200416231 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關含氟樹脂組成物、製造含氟樹脂組成物 之方法、半導體製造裝置及被覆電線。 【先前技術】 四氟乙烯/氟烷氧基三氟乙烯共聚物〔PFA〕爲具有優 良耐藥性、耐熱性及成型性之含氟樹脂，因此可活用其特 性而使用於接觸具有強烈破壞作用之流體（氣體、液體） 搬運系統用之管子或瓶子等，又，作爲半導體製造裝置用 零件時，可使用於含臭氧媒體流通用管子、含硏磨劑之淤 漿送液用管子等。 近年來爲了因應半導體製造高速化之需求，而使流通 於管內之含臭氧媒體中的臭氧高濃度化，因此PFA所得 之材料會有快速惡化及提高裝置維護頻率之生產性問題。 先前PFA所得之零件的管內面不具充分平滑性，因 此特別是移送含硏磨劑淤漿時，硏磨作用今造成管料混入 送液系統內，而成爲降低硏磨效率、硏磨異常、降低所得 半導體之電特性的原因，而大幅降低製品合格率。另外， 含臭氧媒體流通時易堆積污染物質，而使維護上產生問題 〇 故需求半導體製造裝置零件用之管子不易惡化及內面 具有平滑性質。 目前已嘗試於製粒階段，使PFA成形時會產生氣泡 -5- (2) (2)200416231 而造成平滑性惡化之不安定的末端官能基接觸含氟氣體而 安定化（例如參考特公平8 — 3 0097號公報）。但，PFA 本身仍存在耐臭氧性差之問題。 又，曾提案具有熱安定性及既使長時間保持高溫熔融 狀態下也不會降低熔融粘度，且每碳數1 06個殘留7至40 個一 CH2OH末端基而使其他不安定末端基安定化之PFA (例如參考持開平1 0 - 1 762 1號公報）。但該PFA仍有 耐臭氧性差之問題。 另曾多次提案以PFA及FEP之混合物作爲抗惡化之 管材料（例如參考特開平1 1 — 2 1 0942號公報、特開2002 —1 7 3 5 7 0號公報）。但，熔融混練P F A及F E P所形成之 混合物以製造相熔物時，可觀察到熔融粘度增加且會暫時 性使剪斷力上升之現象，因此由相熔物而得之管內面的最 大粗糙度將難低於0 · 3 // m，又，其未接觸含氟氣體。 爲了提升所得成型物內面之平滑性，曾提案PFA添 加聚四氟乙烯而得之組成物（例如參考特開平7 — 7 〇 3 9 7 號公報）。但其中未曾記載及提示有關製造該組成物時， 未接觸含氟氣體、增加熔融粘度及短暫提升剪斷力之事。 PFA除了使用於管料之用途外，也可作爲電線被覆物 ’但因具有局熔點等，故難提升成型時生產速度，又，提 高速度時會產生被覆物外表面龜裂等成型加工上大問題。 以具有良好成型加工性之FEP作爲被覆物時，因耐 熱性、電特性方面比PFA差，故近年來無法符合電線被 覆物所要求之絕緣性、耐熱性等性能水準之事件逐漸增加 -6- (3) (3)200416231 曾揭示主要作爲電線被覆物之PFA、FEP及改性 PTFE所形成的組成物（例如參考美國專利第5 3 1 7 06 1號 公報說明書），但該組成物未接觸含氟氣體。 【發明內容】 發明之要旨 本鑑於此，故本發明第1項目的爲，提供有關具有耐 臭氧性及表面平滑性之半導體製造裝置用零件，本發明第 2項目的爲，提供具有優良成型加工性之四氟乙烯/氟烷氧 基三氟乙烯共聚物所形成的含氟樹脂組成物。 本發明含氟樹脂組成物之特徵爲，四氟乙烯/氟烷氧 基三氟乙烯共聚物及四氟乙烯/六氟丙烯共聚物所形成之 含氟樹脂組成物中，四氟乙烯/六氟丙烯共聚物對四氟乙 烯/六氟丙烯共聚物及四氟乙烯/氟烷氧基三氟乙烯共聚物 之合計固體成分質量爲0.5至60質量％，又，含氟樹脂組 成物所形成之測定用管狀成型物爲，內面平均粗糙度〔Ra 〕爲0.035//m以下，最大粗糙度〔Rt〕低於〇.3//m。 本發明製造含氟樹脂組成物之方法的特徵爲，依序利 用將四氟乙烯/氟烷氧基三氟乙烯共聚物及四氟乙烯/六氟 丙烯共聚物所形成之混合組成物熔融混練的熔融混練步驟 ’及使用含氟氣體精製處理之精製步驟製造含氟樹脂組成 物之製造含氟樹脂組成物方法中，熔融混練時係利用汽缸 內混合組成物溫度控制於3 5 0至3 9 5 °C之擠押成形機，於 (4) (4)200416231 混合組成物之粘度不產生變化下進行，又，該含氟氣體爲 含有5質量％以上氟，且精製處理步驟爲，將熔融混練步 驟所得之擠出物曝露於含氟氣體中，以分解去除低分子量 物。 發明之詳細揭示 下面將詳細說明本發明。 本發明之含氟樹脂組成物爲，四氟乙烯/氟烷氧基三 氟乙烯共聚物及四氟乙烯/六氟丙烯共聚物所形成之測定 用管狀成型物的內面平均粗糙度〔Ra〕爲0.03 5 μ m以下 。長時間使含硏磨劑等之流體流通於內面平均粗糙度〔Ra 〕超過0.03 5 // m之管子時，易造成磨損，且長時間接觸 具有強烈化學性破壞作用之流體時，易使管內面遭破壞之 部分堆積污染物質等。平均粗糙度〔Ra〕之上限較佳爲 0.0 3 // m。平均粗糙度〔Ra〕爲該範圍下，受限於製造測 定用管狀成型物之方法的下限可爲0.005// m。 本發明之含氟樹脂組成物爲，四氟乙烯/氟烷氧基三 氟乙烯共聚物及四氟乙烯/六氟丙烯共聚物所形成之測定 用管狀成型物的內面平均粗糙度〔Ra〕爲上述範圍，且最 大粗糙度〔Rt〕低於〇·3 // m。〔 Rt〕爲0.3 // m以上時， 將無法符合各種製品所要求的規格水準而不宜。較佳之上 限爲〇 · 2 5 // m。最大粗糙度〔Rt〕爲該範圍下，受限於製 造測定用管狀成型物之方法的下限可爲〇. 1 // m。 上述平均粗糙度〔Ra〕及最大粗糙度〔Rt〕係依據 -8- (5) (5)200416231 JI S B 0 6 0 1所測得之値。 上述測定用管狀成型物之內面平均粗糙度〔Ra〕及最 大粗縫度〔Rt〕一般存在後述之低分子量物。確認方法可 爲，熔融混練數種經r線照射而降低分子量之四氟乙烯/ 氯院氧基二氯乙細共聚物及/或四氣乙儲/六氣丙細共聚物 後，觀察成型所得管子內面。 該測定用管子爲，利用汽缸徑30mm，L/D = 22 ’模頭/ 尖端=2 0mm 0 /12mm 0之擠押成型機，將四氟乙烯/氟烷 氧基三氟乙烯共聚物及四氟乙烯/六氟丙烯共聚物之混合 物熔融混練後，利用管狀成型用模具以40cm/分之拉取速 度濟押而得之內徑9.5mm、外徑11.5mm的管子。又’熔 融混練係於汽缸內混合物溫度控制於340°C至3 95 °C ’且 旋轉回轉數爲8rpm下進行8至10分鐘。 如上述般，因該測定用管狀成型物同一般管子係於擠 押成型時外表面接觸模具等之外物時成型、冷卻而得，故 外表面凹凸情形一般比模具等之表面平滑，但內表面於冷 卻時未持續接觸模具等，因此表面凹凸情形比模具等之外 物不規律，而易形成晶球及表面粗糙。且，使用本發明之 含氟樹脂組成物而得的測定用管狀成型物，既使內面也可 得表面平滑性，且平均粗糙度〔Ra〕及最大粗糙度〔Rt〕 符合上述範圍。 本發明之含氟樹脂組成物的測定用管狀成型物內面之 平均粗糙度〔Ra〕及最大粗糙度〔Rt〕符合上述範圍時， 平滑性比其他一般性成型物更充分。該其他一般性成型物 -9- (6) (6)200416231 並無特別限制，可爲同上述管內面之目前表面易粗糙之物 ，例如利用圓錐而得之電線被覆物、鑄造膜而得之薄膜等 〇 本發明之含氟樹脂組成物係由四氟乙烯/氟烷氧基三 氟乙烯共聚物〔TFE/FTE共聚物〕所形成。 本說明書之TFE/FTE共聚物係指，以氟烷氧基三氟 乙烯〔FTE〕爲四氟乙烯〔TFE〕之共聚單體的共聚物， 且FTE對TFE及FTE之合計質量爲1至15質量％。又， 本說明書中以對全部單體之質量％表示的共聚單體量係指 ’共聚物之分子構造中，「來自單體之全部單體」中來自 該共聚單體之共聚單體單位所佔質量％。該「共聚單體單 位」例如來自後述之 HFP時，以—CF2— CF ( CF3 )—表 示。又，氟烷氧基三氟乙烯之氟烷氧基可爲，烷氧基之碳 -氫鍵全部成爲碳-氟鍵的全氟烷氧基，或碳-氫鏈之部 分氫受氟取代之烷氧基。 上述TFE/FTE共聚物較佳爲，熔融指數〔MFR〕爲9 (g/ΙΟ分）以下之物。超過9(g/10分）時，會因分子量 過低而易降低所得成型物之耐臭氧性及耐熱性。上限較佳 爲4(g/l〇分），更佳爲3.5(g/10分）。]V[FR爲該範圍 時’就成型加工觀點下限例如可爲0 · 5 ( g/1 0分）。 本說明書之MFR係指，依據ASTM D3307(1998年 )於3 72 1：下荷重5kg所測得之値。 本發明之含氟樹脂組成物係由上述TFE/FTE共聚物 及四氟乙烯/六氟丙烯共聚物〔TFE/HFP共聚物〕所形成 -10- (7) (7)200416231 ，又，添加該TFE/HFP共聚物可強化耐臭氧性。 本說明書之TFE/HEP共聚物係指，以六氟丙烯〔HFP 〕爲TFE之共聚單體的共聚物，且HFP對TFE及HFP之 合計質量爲1至2 0質量％以上。 又，該TFE/HFP共聚物可爲，以HFP爲TFE之共聚 單體，且依所需使用乙烯醚而得之3元以上共聚物。 TFE/HFP共聚物爲3元以上共聚物時，一般乙烯醚對TFE 、HFP及乙烯醚之合計質量爲1質量％以下，但對TFE、 HFP及乙烯醚之合計質量可超過1質量％，超過1質量％ 時上限較佳如2 · 5質量％，更佳如2質量％。200416231 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a fluorine-containing resin composition, a method for manufacturing a fluorine-containing resin composition, a semiconductor manufacturing apparatus, and a covered electric wire. [Prior technology] Tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer [PFA] is a fluororesin with excellent chemical resistance, heat resistance and moldability, so it can make full use of its characteristics and have a strong destructive effect on contact. Fluids (gases, liquids) Pipes or bottles used in conveying systems, and parts for semiconductor manufacturing equipment can be used for general-purpose pipes containing ozone-containing media streams, pipes for slurry-feeding containing honing agents, and the like. In recent years, in order to meet the demand for high-speed semiconductor manufacturing, the concentration of ozone in the ozone-containing medium circulating in the tube has been increased. Therefore, the materials obtained from PFA have the problems of rapid deterioration and productivity maintenance. The inner surface of the tube of the previous PFA parts did not have sufficient smoothness, so especially when transferring the slurry containing honing agent, the honing effect caused the pipe material to be mixed into the liquid feeding system, which reduced the honing efficiency, honing abnormality, The reason for reducing the electrical characteristics of the obtained semiconductor is to greatly reduce the yield of the product. In addition, when the ozone-containing medium is in circulation, it is easy to accumulate pollutants and cause maintenance problems. Therefore, it is required that the tubes for semiconductor manufacturing device parts are not easily deteriorated and the inner surface has smooth properties. At present, it has been attempted in the granulation stage to make bubbles in the formation of PFA-5- (2) (2) 200416231 and the unstable terminal functional group that causes the deterioration of smoothness is stabilized by contacting the fluorine-containing gas (for example, refer to Special Fair 8) — 3 0097). However, PFA itself still has the problem of poor ozone resistance. In addition, it has been proposed that it has thermal stability and does not reduce the melt viscosity even if it is maintained at a high temperature for a long time, and it has 7 to 40 residues per carbon number of 1 to 2 CH2OH terminal groups to stabilize other unstable terminal groups. PFA (for example, refer to Hirakai No. 10-1 762 1). However, the PFA still has a problem of poor ozone resistance. It has also been proposed many times that a mixture of PFA and FEP is used as the anti-deterioration tube material (for example, refer to JP-A No. 11 — 2 1 0942, JP No. 2002 — 1 7 3 5 7 0). However, when the mixture of PFA and FEP is melt-kneaded to produce a phase melt, the increase in melt viscosity and the temporary increase in shear force are observed. Therefore, the maximum roughness of the inner surface of the tube obtained from the phase melt The degree will be hardly lower than 0 · 3 // m, and it is not exposed to the fluorine-containing gas. In order to improve the smoothness of the inner surface of the obtained molded product, a composition obtained by adding polytetrafluoroethylene to PFA has been proposed (for example, refer to Japanese Patent Application Laid-Open No. 7-7007397). However, there is no record or suggestion in the manufacture of this composition that it did not come into contact with fluorine-containing gas, increased melt viscosity, and temporarily increased shearing force. In addition to being used for pipe materials, PFA can also be used as a wire coating. However, because of its local melting point, it is difficult to increase the production speed during molding, and when the speed is increased, the outer surface of the coating will crack, such as cracking. problem. When FEP with good moldability is used as a coating, the heat resistance and electrical characteristics are inferior to PFA. Therefore, in recent years, the number of incidents that cannot meet the performance standards such as insulation and heat resistance required for wire coatings has gradually increased. (3) (3) 200416231 A composition formed by PFA, FEP, and modified PTFE, which are mainly used as wire coverings, has been disclosed (for example, refer to the specification of US Patent No. 5 3 1 7 06 1), but the composition is not in contact Fluorine-containing gas. [Summary of the Invention] In view of this, the first item of the present invention is to provide components for semiconductor manufacturing devices having ozone resistance and surface smoothness, and the second item of the present invention is to provide excellent molding processing Fluorine-containing resin composition formed of a tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer. The fluorine-containing resin composition of the present invention is characterized in that, in a fluorine-containing resin composition formed of a tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / hexafluoro The total solid content mass of the propylene copolymer to the tetrafluoroethylene / hexafluoropropylene copolymer and the tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer is 0.5 to 60% by mass, and the formation of the fluorine-containing resin composition is measured. The tubular molded product has an average inner surface roughness [Ra] of 0.035 // m or less and a maximum roughness [Rt] of less than 0.3 // m. The method for producing a fluorine-containing resin composition according to the present invention is characterized by sequentially using a melt-kneaded mixed composition formed by a tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer. Melt-kneading step 'and the method for producing a fluororesin composition using a refining step using a fluorine-containing gas refining process, the temperature of the mixed composition in the cylinder is used to control the temperature of the mixture to 3 5 0 to 3 9 5 The extrusion molding machine at ° C is performed without changing the viscosity of (4) (4) 200416231 mixed composition. The fluorine-containing gas contains 5 mass% or more of fluorine, and the refining step is to melt and knead. The extrudate obtained in the step is exposed to a fluorine-containing gas to decompose and remove low molecular weight substances. Detailed Disclosure of the Invention The present invention will be described in detail below. The fluorine-containing resin composition of the present invention is an average inner surface roughness [Ra] of a tubular molded article for measurement formed by a tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer. It is 0.03 5 μm or less. It is easy to cause abrasion when the fluid with honing agent is circulated in the pipe whose average roughness [Ra] is more than 0.03 5 // m for a long time, and it is easy to make a fluid with strong chemical damage for a long time. The damaged part of the inner surface of the tube accumulates pollutants, etc. The upper limit of the average roughness [Ra] is preferably 0.0 3 // m. The average roughness [Ra] is within this range, and the lower limit limited to the method for manufacturing the tubular molded article for measurement may be 0.005 // m. The fluorine-containing resin composition of the present invention is an average inner surface roughness [Ra] of a tubular molded article for measurement formed by a tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer. Is within the above range, and the maximum roughness [Rt] is lower than 0.3 / m. When [Rt] is 0.3 // m or more, it will not be able to meet the specifications required by various products. The preferred upper limit is 0 · 2 5 // m. 1 // m。 The maximum roughness [Rt] is within this range, and the lower limit limited to the method for producing a tubular molded article for measurement may be 0.1 // m. The above average roughness [Ra] and maximum roughness [Rt] are measured based on -8- (5) (5) 200416231 JI S B 0 6 0 1. Generally, the inner surface roughness [Ra] and the maximum shirring degree [Rt] of the tubular molded article for measurement mentioned above are generally low-molecular weight materials described later. The confirmation method may be as follows: melt-kneading several tetrafluoroethylene / chloroethoxy dichloroethylene fine copolymers and / or tetrakisthyl ethylene / hexafluoroacrylic acid fine copolymers whose molecular weight is reduced by r-ray irradiation, and observe the molding results Inside of the pipe. The tube used for this measurement was an extrusion molding machine with a cylinder diameter of 30 mm and L / D = 22 'die / tip = 20 mm 0/12 mm 0. The tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer and four After the mixture of the fluoroethylene / hexafluoropropylene copolymer was melt-kneaded, a tube having a inner diameter of 9.5 mm and an outer diameter of 11.5 mm was obtained by using a tube-forming mold at a drawing speed of 40 cm / min. Also, the 'melting kneading is performed by controlling the temperature of the mixture in the cylinder at 340 ° C to 3 95 ° C' and performing the rotation at 8 rpm for 8 to 10 minutes. As mentioned above, the tube-shaped molded article for measurement is obtained by forming and cooling when the outer surface of the tube is molded and cooled when it is in contact with a foreign object such as a mold during extrusion molding. Therefore, the unevenness of the outer surface is generally smoother than the surface of the mold. The surface does not continuously contact the mold or the like during cooling, so the surface irregularities are more irregular than those of the mold or the like, and crystal balls are easily formed and the surface is rough. In addition, the tubular molded article for measurement obtained by using the fluorine-containing resin composition of the present invention can obtain surface smoothness even on the inner surface, and the average roughness [Ra] and the maximum roughness [Rt] fall within the above range. When the average roughness [Ra] and the maximum roughness [Rt] of the inner surface of the tubular molded article for measurement of the fluorine-containing resin composition of the present invention fall within the above ranges, the smoothness is more sufficient than that of other general molded articles. The other general moldings 9- (6) (6) 200416231 are not particularly limited, and may be those which are easily roughened with the current surface of the inner surface of the tube, for example, a wire covering obtained by using a cone and a casting film. Films, etc. The fluorine-containing resin composition of the present invention is formed of a tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer [TFE / FTE copolymer]. The TFE / FTE copolymer in this specification refers to a copolymer in which fluoroalkoxytrifluoroethylene [FTE] is a comonomer of tetrafluoroethylene [TFE], and the total mass of FTE to TFE and FTE is 1 to 15 quality%. In addition, the comonomer amount expressed in terms of% by mass of all monomers in the present specification refers to a comonomer unit derived from the comonomer in "the entire monomer derived from the monomer" in the molecular structure of the copolymer. Percentage by mass. When the "comonomer unit" is derived from, for example, HFP described later, it is represented by —CF2 — CF (CF3) —. The fluoroalkoxy group of the fluoroalkoxytrifluoroethylene may be a perfluoroalkoxy group in which all carbon-hydrogen bonds of the alkoxy group become carbon-fluorine bonds, or a part of the hydrogen of the carbon-hydrogen chain is replaced by fluorine. Alkoxy. The TFE / FTE copolymer is preferably one having a melt index [MFR] of 9 (g / 10) or less. When it exceeds 9 (g / 10 minutes), the molecular weight is too low, and the ozone resistance and heat resistance of the obtained molded article are liable to be lowered. The upper limit is preferably 4 (g / 10 minutes), and more preferably 3.5 (g / 10 minutes). ] V [When the FR is within this range ', the lower limit in terms of molding processing viewpoint may be, for example, 0 · 5 (g / 10 minutes). The MFR in this specification refers to 値 measured in accordance with ASTM D3307 (1998) at 3 72 1: under load of 5 kg. The fluorine-containing resin composition of the present invention is formed from the above-mentioned TFE / FTE copolymer and tetrafluoroethylene / hexafluoropropylene copolymer [TFE / HFP copolymer]. -10- (7) (7) 200416231 TFE / HFP copolymer can enhance ozone resistance. The TFE / HEP copolymer in this specification refers to a copolymer using hexafluoropropylene [HFP] as a comonomer of TFE, and the total mass of HFP to TFE and HFP is 1 to 20% by mass or more. The TFE / HFP copolymer may be a ternary or higher copolymer obtained by using HFP as a comonomer and using vinyl ether as needed. When the TFE / HFP copolymer is a ternary copolymer or more, the total mass of vinyl ether to TFE, HFP, and vinyl ether is generally 1 mass% or less, but the total mass of TFE, HFP, and vinyl ether may exceed 1 mass%, exceeding The upper limit at 1% by mass is preferably 2.5% by mass, and more preferably 2% by mass.
該乙烯醚並無特別限制，例如下列一般式（I ) CY^^CY2 - OR (式中，Y1及Y2爲相同或相異之氫原子或氟原子。 R爲部分或全部鍵結於碳原子之氫原子可受氟原子取代的 可具有醚氧之有機基） 所示含醚氧化合物等。其中，就經濟面有機基較佳爲 碳數1至4之烷基，就耐臭氧性觀點更佳爲碳數2至4之 烷基。 上述TFE/HFP共聚物較佳爲，熔融指數〔MFR〕爲9 (g/ΙΟ分）以下之物。超過9(g/l〇分）時，會因分子量 過低而易降低所得成型物之耐臭氧性及耐熱性。上限較佳 爲4(g/l〇分），更佳爲3(g/l〇分）〇MFR爲該範圍下 ，就成型加工性觀點下限可爲0.5 ( g/1 0分）。 組合具有上述範圍之TFE/HFP共聚物及TFE/FTE共 -11 - (8) (8)200416231 聚物時’可使所得測定用管狀成型物之內面平均粗糙度〔 Ra〕及最大粗糙度〔Rt〕爲上述範圍。又，利用後述含氟 氣體進行精製處理時，可縮小測定用管狀成型物之內面平 均粗糙度〔Ra〕及最大粗糙度〔Rt〕。 本發明之含氟樹脂組成物可爲，未使用後述含氟氣體 進行精製處理之物，又，使用MFR爲1.0至3.5 ( g/ΙΟ分 )之TFE/FTE共聚物及MFR爲0.5至3 ( g/ΙΟ分）之 TFE/HFP共聚物時，可使測定用管狀成型物之內面平均粗 糙度〔Ra〕及最大粗糙度〔Rt〕爲上述範圍。 上述TFE/HFP共聚物對TFE/HFP共聚物及TFE/FTE 共聚物之合計固體成分質量爲0.5至60質量％。低於0.5 質量％時，會使使用本發明之含氟樹脂組成物而得的成型 物之表面平滑性變差，又，超過60質量％時，會使所得 成型物之耐彎曲性及高溫下機械特性變差。就提升成型速 度觀點，上限較佳爲5 0質量％，就不降低所得成型物之 耐熱性下既使使用實用性洗淨溫度也無損尺寸安定性觀點 ，上限更佳爲3 0質量％。就後述高熔點觀點，上限更佳 爲1 0質量％，但最佳組成係具有均衡成型性及具有性能 下依用途設定。 本發明之含氟樹脂組成物較佳爲，對上述TFE/FTE 共聚物與TFE/HFP共聚物進行熔融混練。 本說明書中將進行熔融混練之前及熔融混練中之 TFE/FTE共聚物及TFE/HFP共聚物之混合物稱爲「混合 組成物」。 -12- (9) (9)200416231 熔融混練係利用擠押成形機進行，又，本說明書中’ 將上述混合組成物進行熔融混練時，擠押成形機所擠出之 物稱爲「擠出物」。 就TFE/HFP共聚物與TFE/FTE共聚物熔融混練後之 耐熱性觀點，上述混合組成物之合計固體成分質量中’ TFE/HFP共聚物所佔比率最佳爲〇·5至約10質量％。比率 爲該範圍下，可由差示掃描型熱量計分析得知，上述擠出 物之熔點比進行熔融混練前單獨之TFE/FTE共聚物高或 具有相同熔點，因此可提升耐熱性。當TFE/HFP共聚物 對混合組成物之合計固體成分質量超過1 0質量％且約3 5 質量％以下時，擠出物之熔解熱量比熔融混練前之 TFE/HFP共聚物高，又，超過約35質量％時，比熔融混 練前之TFE/HFP共聚物低。本發明之含氟樹脂組成物係 經歷熔融混練之物，因此可得前述般特異之熱特性。 因本發明之含氟樹脂組成物經歷熔融混練，故如上述 般可調整熔解熱量及控制平均分子量與熔融粘度。 又，對本發明含氟樹脂組成物之上述混合組成物進行 加壓粉碎處理時，可如上述般調整熔解熱量，平均分子量 及熔融粘度。進行加壓粉碎處理時係採用搭載於成型裝置 之具高混練效果的螺旋。 本發明之含氟樹脂組成物可爲，TFE/FTE共聚物及 TFE/HFP共聚物與四氟乙烯聚合物所形成之物。由四氟乙 烯聚合物形成時，可更進一步改善所得成型物之耐彎曲性 及耐斷裂性。又，添加該四氟乙烯聚合物時，可如後述般 -13- 200416231 (ίο) 具有改善成型時之成型加工性效果，因此可作爲成型助劑 〇 本說明書之「四氟乙烯聚合物」係指，四氟乙烯之單 獨聚合物及/或該四氟乙烯與其他共聚單體之共聚物，且 該其他共聚單體對四氟乙烯及其他共聚單體之合計質量爲 低於1質量％。 該四氟乙烯聚合物係以四氟乙烯以外之共聚成分含量 低於 1質量％的觀點，與上述 TFE/FTE共聚物及 TFE/HFP共聚物區別。 上述之其他共聚單體並無特別限制，例如氯三氟乙烯 〔TFE〕、HFP、全氟（烷基乙烯醚）〔PAVE〕等。 所使用之四氟乙烯聚合物的熔融熱量較佳爲60j/g以 上。熱量爲該範圍下可得，製造具有優良耐彎曲性及耐斷 裂性之成型物時’於熔融成型時具有良好成型加工性之含 氟樹脂組成物。該四氟乙烯聚合物之熔融熱量可低於 6〇J/g，例如35至48J/g，如此可改善若干成型加工性及 耐彎曲性、耐斷裂性。 本發明之含氟樹脂組成物係由上述四氟乙烯聚合物形 成時’四氟乙烯聚合物對上述含氟樹脂組成物之固體成分 質量較佳爲0·2至5質量％。低於0.2質量％時，使用該四 氟乙烯聚合物時無法明顯改善成型加工性，又，超過5質 量％時’會使所得成型物之表面平滑性變差。其下限更佳 爲〇 · 5質量％，上限更佳爲3質量％。 本發明之含氟樹脂組成物除了上述TFE/FTE共聚物 -14- (11) (11)200416231 、TFE/HFP共聚物及所需之四氟乙烯聚合物外，可含有添 加劑類。 該添加劑類並無特別限制，例如塡充劑、潤滑劑、成 型助劑、顏料等，但將所得成型物使用於半導體製造裝置 時，就無損純度觀點又以不使用添加劑爲佳。 上述TFE/FTE共聚物及TFE/HFP共聚物較佳爲，已 調整末端官能基數之物。又，可於未熔融混練前調整該末 端官能基數。調整末端官能基數之方法如後述。 上述含氟樹脂組成物較佳爲，經含氟氣體處理之物。 本說明書中利用「含氟氣體處理」之目的爲，除了調 整未熔融混練前之末端官能基數及抑制成型時起泡外，可 分解去除熔融混練後所得擠出物所含之低分子量物。 該含截氣體處理爲’使用含每氣體之精製處理。即’ 曝露於含氟氣體中，可分解去除熔融混練後所得擠出物所 含之低分子量物。 本發明含氟樹脂組成物之分子量分而較佳爲1 ·〇至 2.2 〇 該分子量分布於僅由特定分子量之物構成時，將指以 單分散之値爲1.0時表示偏差程度之値。該分子量分布超 過2.2時，會增加分子量偏差程度而存在低分子量物’因 此不依靠模具等形成管內面等表面之凹凸情形的成型物時 ，會使低分子量物溢流於表面而易降低表面平滑性。上限 更佳爲1 . 6。 上述分子量分布爲上述本發明含氟樹脂組成物之値’ -15- (12) 200416231 又，使用含氟氣體對本發明之含氟樹脂組成物進行精 理時，係指經含氟氣體之精製處理後之値。使用含氟 進行精製處理後，可去除低分子量物而將分子量分布 於上述範圍內。又，使用含氟氣體進行精製處理時， 處理前之分子量分布値可超出上述範圍。 判斷去除低分子量物之方法可爲，經含氟氣體之 處理後，可減少分子量分布値及降低MFR。僅依據 量分而減少而無法判斷去除低分子量物之原因爲，爲 熔融粘彈性測定結果適合正規分布曲線，而進行接近 曲線之操作下，即使具有分布廣指標也無法評估分布 〇 熔融混練後含氟樹脂組成物之MFR測定方法同 〇 上述分子量分布爲，依據Pol ym· Eng· Sci·，29 ( ),64 5 ( W. H. Tuminello )及 M a c r o m o 1 ·，2 6 ( 1 9 9 3 ) (W. H. Tuminello et. al.)所記載之方法測定而得的 本發明之含氟樹脂組成物中，一CF2 — CH2OH CONH2、COOH、— COF群中所選出至少1個之末端 基對每碳數1 〇6較佳爲低於1 〇個。1 〇個以上時，熔 型時易起泡。又，本發明之含氟樹脂組成物可不存該 官能基。 該末端官能基數爲，利用紅外分光法測得之値。 上述末端官能基數如上述般爲本發明含氟樹脂組 之値，又，本發明之含氟樹脂組成物使用含氟氣體進 製處 氣體 抑制 精製 精製 分子 了使 理想 偏移 上述 198 9 ,499 直。 > — 官能 融成 末端 成物 行精 -16- (13) (13)200416231 製處理時，係指精製處理後之値。 上述碳數係指TFE/FTE共聚物之碳數及TFE/HFP共 聚物之碳數的合計數。本發明之含氟樹脂組成物係由上述 四氟乙烯聚合物形成時，該碳數及末端官能基數係包含四 氟乙烯聚合物之碳數及末端官能基數。 上述末端官能基爲，存在於TFE/FTE共聚物及/或 TFE/HFP共聚物之分子鏈末端的基。該分子鏈末端可爲主 鏈末端或支鏈末端。該末端官能基可於TFE/FTE共聚物 及/或TFE/HFP共聚物聚合時，使用鏈轉移劑1價低級醇 而導入主鏈末端及/或支鏈末端。 本發明製造含氟樹脂組成物之方法係製造上述含氟樹 脂組成物用。 本發明製造含氟樹脂組成物之方法爲，特徵係依序進 行將TFE/FTE共聚物及TFE/HFP共聚物所形成的混合組 成物熔融混練之熔融混練步驟，及使用含氟氣體進行精製 處理之精製步驟。 上述熔融混練步驟中含有，使上述混合組成物之 TFE/FTE共聚物、TFE/HFP共聚物及所需之四氟乙烯聚合 物的分子鏈所具有之末端官能基們鍵結的反應（以下稱爲 偶合反應）。 確認上述混合組成物中 TFE/FTE共聚物、TFE/HFP 共聚物之各分子的至少一部分末端官能基間產生偶合反應 的方法可爲，總合①熔融混練前後利用差示掃描型熱量分 析〔DSC〕而得之熱收支曲線槪略圖形會產生較大變化， -17- (14) (14)200416231 ②熔融混練後利用DSC觀測熔融混練前來自TFE/HFP共 聚物之264 t附近的吸熱峰會完全消失，③熔融混練時利 用DSC觀測熔融混練前來自TFE/FTE共聚物之2個吸熱 峰的形狀及位置會產生變化，及④既使高溫下長時間保存 仍能抑制PFA熔融粘度降低之4個現象而加以判斷。 上述熔融混練步驟可利用末端官能基之偶合反應生成 偶合物，因此可作爲製造耐臭氧性優良之成型物用步驟。 目前進行樹脂熔融混練時，隨著偶合反應會增加分子 量及熔融粘度，因此會使混合組成物之剪斷力短暫上升而 造成局部分子鏈斷裂，故無法避免降低熔融粘度及生成低 分子量物。但本發明之熔融混練步驟係以均衡調整後述熔 融混練時間、熔融混練溫度、剪斷速度、末端官能基數等 ，而抑制末端官能基之偶合反應進行，故既使一旦切斷分 子鏈而降低分子量時，仍能利用偶合反應鍵結其他分子鏈 ，而保有同切斷前之分子量，而得抑制低分子量物存在率 之具有優良耐臭氧性的成型物。 本發明之熔融混練步驟係於超越因剪斷作用而使分子 鏈斷裂之速度下進行偶合反應，故可控制過度提升熔融粘 度，而防止熔融成型時成型加工性變差。 上述熔融混練步驟係進行至混合組成物之粘度不產生 變化爲止。混合組成物之熔融混練中粘度變化可由，介有 螺旋利用轉矩計器觀測回轉轉矩之經時變化而得知。該「 混合組成物之粘度不產生變化爲止」係指，混合組成物無 粘度變化狀態爲止。又，該「混合組成物無粘度變化狀態 -18- (15) (15)200416231 」係指，回轉轉矩値之變化爲一定時間以上中心値至5 % 以內狀態。 該「一定時間」例如1 〇分鐘已足夠。 熔融混練所需時間可依進行後述熔融混練之溫度、混 合組成物之混合比率、螺旋形狀等而異，一般爲2分鐘以 上。 就經濟性及生產性觀點，熔融混練所需時間之上限可 爲1 〇分鐘，例如將質量比90 : 1 0的具有1 7個末端官能 基之TFE/FTE共聚物與末端全爲活性基之TFE/HFP共聚 物混練時，3 90 °C下需4至9分鐘，又，利用實驗式塑料 混練型雙軸擠押機（東洋精機公司製）混練時，相當於通 過時間2.5至5分鐘。該通過時間可依預先測定利用分批 式混練機之粘度經時變化，再依據經時變化之數據設定。 上述熔融混練步驟中，係將汽缸內 TFE/FTE共聚物 及TFE/HFP共聚物之混合組成物溫度控制於3 5 0至3 95 t 下，利用擠押成型機進行熔融混練。混練溫度爲該範圍時 ，易得成型時成型物表面平滑化之含氟樹脂組成物。混練 溫度之下限較佳爲3 60 t。 該熔融混練步驟中，控制擠押成型機之汽缸內溫度的 方法爲，於未加入混合組成物之狀態下輸入控制條件後， 安定狀態下利用複數根長度爲一定內徑汽缸之1 0%以上的 熱電對測定目的溫度。 該熔融混練步驟可使用備有高混練效果之螺旋的單軸 型擠押成型機、或雙軸型擠押成型機。 -19- (16) (16)200416231 所選用之雙軸型擠押成型機較佳爲，螺旋構造具有充 分混練效果，且對混合組成物無過多剪斷力。 剪斷速度於上述溫度範圍下較佳爲，因應混合組成物 之組成比率設定。 熔融混練步驟中所使用之 TFE/FTE 共聚物及 TFE/HEP共聚物較佳爲，可提升聚合之粉狀物，該粉狀物 較佳爲粒徑小之物。又，熔融混練前利用含氟氣體如後述 般調整末端官能基數時，除了易處理外，可得均勻之熔融 混練狀態。該提升聚合之粉狀物係指，結束聚合反應後乾 燥而得之粉狀物。 熔融混練前又以未加熱狀態下混合TFE/FTE共聚物 之粉狀物及TFE/HFP共聚物之粉狀物爲佳。混合該粉狀 物時可使用已知之裝置進行。 又，熔融混練前較佳爲，調整 TFE/FTE共聚物及 丁FE/HFP共聚物之末端官會g基板。調整末端官會g基板時， 熔融混練過程中可保有能製造耐臭氧性之成型物用偶合物 的末端官能基數及抑制混合組成物因過度提升剪斷力而產 生低分子量物之末端官能基數。 調整後末端官能基數較佳爲，使末端官能基數對每 TFE/FTE共聚物之碳數及TFE/HFP共聚物之碳數合計1〇6 個爲4至1 〇 0個。上限更佳爲7 0個，下限更佳爲5 0個。 又，使用四氟乙烯聚合物時，較佳於熔融混練前調整該四 氟乙烯聚合物之末端官能基數。此時調整後碳數及末端官 能基數較佳爲TFE/FTE共聚物、TFE/HFP共聚物及四氟 -20- (17) (17)200416231 乙烯聚合物之組合物的數値。 調整末端官能基數之方法雖可爲，分別調整原先聚合 階段爲〇或後述末端官能基不活性化而爲〇之物（A )， 及完全未經後述末端官能基不活性化之物（B )混合而得 的末端官能基數。但熔融混練時，相對於（B )會因偶合 反應而增加分子量之情形下，（A )僅會因主鏈斷裂而變 差，因此無法避免低分子量物產量增加。故調整末端官能 基數之方法較佳爲，對TFE/FTE共聚物、TFE/HFP共聚 物及四氟乙烯聚合物之混合組成物一樣進行而使分子間均 勻調整。 本發明製造含氟樹脂組成物之方法中，精製步驟可去 除上述熔融混練步驟所生成之低分子量物，而使本發明之 含氟樹脂組成物具有均勻組成。 精製步驟所使用之含氟氣體爲，含有5質量％以上之 氟。含氟氣體爲該範圍下，可爲含有1〇〇質量％以下氟之 物或氟氣。 該精製步驟之精製處理方法爲，將上述熔融混練步驟 所得之擠出物曝露於含氟氣體中，以分解去除低分子量物 。又，該精製處理除了可去除低分子量物外，可如後述般 使末端官能基不活性化。 去除低分子量物之方法可爲，如歐洲專利第472908 號說明書（1 9 9 2年）、特開平0 4 — 0 8 5 3 0 5號公報及專利 3 0 06049號公報所揭示，使用氯氟化碳類等含氟溶劑進行 ，但該步驟煩雜，因此以上述使用含氟氣體之方法爲佳。 -21 - (18) (18)200416231 經上述熔融混練步驟及精製步驟而得之本發明含氟樹 脂組成物係供給熔融成型用，但今因成型條件，而產生起 因於殘存之末端官能基的起泡情形。因此爲了抑制熔融成 型時起泡，較佳於熔融混練後將殘存之末端官能基不活性 化。 將末端官能基不活性化之方法並無特別限制，例如， 曝露於上述含氟氣體而使末端變化爲三氟甲基之方法、或 浸漬於苯胺之甲醇溶液後，於高壓鍋內高溫高壓下進行處 理而受苯基取代之方法等，又，高溫下能變爲成型時不分 解之末端下，方法並無限制。 本發明之含氟樹脂組成物因具有上述組成及係利用上 述製造方法製得，故可得具有耐臭氧性及表面平滑性之成 型物。 雖未淸楚本發明之含氟樹脂組成物得到上述優良效果 之機構，但可由後述推論得知。即，本發明之含氟樹脂組 成物係使用含氟氣體進行精製處理以去除低分子量物，因 此既使不依靠模具等外物製造具有管內表面等表面之成形 物’也不易使低分子量物溢流於成型物表面，故可提升所 得成型物之表面平滑性。 又，本發明之含氟樹脂組成物於上述熔融混練過程中 ，可控制末端官能基之間的偶合反應，故難生成低分子量 物，且既使生成低分子量物也可利用熔融混練後之含氟氣 體精製處理去除低分子量物。 本發明之含氟樹脂組成物因係由難接受臭氧分解之 -22- (19) (19)200416231 TFE/HFP共聚物成分所形成，故可稍微抑制曝露於臭氧後 降低成型物之耐斷裂性等。 又，本發明之含氟樹脂組成物爲，使用含氟氣體精製 處理後，使殘存之末端官能基不活性化之物，因此末端官 能基不活性化後進行製造成型物用之熔融成型時，可抑制 伴隨末端官能基分解及/或末端官能基之偶合反應的起泡 情形，而提升所得成型物之表面平滑性。 本發明之一項爲成型物，其特徵係由上述含氟樹脂組 成物所形成。 本發明另一項爲上述成型物所形成之半導體製造裝置 ，其特徵爲使用60°C以上含10體積％之臭氧的含臭氧媒 體。 使用於半導體製造裝置之成型物並無特別限制，例如 可爲管子等。 由上述含氟樹脂組成物所得之管子因具有高耐臭氧性 ，故使用於使用含臭氧水或含臭氧氣體等含臭氧媒體之半 導體製造裝置時，耐久性比現在氟樹脂製管子高，因此可 降低裝置維護頻率、提高裝置生產率及削減維護所需成本 ，而以更廉價方式製造半導體。又，由本發明之含氟樹脂 組成物而得的管子因內面平均粗糙度〔Ra〕及最大粗糙度 〔Rt〕較低，故可得優良表面平滑性及耐摩損性，又，既 使使用於製造半導體過程之硏磨系統上也能具有高耐久性 ，因此能以更廉價方式製造半導體。 本發明另一項爲由上述成型物而得之半導體製造裝置 -23- (20) (20)200416231 ，其特徵爲使用1 5 °C以上含粒子淤漿，且該含粒子淤漿 爲含氧化鋁及/或二氧化矽所形成之粒子。 本發明另一項爲圓筒狀成型物用連接器，其特徵爲由 上述含氟樹脂組成物而得。 該圓筒狀成型物用連接器爲，接連圓筒狀成型物們及 接連圓筒狀成型物與其他零件用零件。 利用圓筒狀成型物用連接器接連之圓筒狀成型物較佳 爲，同圓筒狀成型物用連接器係由含氟樹脂組成物形成， 但連接處無需爲圓筒狀，且無厚度、長短、剖面形狀等尺 寸約束，又，使用上述含氟樹脂組成物就物性面因具優 越性，故用途並無特別限制。適用於半導體製造裝置之圓 筒狀成型物如，熱收縮管、厚肉管等各種形狀物。 上述圓筒狀成型物比僅由TFE/FTE共聚物而得之圓 筒狀成型物具有更優良之表面平滑性、耐斷裂性及耐臭氧 性。 上述圓筒狀成型物用連接器不使用上述含氟樹脂組成 物時，會使表面平滑性變差，因此運送含硏磨劑之淤漿時 ，會集中於連接處產生磨損，且會因磨損所造成的偏差而 使圓筒狀成型物內面與淤漿間產生異常摩擦，而無法得到 所需耐摩損性。 本發明另一項爲被覆電線，其特徵爲利用上述含氟樹 脂組成物所得之被覆物被覆電線。 因上述含氟樹脂組成物之熔解熱量之熔融混練前之 TFE/HFP共聚物低，故可高速製造含氟樹月旨被覆電線。又 -24- (21) (21)200416231 ’該含氟樹脂組成物之熔融粘度較低，故成型加工性優於 僅使用 TFE/HFP共聚物而得之被覆電線。另外因含有 TFE/FTE共聚物成分，故高溫下可得比僅由TFE/HFP共 聚物而得之被覆電線更高的體積電阻率。 比較一般僅由 TFE/FTE共聚物而得之成型物，生成 於由本發明之含氟樹脂組成物而得的成型物表面上之晶球 較小，因此可減小粒表面積，而減小的粒表面尺寸可減少 應力局部集中性，故可提升對疲勞性破壞之耐久性及耐彎 曲性，而適用於上述被覆電線等。 【實施方式】 實施發明之最佳形態 下面將以實施例更詳細說明本發明，但本發明非限於 該實施例。 實施例1 預先依表1所示組成比混合粉狀TFE/FTE共聚物（ 熔融指數〔MFR〕=2.0g/l 0分）及 TFE/HFP共聚物（ MFR=1.9g/10分），再以所得混合組成物爲基礎原料。所 得混合組成物之末端官能基數對 TFE/FTE共聚物及 TFE/HFP共聚物之合計與碳數106個爲17個。利用0 1 5mm之備螺旋雙軸型熔融混練機，於混合組成物溫度保 有3 8 0至3 9(TC下進行混練再擠出，得顆粒狀擠出物。 1 85 °C下於高壓鍋內將擠出物曝露於20質量％之含氟氣體 -25- (22) (22)200416231 中，精製處理後得含氟樹脂組成物。 所得含氟樹脂組成物之分子量分布〔MWD〕爲1.45 ，因此比精製處理前之値1 · 6 3少，且可將精製處理前之 MFR値2· 1 ( g/1 0分）降低爲精製處理後之値1 .7 ( g/1 0 分），而由減少MWD及降低MFR可判斷已由擠出物去 除低分子量物。此時利用紅外線分光法測得之含氟樹脂組 成物所含的末端官能基數爲，對每碳數1 0 6個爲4至1 0 個。 上述 MFR 係依據 ASTM D 3 3 07 ( 1 998 年）於 3 72 t： 下以荷重5kg方式測定。 以所得顆粒狀含氟樹脂組成物作爲原料，利用熱板溫 度3 60 °C進行熔融壓縮成型，得厚2mm片物後，將所得 片物靜置於預熱37(TC之烤箱內，2小時後以目測觀察， 結果並未起泡。 使用所得含氟樹脂組成物形成測定用管狀成型物及片 物，再進行下列評估。 表面粗f造度： 以上述製法使用含氟樹脂組成物形成測定用管狀成型 物，再依JIS B 060 1測定內面平均粗糙度〔Ra〕及最大 粗糙度〔Rt〕。 漱獎送液試驗： 溫度25 °C下使淤漿（粒子：氧化鋁，濃度50 g/L)以 -26- (23) 200416231 流速1 0L/分方式流通於上述測定用管狀成型物內 時後利用電子顯微鏡觀察淤漿送液前後測定用管 之內面，結果如圖1所示附著於內表面之粒子少 痕等。 實施例2 除了對基礎原料1 00質量份添加四氟乙烯聚 聚單體：HFP，〇.〇8質量％，熔解熱量 45 J/g， 1 8 0萬）0 · 8質量份外，其他同實施例1之方法 脂組成物，再進行淤漿送液試驗以外之評估。 實施例3 除了未將所得之擠出物曝露於含氟氣體外， 施例1之方法得含氟樹脂組成物，再進行淤漿送 外之評估。 比較例1 除了僅以TFE/FTE共聚物樹脂成爲基礎原 他同實施例1之方法得含氟樹脂組成物，再進行 。又，淤漿送液試驗前後測定用管狀成型物內面 微鏡像如圖2所示。結果可觀測看比實施例1之 顯的筋狀摩損痕跡。 比較例2 ，8 00 小 狀成型物 ，且無傷 合物（共 分子量約 得含氟樹 其他同實 液試驗以 料外，其 相同評估 之電子顯 管子更明 •27- (24) 200416231 除了將熔融混練時之混合組成物溫度設定爲40 5 °C外 ，其他同實施例1之方法得含氟樹脂組成物，再進行淤漿 送液試驗以外之評估。 -28- (25)200416231 表1 TFE/FTE TFE/HFP TFE系 精製 分子量 熔融指數 平均粗糙度 最大粗糙度 共聚物 共聚物 聚合物 處理 分布 (g/ΐο 分） 网 [Rt] (質量份） (質量份） (質量份) ("m) ("m) 實施例1 90 10 一 前 1.63 21. 0.023 0.161 後 1.45 1.7 實施例2 90 10 0.8 _.v/- 刖 — 1.5 0.024 0.144 後 — 1.1 實施例3 90 10 — 未進行 — 2.1 0.031 0.256 比較例1 100 一 — 前 一 2 0.050 0.329 後 一 1.9 比較例2 90 10 一 刖 — 3.7 0.101 0.637 後 — 2.8 -29- (26) (26)200416231 由表1得知，實施例1至3之測定用管狀成型物的內 面平均粗糙度及最大粗糙度比比較例1至2小。 實施例4 除了將混合組成物之TFE/HFP共聚物成分率改爲50 質量％以外，其他同實施例1之方法熔融混練，再使用含 氟氣體進行處理，得含氟樹脂組成物。利用DSC由292 °C 附近之吸熱峰面積測定該含氟樹脂組成物之熔解熱量。又 ，以汽缸徑0 30mm、螺旋L/D = 22、模頭/尖端=0 1 3mm/ 0 7mm、擠出溫度3 4 0°C至3 95 °C，螺旋回轉數48rpm、 拉取速度6 1 m/分之條件將含氟樹脂組成物熔融擠出成型 ，得被覆厚度〇.3mm之電線被覆物。依據AS TM D 1 50 ( 1 9 8 7年）以測定周波數106Hz測定所得電線被覆物之介 電率及介電質損耗因數。 結果熔解熱量、介電率、介電質損耗因數及製造電線 被覆物時之拉取速度如表2所示。 電線被覆物之成型速度爲比較例3之1.2倍，故可確 認提升生產性。 所得電線被覆物之1 2 0 °C下體積電阻率爲1 x 1 〇 18 Ω · cm以上，因此比一般TFE/HFP共聚物之體積電阻率（ 1 0 17 Ω · cm以下）具有更優良絕緣性。 比較例3 僅使用TFE/FTE共聚物顆粒製造被覆厚度同實施例4 -30- (27) 200416231 之電源被覆物，再以同實施例4之方法進行評估。結果如 表2所示。 表2 TFE/FTE TFE/HFP 介電率 介電質損耗因數 熔解熱量 拉取速度 共聚物 (質量％) 共聚物 (質量％) (25°C?1〇6Hz) (25〇C51〇6Hz) (J/g) (m/分） 實施例4 50 50 2.08 0.0003 11.2 61 _ 比較例3 100 一 2.06 0.0003 19.4 50〜55_ 由表2得知，添加TFE/HFP共聚物之實施例4除了 具有與比較例3同等之電特性外，可得熔解熱量較低之含 氟樹脂組成物。 實施例5 除了以TFE/FTE共聚物（MFR = 3.5至8.5g/10分）及 TFE/HEP共聚物（MFR = 4.3至8.7g/10分）所形成的混合 組成物爲基礎原料外，其他同實施例1之方法得含氟樹脂 組成物後’將其射出成型爲接連2根實施例1所得之測定 用管狀成型物用的連接器。組合2根測定用管狀成型物及 該連接器作爲藥液循環系統用，再以同實施例1之條件進 行游漿送液試驗。利用電子顯微鏡觀察淤漿送液試驗後連 接器之內面’結果連接處未見氧化鋁沈澱及附著，連接器 及管子亦無明顯摩損。 -31 - (28)200416231 比較例4 同實施例5將2根實施例1所 及由比較例1之組成物而得的連接 統後，同實施例5進行淤漿送液試 察淤漿送液試驗後連接器內面，結 鋁，且堆積氧化鋁部分出現筋狀摩 實施例6 對實施例5所得之連接器進行 氧曝露後連接器內面未見圖3所示 臭氧曝露試驗： 進行臭氧曝露試驗之方法爲， 列內徑 5 0 m m之管內，再利用臭1 SGX — A1 1MN，住友精密公司製） 濃度12體積％濕氣流通於管內21 ，使乾臭氧氣經過離子交換水之閥 得之測定用管狀成型物 器組合成爲藥液循環系 驗。利用電子顯微鏡觀 果連接器內面堆積氧化 損痕跡。 臭氧曝露試驗。結果臭 裂痕。 將上述連接器靜置於直 氧發生裝置（商品名： 以0.7L/分流量使臭氧 〇天。又，該濕氣係由 而得。 比較例5 對由比較例1之組成物而得的 之臭氧曝露試驗。結果臭氧曝露試 圖3所示裂痕。 連接器進行同實施例6 驗後之連接器剖面出現 -32- (29) (29)200416231 產業上利用可能性 本發明之含氧樹脂組成物係由上述方法構成，因此保 有T F E / F T E共聚物原有之優良耐熱性及電特性的同時， 可得具優良耐臭氧性及表面平滑性之成型物。 【圖式簡單說明】 圖1爲，實施例1之淤漿送液試驗後測定用管狀成型 物內表面的電子顯微鏡像。 圖2爲，比較例1之淤漿送液試驗後測定用管狀成型 物內表面的電子顯微鏡像。 圖3爲，比較例5之臭氧曝露試驗後產生裂痕之連接 器厚度方向剖面圖。 符號說明 1 :曝露表面 2 :裂痕影像 3 :主體 -33-The vinyl ether is not particularly limited, for example, the following general formula (I) CY ^^ CY2-OR (wherein Y1 and Y2 are the same or different hydrogen atom or fluorine atom. R is partially or completely bonded to a carbon atom An organic oxygen group-containing compound such as an organic group in which a hydrogen atom may be substituted by a fluorine atom may have an ether oxygen). Among them, an organic group having an alkyl group having 1 to 4 carbon atoms is preferred from the economic point of view, and an alkyl group having 2 to 4 carbon atoms is more preferable from the viewpoint of ozone resistance. The TFE / HFP copolymer is preferably one having a melt index [MFR] of 9 (g / 10) or less. When it exceeds 9 (g / l0 minutes), the molecular weight of the molded article is too low, and the ozone resistance and heat resistance of the obtained molded article are likely to be lowered. The upper limit is preferably 4 (g / 10 minutes), and more preferably 3 (g / 10 minutes). The MFR is within this range, and the lower limit may be 0.5 (g / 10 minutes) from the viewpoint of molding processability. When a TFE / HFP copolymer and a TFE / FTE copolymer having the above ranges are combined-(8) (8) 200416231 polymer, 'the average roughness [Ra] and the maximum roughness of the inner surface of the obtained tubular molded article can be obtained [Rt] is the above range. In addition, when performing a refining treatment using a fluorine-containing gas described later, the inner surface average roughness [Ra] and the maximum roughness [Rt] of the tubular molded article for measurement can be reduced. The fluorine-containing resin composition of the present invention may be one that has not been subjected to a refining treatment using a fluorine-containing gas described later, and a TFE / FTE copolymer having an MFR of 1.0 to 3.5 (g / 10 minutes) and an MFR of 0.5 to 3 ( g / 10 points) of the TFE / HFP copolymer, the average roughness [Ra] and the maximum roughness [Rt] of the inner surface of the tubular molded article for measurement can be set within the above ranges. The total solid content mass of the TFE / HFP copolymer to the TFE / HFP copolymer and the TFE / FTE copolymer is 0.5 to 60% by mass. When it is less than 0.5% by mass, the surface smoothness of the molded article obtained by using the fluororesin composition of the present invention is deteriorated. When it exceeds 60% by mass, the obtained molded article is resistant to bending and high temperature. Deterioration of mechanical characteristics. From the viewpoint of increasing the molding speed, the upper limit is preferably 50% by mass, and the upper limit is more preferably 30% by mass from the viewpoint of not impairing the dimensional stability even when the practical washing temperature is used without reducing the heat resistance of the obtained molded article. From the viewpoint of the high melting point described later, the upper limit is more preferably 10% by mass. However, the optimum composition has balanced moldability and performance and is set depending on the application. The fluorine-containing resin composition of the present invention preferably melt-kneads the TFE / FTE copolymer and the TFE / HFP copolymer. In this specification, a mixture of the TFE / FTE copolymer and the TFE / HFP copolymer before and during melt-kneading is referred to as a "mixed composition". -12- (9) (9) 200416231 Melt-kneading is performed using an extrusion molding machine. In this specification, when the above-mentioned mixed composition is melt-kneaded, the material extruded from the extrusion molding machine is called "extrusion. Thing. " From the viewpoint of heat resistance of the TFE / HFP copolymer and the TFE / FTE copolymer after melt-kneading, the ratio of the TFE / HFP copolymer to the total solid mass of the above-mentioned mixed composition is preferably 0.5 to about 10% by mass . When the ratio is within this range, it can be known from the analysis of a differential scanning calorimeter that the melting point of the extrudate is higher than that of the TFE / FTE copolymer alone before melt-kneading or has the same melting point, so that heat resistance can be improved. When the total solids mass of the TFE / HFP copolymer to the mixed composition exceeds 10% by mass and less than about 35% by mass, the heat of fusion of the extrudate is higher than that of the TFE / HFP copolymer before melt-kneading. At about 35% by mass, it was lower than the TFE / HFP copolymer before melt-kneading. The fluorine-containing resin composition of the present invention is a material that has undergone melt-kneading, so that the aforementioned specific thermal characteristics can be obtained. Since the fluorine-containing resin composition of the present invention undergoes melt-kneading, the heat of fusion can be adjusted and the average molecular weight and melt viscosity can be controlled as described above. When the above-mentioned mixed composition of the fluorine-containing resin composition of the present invention is subjected to a pressure pulverization treatment, the heat of fusion, the average molecular weight, and the melt viscosity can be adjusted as described above. The pressure pulverization process uses a screw with a high kneading effect mounted on a molding device. The fluorine-containing resin composition of the present invention may be a product formed of a TFE / FTE copolymer, a TFE / HFP copolymer, and a tetrafluoroethylene polymer. When formed from a tetrafluoroethylene polymer, the bending resistance and fracture resistance of the obtained molded article can be further improved. In addition, when the tetrafluoroethylene polymer is added, as described below, 13-200416231 (ίο) has the effect of improving the moldability at the time of molding, so it can be used as a molding aid. The "tetrafluoroethylene polymer" system in this specification It means that the single polymer of tetrafluoroethylene and / or the copolymer of the tetrafluoroethylene and other comonomers, and the total mass of the other comonomer to the tetrafluoroethylene and other comonomers is less than 1% by mass. This tetrafluoroethylene polymer is different from the above-mentioned TFE / FTE copolymer and TFE / HFP copolymer from the viewpoint that the content of copolymerization components other than tetrafluoroethylene is less than 1% by mass. The other comonomers mentioned above are not particularly limited, such as chlorotrifluoroethylene [TFE], HFP, perfluoro (alkyl vinyl ether) [PAVE], and the like. The heat of fusion of the tetrafluoroethylene polymer used is preferably 60 j / g or more. When the amount of heat is within this range, a fluororesin composition having good moldability during melt molding is produced when a molded article having excellent bending resistance and crack resistance is produced. The heat of fusion of the tetrafluoroethylene polymer can be lower than 60J / g, for example, 35 to 48J / g, which can improve the molding processability, bending resistance, and fracture resistance. When the fluororesin composition of the present invention is formed from the above-mentioned tetrafluoroethylene polymer, the solid content of the 'tetrafluoroethylene polymer to the above-mentioned fluororesin composition is preferably from 0.2 to 5% by mass. When it is less than 0.2% by mass, molding processability cannot be significantly improved when the tetrafluoroethylene polymer is used, and when it exceeds 5% by mass', the surface smoothness of the obtained molded article is deteriorated. The lower limit is more preferably 0.5% by mass, and the upper limit is more preferably 3% by mass. The fluorine-containing resin composition of the present invention may contain additives in addition to the above-mentioned TFE / FTE copolymer -14- (11) (11) 200416231, TFE / HFP copolymer, and a desired tetrafluoroethylene polymer. The additives are not particularly limited, for example, fillers, lubricants, molding aids, pigments, and the like. However, when the obtained molded product is used in a semiconductor manufacturing device, it is preferable not to use an additive in terms of non-destructive purity. The TFE / FTE copolymer and the TFE / HFP copolymer are preferably those having adjusted the number of terminal functional groups. The number of terminal functional groups can be adjusted before the melt-kneading. The method of adjusting the number of terminal functional groups is described later. The fluorine-containing resin composition is preferably a fluorine-containing gas-treated product. The purpose of using "fluorine-containing gas treatment" in this specification is to decompose and remove the low molecular weight substances contained in the extrudate obtained after melt-kneading, in addition to adjusting the number of terminal functional groups before melt-kneading and suppressing foaming during molding. This gas interception treatment is a 'refining treatment using per gas. That is, 'exposure to a fluorine-containing gas can decompose and remove the low molecular weight substances contained in the extrudate obtained after melt-kneading. The molecular weight of the fluorine-containing resin composition of the present invention is preferably from 1.0 to 2.2. When the molecular weight distribution is composed of only a specific molecular weight substance, it means that the degree of deviation is expressed when the monodisperse 値 is 1.0. When the molecular weight distribution exceeds 2.2, the degree of molecular weight deviation will increase and low-molecular-weight substances will be present. Therefore, when a molded article that does not rely on a mold or the like to form unevenness on the inner surface of a tube, the low-molecular-weight substances will overflow on the surface and the surface will be easily lowered Smoothness. The upper limit is more preferably 1.6. The above molecular weight distribution is the 値 of the above-mentioned fluorine-containing resin composition of the present invention. -15- (12) 200416231 When the fluorine-containing resin composition of the present invention is refined by using a fluorine-containing gas, it means that the fluorine-containing gas is refined. Later After refining with fluorine, low molecular weight substances can be removed and the molecular weight distribution can be within the above range. When the fluorine-containing gas is used for refining treatment, the molecular weight distribution 値 before the treatment may exceed the above range. The method for judging the removal of low-molecular-weight substances may be to reduce the molecular weight distribution and the MFR after treatment with a fluorine-containing gas. The reason why it is impossible to judge the removal of low-molecular-weight substances only based on the quantity is that the melt viscoelasticity measurement results are suitable for the regular distribution curve, and the distribution curve cannot be evaluated even with a broad distribution index under the operation of the approximate curve. The MFR measurement method of the fluororesin composition is the same as above. The molecular weight distribution is based on Pol ym · Eng · Sci ·, 29 (), 64 5 (WH Tuminello) and Macromo 1 ·, 2 6 (1 9 9 3) (WH In the fluorine-containing resin composition of the present invention obtained by the method described in Tuminello et. Al.), At least one terminal group selected from a CF2—CH2OH CONH2, COOH, and COF group has a number of 1 per carbon. 6 is preferably less than 10 pieces. When it is 10 or more, foaming is liable to occur during melting. The fluorine-containing resin composition of the present invention may not contain the functional group. The number of the terminal functional groups is measured by infrared spectrometry. The number of the above-mentioned terminal functional groups is the same as that of the fluorine-containing resin group of the present invention, and the fluorine-containing resin composition of the present invention uses a fluorine-containing gas to suppress the refining and refinement of molecules. . > — Functional melting End product Refining -16- (13) (13) 200416231 In the case of processing, it means the product after the processing. The above carbon number refers to the total number of carbon numbers of the TFE / FTE copolymer and the carbon number of the TFE / HFP copolymer. When the fluorine-containing resin composition of the present invention is formed of the above-mentioned tetrafluoroethylene polymer, the number of carbons and terminal functional groups include the number of carbons and terminal functional groups of the tetrafluoroethylene polymer. The terminal functional group is a group existing at the molecular chain terminal of the TFE / FTE copolymer and / or the TFE / HFP copolymer. The molecular chain end may be a main chain end or a branched chain end. This terminal functional group can be introduced into the main chain end and / or the branched chain end using a chain transfer agent monovalent lower alcohol during the polymerization of the TFE / FTE copolymer and / or the TFE / HFP copolymer. The method for producing a fluorine-containing resin composition of the present invention is for producing the above-mentioned fluorine-containing resin composition. The method for producing a fluorine-containing resin composition according to the present invention is characterized in that a melt-kneading step of melt-kneading a mixed composition formed by a TFE / FTE copolymer and a TFE / HFP copolymer is sequentially performed, and the fluorine-containing gas is used for refining treatment. Refining steps. The above-mentioned melt-kneading step includes a reaction (hereinafter referred to as a reaction in which the terminal functional groups of the molecular chain of the TFE / FTE copolymer, TFE / HFP copolymer and the desired tetrafluoroethylene polymer of the mixed composition are bonded) Is a coupling reaction). The method for confirming the coupling reaction between at least a part of the terminal functional groups of each of the molecules of the TFE / FTE copolymer and the TFE / HFP copolymer in the above mixed composition may be as follows: ① using differential scanning calorimetry before and after melt-kneading [DSC The resulting thermal budget curve will have a large change. -17- (14) (14) 200416231 ②After melt kneading, use DSC to observe the endothermic peak near 264 t from the TFE / HFP copolymer before melt kneading. Completely disappeared. ③ Use DSC to observe the shape and position of the two endothermic peaks from the TFE / FTE copolymer before melt-kneading during melt-kneading. ④ Even if stored at high temperature for a long time, the decrease in PFA melt viscosity can be suppressed. 4 This phenomenon. The above-mentioned melt-kneading step can be used as a step for producing a molded article having excellent ozone resistance because a coupling compound can be formed by a coupling reaction of terminal functional groups. At present, when the resin is melt-kneaded, the molecular weight and melt viscosity will increase with the coupling reaction. Therefore, the shearing force of the mixed composition will be temporarily increased and local molecular chains will be broken. Therefore, it is unavoidable to reduce the melt viscosity and generate low molecular weight substances. However, the melt-kneading step of the present invention adjusts the below-mentioned melt-kneading time, melt-kneading temperature, shearing speed, number of terminal functional groups, etc. in a balanced manner, and inhibits the coupling reaction of the terminal functional groups from proceeding. In this case, it is still possible to use a coupling reaction to bond other molecular chains, while maintaining the same molecular weight as before the cleavage, and obtaining a molded article with excellent ozone resistance that suppresses the presence of low molecular weight materials. The melt-kneading step of the present invention is to perform the coupling reaction at a speed beyond the breakage of the molecular chain due to the shearing action, so that the melt viscosity can be controlled to be excessively increased, and the moldability during melt molding is prevented from being deteriorated. The above-mentioned melt-kneading step is performed until the viscosity of the mixed composition does not change. The viscosity change during melt-kneading of the mixed composition can be obtained by observing the change in the turning torque over time with a torque meter through a spiral. This "until the viscosity of the mixed composition does not change" means that the mixed composition has no viscosity change state. The "mixed composition has no viscosity change state -18- (15) (15) 200416231" refers to a state in which the change in the turning torque 为 is within a certain time from the center 値 to within 5%. The "certain time", for example, 10 minutes is sufficient. The time required for the melt-kneading may vary depending on the temperature of the later-mentioned melt-kneading, the mixing ratio of the mixed composition, the spiral shape, etc., and is generally 2 minutes or more. From the viewpoint of economics and productivity, the upper limit of the time required for melt-kneading can be 10 minutes. For example, a TFE / FTE copolymer having 17 terminal functional groups with a mass ratio of 90:10 and the terminals are all active groups. The TFE / HFP copolymer is kneaded at 4 to 9 minutes at 3 90 ° C. When mixed with an experimental plastic kneading type twin-shaft extruder (manufactured by Toyo Seiki Co., Ltd.), the passage time is equivalent to 2.5 to 5 minutes. The passing time can be determined by measuring the viscosity of the batch-type kneader with time, and then set according to the time-varying data. In the above-mentioned melt-kneading step, the temperature of the mixed composition of the TFE / FTE copolymer and the TFE / HFP copolymer in the cylinder is controlled at 350 to 3 95 t, and the melt-kneading is performed by using an extrusion molding machine. When the kneading temperature is within this range, it is easy to obtain a fluororesin composition having a smooth surface of a molded article during molding. The lower limit of the kneading temperature is preferably 3 60 t. In this melt-kneading step, the method of controlling the temperature in the cylinder of the extrusion molding machine is to input the control conditions without adding the mixed composition, and use a plurality of cylinders with a length of more than 10% of a certain inner diameter in a stable state. The thermoelectric pair is used to determine the target temperature. In this melt-kneading step, a single-shaft type extrusion molding machine equipped with a spiral having a high kneading effect, or a double-shaft type extrusion molding machine can be used. -19- (16) (16) 200416231 The biaxial extrusion molding machine selected is preferably a spiral structure with sufficient mixing effect without excessive shearing force on the mixed composition. The shearing speed is preferably in the above-mentioned temperature range, and is set in accordance with the composition ratio of the mixed composition. The TFE / FTE copolymer and TFE / HEP copolymer used in the melt-kneading step are preferably powders capable of improving polymerization, and the powders are preferably those having a small particle size. In addition, when the number of terminal functional groups is adjusted using a fluorine-containing gas as described below before melt-kneading, in addition to being easy to handle, a uniform melt-kneading state can be obtained. The powdery substance for lifting polymerization refers to a powdery substance obtained by drying after the polymerization reaction is completed. It is better to mix the powder of TFE / FTE copolymer and powder of TFE / HFP copolymer in the unheated state before melt-kneading. Mixing the powder can be performed using a known device. In addition, before melt-kneading, it is preferable to adjust the terminal board of the TFE / FTE copolymer and the DFE / HFP copolymer. When the end-of-government substrate is adjusted, the number of terminal functional groups of the coupler capable of producing ozone-resistant molded articles can be maintained during the melt-kneading process, and the number of terminal functional groups of the low-molecular-weight compound produced by the excessively increased shearing force of the mixed composition can be suppressed. The number of terminal functional groups after the adjustment is preferably such that the number of terminal functional groups is from 4 to 1,000, with respect to the total number of carbons per TFE / FTE copolymer and the number of carbons of TFE / HFP copolymer. The upper limit is more preferably 70, and the lower limit is more preferably 50. When using a tetrafluoroethylene polymer, it is preferable to adjust the number of terminal functional groups of the tetrafluoroethylene polymer before melt-kneading. The adjusted carbon number and terminal functional base number at this time are preferably the number of the composition of the TFE / FTE copolymer, TFE / HFP copolymer, and tetrafluoro-20- (17) (17) 200416231 ethylene polymer. Although the method of adjusting the number of terminal functional groups may be adjusted respectively to the original polymerization stage is 0 or the later-mentioned terminal functional group is inactivated and becomes 0 (A), and the terminal functional group is not completely inactivated as described below (B) Number of terminal functional groups obtained by mixing. However, in the case of melt-kneading, as compared with the case where (B) increases molecular weight due to the coupling reaction, (A) deteriorates only due to the main chain rupture. Therefore, an increase in the production of low-molecular-weight substances cannot be avoided. Therefore, the method of adjusting the number of terminal functional groups is preferably to perform the same adjustment on the mixed composition of TFE / FTE copolymer, TFE / HFP copolymer and tetrafluoroethylene polymer to uniformly adjust intermolecular. In the method for producing a fluorine-containing resin composition of the present invention, the refining step can remove the low-molecular-weight substances generated in the melt-kneading step, so that the fluorine-containing resin composition of the present invention has a uniform composition. The fluorine-containing gas used in the refining step contains 5 mass% or more of fluorine. Within this range, the fluorine-containing gas may be a substance or fluorine gas containing 100% by mass or less of fluorine. The refining process of this refining step is to expose the extrudate obtained in the above-mentioned melt-kneading step to a fluorine-containing gas to decompose and remove low molecular weight substances. In addition to this purification treatment, in addition to removing low-molecular-weight substances, terminal functional groups can be inactivated as described later. Methods for removing low-molecular-weight substances can be, for example, disclosed in European Patent No. 472908 (1992), Japanese Patent Application Laid-Open No. 0 4-0 8 5 3 0 5 and Patent No. 3 0 06049, using chlorofluoro The fluorinated solvent such as carbonization is performed, but this step is complicated, so the above method using a fluorinated gas is preferable. -21-(18) (18) 200416231 The fluorine-containing resin composition of the present invention obtained through the above-mentioned melt-kneading step and refining step is used for melt molding, but today, due to the molding conditions, the Bubble situation. Therefore, in order to suppress foaming during melt molding, it is preferable to inactivate the remaining terminal functional groups after melt kneading. The method for inactivating the terminal functional group is not particularly limited, for example, a method in which the terminal is changed to a trifluoromethyl group by being exposed to the above-mentioned fluorine-containing gas, or the solution is immersed in a methanol solution of aniline, and then performed in a pressure cooker under high temperature and pressure There is no limitation on the method of treatment and substitution by a phenyl group, and the method can be changed to a terminal that does not decompose during molding at a high temperature. Since the fluorine-containing resin composition of the present invention has the above-mentioned composition and is produced by the above-mentioned manufacturing method, a molded article having ozone resistance and surface smoothness can be obtained. Although the mechanism that the fluorine-containing resin composition of the present invention obtains the above-mentioned excellent effects is not known, it can be known from the reasoning described later. That is, the fluorine-containing resin composition of the present invention is subjected to a refining treatment using a fluorine-containing gas to remove low-molecular-weight substances. Therefore, it is not easy to make low-molecular-weight substances even if a molded article having a surface such as a tube inner surface is produced without relying on a foreign object such as a mold. Overflow on the surface of the molded article, so the surface smoothness of the obtained molded article can be improved. In addition, in the above-mentioned melt-kneading process, the fluororesin composition of the present invention can control the coupling reaction between terminal functional groups, so it is difficult to form a low-molecular-weight substance. Removal of fluorine gas removes low molecular weight substances. The fluorine-containing resin composition of the present invention is formed of -22- (19) (19) 200416231 TFE / HFP copolymer component which is difficult to accept ozone decomposition, so it can slightly reduce the fracture resistance of the molded article after being exposed to ozone. Wait. In addition, the fluorine-containing resin composition of the present invention is a substance that inactivates the remaining terminal functional groups after purification treatment with a fluorine-containing gas, and therefore, the terminal functional groups are inactivated and then melt-molded for manufacturing a molded product. It is possible to suppress the foaming caused by the decomposition of the terminal functional group and / or the coupling reaction of the terminal functional group, and improve the surface smoothness of the obtained molded article. One aspect of the present invention is a molded article, which is characterized by being formed from the above-mentioned fluororesin composition. Another aspect of the present invention is a semiconductor manufacturing device formed by the above-mentioned molded article, which is characterized by using an ozone-containing medium containing 60% by volume of ozone at 60 ° C or higher. The molded article used in the semiconductor manufacturing apparatus is not particularly limited, and may be, for example, a pipe. The tube obtained from the above-mentioned fluororesin composition has high ozone resistance, so when it is used in a semiconductor manufacturing device using an ozone-containing medium such as ozone-containing water or an ozone-containing gas, the durability is higher than that of a conventional fluororesin tube. Reduce the frequency of device maintenance, increase device productivity, and reduce the cost of maintenance, and manufacture semiconductors more cheaply. In addition, the pipe obtained from the fluororesin composition of the present invention has a low average surface roughness [Ra] and a maximum roughness [Rt] of the inner surface, and therefore, excellent surface smoothness and abrasion resistance can be obtained. It can also have high durability on a honing system for manufacturing semiconductors, so that semiconductors can be manufactured in a cheaper manner. Another aspect of the present invention is a semiconductor manufacturing device obtained from the molded article-23- (20) (20) 200416231, characterized in that a particle-containing slurry having a temperature of 15 ° C or more is used, and the particle-containing slurry is oxidized Particles formed from aluminum and / or silicon dioxide. Another aspect of the present invention is a connector for a cylindrical molded article, which is obtained from the above-mentioned fluororesin composition. The connector for a cylindrical molded product is a continuous cylindrical molded product, a continuous cylindrical molded product, and other parts. It is preferable that the cylindrical molded product connected by the connector for a cylindrical molded product is formed of a fluorine-containing resin composition similar to the connector for the cylindrical molded product, but the connection portion does not need to be cylindrical and has no thickness. Dimensional constraints such as length, length, cross-sectional shape, and the use of the above-mentioned fluororesin composition are superior in terms of physical properties, so there are no particular restrictions on its use. It is suitable for various shaped articles such as heat-shrinkable tubes, thick meat tubes, and the like for semiconductor manufacturing equipment. The above-mentioned cylindrical shaped article has more excellent surface smoothness, fracture resistance, and ozone resistance than a cylindrical shaped article obtained only from a TFE / FTE copolymer. When the above-mentioned connector for cylindrical moldings does not use the above-mentioned fluorine-containing resin composition, the surface smoothness is deteriorated. Therefore, when the slurry containing a honing agent is transported, the abrasion occurs at the joints, and wear is caused by the abrasion. The deviation caused abnormal friction between the inner surface of the cylindrical molding and the slurry, and the required abrasion resistance could not be obtained. Another aspect of the present invention is a covered electric wire, which is characterized in that the covered electric wire is obtained by using the covering obtained by using the above-mentioned fluorine-containing resin composition. Because the TFE / HFP copolymer before the melt-kneading of the above-mentioned fluorine-containing resin composition has low melting and kneading, the fluorine-containing tree-coated wire can be manufactured at high speed. -24- (21) (21) 200416231 ′ This fluororesin composition has a low melt viscosity, so it has better molding processability than a coated wire obtained by using only TFE / HFP copolymer. In addition, because it contains a TFE / FTE copolymer component, a higher volume resistivity can be obtained at high temperatures than a covered wire obtained only from a TFE / HFP copolymer. Compared with moldings generally obtained only from TFE / FTE copolymers, the crystal spheres formed on the surface of the moldings obtained from the fluororesin composition of the present invention are smaller, so the surface area of the particles can be reduced, and the surface of the particles can be reduced. The size can reduce the local concentration of stress, so it can improve the durability and bending resistance to fatigue damage, and is suitable for the covered electric wires. [Embodiment] Best Mode for Carrying Out the Invention The present invention will be described in more detail by way of examples, but the present invention is not limited to this embodiment. Example 1 A powdery TFE / FTE copolymer (melt index [MFR] = 2.0 g / l 0 minutes) and a TFE / HFP copolymer (MFR = 1.9 g / 10 minutes) were mixed in advance according to the composition ratio shown in Table 1, and then The obtained mixed composition was used as a basic raw material. The number of terminal functional groups of the obtained mixed composition was 17 with a total number of 106 carbons and a TFE / FTE copolymer and a TFE / HFP copolymer. Using a prepared spiral biaxial melt kneading machine of 0 1 5 mm, kneading and extruding at a temperature of the mixed composition of 3 8 to 3 9 (TC, to obtain a granular extrudate. 1 85 ° C in an autoclave The extrudate was exposed to 20% by mass of fluorine-containing gas-25- (22) (22) 200416231, and a fluorine-containing resin composition was obtained after refining. The molecular weight distribution [MWD] of the obtained fluorine-containing resin composition was 1.45, Therefore, it is less than 値 1 · 6 3 before refining treatment, and MFR 値 2 · 1 (g / 1 0 points) before refining treatment can be reduced to. 1.7 (g / 1 0 points) after refining treatment. And by reducing MWD and MFR, it can be judged that low molecular weight materials have been removed from the extrudate. At this time, the number of terminal functional groups contained in the fluororesin composition measured by infrared spectrometry is, for each carbon number of 106 is 4 to 10 pieces. The above MFR is measured in accordance with ASTM D 3 3 07 (1998) at 3 72 t under a load of 5 kg. Using the obtained particulate fluororesin composition as a raw material, a hot plate temperature of 3 60 is used. ° C for melt compression molding to obtain a 2mm thick sheet, then place the obtained sheet in a preheated 37 ° C oven for 2 hours Visual inspection showed no foaming. Using the obtained tubular molded article and sheet for measuring the formation of the fluororesin composition, the following evaluations were performed. Surface roughness: Using the fluororesin composition formation measurement according to the above-mentioned production method. The tubular shaped article was then measured for the average roughness [Ra] and maximum roughness [Rt] of the inner surface in accordance with JIS B 060 1. Liquid delivery test: Slurry (particles: alumina, concentration 50 g) at a temperature of 25 ° C / L) -26- (23) 200416231 The flow rate of 10L / min was passed through the above-mentioned measuring tube shaped article, and the inner surface of the measuring tube before and after the slurry was fed was observed with an electron microscope. The results are shown in Fig. 1 There are few traces of particles adhering to the inner surface, etc. Example 2 In addition to adding 100 parts by mass of a basic raw material to a tetrafluoroethylene polymonomer: HFP, 0.08 mass%, melting heat 45 J / g, 1.8 million ) Except for 0. 8 parts by mass, the lipid composition was evaluated in the same manner as in Example 1, except that the slurry delivery test was performed. Example 3 Except that the obtained extrudate was not exposed to a fluorine-containing gas, Examples 1 method to obtain a fluororesin composition, and then Evaluation of slurry delivery. Comparative Example 1 Except that only the TFE / FTE copolymer resin was used as the basis, the same method as in Example 1 was used to obtain a fluororesin composition. Then, the tube was used for measurement before and after the slurry delivery test. The micromirror image of the inner surface of the molded product is shown in Fig. 2. As a result, the tendon-like abrasion marks that are more obvious than those in Example 1 can be observed. Comparative Example 2, a small molded product without a wound compound (the total molecular weight is about fluorinated) Other than the material test, the electronic display tube with the same evaluation is more clear. • 27- (24) 200416231 except that the temperature of the mixed composition during melt-kneading is set to 40 5 ° C, the other is the same as in Example 1. Methods: Fluorine-containing resin composition was obtained, and evaluations other than the slurry delivery test were performed. -28- (25) 200416231 Table 1 TFE / FTE TFE / HFP TFE series refined molecular weight melt index average roughness maximum roughness copolymer copolymer polymer treatment distribution (g / ΐο points) net [Rt] (parts by mass) ( (Parts by mass) (parts by mass) (" m) (" m) Example 1 90 10 first 1.63 21. 0.023 0.161 after 1.45 1.7 Example 2 90 10 0.8 _.v /-刖 — 1.5 0.024 0.144 after — 1.1 Example 3 90 10 — Not carried out — 2.1 0.031 0.256 Comparative Example 1 100 1 — Previous 2 0.050 0.329 Next 1 1.9 Comparative Example 2 90 10 1 — 3.7 0.101 0.637 After — 2.8 -29- (26) (26) 200416231 As can be seen from Table 1, the inner surface average roughness and the maximum roughness of the tubular molded articles for measurement of Examples 1 to 3 are smaller than those of Comparative Examples 1 to 2. Example 4 Except that the TFE / HFP copolymer component ratio of the mixed composition was changed to 50% by mass, the method was melt-kneaded in the same manner as in Example 1 and then treated with a fluorine-containing gas to obtain a fluorine-containing resin composition. The heat of fusion of the fluororesin composition was determined by DSC from the endothermic peak area near 292 ° C. In addition, with a cylinder bore of 0 30mm, a spiral L / D = 22, a die / tip = 0 1 3mm / 0 7mm, an extrusion temperature of 3 4 0 ° C to 3 95 ° C, a spiral rotation number of 48 rpm, and a pulling speed of 6 The fluororesin composition was melt-extruded under the condition of 1 m / min to obtain a wire coating having a thickness of 0.3 mm. The dielectric constant and dielectric loss factor of the obtained wire covering were measured in accordance with AS TM D 1 50 (1989) at a measuring frequency of 106 Hz. Results Table 2 shows the melting heat, dielectric rate, dielectric loss factor, and pull speed when the wire covering is manufactured. Since the molding speed of the wire covering was 1.2 times that of Comparative Example 3, it was confirmed that the productivity was improved. The volume resistivity of the obtained wire covering at 120 ° C is 1 x 1 〇18 Ω · cm or more, so it has better insulation than the volume resistivity of general TFE / HFP copolymer (less than 10 17 Ω · cm). Sex. Comparative Example 3 Only the TFE / FTE copolymer particles were used to make the coating thickness as in Example 4 -30- (27) 200416231, and then evaluated in the same manner as in Example 4. The results are shown in Table 2. Table 2 TFE / FTE TFE / HFP Dielectric Rate Dielectric Loss Factor Melting Heat Pull Speed Copolymer (mass%) Copolymer (mass%) (25 ° C? 106Hz) (25 ° C51〇6Hz) ( J / g) (m / min) Example 4 50 50 2.08 0.0003 11.2 61 _ Comparative Example 3 100-2.06 0.0003 19.4 50 ~ 55_ It is known from Table 2 that the addition of TFE / HFP copolymer in Example 4 has In addition to the equivalent electrical characteristics of Example 3, a fluororesin composition having a low melting heat can be obtained. Example 5 Except for using a mixed composition formed of a TFE / FTE copolymer (MFR = 3.5 to 8.5 g / 10 minutes) and a TFE / HEP copolymer (MFR = 4.3 to 8.7 g / 10 minutes) as the basic raw materials, After the fluororesin composition was obtained in the same manner as in Example 1, it was injection-molded to form two connectors for measuring the tubular molded article obtained in Example 1. The two tube-shaped molded articles for measurement and the connector were used as a chemical liquid circulation system, and the slurry feeding test was performed under the same conditions as in Example 1. Observation of the inner surface of the connector after the slurry feeding test with an electron microscope showed that there was no alumina precipitation and adhesion at the connection, and there was no significant abrasion of the connector or pipe. -31-(28) 200416231 Comparative Example 4 In the same way as in Example 5, two joints obtained from Example 1 and the composition of Comparative Example 1 were used. Then, a slurry delivery test was performed in Example 5 to check the slurry delivery. After the liquid test, the inner surface of the connector was agglomerated with aluminum and the alumina was piled up. Example 6 After the connector obtained in Example 5 was exposed to oxygen, the inner surface of the connector was not shown in Figure 3. The ozone exposure test was performed: The method for the ozone exposure test is to use a odor 1 SGX — A1 1MN in a tube with an inner diameter of 50 mm, and use a humid air stream with a concentration of 12% by volume to pass through the tube 21 to allow dry ozone to pass through the ion exchange. The measurement of the valve obtained by the water valve is combined with a tube-shaped molding device to form a chemical liquid circulation system test. Observe the traces of oxidation damage on the inner surface of the connector with an electron microscope. Ozone exposure test. The result was stinky cracks. The connector was placed in a direct oxygen generator (trade name: ozone at a flow rate of 0.7 L / min for 0 days.) This moisture was obtained. Comparative Example 5 A composition obtained from the composition of Comparative Example 1 The ozone exposure test. The results showed that the ozone exposure attempted a crack as shown in 3. The connector was examined in the same manner as in Example 6. The cross section of the connector appeared after inspection. -32- (29) (29) 200416231 Industrial application possibility The oxygen-containing resin composition of the invention The material is composed of the above method, so while retaining the excellent heat resistance and electrical characteristics of the original TFE / FTE copolymer, a molded article with excellent ozone resistance and surface smoothness can be obtained. [Schematic description] Figure 1 is The electron microscope image of the inner surface of the tubular shaped article for measurement after the slurry liquid feed test in Example 1. Figure 2 is an electron microscope image of the inner surface of the tubular shaped article for measurement after the slurry liquid feed test in Comparative Example 1. Fig. 3 is a cross-sectional view in the thickness direction of the connector that produced cracks after the ozone exposure test in Comparative Example 5. Symbol Description 1: Exposed Surface 2: Crack Image 3: Main Body-33-