JP2728717B2 - High-strength, high-modulus fiber with improved wear resistance - Google Patents
High-strength, high-modulus fiber with improved wear resistanceInfo
- Publication number
- JP2728717B2 JP2728717B2 JP1028390A JP2839089A JP2728717B2 JP 2728717 B2 JP2728717 B2 JP 2728717B2 JP 1028390 A JP1028390 A JP 1028390A JP 2839089 A JP2839089 A JP 2839089A JP 2728717 B2 JP2728717 B2 JP 2728717B2
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- strength
- fibers
- wear resistance
- organopolysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 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、耐摩耗性が改良された高強力、高弾性率繊
維に関する。The present invention relates to a high-strength, high-modulus fiber having improved abrasion resistance.
最近有機繊維で強度10g/d以上かつ弾性率400g/d以上
を有するものが、種々開発されており、主に前記の産業
資材分野で利用され始めだした。特に芳香族ポリエステ
ル繊維やアラミド繊維は、耐熱性も優れているため注目
されている。Recently, various organic fibers having a strength of 10 g / d or more and an elastic modulus of 400 g / d or more have been developed, and have begun to be used mainly in the above-mentioned industrial materials. In particular, aromatic polyester fibers and aramid fibers have attracted attention because of their excellent heat resistance.
〔発明が解決しようとする課題〕 これらの有機繊維は、高強度、高弾性率の性能を達成
するため、ポリマー組成や繊維成型時の条件に工夫を凝
らしており、繊維構造として分子鎖が繊維軸方向に高度
に配向している。このため繊維軸に対して垂直な方向に
は弱く、摩擦によつて容易にフイブリル化し、それが更
に表面の平滑性を悪くして耐摩耗性を低下させるため、
ロープ、コード、魚網等の用途分野で改良が望まれてい
た。[Problems to be Solved by the Invention] In order to achieve high strength and high elasticity performance, these organic fibers are devised in terms of polymer composition and fiber molding conditions. Highly oriented in the axial direction. For this reason, it is weak in the direction perpendicular to the fiber axis and easily fibrillates by friction, which further deteriorates the surface smoothness and lowers the abrasion resistance,
Improvements have been desired in application fields such as ropes, cords and fish nets.
ロープやコードなどで使用する際、この性能を補うた
め、ヤーンに表面平滑性を付与するワツクス系の油剤を
付着させるとか、撚糸や合糸で形態を特定のものとする
とか、あるいはまたこれら加工品をさらに熱可塑性樹脂
で被覆する等して耐摩耗性や更に耐屈曲疲労性を向上さ
せている。しかし耐摩耗性向上に適した油剤は見出され
てなく、更に湿潤時にも乾燥時と同じ耐摩耗性を保持す
る安価な油剤が望まれていた。In order to supplement this performance when used with ropes and cords, a wax type oil agent that imparts surface smoothness is attached to the yarn, the form is specified with twisted or plied yarns, or these are processed. The product is further coated with a thermoplastic resin or the like to improve the wear resistance and the bending fatigue resistance. However, no oil agent suitable for improving abrasion resistance has been found, and an inexpensive oil agent which maintains the same abrasion resistance as when dry even when wet has been desired.
また四沸化エチレン樹脂(PTFE)の水分散剤を上記繊
維に付着させた後、加熱焼成してPTFE樹脂で被覆するこ
とで乾燥、湿潤時の耐摩耗性を向上させたものがある
が、その向上効果はいまだ満足すべきものでなく、焼成
温度が350℃以上と高いため繊維の性能低下がおこり、
コスト的にも高いので問題があつた。In addition, after attaching a water dispersant of tetrafluoroethylene resin (PTFE) to the above fibers, heating and sintering and coating with a PTFE resin, the abrasion resistance when dry and wet is improved. The improvement effect is still unsatisfactory, and the firing temperature is as high as 350 ° C or higher, resulting in a decrease in fiber performance.
There was a problem because of the high cost.
本発明は強度10g/d以上かつ弾性率400g/d以上を有す
る繊維に対して下記一般式(A)で示されるオルガノポ
リシロキサンおよびフッソ樹脂を付着してなる産業資材
用高強度・高弾性率繊維にある 〔式中、m、nは1以上の整数、XはOH、NH2、ROH又は
RNH2を示す。但しRはアルキル基又はフエニル基を示
す。〕 上記繊維は、強度10g/d以上かつ弾性率400g/d以上を
有する繊維に上記一般式(A)で示されるオルガノポリ
シロキサンおよびフツ素樹脂のエマルジヨン又は分散液
を別々に2段で付着するあるいは混合液として1段で付
着することにより得ることが出来る。The present invention provides a high strength and high elastic modulus for industrial materials obtained by adhering an organopolysiloxane represented by the following general formula (A) and a fluorine resin to a fiber having a strength of 10 g / d or more and an elastic modulus of 400 g / d or more. In the fiber [Wherein, m and n are integers of 1 or more, X is OH, NH 2 , ROH or
RNH 2 is shown. However, R represents an alkyl group or a phenyl group. In the above-mentioned fiber, an emulsion or dispersion of an organopolysiloxane and a fluorine resin represented by the above general formula (A) is separately attached in two steps to a fiber having a strength of 10 g / d or more and an elastic modulus of 400 g / d or more. Alternatively, it can be obtained by adhering in a single step as a mixed solution.
本発明の対象とする繊維とは、例えば、高分子量ポリ
エチレン繊維である東洋紡(株)の「ダイニーマ」、ア
ライド社の「スペクトラ」、三井石油化学(株)の「テ
クミクロン」、特開昭62−85013、特開昭62−162010等
に記載される高分子量ポリビニルアルコール繊維、パラ
系アラミド繊維であるデュポン社の「ケブラー」、帝人
(株)の「テクノーラ」、エンカ社の「トアロン」、芳
香族ポリエステル繊維である、(株)クラレの「ベクト
ラン」等がある。The fibers to be used in the present invention are, for example, "Dyneema" of Toyobo Co., Ltd., "Spectra" of Allied, "Techmicron" of Mitsui Petrochemical Co., Ltd., which is a high molecular weight polyethylene fiber, and Japanese Patent Application Laid-Open No. Sho 62. -85013, high molecular weight polyvinyl alcohol fiber described in JP-A-62-162010, etc., "Kevlar" of DuPont, which is a para-aramid fiber, "Technola" of Teijin Limited, "Toaron" of Enca, aromatic And "Vectran" manufactured by Kuraray Co., Ltd., which is an aromatic polyester fiber.
なかでも特に異方性溶融物を形成する芳香族ポリエス
テル繊維は他の高強度・高弾性率繊維に比べ耐摩耗性が
優れているため本発明の対象繊維としてより望ましい。In particular, aromatic polyester fibers forming an anisotropic melt are more desirable as the target fibers of the present invention because of their excellent abrasion resistance as compared with other high-strength and high-modulus fibers.
異方性溶融物を形成する芳香族ポリエステル化合物の
好ましい例としては、下記に示す反復成分の組合せから
なるものである。Preferred examples of the aromatic polyester compound forming the anisotropic melt include a combination of the following repeating components.
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
報等で公知で開示されている。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 It is known and disclosed in JP-A-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〕の反復構成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] or [II] is at least 80 mol%, particularly 5 to 45 mol of the component [II]. % Of the 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、特願昭62−31
1668号に詳しく記載されている。 A method of spinning fibers from this compound is disclosed in Japanese Patent Application No. 62-31.
It is described in detail in 1668.
本発明におけるオルガノポリシロキサンとは、前記一
般式(A)で表わされ、一般に繊維や織物に潤滑性、発
水性、発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。一般式(A)は、25
℃における粘度が10〜100,000センチストークス(cS)
である水酸基又はアミノ基による変成ジメチルポリシロ
キサンであり、繊維へ付着するためエマルジヨン化した
ものが使用される。さらに平滑性を繊維に付与する場合
は、アミノポリシロキサン系の化合物(B)を前記式
(A)の固形分に対して添加し、さらに架橋反応を起こ
させる触媒を入れて繊維に付着後、通常120〜250℃程度
の温度で熱処理することで得られる。The organopolysiloxane in the present invention is a surface treatment agent represented by the general formula (A), which generally gives lubricity, water repellency, oil repellency, etc. to fibers and woven fabrics, and imparts considerable smoothness to fibers. be able to. The general formula (A) is 25
Viscosity at ℃ is 10-100,000 centistokes (cS)
A modified dimethylpolysiloxane with a hydroxyl group or an amino group, which is emulsified to adhere to fibers, is used. In order to further impart smoothness to the fiber, the aminopolysiloxane-based compound (B) is added to the solid content of the formula (A), and a catalyst for causing a crosslinking reaction is added. It is usually obtained by heat treatment at a temperature of about 120 to 250 ° C.
化合物(B)の添加量は、好ましくは50重量%以下、
より好ましくは5〜25重量%であり、触媒としては、亜
鉛、すず、鉛、チタン、カリウム、マグネシウムの有機
酸塩などが良い。The amount of the compound (B) to be added is preferably 50% by weight or less,
More preferably, it is 5 to 25% by weight. As the catalyst, zinc, tin, lead, titanium, potassium, magnesium organic acid salts and the like are preferable.
本発明に係わる組成物を水中でエマルジヨン化するに
は、ノニオン系、アニオン系及びカチオン系乳化剤を使
用してエマルジヨン化すれば良く、例えばポリオキシエ
チレンアルキルフエニルエーテル、第4級アンモニウム
塩、アルキルベンゼンスルホン酸ナトリウム等をあげる
ことが出来る。The composition of the present invention can be emulsified in water by using a nonionic, anionic or cationic emulsifier, for example, polyoxyethylene alkylphenyl ether, quaternary ammonium salt, alkylbenzene. And sodium sulfonate.
この乳化剤の使用量は、ポリシロキサンの固形分合計
量100重量%に対して概ね1〜50重量%の範囲が適当で
ある。The amount of the emulsifier used is suitably in the range of about 1 to 50% by weight based on 100% by weight of the total solid content of the polysiloxane.
本発明に言うフツソ樹脂とは、テトラフルオロエチレ
ン(以下PTFEと略)、テトラフルオロエチレン−エチレ
ン共重合体(以下ETFEと略)、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(FEP)、ポリク
ロロトリフルオロエチレン(PCFE)等があり、これらを
エマルジヨン化、あるいは分散するため、乳化剤、変性
剤等を加えても良い。The fluororesin referred to in the present invention includes tetrafluoroethylene (hereinafter abbreviated as PTFE), tetrafluoroethylene-ethylene copolymer (hereinafter abbreviated as ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychloroethylene There are trifluoroethylene (PCFE) and the like, and an emulsifier, a modifier and the like may be added in order to emulsify or disperse these.
これらの樹脂の例としては、ダイキン工業(株)製、
「ポリフロン」、「ネオフロン」、「ダイフロン」や、
日本アチソン(株)製「エムラロン」、住友化学工業
(株)製「スミフルノン」、旭硝子(株)製「ルミフロ
ン」等の使用が可能である。Examples of these resins include Daikin Industries, Ltd.
"Polyflon", "Neoflon", "Diflon",
"Emuralon" manufactured by Acheson Japan, "Sumiflunon" manufactured by Sumitomo Chemical Co., Ltd., "Lumiflon" manufactured by Asahi Glass Co., Ltd. can be used.
本発明に用いるオルガノポリシロキサンは、高強力・
高弾性率繊維の耐摩耗性を著しく向上させる効果がある
が、湿潤時および高温度には、その効果が低下する。一
方フツソ樹脂単独では、繊維付着時に行う焼成で繊維そ
のものを劣化させたり、目的の効果を出すためには、繊
維に対して、10〜50%という高付着の必要がありヤーン
径が太くなりすぎたり、コスト的にも高いものとなつて
いた。The organopolysiloxane used in the present invention has high strength
It has the effect of significantly improving the abrasion resistance of the high modulus fiber, but its effect decreases when wet and at high temperatures. On the other hand, in the case of fusso resin alone, in order to degrade the fiber itself by baking performed at the time of fiber attachment or to achieve the intended effect, it is necessary to attach 10 to 50% to the fiber, and the yarn diameter becomes too large. And cost was high.
本発明によれば、オルガノポリシロキサンとフツソ樹
脂の該繊維に対する付着量は合計で1重量%以上が良
く、好ましくは1〜20重量%、より好ましくは3〜10重
量%である。該繊維に付着しているオルガノポリシロキ
サンとフツソ樹脂の比は1:9〜9:1が好ましく、オルガノ
ポリシロキサンとフツソ樹脂の比が1:9よりフツソ樹脂
が多くなると、使用中に樹脂の脱落を生じ好ましくな
い。逆に9:1よりフツソ樹脂が少なくなると、高温時、
湿潤時の耐摩耗性が低下する。より好ましくは5:5〜9:1
である。According to the present invention, the total amount of the organopolysiloxane and the fluororesin adhered to the fiber is preferably 1% by weight or more, preferably 1 to 20% by weight, more preferably 3 to 10% by weight. The ratio of the organopolysiloxane and the fluorine resin adhering to the fiber is preferably 1: 9 to 9: 1.If the ratio of the organopolysiloxane to the fluorine resin is more than 1: 9, the ratio of the resin during use is reduced. Dropping occurs, which is not preferable. Conversely, if the amount of fusso resin is less than 9: 1, at high temperatures,
Abrasion resistance when wet is reduced. More preferably 5: 5 to 9: 1
It is.
繊維への付着法は、オルガノポリシロキサンおよびフ
ツソ樹脂のエマルジヨン又は分散溶液等を別々に2段に
付着したり、あるいは、混合液として1段で行つても良
い。The method of adhering to the fiber may be such that the emulsion or dispersion solution of the organopolysiloxane and the fluorine resin is separately applied in two stages, or may be carried out in one stage as a mixed solution.
付着は、一定量の液が吐出されるノズル付ガイド、あ
るいは、エマルジヨン又は分散液に一部浸した回転ロー
ラー等に糸を接触させ行うことが出来る。The adhesion can be performed by bringing the yarn into contact with a guide with a nozzle from which a fixed amount of liquid is discharged, a rotating roller partially immersed in an emulsion or a dispersion liquid, or the like.
次にエマルジヨンあるいは分散溶液を乾燥させて巻き
とることで達成できるが、架橋反応が必要な場合には更
に熱処理を行うか乾燥と熱処理を同時に高温で行うかす
る、例えば、連続処理できる熱風処理機を通過させる方
法がある。Next, it can be achieved by drying and winding the emulsion or dispersion solution. If a cross-linking reaction is required, further heat treatment or simultaneous drying and heat treatment at a high temperature, for example, a hot-air treatment machine capable of continuous treatment There is a way to pass.
本発明により、高強度・高弾性率繊維本来の性能を損
なうこと無しに、耐摩耗性を著しく改良し、かつ、高温
時、あるいは湿潤時でのその性能低下の非常に少ない高
強度・高弾性率繊維の供給が可能となつた。本発明の繊
維は産業資材用などに有用である。According to the present invention, high-strength and high-elasticity fibers have significantly improved abrasion resistance without impairing the inherent performance of the high-strength and high-elasticity fibers, and have very little deterioration in performance at high temperatures or when wet. Rate fiber can be supplied. The fiber of the present invention is useful for industrial materials and the like.
以下、実施例により本発明に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 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耐摩耗性試験とは、60回/mの撚
りを持つ試験糸1本を反転プーリーと他端のフリーロー
ラーとの間に5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、76回/分の速
度の反転プーリー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と、同じく60回/m
の撚りを持つ試験糸1本の一端を固定し他端に1/10g/d
の荷重をかけ、直径10cmの丸砥石を接触角100度、接触
長9cm、回転数100回/分で回転させて切断までの回転数
で示すグラインダー摩耗試験の両者で測定した。In the abrasion resistance test described in the examples, one test yarn having a twist of 60 turns / m is twisted 5 times between the reversing pulley and the free roller at the other end to form a figure 8 shape. Attaching, applying a 2kg load to the free roller, twisting and abrading the test yarn with a reversing pulley at a speed of 76 times / minute, and measuring the number of times until cutting by twisting abrasion test, also 60 times / m
One end of a test yarn with a twist of 1 / 10g / d at the other end
And a grindstone having a diameter of 10 cm was rotated at a contact angle of 100 degrees, a contact length of 9 cm, and a rotation speed of 100 times / minute, and a grinder abrasion test indicated by the rotation speed until cutting was performed.
実施例1〜6、比較例1、2 前期構造単位〔I〕、〔II〕からなる強度28g/d、伸
度4.6%、弾性率600g/dである1500dr/300fの芳香族ポリ
エステル繊維に、下記構造式(C)のオルガノポリシロ
キサンの30%デイスパージヨンと、PTFEの60%デイスパ
ージヨンを第1表に示す割合いで混合し、ギヤポンプで
計量し、ノズル付ガイドより繊維に付け、所定量の付着
量とした。付着後、200℃の乾燥熱処理を行つた。Examples 1 to 6, Comparative Examples 1 and 2 An aromatic polyester fiber of 1500 dr / 300f having a strength of 28 g / d, an elongation of 4.6%, and an elastic modulus of 600 g / d, comprising the above structural units [I] and [II], 30% disposable organopolysiloxane of the following structural formula (C) and 60% disposable PTFE are mixed in the proportions shown in Table 1, weighed with a gear pump, and attached to the fiber from a guide with a nozzle. The amount was determined as the fixed amount. After the adhesion, a drying heat treatment at 200 ° C. was performed.
得られた繊維の性質を1表に示す。 Table 1 shows the properties of the obtained fibers.
本発明の繊維は、湿潤時の性能が著しく改良されてい
る。 The fibers of the present invention have significantly improved wet performance.
Claims (1)
する繊維に対して、下記一般式で示されるオルガノポリ
シロキサンおよびフッソ樹脂を付着した産業資材用高強
度・高弾性率繊維。 〔式中、m、nは1以上の整数、XはOH、NH2、R−O
H、又はR−NH2を示す。但しRはアルキル基又はフェニ
ル基を示す。〕1. A high-strength, high-modulus fiber for industrial materials obtained by adhering an organopolysiloxane and a fluorine resin represented by the following general formula to a fiber having a strength of 10 g / d or more and an elastic modulus of 400 g / d or more. [Wherein, m and n are integers of 1 or more, X is OH, NH 2 , R—O
H, or an R-NH 2. Here, R represents an alkyl group or a phenyl group. ]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1028390A JP2728717B2 (en) | 1989-02-06 | 1989-02-06 | High-strength, high-modulus fiber with improved wear resistance |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1028390A JP2728717B2 (en) | 1989-02-06 | 1989-02-06 | High-strength, high-modulus fiber with improved wear resistance |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02210072A JPH02210072A (en) | 1990-08-21 |
JP2728717B2 true JP2728717B2 (en) | 1998-03-18 |
Family
ID=12247328
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1028390A Expired - Fee Related JP2728717B2 (en) | 1989-02-06 | 1989-02-06 | High-strength, high-modulus fiber with improved wear resistance |
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Country | Link |
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JP (1) | JP2728717B2 (en) |
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DE69208294D1 (en) * | 1991-06-24 | 1996-03-28 | Kuraray Co | Synthetic fiber based on polyvinyl alcohol and process for its production |
AU2009230655B2 (en) | 2008-03-25 | 2014-01-09 | Kuraray Co., Ltd. | Organopolysiloxane composition and process for producing rope structure with the same |
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JPS57205588A (en) * | 1981-06-05 | 1982-12-16 | Toray Industries | Fiber structure having color forming durability |
JPH0726250B2 (en) * | 1986-03-27 | 1995-03-22 | 住友化学工業株式会社 | Polyester fiber |
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