JPS59152825A - Polytetrafluoroethylene semi-sintered body and manufacture thereof - Google Patents
Polytetrafluoroethylene semi-sintered body and manufacture thereofInfo
- Publication number
- JPS59152825A JPS59152825A JP58155649A JP15564983A JPS59152825A JP S59152825 A JPS59152825 A JP S59152825A JP 58155649 A JP58155649 A JP 58155649A JP 15564983 A JP15564983 A JP 15564983A JP S59152825 A JPS59152825 A JP S59152825A
- Authority
- JP
- Japan
- Prior art keywords
- semi
- fired
- film
- fired body
- unfired
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
- B29C67/205—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising surface fusion, and bonding of particles to form voids, e.g. sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
- B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Molding Of Porous Articles (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、ボリテ１−ラフルＡロエチレン（以下、ｒ
Ｐ Ｔト［」という。）半焼成１木Ｊ３まひでの製？人
に関し、更に詳しくは二軸延伸可能なＰＴＦＥ半ｌＡ成
体およびその製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides bolite 1-rafur A roethylene (hereinafter referred to as r
It is called PT. ) Made of semi-fired 1 wood J3 mahi? The present invention relates to humans, and more particularly to a biaxially stretchable PTFE semi-IA composite and a method for producing the same.
ペース１〜押出により得られた１つＴ ＩＴ Ｅに未焼
成物品を延伸して多孔体を製造づる方法と（）て、（１
）結晶化度９５％以上のＰＴＦＥ−ノｉ）インパウダー
をその融点、」；り低い４度でベースト押し出しし、押
出助剤の抽出および乾燥などをイうった後、ＰＴＦＥの
結晶融点より（ｉＬい湿度で延伸を行って多孔体を得る
方法（持久＋＋１イ／１８−４／１６６４号公報ｊ３よ
び持久ｔ＋ｉ３５１−１８９９１号公報参照）（２）Ｐ
Ｔ’ＦＥ焼成体を３２７°０より高い温度で加熱し、次
い−Ｃぎわめでゆるやかに冷却しく”結晶化を高めた後
、延伸する方法（・特公昭５３−４２７９４号公報参照
）、および
（３）Ｐ−ｒＦｆ三フィルムを３２７°Ｃ、Ｊ、り低く
４ｇい温度で焼成し、焼成フィルムをカレンダプノ向に
垂直な方向へ延伸りる方法（４：Ｉ開明５５−５５３７
８号公報参照）
などが知られ（いる、。Pace 1 - A method of producing a porous body by stretching an unfired article into one piece obtained by extrusion ()
) PTFE powder with crystallinity of 95% or more is extruded at 4 degrees lower than its melting point, and after extraction and drying of extrusion aids, A method of obtaining a porous body by stretching at low humidity (Refer to Endurance ++1 I/18-4/1664 Publication J3 and Endurance t+i 351-18991) (2) P
A method in which a T'FE fired body is heated at a temperature higher than 327° 0, then slowly cooled with -C to enhance crystallization, and then stretched (see Japanese Patent Publication No. 53-42794), and (3) A method in which a P-rFf film is fired at a temperature of 327°C, J, and 4g lower, and the fired film is stretched in a direction perpendicular to the direction of the calender (4: I Kaimei 55-5537
(See Publication No. 8) are known.
上記（１）の方法によると、得られたＰＴＦＥ材料は、
二軸延伸ｅさ、大きい引張強度および非常に低い見掛（
、プ比重を有している。しかし、この方法では、結晶化
度が少くとも９５％のＰＴＦＥ）７フインパウターをＩ
ＴＪ ｌ、＼なＩプればならない。さらに、□延伸多孔
体をＰＴＦＥの融点以上に加熱してセットする」ニ稈が
必要であり、得られる多孔体の表面は粘着性があり、汚
れやづい。According to the method (1) above, the obtained PTFE material is
Biaxial stretching, large tensile strength and very low appearance (
, has a specific gravity. However, in this method, a 7-fine powder (PTFE) with a crystallinity of at least 95% is
TJ l,\na I must. Furthermore, it is necessary to set the stretched porous material by heating it above the melting point of PTFE, and the surface of the resulting porous material is sticky and easily stained.
上記（２）の方法では、延伸後のヒー１へヒラｊ・工程
は不要で、気体透過性は未延伸物に比べてり“くれでい
る。（プれども、ＰＴＦＥ焼成体は一軸延伸しかできず
、延伸倍率も４倍程度までと低い。In method (2) above, the heating step after stretching is not necessary, and the gas permeability is lower than that of the unstretched material. This is not possible, and the stretching ratio is as low as about 4 times.
さらに工程が長く、少くとも２回の加熱工程を含むから
エネルギーの消費が大きい。、得られるＰＴＦ［多孔体
の見掛り密度は比較的高い。Furthermore, since the process is long and includes at least two heating steps, energy consumption is large. , the apparent density of the resulting porous material is relatively high.
上記〈３）の方法では、ＰＴＦＦ焼成シー；へ（−１カ
レンダ方向に垂直な方向へ、２５０℃以下の温度におい
て延伸倍率４．２以下でしか延伸できず、しかもＩｓ？
られたＰ Ｔ Ｆ Ｅ多孔体の見掛は密度は比較的高く
なる。In the method of <3) above, the PTFF can only be stretched in the direction perpendicular to the (-1 calendar direction) at a stretching ratio of 4.2 or less at a temperature of 250°C or less, and furthermore, Is?
The apparent density of the P TFE porous body obtained is relatively high.
本発明者らは、ＰＴＦＥ多孔体の製法について仙究を小
ねろうら、Ｐ Ｔ Ｆ Ｅ半焼成体は二軸延伸可能であ
り、１へれた引張強度ｄ）よび滑らかな表面を持一つ多
孔体を製造り゛ることかでき、しかも多孔体の密度また
は見掛【プ比Φ（ま用途に応して調節できることを児い
出し、本発明を完成するに〒つた。The present inventors have conducted a small study on the manufacturing method of porous PTFE bodies, and have found that PTFE semi-fired bodies can be stretched biaxially and have a tensile strength of 1) and a smooth surface. The present invention has been completed by discovering that it is possible to manufacture a porous body with a single porous body, and that the density or apparent ratio Φ (Φ) of the porous body can be adjusted depending on the intended use.
１なわち、本発明の要旨は、ボリラ［〜ラフルＡ［」エ
ヂレン未焼成イホをポリテトラノルΔロー［チレン焼成
体の８１！点以上の温度で加熱づることにより製造され
、示差走査熱偵計による結晶融解曲線上で３４５±５°
Ｃの温度に吸熱カーブを持ち、未焼成体、半焼成体およ
び焼成体の融解熱量により定義される結晶転化率が０．
１０〜０．８５であり、Ｘ線回折により測りｒした結晶
化度′が８０〜９３％であることを特徴とするボリンド
ラフルオロ［チレン半焼成体に存覆る。1 That is, the gist of the present invention is to convert Borilla [~Rahul A] ethylene unfired Iho to polytetranol ΔRho [81! of tyrene fired body! 345±5° on the crystal melting curve by differential scanning thermal reconnaissance.
It has an endothermic curve at a temperature of C, and has a crystal conversion rate of 0.
10 to 0.85, and the degree of crystallinity measured by X-ray diffraction is 80 to 93%.
ここてｒＰＴＦＥｌとは、う１−）゛ノルＡ口にチレン
のポモポリマーだ【フＣ・なく、テトラフルΔ１」エチ
レンと２重傷％を越えない共Φ合可能な他のモノマーと
の共重合体をも包含りる。Here, rPTFE1 is a pomopolymer of ethylene and tetrafluor Δ1, which is a copolymer of ethylene and other monomers that can be co-formed at not more than 2%. It also includes.
本発明のＰＴＦＥ半焼成体に１、ペースト押出または圧
縮成形により得られる１−）１’ にＥ未焼成成形品を
、Ｐ Ｔ Ｆ ＩＥ焼成体の融点以上、好ましくはト）
ＴＦＥ焼成体の融点とＰＴＦＥ未焼成体の融点との間の
温度において、加熱することにより製造できる。まｌζ
、本発明の半焼成体は、ＰＴＦＥ未焼成成形品を、Ｐ
Ｔ Ｆ Ｅ未焼成体の融点Ｊζり高い温度において非常
に短時間、たとえば、３６０℃で２０秒以下加熱するこ
とによっても製造できる。1 to the PTFE semi-fired body of the present invention, 1-) obtained by paste extrusion or compression molding, and an E unfired molded product to the PTFE semi-fired body of the present invention;
It can be produced by heating at a temperature between the melting point of the TFE fired body and the melting point of the PTFE green body. ζ
, the semi-fired body of the present invention is a PTFE unfired molded product,
It can also be produced by heating at a temperature higher than the melting point Jζ of the TFE green body for a very short time, for example, at 360° C. for 20 seconds or less.
しかし、Ｐ ”ｒ Ｆ Ｅ未焼成体をＰＴＦＥ焼成体の
融点より低い温度でいくら長く加熱しても半焼成体は得
られない。However, no matter how long the P"rFE green body is heated at a temperature lower than the melting point of the PTFE fired body, a semi-fired body cannot be obtained.
本発明の製法で必要どされる加熱時間は、加熱物の見掛
は比重を測定することにより定めることができるａＰＴ
ＦＥ未焼成体は多孔性であり、その見掛り比重は通常１
．２〜１．７、好ましくは１．４〜１．７であり、Ｐ
−ｒ Ｆ Ｅ自身の比重（一般に約２．２）より小さい
。多孔性のＰＴＦＥ未焼成体を、ＰＴＦＥの通常の焼成
温度である３５０〜４００″Ｃで加熱すると、物品中の
多孔がなくなり、物品が収縮して見掛′（）比重がＰＴ
ＦＥの真の比重に近づくことが知られている。本発明の
加熱処理も未焼成１木に同様の動床を承り。加熱したＰ
Ｔ Ｆ 「の比重は、一般に少くとＵ）１８である。The heating time required in the production method of the present invention can be determined by measuring the apparent specific gravity of the heated material.
FE green bodies are porous and their apparent specific gravity is usually 1.
．． 2 to 1.7, preferably 1.4 to 1.7, P
-r FE Smaller than the specific gravity of E itself (generally about 2.2). When a porous PTFE green body is heated at 350-400''C, which is the normal firing temperature for PTFE, the porosity in the article disappears and the article shrinks, reducing the apparent specific gravity to PTFE.
It is known that it approaches the true specific gravity of FE. The heat treatment of the present invention also applies a similar moving bed to unburned wood. heated P
The specific gravity of T F is generally at least U)18.
さらに見掛【プ比槍が２．２０〜２．２Ｆ）稈１ｑの本
発明のＰ Ｔ Ｆ ＩＥ半焼成体でｂ延伸しτＰ Ｔ
Ｆ Ｅ多孔体とづることＩ）りできる。フィルム、シー
ト、ブユーブ、棒等のＩＩ！厚、ｌ：ｉ９１９またＩｔ
直イイが０．２１１１１１１より小さい場合は加熱変性
は比較的り、０時間でその厚みの大部分の変性が可能ひ
あるか、膜斤、壁厚または西経７ＪＸ０ 、 ２〜２
ｍｍの場合Ｇ；１０ 、 ２ ｍｍより小さい場合に比
しく長口）間の加熱が必要である。Further, b is stretched with the P T F IE semi-fired body of the present invention of 1 q of culm (apparent ratio is 2.20 to 2.2 F) and τ P T
FE can be used as a porous material. Films, sheets, tubes, rods, etc. II! Thickness, l: i919 also It
If the thickness is less than 0.2111111, thermal denaturation is relatively slow, and most of the thickness can be denatured in 0 hours, or the membrane thickness, wall thickness, or west longitude 7JX0, 2 to 2
In the case of a diameter of less than 10 mm, heating is required for a longer distance than in the case of a diameter of less than 2 mm.
いずれの場合もＰＴＦＥの加熱による変性は成形体の表
面から内部に向かって進行゛りる。In either case, the modification of PTFE by heating proceeds from the surface of the molded body toward the inside.
本発明のＰ Ｔ Ｆ Ｆ半焼成体の他の特１跋の一つは
、その表面がはは無孔であることである。従・）Ｃ１加
熱時間は加熱物品の表面の多孔状態をｆｔ、察りること
によっても定めることができる。多孔状態は、たとえば
表面に溶剤を塗布しで調べる。まず１表面にマーカーイ
ンキを塗布した後、トルーＩ−ンの様な溶剤を含浸させ
た布でふぎとり、インキがふきとれれば、表面は無孔で
ある１゜
上記の半焼成体にみられる変化に加え、Ｐ Ｔ ＦＦ物
品の透明性も変化する。加熱温度がＰ Ｔ Ｆ Ｅ焼成
体の融点より低ければ、物品は不透明のままである。薄
いまたは小さいＰＴＦＥ半焼成体は一般に透明である。One of the other special features of the PTF semi-fired body of the present invention is that its surface is non-porous. The C1 heating time can also be determined by observing the porosity of the surface of the heated article. The state of porosity is examined, for example, by applying a solvent to the surface. First, marker ink is applied to one surface, and then wiped off with a cloth impregnated with a solvent such as Trou-Ine. If the ink is wiped off, the surface is non-porous. In addition to the changes, the transparency of the PTFF article also changes. If the heating temperature is below the melting point of the P T F E fired body, the article remains opaque. Thin or small PTFE semi-fired bodies are generally transparent.
加えて、本発明のＰ Ｔ Ｆ Ｅ半焼成体の無定形指数
は、未焼成体より大ぎく、かつ焼成体より小さいことも
特徴の１つである。In addition, one of the characteristics of the P T F E semi-fired body of the present invention is that the amorphous index is larger than that of the unfired body and smaller than that of the fired body.
ｐ Ｔ Ｆ Ｅ半焼成体を得るために焼成炉またはソル
トバス中で適当な湿度に十分な時間、未焼成体を加熱し
た後、ＰＴ Ｆ Ｅ半焼成体は、炉またはバスから取り
出きれ、冷却され、別の工程で延伸される。また、加熱
した物品を熱いうちに続いて延伸してもよい。After heating the green body for a sufficient period of time at suitable humidity in a kiln or salt bath to obtain a PT F E semi-fired body, the PT F E semi-fired body can be removed from the furnace or bath; It is cooled and stretched in another step. Alternatively, the heated article may be subsequently stretched while still hot.
本発明のＰ Ｔ Ｆ Ｅ半焼成体の結晶転化率は、次の
様にして決定される。The crystal conversion rate of the PTFE semi-fired body of the present invention is determined as follows.
まず、半焼成体から１０．０＋０．１ｍｇ秤但しＣ切取
り試別とする。上述のとおりＰ Ｔ Ｆ Ｅの加熱変性
は表面から内部へ進行するので、半焼成の度合は試料の
各部分において必ずしも均一ではない。この（σ１向は
当然Ｉ１５！厚の１９いものにａ５いて顕著である７、
前記の試Ｈの採取に際ｌ）ては試料の厚Ｉ味方向に（ｂ
いて各変性度合のものが平均化して含まれるように配慮
されイヱりれならない。ｒ）、 ｌの試１′＋１を用い
てまず結晶融解曲線ｉを求める。First, 10.0+0.1 mg of the semi-fired body was cut out on a scale and tested. As mentioned above, the thermal denaturation of P TFE proceeds from the surface to the inside, so the degree of semi-baking is not necessarily uniform in each part of the sample. This (σ1 direction is naturally noticeable in the I15! thickness of the 19-thick A57,
When collecting the sample H mentioned above, the thickness of the sample was measured in the direction (b).
Care must be taken to ensure that each degree of modification is averaged and included. First, obtain the crystal melting curve i using test 1'+1 of r) and l.
上記と同様の方法により、Ｐ Ｔ Ｆト未焼成体の試料
１０．Ｏ±０．１１１１！ＩをＢＪ製田る。Sample 10 of PTF green body was prepared by the same method as above. O±0.1111! I made BJ.
結晶融解曲線は、示差走査熱量計〈以下、「１）ＳＣｊ
という。例えばＰ ｅｒｋｉｎ −Ｆ１ｍｅｒネｌ ’
ＦＪ ［’） ５Ｃ−２型）を用い−Ｃ記録りる。よ７
１” Ｐ −ｒ ＋ニド未焼成体の試料を、Ｄ Ｓ Ｃ
のアルミニウム製パンにイ」込み、未焼成体の融解熱お
よび・綽・′成体の融解熱を次の手順で測定する：
（１）試料を１６０’Ｃ／分の加熱速度Ｃ２７７°Ｃに
加熱し、次いで１０’Ｃ／分の、加熱速度で２７７°Ｃ
から３６０℃まで加熱する。。The crystal melting curve was measured using a differential scanning calorimeter (hereinafter referred to as “1) SCj
That's what it means. For example Perkin-F1mer '
-C recording using FJ [') 5C-2 type). Yo7
A sample of the 1” P −r + nide green body was subjected to D S C
Place the sample in an aluminum pan and measure the heat of fusion of the unfired product and the heat of fusion of the finished product using the following steps: (1) Heat the sample at a heating rate of 160°C/min to 277°C. and then 277°C at a heating rate of 10'C/min.
Heat from to 360°C. .
この加熱工程において記録された結晶融解曲線の１例を
第１図に示Ｊ。この−Ｙ稈に（１３いて現われる吸熱カ
ーブの位置を、ｒ Ｐ Ｔ−ニド未焼成体の融点」また
はＰ Ｔ Ｆ ［ファインパウダーの融点と定義する。An example of a crystal melting curve recorded in this heating process is shown in Figure 1. The position of the endothermic curve that appears in this -Y culm (13) is defined as the melting point of r P T-nide green body or P T F [melting point of fine powder.
（２）３６０℃まで加熱した直後、試料を８０’Ｃ／分
の冷却速度で２７７°０に冷月１する′。(2) Immediately after heating to 360°C, cool the sample to 277°C at a cooling rate of 80°C/min.
（３）試料を角ひ１０℃／分の加熱速度で３６０°Ｃに
加熱づる。(3) Heat the sample to 360°C at a heating rate of 10°C/min.
加熱工程（３）において記録される結晶融解曲線の１例
を第２図に示す。加熱工程（３）において現われる吸熱
カーブの位置を、ｒｐ−ｒｔ二、ａ焼成体の融点」と定
義する。An example of a crystal melting curve recorded in the heating step (3) is shown in FIG. The position of the endothermic curve that appears in the heating step (3) is defined as the melting point of the fired body.
ＰＴＦＥ未焼成体また（よ焼成体の融解熱は、吸熱カー
ブとベースラインとの間の面積に比例する。The heat of fusion of a PTFE green or pre-fired body is proportional to the area between the endothermic curve and the baseline.
ベースラインは、Ｄ Ｓ Ｃチャート上の３０ ／ ’
Ｃ（５８０°Ｋ）の点から吸熱カーブの右端の基部に接
′りるように引いた直線である。The baseline is 30/' on the DSC chart.
This is a straight line drawn from point C (580°K) so as to touch the base of the right end of the endothermic curve.
続いて、ＰＴＦＥ半焼成体について結晶融解曲線を工程
（１）に従って記録する。この場合の曲線の１例を第３
図に示づ−０
そこで、結晶転化率は次の式によっＣ４算される：
結晶転化率−（Ｓｔ −８３）／ （Ｓｔ −８２）こ
こで、ＳｌはＰ Ｔ Ｆ Ｅ、！＜焼成体の吸熱ノｊ−
７の面積（第１図参照）であり、Ｓ２はＰ Ｔ−Ｆ Ｉ
Ｅ焼成体の吸熱カー１の面積〈第２図参照）Ｃ′あり、
Ｓ、ｑＬユＰ Ｔ’ Ｆ ＩＥ半焼成体の吸熱カーブの
ｍ）積（第３図参照）である。Subsequently, a crystal melting curve is recorded for the PTFE semi-fired body according to step (1). An example of the curve in this case is shown in the third example.
-0 As shown in the figure, the crystal conversion rate is calculated by the following formula: Crystal conversion rate - (St -83)/ (St -82) where Sl is P T F E,! <The heat absorption of the fired body
7 (see Figure 1), and S2 is P T-F I
E The area of the endothermic car 1 of the fired body (see Figure 2) C' is present,
S, qL UPT'F IE is the product of the endothermic curve of the semi-fired body (see Figure 3).
一般に、本発明の１つＴ Ｕ Ｅ Ｍ’ ＩＩ；ｌ’ｌ
！成体の結晶転化率は、０．１０へ−０，８５，９１′
ましくは０．１５・〜０．７０である。In general, one of the invention T U E M'II;l'l
! The crystal conversion rate of the adult is 0.10-0,85,91'
Preferably it is 0.15-0.70.
結晶化度は、Ｘ線回折により次の手順で決定される：
用いたＸ線回折用はＱ ｅｉｇｃｒ Ｆ ｌｅＸ Ｒａ
（１−ＩＩ Ａ（理学電機株式会ネ」製）である。・′
×線源は、ＣＵ−にαてあり、Ｘ線はピンクＩＮメータ
を用い０１１色化した１、
Ｐ Ｔ Ｆ Ｅ半焼成イホの試料を７ノルミニウム製、
Ｉ＼ルダーに入れ、Ｘ線回折パターンＣ，４，１０°〜
２５°の２θニａ３ イＴ ａｌ定Ｌ タ、 ＩＩＱ型
的４＞ Ｘ 線回折パターンを第４図に示す。Crystallinity is determined by X-ray diffraction using the following procedure:
(1-II A (manufactured by Rigaku Denki Co., Ltd.).・'
The x-ray source is α at CU-, and the X-rays are colored using a pink IN meter.
X-ray diffraction pattern C, 4, 10°~
FIG. 4 shows the 25° 2θ ni a3 I T al constant L ta, IIQ type 4> X-ray diffraction pattern.
結晶化度は、結晶部分に対応り−る２θ−′Ｉε３゜で
のピークおにび無定形部分に対応づる２θ−・１６″の
ピークから次のようにして決定した：×線回折ピークに
おけ゛る結晶部分に対応り゛る面積と無定形部分に対応
する面積を分けるため、２θ−１６°に対応する曲線上
の点からピークの右側基部へ第４図に示ツにうに直線を
引いた。The degree of crystallinity was determined from the peak at 2θ-'Iε3° corresponding to the crystalline portion and the peak at 2θ-16'' corresponding to the amorphous portion as follows: In order to separate the area corresponding to the crystalline part and the area corresponding to the amorphous part, draw a straight line from the point on the curve corresponding to 2θ-16° to the right base of the peak as shown in Figure 4. I pulled it.
結晶化度は次の式に従って計算される：結晶化度く％）
−
００１ｃ
ＩＣ＋０．６６Ｉａ
ここでＩＣは結晶部分に対応する面積であり、Ｉａは無
定形部分に対応する面積である。Crystallinity is calculated according to the following formula: crystallinity %)
- 001c IC+0.66Ia Here, IC is the area corresponding to the crystal part, and Ia is the area corresponding to the amorphous part.
一般に、本発明のＰＴＦＥ半焼成体の結晶化度は、８０
〜９３％、好ましくは８５〜９２％である、。Generally, the crystallinity of the PTFE semi-fired body of the present invention is 80
~93%, preferably 85-92%.
本発明のＰＴＦＥ半焼成体は、ＰＴＦＥ未焼成体および
焼成体と比較して特異的な表面状態を有していることが
見出された。このことは、第５５〜７図に示されている
。これら図面は、ＰＴＦＥ未焼成体〈実施例３のフィル
ムＮ０１９、第８表）、Ｐ Ｔ ［：″［三半焼成体〈
実施例３のフィルムＮＯ１２、第８表）およびＰ １”
ｌ−Ｅ焼成体〈実施例３のフィルムＮｏ、１８．、第
８表）の表ｍｊのレブリ）ノの走査型電子顕微鏡写真で
ある（夫々１６’、 ００’ＣＮ呂）。It has been found that the PTFE semi-fired body of the present invention has a unique surface condition compared to PTFE green bodies and fired bodies. This is illustrated in Figures 55-7. These drawings show PTFE unfired body (film N019 of Example 3, Table 8), PTFE green body (film N019 of Example 3, Table 8), PTFE green body
Film No. 12 of Example 3, Table 8) and P 1”
1-E fired body <Film No. of Example 3, 18. , Table 8) are scanning electron micrographs of Table mj of Table 8) (16' and 00'CNro, respectively).
第５図に示されたＰ Ｔ Ｆ ＩＥ半焼成体の表面には
、多数の粒子が見られる。第７図に示された１丁［：Ｅ
焼成体の表面には、Ｉ） Ｔ Ｆ Ｅの特徴であるよく
発達したパン１く構造が見られる。これに対し、本発明
のＰ ”Ｉ−Ｆ Ｅ半焼成体の表１１１１には、粒子や
バンド構造は全くないしほとんど見られｔＺい。第０図
では、粒子またはバンド構造に１全く見られない。A large number of particles can be seen on the surface of the PTF IE semi-fired body shown in FIG. One gun shown in Figure 7 [:E
A well-developed bread structure, which is a characteristic of I) TFE, can be seen on the surface of the fired product. In contrast, in Table 1111 of the P"I-F E semi-fired body of the present invention, there are no or almost no grains or band structures. In Figure 0, no grains or band structures are seen at all. .
本発明のＰ’ Ｔ Ｆ Ｅ半焼成体１．Ｊ、通常の形状
、例えばフィルム、シート、チ旦−ブパ、捧４Ｔとてあ
ってよい。P' T F E semi-fired body of the present invention 1. J. It may be in any conventional shape, such as a film, sheet, chip, or 4T.
本発明のＰ Ｔ Ｆ ｌ＝半焼成体には、１人械的、物
理的および化学的性質を改良し、Ｐ Ｔ Ｆ Ｅ半焼成
体に種々の法化を（＝Ｊ与Ｊるため、０機またＣａｌ
７！’、’ ｆｊＭの充填剤を配合してもＪ、い１．充
填剤の例には、ガラス、カーボン、グラフ１イＩ〜、シ
リカ、ｎ長生ブタン、酸化亜鉛、チタン酸カリウムいク
ルク、ポリマー類（例えばテ１〜ラフルＪ「−、ｌ 、
ｌニブレンボリマー類、ポリアミドシ；１、ポリアミド
イミドなど）か包含される。In order to improve the mechanical, physical and chemical properties of the P T F l = semi-fired body of the present invention, and to apply various methods to the P T F E semi-fired body, 0 aircraft also Cal
7! ',' Even if fjM filler is blended, J, 1. Examples of fillers include glass, carbon, graphite, silica, long-lived butane, zinc oxide, potassium titanate, curcum, polymers (e.g.
1, polyamide polymers, polyamide polymers; 1, polyamideimide, etc.).
本発明のＰ Ｔ Ｆ Ｅ半焼成体の表面における接着性
を改良するため、自体既知の方法により、例えばナフタ
レン１１）イホをす１〜す１クムのアンエニア水または
環状エーテル溶液に溶解したものにより表面を処理する
か、またはスパッターエツチングにより処理づることに
よりエツチングしてもよい。In order to improve the adhesion on the surface of the P T F E semi-fired body of the invention, it is possible to improve the adhesion by methods known per se, for example by dissolving naphthalene 11) ipho in 1 to 1 cum of aqueous aqueous or cyclic ether solution. Etching may be performed by treating the surface or by treating with sputter etching.
本発明のＰ Ｔ Ｆ Ｅ半焼成体は、それ自体有用なも
のである。例えば、Ｐ １− Ｆ Ｅ半焼成体のフィル
ムは溶媒用の容器のキ１ツブとしで用いることができる
。半焼成体の表面は延伸前には無孔であるので効果的に
溶媒をシールすることができる。半焼成体のフィルムは
、例えば指により圧を加えることによって延伸ず４ると
、多孔性になり、溶媒は多孔性フィルムを透過すること
ができる。The PTFE semi-fired body of the present invention is useful in itself. For example, a film of P 1-FE semi-fired product can be used as a key for a container for a solvent. Since the surface of the semi-fired body is non-porous before stretching, the solvent can be effectively sealed. If the film of the semi-fired body is not stretched, for example by applying pressure with the fingers, it becomes porous and the solvent can pass through the porous film.
本発明のＰＴＦＥ半焼成体は、自体相互にまたは他の基
材に対して溶融接着できる。また積層しあるいはガスケ
ットに成形することができる。The PTFE semi-fired bodies of the present invention can be melt bonded to themselves or to other substrates. It can also be laminated or formed into a gasket.
さらに、本発明の半焼成体は、膨張または延伸すること
ができ、ＰＴＦＥ多孔Ｄｉ＼を形成する。Furthermore, the semi-fired body of the present invention can be expanded or stretched to form PTFE porous Di\.
Ｐ Ｔ Ｆ ［半°焼成イホの１影服よ１．−は延伸は
、自体既知の方法により、室温からＰ Ｔ ）−Ｆ未焼
成体の融点の間の濡１９にａ３いて行うことがＣきる、
７延伸倍キＣＪｌ、用）♂にＪ、つ−でｒ／２るが通常
的１０侶までである。PT - The stretching can be carried out by a method known per se at a temperature between room temperature and the melting point of the green body (P T )-F.
7 stretching times: CJl, ♂ to J, two to r/2, but usually up to 10 times.
本発明のＰ Ｔ Ｆ Ｅ半焼成体４Ｊ、０．５％、７部
秒程度の延伸速度で延伸でき、指（、二よっても延伸す
ることができる。The P T F E semi-fired product of the present invention 4J, 0.5%, can be stretched at a stretching speed of about 7 parts per second, and can also be stretched by fingers.
ＰＴＩ−Ｅ半焼成体の延伸にＪＪいて、 −；Ｊ ン人
的な変化は、従来のＰ Ｔ Ｆ Ｅ物品の砂止よりも大
さい。The human variation in stretching of PTI-E semi-fired bodies is greater than that of conventional PTFE articles.
例えば、２５μより薄いフィルムを％ 、、Ｂ ？ｌる
」ｂ合、未焼成フィルムを延伸する場合には大きな用法
変化が生じないので、非常に薄い未焼成−フィルムを延
伸する必要がある。しかし′／ヱがら、）Ｊレンダ成形
・された未焼成フィルｌオはわかめ状になり、Ｉ：ｉｔ
子の配向は均一ではないのて、フィルムの強度し不均一
になる。従って、従来の７ｊ法によって薄いＰｌ−Ｆ
Ｅ多孔性フィルムをＴ”２’−的に製Ｆ ９ることは非
常に困難である′。また市販３されている）） −ｒ
Ｆ Ｅ多孔性フィルｌ＼は５０μにり大きい厚さを有し
ている。これに対し、本発明によれば、厚いＰ Ｔ 「
Ｅ多孔性フィルムだけでなく薄いＰ丁ＩＴ Ｆ多孔ｆｌ
フィルムも容易に製造できる。For example, a film thinner than 25μ is %,,B? In this case, it is necessary to stretch a very thin green film, since there is no significant change in usage when stretching a green film. However, the unfired film that has been rendered and molded becomes wakame-like, and I:it
Since the orientation of the particles is not uniform, the strength of the film is non-uniform. Therefore, by the conventional 7j method, thin Pl-F
It is very difficult to produce a porous film manually.It is also commercially available3)) -r
The FE porous film has a thickness greater than 50μ. On the other hand, according to the present invention, thick P T "
E Not only porous film but also thin P-Ting IT F porous fl
Films can also be easily produced.
本発明のＰ １− Ｆ ｌｘ半焼成体を延伸して作られ
た多孔性ＰＴＦＥ材料は、結晶融解曲線において３４５
±５°Ｃに吸熱カーブを持つ。多孔性１） Ｔ Ｆト月
利の吸熱カーブの面積は、Ｐ Ｔ Ｆ Ｆ ’４ニカ゛
ｄ成体の吸熱カーブの面積よりも小さい。The porous PTFE material made by stretching the P1-F lx semi-fired body of the present invention has a crystalline melting curve of 345
It has an endothermic curve at ±5°C. Porosity 1) The area of the endothermic curve of T F 4-d adult is smaller than the area of the endothermic curve of P T F F '4 d adult.
１） Ｔ Ｆ Ｅ多孔性材料をフィルターとして用いる
場合、月料はできるだ（づ目詰まりしないのが好ましく
、かつ曜過物の透過速度が大ぎいことが望ましい。さら
にすぐれた機械的性質を持つことが望ましい。本発明に
より賀られるＰＴＦＥ多孔性拐料は、表面におりる孔の
割合が内部における孔の割合にりら小さいという特異的
な構造をイ〕しでいる。この構造上の特徴は、第８図お
よび第９図に示されている。両図面は、実施例１の第４
表のフィルムＮｏ ４ （ヒートセットなし）のｐ Ｔ
＋−Ｅ多孔性材料の表面の走査型顕微鏡写冥（３’、
０００培） ｉ１５よび実施例１の第４表のフィルムＮ
０２（ヒーｌ−レツ１〜＾Ｉｌ）の断面の走台型顕微鏡
写真（３，０００倍）である。従−）で、１つＴＦＦ多
孔性材利は、非常に目詰まりし、に＜＜、薄い場合にＪ
３いても比較的）５過性が高い１゜
従来のカレンダ成形未焼成し”Ｉ’ Ｆ Ｅフィルムを
カレンダ方向に垂直な方向へ延伸した場合、機械的強度
がＩＬｌわれ、い−！ｖ゛れのＩ）向に６等しい強度を
持つフィルムを１１Ｊ１ようとすれ（、；積層しなりれ
ばなら４ｆい。しかしながら、／ｌ（発明の半焼成体か
ら得られるｐｒｒＥ多孔性゛フイルノ、（、Ｌ、カレン
ダ方向【ごヌ・１し垂直および平イｊな方向１・ｒ ＜
れた強度を有しており、中層フィルムとし１用いること
ができる。1) When using a TFE porous material as a filter, it is preferable that it not be clogged, and that the permeation rate of the filter material is high.It should also have excellent mechanical properties. The porous PTFE material provided by the present invention has a unique structure in which the proportion of pores on the surface is smaller than the proportion of pores in the interior.This structural feature is , FIG. 8 and FIG. 9. Both figures show the fourth example of Example 1.
Film No. 4 (no heat set) p T in the table
+-E Scanning micrograph of the surface of porous material (3',
000 culture) i15 and Film N of Table 4 of Example 1
02 (Heal-Lets 1-^Il) is a table-type micrograph (3,000x magnification) of the cross section. In one case, the TFF porous material is very clogged and very thin.
When a conventional calender-formed, unbaked "I'FE film is stretched in a direction perpendicular to the calender direction, its mechanical strength decreases, and 11J1 films having a strength equal to 6 in the I) direction (,; if laminated, it would be 4F. L, calendar direction [gonu・1, vertical and horizontal direction 1・r <
It has excellent strength and can be used as an intermediate layer film.
次に実施例および比較例をｌｊ、し、本発明を訂１１＋
＋に説明Ｊ８ｏ尚、ｙｉｌｉとあるの（二いＢ Ｓ３部
を現ねづ。Next, Examples and Comparative Examples are given, and the present invention is revised 11+
In the + explanation J8o, it says yili (2 BS S3 part is shown).
実施例１
（１）Ｐｌ”ＦＥ未焼成体の製造
Ｐ Ｔ Ｆ Ｅファインパウダ゛−（ダイキン王Ｅ １
′ＡζＪ（会社製「ポリフロン・ファインパウダーＦ−
１０４Ｊ）１０．０部に押し出し助剤どし−Ｃ炭化水索
油（エッソ石油「アイソパーＭ」）２４部を加え、シリ
ンダー内径１３０ｍｍ、押し出し金型ダイス内径１２ｍ
ｍの押し出し機により丸棒のペースト押し出しを行い、
これを７０℃に加熱したカレンダロールにより２８ｍｍ
／分の速度でカレンダｆｉ） ＆ｉしてフィルムとし、
このフィルムを５０℃の１〜リク［１０エチレンに浸漬
して押し出し助剤を抽出除去した俊ＪｆＡ乾し、平均厚
さ１Ｑ□Ｉ１ｍ、平均幅２００…ｍのＰＴＦＥ未焼成フ
ィルムを作成した。このフィルムの見掛は密度は１−５
Ｑ／ ０ｌｌｌ”であり、１部ｍｍ幅のデーゾを切取
り、２００ｍ１ｌ＋／分の引張速度で測定したフィルム
の押し出し縦方向および横方向の仔（械的強度は第１表
に示ず通りであった。Example 1 (1) Production of Pl"FE green body
'AζJ (manufactured by the company ``Polyflon Fine Powder F-
Add 24 parts of extrusion aid Doshi-C hydrocarbon oil (Esso Oil "Isopar M") to 10.0 parts of 104J), and make a cylinder with an inner diameter of 130 mm and an extrusion die with an inner diameter of 12 m.
Paste is extruded into a round bar using an extruder.
This was heated to 70℃ using a calender roll to 28mm.
Calendar fi) &i to film at a speed of /min,
This film was immersed in 1 to 10 ml of ethylene at 50° C., the extrusion aid was extracted and dried, and an unfired PTFE film having an average thickness of 1Q□I1 m and an average width of 200 m was prepared. The apparent density of this film is 1-5
Q/0lll'', cut out 1 part mm wide deso and measured the lengthwise and crosswise extrusion of the film at a pulling speed of 200ml+/min (mechanical strength was as shown in Table 1). .
第１表
（２）未焼成フ・Ｃルムの加熱
このＪ、うにして得られたＩ） ｌ−Ｐ ＩＦ未焼成フ
ィルムを、２００ ’Ｃ１３００’Ｃ１３２０℃、３３
０°Ｃまたは３６０ ’Ｃに加熱した焼成炉に入れ、所
定の時間加熱した後苗温に冷却した。加熱されたフィル
ムの性質を次のようにして測定した：ｌ良
Ｊ １ｓ６８９２−１９７６に従って測定。Table 1 (2) Heating of unfired film/C film.
It was placed in a firing furnace heated to 0°C or 360'C, heated for a predetermined time, and then cooled to seedling temperature. The properties of the heated film were determined as follows: Measured according to Iryo J 1s6892-1976.
透明性 目視により？睨察、１ ＤＳＣにおける吸熱カーブ 上述のようにして測定。transparency By visual inspection? Glare, 1 Endothermic curve in DSC Measure as described above.
Ｍ災
赤外線吸収スベク１〜ルにお（）る７ ７３ ｃｍ′□
１の吸収と２ 、３６７ｃｍ−１の吸収の比として決定
。7 73 cm'□
Determined as the ratio of the absorption at 1 and the absorption at 2,367 cm.
Ｐ２“２ケ および１」ひ
フィルムＮＯ１，２および３の場合には、フィルムをカ
レンダ方向に沿っで幅１Ｑｍｍのス１−リップに切断し
、フィルムＮＯ４−８の場合には、フィルムをＪＩＳＮ
ｏ３ダンベル型に切断した。引張強度Ｊ５よび沖ひは、
空温において引張速度２゜Ｏｍｌ＋／分て測定した。P2 "2 pieces and 1" In the case of film Nos. 1, 2 and 3, the film is cut into slips of width 1Qmm along the calender direction, and in the case of film No. 4-8, the film is cut into JIS N.
Cut into o3 dumbbell shape. Tensile strength J5 and Okihiha,
Measurements were made at air temperature at a tensile rate of 2° Oml+/min.
マーカーインキの透過性
市販のマーカーインキ（商品名「マジックインキ」）を
２イ１３是の１〜ルエンで希釈し、刷毛でフィルム上に
塗布した。乾燥後、インキの（Ｊいた表面をトルエンの
含浸された布で拭った。Permeability of Marker Ink A commercially available marker ink (trade name "Magic Ink") was diluted with 2 to 13 parts of luene and applied onto the film with a brush. After drying, the surface of the ink was wiped with a toluene-impregnated cloth.
結果を第２−１表および第２−２表に示すこの実施例に
おいては、フィルム４および６が本発明の範囲内であり
、他のものは比較である。In this example, the results of which are shown in Tables 2-1 and 2-2, films 4 and 6 are within the scope of the invention, and the others are comparative.
（３）加熱フィルムの延伸
工 裁断フィルムの延伸
加熱したフィルム夫々を幅２Ｑｍｍ、長さ５０′ｎｌｌ
１１のストリップに裁断した。ストリップはカレンダ方
向に対し平行または垂直方向に引張速度１００％／秒で
７００％まで自由端一軸延伸した。(3) Stretching of heating film The stretched and heated cut film was each stretched to a width of 2Qmm and a length of 50'nll.
Cut into 11 strips. The strips were free-end uniaxially stretched to 700% in a direction parallel or perpendicular to the calender direction at a pulling rate of 100%/sec.
ストリップの延伸可能性およびこのようにして形成され
たＰＴＦＥ多孔性フィルムの厚さおよ□び幅の減少率、
密度および引張強度を第３表に示り。the stretchability of the strip and the rate of reduction in the thickness and width of the PTFE porous film thus formed;
The density and tensile strength are shown in Table 3.
引張強度は、幅が１０１１１ｍ以上のものについては幅
１０ｍｍのストリップについて、または幅が１０ｍｍ未
満のものについてはそのままの幅で引張速度２００ｍｍ
／分で測定した。The tensile strength is measured for strips with a width of 10 mm for strips with a width of 10111 m or more, or at a tensile speed of 200 mm at the same width for strips with a width of less than 10 mm.
/min.
第３表に示した結果から理解されるようにフーｒルムＮ
ｏ４および６から形成されたＰＴＦＥ多孔性フィルムは
カレンダ方向の横断方向について延伸可能であり、この
方向にすぐれた引張強度を有している。As understood from the results shown in Table 3, the full N
The porous PTFE films formed from O4 and O6 are stretchable transversely to the calendering direction and have excellent tensile strength in this direction.
■ 未裁断フィルムの延伸
長ｇ１００ｍｍの熱処理したフィルムＮｏ４を、３００
″Ｃに保った炉内で引張速度２５０％／秒においてカレ
ンダ方向に平行な方向へ所定の延伸倍率まで延伸した。■ Heat-treated film No. 4 with an uncut film stretching length g of 100 mm was
The film was stretched to a predetermined stretching ratio in a direction parallel to the calender direction at a tensile rate of 250%/sec in a furnace maintained at a temperature of 1.
厚さおよび幅の減少率、密度、引張強度およびマトリッ
クス強麿を第４表に示す。The percentage reduction in thickness and width, density, tensile strength and matrix strength are shown in Table 4.
上述と同様の方法により、加熱したフィルムＮｏ２およ
び４を６．００％まで延伸した。次いで炉の温度を３５
０°Ｃに上昇し、その温度で１０分間保ったくと−１〜
セツテイング）。炉からフィルムを取出すと、フィルム
はさらに収縮した。The heated films No. 2 and 4 were stretched to 6.00% by the same method as described above. Then set the furnace temperature to 35
-1 to 0°C and kept at that temperature for 10 minutes
setting). When the film was removed from the oven, it shrank further.
このようにして得られたＰＴＦＥ多孔性フィルムの厚さ
および幅の減少率、密度、引張強度およびマトリックス
強度を第５表に示す。Table 5 shows the thickness and width reduction, density, tensile strength and matrix strength of the PTFE porous film thus obtained.
フィルムの厚さｄ５よび幅の減少率は、延伸前および延
伸後のフィルムの中火部分のＪｈす３よび幅から計算し
た。フィルムの密度は、フィルム中央部分から裁断した
５ ＣＩＩＩＸ ５ Ｃｌ１ｌのピースの重さおにび厚
ざから計算した。The reduction rate of the thickness d5 and width of the film was calculated from Jh3 and width of the medium-heated portion of the film before and after stretching. The density of the film was calculated from the weight and thickness of a 1 liter piece of 5 CIIIX 5 Cl cut from the center of the film.
フィルムの引張強度は、フィルムから長さ１００ｍｍ、
幅１０ｍｍのストリップ５）木を裁断し、引張速度２０
０ ｍｍ／分で各ストリップの引張強度を測定して得た
値の平均である。The tensile strength of the film is 100 mm long from the film,
10mm wide strip 5) Cut the wood and pull speed 20
It is the average of the values obtained by measuring the tensile strength of each strip at 0 mm/min.
第４表および第５表に示すマトリックス強度は次の式に
従って削算したニ
ア１〜リックス強度＝
弓張強「−×２．２
延伸フィルムの密度
■ 延伸速度５％／秒以下での延伸性
幅２０ｍｍ、長さ５０ｍｍの熱処理したフィルム４を、
５０℃においてカレンダ方向と平行な方向へは５００％
ｊ３よびカレンダ方向と垂直な方向へは８００％まで所
定の延伸速度で自由端一軸固定延伸した。The matrix strengths shown in Tables 4 and 5 are calculated according to the following formula: Near 1~Rix strength = Bow tensile strength - x 2.2 Density of stretched film ■ Stretchability width at a stretching speed of 5%/sec or less A heat-treated film 4 with a length of 20 mm and a length of 50 mm is
500% in the direction parallel to the calendar direction at 50℃
j3 and the direction perpendicular to the calendar direction, the free end was uniaxially fixed and stretched to 800% at a predetermined stretching speed.
引張強度は、幅が１Ｑ、ｍｍ以上の場合は幅１ｏＩｎｍ
のストリップについて、または幅が’ｌＱＩＩ１ｍ未満
の場合はその幅のフィルムについて、カレンダ方向に平
行な方向へ引張速度２００ ｍｍ７分において測定した
。Tensile strength is 1Q, width is 1oInm if the width is more than mm.
or, if the width was less than 1 m, a film of that width in a direction parallel to the calender direction at a tensile speed of 200 mm for 7 minutes.
延伸したフィルムの密度は、フィルムピースの体積（幅
ＣＩＩＩＸ長さｃｍｘ厚ざｃｍ）に対するフィルムピー
スの重さくａ ンの比として決定した。The density of the stretched film was determined as the ratio of the weight of the film piece a to the volume of the film piece (width CIIIX length cm x thickness cm).
結果を第６表に示す。The results are shown in Table 6.
同じフィルムは、カレンダ方向に対し平行おＪ、び垂直
な方向の両方へ指により容易に延伸することができ、密
度１．１ ９／ｃｍ３のＰ Ｔ Ｆ Ｅ多孔性フィルム
が得られた。The same film could be easily stretched by fingers in both parallel and perpendicular directions to the calendering direction, resulting in a P TFE porous film with a density of 1.19/cm 3 .
ＩＶ 圧縮成形物の延伸性
２００ ｋｇ／ ｃｍ２の加圧下に圧縮成形して実施例
１で用いたのと同じＰＴＦＥファインパウダーから幅１
００ ｍｍｔＪ３よび１ワさ１０１ｍの１） −１’
Ｆ Ｅシートを成形した。このシーｈを所定温度に保っ
たツル］〜バス中で所定時間加熱した。IV. Stretchability of compression molded product Compression molded under a pressure of 200 kg/cm2 and made from the same PTFE fine powder used in Example 1 with a width of 1
00 mmtJ3 and 1W 101m 1) -1'
FE sheet was molded. This seaweed was heated for a predetermined time in a bath kept at a predetermined temperature.
このように加熱したシー１〜を幅５ｍｍおよび長さ２５
ＩＩＩＩｌｌのス１〜リップに裁断した３、ス１〜リッ
プをカレンダ方向と平行な方向へｉ、ｏｏｏ％／秒の引
張速度で３００℃に保った炉内ｒ１．００に）％まで延
伸した。Seats 1 to 1 heated in this way are made into a sheet with a width of 5 mm and a length of 25 mm.
3. The slips 1 to 3, which were cut into 1 to 3 sheets of IIIll, were stretched in a direction parallel to the calender direction at a tensile rate of 1,00%/sec to r1.00% in a furnace maintained at 300°C.
未延伸シートの比重、シートの延伸性および延伸したシ
ートの密度を第７表に承り。The specific gravity of the unstretched sheet, the stretchability of the sheet, and the density of the stretched sheet are shown in Table 7.
第６表
第７表
実施例２
フィルムを２５°０±２℃で延伸する以外は実施例１と
同じ手順によりｆＤ Ｔ’ Ｆ Ｌ延伸フィルムを製造
した。Table 6 Table 7 Example 2 An fD T' F L stretched film was produced by the same procedure as in Example 1 except that the film was stretched at 25°0±2°C.
このように−して得たフィル１１の性質を第８表に示す
。ここでフィルムＮｏ１６〜１９は比較例である。The properties of the fill 11 thus obtained are shown in Table 8. Films Nos. 16 to 19 are comparative examples.
実施例３
実施例１（１）で得たフィルムおよび熱処理した裁断フ
ィルムＮｏ４および５を長さ５ｏｌｌｌｌＩ１幅１０ｍ
ｍのストリップに裁断した。同じフィルムから裁断した
２本のストリップを相互に小ね合わけ、重ね合わせたフ
ィルムの幅の狭い方の端部を１Ｏ１０ｎ１５ ｍｎ＋の
面積でボッｌ−プレス中で押し付（プ、１Ｍ Ｐ ａの
圧力下３７０°Ｃ２分間保持して端部分を結合した。Example 3 The film obtained in Example 1 (1) and the heat-treated cut films No. 4 and 5 were cut into lengths of 5 ollll I and width of 10 m.
It was cut into strips of m. Two strips cut from the same film were pressed together, and the narrow end of the overlapped film was pressed in a bolt press with an area of 1O10n15 mn+. The end portions were bonded by holding at 370° C. for 2 minutes under pressure.
結合したフィルムの接着強度を、結合していない狭い方
の端部を引張試験機により引離して測定し ｌこ 。The adhesive strength of the bonded films was measured by pulling the unbonded narrow ends apart using a tensile tester.
同様のテストを、Ｖポリフロンファインパウタ−Ｆ−１
０４Ｊの代りに「テフロン６Ｊ」 （商品名）を用いて
繰返した。A similar test was conducted using V Polyflon Fine Powder F-1.
The process was repeated using "Teflon 6J" (trade name) instead of 04J.
結果を第９表のＡ欄に示す。The results are shown in column A of Table 9.
結合したフィルノ＼を３７０℃で３０分間さらに加熱し
て接も一強度を測定した。The bonded Firno\ was further heated at 370°C for 30 minutes and the bond strength was measured.
この結果を第９表のＢ欄に承り、。Enter this result in column B of Table 9.
第９表
第９表の結果から理解されるように、フィルムをビー１
ヘブレスした揚台、ＰＴＦＥ未焼成フィルムとｌ１５１
４’Ｊ＞ Ｐ −ｌ−Ｆ Ｅ半焼成フィルムについても
強力な接着・１」が得られる。これに対し焼成フィルム
は劣った接着性しか有していなかった。さらにこの結果
から、本発明の目的はＰ Ｔ Ｆ Ｅファインパウダー
の１ｒＩＴｉ：（ｉによらず達成できることか解る。Table 9 As can be seen from the results in Table 9, the film was
Hebless lifting platform, PTFE unfired film and l151
4'J>P-l-F Strong adhesion 1'' can also be obtained for E semi-baked films. In contrast, the fired film had poor adhesion. Further, from this result, it can be seen that the object of the present invention can be achieved regardless of the 1rITi:(i) of the P T F E fine powder.
第１図、第２図および第３図は、夫々Ｐ Ｔ Ｆ Ｅ未
焼成体、焼成体ｄ５よび半焼成体の示差走査熱量計によ
る結晶融解曲線を示す。第４図はＰ丁ＦＦ半焼成体のＸ
線回折図である。第５図、第６図および第７図は、Ｐ
−Ｉ−Ｆ Ｅ未焼成体、半焼成体Ｊ′３よび焼成体の表
面の走査型顕微鏡写真である。第８図および第９図は本
発明のＰ王ＦＥ半焼成体から得られるＰＴＦＥ多孔性材
料の表面および内部の走査型顕微鏡写真である。
特 許 出 願 人 ダイキン工業株式会社代 理 人
弁理士 青白 葆 ばか２名第１図
５８０’Ｋ ６００”Ｋ ６１
０”Ｋ ６２０’に第２図
￥
第３図
第４図
１０ １２ １４ １６
旧 ２０ ２２ ２４
ｅFIGS. 1, 2, and 3 show crystal melting curves measured by differential scanning calorimetry of the P T F E green body, fired body d5, and semi-fired body, respectively. Figure 4 shows the X of the Pcho FF semi-fired body.
It is a line diffraction diagram. Figures 5, 6 and 7 are
-I-F E is a scanning micrograph of the surfaces of an unfired body, a semi-fired body J'3, and a fired body. FIGS. 8 and 9 are scanning micrographs of the surface and interior of the PTFE porous material obtained from the P-Ko FE semi-fired body of the present invention. Patent applicant: Daikin Industries, Ltd. Representative: Patent attorney: Two idiots: 580'K 600"K 61
0"K 620' to Figure 2 ￥ Figure 3 Figure 4 10 12 14 16
Old 20 22 24
e
Claims (1)
う゛フルＡロエヂレン焼成体の融点以上の）温度で加熱
づ−ることにより製造され、示差走査熱量削による結晶
融解曲線上で３４５±５℃の温度［こ吸熱カーブを持ち
、未焼成体、半焼成体および焼成体の融解熱量により定
義８れる結晶転化率が０゜１０−０．８５であり、Ｘ線
回折により測定した結晶化度が８０〜９３％であること
を特徴とづるボリア（ヘラフルオロエチレン半焼成体。 ２、結晶転化率が０．１５〜０．７０であるＭ許請求の
範囲第１項記載の生焼成体。 ３、結晶化１σが８５〜９２％である１）許請求の範囲
第１項記載の半焼成体。 ４、半焼成イホの加熱された部分の比重が少くとも１，
８ｅある特；、′１品求の範囲第１項記載の半すｙコ成
体、。 ５、未焼成体が少くとし１．／ｌの比重を１．５゛つ特
許請求の範囲第１項記載の４’ １．ｉ’ａ成体。 ６、未焼成体が、丹４み／ｊ＼０ 、２ ｍｍ、ｉ、り
小さいシートもしくはフィルム、壁厚ｊｉｒ ０ 、２
ｍｍより小ざいデユープもしくは直杆がＱ、２＋ｎｍ
Ｊ、り小さい棒である特許請求の範囲第１〜５檀の何れ
かに記載の半焼成体。 ７、未焼成体が、厚みか０．２〜・２ｎｖＪ：り小さい
シー１〜またはフィルム、壁ルが０．２〜２ｍｍのデユ
ープもしくは直イ子か０２へ、ｔ’ ２ Ｉｌｌ Ｉｌ
ｌ （７）棒Ｃあイ；）特許請求の範囲第１〜５項のい
ずれかに記載の」′焼成体。 ８、ボリテｈラフルΔ１：１エチレン未焼成体をボリア
１〜ラフルオロエチレン焼成体の融点」メ上の温度で加
熱し、示差走査熱量ｉ１に」、る結晶Ｅ４１１解曲線士
、 ｒ ３ ／ｌ ５±５°Ｃ（７） 濡Ｗ ｋ吸Ｈ％
ノ＋ ７Ｊ７’ （Ｈ持ら未゛ハに成体、半焼成体、ｊ
−３よひ焼成１木の融解熱量により定義される結晶転化
率が０．１０−・０．８５であり、Ｘ線回折により測定
した結晶化度が８０〜９３％である物品を得ることを特
徴とり−るポリテトラフルオロエチレン未焼成体の製法
。 ９、焼成体の融点から未焼成体の融点までの温度で加熱
する特許請求の範囲第８項記載の製法。 １０、ポリテトラフルオロエチレン未焼成体をポリテト
ラフルオロエチレン焼成体の融点以上の温度で加熱覆る
ことにより製造され、示差走査熱量計による結晶融解曲
線上で３４５±５°Ｃａ） ？ＡＡ度に吸熱カーブを持
ち、未焼成体、半焼成体および焼成体の融解熱量により
定義される結晶転化率が０゜１０〜０，８５であり、Ｘ
線回折ににり測定した結晶化度が８０〜９３％であるこ
とを特徴とするボリテ［・ラフルＡロエチレン半焼成体
から形成された溶媒用容器のキ１ｊツブ。[Claims] 1. The polytetrafluoroethylene green body is made of boria 1~
It is manufactured by heating at a temperature (above the melting point of the sintered body of Ufuru A Roedylene), and has an endothermic curve of 345±5°C on the crystal melting curve by differential scanning calorimetry. Boria (Hera) is characterized by having a crystal conversion rate defined by the fired body and the heat of fusion of the fired body of 0°10-0.85, and a degree of crystallinity measured by X-ray diffraction of 80-93%. A semi-fired fluoroethylene body. 2. A raw fired body according to claim 1 having a crystal conversion rate of 0.15 to 0.70. 3. A semi-fired body having a crystallization 1σ of 85 to 92%. A semi-fired body according to claim 1. 4. The specific gravity of the heated part of the semi-baked iho is at least 1,
8e Certain characteristics; '1. Scope of requirements: The semi-cylindrical body described in item 1. 5. Less unfired material 1. 4' as set forth in claim 1 having a specific gravity of 1.5/l i'a adult. 6. The unfired body has a small sheet or film, wall thickness jir 0, 2
Duplex or straight rod smaller than mm is Q, 2+nm
J. The semi-fired body according to any one of claims 1 to 5, which is a small rod. 7. If the unfired body has a thickness of 0.2~2nvJ: a small sheet 1~ or a film, a duplex or a straight child with a wall thickness of 0.2~2mm, t' 2 Ill Il
(7) Rod C;) ``' fired body according to any one of claims 1 to 5. 8. Heating the unfired ethylene body of 1:1 fluoroethylene at a temperature above the melting point of the fired body of boria 1 to the melting point of the fired body of fluoroethylene to give a differential scanning calorific value i1, crystal E411 solver, r 3 /l. 5±5°C (7) Wet W k H%
ノ+ 7J7' (H has not yet matured, semi-fired body, j
-3 - To obtain an article having a crystal conversion rate defined by the heat of fusion of 1 wood of 0.10-0.85 and a crystallinity of 80 to 93% as measured by X-ray diffraction. A method for producing a polytetrafluoroethylene green body with characteristics. 9. The manufacturing method according to claim 8, wherein heating is performed at a temperature between the melting point of the fired body and the melting point of the unfired body. 10. Produced by heating and covering an unfired polytetrafluoroethylene body at a temperature higher than the melting point of the fired polytetrafluoroethylene body, the crystal melting curve measured by a differential scanning calorimeter was 345±5°Ca)? It has an endothermic curve at AA degree, and the crystal conversion rate defined by the heat of fusion of the unfired, semi-fired, and fired bodies is 0°10 to 0.85, and
A container for a solvent formed from a semi-fired ethylene body characterized by having a degree of crystallinity of 80 to 93% as measured by line diffraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/642,770 US4596837A (en) | 1982-02-22 | 1984-08-21 | Semisintered polytetrafluoroethylene article and production thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP83101633A EP0087149B1 (en) | 1982-02-22 | 1983-02-19 | Semisintered polytetrafluoroethylene article and production thereof |
| EP831016332 | 1983-02-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59152825A true JPS59152825A (en) | 1984-08-31 |
| JPH0353103B2 JPH0353103B2 (en) | 1991-08-14 |
Family
ID=8190303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58155649A Granted JPS59152825A (en) | 1982-02-22 | 1983-08-25 | Polytetrafluoroethylene semi-sintered body and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59152825A (en) |
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| JPH03221541A (en) * | 1990-01-29 | 1991-09-30 | Daikin Ind Ltd | Polytetrafluoroethylene porous membrane and preparation thereof |
| US5217666A (en) * | 1991-05-29 | 1993-06-08 | Daikin Industries Ltd. | Process for producing porous polytetrafluoroethylene film |
| US5910277A (en) * | 1996-05-17 | 1999-06-08 | Nitto Denko Corporation | Process of making a porous PTFE membrane |
| US6395159B2 (en) | 1997-08-29 | 2002-05-28 | Ngk Spark Plug Co., Ltd. | Oxygen sensor |
| US6548023B1 (en) | 1998-06-18 | 2003-04-15 | Ngk Spark Plug Co., Ltd. | Gas sensor |
| JP2015514579A (en) * | 2012-04-27 | 2015-05-21 | ダブリュ．エル．ゴア アンド アソシエイツ，インコーポレイティドＷ．Ｌ． Ｇｏｒｅ ＆ Ａｓｓｏｃｉａｔｅｓ， Ｉｎｃｏｒｐｏｒａｔｅｄ | Seam seal type filter and method for manufacturing the same |
| WO2015080294A1 (en) | 2013-11-29 | 2015-06-04 | 旭化成イーマテリアルズ株式会社 | Polymer electrolyte membrane |
| JP2015160882A (en) * | 2014-02-27 | 2015-09-07 | 日東電工株式会社 | adhesive sheet |
| JP2015160884A (en) * | 2014-02-27 | 2015-09-07 | 日東電工株式会社 | adhesive sheet |
| JP2015160883A (en) * | 2014-02-27 | 2015-09-07 | 日東電工株式会社 | adhesive sheet |
| JP2018184614A (en) * | 2018-07-26 | 2018-11-22 | 日東電工株式会社 | Adhesive sheet |
| JP2022536768A (en) * | 2019-06-13 | 2022-08-18 | ダブリュ．エル．ゴア アンド アソシエイツ，インコーポレイティド | Lightweight expanded polytetrafluoroethylene membrane with high intrinsic strength and optical transparency |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101142831B1 (en) * | 2010-07-27 | 2012-05-18 | 강성만 | Fixing unit of cleaning pad |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5118991A (en) * | 1974-06-28 | 1976-02-14 | Cyprus Metallurg Process | Kinzokuryukabutsuno sankaho |
| JPS5617216A (en) * | 1979-07-24 | 1981-02-19 | Central Jidosha Kk | Plastic press die and production thereof |
-
1983
- 1983-08-25 JP JP58155649A patent/JPS59152825A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5118991A (en) * | 1974-06-28 | 1976-02-14 | Cyprus Metallurg Process | Kinzokuryukabutsuno sankaho |
| JPS5617216A (en) * | 1979-07-24 | 1981-02-19 | Central Jidosha Kk | Plastic press die and production thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03221541A (en) * | 1990-01-29 | 1991-09-30 | Daikin Ind Ltd | Polytetrafluoroethylene porous membrane and preparation thereof |
| JPH0689165B2 (en) * | 1990-01-29 | 1994-11-09 | ダイキン工業株式会社 | Polytetrafluoroethylene porous membrane and method for producing the same |
| US5217666A (en) * | 1991-05-29 | 1993-06-08 | Daikin Industries Ltd. | Process for producing porous polytetrafluoroethylene film |
| US5910277A (en) * | 1996-05-17 | 1999-06-08 | Nitto Denko Corporation | Process of making a porous PTFE membrane |
| US6030428A (en) * | 1996-05-17 | 2000-02-29 | Nitto Denko Corporation | Porous polytetrafluoroethylene membrane, process for producing the same, sheet-form polytetrafluoroethylene molding, and air filter medium |
| US6395159B2 (en) | 1997-08-29 | 2002-05-28 | Ngk Spark Plug Co., Ltd. | Oxygen sensor |
| US6548023B1 (en) | 1998-06-18 | 2003-04-15 | Ngk Spark Plug Co., Ltd. | Gas sensor |
| JP2015514579A (en) * | 2012-04-27 | 2015-05-21 | ダブリュ．エル．ゴア アンド アソシエイツ，インコーポレイティドＷ．Ｌ． Ｇｏｒｅ ＆ Ａｓｓｏｃｉａｔｅｓ， Ｉｎｃｏｒｐｏｒａｔｅｄ | Seam seal type filter and method for manufacturing the same |
| WO2015080294A1 (en) | 2013-11-29 | 2015-06-04 | 旭化成イーマテリアルズ株式会社 | Polymer electrolyte membrane |
| JP2015128060A (en) * | 2013-11-29 | 2015-07-09 | 旭化成イーマテリアルズ株式会社 | Polymer electrolyte membrane |
| JP2015160882A (en) * | 2014-02-27 | 2015-09-07 | 日東電工株式会社 | adhesive sheet |
| JP2015160884A (en) * | 2014-02-27 | 2015-09-07 | 日東電工株式会社 | adhesive sheet |
| JP2015160883A (en) * | 2014-02-27 | 2015-09-07 | 日東電工株式会社 | adhesive sheet |
| JP2018184614A (en) * | 2018-07-26 | 2018-11-22 | 日東電工株式会社 | Adhesive sheet |
| JP2022536768A (en) * | 2019-06-13 | 2022-08-18 | ダブリュ．エル．ゴア アンド アソシエイツ，インコーポレイティド | Lightweight expanded polytetrafluoroethylene membrane with high intrinsic strength and optical transparency |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0353103B2 (en) | 1991-08-14 |
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| LAPS | Cancellation because of no payment of annual fees |