201035124 六、發明說明： 【發明所屬之技術領域】 本發明關於一種藉由將全氟彈性體組成物交聯並模製 而製得之經交聯模製物件，且進一步關於全氟彈性體組成 物。 【先前技術】 含氟彈性體，尤其是主要包含四氟乙烯（TFE)單元 之全氟彈性體，因爲其極佳的耐化學性 '耐溶劑性及耐熱 性，而廣泛用作在嚴苛環境下使用的密封材料等。尤其是 適合用作半導體及液晶製造設備之密封材料的多種全氟彈 性體組成物已有提出。 WO 01/23470揭示一種其中將含氟樹脂細粒細微地分 散於全氟彈性體中的全氟彈性體組成物及一種藉由將該組 成物交聯並模製而製得之彈性體模製物件。在 WO 01/23470中，述及以TFE單元與全氟（烷基乙烯醚）（ PAVE )單元之共聚物作爲全氟彈性體。因爲含有作爲塡 充劑之含氟樹脂細粒，所以從模製物件製造步驟複雜的觀 點來看，有改進的空間，而且在使用經交聯模製物件作爲 半導體製造設備之密封材料的情況中，會發生粒子產生現 象。 JP2003 - 1 3 793 0A揭示一種在其鏈及/或末端中具有碘 原子及/或溴原子之全氟彈性體，其係藉由將TFE、全氟 乙烯醚（諸如 cf2=cfocf2ocf2cf3 或 CF2=CFOCF2OCF2CF2OCF3) 201035124 與雙烯烴（bisolefin )聚合而製得，以及一種從該全氟彈 性體製得之模製物件。在J P 2 0 0 3 - 1 3 7 9 3 0 A所揭示之模製 物件中，係將碳黑與氧化鋅作爲塡充劑摻合’以賦予極佳 的機械特性。結果，所製得之模製物件不透明’因此不能 偵測出在製造模製物件之步驟中所可能混入的污染物及外 來物質。另外，從使用該經交聯模製物件作爲半導體製造 設備之密封材料的情況中會產生粒子的觀點來看，有改進 的空間。 JP2002-507640A揭示一種全氟彈性體組成物，其包 含全氟烯烴、全氟乙烯醚、包含具有能夠進行過氧化物硫 化反應之可硫化位置的組份之全氟彈性體及過氧化物硫化 劑，以及一種由其所製得之模製物件。在此全氟彈性體組 成物中，TFE被提出作爲全氟烯烴，而PAVE及全氟烷氧 基乙烯醚被提出作爲全氟乙烯醚。碳黑與氧化鋅則作爲塡 充劑而摻合在此組成物中。結果，所製得之模製物件不透 明，因此不能偵測出在製造模製物件之步驟中所可能混入 的污染物及外來物質。另外，從使用該經交聯模製物件作 爲半導體製造設備之密封材料的情況中會產生粒子的觀點 來看，有改進的空間。 JP2003-526705A揭示一種可交聯之全氟彈性體組成 物，其包含全氟烯烴、全氟乙烯醚、包含具有能夠進行過 氧化物硬化反應之硬化位置的組份之全氟彈性體、選自有 機鑰、磷酸鹽 '氧化膦、氧化胺、烷胺、多環鹽和多環胺 鹽之添加劑、過氧化物硬化劑及助劑。在該可交聯之全氟 -6 - 201035124 彈性體組成物中’ TFE被提出作爲全氟烯烴，而PAVE及 全氟烷氧基乙烯醚被提出作爲全氟乙烯醚。在此組成物中 摻合有碳黑與氧化鋅。結果，所製得之模製物件不透明’ 因此不能偵測出在製造模製物件之步驟中所可能混入的污 染物及外來物質。另外，從使用經交聯模製物件作爲半導 體製造設備之密封材料的情況中會產生粒子的觀點來看’ 有改進的空間，且混合之金屬的溶析對半導體製造設備有 ^ 不利的影響。 Ο JP2005-220161A敘述一種可交聯之全氟彈性體組成 物，其包含可交聯之全氟彈性體及含氟溶劑。另外，其敘 述該可交聯之全氟彈性體包含TFE、PAVE或全氟烷氧基 乙烯醚及具有至少一個溴基團或碘基團之含硬化位置之單 體。然而，因爲 PFA樹脂粉末作爲塡充劑而包含在 J P 2 0 0 5 - 2 2 0 1 6 1 A的可交聯全氟彈性體組成物中，所以從 複雜的模製物件製造步驟及在使用經交聯模製物件作爲半 Q 導體製造設備之密封材料的情況中的粒子產生的觀點來看 ，有改進的空間。 JP2002-265733A 及 JP2000-53835A 揭示可交聯之全 氟彈性體組成物，其包含具有碘原子及/或溴原子之 TFE/PAVE共聚物、有機過氧化物及共交聯劑。然而，將 菱水鎂鋁石作爲酸受體摻合。結果，所製得之模製物件不 透明，因此不能偵測出在製造模製物件之步驟中所可能混 合的污染物及外來物質。另外，從使用經交聯模製物件作 爲半導體製造設備之密封材料的情況中會產生粒子的觀點 201035124 來看，有改進的空間，且混合之金屬的溶析對半導體製造 設備有不利的影響。 WO 02/48200 及 JP2004-532902A 揭示一種製備全氟 彈性體模製物件之方法，該物件包含T F E、全氟乙烯醚（ 諸如PAVE)或全氟烷氧基乙烯醚與具有硬化位置之單體 (諸如含腈之氟化烯烴或含腈之氟化乙烯醚）之共聚物及 硬化劑。此全氟彈性體模製物件爲半透明或透明，具有淡 色或爲無色且具有好的抗張性質及壓縮定形。.然而，必需 以具有腈硬化位置之單體作爲基本組份。 JP2005-290011A揭示一種製備氟化碘烷腈之方法， 該氟化碘烷腈係用作供製備全氟彈性體用之鏈轉移劑，並 敘述一種藉由使用以該鏈轉移劑改質之TFE/PMVE/全氟 (8-氰基-5-甲基-3,6-二氧雜-1-辛烯）（8CNVE)而製備 之全氟彈性體及從該全氟彈性體製得之經交聯模製物件。 在該經交聯模製物件中摻合有碳黑。結果，所製得之模製 物件不透明，因此不能偵測出在製造模製物件之步驟中所 可能混入的污染物及外來物質。另外，從使用該經交聯模 製物件作爲半導體製造設備之密封材料的情況中會產生粒 子的觀點來看，有改進的空間。 美國專利第4,98 3,697號揭示一種TFE/PMVE共聚物 。此共聚物具有腈基團及碘原子作爲硬化位置，且敘述以 過氧化物作爲交聯劑及以異氰尿酸三烯丙酯作爲共交聯劑 。在其經交聯模製物件中摻合有碳黑。結果，所製得之模 製物件不透明，因此不能偵測出在製造模製物件之步驟中 -8- 201035124 所可能混入的污染物及外來物質。另外’從使用經交聯模 製物件作爲半導體製造設備之密封材料的情況中會產生粒 子的觀點來看，有改進的空間。 美國專利第 5,447,993 號及 JP9-5 1 2569A揭示 TFE/PM VE共聚物。該等共聚物具有腈基團及碘原子作爲 硬化位置，且過氧化物被提出作爲交聯劑及異氰尿酸三烯 丙酯作爲共交聯劑。在其經交聯模製物件中摻合有碳黑。 結果，所製得之模製物件不透明，因此不能偵測出在製造 〇 ' 模製物件之步驟中所可能混入的污染物及外來物質。另外 ，從使用經交聯模製物件作爲半導體製造設備之密封材料 的情況中會產生粒子的觀點來看，有改進的空間。 JP4-505633A揭示一種全氟彈性體，其包含TFE單元 、PAVE單元及具有溴原子和碘原子作爲硬化位置之單體 。從J P 4 - 5 0 5 6 3 3 A之全氟彈性體所製備之組成物具有極佳 的可硬化性及脫模性質。然而，此組成物中摻合有碳黑以 ^ 改進機械強度。結果，所製得之模製物件不透明，因此不 能偵測出在製造模製物件之步驟中所可能混入的污染物及 外來物質。另外，從使用經交聯模製物件作爲半導體製造 設備之密封材料的情況中會產生粒子的觀點來看，有改進 的空間。 JP9- 5 00 1 63 A揭示一種全氟彈性體組成物，其包含過 氧化物可交聯之全氟彈性體且既不含有萃出之金屬，亦不 實質含有金屬化合物，以及一種藉由將該組成物模製而製 得之經交聯物件。該組成物及由其製得之經交聯物件可用 -9 - 201035124 於需要高純度之應用’但是其摻合有碳黑以改進機械強度 ，使用分散在無活性載劑中的有機過氧化物且摻合質子海 綿作爲酸受體。結果，所製得之模製物件不透明，因此不 能偵測出在製造模製物件之步驟中所可能混入的污染物及 外來物質。另外，從使用經交聯模製物件作爲半導體製造 設備之密封材料的情況中會產生粒子及出氣的觀點來看， 有改進的空間。 【發明內容】 本發明者對於除了交聯反應所必需的交聯劑以外不使 用塡充劑、加工助劑或類似物，以避免應用時產生粒子及 出氣（從經模製之密封材料產生的氣體）的技術進行硏究 ，尤其是在使用經交聯模製物件作爲半導體及液晶製造設 備之密封材料的情況，且發現在具有碘及/或溴之待接受 過氧化物交聯的全氟彈性體的情況中，當不摻合塡充劑（ 諸如碳黑）時，有改進抗張強度的空間。 本發明的目的係提供一種藉由將全氟彈性體組成物交 聯並模製而製得之經交聯模製物件，該全氟彈性體組成物 不包含造成出氣或產生粒子之添加劑諸如碳黑、氧化鋅及 質子海綿且能夠提供具有顯著改進之抗張強度的經交聯模 製物件。該經交聯模製物件爲透明並具有令人滿意的機械 性質。 本發明關於一種藉由將全氟彈性體組成物交聯並模製 而製得之經交聯模製物件，該全氟彈性體組成物係由下列 -10- 201035124 所組成： (A)全氟彈性體’其具有碘原子及/或溴原子且包含 20至35莫耳％之全氟乙烯醚單元（a)及65至80莫耳％ 之四氟乙烯單元（b) ’ (B )有機過氧化物’及 (C)分子中具有至少兩個雙鍵的化合物。 較佳的是有機過氧化物（B)與分子中具有至少兩個 0 雙鍵的化合物（c )之總量以1 〇〇質量份之該全氟彈性體 (A)爲基準計爲0.5至3.0質量份。 較佳的是全氟乙烯醚單元（a)爲以式（1)代表的單 元： —CF2-CF— ⑴ 0—Rf 其中Rf爲具有1至10個碳原子之全氟烷基。 較佳的是該全氟乙烯醚單元（a)爲全氟（甲基乙烯 〇 醒）單元。 較佳的是該經交聯模製物件之金屬含量不超過1 00 ppm。 較佳的是該經交聯模製物件之霧値不超過50%。 較佳的是該經交聯模製物件之抗張強度不低於8 MP a 〇 較佳的是該經交聯模製物件爲密封材料。 較佳的是該經交聯模製物件爲用於半導體製造設備之 密封材料。 -11 - 201035124 本發明亦關於一種全氟彈性體組成物，其係由下列所 組成： (A)全氟彈性體’其具有碘原子及/或溴原子且包含 20至35莫耳％之全氟乙嫌醚單元（a)及65至80莫耳％ 之四氟乙烯單元（b)， (B )有機過氧化物，及 (C)分子中具有至少兩個雙鍵的化合物。 較佳的是有機過氧化物（B)與分子中具有至少兩個 雙鍵的化合物（C )之總量以1 〇 〇質量份之該全氟彈性體 (A)爲基準計爲0.5至3.0質量份。 實施本發明的較佳模式 藉由將全氟彈性體組成物交聯並模製而製得之本發明 的經交聯模製物件係由（A )全氟彈性體，其具有碘原子 及/或溴原子且包含全氟乙烯醚（以下亦被稱爲PVE)單 元（a)及四氟乙烯（以下亦被稱爲TFE)單元（b)、（ B)有機過氧化物及（C)分子中具有至少兩個雙鍵的化 合物所組成。 從不損失彈性橡膠的性質且使其性質不變得與樹脂性 質相似的觀點來看，在全氟彈性體（A )中的PVE單元（ a )之含量不低於2 0莫耳％，更佳爲不低於2 2莫耳％。另 外，從經交聯模製物件的優異機械強度的觀點來看，在全 氟彈性體（A )中的PVE單元（a)之含量較佳地不超過 3 5莫耳％。 -12- 201035124 較佳的PVE單元爲一種以式（1)代表的單元： ——CF2 — CF~~~ I ⑴ 0—Rf 其中Rf爲具有1至1〇個，較佳爲1至5個，更佳爲1至 3個碳原子之全氟烷基。 P VE單元（a )的實例爲例如全氟（甲基乙烯醚）（ 以下被稱爲PMVE)、全氟（丙基乙烯醚）及類似物。在 〇 該等之中’從可降低經硬化物件之玻璃轉換溫度、維持彈 性橡膠之性質及極佳的機械強度的觀點來看，以Ρ Μ V E較 其他的PVE單元（a)的實例爲一種以CFpCF-ORf1 代表的單元’在式中’ Rf1爲具有3至12個碳原子及1至 3個氧原子之全氟烷基（聚）醚基團。具體實例有 CF2=CF0(CF2CFCF30)2CF2CF2CF3 及 CF2=CFOCF2CFCF3OCF2CF2CF3。 從經交聯模製物件的優異抗張強度的觀點來看，在全 〇 氟彈性體（A )中的T F E單元（b )之含量較佳地不低於 6 5莫耳％。從不損失彈性橡膠的性質且使其性質不變得與 樹脂性質相似的觀點來看，在全集彈性體（A )中的T F E 單元（b)之含量亦不超過80莫耳％，較佳爲不超過78 莫耳％。 全氟彈性體（A )具有碘原子及/或溴原子。從所製得 之聚合物具有窄的分子量分佈、容易控制分子量、碘原子 可引入聚合物末端及聚合物末端可用作爲硬化位置的觀點 來看’較佳的是以一種已知的碘轉移聚合法作爲製備具有 -13- 201035124 碘原子及/或溴原子之全氟彈性體（A )的方法。 例如，有一種以構成上述彈性體之單體與若必要時提 供硬化位置之單體在碘及/或溴化合物，較佳爲二碑及/或 二溴化合物，更佳爲二碘化合物的存在下，在水性介質中 ，在壓力下，同時在自由基聚合起始劑存在下及在實質上 無氧大氣中攪拌進行乳液聚合、溶液聚合或懸浮聚合之方 法。 待用之碘或溴化合物的代表實例爲以式（2 )代表的 化合物： R2IxBry ( 2 ) 其中每一 X及y爲0或1至4之整數，且滿足i$x + y$4 ;R2爲具有1至8個碳原子之飽和或不飽和氟烴基或氯 氟烴基或具有1至3個碳原子之烴基，並可含有氧原子。 具體例子有單碘甲烷、1-碘甲烷、1-碘正丙烷、異丙 基碘、二碘甲烷、1,2-二碘乙烷、1,3-二碘正丙烷及類似 物。 更佳的是以通式：Rf1 . Ix代表的碘化合物作爲待用 之碘或溴化合物。201035124 VI. Description of the Invention: [Technical Field] The present invention relates to a cross-linked molded article obtained by crosslinking and molding a perfluoroelastomer composition, and further relates to a perfluoroelastomer composition Things. [Prior Art] Fluoroelastomers, especially perfluoroelastomers mainly comprising tetrafluoroethylene (TFE) units, are widely used in harsh environments because of their excellent chemical resistance, solvent resistance and heat resistance. Sealing materials used below. In particular, a variety of perfluoroelastomer compositions suitable for use as sealing materials for semiconductor and liquid crystal manufacturing equipment have been proposed. WO 01/23470 discloses a perfluoroelastomer composition in which fine particles of a fluorine-containing resin are finely dispersed in a perfluoroelastomer and an elastomer molded by crosslinking and molding the composition. object. In WO 01/23470, a copolymer of a TFE unit and a perfluoro(alkyl vinyl ether) (PAVE) unit is mentioned as a perfluoroelastomer. Since the fluorine-containing resin fine particles as the chelating agent are contained, there is room for improvement from the viewpoint of complicated manufacturing steps of the molded article, and in the case of using the cross-linked molded article as the sealing material of the semiconductor manufacturing equipment , particle generation will occur. JP 2003 - 1 3 793 0 A discloses a perfluoroelastomer having an iodine atom and/or a bromine atom in its chain and/or terminal by using TFE, perfluorovinyl ether (such as cf2 = cfocf2ocf2cf3 or CF2 = CFOCF2OCF2CF2OCF3) 201035124 is prepared by polymerization with a bisolefin, and a molded article obtained from the perfluoroelastomer. In the molded article disclosed in J P 2 0 0 3 - 1 3 7 9 3 0 A, carbon black is blended with zinc oxide as a chelating agent to impart excellent mechanical properties. As a result, the molded article produced is opaque, and thus it is impossible to detect contaminants and foreign matter which may be mixed in the step of manufacturing the molded article. Further, there is room for improvement from the viewpoint that particles are generated in the case where the crosslinked molded article is used as a sealing material for a semiconductor manufacturing apparatus. JP 2002-507640 A discloses a perfluoroelastomer composition comprising a perfluoroolefin, a perfluorovinyl ether, a perfluoroelastomer comprising a component having a vulcanizable position capable of undergoing a peroxide vulcanization reaction, and a peroxide vulcanizing agent. And a molded article made therefrom. In this perfluoroelastomer composition, TFE is proposed as a perfluoroolefin, and PAVE and perfluoroalkoxyvinyl ether are proposed as perfluorovinyl ether. Carbon black and zinc oxide are blended as a smear in this composition. As a result, the molded article produced is opaque, and therefore it is impossible to detect contaminants and foreign matter which may be mixed in the step of manufacturing the molded article. Further, from the viewpoint of the generation of particles in the case where the crosslinked molded article is used as a sealing material for a semiconductor manufacturing apparatus, there is room for improvement. JP 2003-526705 A discloses a crosslinkable perfluoroelastomer composition comprising a perfluoroolefin, a perfluorovinyl ether, a perfluoroelastomer comprising a component having a hardening position capable of undergoing a peroxide hardening reaction, and being selected from the group consisting of Organic key, phosphate 'phosphine oxide, amine oxide, alkylamine, polycyclic salt and polycyclic amine salt additives, peroxide hardener and additives. In the crosslinkable perfluoro-6 - 201035124 elastomer composition, 'TFE was proposed as a perfluoroolefin, and PAVE and perfluoroalkoxyvinyl ether were proposed as perfluorovinyl ether. Carbon black and zinc oxide are blended in this composition. As a result, the molded article produced is opaque, so that it is impossible to detect the contaminants and foreign matter which may be mixed in the step of manufacturing the molded article. Further, from the viewpoint of the use of the crosslinked molded article as the sealing material of the semiconductor manufacturing apparatus, there is room for improvement, and the elution of the mixed metal has an adverse effect on the semiconductor manufacturing equipment. Ο JP2005-220161A describes a crosslinkable perfluoroelastomer composition comprising a crosslinkable perfluoroelastomer and a fluorochemical solvent. Further, it is stated that the crosslinkable perfluoroelastomer comprises TFE, PAVE or perfluoroalkoxyvinyl ether and a monomer having a hardened position having at least one bromine group or an iodine group. However, since the PFA resin powder is contained as a chelating agent in the crosslinkable perfluoroelastomer composition of JP 2 0 0 5 - 2 2 0 1 6 1 A, the manufacturing steps and the use of the complicated molded article are used. There is room for improvement from the viewpoint of particle generation in the case where the crosslinked molded article is used as a sealing material for a semi-Q conductor manufacturing apparatus. JP2002-265733A and JP2000-53835A disclose a crosslinkable perfluoroelastomer composition comprising a TFE/PAVE copolymer having an iodine atom and/or a bromine atom, an organic peroxide, and a co-crosslinking agent. However, the magnesite is blended as an acid acceptor. As a result, the molded article produced is opaque and therefore cannot detect contaminants and foreign matter which may be mixed in the step of manufacturing the molded article. Further, from the viewpoint of the use of a crosslinked molded article as a sealing material for a semiconductor manufacturing apparatus, it is seen that there is room for improvement in 201035124, and the elution of the mixed metal adversely affects the semiconductor manufacturing equipment. WO 02/48200 and JP 2004-532902 A disclose a method of preparing a perfluoroelastomer molded article comprising TFE, perfluorovinyl ether (such as PAVE) or perfluoroalkoxyvinyl ether and a monomer having a hardened position ( Copolymers and hardeners such as nitrile-containing fluorinated olefins or nitrile-containing fluorinated vinyl ethers. The perfluoroelastomer molded article is translucent or transparent, has a light color or is colorless and has good tensile properties and compression set. However, it is necessary to use a monomer having a nitrile hardening position as a basic component. JP2005-290011A discloses a process for preparing a fluorinated iodocarbonitrile which is used as a chain transfer agent for preparing a perfluoroelastomer, and describes a TFE which is modified by using the chain transfer agent. Perfluoroelastomer prepared by /PMVE/perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene) (8CNVE) and its cross-linking from the perfluoroelastomer Co-molded objects. Carbon black is blended in the crosslinked molded article. As a result, the molded article produced is opaque, and therefore it is impossible to detect contaminants and foreign matter which may be mixed in the step of manufacturing the molded article. Further, there is room for improvement from the viewpoint that particles are generated in the case where the crosslinked molded article is used as a sealing material for a semiconductor manufacturing apparatus. A TFE/PMVE copolymer is disclosed in U.S. Patent No. 4,98,697. This copolymer has a nitrile group and an iodine atom as a hardening site, and a peroxide is used as a crosslinking agent and triallyl isocyanurate is used as a co-crosslinking agent. Carbon black is blended in its crosslinked molded article. As a result, the molded article produced is opaque, and therefore it is impossible to detect contaminants and foreign matter which may be mixed in the step of manufacturing the molded article -8-201035124. Further, there is room for improvement from the viewpoint that particles are generated in the case where a crosslinked molded article is used as a sealing material for a semiconductor manufacturing apparatus. TFE/PM VE copolymers are disclosed in U.S. Patent Nos. 5,447,993 and JP 9-5 1 2569A. These copolymers have a nitrile group and an iodine atom as a hardening site, and a peroxide is proposed as a crosslinking agent and triallyl isocyanurate as a co-crosslinking agent. Carbon black is blended in its crosslinked molded article. As a result, the molded article produced is opaque, and therefore it is impossible to detect contaminants and foreign matter which may be mixed in the step of manufacturing the molded article. Further, there is room for improvement from the viewpoint that particles are generated in the case where a cross-linked molded article is used as a sealing material for a semiconductor manufacturing apparatus. JP 4-505633 A discloses a perfluoroelastomer comprising a TFE unit, a PAVE unit, and a monomer having a bromine atom and an iodine atom as a hardening position. The composition prepared from the perfluoroelastomer of J P 4 - 5 0 5 6 3 3 A has excellent hardenability and mold release properties. However, this composition is blended with carbon black to improve mechanical strength. As a result, the molded article produced is opaque, and therefore it is impossible to detect contaminants and foreign matter which may be mixed in the step of manufacturing the molded article. Further, there is room for improvement from the viewpoint that particles are generated in the case where a cross-linked molded article is used as a sealing material for a semiconductor manufacturing apparatus. JP 9- 5 00 1 63 A discloses a perfluoroelastomer composition comprising a peroxide crosslinkable perfluoroelastomer and containing neither a extracted metal nor a metal compound, and The composition is molded to produce a crosslinked article. The composition and the crosslinked article made therefrom can be used in -9 - 201035124 for applications requiring high purity 'but it is blended with carbon black to improve mechanical strength, using organic peroxide dispersed in an inactive carrier And a proton sponge is blended as an acid acceptor. As a result, the molded article produced is opaque, and therefore it is impossible to detect contaminants and foreign matter which may be mixed in the step of manufacturing the molded article. Further, there is room for improvement from the viewpoint of generating particles and gas out in the case of using a crosslinked molded article as a sealing material for a semiconductor manufacturing apparatus. SUMMARY OF THE INVENTION The present inventors do not use a hydrating agent, a processing aid or the like for the crosslinking agent necessary for the crosslinking reaction to avoid generation of particles and gas (from the molded sealing material). The technology of gas) is studied, especially in the case of using cross-linked molded articles as sealing materials for semiconductor and liquid crystal manufacturing equipment, and it has been found that perfluoro-crosslinking with iodine and/or bromine is to be accepted. In the case of an elastomer, there is room for improvement of tensile strength when a filler (such as carbon black) is not blended. SUMMARY OF THE INVENTION It is an object of the present invention to provide a crosslinked molded article obtained by crosslinking and molding a perfluoroelastomer composition which does not contain an additive such as carbon which causes outgassing or particle generation. Black, zinc oxide and proton sponges and capable of providing crosslinked molded articles with significantly improved tensile strength. The crosslinked molded article is transparent and has satisfactory mechanical properties. The present invention relates to a crosslinked molded article obtained by crosslinking and molding a perfluoroelastomer composition consisting of the following -10-201035124: (A) A fluoroelastomer having an iodine atom and/or a bromine atom and comprising 20 to 35 mol% of a perfluorovinyl ether unit (a) and 65 to 80 mol% of a tetrafluoroethylene unit (b) '(B) organic a compound having at least two double bonds in the peroxide 'and (C) molecule. It is preferred that the total amount of the organic peroxide (B) and the compound (c) having at least two 0 double bonds in the molecule is 0.5 to 1 part by mass based on the perfluoroelastomer (A). 3.0 parts by mass. Preferably, the perfluorovinyl ether unit (a) is a unit represented by the formula (1): -CF2-CF-(1) 0-Rf wherein Rf is a perfluoroalkyl group having 1 to 10 carbon atoms. Preferably, the perfluorovinyl ether unit (a) is a perfluoro(methyl vinyl oxime) unit. Preferably, the crosslinked molded article has a metal content of not more than 100 ppm. Preferably, the cross-linked molded article has a haze of no more than 50%. Preferably, the crosslinked molded article has a tensile strength of not less than 8 MP a 。 Preferably, the crosslinked molded article is a sealing material. Preferably, the crosslinked molded article is a sealing material for a semiconductor manufacturing apparatus. -11 - 201035124 The present invention also relates to a perfluoroelastomer composition which is composed of the following: (A) a perfluoroelastomer having an iodine atom and/or a bromine atom and containing from 20 to 35 mol% A fluoroethylene ether unit (a) and 65 to 80 mol% of a tetrafluoroethylene unit (b), (B) an organic peroxide, and (C) a compound having at least two double bonds in the molecule. It is preferred that the total amount of the organic peroxide (B) and the compound (C) having at least two double bonds in the molecule is from 0.5 to 3.0 based on 1 part by mass of the perfluoroelastomer (A). Parts by mass. BEST MODE FOR CARRYING OUT THE INVENTION The crosslinked molded article of the present invention obtained by crosslinking and molding a perfluoroelastomer composition is composed of (A) a perfluoroelastomer having an iodine atom and/or Or a bromine atom and comprising perfluorovinyl ether (hereinafter also referred to as PVE) unit (a) and tetrafluoroethylene (hereinafter also referred to as TFE) unit (b), (B) organic peroxide and (C) molecule Composed of a compound having at least two double bonds. The content of the PVE unit (a) in the perfluoroelastomer (A) is not less than 20% by mol from the viewpoint of not losing the properties of the elastic rubber and making its properties not similar to those of the resin. Good is not less than 2 2 mol%. Further, the content of the PVE unit (a) in the perfluoroelastomer (A) is preferably not more than 35 mol% from the viewpoint of excellent mechanical strength of the crosslinked molded article. -12- 201035124 The preferred PVE unit is a unit represented by the formula (1): ——CF2 — CF~~~ I (1) 0—Rf where Rf has 1 to 1〇, preferably 1 to 5 More preferably, it is a perfluoroalkyl group of 1 to 3 carbon atoms. Examples of the P VE unit (a) are, for example, perfluoro(methyl vinyl ether) (hereinafter referred to as PMVE), perfluoro(propyl vinyl ether), and the like. In the case of 'from the viewpoint of reducing the glass transition temperature of the hardened article, maintaining the properties of the elastic rubber, and excellent mechanical strength, an example of the Ρ VE compared to other PVE units (a) is The unit represented by CFpCF-ORf1 'in the formula' Rf1 is a perfluoroalkyl (poly)ether group having 3 to 12 carbon atoms and 1 to 3 oxygen atoms. Specific examples are CF2=CF0(CF2CFCF30)2CF2CF2CF3 and CF2=CFOCF2CFCF3OCF2CF2CF3. The content of the T F E unit (b ) in the total fluorinated elastomer (A ) is preferably not less than 65 mol% from the viewpoint of excellent tensile strength of the crosslinked molded article. The content of the TFE unit (b) in the total assembly elastomer (A) is also not more than 80 mol%, from the viewpoint of not losing the properties of the elastic rubber and making its properties not similar to those of the resin. No more than 78% of the mole. The perfluoroelastomer (A) has an iodine atom and/or a bromine atom. From the viewpoint that the obtained polymer has a narrow molecular weight distribution, easy control of molecular weight, iodine atoms can be introduced into the polymer end, and the polymer end can be used as a hardening position, it is preferably a known iodine transfer polymerization method. As a method of preparing a perfluoroelastomer (A) having an iodine atom and/or a bromine atom of -13 to 201035124. For example, there is a iodine and/or bromine compound, preferably a di- and/or dibromo compound, preferably a diiodide compound, in a monomer constituting the above elastomer and, if necessary, a monomer providing a hardening position. The method of emulsion polymerization, solution polymerization or suspension polymerization is carried out in an aqueous medium under pressure while stirring in the presence of a radical polymerization initiator and in a substantially oxygen-free atmosphere. A representative example of the iodine or bromine compound to be used is a compound represented by the formula (2): R2IxBry ( 2 ) wherein each X and y is an integer of 0 or 1 to 4, and satisfies i$x + y$4; R2 is A saturated or unsaturated fluorohydrocarbon or chlorofluorocarbon group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 3 carbon atoms, and may contain an oxygen atom. Specific examples are monoiodomethane, 1-iodomethane, 1-iodo-n-propane, isopropyl iodide, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane and the like. More preferably, the iodine compound represented by the formula: Rf1.Ix is used as the iodine or bromine compound to be used.
Rf1爲具有1至16個碳原子之飽和或不飽和氟烴基或 氯氟烴基，而以具有4至8個碳原子之全氟烷基較佳。若 碳原子數量超過1 6個，則反應性傾向降低。 在以通式：Rf1 · Ix代表的碘化合物中，X代表Rf1之 -14 - 201035124 鍵數量並爲不低於1且不超過4之整數’較佳爲不低於2 且不超過3之整數。即使X超過4，仍可使用此化合物， 但是從合成成本的觀點來看，並不理想。從所製得之聚合 物具有較少分支的觀點來看，最佳的是X爲2。 此碘化合物之碳-碘鍵爲相對弱的鍵，並在自由基釋 出源的存在下容易以自由基的形式分裂。因爲釋出之自由 基具有高反應性，所以單體進行加成生成反應，並接著藉 由從碘化合物移除碘而終止反應。在因此製得之其中碘與 在其分子末端上的碳鍵結的含氟彈性體中，末端碘變成有 效的硬化位置而可有效地進行交聯。 Ο 以通式：Rf1 . Ιχ代表的碘化合物的實例爲例如單姚 全氟甲烷、單碘全氟乙烷、單碘全氟丙烷、單碘全氟丁院 (例如’ 2 -碘全氟丁烷、1-碘全氟（1，1_二甲基乙烷）） 、單碘全氟戊烷（例如，1-碘全氟（4 -甲基丁院））、卜 硤全氟正辛院、單确全氟環丁院、2 -蛛全氟（1-環丁基乙 烷）環己烷、單碘全氟環己烷、單碘三氟環丁烷、單蛾二 氟甲烷、單碘單氟甲烷、2 -碘-i_氫全氟乙烷、3_碘-1_氫 全氟丙烷、單碘單氯二氟甲烷、單碘二氯單氟甲烷、2_ 碘-1，2-二氯-1,12-三氟乙烷、4_碘-^-二氯全氟丁烷、6_ 碘-1，2-一氯全氟己烷、4-碘-1，2，4-三氯全氟丁烷、丨·碘· 2,2 -一氫全氟丙烷、1-碘氫全氟丙烷、單碘三氟乙烯、 3-碘全氟丙烯-1、4-碘全氟戊烯、4_碘_5_氯全氟戊烯q 、2 -撫全氟（1-環丁烯基乙烷）、1,2 -二碘全氟乙烷、 1，3-—碑全氟丙烷' l，4 -一腆全氟正丁烷、丨^-二碘全氟 -15- 201035124 正戊烷、1,6 -二碘全氟正己烷、1，7 -二碘全氟正庚烷、 1,3-二碘·2-氯全氟丙烷、1，5-二碘-2,4_二氯全氟正戊烷、 1，8-二碘全氟正辛烷、1，2-二（碘二氟甲基）全氟環丁烷 、2-碘-1,1,1-三氟乙烷、1-碘-卜氫全氟（2-甲基乙烷）、 2-碘-2,2-二氯-1,1，丨-三氟乙烷、2-碘-2-氯_1,1,1-三氟乙烷 及類似物。再者，Rf1之烴基可含有諸如可形成醚鍵聯之 氧原子、可形成硫醚鍵聯之硫原子或羧基的官能基，且具 有此類官能基之化合物的實例爲2-碘全氟乙基全氟乙烯 醚、2-碘全氟乙基全氟異丙醚、3-捵-2-氯全氟丁基全氟甲 基硫醚及3-碘-4-氯全氟丁酸。 其中，從容易合成、反應性、經濟效率及穩定性的觀 點來看，以1,4-二碘全氟正丁烷及1,6-二碘全氟正己烷較 佳，並從在室溫下爲液體及容易處置的觀點來看，以1，4-二碘全氟正丁烷較佳。 將碘原子或溴原子引入使用此類碘化合物及/或溴化 合物所製備之全氟彈性體（A )中（例如，參考 WO 97/24381)。 製備具有碘原子或溴原子之全氟彈性體（A )的^他 方法的實例爲全氟彈性體與含碘-或溴-單體共聚合之方法 〇 具有碘原子或溴原子之單體的實例爲以通式（3 )代 表的含碘-或溴-單體： CY12=CY1-Rf2(CHR3)nX1 (3) 其中Y1爲氫原子、氟原子或- CH3; Rf2爲氟伸烷基、全氟 -16- 201035124 伸烷基、氟多氧伸烷基或全氟多氧伸院基；R3爲氫原子 或- CH^X1爲碗原子或溴原子，η爲〇或1;以通式（4 )代表的單體： CF2=CFO(CF2CF(CF3)0)m(CF2)n-X2 (4) 其中m爲0或1至5之整數；！！爲〗至3之整數，X2爲 溴原子或碘原子；及以通式（5)代表的單體： CH2=CH(CF2)nI (5) 其中η爲1至10之整數。例如，有含碘單體，諸如在 JP5-63 4 8 2B 和 JP 7-3 1 623 4A 中所揭示之全氟（6,6-二氫-6 -碘-3-氧雜-1-己烯）和全氟（5 -碘-3 -氧雜-1-戊烯）、 CH2 = CH ( CF2 ) 41 及 ch2 = ch ( cf2 ) 61。 這些含碘-或溴-單體可藉由使用上述碘及/或溴化合物 的反應而增加待引入全氟彈性體中的碘/溴量。 在本發明使用的全氟彈性體（A )可以慣用的聚合法 製備’諸如乳液聚合法、懸浮聚合法或溶液聚合法。諸如 聚合溫度及時間之聚合條件可取決於單體種類及所欲使用 之彈性體而隨意地決定。可添加乳化劑、分子量調節劑、 pH調節劑及類似物。分子量調節劑可在聚合初期階段分 批添加或可連續或不連續添加。 可以各種乳化劑用於乳化聚合反應。從抑制聚合期間 所發生之對乳化劑分子的鏈轉移反應的觀點來看，適宜的 乳化劑爲具有氟碳鏈或氟聚醚鏈之羧酸鹽。另外，也適合 使用反應性乳化劑。 可使用油溶性自由基聚合起始劑或水溶性自由基聚合 -17- 201035124 起始劑作爲聚合起始劑。水溶性自由基聚合起始 爲例如過硫酸銨（AP S )、過硫酸鉀（KP S )及翔 用於聚合系統之pH調節劑的實例爲具有緩 電解質物質，諸如磷酸鹽、碳酸鹽及硼酸鹽或氫 氫氧化鉀及氫氧化銨。 分子量調節劑的實例爲上述舉例之碘化合物 物。 關於從聚合反應混合物分離聚合產物之方法 藉由將聚合反應混合物與氫氯酸、硝酸或類似物 處理之凝聚方法及藉由將聚合反應混合物冷凍並 解凍之凝聚方法。再者，可採用以超聲波之凝聚 機械力之凝聚方法。 從聚合反應混合物分離聚合產物之其他方法 藉由添加例如金屬鹽，諸如氯化鎂、氯化鈣、氯 化鋁、硫酸鎂、硫酸鋇或硫酸鋁之凝聚方法。 爲了減少聚合產物的金屬含量，以不使用含 物（諸如金屬鹽）的從聚合反應混合物分離聚合 法較佳，且以酸處理或以冷凍及接著解凍之上述 較佳。 從使用全氟彈性體所製造之模製物件的令人 縮定形的觀點來看，在全氟彈性體（A)中的姚 溴原子之含量較佳爲不低於0.05質量％，更佳 〇. 1 0質量％，更佳爲不低於0.1 5質量％。另外， 貴的碘/溴化合物使用量及使用全氟彈性體所製 劑的實例 I似物。 衝能力之 氧化鈉、 及溴化合 ，可採用 混合的酸 接著將其 方法或以 的實例爲 化鈉、氯 金屬化合 產物之方 凝聚方法 .滿意的壓 原子及/或 爲不低於 從減少昂 造之模製 -18- 201035124 物件的令人滿意的抗張強度的觀點來看，碘原子及/或溴 原子之含量較佳爲不超過1.5質量％，更佳爲不超過1,2 質量％，更佳爲不超過1. 〇質量％。 從用於合成具有硬化位置之單體的成本及長期路徑的 觀點來看，較佳的是本發明的全氟彈性體（A)不包含具 有硬化位置之單體，諸如含腈之氟化烯烴或含腈之氟化乙 烯醚。 有機過氧化物（B)通常可爲在熱或還原劑存在下輕 易產生自由基之有機過氧化物。其實例爲例如1，1 -雙（第 三丁基過氧基）-3,5,5 -三甲基環己烷、2,5 -二甲基己烷· 2,5-二羥基過氧化物、二-第三丁基過氧化物、第三丁基異 丙苯基過氧化物、二異丙苯基過氧化物、α,α’-雙（第三 丁基過氧基）-對-二異丙基苯、2,5-二甲基-2,5·二（第三 丁基過氧基）己烷、2,5-二甲基-2,5-二（第三丁基過氧基 )己炔-3'苯甲醯基過氧化物、第三丁基過氧苯、2，5·二 甲基-2,5-二（苯甲醯基過氧基）己烷、過氧苯甲酸第三丁 酯、過氧馬來酸第三丁酯 '過氧異丙基碳酸第三丁酯及類 似物。在該等之中，以二烷基過氧化物（諸如二異丙苯基 過氧化物）、2,5-二甲基-2,5-二（第三丁基過氧基）己院 及2，5 -二甲基-2,5 -二（第三丁基過氧基）己炔-3較佳。 有機過氧化物的種類及量通常以考慮活性的量、分 解溫度等予以選擇。另外，從分解溫度的觀點來看’以具 有100。至14(TC之10小時半生期溫度的有機過氧化物較 佳，例如過氧苯甲酸第三丁酯、二異丙苯基過氧化物、 -19- 201035124 2.5- 二甲基-2,5-二（第三丁基過氧基）己烷及2,5-二甲 基-2,5-二（第三丁基過氧基）己炔-3。 從改進所製得之全氟彈性體組成物的交聯程度的觀點 來看，有機過氧化物（B )之量以1 〇〇質量份之全氟彈性 體（A)爲基準計較佳爲不低於0.1質量份，更佳爲不低 於0.2質量份，更佳爲不低於0.3質量份。另外，從可降 低難以捏和之有機過氧化物（B )之量的觀點來看，有機 過氧化物（B )之量以1 0 〇質量份之全氟彈性體（A )爲 基準計較佳爲不超過2.5質量份，更佳爲不超過2質量份 。從不降低透明度的觀點來看，應避免使用分散在無活性 載劑中之狀態的有機過氧化物。 本發明的組成物包含分子中具有至少兩個雙鍵的化合 物（C )，其係爲交聯劑。分子中具有至少兩個雙鍵的化 合物（C)可爲對從有機過氧化物（B)所衍生之自由基 及聚合物自由基具有反應性之化合物。其實例爲例如具有 諸如 CH2 = CH-、CH2 = CHCH2-或 CF2-CF-之官能基的多官 能性化合物。例如，有氰尿酸三烯丙酯、異氰尿酸三烯丙 酯（TAIC) 、TAIC預聚物、異氰尿酸三甲基烯丙酯、三 丙烯基甲縮醛、苯三甲酸三烯丙酯、Ν,Ν’-正苯撐雙馬來 醯亞胺、苯二甲酸二烯丙酯、對苯二甲酸四烯丙酯醯胺。 磷酸三烯丙酯、雙馬來醯亞胺、氟化異氰尿酸三烯丙酯（ 1.3.5- 參（2,3,3-三氟-2-丙烯基）-1，3,5-三哄-2,4,6-三酮 )、參（二烯丙胺）-S-三哄、亞磷酸三烯丙酯、Ν,Ν-二 烯丙基丙烯醯胺、六烯丙基磷醯胺、Ν,Ν,Ν’，Ν’-四烯丙基 -20- 201035124 對苯二甲醯胺、Ν,Ν,Ν’，Ν’-四烯丙基丙二醯胺、異氰尿酸 三乙烯酯、2,4,6-三乙烯基甲基三矽氧烷、三（5-降茨燦_ 2-亞甲基）氰尿酸酯、CH2 = CH- ( CF2 ) 6-CH = ch2、 CH2 = CH- ( CF2 ) 4-CH = CH2及類似物。在該等化合物之中 ，從經交聯物件令人滿意的交聯性和物理性質的觀點來看 ，以具有二或三個CXikCX3- ( X1、X2及X;爲H或F )官能基之化合物較佳，且從低價格和可得性的觀點來看 ，以具有二或三個CXl^CX3- ( X1、X2及X3爲Η)官 能基之化合物較佳，且從經交聯物件令人滿意的交聯性和 物理性質、低價格和可得性的觀點來看，以TAIC較佳。 從改進所製得之全氟彈性體組成物的交聯程度的觀點 來看，分子中具有至少兩個雙鍵的化合物（C)之量以 1 〇〇質量份之全氟彈性體（A )爲基準計較佳爲不低於〇. i 質量份，更佳爲不低0.2質量份，更佳爲不低於0.3質量 份。另外，從可降低難以捏和之分子中具有至少兩個雙鍵 的化合物（C)之量的觀點來看，分子中具有至少兩個雙 鍵的化合物（C )之量以1 〇〇質量份之全氟彈性體（A ) 爲基準計較佳爲不超過2.5質量份，更佳爲不超過2質量 份。 再者，從改進所製得之全氟彈性體組成物的交聯程度 的觀點來看，有機過氧化物（B)與分子中具有至少兩個 雙鍵的化合物（C )之總量以100質量份之全氟彈性體（ A)爲基準計較佳爲不低於0·5質量份，更佳爲不低於0.8 質量份。另外，從可降低難以捏和之有機過氧化物（Β ) -21 - 201035124 與化合物（C)之量的觀點來看，有機過氧化物（B)與 分子中具有至少兩個雙鍵的化合物（C )之總量以1 00質 量份之全氟彈性體（A)爲基準計較佳爲不超過3.0質量 份，更佳爲不超過2.5質量份，更佳爲不超過2.0質量份 〇 用於本發明的經交聯模製物件之全氟彈性體組成物可 藉由將每一上述組份以慣用的彈性體加工設備，例如開放 式滾輥、班布里（Banbury )混合機或捏合機混合而製備 。另外，組成物亦可以使用內部混合機的方法製備。 本發明的經交聯模製物件不含有可爲粒子及出氣產生 源之添加劑。此等添加劑的實例爲例如塡充劑、加工助劑 、增塑劑、著色劑、抗氧化劑、交聯促進劑、酸受體及類 似物。 塡充劑的實例爲無機塡充劑及有機塡充劑。有機塡充 劑的實例爲具有醯亞胺結構之醯亞胺塡充劑，諸如聚醯亞 胺、聚醯胺醯亞胺和聚醚醯亞胺；酮工程塑料，諸如聚醚 醚酮（PEEK)和聚醚酮（PEK) •，及工程塑料，諸如聚丙 酸酯、聚楓、聚醚颯 '聚苯硫和聚氧苯甲酸酯。亦有氟聚 合物，諸如聚四氟乙烯（PTFE)、全氟烯烴與全氟（院 基乙烯醚）之共聚物（PFA)、四氟乙烯/六氟丙烯共聚物 、聚偏二氟乙烯、聚氟乙烯及聚氯三氟乙烯粉末。其他的 實例爲高苯乙烯樹脂、酚樹脂、薰草酮樹脂及類似物。無 機塡充劑的實例爲金屬氧化物塡充劑，諸如氧化鋁、氧化 矽、氧化釔和氧化鈦；金屬碳化物，諸如碳化矽和碳化鋁 -22- 201035124 :金屬氮化物，諸如氮化矽和氮化鋁；氟化物塡充劑’諸 如氟化銘和氟化碳；及一般使用的塡充劑’諸如硫酸鋇、 碳黑、矽石、黏土、滑石和碳酸鈣。 加工助劑的實例爲高碳脂肪酸，諸如硬脂酸、油酸， 棕櫚酸和月桂酸；高碳脂肪酸鹽’諸如硬脂酸鈉和硬脂酸 鋅：高碳脂肪酸醯胺，諸如硬脂酸醯胺和油酸醯胺；高碳 脂肪酸酯，諸如油酸乙酯；高碳脂肪酸胺，諸如硬脂胺和 ^ 油胺；石油蠟，諸如棕櫚蠟和地蠟；聚二醇，諸如乙二醇 、甘油和二伸乙甘醇；脂族烴，諸如凡士林和石蠟；聚矽 氧油、聚矽氧聚合物、低分子量聚乙烯、苯二甲酸酯、磷 酸酯、松香、（氫化）二院基胺、（氫化）二院基楓、界 面活性劑及類似物。 增塑劑的實例爲例如苯二甲酸衍生物及癸二酸衍生物 。亦有含氟油，諸如全氟聚醚。 著色劑的實例爲縮合偶氮顏料、異嘲哄滿酮（ 〇 isoind〇lenone )顏料、喹吖酮顏料、二酮吡咯並吡咯顏料 及蒽酿顏料。另外有碳黑、硫酸鋇、氧化欽、氧化鋅、石夕 石、碳酸鎂、碳酸鈣、黏土及類似物。 抗氧化劑的實例爲胺、酚、硫及磷化合物，且其非限 制實例爲亞磷酸三苯酯及聚苯硫樹脂。具有對抗電黎之抗 氧化效果之化合物爲該等用作爲有機顔料及抗氧化劑者。 例如’有異吲哚滿酮顏料、喹吖酮顏料、二酮吡略並啦略 顔料及蒽醌顏料。 交聯促進劑的實例爲無機氧化物、無機氮化物及碳材 -23- 201035124 料。尤其是具有水和醇吸附性之化合物及具有鹼 合物。具有水和醇吸附性之化合物的實例爲例如 硫酸鎂、硫酸鈉、活性碳及中孔矽石。具有鹼位 物的實例爲例如（η鹼金屬、鹼土金屬和氧化衫 含有鹼金屬、鹼土金屬和氧化物之矽石、氧化鋁 性碳，（3 )無機氮化物，諸如氮化矽（Si3N4 ) 5 及（4)在表面上具有胺官能基之矽石、氧化鋁 性碳。（1 )至（4 )之化合物的實例爲氧化鎂、 氧化鈉、氧化鋅、氧化銀、氧化鋁、氧化鈦、氧 水鎂鋁石、硬矽鈣石、矽灰石、滑石、鎂鋁海泡 、沸石、黏土、葉蠟石及亞硒酸鹽。另外，有機 四級銨鹽及鐵鹽係例舉爲交聯促進劑。 酸受體的實例爲氧化鎂、氧化鈣、氫氧化鎂 鈣、鎂鋁海泡石、質子海綿（1,8-雙-(二甲胺基 自Aldrich)及十八院胺。 可使用慣用的方法從上述組成物製造預模製 如在金屬模具中加熱並壓縮之方法，在壓力下放 金屬模具中之方法及以擠壓器擠壓之方法。在擠 的例子中，諸如管子及電線，經交聯模製物件可 壓之後以蒸汽交聯而製得。 在本發明中，交聯條件未受到特殊的限制， 可在全氟彈性體慣用的交聯條件下進行。例如’ 件可藉由將上述全氟彈性體組成物進料至金屬模 由固定在壓力下以120°至250°C (較佳爲140°至 位置之化 分子篩、 置之化合 ?，( 2 ) 、碳和活 fU AIN > 、碳和活 氧化鋁、 化錫、菱 石、膨土 鹽，諸如 、氫氧化 )萘，取 物件，諸 入加熱之 壓之產品 藉由在擠 並且交聯 經交聯物 具中，藉 1 8 0°C ) -24- 201035124 進行加壓交聯1至120分鐘及接著藉由固定在爐內的 或惰性氣體中以120°至320°c (較佳爲14〇°至24〇°C 佳爲160°至220°C )進行爐內交聯〇至48小時（較佳 至12小時）而製得。 從防止因微量金屬的溶析而污染半導體製造設備 點來看，藉由將全氟彈性體組成物交聯並模製而製得 交聯模製物件的金屬含量較佳爲不超過1〇〇 PPm，更 0 不超過50ppm，更佳爲不超過30ppm。 從可偵測出在製造模製物件之步驟中所可能混入 物及外來物質的觀點來看，藉由將全氟彈性體組成物 並模製而製得之經交聯模製物件的霧値較佳爲不超過 ，更佳爲不超過40%，更佳爲不超過30%。 爲了降低經交聯模製物件的霧値至50%或更低， 種既不添加塡充劑、加工助劑、增塑劑、著色劑、抗 劑，亦不添加酸受體之方法。 Q 藉由將全氟彈性體組成物交聯並模製而製得之經 模製物件的抗張強度較佳爲不低於8 MP a，更佳爲不 9 MPa，更佳爲不低於1 0 MPa。抗張強度可根據 K62 5 1測量。 本發明的經交聯模製物件具有極佳的耐化學性、 強度及耐熱性，並適合例如作爲半導體設備之密封材 密封材料的實例爲0型環、方型環、襯墊、包裝、 、軸承封、端頭封等。 在本發明中，半導體製造設備不特別受限於製造 空氣 ，更 爲2 的觀 之經 佳爲 污染 交聯 5 0% 有一 氧化 交聯 低於 JIS 機械 料。 油封 半導 -25- 201035124 體的設備，而是包含在其中需要高清晰程度之半導體領域 中所使用的所有製造設備，諸如製造液晶面板及電漿面板 之設備。半導體製造設備的實例如下。 (1 )蝕刻系統 乾蝕刻設備 電漿蝕刻機 反應性離子蝕刻機 反應性離子束蝕刻機 濺射鈾刻機 離子束蝕刻機 濕式鈾刻設備 灰燼設備 (2 )清潔系統 乾式蝕刻清潔設備 UV/03清潔機 離子束清潔機 雷射光束清潔機 電漿清潔機 氣體蝕刻清潔機 萃取清潔設備 索克斯雷特（Soxhlet)萃取清潔機 高溫高壓萃取清潔機 微波萃取清潔機 超臨界萃取清潔機 -26- 201035124 (3 )曝光系統 步進機 塗布機及顯影機 (4 )磨光系統 CMP設備 (5 )成膜系統 CVD設備 π 濺射設備 〇 (6 )擴散及離子植入系統 氧化及擴散設備 離子植入設備 【實施方式】 實例 於此等實 接著本發明係以實驗例方式說明，但不受限 0 驗例。 實例1 1.聚合步驟 3 0 公克 公克 葉片作爲 以氮氣充 rpm下以 將 3，0 0 0公克純水與作爲乳化劑之 C3F7OCF(CF3)CF2OCF(CF3)COONH4 及 0.27 (NH4)2C03傾注於不具火源並配備MAXBLEND 攪拌器的6公升不銹鋼高壓鍋中，並在系統內部 分置換且排氣之後，將高壓鍋的內部溫度在600 -27- 201035124 攪拌加熱至多50C。並引入四氟乙輝（tfe)與全氟（甲 基乙燃酸）（PMVE)之氣體混合物（TFE/PMVE = 44/56 之莫耳百分比）的初進料，所以內部壓力變成〇·83 MPaG 。接著將0.558公克過硫酸銨（APS)溶解在ι〇公克純水 中所製備之溶液以加壓氮氣引入，以引發反應。 在進行聚合時’當內部壓力下降至0.73 MPaG時，將 3.03公克I(CF1 2CF；2) 1i以加壓氮氣引入，並在壓力下供 應10公克純水清洗管子。接著引入TFE及PMVE ( TFE/PMVE = 75/25之莫耳百分比），所以內部壓力變成 0.83 MPaG。之後當內部壓力隨著聚合進行下降至〇73 MPaG時，將TFE及PMVE以75/23之莫耳百分比與上述 相同的方式進料’直到內部壓力達到0· 8 3 MPaG爲止，並 因此在0.73 MPaG與〇.83 MPaG之間重複壓力的增加及 降低。 當TFE之總添加量及PMVE之總添加量在開始聚合 之後8 3小時分別達到3 8 2公克及2 1 1公克時，將高壓鍋 冷卻及釋出未反應之單體，製得具有I4.5質量％之固體含 量的3，6 4 7公克水性分散液。 -28- 1 .後處理步驟 2 將1，〇〇〇公克所製得之水性分散液以1,000公克純水 3 3.5質量％之氫氯酸水溶液中。在加完之後，將溶液攪拌5 4 分鐘，並接著將凝聚之聚合物濾出，並將製得之聚合物傾 5 稀釋，並將稀釋之分散液以攪拌緩慢添加至8,000公克 201035124 注於5,000公克純水中，接著攪拌5分鐘及再濾出。接著 重複以水清洗及濾出’並當清洗之後的清洗水之pH値變 成6或更高時，將聚合物取出。將聚合反應製得之3,647 公克水性分散液與上述相同的方處理，並將所製得之全部 聚合物在1 2 0 °C下進行2 4小時真空乾燥，以製得5 9 8公 克乾燥聚合物（全氟彈性體A)。 19F-NMR分析（熔融法，270°C )結果，此爲一種包 0 含具有75.9/24.1之莫耳百分比的TFE/PMVE之單體單元 的聚合物。此聚合物的孟納（Μ ο ο n e y )黏度（M L 1 + 2 0， MO °C )爲86。在聚合物中的碘含量爲〇·ΐ6質量％。聚合 物在1 00 °C下不足以熔融且不能測到孟納黏度。將評估結 果顯示於表1和2中。 3.經交聯模製物件之評估 將所製得之全氟彈性體A、作爲在分子中具有至少兩 Q 個雙鍵的化合物之異氰尿酸三烯丙酯（可取自Nippon Kasei Chemical Co.，Ltd.之 TAIC)與作爲有機過氧化物 之取自 NOF CORPORATION 之 PERHEXA 258(2,5-二甲 基-2,5-二（第三丁基過氧基）己烷以100/0.5/0.5之質量 比以開放式滾輥捏和，以製備可交聯之全氟彈性體組成物 0 此全氟彈性體組成物之硫化曲線係根據JIS K63 00-2 在160°C下使用橡膠加工分析儀RPA2000 (取自 Alfa Technologies Japan LLC)獲得，並測定誘導時間（T10) -29- 201035124 、90%之硫化時間（T90 )、最大扭力及最小扭力。將評 估結果顯示於表2中。 接著將此全氟彈性體組成物在1 60 °C下接受加壓交聯 10分鐘及在爐內於180 °C之空氣中進一步加熱4小時’以 製得2毫米厚度的透明薄片並作爲經交聯模製物件之p-24標準（JIS B2401)的〇型環。 此模製物件在正常狀態下的物理性質、壓縮定形、霧 値、比重及金屬含量係以下列測量方法測量。將評估結果 顯示於表3中。 (在正常狀態下的物理性質） 經交聯模製物件之2毫米厚度薄片在1 00%伸長率下 的張應力（M100)、在斷裂時的張應力（TSb)及在斷裂 時的伸長率（Eb )係根據JIS K625 l在正常狀態下使用6 號啞鈴測量。 (硬度） 模製物件之硬度（蕭氏（Shore ) a )係根據 JIS K625 3測量。 (比重） 模製物件之比重係根據JIS K0268測量。 (壓縮定形） -30- 201035124 經交聯〇型環之樣品的壓縮定形係根據JIS B 2401在 200°C下以20%壓縮5小時而測量。 (霧値） 經交聯模製物件之2毫米厚度薄片的霧値係根據 ASTM D 1 003 使用比濁計（取自 Kabushiki Kaisha Toyo Seiki Seisakusho 之 Haze Guard II)而測量。 Ο (金屬含量） 測量出2公克模製物件並放在鉑盤上，接著在5 5 〇。(3 加熱30分鐘而灰化。將25公克稀釋之氫氯酸添加至灰末 中，接著在水浴上以8 0 °C加熱以溶解灰末。將此水溶液 以發射光譜化學分析儀 SPS3 000ICP (取自 Seik0 Instruments Co., Ltd.)分析。 在表3中，ND意謂未偵測到任何金屬組份。 〇 實例2 聚合反應係在與實例1相同的聚合條件下進行，除了 初進料的混合氣體改變成TFE/PMVE = 3 8/62之莫耳百分比 ，另外添加之TFE/PMVE改變成70/30之莫耳百分比，添 加之TFE的總量改變成3 5 3公克及添加之PMVE的總量 改變成2 5 1公克。結果製得全氟彈性體B。將結果顯示於 表1中，並將物理性質的評估結果顯不於表2和3中。 -31 - 201035124 實例3 聚合反應係在與實例1相同的聚合條件 初進料的混合氣體改變成TFE/PMVE = 36/64 ，另外添加之TFE/PMVE改變成6 8/3 2之莫 加之TFE的總量改變成338公克及添加之 改變成264公克。結果製得全氟彈性體c。 表1中，並將物理性質的評估結果顯示於表 實例4 聚合反應係在與實例1相同的聚合條件 初進料的混合氣體改變成TFE/PMVE = 32/68 ’另外添加之TFE/PMVE改變成65/35之莫 加之TFE的總量改變成318公克及添加之 改變成2 8 8公克。結果製得全氟彈性體D。 表1中，並將物理性質的評估結果顯示於表 比較性實例1 聚合反應係在與實例1相同的聚合條件 初進料的混合氣體改變成TFE/PMVE = 28/72 ，另外添加之TFE/PMVE改變成62/38之莫 加之TFE的總量改變成294公克及添加之 改變成299公克。結果製得全氟彈性體E。 表1中，並將物理性質的評估結果顯示於表 下進行，除了 之莫耳百分比 耳百分比，添 PMVE的總量 將結果顯示於 2和3中。 下進行，除了 之莫耳百分比 耳百分比，添 Ρ Μ V E的總量 將結果顯不於 2和3中。 下進行，除了 之莫耳百分比 耳百分比，添 PMVE的總量 將結果顯不於 2和3中。 -32 - 201035124Rf1 is a saturated or unsaturated fluorohydrocarbon group or a chlorofluorocarbon group having 1 to 16 carbon atoms, and a perfluoroalkyl group having 4 to 8 carbon atoms is preferred. If the number of carbon atoms exceeds 16, the reactivity tends to decrease. In the iodine compound represented by the general formula: Rf1 · Ix, X represents the number of the bonds -14 to 35,535,124 of Rf1 and is an integer of not less than 1 and not more than 4', preferably not less than 2 and not more than 3 . Even if X exceeds 4, this compound can be used, but it is not preferable from the viewpoint of synthesis cost. From the standpoint that the produced polymer has less branching, it is most preferable that X is 2. The carbon-iodine bond of this iodine compound is a relatively weak bond and is easily cleaved in the form of a radical in the presence of a source of free radical release. Since the released free radical is highly reactive, the monomer undergoes an addition reaction, and then the reaction is terminated by removing iodine from the iodine compound. In the thus obtained fluoroelastomer in which iodine is bonded to carbon at the end of its molecule, terminal iodine becomes an effective hardening position and can be effectively crosslinked.实例 Examples of the iodine compound represented by the formula: Rf1. 为 are, for example, monomethyl perfluoromethane, monoiodoperfluoroethane, monoiodoperfluoropropane, monoiodoperfluorobutanin (for example, '2-iodoprolate Alkane, 1-iodoperfluoro(1,1-dimethylethane), monoiodoperfluoropentane (for example, 1-iodoperfluoro (4-methylbutyl)), dithizone Mono-perfluorocyclobutylene, 2-arachto-perfluoro(1-cyclobutylethane)cyclohexane, monoiodoperfluorocyclohexane, monoiodotrifluorocyclobutane, monomolyte difluoromethane, monoiodine Monofluoromethane, 2-iodo-i-hydroperfluoroethane, 3-iodo-1-hydroperfluoropropane, monoiodo-dichlorodifluoromethane, monoiododichloromonofluoromethane, 2_iodine-1,2- Dichloro-1,12-trifluoroethane, 4-iodo-^-dichloroperfluorobutane, 6-iodo-1,2-chloroperfluorohexane, 4-iodo-1,2,4-tri Chloroperfluorobutane, hydrazine·iodine·2,2-hydroperfluoropropane, 1-iodohydroperfluoropropane, monoiodotrifluoroethylene, 3-iodoperfluoropropene-1, 4-iodoperfluoropentene , 4_iodine_5_chloroperfluoropentene q, 2-propanol (1-cyclobutenylethane), 1,2-diiodoperfluoroethane, 1,3-s-perfluoropropane ' l,4 -one perfluoro-n-butyl ,丨^-diiodoperfluoro-15- 201035124 n-pentane, 1,6-diiodoperfluoro-n-hexane, 1,7-diiodoperfluoro-n-heptane, 1,3-diiodo·2-chloro Fluoropropane, 1,5-diiodo-2,4-dichloroperfluoro-n-pentane, 1,8-diiodoperfluoro-n-octane, 1,2-di(iododifluoromethyl)perfluorocyclobutane Alkane, 2-iodo-1,1,1-trifluoroethane, 1-iodo-dihydroperfluoro(2-methylethane), 2-iodo-2,2-dichloro-1,1, anthracene Trifluoroethane, 2-iodo-2-chloro-1, 1,1-trifluoroethane and the like. Further, the hydrocarbon group of Rf1 may contain a functional group such as an oxygen atom capable of forming an ether linkage, a sulfur atom or a carboxyl group capable of forming a thioether linkage, and an example of a compound having such a functional group is 2-iodo perfluoroethylene Perfluorovinyl ether, 2-iodoperfluoroethyl perfluoroisopropyl ether, 3-indole-2-chloroperfluorobutyl perfluoromethyl sulfide and 3-iodo-4-chloroperfluorobutyric acid. Among them, from the viewpoints of ease of synthesis, reactivity, economic efficiency, and stability, it is preferred to use 1,4-diiodoperfluoro-n-butane and 1,6-diiodoperfluoro-n-hexane, and from room temperature From the viewpoint of being liquid and easy to handle, 1,4-diiodoperfluoro-n-butane is preferred. An iodine atom or a bromine atom is introduced into the perfluoroelastomer (A) prepared using such an iodine compound and/or a bromine compound (for example, refer to WO 97/24381). An example of a method for preparing a perfluoroelastomer (A) having an iodine atom or a bromine atom is a method in which a perfluoroelastomer is copolymerized with an iodine- or bromine-containing monomer, and a monomer having an iodine atom or a bromine atom. An example is an iodine- or bromine-containing monomer represented by the general formula (3): CY12=CY1-Rf2(CHR3)nX1 (3) wherein Y1 is a hydrogen atom, a fluorine atom or -CH3; Rf2 is a fluorine alkyl group, Perfluoro-16- 201035124 alkyl, fluoropolyoxyalkylene or perfluoropolyoxyl extension; R3 is a hydrogen atom or -CH^X1 is a bowl atom or a bromine atom, η is 〇 or 1; (4) Represented monomer: CF2=CFO(CF2CF(CF3)0)m(CF2)n-X2 (4) where m is 0 or an integer from 1 to 5; ! An integer of from 〖 to 3, X2 is a bromine atom or an iodine atom; and a monomer represented by the formula (5): CH2=CH(CF2)nI (5) wherein η is an integer of from 1 to 10. For example, there are iodine-containing monomers such as perfluoro(6,6-dihydro-6-iodo-3-oxa-1-hexyl disclosed in JP 5-63 4 8 2B and JP 7-3 1 623 4A Alkene) and perfluoro(5-iodo-3-oxa-1-pentene), CH2=CH(CF2)41 and ch2=ch(cf2)61. These iodine- or bromine-containing monomers can increase the amount of iodine/bromine to be introduced into the perfluoroelastomer by the reaction using the above iodine and/or bromine compound. The perfluoroelastomer (A) used in the present invention can be produced by a conventional polymerization method such as an emulsion polymerization method, a suspension polymerization method or a solution polymerization method. The polymerization conditions such as the polymerization temperature and time may be arbitrarily determined depending on the kind of the monomer and the elastomer to be used. Emulsifiers, molecular weight regulators, pH adjusters, and the like can be added. The molecular weight modifier may be added in portions at the initial stage of polymerization or may be added continuously or discontinuously. Various emulsifiers can be used for the emulsion polymerization. From the viewpoint of suppressing the chain transfer reaction to the emulsifier molecule which occurs during the polymerization, a suitable emulsifier is a carboxylate having a fluorocarbon chain or a fluoropolyether chain. In addition, reactive emulsifiers are also suitable. An oil-soluble radical polymerization initiator or a water-soluble radical polymerization -17-201035124 initiator can be used as a polymerization initiator. Examples of water-soluble radical polymerization starting from, for example, ammonium persulfate (AP S ), potassium persulfate (KP S ), and pH adjusting agents used in polymerization systems are slow electrolyte materials such as phosphates, carbonates, and boric acid. Salt or potassium hydroxide and ammonium hydroxide. Examples of the molecular weight modifier are the above-exemplified iodine compounds. A method for separating a polymerization product from a polymerization mixture, a coacervation method by treating a polymerization mixture with hydrochloric acid, nitric acid or the like, and a coagulation method by freezing and thawing the polymerization mixture. Further, a coagulation method of agglomerating mechanical force by ultrasonic waves can be employed. Other methods of separating the polymerization product from the polymerization mixture are by agglomeration methods such as a metal salt such as magnesium chloride, calcium chloride, aluminum chloride, magnesium sulfate, barium sulfate or aluminum sulfate. In order to reduce the metal content of the polymerization product, it is preferred to separate the polymerization from the polymerization mixture without using a substance such as a metal salt, and to treat it with acid or to freeze and then to thaw it. The content of the bromine atom in the perfluoroelastomer (A) is preferably not less than 0.05% by mass, more preferably from the viewpoint of the shape of the molded article produced by using the perfluoroelastomer. 10% by mass, more preferably not less than 0.15% by mass. Further, the amount of the iodine/bromine compound used and the example of the preparation of the perfluoroelastomer are similar. The sodium oxide and bromination of the rushing ability, the mixed acid may be used, and the method or the example thereof is a method of agglomerating the sodium and chlorometal compound products. The satisfactory pressure atom and/or is not lower than Molding -18- 201035124 From the viewpoint of satisfactory tensile strength of the article, the content of the iodine atom and/or the bromine atom is preferably not more than 1.5% by mass, more preferably not more than 1,2% by mass. More preferably, it is not more than 1. 〇 mass%. From the viewpoints of cost and long-term route for synthesizing a monomer having a hardened position, it is preferred that the perfluoroelastomer (A) of the present invention does not contain a monomer having a hardened position, such as a nitrile-containing fluorinated olefin. Or a nitrile-containing fluorinated vinyl ether. The organic peroxide (B) can usually be an organic peroxide which is lightly free to generate free radicals in the presence of heat or a reducing agent. Examples thereof are, for example, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane·2,5-dihydroxyperoxidation , di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α,α'-bis(t-butylperoxy)-pair -diisopropylbenzene, 2,5-dimethyl-2,5.di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butyl Peroxy)hexyne-3' benzhydryl peroxide, tert-butylperoxybenzene, 2,5·dimethyl-2,5-bis(benzhydrylperoxy)hexane, Tert-butyl peroxybenzoate, tert-butyl peroxymaleate, tert-butyl peroxyisopropyl carbonate, and the like. Among these, dialkyl peroxides (such as dicumyl peroxide), 2,5-dimethyl-2,5-di(t-butylperoxy) 2,5-Dimethyl-2,5-di(t-butylperoxy)hexyne-3 is preferred. The type and amount of the organic peroxide are usually selected in consideration of the amount of activity, the decomposition temperature, and the like. Further, from the viewpoint of decomposition temperature, it has 100. Organic peroxides up to 14 (TC's 10-hour half-life temperature, such as tert-butyl peroxybenzoate, dicumyl peroxide, -19-201035124 2.5-dimethyl-2,5 - bis(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3. Perfluoroelastomers prepared from the improvement The amount of the organic peroxide (B) is preferably not less than 0.1 part by mass, more preferably not less than 0.1 part by mass based on 1 part by mass of the perfluoroelastomer (A), from the viewpoint of the degree of crosslinking of the bulk composition. Not less than 0.2 parts by mass, more preferably not less than 0.3 parts by mass. Further, from the viewpoint of reducing the amount of the organic peroxide (B) which is difficult to knead, the amount of the organic peroxide (B) is The amount of the perfluoroelastomer (A) of 10 parts by mass is preferably not more than 2.5 parts by mass, more preferably not more than 2 parts by mass. From the viewpoint of not reducing transparency, dispersion in the inactive load should be avoided. The organic peroxide in the state of the agent. The composition of the present invention comprises a compound (C) having at least two double bonds in the molecule, which is a crosslinking agent. The compound (C) having at least two double bonds may be a compound reactive with a radical derived from the organic peroxide (B) and a polymer radical, and examples thereof are, for example, such as CH2 = CH-, CH2 = A polyfunctional compound having a functional group of CHCH2- or CF2-CF-. For example, triallyl cyanurate, triallyl isocyanurate (TAIC), TAIC prepolymer, trimethyl allylic isocyanurate Ester, tripropylene-based acetal, triallyl benzenetricarboxylate, hydrazine, Ν'-n-phenylene bismaleimide, diallyl phthalate, tetraallyl terephthalate Triallyl phosphate, bismaleimide, triallyl isocyanurate ( 1.3.5- ginseng (2,3,3-trifluoro-2-propenyl)-1,3,5 - triterpene-2,4,6-trione), ginseng (diallylamine)-S-triazine, triallyl phosphite, hydrazine, hydrazine-diallyl acrylamide, hexenylphosphine Guanamine, hydrazine, hydrazine, Ν', Ν'-tetraallyl-20- 201035124 p-xylyleneamine, hydrazine, hydrazine, hydrazine, Ν'-tetraallylpropanediamine, isocyanuric acid Trivinyl ester, 2,4,6-trivinylmethyltrioxane, tris(5-norzcan_2- Methyl) cyanurate, CH2 = CH-(CF2) 6-CH = ch2, CH2 = CH-(CF2) 4-CH = CH2 and the like. Among these compounds, from crosslinked articles From the standpoint of satisfactory crosslinkability and physical properties, compounds having two or three CXikCX3- (X1, X2 and X; H or F) functional groups are preferred, and are low in price and availability. From the viewpoints, a compound having two or three CXl^CX3- (X1, X2 and X3 are oxime) functional groups is preferred, and satisfactory crosslinkability and physical properties from the crosslinked article, low price and From the standpoint of availability, TAIC is preferred. From the viewpoint of improving the degree of crosslinking of the perfluoroelastomer composition prepared, the amount of the compound (C) having at least two double bonds in the molecule is 1 part by mass of the perfluoroelastomer (A). The basis weight is preferably not less than 〇. i parts by mass, more preferably not less than 0.2 parts by mass, more preferably not less than 0.3 parts by mass. Further, from the viewpoint of reducing the amount of the compound (C) having at least two double bonds in the molecule which is difficult to knead, the amount of the compound (C) having at least two double bonds in the molecule is 1 part by mass. The perfluoroelastomer (A) is preferably not more than 2.5 parts by mass, more preferably not more than 2 parts by mass. Further, from the viewpoint of improving the degree of crosslinking of the perfluoroelastomer composition obtained, the total amount of the organic peroxide (B) and the compound (C) having at least two double bonds in the molecule is 100. The parts by mass of the perfluoroelastomer (A) is preferably not less than 0.5 parts by mass, more preferably not less than 0.8 parts by mass. Further, the organic peroxide (B) and a compound having at least two double bonds in the molecule are from the viewpoint of reducing the amount of the organic peroxide (Β) -21 - 201035124 and the compound (C) which are difficult to knead. The total amount of (C) is preferably not more than 3.0 parts by mass, more preferably not more than 2.5 parts by mass, more preferably not more than 2.0 parts by mass, based on 100 parts by mass of the perfluoroelastomer (A). The perfluoroelastomer composition of the crosslinked molded article of the present invention can be processed by conventional elastomer processing equipment such as an open roll, a Banbury mixer or a kneader by using each of the above components. Prepared by mixing. Alternatively, the composition can be prepared by an internal mixer. The crosslinked molded article of the present invention does not contain an additive which can be a source of particles and a gas generating source. Examples of such additives are, for example, chelating agents, processing aids, plasticizers, colorants, antioxidants, crosslinking accelerators, acid acceptors, and the like. Examples of the chelating agent are inorganic chelating agents and organic chelating agents. Examples of organic chelating agents are quinone imine oximes having a quinone imine structure, such as polyimine, polyamidimide and polyether phthalimide; ketone engineering plastics such as polyetheretherketone (PEEK) And polyether ketone (PEK) •, and engineering plastics such as polypropionate, poly maple, polyether oxime 'polyphenyl sulphide and polyoxybenzoate. There are also fluoropolymers such as polytetrafluoroethylene (PTFE), copolymers of perfluoroolefins and perfluoro(household vinyl ether) (PFA), tetrafluoroethylene/hexafluoropropylene copolymers, polyvinylidene fluoride, Polyvinyl fluoride and polychlorotrifluoroethylene powder. Other examples are high styrene resins, phenol resins, xanthones resins and the like. Examples of inorganic chelating agents are metal oxide chelating agents such as alumina, cerium oxide, cerium oxide and titanium oxide; metal carbides such as lanthanum carbide and aluminum carbide-22-201035124: metal nitrides such as tantalum nitride And aluminum nitride; fluoride chelants 'such as fluoride and carbon fluoride; and commonly used enthalpy' such as barium sulfate, carbon black, vermiculite, clay, talc and calcium carbonate. Examples of processing aids are high carbon fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; high carbon fatty acid salts such as sodium stearate and zinc stearate: high carbon fatty acid decylamines such as stearic acid Indoleamine and decyl oleate; high carbon fatty acid esters such as ethyl oleate; high carbon fatty acid amines such as stearylamine and oleylamine; petroleum waxes such as palm wax and ceresin; polyglycols such as B Glycols, glycerol and diethylene glycol; aliphatic hydrocarbons such as petrolatum and paraffin; polyoxygenated oils, polyoxyalkylene polymers, low molecular weight polyethylenes, phthalates, phosphates, rosins, (hydrogenated) Second home base amine, (hydrogenated) two-yard base maple, surfactants and the like. Examples of the plasticizer are, for example, a phthalic acid derivative and a sebacic acid derivative. There are also fluorine-containing oils such as perfluoropolyether. Examples of colorants are condensed azo pigments, oxime isoindlenone pigments, quinacridone pigments, diketopyrrolopyrrole pigments and broth pigments. In addition, there are carbon black, barium sulfate, oxidized chin, zinc oxide, stone stone, magnesium carbonate, calcium carbonate, clay and the like. Examples of the antioxidant are amine, phenol, sulfur and phosphorus compounds, and non-limiting examples thereof are triphenyl phosphite and polyphenylene sulfide. Compounds having an anti-oxidation effect against electric ray are those used as organic pigments and antioxidants. For example, 'isoindolinone pigment, quinophthalone pigment, diketopyrrole pigment and anthraquinone pigment. Examples of crosslinking accelerators are inorganic oxides, inorganic nitrides, and carbon materials -23-201035124. In particular, it has a water and alcohol adsorbing compound and has a basic compound. Examples of the compound having water and alcohol adsorption properties are, for example, magnesium sulfate, sodium sulfate, activated carbon, and mesoporous vermiculite. Examples of the base site are, for example, (n alkali metal, alkaline earth metal, and oxidized shirt containing an alkali metal, an alkaline earth metal and an oxide of vermiculite, alumina carbon, and (3) an inorganic nitride such as tantalum nitride (Si3N4). 5 and (4) vermiculite or aluminaous carbon having an amine functional group on the surface. Examples of the compounds of (1) to (4) are magnesium oxide, sodium oxide, zinc oxide, silver oxide, aluminum oxide, titanium oxide. , oxyapatite, hard strontite, ash, talc, magnesium aluminum blisters, zeolites, clay, pyrophyllite and selenite. In addition, organic quaternary ammonium salts and iron salts are exemplified as Crosslinking accelerators. Examples of acid acceptors are magnesium oxide, calcium oxide, calcium magnesium hydroxide, magnesium aluminum sepiolite, proton sponge (1,8-bis-(dimethylamino) from Aldrich) and octadecylamine. A method of pre-molding, such as heating and compression in a metal mold, a method of placing a metal mold under pressure, and a method of extruding by an extruder, can be produced from the above-mentioned composition by a conventional method. Pipes and wires, which are made by cross-linking molded articles and then cross-linked by steam In the present invention, the crosslinking conditions are not particularly limited and may be carried out under the usual crosslinking conditions of the perfluoroelastomer. For example, the article may be fixed by feeding the above-mentioned perfluoroelastomer composition to a metal mold. Under pressure, 120° to 250°C (preferably 140° to position molecular sieve, compounding?, (2), carbon and live fU AIN >, carbon and activated alumina, tin, sapphire, A bentonite salt, such as, for example, hydrogenated naphthalene, an object, and a product which is pressed into a heated product, by pressurizing and crosslinking the crosslinked article, by using 180 ° C) -24 - 201035124 Induction in the furnace for 1 to 120 minutes and then by means of fixing in the furnace or in an inert gas at 120 to 320 ° C (preferably 14 ° to 24 ° C, preferably 160 to 220 ° C) It is prepared by coupling to 48 hours (preferably 12 hours). From the viewpoint of preventing contamination of semiconductor manufacturing equipment due to elution of trace metals, it is obtained by crosslinking and molding a perfluoroelastomer composition. The metal content of the crosslinked molded article is preferably not more than 1 〇〇 PPm, more preferably not more than 50 ppm, more preferably not more than 30 ppm. The smog of the crosslinked molded article obtained by molding and molding the perfluoroelastomer composition is preferably from the viewpoint of detecting possible inclusions and foreign substances in the step of manufacturing the molded article. It is not more than, more preferably not more than 40%, more preferably not more than 30%. In order to reduce the haze of the cross-linked molded article to 50% or less, the product is neither added with a hydrating agent, a processing aid, A plasticizer, a colorant, an anti-agent, and a method of not adding an acid acceptor. Q The tensile strength of the molded article obtained by crosslinking and molding the perfluoroelastomer composition is preferably not Below 8 MP a, more preferably not 9 MPa, more preferably not less than 10 MPa. Tensile strength can be measured according to K62 5 1. The crosslinked molded article of the present invention has excellent chemical resistance, strength and heat resistance, and is suitable, for example, as a sealing material for a semiconductor device, as a 0-ring, a square ring, a gasket, a package, Bearing seal, end seal, etc. In the present invention, the semiconductor manufacturing equipment is not particularly limited to the production of air, and the effect of 2 is better than that of the cross-linking of 50% of which has an oxidized cross-linking lower than that of the JIS mechanical material. Oil seals Semi-conductor -25- 201035124 Body equipment, but all manufacturing equipment used in the semiconductor field where high definition is required, such as equipment for manufacturing liquid crystal panels and plasma panels. Examples of semiconductor manufacturing equipment are as follows. (1) Etching system dry etching equipment plasma etching machine reactive ion etching machine reactive ion beam etching machine sputtering uranium engraving machine ion beam etching machine wet uranium engraving equipment ash equipment (2) cleaning system dry etching cleaning equipment UV / 03 cleaning machine ion beam cleaning machine laser beam cleaning electromechanical pulp cleaning machine gas etching cleaning machine extraction cleaning equipment Soxhlet extraction cleaning machine high temperature and high pressure extraction cleaning machine microwave extraction cleaning machine supercritical extraction cleaning machine -26- 201035124 (3) Exposure system stepper coating machine and developing machine (4) polishing system CMP equipment (5) film forming system CVD equipment π sputtering equipment 〇 (6) diffusion and ion implantation system oxidation and diffusion equipment ion implantation [Embodiment] EXAMPLES The present invention is described by way of experimental examples, but is not limited to the example. Example 1 1. Polymerization step 30 g gram of vane was used as a nitrogen-filled rpm to pour 3,0 0 g of pure water with C3F7OCF(CF3)CF2OCF(CF3)COONH4 and 0.27(NH4)2C03 as emulsifiers. After the fire source is equipped with a MAXBLEND stirrer in a 6-liter stainless steel pressure cooker and partially replaced and vented in the system, the internal temperature of the pressure cooker is heated up to 50C at 600 -27- 201035124. And introduce the initial feed of a gas mixture of tetrafluoroethylene (tfe) and perfluoro(methyl ethanoic acid) (PMVE) (% of molars of TFE/PMVE = 44/56), so the internal pressure becomes 〇·83 MPaG. Next, a solution prepared by dissolving 0.558 g of ammonium persulfate (APS) in ι gram of pure water was introduced under pressurized nitrogen to initiate the reaction. While the polymerization was being carried out, when the internal pressure was lowered to 0.73 MPaG, 3.03 g of I(CF1 2CF; 2) 1i was introduced under pressurized nitrogen, and 10 g of pure water was supplied under pressure to clean the tube. Then TFE and PMVE (% of TFE/PMVE = 75/25) were introduced, so the internal pressure became 0.83 MPaG. Then, when the internal pressure drops to 〇73 MPaG with polymerization, TFE and PMVE are fed in the same manner as above in a molar percentage of 75/23 until the internal pressure reaches 0·83 MPaG, and thus at 0.73 The increase and decrease of repeated pressure between MPaG and 〇.83 MPaG. When the total addition amount of TFE and the total addition amount of PMVE reached 382 g and 21 g, respectively, at 83 hours after the start of polymerization, the autoclave was cooled and released unreacted monomer to obtain I4.5. A mass fraction of 3,6 4 7 g aqueous dispersion of solid content. -28- 1. Post-treatment step 2 An aqueous dispersion prepared by the method of 1, gram is used in 1,000 g of pure water 3 3.5% by mass aqueous hydrochloric acid. After the addition was completed, the solution was stirred for 5 minutes, and then the agglomerated polymer was filtered off, and the obtained polymer was diluted 5 times, and the diluted dispersion was slowly added to 8,000 g of 201035124 with stirring. In grams of pure water, stir for 5 minutes and filter again. Then, the water was washed and filtered out repeatedly, and when the pH of the washing water after washing was changed to 6 or higher, the polymer was taken out. 3,647 g of the aqueous dispersion prepared by the polymerization was treated in the same manner as above, and all the obtained polymers were vacuum dried at 120 ° C for 24 hours to obtain 5 9 8 g of dry polymerization. (perfluoroelastomer A). 19F-NMR analysis (melting method, 270 ° C) As a result, this was a polymer containing a monomer unit of TFE/PMVE having a molar percentage of 75.9/24.1. The Mona (Μ ο e n e y ) viscosity (M L 1 + 2 0, MO °C ) of this polymer was 86. The iodine content in the polymer was 〇·ΐ 6 mass%. The polymer was not sufficiently melted at 100 ° C and the Menner viscosity could not be measured. The evaluation results are shown in Tables 1 and 2. 3. Evaluation of Crosslinked Molded Articles The perfluoroelastomer A produced, as a triallyl isocyanurate having at least two Q double bonds in the molecule (available from Nippon Kasei Chemical Co ., TAIC of Ltd. and PERHEXA 258 (2,5-dimethyl-2,5-di(t-butylperoxy)hexane taken from NOF CORPORATION as an organic peroxide at 100/0.5 The mass ratio of /0.5 is kneaded by an open roll to prepare a crosslinkable perfluoroelastomer composition. The vulcanization curve of the perfluoroelastomer composition is based on JIS K63 00-2 at 160 ° C. The processing analyzer RPA2000 (taken from Alfa Technologies Japan LLC) was obtained, and the induction time (T10) -29-201035124, 90% vulcanization time (T90), maximum torque and minimum torque were measured. The evaluation results are shown in Table 2. Then, the perfluoroelastomer composition was subjected to pressure crosslinking at 10 ° C for 10 minutes and further heated in an air at 180 ° C for 4 hours in a furnace to obtain a transparent sheet having a thickness of 2 mm and used as a Cross-linked molded parts of the p-24 standard (JIS B2401) 〇-type ring. This molded object is in normal condition. The physical properties, compression set, haze, specific gravity and metal content of the state are measured by the following measurement methods. The evaluation results are shown in Table 3. (Physical properties under normal conditions) 2 mm of cross-linked molded articles The tensile stress (M100) of the thickness sheet at 100% elongation, the tensile stress at break (TSb), and the elongation at break (Eb) were measured under normal conditions using a No. 6 dumbbell according to JIS K625 l. (Hardness) The hardness of the molded article (Shore a) is measured in accordance with JIS K625 3. (Specific gravity) The specific gravity of the molded article is measured in accordance with JIS K0268. (Compression set) -30- 201035124 Crosslinked type The compression setting of the sample of the ring was measured according to JIS B 2401 at 20% compression for 5 hours at 200 ° C. (Haze) The haze of the 2 mm thickness sheet of the crosslinked molded article was used in accordance with ASTM D 1 003. The turbidimeter (taken from Kazeshiki Kaisha Toyo Seiki Seisakusho's Haze Guard II) was measured. Ο (Metal content) 2 g of molded object was measured and placed on a platinum plate, followed by 5 5 〇. (3 heating for 30 minutes Ashing. 25 grams of diluted hydrogen Chloro acid was added to the ash, followed by heating on a water bath at 80 ° C to dissolve the ash. This aqueous solution was analyzed by an emission spectrochemical analyzer SPS3 000 ICP (taken from Seik0 Instruments Co., Ltd.). In Table 3, ND means that no metal component was detected. 〇 Example 2 The polymerization was carried out under the same polymerization conditions as in Example 1, except that the mixed gas of the initial feed was changed to the molar percentage of TFE/PMVE = 3 8/62, and the added TFE/PMVE was changed to 70/30. The percentage of moles, the total amount of TFE added was changed to 3 5 3 grams and the total amount of added PMVE was changed to 2 5 1 gram. As a result, perfluoroelastomer B was obtained. The results are shown in Table 1, and the evaluation results of the physical properties are not shown in Tables 2 and 3. -31 - 201035124 Example 3 The polymerization reaction was changed to TFE/PMVE = 36/64 in the same polymerization conditions as in Example 1, and the additional TFE/PMVE was changed to 6 8/3 2 Moga TFE The total amount was changed to 338 grams and the addition was changed to 264 grams. As a result, a perfluoroelastomer c was obtained. In Table 1, the evaluation results of the physical properties are shown in Table 4. The polymerization reaction was changed to the TFE/PMVE = 32/68 in the initial polymerization of the same polymerization conditions as in Example 1. The TFE/PMVE was additionally added. The total amount of TFE in the 65/35 Moga was changed to 318 grams and the addition was changed to 2 8 8 grams. As a result, a perfluoroelastomer D was obtained. In Table 1, the evaluation results of the physical properties are shown in the table. Comparative Example 1 The polymerization reaction was changed to TFE/PMVE = 28/72 in the initial polymerization conditions of the same polymerization conditions as in Example 1, and TFE/ was additionally added. The total amount of TFE in which PMVE was changed to 62/38 was changed to 294 g and the addition was changed to 299 g. As a result, a perfluoroelastomer E was obtained. In Table 1, the results of the evaluation of the physical properties are shown in the table below, except for the percentage of ears in the molar percentage, and the total amount of added PMVE is shown in 2 and 3. In the next step, except for the percentage of the ear percentage, the total amount of Ρ Μ V E is not shown in 2 and 3. In the next step, except for the percentage of the ear percentage, the total amount of PMVE added will be less than 2 and 3. -32 - 201035124
(NsΖ;9ε/ε·ε9 165 SI Ζ.ΊΙ 66(n 寸 6(n 8ε/(Ν9 TmrJ I 寸Γ0ε·εε//..99 i6ς9《ε 9.91 6.U 008ZοοΙε si 89/(Νε 寸 寸s 6·§·89 609 Z/9I 0·ΙΙ 寸 9CN οοεε (Νε/89 s/9£ 寸s 9·§ 寸·0/, S9 iNs ^.91 6·8 s s Orn/OA CN_ 9ΙΌ I·寸<ν/6.ρ 0065sw 寸.91 ε·8 s cn8£ LrlmL 9S/寸寸 (is_— (％WM)(HAWJ/3J1) §0$0 (职<4)¥鬆40齡爷#: (职SIW侧 (％¥»)Ϊ<ΙΏ鹦画 (盤令)酲您如厳 (职负)mAIMJ s<4) S1 (％wM)(3AlAId/3dH) 鬆4Π鹧 ϋ 嫉ΝαίΜ (0/0wM)(3AsCI/Hdl) -33- 201035124 CN撇 比較性實例 r-H § in 2 d ο 74 0.3 16.2 0.9 2.5 寸 〇 in m 2 d d 68 0.3 16.9 0.8 2.1 卹 m 〇 ι〇 2 〇 〇 77 0.3 16.6 0.8 2.5 (N 〇 »〇 m 2 d d B 〇 in 2 d d 86 1.6 15.2 1.0 2.6 am sn }E PQ ^CcquQw^jq 、j CffiL nKL UmL nniL QmL nV W ^激激献献幽脸PC 咖]虐ίϊ廳虐廳贓S 惡啪制釗制糾輒g S ^ ^ 裏' 妾灏姿 P P 1 1Φ S ? 5|2gi W W S S H 4flp 2 豸 Μ + + 珀珀盤渥 露2 2与酿囀饀g 担_ 渥 -34- 201035124 o(NsΖ;9ε/ε·ε9 165 SI Ζ.ΊΙ 66(n inch 6(n 8ε/(Ν9 TmrJ I inch Γ0ε·εε//..99 i6ς9“ε 9.91 6.U 008ZοοΙε si 89/(Νε inch inch s 6.············· <ν/6.ρ 0065sw Inch.91 ε·8 s cn8£ LrlmL 9S/inch inch (is_—(%WM)(HAWJ/3J1) §0$0 (职<4)¥松40龄爷#: ( SIW side (%¥»)Ϊ&ΙΏ;ΙΏ画画(盘令)酲如如(职负)mAIMJ s<4) S1 (%wM)(3AlAId/3dH) 松4Π鹧ϋ 嫉ΝαίΜ (0/0wM )(3AsCI/Hdl) -33- 201035124 CN撇Comparative example rH § in 2 d ο 74 0.3 16.2 0.9 2.5 inches 〇in m 2 dd 68 0.3 16.9 0.8 2.1 shirt m 〇ι〇2 〇〇77 0.3 16.6 0.8 2.5 (N 〇»〇m 2 dd B 〇in 2 dd 86 1.6 15.2 1.0 2.6 am sn }E PQ ^CcquQw^jq , j CffiL nKL UmL nniL QmL nV W ^Exciting Dedicated Face PC Coffee]赃S 啪 啪 辄 辄 g S ^ ^ 里 ' 妾灏 PP PP 1 1Φ S ? 5|2gi WWSSH 4flp 2 豸Μ + + 珀珀盘渥露 2 2 with 啭饀 啭饀 g _ 渥-34 - 201035124 o
比較性實例 評估 寸 W m CN SO.CNςς οοςl.s ΓΙ loo.CNsς〇ε 5 9S 6lns OSο·πL.lComparative example evaluation Inch W m CN SO.CNςς οοςl.s ΓΙ loo.CNsς〇ε 5 9S 6lns OSο·πL.l
90.(n 99 ILs I 6T 80.(n £8 68 091 3.91 L·% S-L4 (#i^-n)(v^_)sh Mi®)(v^ll)SH (％) s2S) esl(Ms) 0012 00 1 1 m ^Τ) (N 壓縮定形(2〇〇°C，168小時， P24 0型環，25%壓縮)(％) 霧値（％) -35- 201035124 ϊ) ε嗽 匡fc {UIdd)剩釦國領^#:鬆^遞1§ 6ε,ειsri 18Ό I 寸rsi 寸8,s § 3 8寸Ό § § ς(Ν·ι 98·6 i (Νοοο (Νε.Ι I寸·寸 § 6ΓΙ 寸S § § S90 6Γ001 III 8ΓΙ 89·(ν 寸9·Α § 寸8·Ι S2 寸2αζ S6csi 口1'| IVuz ss s ΰ <ui -36- 201035124 產業利用性 根據本發明，抗張強度可藉由增加包含TFE單元及 PAVE單元之共聚物的TFE單元含量而顯著地改進。再者 ，因爲藉由將全氟彈性體組成物交聯並模製而製得之經交 聯模製物件包含形成經交聯模製物件之全氟彈性體及交聯 - 劑，而且不含有任何添加劑，所以其爲透明的，具有令人 滿意的機性性質且尤其可預期爲用作供半導體製造設備用 I 的密封材料。 〇90.(n 99 ILs I 6T 80.(n £8 68 091 3.91 L·% S-L4 (#i^-n)(v^_)sh Mi®)(v^ll)SH (%) s2S) Esl(Ms) 0012 00 1 1 m ^Τ) (N compression set (2〇〇°C, 168 hours, P24 0 type ring, 25% compression) (%) haze (%) -35- 201035124 ϊ) ε嗽匡fc {UIdd) 扣扣国领^#:松^递1§ 6ε,ειsri 18Ό I inch rsi inch 8,s § 3 8 inch Ό § § ς(Ν·ι 98·6 i (Νοοο (Νε. Ι I inch·inch § 6ΓΙ inch S § § S90 6Γ001 III 8ΓΙ 89·(ν 寸 9·Α § inch 8·Ι S2 inch 2αζ S6csi mouth 1'| IVuz ss s ΰ <ui -36- 201035124 Industrial use According to the present invention, the tensile strength can be remarkably improved by increasing the TFE unit content of the copolymer comprising the TFE unit and the PAVE unit. Furthermore, since it is obtained by crosslinking and molding the perfluoroelastomer composition. The cross-linked molded article comprises a perfluoroelastomer and a cross-linking agent which form a cross-linked molded article, and does not contain any additives, so it is transparent, has satisfactory mechanical properties and is particularly expected Used as a sealing material for I used in semiconductor manufacturing equipment.
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