JP2013204181A - Polytetrafluoroethylene impregnated fiber and method for producing the same - Google Patents
Polytetrafluoroethylene impregnated fiber and method for producing the same Download PDFInfo
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- JP2013204181A JP2013204181A JP2012073242A JP2012073242A JP2013204181A JP 2013204181 A JP2013204181 A JP 2013204181A JP 2012073242 A JP2012073242 A JP 2012073242A JP 2012073242 A JP2012073242 A JP 2012073242A JP 2013204181 A JP2013204181 A JP 2013204181A
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 109
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 109
- 239000000835 fiber Substances 0.000 title claims abstract description 51
- -1 Polytetrafluoroethylene Polymers 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 239000011347 resin Substances 0.000 claims abstract description 67
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 14
- 238000002411 thermogravimetry Methods 0.000 claims abstract description 10
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 230000004580 weight loss Effects 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 239000013585 weight reducing agent Substances 0.000 abstract 1
- 238000004804 winding Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 238000009954 braiding Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 210000004907 gland Anatomy 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920000271 Kevlar® Polymers 0.000 description 2
- 229920000784 Nomex Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004763 nomex Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、フィラメント表面に保持された未焼成ポリテトラフルオロエチレン（以下「ＰＴＦＥ」ともいう。）樹脂が脱落しにくく、加工性に優れたＰＴＦＥ含浸糸およびその製造方法に関するものである。 The present invention relates to a PTFE-impregnated yarn excellent in processability and a non-fired polytetrafluoroethylene (hereinafter also referred to as “PTFE”) resin held on a filament surface, which is less likely to fall off.
ＰＴＦＥ樹脂はその優れた潤滑性、耐久性、耐熱性、耐薬品性からさまざまな用途に幅広く使用されている。ＰＴＦＥ樹脂から製造されるＰＴＦＥ繊維も、その優れた耐熱性、耐薬品性、耐蒸熱性、電気絶縁性、また表面抵抗の低い材料として知られている。 PTFE resin is widely used in various applications because of its excellent lubricity, durability, heat resistance, and chemical resistance. PTFE fiber produced from PTFE resin is also known as a material having excellent heat resistance, chemical resistance, heat resistance, electrical insulation and low surface resistance.
それら特性を活かし、ＰＴＦＥ樹脂水性分散液をＰＴＦＥやカーボンファイバー、ケブラー、ノーメックス、ＰＰＳ（ポリフェニレンサルファイド）などの繊維に含浸させた含浸糸を編組にした編組製品や、繊維を編組した後にＰＴＦＥ樹脂水性分散液を含浸させた編組製品は、ポンプ、攪拌機、バルブなど各種流体機器の軸封部などに用いられるグランドパッキンとして幅広く使用されている（特許文献１）。 Taking advantage of these characteristics, braided products made by braiding impregnated yarn in which PTFE resin aqueous dispersion is impregnated in fibers such as PTFE, carbon fiber, Kevlar, Nomex, PPS (polyphenylene sulfide), and PTFE resin aqueous solution after braiding the fiber The braided product impregnated with the dispersion is widely used as a gland packing used in shaft seals of various fluid devices such as pumps, agitators, and valves (Patent Document 1).
ＰＴＦＥ含浸糸はフィラメント状の繊維にＰＴＦＥ樹脂水性分散液を含浸させた後に乾燥させ、ＰＴＦＥ樹脂のみを繊維表面に未焼成の状態で露出させた繊維である。このＰＴＦＥ含浸糸は未焼成ＰＴＦＥ樹脂を良好に保持し、このＰＴＦＥ含浸糸を編組した製品はパッキン表面に常に安定した潤滑性を付与することが出来るとともに、柔軟性も保持し、長期間にわたるシール性を一層良好に確保できることが知られている（特許文献２）。 The PTFE-impregnated yarn is a fiber in which filamentary fibers are impregnated with an aqueous PTFE resin dispersion and then dried to expose only the PTFE resin on the fiber surface in an unfired state. This PTFE-impregnated yarn keeps the unfired PTFE resin well, and the products braided with this PTFE-impregnated yarn can always give a stable lubricity to the packing surface, and also maintain flexibility and seal over a long period of time. It is known that the property can be secured better (Patent Document 2).
しかしながら、ＰＴＦＥ含浸糸は、フィラメント状の繊維にＰＴＦＥ樹脂水性分散液を含浸した後に乾燥させ水分を除去することにより、未焼成ＰＴＦＥ樹脂の状態でフィラメント状の繊維表面にＰＴＦＥ樹脂を保持しているため、その過程においてガイド等への擦過によりＰＴＦＥ樹脂が脱落し易いという欠点がある。 However, the PTFE-impregnated yarn retains the PTFE resin on the surface of the filament-like fiber in the state of the unfired PTFE resin by impregnating the filament-like fiber with the PTFE resin aqueous dispersion and drying it to remove moisture. Therefore, in the process, there is a drawback that the PTFE resin is easily dropped due to rubbing against a guide or the like.
本発明の目的は、フィラメント状の繊維表面に保持された未焼成ＰＴＦＥ樹脂が脱落しにくく、加工性に優れたＰＴＦＥ含浸糸およびその製造方法を提供することである。 An object of the present invention is to provide a PTFE-impregnated yarn excellent in processability and a method for producing the same, in which an unsintered PTFE resin held on a filament-like fiber surface is less likely to fall off.
上述した目的を達成するために、本発明に係るＰＴＦＥ含浸糸およびその製造方法は次の構成を有する。 In order to achieve the above-described object, the PTFE-impregnated yarn and the method for producing the same according to the present invention have the following configurations.
（１）フィラメント状繊維に、ポリテトラフルオロエチレン樹脂を５５〜６５質量％含有し、熱重量測定（ＴＧＡ）によって測定した２２０℃における重量減少が２０質量％以下であるノニオン系界面活性剤をポリテトラフルオロエチレン樹脂に対し２．５質量％以上１０質量％以下含有するポリテトラフルオロエチレン樹脂水性分散液を含浸させた後、乾燥させることを特徴とするポリテトラフルオロエチレン含浸糸の製造方法。 (1) Polynonfluorosurfactant containing 55 to 65% by mass of polytetrafluoroethylene resin in a filamentous fiber and having a weight loss at 220 ° C. measured by thermogravimetry (TGA) of 20% by mass or less A method for producing a polytetrafluoroethylene-impregnated yarn, comprising impregnating a polytetrafluoroethylene resin aqueous dispersion containing 2.5% by mass to 10% by mass with respect to a tetrafluoroethylene resin, followed by drying.
（２）前記フィラメント状繊維に、前記ポリテトラフルオロエチレン樹脂水性分散液を含浸させた後、１５０℃以上２２０℃以下の乾燥温度で２分以上１０分以下の乾燥時間にて乾燥させる、（１）のＰＴＦＥ含浸糸の製造方法。 (2) The filamentous fiber is impregnated with the aqueous polytetrafluoroethylene resin dispersion, and then dried at a drying temperature of 150 ° C. or higher and 220 ° C. or lower for a drying time of 2 minutes or longer and 10 minutes or shorter. ) PTFE-impregnated yarn production method.
（３）前記フィラメント状繊維に対して、６０質量％以上１２０質量％以下の割合で未焼成ＰＴＦＥ樹脂を塗着させる、（１）または（２）のＰＴＦＥ含浸糸の製造方法。 (3) The method for producing a PTFE-impregnated yarn according to (1) or (2), wherein an unsintered PTFE resin is applied to the filamentous fiber at a ratio of 60% by mass to 120% by mass.
（４）前記フィラメントの繊維がポリテトラフルオロエチレン樹脂からなる、（１）〜（３）のいずれかのポリテトラフルオロエチレン含浸糸の製造方法。 (4) The method for producing a polytetrafluoroethylene-impregnated yarn according to any one of (1) to (3), wherein the filament fibers are made of a polytetrafluoroethylene resin.
（５）ジメチルポリシロキサンを８質量％以上１５質量％以下の割合で付着させる、（１）〜（４）のいずれかのポリテトラフルオロエチレン含浸糸の製造方法。 (5) The method for producing a polytetrafluoroethylene-impregnated yarn according to any one of (1) to (4), wherein dimethylpolysiloxane is adhered at a ratio of 8% by mass to 15% by mass.
（６）（１）〜（５）のいずれかの製造方法によって得られるポリテトラフルオロエチレン含浸糸。 (6) A polytetrafluoroethylene-impregnated yarn obtained by the production method of any one of (1) to (5).
本発明によれば、フィラメント状の繊維の表面に未焼成ＰＴＦＥ樹脂が脱落しにくく、加工性に優れたＰＴＦＥ樹脂水性分散液を含浸したＰＴＦＥ含浸糸を提供することができる。 According to the present invention, it is possible to provide a PTFE-impregnated yarn impregnated with an aqueous PTFE resin dispersion that is excellent in processability because the unsintered PTFE resin is unlikely to fall off on the surface of filamentous fibers.
以下に本発明の一実施態様に係るＰＴＦＥ含浸糸の詳細について説明する。本実施態様によれば、フィラメント状の繊維表面に未焼成ＰＴＦＥ樹脂が脱落しにくく、加工性に優れたＰＴＦＥ樹脂水性分散液を含浸したＰＴＦＥ含浸糸を提供することができる。ここでＰＴＦＥ含浸糸とは、フィラメント状の繊維に未焼成ＰＴＦＥ樹脂を含浸させ、または未焼成ＰＴＦＥ樹脂と液体潤滑剤としてのジメチルポリシロキサンとを含浸させた製品である。このＰＴＦＥ含浸糸を編組した製品は、たとえばポンプ、攪拌機、バルブなど各種流体機器の軸封部などのグランドパッキンとして広く用いられる。 Details of the PTFE-impregnated yarn according to one embodiment of the present invention will be described below. According to this embodiment, it is possible to provide a PTFE-impregnated yarn impregnated with an aqueous PTFE resin dispersion that is excellent in processability because the unsintered PTFE resin is less likely to fall off on the filament-like fiber surface. Here, the PTFE-impregnated yarn is a product obtained by impregnating filamentary fibers with unsintered PTFE resin or impregnated with unsintered PTFE resin and dimethylpolysiloxane as a liquid lubricant. Products obtained by braiding the PTFE-impregnated yarn are widely used as gland packings for shaft seals of various fluid devices such as pumps, stirrers, and valves.
ＰＴＦＥ含浸糸は編組した際にも未焼成のＰＴＦＥ樹脂や液体潤滑剤であるジメチルポリシロキサンを良好に保持して、パッキンの表面部及び内部からＰＴＦＥ樹脂、またはＰＴＦＥ樹脂と液体潤滑剤であるジメチルポリシロキサンをにじみ出させて、パッキン表面に常に安定した潤滑剤を付与することが出来るとともに、柔軟性も保持し、長期間にわたるシール性を一層良好に確保できるものである。 PTFE impregnated yarn retains unsintered PTFE resin and dimethylpolysiloxane, which is a liquid lubricant, even when braided, and PTFE resin, or PTFE resin and dimethyl, which is a liquid lubricant, from the surface and inside of the packing. Polysiloxane can be exuded and a stable lubricant can be constantly applied to the packing surface, and flexibility can be maintained, and a long-term sealing performance can be ensured better.
含浸させるフィラメント状の繊維としてはカーボンファイバーやケブラー、ノーメックスなどのアラミド繊維、ＰＰＳ（ポリフェニレンサルファイド）、ＰＴＦＥ繊維などの高強力繊維や耐熱・耐薬品繊維を用いることが出来るが、特に限定はされない。 As the filament-like fibers to be impregnated, carbon fiber, aramid fibers such as Kevlar and Nomex, high strength fibers such as PPS (polyphenylene sulfide) and PTFE fibers, and heat and chemical resistant fibers can be used, but there is no particular limitation.
その中でも、特に耐熱や耐薬品性の観点からＰＴＦＥ繊維であることが好ましい。その際のＰＴＦＥ繊維は従来公知のマトリックス法（エマルジョン法ともいう）、スプリット剥離法、あるいはペースト押出法などの生産方式が知られているが、繊維断面が均一で繊度バラツキが小さいという観点から、マトリックス紡糸法によって得られるＰＴＦＥ繊維であることが好ましい。スプリット剥離法あるいはペースト押出法によって得られるＰＴＦＥ繊維では、細かく切り裂いて繊維を製造するために最終繊維状物の断面は扁平形状となり、しかも、繊度がランダムであって均一性に劣り、安定した繊維物性を得ることが難しい。 Among them, PTFE fiber is particularly preferable from the viewpoint of heat resistance and chemical resistance. PTFE fibers at that time are conventionally known production methods such as a matrix method (also called an emulsion method), a split peeling method, or a paste extrusion method, but from the viewpoint of uniform fiber cross-section and small variation in fineness, PTFE fibers obtained by a matrix spinning method are preferred. In PTFE fiber obtained by split peeling method or paste extrusion method, the final fiber-like product has a flat cross section because it is cut into small pieces, and the fineness is random, inferior in uniformity, and stable. It is difficult to obtain physical properties.
ＰＴＦＥ繊維は、繊度５０００ｄｔｅｘ以上１５００００ｄｔｅｘ以下、単糸繊度２ｄｔｅｘ以上１４ｄｔｅｘ以下とする構成のマルチフィラメントであることが好ましい。さらには繊度８０００ｄｔｅｘ以上１２００００ｄｔｅｘ以下、単糸繊度３ｄｔｅｘ以上１０ｄｔｅｘ以下がより好ましい。繊度５０００ｄｔｅｘ未満、単糸繊度２ｄｔｅｘ未満の繊維は単糸繊度が細いため、安定した糸の生産が困難となる。繊度１５００００ｄｔｅｘおよび単糸繊度１４ｄｔｅｘを超えると繊維間の隙間をＰＴＦＥ樹脂微粒子や液体潤滑剤で抑えられず、編組製品として安定したシール性を付与することが出来なくなる恐れがある。 The PTFE fiber is preferably a multifilament having a fineness of 5000 dtex to 150,000 dtex and a single yarn fineness of 2 dtex to 14 dtex. More preferably, the fineness is 8000 dtex or more and 120,000 dtex or less, and the single yarn fineness is 3 dtex or more and 10 dtex or less. A fiber having a fineness of less than 5000 dtex and a single yarn fineness of less than 2 dtex has a fine single yarn fineness, making it difficult to produce a stable yarn. If the fineness exceeds 150,000 dtex and the single yarn fineness of 14 dtex, the gap between the fibers cannot be suppressed by the PTFE resin fine particles or the liquid lubricant, and there is a possibility that stable sealing performance cannot be provided as a braided product.
ＰＴＦＥ繊維の単糸強度は０．３ｃＮ／ｄｔｅｘ以上２ｃＮ／ｄｔｅｘ以下であることが好ましい。さらには０．４ｃＮ／ｄｔｅｘ以上１．０ｃＮ／ｄｔｅｘ以下であることが好ましい。単糸強度が０．３ｃＮ／ｄｔｅｘ未満であれば強度が弱いため、繊維切れが頻発し高次加工性が劣り、さらには編組製品としての強力も低くなることで、その寿命が短くなる恐れがある。２ｃＮ／ｄｔｅｘを超える繊維は、ＰＴＦＥ繊維製造過程において、その条件が高度化し、安定した品質の繊維を得ることが難しくなる。 The single yarn strength of the PTFE fiber is preferably 0.3 cN / dtex or more and 2 cN / dtex or less. Further, it is preferably 0.4 cN / dtex or more and 1.0 cN / dtex or less. If the single yarn strength is less than 0.3 cN / dtex, the strength is weak, so that fiber breakage frequently occurs and inferior high-order processability, and further, the strength as a braided product may be reduced, and the life may be shortened. is there. Fibers exceeding 2 cN / dtex have advanced conditions in the PTFE fiber production process, making it difficult to obtain stable quality fibers.
ＰＴＦＥ繊維の２３０℃×３０分の乾燥処理時における乾熱収縮率は３％以下であることが好ましい。３％を超えると編組製品としての寸法安定性が満足できなくなる。 It is preferable that the dry heat shrinkage rate of the PTFE fiber during drying at 230 ° C. for 30 minutes is 3% or less. If it exceeds 3%, the dimensional stability as a braided product cannot be satisfied.
ＰＴＦＥ繊維はＰＴＦＥ樹脂水性分散液を含浸させることで、フィラメント状の繊維表面に未焼成のＰＴＦＥ樹脂を保持することができる。 By impregnating the PTFE fiber with an aqueous PTFE resin dispersion, the unfired PTFE resin can be retained on the filament-like fiber surface.
ＰＴＦＥ樹脂水性分散液のＰＴＦＥ濃度は５５質量％以上６５質量％以下であることが好ましい。５５質量％未満であると、フィラメントに塗着するＰＴＦＥ量が少なくなるため、目的の半焼成ＰＴＦＥ量を含浸させるために含浸回数を増やし、ライン速度を下げるなどの対策が必要となり、経済的に不利である。また、６５質量％を超えるとＰＴＦＥ塗着量の微妙なコントロールが難しくなる。 The PTFE concentration of the aqueous PTFE resin dispersion is preferably 55% by mass or more and 65% by mass or less. If the amount is less than 55% by mass, the amount of PTFE to be applied to the filament is reduced. Therefore, it is necessary to take measures such as increasing the number of impregnations and lowering the line speed in order to impregnate the desired semi-baked PTFE amount. It is disadvantageous. On the other hand, if it exceeds 65% by mass, delicate control of the PTFE coating amount becomes difficult.
ＰＴＦＥ樹脂水性分散液中の特定のノニオン系界面活性剤は、ＪＩＳ Ｋ０１２９の熱重量測定（ＴＧＡ）によって測定した２２０℃における重量減少が２０質量％以下である。 The specific nonionic surfactant in the PTFE resin aqueous dispersion has a weight loss of 20% by mass or less at 220 ° C. measured by thermogravimetry (TGA) of JIS K0129.
上記２２０℃における重量減少が２０質量％以下であるノニオン系界面活性剤は、疎水基として芳香族環を含まない直鎖あるいは／および分岐あるいは／および環状構造を有する炭化水素基を持ち、親水基としてポリオキシエチレン基を有するものであれば、特に構造は限定されないが、下記化学式で示されるものが好ましく使用される。 The nonionic surfactant having a weight loss of 20% by mass or less at 220 ° C. has a hydrocarbon group having a linear or / and branched or / and cyclic structure not containing an aromatic ring as a hydrophobic group, and a hydrophilic group As long as it has a polyoxyethylene group, the structure is not particularly limited, but those represented by the following chemical formula are preferably used.
Ｒ１（ＯＣＨ２ＣＨ２）ｎＯＨ 式（１）
（Ｒ１は炭素数が１０〜１５である直鎖および／または分岐構造有する脂肪族炭化水素、ｎは平均５〜２０の整数）
R 1 (OCH 2 CH 2 ) n OH Formula (1)
(R 1 is an aliphatic hydrocarbon having a linear and / or branched structure having 10 to 15 carbon atoms, and n is an integer having an average of 5 to 20)
本発明において好ましい熱重量減少範囲である２２０℃において２０質量％以下であるためには、Ｒ１が分岐デシル、イソデシルの場合には、ｎの平均が１１以上であることが好ましい。 In order to be 20% by mass or less at 220 ° C., which is a preferred thermogravimetric reduction range in the present invention, when R 1 is branched decyl or isodecyl, the average of n is preferably 11 or more.
また、Ｒ１が分岐トリデシルの場合にはｎの平均が７〜１２であることが好ましい。 Further, it is preferable in the case of R 1 is branched tridecyl average of n is 7 to 12.
また、Ｒ１が炭素数が１１〜１４の分岐アルキル基混合物の場合には、ｎの平均が１０〜１３であることが好ましい。 In addition, when R 1 is a branched alkyl group mixture having 11 to 14 carbon atoms, the average of n is preferably 10 to 13.
さらに、上記ノニオン系界面活性剤を混合して使用することもできる。上記ノニオン系界面活性剤あるいはその混合物の曇点は３０℃〜８０℃であることが好ましく、さらに４５℃から７０℃であることが好ましい。 Furthermore, the nonionic surfactant can be mixed and used. The cloud point of the nonionic surfactant or mixture thereof is preferably 30 ° C to 80 ° C, more preferably 45 ° C to 70 ° C.
本発明のノニオン系界面活性剤は、分岐、直鎖あるいは環状の一級アルコールに公知の方法によってエチレンオキサイドおよび／あるいはポリプロピレンオキサイドを付加することによって得ることができる。また、２級、３級のアルコールにエチレンオキサイドおよび／あるいはポリプロピレンオキサイドを付加することによっても得ることができる。 The nonionic surfactant of the present invention can be obtained by adding ethylene oxide and / or polypropylene oxide to a branched, linear or cyclic primary alcohol by a known method. It can also be obtained by adding ethylene oxide and / or polypropylene oxide to secondary and tertiary alcohols.
エチレンオキサイドおよび／あるいはポリプロピレンオキサイドの付加は、単分散、あるいは、単分散を混合したバイモーダルであることができる。 The addition of ethylene oxide and / or polypropylene oxide can be monodispersed or bimodal mixed with monodisperse.
さらに、本発明の目的を損なわない範囲で、目的に応じてさらにノニオン系界面活性剤、アニオン系界面活性剤などを併用することができる。 Furthermore, a nonionic surfactant, an anionic surfactant, etc. can be used together according to the objective in the range which does not impair the objective of this invention.
ＰＴＦＥ繊維表面から半焼成ＰＴＦＥが脱落しにくい理由については、発明者は、半焼成ＰＴＦＥ中に残存しているノニオン系界面活性剤が、ＰＴＦＥ粒子のバインダーとして適度な保持力を発現していると考えている。このため、半焼成温度付近におけるノニオン系界面活性剤の分解が多すぎると、このバインダー成分としてのノニオン界面活性剤量の残存量が少なくなり、保持力が不足するものと考えられる。熱重量測定（ＴＧＡ）によって測定される、２２０℃における重量減少割合が２０質量％超であると、半焼成工程において分解揮発するノニオン系界面活性剤量が過剰となりバインダー成分が不足する恐れがある。その結果、ＰＴＦＥ樹脂水性分散液を含浸後、乾燥工程のガイドへの擦過によりＰＴＦＥ樹脂が脱落し易くなり、フィラメント状の繊維表面に目標とする未焼成ＰＴＦＥ樹脂を保持することが難しくなると考えられる。 Regarding the reason why the semi-fired PTFE is not easily removed from the surface of the PTFE fiber, the inventor said that the nonionic surfactant remaining in the semi-fired PTFE expresses an appropriate holding force as a binder of the PTFE particles. thinking. For this reason, when there is too much decomposition | disassembly of nonionic surfactant in the semi-baking temperature vicinity, the residual amount of the nonionic surfactant amount as this binder component will decrease, and it is thought that holding power is insufficient. If the weight loss rate at 220 ° C. measured by thermogravimetry (TGA) is more than 20% by mass, the amount of nonionic surfactant that decomposes and volatilizes in the semi-baking process may be excessive, and the binder component may be insufficient. . As a result, after impregnating the aqueous PTFE resin dispersion, the PTFE resin is likely to fall off by rubbing the guide in the drying step, and it is considered difficult to hold the target unsintered PTFE resin on the filament-like fiber surface. .
フィラメント状繊維に対して、６０質量％以上１２０質量％以下の割合で未焼成ＰＴＦＥ樹脂が塗着していることが好ましい。未焼成ＰＴＦＥ樹脂の塗着割合は、より好ましくは７０質量％以上１１０質量％以下である。６０質量％未満であると、編組製品として安定したシール性を付与することが出来ない恐れがある。１２０質量％を超えても、それ以上のシール性の効果はなく、コスト悪化に繋がる。 It is preferable that the unsintered PTFE resin is applied to the filamentous fiber at a ratio of 60% by mass or more and 120% by mass or less. The coating ratio of the unsintered PTFE resin is more preferably 70% by mass or more and 110% by mass or less. If it is less than 60% by mass, there is a possibility that a stable sealing property cannot be imparted as a braided product. Even if it exceeds 120% by mass, there is no further sealing effect, leading to cost deterioration.
ＰＴＦＥ樹脂水性分散液を含浸後、乾燥温度を１５０℃以上２２０℃以下、乾燥時間を２分以上１０分以下とすることが好ましい。乾燥温度１６０℃未満であるとＰＴＦＥ樹脂水性分散液中の水分揮発が十分ではなく、ＰＴＦＥ樹脂の塗着性が悪化する恐れがある。乾燥温度２２０℃を超えると界面活性剤の分解が進み、ＰＴＦＥ樹脂の塗着性が悪化する。乾燥時間２分未満であるとＰＴＦＥ樹脂水性分散液の水分揮発が十分ではなく、ＰＴＦＥ樹脂の塗着性が悪化する恐れがある。乾燥時間１０分を超えてもＰＴＦＥ含浸糸は十分に水分除去が完了しており、それ以上の乾燥はエネルギーの悪化に繋がる。 After impregnating with the aqueous PTFE resin dispersion, the drying temperature is preferably 150 ° C. or higher and 220 ° C. or lower, and the drying time is preferably 2 minutes or longer and 10 minutes or shorter. If the drying temperature is lower than 160 ° C., the water volatilization in the aqueous PTFE resin dispersion is not sufficient, and the applicability of the PTFE resin may be deteriorated. When the drying temperature exceeds 220 ° C., the decomposition of the surfactant proceeds and the coating property of the PTFE resin deteriorates. If the drying time is less than 2 minutes, the PTFE resin aqueous dispersion will not have sufficient water volatilization, and the coating property of the PTFE resin may be deteriorated. Even when the drying time exceeds 10 minutes, the PTFE-impregnated yarn has sufficiently removed water, and further drying leads to deterioration of energy.
ＰＴＦＥ含浸糸に対して、液体潤滑剤であるジメチルポリシロキサンが８質量％以上１５質量％以下の割合で付着していることが好ましい。ジメチルポリシロキサンの付着割合は、より好ましくは１０質量％以上１３質量％以下である。８質量％未満であると編組の流体機器における初期潤滑性が悪化する恐れがある。１５質量％を超えてもそれ以上の初期潤滑性が得られず、コスト悪化に繋がる。 It is preferable that dimethylpolysiloxane, which is a liquid lubricant, adheres to the PTFE-impregnated yarn at a ratio of 8% by mass to 15% by mass. The adhesion ratio of dimethylpolysiloxane is more preferably 10% by mass or more and 13% by mass or less. If it is less than 8% by mass, the initial lubricity in the braided fluid device may be deteriorated. Even if it exceeds 15% by mass, no further initial lubricity can be obtained, leading to cost deterioration.
これら得られたＰＴＦＥ含浸糸を編組した製品は、たとえばポンプ、攪拌機、バルブなど各種流体機器の軸封部などのグランドパッキンとして広く用いられる。 Products obtained by braiding these obtained PTFE-impregnated yarns are widely used as gland packings for shaft seals of various fluid devices such as pumps, agitators and valves.
以下、実施例を挙げて本発明を具体的に説明する。なお、繊維の各物性の測定方法は以下の通りである。 Hereinafter, the present invention will be specifically described with reference to examples. In addition, the measuring method of each physical property of a fiber is as follows.
（１）ＰＴＦＥフィラメントの繊度
ＪＩＳ Ｌ １０１３：１９９９に準じて測定した。
(1) Fineness of PTFE filament Measured according to JIS L 1013: 1999.
（２）ＰＴＦＥフィラメントへの未焼成ＰＴＦＥ樹脂塗着率
ＪＩＳ Ｌ １０１３：１９９９に準じてＰＴＦＥ含浸糸の繊度を測定し、ＰＴＦＥ樹脂含浸前のＰＴＦＥフィラメントの繊度より算出した。
(2) Coating rate of unsintered PTFE resin on PTFE filament The fineness of the PTFE-impregnated yarn was measured according to JIS L 1013: 1999, and calculated from the fineness of the PTFE filament before impregnation with the PTFE resin.
未焼成ＰＴＦＥ樹脂塗着率＝（ＰＴＦＥ含浸糸繊度−ＰＴＦＥフィラメント繊度）／ＰＴＦＥフィラメント繊度×１００ Unbaked PTFE resin coating rate = (PTFE impregnated yarn fineness−PTFE filament fineness) / PTFE filament fineness × 100
（３）２２０℃における熱重量減少割合
セイコー電子社製示差熱・熱重量測定装置（ＴＧ−ＤＴＡ６２００）を使用し、下記条件下で得られた熱重量減少カーブより、２２０℃における熱重量減少割合を１００分率で求めた。
(3) Thermogravimetric decrease rate at 220 ° C. Using a differential thermal / thermogravimetric measuring device (TG-DTA6200) manufactured by Seiko Electronics Co., Ltd. Was obtained at a rate of 100 minutes.
試料：１０ｍｇ、アルミニウムセル使用
温度範囲：２０℃〜６００℃、昇温レート：１０℃／ｍｉｎ
雰囲気：空気２００ｍｌ／ｍｉｎ
Sample: 10 mg, aluminum cell operating temperature range: 20 ° C. to 600 ° C., temperature rising rate: 10 ° C./min
Atmosphere: Air 200ml / min
（４）ＰＴＦＥ樹脂塗着性確認
ＰＴＦＥフィラメントにＰＴＦＥ樹脂水性分散液を含浸させ乾燥後、巻取り前のテンショナーユニットガイド下部に脱落したＰＴＦＥ樹脂重量を測定した。
(4) Confirmation of PTFE resin coatability
After the PTFE filament was impregnated with an aqueous PTFE resin dispersion and dried, the weight of the PTFE resin dropped off under the tensioner unit guide before winding was measured.
［実施例１］
カセ巻き工程の後に、ＰＴＦＥフィラメント（繊度１００００ｄｔｅｘ、単糸繊度９．５ｄｔｅｘ）を連続的に、ＰＴＦＥ水性分散液１（ＰＴＦＥ濃度６１質量％、疎水基が、分岐トリデシルであり、エチレンオキサイドの平均付加数が８．６モルであるノニオン系界面活性剤（２２０℃における熱重量減少が１０質量％）をＰＴＦＥに対して５．５質量％含む水性分散液）中を通して含浸させた後、１８０℃の熱風炉中で４分間乾燥させ、ＰＴＦＥフィラメントへの未焼成ＰＴＦＥ樹脂塗着率を１００％とする含浸糸を得た。巻き取り前のテンショナーユニットガイド下部に発生したＰＴＦＥ樹脂脱落物量は、ＰＴＦＥ含浸糸１０００ｍあたり８ｇと非常に少なかった。
[Example 1]
After the winding process, PTFE filament (fineness: 10000 dtex, single yarn fineness: 9.5 dtex) is continuously added, PTFE aqueous dispersion 1 (PTFE concentration 61 mass%, hydrophobic group is branched tridecyl, and average addition of ethylene oxide) After impregnating through a nonionic surfactant having a number of 8.6 mol (an aqueous dispersion containing 5.5% by mass of thermal weight at 220 ° C. of 10% by mass) with respect to PTFE), 180 ° C. It was dried in a hot air oven for 4 minutes to obtain an impregnated yarn having a non-fired PTFE resin coating rate of 100% on the PTFE filament. The amount of PTFE resin dropout generated at the lower part of the tensioner unit guide before winding was as small as 8 g per 1000 m of PTFE-impregnated yarn.
［実施例２］
実施例１において、２１０℃の熱風炉中で３分間乾燥させた以外は、実施例１と同様にして含浸糸を得た。巻き取り前のテンショナーユニットガイド下部に発生したＰＴＦＥ樹脂脱落物量は、ＰＴＦＥ含浸糸１０００ｍあたり１０ｇと非常に少なかった。
[Example 2]
In Example 1, an impregnated yarn was obtained in the same manner as in Example 1 except that it was dried in a hot air oven at 210 ° C. for 3 minutes. The amount of the PTFE resin dropout generated at the lower part of the tensioner unit guide before winding was as small as 10 g per 1000 m of PTFE-impregnated yarn.
［比較例１］
実施例１において、ＰＴＦＥ水性分散液１を、ＰＴＦＥ水性分散液２（ＰＴＦＥ濃度６１質量％、疎水基が、炭素数１１〜１４の分岐アルキル基（平均炭素数１２．８）であり、エチレンオキサイドの平均付加数が９．２モルであるノニオン系界面活性剤（２２０℃における熱重量減少が２６質量％）をＰＴＦＥに対して５．５質量％含む水性分散液）に変更した以外は、実施例１と同様にして含浸糸を得た。巻き取り前のテンショナーユニットガイド下部に発生したＰＴＦＥ樹脂脱落物量は、ＰＴＦＥ含浸糸１０００ｍあたり４０ｇと非常に多く、生産性面で不利であった。
[Comparative Example 1]
In Example 1, PTFE aqueous dispersion 1 was treated with PTFE aqueous dispersion 2 (PTFE concentration 61 mass%, hydrophobic group was a branched alkyl group having 11 to 14 carbon atoms (average carbon number 12.8), and ethylene oxide. The nonionic surfactant having an average addition number of 9.2 mol (an aqueous dispersion containing 5.5% by mass of thermal weight at 220 ° C.) is changed to 5.5% by mass with respect to PTFE. In the same manner as in Example 1, an impregnated yarn was obtained. The amount of the PTFE resin dropout generated at the lower part of the tensioner unit guide before winding was as large as 40 g per 1000 m of PTFE-impregnated yarn, which was disadvantageous in terms of productivity.
［比較例２］
実施例１において、１３０℃の熱風炉中で９分間乾燥させた以外は、実施例１と同様にして含浸糸を得た。巻き取り前のテンショナーユニットガイド下部に発生したＰＴＦＥ樹脂脱落物量は、ＰＴＦＥ含浸糸１０００ｍあたり４５ｇと非常に多く、生産性面で不利であった。
[Comparative Example 2]
In Example 1, an impregnated yarn was obtained in the same manner as in Example 1 except that it was dried in a hot air oven at 130 ° C. for 9 minutes. The amount of the PTFE resin dropout generated at the lower part of the tensioner unit guide before winding was as large as 45 g per 1000 m of PTFE-impregnated yarn, which was disadvantageous in terms of productivity.
［比較例３］
実施例１において、熱風炉中で１分間乾燥させた以外は、実施例１と同様にして含浸糸を得た。巻き取り前のテンショナーユニットガイド下部に発生したＰＴＦＥ樹脂脱落物量は、ＰＴＦＥ含浸糸１０００ｍあたり３３ｇと非常に多く、生産性面で不利であった。
[Comparative Example 3]
In Example 1, an impregnated yarn was obtained in the same manner as in Example 1 except that it was dried in a hot air oven for 1 minute. The amount of the PTFE resin dropout generated at the lower part of the tensioner unit guide before winding was as large as 33 g per 1000 m of PTFE-impregnated yarn, which was disadvantageous in terms of productivity.
［比較例４］
実施例１において、２４０℃の熱風炉中で４分間乾燥させた以外は、実施例１と同様にして含浸糸を得た。巻き取り前のテンショナーユニットガイド下部に発生したＰＴＦＥ樹脂脱落物量は、ＰＴＦＥ含浸糸１０００ｍあたり５６ｇと非常に多く、生産性面で不利であった。
[Comparative Example 4]
In Example 1, an impregnated yarn was obtained in the same manner as in Example 1 except that drying was performed in a hot air oven at 240 ° C. for 4 minutes. The amount of the PTFE resin dropout generated at the lower portion of the tensioner unit guide before winding was as large as 56 g per 1000 m of PTFE-impregnated yarn, which was disadvantageous in terms of productivity.
上述の実施例および比較例で得られた結果を表１に示す。 Table 1 shows the results obtained in the above examples and comparative examples.
本発明のＰＴＦＥ含浸糸を編組した製品は、たとえばポンプ、攪拌機、バルブなど各種流体機器の軸封部などのグランドパッキンとして広く用いられる。
A product obtained by braiding the PTFE-impregnated yarn of the present invention is widely used as a gland packing such as a shaft seal portion of various fluid devices such as a pump, a stirrer and a valve.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912815A (en) * | 2019-03-05 | 2019-06-21 | 山东东岳高分子材料有限公司 | A kind of high redispersibility fluoroplastics aqueous liquid dispersion and the preparation method and application thereof |
| CN109912815B (en) * | 2019-03-05 | 2021-11-05 | 山东东岳高分子材料有限公司 | High-redispersibility fluoroplastic aqueous dispersion liquid and preparation method and application thereof |
| JP2021060184A (en) * | 2019-10-08 | 2021-04-15 | 日本ピラー工業株式会社 | Operation control method for dryer, and operation method for dryer |
| JP7478542B2 (en) | 2019-10-08 | 2024-05-07 | 日本ピラー工業株式会社 | Method for controlling operation of drying device and method for operating drying device |
| WO2022009918A1 (en) * | 2020-07-09 | 2022-01-13 | Ａｇｃ株式会社 | Sizing agent, sized fibers, prepreg, and dispersion |
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| JP5981188B2 (en) | 2016-08-31 |
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