JP4762741B2 - Method for manufacturing structure with PTFE resin molded body bonded - Google Patents
Method for manufacturing structure with PTFE resin molded body bonded Download PDFInfo
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- JP4762741B2 JP4762741B2 JP2006025385A JP2006025385A JP4762741B2 JP 4762741 B2 JP4762741 B2 JP 4762741B2 JP 2006025385 A JP2006025385 A JP 2006025385A JP 2006025385 A JP2006025385 A JP 2006025385A JP 4762741 B2 JP4762741 B2 JP 4762741B2
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- ptfe resin
- molded body
- insulated wire
- inorganic oxide
- polytetrafluoroethylene resin
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims description 133
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims description 133
- 229920005989 resin Polymers 0.000 title claims description 133
- 239000011347 resin Substances 0.000 title claims description 133
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- -1 polytetrafluoroethylene Polymers 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 238000000465 moulding Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- 239000011737 fluorine Substances 0.000 description 17
- 229910052731 fluorine Inorganic materials 0.000 description 17
- 238000000576 coating method Methods 0.000 description 14
- 229920002313 fluoropolymer Polymers 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 13
- 239000004811 fluoropolymer Substances 0.000 description 13
- 238000001246 colloidal dispersion Methods 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229920001973 fluoroelastomer Polymers 0.000 description 10
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000012790 confirmation Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Insulated Conductors (AREA)
Description
本発明は、ポリテトラフルオロエチレン樹脂成型体が接着された構造体、及び、ＰＴＦＥ樹脂成型体の接着方法に係り、特に、初期の密着強度に優れるとともに、高温環境においても優れた密着強度を維持することが可能なものに関する。 The present invention relates to a structure bonded with a polytetrafluoroethylene resin molded body and a method for bonding a PTFE resin molded body. Particularly, the present invention has excellent initial adhesion strength and maintains excellent adhesion strength even in a high temperature environment. About what can be done.
フッ素系ポリマーは、耐熱性、耐油性、耐薬品性などに優れる材料であり、シール部材（ブッシング、グロメット、パッキング、Ｏ−リング）、電線被覆、ホース、チューブ、ロール、ダイヤフラムなど種々の用途で使用されている。特に、ポリテトラフルオロエチレン樹脂（以下、ＰＴＦＥ樹脂と記す。）は、耐熱性に優れ、より過酷な条件下においても使用可能な材料として知られている。このような用途の具体的な例として、例えば、特許文献１のように、高温下で使用されるセンサのリード線被覆材、及び、その外周に配置されるシール部材への適用が知られている。この特許文献１では、リード線被覆材としてＰＴＦＥ樹脂、シール部材としてフッ素ゴムを使用し、リード線をシール部材に挿通した状態で、シール部材を外部からカシメ圧縮し、フッ素ゴムの反発弾性力によってリード線とシール部材の間の水密性を得ることが開示されている。しかしながら、この特許文献１のような場合、フッ素ゴムの圧縮永久歪により反発弾性力が得られなくなる点、圧縮により防水シールに割れが発生する点、高温での圧縮によってＰＴＦＥ樹脂が加熱変形し、リード線被覆材が肉痩せしてしまう点が問題点として挙げられている。 Fluoropolymer is a material that excels in heat resistance, oil resistance, chemical resistance, etc., and is used in various applications such as seal members (bushings, grommets, packing, O-rings), wire coating, hoses, tubes, rolls, diaphragms, etc. in use. In particular, polytetrafluoroethylene resin (hereinafter referred to as PTFE resin) is known as a material that has excellent heat resistance and can be used even under more severe conditions. As a specific example of such an application, for example, as disclosed in Patent Document 1, application to a lead wire covering material of a sensor used at a high temperature and a seal member disposed on the outer periphery thereof is known. Yes. In this Patent Document 1, PTFE resin is used as a lead wire covering material, and fluororubber is used as a seal member. With the lead wire inserted into the seal member, the seal member is caulked and compressed from the outside by the repulsive elastic force of the fluororubber. It is disclosed to obtain water tightness between the lead wire and the seal member. However, in the case of this Patent Document 1, the point where the rebound elastic force cannot be obtained due to the compression set of the fluororubber, the point where the waterproof seal is cracked due to the compression, the PTFE resin is thermally deformed due to the compression at a high temperature, The problem that the lead wire covering material is thin is cited as a problem.
この問題を解消する方法としては、ＰＴＦＥ樹脂からなるリード線被覆材とフッ素ゴムからなるシール部材を接着することにより水密性を保つことが考えられる。しかしながら、ＰＴＦＥ樹脂は、接着が非常に困難な材料であるため、その接着技術については、これまで種々の検討が重ねられてきた。例えば、特許文献２には、ＰＴＦＥ樹脂からなるリード線の被覆膜と、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体樹脂（以下、ＰＦＡ樹脂と記す。）やテトラフルオロエチレン−ヘキサフルオロプロピレン共重合体樹脂のシール部材との接着に関し、上記シール部材を加熱することによって溶融させ、リード線の被覆膜とシール部材とを接着する技術が開示されている。 As a method for solving this problem, it is conceivable to maintain water tightness by bonding a lead wire covering material made of PTFE resin and a seal member made of fluoro rubber. However, since PTFE resin is a material that is very difficult to bond, various studies have been repeated on its bonding technology. For example, Patent Document 2 discloses a lead wire coating film made of PTFE resin, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (hereinafter referred to as PFA resin), and a tetrafluoroethylene-hexafluoropropylene copolymer. Regarding the adhesion of the polymer resin to the seal member, a technique is disclosed in which the seal member is melted by heating to bond the lead wire coating film and the seal member.
又、特許文献３には、ＰＴＦＥ樹脂からなる絶縁電線及びシール部材の接着に関し、絶縁電線又はシール部材のいずれか一方のＰＴＦＥ樹脂にＰＦＡ樹脂を混合し、加熱加圧によりＰＦＡ樹脂を溶融させ、絶縁電線とシール部材を接着する技術が開示されている。 Patent Document 3 relates to the bonding of an insulated wire and a seal member made of PTFE resin, mixing PFA resin with either PTFE resin of the insulated wire or seal member, melting the PFA resin by heating and pressurization, A technique for bonding an insulated wire and a seal member is disclosed.
又、特許文献４には、フッ素樹脂層（ＰＴＦＥ樹脂を含む）とパーフルオロゴム層の間にシランカップリング剤等を主成分とした接着層を形成し、フッ素樹脂層とパーフルオロゴム層を接着して積層体を得る技術が開示されている。 In Patent Document 4, an adhesive layer mainly composed of a silane coupling agent or the like is formed between a fluororesin layer (including PTFE resin) and a perfluororubber layer, and the fluororesin layer and the perfluororubber layer are provided. A technique for obtaining a laminate by bonding is disclosed.
又、特許文献５には、フッ素含有樹脂（ＰＴＦＥ樹脂を含む）からなるリード線被覆材とフッ素含有樹脂（ＰＴＦＥ樹脂を含む）からなるシール部材の間に金属膜を介在させることにより、リード線被覆材とシール部材を接着する技術が開示されている。 Patent Document 5 discloses a lead wire by interposing a metal film between a lead wire covering material made of a fluorine-containing resin (including PTFE resin) and a seal member made of a fluorine-containing resin (including PTFE resin). A technique for bonding a covering material and a seal member is disclosed.
又、高温での圧縮によるＰＴＦＥ樹脂の加熱変形を防止する技術として、例えば、特許文献６には、ＰＴＦＥ樹脂粉末にガラスビーズなどのガラス粉末、シリカ粉末、アルミナ粉末等の充填材を混合して製造したＰＴＦＥ樹脂造粒粉末によるＰＴＦＥ樹脂成型体が開示されている。ここで、充填材としては、粒径２００〜１０００μｍ程度のものが使用されている。 In addition, as a technique for preventing heat deformation of PTFE resin due to compression at high temperature, for example, in Patent Document 6, a filler such as glass powder such as glass beads, silica powder, and alumina powder is mixed with PTFE resin powder. A PTFE resin molding using the produced PTFE resin granulated powder is disclosed. Here, a filler having a particle size of about 200 to 1000 μm is used.
尚、本発明に関連するものとして、当該出願人から特許文献７が出願されている。
しかしながら、上記特許文献２〜５による接着方法は、初期の密着強度こそ優れたものが得られるものの、高温環境下での長期間の使用により、徐々に密着強度が低下し、水密性が低下してしまう恐れがあるという問題がある。又、特許文献４のようにシランカップリング剤等を主成分とした接着層を形成する場合、フッ素系ポリマーは撥水性が高いため、接着層の形成自体が非常に困難という問題もある。 However, although the adhesion methods according to Patent Documents 2 to 5 are excellent in initial adhesion strength, the adhesion strength gradually decreases and the watertightness decreases due to long-term use in a high temperature environment. There is a problem that there is a risk that. Further, when forming an adhesive layer containing a silane coupling agent or the like as a main component as in Patent Document 4, there is a problem that the formation of the adhesive layer itself is very difficult because the fluorine-based polymer has high water repellency.
又、上記特許文献６によるＰＴＦＥ樹脂成型体は、高温での圧縮による加熱変形の防止には一定の効果が得られるものの、十分な水密性を得るには至っていない。そのため、このＰＴＦＥ樹脂成型体とフッ素系ポリマーシール部材とを接着させることも考えられるのだが、このＰＴＦＥ樹脂成型体も、充填材を混合していないＰＴＦＥ樹脂成型体と同様に接着が困難なものである。これは、充填材がＰＴＦＥ樹脂成型体の表面に現れていないため、ＰＴＦＥ樹脂成型体の表面状態が充填材を混合していないものと何ら変わりないことが原因である。ここで、充填材がＰＴＦＥ樹脂成型体の表面に現れるように、充填材の混合量を増加すると、充填材の粒径が粗大であるためＰＴＦＥ樹脂成型体がポーラスな状態になってしまい、成型体の機械的強度が大幅に低下してしまうことになる。又、粒径が小さい充填材を混合した場合は、充填材の粒子同士が凝集してしまうため、結果的に粒径が粗大のものを使用した場合と同じ結果となってしまう。 Moreover, although the PTFE resin molding by the said patent document 6 has a certain effect for prevention of the heat deformation by compression at high temperature, it has not reached sufficient water-tightness. For this reason, it is conceivable to bond this PTFE resin molded body to a fluoropolymer seal member, but this PTFE resin molded body is also difficult to bond in the same manner as a PTFE resin molded body in which no filler is mixed. It is. This is because the filler does not appear on the surface of the PTFE resin molding, and therefore the surface state of the PTFE resin molding is not different from that in which the filler is not mixed. Here, when the mixing amount of the filler is increased so that the filler appears on the surface of the PTFE resin molded body, the PTFE resin molded body becomes porous due to the coarse particle size of the filler. The mechanical strength of the body will be greatly reduced. Further, when a filler having a small particle size is mixed, the particles of the filler are aggregated, and as a result, the same result as when a coarse particle size is used is obtained.
本発明は、このような従来技術の問題を解決するためになされたものであって、その目的とするところは、初期の密着強度に優れるとともに、高温環境においても優れた密着強度を維持することが可能なＰＴＦＥ樹脂成型体が接着された構造体、及び、ＰＴＦＥ樹脂成型体の接着方法を提供することにある。 The present invention has been made to solve such problems of the prior art, and the object thereof is to maintain excellent adhesion strength even in a high temperature environment as well as excellent initial adhesion strength. An object of the present invention is to provide a structure to which a PTFE resin molding that can be bonded is bonded, and a method for bonding the PTFE resin molding.
上記目的を達成するべく、本発明の請求項１によるＰＴＦＥ樹脂成型体が接着された構造体の製造方法は、ポリテトラフルオロエチレン樹脂成型体と、他の部材とが接着された構造体の製造方法であって、上記ポリテトラフルオロエチレン樹脂成型体として、未焼成且つ多孔質のポリテトラフルオロエチレン樹脂からなる成型体を、処理液に含浸させた後、上記ポリテトラフルオロエチレン樹脂を焼成することによって得られたものを用い、且つ、上記処理液として、焼成後に無機酸化物が残存するものを用いるとともに、上記ポリテトラフルオロエチレン樹脂の焼成により、ポリテトラフルオロエチレン樹脂成型体の表面において、上記無機酸化物の一部を埋め込まれるような状態に保持させることを特徴とするものである。
又、請求項２によるＰＴＦＥ樹脂成型体が接着された構造体の製造方法は、上記処理液は、上記無機酸化物が、焼成後に少なくとも一部が０．５μｍ以下の粒径で残存するものであることを特徴とするものである。
又、請求項３によるＰＴＦＥ樹脂成型体が接着された構造体の製造方法は、上記処理液は、シリカを含有するものであることを特徴とするものである。
又、請求項４によるＰＴＦＥ樹脂成型体が接着された構造体の製造方法は、上記処理液は、有機シラン化合物を含有するものであることを特徴とするものである。
To achieve the above object, a manufacturing method of claim 1 is PTFE resin molded body is adhered by the structure of the present invention, the production of a polytetrafluoroethylene resin molded body and the other member and are bonded structure A method comprising impregnating a treatment liquid with a molded body made of an unfired and porous polytetrafluoroethylene resin as the polytetrafluoroethylene resin molded body, and then firing the polytetrafluoroethylene resin. used those obtained by, and, as the treatment solution, with using those inorganic oxide remains after firing, the firing of the polytetrafluoroethylene resin, the surface of the polytetrafluoroethylene resin molded body, the It is characterized in that a part of the inorganic oxide is kept buried .
According to a second aspect of the present invention, there is provided a method for producing a structure to which a molded PTFE resin is adhered , wherein the treatment liquid is such that the inorganic oxide remains at least partially with a particle size of 0.5 μm or less after firing. It is characterized by being.
According to a third aspect of the present invention, there is provided a method for producing a structure to which a molded PTFE resin is adhered , wherein the treatment liquid contains silica.
According to a fourth aspect of the present invention, there is provided a method for producing a structure to which a molded PTFE resin is adhered , wherein the treatment liquid contains an organosilane compound.
本発明においては、無機酸化物の少なくとも一部が０．５μｍ以下の粒径で分散されていることから、この無機酸化物は極めて大きな表面積を有することになる。そのため、例えば、ＰＴＦＥ樹脂成型体を他部材と接着させる際には、この他の部材に含有されるフィラー成分や金属成分などと無機酸化物の接触面積が増加するため、優れた密着強度をもって他の部材と接着させることができる。しかも、ＰＴＦＥ樹脂成型体の表面において、無機酸化物の一部が埋め込まれるような状態となって確実に保持されることになるため、高温下においても優れた密着強度が持続することになる。
又、本発明のような接着方法であれば、多孔質のＰＴＦＥ樹脂の孔の部分に処理液が侵入し、焼成によりＰＴＦＥ樹脂の孔が閉じられ無機酸化物が保持されることになる。そのため、ＰＴＦＥ樹脂成型体の表面において、無機酸化物の一部が埋め込まれるような状態となって確実に保持されることになる。又、焼成の際の加熱により無機酸化物をＰＴＦＥ樹脂成型体に保持させることになるため、無機酸化物が凝集することなく小さい粒径を保ったままＰＴＦＥ樹脂成型体に分散されることになる。
従って、本発明によれば、初期の密着強度に優れるとともに、高温環境においても優れた密着強度を維持することが可能なＰＴＦＥ樹脂成型体が接着された構造体、及び、ＰＴＦＥ樹脂成型体の接着方法を得ることができる。
In the present invention, since at least a part of the inorganic oxide is dispersed with a particle size of 0.5 μm or less, the inorganic oxide has a very large surface area. Therefore, for example, when a PTFE resin molded body is bonded to another member, the contact area between the filler component, metal component, etc. contained in the other member and the inorganic oxide increases. It can be made to adhere to. In addition, since the surface of the PTFE resin molding is surely held in a state in which a part of the inorganic oxide is embedded, excellent adhesion strength is maintained even at high temperatures.
Further, in the case of the adhesion method as in the present invention, the treatment liquid enters the hole portion of the porous PTFE resin, and the pores of the PTFE resin are closed by baking to retain the inorganic oxide. Therefore, on the surface of the PTFE resin molded body, a part of the inorganic oxide is embedded and reliably held. Moreover, since the inorganic oxide is held in the PTFE resin molding by heating at the time of firing, the inorganic oxide is dispersed in the PTFE resin molding while maintaining a small particle size without agglomeration. .
Therefore, according to the present invention, the structure to which the PTFE resin molded body that is excellent in the initial adhesion strength and can maintain the excellent adhesion strength even in a high-temperature environment is bonded, and the PTFE resin molded body is bonded. You can get the method.
以下に、図１を参照して本発明による実施の形態１を説明する。尚、本実施の形態１は、ＰＴＦＥ樹脂絶縁電線とフッ素ゴムシール部材の接着に適用したものである。 A first embodiment of the present invention will be described below with reference to FIG. In addition, this Embodiment 1 is applied to adhesion | attachment of a PTFE resin insulated wire and a fluororubber seal member.
まず、ＰＴＦＥ樹脂粉末と市販の石油系押出助剤を混合したものを所定時間熟成した後、シリンダーに充填して加圧しＰＴＦＥ樹脂プリフォームを調整した。次いで、このＰＴＦＥ樹脂プリフォームをペースト押出機によって、ニッケルメッキ銅被覆鋼線からなる中心導体１ａの外周に押出被覆した後、２００℃の加熱炉に通して押出助剤を乾燥除去し、未焼成且つ多孔質のＰＴＦＥ樹脂からなる被覆１ｂが形成された、外径１．７ｍｍのＰＴＦＥ樹脂絶縁電線１を作製した。 First, a mixture of PTFE resin powder and a commercially available petroleum-based extrusion aid was aged for a predetermined time, then filled in a cylinder and pressurized to prepare a PTFE resin preform. Next, this PTFE resin preform is extrusion coated on the outer periphery of the central conductor 1a made of nickel-plated copper-coated steel wire by a paste extruder, and then passed through a heating furnace at 200 ° C. to dry-remove the extrusion aid, and is not fired. A PTFE resin insulated wire 1 having an outer diameter of 1.7 mm, on which a coating 1b made of porous PTFE resin was formed, was produced.
次に、このＰＴＦＥ樹脂絶縁電線１を、有機シラン化合物を含有する処理液としてシランカップリング剤に含浸させ、その後、５００℃の加熱炉にて焼成することにより、ＰＴＦＥ樹脂からなる被覆１ｂに無機酸化物としてのシリカを分散させて保持させた。尚、このＰＴＦＥ樹脂からなる被覆１ｂの表面を走査型電子顕微鏡にて５０００倍に拡大し観察したところ、図３に示すように、粒径０．５μｍを超えるような無機酸化物粒子は確認されなかった。ここで、本実施の形態１では、無機酸化物としてシリカを分散させて保持させたが、これに限定されることはない。無機酸化物としては、例えば、シリカ以外にも、アルミナ、チタニア、ジルコニアなどが挙げられ、これらの内の一種又は複数種がＰＴＦＥ樹脂に分散させて保持させれば良い。又、本実施の形態１では、処理液としてシランカップリング剤を使用したが、これに限定されることはない。処理液としては、焼成後に上記した無機酸化物が残存するような液状体であれば良く、例えば、アルミネート系カップリング剤やチタネート系カップリング剤のような有機金属溶液、各種無機酸化物微粒子のコロイド分散体などが挙げられる。これらの中でも、焼成後に、上記した無機酸化物が、少なくとも一部が０．５μｍ以下の粒径で残存するものが好ましいため、各種無機酸化物微粒子のコロイド分散体を使用する場合は、少なくとも一部が０．５μｍ以下の粒径である無機物微粒子を分散相としたコロイド分散体とする。尚、焼成の条件については、ＰＴＦＥ樹脂絶縁電線の寸法等により温度と時間を適宜に設定すれば良い。 Next, the PTFE resin insulated wire 1 is impregnated with a silane coupling agent as a treatment liquid containing an organic silane compound, and then fired in a heating furnace at 500 ° C., whereby the coating 1b made of PTFE resin is inorganic. Silica as an oxide was dispersed and held. When the surface of the coating 1b made of PTFE resin was observed with a scanning electron microscope at a magnification of 5000 times, inorganic oxide particles having a particle size exceeding 0.5 μm were confirmed as shown in FIG. There wasn't. Here, in Embodiment 1, silica is dispersed and held as the inorganic oxide, but the present invention is not limited to this. Examples of the inorganic oxide include alumina, titania, zirconia, and the like in addition to silica, and one or more of these may be dispersed and held in the PTFE resin. In the first embodiment, the silane coupling agent is used as the treatment liquid. However, the present invention is not limited to this. The treatment liquid may be a liquid in which the above-described inorganic oxide remains after firing. For example, organometallic solutions such as aluminate coupling agents and titanate coupling agents, and various inorganic oxide fine particles. And colloidal dispersions. Among these, after firing, it is preferable that at least a part of the above-described inorganic oxide remains with a particle size of 0.5 μm or less. Therefore, when using a colloidal dispersion of various inorganic oxide fine particles, at least one A colloidal dispersion having a dispersed phase of inorganic fine particles having a particle size of 0.5 μm or less in part is used. In addition, about the conditions of baking, what is necessary is just to set temperature and time suitably by the dimension of a PTFE resin insulated wire, etc.
このようにして無機酸化物を分散させて保持させたＰＴＦＥ樹脂絶縁電線１の外周に、インサート成型によって、フッ素系ポリマーとしてのフッ素ゴムからなるシール部材２を形成した。シール部材２は、直径７ｍｍ、長さ５０ｍｍの円筒形状とした。上記のような成型により、ＰＴＦＥ樹脂絶縁電線１をフッ素系ポリマーシール部材２に挿通させた状態とした後、２００℃、１５ＭＰａの熱間プレスによりＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシール部材２を接着させた。尚、本実施の形態１では、シール部材２としてフッ素系ポリマーであるフッ素ゴムを使用したが、これに限定されることはない。フッ素系ポリマーとしては、例えば、ポリテトラフルオロエチレン、変性ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライド、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−パーフルオロビニルエーテル共重合体、エチレン−テトラフルオロエチレン、ビニリデンフルオライド−テトラフルオロエチレン共重合体、ビニリデンフルオライド−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−プロピレン共重合体などが挙げられ、目的とする用途に応じて適宜選択すれば良い。又、成型方法も特に限定はなく、従来公知の種々の方法により成型すれば良い。 A seal member 2 made of fluororubber as a fluoropolymer was formed by insert molding on the outer periphery of the PTFE resin insulated wire 1 in which the inorganic oxide was dispersed and held in this manner. The seal member 2 has a cylindrical shape with a diameter of 7 mm and a length of 50 mm. After the PTFE resin insulated wire 1 is inserted through the fluorine-based polymer seal member 2 by molding as described above, the PTFE resin insulated wire 1 and the fluorine-based polymer seal member 2 are hot-pressed at 200 ° C. and 15 MPa. Glued. In the first embodiment, fluorine rubber, which is a fluorine-based polymer, is used as the seal member 2, but the present invention is not limited to this. Examples of the fluorine-based polymer include polytetrafluoroethylene, modified polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluorovinyl ether copolymer Polymers, ethylene-tetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, and the like. What is necessary is just to select suitably. Also, the molding method is not particularly limited, and may be molded by various conventionally known methods.
上記のようにしてＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシール部材２を接着させたものについて、密着強度の確認として、引抜強度の測定を行った。引抜強度の測定方法は、フッ素系ポリマーシール部材２を治具にて押さえるとともに、ＰＴＦＥ樹脂絶縁電線１を速度５０ｍｍ／分で引抜いた際の荷重を測定した。尚、引抜強度の測定は、接着直後（初期値）、２８０℃×７２時間の加熱後、２８０℃×２００時間の加熱後の３回測定を行った。結果を表１に示す。 With respect to the case where the PTFE resin insulated wire 1 and the fluoropolymer seal member 2 were bonded as described above, the pullout strength was measured as confirmation of the adhesion strength. The pulling strength was measured by pressing the fluoropolymer seal member 2 with a jig and measuring the load when the PTFE resin insulated wire 1 was pulled out at a speed of 50 mm / min. The pull-out strength was measured three times immediately after bonding (initial value), after heating at 280 ° C. for 72 hours and after heating at 280 ° C. for 200 hours. The results are shown in Table 1.
比較のため、実施の形態１において、ＰＴＦＥ樹脂絶縁電線１をシランカップリング剤からなる処理液に含浸させず、無機酸化物がＰＴＦＥ樹脂絶縁電線に分散されていないものを比較の形態１とし、実施の形態１と同様に引抜強度の測定を行った。結果を表１に併せて示す。 For comparison, in Embodiment 1, the PTFE resin insulated wire 1 is not impregnated with a treatment liquid composed of a silane coupling agent, and the inorganic oxide is not dispersed in the PTFE resin insulated wire as Comparative Embodiment 1. The pullout strength was measured in the same manner as in the first embodiment. The results are also shown in Table 1.
表１に記載のように、本実施の形態１によれば、引抜強度の初期値が優れているだけでなく、２８０℃の加熱後において更に引抜強度が向上する傾向にあり、高温環境下においても優れた密着強度を維持できることが確認された。これに対して、比較の形態１は、引抜強度の初期値が低く、又、２８０℃の加熱後における引抜強度の向上度合いも低かった。 As shown in Table 1, according to the first embodiment, not only the initial value of the pulling strength is excellent, but the pulling strength tends to be further improved after heating at 280 ° C. It was also confirmed that excellent adhesion strength can be maintained. On the other hand, Comparative Example 1 had a low initial value of the pulling strength, and the degree of improvement of the pulling strength after heating at 280 ° C. was also low.
次いで、図２を参照して本発明による実施の形態２を説明する。尚、本実施の形態２は、ＰＴＦＥ樹脂絶縁電線とフッ素ゴムシートの接着に適用したものである。 Next, a second embodiment of the present invention will be described with reference to FIG. In addition, this Embodiment 2 is applied to adhesion | attachment of a PTFE resin insulated wire and a fluororubber sheet.
上記実施の形態１と同様に、中心導体１ａの外周にＰＴＦＥ樹脂からなる被覆１ｂが形成されたＰＴＦＥ樹脂絶縁電線１を作製し、ＰＴＦＥ樹脂からなる被覆１ｂに、無機酸化物としてのシリカを分散させて保持させた。 As in the first embodiment, a PTFE resin insulated wire 1 is produced in which a coating 1b made of PTFE resin is formed on the outer periphery of the center conductor 1a, and silica as an inorganic oxide is dispersed in the coating 1b made of PTFE resin. Allowed to hold.
このようにして無機酸化物を分散させて保持させたＰＴＦＥ樹脂絶縁電線１を、フッ素系ポリマーとしてのフッ素ゴムからなるシート３の上に配置した。シート３は、縦１５０ｍｍ、横２００ｍｍ、厚さ５ｍｍとし、ＰＴＦＥ樹脂絶縁電線１が配置される部分は、ＰＴＦＥ樹脂絶縁電線１外周の半分が埋め込まれるように溝を形成した。これらのＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシート３に、２００℃、１５ＭＰａの熱間プレスを施し、ＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシート３を接着させた。 Thus, the PTFE resin insulated wire 1 in which the inorganic oxide was dispersed and held was disposed on the sheet 3 made of fluororubber as a fluoropolymer. The sheet 3 had a length of 150 mm, a width of 200 mm, and a thickness of 5 mm, and a groove was formed in the portion where the PTFE resin insulated wire 1 was arranged so that the half of the outer periphery of the PTFE resin insulated wire 1 was embedded. The PTFE resin insulated electric wire 1 and the fluorine-based polymer sheet 3 were hot-pressed at 200 ° C. and 15 MPa to adhere the PTFE resin-insulated electric wire 1 and the fluorine-based polymer sheet 3.
上記のようにして接着させたＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシート３について、密着強度の確認として、剥離強度の測定を行った。剥離強度の測定方法は、フッ素系ポリマーシート３を固定し、ＰＴＦＥ樹脂絶縁電線１の端部を掴んでフッ素系ポリマーシート３の上方へ速度３０ｍｍ／分で引剥がした際の荷重を測定した。尚、剥離強度の測定は、接着直後（初期値）、２８０℃×７２時間の加熱後、２８０℃×２００時間の加熱後の３回測定を行った。結果を表２に示す。 For the PTFE resin insulated wire 1 and the fluoropolymer sheet 3 bonded as described above, the peel strength was measured as confirmation of the adhesion strength. The peel strength was measured by fixing the fluorine polymer sheet 3, grasping the end of the PTFE resin insulated wire 1, and measuring the load at the time of peeling off the fluorine polymer sheet 3 at a speed of 30 mm / min. The peel strength was measured three times immediately after bonding (initial value), after heating at 280 ° C. for 72 hours and after heating at 280 ° C. for 200 hours. The results are shown in Table 2.
比較のため、実施の形態２において、ＰＴＦＥ樹脂絶縁電線１をシランカップリング剤からなる処理液に含浸させず、無機酸化物がＰＴＦＥ樹脂絶縁電線に分散され保持されていないものを比較の形態２とし、実施の形態２と同様に引抜強度の測定を行った。結果を表２に併せて示す。 For comparison, in the second embodiment, the PTFE resin insulated wire 1 is not impregnated with a treatment liquid made of a silane coupling agent, and the inorganic oxide is not dispersed and held in the PTFE resin insulated wire. Then, the pull-out strength was measured in the same manner as in the second embodiment. The results are also shown in Table 2.
表２に記載のように、本実施の形態２によれば、剥離強度の初期値が優れているだけでなく、２８０℃の加熱後においても剥離強度の低下はほとんどなく、高温環境下においても優れた密着強度を維持できることが確認された。これに対して、比較の形態２は、接着されることはなく、手で触れただけで剥がれてしまったことから、剥離強度を測定することができなかった。 As shown in Table 2, according to the second embodiment, not only is the initial value of the peel strength excellent, but there is almost no decrease in the peel strength even after heating at 280 ° C., even under a high temperature environment. It was confirmed that excellent adhesion strength can be maintained. On the other hand, Comparative Example 2 was not adhered, and peeled off only by touching with a hand, so that the peel strength could not be measured.
次いで、図４を参照して本発明による実施の形態３を説明する。尚、本実施の形態３は、ＰＴＦＥ樹脂絶縁電線とフッ素ゴムシール部材の接着に適用したものである。 Next, a third embodiment according to the present invention will be described with reference to FIG. In addition, this Embodiment 3 is applied to adhesion | attachment of a PTFE resin insulated wire and a fluororubber seal member.
まず、ＰＴＦＥ樹脂粉末と市販の石油系押出助剤を混合したものを所定時間熟成した後、シリンダーに充填して加圧しＰＴＦＥ樹脂プリフォームを調整した。次いで、このＰＴＦＥ樹脂プリフォームをペースト押出機によって、ニッケルメッキ銅被覆鋼線からなる中心導体１ａの外周に押出被覆し、未焼成且つ多孔質のＰＴＦＥ樹脂からなる被覆１ｂが形成された、外径１．７ｍｍのＰＴＦＥ樹脂絶縁電線１を作製した。 First, a mixture of PTFE resin powder and a commercially available petroleum-based extrusion aid was aged for a predetermined time, then filled in a cylinder and pressurized to prepare a PTFE resin preform. Next, this PTFE resin preform was extrusion coated on the outer periphery of the central conductor 1a made of nickel-plated copper-coated steel wire by a paste extruder, and the outer diameter of the coating 1b made of unfired and porous PTFE resin was formed. A 1.7 mm PTFE resin insulated wire 1 was produced.
次にこのＰＴＦＥ樹脂絶縁電線１を、粒径２０ｎｍのシリカ微粒子を分散相としたコロイド分散体からなる処理液に含浸させた。その後、１５０℃の乾燥炉にて押出助剤、及び、コロイド分散体の分散媒を乾燥除去し、更に５００℃の加熱炉にて焼成することにより、ＰＴＦＥ樹脂からなる被覆１ｂに、無機酸化物としてのシリカを分散させて保持させた。尚、このＰＴＦＥ樹脂からなる被覆の表面を走査型電子顕微鏡にて５０００倍に拡大し観察したところ、図５に示すように、粒径０．５μｍを超えるような無機酸化物粒子は確認されなかった。ここで、本実施の形態３では、シリカ微粒子を分散相としたコロイド分散体を使用したが、これに限定されることはない。分散相としては、例えば、チタニア微粒子、アルミナ微粒子など種々の無機酸化物が考えられる。これらの中でも、焼成後に、上記した無機酸化物が、少なくとも一部が０．５μｍ以下の粒径で残存するものが好ましいため、少なくとも一部が０．５μｍ以下の粒径である無機物微粒子を分散相したものとする。又、分散媒としては、ＰＴＦＥ樹脂の焼成温度以下で気化するものであれば特に限定はなく、各種有機溶剤や水など適宜に選定すればよい。尚、焼成の条件については、ＰＴＦＥ樹脂絶縁電線の寸法等により温度と時間を適宜に設定すれば良い。 Next, this PTFE resin insulated wire 1 was impregnated with a treatment liquid composed of a colloidal dispersion in which silica fine particles having a particle diameter of 20 nm were dispersed. Thereafter, the extrusion aid and the dispersion medium of the colloidal dispersion are dried and removed in a drying furnace at 150 ° C., and further baked in a heating furnace at 500 ° C., whereby the coating 1b made of PTFE resin is coated with an inorganic oxide. The silica as was dispersed and held. When the surface of the coating made of PTFE resin was observed with a scanning electron microscope at a magnification of 5000 times, no inorganic oxide particles having a particle size exceeding 0.5 μm were confirmed as shown in FIG. It was. Here, in Embodiment 3, a colloidal dispersion using silica fine particles as a dispersed phase is used. However, the present invention is not limited to this. Examples of the dispersed phase include various inorganic oxides such as titania fine particles and alumina fine particles. Among these, after firing, it is preferable that at least a part of the above-described inorganic oxide remains with a particle size of 0.5 μm or less, so that at least a part of inorganic fine particles with a particle size of 0.5 μm or less is dispersed. Shall be compatible. The dispersion medium is not particularly limited as long as it vaporizes below the firing temperature of the PTFE resin, and various organic solvents and water may be appropriately selected. In addition, about the conditions of baking, what is necessary is just to set temperature and time suitably by the dimension of a PTFE resin insulated wire, etc.
このようにして無機酸化物を分散させて保持させたＰＴＦＥ樹脂絶縁電線１の外周に、フッ素系ポリマーとしてのフッ素ゴムからなり、予め直径３ｍｍ、長さ４ｍｍの円筒形状に成型するとともに、半加硫状態としたフッ素系ポリマーシール部材２を配置した。その後、これらを１７０℃で１時間加熱して、フッ素系ポリマーシール部材２を加硫するとともに、ＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシール部材２を接着させた。尚、フッ素系ポリマーシール部材２の成型方法については特に限定はなく、従来公知の種々の方法により成型すれば良い。 The outer periphery of the PTFE resin insulated wire 1 in which the inorganic oxide is dispersed and held in this way is made of fluororubber as a fluoropolymer and is previously molded into a cylindrical shape having a diameter of 3 mm and a length of 4 mm. A fluorinated polymer seal member 2 in a sulfur state was disposed. Thereafter, these were heated at 170 ° C. for 1 hour to vulcanize the fluorine-based polymer seal member 2 and to bond the PTFE resin insulated wire 1 and the fluorine-based polymer seal member 2 together. In addition, there is no limitation in particular about the shaping | molding method of the fluorine-type polymer seal member 2, What is necessary is just to shape | mold by a conventionally well-known various method.
上記のようにしてＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシール部材２を接着させたものについて、密着強度の確認として、引抜強度の測定を行った。引抜強度の測定方法は、フッ素系ポリマーシール部材２を治具にて押さえるとともに、ＰＴＦＥ樹脂絶縁電線１を速度５０ｍｍ／分で引抜いた際の荷重を測定した。尚、引抜強度の測定は、接着直後（初期値）、２８０℃×２００時間の加熱後、２８０℃×３５０時間の加熱後の３回測定を行った。結果を表３に示す。 With respect to the case where the PTFE resin insulated wire 1 and the fluoropolymer seal member 2 were bonded as described above, the pullout strength was measured as confirmation of the adhesion strength. The pulling strength was measured by pressing the fluoropolymer seal member 2 with a jig and measuring the load when the PTFE resin insulated wire 1 was pulled out at a speed of 50 mm / min. The pull-out strength was measured three times immediately after bonding (initial value), after heating at 280 ° C. × 200 hours and after heating at 280 ° C. × 350 hours. The results are shown in Table 3.
比較のため、実施の形態３において、ＰＴＦＥ樹脂絶縁電線１を、シリカ微粒子を分散相としたコロイド分散体からなる処理液に含浸させず、無機酸化物がＰＴＦＥ樹脂絶縁電線に分散され保持されていないものを比較の形態３とし、実施の形態３と同様に引抜強度の測定を行った。結果を表３に併せて示す。 For comparison, in Embodiment 3, the PTFE resin insulated wire 1 is not impregnated with a treatment liquid composed of a colloidal dispersion in which silica fine particles are dispersed, and the inorganic oxide is dispersed and held in the PTFE resin insulated wire. The one without comparison was designated as Comparative Example 3, and the pull-out strength was measured in the same manner as in Example 3. The results are also shown in Table 3.
表３に記載のように、本実施の形態３によれば、引抜強度の初期値、及び、２８０℃の加熱後において、充分な強度が得られることが確認された。これに対して、比較の形態３は、引抜強度の初期値が低く、２８０℃の加熱後においては更に引抜強度が低下しており、充分な強度が得られるとは言えなかった。尚、上記の表１に記載した実施の形態１と実施の形態３を比較した場合、実施の形態３は実施の形態１よりも引抜強度の値が小さくなっている。これは、実施の形態３は、フッ素系ポリマーシール材２の長さが短く、又、ＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシール部材２を接着させる際に加圧をしていないことによるものである。 As shown in Table 3, according to the third embodiment, it was confirmed that a sufficient strength was obtained after the initial value of the pulling strength and after heating at 280 ° C. On the other hand, in Comparative Example 3, the initial value of the pulling strength was low, and the pulling strength was further lowered after heating at 280 ° C., and it could not be said that sufficient strength was obtained. When the first embodiment described in Table 1 is compared with the third embodiment, the pull-out strength value of the third embodiment is smaller than that of the first embodiment. This is because Embodiment 3 has a short length of the fluorine-based polymer sealing material 2 and is not pressurized when bonding the PTFE resin insulated wire 1 and the fluorine-based polymer sealing member 2. is there.
この実施の形態３及び比較の形態３について、密着強度の更なる確認として、耐熱リーク試験を行った。試験方法としては、接着させたＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシール部材２を金属筒中に配置して、この金属筒をかしめたものをサンプルとし、このサンプルを２８０℃の雰囲気中に配置した後、常温で金属筒の片端に１００ｋＰａの気圧を加えてもう一方の端から空気がリークするまでの時間を測定した。測定結果を表４に示す。 About this Embodiment 3 and Comparative Embodiment 3, as a further confirmation of the adhesion strength, a heat-resistant leak test was conducted. As a test method, the bonded PTFE resin insulated wire 1 and the fluorine-based polymer seal member 2 are arranged in a metal tube, and the sample obtained by caulking the metal tube is used as a sample, and the sample is arranged in an atmosphere of 280 ° C. Thereafter, a pressure of 100 kPa was applied to one end of the metal tube at room temperature, and the time until air leaked from the other end was measured. Table 4 shows the measurement results.
表４に記載のように、実施の形態３は、空気がリークするまでの時間が２５０時間であり、高温環境においてもＰＴＦＥ樹脂絶縁電線１とフッ素系ポリマーシール部材２とが優れた密着強度を維持して接着していることが確認された。これに対して、比較の形態３は、空気がリークするまでの時間が１５０時間と短く、高温環境における密着強度の維持という点で充分なものとは言えなかった。 As shown in Table 4, in the third embodiment, the time until the air leaks is 250 hours, and the PTFE resin insulated wire 1 and the fluoropolymer seal member 2 have excellent adhesion strength even in a high temperature environment. It was confirmed that it was maintained and adhered. On the other hand, in Comparative Example 3, the time until the air leaked was as short as 150 hours, which was not sufficient in terms of maintaining the adhesion strength in a high temperature environment.
次いで、図６を参照して本発明による実施の形態４を説明する。尚、本実施の形態４は、ＰＴＦＥ樹脂絶縁電線とエポキシ樹脂の接着に適用したものである。 Next, a fourth embodiment according to the present invention will be described with reference to FIG. In addition, this Embodiment 4 is applied to adhesion | attachment of a PTFE resin insulated wire and an epoxy resin.
まず、ＰＴＦＥ樹脂粉末と市販の石油系押出助剤を混合したものを所定時間熟成した後、シリンダーに充填して加圧しＰＴＦＥ樹脂プリフォームを調整した。次いで、このＰＴＦＥ樹脂プリフォームをペースト押出機によって、ニッケルメッキ銅被覆鋼線からなる中心導体１ａの外周に押出被覆し、未焼成且つ多孔質のＰＴＦＥ樹脂からなる被覆１ｂが形成された、外径１．７ｍｍのＰＴＦＥ樹脂絶縁電線１を作製した。 First, a mixture of PTFE resin powder and a commercially available petroleum-based extrusion aid was aged for a predetermined time, then filled in a cylinder and pressurized to prepare a PTFE resin preform. Next, this PTFE resin preform was extrusion coated on the outer periphery of the central conductor 1a made of nickel-plated copper-coated steel wire by a paste extruder, and the outer diameter of the coating 1b made of unfired and porous PTFE resin was formed. A 1.7 mm PTFE resin insulated wire 1 was produced.
次にこのＰＴＦＥ樹脂絶縁電線１を、粒径２０ｎｍのシリカ微粒子を分散相としたコロイド分散体からなる処理液に含浸させた。その後、１５０℃の乾燥炉にて押出助剤、及び、コロイド分散体の分散媒を乾燥除去し、更に５００℃の加熱炉にて焼成することにより、ＰＴＦＥ樹脂からなる被覆１ｂに、無機酸化物としてのシリカを分散させて保持させた。 Next, this PTFE resin insulated wire 1 was impregnated with a treatment liquid composed of a colloidal dispersion in which silica fine particles having a particle diameter of 20 nm were dispersed. Thereafter, the extrusion aid and the dispersion medium of the colloidal dispersion are dried and removed in a drying furnace at 150 ° C., and further baked in a heating furnace at 500 ° C., whereby the coating 1b made of PTFE resin is coated with an inorganic oxide. The silica as was dispersed and held.
このようにして無機酸化物を分散させて保持させたＰＴＦＥ樹脂絶縁電線１の外周に、２液混合性エポキシ樹脂を混合したものを塗布した後、２４時間常温で放置して硬化させ、エポキシ樹脂による肉盛部４を形成した。 After applying a mixture of a two-component mixed epoxy resin to the outer periphery of the PTFE resin insulated wire 1 in which the inorganic oxide is dispersed and held in this way, the epoxy resin is left to cure at room temperature for 24 hours. The build-up part 4 was formed.
上記のようにしてＰＴＦＥ樹脂絶縁電線１に肉盛部４を形成させたものについて、密着強度の確認として、引抜強度の測定を行った。引抜強度の測定方法は、肉盛部４を治具にて押さえるとともに、ＰＴＦＥ樹脂絶縁電線１を速度５０ｍｍ／分で引抜いた際の荷重を測定した。結果を表５に示す。 As described above, the tensile strength of the PTFE resin insulated wire 1 formed with the built-up portion 4 was measured as confirmation of the adhesion strength. The pulling strength was measured by holding the build-up portion 4 with a jig and measuring the load when the PTFE resin insulated wire 1 was pulled out at a speed of 50 mm / min. The results are shown in Table 5.
比較のため、実施の形態４において、ＰＴＦＥ樹脂絶縁電線１を、シリカ微粒子を分散相としたコロイド分散体からなる処理液に含浸させず、無機酸化物がＰＴＦＥ樹脂絶縁電線に分散され保持されていないものを比較の形態４とし、実施の形態４と同様に引抜強度の測定を行った。結果を表５に併せて示す。 For comparison, in Embodiment 4, the PTFE resin insulated wire 1 is not impregnated with a treatment liquid composed of a colloidal dispersion in which silica fine particles are dispersed, and the inorganic oxide is dispersed and held in the PTFE resin insulated wire. Those not present were designated as Comparative Example 4, and the pull-out strength was measured in the same manner as in Example 4. The results are also shown in Table 5.
表５に記載のように、本実施の形態４によれば、充分な引抜強度が得られることが確認された。これに対して、比較の形態４は、充分な引抜強度が得られるとは言えなかった。 As shown in Table 5, according to the fourth embodiment, it was confirmed that sufficient pulling strength was obtained. On the other hand, Comparative Form 4 could not be said to provide sufficient pulling strength.
上記実施の形態１及び実施の形態２では、シランカップリング剤からなる処理液を使用し、上記実施の形態３及び実施の形態４では、シリカ微粒子を分散相としたコロイド分散体からなる処理液を使用したが、これらを組合せても構わない。即ち、シランカップリング剤にシリカ微粒子を分散させた処理液を使用しても良い。 In the first embodiment and the second embodiment, a treatment liquid made of a silane coupling agent is used, and in the third and fourth embodiments, a treatment liquid made of a colloidal dispersion using silica fine particles as a dispersed phase. However, these may be combined. That is, a treatment liquid in which silica fine particles are dispersed in a silane coupling agent may be used.
上記の実施の形態では、電線被覆とシール部材の接着、電線被覆とシートの接着について説明したが、本発明はこれらに限定されるものではない。例えば、シート同士の接着、多層ホースの内層と外層の接着、シール材と構造体の接着など、ＰＴＦＥ樹脂からなる成型体に関する接着であれば、全て応用が可能である。 In the above embodiment, the adhesion between the wire covering and the sealing member and the adhesion between the wire covering and the sheet have been described, but the present invention is not limited to these. For example, all applications can be applied as long as they are adhesions related to a molded body made of PTFE resin, such as adhesion between sheets, adhesion between inner and outer layers of a multilayer hose, adhesion between a sealing material and a structure.
又、上記の実施の形態４では、ＰＴＦＥ樹脂とエポキシ樹脂の接着について説明したが、他のポリマーとの接着に応用することも勿論可能である。更に、エポキシ樹脂などポリマーを接着剤として使用することで、更に別の部材、例えば、ポリマーのみでなく、金属、セラミック、ガラス、鉱物、木質材、などと接着させるといった展開も考えられる。即ち、本発明によれば、接着が非常に困難な材料であったＰＴＦＥ樹脂が、公知の接着剤によって接着することも可能となるという優れた効果を得ることができる。 In the fourth embodiment, the bonding between the PTFE resin and the epoxy resin has been described. However, it is of course possible to apply the bonding to other polymers. Further, by using a polymer such as an epoxy resin as an adhesive, it is also possible to develop such a structure that not only a polymer but also a metal, ceramic, glass, mineral, wood material, and the like are adhered. That is, according to the present invention, it is possible to obtain an excellent effect that the PTFE resin, which is a material that is very difficult to bond, can be bonded by a known adhesive.
以上詳述したように、本発明は、初期の密着強度に優れるとともに、高温環境においても優れた密着強度を維持することが可能なＰＴＦＥ樹脂成型体が接着された構造体、及び、ＰＴＦＥ樹脂成型体の接着方法に関するものである。従って、例えば、シール部材（グロメット、ブッシング、パッキング、Ｏ−リング）、電線被覆、ホース、チューブ、ロール、ダイヤフラム、ウェザーストリップ、などに使用される接着技術として有用なものである。又、これらの他に、ＰＴＦＥ樹脂からなるフィルタとこのフィルタを保持するグロメットとを接着する際の技術としても、応用することが可能である。 As described above in detail, the present invention is excellent in initial adhesion strength, and has a structure bonded with a PTFE resin molding capable of maintaining excellent adhesion strength even in a high-temperature environment, and PTFE resin molding. The present invention relates to a body bonding method. Therefore, for example, it is useful as an adhesion technique used for seal members (grommets, bushings, packing, O-rings), electric wire coatings, hoses, tubes, rolls, diaphragms, weather strips, and the like. In addition to these, the present invention can also be applied as a technique for bonding a filter made of PTFE resin and a grommet holding the filter.
１ ＰＴＦＥ樹脂絶縁電線
２ フッ素系ポリマーシール部材
３ フッ素系ポリマーシート
４ 肉盛部
1 PTFE resin insulated wire 2 Fluoropolymer seal member 3 Fluoropolymer sheet 4 Overlay
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