JP2008101289A - Polyester monofilament for screen gauze, which is excellent in electrostatic property - Google Patents
Polyester monofilament for screen gauze, which is excellent in electrostatic property Download PDFInfo
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- 229920000728 polyester Polymers 0.000 title claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 239000002216 antistatic agent Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 24
- 230000037303 wrinkles Effects 0.000 claims description 18
- 239000000306 component Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- 239000008358 core component Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 6
- 230000006866 deterioration Effects 0.000 claims description 4
- 238000009941 weaving Methods 0.000 abstract description 15
- 238000007639 printing Methods 0.000 abstract description 14
- 239000004744 fabric Substances 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 16
- -1 ion compound Chemical class 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 230000007547 defect Effects 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 238000011282 treatment Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000007790 scraping Methods 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
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- 238000000034 method Methods 0.000 description 4
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- 238000009987 spinning Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000270506 Tupinambis Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- SIFUVXFIMXORMW-UHFFFAOYSA-N benzyl(triphenyl)phosphanium;dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 SIFUVXFIMXORMW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- VBVCYAZECWLFHP-UHFFFAOYSA-N dodecyl benzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 VBVCYAZECWLFHP-UHFFFAOYSA-N 0.000 description 1
- XWTOMWARSPYOAY-UHFFFAOYSA-N dodecyl benzenesulfonate;tetraphenylphosphanium Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XWTOMWARSPYOAY-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IRDCEJVOXCGYAV-UHFFFAOYSA-M lithium;2-dodecylbenzenesulfonate Chemical compound [Li+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O IRDCEJVOXCGYAV-UHFFFAOYSA-M 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KBAFDSIZQYCDPK-UHFFFAOYSA-M sodium;octadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O KBAFDSIZQYCDPK-UHFFFAOYSA-M 0.000 description 1
- HRQDCDQDOPSGBR-UHFFFAOYSA-M sodium;octane-1-sulfonate Chemical compound [Na+].CCCCCCCCS([O-])(=O)=O HRQDCDQDOPSGBR-UHFFFAOYSA-M 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Abstract
Description
本発明は、表面が改質されたモノフィラメントに関する。さらに詳細には、スクリーン印刷用のメッシュ織物、特にプリント配線基盤の製造などの高度な精密性を要求されるハイメッシュでハイモジュラスのスクリーン紗を得るのに好適なモノフィラメントに関する。 The present invention relates to a monofilament having a modified surface. More particularly, the present invention relates to a monofilament suitable for obtaining a high-mesh, high-modulus screen wrinkle that requires a high degree of precision, such as a mesh fabric for screen printing, particularly manufacturing a printed wiring board.
モノフィラメントは衣料分野ではもちろん、産業資材の分野でも幅広く利用されてきている。特に後者の産業資材の分野での用途の例として、タイヤコード、ロープ、ネット、テグス、ターポリン、テント、スクリーン、パラグライダー、およびセールクロス用などの原糸としてのモノフィラメントがある。そして、このモノフィラメントに要求される物性も厳しくなり、ゴムとの接着性、耐疲労性、染色性、耐摩耗性、結節強力などの改善が迫られている。特に最近の電子回路分野での印刷においては集積度が高まる一方であり、スクリーン紗としての印刷緻密さのためハイメッシュ、ハイモジュラス化及び印刷性向上、特に連続印刷における寸法安定性の要求が強くなっている。 Monofilaments have been widely used not only in the clothing field but also in the industrial material field. Examples of applications in the latter field of industrial materials in particular include monofilaments as raw yarns for tire cords, ropes, nets, tegus, tarpaulins, tents, screens, paragliders and sailcloths. The physical properties required for this monofilament are becoming strict, and improvements such as adhesion to rubber, fatigue resistance, dyeability, abrasion resistance, and knot strength are being urged. Especially in the recent printing in the electronic circuit field, the degree of integration is increasing, and due to the printing density as a screen flaw, there is a strong demand for high mesh, high modulus and improved printability, especially dimensional stability in continuous printing. It has become.
又、ハイメッシュ、ハイモジュラススクリーン紗を用いることによって、紗の目開き量が小さい緻密性の高い印刷が可能になり、今まで問題にならなかったごく僅かな印刷欠点も著しく目立つようになってきた。このような印刷欠点の中には糸削れによるものばかりでなく、使用する紗が帯電することにより起因するものが多い。例えば、加工工程において紗への摩擦などによって静電気が紗に帯電すると塵やゴミの付着に伴う印刷欠点が生じたり、静電気を帯電した静電気によって印刷時に印刷インキが飛散したりすることにより、印刷欠点が生ずるという問題があった。それらに対応した原糸が要求されている。 In addition, by using a high mesh, high modulus screen wrinkle, it is possible to print with high density with a small opening amount of wrinkles, and even a few printing defects that have not been a problem until now have become noticeable. It was. Many of these printing defects are caused not only by thread scraping but also by charging of the wrinkles used. For example, if static electricity is charged to the cocoon due to friction on the cocoon in the processing process, printing defects due to adhesion of dust or dirt may occur, or printing ink may be scattered during printing due to static electricity charged with static electricity. There was a problem that occurred. The raw yarn corresponding to them is requested | required.
スクリーン紗用原糸を設計する上で特許文献１（特開平２−２８９１２０号公報）では、ポリエステル芯鞘型モノフィラメントの破断強度や破断伸度、１０％伸長時のモジュラス、及び鞘部のポリエステルのＴｇを特定し、芯部で高モジュラス、高強度を取り、鞘部で製織時の筬による糸削れ防止、スカムの発生防止することが提案されている。確かに該方法により高強力、高モジュラススクリーン紗が得られ且つ糸削れを減少させることは可能であるが、スクリーン紗製造にあたり、織目調整や湿熱セットや紗張りの工程を経過する際、原糸は収縮し、糸の荷重曲線が収縮前と異なったものとなるため、スクリーン紗としての寸法安定性が悪く、連続印刷性の良いものが得られなかった。 In designing screen silk yarn, Patent Document 1 (Japanese Patent Application Laid-Open No. 2-289120) describes the breaking strength and breaking elongation of polyester core-sheath monofilament, the modulus when stretched by 10%, and the polyester of the sheath portion. It has been proposed that Tg is specified, the core portion has high modulus and high strength, and the sheath portion prevents yarn scraping due to wrinkles during weaving and the occurrence of scum. It is possible to obtain a high-strength, high-modulus screen wrinkle with this method and to reduce thread shaving. However, in the production of the screen wrinkle, when the process of texture adjustment, moist heat setting and tensioning is passed, Since the yarn contracted and the load curve of the yarn became different from that before the contraction, the dimensional stability as a screen wrinkle was poor and a continuous printability good product could not be obtained.
又帯電抑制については特許文献２（特開平２−２８９１１９号公報）、特許文献３（特開２００１−２６２４３８号公報）でポリアルキレンエーテルを含有するポリエステルを芯成分とした芯鞘型複合モノフィラメントを提案されているが、芯側に制電剤が含有し、表面に露出しないため、良好な制電性能を得ることができない。特許文献１ではポリエチレングリコールを鞘成分ポリエステルに共重合することが示されているが、ある程度効果はあるものの共重合量には物性上限度があり、十分帯電防止効果をもたらすものではなかった。 As for charge suppression, Patent Document 2 (Japanese Patent Laid-Open No. 2-289119) and Patent Document 3 (Japanese Patent Laid-Open No. 2001-262438) propose a core-sheath type composite monofilament having a polyalkylene ether-containing polyester as a core component. However, since the antistatic agent is contained on the core side and is not exposed on the surface, good antistatic performance cannot be obtained. Patent Document 1 shows that polyethylene glycol is copolymerized with a sheath component polyester, but although there is an effect to some extent, the copolymerization amount has an upper limit of physical properties and does not sufficiently provide an antistatic effect.
又、これらの種の問題に対処するためにポリエステルモノフィラメント織物の一部に、銅線などの金属線を交織した工業用織物が知られているが、これは使用中に金属線に錆が発生したり、織物が接触するローラーを擦過するなどの問題があるため、実用的ではなかった。また、高導電性カーボンブラックを高濃度にブレンドした導電性ナイロン樹脂組成物を鞘成分に用いた導電性芯鞘ナイロンモノフィラメントを、ポリエステルモノフィラメント織物に交織した工業用織物も用いられてきたが、この場合、ポリエステルモノフィラメントと導電性芯鞘ナイロンモノフィラメントとの吸湿時の寸法安定性が異なるため、乾燥機内などで織物にうねりが発生するばかりか、カーボンブラックを高濃度にブレンドしたナイロン樹脂の流動性が悪いため、均一な導電性芯鞘ナイロンモノフィラメントが得られないなどの問題があった。 In addition, in order to cope with these kinds of problems, there is known an industrial fabric in which a metal wire such as a copper wire is interwoven with a part of a polyester monofilament fabric, which causes rust on the metal wire during use. And it is not practical due to problems such as rubbing the roller that the fabric contacts. In addition, industrial fabrics in which a conductive core-sheath nylon monofilament using a conductive nylon resin composition blended in a high concentration of highly conductive carbon black as a sheath component is interwoven with a polyester monofilament fabric have also been used. In this case, the polyester monofilament and the conductive core-sheath nylon monofilament have different dimensional stability at the time of moisture absorption. Since it was bad, there existed problems, such as being unable to obtain a uniform conductive core-sheath nylon monofilament.
又、特許文献４（特開昭５６−８５４２３号公報）にあるような芳香族ポリエステル／脂肪族ポリエステル（混合重量比率８０／２０〜９８／２）のポリエステル混合物と導電性カーボンブラックとからなる組成物を芯成分とし、芳香族ポリエステルからなる鞘成分とする導電性複合繊維が提案されているが、鞘成分に導電性カーボンブラックが存在しないため導電性が不十分であり、カーボンブラックが２０〜３０重量％と多量に混合する必要があるため、紡糸口金面汚れが発生し、長時間安定した生産が困難であるという問題を有していた。又、特許文献５（特開平８−７４１２５号公報）にあるような高導電性カーボンブラック４〜１５重量％からなる鞘成分とポリエステル組成物９６〜８５重量％からなる芯成分にて構成される芯鞘複合型導電性ポリエステルモノフィラメントが提案されているが、カーボンが表面に露出しているため、製織時での筬摩耗や織物が接触するローラーを擦過するなどの問題があり、又スクリーン紗作成時、乳剤を塗布をして感光させる際に発生するハレーション防止するための染色が出来ないという問題もあった。
こうした現状に鑑み、製織安定性、寸法安定性と帯電防止性を兼ね備えたスクリーン紗の開発が大いに望まれていた。
Also, a composition comprising an aromatic polyester / aliphatic polyester (mixed weight ratio 80/20 to 98/2) polyester mixture and conductive carbon black as disclosed in Patent Document 4 (Japanese Patent Laid-Open No. 56-85423). A conductive composite fiber having a core component and a sheath component made of an aromatic polyester has been proposed, but the conductivity is insufficient because there is no conductive carbon black in the sheath component. Since it was necessary to mix in a large amount of 30% by weight, the spinneret surface was soiled, and there was a problem that stable production for a long time was difficult. Further, it is composed of a sheath component composed of 4 to 15% by weight of a highly conductive carbon black and a core component composed of 96 to 85% by weight of a polyester composition as disclosed in Patent Document 5 (JP-A-8-74125). Core-sheath composite type conductive polyester monofilament has been proposed. However, since carbon is exposed on the surface, there are problems such as wrinkle wear during weaving and rubbing the roller with which the fabric comes into contact. There is also a problem that dyeing for preventing halation, which occurs when an emulsion is coated and exposed, cannot be dyed.
In view of the current situation, the development of a screen bag having both weaving stability, dimensional stability and antistatic properties has been highly desired.
本発明はスクリーン印刷に用いられるメッシュ織物に好適なポリエステルモノフィラメント、詳しくは加工時の製織安定性、スクリーン紗としての連続印刷性能（寸法安定性）に優れ、高度な精密性を要求されるハイメッシュで更に帯電性に優れたハイモジュラスのスクリーン紗を得るのに好適なモノフィラメントに提供することにある。 The present invention is a polyester monofilament suitable for mesh fabrics used in screen printing. Specifically, it is excellent in weaving stability during processing, continuous printing performance (dimensional stability) as a screen wrinkle, and requires high precision. It is another object of the present invention to provide a monofilament suitable for obtaining a high modulus screen with excellent charging properties.
繊維成形性ポリマーを芯成分、ポリエステルを鞘成分で構成される芯鞘型複合モノフィラメントにおいて下記Ａ〜Ｉを満足することを特徴とする芯鞘型複合モノフィラメントにより達成される。
Ａ．モノフィラメントの湿熱処理前の原糸最大点強力が５．５〜８．０ｃＮ／ｄｔｅｘ、５％伸張時の強度が３．５〜５．０ｃＮ／ｄｔｅｘ、最大点伸度が２０〜３５％、湿熱収縮率が２．５〜９．０％であること。
Ｂ．モノフィラメントの湿熱処理後の原糸最大点強力が５．０〜７．５ｃＮ／ｄｔｅｘ、１５％伸張時の強度が４．０〜７．０ｃＮ／ｄｔｅｘ、最大点伸度が２０〜４０％であること。
Ｃ．芯側ポリマーの固有粘度が０．７０〜１．００ｄＬ／ｇであること。
Ｄ．鞘側ポリマーが、芳香族ポリエステル１００重量部に対して、制電剤としてポリオキシアルキレン系ポリエーテルを０．２〜３０重量部及び該ポリエステルと実質的に非反応性の有機イオン性化合物を０．０５〜１０重量部含有するポリエステルであること。
Ｅ．鞘側ポリマーの固有粘度が０．４０〜０．５５ｄＬ／ｇであること。
Ｆ．鞘側ポリマーの複屈折率が１４０×１０−３〜１７０×１０−３であること。
Ｇ．ポリマーの芯鞘比率が３０：７０〜７０：３０であること。
Ｈ．単糸繊度が４〜２４ｄｔｅｘであること。
Ｉ．モノフィラメントの繊維長手方向５０万メートルで繊維直径に対し１．１倍以上の節糸が１個以下であること。
The core-sheath type composite monofilament comprising a fiber moldable polymer as a core component and polyester as a sheath component satisfies the following A to I.
A. Monofilament maximum strength before wet heat treatment of 5.5 to 8.0 cN / dtex, strength at 5% elongation of 3.5 to 5.0 cN / dtex, maximum elongation of 20 to 35%, wet heat The shrinkage rate is 2.5 to 9.0%.
B. The monofilament has a maximum yarn point strength after wet heat treatment of 5.0 to 7.5 cN / dtex, a strength at 15% elongation of 4.0 to 7.0 cN / dtex, and a maximum elongation of 20 to 40%. thing.
C. The intrinsic viscosity of the core side polymer is 0.70 to 1.00 dL / g.
D. The sheath side polymer is 0.2 to 30 parts by weight of a polyoxyalkylene polyether as an antistatic agent and 100% by weight of an organic ionic compound substantially nonreactive with the polyester with respect to 100 parts by weight of the aromatic polyester. .05 to 10 parts by weight of polyester.
E. The intrinsic viscosity of the sheath side polymer is 0.40 to 0.55 dL / g.
F. The birefringence of the sheath side polymer is 140 × 10 −3 to 170 × 10 −3 .
G. The core-sheath ratio of the polymer is 30:70 to 70:30.
H. The single yarn fineness is 4 to 24 dtex.
I. The number of knots is 1.1 or more times the fiber diameter in the monofilament longitudinal direction of 500,000 meters.
スクリーン紗の湿熱セット前後の原糸物性の適正化、特に湿熱セット後の原糸の最大点強度、伸度、１５％伸長時の強度を特定することで、連続印刷性に優れたスクリーン紗とし、また、鞘側のポリマーとして、ポリオキシアルキレンエーテルと有機イオン化合物が配合されたポリエステルで構成することで帯電防止に優れたものとすることができる。 Screen wrinkles with excellent continuous printability by optimizing the properties of the yarn before and after wet heat setting of the screen, especially by specifying the maximum point strength, elongation, and 15% strength of the yarn after wet heat setting Moreover, it can be set as the thing excellent in antistatic by comprising by the polyester by which polyoxyalkylene ether and the organic ion compound were mix | blended as a polymer of a sheath side.
精密印刷に適したハイメッシュスクリーン（２００〜５００メッシュ）用として２４ｄｔｅｘ以下の細繊度モノフィラメントが用いられる。紗織物用フィラメントには製織性の低下や印刷時のスクリーン紗の伸び（寸法安定性の低下）などの発生を抑えるだけの特定の強度、伸度等の物性が必要である。一般的には原糸の伸度５％時の応力（モジュラス、以下５％ＬＡＳＥ）により性能を評価することが行われているが、本発明者は更に高度な寸法安定性を得るためにはそれだけでなく、スクリーン紗の製造工程での湿熱処理により原糸が受ける影響を考慮することが重要であることを見出した。（湿熱処理とは、通常製織されたスクリーン紗を精錬や染色等の処理時における温水、蒸気処理することを意味する）これらの知見に基づいてなされたもので、本発明のスクリーン紗用モノフィラメントは、高ＩＶのポリエステルを芯成分、低ＩＶのポリエステルを鞘成分とする単糸繊度が４〜２４ｄｔｅｘの芯鞘型複合ポリエステルモノフィラメントからなり、該モノフィラメントの湿熱処理前の最大点強力を５．５〜８．０ｃＮ／ｄｔｅｘ、５％伸張時の強度を３．５〜５．０ｃＮ／ｄｔｅｘ、最大点伸度を２０〜３５％、湿熱収縮率を２．５〜９．０％とし、湿熱処理後の最大点強力を５．０〜７．５ｃＮ／ｄｔｅｘ、１５％伸張時の強度（モジュラス、以下１５％ＬＡＳＥ）を４．０〜７．０ｃＮ／ｄｔｅｘ、最大点伸度を２０〜４０％とすることにより、スクリーン紗として織目調整や湿熱セットや紗張りの工程経過後、高度に寸法安定性に優れるスクリーン紗とすることができる。最大点強度、伸度とは原糸の荷伸曲線における切断時の強度、伸度を意味する。 A fine filament monofilament of 24 dtex or less is used for a high mesh screen (200 to 500 mesh) suitable for precision printing. The filaments for woven fabrics must have specific properties such as strength and elongation enough to suppress the occurrence of deterioration in weaving properties and the elongation of screen creases during printing (decrease in dimensional stability). In general, the performance is evaluated by the stress (modulus, hereinafter 5% LASE) when the elongation of the raw yarn is 5%. However, in order to obtain a higher degree of dimensional stability, the present inventor In addition, it has been found that it is important to consider the influence of the raw yarn on the wet heat treatment in the production process of the screen koji. (Humidity heat treatment means that the woven screen cocoon is usually treated with warm water and steam during the refining and dyeing treatments.) The monofilament for the screen cocoon of the present invention is based on these findings. And a core-sheath type composite polyester monofilament having a single yarn fineness of 4 to 24 dtex with a high IV polyester as a core component and a low IV polyester as a sheath component, and having a maximum point strength before wet heat treatment of 5.5 to 5.5 8.0 cN / dtex 5% stretch strength 3.5-5.0 cN / dtex, maximum point elongation 20-35%, wet heat shrinkage 2.5-9.0%, after wet heat treatment The maximum point strength is 5.0 to 7.5 cN / dtex, the strength at 15% elongation (modulus, hereinafter 15% LASE) is 4.0 to 7.0 cN / dtex, and the maximum point elongation is 20 to 4 By% to, after the step has elapsed weave adjustments and wet heat set or gauze-covered as screen mesh cloth may be a screen mesh having excellent highly dimensional stability. The maximum point strength and elongation mean strength and elongation at the time of cutting in the unloading curve of the raw yarn.
本発明に使用する芯側へのポリマーの種類はポリエチレン、ポリエステルなどが挙げられ、許容ＩＶが０．７〜１．０ｄＬ／ｇあれば、限定せず、使用することができる。中でもポリエステルは、特に好ましい。又鞘成分としては、０．４５〜０．５５の低ＩＶのポリエステルにポリオキシアルキレンエーテル及び後述する有機イオン化合物を含有するポリエステルを使用する。通常の複合紡糸装置を用いて芯鞘型モノフィラメントとする。断面形状については安定した製糸性および高次加工性が得やすいという点や製織後の乳剤を塗布して感光させる際に発生するハレーションを防止する点、スクリーン紗の目開きの安定性などにより丸断面が好ましい。断面での芯と鞘部が相似形、或いは同心円状である必要はないが、芯部は鞘部で十分に覆われていることが必要である。好ましい芯：鞘面積比率は３０：７０〜７０：３０である。 Examples of the polymer on the core side used in the present invention include polyethylene, polyester, and the like. If the allowable IV is 0.7 to 1.0 dL / g, the polymer can be used without limitation. Of these, polyester is particularly preferable. Moreover, as a sheath component, the polyester containing polyoxyalkylene ether and the organic ionic compound mentioned later is used for the low IV polyester of 0.45-0.55. It is set as a core-sheath type monofilament using a normal composite spinning apparatus. The cross-sectional shape is round due to the fact that stable yarn-making and high-order processability are easily obtained, halation that occurs when the emulsion after weaving is exposed and exposed to light, and the stability of the screen mesh opening. A cross section is preferred. The core and the sheath in the cross section need not be similar or concentric, but the core must be sufficiently covered with the sheath. A preferable core: sheath area ratio is 30:70 to 70:30.
芯部のポリエステルのＩＶは０．７以上とすることにより高い強伸度、高モジュラスとすることができ、鞘部のポリエステルのＩＶを０．４５〜０．５５とすることによりソフトであるため製織時の筬による糸削れが減少する。 Since the polyester of the core part has an IV of 0.7 or higher, it can have a high strength and high modulus, and the IV of the polyester of the sheath part is soft by setting the IV of the polyester to 0.45 to 0.55. Yarn cutting due to wrinkles during weaving is reduced.
使用するポリエステルの種類としてはポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）のような芳香族ポリエステルが挙げられ、いずれでもよい。中でもＰＥＴは溶融紡糸を行う際の操業性、コストの面でももっとも好まれる。 Examples of the polyester used include aromatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), and any of them may be used. Among these, PET is most preferred in terms of operability and cost when performing melt spinning.
本発明のモノフィラメントは湿熱処理前の最大点強力が５．５〜８．０ｃＮ／ｄｔｅｘ、５％ＬＡＳＥが３．５〜５．０ｃＮ／ｄｔｅｘ、最大点伸度が２０〜３５％、湿熱収縮率が２．５〜９．０％に設計することが必要である。
５％ＬＡＳＥは高い方が好ましいが、５．０ｃＮ／ｄｔｅｘを超えると製織時に筬による削れが発生し、織物に織込まれ、欠点となってしまうため好ましくない。逆に３．５ｃＮ／ｄｔｅｘ以下ではスクリーン連続印刷時での寸法安定性が悪くなり、目ズレが発生しやすくなり、印刷物の欠点となるため好ましくない。
The monofilament of the present invention has a maximum point strength before wet heat treatment of 5.5 to 8.0 cN / dtex, 5% LASE of 3.5 to 5.0 cN / dtex, maximum point elongation of 20 to 35%, wet heat shrinkage Is required to be designed to be 2.5 to 9.0%.
A higher 5% ASE is preferable, but if it exceeds 5.0 cN / dtex, it is not preferable because scraping due to wrinkles occurs during weaving and is woven into the woven fabric, resulting in a defect. On the contrary, if it is 3.5 cN / dtex or less, the dimensional stability at the time of continuous screen printing becomes poor, the misalignment is likely to occur, and it becomes a defect of the printed matter, which is not preferable.
湿熱処理後の最大点強度が５．０ｃＮ／ｄｔｅｘ以下ではスクリーン紗強度が不足し、スクリーン連続印刷時に目ズレが発生し易くなったり、印刷時の被印刷物との紗離れが良くない。７．５ｃＮ／ｄｔｅｘ以上では、製織時に筬による削れが発生しやすくなる。
又最大点伸度が２０％未満では製織糸切れが多発するなど糸の取り扱い性が悪くなる。最大点伸度が４０％以上では紗伸びが発生し易くなる。
When the maximum point strength after the wet heat treatment is 5.0 cN / dtex or less, the screen wrinkle strength is insufficient, and misalignment is likely to occur during continuous screen printing, or the wrinkle separation from the printing material during printing is not good. If it is 7.5 cN / dtex or more, scraping due to wrinkles easily occurs during weaving.
On the other hand, if the maximum point elongation is less than 20%, the yarn handleability deteriorates, such as frequent weaving of woven yarn. If the maximum point elongation is 40% or more, wrinkle elongation tends to occur.
湿熱収縮率は２．５〜９．０％の範囲が好ましく、この範囲外では湿熱処理後の１５％ＬＡＳＥを特定の範囲内にすることができず好ましくない。（湿熱処理後の糸の１５％ＬＡＳＥと、湿熱処理を経たスクリーン紗の寸法安定性が相関することに基づくものであり、本発明のモノフィラメントの湿熱処理後の１５％ＬＡＳＥが４．０〜７．０ｃＮ／ｄｔｅｘであることが必要である） The wet heat shrinkage rate is preferably in the range of 2.5 to 9.0%. Outside this range, 15% LASE after the wet heat treatment cannot be within a specific range, which is not preferable. (This is based on the correlation between the 15% LASE of the yarn after the wet heat treatment and the dimensional stability of the screen ridge after the wet heat treatment, and the 15% ASE after the wet heat treatment of the monofilament of the present invention is 4.0 to 7 0.0 cN / dtex)
本発明に使用する鞘側のポリエステルに配合するポリオキシアルキレン系ポリエーテルは、ポリエステルに実質的に不溶性のものであれば、単一のオキシアルキレン単位からなるポリオキシアルキレングリコールであっても、二種以上のオキシアルキレン単位からなる共重合ポリオキシアルキレングリコールであってもよく、また、下記一般式（Ｉ）、
Ｚ−［（ＣＨ２ＣＨ２Ｏ）ｎ（Ｒ１Ｏ）ｍ−Ｒ２］ｋ ・・・式Ｉ
［式中、Ｚは１〜６個の活性水素原子を有する有機化合物残基、Ｒ１ は炭素原子数６以上のアルキレン基又は置換アルキレン基、Ｒ２ は水素原子、炭素原子数１〜４０の一価の炭化水素基、炭素原子数２〜４０の一価のヒドロキシ炭化水素又は炭素原子数２〜４０の一価のアシル基、ｋは１〜６の整数、ｎはｎ≧７０／ｋを満足する整数、ｍは１以上の整数］で表わされるポオキシエチレン系ポリエーテルであってもよい。
The polyoxyalkylene polyether to be blended with the sheath side polyester used in the present invention may be a polyoxyalkylene glycol composed of a single oxyalkylene unit as long as it is substantially insoluble in the polyester. It may be a copolymerized polyoxyalkylene glycol composed of two or more kinds of oxyalkylene units, and the following general formula (I),
Z - [(CH 2 CH 2 O) n (R 1 O) m-R 2] k ··· formula I
[Wherein, Z is an organic compound residue having 1 to 6 active hydrogen atoms, R 1 is an alkylene group or substituted alkylene group having 6 or more carbon atoms, R 2 is a hydrogen atom, having 1 to 40 carbon atoms. A monovalent hydrocarbon group, a monovalent hydroxy hydrocarbon having 2 to 40 carbon atoms or a monovalent acyl group having 2 to 40 carbon atoms, k is an integer of 1 to 6, and n is n ≧ 70 / k. A satisfactory integer, m is an integer of 1 or more] may be used.
上記のポリオキシアルキレン系ポリエーテルの具体例としては、分子量が４０００以上のポリオキシエチレングリコール、分子量が１０００以上のポリオキシプロピレングリコール、ポリオキシテトラメチレングリコール、分子量が２０００以上のエチレンオキサイド、プロピレンオキサイド共重合体、分子量４０００以上のトリメチロールプロパンエチレンオキサイド付加物、分子量３０００以上のノニルフェノールエチレンオキサイド付加物、並びにこれらの末端ＯＨ基に炭素数が６以上の置換エチレンオキサイドが付加した化合物があげられ、なかでも分子量が１００００〜１０００００のポリオキシエチレングコール、及び分子量が５０００〜１６０００の、ポリオキシエチレングリコールの両末端に炭素数が８〜４０のアルキル基置換エチレンオキサイドが付加した化合物が好ましい。 Specific examples of the polyoxyalkylene polyether include polyoxyethylene glycol having a molecular weight of 4000 or more, polyoxypropylene glycol having a molecular weight of 1000 or more, polyoxytetramethylene glycol, ethylene oxide having a molecular weight of 2000 or more, and propylene oxide. A copolymer, a trimethylolpropane ethylene oxide adduct having a molecular weight of 4000 or more, a nonylphenol ethylene oxide adduct having a molecular weight of 3000 or more, and a compound in which a substituted ethylene oxide having 6 or more carbon atoms is added to these terminal OH groups. Among them, polyoxyethylene glycol having a molecular weight of 10,000 to 100,000 and an alkyl group having 8 to 40 carbon atoms at both ends of the polyoxyethylene glycol having a molecular weight of 5000 to 16000. Compound conversion of ethylene oxide are added are preferred.
又ポリオキシアルキレン系ポリエーテル化合物の配合量は、前記芳香族ポリエステル１００重量部に対して０．２〜３０重量部の範囲である。０．２重量部より少ないときは親水性が不足して充分な制電性を呈することができない。一方３０重量部より多くしても最早制電性の向上効果は認められず、かえって得られる組成物の機械的性質を損うようになる上、該ポリエーテルがブリードアウトし易くなるため溶融成形時チップのルーダーへのかみこみ性が低下して、成形安定性も悪化するようになる。 The blending amount of the polyoxyalkylene polyether compound is in the range of 0.2 to 30 parts by weight with respect to 100 parts by weight of the aromatic polyester. When the amount is less than 0.2 parts by weight, the hydrophilicity is insufficient and sufficient antistatic property cannot be exhibited. On the other hand, even if the amount exceeds 30 parts by weight, the antistatic effect is no longer recognized, but the mechanical properties of the resulting composition are deteriorated, and the polyether is easily bleed out, so that it is melt molded. In some cases, the insertability of the chip into the ruder is reduced, and the molding stability is also deteriorated.
本発明の鞘成分のポリエステルには、更に制電性を向上させるために有機イオン性化合物を配合する。有機イオン性化合物としては、例えば下記一般式（ＩＩ），（ＩＩＩ）で示されるスルホン酸金属塩及びスルホン酸第４級ホスホニウム塩を好ましいものとしてあげることができる。
ＲＳＯ３Ｍ ・・・式（ＩＩ）
［式中、Ｒは炭素原子数３〜３０のアルキル基又は炭素原子数７〜４０のアリール基、Ｍはアルカリ金属又はアルカリ土類金属を示す：Ｒがアルキル基のときはアルキル基は直鎖状であっても又は分岐した側鎖を有していてもよい：ＭはＮａ，Ｋ，Ｌｉ等のアルカリ金属又はＭｇ，Ｃａ等のアルカリ土類金属であり、なかでもＬｉ，Ｎａ，Ｋが好ましい］
In order to further improve the antistatic property, an organic ionic compound is blended with the polyester of the sheath component of the present invention. Preferred examples of the organic ionic compound include sulfonic acid metal salts and sulfonic acid quaternary phosphonium salts represented by the following general formulas (II) and (III).
RSO 3 M Formula (II)
[Wherein, R represents an alkyl group having 3 to 30 carbon atoms or an aryl group having 7 to 40 carbon atoms, M represents an alkali metal or an alkaline earth metal: when R is an alkyl group, the alkyl group is linear Or may have branched side chains: M is an alkali metal such as Na, K, Li or an alkaline earth metal such as Mg, Ca, among which Li, Na, K are preferable]
上記スルホン酸金属塩は１種のみを単独で用いても２種以上を混合して使用してもよく、好ましい具体例としてはステアリルスルホン酸ナトリウム、オクチルスルホン酸ナトリウム、ドデシルスルホン酸ナトリウム、炭素原子数の平均が１４であるアルキルスルホン酸ナトリウム混合物、ドデシルベンゼンスルホン酸ナトリウム混合物、ドデシルベンゼンスルホン酸ナトリウム（ハード型、ソフト型）、ドデシルベンゼンスルホン酸リチウム（ハード型、ソフト型）、ドデシルベンゼンスルホン酸マグネシウム（ハード型、ソフト型）等をあげることができる。
ＲＳＯ３ −Ｐ＋Ｒ１Ｒ２Ｒ３Ｒ４ ・・・式（ＩＩＩ ）
［式中、Ｒは上記式（ＩＩ）におけるＲの定義と同じであり、Ｒ１ ，Ｒ２ ，Ｒ３ 及びＲ４ はアルキル基又はアリール基でなかでも低級アルキル基、フェニル基又はベンジル基が好ましい］
The above sulfonic acid metal salts may be used alone or in combination of two or more. Preferred specific examples include sodium stearyl sulfonate, sodium octyl sulfonate, sodium dodecyl sulfonate, carbon atom Sodium alkyl sulfonate mixture having an average number of 14, sodium dodecyl benzene sulfonate mixture, sodium dodecyl benzene sulfonate (hard type, soft type), lithium dodecyl benzene sulfonate (hard type, soft type), dodecyl benzene sulfonic acid Examples thereof include magnesium (hard type and soft type).
RSO 3 - P + R 1 R 2 R 3 R 4 ··· formula (III)
[In the formula, R is the same as the definition of R in the above formula (II), and R 1 , R 2 , R 3 and R 4 are alkyl groups or aryl groups, especially a lower alkyl group, a phenyl group or a benzyl group. preferable]
上記スルホン酸第４級ホスホニウム塩は１種のみを単独で用いても２種以上を混合して使用してもよい。好ましい具体例としては炭素原子数の平均が１４であるアルキルスルホン酸テトラブチルホスホニウム、炭素原子数の平均が１４であるアルキルスルホン酸テトラフェニルホスホニウム、炭素原子数の平均が１４であるアルキルスルホン酸ブチルトリフェニルホスホニウム、ドデシルベンゼンスルホン酸テトラブチルホスホニウム（ハード型、ソフト型）、ドデシルベンゼンスルホン酸テトラフェニルホスホニウム（ハード型、ソフト型）、ドデシルベンゼンスルホン酸ベンジルトリフェニルホスホニウム（ハード型、ソフト型）等をあげることができる。 The sulfonic acid quaternary phosphonium salts may be used alone or in combination of two or more. Preferred examples include tetrabutylphosphonium alkyl sulfonate having an average of 14 carbon atoms, tetraphenyl phosphonium alkyl sulfonate having an average of 14 carbon atoms, and butyl alkyl sulfonate having an average of 14 carbon atoms. Triphenylphosphonium, tetrabutylphosphonium dodecylbenzenesulfonate (hard type, soft type), tetraphenylphosphonium dodecylbenzenesulfonate (hard type, soft type), benzyltriphenylphosphonium dodecylbenzenesulfonate (hard type, soft type), etc. Can give.
又有機のイオン性化合物は１種でも、２種以上併用してもよく、その配合量は、芳香族ポリエステル１００重量部に対して０．０５〜１０重量部の範囲が好ましい。０．０５重量部未満では制電性向上の効果が小さく、１０重量部を越えると組成物の機械的性質を損なうようになる上、該イオン性化合物もブリードアウトし易くなるため、溶融成形時のチップのルーダーかみこみ性が低下して、成形安定性も悪化するようになる。 The organic ionic compound may be used alone or in combination of two or more, and the blending amount is preferably in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of the aromatic polyester. If the amount is less than 0.05 parts by weight, the effect of improving antistatic properties is small. If the amount exceeds 10 parts by weight, the mechanical properties of the composition are impaired, and the ionic compound also tends to bleed out. As a result, the insertability of the chip of the chip decreases, and the molding stability also deteriorates.
次に本発明の芯鞘型複合モノフィラメントを得るための具体的な製造法について説明するが、必ずしもこれに限定されるものではない。
前記した芯成分用ポリマー、鞘成分用ポリマーを常法により複合紡糸口金を用いて、溶融紡糸し芯鞘型複合モノフィラメントとし、続いて延伸を施すことにより得られる。紡糸工程で一旦未延伸糸として巻き取り改めて延伸工程に供することもできるが、紡糸工程と直結して延伸を行うことが好ましい。
Next, although the specific manufacturing method for obtaining the core-sheath-type composite monofilament of this invention is demonstrated, it is not necessarily limited to this.
The core component polymer and the sheath component polymer are melt-spun using a composite spinneret by a conventional method to obtain a core-sheath type composite monofilament, followed by stretching. Although it can be wound up as an undrawn yarn once in the spinning step and used for the drawing step, it is preferable to carry out drawing in direct connection with the spinning step.
直接紡糸延伸においては、数対の加熱ロールを用い、一段又は多段で延伸することが好ましく、最終的に強度、伸度、収縮率が所定の範囲に入るように延伸倍率を定める。この延伸にはリラックス延伸等の弛緩処理を含めることができ、湿熱収縮率を所定の範囲に入るよう調整することができる。 In direct spinning drawing, it is preferable to use several pairs of heated rolls and draw in one or more stages, and finally, the draw ratio is determined so that the strength, elongation, and shrinkage rate fall within a predetermined range. This stretching can include a relaxation treatment such as relaxing stretching, and the wet heat shrinkage rate can be adjusted to fall within a predetermined range.
このように製織前の原糸物性を調整し、しかる後製織工程に供し、必要に応じて精錬、染色、等の湿熱処理を経ることにより収縮し、糸は湿熱収縮後の所定の強伸度特性を有するものとなり、スクリーン紗は高度の寸法安定性を有するものと成る。 In this way, the properties of the original yarn before weaving are adjusted, and then subjected to the weaving process, and if necessary, shrinkage is performed through wet heat treatment such as refining, dyeing, etc., and the yarn has a predetermined high elongation after wet heat shrinkage. The screen has a high degree of dimensional stability.
モノフィラメントの表面に生じる節は製織時において糸の切断やスカム発生の原因となり好ましくなく、出来るだけ発生を防止する必要がある。節の発生要因としてはポリマーに含有する未溶融異物やポリマー自身の劣化が挙げられる。ポリマー内の未溶融異物については、パック入り口から口金吐出口までに濾過層を形成することでその排出を抑制させたり、分散させたりすることができる。この濾過層についてはモノフィラメント直径の約２０〜３０％の目開き量が好ましく、２０％以下にするとパック内に異常な圧力がかかり、パック内部品とパック本体の破損につながる。３０％以上にすると節糸の主因となる未溶融異物が粗大粒子のまま糸に含有し、節の発生リスクが大きくなる。また、ポリマー自身の劣化についてはポリマー送液に関し、配管の曲がりを減らし、パック導入から吐出までの時間を１分以内とし、ポリマーが受ける熱量を出来る限り軽減することによって節の発生リスクを低減させることができる。 Nodes generated on the surface of the monofilament are undesirable because they cause yarn breakage and scum during weaving, and it is necessary to prevent them from occurring as much as possible. As the cause of the knot, there are unmelted foreign matters contained in the polymer and deterioration of the polymer itself. About the unmelted foreign material in a polymer, the discharge | emission can be suppressed or disperse | distributed by forming a filtration layer from a pack entrance to a nozzle | cap | die discharge port. About this filtration layer, the opening amount of about 20 to 30% of the monofilament diameter is preferable, and if it is 20% or less, abnormal pressure is applied in the pack, leading to breakage of the parts in the pack and the pack body. If it is 30% or more, unmelted foreign matter, which is the main cause of knot yarn, is contained in the yarn as coarse particles, and the risk of knot generation increases. In addition, with regard to the deterioration of the polymer itself, with regard to polymer feeding, the bending of the pipe is reduced, the time from introduction of the pack to discharge is within 1 minute, and the amount of heat received by the polymer is reduced as much as possible to reduce the risk of occurrence of nodes be able to.
以下の実施例を挙げて、本発明をさらに具体的に説明する。
実施例中、固有粘度、強度、伸度、湿熱時収縮率、湿熱処理後の強度、湿熱処理後の伸度、１５％伸張時の強度、節数の数の評価、糸削れ評価、ヒステリシスの評価は、以下の定義で行った。
The present invention will be described more specifically with reference to the following examples.
In Examples, intrinsic viscosity, strength, elongation, shrinkage rate during wet heat treatment, strength after wet heat treatment, elongation after wet heat treatment, strength at 15% elongation, evaluation of the number of nodes, evaluation of thread scraping, hysteresis Evaluation was performed according to the following definitions.
固有粘度：
３５℃でオルトクロロフェノールにサンプルを溶解した各濃度（Ｃ）の希釈溶液を作成し、それら溶液の粘度（ηｒ）から下記式によってＣを０に近づけることで算出した。
η＝ｌｉｍｉｔ（ｌｎ（ηｒ／Ｃ））
なお、芯鞘の各成分は製糸時に使用する口金と溶融での滞留時間が同等となると共に芯と鞘のポリマーが別々に吐出できるよう設計した口金を作成し、十分に放流状態を安定させた上で、放流ポリマーをそれぞれ採取して測定した。
Intrinsic viscosity:
Dilution solutions of each concentration (C) in which the sample was dissolved in orthochlorophenol at 35 ° C. were prepared, and C was brought close to 0 from the viscosity (ηr) of these solutions by the following formula.
η = limit (ln (ηr / C))
In addition, each component of the core sheath is equivalent to the base used at the time of yarn production and the residence time in melting, and a base designed so that the core and sheath polymers can be discharged separately has been sufficiently stabilized. Above, the release polymer was sampled and measured.
強度、伸度：
繊維の強度および伸度はＪＩＳ−Ｌ１０１７に準拠し、オリエンテック社製のテンシロンを用いてサンプル長２５ｃｍ、伸張速度３０ｃｍ／ｍｉｎで測定し、サンプル破断した時の強度と伸度である。５％ＬＡＳＥは上記の測定時のサンプルが５％伸張した時の応力を測定した。
Strength and elongation:
The strength and elongation of the fiber are the strength and elongation when the sample breaks in accordance with JIS-L1017, measured using a Tensilon manufactured by Orientec Co., Ltd. at a sample length of 25 cm and an elongation rate of 30 cm / min. For 5% ASE, the stress was measured when the sample at the time of the above measurement was stretched by 5%.
湿熱収縮率：
５０００ｍ採取して、かせ状態にし、高圧内１３０℃の湿熱雰囲気内に繊度×０．１倍（ｇ）をかけつつ、１０分間入れた。処置終了後の糸は自然乾燥を行い、糸長を再度測定した。処置後の糸長を処置前の糸長５０００ｍで割って百分率表示として湿熱処置後の収縮率とした。
Moist heat shrinkage:
5000 m was sampled and placed in a skein state, and placed in a high-pressure, 130 ° C., moist heat atmosphere for 10 minutes while applying a fineness × 0.1 times (g). The yarn after the treatment was naturally dried and the yarn length was measured again. The yarn length after the treatment was divided by the yarn length of 5000 m before the treatment, and the percentage of shrinkage after the wet heat treatment was expressed as a percentage.
湿熱処理後の強度、伸度、１５％ＳＳＣ：
湿熱処理後の繊維の強度および伸度は湿熱処置後の糸をオリエンテック社製のテンシロンを用いてサンプル長２５ｃｍ、伸張速度３０ｃｍ／ｍｉｎで測定し、サンプル破断した時の強度と伸度である。１５％ＬＡＳＥは上記の測定時のサンプルが１５％伸張した時の応力を測定した。
Strength and elongation after wet heat treatment, 15% SSC:
The strength and elongation of the fiber after wet heat treatment are the strength and elongation when the yarn after wet heat treatment is measured using a Tensilon made by Orientec Co., Ltd. with a sample length of 25 cm and an elongation rate of 30 cm / min, and the sample is broken. . For 15% ASE, the stress was measured when the sample at the time of the above measurement was stretched by 15%.
節数の数の評価：
整経機のクリール出口に設置されているドロッパー前に隙間が糸径×１．１倍で公差±２μｍとなる１２本通しのスリットガイド設置した。そのスリットガイドに糸を通し、１２本×８段＝９６本をそれぞれ糸速５００ｍ／ｍｉｎにて各糸長２０万ｍ整経した。その際、スリットガイドにて断糸した回数を節の数と見なし、整経中での断糸回数を測定した。検出した断糸回数を糸長１０万ｍ換算して評価を行った。
Evaluation of the number of clauses:
In front of the dropper installed at the creel outlet of the warping machine, 12 slit guides having a clearance of thread diameter × 1.1 times and a tolerance of ± 2 μm were installed. Threads were passed through the slit guide, and 12 yarns × 8 stages = 96 yarns were warped at a yarn speed of 500 m / min, and each yarn length was 200,000 m. At that time, the number of yarn breaks with the slit guide was regarded as the number of knots, and the number of yarn breaks during warping was measured. Evaluation was performed by converting the detected number of times of yarn breakage into a yarn length of 100,000 m.
糸削れの評価：
スルーザー型織機により、織機の回転数２５０ｒｐｍとして織幅１インチあたり３００本の経糸を用いてメッシュ織物を製織し、織りあがった反物を検反機にて目視検査を行った。この時、通常黒に見えるメッシュ模様が白色化して見える織物欠点の数を数えて評価した。
織幅１．５ｍ×織物長さ３００ｍあたり糸削れによる欠点５個未満を○、５以上１０ヶ未満を△、１０ヶ以上を×と判定した。
Evaluation of thread cutting:
A mesh fabric was woven using 300 warps per inch of weaving width with a slewer type loom at a rotation speed of 250 rpm, and the woven fabric was visually inspected with the inspection machine. At this time, the number of fabric defects in which the mesh pattern that normally appears black was whitened was counted and evaluated.
Less than 5 defects caused by thread cutting per woven width 1.5 m × woven fabric length 300 m were evaluated as “◯”, 5 or more and less than 10 as “Δ”, and 10 or more as “×”.
ヒステリシス評価（スクリーン紗寸法安定性代用特性）：
湿熱処理後の原糸に７％伸長時の荷重を初期荷重としてかけ、そこから更に１．５％連続伸長を１０００回させた時の荷重（Ｂ）が３０回目の荷重（Ａ）対比、Ｃ＝Ｂ／Ａ×１００により得られるＣの値が９８％以下となる連続荷重回数が１０００回以下は×、１０００回以上は○とした。
Hysteresis evaluation (screen 紗 dimensional stability substitute characteristics):
A load at the time of 7% elongation is applied as an initial load to the raw yarn after the wet heat treatment, and then the load (B) when the 1.5% continuous elongation is further increased 1000 times is compared with the load (A) at the 30th time, C = The value of C obtained by B / A × 100 is 98% or less.
制電性能評価：
延伸糸を筒編みもしくは織物として精練を行い、ＪＩＳ−Ｌ−１０９４法に準じ、摩擦布は羊毛とし、測定室温を２０℃、湿度４０％とし、摩擦帯電圧を測定した。摩擦６０秒後の帯電圧が５００Ｖ以下を○、１０００Ｖ以下を△、１０００Ｖ以上を×とした。
Antistatic performance evaluation:
The drawn yarn was scoured as a knitted or woven fabric, and in accordance with JIS-L-1094, the friction fabric was wool, the measurement room temperature was 20 ° C., the humidity was 40%, and the frictional voltage was measured. When the charged voltage after 60 seconds of friction is 500 V or less, the symbol is ◯, when 1000 V or less is Δ, and when the voltage is 1000 V or more, ×.
［実施例１］
芯側に固有粘度０．８７ｄＬ／ｇのポリエチレンテレフタレート、鞘側に制電剤として分子量１００００のポリエチレングリコールとドデシルスルホン酸ソーダをポリエステル全重量に対してそれぞれ３重量％重合の末期に添加した固有粘度０．６８ｄＬ／ｇの制電性ポリエチレンテレフタレートを使用し、双方とも２９５℃の温度にて溶融し放流開始から２時間後にサンプリングした。芯側の固有粘度は０．７５ｄＬ／ｇで、鞘側の固有粘度は０．５０ｄＬ／ｇであった。１２００ｍ／分の紡速にて巻き取りつつ、オイリングローラーにて油剤を付着させながら、未延伸糸を得た。その後、加熱されたホットローラーにて予熱後、スリットヒーター２００℃で加熱しながら３．８倍で延伸し、０．０３倍のリラックス処理を施した後、巻き取り、１３ｄｔｅｘ−１ｆｉｌの延伸糸を得た。得られた延伸糸は強度６．０ｃＮ／ｄｔｅｘ、伸度２５％、５％ＬＡＳＥ ３．９ｃＮ／ｄｔｅｘ、湿熱収縮率７．０％、沸水処理後の強度は６．０ｃＮ／ｄｔｅｘ、伸度３２％、１５％ＬＡＳＥは４．２ｃＮ／ｄｔｅｘであった。原糸の節糸発生個数は０個であった。この原糸をスルーザー型織機で製織した際、糸削れ発生による織物欠点は３００ｍあたり０ヶであった。ヒステリシス評価は○であった。制電評価は○であった。仕上げ加工したスクリーン紗を連続印刷したところ、伸びが少なく寸法安定性に優れるものであった。
[Example 1]
Intrinsic viscosity in which polyethylene terephthalate having an intrinsic viscosity of 0.87 dL / g on the core side and polyethylene glycol having a molecular weight of 10,000 and sodium dodecyl sulfonate as antistatic agents on the sheath side were respectively added at the end of the polymerization at 3% by weight with respect to the total weight of the polyester. 0.68 dL / g antistatic polyethylene terephthalate was used, both melted at a temperature of 295 ° C. and sampled 2 hours after the start of discharge. The intrinsic viscosity on the core side was 0.75 dL / g, and the intrinsic viscosity on the sheath side was 0.50 dL / g. While being wound at a spinning speed of 1200 m / min, an unstretched yarn was obtained while attaching an oil agent with an oiling roller. Then, after preheating with a heated hot roller, it is stretched at 3.8 times while being heated at 200 ° C. with a slit heater, subjected to a relaxation treatment of 0.03 times, wound up, and stretched with 13 dtex-1 file. Obtained. The obtained drawn yarn had a strength of 6.0 cN / dtex, an elongation of 25%, a 5% ASE of 3.9 cN / dtex, a wet heat shrinkage of 7.0%, and a strength after boiling water treatment of 6.0 cN / dtex, an elongation of 32. %, 15% LASE was 4.2 cN / dtex. The number of node yarn generation of the raw yarn was zero. When this raw yarn was woven with a slewer type loom, the number of fabric defects due to the occurrence of yarn shaving was 0 per 300 m. Hysteresis evaluation was (circle). The antistatic evaluation was ○. When the finished screen koji was continuously printed, it had little elongation and excellent dimensional stability.
［比較例１］
実施例１においてリラックス延伸を止め、その部分で１．２倍延伸を実施し、得られた延伸糸を１３ｄｔｅｘと合せた。得られた延伸糸は強度６．２ｃＮ／ｄｔｅｘ、伸度２０％、５％ＬＡＳＥ ４．４ｃＮ／ｄｔｅｘ、湿熱収縮率１０．０％、沸水処理後の強度は６．１ｃＮ／ｄｔｅｘ、伸度３８％、１５％ＬＡＳＥは３．５ｃＮ／ｄｔｅｘであった。原糸の節糸発生個数は０個であった。この原糸をスルーザー型織機で製織した際、糸削れ発生による織物欠点は３００ｍあたり３ヶであり、ヒステリシス評価は×であった。制電評価は○であった。仕上げ加工したスクリーン紗を連続印刷したところ、伸びが大きく寸法安定性に問題があった。
[Comparative Example 1]
In Example 1, relaxation stretching was stopped, 1.2-fold stretching was performed at that portion, and the obtained stretched yarn was combined with 13 dtex. The obtained drawn yarn has a strength of 6.2 cN / dtex, an elongation of 20%, a 5% ASE of 4.4 cN / dtex, a wet heat shrinkage of 10.0%, a strength after boiling water treatment of 6.1 cN / dtex, and an elongation of 38. %, 15% LASE was 3.5 cN / dtex. The number of node yarn generation of the raw yarn was zero. When this raw yarn was woven with a slewer type loom, the number of fabric defects due to the occurrence of yarn shaving was 3 pieces per 300 m, and the hysteresis evaluation was x. The antistatic evaluation was ○. When the finished screen was continuously printed, the elongation was large and there was a problem with dimensional stability.
［実施例２］
実施例１において、延伸実施時のスリットヒーター温度を２００⇒２３０℃に変更した以外は実施例１と同様な方法で延伸糸を得た。得られた延伸糸は強度６．１ｃＮ／ｄｔｅｘ、伸度２４％、５％ＬＡＳＥ ３．９ｃＮ／ｄｔｅｘ、湿熱収縮率５．８％、沸水処理後の強度は６．１ｃＮ／ｄｔｅｘ、伸度３２％、１５％ＬＡＳＥは４．３ｃＮ／ｄｔｅｘであった。原糸の節糸発生個数は０個であった。この原糸をスルーザー型織機で製織した際、糸削れ発生による織物欠点は３００ｍあたり０ヶであった。ヒステリシス評価は○であった。制電評価は○であった。仕上げ加工したスクリーン紗を連続印刷したところ、伸びが少なく寸法安定性に優れるものであった。
[Example 2]
In Example 1, a drawn yarn was obtained in the same manner as in Example 1 except that the slit heater temperature at the time of drawing was changed from 200 to 230 ° C. The drawn yarn obtained had a strength of 6.1 cN / dtex, an elongation of 24%, a 5% ASE of 3.9 cN / dtex, a wet heat shrinkage of 5.8%, and a strength after boiling water treatment of 6.1 cN / dtex, an elongation of 32. %, 15% LASE was 4.3 cN / dtex. The number of node yarn generation of the raw yarn was zero. When this raw yarn was woven with a slewer type loom, the number of fabric defects due to the occurrence of yarn shaving was 0 per 300 m. Hysteresis evaluation was (circle). The antistatic evaluation was ○. When the finished screen koji was continuously printed, it had little elongation and excellent dimensional stability.
［比較例２］
実施例１において、芯鞘の比率を９５：５にて紡糸した以外は、実施例１と同様な方法で延伸糸を得た。得られた延伸糸は強度５．９ｃＮ／ｄｔｅｘ、伸度２４％、５％ＬＡＳＥ４．２ｃＮ／ｄｔｅｘ、湿熱収縮率１５．０％、沸水処理後の強度は５．８ｃＮ／ｄｔｅｘ、伸度３３％、１５％ＬＡＳＥは４．５ｃＮ／ｄｔｅｘであった。芯成分が糸表面に露出した部分が多い影響で糸削れによる織物欠点が多く、織物欠点は３００ｍあたり８ヶであった。また、鞘成分の吐出量が下がった影響で溶融領域内での滞留が長くなり、若干節糸が発生した。原糸の節糸発生個数は６個であった。ヒステリシス評価は○であった。制電性評価も鞘側が薄く、芯側の露出が多く×であった。
実施例１〜２、比較例１〜２の結果を表１にまとめる。
[Comparative Example 2]
In Example 1, a drawn yarn was obtained in the same manner as in Example 1, except that the core-sheath ratio was spun at 95: 5. The obtained drawn yarn has a strength of 5.9 cN / dtex, an elongation of 24%, a 5% ASE 4.2 cN / dtex, a wet heat shrinkage of 15.0%, and a strength after boiling water treatment of 5.8 cN / dtex, an elongation of 33%. 15% LASE was 4.5 cN / dtex. There were many fabric defects due to thread shaving due to the many portions where the core component was exposed on the yarn surface, and the fabric defects were 8 pieces per 300 m. In addition, the stay in the melted region became longer due to the decrease in the discharge amount of the sheath component, and some knots were generated. The number of node yarn generation of the raw yarn was 6. Hysteresis evaluation was (circle). In the antistatic evaluation, the sheath side was thin, and the core side was exposed with a large X.
The results of Examples 1-2 and Comparative Examples 1-2 are summarized in Table 1.
本発明は、表面が改質された芯鞘複合モノフィラメントに関し、ハイメッシュでハイモジュラスで且つ寸法安定性、帯電防止性に優れたスクリーン紗を得るのに好適であり、スクリーン印刷用のメッシュ織物としてプリント配線基盤の製造などの高度な精密性を要求される用途に有用である。 The present invention relates to a core-sheath composite monofilament having a modified surface, suitable for obtaining a screen mesh having a high mesh, a high modulus, excellent dimensional stability and antistatic property, and a mesh fabric for screen printing. It is useful for applications that require high precision, such as the manufacture of printed wiring boards.
Claims (2)
Ａ．モノフィラメントの湿熱処理前の原糸最大点強力が５．５〜８．０ｃＮ／ｄｔｅｘ、５％伸張時の強度が３．５〜５．０ｃＮ／ｄｔｅｘ、最大点伸度が２０〜３５％、湿熱収縮率が２．５〜９．０％であること。
Ｂ．モノフィラメントの湿熱処理後の原糸最大点強力が５．０〜７．５ｃＮ／ｄｔｅｘ、１５％伸張時の強度が４．０〜７．０ｃＮ／ｄｔｅｘ、最大点伸度が２０〜４０％であること。
Ｃ．芯側ポリマーの固有粘度が０．７０〜１．００ｄＬ／ｇであること。
Ｄ．鞘側ポリマーが、芳香族ポリエステル１００重量部に対して、制電剤としてポリオキシアルキレン系ポリエーテルを０．２〜３０重量部及び該ポリエステルと実質的に非反応性の有機イオン性化合物を０．０５〜１０重量部含有するポリエステルであること。
Ｅ．鞘側ポリマーの固有粘度が０．４０〜０．５５ｄＬ／ｇであること。
Ｆ．ポリマーの芯鞘比率が３０：７０〜７０：３０であること。
Ｇ．鞘側の複屈折率が１４０×１０−３〜１７０×１０−３であること。
Ｈ．単糸繊度が４〜２４ｄｔｅｘであること。
Ｉ．モノフィラメントの繊維長手方向５０万メートルで繊維直径に対し１．１倍以上の節糸が１個以下であること。 A core-sheath type composite monofilament composed of a fiber-forming polymer as a core component and polyester as a sheath component, wherein the core-sheath type composite monofilament for screen cocoons satisfies the following A to I.
A. Monofilament maximum strength before wet heat treatment of 5.5 to 8.0 cN / dtex, strength at 5% elongation of 3.5 to 5.0 cN / dtex, maximum elongation of 20 to 35%, wet heat The shrinkage rate is 2.5 to 9.0%.
B. The monofilament has a maximum yarn point strength after wet heat treatment of 5.0 to 7.5 cN / dtex, a strength at 15% elongation of 4.0 to 7.0 cN / dtex, and a maximum elongation of 20 to 40%. thing.
C. The intrinsic viscosity of the core side polymer is 0.70 to 1.00 dL / g.
D. The sheath side polymer is 0.2 to 30 parts by weight of a polyoxyalkylene polyether as an antistatic agent and 100% by weight of an organic ionic compound substantially nonreactive with the polyester with respect to 100 parts by weight of the aromatic polyester. .05 to 10 parts by weight of polyester.
E. The intrinsic viscosity of the sheath side polymer is 0.40 to 0.55 dL / g.
F. The core-sheath ratio of the polymer is 30:70 to 70:30.
G. The birefringence on the sheath side is 140 × 10 −3 to 170 × 10 −3 .
H. The single yarn fineness is 4 to 24 dtex.
I. The number of knots is 1.1 or more times the fiber diameter in the monofilament longitudinal direction of 500,000 meters.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008101287A (en) * | 2006-10-18 | 2008-05-01 | Teijin Fibers Ltd | Monofilament for screen gauze |
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| JPH02289120A (en) * | 1989-01-19 | 1990-11-29 | Toray Ind Inc | Polyester monofilament for screen gauze |
| JP2001262438A (en) * | 2000-01-11 | 2001-09-26 | Kanebo Ltd | Antistatic conjugate filament |
| JP2004143659A (en) * | 2002-10-24 | 2004-05-20 | Teijin Monofilament Germany Gmbh | Sheath-core fiber having high chemical-resistance, electroconductivity and stain repellency, method for manufacturing the same, and usage of the same |
| JP2004232182A (en) * | 2003-01-10 | 2004-08-19 | Toray Ind Inc | Polyester monofilament for screen gauze and method for producing the same |
| JP2005240266A (en) * | 2004-01-26 | 2005-09-08 | Toray Ind Inc | Polyester monofilament for screen mesh |
| JP2005248357A (en) * | 2004-03-03 | 2005-09-15 | Teijin Techno Products Ltd | Polyester monofilament for screen gauze |
| JP2008101288A (en) * | 2006-10-18 | 2008-05-01 | Teijin Fibers Ltd | Monofilament for screen gauze, excellent in dimensional stability |
| JP2008101287A (en) * | 2006-10-18 | 2008-05-01 | Teijin Fibers Ltd | Monofilament for screen gauze |
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| JPH02289120A (en) * | 1989-01-19 | 1990-11-29 | Toray Ind Inc | Polyester monofilament for screen gauze |
| JP2001262438A (en) * | 2000-01-11 | 2001-09-26 | Kanebo Ltd | Antistatic conjugate filament |
| JP2004143659A (en) * | 2002-10-24 | 2004-05-20 | Teijin Monofilament Germany Gmbh | Sheath-core fiber having high chemical-resistance, electroconductivity and stain repellency, method for manufacturing the same, and usage of the same |
| JP2004232182A (en) * | 2003-01-10 | 2004-08-19 | Toray Ind Inc | Polyester monofilament for screen gauze and method for producing the same |
| JP2005240266A (en) * | 2004-01-26 | 2005-09-08 | Toray Ind Inc | Polyester monofilament for screen mesh |
| JP2005248357A (en) * | 2004-03-03 | 2005-09-15 | Teijin Techno Products Ltd | Polyester monofilament for screen gauze |
| JP2008101288A (en) * | 2006-10-18 | 2008-05-01 | Teijin Fibers Ltd | Monofilament for screen gauze, excellent in dimensional stability |
| JP2008101287A (en) * | 2006-10-18 | 2008-05-01 | Teijin Fibers Ltd | Monofilament for screen gauze |
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| JP2008101287A (en) * | 2006-10-18 | 2008-05-01 | Teijin Fibers Ltd | Monofilament for screen gauze |
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