JP2886946B2 - Insulation material composed of melt anisotropic aromatic polyester fiber - Google Patents
Insulation material composed of melt anisotropic aromatic polyester fiberInfo
- Publication number
- JP2886946B2 JP2886946B2 JP12751590A JP12751590A JP2886946B2 JP 2886946 B2 JP2886946 B2 JP 2886946B2 JP 12751590 A JP12751590 A JP 12751590A JP 12751590 A JP12751590 A JP 12751590A JP 2886946 B2 JP2886946 B2 JP 2886946B2
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- Prior art keywords
- fiber
- aromatic polyester
- yarn
- polysiloxane
- polyester fiber
- Prior art date
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- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、溶融異方性芳香族ポリエステル繊維からな
る絶縁材料に関する。Description: TECHNICAL FIELD The present invention relates to an insulating material comprising a melt-anisotropic aromatic polyester fiber.
〔従来の技術〕 溶融異方性を示すポリマーを紡糸して高強度・高弾性
率の繊維が得られることは特開昭54−77691号および特
開平１−92408号公報等で公知である。オルガノポリシ
ロキサンを有機繊維の油剤として用いることは特開昭57
−171769号等で公知である。2. Description of the Related Art It is known from JP-A-54-77691 and JP-A-1-92408 that spinning a polymer exhibiting melt anisotropy to obtain a fiber having a high strength and a high elastic modulus. The use of organopolysiloxane as an oil agent for organic fibers is disclosed in
It is known in US Pat.
高強度・高弾性率のアラミド繊維や芳香族ポリエステ
ル繊維を電線材料の芯材として用いた場合、相対湿度60
％で従来品では1013（Ω/cm）オーダー以下の電気抵抗
しか得られず、電気抵抗性に優れた高強度・高弾性率繊
維が望まれている。When high-strength, high-modulus aramid fiber or aromatic polyester fiber is used as the core material of the wire material, the relative humidity is 60%.
%, The conventional product can provide an electric resistance of only 10 13 (Ω / cm) or less, and a high-strength and high-modulus fiber having excellent electric resistance is desired.
また、溶融異方性芳香族ポリエステル繊維は、ロープ
等として用いられることもあり、電気抵抗性を併せて耐
摩耗性についてもその特性が要望されている。Further, the melt-anisotropic aromatic polyester fiber is sometimes used as a rope or the like, and its characteristics are required for abrasion resistance as well as electric resistance.
本発明は、下記一般式（Ａ）で示される繰り返し単位
からなるポリシロキサンを繊維に対して0.1重量％以上
付着した溶融異方性芳香族ポリエステル繊維からなる絶
縁材料である。The present invention is an insulating material composed of a melt-anisotropic aromatic polyester fiber having a polysiloxane composed of a repeating unit represented by the following general formula (A) adhered to the fiber in an amount of 0.1% by weight or more based on the fiber.
（ただし、式中、R1、R2は水素原子、アルキル基又はア
リール基を表す。） 本発明にいう溶融異方性芳香族ポリエステルの好まし
い例としては、下記に示す繰り返し単位の組合せからな
るものである。 (Wherein, R 1 and R 2 represent a hydrogen atom, an alkyl group or an aryl group.) A preferred example of the melt anisotropic aromatic polyester according to the present invention comprises a combination of the following repeating units. Things.
上記芳香族ポリエステル化合物から溶融紡糸法によつ
て従来の衣料用ポリエステル繊維より高強度低伸度な芳
香族ポリエステル繊維が得られることは、特開昭54−77
691号、特開昭50−43223号、特開昭58−191219号等に開
示されている。 Japanese Patent Application Laid-Open No. 54-77 discloses that aromatic polyester fibers having higher strength and lower elongation than conventional polyester fibers for clothing can be obtained from the aromatic polyester compound by a melt spinning method.
No. 691, JP-A-50-43223 and JP-A-58-191219.
さらに異方性溶融物を形成し得る芳香族ポリエステル
ポリマーを適当な条件で紡糸し（必要によつては熱処理
および／又は延伸し）て高強力高弾性率繊維を製造する
技術は特公昭55−20008号公報、特開昭60−239600号公
報等に開示されている。Furthermore, a technique for producing a high-strength, high-modulus fiber by spinning an aromatic polyester polymer capable of forming an anisotropic melt under appropriate conditions (heat treatment and / or stretching if necessary) is disclosed in No. 20008, JP-A-60-239600 and the like.
本発明の効果が最も顕著に発揮されるのは、下記
〔Ｉ〕、〔II〕の繰り返し単位から成る部分が、80モル
％以上であるポリマー、特に〔II〕の成分が５〜45モル
％である芳香族ポリエステル化合物である。The effect of the present invention is most remarkably exhibited when the polymer comprising the repeating unit of the following [I] and [II] is at least 80 mol%, particularly 5 to 45 mol% of the component [II]. Is an aromatic polyester compound.
また第３成分として、例えば下記に挙げる構造単位の
１個又は複数個を20モル％以下含んでいても良い。 As the third component, for example, one or more of the following structural units may be contained in an amount of 20 mol% or less.
この化合物から繊維を紡糸する方法は、特開平１−25
410号公報に詳しく記載されている。 A method of spinning a fiber from this compound is disclosed in
This is described in detail in Japanese Patent Publication No. 410.
本発明におけるポリシロキサンとは、前記一般式
（Ａ）で表わされる繰り返し単位からなり、式中、R1、
R2は水素原子、−CH3、−CH2CH3等のアルキル基または
−C6H5等のアリール基を示す。好ましくはR1、R2がメチ
ル基よりなるものが電気抵抗が高く良い。The polysiloxane in the present invention comprises a repeating unit represented by the general formula (A), wherein R 1 ,
R 2 represents a hydrogen atom, an alkyl group such as —CH 3 or —CH 2 CH 3 or an aryl group such as —C 6 H 5 . Preferably, those in which R 1 and R 2 are each a methyl group have a high electric resistance and are good.
本発明に用いるポリシロキサンは繊維や織物に潤滑
性、撥水性、撥油性などを与える表面処理剤で、かなり
の平滑性を繊維に付与することができる。本発明に用い
るポリシロキサンは、25℃における粘度が１〜100,000
センチストークス（cst）が好ましい。The polysiloxane used in the present invention is a surface treatment agent that imparts lubricity, water repellency, oil repellency, and the like to fibers and fabrics, and can impart considerable smoothness to fibers. The polysiloxane used in the present invention has a viscosity at 25 ° C of 1 to 100,000.
Centistokes (cst) are preferred.
絶縁材料として使用する油剤としては、電気抵抗性を
補うため、繊維表面に植物性絶縁油（例えば、ヤシ油、
キリ油、アマニ油、ヒマシ油、大豆油）、鉱物性絶縁油
（主成分がパラフイン系炭化水素及びナフテン系炭化水
素）系の油剤を付着させる改善が考えられるが、芳香族
ポリエステルにこれらの油剤を付着しても電気抵抗性、
耐摩耗性が不十分である。As an oil agent used as an insulating material, a vegetable insulating oil (for example, coconut oil,
It is possible to improve the adhesion of oils of tung oil, linseed oil, castor oil, soybean oil) and mineral insulating oils (mainly paraffinic hydrocarbons and naphthenic hydrocarbons). Even if you attach electrical resistance,
Insufficient wear resistance.
ポリシロキサンを繊維表面へ均一に付着させるため低
粘度鉱物油により希釈されたポリシロキサンを用いても
良い。Polysiloxane diluted with low-viscosity mineral oil may be used to uniformly adhere the polysiloxane to the fiber surface.
しかし、一般に用いられるエマルジヨンタイプ付着法
すなわちノニオン系、アニオン系及びカチオン系乳化剤
を使用し、本発明に係わる組成物を水中でエマルジヨン
化し、繊維に添付する方法は、繊維中に界面活性剤が残
存するため、乾燥繊維の電気抵抗が低くなり、本発明の
主旨からはずれる。具体的な繊維への付着法は、一定濃
度（原液または希釈された液）にした溶液を一定速度の
走行糸にカラス口等から吐出させる法、ポリシロキサン
溶液に一部浸した回転ローラー上で糸を走行させる方
法、ポリシロキサン溶液中を走行させアングル等で絞る
方法等があり、目的の付着量が得られるならいずれの方
法でも良い。次にポリシロキサン溶液を乾燥させて巻き
とることで達成できる。However, a commonly used emulsion type deposition method, that is, a method of using a nonionic, anionic or cationic emulsifier, emulsifying the composition according to the present invention in water, and attaching the composition to the fiber, a surfactant is contained in the fiber. Since it remains, the electrical resistance of the dried fiber becomes low, deviating from the gist of the present invention. A specific method of adhering to fibers is to discharge a solution of a certain concentration (a stock solution or a diluted solution) onto a traveling yarn at a certain speed from a crow's mouth or the like, or on a rotating roller partially immersed in a polysiloxane solution. There are a method of running the yarn, a method of running the yarn in a polysiloxane solution, and squeezing by an angle or the like, and any method may be used as long as a desired amount of adhesion can be obtained. Next, it can be achieved by drying and winding the polysiloxane solution.
ポリシロキサンの繊維への付着量は、繊維表面をむら
なく均一に覆うことができれば良く、繊維に対して0.1
重量％以上であれば良く、好ましくは0.5から20重量％
である。The amount of polysiloxane adhering to the fiber may be any value as long as the fiber surface can be evenly and uniformly covered.
% By weight or more, preferably 0.5 to 20% by weight
It is.
本発明により強度15g/d以上かつ弾性率400g/d以上を
有する高強度・高弾性率溶融異方性芳香族ポリエステル
繊維に、ポリシロキサンを該繊維に対して0.1重量％以
上付着することで、これらの繊維の電気抵抗を著しく発
現させることが可能となつた。By attaching a polysiloxane to the high-strength and high-modulus melt-anisotropic aromatic polyester fiber having a strength of 15 g / d or more and an elastic modulus of 400 g / d or more according to the present invention, at least 0.1% by weight of the fiber, It has become possible to significantly develop the electrical resistance of these fibers.
本発明の絶縁材料の具体的用途としては以下のような
ものが挙げられる 1.フイラメント、紡績糸、ヤーン状で使用されるもの、
光フアイバー、高電圧下光フアイバー用テンシヨンメン
バー、電線ケーブル、芯材等絶縁材料等が挙げられる。
ロープ、ホース、コード、ケーブル、縫糸等の形態で使
用してもかまわない。Specific applications of the insulating material of the present invention include the following 1. Filament, spun yarn, those used in a yarn shape,
Examples include optical fibers, tension members for optical fibers under high voltage, electric cables, insulating materials such as core materials, and the like.
It may be used in the form of a rope, a hose, a cord, a cable, a sewing thread, or the like.
2.カツトフアイバー、チヨツプドヤーン状で使用される
もの、紙（絶縁紙）、IC等基盤用補強材、テレビ、ビデ
オ、オーデイオ等電気部品用樹脂補強材、一般用樹脂補
強材等が挙げられる。2. Cut fiber, used in the form of chopped yarn, paper (insulating paper), reinforcing material for bases such as IC, resin reinforcing material for electric parts such as TV, video, audio, and general resin reinforcing material.
以下、実施例により本発明をより具体的に説明する
が、本発明はこれら実施例により限定されるものではな
い。Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
尚実施例中に記載した繊度（DB）｛デニール（d
r）｝、強度DT（g/d）、伸度DE（％）及び弾性率YM（g/
d）の測定値はヤーンに80回/mの撚りを与えた試料を用
い、JIS L1013に準じ、調湿した繊維を試長20cmで10cm/
minの引張速度で室温にて測定して得たものである。繊
度は重量法により求めた。The fineness (DB) ｛denier (d
r)｝, strength DT (g / d), elongation DE (%), and elasticity YM (g / d)
The measured value of d) is based on JIS L1013 using a sample in which the yarn is twisted at 80 turns / m.
It was obtained by measuring at room temperature at a tensile speed of min. The fineness was determined by a gravimetric method.
繊維の電気抵抗Ｒ（Ω/cm）は試長1cm、印加電圧1000
Vで測定環境湿度を変化させて測定した。繊維間摩耗と
は、80回/mの撚りを持つヤーン試験糸（例えば1500デニ
ール/300フイラメント）を反転プーリーと他端のフリー
ローラーとの間に３回撚合せることで８の字状として取
付けフリーローラーに2kgの荷重をかけ、35回／分の速
度で試験糸を往復撚合せ摩耗させて切断までの回数を測
定する撚合せ摩耗試験で測定した。The electrical resistance R (Ω / cm) of the fiber is test length 1cm, applied voltage 1000
The measurement was performed by changing the measurement environment humidity at V. The inter-fiber abrasion means that a yarn test yarn with a twist of 80 turns / m (for example, 1500 denier / 300 filament) is twisted three times between the reversing pulley and the free roller at the other end and attached as a figure-eight. A 2 kg load was applied to the free roller, and the test yarn was reciprocally twisted and worn at a speed of 35 times / min.
対数粘度は次のようにして求めた。 The logarithmic viscosity was determined as follows.
試料をペンタフルオロフエノールに0.1重量％溶解し
（60〜80℃）、60℃の恒温槽中でウベローデ型毛管粘度
計（例えば高分子学会編“高分子科学実験法”東京化学
同人P179（1986）東京）で測定する。A sample is dissolved in pentafluorophenol at 0.1% by weight (60-80 ° C), and an Ubbelohde capillary viscometer (for example, “Polymer Science Experimental Method” edited by The Society of Polymer Science, Tokyo Chemical Dojin P179 (1986)) in a thermostat at 60 ° C. Tokyo).
〔ηrel;相対粘度,C;測定溶液濃度（g/dl）〕 Tmは融点でありDSCによつて測定された吸熱ピーク温
度である。 [Ηrel; relative viscosity, C; measured solution concentration (g / dl)] Tm is a melting point and an endothermic peak temperature measured by DSC.
実施例１ 前記構成単位〔Ｉ〕、〔II〕が70/30モル％比である
芳香族ポリエステルポリマーを溶融紡糸に使用した。Example 1 An aromatic polyester polymer in which the structural units [I] and [II] had a 70/30 mol% ratio was used for melt spinning.
このポリマーの物性は、 ηinh＝5.9dl/g Tm＝281℃ であつた。 Physical properties of this polymer were ηinh = 5.9 dl / g Tm = 281 ° C.
このポリマーを単軸ベント型押出機より押出し、サン
ド（ステンレスパウダー）層、金属細線からなるフイル
ターを通過させたのち、320℃で紡糸した。ノズルは、
0.12mmφ×300Hである。吐出量125g/min、紡速800m/min
で巻取つた。The polymer was extruded from a single-screw vent type extruder, passed through a sand (stainless powder) layer, and a filter made of a fine metal wire, and then spun at 320 ° C. The nozzle is
It is 0.12mmφ × 300H. Discharge rate 125g / min, spinning speed 800m / min
It was wound up.
この紡糸原糸を穴あきボビンに巻密度0.57g/CCで巻
き、260℃で１時間、270℃から280℃まで３時間、280℃
から285℃まで５時間熱処理をした。得られた熱処理糸
の力学的性能は、 ヤーンデニール（DR）:1510dr 強 度 （DT）:26.8g/d 伸 度 （DE）:3.8％ 弾 性 率 （YM）:587g/d であつた。This spun yarn is wound around a bobbin with a winding density of 0.57 g / CC, at 260 ° C for 1 hour, from 270 ° C to 280 ° C for 3 hours, at 280 ° C.
To 285 ° C. for 5 hours. The mechanical properties of the obtained heat-treated yarn were as follows: yarn denier (DR): 1510dr strength (DT): 26.8 g / d elongation (DE): 3.8% elastic modulus (YM): 587 g / d.
この熱処理糸に下記構造式（Ｂ）のポリジメチルシロ
キサン（10cst）をカラス口より0.34g/min〜6.8g/min吐
出して速度200m/minの走行糸に付着（１、２、４、10、
20重量％）させ、200℃に保つた加熱ローラーへ導いて
乾燥熱処理をした。A 0.34 g / min to 6.8 g / min polydimethylsiloxane (10) of the following structural formula (B) is discharged from the crow mouth to the heat-treated yarn and adheres to the running yarn at a speed of 200 m / min (1, 2, 4, 10 ,
20% by weight) and guided to a heating roller maintained at 200 ° C. for dry heat treatment.
〔式中ｎは自然数を表す〕 得られた各加工糸の力学的性質及び相対湿度60％、室
温における電気抵抗を表１に示す。 [Where n represents a natural number] Table 1 shows the mechanical properties and the electrical resistance of the obtained processed yarns at a relative humidity of 60% and room temperature.
実施例２ 実施例１で得られた熱処理糸に実施例１と同様にして
下記構造式（Ｃ）で示されるポリシロキサンを１及び４
重量％付着させて、得られた力学的性質及び相対湿度60
％、室温における電気抵抗の結果も表１に示す。Example 2 In the same manner as in Example 1, the polysiloxane represented by the following structural formula (C) was added to the heat-treated yarn obtained in Example 1 in the same manner as in Examples 1 and 4.
Wt% deposited, resulting mechanical properties and relative humidity 60
Table 1 also shows the results of% and the electrical resistance at room temperature.
〔式中ｎは自然数を表す〕 比較例１ 実施例１で得られた熱処理糸に下記構造式（Ｄ）で示
されるポリシロキサンをエマルジヨン化した水溶液より
１重量％付着させて、得られた繊維の力学的性質及び相
対湿度60％、室温における電気抵抗の結果も表１に示
す。 [In the formula, n represents a natural number] Comparative Example 1 A fiber obtained by adhering 1% by weight of an aqueous solution obtained by emulsifying a polysiloxane represented by the following structural formula (D) to the heat-treated yarn obtained in Example 1 Table 1 also shows the results of the mechanical properties and the electrical resistance at a relative humidity of 60% and room temperature.
〔式中m,nは自然数を表す〕 実施例３ 実施例１で得られた熱処理糸に前記構造式（Ｃ）で示
されるポリシロキサン重量１に対して９の鉱物油（流動
パラフイン）を加え10重量％溶液とし、カラス口より3.
4g/min〜13.6g/min吐出して速度200m/minの走行糸に付
着（1,2、４重量％）させ、実施例１と同様に乾燥熱処
理した。得られた測定結果を表２に示す。 (Where m and n represent natural numbers) Example 3 To the heat-treated yarn obtained in Example 1, 9 mineral oil (liquid paraffin) was added to 1 part by weight of the polysiloxane represented by the structural formula (C) to form a 10% by weight solution.
4 g / min to 13.6 g / min was discharged and adhered to the running yarn at a speed of 200 m / min (1, 2, 4% by weight), and dried and heat-treated in the same manner as in Example 1. Table 2 shows the obtained measurement results.
比較例２ 実施例１で得られた熱処理糸にやし油をカラス口より
1.36g/min吐出して速度200nm/minの走行糸に４重量％付
着させ、実施例１と同様に乾燥熱処理した。得られた測
定結果を表２に示す。Comparative Example 2 Palm oil was added to the heat-treated yarn obtained in Example 1 through a crow mouth.
1.36 g / min was discharged and adhered to a running yarn at a speed of 200 nm / min at 4% by weight, and dried and heat-treated in the same manner as in Example 1. Table 2 shows the obtained measurement results.
比較例３ 実施例１で得られた熱処理糸に鉱物油（流動パラフイ
ン）をカラス口より1.36g/min吐出して速度200m/minの
走行糸に４重量％の目安で付着させ、150℃に保つた加
熱ローラーへ導いて乾燥熱処理をした。得られた結果を
表２に示す。Comparative Example 3 Mineral oil (liquid paraffin) was discharged at 1.36 g / min from the crow mouth to the heat-treated yarn obtained in Example 1 and adhered to the running yarn at a speed of 200 m / min at a standard of 4% by weight. It was led to a heated heating roller and subjected to a dry heat treatment. Table 2 shows the obtained results.
比較例４ 下記力学的性質を有するパラ系アラミドを試料とし
て、表面に付着している油剤や汚れを除去するため、ｎ
−ヘキサン溶液中で10分間、次に水中で10分間攪拌洗浄
して乾燥させた。Comparative Example 4 Using a para-aramid having the following mechanical properties as a sample, n was used to remove oil and dirt attached to the surface.
-Washed with stirring in a hexane solution for 10 minutes and then in water for 10 minutes and dried.
（洗浄後） ヤーンデニール（DR）:1531dr 強 度（DT）:22.6g/d 伸 度（DE）:3.7％ 弾 性 率（YM）:558g/d この糸に前記構造式（Ｂ）のポリシロキサンをカラス
口より0.34g/min〜3.4g/min吐出して速度200m/minの走
行糸に付着（４重量％）させ、実施例１と同様に乾燥熱
処理した。得られた各加工糸の力学的性質及び電気抵抗
の結果を表２に示す。(After washing) Yarn denier (DR): 1531dr Strength (DT): 22.6 g / d Elongation (DE): 3.7% Elastic modulus (YM): 558 g / d The yarn of the above structural formula (B) Siloxane was discharged from the crow mouth at 0.34 g / min to 3.4 g / min and adhered (4% by weight) to the running yarn at a speed of 200 m / min, and dried and heat-treated in the same manner as in Example 1. Table 2 shows the results of the mechanical properties and electric resistance of each of the obtained processed yarns.
〔発明の効果〕 本発明はポリシロキサンを溶融異方性芳香族ポリエス
テル繊維に付着させることにより電気抵抗性及び耐摩耗
性に優れた絶縁材料とできる。 [Effects of the Invention] According to the present invention, an insulating material having excellent electric resistance and abrasion resistance can be obtained by attaching polysiloxane to a melt anisotropic aromatic polyester fiber.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 杉田 幸男 岡山県倉敷市酒津1621番地 株式会社ク ラレ内 審査官 松縄 正登 (56)参考文献 特開 昭57−171769（ＪＰ，Ａ) 特開 昭54−77691（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) D06M 15/00 - 15/72 D01F 11/08 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yukio Sugita 1621 Sazu, Kurashiki-shi, Okayama Pref. −77691 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) D06M 15/00-15/72 D01F 11/08
Claims (1)
からなるポリシロキサンを繊維に対して0.1重量％以上
付着した溶融異方性芳香族ポリエステル繊維からなる絶
縁材料。 （ただし、式中、R1、R2は水素原子、アルキル基又はア
リール基を表す。）1. An insulating material comprising a melt-anisotropic aromatic polyester fiber having a polysiloxane comprising a repeating unit represented by the following general formula (A) adhered to the fiber in an amount of 0.1% by weight or more based on the fiber. (Wherein, R 1 and R 2 represent a hydrogen atom, an alkyl group or an aryl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12751590A JP2886946B2 (en) | 1990-05-16 | 1990-05-16 | Insulation material composed of melt anisotropic aromatic polyester fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12751590A JP2886946B2 (en) | 1990-05-16 | 1990-05-16 | Insulation material composed of melt anisotropic aromatic polyester fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0424289A JPH0424289A (en) | 1992-01-28 |
| JP2886946B2 true JP2886946B2 (en) | 1999-04-26 |
Family
ID=14961920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12751590A Expired - Fee Related JP2886946B2 (en) | 1990-05-16 | 1990-05-16 | Insulation material composed of melt anisotropic aromatic polyester fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2886946B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111819322B (en) * | 2018-03-07 | 2023-05-12 | 株式会社可乐丽 | Molten anisotropic aromatic polyester multifilament yarn |
-
1990
- 1990-05-16 JP JP12751590A patent/JP2886946B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0424289A (en) | 1992-01-28 |
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