JP3667913B2 - Polyamide-based mixed spinning fiber - Google Patents
Polyamide-based mixed spinning fiber Download PDFInfo
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- JP3667913B2 JP3667913B2 JP1109397A JP1109397A JP3667913B2 JP 3667913 B2 JP3667913 B2 JP 3667913B2 JP 1109397 A JP1109397 A JP 1109397A JP 1109397 A JP1109397 A JP 1109397A JP 3667913 B2 JP3667913 B2 JP 3667913B2
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- polyamide
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- polyethylene glycol
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Description
【０００１】
【発明の属する技術分野】
本発明は、ポリアミド系混合紡糸繊維に関し、更に詳しくは紡糸調子が良好で、カード通過性、ニードルパンチ性に優れる混合紡糸繊維に関する。
【０００２】
【従来の技術】
ポリアミドとポリオレフィンとからなる混合紡糸繊維は、繊維特性が改善され、あるいは繊維構成成分の一方を除去して、人工皮革、フィルター、保温材などに使用する特殊形状の繊維シートとすることができるため、広く用いられている（例えば、特開昭６３−２４３３１４号公報）。
【０００３】
しかし、ポリアミドとポリオレフィンとを同一溶液系で溶融し、混合紡糸して混合紡糸繊維を製造する場合、紡糸時にベンデイングや断糸が多発して安定な紡糸が行えないという問題があった。
【０００４】
この問題を解決しようとして、これまで数多くの提案が行われてきた。例えば、特公昭４１−１１６５号公報では、紡糸ノズルを通過する両ポリマーの溶融粘度を同一剪断速度においてほぼ同程度とすることが提案されている。
【０００５】
また、このポリアミドとポリオレフィンからなる混合紡糸繊維では、ウエブを作り、ニードルパンチ等を施して不織布とする場合に、カードでシリンダーやドッファーへの巻き付きが発生しやすく、カード通過性が悪いという問題と、ニードルパンチ工程において、不織布の層間剥離強力が上がらないというニードルパンチ特性不良の問題があった。
【０００６】
しかし、従来提案されている技術では、十分に満足できるカード通過性、ニードルパンチ性は得られなかった。
【０００７】
【発明が解決しようとする課題】
本発明は、ポリアミドとポリオレフィンとからなる混合紡糸繊維のカード通過性及びニードルパンチ特性を改善するとともに、紡糸時のベンデイング、断糸を減少させて、紡糸性を向上させることを目的とする。
【０００８】
【課題を解決するための手段】
本発明者らは、かかる課題を解決すべく鋭意検討を重ねた結果、両末端封鎖型ポリエチレングリコールをポリアミドとポリオレフィンの溶融混合系に添加すると、驚くべきことに、得られた混合紡糸繊維のカード通過性、ニードルパンチ特性が著しく改善され、紡糸性も大幅に向上することを見出し、本発明を完成するに至った。
【０００９】
すなわち、本発明は、ポリアミドとポリオレフィンとからなる混合紡糸繊維であって、該ポリオレフィンに対して、０．１〜５重量％の両末端封鎖型ポリエチレングリコールを含有することを特徴とするポリアミド系混合紡糸繊維である。
【００１０】
ポリアミドとポリオレフィンとからなる混合紡糸繊維において、両末端封鎖型ポリエチレングリコールの添加により、カード通過性、ニードルパンチ特性が向上する理由は、未だ明らかでないが、おそらく両末端封鎖型ポリエチレングリコールがポリアミド、ポリオレフィン相互の分散性あるいは相溶性を高め、混合紡糸繊維の表面が平滑になり、その結果、繊維表面の摩擦係数が低下することに起因するものと推定される。
【００１１】
同様に、紡糸時のベンデイングや断糸が減少し、安定した紡糸が行えるようになるのも、両末端封鎖型ポリエチレングリコールがポリアミド、ポリオレフィン相互の分散性あるいは相溶性を高めることに起因するものと推定される。
【００１２】
すなわち、ポリアミドとポリオレフィンとは、もともと異質のポリマーであり、相互の分散性あるいは相溶性は必ずしもよいとはいえない。そのため、溶融紡糸時には、紡糸ノズルから吐出された際に、両者が分離し、主としてポリアミド成分が紡糸口金の紡糸ノズル周辺に異物として炭化し、堆積し、ベンデイング、断糸を多発させる原因となっている。
【００１３】
ところが、両末端封鎖型ポリエチレングリコールを添加すると、ポリアミドとポリオレフィンとの分散性あるいは相溶性が向上し、紡糸時の紡糸ノズル周辺への異物の堆積が減少し、ベンデイング、断糸が少なくなり、安定した紡糸が可能になるものと考えられる。
【００１４】
【発明の実施の形態】
本発明において、ポリアミドは、ナイロン４、ナイロン６、ナイロン６６、ナイロン７、ナイロン６１０、ナイロン１１、ナイロン１２、ビス（アミノシクロヘキシル）メタンと１，１０デカメチレンジカルボン酸もしくは１，９−ノナメチレンジカルボン酸からのポリアミド、これらのポリアミドに１５モル％未満の第三成分を共重合した共重合ポリアミド及びこれらの２種類以上の共重合物若しくは混合物が例示できるが、特にナイロン６が好適である。
【００１５】
また、ポリオレフィンは、熱トルエン、ハロゲン化炭化水素などの溶剤に可溶であれば特に限定されないが、ポリエチレン、ポリプロピレン及びポリブチレンからなる群より選ばれた少なくとも１種のポリマーであることが好ましい。
【００１６】
ポリアミドとポリオレフィンとの混合割合（重量比）は、要求特性、用途などにもよるが、通常は２５：７５〜７５：２５の範囲が好ましく、特に好ましくは４０：６０〜６０：４０である。
【００１７】
なお、本発明においては、ポリアミドとポリオレフィンの混合分散状態を、ポリオレフィン（分散成分）中にポリアミド（分散成分）が分散した形態とするのが、顕著な効果を期待できるので好ましいが、逆にポリアミドを分散媒成分として、その中にポリオレフィンを分散させるようにしてもよい。
【００１８】
さらに、本発明においては、任意の両末端封鎖型ポリエチレングリコールを用いることができる。なかでも、下記式（１）で表される化合物を用いるのが好ましい。
【００１９】
【化２】
（Ｃm Ｈ2m+1ＣＯＯ）-(ＣＨ2 - ＣＨ2 - Ｏ）n - （ＣＯＣm Ｈ2m+1) ・・・（１）
（式中、ｎは１０〜１０００、ｍは８〜２０の整数を示す）
【００２０】
両末端封鎖型ポリエチレングリコールの含有量は、ポリオレフィンに対して、０．１重量％から５重量％までの範囲であることが必要である。０．１重量％未満では、両末端封鎖型ポリエチレングリコール添加の効果がなく、紡糸時のベンデイング、断糸が多発し、不織布製造工程でのカード通過性が悪く、ニードルパンチにおける層間剥離強度が上がらす、ニードルパンチ特性が劣る。一方、５重量％を超えても、含有量に見合うだけの効果が得られず、むしろ、紡糸時のベンデイング、断糸が多くなり、不織布製造工程でのカード通過性やニードルパンチ特性も悪くなる傾向があるので不利である。両末端封鎖型ポリエチレングリコール含有両の特に好ましい範囲は０．５〜３重量％である。
【００２１】
両末端封鎖型ポリエチレングリコールのポリオレフィン及びポリアミドの添加は、公知の方法で行うことができる。例えば、溶融紡糸前にポリアミド、ポリオレフィン、両末端封鎖型ポリエチレングリコールの三者をブレンダーで粉体混合してもよいし、予めポリオレフィンに高濃度の両末端封鎖型ポリエチレングリコールを溶融添加したマスターバッチを作っておき、これを溶融紡糸前に希釈用のポリアミド及びポリオレフィンと混合して押出機に供給して溶融紡糸してもよい。さらに、ポリアミドとポリオレフィンとを押出機で溶融し、両末端封鎖型ポリエチレングリコールを粉体のままか、あるいは溶融して、押出機内の溶融したポリアミドとポリオレフィンに直接添加してもよい。
【００２２】
本発明のポリアミドとポリオレフィンとからなる混合紡糸繊維は、必要に応じて、帯電防止剤、二酸化チタンの如き艶消し剤、カーボンブラックの如き着色剤、熱安定を得るための酸化防止剤、滑剤などの添加剤を適量含有することもできる。
【００２３】
両末端封鎖型ポリエチレングリコールを添加したポリアミドとポリオレフィンの混合物を溶融紡糸する際の紡糸温度は２４０〜２６０℃、紡糸引取速度は５００〜１５００ｍ／分が好ましい。
【００２４】
得られた未延伸糸は、通常、延伸され、単繊維繊度が１〜１０デニールの混合紡糸繊維になる。延伸温度は４０〜９５℃、延伸倍率は２〜４倍、延伸速度は５０〜３００ｍ／分が好ましい。
【００２５】
延伸後、２５〜２００ｍｍの繊維長となるように切断して、カードを通してウエブを作り、ニードルパンチ等を施して不織布とする。次いで、ポリオレフィンを熱トルエンのような可溶性の溶剤で溶出して、極細ポリアミド繊維構造体を得、この構造体にポリウレタン樹脂等を含浸させれば、良好な人工皮革を得ることができる。
【００２６】
【実施例】
以下、本発明を実施例により詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例中、部は重量部である。また、紡糸性及び後加工性は次のようにして評価した。
【００２７】
１．紡糸性
（１）異物堆積高さ
１日間紡糸を行った後、紡糸口金の紡糸ノズル周辺に堆積した異物の高さを測定した。
（２）紡糸断糸
１日間紡糸を行った際の断糸発生回数を数えた。
【００２８】
２．後加工性
（１）カード通過性
ドッファーの表面速度３５ｍ／分、紡出ウエブの目付が１５ｇ／ｍ2 となる条件でカードにかけ、１時間運転を行った際にウエブがドッファーに巻き付いた回数を数えた。
（２）ニードルパンチ特性（層間剥離強度）
カードウエブを目付５００ｇ／ｍ2 となるように積層後、３６番手レギュラーバーブを用い針深度１０ｍｍ、パンチ密度１０００本／ｃｍ2 の条件でニードルパンチを施し、得られた不織布の層間剥離強度（ｋｇ／ｃｍ）を測定した。
【００２９】
〔実施例１〜４、比較例１〜２〕
２６０℃で測定したメルトインデックスが７０のポリエチレンに、ポリエチレングリコール（ＰＥＧ６０００：ｎ＝１３６）ジステアレートを２８０℃で溶融して、両末端封鎖型ポリエチレングリコールのマスターバッチを作成した。
【００３０】
このマスターバッチＸ部、該マスターバッチに使用したものと同じポリエチレン（５０−Ｘ）部、及び２６０℃で測定したメルトインデックスが２０のナイロン６を５０部チップブレンドして押出機に供給し、溶融部とスクリュー先端部の温度を２７０℃、紡糸パック、紡糸口金の温度を２４５℃にして、ノズル径０．４ｍｍ、ノズル数１６０の紡糸口金から７００ｍ／分の引取速度で紡糸した。
【００３１】
得られた混合紡糸未延伸糸を、６０℃で２．５倍に延伸し、機械捲縮を付与した後、５１ｍｍの長さに切断して、混合紡糸繊維を得た。該繊維の単繊維繊度は５デニールであった。
【００３２】
この混合紡糸繊維をカードにかけ、さらにニードルパンチを行い、後加工特性を評価した。
紡糸性及び後加工性を表１に示す。
【００３３】
【表１】
表１にみるとおり、両末端封鎖型ポリエチレングリコールの含有量が０．１〜５重量％である本発明方法の場合、紡糸性が向上し、カード通過性、ニードルパンチ特性も改善されている。特に、両末端封鎖型ポリエチレングリコールの含有量が０．５〜３重量％の場合にその効果が大きい。
【００３５】
〔実施例５〜７〕
実施例３において、ポリエチレンの代わりに、２６０℃で測定したメルトインデックスが３０のポリプロピレンを用い、非水溶性ポリエチレングリコールを前記式（１）で表される化合物でｎとｍを表２に示すように変更したものに代えた以外は実施例３と同様にして、混合紡糸繊維を製造し、後加工特性を評価した。結果は表２に示すとおりであり、紡糸性、後加工性は良好な結果を得た。
【００３６】
【表２】
【発明の効果】
本発明によれば、紡糸時のベンデイングや断糸が大幅に減少し、ポリアミドとポリオレフィンの混合紡糸繊維を安定して製造することができるとともに、後加工工程でのカード通過性、ニードルパンチ特性が優れたおり、良好な生産性のもとで、高品質の不織布を得ることができ、人工皮革用途などに極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyamide-based mixed spun fiber, and more particularly to a mixed spun fiber having a good spinning condition, excellent card passing property and needle punching property.
[0002]
[Prior art]
The mixed spun fiber made of polyamide and polyolefin has improved fiber characteristics, or can remove one of the fiber components to form a specially shaped fiber sheet for use in artificial leather, filters, heat insulation materials, etc. Are widely used (for example, JP-A-63-243314).
[0003]
However, when a mixed spun fiber is produced by melting polyamide and polyolefin in the same solution system and mixing and spinning, there is a problem in that stable spinning cannot be performed due to frequent bending and breakage during spinning.
[0004]
Many proposals have been made to solve this problem. For example, Japanese Patent Publication No. 41-1165 proposes that the melt viscosities of both polymers passing through a spinning nozzle be approximately the same at the same shear rate.
[0005]
Also, with this mixed spinning fiber made of polyamide and polyolefin, when a web is made and a needle punch or the like is used to make a nonwoven fabric, the card is likely to wrap around the cylinder or doffer and the card passing property is poor. In the needle punching process, there has been a problem of poor needle punching characteristics that the delamination strength of the nonwoven fabric does not increase.
[0006]
However, with the conventionally proposed techniques, a sufficiently satisfactory card passing property and needle punching property cannot be obtained.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to improve the cardability and needle punch characteristics of a mixed spun fiber made of polyamide and polyolefin, and to improve spinning performance by reducing bending and yarn breakage during spinning.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve such problems, the present inventors have surprisingly found that when both end-capped polyethylene glycol is added to a melt-mixed system of polyamide and polyolefin, the resulting mixed spun fiber card is obtained. The inventors have found that the passability and needle punch characteristics are remarkably improved and the spinnability is greatly improved, and the present invention has been completed.
[0009]
That is, the present invention is a mixed spinning fiber comprising a polyamide and a polyolefin, and 0.1 to 5 wt% of both end-capped polyethylene glycol is contained with respect to the polyolefin. Spinning fiber.
[0010]
The reason why the card passability and needle punching characteristics are improved by adding both end-capped polyethylene glycol in a mixed spun fiber composed of polyamide and polyolefin is not yet clear, but probably both end-capped polyethylene glycol is polyamide, polyolefin. It is presumed that the mutual dispersibility or compatibility is increased, the surface of the mixed spun fiber becomes smooth, and as a result, the friction coefficient of the fiber surface decreases.
[0011]
Similarly, bending and yarn breakage during spinning are reduced, and stable spinning can be performed because both end-capped polyethylene glycol increases the dispersibility or compatibility between polyamide and polyolefin. Presumed.
[0012]
That is, polyamide and polyolefin are originally different polymers, and their dispersibility or compatibility is not necessarily good. Therefore, at the time of melt spinning, both are separated when discharged from the spinning nozzle, and mainly the polyamide component is carbonized as foreign matter around the spinning nozzle of the spinneret and accumulates, causing bending and yarn breakage frequently. Yes.
[0013]
However, when both end-capped polyethylene glycol is added, the dispersibility or compatibility of polyamide and polyolefin is improved, the accumulation of foreign matter around the spinning nozzle during spinning is reduced, bending and yarn breakage are reduced, and stability is improved. It is considered that the spun yarn can be made.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the polyamide is nylon 4, nylon 6, nylon 66, nylon 7, nylon 610, nylon 11, nylon 12, bis (aminocyclohexyl) methane and 1,10 decamethylene dicarboxylic acid or 1,9-nonamethylene dicarboxylic acid. Examples include polyamides from acids, copolymerized polyamides obtained by copolymerizing these polyamides with a third component of less than 15 mol%, and copolymers or mixtures of two or more of these, with nylon 6 being particularly preferred.
[0015]
The polyolefin is not particularly limited as long as it is soluble in a solvent such as hot toluene and halogenated hydrocarbon, but is preferably at least one polymer selected from the group consisting of polyethylene, polypropylene and polybutylene.
[0016]
The mixing ratio (weight ratio) of polyamide and polyolefin is preferably in the range of 25:75 to 75:25, particularly preferably 40:60 to 60:40, although it depends on the required characteristics and applications.
[0017]
In the present invention, it is preferable that the mixed dispersion state of the polyamide and the polyolefin is in a form in which the polyamide (dispersion component) is dispersed in the polyolefin (dispersion component) because a remarkable effect can be expected. As a dispersion medium component, polyolefin may be dispersed therein.
[0018]
Furthermore, in the present invention, any end-capped polyethylene glycol can be used. Especially, it is preferable to use the compound represented by following formula (1).
[0019]
[Chemical formula 2]
(C m H 2m + 1 COO ) - (CH 2 - CH 2 - O) n - (COC m H 2m + 1) ··· (1)
(In the formula, n represents an integer of 10 to 1000, and m represents an integer of 8 to 20)
[0020]
The content of both end-capped polyethylene glycols needs to be in the range of 0.1% to 5% by weight with respect to the polyolefin. If it is less than 0.1% by weight, there is no effect of adding both end-capped polyethylene glycol, bending and spinning frequently occur during spinning, card passing properties in the nonwoven fabric manufacturing process are poor, and delamination strength in the needle punch is increased. The needle punch characteristic is inferior. On the other hand, even if it exceeds 5% by weight, the effect sufficient for the content cannot be obtained, but rather bending and yarn breakage during spinning increase, and the card passing property and needle punch characteristics in the nonwoven fabric manufacturing process also deteriorate. It is disadvantageous because there is a tendency. A particularly preferred range of both end-capped polyethylene glycol-containing groups is 0.5 to 3% by weight.
[0021]
Addition of both end-capped polyethylene glycol polyolefin and polyamide can be carried out by a known method. For example, before melt spinning, polyamide, polyolefin, and both end-capped polyethylene glycol may be powder mixed with a blender, or a master batch in which high-concentration both-end capped polyethylene glycol is previously melt-added to polyolefin. It may be prepared and mixed with a diluting polyamide and polyolefin before melt spinning, and supplied to an extruder for melt spinning. Furthermore, polyamide and polyolefin may be melted by an extruder, and both end-capped polyethylene glycol may be powdered or melted and added directly to the melted polyamide and polyolefin in the extruder.
[0022]
The mixed spun fiber composed of the polyamide and polyolefin of the present invention may contain an antistatic agent, a matting agent such as titanium dioxide, a colorant such as carbon black, an antioxidant for obtaining thermal stability, a lubricant, etc. An appropriate amount of these additives can also be contained.
[0023]
The spinning temperature at the time of melt spinning a mixture of polyamide and polyolefin to which both end-capped polyethylene glycol is added is preferably 240 to 260 ° C., and the spinning take-up speed is preferably 500 to 1500 m / min.
[0024]
The obtained undrawn yarn is usually drawn into a mixed spun fiber having a single fiber fineness of 1 to 10 denier. The stretching temperature is preferably 40 to 95 ° C., the stretching ratio is 2 to 4 times, and the stretching speed is preferably 50 to 300 m / min.
[0025]
After stretching, it is cut so as to have a fiber length of 25 to 200 mm, a web is made through a card, and needle punching or the like is applied to obtain a nonwoven fabric. Next, if the polyolefin is eluted with a soluble solvent such as hot toluene to obtain an ultrafine polyamide fiber structure, and this structure is impregnated with a polyurethane resin or the like, a good artificial leather can be obtained.
[0026]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In the examples, parts are parts by weight. Spinnability and post-processability were evaluated as follows.
[0027]
1. Spinnability (1) Foreign matter deposition height After spinning for 1 day, the height of foreign matter deposited around the spinning nozzle of the spinneret was measured.
(2) Spinning breakage The number of occurrences of yarn breakage when spinning for 1 day was counted.
[0028]
2. Post-processability (1) The number of times the web is wound around the doffer when the card is applied to the card under the conditions that the surface speed of the doppler is 35 m / min and the basis weight of the spinning web is 15 g / m 2. I counted.
(2) Needle punch characteristics (delamination strength)
After laminating the card web so as to have a basis weight of 500 g / m 2 , needle punching was performed using a 36 th regular barb at a needle depth of 10 mm and a punch density of 1000 / cm 2 , and the delamination strength (kg / Cm) was measured.
[0029]
[Examples 1-4, Comparative Examples 1-2]
Polyethylene glycol (PEG 6000: n = 136) distearate was melted at 280 ° C. in polyethylene having a melt index of 70 measured at 260 ° C. to prepare a master batch of both end-capped polyethylene glycol.
[0030]
This masterbatch X part, the same polyethylene (50-X) part used for the masterbatch, and 50 parts of nylon 6 having a melt index of 20 measured at 260 ° C. are chip-blended and supplied to an extruder for melting. Spinning was performed at a take-up speed of 700 m / min from a spinneret having a nozzle diameter of 0.4 mm and a nozzle number of 160 with the temperature of the head and the screw tip being 270 ° C, the temperature of the spinning pack and the spinneret being 245 ° C.
[0031]
The obtained mixed-spun undrawn yarn was drawn 2.5 times at 60 ° C. to give mechanical crimps, and then cut into a length of 51 mm to obtain a mixed-spun fiber. The single fiber fineness of the fiber was 5 denier.
[0032]
This mixed spun fiber was put on a card and further subjected to needle punching to evaluate post-processing characteristics.
The spinnability and post-processability are shown in Table 1.
[0033]
[Table 1]
As shown in Table 1, in the case of the method of the present invention in which the content of both end-capped polyethylene glycol is 0.1 to 5% by weight, the spinnability is improved, and the card passability and needle punch characteristics are also improved. In particular, the effect is great when the content of both end-capped polyethylene glycol is 0.5 to 3% by weight.
[0035]
[Examples 5 to 7]
In Example 3, polypropylene having a melt index of 30 measured at 260 ° C. was used instead of polyethylene, and water-insoluble polyethylene glycol was a compound represented by the above formula (1), and n and m are shown in Table 2. A mixed spun fiber was produced in the same manner as in Example 3 except that the post-process characteristics were evaluated. The results are as shown in Table 2, and good results were obtained for spinnability and post-processability.
[0036]
[Table 2]
【The invention's effect】
According to the present invention, bending and yarn breakage during spinning are greatly reduced, and a mixed spun fiber of polyamide and polyolefin can be stably produced, and card passing properties and needle punching characteristics in a post-processing step are improved. It is excellent and can produce a high-quality nonwoven fabric with good productivity, which is extremely useful for artificial leather.
Claims (4)
で示される請求項１記載のポリアミド系混合紡糸繊維。Both end-capped polyethylene glycol is represented by the following formula (1)
The polyamide-based mixed spun fiber according to claim 1, represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1109397A JP3667913B2 (en) | 1996-10-01 | 1997-01-24 | Polyamide-based mixed spinning fiber |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26073796 | 1996-10-01 | ||
| JP8-260737 | 1996-10-01 | ||
| JP1109397A JP3667913B2 (en) | 1996-10-01 | 1997-01-24 | Polyamide-based mixed spinning fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10158933A JPH10158933A (en) | 1998-06-16 |
| JP3667913B2 true JP3667913B2 (en) | 2005-07-06 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1109397A Expired - Fee Related JP3667913B2 (en) | 1996-10-01 | 1997-01-24 | Polyamide-based mixed spinning fiber |
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| Country | Link |
|---|---|
| JP (1) | JP3667913B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116145329B (en) * | 2023-01-10 | 2023-10-13 | 恒天嘉华非织造有限公司 | Antibacterial antistatic non-woven fabric and preparation method thereof |
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Also Published As
| Publication number | Publication date |
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| JPH10158933A (en) | 1998-06-16 |
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