JP4498001B2 - Polyester composite fiber - Google Patents
Polyester composite fiber Download PDFInfo
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- JP4498001B2 JP4498001B2 JP2004135772A JP2004135772A JP4498001B2 JP 4498001 B2 JP4498001 B2 JP 4498001B2 JP 2004135772 A JP2004135772 A JP 2004135772A JP 2004135772 A JP2004135772 A JP 2004135772A JP 4498001 B2 JP4498001 B2 JP 4498001B2
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- composite fiber
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- polyester
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- fiber
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- 239000000835 fiber Substances 0.000 title claims description 207
- 229920000728 polyester Polymers 0.000 title claims description 131
- 239000002131 composite material Substances 0.000 title claims description 126
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 92
- 239000004626 polylactic acid Substances 0.000 claims description 91
- 125000003118 aryl group Chemical group 0.000 claims description 70
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000002788 crimping Methods 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 28
- 230000008018 melting Effects 0.000 claims description 28
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 24
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 17
- 229940022769 d- lactic acid Drugs 0.000 claims description 17
- 229930182843 D-Lactic acid Natural products 0.000 claims description 15
- 239000002361 compost Substances 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000004927 fusion Effects 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 5
- 238000009987 spinning Methods 0.000 description 25
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 21
- 239000004745 nonwoven fabric Substances 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- -1 polyethylene terephthalate Polymers 0.000 description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 description 18
- 239000005020 polyethylene terephthalate Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 13
- 238000002074 melt spinning Methods 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000155 melt Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 description 8
- 238000006065 biodegradation reaction Methods 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000009264 composting Methods 0.000 description 5
- 238000009940 knitting Methods 0.000 description 5
- 229920001432 poly(L-lactide) Polymers 0.000 description 5
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 5
- 229920002994 synthetic fiber Polymers 0.000 description 5
- 239000012209 synthetic fiber Substances 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 3
- 229960000448 lactic acid Drugs 0.000 description 3
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000433 Lyocell Polymers 0.000 description 2
- 229920001407 Modal (textile) Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- RGMMREBHCYXQMA-UHFFFAOYSA-N 2-hydroxyheptanoic acid Chemical compound CCCCCC(O)C(O)=O RGMMREBHCYXQMA-UHFFFAOYSA-N 0.000 description 1
- JKRDADVRIYVCCY-UHFFFAOYSA-N 2-hydroxyoctanoic acid Chemical compound CCCCCCC(O)C(O)=O JKRDADVRIYVCCY-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- XGIAHMUOCFHQTI-UHFFFAOYSA-N Cl.Cl.Cl.Cl.CC Chemical compound Cl.Cl.Cl.Cl.CC XGIAHMUOCFHQTI-UHFFFAOYSA-N 0.000 description 1
- 240000001980 Cucurbita pepo Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007378 ring spinning Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Landscapes
- Multicomponent Fibers (AREA)
Description
本発明は、植物由来のポリ乳酸を一成分とする複合繊維であって、耐湿熱分解性、強度、耐摩耗性に優れ、様々な用途に使用することができるポリエステル複合繊維に関するものである。 The present invention relates to a polyester composite fiber that is a composite fiber containing plant-derived polylactic acid as a component and has excellent resistance to wet thermal decomposition, strength, and wear resistance, and can be used in various applications.
合成繊維の中でも特にポリエステル繊維は、その優れた寸法安定性、耐候性、機械的特性、耐久性、さらにはリサイクル性等から、衣料、産業資材として不可欠のものとなっており、様々な分野、用途において広く使用されている。 Among synthetic fibers, especially polyester fibers are indispensable as clothing and industrial materials due to their excellent dimensional stability, weather resistance, mechanical properties, durability, and recyclability. Widely used in applications.
従来の合成繊維は、その大部分が石油などの限りある貴重な化石資源を原料としている。またこれらは自然環境下ではほとんど分解されず、廃棄処理が問題となっている。これに対し、ポリ乳酸はトウモロコシなどの植物資源を原料としており、ポリ乳酸を繊維化したポリ乳酸系繊維は、種々の製品に加工された後、コンポストまたは土壌中などの自然環境下では最終的に炭酸ガスと水に分解される完全生分解性を持つ。 Most of the conventional synthetic fibers are made from valuable fossil resources such as petroleum. Also, they are hardly decomposed in the natural environment, and disposal is a problem. Polylactic acid, on the other hand, is made from plant resources such as corn. Polylactic acid fibers made from polylactic acid are processed into various products, and are finally used in natural environments such as compost or soil. It is completely biodegradable and is decomposed into carbon dioxide and water.
しかしながら、ポリ乳酸繊維は、強度、耐摩耗性が従来の合成繊維よりも劣っている。また、染色等の湿熱処理による重合度の低下が大きく、これによっても強度の低下が生じるという問題点があった。 However, polylactic acid fibers are inferior in strength and wear resistance to conventional synthetic fibers. Further, there is a problem that the degree of polymerization is greatly reduced by wet heat treatment such as dyeing, and this also causes a reduction in strength.
このため、従来のポリ乳酸繊維は、ディスポーザブルの日用資材、農林園芸資材等の用途が主流であり、衣料用、土木建築用、水産資材用、自動車資材用等の強度が要求される分野での使用は限定されているのが現状である。 For this reason, conventional polylactic acid fibers are mainly used for disposable daily materials, agriculture, forestry and horticultural materials, and in fields where strength is required for clothing, civil engineering, marine materials, automotive materials, etc. The use of is currently limited.
このようなポリ乳酸繊維の問題点を解決する手段の一つとしては、強度が要求される用途に使用する場合、質量や厚みを増大させて強度や耐摩耗性をカバーしている。 As one of means for solving such problems of polylactic acid fibers, when used in applications requiring strength, the strength and wear resistance are covered by increasing the mass and thickness.
また、特許文献１では、ポリ乳酸の耐久性を上げるために、カルボジイミドなどの末端封鎖剤により、ポリマーの末端を封鎖し、耐加水分解性を向上させることが提案されている。しかしながら、この繊維では、加水分解を促進する末端基の数を減らすことはできたが、ポリ乳酸のみを使用する繊維であるため、耐湿熱分解性の向上効果は不十分であった。 Patent Document 1 proposes that the end of the polymer is blocked with a terminal blocking agent such as carbodiimide to improve the hydrolysis resistance in order to increase the durability of polylactic acid. However, with this fiber, the number of end groups that promote hydrolysis could be reduced, but since the fiber uses only polylactic acid, the effect of improving wet heat decomposition resistance was insufficient.
特許文献２には、ポリ乳酸と他の成分とからなる複合繊維として、ポリ乳酸が単繊維の表面の全部または一部を形成し、他の成分としてポリエチレンテレフタレート等のポリエステルを芯部に用いた複合繊維が提案されている。しかしながら、この繊維はポリ乳酸成分が繊維の外周部を占め、ポリ乳酸成分を接着成分するバインダー繊維であり、上記したような衣料用、土木建築用、水産資材用、自動車資材用等の強度が要求される分野で使用するものではなかった。
本発明は、上記の問題点を解決し、ポリ乳酸を構成成分としながらも、強度、耐湿熱分解性、耐摩耗性に優れ、様々な用途に使用することが可能なポリエステル複合繊維を提供しようとするものである。また、機械捲縮やスパイラル捲縮、潜在（スパイラル）捲縮性能を有しており、嵩高性が要求される用途として、詰め綿やクッション材にも好適に使用することができるポリエステル複合繊維を提供しようとするものである。 The present invention solves the above-mentioned problems and provides a polyester composite fiber that is excellent in strength, moist heat resistance, and abrasion resistance, and can be used in various applications, while using polylactic acid as a constituent component. It is what. In addition, polyester composite fibers that have mechanical crimping, spiral crimping, and latent (spiral) crimping performance, and can be suitably used for stuffed cotton and cushioning materials are also required for bulkiness. It is something to be offered.
本発明者らは、上記の課題を解決するために鋭意検討の結果、本発明に到達した。
すなわち、本発明は次の（１）〜（６）を要旨とするものである。（１）全酸成分が芳香族ジカルボン酸である芳香族ポリエステルとポリ乳酸よりなる複合繊維であって、横断面形状が芯鞘形状を呈しており、鞘部が上記芳香族ポリエステルで構成され、芯部がポリ乳酸で構成されており、芳香族ポリエステルの融点とポリ乳酸の融点との差が０〜６０℃であることを特徴とするポリエステル複合繊維。
（２）芯部と鞘部がほぼ同心円上に配置された同心芯鞘型の複合繊維であって、機械捲縮が付与されている（１）記載のポリエステル複合繊維。
（３）芯部と鞘部が偏心的に配置された偏心芯鞘型の複合繊維であって、捲縮数５個／２５ｍｍ以上、捲縮率８％以上を同時に満足するスパイラル捲縮を有している（１）記載のポリエステル複合繊維。
（４）芯部と鞘部が偏心的に配置された偏心芯鞘型の複合繊維であって、１５０℃乾熱処理後に５０個／２５ｍｍ以上のスパイラル捲縮を発現する潜在捲縮性能を有している（１）記載のポリエステル複合繊維。
（５）芯部のポリ乳酸は、Ｌ−乳酸および／またはＤ−乳酸からなり、融点１２０℃以上、融解熱１０Ｊ／ｇ以上である（１）〜（４）のいずれかに記載のポリエステル複合繊維。
（６）ＪＩＳ Ｋ ６９５３に準じるコンポスト試験において、４５日間で６０％以上の生分解度を示す（１）〜（５）のいずれかに記載のポリエステル複合繊維。
The inventors of the present invention have reached the present invention as a result of intensive studies in order to solve the above problems.
That is, the gist of the present invention is the following (1) to (6) . (1) A composite fiber total acid component consisting of the aromatic polyester and the polylactic acid is an aromatic dicarboxylic acid, cross-sectional shape has exhibited a core-sheath configuration, the sheath portion is composed of the aromatic polyester, A polyester composite fiber, characterized in that the core is composed of polylactic acid, and the difference between the melting point of the aromatic polyester and the melting point of polylactic acid is 0 to 60 ° C.
(2) The polyester composite fiber according to (1), which is a concentric core-sheath type composite fiber in which a core part and a sheath part are arranged substantially concentrically, and mechanically crimped.
(3) Eccentric core-sheath type composite fiber in which the core part and the sheath part are arranged eccentrically, and has a spiral crimp that simultaneously satisfies the number of crimps of 5/25 mm or more and a crimp rate of 8% or more. The polyester conjugate fiber according to (1).
(4) An eccentric core-sheath type composite fiber in which a core part and a sheath part are arranged eccentrically, and has a latent crimping performance to express 50/25 mm or more spiral crimps after a dry heat treatment at 150 ° C. The polyester composite fiber according to (1).
(5) The polyester composite according to any one of (1) to (4), wherein the polylactic acid in the core is composed of L-lactic acid and / or D-lactic acid and has a melting point of 120 ° C. or higher and a heat of fusion of 10 J / g or higher. fiber.
(6) The polyester composite fiber according to any one of (1) to (5), which exhibits a degree of biodegradation of 60% or more in 45 days in a compost test according to JIS K 6953.
本発明のポリエステル複合繊維は、ポリ乳酸成分を構成成分としながらも、強度、耐摩耗性、耐湿熱分解性に優れており、衣料、産業資材用途等に幅広く用いることが可能となる。
中でも、機械捲縮を有している本発明のポリエステル複合繊維は、紡績糸や不織布用等に好適に使用することができる。
スパイラル捲縮を有している本発明のポリエステル複合繊維は、嵩高性が要求される用途として、詰め綿やクッション材に好適に使用することができる。
潜在（スパイラル）捲縮性能を有している本発明のポリエステル複合繊維は、操業性よく伸縮性に優れた不織布や織編物等の布帛を得ることができる。
さらに、コンポストでの生分解性に優れた本発明のポリエステル複合繊維は、使用時は十分な強度、耐湿熱分解性を有していながら、使用後は速やかに分解するので特に地球環境に優しい繊維となる。
The polyester composite fiber of the present invention is excellent in strength, wear resistance, and moisture and heat decomposability while having a polylactic acid component as a constituent component, and can be widely used for clothing, industrial materials and the like.
Among these, the polyester composite fiber of the present invention having mechanical crimps can be suitably used for spun yarns and nonwoven fabrics.
The polyester composite fiber of the present invention having spiral crimps can be suitably used for stuffed cotton and cushion materials as an application requiring bulkiness.
The polyester composite fiber of the present invention having a latent (spiral) crimping performance can provide a fabric such as a nonwoven fabric or a woven or knitted fabric with excellent operability and excellent stretchability.
Furthermore, the polyester composite fiber of the present invention, which is excellent in biodegradability in compost, is a fiber that is particularly friendly to the global environment because it decomposes quickly after use, while having sufficient strength and resistance to moist heat decomposition during use. It becomes.
以下、本発明を詳細に説明する。
本発明のポリエステル複合繊維は、横断面形状が芯鞘形状を呈する芯鞘型複合繊維であって、鞘部が芳香族ポリエステル、芯部がポリ乳酸で構成されている。本発明のポリエステル複合繊維は単繊維形状を示すものであるので、本発明のポリエステル複合繊維（単繊維）を複数本集合させた繊維として、長繊維や短繊維として使用することができる。また、複数本集合させることなくモノフィラメントとして用いてもよい。
Hereinafter, the present invention will be described in detail.
The polyester composite fiber of the present invention is a core-sheath type composite fiber having a cross-sectional shape of a core-sheath shape, wherein the sheath part is composed of aromatic polyester and the core part is composed of polylactic acid. Since the polyester composite fiber of the present invention exhibits a single fiber shape, it can be used as a long fiber or a short fiber as a fiber in which a plurality of the polyester composite fibers (single fibers) of the present invention are assembled. Moreover, you may use as a monofilament, without making multiple sets gather.
本発明のポリエステル複合繊維の芯部を構成するポリ乳酸としては、ポリＤ−乳酸、ポリＬ−乳酸、ポリＤ−乳酸とポリＬ−乳酸との共重合体であるポリＤＬ−乳酸、ポリＤ−乳酸とポリＬ−乳酸との混合物（ステレオコンプレックス）、ポリＤ−乳酸とヒドロキシカルボン酸との共重合体、ポリＬ−乳酸とヒドロキシカルボン酸との共重合体、ポリＤ−乳酸又はポリＬ−乳酸と脂肪族ジカルボン酸及び脂肪族ジオールとの共重合体、あるいはこれらのブレンド体とすることが好ましい。 Polylactic acid constituting the core of the polyester composite fiber of the present invention includes poly-D-lactic acid, poly-L-lactic acid, poly-DL-lactic acid that is a copolymer of poly-D-lactic acid and poly-L-lactic acid, and poly-D. -Lactic acid and poly L-lactic acid mixture (stereo complex), poly D-lactic acid and hydroxycarboxylic acid copolymer, poly L-lactic acid and hydroxycarboxylic acid copolymer, poly D-lactic acid or poly L -It is preferable to use a copolymer of lactic acid, aliphatic dicarboxylic acid and aliphatic diol, or a blend thereof.
そして、ポリ乳酸は、上記のようにＬ−乳酸とＤ−乳酸が単独で用いられているもの、もしくは併用されているものであるが、中でも融点が１２０℃以上、融解熱が１０Ｊ／ｇ以上であることが好ましい。 The polylactic acid is one in which L-lactic acid and D-lactic acid are used alone or in combination as described above. Among them, the melting point is 120 ° C. or more, and the heat of fusion is 10 J / g or more. It is preferable that
ポリ乳酸のホモポリマーであるＬ−乳酸やＤ−乳酸の融点は約180℃であるが、Ｄ−乳酸とＬ−乳酸との共重合体の場合、いずれかの成分の割合を１０モル％程度とすると、融点はおよそ１３０℃程度となる。さらに、いずれかの成分の割合を１８モル％以上とすると、融点は１２０℃未満、融解熱は１０Ｊ／ｇ未満となって、ほぼ完全に非晶性の性質となる。このような非晶性のポリマーとなると、製造工程において特に熱延伸し難くなり、高強度の繊維が得られ難くくなるという問題が生じたり、繊維が得られたとしても、耐熱性、耐摩耗性に劣ったものとなるため好ましくない。 The melting point of L-lactic acid and D-lactic acid, which are homopolymers of polylactic acid, is about 180 ° C., but in the case of a copolymer of D-lactic acid and L-lactic acid, the proportion of any component is about 10 mol%. Then, the melting point is about 130 ° C. Furthermore, when the proportion of any of the components is 18 mol% or more, the melting point is less than 120 ° C. and the heat of fusion is less than 10 J / g, which is almost completely amorphous. When such an amorphous polymer is used, it becomes difficult to heat-stretch particularly in the production process, and it becomes difficult to obtain high-strength fibers, and even if fibers are obtained, heat resistance, abrasion resistance Since it becomes inferior in property, it is not preferable.
そこで、ポリ乳酸としては、ラクチドを原料として重合する時のＬ−乳酸やＤ−乳酸の含有割合で示されるＬ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが、８２／１８以上のものが好ましく、中でも９０／１０以上、さらには９５／１５以上とすることが好ましい。 Therefore, as polylactic acid, L / D or D / which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid indicated by the content ratio of L-lactic acid or D-lactic acid when polymerizing using lactide as a raw material. L is preferably 82/18 or more, more preferably 90/10 or more, and even more preferably 95/15 or more.
また、ポリ乳酸の中でも、上記したようなポリＤ−乳酸とポリＬ−乳酸との混合物（ステレオコンプレックス）は、融点が200〜230℃と高く、布帛にした後の高温染色やアイロン加工も可能となり、特に好ましい。 Among polylactic acids, the mixture of poly D-lactic acid and poly L-lactic acid (stereo complex) as described above has a high melting point of 200-230 ° C, and can be dyed at high temperatures and ironed after being made into a fabric. And is particularly preferable.
ポリ乳酸とヒドロキシカルボン酸の共重合体である場合は、ヒドロキシカルボン酸の具体例としてはグリコール酸、ヒドロキシ酪酸、ヒドロキシ吉草酸、ヒドロキシカプロン酸、ヒドロキシペンタン酸、ヒドロキシヘプタン酸、ヒドロキシオクタン酸等が挙げられる。中でもヒドロキシカプロン酸またはグリコール酸を用いることがコスト面からも好ましい。 In the case of a copolymer of polylactic acid and hydroxycarboxylic acid, specific examples of hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxypentanoic acid, hydroxyheptanoic acid, hydroxyoctanoic acid, etc. Can be mentioned. Of these, the use of hydroxycaproic acid or glycolic acid is preferable from the viewpoint of cost.
ポリ乳酸と脂肪族ジカルボン酸及び脂肪族ジオールとの共重合体の場合は、脂肪族ジカルボン酸及び脂肪族ジオールとしては、セバシン酸、アジピン酸、ドデカン二酸、トリメチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール等が挙げられる。 In the case of a copolymer of polylactic acid, aliphatic dicarboxylic acid and aliphatic diol, the aliphatic dicarboxylic acid and aliphatic diol include sebacic acid, adipic acid, dodecanedioic acid, trimethylene glycol, 1,4-butane. Diol, 1,6-hexanediol, etc. are mentioned.
このようにポリ乳酸に他の成分を共重合させる場合は、ポリ乳酸を８０モル％以上とすることが好ましい。８０モル％未満であると、共重合ポリ乳酸の結晶性が低くなり、融点１２０℃未満、融解熱１０Ｊ／ｇ未満となりやすい。 Thus, when making polylactic acid copolymerize another component, it is preferable that polylactic acid shall be 80 mol% or more. If it is less than 80 mol%, the crystallinity of the copolymerized polylactic acid tends to be low, and the melting point is less than 120 ° C. and the heat of fusion is less than 10 J / g.
また、ポリ乳酸の分子量としては、分子量の指標として用いられるASTM D−1238法に準じ、温度２１０℃、荷重2160gで測定したメルトフローレートが、１〜１００（ｇ／１０分）であることが好ましく、より好ましくは５〜５０（ｇ／１０分）である。メルトフローレートをこの範囲とすることにより、強度、湿熱分解性、耐摩耗性が向上する。 In addition, the molecular weight of polylactic acid is 1 to 100 (g / 10 min) as measured by a temperature of 210 ° C. and a load of 2160 g according to the ASTM D-1238 method used as an index of molecular weight. More preferably, it is 5-50 (g / 10min). By setting the melt flow rate within this range, strength, wet heat decomposability, and wear resistance are improved.
また、ポリ乳酸の耐久性を高める目的で、ポリ乳酸に脂肪族アルコール、カルボジイミド化合物、オキサゾリン化合物、オキサジン化合物、エポキシ化合物などの末端封鎖剤を添加してもよい。 For the purpose of enhancing the durability of polylactic acid, a terminal blocking agent such as an aliphatic alcohol, a carbodiimide compound, an oxazoline compound, an oxazine compound, or an epoxy compound may be added to polylactic acid.
さらに、本発明の目的を損なわない範囲であれば、必要に応じて、ポリ乳酸中に熱安定剤、結晶核剤、艶消剤、顔料、耐光剤、耐候剤、滑剤、酸化防止剤、抗菌剤、香料、可塑剤、染料、界面活性剤、難燃剤、表面改質剤、各種無機及び有機電解質、その他類似の添加剤を添加してもよい。 Furthermore, as long as it does not impair the purpose of the present invention, a heat stabilizer, a crystal nucleating agent, a matting agent, a pigment, a light-proofing agent, a weathering agent, a lubricant, an antioxidant, an antibacterial agent are included in polylactic acid as necessary. Agents, fragrances, plasticizers, dyes, surfactants, flame retardants, surface modifiers, various inorganic and organic electrolytes, and other similar additives may be added.
次に、本発明のポリエステル複合繊維の鞘部を構成する芳香族ポリエステルとしては、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、ポリトリメチレンテレフタレートなどのポリアルキレンテレフタレートを主体としたポリエステルであって、イソフタル酸、５−スルホイソフタル酸などの芳香族ジカルボン酸、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，４−シクロヘキサンジメタノールなどの脂肪族ジオールの少なくともいずれか一方を共重合させることが必要である。 Next, the aromatic polyester constituting the sheath of the polyester composite fiber of the present invention is a polyester mainly composed of polyalkylene terephthalate such as polyethylene terephthalate (PET), polybutylene terephthalate, polytrimethylene terephthalate, and the like. acid, 5-sulfo aromatic dicarboxylic acids such as isophthalic acid, d Ji glycol, propylene glycol, 1,4-butanediol, be copolymerized with at least one of aliphatic diols such as 1,4-cyclohexane dimethanol is required.
本発明の芳香族ポリエステルとしては、芳香族ジカルボン酸成分が全酸成分である芳香族ポリエステルであることが必要である。芳香族ジカルボン酸成分以外の酸成分が含有されている場合には、芳香族ポリエステルの耐湿熱分解性、耐候性などが低下しやすくなる。 The aromatic polyesters of the present invention, it is necessary that Kaoru aromatic dicarboxylic acid component is an aromatic polyester is the total acid components min. When an acid component other than the aromatic dicarboxylic acid component is contained , the wet heat decomposition resistance and weather resistance of the aromatic polyester are likely to deteriorate.
また、芳香族ポリエステルの融点は、芯部のポリ乳酸との融点差が大きすぎると、複合紡糸に際して紡糸操業性を阻害したり、ポリ乳酸の熱分解を引き起こすことがあるので、融点が２００〜２５５℃程度のものを用いることが好ましく、芯部のポリ乳酸の融点との差は０〜６０℃とすることが必要である。 The melting point of the aromatic polyester is such that if the difference in melting point from the polylactic acid in the core is too large, the spinning operability may be hindered during composite spinning or the thermal decomposition of the polylactic acid may occur. It is preferable to use one having a temperature of about 255 ° C., and the difference from the melting point of the polylactic acid in the core is required to be 0 to 60 ° C.
このような融点を有し、芳香族ジカルボン酸成分が全酸成分である芳香族ポリエステルとしては、イソフタル酸を共重合したＰＥＴ、ポリトリメチレンテレフタレート（ホモポリエステル）、ポリブチレンテレフタレート（ホモポリエステル）を用いることが好ましい。 Having such a melting point, as the aromatic polyester aromatic dicarboxylic acid component is whole acid components fraction, PET obtained by copolymerizing isophthalic acid, polytrimethylene terephthalate (homopolyester), polybutylene terephthalate (homopolyester) Is preferably used.
また、芳香族ポリエステル中にも、本発明の目的を損なわない範囲であれば、必要に応じて、熱安定剤、結晶核剤、艶消剤、顔料、耐光剤、耐候剤、滑剤、酸化防止剤、抗菌剤、香料、可塑剤、染料、界面活性剤、難燃剤、表面改質剤、各種無機及び有機電解質、その他類似の添加剤を添加することができる。 Also, in the aromatic polyester, as long as the purpose of the present invention is not impaired, a thermal stabilizer, a crystal nucleating agent, a matting agent, a pigment, a light-resistant agent, a weathering agent, a lubricant, an antioxidant, if necessary. Agents, antibacterial agents, fragrances, plasticizers, dyes, surfactants, flame retardants, surface modifiers, various inorganic and organic electrolytes, and other similar additives can be added.
次に、本発明のポリエステル複合繊維の形状について説明する。本発明のポリエステル複合繊維は、横断面形状、すなわち、繊維の長さ方向に対して垂直に切断した断面の形状が芯鞘形状を呈する芯鞘型複合繊維であって、上記のような芳香族ポリエステルが鞘部に配され、ポリ乳酸が芯部に配されている。芳香族ポリエステルが鞘部に配されるということは、繊維の表面全体を芳香族ポリエステルが覆うように配置されていることであるが、このとき、芯部は１つであっても複数であってもよい。つまり、芯鞘形状としては、芯部が１つである同心芯鞘型や偏心芯鞘型、芯部が複数個である海島型等の複合形態のものが挙げられる。 Next, the shape of the polyester composite fiber of the present invention will be described. The polyester conjugate fiber of the present invention is a core-sheath type conjugate fiber in which a cross-sectional shape, that is, a shape of a cross-section cut perpendicularly to the length direction of the fiber exhibits a core-sheath shape, and is aromatic as described above Polyester is disposed on the sheath and polylactic acid is disposed on the core. The fact that the aromatic polyester is arranged in the sheath means that the entire surface of the fiber is covered with the aromatic polyester, but at this time, even if there is one core, there are a plurality of cores. May be. In other words, examples of the core-sheath shape include composite forms such as a concentric core-sheath type having one core part, an eccentric core-sheath type, and a sea-island type having a plurality of core parts.
このような芯鞘型の複合形状とすることにより、芳香族ポリエステルがポリ乳酸の劣る性能である強度や耐湿熱分解性、耐摩耗性等をカバーできるので、繊維全体として強度や耐湿熱分解性、耐摩耗性に優れたものとなる。 By adopting such a core-sheath type composite shape, the aromatic polyester can cover the inferior performance of polylactic acid, such as strength, moisture pyrolysis resistance, wear resistance, etc., so the strength and moisture pyrolysis resistance of the whole fiber It is excellent in wear resistance.
上記のような芯鞘型の複合形状を呈していれば、本発明の複合繊維は丸断面に限定されるものではなく、扁平断面、多角形、多葉形、ひょうたん形、アルファベット形（Ｔ型、Ｙ型等）、井型等の各種の異形のものであってもよい。また、これらの形状において中空部を有するものでもよい。 If the core-sheath type composite shape as described above is exhibited, the composite fiber of the present invention is not limited to a round cross section, but a flat cross section, a polygonal shape, a multileaf shape, a gourd shape, an alphabet shape (T type) , Y type, etc.), various types of irregular shapes such as a well type. Moreover, you may have a hollow part in these shapes.
そして、本発明のポリエステル複合繊維は、中でも以下の（Ａ）〜（Ｃ）の形状のものとすることが好ましい。
（Ａ）芯部と鞘部がほぼ同心円上に配置された同心芯鞘型の複合繊維であって、機械捲縮が付与されている。
（Ｂ）芯部と鞘部が偏心的に配置された偏心芯鞘型の複合繊維であって、捲縮数が５個／２５ｍｍ以上、捲縮率が８％以上を同時に満足するスパイラル捲縮を有している。
（Ｃ）芯部と鞘部が偏心的に配置された偏心芯鞘型の複合繊維であって、１５０℃乾熱処理後に５０個／２５ｍｍ以上のスパイラル捲縮を発現する潜在捲縮性能を有している。
And it is preferable that especially the polyester composite fiber of this invention shall be a thing of the shape of the following (A)-(C).
(A) A concentric core-sheath type composite fiber in which a core part and a sheath part are arranged substantially concentrically, and mechanical crimps are imparted.
(B) Eccentric core-sheath type composite fiber in which the core part and the sheath part are eccentrically arranged, and the spiral crimp that satisfies the crimp number of 5/25 mm or more and the crimp rate of 8% or more simultaneously. have.
(C) An eccentric core-sheath type composite fiber in which a core part and a sheath part are arranged eccentrically, and has a latent crimping performance that exhibits 50/25 mm or more spiral crimps after dry heat treatment at 150 ° C. ing.
まず、（Ａ）の形状を有するポリエステル複合繊維について説明する。図１は、（Ａ）の形状を有するポリエステル複合繊維の一実施態様を示す横断面図である。（Ａ）の形状において、ほぼ同心円上に配置されている同心芯鞘型とは、鞘部の形状と芯部の形状が異なる場合（例えば、鞘部が丸型形状、芯部が四角形状）であっても、それぞれの中心（重心）点がほぼ一致するように配置されているものをいう。 First, the polyester composite fiber having the shape (A) will be described. FIG. 1 is a cross-sectional view showing an embodiment of a polyester composite fiber having the shape of (A). In the shape of (A), when the shape of the sheath part and the shape of the core part are different from the concentric core-sheath type arranged substantially concentrically (for example, the sheath part is round and the core part is square) Even so, the center (center of gravity) points are arranged so as to substantially coincide with each other.
また、このような形状において、鞘部の最も厚い部分の厚みをａとし、最も薄い部分の厚みをｂとして、偏心度＝ａ／ｂとした場合に、偏心度が２．０以下となるようにすることが好ましく、中でも１．５以下となるようにすることが好ましい。 In such a shape, when the thickness of the thickest part of the sheath is a, the thickness of the thinnest part is b, and the degree of eccentricity is a / b, the degree of eccentricity is 2.0 or less. It is preferable to set it to 1.5 or less.
なお、鞘部の厚みは、光学顕微鏡にて繊維の横断面（繊維の長さ方向に対して垂直に切断した断面）を５００倍で撮影し、顕微鏡写真より測定したものであり、ｎ＝２０の平均値とする。 In addition, the thickness of the sheath part was measured by taking a cross section of the fiber (cross section cut perpendicularly to the length direction of the fiber) with an optical microscope at a magnification of 500, and measured from a micrograph, n = 20 The average value of
（Ａ）の形状における芯鞘複合比率は、鞘部が繊維表面全体を覆うためには、質量比率（芯／鞘）で２０／８０〜８０／２０とすることが好ましい。 The core / sheath composite ratio in the shape of (A) is preferably 20/80 to 80/20 in mass ratio (core / sheath) so that the sheath part covers the entire fiber surface.
そして、（Ａ）の形状を有するポリエステル複合繊維は、機械捲縮が付与されたものである。機械捲縮とは、押し込み式クリンパーやスタフィングボックス等の捲縮付与装置により捲縮を付与されたものをいい、通常、これらの捲縮付与装置によると山部と谷部が連続して存在するジグザグ状の捲縮が付与される。捲縮付与装置により付与する捲縮数は５個／２５ｍｍ〜２５個／２５ｍｍとすることが好ましく、捲縮率は５〜３０％とすることが好ましい。 And the polyester composite fiber which has a shape of (A) is a thing to which the mechanical crimp was provided. Mechanical crimps are those that have been crimped by a crimping device such as a push-in crimper or a stuffing box. Normally, these crimping devices have continuous peaks and valleys. Zigzag crimps are applied. The number of crimps applied by the crimp application device is preferably 5/25 mm to 25/25 mm, and the crimp rate is preferably 5 to 30%.
このような（Ａ）の形状を有するポリエステル複合繊維は、紡績糸や不織布用途に適しており、本発明のポリエステル複合繊維を数千〜数百万本を集合させた繊維束とし、繊維長５〜１５０ｍｍ程度の短繊維として用いることが好ましい。また、本発明の複合繊維は単独で用いてもよいが、他の繊維と混用する用途にも適しており、混紡、交撚、精紡交撚を行ったり、交織、交編して用いてもよい。混用する他の繊維としては、ポリエステル、ナイロン、アクリル、アラミド等の合成繊維、ビスコース、キュプラ、ポリノジック等のレーヨン系繊維、リヨセル等の溶剤紡糸セルロース繊維、絹、綿、麻、羊毛その他の獣毛繊維が挙げられる。 The polyester composite fiber having such a shape (A) is suitable for use in spun yarns and nonwoven fabrics. The polyester composite fiber of the present invention is made into a fiber bundle in which several thousand to several millions are assembled, and the fiber length is 5 It is preferably used as a short fiber of about ~ 150 mm. In addition, the composite fiber of the present invention may be used alone, but is also suitable for use with other fibers, and is used by mixing, knitting, fine spinning, knitting, knitting, knitting. Also good. Other fibers that can be mixed include synthetic fibers such as polyester, nylon, acrylic and aramid, rayon fibers such as viscose, cupra and polynosic, solvent-spun cellulose fibers such as lyocell, silk, cotton, hemp, wool and other beasts. A hair fiber is mentioned.
このような用途に適するものとしては、本発明の複合繊維の繊度（単繊維繊度）は１〜１００dtexとすることが好ましい。 As suitable for such applications, the fineness (single fiber fineness) of the composite fiber of the present invention is preferably 1 to 100 dtex.
（Ａ）の形状を有する本発明のポリエステル複合繊維の製造方法について、上記したような数千〜数百万本を集合させた繊維束とし、短繊維とする場合の製造例を用いて説明する。ポリ乳酸と芳香族ポリエステルを通常の複合紡糸装置（同心芯鞘型の複合紡糸装置）を用いて溶融紡糸し、冷却、油剤を付与した後、延伸することなく一旦巻取る。この未延伸糸を数十万〜二百万dtexのトウに集束して、延伸倍率２〜５倍、延伸温度４０〜８０℃で延伸を行い、８０〜１６０℃で熱処理を施す。続いて、押し込み式クリンパーにより機械捲縮を施した後、ＥＣカッター等のカッターで目的とする長さに切断して短繊維とする。 The manufacturing method of the polyester composite fiber of the present invention having the shape of (A) will be described with reference to a manufacturing example in the case where the above-described fiber bundle is assembled from several thousand to several millions, and short fibers are used. . Polylactic acid and aromatic polyester are melt-spun using a normal composite spinning device (concentric core-sheath type composite spinning device), cooled, provided with an oil agent, and then wound up without stretching. The undrawn yarn is focused on a tow of several hundred thousand to two million dtex, drawn at a draw ratio of 2 to 5 times, a draw temperature of 40 to 80 ° C., and subjected to heat treatment at 80 to 160 ° C. Subsequently, after mechanical crimping by a push-in type crimper, it is cut into a target length with a cutter such as an EC cutter to obtain short fibers.
なお、長繊維とする際には、未延伸糸（マルチフィラメント状）を巻き取った後、トウとして集束することなく延伸を施すか、もしくは未延伸糸のまま、撚糸や仮撚加工等を行って加工糸を得る方法がある。 In addition, when making a long fiber, after winding an unstretched yarn (multifilament shape), it is stretched without converging as a tow, or the unstretched yarn is subjected to twisting or false twisting. There is a method to obtain processed yarn.
次に、（Ｂ）の形状を有するポリエステル複合繊維について説明する。図２は、（Ｂ）の形状を有するポリエステル複合繊維の一実施態様を示す横断面図である。（Ｂ）の形状において、芯部と鞘部が偏心的に配置されているとは、鞘部の形状と芯部の形状が同じ場合や異なる場合（例えば、鞘部が丸型形状、芯部が四角形状）において、それぞれの中心（重心）点が一致していない状態で配置されているものをいう。そして、（Ａ）の形状において前記したように、鞘部の最も厚い部分の厚みをａとし、最も薄い部分の厚みをｂとしたときの偏心度＝ａ／ｂにおいて、偏心度が２．０以上となるようにすることが好ましく、中でも３．０以上、さらには４．０以上であることが好ましい。 Next, the polyester composite fiber having the shape (B) will be described. FIG. 2 is a cross-sectional view showing one embodiment of a polyester composite fiber having the shape (B). In the shape of (B), when the core part and the sheath part are arranged eccentrically, the shape of the sheath part and the shape of the core part are the same or different (for example, the sheath part has a round shape, the core part) In the shape of a quadrangle), the center (center of gravity) points are not aligned. As described above in the shape of (A), when the thickness of the thickest portion of the sheath is a and the thickness of the thinnest portion is b, the eccentricity is 2.0 when the eccentricity is a / b. It is preferable to make it above, and among them, it is preferably 3.0 or more, more preferably 4.0 or more.
なお、偏心度が大きくなりすぎると、紡糸操業性が悪化したり、強度等の物性が低下しやすいため、偏心度は１０．０以下とすることが好ましい。 If the degree of eccentricity becomes too large, the spinning operability is deteriorated and physical properties such as strength are easily lowered. Therefore, the degree of eccentricity is preferably 10.0 or less.
このように、芳香族ポリエステルとポリ乳酸を偏心的に複合させることで、両ポリマーの粘度差や熱収縮差によってスパイラル捲縮を発現させることができる。つまり、スパイラル捲縮とは、コイル（螺旋）状の微細な捲縮であって、三次元的な立体捲縮のことであり、上記（Ａ）の形状のように捲縮付与装置により機械捲縮を付与したものとは形状が異なるものである。
偏心度が２．０より小さいと、スパイラル捲縮の発現性が悪くなるため好ましくない。
Thus, by crimping the aromatic polyester and polylactic acid in an eccentric manner, spiral crimps can be expressed by the difference in viscosity or thermal contraction between the two polymers. That is, the spiral crimp is a coil (spiral) -like fine crimp, which is a three-dimensional solid crimp, and is mechanically crimped by a crimp imparting device as in the shape of (A) above. The shape is different from that of the contracted one.
If the degree of eccentricity is less than 2.0, the expression of spiral crimps is deteriorated, which is not preferable.
（Ｂ）の形状を有するポリエステル複合繊維は、このような立体的なスパイラル捲縮を有することから、嵩高性に優れており、クッション材や詰め綿用途に適している。また、このような用途に用いる際には、本発明のポリエステル複合繊維を数千〜数百万本を集合させた繊維束とし、繊維長５〜１５０ｍｍ程度の短繊維として用いることが好ましい。 Since the polyester composite fiber having the shape (B) has such a three-dimensional spiral crimp, it is excellent in bulkiness and is suitable for cushioning materials and stuffed cotton applications. Moreover, when using for such a use, it is preferable to use the polyester composite fiber of this invention as a fiber bundle which aggregated several thousand to several million, and to use as a short fiber about 5-150 mm in fiber length.
本発明のポリエステル複合繊維のスパイラル捲縮は、捲縮数が５個／２５ｍｍ以上であることが好ましく、中でも６個／２５ｍｍ〜３０個／２５ｍｍ、さらには７個／２５ｍｍ〜２０個／２５ｍｍであることが好ましい。また、捲縮率は８％以上であることが好ましく、中でも１０〜４０％、さらには１５〜３０％であることが好ましい。 The spiral crimp of the polyester composite fiber of the present invention preferably has a number of crimps of 5 pieces / 25 mm or more, particularly 6 pieces / 25 mm to 30 pieces / 25 mm, and more preferably 7 pieces / 25 mm to 20 pieces / 25 mm. Preferably there is. The crimp rate is preferably 8% or more, more preferably 10 to 40%, and further preferably 15 to 30%.
スパイラル捲縮の数が５個／２５ｍｍより少なかったり、捲縮率が８％未満であると、嵩高性が乏しくなり、クッション性が低下したり、カード通過性が悪くなりやすい。 When the number of spiral crimps is less than 5 pieces / 25 mm or the crimp rate is less than 8%, the bulkiness is poor, the cushioning property is lowered, and the card passing property is liable to be deteriorated.
（Ｂ）の形状を有するポリエステル複合繊維は、芳香族ポリエステルとポリ乳酸の粘度や共重合量及び複合繊維の偏心度を適宜調整することによって、上記範囲の捲縮数や捲縮率のものとすることができる。つまり、これらの性能差により複合繊維内でポリマーの収縮差が生じ、延伸や熱処理時にスパイラル捲縮が発現するものである。芳香族ポリエステル、ポリ乳酸のいずれが高収縮側、低収縮側であってもよい。なお、ポリ乳酸は芳香族ポリエステルに比較して、熱収縮が高い傾向にあるため、ポリ乳酸を高収縮側にする方が、製糸面、性能面で適している。 The polyester composite fiber having the shape of (B) has a number of crimps and a crimp rate in the above range by appropriately adjusting the viscosity and copolymerization amount of the aromatic polyester and polylactic acid and the eccentricity of the composite fiber. can do. That is, the difference in performance causes a difference in the shrinkage of the polymer in the composite fiber, and a spiral crimp is developed during stretching and heat treatment. Either aromatic polyester or polylactic acid may be on the high shrinkage side or the low shrinkage side. Since polylactic acid tends to have higher thermal shrinkage than aromatic polyester, it is more suitable in terms of yarn production and performance to make polylactic acid highly shrinkable.
ポリ乳酸を高収縮側とする場合、低収縮側となる芳香族ポリエステルの好ましい例としては、ＰＥＴを主体とし、かつ、他の共重合成分の共重合量が低い（共重合量が３０モル％以下）ものが好ましい。 When polylactic acid is used on the high shrink side, preferred examples of the aromatic polyester on the low shrink side include PET as a main component and a low copolymerization amount of other copolymer components (the copolymerization amount is 30 mol%). The following are preferred.
また、スパイラル捲縮を発現しやすくするために、芳香族ポリエステルの溶融粘度をポリ乳酸の溶融粘度よりも低くなるようにすることが好ましい。 Moreover, in order to make it easy to express spiral crimp, it is preferable to make the melt viscosity of the aromatic polyester lower than the melt viscosity of polylactic acid.
逆に、ポリ乳酸を低収縮側とする場合、芳香族ポリエステルを熱収縮性の高いポリマーとする必要がある。このような芳香族ポリエステルとしては、ＰＥＴにイソフタル酸や５−スルホイソフタル酸などを３０〜５０ｍｏｌ％共重合したものや、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート等のポリマーが挙げられる。 Conversely, when polylactic acid is used on the low shrinkage side, the aromatic polyester needs to be a polymer having high heat shrinkability. Examples of such aromatic polyesters include those obtained by copolymerizing 30 to 50 mol% of isophthalic acid or 5-sulfoisophthalic acid with PET, and polymers such as polybutylene terephthalate and polytrimethylene terephthalate.
ポリ乳酸を収縮性の低いものとするためには、Ｌ−乳酸もしくはＤ−乳酸の割合が９８モル％以上のポリ乳酸を用いることが好ましい。 In order to make polylactic acid low in contractility, it is preferable to use polylactic acid having a ratio of L-lactic acid or D-lactic acid of 98 mol% or more.
また、スパイラル捲縮を発現しやすくするために、芳香族ポリエステルの溶融粘度をポリ乳酸の溶融粘度よりも高くなるようにすることが好ましい。 Moreover, in order to make it easy to express spiral crimp, it is preferable to make the melt viscosity of the aromatic polyester higher than the melt viscosity of polylactic acid.
（Ｂ）の形状を有するポリエステル複合繊維においては、芯鞘複合比率は、捲縮発現性、コスト、操業性の面から、質量比率（芯／鞘）で３０／７０〜７０／３０とすることが好ましい。 In the polyester composite fiber having the shape of (B), the core / sheath composite ratio is 30/70 to 70/30 in terms of mass ratio (core / sheath) in terms of crimp development, cost, and operability. Is preferred.
ポリエステル複合繊維の繊度（単繊維繊度）としては、クッション性能、生産性、操業安定性等を考慮して、１．０〜８０ｄｔｅｘ程度が好ましく、５．０〜４０ｄｔｅｘがより好ましい。 The fineness (single fiber fineness) of the polyester composite fiber is preferably about 1.0 to 80 dtex, more preferably 5.0 to 40 dtex in consideration of cushion performance, productivity, operational stability, and the like.
（Ｂ）の形状を有するポリエステル複合繊維においては、上記のような芯鞘形状やポリマー組成とすることにより、スパイラル捲縮を発現、調整できるものであるが、このようなスパイラル捲縮は製造工程において発現させるものであるので、特に延伸温度や延伸倍率の影響を受ける。このため、スパイラル捲縮を十分に発現させるためにはこれらの条件を適切に選定することも重要である。 In the polyester composite fiber having the shape of (B), the spiral crimp can be expressed and adjusted by using the core-sheath shape and the polymer composition as described above, but such a spiral crimp is a manufacturing process. In particular, it is influenced by the stretching temperature and the stretching ratio. For this reason, it is also important to select these conditions appropriately in order to fully manifest the spiral crimp.
次に、（Ｂ）の形状を有する本発明のポリエステル複合繊維の製造方法について、上記したような数千〜数百万本を集合させた繊維束とし、短繊維とする場合の製造例を用いて説明する。まず、ポリ乳酸と芳香族ポリエステルを通常の複合紡糸装置を用いて溶融紡糸し、冷却、油剤を付与した後、延伸することなく一旦巻取る。この未延伸糸を数十万〜二百万dtexのトウに集束して、延伸倍率２〜５倍、延伸温度４０〜８０℃で延伸を行うことによってスパイラル捲縮を発現させ、仕上げ油剤を付与後、７０℃〜１８０℃で乾燥熱処理を施す。そして、ＥＣカッター等のカッターで目的とする長さに切断して短繊維とする。 Next, about the manufacturing method of the polyester composite fiber of this invention which has the shape of (B), it is set as the fiber bundle which gathered thousands-millions as mentioned above, and the manufacture example in the case of setting it as a short fiber is used. I will explain. First, polylactic acid and aromatic polyester are melt-spun using an ordinary composite spinning device, cooled, provided with an oil agent, and then wound up without stretching. This undrawn yarn is focused on a tow of several hundred thousand to two million dtex, and is drawn at a draw ratio of 2 to 5 times and a draw temperature of 40 to 80 ° C. to express a spiral crimp and give a finishing oil. Thereafter, a drying heat treatment is performed at 70 to 180 ° C. And it cut | disconnects to the target length with cutters, such as EC cutter, and is set as a short fiber.
上記のように、本発明のポリエステル複合繊維は、製造工程時（延伸を施すことによって延伸直後）にスパイラル捲縮を発現させる、いわゆる顕在捲縮タイプである。そして、本発明のポリエステル複合繊維から得られる製品の寸法安定性を良好とするために、製品とした後に顕在化されずに残った捲縮が発現することを抑えることが好ましい。製品とした後の捲縮の発現を抑制する方法としては、製造時にスパイラル捲縮を発現させた後に、乾燥機などで熱処理を行うことが好ましい。熱処理温度としては７０℃〜１８０℃が好ましく、中でも１００℃から１５０℃が好ましい。 As described above, the polyester conjugate fiber of the present invention is a so-called manifested crimp type in which spiral crimps are developed during the manufacturing process (immediately after stretching by stretching). And in order to make the dimensional stability of the product obtained from the polyester composite fiber of the present invention good, it is preferable to suppress the occurrence of crimps that are not manifested after the product is produced. As a method for suppressing the occurrence of crimp after the product is produced, it is preferable to cause a heat treatment with a dryer or the like after the spiral crimp is developed at the time of production. As heat processing temperature, 70 to 180 degreeC is preferable, and 100 to 150 degreeC is especially preferable.
次に、（Ｃ）の形状を有するポリエステル複合繊維について説明する。（Ｃ）の形状を有するポリエステル複合繊維の一実施態様を示す横断面図は、図２と同様のものである。 Next, the polyester composite fiber having the shape (C) will be described. The cross-sectional view showing one embodiment of the polyester composite fiber having the shape of (C) is the same as FIG.
（Ｃ）の形状において、芯部と鞘部が偏心的に配置されているとは、（Ｂ）の形状において前記したように、鞘部の形状と芯部の形状が同じ場合や異なる場合（例えば、鞘部が丸型形状、芯部が四角形状）において、それぞれの中心（重心）点が一致していない状態で配置されているものをいう。そして、鞘部の最も厚い部分の厚みをａとし、最も薄い部分の厚みをｂとしたときの偏心度＝ａ／ｂにおいて、偏心度が２．０以上となるようにすることが好ましく、中でも３．０以上、さらには４．０以上であることが好ましい。 In the shape of (C), the core and the sheath are arranged eccentrically, as described above in the shape of (B), when the shape of the sheath and the shape of the core are the same or different ( For example, in the case where the sheath part is round and the core part is quadrilateral, the center (center of gravity) points are not aligned. And, when the thickness of the thickest part of the sheath part is a and the thickness of the thinnest part is b, it is preferable that the eccentricity is 2.0 or more at the eccentricity = a / b, It is preferably 3.0 or more, more preferably 4.0 or more.
なお、偏心度が大きくなりすぎると、紡糸操業性が悪化したり、強度等の物性が低下しやすいため、偏心度は１０．０以下とすることが好ましい。 If the degree of eccentricity becomes too large, the spinning operability is deteriorated and physical properties such as strength are easily lowered. Therefore, the degree of eccentricity is preferably 10.0 or less.
このように、芳香族ポリエステルとポリ乳酸を偏心的に複合することで、両ポリマーの粘度差や熱収縮差によって、１５０℃の乾熱処理後にスパイラル捲縮を発現する潜在捲縮性能を有するものとすることができる。ここで、スパイラル捲縮とは、上記（Ｂ）の形状のように、コイル（螺旋）状の微細な捲縮であって、三次元的な立体捲縮のことであり、上記（Ａ）の形状のように捲縮付与装置により機械捲縮を付与したものとは形状が異なるものである。 Thus, by having an eccentric composite of aromatic polyester and polylactic acid, it has a latent crimping performance that develops spiral crimping after dry heat treatment at 150 ° C. due to the difference in viscosity and thermal shrinkage of both polymers. can do. Here, the spiral crimp is a fine crimp of a coil (spiral) like the shape of (B) above, which is a three-dimensional solid crimp, Like the shape, the shape is different from that obtained by applying the mechanical crimp by the crimp applying device.
偏心度が２．０より小さいと、乾熱処理後のスパイラル捲縮の発現性が悪くなるため好ましくない。 If the degree of eccentricity is less than 2.0, the expression of spiral crimp after the dry heat treatment is deteriorated, which is not preferable.
本発明のポリエステル複合繊維は、１５０℃の乾熱処理によりスパイラル捲縮を発現するものであるが、１５０℃の乾熱処理とは、２ｍｇ／１dtexの荷重下で１５分間、１５０℃で熱処理を行うことである。 The polyester conjugate fiber of the present invention exhibits spiral crimping by a dry heat treatment at 150 ° C. The 150 ° C. dry heat treatment is a heat treatment at 150 ° C. for 15 minutes under a load of 2 mg / 1 dtex. It is.
１５０℃の乾熱処理で発現する捲縮数は、５０個／２５ｍｍ以上であることが好ましく、中でも６０個／２５ｍｍ〜１３０個／２５ｍｍ、さらには７０個／２５ｍｍ〜１１０個／２５ｍｍであることが好ましい。発現するスパイラル捲縮の数が５０個／２５ｍｍより少ないと、得られる織編物、不織布等の製品の伸縮性が乏しいものとなりやすい。 The number of crimps developed by dry heat treatment at 150 ° C. is preferably 50 pieces / 25 mm or more, more preferably 60 pieces / 25 mm to 130 pieces / 25 mm, and more preferably 70 pieces / 25 mm to 110 pieces / 25 mm. preferable. If the number of spiral crimps that develop is less than 50/25 mm, the resulting woven or knitted fabric, nonwoven fabric or other product tends to have poor stretchability.
このような（Ｃ）の形状を有するポリエステル複合繊維は、紡績糸や不織布用途に適しており、伸縮性に優れた織編物や不織布等の布帛を得ることができるものである。このような用途に用いる際には、本発明のポリエステル複合繊維を数千〜数百万本を集合させた繊維束とし、繊維長５〜１５０ｍｍ程度の短繊維として用いることが好ましい。また、本発明の複合繊維は、潜在捲縮性能が発現後、十分な伸縮性を有するため、紡績糸や不織布中の一部にのみ本発明の複合繊維を用い、他の繊維と混用しても、伸縮性に優れた製品とすることができる。 The polyester composite fiber having such a shape (C) is suitable for spun yarns and nonwoven fabrics, and can be used to obtain a fabric such as a woven or knitted fabric or a nonwoven fabric having excellent stretchability. When used in such applications, the polyester composite fiber of the present invention is preferably used as a short fiber having a fiber length of about 5 to 150 mm by collecting a bundle of thousands to millions of fibers. In addition, since the conjugate fiber of the present invention has sufficient stretchability after the latent crimping performance is expressed, the conjugate fiber of the present invention is used only in a part of the spun yarn and the nonwoven fabric and mixed with other fibers. Can also be made into a product with excellent elasticity.
混用する他の繊維としては、ポリエステル、ナイロン、アクリル、アラミド等の合成繊維、ビスコース、キュプラ、ポリノジック等のレーヨン系繊維、リヨセル等の溶剤紡糸セルロース繊維、絹、綿、麻、羊毛その他の獣毛繊維が挙げられる。 Other fibers that can be mixed include synthetic fibers such as polyester, nylon, acrylic and aramid, rayon fibers such as viscose, cupra and polynosic, solvent-spun cellulose fibers such as lyocell, silk, cotton, hemp, wool and other beasts. A hair fiber is mentioned.
（Ｃ）の形状を有するポリエステル複合繊維は、潜在捲縮性能が発現することによりスパイラル捲縮を有するものとなるが、潜在捲縮性能が発現する前の形状としては、短繊維とする場合には、梳綿工程でネップや未開繊部の発生がないものとすることが好ましいため、捲縮付与装置による機械捲縮が付与されていることが好ましい。 The polyester composite fiber having the shape of (C) has a spiral crimp when the latent crimping performance is exhibited, but the shape before the latent crimping performance is exhibited is a short fiber. Since it is preferable that there is no generation of a nep or an unopened part in the crimping step, it is preferable that mechanical crimping by a crimping device is applied.
ここでいう機械捲縮とは、上記の（Ａ）の形状を有する複合繊維で説明したものと同じであり、捲縮数が８個／２５ｍｍ〜１８個／２５ｍｍであることが好ましい。機械捲縮の捲縮数が８個／２５ｍｍ未満であると、未開繊部が発生しやすく、１８個／２５ｍｍを超えるとネップが発生しやすい。 The mechanical crimp here is the same as that described for the composite fiber having the shape (A), and the number of crimps is preferably 8 pieces / 25 mm to 18 pieces / 25 mm. When the number of crimps of mechanical crimp is less than 8 pieces / 25 mm, an unopened portion is likely to occur, and when it exceeds 18 pieces / 25 mm, nep is likely to occur.
（Ｃ）の形状を有するポリエステル複合繊維は、芳香族ポリエステルとポリ乳酸の粘度や共重合量及び複合繊維の偏心度を適宜調整することによって、熱処理により発現する捲縮数（潜在捲縮数）を上記範囲のものとすることができる。本発明のポリエステル複合繊維は、ポリマーの収縮差によって、熱処理後にスパイラル捲縮が発現するものであり、芳香族ポリエステル、ポリ乳酸のいずれが高収縮側、低収縮側であってもよい。なお、ポリ乳酸は芳香族ポリエステルに比較して、熱収縮が高い傾向にあるため、ポリ乳酸を高収縮側にする方が、製糸面、性能面で適している。 The polyester composite fiber having the shape of (C) has a number of crimps (latent number of crimps) expressed by heat treatment by appropriately adjusting the viscosity and copolymerization amount of the aromatic polyester and polylactic acid and the eccentricity of the composite fiber. Can be in the above range. The polyester conjugate fiber of the present invention exhibits spiral crimp after heat treatment due to a difference in shrinkage of the polymer, and either aromatic polyester or polylactic acid may be on the high shrinkage side or the low shrinkage side. Since polylactic acid tends to have higher thermal shrinkage than aromatic polyester, it is more suitable in terms of yarn production and performance to make polylactic acid highly shrinkable.
ポリ乳酸を高収縮側とする場合、低収縮側となる芳香族ポリエステルの好ましい例としては、ＰＥＴを主体とし、かつ、共重合量が低い（共重合量が３０モル％以下）ものが好ましい。 When polylactic acid is used on the high shrinkage side, a preferred example of the aromatic polyester on the low shrinkage side is preferably one having PET as a main component and a low copolymerization amount (copolymerization amount of 30 mol% or less).
また、スパイラル捲縮を発現しやすくするために、芳香族ポリエステルの溶融粘度をポリ乳酸の溶融粘度よりも低くなるようにすることが好ましい。 Moreover, in order to make it easy to express spiral crimp, it is preferable to make the melt viscosity of the aromatic polyester lower than the melt viscosity of polylactic acid.
逆に、ポリ乳酸を低収縮側とする場合、芳香族ポリエステルを熱収縮性の高いポリマーとする必要がある。このような芳香族ポリエステルとしては、ＰＥＴに、イソフタル酸や５−スルホイソフタル酸などを２０〜５０ｍｏｌ％共重合したものや、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート等のポリマーが挙げられる。 Conversely, when polylactic acid is used on the low shrinkage side, the aromatic polyester needs to be a polymer having high heat shrinkability. Examples of such aromatic polyesters include those obtained by copolymerizing PET with 20 to 50 mol% of isophthalic acid or 5-sulfoisophthalic acid, and polymers such as polybutylene terephthalate and polytrimethylene terephthalate.
ポリ乳酸を収縮性の低いものとするためには、Ｌ−乳酸もしくはＤ−乳酸の割合が９８モル％以上のポリ乳酸を用いることが好ましい。 In order to make polylactic acid low in contractility, it is preferable to use polylactic acid having a ratio of L-lactic acid or D-lactic acid of 98 mol% or more.
また、スパイラル捲縮を発現しやすくするために、芳香族ポリエステルの溶融粘度をポリ乳酸の溶融粘度よりも高くなるようにすることが好ましい。 Moreover, in order to make it easy to express spiral crimp, it is preferable to make the melt viscosity of the aromatic polyester higher than the melt viscosity of polylactic acid.
（Ｃ）の形状を有するポリエステル複合繊維においては、芯鞘複合比率は、捲縮発現性、コスト、操業性の面から、質量比率（芯／鞘）で３０／７０〜７０／３０とすることが好ましい。 In the polyester composite fiber having the shape of (C), the core / sheath composite ratio is 30/70 to 70/30 in terms of mass ratio (core / sheath) in terms of crimp development, cost, and operability. Is preferred.
本発明のポリエステル複合繊維の繊度（単繊維繊度）としては、得られる製品の伸縮性、生産性、操業安定性等を考慮して、１．０〜８０ｄｔｅｘ程度が好ましく、５．０〜４０ｄｔｅｘがより好ましい。 The fineness (single fiber fineness) of the polyester composite fiber of the present invention is preferably about 1.0 to 80 dtex, preferably 5.0 to 40 dtex in consideration of the stretchability, productivity, operational stability, and the like of the resulting product. More preferred.
（Ｃ）の形状を有する本発明のポリエステル複合繊維の製造方法について、上記したような数千〜数百万本を集合させた繊維束とし、短繊維とする場合の製造例を用いて説明する。まず、ポリ乳酸と芳香族ポリエステルを通常の複合紡糸装置を用いて溶融紡糸し、冷却、油剤を付与した後、延伸することなく一旦巻取る。この未延伸糸を数十万〜二百万dtexのトウに集束して、延伸倍率２〜５倍、延伸温度４０〜８０℃で延伸を行い、次に８０〜１６０℃で熱処理を施す。続いて、押し込み式クリンパーにより機械捲縮を施した後、ＥＣカッター等のカッターで目的とする長さに切断して短繊維とする。 About the manufacturing method of the polyester composite fiber of this invention which has the shape of (C), it is set as the fiber bundle which gathered several thousands-millions as mentioned above, and it demonstrates using the manufacture example in the case of setting it as a short fiber. . First, polylactic acid and aromatic polyester are melt-spun using an ordinary composite spinning device, cooled, provided with an oil agent, and then wound up without stretching. The undrawn yarn is focused on a tow of several hundred thousand to two million dtex, drawn at a draw ratio of 2 to 5 times, a draw temperature of 40 to 80 ° C., and then heat treated at 80 to 160 ° C. Subsequently, after mechanical crimping by a push-in type crimper, it is cut into a target length with a cutter such as an EC cutter to obtain short fibers.
なお、長繊維とする際には、未延伸糸（マルチフィラメント状）を巻き取った後、トウとして集束することなく延伸を施すか、もしくは未延伸糸のまま、撚糸や仮撚加工等を行って加工糸を得る方法がある。 In addition, when making a long fiber, after winding an unstretched yarn (multifilament shape), it is stretched without converging as a tow, or the unstretched yarn is subjected to twisting or false twisting. There is a method to obtain processed yarn.
なお、本発明のポリエステル複合繊維は、上記のように、繊維の製造工程時にスパイラル捲縮を発現させることなく、例えば、製品を得る工程において熱処理を施すことにより捲縮を発現させるものである、いわゆる潜在捲縮タイプである。製品によっては、製造する途中の工程でスパイラル捲縮を発現させると、ネップが発生しやすくなり、得られる製品の均斉度が悪くなったり、工程通過性が悪くなるものがある。このような場合には、製品にした最終の段階で熱処理を施すことにより潜在捲縮性能を発現させることが好ましい。 In addition, as described above, the polyester conjugate fiber of the present invention expresses crimps by, for example, applying heat treatment in a process of obtaining a product without expressing spiral crimps during the fiber manufacturing process. This is a so-called latent crimp type. Depending on the product, if spiral crimps are developed in the course of manufacturing, neps are likely to occur, resulting in poor uniformity of the product or poor processability. In such a case, it is preferable to develop latent crimping performance by performing a heat treatment in the final stage of the product.
本発明のポリエステル複合繊維は、100〜180℃の熱処理により捲縮が発現する。そこで、織編物とする際には染色や精練工程での熱処理において捲縮を発現させ、不織布とする際にはニードルパンチ処理やウオータージェット処理をした後の熱処理により発現させることが好ましい。 The polyester composite fiber of the present invention exhibits crimps by heat treatment at 100 to 180 ° C. Therefore, it is preferable that crimping is expressed in the heat treatment in the dyeing or scouring process when the knitted or knitted fabric is formed, and the heat treatment after the needle punching process or the water jet process is performed when forming the nonwoven fabric.
さらに、本発明のポリエステル複合繊維は、ＪＩＳ Ｋ ６９５３に準じるコンポスト試験において、処理期間４５日間で６０％以上の生分解度を示すことが好ましい。本発明のポリエステル複合繊維は、植物由来のポリ乳酸を一成分とする複合繊維でありながら、耐湿熱分解性、強度、耐摩耗性等に優れるものであるが、この生分解度を満足することによって、コンポスト処理による速やかな生分解性をも示すものとなる。 Furthermore, the polyester composite fiber of the present invention preferably exhibits a biodegradability of 60% or more in a treatment period of 45 days in a compost test according to JIS K 6953. Although the polyester composite fiber of the present invention is a composite fiber containing plant-derived polylactic acid as a component, it is excellent in moist heat resistance, strength, wear resistance, etc., but satisfies this biodegradability. By this, rapid biodegradability by composting is also shown.
ＪＩＳ Ｋ ６９５３とは、プラスチックの制御されたコンポスト条件下の好気的究極生分解度および崩壊度の求め方についての基準である。ＪＩＳ Ｋ ６９５３における生分解度が処理期間４５日間で６０％未満であると、コンポストの処理効率が悪くなるため好ましくない。 JIS K 6953 is a standard for determining the degree of aerobic ultimate biodegradation and disintegration under controlled composting conditions of plastics. If the biodegradation degree in JIS K 6953 is less than 60% in a treatment period of 45 days, the processing efficiency of compost deteriorates, which is not preferable.
コンポスト下での複合繊維の生分解度は、芳香族ポリエステル（鞘成分）の厚み（芯鞘比）、芳香族ポリエステルのポリマー組成、繊度等に影響されるので、上記したような（Ａ）〜（Ｃ）の形状を呈する複合繊維においても、後述するような好適な条件を適宜選択することが好ましい。 The degree of biodegradation of the composite fiber under compost is affected by the thickness (core-sheath ratio) of the aromatic polyester (sheath component), the polymer composition of the aromatic polyester, the fineness, and the like (A) to Also in the composite fiber exhibiting the shape of (C), it is preferable to appropriately select suitable conditions as described below.
まず、処理期間４５日間で６０％以上の生分解度を示すためには、鞘部を構成する芳香族ポリエステルの厚みを薄くする、すなわち鞘部の比率を低くすることが好ましく、質量比率（芯／鞘）を６０／４０〜９０／１０、中でも６０／４０〜８０／２０とすることが好ましい。 First, in order to show a biodegradability of 60% or more in a treatment period of 45 days, it is preferable to reduce the thickness of the aromatic polyester constituting the sheath, that is, to reduce the ratio of the sheath, and to reduce the mass ratio (core / Sheath) is preferably 60/40 to 90/10, and more preferably 60/40 to 80/20.
また、芯部と鞘部は、上記で定義する偏心度が６．０以下であることが好ましく、中でも３．０以下とすることが好ましい。偏心度が６．０より大きいと、鞘部の芳香族ポリエステルの厚みが厚い部分と、薄い部分の差が大きく、本発明の効果である、使用中の耐久性とコンポスト下での速やかな分解性を両立することが困難となる。すなわち、複合繊維の保管中、あるいは使用中において、鞘部の厚みが薄い部分が摩耗などによって浸食された場合、芯部のポリ乳酸成分が繊維表面に露出してしまうため、複合繊維の耐久性が劣るものになる。そして、鞘部の厚みが厚い箇所は、コンポスト時の分解に長期を要するため好ましくない。 Moreover, it is preferable that the eccentricity degree defined above is 6.0 or less, and it is preferable to set it as 3.0 or less especially in a core part and a sheath part. If the degree of eccentricity is greater than 6.0, the difference between the thick part and the thin part of the aromatic polyester in the sheath part is large, which is the effect of the present invention, durability during use and rapid decomposition under compost. It becomes difficult to achieve both properties. That is, when the composite fiber is being stored or used, when the thin sheath portion is eroded due to wear or the like, the polylactic acid component in the core is exposed to the fiber surface. Is inferior. And the location where the thickness of a sheath part is thick is unpreferable since decomposition | disassembly at the time of composting requires a long time.
コンポスト下での分解性に優れるものとするために、芳香族ポリエステルとして、ＰＥＴに全ジオール成分に対してブタンジオールを４０〜６０ｍｏｌ％共重合したもの、ＰＥＴに全酸成分に対して、イソフタル酸を２０〜５０ｍｏｌ％共重合したもの、ポリアルキレンテレフタレートに芳香族ジカルボン酸、脂肪族ジオールなどを共重合したものが好ましい。 In order to be excellent in decomposability under compost, aromatic polyester is obtained by copolymerizing PET with 40 to 60 mol% of butanediol with respect to the total diol component, and isophthalic acid with respect to the total acid component of PET. a material obtained by polymerizing 20 to 50 mol% both aromatic dicarboxylic acid polyalkylene down terephthalate, obtained by copolymerizing such fat aliphatic diols are preferred.
なお、これらの芳香族ポリエステルは、通常の環境下では、ほとんど分解しないにもかかわらず、コンポスト下でこれらの芳香族ポリエステルが分解されるというメカニズムは未だ明確になっていないが、本発明者等は以下のように考える。つまり、芳香族ポリエステルが加水分解しやすいポリ乳酸と複合されているので、ポリ乳酸がコンポスト下の湿熱作用によって加水分解されて生じる酸とアルコールが芳香族ポリエステルにも接触するため、これらの酸やアルコールの作用により芳香族ポリエステルの加水分解が促進され、低分子化合物となり、その後、微生物によって分解されると考えられる。 Although these aromatic polyesters are hardly decomposed under a normal environment, the mechanism that these aromatic polyesters are decomposed under compost has not yet been clarified. Thinks as follows. In other words, since the aromatic polyester is complexed with polylactic acid that is easily hydrolyzed, the acid and alcohol produced by hydrolysis of the polylactic acid by the wet heat action under compost also contact the aromatic polyester. It is considered that the hydrolysis of the aromatic polyester is promoted by the action of alcohol, resulting in a low molecular weight compound, which is then decomposed by microorganisms.
また、複合繊維の繊度が太いほど、鞘部の芳香族ポリエステルの厚みが厚くなり、コンポスト下での分解性が遅くなるため、太繊度の場合には、鞘部の比率を低くしたり、比較的分解速度の速い芳香族ポリエステルを使用することが好ましい。繊度（単繊維繊度）としては、生産性、操業安定性や、コンポスト下での分解性を考慮して１．０〜４０ｄｔｅｘ程度が好ましく、中でも２．０〜２０ｄｔｅｘが好ましい。 In addition, the thicker the fineness of the composite fiber, the thicker the aromatic polyester in the sheath, and the slower the decomposability under composting. It is preferable to use an aromatic polyester having a high chemical degradation rate. The fineness (single fiber fineness) is preferably about 1.0 to 40 dtex, more preferably 2.0 to 20 dtex in consideration of productivity, operational stability, and decomposability under compost.
以下、実施例により本発明を具体的に説明する。なお、実施例中の各物性値の測定法及び評価法は次のとおりである。
(1)ポリ乳酸のメルトフローレート値（ｇ／１０分）：前記の方法で測定した。
(2)芳香族ポリエステルの相対粘度：フェノールと四塩化エタンの等質量混合物を溶媒とし、ウベローデ粘度計を使用して、試料濃度０．５ｇ／１００ｃｃ、温度２０℃の条件で測定した。
(3)ポリ乳酸の融点（℃）、融解熱（Ｊ／ｇ）：パーキンエルマー社製の示差走査熱量計ＤＳＣ−２型を使用し、昇温速度２０℃／分の条件で測定した。
(4)ポリ乳酸のＬ−乳酸とＤ−乳酸の含有比（モル比）：超純水と１Ｎの水酸化ナトリウムのメタノール溶液の等質量混合溶液を溶媒とし、高速液体クロマトグラフィー（ＨＰＬＣ）法により測定した。カラムにはｓｕｍｉｃｈｉｒａｌ ＯＡ６１００を使用し、ＵＶ吸収測定装置により検出した。
(5)偏心度：前記の方法で測定、算出した。
(6)単繊維繊度（ｄｔｅｘ）：ＪＩＳ Ｌ−１０１５ 正量繊度Ａ法に準じて測定した。
(7)強度（ｃＮ／ｄｔｅｘ）：ＪＩＳ Ｌ−１０１５ 引張強さ及び伸び率の標準時試験に準じて測定した。
(8)捲縮数（個／２５ｍｍ）、捲縮率（％）：ＪＩＳ Ｌ−１０１５ けん縮のけん縮数及びけん縮率に準じて測定した。
なお、１５０℃乾熱処理後の捲縮数は、複合繊維を２mg／1dtexの荷重下で、１５０℃、１５分間熱処理した後に測定した。
(9)耐湿熱分解性：複合繊維を50℃、９５％相対湿度の条件下で1000時間保持し、処理前の強度に対する処理後の強度の比を次式にて算出した。なお、これらの強度は前記の(7)にしたがって測定した。
耐湿熱分解性（％）＝（処理後強度／処理前強度）×１００
(10)耐摩耗性：得られた複合繊維をリング精紡機にかけて、綿番手１０番の単糸（10/1）の紡績糸を得、この紡績糸を筒編みにしたものを用いて、耐摩耗性をＪＩＳ Ｌ１０１８ 摩耗強さのＡ法（ユニホーム形法）に準じて測定した。
(11)嵩高性：複合繊維をカード開繊機にかけてシート状ウェブにした後、２０×２０ｃｍの大きさに切り、質量が８０ｇになるように積み重ね、初荷重（測定板２０×２０ｃｍ、質量１７０ｇ）時の比容積を測定したものを初荷重時比容積（ｃｍ３／ｇ）とし、荷重（測定板２０×２０ｃｍ、質量１７０ｇ＋５．２３ｋｇ）時の比容積を測定したものを荷重時比容積（ｃｍ３／ｇ）とする。
初荷重時比容積８０ｃｍ３／ｇ以上、荷重時比容積２０ｃｍ３／ｇ以上を嵩高性があると判断した。
(12)不織布の伸縮性：得られた不織布を長さ１５ｃｍ、幅５ｃｍに切断し、３０ｇ荷重時の長さＬ０と２４０ｇ荷重時の長さＬ１を測定し、次式より伸長率を算出した。
伸長率（％）＝〔（Ｌ１−Ｌ０）／Ｌ０〕×１００
伸長率１００％以上を伸縮性があると判断した。
(13)生分解度：ＪＩＳ Ｋ ６９５３（プラスチックの制御されたコンポスト条件下の好気的究極生分解度および崩壊度の求め方）に準じて、得られた不織布を試験材料とし、処理期間４５日間後の生分解度を測定した。
(14)不織布の崩壊度：(13)での測定において、処理期間４５日間後の不織布の形状を目視で観察し、以下の基準で崩壊度を評価した。
○：不織布の形状を維持しておらず、繊維状のものも確認できない。
△：不織布の形状を維持していないが、繊維状のものが確認できる。
×：不織布の形状を維持している。
Hereinafter, the present invention will be described specifically by way of examples. In addition, the measuring method and evaluation method of each physical property value in an Example are as follows.
(1) Melt flow rate value of polylactic acid (g / 10 min): Measured by the method described above.
(2) Relative viscosity of aromatic polyester: Measured under the conditions of a sample concentration of 0.5 g / 100 cc and a temperature of 20 ° C. using an equal mass mixture of phenol and ethane tetrachloride as a solvent and an Ubbelohde viscometer.
(3) Melting point (° C.) and heat of fusion (J / g) of polylactic acid: A differential scanning calorimeter DSC-2 manufactured by Perkin Elmer was used and measured under conditions of a temperature rising rate of 20 ° C./min.
(4) Content ratio (molar ratio) of L-lactic acid and D-lactic acid in polylactic acid: High-performance liquid chromatography (HPLC) method using an equimolar mixed solution of ultrapure water and 1N sodium hydroxide in methanol as a solvent. It was measured by. The column used was sumichiral OA6100, and was detected by a UV absorption measuring device.
(5) Eccentricity: measured and calculated by the method described above.
(6) Single fiber fineness (dtex): measured according to JIS L-1015 positive fineness A method.
(7) Strength (cN / dtex): Measured according to JIS L-1015 standard time test of tensile strength and elongation.
(8) Crimp number (pieces / 25 mm), crimp rate (%): Measured according to the crimp number and crimp rate of JIS L-1015.
The number of crimps after 150 ° C. dry heat treatment was measured after heat treating the composite fiber at 150 ° C. for 15 minutes under a load of 2 mg / 1 dtex.
(9) Humidity and thermal decomposition resistance: The composite fiber was held at 50 ° C. and 95% relative humidity for 1000 hours, and the ratio of the strength after treatment to the strength before treatment was calculated by the following formula. These strengths were measured according to the above (7).
Moisture and heat resistance (%) = (strength after treatment / strength before treatment) × 100
(10) Abrasion resistance: The obtained composite fiber is put on a ring spinning machine to obtain a single yarn (10/1) yarn of cotton count No. 10, and this spun yarn is made into a cylindrical knitting, Abrasion was measured according to JIS L1018 Abrasion Strength Method A (Uniform Type Method).
(11) Bulkiness: After a composite fiber is passed through a card opening machine to form a sheet-like web, it is cut into a size of 20 × 20 cm, stacked so as to have a mass of 80 g, and an initial load (measuring plate 20 × 20 cm, mass 170 g) The specific volume at the time of initial load was measured (cm 3 / g), and the specific volume at the time of load (measuring plate 20 × 20 cm, mass 170 g + 5.23 kg) was measured. 3 / g).
The specific volume at the initial load of 80 cm 3 / g or more and the specific volume at the load of 20 cm 3 / g or more were judged to be bulky.
(12) Elasticity of nonwoven fabric: The obtained nonwoven fabric was cut into a length of 15 cm and a width of 5 cm, the length L0 at 30 g load and the length L1 at 240 g load were measured, and the elongation rate was calculated from the following formula: .
Elongation rate (%) = [(L1-L0) / L0] × 100
An elongation rate of 100% or more was judged to be stretchable.
(13) Degree of biodegradation: According to JIS K 6953 (determination of aerobic ultimate biodegradation and disintegration under controlled composting conditions of plastics), the obtained non-woven fabric is used as a test material, and the treatment period is 45. The degree of biodegradation after the day was measured.
(14) Disintegration degree of nonwoven fabric: In the measurement in (13), the shape of the nonwoven fabric after 45 days of the treatment period was visually observed, and the disintegration degree was evaluated according to the following criteria.
○: The shape of the nonwoven fabric is not maintained, and the fibrous shape cannot be confirmed.
(Triangle | delta): Although the shape of a nonwoven fabric is not maintained, a fibrous thing can be confirmed.
X: The shape of the nonwoven fabric is maintained.
実施例１
ポリ乳酸として、融点１７０℃、融解熱３８Ｊ／ｇ、Ｌ−乳酸とＤ−乳酸の含有比であるＬ／Ｄが９８．５／１．５、メルトフローレート値（以降、ＭＦＲとする。）が２３ｇ／１０分、相対粘度１．８５のものを用い、芳香族ポリエステルとして、相対粘度1.37、融点217℃のイソフタル酸15モル％共重合したＰＥＴを用い、それぞれのチップを減圧乾燥した後、同心芯鞘型複合溶融紡糸装置に供給して溶融紡糸を行った。このとき、共重合ＰＥＴが鞘部、ポリ乳酸が芯部となるように配し、複合比（質量比）を５０／５０とし、紡糸温度２４０℃で溶融紡糸を行った。紡出糸条を冷却した後、引取速度１０００ｍ／分で引き取って未延伸糸条を得た。得られた糸条を集束して３３万dtexのトウにし、延伸倍率３．２倍、温度６０℃で延伸し、温度１４０℃のヒートドラムで熱処理してから、押し込み式クリンパーを使用して機械捲縮を付与した後、繊維長５１ｍｍに切断し、短繊維を得た。
得られた複合繊維は、繊度（単繊維繊度）が３．３dtexの丸断面形状のものであり、偏心度が１．５、捲縮数11.2個／２５ｍｍ、捲縮率11.1％、強度4.31ｃN/dtex、耐湿熱分解性が89％、耐摩耗性が3650回のものであった。
Example 1
Polylactic acid has a melting point of 170 ° C., a heat of fusion of 38 J / g, an L / D content ratio of L-lactic acid and D-lactic acid of 98.5 / 1.5, a melt flow rate value (hereinafter referred to as MFR). Was 23 g / 10 min and a relative viscosity of 1.85 was used, and as aromatic polyester, 15 mol% isophthalic acid copolymerized with a relative viscosity of 1.37 and a melting point of 217 ° C. was used, and each chip was dried under reduced pressure. The melt was spun by supplying it to a concentric core-sheath type composite melt spinning apparatus. At this time, the copolymer PET was arranged so as to be a sheath part and polylactic acid was a core part, the composite ratio (mass ratio) was 50/50, and melt spinning was performed at a spinning temperature of 240 ° C. After cooling the spun yarn, it was drawn at a take-up speed of 1000 m / min to obtain an undrawn yarn. The resulting yarn is converged into a 330,000 dtex tow, drawn at a draw ratio of 3.2 times, at a temperature of 60 ° C., heat-treated with a heat drum at a temperature of 140 ° C., and then machined using a push-in crimper. After crimping, the fiber length was cut to 51 mm to obtain short fibers.
The obtained composite fiber has a round cross-sectional shape with a fineness (single fiber fineness) of 3.3 dtex, an eccentricity of 1.5, a number of crimps of 11.2 pieces / 25 mm, a crimp rate of 11.1%, and a strength of 4.31 cN. / dtex, 89% wet thermal decomposition, and 3650 wear resistance.
実施例２〜３
芯部と鞘部の複合比率を表１に示すように変更した以外は、実施例１と同様にして行った。
Examples 2-3
The same procedure as in Example 1 was performed except that the composite ratio of the core part and the sheath part was changed as shown in Table 1.
実施例４
芳香族ポリエステルとして、ポリトリメチレンテレフタレート（相対粘度1.44、融点215℃）を用いた以外は、実施例１と同様に行った。
Example 4
The same procedure as in Example 1 was performed except that polytrimethylene terephthalate (relative viscosity 1.44, melting point 215 ° C.) was used as the aromatic polyester.
実施例５
芳香族ポリエステルとして、ポリブチレンテレフタレート（相対粘度1.46、融点218℃）を用いた以外は、実施例１と同様に行った。
Example 5
The same procedure as in Example 1 was performed except that polybutylene terephthalate (relative viscosity 1.46, melting point 218 ° C.) was used as the aromatic polyester.
比較例１
複合繊維ではなく、ポリ乳酸のみの単一型の繊維とし、通常の紡糸装置を用いて紡糸温度２３０℃で溶融紡糸した以外は、実施例１と同様に行った。
Comparative Example 1
It was carried out in the same manner as in Example 1 except that it was not a composite fiber but a single type fiber of only polylactic acid and was melt-spun at a spinning temperature of 230 ° C. using a normal spinning device.
参考例１
複合繊維ではなく、芳香族ポリエステルのみの単一型の繊維とし、通常の紡糸装置を用いて紡糸温度２５０℃で溶融紡糸した以外は、実施例１と同様に行った。
Reference example 1
It was carried out in the same manner as in Example 1 except that it was not a composite fiber but a single type fiber of only aromatic polyester, and melt spinning at a spinning temperature of 250 ° C. using a normal spinning device.
実施例１〜５で得られた複合繊維、比較例１、参考例１で得られた繊維の物性値及び評価結果を表１に示す。 Table 1 shows the physical property values and evaluation results of the composite fibers obtained in Examples 1 to 5, Comparative Example 1, and the fibers obtained in Reference Example 1.
表１から明らかなように、実施例１〜５の複合繊維は、強度、耐湿熱分解性、耐摩耗性が高く、様々な用途に使用するのに十分な特性を有していた。一方、比較例１の繊維は、ポリ乳酸のみからなる繊維であったため、強度、耐摩耗性が低く、耐湿熱分解性を測定する際、湿熱処理後の強度が低下しすぎて繊維はボロボロとなり、処理後の強度の測定ができず、耐湿熱分解性を算出することが不可能であった。 As is clear from Table 1, the composite fibers of Examples 1 to 5 had high strength, wet heat decomposition resistance, and wear resistance, and had sufficient characteristics for use in various applications. On the other hand, since the fiber of Comparative Example 1 was a fiber composed only of polylactic acid, the strength and abrasion resistance were low, and when measuring the resistance to wet thermal decomposition, the strength after wet heat treatment was too low, and the fiber became tattered. The strength after the treatment could not be measured, and it was impossible to calculate the wet heat decomposition resistance.
実施例６Example 6
実施例１と同様のポリ乳酸で相対粘度１．８５のものを用い、芳香族ポリエステルとして、イソフタル酸２０モル％共重合したＰＥＴ（相対粘度１．３８、融点２０６℃）を鞘部とし、偏心芯鞘型複合溶融紡糸装置に供給して溶融紡糸を行った。 The same polylactic acid as in Example 1 and having a relative viscosity of 1.85 was used. As an aromatic polyester, PET (relative viscosity 1.38, melting point 206 ° C.) copolymerized with 20 mol% of isophthalic acid was used as the sheath, and the eccentricity. The melt-spinning was performed by supplying the core-sheath type composite melt spinning apparatus.
このとき、イソフタル酸２０モル％共重合したＰＥＴが鞘部、ポリ乳酸が芯部となるように配し、複合比（質量比）を５０／５０とし、孔数２２５孔の紡糸口金より紡糸温度２４０℃で溶融紡糸を行った。紡出糸条を冷却した後、引取速度８００ｍ／分で引き取って未延伸糸条を得た。得られた糸条を集束して３３万detexのトウにし、延伸倍率３．５倍、温度６０℃で延伸することによって、延伸直後にスパイラル捲縮を発現させた。続いて、仕上げ油剤を付与し、１００℃で乾燥させた後、繊維長６４ｍｍに切断し、短繊維を得た。 At this time, PET copolymerized with 20 mol% of isophthalic acid is arranged so that the sheath part and the polylactic acid become the core part, the composite ratio (mass ratio) is 50/50, and the spinning temperature is from the spinneret having 225 holes. Melt spinning was performed at 240 ° C. After cooling the spun yarn, it was drawn at a take-up speed of 800 m / min to obtain an undrawn yarn. The obtained yarn was converged into a tow of 330,000 detex, and drawn at a draw ratio of 3.5 times and at a temperature of 60 ° C., so that spiral crimp was expressed immediately after drawing. Subsequently, a finishing oil was applied and dried at 100 ° C., and then cut to a fiber length of 64 mm to obtain short fibers.
得られた複合繊維は、繊度（単繊維繊度）が６．６dtexの丸断面形状のものであり、偏心度が４．０、スパイラル捲縮が発現したものであり、その捲縮数７．５個／２５ｍｍ、捲縮率２１．１％、強度３．４１cN/detexであった。また、嵩高性評価の初荷重時比容積、荷重時比容積ともに高く嵩高性に優れており、耐湿熱分解性が９０％のものであった。 The obtained composite fiber has a round cross-sectional shape with a fineness (single fiber fineness) of 6.6 dtex, an eccentricity of 4.0, and spiral crimps. The number of crimps is 7.5. Pieces / 25 mm, crimp rate 21.1%, strength 3.41 cN / detex. Moreover, both the specific volume at the time of initial load and the specific volume at the time of load of the bulkiness evaluation were high and excellent in bulkiness, and the moisture and heat decomposition resistance was 90%.
実施例７
芳香族ポリエステルとして、エチレングリコール（ＥＧ）を４５モル％共重合したＰＢＴ（相対粘度１．４０、融点１８０℃）を用い、紡糸温度を２３０℃とした以外は、実施例６と同様に行った。
Example 7
The same procedure as in Example 6 was performed except that PBT (relative viscosity 1.40, melting point 180 ° C.) copolymerized with 45 mol% of ethylene glycol (EG) was used as the aromatic polyester and the spinning temperature was 230 ° C. .
比較例２
鞘部ポリマーとして、実施例１と同様のポリ乳酸で相対粘度1.61のものを用い、紡糸温度を２３０℃とした以外は、実施例６と同様に行った。
Comparative Example 2
The sheath polymer was the same as in Example 6 except that the same polylactic acid as in Example 1 with a relative viscosity of 1.61 was used and the spinning temperature was 230 ° C.
実施例６、７、比較例２で得られた複合繊維の物性値及び評価結果を表２に示す。 Table 2 shows the physical property values and evaluation results of the conjugate fibers obtained in Examples 6 and 7 and Comparative Example 2.
表２から明らかなように、実施例６、７の複合繊維は、スパイラル捲縮が発現されており、嵩高性に優れ、耐湿熱分解性にも優れており、様々な用途に使用するのに十分な特性を有していた。
一方、比較例２の複合繊維は、ポリ乳酸のみからなる繊維であったため、耐湿熱分解性を測定する際、湿熱処理後の強度が低下しすぎて繊維はボロボロとなり、処理後の強度の測定ができず、耐湿熱分解性を算出することができなかった。
As is apparent from Table 2 , the composite fibers of Examples 6 and 7 exhibit spiral crimping, are excellent in bulkiness, are excellent in resistance to moist heat decomposition, and are used for various applications. It had sufficient characteristics .
On the other hand, since the composite fiber of Comparative Example 2 was a fiber composed only of polylactic acid, when measuring the resistance to moist heat degradation, the strength after the wet heat treatment was too low, and the fiber became tattered, and the strength after the treatment was measured. It was not possible to calculate the resistance to wet thermal decomposition.
実施例８
実施例１と同様のポリ乳酸で相対粘度１．８５のものを用い、芳香族ポリエステルとして、イソフタル酸２０モル％共重合したＰＥＴ（相対粘度１．３８、融点２０６℃）を鞘部とし、偏心芯鞘型複合溶融紡糸装置に供給して溶融紡糸を行った。
このとき、イソフタル酸２０モル％共重合したＰＥＴが鞘部、ポリ乳酸が芯部となるように配し、複合比（質量比）を５０／５０とし、孔数６３９孔の紡糸口金より紡糸温度２４０℃で溶融紡糸を行った。紡出糸条を冷却した後、引取速度９００ｍ／分で引き取って未延伸糸条を得た。得られた糸条を集束して３３万detexのトウにし、延伸倍率３．５倍、温度６０℃で延伸し、１１０℃で緊張熱処理をしてから、押し込み型クリンパーにて機械捲縮を付与し、仕上げ油剤を付与後に、６５℃で乾燥させ、繊維長４４ｍｍに切断し、短繊維を得た。
得られた複合繊維は、繊度（単繊維繊度）が３．３dtexの丸断面形状のものであり、偏心度が４．０、機械捲縮の捲縮数１２．１個／２５ｍｍ、強度３．８７cN/detexであった。また、１５０℃熱処理後のスパイラル捲縮の捲縮数は９４個／２５ｍｍ、耐湿熱分解性が９０％であった。
次に、得られた短繊維をカード機で開繊し、目付５０ｇ／ｍ ２ のウエブを作成した。次いで、このウエブを１００メッシュスクリーンからなるネットコンベアーに載置し、孔径０．１２ｍｍ、孔間隔１．０ｍｍの噴射孔を複数個有する噴射ノズルを３段階に設け、前段４０００ｋＰａ、中段９０００ｋＰａ，後段９０００ｋＰａの水圧でウエブの表裏に水流交絡処理を施して、不織布を得た。得られた不織布の伸長率は１９４％であった。
Example 8
The same polylactic acid as in Example 1 and having a relative viscosity of 1.85 was used. As an aromatic polyester, PET (relative viscosity 1.38, melting point 206 ° C.) copolymerized with 20 mol% of isophthalic acid was used as the sheath, and the eccentricity. The melt-spinning was performed by supplying the core-sheath type composite melt spinning apparatus.
At this time, PET copolymerized with 20 mol% of isophthalic acid is arranged so that the sheath part and the polylactic acid become the core part, the composite ratio (mass ratio) is 50/50, and the spinning temperature is from the spinneret having 639 holes. Melt spinning was performed at 240 ° C. After cooling the spun yarn, it was drawn at a take-up speed of 900 m / min to obtain an undrawn yarn. The obtained yarn is converged to a toe of 330,000 detex, stretched at a stretching ratio of 3.5 times, at a temperature of 60 ° C., subjected to tension heat treatment at 110 ° C., and then subjected to mechanical crimping by an indentation type crimper. After applying the finishing oil, it was dried at 65 ° C. and cut into a fiber length of 44 mm to obtain short fibers.
The obtained composite fiber has a round cross-sectional shape with a fineness (single fiber fineness) of 3.3 dtex, an eccentricity of 4.0, a number of mechanical crimps of 12.1 pieces / 25 mm, and a strength of 3. It was 87 cN / detex. Moreover, the number of crimps of spiral crimps after heat treatment at 150 ° C. was 94 pieces / 25 mm, and the resistance to wet thermal decomposition was 90%.
Next, the obtained short fiber was opened with a card machine to prepare a web having a basis weight of 50 g / m 2 . Next, this web was placed on a net conveyor composed of a 100 mesh screen, and provided with three injection nozzles having a plurality of injection holes with a hole diameter of 0.12 mm and a hole interval of 1.0 mm, a front stage of 4000 kPa, a middle stage of 9000 kPa, and a rear stage of 9000 kPa. The nonwoven fabric was obtained by subjecting the front and back of the web to hydroentanglement with a water pressure of. The elongation percentage of the obtained nonwoven fabric was 194%.
実施例９
芳香族ポリエステルとして、エチレングリコール（ＥＧ）を４５モル％共重合したＰＢＴ（相対粘度１．４０、融点１８０℃）を用い、紡糸温度を２３０℃とし、偏心度４．３となるようにした以外は、実施例８と同様に行った。
Example 9
Except that PBT (relative viscosity 1.40, melting point 180 ° C) copolymerized with 45 mol% of ethylene glycol (EG) was used as the aromatic polyester, the spinning temperature was 230 ° C, and the eccentricity was 4.3. Was carried out in the same manner as in Example 8 .
比較例３
鞘部ポリマーとして、融点１５３℃、融解熱２１Ｊ／ｇ、Ｌ−乳酸とＤ−乳酸の含有比であるＬ／Ｄが９４．２／５．８、メルトフローレート値（以降、ＭＦＲとする。）が２１ｇ／１０分、相対粘度１．８１のポリ乳酸を用い、紡糸温度を２３０℃とし、偏心度４．４となるようにした以外は、実施例８と同様に行った。
Comparative Example 3
The sheath polymer has a melting point of 153 ° C., a heat of fusion of 21 J / g, an L / D content ratio of L-lactic acid and D-lactic acid of 94.2 / 5.8, a melt flow rate value (hereinafter referred to as MFR). ) is 21g / 10 min, using a polylactic acid having a relative viscosity of 1.81, a spinning temperature of 230 ° C., except that as the eccentricity 4.4, was carried out in the same manner as in example 8.
実施例８、９、比較例３で得られた複合繊維、不織布の物性値及び評価結果を表３に示す。 Table 3 shows the physical properties and evaluation results of the composite fibers and nonwoven fabrics obtained in Examples 8 and 9 and Comparative Example 3.
表３から明らかなように、実施例８、９の複合繊維は、熱処理によりスパイラル捲縮が発現するものであり、耐湿熱分解性にも優れており、得られた不織布は伸縮性に優れるものであった。
一方、比較例３の複合繊維は、ポリ乳酸のみからなる繊維であったため、耐湿熱分解性を測定する際、湿熱処理後の強度が低下しすぎて繊維はボロボロとなり、処理後の強度の測定ができず耐湿熱分解性を算出することができなかった。
As is apparent from Table 3, the composite fibers of Examples 8 and 9 exhibit spiral crimping by heat treatment, are excellent in resistance to wet thermal decomposition, and the obtained nonwoven fabric is excellent in stretchability. It was .
On the other hand, since the composite fiber of Comparative Example 3 was a fiber made only of polylactic acid, when measuring the resistance to moist heat decomposition, the strength after the wet heat treatment was too low, and the fiber was tattered, and the strength after the treatment was measured. It was not possible to calculate the resistance to wet thermal decomposition.
実施例１０
実施例１と同様のポリ乳酸で相対粘度１．８５のものを用い、芳香族ポリエステルとしてエチレングリコール（ＥＧ）を４５モル％共重合したＰＢＴ（相対粘度１．４０、融点１８０℃）を用い、それぞれのチップを減圧乾燥した後、同心芯鞘型複合溶融紡糸装置に供給して溶融紡糸を行った。このとき、共重合ＰＥＴが鞘部、ポリ乳酸が芯部となるように配し、複合比（質量比：芯／鞘）を７５／２５とし、紡糸温度２３０℃で溶融紡糸を行った。紡出糸条を冷却した後、引取速度１１００ｍ／分で引き取って未延伸糸条を得た。得られた糸条を集束して３３万detexのトウにし、延伸倍率３．５倍、温度６０℃で延伸し、温度１４０℃のヒートドラムで熱処理してから、押し込み式クリンパーを使用して機械捲縮を付与した後、繊維長５１ｍｍに切断し、短繊維を得た。
得られた複合繊維は、単繊維繊度が３３detexの丸断面形状のものであり、偏心度が１．５、捲縮数１２．３個／２５ｍｍ、捲縮率１１．２％、強度３．９５ｃＮ／detex、耐湿熱分解性８７％であった。
次に、得られた短繊維をカード機で開繊し、目付５０ｇ／ｍ２のウエブを作成した。次いで、このウエブを１００メッシュスクリーンからなるネットコンベアーに載置し、孔径０．１２ｍｍ、孔間隔１．０ｍｍの噴射孔を複数個有する噴射ノズルを３段階に設け、前段４０００ｋＰａ、中段９０００ｋＰａ、後段９０００ｋＰａの水圧でウエブの表裏に水流交絡処理を施して、不織布を得た。 Example 10
The same polylactic acid as in Example 1 having a relative viscosity of 1.85 was used, and PBT copolymerized with 45 mol% of ethylene glycol (EG) as an aromatic polyester (relative viscosity 1.40, melting point 180 ° C.) was used. Each chip was dried under reduced pressure, and then supplied to a concentric core-sheath type composite melt spinning apparatus to perform melt spinning. At this time, melt-spinning was performed at a spinning temperature of 230 ° C. with a copolymer ratio of 75/25 and a composite ratio (mass ratio: core / sheath) of copolymerized PET as a sheath and polylactic acid as a core. After cooling the spun yarn, it was drawn at a take-up speed of 1100 m / min to obtain an undrawn yarn. The resulting yarn is converged into a tow of 330,000 detex, stretched at a draw ratio of 3.5 times, at a temperature of 60 ° C., heat-treated with a heat drum at a temperature of 140 ° C., and then machined using a push-in crimper. After crimping, the fiber length was cut to 51 mm to obtain short fibers.
The obtained conjugate fiber has a round cross-sectional shape with a single fiber fineness of 33 detex, an eccentricity of 1.5, a number of crimps of 12.3 pieces / 25 mm, a crimp rate of 11.2%, and a strength of 3.95 cN. / Detex, resistance to moist heat decomposition was 87%.
Next, the obtained short fiber was opened with a card machine to prepare a web having a basis weight of 50 g / m 2 . Next, this web was placed on a net conveyor consisting of a 100 mesh screen, and provided with three stages of injection nozzles having a plurality of injection holes with a hole diameter of 0.12 mm and a hole interval of 1.0 mm, the front stage 4000 kPa, the middle stage 9000 kPa, and the rear stage 9000 kPa. The nonwoven fabric was obtained by subjecting the front and back of the web to hydroentanglement with a water pressure of .
実施例１１〜１３
複合溶融紡糸装置のノズルの形状を変更し、偏心度を表４に示す値に変更した以外は、実施例１０と同様に行った。
Examples 11-13
The same procedure as in Example 10 was performed except that the shape of the nozzle of the composite melt spinning apparatus was changed and the eccentricity was changed to the values shown in Table 4.
実施例１４
芳香族ポリエステルとして、イソフタル酸４０モル％共重合したＰＥＴ（相対粘度１．３８）を用い、紡糸温度を２３０℃とした以外は、実施例１０と同様に行った。
Example 14
The same procedure as in Example 10 was performed except that PET (relative viscosity: 1.38) copolymerized with 40 mol% of isophthalic acid was used as the aromatic polyester, and the spinning temperature was 230 ° C.
実施例１５
芳香族ポリエステルとして、イソフタル酸１５モル％共重合したＰＥＴ（相対粘度１．３７、融点２１７℃）を用い、紡糸温度を２４０℃とし、偏心度を１．６となるように変更した以外は、実施例１０と同様に行った。
Example 15
As aromatic polyester, except that PET (relative viscosity 1.37, melting point 217 ° C.) copolymerized with 15 mol% of isophthalic acid was used, the spinning temperature was 240 ° C., and the eccentricity was changed to 1.6. The same operation as in Example 10 was performed.
比較例４
複合繊維ではなく、ポリ乳酸のみの単一型の繊維とし、通常の紡糸装置を用いて紡糸温度２３０℃で溶融紡糸した以外は、実施例１０と同様に行った。
Comparative Example 4
It was carried out in the same manner as in Example 10 except that it was not a composite fiber but a single type fiber of only polylactic acid and was melt-spun at a spinning temperature of 230 ° C. using a normal spinning device.
実施例１０〜１５で得られた複合繊維、比較例４で繊維の物性値及び評価結果を表４に示す。 Table 4 shows the physical properties and evaluation results of the composite fibers obtained in Examples 10 to 15 and the fibers in Comparative Example 4.
表４から明らかなように、実施例１０〜１５の複合繊維は、強度と耐湿熱分解性に優れていた。 As is clear from Table 4, the composite fibers of Examples 10 to 15 were excellent in strength and wet heat decomposition resistance .
一方、比較例４の繊維は、ポリ乳酸のみからなる繊維であったため、耐湿熱分解性を測定する際、湿熱処理後の強度が低下しすぎて繊維はボロボロとなり、処理後の強度の測定ができず、耐湿熱分解性を算出することができなかった。 On the other hand, since the fiber of Comparative Example 4 was a fiber made only of polylactic acid, when measuring the resistance to moist thermal decomposition, the strength after the wet heat treatment was too low, and the fiber became tattered. It was not possible to calculate the wet heat decomposition resistance.
Ａ ポリ乳酸
Ｂ 芳香族ポリエステル
C 中心点
A Polylactic acid B Aromatic polyester
C center point
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