JPH11116710A - High-purity reforming method for fluororesin moldings - Google Patents
High-purity reforming method for fluororesin moldingsInfo
- Publication number
- JPH11116710A JPH11116710A JP28686497A JP28686497A JPH11116710A JP H11116710 A JPH11116710 A JP H11116710A JP 28686497 A JP28686497 A JP 28686497A JP 28686497 A JP28686497 A JP 28686497A JP H11116710 A JPH11116710 A JP H11116710A
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- Prior art keywords
- copolymer
- tetrafluoroethylene
- perfluoro
- molded article
- water
- Prior art date
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、表面が高度にフッ
素化されフッ素イオンの溶出が低減化されたテトラフル
オロエチレン／パーフルオロ（アルキルビニルエーテ
ル）共重合体（ＰＦＡ）またはテトラフルオロエチレン
／ヘキサフルオロプロピレン共重合体（ＦＥＰ）の溶融
成形体および該成形体をうるための改質法に関する。TECHNICAL FIELD The present invention relates to a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA) or tetrafluoroethylene / hexafluoro which has a highly fluorinated surface and reduced elution of fluorine ions. The present invention relates to a melt molded article of a propylene copolymer (FEP) and a modification method for obtaining the molded article.
【０００２】[0002]
【従来の技術】ＰＦＡやＦＥＰは耐熱性、耐薬品性、非
粘着性、低摩擦性というフッ素樹脂に特有の性質を有し
ているうえ溶融成形ができるため、各種分野に成形材料
として幅広く使用されている。特にＰＦＡは、不純物の
混入を嫌う半導体関連分野で、その優れた化学的熱的安
定性と成形性の点から、シート、チューブ、継手、容
器、キャリアー、ベローズなどの成形品として実用化さ
れている。2. Description of the Related Art PFA and FEP have properties such as heat resistance, chemical resistance, non-adhesion and low friction characteristic of fluororesin and can be melt-molded, so that they are widely used as molding materials in various fields. Have been. In particular, PFA has been put into practical use as a molded product such as sheets, tubes, joints, containers, carriers, bellows, etc. in the semiconductor-related field which refuses to mix impurities, due to its excellent chemical thermal stability and moldability. I have.
【０００３】ところで、ＰＦＡおよびＦＥＰはその共重
合の際に使用する重合開始剤や分子量調整剤に由来する
−ＣＯＯＨ、−ＣＨ2ＯＨ、−ＣＯＯＣＨ3などの熱的に
不安定な基が分子末端などに存在し、溶融成形時の熱に
より分解して−ＣＯＦを生成する。この−ＣＯＦが水と
接触すると加水分解しフッ素イオンを溶出する。そこ
で、特に厳しいクリーンな条件が要求される半導体のウ
ェットプロセス用のＰＦＡやＦＥＰの一部には、製造さ
れた共重合体の段階でフッ素化処理を施し、不安定基を
安定化したものが使用されている。Meanwhile, PFA and FEP polymerization -COOH derived from the initiator or the molecular weight modifier, -CH 2 OH, thermally labile group is the molecular terminal, such as -COOCH 3 for use in the copolymerization Etc., which are decomposed by heat at the time of melt molding to generate -COF. When -COF comes into contact with water, it hydrolyzes and elutes fluorine ions. Therefore, some PFAs and FEPs for semiconductor wet processes, which require particularly strict clean conditions, have undergone fluorination at the stage of the produced copolymer to stabilize unstable groups. in use.
【０００４】しかし、確かに安定化処理されたＰＦＡま
たはＦＥＰそれ自体は極めて安定した状態であり溶出フ
ッ素イオンも約１ppm 以下に低減できるが、これらの安
定化処理されたＰＦＡなども成形品にするためには約３
８０℃という高温で溶融成形しなければならない。その
際、不可避的に僅かではあるが熱分解が生じたり、金型
離型剤の使用の結果、成形品では溶出フッ素イオンが数
ppm から十数ppmまで大きくなってしまう。この程度の
フッ素イオンの溶出でも半導体ウェットプロセスには大
きな影響を及ぼすことがある。ましてや不安定基の安定
化処理がされていないＰＦＡなどでは溶出フッ素イオン
は十数ppmを超えている。[0004] However, stabilized PFA or FEP itself is in an extremely stable state, and the eluted fluorine ions can be reduced to about 1 ppm or less. However, such stabilized PFA or the like is also used as a molded article. About 3
It must be melt molded at a high temperature of 80 ° C. At that time, thermal decomposition may occur inevitably, but as a result of the use of the mold release agent, the number of eluted fluorine ions in
From ppm to over a dozen ppm. This level of fluorine ion elution can have a significant effect on the semiconductor wet process. In the case of PFA or the like in which unstable groups have not been stabilized, the eluted fluoride ion exceeds 10 ppm.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、ＰＦＡやＦ
ＥＰの成形体の溶出フッ素イオンを大幅に減少できる高
純度化改質法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention relates to PFA or F
It is an object of the present invention to provide a high-purity reforming method capable of greatly reducing the fluoride ions eluted from a molded article of EP.
【０００６】[0006]
【課題を解決するための手段】本発明は、ＰＦＡまたは
ＦＥＰの成形体の少なくとも表面をフッ素ガスによりフ
ッ素化処理するＰＦＡまたはＦＥＰ成形体の高純度化改
質法に関する。SUMMARY OF THE INVENTION The present invention relates to a method for purifying and reforming a PFA or FEP molded article by fluorinating at least the surface of the PFA or FEP molded article with fluorine gas.
【０００７】本発明においては、前記フッ素化処理後、
２００〜２５０℃で熱処理を行なうことが好ましい。In the present invention, after the fluorination treatment,
The heat treatment is preferably performed at 200 to 250 ° C.
【０００８】本発明の改質法は、フッ素化処理前の成形
体が、ＰＦＡまたはＦＥＰを溶融成形してえられた成形
体であるばあいに特に優れた効果が発揮される。The reforming method of the present invention is particularly effective when the molded body before the fluorination treatment is a molded body obtained by melt-molding PFA or FEP.
【０００９】対象とするＰＦＡまたはＦＥＰとしては、
末端不安定基を安定化処理したものが好ましい。The target PFA or FEP includes:
What stabilized the terminal unstable group is preferable.
【００１０】本発明はさらに、２５℃での対水接触角が
１０５度以上、１２１℃での水への溶出フッ素イオン濃
度が０．５ppm以下、かつ１２１℃での水へ溶出する全
有機炭素量が３０ppm以下であるＰＦＡまたはＦＥＰの
溶融成形体に関する。[0010] The present invention further relates to a total organic carbon eluted in water having a contact angle with water at 25 ° C of not less than 105 °, an elution of fluorine ions in water at 121 ° C of 0.5 ppm or less, and water of 121 ° C. The present invention relates to a melt molded product of PFA or FEP having an amount of 30 ppm or less.
【００１１】かかる溶融成形体は、前記本発明の改質法
により製造することができる。Such a melt molded article can be produced by the above-mentioned modification method of the present invention.
【００１２】本発明の改質法によれば、溶出フッ素イオ
ン量を大幅に減少できるだけでなく、溶出する全有機炭
素量（ＴＯＣ）をも低減することができる。さらに、対
水接触角を大きくすることができ、液濡れ性も改善でき
るので、金属イオンの溶出も低減できる。According to the reforming method of the present invention, not only can the amount of eluted fluorine ions be significantly reduced, but also the total amount of eluted organic carbon (TOC) can be reduced. Furthermore, since the contact angle with respect to water can be increased and the liquid wettability can be improved, the elution of metal ions can be reduced.
【００１３】[0013]
【発明の実施の形態】本発明の改質法は、ＰＦＡまたは
ＦＥＰの成形体の少なくとも表面をフッ素ガスでフッ素
化処理する方法である。BEST MODE FOR CARRYING OUT THE INVENTION The reforming method of the present invention is a method of fluorinating at least the surface of a molded article of PFA or FEP with fluorine gas.
【００１４】フッ素化処理は、成形体の表面を室温ない
し３００℃の処理温度でフッ素ガスと接触させることに
より行なう。処理温度は処理（フッ素化）速度を上げる
ためには高い方がよく、好ましくは１５０〜２５０℃、
特に好ましくは２００〜２５０℃である。反応に供する
フッ素ガスはチッ素やヘリウムガスなどの不活性ガスで
希釈して用いるのが好ましく、通常５〜３０容量％、好
ましくは１０〜３０容量％の濃度で成形体表面と接触さ
せる。処理に要する時間は反応温度、フッ素濃度によっ
て異なるが、通常４〜１６時間である。The fluorination treatment is performed by bringing the surface of the molded body into contact with fluorine gas at a treatment temperature of room temperature to 300 ° C. The treatment temperature is preferably higher in order to increase the treatment (fluorination) rate, and is preferably 150 to 250 ° C.
Especially preferably, it is 200-250 degreeC. The fluorine gas to be used for the reaction is preferably diluted with an inert gas such as nitrogen or helium gas before use, and is usually brought into contact with the surface of the molded body at a concentration of 5 to 30% by volume, preferably 10 to 30% by volume. The time required for the treatment varies depending on the reaction temperature and the fluorine concentration, but is usually 4 to 16 hours.
【００１５】本発明において、フッ素化処理してえられ
た表面フッ素化成形体を熱処理（アニーリング処理）す
ることにより、残留するフッ素ガスおよび副生するフッ
酸を除去することとなり、好ましい。熱処理温度は残留
フッ素ガスおよび副生フッ酸除去の点から約２００〜２
５０℃、好ましくは２３０〜２５０℃である。熱処理雰
囲気は空気中、好ましくはチッ素ガス中とするのが、熱
酸素劣化の防止の点から好ましい。熱処理時間は２〜１
０時間、通常４〜８時間とするのが好ましい。In the present invention, the heat treatment (annealing treatment) of the surface fluorinated molded product obtained by the fluorination treatment preferably removes residual fluorine gas and by-product hydrofluoric acid. The heat treatment temperature is about 200 to 2 from the viewpoint of removing residual fluorine gas and by-product hydrofluoric acid.
The temperature is 50C, preferably 230-250C. The heat treatment atmosphere is preferably in air, preferably in nitrogen gas, from the viewpoint of preventing thermal oxygen deterioration. Heat treatment time is 2-1
It is preferably 0 hours, usually 4 to 8 hours.
【００１６】本発明における処理対象であるＰＦＡおよ
びＦＥＰはつぎの含フッ素ポリマーである。PFA and FEP to be treated in the present invention are the following fluoropolymers.
【００１７】ＰＦＡは、テトラフルオロエチレンと式：
Ｒf−Ｏ−ＣＦ＝ＣＦ2（式中、Ｒfは炭素数１〜８のパ
ーフルオロアルキル基）で示されるパーフルオロ（アル
キルビニルエーテル）との共重合体であり、パーフルオ
ロ（アルキルビニルエーテル）単位が０．４〜４モル％
含まれている。パーフルオロ（アルキル）ビニルエーテ
ル）としては、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（ブ
チルビニルエーテル）、パーフルオロ（ヘプチルビニル
エーテル）などがあげられる。ＦＥＰはテトラフルオロ
エチレンとヘキサフルオロプロピレンとの９６．７〜８
６／３．３〜１４（モル比）の共重合体である。これら
にはいずれも重合時にパーオキサイド、過硫酸塩などの
重合開始剤、メタノール、メタン、エタンなどの分子量
調製剤、重合緩衝剤、乳化剤などの残渣が含まれてお
り、前記のとおり、不安定基となっている。PFA is represented by the formula:
A copolymer with perfluoro (alkyl vinyl ether) represented by R f —O—CF ＝ CF 2 (where R f is a perfluoroalkyl group having 1 to 8 carbon atoms); Unit is 0.4 to 4 mol%
include. Examples of the perfluoro (alkyl) vinyl ether) include perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (heptyl vinyl ether) and the like. FEP is 96.7-8 of tetrafluoroethylene and hexafluoropropylene.
6 / 3.3 to 14 (molar ratio). All of these include peroxides, polymerization initiators such as persulfates, molecular weight regulators such as methanol, methane, and ethane, polymerization buffers, and residues such as emulsifiers during polymerization, and as described above, are unstable. It is the basis.
【００１８】また、前記のようにこれらのＰＦＡはＦＥ
Ｐの不安定基を安定化処理した安定化処理ＰＦＡまたは
ＦＥＰも成形体の材料として採用しうる。As described above, these PFAs are FE
Stabilized PFA or FEP obtained by stabilizing an unstable group of P can also be used as a material of the molded article.
【００１９】表面フッ素化の程度は、たとえばフッ素化
処理成形体の表面のフッ素原子と炭素原子とのモル比
（Ｆ／Ｃ）の増加を電子分光法（ＥＳＣＡ）で測定する
ことによって追跡できる。しかし、フッ素化の処理条件
によってはＦ／Ｃには変化が認められないにもかかわら
ず、対水接触角の増大、溶出フッ素イオン量、および溶
出ＴＯＣの抑制などの本発明の効果がえられるばあいが
ある。The degree of surface fluorination can be monitored, for example, by measuring the increase in the molar ratio of fluorine atoms to carbon atoms (F / C) on the surface of the fluorinated molded article by electron spectroscopy (ESCA). However, despite no change in F / C depending on the fluorination treatment conditions, the effects of the present invention such as an increase in the contact angle with water, the amount of eluted fluoride ions, and the suppression of eluted TOC can be obtained. There is a case.
【００２０】ＰＦＡおよびＦＥＰはポリテトラフルオロ
エチレン（ＰＴＦＥ）と異なり溶融成形が可能であり、
射出成形法、押出成形法などの溶融成形法が採用され
る。もちろんＰＴＦＥと同様の圧縮成形法や切削加工法
も適用できる。本発明はいずれの成形法で製造された成
形体をも処理対象とするが、特に溶融成形法で製造され
た成形体は、前述のように、たとえ安定化処理されてい
ても成形前よりも不安定基が増加するため、特に本発明
の改質の効果が奏されている。PFA and FEP can be melt-molded unlike polytetrafluoroethylene (PTFE).
A melt molding method such as an injection molding method or an extrusion molding method is employed. Of course, the same compression molding method and cutting method as PTFE can be applied. The present invention is intended to process molded articles produced by any of the molding methods, but in particular, molded articles produced by the melt molding method, as described above, even if subjected to stabilization treatment than before molding. Since the number of unstable groups increases, the effect of the modification of the present invention is particularly exhibited.
【００２１】成形体の形状は特に制限されず、たとえば
シート、フィルム、板、棒、チューブ、角柱などのほ
か、種々の形状の容器など各種の具体的製品であっても
よい。本発明の改質法は製品の作製の最終段階で実施す
るのが効果的であるから、最終製品の形状とした成形体
を対象とするのが好ましい。最終製品としては種々のも
のがあるが、たとえばウェハーキャリア、継ぎ手、ナッ
ト、チューブ、ベローズ、ダイヤフラム、フィルターハ
ウジングなどがあげられる。The shape of the molded article is not particularly limited, and may be various specific products such as sheets, films, plates, rods, tubes, prisms, and containers of various shapes. Since the modification method of the present invention is effective to be carried out at the final stage of production of a product, it is preferable to target a molded product having the shape of the final product. Although there are various types of final products, examples include a wafer carrier, a joint, a nut, a tube, a bellows, a diaphragm, and a filter housing.
【００２２】本発明の改質法によれば、ＰＦＡまたはＦ
ＥＰ成形体のフッ素イオンの水への溶出を抑えることが
でき、さらに全有機炭素（ＴＯＣ）の溶出量も抑えるこ
とができるので、接触する液体を汚染することが抑制で
きる。また、対水接触角（２５℃）を大きくすることが
でき、液濡れ性を向上させることができる。かかる改質
高純度化の効果は、成形体が溶融成形法で製造されたば
あいに従来にない特に顕著にえられる。According to the reforming method of the present invention, PFA or F
Since the elution of fluorine ions from the EP molded body into water can be suppressed and the amount of total organic carbon (TOC) eluted can also be suppressed, contamination of the contacting liquid can be suppressed. Further, the contact angle with water (25 ° C.) can be increased, and the liquid wettability can be improved. The effect of the modification and high purification is particularly remarkable when a molded article is produced by a melt molding method.
【００２３】したがって、本発明は、溶融成形法で製造
されたＰＦＡまたはＦＥＰ成形体であって、対水接触角
（２５℃）が１０５度以上、、水（１２１℃）への溶出
フッ素イオン濃度が０．５ｐｐｍ以下、および水（１２
１℃）への溶出全有機炭素量（ＴＯＣ）が３０ppm以下
である新規な成形体にも関する。また、硫酸（濃度９８
％、１８０℃）浸漬試験による重量変化が０．０１％以
下である成形体をも提供できる。Therefore, the present invention relates to a PFA or FEP molded article produced by a melt molding method, wherein the contact angle with water (25 ° C.) is 105 ° or more, and the concentration of eluted fluorine ions in water (121 ° C.) Is 0.5 ppm or less, and water (12
(1 ° C.). The present invention also relates to a novel molded product having a total organic carbon content (TOC) of 30 ppm or less. In addition, sulfuric acid (concentration 98
%, 180 ° C.) It is also possible to provide a molded article whose weight change by an immersion test is 0.01% or less.
【００２４】さらに、フッ素化処理後に熱（アニーリン
グ）処理を施すことにより、接触角（２５℃）が１０５
度以上、水（１２１℃）への溶出フッ素イオン濃度が
０．３ppm以下、および水（１２１℃）へのＴＯＣが２
５ppm以下のＰＦＡまたはＦＥＰ成形体を提供すること
ができる。Further, by performing a heat (annealing) treatment after the fluorination treatment, the contact angle (25 ° C.) is 105 ° C.
Degree, the elution fluoride ion concentration to water (121 ° C.) is 0.3 ppm or less, and the TOC to water (121 ° C.) is 2 ppm.
A PFA or FEP molded article of 5 ppm or less can be provided.
【００２５】[0025]
【実施例】つぎに本発明を実施例に基づいて説明する
が、本発明はかかる実施例のみに限定されるものではな
い。Next, the present invention will be described based on examples, but the present invention is not limited to only these examples.
【００２６】実施例１ ＰＦＡ（ダイキン工業（株）製のネオフロンＰＦＡ Ａ
Ｐ−２１０）を用いてＰＦＡ成型体（１３０トン射出成
形機（東芝機器（株）製。成形温度３９０℃）で成形し
た２インチキャリア）を熱風式オーブン中に設けられた
モネル製の箱型容器（（８０×４０×５０ｃｍ）に入
れ、容器内を充分にチッ素ガスで置換した。ついで、オ
ーブン内を２００℃に昇温したのちフッ素ガス（チッ素
ガスで１０容量％に希釈されている）を０．５リットル
／分の流速で箱型容器に導入しフッ素化処理を開始し
た。この条件で５時間フッ素化処理を行なったのち放冷
し、箱型容器内をチッ素で置換してフッ素化処理ＰＦＡ
成形体（１−Ａ）をえた。Example 1 PFA (Neoflon PFA A manufactured by Daikin Industries, Ltd.)
P-210) and a Monel box mold provided in a hot-air oven with a PFA molded body (2 inch carrier molded by a 130-ton injection molding machine (manufactured by Toshiba Instruments Co., Ltd., molding temperature: 390 ° C.)) The container was placed in a container ((80 × 40 × 50 cm), and the inside of the container was sufficiently replaced with nitrogen gas. Then, the inside of the oven was heated to 200 ° C., and then fluorine gas (diluted to 10% by volume with nitrogen gas. Was introduced into the box-shaped container at a flow rate of 0.5 liter / min to start the fluorination treatment.After performing the fluorination treatment under these conditions for 5 hours, the mixture was allowed to cool, and the inside of the box-shaped container was replaced with nitrogen. Fluorinated PFA
A molded article (1-A) was obtained.
【００２７】フッ素化処理条件を表１に示す条件に変え
たほかは同様に処理してフッ素化処理してフッ素化処理
ＰＦＡ成形体（１−Ｂおよび１−Ｃ）をえた。The fluorination treatment was carried out in the same manner except that the fluorination treatment conditions were changed to the conditions shown in Table 1 to obtain fluorinated PFA molded articles (1-B and 1-C).
【００２８】さらに、フッ素化処理ＰＦＡ成形体１−Ｂ
（２１０℃で８時間処理したもの）をさらに空気雰囲気
中で２５０℃にて５時間熱処理してフッ素化処理ＰＦＡ
成形体１−Ｄをえた。Further, a fluorinated PFA molded article 1-B
(Treated at 210 ° C. for 8 hours) and further heat-treated at 250 ° C. for 5 hours in an air atmosphere to obtain a fluorinated PFA
A molded article 1-D was obtained.
【００２９】これらのフッ素化処理ＰＦＡ成形体につい
て、つぎの性質を調べた。結果を表１に示す。The following properties of these fluorinated PFA molded articles were examined. Table 1 shows the results.
【００３０】［溶出フッ素イオン濃度］被験成形体２５
ｇを純水５０ｇに浸漬し、加圧式滅菌機で１２１℃１時
間抽出し、抽出中のフッ素イオン量をイオンクロマトグ
ラフィー（ＹＯＫＯＧＡＷＡ製の１Ｃ７０００式液体ク
ロマトグラム）で定量する。[Eluted Fluorine Ion Concentration] Test compact 25
g was immersed in 50 g of pure water and extracted with a pressure sterilizer at 121 ° C. for 1 hour, and the amount of fluorine ions during the extraction was determined by ion chromatography (1C7000 liquid chromatogram manufactured by YOKOGAWA).
【００３１】［対水接触角］協和界面科学（株）製の接
触角計により測定する。[Contact angle with water] Measured with a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.
【００３２】［溶出ＴＯＣ］被験成形体２５ｇを純水５
０ｇに浸漬し、加圧式滅菌機で１２１℃にて１時間抽出
し、抽出中のＴＯＣ量をＴＯＣメーター（（株）島津製
作所製の全有機炭素計）で定量する。[Eluted TOC] 25 g of the test compact was purified with 5
Then, the sample was immersed in 0 g, extracted with a pressure sterilizer at 121 ° C. for 1 hour, and the amount of TOC during the extraction was quantified using a TOC meter (Total Organic Carbon Meter manufactured by Shimadzu Corporation).
【００３３】［硫酸浸漬後の重量変化］被験成形体２５
ｇを硫酸（９８％）中に１８０℃にて３０時間浸漬後、
成形体をとり出し、純水で数回すすぎ、重量を測定し
た。[Change in weight after immersion in sulfuric acid] Test compact 25
g in sulfuric acid (98%) at 180 ° C. for 30 hours,
The molded body was taken out, rinsed several times with pure water, and weighed.
【００３４】［Ｆ／Ｃ］ＥＳＣＡ（（株）島津製作所製
のＸ線光電子分光計）により測定する。[F / C] Measured by ESCA (X-ray photoelectron spectrometer manufactured by Shimadzu Corporation).
【００３５】表１の結果からフッ素化処理を２００〜２
５０℃の温度範囲内で行なうと溶出フッ素イオン量およ
びＴＯＣが低減し、さらに熱処理を加えたばあいさらに
溶出フッ素イオン量が低減することがわかる。From the results shown in Table 1, the fluorination treatment was performed for 200 to 2 times.
It can be seen that when performed within a temperature range of 50 ° C., the amount of eluted fluorine ions and TOC are reduced, and the amount of eluted fluorine ions is further reduced when heat treatment is further applied.
【００３６】比較例１ 実施例１で用いた原料ＰＦＡのペレットを実施例１の１
−Ｂと同様にしてフッ素化処理（２１０℃８時間）し
た。このフッ素化処理ＰＦＡペレットの溶出フッ素イオ
ン濃度は０．２ppmにまで減少していた。ついで、この
フッ素化処理ペレットを用いて実施例１と同じ条件で射
出成形してＰＦＡ成形体を作製した。このＰＦＡ成形体
の溶出フッ素イオン濃度は３．０ｐｐｍと上昇してい
た。これは射出成形時にフッ素化処理ＰＦＡが不安定基
を生じたことを示す。Comparative Example 1 The raw material PFA pellets used in Example 1 were used in Example 1
It was fluorinated (210 ° C. for 8 hours) in the same manner as in −B. The eluted fluorine ion concentration of the fluorinated PFA pellet was reduced to 0.2 ppm. Next, the fluorinated pellets were injection molded under the same conditions as in Example 1 to produce a PFA molded body. The eluted fluorine ion concentration of this PFA molded article was increased to 3.0 ppm. This indicates that the fluorinated PFA produced an unstable group during injection molding.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【発明の効果】本発明のＰＦＡまたはＦＥＰ成形体の高
純度化改質法によれば、溶出するフッ素イオン量だけで
なく溶出全有機炭素量をも低減することができる。しか
も対水接触角も大きくなるので液濡れ性が向上し、成形
体中の金属不純物の溶出も抑制できる。したがって、溶
融成形可能なＰＦＡやＦＥＰの使用が難しかった極めて
高度なクリーン環境が要求される半導体分野のウェット
プロセスにおける各種成形体として有用である。さらに
ＰＦＡおよびＦＥＰ成形体の製品寿命を延ばすことがで
きる。According to the method for purifying and reforming a PFA or FEP molded article of the present invention, not only the amount of eluted fluorine ions but also the total amount of eluted organic carbon can be reduced. In addition, since the contact angle with water is increased, the liquid wettability is improved, and the elution of metal impurities in the molded body can be suppressed. Therefore, it is useful as various molded articles in a wet process in the semiconductor field which requires an extremely high clean environment in which use of PFA or FEP which is melt-moldable is difficult. Further, the product life of the PFA and FEP molded products can be extended.
フロントページの続き (72)発明者 長谷川 雅典 大阪府摂津市西一津屋１番１号 ダイキン 工業株式会社淀川製作所内 (72)発明者 石割 和夫 大阪府摂津市西一津屋１番１号 ダイキン 工業株式会社淀川製作所内Continued on the front page (72) Inventor Masanori Hasegawa 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Kazuo Ishiwari 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Inside the factory
Claims (6)
（アルキルビニルエーテル）共重合体またはテトラフル
オロエチレン／ヘキサフルオロプロピレン共重合体の成
形体の少なくとも表面をフッ素ガスによりフッ素化処理
するテトラフルオロエチレン／パーフルオロ（アルキル
ビニルエーテル）共重合体またはテトラフルオロエチレ
ン／ヘキサフルオロプロピレン共重合体の成形体の高純
度化改質法。Claims: 1. A tetrafluoroethylene / perfluoro (perfluoro (alkyl vinyl ether) copolymer or a tetrafluoroethylene / hexafluoropropylene copolymer formed article, wherein at least the surface of a molded article is fluorinated with fluorine gas. (Alkyl vinyl ether) copolymer or tetrafluoroethylene / hexafluoropropylene copolymer molded article with high purity.
で熱処理を行なう請求項１記載の高純度化改質法。2. After the fluorination treatment, 200 to 250 ° C.
The high-purity reforming method according to claim 1, wherein the heat treatment is performed.
フルオロエチレン／パーフルオロ（アルキルビニルエー
テル）共重合体またはテトラフルオロエチレン／ヘキサ
フルオロプロピレン共重合体を溶融成形してえられた成
形体である請求項１または２記載の高純度化改質法。3. The molded product before the fluorination treatment is a molded product obtained by melt-forming a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer or a tetrafluoroethylene / hexafluoropropylene copolymer. 3. The high-purity reforming method according to claim 1 or 2.
処理したテトラフルオロエチレン／パーフルオロ（アル
キルビニルエーテル）共重合体またはテトラフルオロエ
チレン／ヘキサフルオロプロピレン共重合体である請求
項１〜３のいずれかに記載の高純度化改質法。4. The copolymer according to claim 1, wherein the copolymer is a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer or a tetrafluoroethylene / hexafluoropropylene copolymer in which a terminal unstable group has been stabilized. 3. The method for high-purity reforming according to any one of 3.
１２１℃での水への溶出フッ素イオン濃度が０．５ppm
以下、かつ１２１℃での水へ溶出する全有機炭素量が３
０ppm以下であるテトラフルオロエチレン／パーフルオ
ロ（アルキルビニルエーテル）共重合体またはテトラフ
ルオロエチレン／ヘキサフルオロプロピレン共重合体の
溶融成形体。5. A contact angle with water at 25 ° C. of 105 degrees or more,
Fluoride ion concentration eluted in water at 121 ° C is 0.5ppm
Below, and the total amount of organic carbon eluted into water at 121 ° C. is 3
A melt molded article of a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer or a tetrafluoroethylene / hexafluoropropylene copolymer having a concentration of 0 ppm or less.
求項５記載の溶融成形体。6. The melt-molded article according to claim 5, which is modified by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28686497A JPH11116710A (en) | 1997-10-20 | 1997-10-20 | High-purity reforming method for fluororesin moldings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28686497A JPH11116710A (en) | 1997-10-20 | 1997-10-20 | High-purity reforming method for fluororesin moldings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11116710A true JPH11116710A (en) | 1999-04-27 |
Family
ID=17710013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28686497A Pending JPH11116710A (en) | 1997-10-20 | 1997-10-20 | High-purity reforming method for fluororesin moldings |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11116710A (en) |
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