JPS63211322A - Production of polyester ultrathin yarn - Google Patents
Production of polyester ultrathin yarnInfo
- Publication number
- JPS63211322A JPS63211322A JP62041532A JP4153287A JPS63211322A JP S63211322 A JPS63211322 A JP S63211322A JP 62041532 A JP62041532 A JP 62041532A JP 4153287 A JP4153287 A JP 4153287A JP S63211322 A JPS63211322 A JP S63211322A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- yarn
- ultrafine
- sulfonic acid
- group
- 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.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- -1 sulfonic acid phosphonium salt Chemical class 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 4
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims 1
- 230000001588 bifunctional effect Effects 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 5
- 238000002074 melt spinning Methods 0.000 abstract description 3
- QCSIRLGSMWDFMF-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tetrabutylphosphanium Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC QCSIRLGSMWDFMF-UHFFFAOYSA-K 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000009987 spinning Methods 0.000 description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000000981 basic dye Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- MMJOUBUIEZZWDJ-UHFFFAOYSA-M 3,5-bis(methoxycarbonyl)benzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 MMJOUBUIEZZWDJ-UHFFFAOYSA-M 0.000 description 1
- HTXMGVTWXZBZNC-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S(O)(=O)=O)=C1 HTXMGVTWXZBZNC-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- RXQGGECQTVPOOB-UHFFFAOYSA-L disodium 4,6-dimethyl-2-sulfobenzene-1,3-dicarboxylate Chemical compound CC1=CC(=C(C(=C1C(=O)[O-])S(=O)(=O)O)C(=O)[O-])C.[Na+].[Na+] RXQGGECQTVPOOB-UHFFFAOYSA-L 0.000 description 1
- VVTXSHLLIKXMPY-UHFFFAOYSA-L disodium;2-sulfobenzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1=C(C([O-])=O)C=CC=C1C([O-])=O VVTXSHLLIKXMPY-UHFFFAOYSA-L 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical class C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
く利用分野〉
本発明はポリエステル１ＩＳＩ糸の製造法、更に詳しく
は塩基性染料で染色可能で且つ力学特性や製糸特性に優
れたポリエステル極細糸の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Application The present invention relates to a method for producing polyester 1ISI yarn, and more particularly to a method for producing ultrafine polyester yarn that can be dyed with basic dyes and has excellent mechanical properties and spinning properties.
〈従来技術〉
ポリエステルは、多くの優れた特性を有するがゆえに、
繊維として広く用いられているが、染色性が低く、特に
塩基性染料では染色できない、この染色性を改善するた
めに、ナトリウムスルホイソフタル酸成分をポリエステ
ル主鎖中に共重合する方法が知られている。<Prior art> Because polyester has many excellent properties,
Although it is widely used as a fiber, it has poor dyeability and cannot be dyed with basic dyes.In order to improve this dyeability, a method is known in which a sodium sulfoisophthalic acid component is copolymerized into the polyester main chain. There is.
他方、ポリエステル繊維よりなるｌ１編物に、独特のソ
フトで良好な風合を与えるために単糸繊度を小さくする
ことも知られており、この場合２０００〜４０００ｍ
７分の高速紡糸を利用して製造した単糸繊度１．０〜０
．１ｄｅの極細糸が利用されている。On the other hand, it is also known to reduce the single yarn fineness in order to give l1 knitted fabrics made of polyester fibers a unique soft and good texture.
Single yarn fineness 1.0 to 0 manufactured using high speed spinning for 7 minutes
．． 1de ultra-fine thread is used.
しかしながら、上記の金属スルホネート基を含有せしめ
て塩基性染料で染色可能にした変性ポリエステルを用い
て高速紡糸により、単糸繊度１．Ｏｄｅ以下の極細糸を
製造しようとしても、上記変性ポリエステルは曳糸性が
極めて悪く、紡糸中に単糸切れが頻発して紡糸不能であ
ったり、紡糸できたとしても、得られた糸は力学特性が
著しく低く、使用に耐えないなめ、実際には利用されて
いない。However, by high-speed spinning using the above-mentioned modified polyester containing metal sulfonate groups and dyeable with basic dyes, single yarn fineness of 1. Even if an attempt is made to produce ultrafine yarn with a diameter of less than Ode, the above-mentioned modified polyester has extremely poor spinnability, and single filament breakage occurs frequently during spinning, making it impossible to spin, or even if spinning is possible, the resulting yarn is mechanically It is not actually used because its characteristics are extremely low and it cannot withstand use.
かかる問題を解決するため高速紡糸の条件、例えば紡糸
口金吐出孔の形状、紡糸温度、冷却条件。In order to solve this problem, high-speed spinning conditions, such as the shape of the spinneret discharge hole, spinning temperature, and cooling conditions, must be adjusted.
フィラメントの集束１口金〜巻取機間走行長の短縮、イ
ンターレースノズルによる集束付与等の改良を試みたが
、これらの方策では限度があり、大幅な改善は期待でき
なかった。Attempts have been made to improve the filament by shortening the running length between one filament tip and the winder, and by using an interlaced nozzle to provide convergence, but these measures have limitations and no significant improvement could be expected.
〈発明の目的〉
本発明の目的は、塩基性染料可染ポリエステル極細糸に
おける上述の問題を解消して力学特性。<Objective of the Invention> The object of the present invention is to solve the above-mentioned problems in ultrafine polyester yarn dyeable with basic dyes and to improve its mechanical properties.
製糸性、染色性、染色堅牢性に優れたボリエスル極細糸
の製造法を提供するにある。An object of the present invention is to provide a method for producing ultrafine polyester yarn having excellent spinning properties, dyeing properties, and color fastness.
〈発明の構成〉
本発明者等は上記の目的を達成せんとして鋭意研究した
結果、従来のナトリウムスルホイソフタル酸に代えて、
スルホン酸ホスホニウム塩を共重合させた変性ポリエス
テルを用いるとき所望の効果が奏されることを究明し、
本発明に到達しな。<Structure of the Invention> As a result of intensive research aimed at achieving the above-mentioned object, the present inventors found that, in place of the conventional sodium sulfoisophthalate,
It was discovered that the desired effect can be achieved when using a modified polyester copolymerized with a sulfonic acid phosphonium salt,
Don't get to the present invention.
即ち、本発明は下記一般式
％式％
［式中、Ａは芳香族基又は脂肪族基、Ｘｌ及びＸｌは同
−又は異なるエステル形成性官能基、Ｒｓ 、Ｒｚ 、
Ｒ３及びＲ，は水素原子、アルキル基、アリール基及び
ヒドロキシアルキル基より選ばれた同−又は異なる基、
ｎは正の整数を示す］
で表わされるスルホン酸ホスホニウム塩を共重合した極
限粘度が０．５以上のポリエステルを３０００ｍ／分以
上の引取速度で溶融紡糸して単糸の平均繊度が１．０
ｄｅ以下のマルチ糸とすることを特徴とするポリエステ
ル極細糸の製造法である。That is, the present invention is based on the following general formula % [wherein A is an aromatic group or an aliphatic group, Xl and Xl are the same or different ester-forming functional groups, Rs, Rz,
R3 and R are the same or different groups selected from hydrogen atoms, alkyl groups, aryl groups and hydroxyalkyl groups,
n represents a positive integer] A polyester copolymerized with a sulfonic acid phosphonium salt represented by the formula and having an intrinsic viscosity of 0.5 or more is melt-spun at a take-up speed of 3000 m/min or more to obtain a single yarn with an average fineness of 1.0.
This is a method for producing ultrafine polyester yarn, which is characterized in that it is a multi-thread yarn with a diameter of less than de.
本発明でいうポリエステルは、テレフタル酸を主たる酸
成分とし、少なくとも１種のグリコール、好ましくはエ
チレングリコール、トリメチレングリコール、テトラメ
チレングリコールから選ばれた少なくとも１１’Ｊのア
ルキレングリコールを主なるグリコール成分とするポリ
エステルを主たる対象とする。The polyester used in the present invention has terephthalic acid as the main acid component and at least one glycol, preferably at least 11'J alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as the main glycol component. The main target is polyester.
また、テレフタル酸成分の一部を他の二官能性カルボン
酸成分で置換えたポリエステルであってもよく、及び／
又はグリコール成分の一部を主成分以外の上記グリコー
ル若しくは他のジオール成分で置換えたポリエステルで
あってもよい。It may also be a polyester in which part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/
Alternatively, it may be a polyester in which part of the glycol component is replaced with the above-mentioned glycol or other diol component other than the main component.
ここで使用されるテレフタル酸以外の二官能性カルボン
酸としては、例えばイソフタル酸、ナフタリンジカルボ
ン酸、ジフェニルジカルボン酸。Examples of the difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, and diphenyl dicarboxylic acid.
ジフェノキシエタンジカルボン酸、β−しドロキシエト
キシ安息香酸、Ｐ−オキシ安息香酸、アジピン酸、セバ
シン酸、１．４−シクロヘキサンジカルボン酸の如き芳
香族、脂肪族、脂環族の二官能性カルボン酸をあげるこ
とができる。更に本発明の効果が実質的に奏せられる範
囲で５−ナトリウムスルホイソフタル酸等の金属スルホ
ネート基を有するイソフタル酸を共重合成分として用い
てもよいが、この場合、その使用量をテレフタル酸成分
に対して １．８モル％未満の量に抑えることが望まし
い。Aromatic, aliphatic, and alicyclic difunctional carboxylic acid such as diphenoxyethanedicarboxylic acid, β-droxyethoxybenzoic acid, P-oxybenzoic acid, adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. I can give you acid. Furthermore, isophthalic acid having a metal sulfonate group such as 5-sodium sulfoisophthalic acid may be used as a copolymerization component within a range where the effects of the present invention can be substantially achieved. It is desirable to suppress the amount to less than 1.8 mol%.
また、上記グリコール以外のジオール化合物としては例
えばシクロヘキサン−１，４−ジメタツール、ネオペン
チルグリコール、ビスフェノールＡ。Examples of diol compounds other than the above-mentioned glycols include cyclohexane-1,4-dimetatool, neopentyl glycol, and bisphenol A.
ビスフェノールＳの如き脂肪族、脂環族、芳香族のジオ
ール化合物及びポリオキシアルキレングリコール等をあ
げることができる。Examples include aliphatic, alicyclic, and aromatic diol compounds such as bisphenol S, and polyoxyalkylene glycols.
更に、ポリエステルが実質的に線状である範囲でトリメ
リット酸、ピロメリット酸の如きポリカルボン酸、グリ
セリン、トリメチロールプロパン。Additionally, polycarboxylic acids such as trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane to the extent that the polyester is substantially linear.
ペンタエリスリトールの如きポリオールを使用すること
ができる。Polyols such as pentaerythritol can be used.
かかるポリエステルは任意の方法によって合成したもの
でよい０例えばポリエチレンテレフタレートについて説
明すれば、通常、テレフタル酸とエチレングリコールと
を直接エステル化反応させるか、テレフタル酸ジメチル
の如きテレフタル酸の低級アルキルエステルとエチレン
グリコールとをエステル交換反応させるか又はテレフタ
ル酸とエチレンオキサイドとを反応させるかしてテレフ
タル酸のグリコールエステル及び／又はその低重合体を
生成させる第１段階の反応と、第１段階の反応生成物を
減圧上加熱して所望の重合度になるまで重縮合させる第
２段階の反応によって製造される。Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, it is usually a direct esterification reaction of terephthalic acid and ethylene glycol, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene. A first step reaction in which a glycol ester of terephthalic acid and/or a low polymer thereof is produced by transesterifying glycol or reacting terephthalic acid with ethylene oxide, and a first step reaction product. It is produced by a second stage reaction of heating under reduced pressure and polycondensing it until the desired degree of polymerization is achieved.
本発明においては、上記ポリエステルのポリマー鎖の中
に下記一般式
％式％
で表わされるスルホン酸ホスホニウム塩が共重合されて
いることが必要である。上記一般式中Ａは芳香族基又は
脂肪族基であり、芳香族基が好ましい、Ｘｌ及びＸ２は
エステル形成性官能基であり、カルボキシル基、クロロ
カルボキシル基、しドロキシル基、アシルオキシ基等が
例示され、好ましい具体例としては
＋ＣＨｚ）ｐＯＨ。In the present invention, it is necessary that a sulfonic acid phosphonium salt represented by the following general formula % is copolymerized in the polymer chain of the polyester. In the above general formula, A is an aromatic group or an aliphatic group, and an aromatic group is preferable. and a preferred example is +CHz)pOH.
０ （ＣＨｚ −ｒ−ゴｎ−−Ｅ Ｏ（Ｃｌ−１
ｚ １Ｌ−１Ｔ−士−］「 ＯＨ。0 (CHz -r-gon--E O(Cl-1
z 1L-1T-Shi-] “OH.
−Ｃ千〇 （ＣＨｚ−ヒ■十ＴＯＨ
Ｉ３
（但し、Ｒは低級アルキル基又はフェニル基を、］は１
以上の整数を、ｍは２以上の整数を示す）等をあけるこ
とができる。このＸｌ及び×２は同一であっても、異な
っていてもよい、Ｒ１，ＲｚＲ３及びＲ４は水素原子、
アルキル基、アリール基、ヒドロキシアルキル基であり
、アルキル基か好ましく、なかでもブチル基が特に好ま
しい、このＲ１，Ｒｚ 、Ｒ３、ＲＡは同一であって異
なっていてもよい、また、ｎは正の整数であり、通常は
１又は２である。-C thousand
or more integers, m indicates an integer of 2 or more), etc. Xl and x2 may be the same or different, R1, RzR3 and R4 are hydrogen atoms,
These are an alkyl group, an aryl group, and a hydroxyalkyl group, and an alkyl group is preferable, and a butyl group is particularly preferable. R1, Rz, R3, and RA may be the same or different, and n is a positive An integer, usually 1 or 2.
かかるスルホン酸ホスホニウム塩は、一般に対応するス
ルホン酸とホスフィン類との反応又は対応するスルホン
酸金属塩とホスホニウムハライド類との反応により容易
に合成できる。スルホン酸とボスフィンより合成する場
合は必ずしも単離する必要はなく、対応するスルホン酸
とホスフィンを改質すべきポリエステルに添加してポリ
エステル反応系内で塩を生成せしめてらよい。しかしな
がら、スルホン酸金属塩とホスホニウムハライドより合
成する場合は、生成する無機塩による悪影響、例えば過
剰な副反応による軟化点の低下１重合度の上昇が不可能
になる等の悪影響が発生するので無機塩を十分除去した
後ポリエステルに添加しなければならない。Such sulfonic acid phosphonium salts can generally be easily synthesized by reacting the corresponding sulfonic acid with phosphines or by reacting the corresponding sulfonic acid metal salt with phosphonium halides. When synthesizing from sulfonic acid and bosphine, it is not necessarily necessary to isolate them, but the corresponding sulfonic acid and phosphine may be added to the polyester to be modified to form a salt within the polyester reaction system. However, when synthesizing from a sulfonic acid metal salt and a phosphonium halide, the resulting inorganic salt causes negative effects, such as a decrease in the softening point due to excessive side reactions, and the inability to increase the degree of polymerization. It must be added to the polyester after sufficient salt removal.
上記スルホン酸ホスホニウム塩の具体例としては３．５
−ジカルボメトキシベンゼンスルホン酸テトラメチルホ
スポニウム塩、３．５−ジカルボメトキシベンゼンスル
ホン酸テトラブチルポスホニウム塩、３，５−ジカルボ
メトキシベンゼンスルホン酸トリブチルメチルポスホニ
ウム塩、２，６−ジカルボメトキシナフタレンー４−ス
ルポン酸テトラブチルホスポニウム塩、２．６−”ジカ
ルボメトギシベンゼンスルホン酸テトラメチルホスホニ
ウム塩等があげられる。A specific example of the sulfonic acid phosphonium salt is 3.5
-Dicarbomethoxybenzenesulfonic acid tetramethylphosponium salt, 3,5-dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid tributylmethylposphonium salt, 2, Examples include 6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosponium salt, 2.6-'' dicarbomethoxybenzenesulfonic acid tetramethylphosphonium salt, and the like.
上記スルホン酸ホスホニウム塩をポリエステルの主鎖中
に共重合するには、前述したポリエステルの合成が完了
する以前の任意の段階で、好ましくは第１段の反応が終
了する以前の任意の段階で上記化合物を添加すればよい
、この際その使用量は、あまり少ないと最終的に得られ
るポリエステル繊維中の染着座席が不足するために塩基
性染料に対する染色性が不充分になり、逆にあまりに多
いと得られるポリマーの軟化点が低くなり、最終的に得
られるポリエステル繊維の力学特性等の糸物性が悪化す
るようになるので、ポリエステル繊維を構成する二官能
性カルボン酸成分に対して０．５〜３．５モル％、好ま
しくは０．７〜２．０モル％となる範囲で使用する。In order to copolymerize the sulfonic acid phosphonium salt into the main chain of the polyester, the above-mentioned phosphonium salt can be copolymerized at any stage before the synthesis of the polyester described above is completed, preferably at any stage before the first stage reaction is completed. It is sufficient to add a compound. In this case, if the amount used is too small, the dyeing seat in the final polyester fiber obtained will be insufficient, resulting in insufficient dyeing properties for basic dyes, and conversely, if the amount is too large, the dyeability for basic dyes will be insufficient. This lowers the softening point of the resulting polymer and deteriorates the yarn physical properties such as mechanical properties of the polyester fibers finally obtained. It is used in a range of 3.5 mol% to 3.5 mol%, preferably 0.7 to 2.0 mol%.
このようにして得られる変性ポリエステルは、その極限
粘度［η］が０，５以上、好ましくは０．６以上である
ことが必要である。０．５を下回る場合には、得られる
ポリエステル極細糸の力学特性、特に強度が不足し、本
発明の目的が達成されない。The modified polyester thus obtained needs to have an intrinsic viscosity [η] of 0.5 or more, preferably 0.6 or more. If it is less than 0.5, the mechanical properties, especially the strength, of the resulting ultrafine polyester yarn will be insufficient, and the object of the present invention will not be achieved.
なお、極限粘度［ワ］は、 ｕｉｌｆｌｎ（ηｒｅｕ））／ｃ Ｃ→０ で与えられる。In addition, the intrinsic viscosity [wa] is uilfln(ηreu))/c C→0 is given by
ここで７７ｒｃ’ｃはオルソクロルフェノールを溶蝮と
するポリエステル稀薄溶液の粘度と同温度、同単位で測
定した前記溶奴の粘度との比であり、Ｃは１００ＣＣ混
合液中のポリエステルのグラム数である。Here, 77rc'c is the ratio of the viscosity of a dilute polyester solution containing orthochlorophenol as a melt to the viscosity of the melt measured at the same temperature and in the same units, and C is the number of grams of polyester in the 100CC mixture. It is.
本発明にあっては、上記変性ポリエステルを３０００ｍ
／分量上の引取速度で溶融紡糸して単糸の平均繊度が
１．０ｄ８以下、好ましくは０．８６θ以下、更に好ま
しくは０．６６ｅ以下のマルチ糸にする。従来のナトリ
ウムスルホイソフタル酸を共重合した塩基性染料可染ポ
リエステルでは、かかる極細糸は、製糸特性が著しく劣
るため製造不可能であった。In the present invention, the above modified polyester is
The fibers are melt-spun at a take-up speed of 1/2 to obtain a multi-filament yarn having an average fineness of 1.0d8 or less, preferably 0.86θ or less, and more preferably 0.66e or less. With the conventional basic dye-dyable polyester copolymerized with sodium sulfoisophthalic acid, it has been impossible to produce such ultrafine yarns because of extremely poor spinning characteristics.
また、得られるＪ＃ｌＨＪ糸の強度は３．５ｇ／ｄａ以
上、更には４−Ｏｒ／ｄｅ以上にするのが望ましい、従
来の塩基性染料可染ポリエステルでは、かかる強度の繊
維は得られず、その強度は高々２．５〜３．０ｇ／ｄｅ
程度であって、その用途は著しく制限されていた。In addition, it is desirable that the strength of the J#lHJ yarn obtained is 3.5 g/da or more, and more preferably 4-Or/de or more.Fibers with such strength cannot be obtained with conventional basic dye-dyeable polyester. , its strength is at most 2.5~3.0g/de
However, its use was severely limited.
上記変性ポリエステルを３０００ｍ ／分量上の引取速
度で溶融紡糸するに当って、下記の（イ）／（ホ）の手
段の１又は２以上を適宜採用するのが有効である。When melt-spinning the above-mentioned modified polyester at a take-up speed of 3000 m 2 /piece, it is effective to appropriately employ one or more of the following means (a) and (e).
（イ）紡糸口金から最初の引取ローラ迄の距離を４ｍ以
下にして走行糸にかかる空気抵抗を軽減する。(a) The distance from the spinneret to the first take-up roller is set to 4 m or less to reduce air resistance on the running yarn.
（ｏｌ 紡糸口金下流０．３〜２ｍの範囲内で、給油
ガイド等を用いて集束すると共に冷却する。(ol) Within a range of 0.3 to 2 m downstream of the spinneret, it is focused and cooled using an oil supply guide or the like.
（７Ｘ）紡糸口金下流１〜４ｍの範囲内に、雰囲気温度
が１５０℃以上の非接触加熱域を設ける。(7X) A non-contact heating area with an ambient temperature of 150° C. or higher is provided within a range of 1 to 4 m downstream of the spinneret.
（二１ 吐出糸を巻取る迄の工程において、１個又は複
数個のホットローラ等により熱処理する。(21. In the process up to winding up the discharged yarn, heat treatment is performed using one or more hot rollers, etc.
（ホ） 紡糸工程中において必要に応じて空気ノズル及
び／又はガイド等により集束して空気抵抗を軽減する。(E) During the spinning process, air resistance is reduced by converging air nozzles and/or guides as necessary.
このようにして得られた糸は、必要に応じて延伸、熱処
理、捲縮加工等を施すことができる。The yarn thus obtained can be subjected to stretching, heat treatment, crimping, etc., as necessary.
〈発明の作用・効果〉
本発明によれば、従来の塩基性染料可染ポリエステル例
えばナトリウムスルホイソフタル酸成分を共重合した変
性ポリエステルでは決して製造できなかった極細糸を、
生産性良く製造することを可能にした。この理由は以下
のｍ構によるものと考えられる。<Operations and Effects of the Invention> According to the present invention, ultrafine yarns that could never be produced using conventional basic dye-dyeable polyesters, such as modified polyesters copolymerized with sodium sulfoisophthalic acid components, can be produced.
This made it possible to manufacture with high productivity. The reason for this is thought to be due to the following m structure.
即ち、従来の変性剤としてナトリウムスルホイソフタル
酸成分を共重合した変性ポリエステルでは、変性剤の間
に、金属イオンを介してイオン性の結合が発生し、分子
鎖は軽い架橋構造をとる。That is, in a conventional modified polyester copolymerized with a sodium sulfoisophthalic acid component as a modifier, ionic bonds are generated between the modifiers via metal ions, and the molecular chains take on a light crosslinked structure.
かかるポリマーを高速で溶融紡糸すると、強い伸張応力
が架橋点に集中し、高速での曳糸性を著しく悪化させる
。特に、単糸繊度の小さい極細糸のときは、空気の抗力
による張力が著しく増加するため、上記の高速時の曳糸
性の悪化は致命的なものになる。When such a polymer is melt-spun at high speed, strong elongation stress is concentrated at the crosslinking points, which significantly deteriorates the spinnability at high speed. In particular, in the case of ultra-fine yarns with small single filament fineness, the tension due to the drag force of air increases significantly, so the above-mentioned deterioration in spinnability at high speeds becomes fatal.
これに対し本発明では、使用する変性剤のイオン成分を
嵩高な置換基Ｒ１，Ｒｚ 、Ｒ３、Ｒ４で覆ってしまう
ため、その立体障害により分子鎖間のイオン性架橋は相
当抑制される。そのなめ紡糸中の伸張応力の集中が生じ
難くなり、極細糸の高速曳糸性が改善される。この効果
は、本明ｍ＠で述べる他技術、例えば吐出マルチ糸の集
束、走行長の短縮等による空気抵抗の軽減等と組合せた
とき、更に大きくなる。このため、本発明によれば、塩
基性染料可染で且つ良好な力学特性特に高い強度や引裂
強度を有するポリエステル極細糸を容易に製造すること
ができる。得られるｆｉＡｌ［Ｉ糸は、特に防水透湿機
能を有する高密度織編物の分野特にスポーツ衣料分野に
最も適した繊維である。従来この分野に分散染料でのみ
染色可能なポリエステル極細糸を用いたのでは、染色の
堅牢性が不充分で色移行の問題が生じていたし、従来の
塩基性染料可染ポリエステル糸を用いるには、高速曳糸
性の欠除に基づく細デニールに限界があるばかりでなく
、糸強度が低いため、布帛の引裂強力が弱くなる等のｌ
？Ｊｆｆ題があり、現実に供しえなかったものである。On the other hand, in the present invention, since the ionic component of the modifier used is covered with bulky substituents R1, Rz, R3, and R4, ionic crosslinking between molecular chains is considerably suppressed due to the steric hindrance. The concentration of elongation stress during the smooth spinning becomes less likely to occur, and the high-speed spinnability of the ultra-fine yarn is improved. This effect becomes even greater when combined with other techniques described in the present invention, such as reducing air resistance by convergence of discharged multi yarns, shortening of running length, etc. Therefore, according to the present invention, it is possible to easily produce polyester ultrafine yarn that is dyeable with a basic dye and has good mechanical properties, particularly high strength and tear strength. The obtained fiAl[I yarn is a fiber most suitable for use in the field of high-density woven and knitted fabrics, particularly in the field of sports clothing, which has waterproof and moisture-permeable properties. Conventionally, using ultrafine polyester yarns that can only be dyed with disperse dyes in this field has resulted in insufficient dyeing fastness and problems with color migration. Not only is there a limit to fine denier due to the lack of high-speed spinnability, but also the thread strength is low, resulting in a decrease in the tear strength of the fabric, etc.
? There was a Jff title, and it could not be used in reality.
かかる分野については、本発明によりはじめてポリエス
テル糸の使用を可能ならしめたのである。The present invention has made it possible for the first time to use polyester yarn in this field.
〈実施例〉
以下に実施例をあげて本発明を具体的に説明するが、本
発明はこれらの実施例に限定されるものではない。<Examples> The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例１〜５及び比較例１〜５
テレフタル酸ジメチル１００部、エチレングリコール６
６部、第１表に記載した量の３．５−ジカルボキシベン
ゼンスルホン酸テトラブチルホスホニウム塩（Ｏ〜４．
３部の範囲で量を変えて実施した。Examples 1 to 5 and Comparative Examples 1 to 5 100 parts of dimethyl terephthalate, 6 parts of ethylene glycol
6 parts, 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt (O-4.
The test was carried out by changing the amount within three parts.
この量の範囲はテレフタル酸ジメチルに対して０〜３．
５モル％の範囲に相当する。）、酢酸マンガン４水塩０
．０３部（テレフタル酸ジメチルに対しして０．０２４
モル％）をエステル交換缶に仕込み、窒素ガス雰囲気１
４時間かけて１４０℃から２３０℃まで昇温して生成す
るメタノールを系外に留去しながらエステル交換反応さ
ぜな。続いて得られた生成物に正リン酸の５６％水溶液
０．０３部（テレフタル酸ジメチルに対して０．０３３
モル％）及び三酸化アンチモン０．０４部（０，０２部
モル％）を添加して重合毎に移した０次いで１時間かけ
て７６０ ｎｍｔｌｇから１ｍ＋ｔ１ｇまで減圧し、同
時に１時間３０分かけて２３０℃から２８０℃まで昇温
しな、１部ｍｌｌＱ以下の減圧下、重合温度２８０℃で
第１表に記載した極限粘度に達するまで重合した。This amount ranges from 0 to 3.0% based on dimethyl terephthalate.
This corresponds to a range of 5 mol%. ), manganese acetate tetrahydrate 0
．． 03 parts (0.024 parts relative to dimethyl terephthalate)
mol%) into a transesterification tank and put it in a nitrogen gas atmosphere 1.
The temperature was raised from 140°C to 230°C over 4 hours, and the transesterification reaction was carried out while the methanol produced was distilled out of the system. Subsequently, 0.03 parts of a 56% aqueous solution of orthophosphoric acid (0.033 parts relative to dimethyl terephthalate) was added to the obtained product.
mol%) and antimony trioxide (0.02 parts mol%) were added and transferred after each polymerization.Then, the pressure was reduced from 760 nmtlg to 1m+t1g over 1 hour, and at the same time, the pressure was reduced to 230 nm over 1 hour and 30 minutes. The polymerization was carried out at a polymerization temperature of 280° C. under reduced pressure of 1 part mlQ or less until the intrinsic viscosity shown in Table 1 was reached, while the temperature was raised from 280° C. to 280° C.
得られたポリエステを１２０℃で６時間真空乾燥し、孔
径０．１５ｍ＋の円形吐出孔を７２個穿設した紡糸口金
を使用して最高３１０℃で溶融し、引取速度毎分４３０
０ｍで高速紡糸して３６デニール／７２フイラメント（
単糸０．５デニール）の極細糸を得た。なお、の時紡糸
口金から第１引取ローラ（ゴデツトローラ）迄の糸条走
行距離は３ｍにした。この時の紡糸調子、得られた極細
糸の物性を第１表に示す。The obtained polyester was vacuum dried at 120°C for 6 hours and melted at a maximum temperature of 310°C using a spinneret with 72 circular discharge holes with a hole diameter of 0.15 m+, and the take-up speed was 430 m/min.
36 denier/72 filament (
An ultrafine yarn of 0.5 denier (single yarn) was obtained. Incidentally, the yarn running distance from the spinneret to the first take-up roller (godet roller) was 3 m. The spinning conditions at this time and the physical properties of the obtained ultrafine yarn are shown in Table 1.
一方比較のため比較例−４及び−５にナトリウムスルホ
イソフタル酸成分を共重合した変性ポリエステルを用い
、上記と同様の方法で紡糸した結果を第１表に併記した
。On the other hand, for comparison, modified polyesters copolymerized with a sodium sulfoisophthalic acid component were used in Comparative Examples -4 and -5, and the results were also shown in Table 1 by spinning in the same manner as above.
第１表
比較例−１は紡糸調子、力学特性ともに良好であるが、
塩基性染料では染色することができない。Comparative Example-1 in Table 1 has good spinning condition and mechanical properties, but
It cannot be dyed with basic dyes.
比較例−２は剤の添加量が４モル％と多すぎるため紡糸
調子はかなり悪化する上、得られるポリエステル糸の強
度が低下する。比較例−３は極限粘度が低く、紡糸調子
は一応良好であるが、強度がやはり低いレベルに留る。In Comparative Example 2, the amount of the agent added was too large, 4 mol %, so that the spinning condition deteriorated considerably and the strength of the resulting polyester yarn decreased. Comparative Example 3 has a low intrinsic viscosity and a good spinning condition, but the strength still remains at a low level.
比較例−４及び５は従来からカチオン可染剤として用い
られているナトリウムスルホイソフタル酸ジメチルを共
重合した例であり、紡糸調子が極めて劣っている。これ
に対し実施例−１〜５は本発明によるものであり紡糸調
子、得られた極細糸の強度とも充分良好である。Comparative Examples 4 and 5 are examples in which sodium dimethyl sulfoisophthalate, which has been conventionally used as a cationic dyestuff, is copolymerized, and the spinning condition is extremely poor. On the other hand, Examples 1 to 5 are based on the present invention, and both the spinning condition and the strength of the obtained ultrafine yarns are sufficiently good.
Claims (6)
式中、Ａは芳香族基又は脂肪族基、Ｘ＿１及びＸ＿２は
同一又は異なるエステル形成性官能基、Ｒ＿１、Ｒ＿２
、Ｒ＿３及びＲ＿４は水素原子、アルキル基、アリール
基及びヒドロキシアルキル基より選ばれた同一又は異な
る基、ｎは正の整数を示す］ で表わされるスルホン酸ホスホニウム塩を共重合した極
限粘度が０．５以上のポリエステルを３０００ｍ／分以
上の引取速度で溶融紡糸して単糸の平均繊度が１．０ｄ
ｅ以下のマルチ糸とすることを特徴とするポリエステル
極細糸の製造法。(1) The following general formula X_1-A-X_2 (SO_3^■P^■R_1R_2R_3R_4)n[
In the formula, A is an aromatic group or an aliphatic group, X_1 and X_2 are the same or different ester-forming functional groups, R_1, R_2
, R_3 and R_4 are the same or different groups selected from a hydrogen atom, an alkyl group, an aryl group, and a hydroxyalkyl group, n is a positive integer] The intrinsic viscosity of the copolymerized sulfonic acid phosphonium salt represented by 5 or more polyester is melt-spun at a take-up speed of 3000 m/min or more, and the average fineness of the single yarn is 1.0 d.
A method for producing ultrafine polyester yarn, which is characterized in that it is a multi-thread of e or less.
ステルを構成する二官能性カルボン酸成分に対して０．
５〜３．５モル％である特許請求の範囲第１項記載のポ
リエステル極細糸の製造法。(2) The copolymerization amount of the sulfonic acid phosphonium salt is 0.0% relative to the bifunctional carboxylic acid component constituting the polyester.
The method for producing ultrafine polyester yarn according to claim 1, wherein the content is 5 to 3.5 mol%.
１、Ｒ＿２、Ｒ＿３及びＲ＿４がブチル基である特許請
求の範囲第１項又は第２項記載のポリエステル極細糸の
製造法。(3) R_ in the general formula representing sulfonic acid phosnium salt
1. The method for producing ultrafine polyester thread according to claim 1 or 2, wherein R_2, R_3 and R_4 are butyl groups.
構成単位とするポリエステルである特許請求の範囲第１
項〜第３項のいずれか１項記載のポリエステル極細糸の
製造法。(4) Claim 1 in which the polyester is a polyester whose main constituent unit is ethylene terephthalate.
A method for producing ultrafine polyester yarn according to any one of Items 1 to 3.
である特許請求の範囲第１項〜第４項のいずれか１項記
載のポリエステル極細糸の製造法。(5) The method for producing ultrafine polyester yarn according to any one of claims 1 to 4, wherein the ultrafine polyester yarn has a strength of 3.5 g/de or more.
ｅ以下である特許請求の範囲第１項〜第５項のいずれか
１項記載のポリエステル極細糸の製造法。(6) Average fineness of single yarn of polyester ultrafine yarn is 0.6d
The method for producing ultrafine polyester yarn according to any one of claims 1 to 5, wherein the polyester ultrafine yarn is less than or equal to e.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62041532A JPS63211322A (en) | 1987-02-26 | 1987-02-26 | Production of polyester ultrathin yarn |
| US07/144,507 US4851504A (en) | 1987-02-26 | 1988-01-15 | Cationically-dyeable, thermally-resistant copolyester fiber comprising quaternary phosphonium organic sulfonate groups |
| DE3888709T DE3888709T2 (en) | 1987-02-26 | 1988-01-19 | Copolyester fiber. |
| EP88100639A EP0280026B1 (en) | 1987-02-26 | 1988-01-19 | Copolyester fiber |
| KR1019880000450A KR970007431B1 (en) | 1987-02-26 | 1988-01-21 | Copolyester fiber |
| CA000557219A CA1301996C (en) | 1987-02-26 | 1988-01-22 | Copolyester fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62041532A JPS63211322A (en) | 1987-02-26 | 1987-02-26 | Production of polyester ultrathin yarn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63211322A true JPS63211322A (en) | 1988-09-02 |
| JPH0361767B2 JPH0361767B2 (en) | 1991-09-20 |
Family
ID=12611022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62041532A Granted JPS63211322A (en) | 1987-02-26 | 1987-02-26 | Production of polyester ultrathin yarn |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63211322A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0364548A (en) * | 1989-07-28 | 1991-03-19 | Teijin Ltd | Water repellent durable fabric |
| JPH0364547A (en) * | 1989-07-28 | 1991-03-19 | Teijin Ltd | Water repellent durable fabric |
| JP2008223148A (en) * | 2007-03-08 | 2008-09-25 | Teijin Fibers Ltd | Method for producing ultra fine false-twisted yarn dyeable with cation dye at atmospheric pressure |
-
1987
- 1987-02-26 JP JP62041532A patent/JPS63211322A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0364548A (en) * | 1989-07-28 | 1991-03-19 | Teijin Ltd | Water repellent durable fabric |
| JPH0364547A (en) * | 1989-07-28 | 1991-03-19 | Teijin Ltd | Water repellent durable fabric |
| JP2008223148A (en) * | 2007-03-08 | 2008-09-25 | Teijin Fibers Ltd | Method for producing ultra fine false-twisted yarn dyeable with cation dye at atmospheric pressure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0361767B2 (en) | 1991-09-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |