JP2004160902A - Manufacturing process for fluororubber molded body - Google Patents
Manufacturing process for fluororubber molded body Download PDFInfo
- Publication number
- JP2004160902A JP2004160902A JP2002331420A JP2002331420A JP2004160902A JP 2004160902 A JP2004160902 A JP 2004160902A JP 2002331420 A JP2002331420 A JP 2002331420A JP 2002331420 A JP2002331420 A JP 2002331420A JP 2004160902 A JP2004160902 A JP 2004160902A
- Authority
- JP
- Japan
- Prior art keywords
- fluororubber
- compound
- unvulcanized
- molded article
- tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000004073 vulcanization Methods 0.000 claims abstract description 28
- -1 perfluoroalkyl ether Chemical compound 0.000 claims abstract description 14
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 3
- CSJWOWRPMBXQLD-UHFFFAOYSA-N perfluoromethylvinylether group Chemical group FC(=C(C(F)(F)F)F)OC(=C(F)C(F)(F)F)F CSJWOWRPMBXQLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- 230000005855 radiation Effects 0.000 description 7
- 238000005187 foaming Methods 0.000 description 6
- 230000001788 irregular Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000012438 extruded product Nutrition 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920006369 KF polymer Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は耐熱性、耐薬品性などに優れた特殊ゴムの成形品に関する。具体的にはフッ素ゴム成形体の製造方法に関する。
【０００２】
【従来の技術】
近年フッ素ゴムは、優れた耐熱性、耐薬品性を有する弾性体として市販され、その加工品が種々の分野に種々の形状で利用されている。利用される分野の例としては、半導体工業分野、化学工業分野、医療・医薬分野などであり、形状としては、各種のＯ−リングに代表されるシール材形状、チューブ形状、断面が異形の長尺形状品、柔軟なシート状などがある。
【０００３】
［フッ素ゴムの定義］
本発明で用いる用語「フッ素ゴム」とは、炭素原子が共有結合により鎖状に連なった高分子で、分子中にフッ素を結合状態で含む、常温で弾性を示すゴム材料を指すものとする。
而して、すでに種々のフッ素ゴムが開発されあらゆる産業分野に利用されている。フッ素ゴムは一般的に他の合成ゴムと比較して、耐薬品性、耐熱性に優れているが、子細に見ると分子構造の違いによってその性質に違いがある。例えば、強酸に対しては強い耐性を示すが、強アルカリに対しては耐性を示さない種類のフッ素ゴムもあるが、強アルカリ、強酸両者に強い耐性を示すフッ素ゴムもある。第１表に現在市販されている、代表的なフッ素ゴムの分子構造と大まかな性質を示す。
【０００４】
【表１】
注）
ＶＦ２：ビニリデンフルオライド ＣＦ２＝ＣＦ２
ＨＦＰ：ヘキサフルオロプロピレン ＣＦ２＝ＣＦＣＦ３
ＴＦＥ：テトラフルオロエチレン ＣＦ２＝ＣＦ２
ＰＭＶＥ：パーフルオロメチルビニルエーテル ＣＦ２＝ＣＦＯ（ＣＦ３）
Ｐｒ：プロピレン ＣＨ２＝ＣＨＣＨ３
Ｅ：エチレン ＣＨ２＝ＣＨ２
＊：タイプＩのゴムを１としたときの相対値
＊＊：「−」は共重合を表す。例えば、ＶＦ２−ＨＦＰはビニリデンフルオライドとヘキサフルオロプロピレン共重合体の意味である。
【０００６】
タイプＩのフッ素ゴムは、ダイキン工業（株）よりダイエル７００番系（シリーズ）として、デュポン（株）からは、バイトンＡタイプとして市販されている。タイＩＩのフッ素ゴムは、ダイキン工業（株）から、ダイエル９００番系（シリーズ）として、デュポン（株）からはバイトンＢタイプとして市販されている。タイプＩＩＩのフッ素ゴムは、旭硝子（株）からＫＦポリマーなる商品名で市販されている。タイプＩＶのフッ素ゴムは、デュポン（株）よりバイトンＧＬＴなる商品名で市販されている。タイプＶのフッ素ゴムは、デュポン（株）よりバイトンＥＴＰなる商品名で市販されている。タイプＶＩのフッ素ゴムは、ダイキン工業（株）よりダイエルパーフルオロなる商品名で、デュポン（株）からは、カルレッツなる商品名で市販されている。
表１で示されるタイプＩ、ＩＩ、ＩＶのフッ素ゴムは、ビニリデンフルオライドを主成分とするビニリデン系フッ素ゴムであり、タイプＩＶ、Ｖ、ＶＩのフッ素ゴムはパ−フルオロビニルエーテル（ＰＭＶＥ）が共重合されてなるフッ素ゴムである。
この表１から分かる通り、タイプＶＩのフッ素ゴムの性能が最も良好であるがコストが極めて高い。次いで、タイプＩＶ、タイプＶの性能がよいがコストはタイプＩに比べて１０倍程度である。これらに共通していることは、いずれも分子中にＰＭＶＥを含むことであり、このモノマーを共重合したフッ素ゴムは、一般に耐アルカリ性、耐酸性、耐油性、耐薬品性、耐熱性などの諸性質が優れている。しかしながら、ＰＭＶＥは現在の技術では安価に製造することが出来ず、必然的にＰＭＶＥを含むフッ素ゴムはコストが高くなる。
【０００７】
［使用するゴム材料の配合］
本発明で使用するフッ素ゴムは、単独で使用してもよいが、通常は加硫剤のほかに補強剤、必要に応じて加工助剤、可塑剤、着色剤などを充填剤として添加する。
フッ素ゴムの加硫には、アミン系加硫剤、ポリオール系加硫剤及びパーオキサイド系加硫剤が使用されるが、本発明においてはいずれの加硫剤も使用できる。パーオキサイド系加硫剤としては、一般にジクミールパーオキサイドなどの有機過酸化物とトリアリルイソシアヌレート（ＴＡＩＣ）の組み合わせが使用される。ポリオール系加硫剤としては、アンモニュウム塩やホスホニュウム塩とビスフェノールＡやビスフェノールＡＦの組み合わせで用いられる。アミン系加硫剤としては、ヘキサメチレンジアミンカーバメートなどが使用できる。
これらの加硫剤、加硫助剤、補強剤などの添加剤は、分子構造の違うフッ素ゴムでも、ほぼ共通して使用できる特徴がある。
【０００８】
加硫剤以外の添加剤、例えば、加硫反応時に発生するフッ酸を中和する受酸剤として金属酸化物を配合することが出来る。また、成型品の補強を目的として、カーボンブラック、シリカ、クレー、珪藻土など無機粉末が一般的に使用されるが、これらの補強剤を添加することもできる。これらの各種添加剤が混練されていても本発明を阻害するものではない。
【０００９】
［加硫工程］
フッ素ゴムの加硫は、通常２段階で行われる。すなわち、生ゴムに所定量の充填剤、加硫剤などを均一に混合したコンパウンドを所定形状の金型中にて圧力１〜１０メガパスカル加えた状態で、温度１５０℃ないし１９０℃に０．１〜１時間保つ。このような加圧と加熱の同時操作は、通常熱プレス装置により行うのが一般的であるが、高圧釜の中に未加硫の成型品を入れて高圧蒸気を吹き込んで加硫する方法もある。この高圧下、加熱する操作を一般に一次加硫と称している。次いで、一次加硫行程の終わった加工品を、無加圧の状態で２００℃前後の温度で、２〜２４時間加熱処理する。この間に加硫はさらに進み、加硫時に発生するガス状物質が揮発し、加硫物の物性は向上する。
この加硫工程は、表１に示した分子構造の違うフッ素ゴムのいずれにも適用できる。
【００１０】
［本発明品の形状］
本発明はフッ素ゴムに関するものであり、いかなる加工形状にも適用できる加工法である。即ち、Ｏ−リング状、チューブ状、シート状、断面が異形の長尺押出品及び電線被覆などに適用できる加工法である。なかんずく加圧下で加熱することが難しい押出成形で成形する長尺成型品に好適に適用される。
【００１１】
【発明が解決しようとする課題】
形状がチューブ状や異形断面を有する長尺ものである場合には、すでに述べた一般的な金型を使用するプレス加硫を採用することが出来ない。このような長尺押出形状品の場合、押し出された未加硫状態のチューブまたは長尺の異形押出品を、加硫釜などの高圧容器に納めて高圧蒸気加硫を行うのが一般的である。本発明者らもこの方法により、断面異形形状のフッ素ゴムの一次加硫を試みたが、蒸気加圧下での加熱時に変形し、歪んだ形状の異形品しか得られなかった。また、チューブ形状のフッ素ゴムの加硫を試みたが、チューブは圧力によって潰れて形状を保つことが出来ず、変形した形状の加硫品しか得られなかった。
本発明者らはかかる問題は、圧縮成形、ロール成形、押出成形または射出成形により付形された未加硫フッ素ゴムコンパウンドに、電離性放射線を照射して予備加硫を行った後、加熱する事により後加硫を行うことを特徴とするフッ素ゴムの加工方法により解決できることを見出した。即ち、高圧蒸気による一次加硫に代えて、押し出された未加硫の異形長尺品に常温常圧下で放射線照射を行い、しかる後常圧下で加熱加硫を行うことにより変形のない加硫された異形押出フッ素ゴム成型品を得ることが出来ることを見出した。
【００１２】
本発明において、付形された未加硫フッ素ゴムコンパウンドは、異形長尺品に限らず、Ｏリングなど金型により付形される形状の物であってもよい。
【００１３】
【発明が解決するための手段】
本発明のフッ素ゴム成形体の製造方法（請求項１）は、付形された未加硫のフッ素ゴムコンパウンドに、加硫剤が分解しない温度で電離性放射線を照射して予備加橋を行った後、加硫剤が分解する温度で後加硫を行うことを特徴とする。本発明で使用する用語「コンパウンド」とは、生ゴムに少なくとも一種類の加硫剤が必要量均一に混練されたものを意味するものである。
本発明の製造方法において、付形された未加硫フッ素ゴムコンパウンドが、チューブ状未加硫フッ素ゴムコンパウンド（請求項２）、異形断面を有する長尺の未加硫フッ素ゴムコンパウンド（請求項３）またはＯ−リング状未加硫フッ素ゴムコンパウンド（請求項４）であることが好ましい。
また、未加硫のフッ素ゴムコンパウンドが、ビニリデン系フッ素ゴム（請求項５）あるいはパーフルオロアルキルビニルエーテル（請求項６）を主成分としたものであることが好ましい。さらに、パーフルオロアルキルビニルエーテルがパーフルオロメチルビニルエーテルであることが好ましい。
【００１４】
【作用および発明の効果】
本発明のフッ素ゴム成形体の製造方法（請求項１）は、付形された未加硫のフッ素ゴムコンパウンドを、加硫剤が分解しない温度で電離性放射線を照射して予備架橋を行うため、加硫剤の分解による発泡などが発生しない。つまり、その発泡による成形体の変形を防ぐために予備架橋を高圧などの過酷な条件で行う必要がなく、添加剤等の種類も減らすことができる。そのため、付形された未加硫のフッ素ゴムコンパウンドを変形させることなく予備架橋ができる。予備架橋されたフッ素ゴムコンパウンドは、塑性流れが減少し、弾性が増大する。そのため、この予備架橋されたフッ素ゴムコンパウンドを加硫剤が分解する温度で、さらに高圧などの過酷な条件で後加硫を行っても、加硫反応により微量の水分や加硫剤の分解物がガス状になって発生するが、電離性放射線の照射により前架橋が進んでいるので、加工品がスポンジ状になったり型くずれが起る事はない。これに対し、電離性放射線の照射による前架橋をせず加熱加硫のみ行う場合は、コンパウンドの粘度が加熱により低下して、発生するガスにより発泡してスポンジ状の不良品となり、複雑な形状品の場合は、粘度低下により型くずれが起って不良品しか得られない。これに対し、本発明の製造方法ではこれらを防止することができる。
【００１５】
前記付形された未加硫フッ素ゴムコンパウンドが、チューブ状未加硫フッ素ゴムコンパウンドである場合（請求項２）、本発明の製造方法を用いることで、チューブ形状がつぶれることなく製造することができる。また、付形された未加硫フッ素ゴムコンパウンドが、Ｏ−リング状のフッ素ゴムコンパウンドまたは異形断面を有する長尺の未加硫フッ素ゴムコンパウンドである場合（請求項３、４）、蒸気加圧下での加熱時に変形し、歪んだ形状の異形品などの製造を防ぐことができる。また、金型を用いる必要がないため、製造段階を簡素化でき、製造コストも抑えることができる。
【００１６】
本発明の製造方法は、前記未加硫フッ素コンパウンドが、ビニリデン系フッ素ゴム（請求項５）あるいは、パーフルオロアルキルビニルエーテル（請求項６）を主成分としたものである場合、前述した作用及び効果を最大限に奏することができる。また、特にパーフルオロアルキルビニルエーテルがパーフルオロメチルビニルエーテルである場合優れている。
【００１７】
【発明の実施の形態】
次に図面を参照しながら本発明のフッ素ゴム成形体の実施形態を説明する。図１は本発明のフッ素ゴム成形体の実施形態であるフッ素ゴムチューブを示す断面図であり、図２は本発明のフッ素ゴム成形体の他の実施形態である正六角形断面を有するフッ素ゴム成形体の長尺を示す断面図であり、図３は本発明のフッ素ゴム成形体の他の実施形態であるＯ−リングを示す断面図である。
【００１８】
図１のフッ素ゴムチューブ１はフッ素ゴムコンパウンドをチューブ状に押出成形にて成形された、未加硫のフッ素ゴムチューブを予備架橋を行い、さらに、後加硫を行い製造する。
【００１９】
未加硫のフッ素ゴムチューブは、金型が取り付けられた一台のスクリュー押出機により製造することができる。フッ素ゴムコンパウンドを溶融し、押出機を用いて押出す。フッ素ゴムコンパウンドがこの押出機を用いて押出される。この連続した未加硫のフッ素ゴムチューブにガンマー線を常温常圧で５〜５００ｋＧｙ（キログレイ）照射し、予備架橋を行った。
その後、予備架橋された未加硫フッ素ゴムチューブを電気炉中で加硫剤の分解温度以上の温度で１０〜５０時間加熱加硫を行う。この加硫反応により微量の水分や加硫剤の分解物がガス状になって発生するが、電離性放射線の照射により前架橋が進んでいるので、加工品がスポンジ状になったり型くずれが起る等を防ぐことができる。この加熱温度は加硫剤によって異なるが、１５０〜３００℃が好ましい。このフッ素ゴムチューブの大きさは、特に限定されるものではないがチューブ内径０．１〜１００ｍｍ程度、チューブ外径０．５〜２００ｍｍ程度のものが好ましい。これにより、フッ素ゴムチューブを変形させる事なく製造することができる。
【００２０】
［電離性放射線の照射］
電離性放射線としては、Ｘ線、ガンマ線などがあるが、最も簡便に用いられるのは、コバルト６０を線源とするガンマ線がある。照射温度は特に規定されるものではないが、フッ素ゴムコンパウンド中の加硫剤が分解しない温度、通常は８０℃以下が好ましく、特に常温での照射が特別な加熱装置などを使う必要がなく有利である。
照射する線量は、引き続く加熱処理時に発泡することなく、かつ型くずれする事がない程度に架橋することが望ましい。５ｋＧｙ以下では放射線架橋の効果が薄く、３００ｋＧｙ以上では材料の劣化を招くおそれがあるため、５ないし３００ＫＧｙ（キログレイ）、就中１０ないし１００ＫＧｙが好ましい。
【００２１】
図３の正六角形断面を有するフッ素ゴム成形体２は、押出成形により成形される未加硫のフッ素ゴム成形体に前述した放射線による予備架橋および電気炉での加熱を順番に行うことで得ることができる。これにより、従来用いていた圧縮用金型を用いることなく、架橋することができる。
【００２２】
図４のＯ−リング３は、溶融したフッ素ゴムコンパウンドをＯ−リング用の金型に流し込み、その後冷却して生成した未加硫のフッ素ゴム成形体に前述した放射線による予備架橋および電気炉での加熱を順番におこなうことで得ることができる。
【００２３】
【実施例】
次に本発明を実施例に従ってさらに詳しく説明する。
［実施例１］
フッ素ゴムとして、ダイキン工業（株）が市販するダイエルＧ−９０２（第１表のタイプＩＩ相当）とダイエルパーフルオロＧＡ−５５（第１表のタイプＶＩ相当）を用意した。いずれのコンパウンドも、生ゴム１００重量部に対して、加硫剤としてジクミールパーオキサイド１．５重量部、加硫助剤としてトリアリルイソシアヌレート４重量部、補強剤としてＭＴカーボン２０重量部が均一に混練されている。
これらのコンパウンドを、図４に示すごとく金型Ｉを介して配置されたａ、ｂ２台のスクリュー押出機のうち、ｂにダイエルパーフルオロＧＡ−５５コンパウンドを、ａにダイエルＧ−９０２コンパウンドをチャージした。
使用したスクリュー押出機ｂのシリンダー径は３０ミリ、Ｌ／Ｄは２５であり、押出機ａのシリンダー径は、４０ミリ、Ｌ／Ｄは２５である。いずれの押出機も、ホッパー側から４ゾーンに分けて温度調節を行い、各ゾーンの温度を６０℃、６５℃、７０℃、７５℃に保った。金型温度は７５℃である。
金型Ｉの概略組立図を図５に示した。この金型は、外径６ミリ、内径４ミリ、全体の肉厚１ミリのチューブが押し出されるように製作されており、内外層の厚みは、押出機ａ、ｂのスクリュー回転数を制御する事により調節できる。本実施例では、押出機ｂのスクリュー回転数を５ｒｐｍ、押出機ａのスクリュー回転数を１５ｒｐｍで行い、内層厚み０．２ｍｍの分子中にパーフルオロアルキルビニルエーテルを含むフッ素ゴム、外層厚み０．８ｍｍの分子中にパーフルオロアルキルビニルエーテルを含まないフッ素ゴムで構成された、未加硫２層チューブを押し出すことが出来た。チューブの線速は、４．２ｍ／ｍｉｎ．であった。
未加硫２層チューブは、内径４ミリ、外径６ミリで内外層の厚みもほぼ設計通りであった。次いで、この連続した未加硫２層チューブから１５メートルを切り取り、コバルト６０を線源とするガンマ線を５０ＫＧｙ照射して予備加硫を行った。その後さらに電気炉中で１８０℃で５時間加熱加硫を行ない、加硫２層チューブを得た。加熱加硫中に発泡することも型くずれも起らなかった。
【００２４】
［比較例１］
実施例１の押出工程で得られた未加硫２層チューブを１５メートル切り取り、電離性放射線を照射することなく電気炉中で１８０℃で５時間加熱加硫を行った。得られた物は、加硫反応は進んでいたが、形状は潰れてチューブ状を保ち得ず、且つ発泡が見られた。
【００２５】
［実施例２］
シリンダー径４０ミリ、Ｌ／Ｄ２５の押出機を用いて、それぞれダイキン工業（株）が市販するダイエルＧ−７０２（第１表のタイプＩ相当）、ダイエルＧ−９０２（第１表のタイプＩＩ相当）、ダイエルＧ−５０１（第１表のタイプＩＩ相当）、およびダイエルパーフルオロＧＡ−５５（第１表のタイプＶＩ相当）の各種未加硫フッ素ゴムコンパウンドを押出してチューブを得た。チューブの外径は６ミリ、内径４ミリ、全体の肉厚１ミリである。いずれの材料も押出条件は同一である。即ち、シリンダーの温度条件はホッパー側から４ゾーンに分けて６０℃、６５℃、７０℃、７５℃に保った。金型温度は７５℃である。押出機のスクリュー回転数を１８ｒｐｍで行い、チューブ押出の線速は、ゴム材料の種類により多少異なるが、４．２ｍ／ｍｉｎ．前後であった。
次いで、各未加硫押出チューブ１５メートルに、コバルト６０を線源とするガンマ線を５０ＫＧｙ照射した後に、１８０℃で５時間加熱処理した。いずれのチューブも型くずれも発泡もなく、充分使用に耐えるものであった。
【００２６】
【表２】
（注１）テトラブチルアンモニュウムヒドロキシド
（注２）Ｎ，Ｎ−ジシンナミリデン−１，６−ヘキサンジアミン（ダイキン工業の商品名）
（注３）２，５−ジメチル−２，５−ジ−ｔ−ブチルパーオキシヘキサン（日本油脂）
【００２８】
［実施例３］
実施例２で得られた加硫チューブのチューブポンプテストを行った。使用したチューブポンプは、（株）アズワンから発売されている、カートリッジチューブポンプＣＴＰ−３である。使用した液体は水である。結果を表３に示した。
【００２９】
【表３】
【００３０】
この結果実施例２で得られた加硫後の各種フッ素ゴムチューブは、充分実用に耐えるものであることが明らかとなった。
【００３１】
［比較例２］
実施例２の押出工程で得られた未加硫チューブを１５メートル切り取り、電離性放射線を照射することなく電気炉中で１８０℃で５時間加熱加硫を行った。得られた物は、加硫反応は進んでいたが、形状は潰れてチューブ状を保ち得ず、且つ発泡が見られた。
【００３２】
【発明の効果】
本発明のフッ素ゴムの加工方法、即ち、圧縮成形、ロール成形、押出成形または射出成形により付形された未加硫フッ素ゴムコンパウンドに、電離性放射線を照射して予備加硫を行った後、加熱する事により後加硫を行うことを特徴とするフッ素ゴムの加工方法は、異形断面を有する長尺成型品、例えばフッ素ゴムチューブの成形加工に特に有効な方法である。
【図面の簡単な説明】
【図１】本発明のフッ素ゴム成形体の実施形態であるフッ素ゴムチューブを示す断面図である。
【図２】本発明のフッ素ゴム成形体の他の実施形態である正六角形断面を有するフッ素ゴム成形体を示す断面図である。
【図３】本発明のフッ素ゴム成形体の他の実施形態であるＯ−リングを示す断面図である。
【図４】本発明の二層フッ素ゴムチューブを成形する押出機配置概念図を示した一例である。
【図５】本発明の二層フッ素ゴムチューブを成形する金型略図の一例である。
【符号の説明】
１ フッ素ゴムチューブ
２ フッ素ゴム成形体
３ Ｏ−リング
ａ 押出し機
ｂ 押出し機
ｃ スクリュー
Ｉ 金型[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a special rubber molded article having excellent heat resistance, chemical resistance and the like. Specifically, the present invention relates to a method for producing a fluororubber molded article.
[0002]
[Prior art]
In recent years, fluororubber has been marketed as an elastic body having excellent heat resistance and chemical resistance, and processed products thereof have been used in various shapes in various fields. Examples of the fields used are the semiconductor industry, the chemical industry, the medical and pharmaceutical fields, and the shapes are sealing material shapes represented by various O-rings, tube shapes, and sections having irregular shapes. There is a long shape product, a flexible sheet shape, and the like.
[0003]
[Definition of fluororubber]
The term “fluororubber” used in the present invention refers to a rubber material which is a polymer in which carbon atoms are linked in a chain by covalent bonds and which has fluorine in the molecule in a bonded state and exhibits elasticity at normal temperature.
Thus, various fluororubbers have already been developed and used in all industrial fields. Fluorine rubber is generally excellent in chemical resistance and heat resistance as compared with other synthetic rubbers, but has a difference in properties due to differences in molecular structure when viewed in detail. For example, some types of fluororubber exhibit strong resistance to strong acids but do not exhibit resistance to strong alkalis, but some fluororubbers exhibit strong resistance to both strong alkalis and strong acids. Table 1 shows the molecular structure and general properties of typical commercially available fluororubbers.
[0004]
[Table 1]
note)
VF2: vinylidene fluoride CF 2 ＣＦCF 2
HFP: hexafluoropropylene CF 2 = CFCF 3
TFE: tetrafluoroethylene CF 2 ＣＦCF 2
PMVE: perfluoromethyl vinyl ether CF 2 ＣＦCFO (CF 3 )
Pr: propylene CH 2 ＣＨCHCH 3
E: ethylene CH 2 ＣＨCH 2
*: Relative value when the type I rubber is set to 1 **: "-" indicates copolymerization. For example, VF2-HFP means vinylidene fluoride and hexafluoropropylene copolymer.
[0006]
Type I fluororubber is commercially available from Daikin Industries, Ltd., as No. 700 Series (Series), and from DuPont Co., Ltd., as Viton A type. The Thai II fluororubber is commercially available from Daikin Industries, Ltd., as a 900 series (series) and from DuPont, Inc., as Viton B type. Type III fluororubber is commercially available from Asahi Glass Co., Ltd. under the trade name KF Polymer. Type IV fluororubber is commercially available from DuPont under the trade name Viton GLT. Type V fluororubber is commercially available from DuPont under the trade name Viton ETP. Type VI fluororubber is commercially available from Daikin Industries, Ltd. under the trade name Daiel Perfluoro, and from DuPont, under the trade name Kalrez.
The type I, II, and IV fluororubbers shown in Table 1 are vinylidene-based fluororubbers containing vinylidene fluoride as a main component, and the types IV, V, and VI fluororubbers are both perfluorovinylether (PMVE). It is a fluororubber obtained by polymerization.
As can be seen from Table 1, the performance of type VI fluororubber is the best, but the cost is extremely high. Next, the performances of Type IV and Type V are good, but the cost is about 10 times that of Type I. What all of them have in common is that PMVE is included in the molecule, and fluororubber copolymerized with this monomer generally has various properties such as alkali resistance, acid resistance, oil resistance, chemical resistance, and heat resistance. Excellent properties. However, PMVE cannot be manufactured at low cost with current technology, and the cost of fluororubber containing PMVE inevitably increases.
[0007]
[Blend of rubber material used]
The fluororubber used in the present invention may be used alone, but usually, in addition to a vulcanizing agent, a reinforcing agent, and if necessary, a processing aid, a plasticizer, a coloring agent, and the like are added as a filler.
For vulcanizing the fluororubber, amine vulcanizing agents, polyol vulcanizing agents and peroxide vulcanizing agents are used. In the present invention, any vulcanizing agent can be used. As the peroxide-based vulcanizing agent, a combination of an organic peroxide such as dicumyl peroxide and triallyl isocyanurate (TAIC) is generally used. As the polyol vulcanizing agent, a combination of an ammonium salt or a phosphonium salt with bisphenol A or bisphenol AF is used. Hexamethylene diamine carbamate and the like can be used as the amine vulcanizing agent.
These vulcanizing agents, vulcanizing aids, reinforcing agents and other additives have the characteristic that they can be used almost in common even with fluororubbers having different molecular structures.
[0008]
Additives other than the vulcanizing agent, for example, a metal oxide can be blended as an acid acceptor for neutralizing hydrofluoric acid generated during the vulcanization reaction. In addition, inorganic powders such as carbon black, silica, clay, and diatomaceous earth are generally used for the purpose of reinforcing a molded product. These reinforcing agents can be added. Even if these various additives are kneaded, the present invention is not inhibited.
[0009]
[Vulcanization process]
Vulcanization of fluororubber is usually performed in two stages. That is, a compound obtained by uniformly mixing a predetermined amount of a filler, a vulcanizing agent, and the like with raw rubber is applied in a mold having a predetermined shape at a pressure of 1 to 10 megapascals. Hold for ~ 1 hour. Such simultaneous operation of pressurization and heating is generally performed by a hot press device, but a method of vulcanizing by putting an unvulcanized molded product in a high-pressure pot and blowing high-pressure steam is also available. is there. The operation of heating under this high pressure is generally called primary vulcanization. Next, the processed product after the primary vulcanization process is heat-treated at a temperature of about 200 ° C. for 2 to 24 hours without pressurization. During this time, vulcanization further proceeds, and gaseous substances generated during vulcanization are volatilized, and the physical properties of the vulcanized product are improved.
This vulcanization step can be applied to any of the fluororubbers having different molecular structures shown in Table 1.
[0010]
[Shape of the product of the present invention]
The present invention relates to fluororubber and is a processing method applicable to any processing shape. That is, it is a processing method that can be applied to an O-ring shape, a tube shape, a sheet shape, a long extruded product having an irregular cross section, a wire coating, and the like. In particular, it is suitably applied to a long molded product formed by extrusion molding, which is difficult to heat under pressure.
[0011]
[Problems to be solved by the invention]
When the shape is a long shape having a tubular shape or an irregular cross section, the press vulcanization using a general mold described above cannot be adopted. In the case of such a long extruded product, it is common to carry out high-pressure steam vulcanization by placing the extruded unvulcanized tube or long extruded product in a high-pressure container such as a vulcanizing pot. is there. The present inventors have also attempted primary vulcanization of a fluororubber having an irregular cross-sectional shape by this method, but only deformed deformed shapes were obtained upon heating under steam pressurization. Further, an attempt was made to vulcanize the tube-shaped fluororubber, but the tube was crushed by pressure and could not maintain its shape, and only a vulcanized product having a deformed shape was obtained.
The present inventors have found that the problem is that the unvulcanized fluoro rubber compound formed by compression molding, roll molding, extrusion molding or injection molding is irradiated with ionizing radiation, pre-vulcanized, and then heated. It has been found that this problem can be solved by a fluororubber processing method characterized by performing post-vulcanization. That is, in place of primary vulcanization by high-pressure steam, the extruded unvulcanized shaped and elongated product is irradiated with radiation at normal temperature and normal pressure, and then vulcanization without deformation is performed by heating and vulcanizing under normal pressure. It has been found that a shaped extruded fluororubber molded article can be obtained.
[0012]
In the present invention, the shaped unvulcanized fluororubber compound is not limited to a deformed long product, and may be a shape shaped by a mold such as an O-ring.
[0013]
Means for Solving the Invention
In the method for producing a fluororubber molded article of the present invention (claim 1), a pre-crosslinking is performed by irradiating the shaped unvulcanized fluororubber compound with ionizing radiation at a temperature at which the vulcanizing agent does not decompose. After that, post-vulcanization is performed at a temperature at which the vulcanizing agent decomposes. The term “compound” used in the present invention means a raw rubber obtained by uniformly kneading at least one kind of vulcanizing agent in a required amount.
In the production method of the present invention, the shaped unvulcanized fluororubber compound is a tubular unvulcanized fluororubber compound (Claim 2) or a long unvulcanized fluororubber compound having a modified cross section (Claim 3). ) Or an O-ring unvulcanized fluoro rubber compound (claim 4).
Further, it is preferable that the unvulcanized fluorine rubber compound is mainly composed of vinylidene fluorine rubber (claim 5) or perfluoroalkyl vinyl ether (claim 6). Further, it is preferable that the perfluoroalkyl vinyl ether is perfluoromethyl vinyl ether.
[0014]
[Action and effect of the invention]
In the method for producing a fluororubber molded article of the present invention (claim 1), a pre-crosslinking is performed by irradiating the shaped unvulcanized fluororubber compound with ionizing radiation at a temperature at which the vulcanizing agent does not decompose. Also, foaming due to decomposition of the vulcanizing agent does not occur. That is, it is not necessary to perform preliminary crosslinking under severe conditions such as high pressure in order to prevent deformation of the molded article due to the foaming, and the types of additives and the like can be reduced. Therefore, pre-crosslinking can be performed without deforming the shaped unvulcanized fluororubber compound. The pre-crosslinked fluororubber compound has reduced plastic flow and increased elasticity. Therefore, even if the vulcanizing agent decomposes this pre-crosslinked fluororubber compound at a temperature at which the vulcanizing agent decomposes, and even under severe conditions such as high pressure, the vulcanization reaction causes a small amount of moisture or the decomposition product of the vulcanizing agent. Are generated in a gaseous state, but since the pre-crosslinking proceeds by irradiation with ionizing radiation, the processed product does not become sponge-like or lose its shape. On the other hand, when only heat vulcanization is performed without pre-crosslinking by irradiation with ionizing radiation, the viscosity of the compound is reduced by heating, and the compound is foamed by the generated gas, resulting in a sponge-like defective product and a complicated shape. In the case of a product, a mold collapse occurs due to a decrease in viscosity, and only a defective product is obtained. In contrast, the manufacturing method of the present invention can prevent these.
[0015]
When the shaped unvulcanized fluororubber compound is a tubular unvulcanized fluororubber compound (claim 2), by using the production method of the present invention, it is possible to produce the tube without collapsing the tube shape. it can. When the shaped unvulcanized fluororubber compound is an O-ring-shaped fluororubber compound or a long unvulcanized fluororubber compound having an irregular cross-section (claims 3 and 4), In this case, it is possible to prevent the production of deformed and deformed deformed products. Further, since there is no need to use a mold, the manufacturing stage can be simplified and the manufacturing cost can be reduced.
[0016]
According to the production method of the present invention, when the unvulcanized fluorine compound is mainly composed of vinylidene-based fluororubber (Claim 5) or perfluoroalkylvinylether (Claim 6), the above-mentioned action and effect are obtained. Can be played to the maximum. It is particularly excellent when the perfluoroalkyl vinyl ether is perfluoromethyl vinyl ether.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, an embodiment of a fluororubber molded article of the present invention will be described with reference to the drawings. FIG. 1 is a sectional view showing a fluororubber tube which is an embodiment of the fluororubber molded article of the present invention, and FIG. 2 is a fluororubber molded article having a regular hexagonal cross section which is another embodiment of the fluororubber molded article of the present invention. FIG. 3 is a cross-sectional view showing a long body, and FIG. 3 is a cross-sectional view showing an O-ring which is another embodiment of the fluororubber molded body of the present invention.
[0018]
The
[0019]
The unvulcanized fluoro rubber tube can be manufactured by one screw extruder equipped with a mold. The fluororubber compound is melted and extruded using an extruder. A fluororubber compound is extruded using this extruder. The continuous unvulcanized fluororubber tube was irradiated with gamma rays at normal temperature and normal pressure at 5 to 500 kGy (kilo gray) to perform preliminary crosslinking.
Thereafter, the pre-crosslinked unvulcanized fluoro rubber tube is heated and vulcanized in an electric furnace at a temperature not lower than the decomposition temperature of the vulcanizing agent for 10 to 50 hours. This vulcanization reaction produces a slight amount of water and decomposition products of the vulcanizing agent in gaseous form, but the pre-crosslinking has progressed due to the irradiation of ionizing radiation, and the processed product becomes sponge-like or loses its shape. Can be prevented. The heating temperature varies depending on the vulcanizing agent, but is preferably from 150 to 300 ° C. The size of the fluororubber tube is not particularly limited, but a tube having an inner diameter of about 0.1 to 100 mm and an outer diameter of the tube of about 0.5 to 200 mm is preferable. Thereby, it can be manufactured without deforming the fluororubber tube.
[0020]
[Irradiation of ionizing radiation]
Examples of ionizing radiation include X-rays and gamma rays, and the most simple one is a gamma ray using cobalt 60 as a radiation source. The irradiation temperature is not particularly limited, but is preferably a temperature at which the vulcanizing agent in the fluororubber compound does not decompose, usually 80 ° C or lower, and irradiation at room temperature is particularly advantageous because it does not require a special heating device or the like. It is.
The irradiation dose is desirably crosslinked so as not to cause foaming during subsequent heat treatment and to prevent the shape from being lost. If it is 5 kGy or less, the effect of radiation crosslinking is weak, and if it is 300 kGy or more, there is a possibility that the material will be degraded. Therefore, 5 to 300 KGy (kilo gray), especially 10 to 100 KGy is preferable.
[0021]
The fluororubber molded
[0022]
The O-ring 3 shown in FIG. 4 is obtained by pouring the molten fluororubber compound into a mold for the O-ring, and then cooling the resulting unvulcanized fluororubber molded article with the above-mentioned pre-crosslinking by radiation and an electric furnace. Can be obtained by performing the heating in order.
[0023]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[Example 1]
Daiel G-902 (equivalent to Type II in Table 1) and Daiel Perfluoro GA-55 (equivalent to Type VI in Table 1) commercially available from Daikin Industries, Ltd. were prepared as fluororubbers. In each case, 1.5 parts by weight of dicumyl peroxide as a vulcanizing agent, 4 parts by weight of triallyl isocyanurate as a vulcanization aid, and 20 parts by weight of MT carbon as a reinforcing agent were used for 100 parts by weight of raw rubber. Is kneaded.
Of these two screw extruders a and b arranged via a mold I as shown in FIG. 4, these compounds were charged with a Daiel Perfluoro GA-55 compound in b and a Daiel G-902 compound in a. did.
The cylinder diameter of the used screw extruder b is 30 mm and L / D is 25, and the cylinder diameter of the extruder a is 40 mm and L / D is 25. In each extruder, the temperature was adjusted in four zones from the hopper side, and the temperature in each zone was maintained at 60 ° C, 65 ° C, 70 ° C, and 75 ° C. The mold temperature is 75 ° C.
FIG. 5 shows a schematic assembly diagram of the mold I. This mold is manufactured so that a tube having an outer diameter of 6 mm, an inner diameter of 4 mm, and a total wall thickness of 1 mm is extruded. The thickness of the inner and outer layers controls the screw rotation speed of the extruders a and b. It can be adjusted by things. In this example, the screw rotation speed of the extruder b was set to 5 rpm, the screw rotation speed of the extruder a was set to 15 rpm, the inner layer thickness was 0.2 mm, and the outer layer thickness was 0.8 mm. A non-vulcanized two-layer tube composed of a fluororubber containing no perfluoroalkylvinyl ether in the molecule could be extruded. The linear velocity of the tube was 4.2 m / min. Met.
The unvulcanized two-layer tube had an inner diameter of 4 mm and an outer diameter of 6 mm, and the thickness of the inner and outer layers was almost as designed. Next, 15 meters were cut from the continuous unvulcanized two-layer tube, and pre-vulcanized by irradiating 50 KGy of gamma rays using cobalt 60 as a radiation source. Thereafter, the mixture was further vulcanized by heating at 180 ° C. for 5 hours in an electric furnace to obtain a vulcanized two-layer tube. No foaming or shape collapse occurred during the heat vulcanization.
[0024]
[Comparative Example 1]
The unvulcanized two-layer tube obtained in the extrusion step of Example 1 was cut off by 15 m, and was heated and vulcanized at 180 ° C. for 5 hours in an electric furnace without irradiation with ionizing radiation. Although the vulcanization reaction of the obtained product proceeded, the shape was crushed and the tube could not be maintained, and foaming was observed.
[0025]
[Example 2]
Using an extruder with a cylinder diameter of 40 mm and an L / D of 25, Daiel G-702 (equivalent to Type I in Table 1) and G-902 (equivalent to Type II in Table 1) marketed by Daikin Industries, Ltd. ), Daiel G-501 (corresponding to Type II in Table 1), and various unvulcanized fluororubber compounds of Daiel Perfluoro GA-55 (corresponding to Type VI in Table 1) were extruded to obtain tubes. The outer diameter of the tube is 6 mm, the inner diameter is 4 mm, and the overall wall thickness is 1 mm. Extrusion conditions are the same for all materials. That is, the temperature condition of the cylinder was divided into four zones from the hopper side and maintained at 60 ° C, 65 ° C, 70 ° C, and 75 ° C. The mold temperature is 75 ° C. The rotational speed of the screw of the extruder is set at 18 rpm, and the linear speed of the tube extrusion is 4.2 m / min. Before and after.
Next, each unvulcanized extruded tube 15 m was irradiated with 50 KGy of gamma rays using cobalt 60 as a radiation source, and then heated at 180 ° C. for 5 hours. All of the tubes did not lose their shape or foam and were sufficiently usable.
[0026]
[Table 2]
(Note 1) Tetrabutylammonium hydroxide (Note 2) N, N-dicinnamylidene-1,6-hexanediamine (trade name of Daikin Industries)
(Note 3) 2,5-dimethyl-2,5-di-t-butylperoxyhexane (Nippon Oil & Fats)
[0028]
[Example 3]
A tube pump test of the vulcanized tube obtained in Example 2 was performed. The tube pump used is a cartridge tube pump CTP-3 sold by As One Corporation. The liquid used is water. The results are shown in Table 3.
[0029]
[Table 3]
As a result, it became clear that the various vulcanized rubber tubes obtained in Example 2 after vulcanization were sufficiently practical.
[0031]
[Comparative Example 2]
The unvulcanized tube obtained in the extrusion process of Example 2 was cut off by 15 m, and was heated and vulcanized at 180 ° C. for 5 hours in an electric furnace without irradiation with ionizing radiation. Although the vulcanization reaction of the obtained product proceeded, the shape was crushed and the tube could not be maintained, and foaming was observed.
[0032]
【The invention's effect】
Processing method of the fluororubber of the present invention, that is, compression molding, roll molding, unvulcanized fluororubber compound shaped by extrusion molding or injection molding, after pre-vulcanization by irradiating ionizing radiation, The method of processing a fluororubber characterized by performing post-vulcanization by heating is a particularly effective method for forming a long molded article having an irregular cross section, for example, a fluororubber tube.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a fluororubber tube which is an embodiment of a fluororubber molded article of the present invention.
FIG. 2 is a cross-sectional view showing a fluororubber molded article having a regular hexagonal cross section, which is another embodiment of the fluororubber molded article of the present invention.
FIG. 3 is a sectional view showing an O-ring as another embodiment of the fluororubber molded article of the present invention.
FIG. 4 is an example showing a conceptual diagram of an arrangement of an extruder for molding the two-layer fluororubber tube of the present invention.
FIG. 5 is an example of a schematic diagram of a mold for molding the two-layer fluororubber tube of the present invention.
[Explanation of symbols]
DESCRIPTION OF
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002331420A JP3979926B2 (en) | 2002-11-14 | 2002-11-14 | Method for producing fluororubber tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002331420A JP3979926B2 (en) | 2002-11-14 | 2002-11-14 | Method for producing fluororubber tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004160902A true JP2004160902A (en) | 2004-06-10 |
| JP3979926B2 JP3979926B2 (en) | 2007-09-19 |
Family
ID=32808778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002331420A Expired - Fee Related JP3979926B2 (en) | 2002-11-14 | 2002-11-14 | Method for producing fluororubber tube |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3979926B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013132889A (en) * | 2011-12-27 | 2013-07-08 | Okuda Corp | Cushioning material for hot pressing |
| WO2014007348A1 (en) * | 2012-07-05 | 2014-01-09 | ダイキン工業株式会社 | Modified fluorine-containing copolymer, fluorine resin molded article, and method for manufacturing fluorine resin molded article |
-
2002
- 2002-11-14 JP JP2002331420A patent/JP3979926B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013132889A (en) * | 2011-12-27 | 2013-07-08 | Okuda Corp | Cushioning material for hot pressing |
| WO2014007348A1 (en) * | 2012-07-05 | 2014-01-09 | ダイキン工業株式会社 | Modified fluorine-containing copolymer, fluorine resin molded article, and method for manufacturing fluorine resin molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3979926B2 (en) | 2007-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7608216B2 (en) | Methods for preparing articles from processable and dimensionally stable elastomer compositions | |
| JP3323284B2 (en) | Composition based on an elastomeric polymer consisting of vinylidene fluoride, hexafluoropropene and optionally tetrafluoroethylene suitable for the production of microporous foamed products | |
| JPH0359937B2 (en) | ||
| EP3467026B1 (en) | Perfluoroelastomer composition and sealing material | |
| KR102414274B1 (en) | Thermoplastic fluorine resin composition and method for producing cross-linked body | |
| US20250205939A1 (en) | Annular seal material and manufacturing method | |
| EP0759354A1 (en) | Laminate of vulcanizable rubber composition layers, process for producing rubber laminate, and rubber laminate | |
| TW201821515A (en) | Perfluoroelastomer composition and sealing material | |
| CN1308411C (en) | Sealing material for semiconductor device and method for production thereof | |
| JP3979925B2 (en) | Fluoro rubber tube and manufacturing method thereof | |
| JPH0966570A (en) | Fluororesin-based molded product, roll and manufacturing method thereof | |
| JP3979926B2 (en) | Method for producing fluororubber tube | |
| JP2013014640A (en) | Fluorine-containing elastomer composition | |
| WO2016060114A1 (en) | Water-vapor-permselective tube | |
| JP3577578B2 (en) | Composite of fluororubber-based thermoplastic elastomer and molded article thereof | |
| US5198502A (en) | Thermoplastic elastomer composition, method for molding the same and molded article of the same | |
| JP2001114964A (en) | Plasma resistant fluoro rubber composition | |
| JP4129946B2 (en) | O-ring and manufacturing method thereof | |
| EP0404239B1 (en) | Thermoplastic elastomer composition, method for molding the same and molded article of the same | |
| JPH073100A (en) | Method for producing fluororubber composition and vulcanized molded article thereof | |
| US20250215976A1 (en) | Annular seal material and manufacturing method | |
| JP3276419B2 (en) | Manufacturing method of fluorine rubber for vacuum | |
| JP3991143B2 (en) | Method for crosslinking chlorine-containing polymer and fluorine-containing polymer | |
| Dow | Perfluoroelastomers and their functionalization | |
| JPH05148399A (en) | Thermally shrinkable fluororubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051111 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070201 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070313 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070514 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070612 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070626 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 3979926 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100706 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100706 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110706 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110706 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120706 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130706 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |