JPH0713171B2 - Tetrafluoroethylene resin composition - Google Patents
Tetrafluoroethylene resin compositionInfo
- Publication number
- JPH0713171B2 JPH0713171B2 JP26611786A JP26611786A JPH0713171B2 JP H0713171 B2 JPH0713171 B2 JP H0713171B2 JP 26611786 A JP26611786 A JP 26611786A JP 26611786 A JP26611786 A JP 26611786A JP H0713171 B2 JPH0713171 B2 JP H0713171B2
- Authority
- JP
- Japan
- Prior art keywords
- average particle
- ptfe
- particle size
- creep
- ether ketone
- 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.)
- Expired - Fee Related
Links
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- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は四フツ化エチレン樹脂組成物に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a tetrafluoroethylene resin composition.
四フツ化エチレン樹脂（以下これをPTFEと略称する）は
耐熱性、耐薬品性に優れているばかりでなく、摩擦係数
が小さく自己潤滑性を有するので、軸受、歯車のような
摺動部用材料、管、バルブ、その他の成形品等いわゆる
エンジニアリングプラスチツクの代表的なものとして各
方面に広く利用されて来たが、耐摩耗性は必ずしも満足
できないので、種々の充填剤を加えてこれを改善しよう
とする試みが数多くなされて来た。充填剤としては、ガ
ラス繊維粉末、ガラスビーズ、炭素繊維、グラフアイ
ト、二硫化モリブデンなどの無機充填剤または芳香族系
ポリエステル、ポリイミド、ポリフエニレンサルフアイ
ド、芳香族系ポリアミドなどの有機充填剤が挙げられる
が、PTFEからなる材料は荷重による変形（クリープ）が
大きく、高性能シールリングのストレートカツト品とし
て使用する場合、シーリングの合い口すきまが使用時に
なくなつたとき、合い口部に一定の圧縮応力を生じ変形
する。再びシールリングを使用すると合い口部の変形に
よりシール性能が低下する。そこで充填剤の増量または
複合化、さらにはPTFE自体の改質等による数多くのクリ
ープ性の改善策が採られたが、このような方法ではクリ
ープ性の改善ができても機械的強度が低下したり、摺動
特性が劣つたりして好ましくない。また、PTFEの薄肉材
料の周囲にクリープ性の小さい熱可塑性樹脂や熱硬化性
樹脂等を射出成形して積層体もしくは複合体とする方法
もあるが成形に手間がかかり経済上不利である。なお耐
クリープ性の良いPTFEとしてたとえばヘキスト社製ホス
タフロンTFM1700等の商品名で市販されている変性四フ
ツ化エチレン樹脂があるが、この樹脂は通常のPTFEと比
較して遥かに高価であるばかりでなく、摺動特性は著し
く劣つている。Not only is tetrafluoroethylene resin (hereinafter abbreviated as PTFE) excellent in heat resistance and chemical resistance, it also has a small coefficient of friction and self-lubrication properties, so it is used for sliding parts such as bearings and gears. It has been widely used in various fields as a representative of so-called engineering plastics such as materials, pipes, valves and other molded products, but wear resistance is not always satisfactory, so improve it by adding various fillers. Many attempts have been made to try. As the filler, glass fiber powder, glass beads, carbon fiber, graphite, inorganic filler such as molybdenum disulfide or aromatic polyester, polyimide, polyphenylene sulfide, organic filler such as aromatic polyamide. However, the material made of PTFE has large deformation (creep) due to load, and when used as a straight cut product of a high performance seal ring, when the sealing gap of the sealing is eliminated at the time of use, there is a constant It deforms by generating compressive stress. If the seal ring is used again, the sealing performance deteriorates due to the deformation of the abutment. Therefore, many measures were taken to improve the creep property by increasing the amount of the filler or compounding it, and further modifying the PTFE itself.However, even if the creep property could be improved by such a method, the mechanical strength would decrease. And the sliding characteristics are inferior, which is not preferable. There is also a method in which a thermoplastic resin or thermosetting resin having a low creep property is injection-molded around a thin material of PTFE to form a laminate or a composite, but this is time-consuming in molding and is economically disadvantageous. As a PTFE with good creep resistance, for example, there is a modified tetrafluoroethylene resin marketed under the trade name of Hostaflon TFM1700 manufactured by Hoechst Co., Ltd., but this resin is much more expensive than ordinary PTFE. And the sliding characteristics are extremely inferior.
このように従来の技術においては耐熱性、耐薬品性に優
れたPTFEも荷重による変変形（クリープ）が大きく、シ
ールリング用としての性能が充分ではなく、これを改善
するために各種充填剤を混入しても機械的強度または摺
動特性が低下して好ましくなく、成形は容易でなく高価
であるなど、耐クリープ性、機械的強度、摩擦摩耗特
性、シール性能等のすべての面で満足できるものは得ら
れなかつたという問題点があつた。As described above, in the conventional technology, PTFE, which has excellent heat resistance and chemical resistance, also undergoes large deformation and deformation (creep) due to load, and its performance as a seal ring is not sufficient. To improve this, various fillers are used. Even if mixed, it is not preferable because the mechanical strength or sliding property is deteriorated, molding is not easy and expensive, etc., and all aspects such as creep resistance, mechanical strength, friction and wear characteristics, and sealing performance can be satisfied. There was a problem that nothing was obtained.
上記の問題点を解決するためには、この発明はPTFEに平
均粒径１〜50μｍのポリエーテルエーテルケトン微粉末
を必須成分として10〜50重量％添加したPTFE組成物とす
る手段を採用したものである。以下その詳細を述べる。In order to solve the above problems, the present invention adopts means for preparing a PTFE composition by adding 10 to 50% by weight of polyether ether ketone fine powder having an average particle size of 1 to 50 μm to PTFE as an essential component. Is. The details will be described below.
まず、この発明におけるPTFEはテトラフルオロエチレン
（四フツ化エチレン）の単独重合体であつて、アルゴフ
ロン（伊国モンデジソン社製）、テフロン（米国デユポ
ン社製）、フルホン（英国アイ・シー・アイ社製）、ポ
ルフロン（ダイキン工業社製）等の登録商標名で市販さ
れているフツ素樹脂の一種であつて、圧縮成形は可能で
あつても通常の射出成形は不可能であり、この発明にお
いては粉状のものが好ましい。First, PTFE in the present invention is a homopolymer of tetrafluoroethylene (tetrafluoroethylene), which includes Algoflon (manufactured by Ikokumon Digison), Teflon (manufactured by U.S.A. It is a kind of fluorocarbon resin marketed under the registered trade name such as Porflon (manufactured by Daikin Industries, Ltd.) and Porflon (manufactured by Daikin Industries, Ltd.), and compression molding is possible but ordinary injection molding is not possible. In the above, powdery one is preferable.
つぎに、この発明の必須成分として添加されるポリエー
テルエーテルケトンはたとえば英国アイ・シー・アイ社
からビクトレツクスの登録商標名で市販されている重合
体であり、耐熱性、耐燃性、機械的強度など優れた諸特
性を有する の構造をもつた樹脂（以下これをPEEKと略称する）であ
り、この微粉末は市販品であつても、また、たとえば冷
凍粉砕機のような粉砕機を用いて塊状のものを粉砕して
得られるものであつてもよい。ただこの発明の効果を期
待するためには、PEEKの微粉末の平均粒径は１〜50μｍ
であることが望ましい。なぜならば平均粒径が１μｍ未
満であつてもまた50μｍを越えてPEFE中のPEEKの均一分
散が困難となり、耐摩耗性、耐圧縮クリープ特性、シー
ル特性などの著しい向上は期待されなくなるからであ
る。そしてPEEK微粉末の好ましい平均粒径は５〜30μｍ
である。また、PEEK微粉末の添加量はPTFE50〜90重量％
に対してPEEKを50〜10重量％（好ましくは40〜15重量
％）とすることが望ましい。なぜならば、PEEKが10重量
％未満の少量では耐摩耗性、耐圧縮クリープ特性、シー
ル特性の改善効果は期待出来ず、逆に50重量％を越える
多量ではコスト上昇が先行し、それに見合う諸特性の改
善効果が現われず経済的不利を招くからである。Next, the polyether ether ketone added as an essential component of the present invention is, for example, a polymer marketed under the registered trademark of Victorex by ICI Corporation in the United Kingdom, and has heat resistance, flame resistance and mechanical strength. Has excellent characteristics such as It is a resin having the structure of (hereinafter, abbreviated as PEEK). Even if this fine powder is a commercially available product, it can be crushed into a lump using a crusher such as a freeze crusher. It may be obtained. However, in order to expect the effects of this invention, the average particle size of PEEK fine powder is 1 to 50 μm.
Is desirable. This is because even if the average particle size is less than 1 μm, it will be difficult to uniformly disperse PEEK in PEFE even if it exceeds 50 μm, and it will not be possible to expect significant improvement in wear resistance, compression creep resistance, sealing characteristics, etc. . And the preferable average particle size of PEEK fine powder is 5 to 30 μm.
Is. In addition, the amount of PEEK fine powder added is 50 to 90% by weight of PTFE.
On the other hand, it is desirable that PEEK is 50 to 10% by weight (preferably 40 to 15% by weight). Because, if PEEK is less than 10% by weight, the effects of improving wear resistance, compression creep resistance, and sealing properties cannot be expected, and conversely, if the amount is more than 50% by weight, cost increase will precede, and various properties will be matched. This is because the improvement effect of does not appear and causes an economic disadvantage.
以上のPTFEとPEEKのの混合物は、従来から広く行なわれ
ている充填剤入りPTFEの通常の成形条件で成形すればよ
く、たとえば、タンブラーミキサー、ヘンシエルミキサ
ー等の混合機によつて両樹脂を粉状で乾式混合し、これ
を金型に入れて380〜600kg/cm2の圧力を加えて予備成型
した後、金型から取り出された圧縮成形体を370℃で焼
結する方法、その他加熱加圧しながら回分式に圧縮成形
する方法またはラム押出機による連続成形方法などのい
ずれであつてもよい。The above mixture of PTFE and PEEK may be molded under the usual molding conditions of PTFE with a filler that has been widely used in the past.For example, both resins are mixed by a mixer such as a tumbler mixer or a Hensiel mixer. Dry mixing in powder form, putting it in a mold and applying a pressure of 380 to 600 kg / cm 2 for preforming, then sintering the compression molded body taken out from the mold at 370 ° C, other heating Either a batch compression molding method while pressurizing or a continuous molding method using a ram extruder may be used.
〔実施例〕 実施例1: 平均粒径10μｍのポリエーテルエーテルケトン（英国ア
イ・シー・アイ社製ビクトレツクスPEEK−150Pの冷凍粉
砕品）30重量％と平均粒径25μｍのポリエトラフルオロ
エチレン（三井デユポンフロロケミカル社製テトロン7
J）70重量％とをヘンシエルミキサーでよく混合した
後、内径30mmの円筒状の金型に充填し、450kg/cm2の圧
力をかけて予備成形を行ない得られた予備成形体を360
℃で３時間加熱して焼結成形体とし、この成形体から各
種試験方法に規定されている寸法、形状の試験片を作製
した。各特性値を求めるために用いた試験方法はつぎの
とおりである。すなわち、 （１）圧縮クリープ性〔ASTM−D621〕 荷重140kg/cm2、24時間の圧縮クリープ変形率（％）、 （２）引張り強さ（kg/cm2）および伸び（％）〔ASTM−
D638〕 （３）摩擦係数 スラスト型摩擦試験機による滑り速度150m/分、荷重1kg
/cm2、相手材アルミニウム合金A5056（施削仕上げ、表
面粗さ3S）、無潤滑の条件下、 （４）摩耗係数（×10-10cm3/kg・ｍ） スラスト型摩耗試験機による滑り速度128m/分、荷重2.3
kg/cm、相手材アルミニウム合金A5056（施削仕上げ、表
面粗さ3S）、無潤滑の条件下、 （５）シールリングのシール性 図に示すシールリング油漏れ量測定試験機を用い１分間
の油漏れ量（ml）を測定した。この試験機はプーリ１と
一体で回転するシリンダー２の中にピストン３が挿入さ
れ、このピストン３は先端部に設けられた２本のリング
溝４および４′に装着されたシールリング５および５′
を介してシリンダー２の内面に接し、シールリング５お
よび５′の中間に油入口Ａから注入される油が封入され
ている。したがつて、ピストン３を固定してプーリ１を
回転させ油出口ＢおよびＣから漏れ出る油の量によつて
シールリング５および５′のシール性を測定することが
できる。測定条件はつぎのとおりである。[Examples] Example 1: 30% by weight of polyether ether ketone having an average particle size of 10 μm (freeze-milled product of Victorex PEEK-150P manufactured by ICI Corp. in the UK) and 25 μm of an average particle size of polyetrafluoroethylene (Mitsui Deupon Fluorochemical Tetron 7
J) 70% by weight was mixed well with a Henschel mixer, then charged into a cylindrical mold with an inner diameter of 30 mm, and preformed by applying a pressure of 450 kg / cm 2 , and the preformed body obtained was 360
It was heated at ℃ for 3 hours to obtain a sintered compact, and from this compact, test pieces having dimensions and shapes specified in various test methods were prepared. The test method used to obtain each characteristic value is as follows. That is, (1) compressive creep property [ASTM-D621] load 140 kg / cm 2 , compressive creep deformation rate (%) for 24 hours, (2) tensile strength (kg / cm 2 ) and elongation (%) [ASTM-D621]
D638] (3) Coefficient of friction Sliding speed by thrust type friction tester 150m / min, load 1kg
/ cm 2 , mating material aluminum alloy A5056 (machining finish, surface roughness 3S), non-lubricated condition (4) Wear coefficient (× 10 -10 cm 3 / kg ・ m) Sliding by thrust type wear tester Speed 128m / min, load 2.3
kg / cm, mating material aluminum alloy A5056 (machining finish, surface roughness 3S), non-lubricated condition (5) Sealing property of seal ring For 1 minute using the seal ring oil leakage measurement tester shown in the figure. The amount of oil leakage (ml) was measured. In this tester, a piston 3 is inserted into a cylinder 2 which rotates integrally with a pulley 1, and the piston 3 has sealing rings 5 and 5 mounted in two ring grooves 4 and 4'provided at the tip thereof. ′
The oil injected from the oil inlet A is sealed between the seal rings 5 and 5 ′ and is in contact with the inner surface of the cylinder 2 via. Therefore, the sealability of the seal rings 5 and 5'can be measured by fixing the piston 3 and rotating the pulley 1 to measure the amount of oil leaking from the oil outlets B and C. The measurement conditions are as follows.
試料…ストレートカツト品、100℃で１時間試験機にて
運転後のもの、 油……自動変速機油デキシロンII、油圧3kg/cm2、油温4
0℃、 シリンダー回転数5000rpm であつて、得られた結果を表にまとめた。Sample: Straight cut product, after being operated by a tester at 100 ° C for 1 hour, Oil: Automatic transmission fluid Dexilon II, hydraulic pressure 3kg / cm 2 , oil temperature 4
The results obtained are summarized in the table at 0 ° C. and a cylinder speed of 5000 rpm.
実施例2: 平均粒径10μｍのポリエーテルエーテルケトンの代わり
に平均粒径40μｍのポリエーテルエーテルケトンを用い
たこと以外は実施例１と全く同じ方法で成形し、成形体
から各試験片を作製して同様の諸特性を調べた。得られ
た結果は表に併記した。 Example 2: Molded in the same manner as in Example 1 except that polyether ether ketone having an average particle diameter of 40 μm was used instead of polyether ether ketone having an average particle diameter of 10 μm, and each test piece was prepared from the molded body. Then, various similar characteristics were investigated. The obtained results are also shown in the table.
比較例1: 平均粒径10μｍのポリエーテルエーテルケトンの代わり
に平均粒径80μｍのポリエーテルエーテルケトンを用い
た以外は実施例１と全く同じ方法で成形し、成形体から
各試験片を作製し、その諸特性を調べた。得られた結果
は表に併記した。Comparative Example 1: Molded in the same manner as in Example 1 except that polyether ether ketone having an average particle size of 80 μm was used instead of polyether ether ketone having an average particle size of 10 μm, and each test piece was prepared from the molded product. , And examined their characteristics. The obtained results are also shown in the table.
比較例2: 平均粒径10μｍのポリエーテルエーテルケトンの代わり
に平均粒径25μｍのポリフエニレンサルフアイド（米国
フイリツプスペトロリウス社製：ライトンPPS−P4）を
用いたこと以外は実施例１と全く同じ方法で成形、試験
片の作製および諸特性の測定を行なつた。得られた結果
は表に併記した。Comparative Example 2: Completely the same as Example 1 except that polyphenylene sulphide having an average particle diameter of 25 μm (Ryton PPS-P4 manufactured by US Phillips Petroleus Co., Ltd.) having an average particle diameter of 25 μm was used in place of the polyether ether ketone having an average particle diameter of 10 μm. By the same method, molding, production of test pieces and measurement of various properties were performed. The obtained results are also shown in the table.
比較例3: 平均粒径10μｍのポリエーテルエーテルケトンの代わり
に平均粒径25μｍのポリオキシベンゾイル（住友化学工
業社製：エコノールE101）を用いたこと以外は実施例１
と全く同じ方法で成形、試験片の作製および諸特性の測
定を行なつた。得られた測定結果は表に併記した。Comparative Example 3: Example 1 except that polyoxybenzoyl having an average particle size of 25 μm (Econol E101 manufactured by Sumitomo Chemical Co., Ltd.) was used in place of the polyether ether ketone having an average particle size of 10 μm.
Molding, production of test pieces, and measurement of various properties were performed in the same manner as in. The measurement results obtained are also shown in the table.
比較例4: 平均粒径10μｍのポリエーテルエーテルケトンの代わり
に平均粒径μｍの3,3′,4,4′−ビフエニルテトラカル
ボン酸二無水物と4,4′−ジアミノジフエニルエーテル
とを重合およびイミド化した芳香族ポリイミド樹脂粉末
を用いたこと以外は実施例１と全く同じ方法で成形、試
験片の作製およびその諸特性を調べた。得られた結果は
表に併記した。Comparative Example 4: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether having an average particle size of μm instead of polyether ether ketone having an average particle size of 10 μm Molding was performed in the same manner as in Example 1 except that the polymerized and imidized aromatic polyimide resin powder was used. The obtained results are also shown in the table.
以上の実施例１および２ならびに比較例１〜４の測定結
果を比較すれば、この発明に基づく実施例１と実施例２
とは圧縮クリープ変形率、引張り強さ、引張り伸び、摩
擦係数、摩耗係数およびシール性能のすべてにおいて平
衡のとれた好結果を示しているのに対し、比較例１にお
いては圧縮クリープ特性が若干低下し、耐摩耗性および
シール性能は著しく劣り、また比較例２〜４においては
特に圧縮クリープ変形率およびシール性能が著しく劣つ
ていることが明らかである。このような結果からこの発
明の組成物は、その成形体の圧縮クリープ変形率が非常
に小さく、しかもシール性能がきわめて優れていること
から、シール部用材料特にシールリング材料には格好の
ものであるということがわかつた。Comparing the measurement results of the above Examples 1 and 2 and Comparative Examples 1 to 4, Example 1 and Example 2 according to the present invention are compared.
Shows a good result in which all of the compression creep deformation rate, tensile strength, tensile elongation, friction coefficient, wear coefficient and sealing performance are balanced, while in Comparative Example 1, the compression creep characteristics are slightly deteriorated. However, it is clear that the wear resistance and the sealing performance are remarkably inferior, and particularly in Comparative Examples 2 to 4, the compression creep deformation rate and the sealing performance are remarkably inferior. From these results, the composition of the present invention has a very small compression creep deformation rate of the molded body and has an extremely excellent sealing performance, and therefore, it is suitable for a seal part material, particularly a seal ring material. I knew that there was.
この発明の組成物は基材の四フツ化エチレン樹脂本来の
優れた低摩耗特性を充分に保持しながら、さらに優れた
圧縮クリープ特性およびシール性能をも兼備していて、
従来その類を見ないものであり、シール材特にシールリ
ングの成形用材料には最適のものであるということがで
きる。したがつて、この発明の意義はきわめて大きいの
である。The composition of the present invention, while sufficiently retaining the excellent low wear characteristics inherent in the tetrafluoroethylene resin of the base material, also has excellent compression creep characteristics and sealing performance,
It is unprecedented, and can be said to be the most suitable as a molding material for a seal material, especially a seal ring. Therefore, the significance of the present invention is extremely great.
図面はこの発明の実施例においてシール性能の測定に使
用したシールリング油漏れ量測定試験機の一部切欠の側
面図である。 １……プーリ、２……シリンダー、３……ピストン、4,
4′……リング溝、5,5′……シールリングThe drawing is a side view of a partial cutout of a seal ring oil leakage measurement tester used for measuring the sealing performance in the embodiment of the present invention. 1 ... Pulley, 2 ... Cylinder, 3 ... Piston, 4,
4 '... Ring groove, 5, 5' ... Seal ring
Claims (1)
均粒径１〜50μｍのポリエーテルエーテルケトン樹脂10
〜50重量％とからなることを特徴とする四フツ化エチレ
ン樹脂組成物。1. A tetrafluoroethylene resin and an essential component, a polyether ether ketone resin having an average particle size of 1 to 50 μm.
A tetrafluorinated ethylene resin composition, characterized in that the composition is made up to 50% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26611786A JPH0713171B2 (en) | 1986-11-06 | 1986-11-06 | Tetrafluoroethylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26611786A JPH0713171B2 (en) | 1986-11-06 | 1986-11-06 | Tetrafluoroethylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63118357A JPS63118357A (en) | 1988-05-23 |
| JPH0713171B2 true JPH0713171B2 (en) | 1995-02-15 |
Family
ID=17426557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26611786A Expired - Fee Related JPH0713171B2 (en) | 1986-11-06 | 1986-11-06 | Tetrafluoroethylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713171B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102628A (en) * | 2013-02-26 | 2013-05-15 | 无锡市祥健四氟制品有限公司 | Components of polyether-ether-ketone modified polytetrafluoroethylene sheet |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5823540A (en) * | 1996-09-25 | 1998-10-20 | Fisher Controls International, Inc. | Polymer reinforced fluid seal |
| WO2002041325A1 (en) | 2000-11-14 | 2002-05-23 | Coltec Industrial Products Inc | Abrasion-resistant polytetrafluoroethylene tape |
| JP2002213670A (en) * | 2001-01-23 | 2002-07-31 | Asahi Glass Co Ltd | Swivel joint |
| JP4592978B2 (en) * | 2001-02-21 | 2010-12-08 | 瓜生製作株式会社 | Rotating tool |
| JP5474371B2 (en) * | 2009-02-20 | 2014-04-16 | オリンパス株式会社 | Thermoplastic resin composition, medical product and endoscope operation unit |
| JP2013067723A (en) * | 2011-09-22 | 2013-04-18 | Nitto Denko Corp | Adhesive tape and endless belt using same |
| WO2014073682A1 (en) * | 2012-11-12 | 2014-05-15 | ダイキン工業株式会社 | Resin composition and molded article |
| US9856817B2 (en) | 2015-03-31 | 2018-01-02 | Harley-Davidson Motor Company Group, LLC | Bolt-on cylinder kit and method for increasing the displacement of an engine |
| JP7405599B2 (en) * | 2018-12-25 | 2023-12-26 | Ntn株式会社 | Seals for flow control valves and flow control valve devices |
-
1986
- 1986-11-06 JP JP26611786A patent/JPH0713171B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102628A (en) * | 2013-02-26 | 2013-05-15 | 无锡市祥健四氟制品有限公司 | Components of polyether-ether-ketone modified polytetrafluoroethylene sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63118357A (en) | 1988-05-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |