これは、それぞれに対応した結晶構造などの違いが
あると推測されるが、延伸加工においては、その構造が
なくべく同一のものが多いほうが、均一な延伸が可能
で、得られる多孔体の特性に優れるといえる。吸熱比
は、その構造の均一性を示す指標であり、吸熱比が小さ
いほど、ＰＴＦＥ中の構造の乱れが小さいとを示してい
る。吸熱比が０．１５を超えると、高倍率延伸が困難と
なったり、破断強度も小さくなる傾向となる。The PTFE of the present invention has a standard specific gravity and an endothermic ratio in a specific range, and is characterized by this. The standard specific gravity of the PTFE of the present invention (hereinafter referred to as SSG)
) Is 2.160 or less, preferably 2.1.
57 or less. This SSG value can be said to be a low value. SSG tends to decrease with increasing average molecular weight. That is, since the PTFE of the present invention has a small SSG value, it can be predicted that the average molecular weight is considerably high. PTFE with SSG value of 2.160 or less
The extruded product has a stretch ratio of more than 3000% and is excellent in stretch uniformity. The endothermic ratio of the PTFE of the present invention is 0.15
Or less, more preferably 0.13 or less, particularly preferably 0.10 or less. This endothermic ratio is defined in the measurement of the endothermic ratio described later. Generally, a plurality of peaks are observed in the crystal melting behavior of PTFE by differential thermal analysis. It is presumed that there is a difference in the crystal structure and the like corresponding to each, but in the stretching process, it is possible to achieve uniform stretching if there are many identical materials without the structure, and the characteristics of the obtained porous body It can be said that it is excellent. The endothermic ratio is an index indicating the uniformity of the structure, and indicates that the smaller the endothermic ratio is, the smaller the turbulence of the structure in PTFE is. When the endothermic ratio exceeds 0.15, high-magnification stretching becomes difficult and the breaking strength tends to decrease.
【０００９】本発明のＰＴＦＥの延伸物の破断強度は、
１９．６Ｎ（２．０ｋｇｆ）〜４９．０Ｎ（５．０ｋｇ
ｆ）の範囲が好ましく、２９．４Ｎ（３．０ｋｇｆ）〜
４９．０Ｎ（５．０ｋｇｆ）の範囲がより好ましく、特
に好ましくは３４．３Ｎ（３．５ｋｇｆ）〜４９．０Ｎ
（５．０ｋｇｆ）の範囲である。破断強度は、大きいほ
ど耐久性に等に優れるので好ましい。一方、破断強度が
５．０ｋｇｆを超えるＰＴＦＥは、製造が非常に困難と
なる傾向がある。また、本発明のＰＴＦＥは、応力緩和
時間が、少なくとも６５０秒であるものが好ましく、少
なくとも７００秒であるものがより好ましく、少なくと
も７３０秒であるものが特に好ましい。本発明のＰＴＦ
Ｅは、水性分散重合により製造することができる。水性
分散重合は、ＴＦＥ単独、またはＴＦＥと改質モノマー
とを用いて、分散剤および重合開始剤を含有する水系媒
体中で、行うことができる。重合温度は、通常５０〜１
２０℃の範囲であり、好ましくは６０〜１００℃の範囲
である。重合圧力は、適宜選定すればよいが、０．５〜
４．０ＭＰａの範囲になるようにすればよく、好ましく
は１．０〜２．５ＭＰａの範囲である。The breaking strength of the expanded PTFE of the present invention is as follows:
19.6 N (2.0 kgf) to 49.0 N (5.0 kg
The range of f) is preferable, and 29.4 N (3.0 kgf) to
The range of 49.0 N (5.0 kgf) is more preferable, and particularly preferably 34.3 N (3.5 kgf) to 49.0 N.
(5.0 kgf). The larger the breaking strength, the better the durability and the like. On the other hand, PTFE having a breaking strength exceeding 5.0 kgf tends to be very difficult to manufacture. Further, the PTFE of the present invention preferably has a stress relaxation time of at least 650 seconds, more preferably at least 700 seconds, and particularly preferably at least 730 seconds. PTF of the present invention
E can be produced by aqueous dispersion polymerization. The aqueous dispersion polymerization can be performed using TFE alone or using TFE and a modifying monomer in an aqueous medium containing a dispersant and a polymerization initiator. The polymerization temperature is usually 50 to 1
It is in the range of 20C, preferably in the range of 60-100C. The polymerization pressure may be appropriately selected, but is preferably 0.5 to
The pressure may be in the range of 4.0 MPa, preferably in the range of 1.0 to 2.5 MPa.
【００１０】分散剤としては、連鎖移動性の少ないアニ
オン系界面活性剤がより好ましく、フルオロカーボン系
の界面活性剤が特に好ましい。具体例としては、ＸＣｎ
Ｆ２ ｎＣＯＯＭ（ここで、Ｘは水素、塩素、フッ素、
（ＣＦ３）２ＣＦを、Ｍは水素、ＮＨ４、アルカリ金属
を、ｎは６〜１２の整数を示す。）、ＣｍＦ２ｍ＋１Ｏ
（ＣＦ（ＣＦ３）ＣＦ２Ｏ）ｐＣＦ（ＣＦ３）ＣＯＯＭ
（ここで、Ｍは水素、ＮＨ４、アルカリ金属を、ｍは１
〜１２の整数を、ｐは０〜５の整数を示す。）、ＣｎＦ
２ｎ＋１ＳＯ３Ｍ、ＣｎＦ２ｎ＋１ＣＨ２ＣＨ２ＳＯ３
Ｍ等が挙げられる。パーフルオロカーボン系の界面活性
剤がより好ましく、Ｃ７Ｆ１５ＣＯＯＮＨ ４、Ｃ８Ｆ
１７ＣＯＯＮＨ４、Ｃ９Ｆ１９ＣＯＯＮＨ４、Ｃ１０Ｆ
２１ＣＯＯＮＨ４、Ｃ７Ｆ１５ＣＯＯＮａ、Ｃ８Ｆ１７
ＣＯＯＮａ、Ｃ９Ｆ１９ＣＯＯＮａ、Ｃ７Ｆ１５ＣＯＯ
Ｋ、Ｃ８Ｆ１７ＣＯＯＫ、Ｃ９Ｆ１９ＣＯＯＫ、Ｃ３Ｆ
７Ｏ（ＣＦ（ＣＦ３）ＣＦ２Ｏ）２ＣＦ（ＣＦ３）ＣＯ
ＯＮＨ４等が挙げられる。これらは、単独で又は２種以
上を組み合わせて用いてもよい。分散剤の量は、使用さ
れる水の質量基準で、２５０〜５０００ｐｐｍの範囲に
することが好ましい。この範囲にすることで水性分散液
の安定性が向上し、得られるＰＴＦＥの破断強度が高く
なる。また、水性分散液の安定性をさらに向上するため
に重合中に分散剤を追加添加することも好ましい。As a dispersant, an anion having a low chain transfer property is used.
On-surfactants are more preferred, and fluorocarbon
Are particularly preferred. As a specific example, XCn
F2 nCOOM (where X is hydrogen, chlorine, fluorine,
(CF3)2CF, M is hydrogen, NH4, Alkali metal
And n represents an integer of 6 to 12. ), CmF2m + 1O
(CF (CF3) CF2O)pCF (CF3) COOM
(Where M is hydrogen, NH4, An alkali metal, m is 1
And p represents an integer of 0 to 5. ), CnF
2n + 1SO3M, CnF2n + 1CH2CH2SO3
M and the like. Surface activity of perfluorocarbon system
Agents are more preferred and C7FFifteenCOONH 4,C8F
17COONH4, C9F19COONH4, C10F
21COONH4, C7FFifteenCOONa,C8F17
COONa, C9F19COONa, C7FFifteenCOO
K,C8F17COOK, C9F19COOK, C3F
7O (CF (CF3) CF2O)2CF (CF3) CO
ONH4And the like. These may be used alone or in combination of two or more.
The above may be used in combination. The amount of dispersant used
Water in the range of 250-5000 ppm
Is preferred. Aqueous dispersions in this range
Stability is improved, and the breaking strength of the obtained PTFE is high.
Become. Also, to further improve the stability of the aqueous dispersion
It is also preferable to additionally add a dispersant during the polymerization.
【００１１】重合開始剤としては、水溶性ラジカル重合
開始剤や水溶性レドックス系重合開始剤が好ましい。水
溶性ラジカル重合開始剤としては、過硫酸アンモニウ
ム、過硫酸カリウム等の過硫酸塩、ビスコハク酸パーオ
キシド、ビスグルタル酸パーオキシド、ｔｅｒｔ−ブチ
ルヒドロパーオキシド等の水溶性有機過酸化物が好まし
い。これらは、単独で又は２種以上を組み合わせて用い
てもよい。特に、レドックス系重合開始剤を用いるとＳ
ＳＧが低く、吸熱比が小さく、押出し圧力が低く、破断
強度が大きいＰＴＦＥが得られるので好ましい。レドッ
クス系重合開始剤としては、過硫酸塩、臭素酸塩等の水
溶性酸化剤と亜硫酸塩やジイミン等の還元剤の組合せが
好ましい。特に、レドックス系重合開始剤として、臭素
酸塩と亜硫酸塩の組み合わせがより好ましく、臭素酸カ
リウムと亜硫酸アンモニウムの組合せが最も好ましい。
臭素酸塩と亜硫酸塩を用いる場合には、どちらかをあら
かじめ重合槽に仕込み、ついでもう一方を連続的または
断続的に加えて重合を開始させることが好ましく、臭素
酸塩をあらかじめ重合槽に仕込み、ついで亜硫酸塩を連
続的または断続的に加えることがより好ましい。重合開
始剤の量は、適宜選定すればよいが、水の質量基準で２
〜６００ｐｐｍが好ましく、臭素酸塩と亜硫酸塩の組合
せの場合にはそれぞれ５〜３００ｐｐｍが好ましい。ま
た、あらかじめ臭素酸塩を重合槽に仕込む場合は、臭素
酸塩濃度を高くすることにより水性分散液の安定性がさ
らに向上する。重合開始剤の量は、少ないほど吸熱比が
小さいＰＴＦＥが得られる傾向となるので好ましい。ま
た、重合開始剤の量は、あまりに少ないと重合速度が遅
くなりすぎる傾向となり、あまりに多いと生成するＰＴ
ＦＥのＳＳＧが高くなる傾向となる。As the polymerization initiator, a water-soluble radical polymerization initiator and a water-soluble redox polymerization initiator are preferable. As the water-soluble radical polymerization initiator, persulfates such as ammonium persulfate and potassium persulfate, and water-soluble organic peroxides such as bissuccinic peroxide, bisglutaric peroxide and tert-butyl hydroperoxide are preferable. These may be used alone or in combination of two or more. In particular, when a redox polymerization initiator is used, S
This is preferable because PTFE having low SG, low heat absorption ratio, low extrusion pressure, and high breaking strength can be obtained. As the redox polymerization initiator, a combination of a water-soluble oxidizing agent such as persulfate and bromate and a reducing agent such as sulfite and diimine is preferable. In particular, a combination of a bromate and a sulfite is more preferable as the redox polymerization initiator, and a combination of potassium bromate and ammonium sulfite is most preferable.
When using a bromate and a sulfite, it is preferable to charge one of them in a polymerization tank in advance, and then add the other continuously or intermittently to start the polymerization. More preferably, the sulfite is added continuously or intermittently. The amount of the polymerization initiator may be appropriately selected, but may be 2 based on the mass of water.
-600 ppm is preferable, and in the case of a combination of bromate and sulfite, 5-300 ppm is preferable respectively. When the bromate is previously charged into the polymerization tank, the stability of the aqueous dispersion is further improved by increasing the bromate concentration. It is preferable that the amount of the polymerization initiator be smaller, since PTFE having a smaller endothermic ratio tends to be obtained. If the amount of the polymerization initiator is too small, the polymerization rate tends to be too slow, and if the amount is too large, the PT
The SSG of the FE tends to increase.
【００１２】水性分散重合は、安定化助剤の存在下に実
施することが好ましい。安定化助剤としては、パラフィ
ンワックス、フッ素系オイル、フッ素系溶剤、シリコー
ンオイル等が好ましい。これらは、単独で又は２種以上
を組み合わせて用いてもよい。特に、パラフィンワック
スの存在下に行うことが好ましい。パラフィンワックス
としては、室温で液体でも、半固体でも、固体であって
もよいが、炭素数１２以上の飽和炭化水素が好ましい。
パラフィンワックスの融点は、通常４０〜６５℃が好ま
しく、５０〜６５℃がより好ましい。パラフィンワック
スの量は、使用される水の質量基準で０．１〜１２質量
％が好ましく、０．１〜８質量％がより好ましい。水性
分散重合は、通常、水系重合混合物を穏やかに撹拌する
ことにより行われる。生成した水性分散液中のＰＴＦＥ
微粒子が凝集しないように撹拌条件が制御される。水性
分散重合は、通常、水性分散液中のＰＴＦＥ微粒子の濃
度が１５〜４０質量％になるまで行われる。水性分散重
合は、酸を添加して酸性状態で行うことが水性分散液の
安定化のために好ましい。酸としては、硫酸、塩酸、硝
酸等の酸が好ましく、硝酸がより好ましい。硝酸を加え
ることにより水性分散液の安定性がさらに向上する。水
性分散重合によりＰＴＦＥ微粒子が分散した水性分散液
が得られるが、水性分散液中のＰＴＦＥ微粒子の粒径
は、通常０．０２〜１．０μｍと広い分布を有し、平均
粒子径は０．１〜０．４μｍ程度である。得られた水性
分散重合液からＰＴＦＥ微粒子を凝集し、乾燥させてＰ
ＴＦＥファインパウダーを得る。凝集方法としては、水
性分散液を高速撹拌することによってＰＴＦＥ微粒子を
凝集させることが好ましい。このとき、凝析剤を添加す
ることが好ましい。凝析剤としては、炭酸アンモニウム
や多価無機塩類、鉱酸類、陽イオン界面活性剤、アルコ
ール等が好ましく、炭酸アンモニウムがより好ましい。The aqueous dispersion polymerization is preferably carried out in the presence of a stabilizing aid. As the stabilizing aid, paraffin wax, fluorine-based oil, fluorine-based solvent, silicone oil and the like are preferable. These may be used alone or in combination of two or more. In particular, it is preferable to carry out in the presence of paraffin wax. The paraffin wax may be liquid, semi-solid, or solid at room temperature, but is preferably a saturated hydrocarbon having 12 or more carbon atoms.
The melting point of paraffin wax is usually preferably from 40 to 65 ° C, more preferably from 50 to 65 ° C. The amount of paraffin wax is preferably from 0.1 to 12% by mass, more preferably from 0.1 to 8% by mass, based on the mass of water used. The aqueous dispersion polymerization is usually performed by gently stirring the aqueous polymerization mixture. PTFE in the resulting aqueous dispersion
The stirring conditions are controlled so that the fine particles do not aggregate. The aqueous dispersion polymerization is usually performed until the concentration of the PTFE fine particles in the aqueous dispersion becomes 15 to 40% by mass. The aqueous dispersion polymerization is preferably performed in an acidic state by adding an acid for stabilizing the aqueous dispersion. As the acid, acids such as sulfuric acid, hydrochloric acid, and nitric acid are preferable, and nitric acid is more preferable. Addition of nitric acid further improves the stability of the aqueous dispersion. An aqueous dispersion in which the PTFE fine particles are dispersed is obtained by the aqueous dispersion polymerization, and the particle diameter of the PTFE fine particles in the aqueous dispersion generally has a wide distribution of 0.02 to 1.0 μm, and the average particle diameter is 0. It is about 1 to 0.4 μm. PTFE fine particles are agglomerated from the obtained aqueous dispersion polymerization solution and dried to form P
Obtain TFE fine powder. As the aggregating method, it is preferable that the PTFE fine particles are agglomerated by stirring the aqueous dispersion at a high speed. At this time, it is preferable to add a coagulant. As the coagulant, ammonium carbonate, polyvalent inorganic salts, mineral acids, cationic surfactants, alcohols and the like are preferable, and ammonium carbonate is more preferable.
【００１３】凝集により湿潤状態で得られるＰＴＦＥの
乾燥は、任意の温度で行うことができるが、１００〜２
５０℃の範囲で行うことが好ましく、１３０〜２００℃
の範囲で行うことが特に好ましい。乾燥によって、本発
明のＰＴＦＥァインパウダーを得ることができる。この
ＰＴＦＥファインパウダーは、その平均粒径が１００〜
８００μｍの範囲のものが好ましく、４００〜６００μ
ｍの範囲のものが特に好ましい。また、本発明は、上記
の特性を有するＰＴＦＥからなる多孔体およびその物品
を提供する。多孔体は、種々の方法により製造したもの
が挙げられるが、例えば、ペースト押出し成形後に延伸
を施すことにより得られる多孔体および多孔体からなる
フィルム、チューブなどが挙げられる。ペースト押出し
成形とは、ＰＴＦＥファインパウダーを潤滑剤と混合し
て、ＰＴＦＥファインパウダーに流動性を持たせてフィ
ルム、チューブ等の成形物を成形するものである。潤滑
剤の混合割合は、ＰＴＦＥファインパウダーに流動性を
持たせるように、適宜選定すればよく、通常１０〜３０
質量％にすればよい。潤滑剤としては、ナフサ、沸点が
２００℃以上の石油系炭化水素が好ましく用いられる。
また、延伸は、適当な速度、例えば５％／秒〜１０００
％／秒の速度で、適当な延伸倍率、例えば５００％以上
の延伸倍率になるように施せばよい。多孔体の空孔率は
特に制限ないが、通常空孔率が５０〜９７％の範囲が好
ましく、７０〜９５％の範囲が特に好ましい。多孔体で
構成される物品の形状は、シート状、フィルム状、繊維
状など種々の形状にすることができる。Drying of PTFE obtained in a wet state by agglomeration can be performed at any temperature.
It is preferably performed in the range of 50 ° C, and 130 to 200 ° C
It is particularly preferable to perform the reaction in the range described above. By drying, the PTFE fine powder of the present invention can be obtained. This PTFE fine powder has an average particle size of 100 to
It is preferably in the range of 800 μm,
Those having a range of m are particularly preferred. Further, the present invention provides a porous body made of PTFE having the above-mentioned properties and an article thereof. Examples of the porous body include those manufactured by various methods. Examples of the porous body include a porous body obtained by performing stretching after paste extrusion, and a film and a tube made of the porous body. Paste extrusion molding refers to mixing PTFE fine powder with a lubricant to give fluidity to PTFE fine powder to form a molded product such as a film or a tube. The mixing ratio of the lubricant may be appropriately selected so that the PTFE fine powder has fluidity.
What is necessary is just to mass%. As the lubricant, naphtha or a petroleum hydrocarbon having a boiling point of 200 ° C. or more is preferably used.
The stretching is performed at an appropriate speed, for example, 5% / sec to 1000%.
The stretching may be performed at a rate of% / sec so as to obtain an appropriate stretching ratio, for example, a stretching ratio of 500% or more. The porosity of the porous body is not particularly limited, but usually the porosity is preferably in the range of 50 to 97%, particularly preferably in the range of 70 to 95%. The shape of the article formed of the porous body can be various shapes such as a sheet shape, a film shape, and a fiber shape.
【００１４】[0014]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本願発明はこれらに限定されない。以下におい
て、部は質量部を示す。例１〜３が実施例であり、例４
が比較例である。なお、実施例において、延伸性の評
価、破断強度、応力緩和時間の測定は、以下に示す方法
により行った。EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In the following, “parts” indicates “parts by mass”. Examples 1 to 3 are working examples, and Example 4
Is a comparative example. In the examples, evaluation of stretchability, measurement of breaking strength, and measurement of stress relaxation time were performed by the following methods.
【００１５】（１）吸熱比の測定 示差熱分析計（ＤＳＣ−７、ＰＥＲＫＩＮ ＥＬＭＥＲ
社製）を用いて測定した。サンプルの１０．０ｍｇを用
い、初期温度２００℃で１分間保持した後、１０℃／分
で３８０℃まで昇温して、示差熱曲線を得た。得られた
示差熱曲線上の３１０℃の点と３５０℃の点を結んでベ
ースラインとした。示差熱曲線上の最も高いピークから
ベースラインに向けて下した長さをＡとする。最も高い
ピークからベースラインに下した交点より１０℃低温側
のベースライン上の点から示差熱曲線までの長さをＢと
する。Ｂ／Ａの値を吸熱比とした。(1) Measurement of endothermic ratio Differential thermal analyzer (DSC-7, PERKIN ELMER)
(Manufactured by the company). Using 10.0 mg of the sample, the sample was kept at an initial temperature of 200 ° C. for 1 minute, and then heated at a rate of 10 ° C./minute to 380 ° C. to obtain a differential heat curve. A point at 310 ° C. and a point at 350 ° C. on the obtained differential heat curve were connected to each other to obtain a baseline. Let A be the length from the highest peak on the differential thermal curve toward the baseline. Let B be the length from the point on the baseline 10 ° C. lower than the intersection from the highest peak to the baseline to the differential heat curve. The value of B / A was taken as the endothermic ratio.
【００１６】（２）延伸性の評価 室温で２時間以上放置されたＰＴＦＥのファインパウダ
ー１００ｇを内容量９００ｃｃのガラス瓶に入れ、アイ
ソパーＨ（登録商標、エクソン社製）潤滑剤２１．７ｇ
を添加し、３分間混合してＰＴＦＥ混合物を得た。得ら
れたＰＴＦＥ混合物を２５℃恒温槽に２時間放置した後
に、リダクションレシオ（ダイスの入り口の断面積と出
口の断面積の比）１００、押出し速度５１ｃｍ／分の条
件で、２５℃にて、直径２．５ｃｍ、ランド長１．１ｃ
ｍ、導入角３０°のオリフィスを通して、ペースト押出
ししビードを得た。得られたビードを２３０℃で３０分
間乾燥し、潤滑剤を除去した。次いで、ビードの長さを
適当な長さに切断し、クランプ間が３．８ｃｍまたは
５．１ｃｍのいずれかの間隔となるよう、各末端を固定
し、空気循環炉中で３００℃に加熱した。次いで、クラ
ンプが所定の間隔になるまで所定の速度で延伸した。こ
の延伸方法は、押出しスピード（５１ｃｍ／分）が異な
ることを除いて、本質的に米国特許第４,５７６,８６９
号明細書に開示された方法に従った。「延伸」とは、長
さの増加であり、通常元の長さと関連して表わされる。(2) Evaluation of stretchability 100 g of PTFE fine powder left at room temperature for 2 hours or more was put into a glass bottle having a content of 900 cc, and 21.7 g of Isopar H (registered trademark, manufactured by Exxon) lubricant was added.
Was added and mixed for 3 minutes to obtain a PTFE mixture. After leaving the obtained PTFE mixture in a constant temperature bath at 25 ° C. for 2 hours, a reduction ratio (the ratio of the cross-sectional area of the entrance of the die to the cross-sectional area of the exit) of 100 and an extrusion speed of 51 cm / min at 25 ° C. 2.5cm in diameter, land length 1.1c
m, and a paste extruded bead was obtained through an orifice having an introduction angle of 30 °. The obtained bead was dried at 230 ° C. for 30 minutes to remove the lubricant. The length of the bead was then cut to a suitable length, each end was fixed such that the gap between the clamps was either 3.8 cm or 5.1 cm, and heated to 300 ° C. in a circulating air oven. . Then, the clamp was stretched at a predetermined speed until a predetermined interval was reached. This stretching method is essentially U.S. Pat. No. 4,576,869 except that the extrusion speed (51 cm / min) is different.
According to the method disclosed in the above specification. "Stretching" is an increase in length, usually expressed in relation to the original length.
【００１７】（３）応力緩和時間の測定 応力緩和時間の測定用のサンプルは、クランプ間隔３．
８ｃｍ、延伸速度１０００％／秒、総延伸２４００％を
用い、延伸性の評価のように、ビードを延伸することに
より、作製する。この延伸ビードのサンプルの両方の末
端は、固定具につなげることにより、ぴんと張られた全
長２５ｃｍの延伸ビードである。応力緩和時間とは、こ
のサンプルが３９０℃、すなわち、米国特許第５,４７
０,６５５号明細書に開示されている延長鎖形状の溶け
る３８０℃より高い温度でオーブン中に放置した後に破
断するのに要する時間である。固定具におけるサンプル
は、オーブンの側部にある（覆われた）スロットを通し
てオーブンに挿入されるので、サンプルを配置する間に
温度は下降することがなく、それゆえに米国特許第４,
５７６,８６９号明細書に開示されたように回復にしば
しの時間を必要としない。(3) Measurement of stress relaxation time The sample for measuring the stress relaxation time has a clamp interval of 3.
It is produced by stretching a bead as in the evaluation of stretchability using 8 cm, a stretching speed of 1000% / sec, and a total stretching of 2400%. At both ends of the stretch bead sample are stretch beads of 25 cm overall length that are taut by connecting to a fixture. The stress relaxation time is defined as 390 ° C., ie, US Pat.
No. 0,655, the time required to break after standing in an oven at a temperature above 380 ° C. at which the extended chain melts, which melts. Since the sample in the fixture is inserted into the oven through a (covered) slot on the side of the oven, the temperature does not drop during sample placement, and therefore, US Pat.
Recovery does not require a brief period of time as disclosed in 576,869.
【００１８】[例１]１００Ｌの重合槽に、パラフィンワ
ックスの９２８ｇ、超純水の５５Ｌ、パーフルオロオク
タン酸アンモニウムの３６ｇ、コハク酸の１ｇ、１Ｎの
硝酸水溶液の８ｍｌ、臭素酸カリウムの０．４ｇを仕込
んだ。窒素パージ、脱気を行った後に、６５℃に昇温し
た。温度が安定した後にＴＦＥを導入し、１．９ＭＰａ
の圧力とした。内容物を撹拌下に、亜硫酸アンモニウム
１４０ｐｐｍ水溶液１Ｌを６０分連続添加して重合を開
始した。重合が進行すると共にＴＦＥが消費されて重合
槽内の圧力が低下したので、圧力を一定に保つようにＴ
ＦＥを連続的に供給した。亜硫酸アンモニウムの添加終
了後にパーフルオロオクタン酸アンモニウムの１１．１
質量％水溶液１Ｌを添加した。重合開始から２７０分経
過した時点で、撹拌およびＴＦＥの供給を停止し、重合
槽内のＴＦＥをパージし、ついで気相を窒素で置換し
た。得られた固形分２８．９質量％のＰＴＦＥ水性分散
液を炭酸アンモニウム存在下で凝集し、湿潤状態のＰＴ
ＦＥを分離した。得られた湿潤状態のＰＴＦＥを１６０
℃で乾燥して、ＰＴＦＥファインパウダーを得た。そし
て、得られたＰＴＦＥファインパウダーのＳＳＧ、吸熱
比および平均粒径を測定した。また、得られたＰＴＦＥ
ファインパウダーをクランプ間隔５．１ｃｍ、延伸速度
１００％／秒、総延伸２４００％を用い、延伸性の評価
と同様にして、ビードを延伸することにより、破断強度
試験測定用サンプルを作製した。破断強度は、延伸ビー
ドから得られる３つのサンプル、延伸ビードの各末端か
ら１つ（クランプの範囲においてネックダウンがあれば
それを除く）、およびその中心から１つ、の最小引張り
破断負荷（力）として、測定した。５．０ｃｍのゲージ
長である、ジョーにおいてサンプルを挟んで固定し、可
動ジョー３００ｍｍ／分のスピードで駆動させ、引張り
試験機（エーアンドディ社製）を用いて、室温で測定し
た。破断強度は、３７．３Ｎであり、多孔体として有用
な非常に高い破断強度を示した。応力緩和時間は前述の
方法に従い測定した。ついで、ＰＴＦＥファインパウダ
ー６００ｇをガラス製のボトルに２０重量％の割合で潤
滑剤であるアイソパーＧ（Ｅｘｘｏｎ社製）を加え、１
００ｒｐｍで３０分間回転させることにより混合した。
ブレンドした樹脂を室温で２４時間熟成させた。この樹
脂を０．２ＭＰａの圧力を１２０秒間プレスして直径６
８ｍｍのプレフォームを得た。このプレフォームを直径
１１ｍｍのオリフィスを通して押出しを行い、押出し物
を厚さ０．１ｍｍまで圧延した。該圧延シートを長さ５
ｃｍ、幅２ｃｍの短冊状とし、３００℃の温度下、１０
０％／秒の速度で１０倍に延伸した。得られたフィルム
の空孔率は、９０％であった。Example 1 In a 100 L polymerization tank, 928 g of paraffin wax, 55 L of ultrapure water, 36 g of ammonium perfluorooctanoate, 1 g of succinic acid, 8 ml of 1N aqueous nitric acid, and 0.1 ml of potassium bromate. 4 g were charged. After nitrogen purging and degassing, the temperature was raised to 65 ° C. After the temperature was stabilized, TFE was introduced and 1.9 MPa
Pressure. While stirring the contents, 1 L of a 140 ppm aqueous solution of ammonium sulfite was continuously added for 60 minutes to initiate polymerization. As the polymerization progressed, TFE was consumed and the pressure in the polymerization tank decreased.
FE was fed continuously. After completion of the addition of ammonium sulfite, 11.1 of ammonium perfluorooctanoate was added.
1 L of a 1% by weight aqueous solution was added. When 270 minutes had elapsed from the start of the polymerization, the stirring and the supply of TFE were stopped, TFE in the polymerization tank was purged, and then the gas phase was replaced with nitrogen. The obtained PTFE aqueous dispersion having a solid content of 28.9% by mass is aggregated in the presence of ammonium carbonate to form a wet state of PT.
The FE was separated. 160 of the obtained wet PTFE
Drying at ℃ yielded PTFE fine powder. Then, SSG, endothermic ratio and average particle size of the obtained PTFE fine powder were measured. In addition, the obtained PTFE
Using a fine powder with a clamp interval of 5.1 cm, a stretching speed of 100% / sec, and a total stretching of 2400%, a bead was stretched in the same manner as in the evaluation of stretchability to prepare a sample for measuring a breaking strength test. The breaking strength was the minimum tensile breaking load (force) of the three samples obtained from the stretched bead, one from each end of the stretched bead (excluding any neckdown in the range of the clamp) and one from its center. ) Was measured. A sample having a gauge length of 5.0 cm was sandwiched between jaws and fixed. The movable jaw was driven at a speed of 300 mm / min, and measured at room temperature using a tensile tester (manufactured by A & D Corporation). The breaking strength was 37.3N, which showed a very high breaking strength useful as a porous body. The stress relaxation time was measured according to the method described above. Then, Isopar G (manufactured by Exxon), which is a lubricant, was added to a glass bottle containing 600 g of PTFE fine powder at a ratio of 20% by weight.
Mix by rotating at 00 rpm for 30 minutes.
The blended resin was aged at room temperature for 24 hours. This resin is pressed at a pressure of 0.2 MPa for 120 seconds to obtain a resin having a diameter of 6 mm.
An 8 mm preform was obtained. The preform was extruded through an orifice having a diameter of 11 mm, and the extruded product was rolled to a thickness of 0.1 mm. The rolled sheet has a length of 5
cm, 2 cm width, at a temperature of 300 ° C.
The film was stretched 10 times at a rate of 0% / sec. The porosity of the obtained film was 90%.
【００１９】[例２]１００Ｌの重合槽に、パラフィンワ
ックスの９２８ｇ、超純水の５５Ｌ、パーフルオロオク
タン酸アンモニウムの２５ｇ、コハク酸の１ｇ、１Ｎの
硝酸水溶液の８ｍｌ、臭素酸カリウムの０．４ｇを仕込
んだ。窒素パージ、脱気を行った後に、８５℃に昇温し
た。温度が安定した後にＴＦＥを導入し、１．９ＭＰａ
の圧力とした。内容物を撹拌下に、亜硫酸アンモニウム
１４０ｐｐｍ水溶液１Ｌを６０分連続添加して重合を開
始した。重合が進行すると共にＴＦＥが消費されて重合
槽内の圧力が低下したので、圧力を一定に保つようにＴ
ＦＥを連続的に供給した。亜硫酸アンモニウムの添加終
了後にパーフルオロオクタン酸アンモニウムの１１．１
質量％水溶液１Ｌを添加した。重合開始から２５０分経
過した時点で、撹拌およびＴＦＥの供給を停止し、重合
槽内のＴＦＥをパージし、ついで気相を窒素で置換し
た。得られた固形分２４．１質量％のＰＴＦＥ水性分散
液を炭酸アンモニウム存在下で凝集し、湿潤状態のＰＴ
ＦＥを分離した。得られた湿潤状態のＰＴＦＥを１４０
℃で乾燥して、ＰＴＦＥファインパウダーを得た。例１
と同様にして、ＰＴＦＥファインパウダーのＳＳＧ、吸
熱比および平均粒径、延伸ビードの破断強度、応力緩和
時間を測定した。例１と同様に、多孔体の破断強度を測
定したところ、３４．８Ｎであり、多孔体として有用な
非常に高い破断強度を示した。Example 2 In a 100 L polymerization vessel, 928 g of paraffin wax, 55 L of ultrapure water, 25 g of ammonium perfluorooctanoate, 1 g of succinic acid, 8 ml of 1N aqueous nitric acid, and 0.1 ml of potassium bromate. 4 g were charged. After nitrogen purging and degassing, the temperature was raised to 85 ° C. After the temperature was stabilized, TFE was introduced and 1.9 MPa
Pressure. While stirring the contents, 1 L of a 140 ppm aqueous solution of ammonium sulfite was continuously added for 60 minutes to initiate polymerization. As the polymerization progressed, TFE was consumed and the pressure in the polymerization tank decreased.
FE was fed continuously. After completion of the addition of ammonium sulfite, 11.1 of ammonium perfluorooctanoate was added.
1 L of a 1% by weight aqueous solution was added. When 250 minutes had passed from the start of the polymerization, stirring and the supply of TFE were stopped, TFE in the polymerization tank was purged, and then the gas phase was replaced with nitrogen. The obtained PTFE aqueous dispersion having a solid content of 24.1% by mass was aggregated in the presence of ammonium carbonate to form a wet PT
The FE was separated. 140 of the obtained wet PTFE
Drying at ℃ yielded PTFE fine powder. Example 1
In the same manner as in the above, the SSG of the PTFE fine powder, the endothermic ratio and the average particle size, the breaking strength of the stretched bead, and the stress relaxation time were measured. When the breaking strength of the porous body was measured in the same manner as in Example 1, it was 34.8 N, indicating a very high breaking strength useful as a porous body.
【００２０】[例３]１００Ｌの重合槽に、パラフィンワ
ックスの９２８ｇ、超純水の５５Ｌ、パーフルオロオク
タン酸アンモニウムの３６ｇ、コハク酸の１ｇ、１Ｎの
硝酸水溶液の８ｍｌ、臭素酸カリウムの０．４ｇを仕込
んだ。窒素パージ、脱気を行った後に、８５℃に昇温し
た。温度が安定した後にＴＦＥを導入し、１．９ＭＰａ
の圧力とした。内容物を撹拌下に、亜硫酸アンモニウム
１８０ｐｐｍ水溶液１Ｌを６０分連続添加して重合を開
始した。重合が進行すると共にＴＦＥが消費されて重合
槽内の圧力が低下したので、圧力を一定に保つようにＴ
ＦＥを連続的に供給した。重合開始４０分から６０分の
間に連続的にパーフルオロオクタン酸アンモニウムの
３．６質量％水溶液１Ｌを添加した。亜硫酸アンモニウ
ムの添加終了後にパーフルオロオクタン酸アンモニウム
の８．１質量％水溶液１Ｌを添加した。重合開始から２
５０分経過した時点で、撹拌およびＴＦＥの供給を停止
し、重合槽内のＴＦＥをパージし、ついで気相を窒素で
置換した。得られた固形分２９．９質量％のＰＴＦＥ水
性分散液を炭酸アンモニウム存在下で凝集し、湿潤状態
のＰＴＦＥを分離した。得られた湿潤状態のＰＴＦＥを
１６０℃で乾燥して、ＰＴＦＥファインパウダーを得
た。例１と同様にして、ＰＴＦＥファインパウダーのＳ
ＳＧ、吸熱比および平均粒径、延伸ビードの破断強度、
応力緩和時間を測定した。Example 3 In a 100 L polymerization vessel, 928 g of paraffin wax, 55 L of ultrapure water, 36 g of ammonium perfluorooctanoate, 1 g of succinic acid, 8 ml of 1N aqueous nitric acid, and 0.1 ml of potassium bromate. 4 g were charged. After nitrogen purging and degassing, the temperature was raised to 85 ° C. After the temperature was stabilized, TFE was introduced and 1.9 MPa
Pressure. While stirring the content, 1 L of a 180 ppm aqueous solution of ammonium sulfite was continuously added for 60 minutes to initiate polymerization. As the polymerization progressed, TFE was consumed and the pressure in the polymerization tank decreased.
FE was fed continuously. One liter of a 3.6% by mass aqueous solution of ammonium perfluorooctanoate was continuously added from 40 minutes to 60 minutes after the start of the polymerization. After the completion of the addition of ammonium sulfite, 1 L of an 8.1% by mass aqueous solution of ammonium perfluorooctanoate was added. 2 from the start of polymerization
After the elapse of 50 minutes, the stirring and the supply of TFE were stopped, TFE in the polymerization tank was purged, and the gas phase was replaced with nitrogen. The obtained PTFE aqueous dispersion having a solid content of 29.9% by mass was coagulated in the presence of ammonium carbonate to separate wet PTFE. The obtained wet PTFE was dried at 160 ° C. to obtain a PTFE fine powder. In the same manner as in Example 1, PTFE fine powder S
SG, endothermic ratio and average particle size, breaking strength of stretched bead,
The stress relaxation time was measured.
【００２１】[例４]１００Ｌの重合槽に、パラフィンワ
ックスの７３６ｇ、超純水の５９Ｌ、パーフルオロオク
タン酸アンモニウムの３３ｇを仕込んだ。７０℃に昇温
し、窒素パージ、脱気を行った後、ＴＦＥを導入し、
１．９ＭＰａの圧力とした。撹拌下に、ジコハク酸パー
オキサイドの０．５質量％水溶液１Ｌを圧入して重合を
開始した。重合の進行に伴いＴＦＥが消費されて重合槽
内の圧力が低下したので、圧力を一定に保つように重合
中はＴＦＥを連続的に供給した。重合開始から４５分後
から６℃／時で９０℃まで昇温した。また、ＴＦＥの供
給量が６．６ｋｇとなった時点で、パーフルオロオクタ
ン酸アンモニウムの５．６質量％水溶液１Ｌを添加し
た。重合開始から１６０分経過した時点で、撹拌および
ＴＦＥの供給を停止し、重合槽内のＴＦＥをパージして
重合を停止した。得られた固形分２４．３質量％のＰＴ
ＦＥ水性分散液を凝集し、湿潤状態のＰＴＦＥを分離し
た。得られた湿潤状態のＰＴＦＥを２０５℃で乾燥し
て、ＰＴＦＥファインパウダーを得た。例１と同様にし
て、ＰＴＦＥファインパウダーのＳＳＧ、吸熱比および
平均粒径、ペースト押出し時の押出し圧力、応力緩和時
間を測定した。例１と同様に、多孔体の破断強度を測定
したところ、９．８Ｎであり、非常に低いものであっ
た。Example 4 A 100 L polymerization tank was charged with 736 g of paraffin wax, 59 L of ultrapure water, and 33 g of ammonium perfluorooctanoate. After the temperature was raised to 70 ° C., nitrogen purge and degassing were performed, TFE was introduced,
The pressure was set to 1.9 MPa. Under stirring, 1 L of a 0.5% by mass aqueous solution of disuccinic acid peroxide was injected under pressure to initiate polymerization. Since TFE was consumed with the progress of polymerization and the pressure in the polymerization tank decreased, TFE was continuously supplied during polymerization so as to keep the pressure constant. After 45 minutes from the start of the polymerization, the temperature was raised to 90 ° C. at 6 ° C./hour. When the supply amount of TFE reached 6.6 kg, 1 L of a 5.6% by mass aqueous solution of ammonium perfluorooctanoate was added. When 160 minutes had elapsed from the start of the polymerization, the stirring and the supply of TFE were stopped, and TFE in the polymerization tank was purged to stop the polymerization. The obtained PT having a solid content of 24.3% by mass.
The FE aqueous dispersion was agglomerated to separate wet PTFE. The obtained wet PTFE was dried at 205 ° C. to obtain a PTFE fine powder. In the same manner as in Example 1, the SSG of the PTFE fine powder, the endothermic ratio, the average particle size, the extrusion pressure during paste extrusion, and the stress relaxation time were measured. When the breaking strength of the porous body was measured in the same manner as in Example 1, it was 9.8 N, which was extremely low.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【発明の効果】本発明のＰＴＦＥは、標準比重が低く、
吸熱比が低く、ペースト押出成形後の延伸操作に好適に
使用できる。The PTFE of the present invention has a low standard specific gravity,
It has a low heat absorption ratio and can be suitably used for a stretching operation after paste extrusion molding.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 星川 潤 千葉県市原市五井海岸10番地 旭硝子フロ ロポリマーズ株式会社内 (72)発明者 加藤 一雄 千葉県市原市五井海岸10番地 旭硝子フロ ロポリマーズ株式会社内 (72)発明者 神谷 浩樹 千葉県市原市五井海岸10番地 旭硝子株式 会社内 (72)発明者 平井 浩之 千葉県市原市五井海岸10番地 旭硝子株式 会社内 Ｆターム(参考） 4F074 AA39 AB02 CA01 CC02Y CC04Y DA02 4J100 AC26P AC27Q AC29Q AC31Q AC34Q AC42Q AE39Q CA01 CA04 DA11 DA22 EA06 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Jun Hoshikawa 10 Asahi Glass Fluoropolymers Co., Ltd., Ichihara City, Chiba Prefecture (72) Inventor Kazuo Kato 10 Asahi Glass Fluoropolymers Co., Ltd., Ichihara City, Chiba Prefecture ( 72) Inventor Hiroki Kamiya 10 Asahi Glass Co., Ltd., Ichihara City, Chiba Prefecture (72) Inventor Hiroyuki Hirai 10 Asahi Glass Co., Ltd., 10 Asahi Glass Co., Ltd. AC26P AC27Q AC29Q AC31Q AC34Q AC42Q AE39Q CA01 CA04 DA11 DA22 EA06
Claims (8)
加工性を有するテトラフルオロエチレン重合体であっ
て、該重合体が２．１６０以下の標準比重を有し、示差
熱分析測定から算出される吸熱比が０．１５以下である
ことを特徴とするテトラフルオロエチレン重合体。1. A tetrafluoroethylene polymer having stretchability, fibrillation property and non-melt secondary workability, wherein the polymer has a standard specific gravity of 2.160 or less and is calculated from a differential thermal analysis measurement. Wherein the endothermic ratio is 0.15 or less.
載のテトラフルオロエチレン重合体。2. The tetrafluoroethylene polymer according to claim 1, which has an endothermic ratio of 0.13 or less.
は２に記載のテトラフルオロエチレン重合体。3. The tetrafluoroethylene polymer according to claim 1, which has an endothermic ratio of 0.10 or less.
〜３のいずれかに記載のテトラフルオロエチレン重合
体。4. The method according to claim 1, wherein the standard specific gravity is 2.157 or less.
4. The tetrafluoroethylene polymer according to any one of items 1 to 3.
る請求項１〜４のいずれかに記載のテトラフルオロエチ
レン重合体。5. The tetrafluoroethylene polymer according to claim 1, wherein the stress relaxation time is at least 650 seconds.
パウダーである請求項１〜５のいずれかに記載のテトラ
フルオロエチレン重合体。6. The tetrafluoroethylene polymer according to claim 1, wherein the tetrafluoroethylene polymer is a fine powder.
液の分散固体成分である請求項１〜５のいずれかに記載
のテトラフルオロエチレン重合体。7. The tetrafluoroethylene polymer according to claim 1, wherein the tetrafluoroethylene polymer is a solid component dispersed in an aqueous dispersion.
合体からなる多孔体およびその物品。8. A porous body comprising the tetrafluoroethylene polymer according to claim 1 and an article thereof.
Priority Applications (6)
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|---|---|---|---|
| JP2001226179A JP3552686B2 (en) | 2000-10-30 | 2001-07-26 | Porous film made of tetrafluoroethylene polymer for stretching |
| EP20010123224 EP1201689B1 (en) | 2000-10-30 | 2001-10-02 | Tetrafluoroethylene polymer for stretching |
| DE60135894T DE60135894D1 (en) | 2000-10-30 | 2001-10-02 | Tetrafluoroethylene polymer for elongation |
| US09/970,674 US6518381B2 (en) | 2000-10-30 | 2001-10-05 | Tetrafluoroethylene polymer for stretching |
| RU2001129148/04A RU2271367C2 (en) | 2000-10-30 | 2001-10-29 | Stretchable tetrafluoroethylene polymer |
| CNB011377550A CN100478367C (en) | 2000-10-30 | 2001-10-30 | Tetrafluoroethylene polymer for expansion |
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| JP2000331278 | 2000-10-30 | ||
| JP2000-331278 | 2000-10-30 | ||
| JP2001226179A JP3552686B2 (en) | 2000-10-30 | 2001-07-26 | Porous film made of tetrafluoroethylene polymer for stretching |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2005061567A1 (en) * | 2003-12-22 | 2007-07-12 | ダイキン工業株式会社 | Non-melt processable polytetrafluoroethylene and its fine powder |
| WO2007119829A1 (en) * | 2006-04-13 | 2007-10-25 | Daikin Industries, Ltd. | Tetrafluoroethylene polymer and aqueous dispersion thereof |
| JP2010221219A (en) * | 2010-06-28 | 2010-10-07 | Asahi Glass Co Ltd | Gas-liquid mixing apparatus and gas-liquid mixing method, method for manufacturing polymer |
| JP2012144717A (en) * | 2010-12-21 | 2012-08-02 | Daikin Industries Ltd | Polytetrafluoroethylene mixture |
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| JP6218723B2 (en) * | 2013-11-29 | 2017-10-25 | ダイキン工業株式会社 | Biaxially stretched porous membrane |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2005061567A1 (en) * | 2003-12-22 | 2007-07-12 | ダイキン工業株式会社 | Non-melt processable polytetrafluoroethylene and its fine powder |
| JP4951970B2 (en) * | 2003-12-22 | 2012-06-13 | ダイキン工業株式会社 | Non-melt processable polytetrafluoroethylene and its fine powder |
| WO2007119829A1 (en) * | 2006-04-13 | 2007-10-25 | Daikin Industries, Ltd. | Tetrafluoroethylene polymer and aqueous dispersion thereof |
| US7820775B2 (en) | 2006-04-13 | 2010-10-26 | Daikin Industries, Ltd. | Tetrafluoroethylene polymer and aqueous dispersion thereof |
| JP5444712B2 (en) * | 2006-04-13 | 2014-03-19 | ダイキン工業株式会社 | Tetrafluoroethylene polymer and aqueous dispersion thereof |
| JP5732850B2 (en) * | 2008-05-21 | 2015-06-10 | 旭硝子株式会社 | Method for producing polytetrafluoroethylene fine powder |
| JP2010221219A (en) * | 2010-06-28 | 2010-10-07 | Asahi Glass Co Ltd | Gas-liquid mixing apparatus and gas-liquid mixing method, method for manufacturing polymer |
| JP2012144717A (en) * | 2010-12-21 | 2012-08-02 | Daikin Industries Ltd | Polytetrafluoroethylene mixture |
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