JP2891858B2 - Abrasion resistance improving agent - Google Patents

Abrasion resistance improving agent

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Publication number
JP2891858B2
JP2891858B2 JP28675793A JP28675793A JP2891858B2 JP 2891858 B2 JP2891858 B2 JP 2891858B2 JP 28675793 A JP28675793 A JP 28675793A JP 28675793 A JP28675793 A JP 28675793A JP 2891858 B2 JP2891858 B2 JP 2891858B2
Authority
JP
Japan
Prior art keywords
agent
treatment
foaming
fiber
abrasion resistance
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.)
Expired - Lifetime
Application number
JP28675793A
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Japanese (ja)
Other versions
JPH07138881A (en
Inventor
定光 村山
進 小椋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Ltd
Original Assignee
Teijin Ltd
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Filing date
Publication date
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Priority to JP28675793A priority Critical patent/JP2891858B2/en
Publication of JPH07138881A publication Critical patent/JPH07138881A/en
Application granted granted Critical
Publication of JP2891858B2 publication Critical patent/JP2891858B2/en
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Expired - Lifetime legal-status Critical Current

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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】本発明は主として繊維製品、たとえばロー
プ、コード、織物等の耐摩耗性向上に用いられる処理剤
に関するものである。さらに詳しくは、糸単独及びベル
ト状構造物、コード状構造物、織布構造物、ネット状構
造物及びロープ状構造物等に編組、または製織加工され
た繊維構造物、またはフェルト状(不織布)繊維構造物
の耐摩耗性、耐屈曲疲労性を向上させるために用いられ
る処理剤に関するものである。
[0001] The present invention relates to a treatment agent mainly used for improving abrasion resistance of textile products, for example, ropes, cords, woven fabrics and the like. More specifically, a fiber structure braided or woven into a single yarn and a belt-like structure, a cord-like structure, a woven fabric structure, a net-like structure, a rope-like structure, or a felt-like (non-woven fabric) The present invention relates to a treatment agent used for improving abrasion resistance and bending fatigue resistance of a fiber structure.

【0002】[0002]

【従来の技術】従来、繊維製品の耐摩耗性向上手段とし
ては処理剤による表面被膜や含浸加工が多く用いられ、
処理剤としてはポリウレタンやフッ素系樹脂が広く用い
られてきた。ポリウレタンを耐摩耗性向上処理剤に用い
た技術としては、「ポリウレタン、酸化ポリエチレン及
びエチレン尿素化合物を主成分とする混合物で処理され
てなる繊維ロープ」(特公昭62−60511号公報)
或いは「ウレタンプレポリマーブロック化物を主成分と
する樹脂を繊維ベルト類に付与し、加熱処理することに
より耐摩耗性を改善する方法」(特開昭60−1731
74号公報)、さらに「シラン系カップリング剤を主成
分とする第1処理剤で処理した後、ポリウレタン、酸化
ポリエチレンおよびエチレン尿素化合物で処理する方
法」(特公平1−29909号公報)、「ポリウレタ
ン、酸化ポリエチレン、フッ素樹脂、エチレン尿素化合
物を主成分とする処理剤」(特開平3−249280号
公報)等があげられる(以下先行技術という)。確かに
上記先行技術に示された処理剤で表面被覆又は含浸処理
された繊維及び構造物は耐摩耗性、耐屈曲疲労性の改善
されることが認められている。しかしながら、上記先行
技術に開示された処理剤を用いて実際に多量の糸を処理
する場合、処理剤中に泡が多量に発生して長時間消泡せ
ず、処理液がゼリー状になって加工時における剤の粘度
と付着量のコントロールができないという問題、さら
に、処理剤被膜の平滑性、特に水分介在下での平滑性が
不足し、加工時や使用時に毛羽を発生し易いという問題
を有している。
2. Description of the Related Art Conventionally, as a means for improving the abrasion resistance of textile products, surface coating or impregnation with a treating agent is often used.
Polyurethanes and fluororesins have been widely used as treating agents. As a technique using polyurethane as a treatment agent for improving abrasion resistance, a fiber rope treated with a mixture containing polyurethane, polyethylene oxide and an ethylene urea compound as main components is disclosed (Japanese Patent Publication No. Sho 62-60511).
Alternatively, a "method of improving abrasion resistance by applying a resin containing a urethane prepolymer block product as a main component to a fiber belt and subjecting the belt to a heat treatment" (Japanese Patent Laid-Open No. 60-1731)
No. 74) and further "a method of treating with a first treating agent containing a silane-based coupling agent as a main component, followed by treatment with a polyurethane, polyethylene oxide and an ethylene urea compound" (Japanese Patent Publication No. 1-29099). "A treating agent containing polyurethane, polyethylene oxide, fluororesin, and ethylene urea compound as main components" (JP-A-3-249280) and the like (hereinafter referred to as prior art). Indeed, it has been recognized that fibers and structures surface-coated or impregnated with the treatment agents described in the above prior art have improved wear resistance and flex fatigue resistance. However, when actually processing a large amount of yarn using the processing agent disclosed in the above prior art, a large amount of foam is generated in the processing agent and does not disappear for a long time, and the processing solution becomes jelly-like. The problem of not being able to control the viscosity and adhesion amount of the agent at the time of processing, and the problem that the smoothness of the treatment agent film, especially the smoothness under moisture intervening, is insufficient, and the fluff easily occurs at the time of processing and use. Have.

【0003】さらに最近の市場における用途の拡大、多
様化に伴い、製品に対する要求性能は、ますます高度
化、多様化する傾向にあるため、上述の先行技術では不
十分であり、用途によっては十分対応することができな
くなりつつある。例えばパラ系アラミド繊維は21グラ
ム/デニール以上の高強度を有するため、最近、この繊
維を使用した種々の繊維構造物が開発され、ベルト、コ
ード、ロープ等の用途分野で活用されつつあるが、繊維
/繊維間,繊維/物体間などの摩擦によりフィブリル化
し易いため処理剤による処理時や実際の上記用途での使
用時にこのフィブリル化が主因となって毛羽を発生し、
強度劣化を生じて、繊維が本来有するすぐれた高強度特
性を十分に発現できないという欠点が指摘されている。
[0003] Further, with the recent expansion and diversification of applications in the market, the required performance of products tends to be more sophisticated and diversified. It is becoming impossible to respond. For example, para-aramid fiber has a high strength of 21 g / denier or more, and various fiber structures using this fiber have recently been developed and are being used in application fields such as belts, cords, and ropes. Since it is easy to fibrillate due to friction between fibers / fibers, fiber / object, etc., the fibrillation is the main cause during processing with a treating agent or during actual use in the above applications, and fluff is generated.
It has been pointed out that the strength is deteriorated, and the excellent high-strength characteristic inherent to the fiber cannot be sufficiently exhibited.

【0004】この欠点を改善するために耐摩耗性の比較
的良好なナイロン系繊維等をベルト、コード、ロープ等
の表層部に用い、芯体部分にアラミド繊維を用いて複合
体構造にするなどの工夫がなされ実用化されている。し
かしながら、これらの複合体構造の製品でも、まだまだ
不十分であり、特にアラミド繊維のフィブリル化を完全
に防止するには至っていない。また複合する繊維の伸度
が異なるために使用時に受ける応力を芯体のみで受ける
ことになり、例えばロープ、コード類では外径の大きさ
(太さ)に対する製品強力の発現程度が小さくなるとい
う欠点を有するばかりではなく、製品が繰り返し屈曲使
用される過程で芯体繊維相互間の摩擦により、繊維が部
分的にフィブリル化して、その結果、十分な製品強力を
長期にわたって維持できないという欠点を生じている。
更に最近では、このパラ系アラミド繊維の高強力を生か
して水産資材分野へ展開すべく、種々の検討、開発が行
われているが、特に高張力下で使用される場合、前述の
フィブリル化が水の介在により促進されて強度劣化が著
しく、繊維が本来有するすぐれた高強度特性を十分に発
現できない。また、前述の如く処理工程での処理剤の発
泡により、糸への付着量のコントロールができないばか
りではなく、平滑性不足から加工時に毛羽も発生し易
い。加えて処理剤により形成された被膜が水の介在によ
って、吸水、膨潤し、被膜の強度劣化のため被膜性能を
十分発現できず、従って本来目的とするところの耐摩耗
性,耐屈曲疲労性を十分に向上し得ず、水産資材分野に
おける要求性能を満足させることができない。
In order to remedy this drawback, nylon-based fibers having relatively good abrasion resistance are used for the surface layers of belts, cords, ropes and the like, and a composite structure is formed by using aramid fibers for the core. Has been put into practical use. However, even products with these composite structures are still insufficient, and in particular, have not yet completely prevented fibrillation of aramid fibers. Also, since the elongation of the composite fiber is different, the stress received during use is received only by the core body. For example, in ropes and cords, the degree of expression of product strength with respect to the outer diameter (thickness) is reduced. In addition to the drawbacks, the friction between the core fibers in the process of repeated bending of the product causes the fibers to be partially fibrillated, resulting in the inability to maintain sufficient product strength for a long period of time. ing.
More recently, various studies and developments have been carried out in order to exploit the high strength of this para-aramid fiber in the field of marine materials, but the fibrillation described above is particularly difficult when used under high tension. The strength is significantly deteriorated due to the intervention of water, and the excellent high-strength characteristics inherent to the fiber cannot be sufficiently exhibited. Further, as described above, due to the foaming of the treatment agent in the treatment step, not only the amount of adhesion to the yarn cannot be controlled, but also fluff is likely to occur during processing due to insufficient smoothness. In addition, the coating formed by the treating agent absorbs water and swells due to the interposition of water, and the coating performance cannot be sufficiently exhibited due to the deterioration of the strength of the coating. Therefore, the originally intended wear resistance and bending fatigue resistance are reduced. It cannot be sufficiently improved, and the required performance in the field of fishery materials cannot be satisfied.

【0005】[0005]

【発明の目的】本発明の目的は、処理剤の発泡を防止
し、かつ処理剤被膜の低摩擦力化を図り、処理された繊
維構造物に高度の平滑性、耐摩耗性、耐屈曲疲労性等を
付与せしめることができる処理剤を提供することにあ
る。
SUMMARY OF THE INVENTION It is an object of the present invention to prevent foaming of a treating agent, to reduce the frictional force of a treating agent film, and to provide a treated fiber structure with a high degree of smoothness, abrasion resistance, and bending fatigue resistance. An object of the present invention is to provide a treating agent capable of imparting properties and the like.

【0006】[0006]

【発明の構成】即ち本発明は、「(請求項1) ポリウ
レタン(A)、酸化ポリエチレン(B)、エチレン尿素
化合物(C)及びオルガノポリシロキサン(D)を主た
る成分とし、下記方法により測定した発泡率が140%
未満であることを特徴とする耐摩耗性向上処理剤。<配合処理液の攪拌による発泡率の評価方法> 配合処理液を秤量して100ml取り、これを外径4.
0cmの250ml用メスシリンダー中に入れた後、該
メスシリンダーの底面から処理剤液面までの高さを測定
して(H1)とする。次に、最大長さ約2.0cmの2枚の
羽根を有する攪拌機により2000rpmで、約5分
間、処理剤を攪拌した後、約30分間静置し、その後、
処理剤の発泡部分も含めた液面高さを測定して(H2)
とし、下記の計算式により発泡率を算出した。 発泡率(%)=(H2)/(H1)×100 (請求項2) ポリウレタン(A)がポリエステルポリ
オールと脂肪族ポリイソシアネートからなり、酸化ポリ
エチレン(B)の分子量が1000〜7000からな
り、エチレン尿素化合物(C)が下記一般式を満足する
化合物からなり、
More specifically, the present invention relates to a method of measuring the following method using "(Claim 1) polyurethane (A), polyethylene oxide (B), ethylene urea compound (C) and organopolysiloxane (D) as main components. 140% foaming rate
Less than 0.1 % . <Method of Evaluating Foaming Ratio by Stirring Compounding Treatment Liquid > The mixing treatment liquid was weighed and taken in an amount of 100 ml.
After placing in a 0 cm 250 ml graduated cylinder,
Measures the height from the bottom of the measuring cylinder to the liquid level of the processing agent
(H1). Next, two sheets with a maximum length of about 2.0 cm
Approximately 5 minutes at 2000 rpm with a stirrer having blades
Meanwhile, after stirring the treating agent, it is allowed to stand for about 30 minutes.
Measure the liquid level including the foaming part of the treatment agent (H2)
The foaming ratio was calculated by the following formula. Foaming rate (%) = (H2) / (H1) × 100 (Claim 2) The polyurethane (A) comprises a polyester polyol and an aliphatic polyisocyanate, and the polyethylene oxide (B) has a molecular weight of 1,000 to 7000; The urea compound (C) comprises a compound satisfying the following general formula;

【0007】[0007]

【化3】 Embedded image

【0008】さらにオルガノポリシロキサン(D)がジ
メチルポリシロキサン又は、下記の一般式で示される変
性ポリシロキサンなどから選択された群からなる1以上
である請求項1記載の耐摩耗性向上処理剤。
The antiwear agent according to claim 1, wherein the organopolysiloxane (D) is at least one selected from the group consisting of dimethylpolysiloxane and modified polysiloxane represented by the following general formula.

【0009】[0009]

【化4】 Embedded image

【0010】(請求項3) 処理剤の各成分の重量比
が、(A)/[(A)+(B)]=0.5〜0.9、
(C)/[(A)+(B)]=0.05〜0.3、
(D)/[(A)+(B)+(C)]=0.0003〜
0.1である請求項1又は2の耐摩耗性向上処理剤。」
である。
(Claim 3) The weight ratio of each component of the treating agent is (A) / [(A) + (B)] = 0.5 to 0.9,
(C) / [(A) + (B)] = 0.05-0.3,
(D) / [(A) + (B) + (C)] = 0.0003-
The agent for improving abrasion resistance according to claim 1 or 2, which is 0.1. "
It is.

【0011】ここにポリウレタンとはポリエステルポリ
オールとポリイソシアネートとの反応により得られる高
分子重合体であり、ポリエステルポリオールとしてはエ
チレングリコール、ジエチレングリコール、1−4ブタ
ンジオール、グリセリン等の多価アルコールとセバシン
酸、アジピン酸、シュウ酸、コハク酸、フタル酸等の多
価脂肪族カルボン酸と芳香族カルボン酸との縮合反応で
得られるポリエステルポリオール等をあげることができ
る。ポリイソシアネートとしては、ヘキサメチレンジイ
ソシアネート、キシリレンジイソシアネート、イソホロ
ンジイソシアネート、トリレンジイソシアネート、ジフ
ェニルメタンジイソシアネート、トリフェニルメタンジ
イソシアネート、ナフチレンジイソシアネート等の脂肪
族ポリイソシアネートまたは芳香族ポリイソシアネート
を挙げることができるが、耐候性の点から脂肪族ポリイ
ソシアネートが好ましい。酸化ポリエチレンはポリエチ
レンを酸化して低分子量化したものであり、水酸基及び
/またはカルボキシル末端基を有するものが好ましく、
さらに好ましくは高密度ポリエチレンの酸化物であって
分子量が1000〜7000のものである。
The polyurethane is a high molecular polymer obtained by reacting a polyester polyol with a polyisocyanate. Examples of the polyester polyol include a polyhydric alcohol such as ethylene glycol, diethylene glycol, 1-4 butanediol, glycerin and sebacic acid. And polyester polyols obtained by the condensation reaction of polyaliphatic carboxylic acids such as adipic acid, oxalic acid, succinic acid and phthalic acid with aromatic carboxylic acids. Examples of the polyisocyanate include an aliphatic polyisocyanate or an aromatic polyisocyanate such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane diisocyanate, and naphthylene diisocyanate. Aliphatic polyisocyanates are preferred from the viewpoint of properties. The oxidized polyethylene is obtained by oxidizing polyethylene to have a low molecular weight, and preferably has a hydroxyl group and / or a carboxyl terminal group,
More preferably, it is an oxide of high-density polyethylene having a molecular weight of 1,000 to 7000.

【0012】エチレン尿素化合物は次に示す一般式で表
される。
The ethylene urea compound is represented by the following general formula.

【0013】[0013]

【化5】 Embedded image

【0014】代表的化合物としてはオクタデシルイソシ
アネート、ヘキサメチレンジイソシアネート、キシリレ
ンジイソシアネート、イソホロンジイソシアネート、ト
リレンジイソシアネート、ジフェニルメタンジイソシア
ネート、トリフェニルメタンジイソシアネート、ナフチ
レンジイソシアネート等の脂肪族または芳香族のポリイ
ソシアネートとエチレンイミンとの反応生成物があげら
れ、通常水分散液の形で使用される。
Typical compounds include aliphatic or aromatic polyisocyanates such as octadecyl isocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane diisocyanate and naphthylene diisocyanate, and ethyleneimine. And usually used in the form of an aqueous dispersion.

【0015】さらにオルガノポリシロキサンとしては、
通常25℃の粘度が5〜200000センチポイズのシ
リコンオイルと称されるジメチルポリシロキサン、ジフ
ェニルポリシロキサン、メチルフェニルポリシロキサン
などのほか、下記一般式で示される様々の変性ポリシロ
キサンがあげられる。
Further, as the organopolysiloxane,
In addition to dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, and the like, which are generally called silicone oils having a viscosity of 5 to 200,000 centipoise at 25 ° C., various modified polysiloxanes represented by the following general formulas are exemplified.

【0016】[0016]

【化6】 Embedded image

【0017】またこれらのオルガノポリシロキサンの中
で、変性により水分散性を付与されたものは、他の配合
剤が水系組成物である場合、そのまま使用できるが、通
常のシリコンオイルを使用する場合には乳化剤等により
エマルジョン化したものを配合するのが望ましい。
Among these organopolysiloxanes, those which are imparted with water dispersibility by modification can be used as they are when the other compounding agent is an aqueous composition. It is desirable to incorporate a mixture emulsified with an emulsifier or the like.

【0018】また繊維製品とはポリエステル繊維、ナイ
ロン繊維、ビニロン繊維、アラミド繊維等からなる製品
であり、例えばロープ、コードや織物、フェルト等をい
う。
The fiber product is a product made of polyester fiber, nylon fiber, vinylon fiber, aramid fiber and the like, and includes, for example, rope, cord, woven fabric, felt and the like.

【0019】本発明の処理剤による処理法としてはスプ
レー法、コーティング法など従来公知のいかなる方法を
用いてもよいが、ポリウレタン(A)、酸化ポリエチレ
ン(B)、エチレン尿素化合物(C)及びオルガノポリ
オキサン(D)のそれぞれの水分散液を混合した液に繊
維製品を含浸させたのち乾燥させるのが最も簡単であ
る。もちろん糸状の繊維形態で前述の方法により処理剤
を付与してもよい。
As the treatment method using the treatment agent of the present invention, any conventionally known method such as a spray method and a coating method may be used. Examples of the method include polyurethane (A), polyethylene oxide (B), ethylene urea compound (C) and organo urea. It is easiest to impregnate the fiber product with a mixture of the respective aqueous dispersions of the polyoxane (D) and then dry. Of course, the treatment agent may be applied in the form of a thread-like fiber by the above-described method.

【0020】処理剤における各成分の重量比は、 重量比a (A)/[(A)+(B)]=0.5〜0.
9 重量比b (C)/[(A)+(B)]=0.05〜
0.3 重量比c (D)/[(A)+(B)+(C)]=0.
0003〜0.1 であることが好ましい。重量比aが0.5未満では、処
理剤被膜の強度が十分でなく、かつ被膜と繊維製品の界
面接着性も不十分となる。また0.9を越えると被膜の
表面摩擦抵抗が大きくなりすぎて平滑性が不十分とな
る。また重量比bが0.05未満では被膜強度が不十分
となり、0.3を越えると被膜の可撓性が不足し処理後
の繊維製品の曲げ特性が低下する。更に、重量比cが
0.003未満では、処理中における処理剤の発泡を十
分に防ぐことができず、有効な消泡効果を発現できない
ばかりか、処理剤被膜の平滑性も不十分となって、糸へ
の剤の付着量のコントロールや処理時における糸ガイド
部等での毛羽発生の減少効果、処理後の繊維構造物への
撥水効果等も期待できなくなる。また0.1を越えると
処理剤により形成された繊維構造物表面の被膜強度が不
十分となり、かつ、被膜と繊維との界面接着力も低下し
て好ましくない。我々の検討では、0.001〜0.0
9の範囲内に配合した場合が、処理剤液の消泡、処理時
の毛羽発生、処理品の表面摩擦抵抗、耐摩耗性、耐屈曲
疲労性などの諸特性に関して最良の向上効果を示す。
The weight ratio of each component in the treating agent is as follows: weight ratio a (A) / [(A) + (B)] = 0.5 to 0.5.
9 Weight ratio b (C) / [(A) + (B)] = 0.05-
0.3 weight ratio c (D) / [(A) + (B) + (C)] = 0.
It is preferably from 0003 to 0.1. When the weight ratio a is less than 0.5, the strength of the treatment agent coating is not sufficient, and the interfacial adhesion between the coating and the fiber product is also insufficient. On the other hand, if it exceeds 0.9, the surface frictional resistance of the coating film becomes too large and the smoothness becomes insufficient. On the other hand, if the weight ratio b is less than 0.05, the coating strength becomes insufficient, and if it exceeds 0.3, the flexibility of the coating becomes insufficient and the bending properties of the treated fiber product deteriorate. Further, when the weight ratio c is less than 0.003, foaming of the treating agent during the treatment cannot be sufficiently prevented, and not only an effective defoaming effect cannot be exhibited, but also the smoothness of the treating agent film becomes insufficient. Thus, the effect of controlling the amount of the agent attached to the yarn, the effect of reducing the generation of fluff in the yarn guide portion and the like at the time of processing, the effect of water repelling the fibrous structure after the processing, and the like cannot be expected. On the other hand, if it exceeds 0.1, the coating strength on the surface of the fibrous structure formed by the treatment agent becomes insufficient, and the interfacial adhesive strength between the coating and the fiber is undesirably reduced. In our review, 0.001-0.0
When the compounding ratio is within the range of 9, the best improvement effect is exhibited with respect to various properties such as defoaming of the treating agent solution, generation of fluff during the treatment, surface friction resistance, abrasion resistance and bending fatigue resistance of the treated product.

【0021】従って前述の重量比a、重量比b、重量比
cに示した範囲になるように該処理剤液を配合し、各有
効成分の重量比をコントロールすることが好ましい。か
かる重量比範囲内で配合された処理剤液は、処理時にお
ける処理剤液中の発泡や、毛羽の発生を少なくするばか
りではなく、加えて、処理された繊維又は繊維構造物の
耐摩耗性、耐屈曲疲労性は大幅に向上し、特に、水が介
在する場合における耐摩耗性、屈曲疲労性の低下も少な
く非常に良好である。
Therefore, it is preferable that the treating agent liquid is blended so as to be in the range of the above-mentioned weight ratio a, weight ratio b and weight ratio c, and the weight ratio of each active ingredient is controlled. The treating agent liquid blended within such a weight ratio range not only reduces foaming and fluffing in the treating agent solution during treatment, but also increases the abrasion resistance of the treated fiber or fiber structure. In addition, the bending fatigue resistance is greatly improved, and in particular, there is little decrease in wear resistance and bending fatigue resistance when water is interposed, and it is very good.

【0022】処理剤液の固形分濃度としては1〜25重
量%が適当であり、好ましくは5〜20重量%である。
また、乾燥温度は100〜150℃、乾燥時間は0.5
〜20分間が好ましい。乾燥温度が100℃未満では処
理剤の被膜強度が十分ではなく150℃を越えると被膜
強度の劣化が生じる。熱処理温度は160〜240℃、
熱処理時間は0.2〜10分間が好ましく、熱処理温度
が160℃未満では、形成された被膜の架橋が不充分で
良好な被膜強度を発現し得なくなる。また240℃を越
えると被膜が熱劣化して強度が低下する。なお処理後の
繊維製品での処理剤付着量は、固形分で1〜10重量%
が好ましい。1重量%未満では繊維製品の耐摩耗性向上
が不十分であり実用的効果が発現せず、10重量%を越
えると処理後の繊維は著しく粗硬となり曲げ疲労性の低
下が生じてくる。
The concentration of the solid content of the treating agent liquid is suitably from 1 to 25% by weight, preferably from 5 to 20% by weight.
The drying temperature is 100 to 150 ° C., and the drying time is 0.5.
-20 minutes is preferred. If the drying temperature is lower than 100 ° C., the coating strength of the treating agent is not sufficient, and if it exceeds 150 ° C., the coating strength is deteriorated. Heat treatment temperature is 160 ~ 240 ℃,
The heat treatment time is preferably from 0.2 to 10 minutes, and if the heat treatment temperature is lower than 160 ° C., the formed coating film is insufficiently cross-linked and cannot exhibit good coating strength. On the other hand, when the temperature exceeds 240 ° C., the coating is thermally deteriorated and the strength is reduced. The amount of the treatment agent attached to the textile product after the treatment is 1 to 10% by weight in solid content.
Is preferred. If the amount is less than 1% by weight, the abrasion resistance of the fiber product is insufficiently improved, and no practical effect is exhibited. If the amount exceeds 10% by weight, the fiber after treatment becomes extremely coarse and the bending fatigue property is reduced.

【0023】[0023]

【発明の作用効果】本発明の処理剤は、処理時における
処理剤液中の発泡が少なく、且つ、処理工程での毛羽の
発生も少ないばかりでなく、処理剤で処理された繊維、
又は、繊維構造物も耐摩耗性、耐屈曲疲労性に優れてい
る。処理剤で処理された繊維や繊維構造物が耐摩耗性に
すぐれている理由は、耐候性を兼備したポリウレタンに
酸化ポリエチレン及びオルガノポリシロキサンを併用す
ることにより、柔軟で高い平滑性を有し、且つ、吸水性
が少なく耐水性に優れた被膜を繊維表面に形成させ、更
に、エチレン尿素化合物を併用して架橋反応を生じさ
せ、被膜の凝集力を向上させていることにある。従っ
て、処理剤で処理された繊維又は繊維構造物は摩擦係数
も小さく、単繊維相互間の摩擦及び繊維/物体間の摩擦
が減少する為、単繊維のフィブリル化も防止されて、耐
摩耗性、耐屈曲疲労性が向上し、かつ、水分介在下での
特性も向上させる効果を兼備している。
The treatment agent of the present invention not only reduces the amount of foam in the treatment agent solution during treatment, and also reduces the generation of fluff in the treatment step, but also the fibers treated with the treatment agent.
Alternatively, the fiber structure also has excellent wear resistance and bending fatigue resistance. The reason why the fibers and fiber structures treated with the treating agent are excellent in abrasion resistance is that, by using polyethylene oxide and organopolysiloxane in combination with polyurethane having weather resistance, it has flexibility and high smoothness, Another object of the present invention is to form a coating film having low water absorption and excellent water resistance on the fiber surface, and further to cause a crosslinking reaction by using an ethylene urea compound in combination to improve the cohesive force of the coating film. Therefore, the fiber or the fiber structure treated with the treating agent has a small coefficient of friction, and reduces the friction between the single fibers and the friction between the fibers / objects. In addition, it has the effect of improving the resistance to bending fatigue and the characteristics under the presence of moisture.

【0024】すなわち、本発明は以下の効果を有する。 (1)本発明の処理剤液で処理する場合、処理剤液の発
泡が少ないため、粘度コントロール、繊維への処理剤付
着量コントロールが容易である。 (2)本発明の処理剤は、被膜が平滑性に富んでいるた
め、処理工程で毛羽を発生し難いばかりでなく、使用時
における繊維のフィブリル化を防止し、耐久性を向上さ
せる。 (3)本発明の処理剤液で処理された繊維又は繊維構造
物の大気中及び水分介在下での耐摩耗性が極めて優れて
いる。 (4)本発明の処理剤液で処理された繊維又は繊維構造
物の大気中及び水分介在下での耐屈曲疲労性は極めて優
れている。
That is, the present invention has the following effects. (1) In the case of treating with the treating agent liquid of the present invention, the foaming of the treating agent liquid is small, so that it is easy to control the viscosity and the amount of the treating agent attached to the fiber. (2) The treatment agent of the present invention not only does not easily generate fluff in the treatment step because the coating film is rich in smoothness, but also prevents fibrillation of fibers during use and improves durability. (3) The fibers or fibrous structures treated with the treating agent solution of the present invention have extremely excellent abrasion resistance in the air and under the presence of moisture. (4) The fiber or fiber structure treated with the treating agent solution of the present invention has extremely excellent bending fatigue resistance in air and under the presence of moisture.

【0025】以下、摩擦によりフィブリル化し易いパラ
系アラミド繊維からなるロープ状繊維構造物を取り上
げ、本発明の処理剤による処理効果について、実施例に
より、具体的に説明する。なお、耐摩耗性、耐屈曲疲労
性、処理剤液の発泡性、及び、処理工程での毛羽発生等
の評価については、以下の方法に従って実施した。
A rope-like fiber structure made of para-aramid fiber which is liable to fibrillate by friction will now be described in detail with reference to examples. The abrasion resistance, flex fatigue resistance, foaming property of the treating agent solution, and evaluation of fluff generation in the treatment step were performed according to the following methods.

【0026】<耐摩耗性評価方法>評価装置を図1に示
す。図1において、含浸処理ロープ(評価サンプル)1
に対して、表面粗さ120番のサンドグラインダー2を
約3450rpmで回転せしめながら、ロープの引張破
断強力の0.2%の荷重3を掛けた状態で10分間摩耗
試験を実施した。なお、5は含浸処理ロープのガイドロ
ール(自由に回転するロール)である。またロート6
は、必要に応じて水を滴下させる為の水付与装置であ
り、7は水8を滴下させるときに開くコックである。水
を滴下させずに評価する方法をA法、水を滴下させなが
ら評価する方法をB法として区分する。
<Method of Evaluating Wear Resistance> FIG. 1 shows an evaluation apparatus. In FIG. 1, impregnated rope (evaluation sample) 1
On the other hand, an abrasion test was performed for 10 minutes while applying a load 3 of 0.2% of the tensile breaking strength of the rope while rotating a sand grinder 2 having a surface roughness of No. 120 at about 3450 rpm. Reference numeral 5 denotes a guide roll (a roll that freely rotates) of the impregnated rope. Also funnel 6
Is a water application device for dropping water as needed, and 7 is a cock that opens when water 8 is dropped. The method of evaluating without dropping water is classified as method A, and the method of evaluating with dropping water is classified as method B.

【0027】<耐屈曲疲労性評価方法>2対の自由回転
するロールを用いたS曲げ方法により実施する。評価用
ロープを2個の自由回転するロールにS字状にかけ、更
にロープの引張破断強力の1/10の引張力を、ロープ
にかけて、往復運動させ、5000回屈曲疲労させた後
の強力保持率で比較判定した。但し、このとき、自由回
転するロール径(D)とロープ径(d)との比が20
(D/d=20)になる様にロールの径を選択する。
<Evaluation Method for Bending Fatigue Resistance> The bending fatigue resistance is evaluated by an S-bending method using two pairs of freely rotating rolls. The evaluation rope is applied to two freely rotating rolls in an S-shape, and a tensile force of 1/10 of the tensile breaking strength of the rope is applied to the rope. Was determined by comparison. However, at this time, the ratio of the roll diameter (D) to the freely rotating roll diameter (D) is 20.
The diameter of the roll is selected so that (D / d = 20).

【0028】<配合処理剤液の攪拌による発泡性の評価
方法>配合処理剤液を秤量して100ml取り、これを
外径4.0cmの250ml用メスシリンダー中にいれ
た後、該メスシリンダーの底面から処理剤液面までの高
さを測定して(H1)とする。次に、最大長さ約2.0
cmの2枚の羽根を有する攪拌機により2000rpm
で、約5分間、処理剤を攪拌した後、約30分間静置
し、その後、処理剤の発泡部分も含めた液面高さを測定
して(H2)とする。発泡性は、下記の計算式により発
泡率(消泡性)を算出し、発泡性の判断の尺度にした。 発泡率(%)=[攪拌後の発泡部分も含めた液面の高さ
(H2)/攪拌前の液面の高さ(H1)]×100 なお、発泡のしにくさも含めた消泡性については、上記
の算出結果を参考にして、100〜120%未満:◎、
120〜140%未満:○、140〜140%未満:
△、160%以上:×として区分、判定した。
<Evaluation method for foaming property of compounding treatment agent solution by stirring> The compounding treatment agent solution was weighed and taken in 100 ml, placed in a 250 ml measuring cylinder having an outer diameter of 4.0 cm, and then placed in the measuring cylinder. The height from the bottom surface to the liquid level of the processing agent is measured, and is defined as (H1). Next, the maximum length is about 2.0
2000 rpm with a stirrer having two blades
Then, after stirring the treatment agent for about 5 minutes, the mixture is allowed to stand for about 30 minutes, and then the liquid level including the foamed portion of the treatment agent is measured to obtain (H2). The foaming property was calculated by calculating the foaming rate (defoaming property) according to the following formula, and used as a scale for judging the foaming property. Foaming rate (%) = [Height of liquid surface including foamed portion after stirring (H2) / Height of liquid surface before stirring (H1)] × 100 Defoaming including difficulty of foaming Regarding the properties, referring to the above calculation results, 100 to less than 120%: 、,
120 to less than 140%: ○, 140 to less than 140%:
Δ, 160% or more: Classified as X and judged.

【0029】<処理工程での毛羽の発生量評価方法>実
質的に油剤が付着していないパラ型アラミド長繊維糸1
500デニール/1000フィラメント〔テクノーラ:
帝人株式会社製〕を用いて、試験用の含浸処理機によ
り、1kg巻×30本=30kgの処理を行い、紙管に
巻かれた処理後の糸について端面部分と表面部分の毛羽
発生状況を観察して区分し、毛羽発生なし=◎、毛羽発
生微量=○、毛羽発生少量=△、毛羽発生中量=×印で
表示した。
<Evaluation Method of Fuzz Generation in Processing Step> Para-type aramid long fiber yarn 1 substantially free of oil agent
500 denier / 1000 filament [Technola:
Using a test impregnating machine, 1kg winding x 30 strands = 30kg was processed using a test impregnating machine, and the fluff generated on the end face portion and surface portion of the processed yarn wound on a paper tube was measured. Observation was carried out and classified. No fuzz was generated = ◎, fuzz generation amount = 微量, fuzz generation amount = 少量, fuzz generation amount = ×.

【0030】[0030]

【実施例1】アジピン酸と1、4−ブタンジオールから
なるポリエステルジオールとヘキサメチレンジイソシア
ネートとを反応させて得られたポリウレタン(A)の水
分散液 (有効成分25重量%)と分子量4500の酸化
ポリエチレン(B)の水分散液(有効成分25重量
%)、ジフェニルメタンジイソシアネートとエチレンイ
ミンとの反応生成物からなるエチレン尿素化合物(C)
の水分散液(有効成分25重量%)及びジメチルシリコ
ーン(D)を主成分とする水分散液(有効成分40重量
%)を表1に示した有効成分比率(固形成分比;重量
%)になるように各水分散液を配合して、処理剤液を作
成した。この処理剤液の固形分濃度は13重量%であっ
た。油剤の付着量が0.5重量%以下であるパラ型アラ
ミド長繊維糸1500デニール/1000フィラメント
〔テクノーラ:帝人株式会社製〕からなる外径14mm
の3つ打のロープを、前記の配合処理液に浸漬して含浸
処理し、圧空ノズル中を通して処理液の付着量をコント
ロールした後、130℃の温度で15分間乾燥し、続い
て、180℃の温度で3分間熱処理して、ロープを構成
する繊維表面に形成された処理剤被膜の架橋反応を行っ
た。このときのロープ全体に付着した処理剤の固形分付
着量は3.5重量%であった。得られたこの処理ロープ
について、耐摩耗性評価方法AとB、及び、耐屈曲疲労
性試験により評価した結果は、表1の該当箇所に示す通
りであった。なお、この配合処理剤液について測定した
発泡率(消泡性)の区分は、表1の該当箇所に示す如く
○印ランクであった。また、処理工程での毛羽発生状況
について、処理後の紙管に巻かれた処理糸を観察して評
価、判定した結果を表1に示した。
Example 1 Aqueous dispersion of polyurethane (A) obtained by reacting adipic acid, polyester diol composed of 1,4-butanediol and hexamethylene diisocyanate (active ingredient 25% by weight) and oxidation of molecular weight 4500 Aqueous dispersion of polyethylene (B) (active ingredient 25% by weight), ethylene urea compound (C) comprising reaction product of diphenylmethane diisocyanate and ethylene imine
The aqueous dispersion (active ingredient 25% by weight) and the aqueous dispersion containing dimethyl silicone (D) as the main component (active ingredient 40% by weight) were added to the active ingredient ratio (solid component ratio; weight%) shown in Table 1. Each of the aqueous dispersions was blended so as to obtain a treating agent liquid. The solid content concentration of this treating solution was 13% by weight. An outer diameter of 14 mm made of a para-aramid long fiber yarn of 1500 denier / 1000 filament [Technola: manufactured by Teijin Limited] having an oil content of 0.5% by weight or less.
Is immersed in the above-mentioned compounding treatment solution to impregnate it, and the amount of the treatment solution attached is controlled by passing through a compressed air nozzle, followed by drying at a temperature of 130 ° C. for 15 minutes. At 3 ° C. for 3 minutes to effect a cross-linking reaction of the treating agent coating formed on the surface of the fiber constituting the rope. At this time, the solid content of the treatment agent attached to the entire rope was 3.5% by weight. The obtained ropes were evaluated by the abrasion resistance evaluation methods A and B and the bending fatigue resistance test, and the results were as shown in the corresponding portions of Table 1. In addition, the classification of the foaming rate (defoaming property) measured for this compounding treatment agent liquid was a circle mark as shown in the corresponding portion of Table 1. Table 1 shows the results of the evaluation and determination of the state of the fluff occurring in the processing step, by observing the processed yarn wound on the paper tube after the processing.

【0031】[0031]

【実施例2〜5】実施例2〜5は、実施例1で用いた
(A)、(B)、(C)及び(D)の各水分散液を、表
1に示したそれぞれの実施例に該当する固形分比率(重
量%)になるよう配合して処理剤液を作成使用した以外
は、実施例1と同様に行った。それらについて、耐摩耗
性評価法AとB及び耐屈曲疲労性試験により、比較評価
した。その結果は表1に示す。また、各実施例で使用し
た配合処理剤液の発泡率(消泡性)の測定結果及び処理
後の紙管に巻かれた処理糸についての毛羽発生状況の観
察評価結果を表1に示した。
Examples 2 to 5 In Examples 2 to 5, the respective aqueous dispersions (A), (B), (C) and (D) used in Example 1 were subjected to the respective operations shown in Table 1. The procedure was performed in the same manner as in Example 1, except that the treating agent liquid was prepared and used so as to have a solid content ratio (% by weight) corresponding to the example. These were compared and evaluated by the wear resistance evaluation methods A and B and the bending fatigue resistance test. The results are shown in Table 1. In addition, Table 1 shows the measurement results of the foaming ratio (defoaming property) of the compounding treatment solution used in each example, and the results of observation and evaluation of the occurrence of fuzz on the treated yarn wound around the paper tube after the treatment. .

【0032】[0032]

【実施例6、7】実施例6、7は、実施例1で用いたジ
メチルシリコーンの代りに自己乳化型のシリコーン
(D)を主成分とする水分散液を用いて、表1に示した
固形分比率(重量%)に配合した以外は、実施例1と同
様に行った。それらについて、耐摩耗性評価法AとB及
び耐屈曲疲労性試験により比較評価した結果は表1のそ
れぞれの該当箇所に示す通りであった。また、実施例1
と同様に評価した処理剤液の発泡率(消泡性)及び処理
後の紙管に巻かれた処糸についての毛羽発生状況観察判
定結果を表1に示した。
Examples 6 and 7 Examples 6 and 7 are shown in Table 1 using an aqueous dispersion containing a self-emulsifying type silicone (D) as a main component instead of the dimethyl silicone used in Example 1. The procedure was performed in the same manner as in Example 1 except that the solid content ratio (% by weight) was added. The results of comparative evaluation of the wear resistance evaluation methods A and B and the flex fatigue resistance test were as shown in Table 1 at the corresponding locations. Example 1
Table 1 shows the foaming rate (defoaming property) of the treating agent liquid evaluated in the same manner as described above, and the results of the observation and determination of the fluff generation state regarding the yarns wound on the paper tube after the treatment.

【0033】[0033]

【表1】 [Table 1]

【0034】[0034]

【比較例1】比較のため、処理剤液で含浸処理する前の
実施例1で用いたロープについて、実施例1と同様の方
法で比較評価、判定した結果を比較例1として表2に示
した。
[Comparative Example 1] For comparison, the results of comparative evaluation and judgment of the rope used in Example 1 before the impregnation treatment with the treating agent liquid in the same manner as in Example 1 are shown in Table 2 as Comparative Example 1. Was.

【0035】[0035]

【比較例2〜8、比較例10、比較例11】比較例2〜
8と比較例10、比較例11は配合処理剤液の固形分比
率(重量%)の最適範囲並びに配合処理剤液の消泡効果
について、実施例と対比して検討した。実施例1で用い
た(A)、(B)、(C)、(D)の各水分散液を、表
2に示した固形分比率(重量%)になるように配合した
以外は、実施例1と同様に行った。その結果を表2に比
較例として示した。また、処理剤液の消泡性、処理糸の
毛羽発生状況についても実施例1と同様に行って、比較
判定し、結果を表2に示した。
Comparative Examples 2 to 8, Comparative Example 10, and Comparative Example 11 Comparative Examples 2 to
8, Comparative Example 10 and Comparative Example 11 examined the optimal range of the solid content ratio (% by weight) of the compounding treatment solution and the defoaming effect of the compounding treatment solution in comparison with the examples. Except that the aqueous dispersions (A), (B), (C) and (D) used in Example 1 were blended so as to have a solid content ratio (% by weight) shown in Table 2, It carried out like Example 1. The results are shown in Table 2 as a comparative example. In addition, the defoaming property of the treating agent liquid and the state of generation of fluff on the treated yarn were determined in the same manner as in Example 1, and the results were compared and determined. The results are shown in Table 2.

【0036】[0036]

【比較例9】比較のため、実施例1で用いた(A)、
(B)、(C)の各水分散液及び実施例6で用いた自己
乳化型のシリコーン(D)を主成分とする水分散液を用
いて、表2の比較例9に示した固形分比率(重量%)に
配合した以外は、実施例1と同様に行った。結果を表2
に示した。また、処理剤液の発泡率(消泡性)及び処理
後の紙管に巻かれた処理糸の毛羽発生状況についても、
実施例1と同様に評価して表2に示した。
Comparative Example 9 For comparison, (A) used in Example 1 was used,
Using each of the aqueous dispersions (B) and (C) and the self-emulsifying silicone (D) used in Example 6, the solid content shown in Comparative Example 9 in Table 2 was used. The procedure was performed in the same manner as in Example 1 except that the blending was performed in the ratio (% by weight). Table 2 shows the results
It was shown to. Also, regarding the foaming rate (defoaming property) of the treating agent liquid and the generation of fluff of the treated yarn wound on the paper tube after the treatment,
Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2.

【0037】[0037]

【表2】 [Table 2]

【図面の簡単な説明】[Brief description of the drawings]

【図1】耐摩耗性評価装置の側断面図。FIG. 1 is a side sectional view of a wear resistance evaluation device.

【符号の説明】[Explanation of symbols]

1 評価用の含浸ロープ(評価サンプル) 2 表面粗さ120番のサンドグラインダー 3 荷重 4 評価用サンプル1を固定する為の固定具 5 自由に回転するガイドロール 6 ロート 7 開閉用のコック 8 水 DESCRIPTION OF REFERENCE NUMERALS 1 Impregnated rope for evaluation (evaluation sample) 2 Sand grinder with surface roughness No. 120 3 Load 4 Fixing device for fixing evaluation sample 1 5 Guide roll that rotates freely 6 Roto 7 Opening and closing cock 8 Water

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI D06M 15/643 D06M 15/643 (58)調査した分野(Int.Cl.6,DB名) D06M 15/00 - 15/72 ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 identification code FI D06M 15/643 D06M 15/643 (58) Field surveyed (Int.Cl. 6 , DB name) D06M 15/00-15/72

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 ポリウレタン(A)、酸化ポリエチレン
(B)、エチレン尿素化合物(C)及びオルガノポリシ
ロキサン(D)を主たる成分とし、下記方法により測定
した発泡率が140%未満であることを特徴とする耐摩
耗性向上処理剤。<配合処理液の攪拌による発泡率の評価方法> 配合処理液を秤量して100ml取り、これを外径4.
0cmの250ml用メスシリンダー中に入れた後、該
メスシリンダーの底面から処理剤液面までの高さを測定
して(H1)とする。次に、最大長さ約2.0cmの2枚の
羽根を有する攪拌機により2000rpmで、約5分
間、処理剤を攪拌した後、約30分間静置し、その後、
処理剤の発泡部分も含めた液面高さを測定して(H2)
とし、下記の計算式により発泡率を算出した。 発泡率(%)=(H2)/(H1)×100
1. Polyurethane (A), polyethylene oxide (B), ethylene urea compound (C) and organopolysiloxane (D) as main components, measured by the following method.
An abrasion resistance improving agent characterized by having a foaming rate of less than 140% . <Method of Evaluating Foaming Ratio by Stirring Compounding Treatment Liquid > The mixing treatment liquid was weighed and taken in an amount of 100 ml.
After placing in a 0 cm 250 ml graduated cylinder,
Measures the height from the bottom of the measuring cylinder to the liquid level of the processing agent
(H1). Next, two sheets with a maximum length of about 2.0 cm
Approximately 5 minutes at 2000 rpm with a stirrer having blades
Meanwhile, after stirring the treating agent, it is allowed to stand for about 30 minutes.
Measure the liquid level including the foaming part of the treatment agent (H2)
The foaming ratio was calculated by the following formula. Foaming rate (%) = (H2) / (H1) × 100
【請求項2】 ポリウレタン(A)がポリエステルポリ
オールと脂肪族ポリイソシアネートからなり、酸化ポリ
エチレン(B)の分子量が1000〜7000からな
り、エチレン尿素化合物(C)が下記一般式を満足する
化合物からなり、 【化1】 さらにオルガノポリシロキサン(D)がジメチルポリシ
ロキサン又は下記の一般式で示される変性ポリシロキサ
からなる請求項1記載の耐摩耗性向上処理剤。 【化2】
2. A polyurethane (A) comprising a polyester polyol and an aliphatic polyisocyanate, a polyethylene oxide (B) having a molecular weight of 1,000 to 7000, and an ethylene urea compound (C) comprising a compound satisfying the following general formula: , Embedded image 2. The agent according to claim 1, wherein the organopolysiloxane (D) comprises dimethylpolysiloxane or a modified polysiloxane represented by the following general formula. Embedded image
【請求項3】 処理剤の各成分の重量比が、(A)/
[(A)+(B)]=0.5〜0.9、(C)/
[(A)+(B)]=0.05〜0.3、(D)/
[(A)+(B)+(C)]=0.0003〜0.1で
ある請求項1又は2の耐摩耗性向上処理剤。
3. The weight ratio of each component of the treatment agent is (A) /
[(A) + (B)] = 0.5-0.9, (C) /
[(A) + (B)] = 0.05-0.3, (D) /
3. The treatment agent for improving abrasion resistance according to claim 1, wherein [(A) + (B) + (C)] = 0.003 to 0.1.
JP28675793A 1993-11-16 1993-11-16 Abrasion resistance improving agent Expired - Lifetime JP2891858B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP28675793A JP2891858B2 (en) 1993-11-16 1993-11-16 Abrasion resistance improving agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP28675793A JP2891858B2 (en) 1993-11-16 1993-11-16 Abrasion resistance improving agent

Publications (2)

Publication Number Publication Date
JPH07138881A JPH07138881A (en) 1995-05-30
JP2891858B2 true JP2891858B2 (en) 1999-05-17

Family

ID=17708656

Family Applications (1)

Application Number Title Priority Date Filing Date
JP28675793A Expired - Lifetime JP2891858B2 (en) 1993-11-16 1993-11-16 Abrasion resistance improving agent

Country Status (1)

Country Link
JP (1) JP2891858B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9834883B2 (en) * 2009-09-03 2017-12-05 Teijin Aramid Gmbh Textile fabric made from aramid fibers and the use thereof

Also Published As

Publication number Publication date
JPH07138881A (en) 1995-05-30

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