JP5180766B2 - Hollow polyester fiber and method for producing the same - Google Patents
Hollow polyester fiber and method for producing the same Download PDFInfo
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- JP5180766B2 JP5180766B2 JP2008260721A JP2008260721A JP5180766B2 JP 5180766 B2 JP5180766 B2 JP 5180766B2 JP 2008260721 A JP2008260721 A JP 2008260721A JP 2008260721 A JP2008260721 A JP 2008260721A JP 5180766 B2 JP5180766 B2 JP 5180766B2
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- polyester
- sulfoisophthalic acid
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- polyester fiber
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- 229920000728 polyester Polymers 0.000 title claims description 56
- 239000000835 fiber Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 29
- 125000002091 cationic group Chemical group 0.000 claims description 22
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- 150000004714 phosphonium salts Chemical group 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000000034 method Methods 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000004043 dyeing Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000002074 melt spinning Methods 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 208000012886 Vertigo Diseases 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- -1 hydrocarbon dicarboxylic acids Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 229920006307 urethane fiber Polymers 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 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 description 1
- BWLOPTUNEMCWSZ-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tetraphenylphosphanium Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 BWLOPTUNEMCWSZ-UHFFFAOYSA-K 0.000 description 1
- FQVMIQKRLZHUDJ-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tributyl(ethyl)phosphanium Chemical compound CCCC[P+](CC)(CCCC)CCCC.CCCC[P+](CC)(CCCC)CCCC.CCCC[P+](CC)(CCCC)CCCC.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O FQVMIQKRLZHUDJ-UHFFFAOYSA-K 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 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
- MAAPEMRACZBJAD-UHFFFAOYSA-K benzyl(tributyl)phosphanium 5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.CCCC[P+](CCCC)(CCCC)Cc1ccccc1.CCCC[P+](CCCC)(CCCC)Cc1ccccc1.CCCC[P+](CCCC)(CCCC)Cc1ccccc1 MAAPEMRACZBJAD-UHFFFAOYSA-K 0.000 description 1
- BUDPGRUUAXTNRB-UHFFFAOYSA-K benzyl(triphenyl)phosphanium 5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.C(c1ccccc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.C(c1ccccc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.C(c1ccccc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 BUDPGRUUAXTNRB-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHPRWPIHJBDGSI-UHFFFAOYSA-K butyl(triphenyl)phosphanium 5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.CCCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1.CCCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1.CCCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1 JHPRWPIHJBDGSI-UHFFFAOYSA-K 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- JWZDVHOYCNIXDA-UHFFFAOYSA-N tributyl(phenyl)phosphanium Chemical class CCCC[P+](CCCC)(CCCC)C1=CC=CC=C1 JWZDVHOYCNIXDA-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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Description
本発明は軽量感に優れ、且つ常圧下でカチオン染料に可染性であって、布帛の引き裂き強力を上げることが可能となるスポーツ衣料等に適した中空常圧カチオン可染性ポリエステル繊維及びその製造方法に関するものである。 The present invention is a hollow normal pressure cationic dyeable polyester fiber suitable for sports clothing and the like, which is excellent in lightness and dyeable to a cationic dye under normal pressure, and can increase the tearing strength of a fabric, and the like It relates to a manufacturing method.
ポリエステル繊維は機械的特性をはじめ様々な優れた特性を有しており、衣料用途をはじめ各種用途・分野に利用されている。しかしながら天然繊維に比べて風合い的に硬く感じられるという特徴があった。そのため、最近ではポリエステル繊維の機能性を向上させるべく、ポリエステル繊維の断面形状の変更やポリマー改質により、軽量性や深色性を向上させたりしてきた。特にスポーツ衣料用途としては、更なる軽量性及び布帛の強度が必要とされてきている。 Polyester fibers have various excellent properties including mechanical properties, and are used in various applications and fields including clothing. However, it has a feature that it feels harder than natural fibers. Therefore, recently, in order to improve the functionality of the polyester fiber, the lightness and the deep color have been improved by changing the cross-sectional shape of the polyester fiber or modifying the polymer. Especially for sports apparel, further lightness and fabric strength have been required.
その軽量性を発現させるため、紡糸口金を中空形状にして、高中空率を保つことで、その軽量性を謳ったり、複合繊維により中心部にポリビニルアルコール系の樹脂を添加し、紡糸巻取後にその樹脂を溶出させ、実質のポリエステル繊維の中空率を高め、軽量性を発現させる方法が各種提案されてきている。(例えば特許文献1参照)
また、深色性に関しては、ポリエステルにスルホイソフタル酸の金属塩を2〜3モル%共重合する方法が提案されている(例えば特許文献2,3参照)。
In order to express its lightness, the spinneret has a hollow shape and maintains a high hollow ratio, thereby increasing its lightness or adding a polyvinyl alcohol-based resin to the center with a composite fiber. Various methods have been proposed in which the resin is eluted, the substantial hollow ratio of the polyester fiber is increased, and lightness is expressed. (For example, see Patent Document 1)
For deep color, a method of copolymerizing a metal salt of sulfoisophthalic acid with 2 to 3 mol% of polyester has been proposed (see, for example, Patent Documents 2 and 3).
しかしながら、かかる方法によって得られるポリエステル繊維は、高温・高圧下でしか染色することができず、天然繊維やウレタン繊維などと交編、交織した後に染色すると、天然繊維、ウレタン繊維が脆化するという問題があった。これを常圧、100℃付近の温度で十分に染色しようとすれば、スルホイソフタル酸の金属塩を多量に共重合されることが必要となるが、この場合、スルホネート基による増粘効果から、ポリエステルの重合度を高くすることができず、溶融紡糸にて得られるポリエステル繊維の強度が著しく低下し、さらに紡糸操業性が著しく悪化するという問題があった。 However, the polyester fiber obtained by such a method can be dyed only under high temperature and high pressure, and if it is dyed after knitting or weaving with natural fiber or urethane fiber, natural fiber and urethane fiber are embrittled. There was a problem. If this is to be sufficiently dyed at normal pressure and at a temperature around 100 ° C., it is necessary to copolymerize a large amount of the metal salt of sulfoisophthalic acid. In this case, from the thickening effect due to the sulfonate group, There is a problem that the degree of polymerization of the polyester cannot be increased, the strength of the polyester fiber obtained by melt spinning is remarkably lowered, and the spinning operability is remarkably deteriorated.
一方、このような問題を解決するため、イオン結合性分子間力の小さいカチオン可染モノマーを共重合する技術が開示されている(例えば特許文献4,5参照)。イオン結合性分子間力の小さいカチオン可染モノマーとしては、5−スルホイソフタル酸テトラブトキシホスホネートなどが例示されているが、これらのカチオン可染モノマー共重合ポリエステルは熱安定性が悪く、常圧カチオン可染化させるため、共重合量を増加させようとしても、重合反応途中で熱分解が進行し、高分子量化させることが困難であった。さらに溶融紡糸する際の熱履歴による分解が大きく、結果として得られる糸の強度が弱くなるという欠点を有していた。また、使用する5−スルホイソフタル酸テトラブトキシホスホネートは非常に高価であり、結果として得られるカチオン可染性ポリエステルのコストが大幅に増大するという問題があった。 On the other hand, in order to solve such a problem, a technique for copolymerizing a cationic dyeable monomer having a small ion-binding intermolecular force has been disclosed (for example, see Patent Documents 4 and 5). Examples of cationic dyeable monomers having a small ion-binding intermolecular force include 5-sulfoisophthalic acid tetrabutoxyphosphonate and the like, but these cationic dyeable monomer copolymer polyesters have poor thermal stability, and are used as atmospheric pressure cations. Even if an attempt was made to increase the amount of copolymerization for dyeing, thermal decomposition progressed during the polymerization reaction, making it difficult to increase the molecular weight. Furthermore, there is a drawback that the decomposition due to the thermal history during melt spinning is large, and the strength of the resulting yarn is weakened. Further, the 5-sulfoisophthalic acid tetrabutoxyphosphonate used is very expensive, and there is a problem that the cost of the resulting cationic dyeable polyester is greatly increased.
かかる問題を解決する方法として、スルホイソフタル酸の金属塩に加え、分子量が2000以上のポリエチレングリコールを共重合する方法、アジピン酸、セバシン酸などの直鎖炭化水素のジカルボン酸を共重合する方法、あるいはジエチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノールのようなグリコール成分を共重合する方法が提案されている。(例えば特許文献6,7参照) As a method for solving such a problem, in addition to a metal salt of sulfoisophthalic acid, a method of copolymerizing polyethylene glycol having a molecular weight of 2000 or more, a method of copolymerizing a dicarboxylic acid of a linear hydrocarbon such as adipic acid or sebacic acid, Alternatively, a method of copolymerizing glycol components such as diethylene glycol, neopentyl glycol, and cyclohexanedimethanol has been proposed. (For example, see Patent Documents 6 and 7)
一方、耐光性の低下が少なく、且つ常圧可染性を出す方法としてアジピン酸、セバシン酸のような直鎖炭化水素のジカルボン酸、あるいはジエチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノールのようなグリコール成分、また、平均分子量が400〜1000のポリアルキレングリコールをスルホイソフタル酸の金属塩と共重合する方法が提案されている(例えば特許文献8参照)。 On the other hand, as a method for producing a low pressure resistance decrease and normal pressure dyeability, linear hydrocarbon dicarboxylic acids such as adipic acid and sebacic acid, or glycol components such as diethylene glycol, neopentyl glycol, and cyclohexanedimethanol In addition, a method of copolymerizing a polyalkylene glycol having an average molecular weight of 400 to 1000 with a metal salt of sulfoisophthalic acid has been proposed (for example, see Patent Document 8).
しかしながら、これらいずれの方法でも得られたポリエステルを溶融紡糸して得られる常圧カチオン可染性ポリエステル繊維の強度が低くなり、強いては得られる布帛の引き裂き強度が低下する、更には染色堅牢度が低いなどの問題があった。 However, the strength of the atmospheric pressure cationic dyeable polyester fiber obtained by melt spinning the polyester obtained by any of these methods is lowered, and thus the tear strength of the resulting fabric is lowered, and further the dyeing fastness is increased. There was a problem such as low.
また、5−ナトリウムスルホイソフタル酸を共重合したポリエステルを鞘部に、95モル%以上がエチレンテレフタレートの繰返し単位からなるポリエステルを芯部に配した複合繊維が提案されている(例えば特許文献9参照)。しかしながら、鞘部を構成する共重合ポリエステル中のスルホイソフタル酸成分の共重合量には、前述と同様の理由で限界があり、十分な染着性を得ることが困難であること、並びに複合繊維とすることで紡糸工程での加工コストが増加、または繊維断面形状などに制約が生じるなどの課題があった。 Further, there has been proposed a composite fiber in which a polyester copolymerized with 5-sodium sulfoisophthalic acid is disposed in the sheath portion and a polyester having 95 mol% or more of ethylene terephthalate repeating units disposed in the core portion (see, for example, Patent Document 9). ). However, the copolymerization amount of the sulfoisophthalic acid component in the copolyester constituting the sheath part is limited for the same reason as described above, and it is difficult to obtain sufficient dyeing properties. As a result, there are problems such as an increase in processing cost in the spinning process or a restriction on the fiber cross-sectional shape.
本発明は上記の課題を解決するものであり、優れた軽量感を有し、常圧下でカチオン染料に可染性である中空ポリエステル繊維に関するものであり、さらにはそれを布帛とした時にソフトな風合い、優れた深色性を持つと同時に布帛の引き裂き強力を上げることが可能となるスポーツ衣料等に適した常圧カチオン可染性中空断面マルチフィラメントに関する。 The present invention solves the above-mentioned problems, and relates to a hollow polyester fiber having an excellent lightness and being dyeable to a cationic dye under normal pressure. The present invention relates to a normal pressure cationic dyeable hollow cross-section multifilament suitable for sports clothing and the like that can improve the tear strength of a fabric while having a texture and excellent deep color.
上記の課題に鑑み本発明者らは鋭意検討を行った結果、本発明を完成するに至った。
すなわち本発明によれば、
主たる繰返し単位がエチレンテレフタレートより構成されるポリエステルであり、下記要件を満足する常圧カチオン可染中空ポリエステル繊維。
a)ポリエステルを構成する酸成分中に、スルホイソフタル酸の金属塩(A)、および下記化学式(1)で表される化合物(B)を、下記数式(1)及び数式(2)を同時に満足する条件で含有すること。
b)ポリエステル中のジエチレングリコール含有量が2.5重量%以下であること。
c)ポリエステルの固有粘度が0.55〜1.0であること。
d)単糸の中空率が5〜80%であること。
4.0≦A+B≦5.0 (数式1)
0.2≦B/(A+B)≦0.7 (数式2)
[ここで、Aはスルホイソフタル酸の金属塩の共重合量(モル%)、Bは上記化学式(1)で表される化合物の共重合量(モル%)を表す。]
In view of the above problems, the present inventors have intensively studied, and as a result, have completed the present invention.
That is, according to the present invention,
A normal pressure cationic dyeable hollow polyester fiber which is a polyester composed of ethylene terephthalate as a main repeating unit and satisfies the following requirements.
a) In the acid component constituting the polyester, the metal salt of sulfoisophthalic acid (A) and the compound (B) represented by the following chemical formula (1) satisfy the following formulas (1) and (2) at the same time. Contain under conditions to do.
b) The diethylene glycol content in the polyester is 2.5% by weight or less.
c) The intrinsic viscosity of the polyester is 0.55 to 1.0.
d) The hollow ratio of the single yarn is 5 to 80%.
4.0 ≦ A + B ≦ 5.0 (Formula 1)
0.2 ≦ B / (A + B) ≦ 0.7 (Formula 2)
[Here, A represents the copolymerization amount (mol%) of the metal salt of sulfoisophthalic acid, and B represents the copolymerization amount (mol%) of the compound represented by the chemical formula (1). ]
本発明によれば、優れた軽量性を有し、色調が良好で、常圧下でのカチオン染色による染着性が良好なポリエステル繊維を提供することができる。 According to the present invention, it is possible to provide a polyester fiber having excellent lightness, good color tone, and good dyeing property by cationic dyeing under normal pressure.
以下、本発明について詳細に説明する。
本発明のポリエステル中空断面繊維は、単糸の断面形状が中空形状であり、中空率が5〜80%、好ましくは10〜60%、より好ましくは20〜40%である。
本発明の中空断面繊維の断面形状は丸断面または3ケ以上の多角形断面形状の中空部を形成しているポリエステル繊維をあらわす。また中空部は1つに限定されず、2ケ以上の中空部を有する中空繊維であってもよい。また繊維全体の形状も丸断面に限定されることはなく、3ケ以上の多角形断面形状であってもよい。また繊維全体の形状も丸断面に限定されることはなく、3ケ以上の多角形断面形状であっても良く、中空を形成するのに影響がない範囲内で断面形状に凹部を有するような異型断面であってもよい。また、中空繊維の繊度は、特に限定されるものではないが、製糸性や深色性の観点から10〜300dtex、好ましくは30〜200dtex、単糸繊度は0.3〜5.0dtex、好ましくは0.5〜3.0dtexである。
Hereinafter, the present invention will be described in detail.
In the polyester hollow cross-section fiber of the present invention, the cross-sectional shape of the single yarn is hollow, and the hollow ratio is 5 to 80%, preferably 10 to 60%, more preferably 20 to 40%.
The cross-sectional shape of the hollow cross-section fiber of the present invention represents a polyester fiber forming a hollow section having a round cross section or three or more polygonal cross-section shapes. Further, the number of hollow portions is not limited to one, and may be hollow fibers having two or more hollow portions. Further, the shape of the entire fiber is not limited to a round cross section, and may be a polygonal cross section shape of three or more. Further, the shape of the entire fiber is not limited to a round cross section, and may be a polygonal cross section shape of three or more, and has a recess in the cross section within a range that does not affect the formation of a hollow. An irregular cross section may be used. Further, the fineness of the hollow fiber is not particularly limited, but is 10 to 300 dtex, preferably 30 to 200 dtex, and the single yarn fineness is 0.3 to 5.0 dtex, preferably from the viewpoint of yarn-making property and deep color. 0.5 to 3.0 dtex.
また、本発明に使用されるポリエステルとは、テレフタル酸またはそのエステル形成性誘導体と、エチレングリコール成分とを重縮合反応せしめて得られるエチレンテレフタレートを主たる繰返し単位とするポリエステルであり、共重合成分としてスルホイソフタル酸の金属塩(A)、及び下記化学式(1)で表される化合物(B)を、下記数式1及び2を同時に満足する状態で含有する共重合ポリエステルであり、該ポリエステル中のジエチレングリコール含有量が2.5重量%以下、固有粘度が0.55〜1.0であり、これにより得られた繊維の断面形状が偏平形状であり、該偏平形状は長手方向に丸断面単糸の3〜6個が接合したような形状を有している偏平断面であることを特徴とする常圧カチオン可染ポリエステル繊維である。 The polyester used in the present invention is a polyester having ethylene terephthalate as a main repeating unit obtained by polycondensation reaction of terephthalic acid or an ester-forming derivative thereof and an ethylene glycol component. A copolymer polyester containing a metal salt of sulfoisophthalic acid (A) and a compound (B) represented by the following chemical formula (1) in a state satisfying the following mathematical formulas 1 and 2 at the same time, and diethylene glycol in the polyester The content is 2.5% by weight or less, the intrinsic viscosity is 0.55 to 1.0, and the cross-sectional shape of the fiber obtained thereby is a flat shape, and the flat shape is a round cross-section single yarn in the longitudinal direction. It is a normal pressure cationic dyeable polyester fiber characterized by having a flat cross-section having a shape such that 3 to 6 are joined.
4.0≦A+B≦5.0 (数式1)
0.2≦B/(A+B)≦0.7 (数式2)
[ここで、Aはスルホイソフタル酸の金属塩の共重合量(モル%)、Bは上記化学式(1)で表される化合物の共重合量(モル%)を表す。]
4.0 ≦ A + B ≦ 5.0 (Formula 1)
0.2 ≦ B / (A + B) ≦ 0.7 (Formula 2)
[Here, A represents the copolymerization amount (mol%) of the metal salt of sulfoisophthalic acid, and B represents the copolymerization amount (mol%) of the compound represented by the chemical formula (1). ]
(成分Aについての説明)
本発明で使用されるスルホン酸塩基含有芳香族ジカルボン酸成分としては、5−スルホイソフタル酸の金属塩(ナトリウム塩、リチウム塩、カリウム塩)、5−スルホイソフタル酸の4級ホスホニウム塩、または5−スルホイソフタル酸の4級アンモニウム塩が例示される。また、これらのエステル形成性誘導体も好ましく例示される。これらの群の中では、熱安定性、コストなどの面から、5−スルホイソフタル酸の金属塩が好ましく例示され、特に、5−スルホイソフタル酸のナトリウム塩およびそのジメチルエステルである5−スルホイソフタル酸ジメチルのナトリウム塩が特に好ましく例示される。
(Description of component A)
Examples of the sulfonate group-containing aromatic dicarboxylic acid component used in the present invention include a metal salt of 5-sulfoisophthalic acid (sodium salt, lithium salt, potassium salt), a quaternary phosphonium salt of 5-sulfoisophthalic acid, or 5 -Quaternary ammonium salts of sulfoisophthalic acid are exemplified. These ester-forming derivatives are also preferably exemplified. Among these groups, a metal salt of 5-sulfoisophthalic acid is preferably exemplified from the viewpoint of thermal stability, cost, etc., and in particular, a sodium salt of 5-sulfoisophthalic acid and a dimethyl ester thereof, 5-sulfoisophthalic acid. Particularly preferred is the sodium salt of dimethyl acid.
(成分Bについての説明)
また、上記化学式(1)で表される化合物(B)としては、5−スルホイソフタル酸あるいはその低級アルキルアエステルの4級ホスホニウム塩または4級アンモニウム塩である。4級ホスホニウム塩、4級アンモニウム塩としては、アルキル基、ベンジル基、フェニル基が置換された4級ホスホニウム塩、4級アンモニウム塩が好ましく、特に4級ホスホニウム塩であることが好ましい。また、4つある置換基は同一であっても異なっていても良い。上記化学式(1)で表される化合物の具体例としては、5−スルホイソフタル酸テトラブチルホスホニウム塩、5−スルホイソフタル酸エチルトリブチルホスホニウム塩、5−スルホイソフタル酸ベンジルトリブチルホスホニウム塩、5−スルホイソフタル酸フェニルトリブチルホスホニウム塩、5−スルホイソフタル酸テトラフェニルホスホニウム塩、5−スルホイソフタル酸ブチルトリフェニルホスホニウム塩、5−スルホイソフタル酸ベンジルトリフェニルホスホニウム塩、あるいはこれらイソフタル酸誘導体のジメチルエステル、ジエチルエステルが好ましく例示される。
(Description of component B)
The compound (B) represented by the chemical formula (1) is quaternary phosphonium salt or quaternary ammonium salt of 5-sulfoisophthalic acid or its lower alkyl ester. As the quaternary phosphonium salt, the quaternary ammonium salt is preferably a quaternary phosphonium salt or a quaternary ammonium salt substituted with an alkyl group, a benzyl group or a phenyl group, and particularly preferably a quaternary phosphonium salt. The four substituents may be the same or different. Specific examples of the compound represented by the chemical formula (1) include 5-sulfoisophthalic acid tetrabutylphosphonium salt, 5-sulfoisophthalic acid ethyltributylphosphonium salt, 5-sulfoisophthalic acid benzyltributylphosphonium salt, and 5-sulfoisophthalic acid. Acid phenyltributylphosphonium salt, 5-sulfoisophthalic acid tetraphenylphosphonium salt, 5-sulfoisophthalic acid butyltriphenylphosphonium salt, 5-sulfoisophthalic acid benzyltriphenylphosphonium salt, or dimethyl ester or diethyl ester of these isophthalic acid derivatives Preferably exemplified.
(数式1の説明)
本発明において、ポリエステルに共重合させる成分Aと成分Bの合計は酸成分を基準として、A+Bが4.0〜5.0モル%の範囲である必要がある。4.0モル%より少ないと、常圧下でのカチオン染色では十分な染着を得ることができない。一方、5.0モル%より多くなると、得られるポリエステル糸の強度が低下するため実用に適さない。さらに染料を過剰に消費するため、コスト面でも不利である。
(Explanation of Formula 1)
In the present invention, the total of component A and component B copolymerized with polyester needs to be within a range of 4.0 to 5.0 mol% of A + B based on the acid component. If it is less than 4.0 mol%, sufficient dyeing cannot be obtained by cationic dyeing under normal pressure. On the other hand, if it exceeds 5.0 mol%, the strength of the resulting polyester yarn is lowered, which is not suitable for practical use. Further, since the dye is consumed excessively, it is disadvantageous in terms of cost.
(数式2の説明)
また、成分Aと成分Bの成分比は、B/(A+B)が0.2〜0.7の範囲にある必要がある。0.2以下、つまり成分Aの割合が多い状態では、スルホイソフタル酸金属塩による増粘効果により、得られるポリエステルの重合度を上げることが困難になる。一方、0.7以上、つまり成分Bの割合が多い状態では、反応が遅くなり、さらに成分Bの比率が多くなると分解が進むため重合度を上げることができない。さらに、成分Bの比率多くなると熱安定性が悪化し、溶融紡糸段階で再溶融した際の熱分解による分子量の低下が大きくなるため、得られるポリエステル糸の強度が低下するため、好ましくない。
(Explanation of Formula 2)
The component ratio between component A and component B must be such that B / (A + B) is in the range of 0.2 to 0.7. When the ratio is 0.2 or less, that is, in a state where the proportion of component A is large, it is difficult to increase the degree of polymerization of the resulting polyester due to the thickening effect of the metal salt of sulfoisophthalic acid. On the other hand, when the ratio is 0.7 or more, that is, the ratio of the component B is large, the reaction is slow, and when the ratio of the component B is further increased, the decomposition proceeds and the degree of polymerization cannot be increased. Further, when the ratio of component B is increased, the thermal stability is deteriorated, and the decrease in molecular weight due to thermal decomposition when remelted in the melt spinning stage is increased, so that the strength of the resulting polyester yarn is decreased, which is not preferable.
(DEG量の説明)
本発明における常圧カチオン可染性ポリエステルに含有されるジエチレングリコールは、2.5重量%以下であることが好ましい。
一般にカチオン可染性ポリエステルを製造する際には、ポリエステルの製造工程において副生するジエチレングリコール(DEG)量を抑制するために、DEG抑制剤として少々のアルカリ金属塩、アルカリ土類金属塩、水酸化テトラアルキルホスホニウム、水酸化テトラアルキルアンモニウム、トリアルキルアミンなどの少なくとも1種類を、使用するカチオン可染性モノマー(本発明の場合は化合物(A)及び(B))に対して、1〜20モル%程度を添加することが好ましい。
(Description of DEG amount)
The diethylene glycol contained in the normal pressure cationic dyeable polyester in the present invention is preferably 2.5% by weight or less.
In general, when a cationic dyeable polyester is produced, in order to suppress the amount of diethylene glycol (DEG) by-produced in the production process of the polyester, a small amount of alkali metal salt, alkaline earth metal salt, hydroxide is used as a DEG inhibitor. 1 to 20 mol of the cationic dyeable monomer (compounds (A) and (B) in the case of the present invention) at least one of tetraalkylphosphonium, tetraalkylammonium hydroxide, trialkylamine and the like used. It is preferable to add about%.
(固有粘度の説明)
本発明で使用されるポリエステルの固有粘度(溶媒:オルトクロロフェノール、測定温度:35℃)は0.55〜1.0の範囲であることが好ましい。固有粘度が0.55以下である場合、得られるポリエステル繊維の強度不足、溶融粘度不足による中空率の低下が起こり、一方、1.0以上とする場合、溶融粘度が高くなりすぎて溶融成型が困難になるため好ましくなく、また、溶融重合法に引続いて固相重合法により重合ポリエステルの重縮合工程での生産コストが大幅に増大するため好ましくない。常圧カチオン可染性ポリエステルの固有粘度としては、0.60〜0.90の範囲が更に好ましい。
(Explanation of intrinsic viscosity)
The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the polyester used in the present invention is preferably in the range of 0.55 to 1.0. When the intrinsic viscosity is 0.55 or less, the resulting polyester fiber is insufficient in strength and the hollowness is lowered due to insufficient melt viscosity. On the other hand, when it is 1.0 or more, the melt viscosity becomes too high and melt molding occurs. It is not preferable because it becomes difficult, and it is not preferable because the production cost in the polycondensation step of the polymerized polyester greatly increases by the solid phase polymerization method following the melt polymerization method. The intrinsic viscosity of the normal pressure cationic dyeable polyester is more preferably in the range of 0.60 to 0.90.
(ポリエステルの製造方法)
本発明における共重合ポリエステルの製造は特に限定されず、通常知られているポリエステルの製造方法が用いられる。すなわち、テレフタル酸とエチレングリコールの直接重縮合反応させる、あるいはテレフタル酸ジメチルに代表されるテレフタル酸のエステル形成性誘導体とエチレングリコールとをエステル交換反応させて低重合体を製造する。次いでこの反応性生物を重縮合触媒の存在下で減圧加熱して所定の重合度になるまで重縮合反応させることにより製造される。スルホイソフタル酸を含有する芳香族ジカルボン酸および/またはそのエステル誘導体を共重合する方法についても通常知られている製造方法を用いる事ができる。
(Production method of polyester)
The production of the copolyester in the present invention is not particularly limited, and a conventionally known polyester production method is used. That is, a low polymer is produced by a direct polycondensation reaction between terephthalic acid and ethylene glycol, or an ester exchange reaction between an ester-forming derivative of terephthalic acid typified by dimethyl terephthalate and ethylene glycol. Subsequently, this reactive organism is produced by heating under reduced pressure in the presence of a polycondensation catalyst to carry out a polycondensation reaction until a predetermined polymerization degree is reached. As a method for copolymerizing an aromatic dicarboxylic acid containing sulfoisophthalic acid and / or an ester derivative thereof, a generally known production method can be used.
(その他添加剤)
また、本発明における共重合ポリエステルは、必要に応じて少量の添加剤、例えば酸化防止剤、蛍光増白剤、帯電防止剤、抗菌剤、紫外線吸収剤、光安定剤、熱安定剤、遮光剤または艶消し剤などを含んでいても良い。特に酸化防止剤、艶消し剤などは特に好ましく添加される。
(Other additives)
In addition, the copolymer polyester in the present invention contains a small amount of additives as necessary, for example, antioxidants, fluorescent whitening agents, antistatic agents, antibacterial agents, ultraviolet absorbers, light stabilizers, heat stabilizers, and light-shielding agents. Or it may contain a matting agent. In particular, antioxidants and matting agents are particularly preferably added.
(溶融紡糸)
本発明におけるポリエステルの製糸方法は、特に制限は無く、従来公知の方法が採用される。すなわち、乾燥した共重合ポリエステルを270℃〜300℃の範囲で溶融紡糸して製造することが好ましく、溶融紡糸の引取り速度は400〜5000m/分で紡糸することが好ましい。紡糸速度がこの範囲にあると、得られる繊維の強度も十分なものであると共に、安定して巻取りを行うこともできる。さらに、上述の方法で得られた未延伸糸もしくは部分延伸糸を、延伸工程にて1.2倍〜6.0倍程度の範囲で延伸することが好ましい。この延伸は未延伸ポリエステル繊維を一旦巻き取ってから行ってもよく、一旦巻き取ることなく連続的に行ってもよい。
(Melt spinning)
There is no restriction | limiting in particular in the polyester yarn manufacturing method in this invention, A conventionally well-known method is employ | adopted. That is, it is preferable to produce the dried copolyester by melt spinning at a temperature in the range of 270 ° C. to 300 ° C., and the spinning speed of the melt spinning is preferably 400 to 5000 m / min. When the spinning speed is within this range, the strength of the obtained fiber is sufficient, and the winding can be stably performed. Furthermore, it is preferable that the undrawn yarn or the partially drawn yarn obtained by the above method is drawn in a range of about 1.2 times to 6.0 times in the drawing step. This stretching may be performed after winding the unstretched polyester fiber once, or may be performed continuously without winding.
以下、実施例により、本発明を更に具体的に説明する。なお、本発明はこれらの実施例に限られるものではない。実施例における各項目は次の方法で測定した。
(1)固有粘度
ポリエステル組成物を100℃、60分間でオルトクロロフェノールに溶解した希薄溶液を、35℃でウベローデ粘度計を用いて測定した値から求めた。なお、チップの固有粘度をηC、紡糸後の未延伸糸の固有粘度をηFとする。
(2)ジエチレングリコール(DEG)含有量:
ヒドラジンヒドラート(抱水ヒドラジン)を用いてポリエステル組成物チップを分解し、この分解生成物中のジエチレングリコールの含有量をガスクロマトグラフィー(ヒューレットパッカード社製(HP6850型))を用いて測定した。
(3)繊維の引張強度・伸度
JIS L1070記載の方法に準拠して測定を行った。
(4)カチオン可染性
CATHILON BLUE CD−FRLH)0.2g/L、CD−FBLH0.2g/L(いずれも保土ヶ谷化学)、硫酸ナトリウム3g/L、酢酸0.3g/Lの染色液中にて100℃で1時間、浴比1:50で染色し、次式により染着率を求めた。
染着率=(OD0−OD1)/OD0
OD0:染色前の染液の576nmの吸光度
OD1:染色後の染液の576nmの吸光度
本発明では、染着率98%以上のものを可染性良好と判断した。
Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples. Each item in the examples was measured by the following method.
(1) A dilute solution in which the intrinsic viscosity polyester composition was dissolved in orthochlorophenol at 100 ° C. for 60 minutes was determined from the value measured at 35 ° C. using an Ubbelohde viscometer. The intrinsic viscosity of the tip is ηC, and the intrinsic viscosity of the undrawn yarn after spinning is ηF.
(2) Diethylene glycol (DEG) content:
The polyester composition chip was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposition product was measured using gas chromatography (HP Hewlett-Packard (HP 6850)).
(3) Tensile strength / elongation of fiber Measured according to the method described in JIS L1070.
(4) Cationic dyeable CATHILON BLUE CD-FRLH) 0.2 g / L, CD-FBLH 0.2 g / L (both Hodogaya Chemical), sodium sulfate 3 g / L, acetic acid 0.3 g / L And dyed at a bath ratio of 1:50 at 100 ° C. for 1 hour, and the dyeing rate was determined by the following formula.
Dyeing rate = (OD0−OD1) / OD0
OD0: Absorbance at 576 nm of the dye solution before dyeing
OD1: Absorbance at 576 nm of the dyeing solution after dyeing In the present invention, a dyeing rate of 98% or more was judged as good dyeability.
[実施例1]
テレフタル酸ジメチル100重量部、表1の添加量となる5−ナトリウムスルホイソフタル酸ジメチルとエチレングリコール60重量部の混合物に、酢酸マンガン0.03重量部、酢酸ナトリウム三水和物0.12重量部を添加し、140℃から240℃まで徐々に昇温しつつ、反応の結果生成するメタノールを系外に留出させながらエステル交換反応を行った。その後、正リン酸0.03重量部を添加し、エステル交換反応を終了させた。
その後、反応生成物に三酸化アンチモン0.05重量部と表1の添加量となる5−スルホイソフタル酸テトラブトキシホスホネートと水酸化テトラエチルアンモニウム0.3重量部とトリエチルアミン0.003重量部を添加して重合容器に移し、285℃まで昇温し、30Pa以下の高真空にて重縮合反応を行い、重合槽の攪拌機電力が所定電力に到達、もしくは所定時間を経過した段階で反応を終了させ、常法に従いチップ化した。
このポリエチレンテレフタレートチップを、同心円状の二重丸の単糸断面形状となる吐出孔を36個有した紡糸口金から、紡糸温度290℃で紡出し、油剤を付与し、紡糸速度3000m/minで引き取った後、予熱温度85℃、熱セット温度120℃、延伸倍率1.7、800m/minの速度で延伸し、単繊度2.4dtex、総繊度84dtexの本発明の中空断面繊維からなるマルチフィラメントを得た。得られたマルチフィラメントを110本/2.54cmの織密度、経緯無撚で製織し、平織物とした後、定法に従い、染色加工をし、得られた布帛について、上記の各方法で評価を行った。結果を表1に示す。
[Example 1]
In a mixture of 100 parts by weight of dimethyl terephthalate and dimethyl 5-sodium sulfoisophthalate and 60 parts by weight of ethylene glycol as shown in Table 1, 0.03 parts by weight of manganese acetate and 0.12 parts by weight of sodium acetate trihydrate Was added, and the ester exchange reaction was carried out while gradually raising the temperature from 140 ° C. to 240 ° C. while distilling methanol produced as a result of the reaction out of the system. Thereafter, 0.03 part by weight of normal phosphoric acid was added to complete the transesterification reaction.
Thereafter, the reaction product of antimony trioxide and 0.05 parts by weight and the Table 1 amount to become 5-sulfoisophthalate, 0.3 part by weight of phthalic acid tetrabutoxy phosphonate with tetraethylammonium hydroxide and triethylamine 0.003 parts by weight was added Transferred to a polymerization vessel, heated to 285 ° C., and subjected to a polycondensation reaction at a high vacuum of 30 Pa or less, and the reaction was terminated when the agitator power of the polymerization tank reached a predetermined power or a predetermined time passed, Chips were made according to conventional methods.
This polyethylene terephthalate chip was spun at a spinning temperature of 290 ° C. from a spinneret having 36 discharge holes having a concentric double round single yarn cross-sectional shape, applied with an oil agent, and taken up at a spinning speed of 3000 m / min. After that, a multifilament made of the hollow cross-section fiber of the present invention having a preheating temperature of 85 ° C., a heat setting temperature of 120 ° C., a draw ratio of 1.7, and a speed of 800 m / min, and having a single fineness of 2.4 dtex and a total fineness of 84 dtex is obtained. Obtained. The obtained multifilament was woven at a weaving density of 110 yarns / 2.54 cm and untwisted to make a plain woven fabric, then dyed according to a conventional method, and the obtained fabric was evaluated by each of the above methods. went. The results are shown in Table 1.
[実施例2〜3、比較例1〜4]
実施例1において、5−スルホイソフタル酸ナトリウム及び5−スルホイソフタル酸テトラブチルホスホネートの添加量を表1となるように変更した事以外は実施例1と同様に実施した。
[Examples 2 to 3 and Comparative Examples 1 to 4]
In Example 1, it implemented like Example 1 except having changed the addition amount of sodium 5-sulfoisophthalate and 5-sulfoisophthalate tetrabutylphosphonate so that it might become Table 1. FIG.
[比較例5]
実施例3において、重縮合反応での攪拌電力が低い段階で反応終了させること以外は実施例3と同様に実施した。
[Comparative Example 5]
In Example 3, it was carried out in the same manner as in Example 3 except that the stirring power in the polycondensation reaction is the completion of the reaction at a lower stage.
[比較例6]
実施例3において、酢酸ナトリウム三水和物、水酸化テトラエチルアンモニウム、トリエチルアミンを添加しないこと以外は実施例3と同様に実施した。
[Comparative Example 6]
In Example 3, sodium acetate trihydrate, tetraethylammonium hydroxide, except that no triethylamine was added was prepared as in Example 3.
本発明によれば、優れた軽量性を有し、優れた深色性を持つと同時に布帛の引き裂き強力の高い常圧カチオン可染性中空糸としてスポーツ衣料等に適したものとなる。 According to the present invention, it is suitable for sports clothing and the like as an atmospheric pressure cationic dyeable hollow fiber having excellent lightness, excellent deep color and high tear strength of the fabric.
Claims (3)
a)ポリエステルを構成する酸成分中に、スルホイソフタル酸の金属塩(A)、および下記化学式(1)で表される化合物(B)を、下記数式(1)及び数式(2)を同時に満足する条件で含有すること。
b)ポリエステル中のジエチレングリコール含有量が2.5重量%以下であること。
c)ポリエステルの固有粘度が0.55〜1.0であること。
d)単糸の中空率が5〜80%であること。
4.0≦A+B≦5.0 (数式1)
0.2≦B/(A+B)≦0.7 (数式2)
[ここで、Aはスルホイソフタル酸の金属塩の共重合量(モル%)、Bは上記化学式(1)で表される化合物の共重合量(モル%)を表す。] A normal pressure cationic dyeable hollow polyester fiber which is a polyester composed of ethylene terephthalate as a main repeating unit and satisfies the following requirements.
a) In the acid component constituting the polyester, the metal salt of sulfoisophthalic acid (A) and the compound (B) represented by the following chemical formula (1) satisfy the following formulas (1) and (2) at the same time. Contain under conditions to do.
b) The diethylene glycol content in the polyester is 2.5% by weight or less.
c) The intrinsic viscosity of the polyester is 0.55 to 1.0.
d) The hollow ratio of the single yarn is 5 to 80%.
4.0 ≦ A + B ≦ 5.0 (Formula 1)
0.2 ≦ B / (A + B) ≦ 0.7 (Formula 2)
[Here, A represents the copolymerization amount (mol%) of the metal salt of sulfoisophthalic acid, and B represents the copolymerization amount (mol%) of the compound represented by the chemical formula (1). ]
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