JP2010024576A - Polylactic acid fabric and clothing - Google Patents
Polylactic acid fabric and clothing Download PDFInfo
- Publication number
- JP2010024576A JP2010024576A JP2008187105A JP2008187105A JP2010024576A JP 2010024576 A JP2010024576 A JP 2010024576A JP 2008187105 A JP2008187105 A JP 2008187105A JP 2008187105 A JP2008187105 A JP 2008187105A JP 2010024576 A JP2010024576 A JP 2010024576A
- Authority
- JP
- Japan
- Prior art keywords
- component
- polylactic acid
- fabric
- poly
- lactic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 51
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 51
- 239000004744 fabric Substances 0.000 title claims abstract description 50
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims abstract description 26
- 229940022769 d- lactic acid Drugs 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 229930182843 D-Lactic acid Natural products 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002981 blocking agent Substances 0.000 claims description 5
- 238000000691 measurement method Methods 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- -1 polyethylene terephthalate Polymers 0.000 description 58
- 238000002844 melting Methods 0.000 description 22
- 230000008018 melting Effects 0.000 description 22
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 14
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical group C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 238000004043 dyeing Methods 0.000 description 10
- 239000000986 disperse dye Substances 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000004310 lactic acid Substances 0.000 description 7
- 235000014655 lactic acid Nutrition 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000009998 heat setting Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 208000016261 weight loss Diseases 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 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
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 210000004243 sweat Anatomy 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229920002988 biodegradable polymer Polymers 0.000 description 3
- 239000004621 biodegradable polymer Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- PBMIETCUUSQZCG-UHFFFAOYSA-N n'-cyclohexylmethanediimine Chemical compound N=C=NC1CCCCC1 PBMIETCUUSQZCG-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- 239000000178 monomer Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=NC1=C(C(C)C)C=CC=C1C(C)C XLDBGFGREOMWSL-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
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- 239000011591 potassium Substances 0.000 description 2
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- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- 150000003606 tin compounds Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- GGQHNQQPLWRNHD-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-hydroxy-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(O)(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C GGQHNQQPLWRNHD-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、ポリ乳酸繊維からなり、スパナイズ感および均一色のナチュラル外観を呈するポリ乳酸布帛および該布帛を用いてなる衣料に関する。 TECHNICAL FIELD The present invention relates to a polylactic acid fabric made of polylactic acid fibers and exhibiting a feeling of spanization and a uniform natural appearance, and a garment using the fabric.
従来、合成繊維、特にポリエチレンテレフタレートなどの芳香族ポリエステルからなるポリエステル繊維で布帛のスパナイズ感を表現するために、ポリエステル未延伸糸を不均一延伸して太細を付与する方法が知られている（例えば、特許文献１参照）。 Conventionally, in order to express the feeling of fabric spanization with synthetic fibers, particularly polyester fibers made of aromatic polyester such as polyethylene terephthalate, a method of imparting fineness by non-uniform stretching of polyester unstretched yarn is known ( For example, see Patent Document 1).
他方、近年では、地球環境保護の目的から、自然環境下で分解される生分解性ポリマーが注目され、世界中で研究されている。生分解性ポリマーとしては、ポリヒドロキシブチレート、ポリカプロラクトン、脂肪族ポリエステル、ポリ乳酸などが知られている。なかでもポリ乳酸は、ポリ乳酸の原料である乳酸またはラクチドが天然物から製造できるので、単なる生分解性ポリマーとしてではなく、地球環境に配慮した汎用性ポリマーとして利用も検討されている（例えば、特許文献２参照）。 On the other hand, in recent years, for the purpose of protecting the global environment, biodegradable polymers that are decomposed in a natural environment have attracted attention and are being studied all over the world. Known biodegradable polymers include polyhydroxybutyrate, polycaprolactone, aliphatic polyester, polylactic acid, and the like. Among them, polylactic acid is considered to be used not only as a biodegradable polymer but also as a versatile polymer in consideration of the global environment because lactic acid or lactide, which is a raw material of polylactic acid, can be produced from natural products. Patent Document 2).
しかしながら、ポリ乳酸繊維は、ポリエチレンテレフタレート繊維など通常のポリエステル繊維に比べて耐熱性の点で劣るため、染色加工時に硬化し風合いが硬くなるという問題があり、ポリ乳酸繊維からなり、スパナイズ感および均一色のナチュラル外観を呈する布帛はこれまであまり提案されていない。 However, polylactic acid fibers are inferior in heat resistance compared to ordinary polyester fibers such as polyethylene terephthalate fibers, so there is a problem that they are hardened during dyeing and the texture becomes hard. So far, fabrics exhibiting a natural appearance of color have not been proposed so much.
本発明は上記の背景に鑑みなされたものであり、その目的は、ポリ乳酸繊維からなり、スパナイズ感および均一色のナチュラル外観を呈するポリ乳酸布帛および該布帛を用いてなる衣料を提供することにある。 The present invention has been made in view of the above background, and an object of the present invention is to provide a polylactic acid fabric comprising a polylactic acid fiber, exhibiting a spanization feeling and a uniform natural appearance, and a garment using the fabric. is there.
本発明者らは上記の課題を達成するため鋭意検討した結果、ポリＬ−乳酸（Ａ成分）とポリＤ−成分（Ｂ成分）とを特定の燐酸エステル金属塩（Ｃ成分）の存在下で紡糸し、繊維方向にランダムな繊度分布を有するポリ乳酸フィラメントを用いて布帛を得ると、ポリ乳酸繊維からなり、スパナイズ感および均一色のナチュラル外観を呈するポリ乳酸布帛が得られることを見出し、さらに鋭意検討を重ねることにより本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that poly L-lactic acid (A component) and poly D-component (B component) are present in the presence of a specific phosphate ester metal salt (C component). It has been found that when a fabric is obtained using a polylactic acid filament that is spun and has a random fineness distribution in the fiber direction, a polylactic acid fabric that is made of polylactic acid fibers and that exhibits a spanned feeling and a uniform natural appearance is obtained. The present invention has been completed through intensive studies.
かくして、本発明によれば「下記の方法により測定される見掛けの太細比が１．１以上のマルチフィラメント糸から構成され、かつフィラメント単糸がそれぞれ繊維方向にランダムな繊度分布を有し、かつ前記マルチフィラメント糸の太部と細部とが同一色に染色可能である布帛であって、
前記マルチフィラメント糸が、（ｉ）ポリＬ−乳酸（Ａ成分）、（ｉｉ）ポリＤ―乳酸（Ｂ成分）および（ｉｉｉ）Ａ成分とＢ成分との合計１００重量部当たり０．０５〜５重量部の下記式（１）または（２）で表される燐酸エステル金属塩（Ｃ成分）を含有するポリ乳酸組成物から形成されることを特徴とするポリ乳酸布帛。」が提供される。
Thus, according to the present invention, “the apparent thickness ratio measured by the following method is composed of multifilament yarns of 1.1 or more, and each filament single yarn has a random fineness distribution in the fiber direction, And the thick part and the details of the multifilament yarn can be dyed in the same color,
The multifilament yarn is 0.05 to 5 per 100 parts by weight of (i) poly L-lactic acid (component A), (ii) poly D-lactic acid (component B), and (iii) components A and B. A polylactic acid fabric formed from a polylactic acid composition containing parts by weight of a phosphoric acid ester metal salt (component C) represented by the following formula (1) or (2). Is provided.
（見掛けの太細比の測定方法）
布帛を構成する糸条を、少なくとも１０ｃｍの長さに亘って電子顕微鏡を用いて観察し、その電子顕微鏡画面上もしくは写真上で、最も糸が膨らんだ部分（太部）の幅と最も糸が集束した部分（細部）の幅との比を求める。
(Measurement method of apparent thickness ratio)
The yarn constituting the fabric is observed with an electron microscope over a length of at least 10 cm, and the width of the most swollen part (thick part) and the most thread are observed on the electron microscope screen or photograph. Find the ratio to the width of the focused part (detail).
その際、前記マルチフィラメント糸が、その表面に凹凸を付与することにより、水の接触角度を低下させたマルチフィラメント糸であることが好ましい。また、前記ポリ乳酸組成物が、ポリＬ−乳酸成分（Ａ成分）とポリＤ−乳酸成分（Ｂ成分）との合計１００重量部当たり０．１〜５重量部のカルボキシル末端封止剤を含有してなることが好ましい。また、布帛が前記マルチフィラメント糸のみで構成されていることが好ましい。 In that case, it is preferable that the said multifilament yarn is a multifilament yarn which reduced the contact angle of water by providing an unevenness | corrugation to the surface. The polylactic acid composition contains 0.1 to 5 parts by weight of a carboxyl terminal blocking agent per 100 parts by weight in total of the poly L-lactic acid component (A component) and the poly D-lactic acid component (B component). It is preferable that Moreover, it is preferable that the fabric is comprised only with the said multifilament yarn.
また、本発明によれば、前記のポリ乳酸布帛を用いてなる衣料が提供される。 Moreover, according to this invention, the clothing which uses the said polylactic acid fabric is provided.
本発明によれば、ポリ乳酸繊維からなり、スパナイズ感および均一色のナチュラル外観を呈するポリ乳酸布帛および該布帛を用いてなる衣料が得られる。 ADVANTAGE OF THE INVENTION According to this invention, the polylactic acid fabric which consists of a polylactic acid fiber, and exhibits a spanization feeling and a uniform natural appearance and clothing which uses this fabric are obtained.
以下、本発明を詳細に説明する。
本発明で用いるポリＬ−乳酸（Ａ成分）は、主としてＬ−乳酸単位からなる。Ｌ−乳酸単位はＬ−乳酸由来の繰り返し単位である。ポリＬ−乳酸（Ａ成分）は、好ましくは９０〜１００モル％、より好ましくは９５〜１００モル％、さらに好ましくは９８〜１００モル％のＬ−乳酸単位を含有する。他の繰り返し単位としてＤ−乳酸単位、乳酸以外の単位がある。Ｄ−乳酸単位および乳酸以外の単位は、好ましくは０〜１０モル％、より好ましくは０〜５モル％、さらに好ましくは０〜２モル％である。
Hereinafter, the present invention will be described in detail.
The poly L-lactic acid (component A) used in the present invention mainly comprises L-lactic acid units. The L-lactic acid unit is a repeating unit derived from L-lactic acid. The poly L-lactic acid (component A) preferably contains 90 to 100 mol%, more preferably 95 to 100 mol%, and still more preferably 98 to 100 mol% of L-lactic acid units. Other repeating units include D-lactic acid units and units other than lactic acid. The D-lactic acid unit and the units other than lactic acid are preferably 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 2 mol%.
乳酸以外の単位としては、グリコール酸、カプロラクトン、ブチロラクトン、プロピオラクトンなどのヒドロキシカルボン酸類、エチレングリコール、１，３−プロパンジオール、１，２−プロパンジオール、１，４−プロパンジオール、１，５−プロパンジオール、ヘキサンジオール、オクタンジオール、デカンジオール、ドデカンジオール、炭素数が２〜３０の脂肪族ジオール類、コハク酸、マレイン酸、アジピン酸、炭素数２〜３０の脂肪族ジカルボン酸、テレフタル酸、イソフタル酸、ヒドロキシ安息香酸、ヒドロキノンなど芳香族ジオール、芳香族ジカルボン酸などから選ばれる１種以上のモノマー由来の単位が挙げられる。 Examples of units other than lactic acid include hydroxycarboxylic acids such as glycolic acid, caprolactone, butyrolactone, propiolactone, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-propanediol, 1,5 -Propanediol, hexanediol, octanediol, decanediol, dodecanediol, aliphatic diols having 2 to 30 carbon atoms, succinic acid, maleic acid, adipic acid, aliphatic dicarboxylic acids having 2 to 30 carbon atoms, terephthalic acid And units derived from one or more monomers selected from aromatic diols such as isophthalic acid, hydroxybenzoic acid, and hydroquinone, and aromatic dicarboxylic acids.
ポリＬ−乳酸（Ａ成分）は、好ましくは結晶性を有する。融点は、好ましくは１５０〜１９０℃、より好ましくは１６０〜１９０℃である。これらの条件を満足すると、高融点のステレオコンプレックス結晶を形成させることができ、かつ、結晶化度を上げることができるからである。
ポリＬ−乳酸（Ａ成分）において、重量平均分子量が５万〜３０万（より好ましくは１０万〜２５万）であることが好ましい。
The poly L-lactic acid (component A) preferably has crystallinity. The melting point is preferably 150 to 190 ° C, more preferably 160 to 190 ° C. If these conditions are satisfied, a stereocomplex crystal having a high melting point can be formed and the crystallinity can be increased.
In poly L-lactic acid (component A), the weight average molecular weight is preferably 50,000 to 300,000 (more preferably 100,000 to 250,000).
一方、本発明で用いるポリＤ−乳酸（Ｂ成分）は、主としてＤ−乳酸単位からなる。Ｄ−乳酸単位はＤ−乳酸由来の繰り返し単位である。ポリＤ−乳酸は、好ましくは９０〜１００モル％、より好ましくは９５〜１００モル％、さらに好ましくは９８〜１００モル％のＤ−乳酸単位を含有する。他の繰り返し単位としてＬ−乳酸単位、乳酸以外の単位がある。Ｌ−乳酸単位および乳酸以外の単位は、好ましくは０〜１０モル％、より好ましくは０〜５モル％、さらに好ましくは０〜２モル％である。 On the other hand, poly D-lactic acid (B component) used in the present invention mainly comprises D-lactic acid units. The D-lactic acid unit is a repeating unit derived from D-lactic acid. The poly-D-lactic acid preferably contains 90 to 100 mol%, more preferably 95 to 100 mol%, and still more preferably 98 to 100 mol% of D-lactic acid units. Other repeating units include L-lactic acid units and units other than lactic acid. The L-lactic acid unit and the units other than lactic acid are preferably 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 2 mol%.
乳酸以外の単位としては、グリコール酸、カプロラクトン、ブチロラクトン、プロピオラクトンなどのヒドロキシカルボン酸類、エチレングリコール、１，３−プロパンジオール、１，２−プロパンジオール、１，４−プロパンジオール、１，５−プロパンジオール、ヘキサンジオール、オクタンジオール、デカンジオール、ドデカンジオール、炭素数が２〜３０の脂肪族ジオール類、コハク酸、マレイン酸、アジピン酸、炭素数２〜３０の脂肪族ジカルボン酸、テレフタル酸、イソフタル酸、ヒドロキシ安息香酸、ヒドロキノンなど芳香族ジオール、芳香族ジカルボン酸などから選ばれる１種以上のモノマー由来の単位が挙げられる。 Examples of units other than lactic acid include hydroxycarboxylic acids such as glycolic acid, caprolactone, butyrolactone, propiolactone, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-propanediol, 1,5 -Propanediol, hexanediol, octanediol, decanediol, dodecanediol, aliphatic diols having 2 to 30 carbon atoms, succinic acid, maleic acid, adipic acid, aliphatic dicarboxylic acids having 2 to 30 carbon atoms, terephthalic acid And units derived from one or more monomers selected from aromatic diols such as isophthalic acid, hydroxybenzoic acid, and hydroquinone, and aromatic dicarboxylic acids.
ポリＤ−乳酸（Ｂ成分）は、好ましくは結晶性を有する。融点は、好ましくは１５０〜１９０℃、より好ましくは１６０〜１９０℃である。これらの条件を満足すると、高融点のステレオコンプレックス結晶を形成させることができ、かつ、結晶化度を上げることができるからである。
ポリＤ−乳酸（Ｂ成分）において、重量平均分子量が５万〜３０万（より好ましくは１０万〜２５万）であることが好ましい。
Poly D-lactic acid (component B) preferably has crystallinity. The melting point is preferably 150 to 190 ° C, more preferably 160 to 190 ° C. If these conditions are satisfied, a stereocomplex crystal having a high melting point can be formed and the crystallinity can be increased.
In poly D-lactic acid (component B), the weight average molecular weight is preferably 50,000 to 300,000 (more preferably 100,000 to 250,000).
ポリＬ−乳酸（Ａ成分）またはポリＤ−乳酸（Ｂ成分）は、Ｌ−乳酸またはＤ−乳酸を直接脱水縮合する方法で製造したり、Ｌ−乳酸またはＤ−乳酸を一度脱水環化してラクチドとした後に開環重合したりする方法で製造することができる。これらの方法に用いる触媒として、オクチル酸スズ、塩化スズ、スズのアルコキシドなどの２価のスズ化合物、酸化スズ、酸化ブチルスズ、酸化エチルスズなど４価のスズ化合物、金属スズ、亜鉛化合物、アルミニウム化合物、カルシウム化合物、ランタニド化合物などを例示することができる。 Poly-L-lactic acid (component A) or poly-D-lactic acid (component B) can be produced by directly dehydrating condensation of L-lactic acid or D-lactic acid, or once dehydrating and cyclizing L-lactic acid or D-lactic acid. It can be produced by a method of ring-opening polymerization after making lactide. Catalysts used in these methods include divalent tin compounds such as tin octylate, tin chloride, and tin alkoxides, tetravalent tin compounds such as tin oxide, butyltin oxide, and ethyltin oxide, metal tin, zinc compounds, aluminum compounds, Examples thereof include calcium compounds and lanthanide compounds.
ポリＬ−乳酸（Ａ成分）およびポリＤ−乳酸（Ｂ成分）は、重合時使用された重合触媒を溶媒で洗浄除去するか、触媒活性を不活性化しておくのが好ましい。触媒活性を不活性化するには、触媒失活剤を用いることができる。 The poly L-lactic acid (component A) and the poly D-lactic acid (component B) are preferably washed away with a polymerization catalyst used during the polymerization, or the catalytic activity is deactivated. A catalyst deactivator can be used to inactivate the catalyst activity.
触媒失活剤として、イミノ基を有し且つ金属重合触媒に配位し得るキレート配位子の群からなる有機リガンド、リンオキソ酸、リンオキソ酸エステルおよび式（３）で表される有機リンオキソ酸化合物群から選択される少なくとも１種が挙げられる。触媒失活剤は、重合終了の時点において触媒中の金属元素１当量あたり、好ましくは０．３〜２０当量、より好ましくは０．４〜１５当量、さらに好ましくは０．５〜１０当量配合する。
Ｘ１−Ｐ（＝Ｏ）ｍ（ＯＨ）ｎ（ＯＸ２）２−ｎ （３）
式中、ｍは０または１、ｎは１または２、Ｘ１およびＸ２は各々独立に炭素数１〜２０の置換基を有していても良い炭化水素基を表す。炭化水素基として、メチル基、エチル基、プロピル基、ブチル基等の炭素数１〜２０のアルキル基が挙げられる。
As a catalyst deactivator, an organic ligand consisting of a group of chelate ligands having an imino group and capable of coordinating to a metal polymerization catalyst, a phosphorus oxoacid, a phosphorus oxoacid ester, and an organic phosphorus oxoacid compound represented by the formula (3) There may be mentioned at least one selected from the group. The catalyst deactivator is preferably blended in an amount of 0.3 to 20 equivalents, more preferably 0.4 to 15 equivalents, and even more preferably 0.5 to 10 equivalents per equivalent of the metal element in the catalyst at the end of the polymerization. .
X 1 -P (= O) m (OH) n (OX 2) 2-n (3)
In the formula, m is 0 or 1, n is 1 or 2, and X 1 and X 2 each independently represent a hydrocarbon group optionally having a substituent having 1 to 20 carbon atoms. Examples of the hydrocarbon group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.
ポリＬ−乳酸（Ａ成分）およびポリＤ−乳酸（Ｂ成分）中の金属イオン含有量は２０ｐｐｍ以下であることが繊維の耐熱性、耐加水分解性の点から好ましい。金属イオン含有量は、アルカリ土類金属、希土類、第三周期の遷移金属類、アルミニウム、ゲルマニウム、スズおよびアンチモンから選ばれる金属の各々の含有量が２０ｐｐｍ以下であることが好ましい。 The metal ion content in poly L-lactic acid (component A) and poly D-lactic acid (component B) is preferably 20 ppm or less from the viewpoint of heat resistance and hydrolysis resistance of the fiber. The metal ion content is preferably such that the content of each metal selected from alkaline earth metals, rare earths, transition metals of the third period, aluminum, germanium, tin and antimony is 20 ppm or less.
次に、本発明で用いる燐酸エステル金属塩（Ｃ成分）は、下記式（１）または（２）で表される化合物である。燐酸エステル金属塩は１種類を用いても複数種類を併用してもよい。 Next, the phosphoric acid ester metal salt (component C) used in the present invention is a compound represented by the following formula (1) or (2). The phosphoric acid ester metal salt may be used alone or in combination.
式（１）において、Ｒ１は、水素原子または炭素数１〜４のアルキル基を表す。Ｒ１で表される炭素数１〜４のアルキル基として、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｉｓｏ−ブチル基などが例示される。 In Formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms represented by R 1 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and an iso-butyl group. The
Ｒ２、Ｒ３は、各々独立に水素原子または炭素数１〜１２のアルキル基を表す。炭素数１〜１２のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｉｓｏ−ブチル基、ｔｅｒｔ−ブチル基、アミル基、ｔｅｒｔ−アミル基、ヘキシル基、ヘプチル基、オクチル基、ｉｓｏ−オクチル基、ｔｅｒｔ−オクチル基、２−エチルヘキシル基、ノニル基、ｉｓｏ−ノニル基、デシル基、ｉｓｏ−デシル基、ｔｅｒｔ−デシル基、ウンデシル基、ドデシル基、ｔｅｒｔ−ドデシル基などが挙げられる。 R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, amyl group, tert-amyl group, hexyl group, heptyl group, octyl group, iso-octyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, iso-nonyl group, decyl group, iso-decyl group, tert-decyl group, An undecyl group, a dodecyl group, a tert-dodecyl group, etc. are mentioned.
Ｍ１は、Ｎａ、Ｋ、Ｌｉなどのアルカリ金属原子またはＭｇ、Ｃａ等のアルカリ土類金属原子を表す。ｐは１または２を表す。
式（１）で表される燐酸エステル金属塩のうち好ましいものとしては、例えばＲ１が水素原子、Ｒ２、Ｒ３がともにｔｅｒｔ−ブチル基のものが挙げられる。
M 1 represents an alkali metal atom such as Na, K or Li or an alkaline earth metal atom such as Mg or Ca. p represents 1 or 2.
Preferable examples of the phosphoric acid ester metal salt represented by the formula (1) include those in which R 1 is a hydrogen atom and R 2 and R 3 are both tert-butyl groups.
式（２）においてＲ４、Ｒ５、Ｒ６は、各々独立に、水素原子、炭素数１〜１２のアルキル基を表す。炭素数１〜１２のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｉｓｏ−ブチル基、ｔｅｒｔ−ブチル基、アミル基、ｔｅｒｔ−アミル基、ヘキシル基、ヘプチル基、オクチル基、ｉｓｏ−オクチル基、ｔｅｒｔ−オクチル基、２−エチルヘキシル基、ノニル基、ｉｓｏ−ノニル基、デシル基、ｉｓｏ−デシル基、ｔｅｒｔ−デシル基、ウンデシル基、ドデシル基、ｔｅｒｔ−ドデシル基などが挙げられる。 In the formula (2), R 4 , R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, amyl group, tert-amyl group, hexyl group, heptyl group, octyl group, iso-octyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, iso-nonyl group, decyl group, iso-decyl group, tert-decyl group, An undecyl group, a dodecyl group, a tert-dodecyl group, etc. are mentioned.
Ｍ２は、Ｎａ、Ｋ、Ｌｉなどのアルカリ金属原子またはＭｇ、Ｃａ等のアルカリ土類金属原子を表す。ｐは１または２を表す。
式（２）で表される燐酸エステル金属塩のうち好ましいものとしては、例えば、Ｒ４、Ｒ６がメチル基、Ｒ５がｔｅｒｔ−ブチル基のものが挙げられる。燐酸エステル金属塩として、（株）ＡＤＥＫＡ製の商品名、ＮＡ−１１が挙げられる。燐酸エステル金属塩は公知の方法により合成することができる。
M 2 represents an alkali metal atom such as Na, K or Li or an alkaline earth metal atom such as Mg or Ca. p represents 1 or 2.
Preferred examples of the phosphoric acid ester metal salt represented by the formula (2) include those in which R 4 and R 6 are methyl groups and R 5 is a tert-butyl group. As a phosphoric acid ester metal salt, trade name, NA-11, manufactured by ADEKA Co., Ltd. can be mentioned. The phosphoric acid ester metal salt can be synthesized by a known method.
特開２００３−１９２８８４号公報に記載のように、式（１）または（２）で表される化合物はポリ乳酸の結晶核剤として知られた化合物である。しかし、本発明において、式（１）、式（２）中のＭ１およびＭ２は、アルカリ金属原子またはアルカリ土類金属原子であることを特徴とする。式（１）、式（２）中のＭ１およびＭ２が、アルミニウムなどの他の金属である場合、化合物自体の耐熱性が低く、紡糸時に昇華物が発生し、紡糸することが困難な場合がある。 As described in JP-A-2003-192884, the compound represented by the formula (1) or (2) is a compound known as a crystal nucleating agent for polylactic acid. However, in the present invention, M 1 and M 2 in the formulas (1) and (2) are an alkali metal atom or an alkaline earth metal atom. When M 1 and M 2 in the formulas (1) and (2) are other metals such as aluminum, the heat resistance of the compound itself is low, and a sublimate is generated during spinning, which makes it difficult to spin. There is a case.
燐酸エステル金属塩（Ｃ成分）は、平均一次粒径が好ましくは０．０１〜１０μｍ、より好ましくは０．０５〜７μｍである。粒径を０．０１μｍより小さくすることは工業的に困難であり、それほど小さくする必要もない。また１０μｍより大きいと、紡糸、延伸時、断糸の頻度が高まる。 The phosphoric acid ester metal salt (component C) preferably has an average primary particle size of 0.01 to 10 μm, more preferably 0.05 to 7 μm. It is industrially difficult to make the particle size smaller than 0.01 μm, and it is not necessary to make it so small. On the other hand, if it is larger than 10 μm, the frequency of yarn breakage increases during spinning and drawing.
燐酸エステル金属塩（Ｃ成分）の含有量は、ポリＬ−乳酸（Ａ成分）とポリＤ−乳酸（Ｂ成分）との合計１００重量部当たり、０．０１〜５重量部、好ましくは０．０５〜５重量部、より好ましくは０．０５〜４重量部、特に好ましくは０．１〜３重量部である。０．０１重量部より少量であると所望の効果がほとんど認められない。また５重量部より多量に使用すると繊維形成時、熱分解を起こしたり、断糸が起きたりする場合があり好ましくない。 The content of the phosphoric acid ester metal salt (component C) is 0.01 to 5 parts by weight per 100 parts by weight in total of the poly L-lactic acid (component A) and the poly D-lactic acid (component B), preferably 0.00. 05 to 5 parts by weight, more preferably 0.05 to 4 parts by weight, particularly preferably 0.1 to 3 parts by weight. If the amount is less than 0.01 parts by weight, the desired effect is hardly recognized. On the other hand, if it is used in a larger amount than 5 parts by weight, it is not preferable because thermal decomposition or fiber breakage may occur during fiber formation.
ポリＬ−乳酸（Ａ成分）とポリＤ−乳酸（Ｂ成分）との比は、Ａ成分／Ｂ成分（重量）で、好ましくは４０／６０〜６０／４０、より好ましくは４５／５５〜５５／４５、さらに好ましくは５０／５０である。 The ratio of poly L-lactic acid (component A) to poly D-lactic acid (component B) is component A / component B (weight), preferably 40 / 60-60 / 40, more preferably 45 / 55-55. / 45, more preferably 50/50.
Ａ成分、Ｂ成分およびＣ成分の混合は、従来公知の各種方法を使用することができる。例えば、Ａ成分、Ｂ成分およびＣ成分を、タンブラー、Ｖ型ブレンダー、スーパーミキサー、ナウタミキサー、バンバリーミキサー、混練ロール、１軸または２軸の押出機等で混合することができる。 For mixing the A component, the B component, and the C component, various conventionally known methods can be used. For example, the A component, the B component, and the C component can be mixed with a tumbler, a V-type blender, a super mixer, a nauta mixer, a Banbury mixer, a kneading roll, a monoaxial or biaxial extruder, and the like.
こうして得られるポリ乳酸組成物は、溶融混合され、そのまま、または計量ポンプなどを経由して紡糸装置に移送することもできる。溶融混合する温度は、得られるステレオコンプレックスポリ乳酸の融点より高い温度であることが好ましく、２２０℃よりも高いことが好ましい。また、一旦ペレット状にしてから紡糸装置に供給することもできる。ペレット長は１〜７ｍｍ、長径３〜５ｍｍ、短径１〜４ｍｍのものが好ましい。ペレットの形状は、ばらつきのないものが好ましい。ペレット化された組成物は、プレッシャーメルター型や１軸あるいは２軸エクストルーダー型などの通常の溶融押出し機を使用して紡糸装置に移送することもできる。ステレオコンプレックス結晶の形成にあたっては、Ａ成分およびＢ成分を十分に混合することが重要であり、とりわけ剪断応力下、混合することが好ましい。 The polylactic acid composition thus obtained can be melt-mixed and transferred to the spinning device as it is or via a metering pump or the like. The temperature for melting and mixing is preferably higher than the melting point of the resulting stereocomplex polylactic acid, and preferably higher than 220 ° C. Further, it may be once pelletized and then supplied to the spinning device. The pellet length is preferably 1 to 7 mm, the major axis is 3 to 5 mm, and the minor axis is 1 to 4 mm. The pellet shape is preferably uniform. The pelletized composition can be transferred to a spinning device using a normal melt extruder such as a pressure melter type or a single-screw or twin-screw extruder type. In forming the stereocomplex crystal, it is important to sufficiently mix the A component and the B component, and it is particularly preferable to mix them under shear stress.
前記のポリ乳酸組成物には、耐湿熱性改善剤として、特定官能基を有するカルボキシル基末端封止剤が好適に適用できる。かかるカルボキシル末端封止剤としては、エポキシ化合物、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、イソシアネート化合物から選択される少なくとも１種の化合物を使用することが好ましい。末端カルボキシル基末端封止剤を含有することで、耐湿熱性改善の作用を向上させることができるのみならず、紡糸性、力学特性、耐熱性、耐久性に優れた繊維を得ることができる。 In the polylactic acid composition, a carboxyl group end-capping agent having a specific functional group can be suitably applied as a wet heat resistance improver. As such a carboxyl terminal blocking agent, it is preferable to use at least one compound selected from an epoxy compound, a carbodiimide compound, an oxazoline compound, an oxazine compound, and an isocyanate compound. By containing the terminal carboxyl group terminal blocking agent, not only the effect of improving the heat and moisture resistance can be improved, but also a fiber excellent in spinnability, mechanical properties, heat resistance and durability can be obtained.
ここで、エポキシ化合物として、グリシジルエーテル化合物、グリシジルエステル化合物、グリジジルアミン化合物、グリシジルイミド化合物、グリシジルアミド化合物、脂環式エポキシ化合物を好ましく使用することができる。 Here, as an epoxy compound, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, a glycidyl amide compound, and an alicyclic epoxy compound can be preferably used.
また、カルボジイミド化合物としては、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、ジメチルカルボジイミド、ジイソブイチルカルボジイミド、ジオクチルカルボジイミド、オクチルデシルカルボジイミド、ジ−ｔ−ブチルカルボジイミド、ｔ−ブチルイソプロピルカルボジイミド、ジベンジルカルボジイミド、ジフェニルカルボジイミド、Ｎ−オクタデシル−Ｎ’−フェニルカルボジイミド、Ｎ−ベンジル−Ｎ’−フェニルカルボジイミド、Ｎ−ベンジル−Ｎ’−トリルカルボジイミド、ジ−ｏ−トルイルカルボジイミド、ジ−ｐ−トルイルカルボジイミド、ビス（ｐ−ニトロフェニル）カルボジイミド、ビス（ｐ−アミノフェニル）カルボジイミド、ビス（ｐ−ヒドロキシフェニル）カルボジイミド、ビス（ｐ−クロロフェニル）カルボジイミド、ビス（ｏ−クロロフェニル）カルボジイミド、ビス（ｏ−エチルフェニル）カルボジイミド、ビス（ｐ−エチルフェニル）カルボジイミドビス（ｏ−イソプロピルフェニル）カルボジイミド、ビス（ｐ−イソプロピルフェニル）カルボジイミド、ビス（ｏ−イソブチルフェニル）カルボジイミド、ビス（ｐ−イソブチルフェニル）カルボジイミド、ビス（２，５−ジクロロフェニル）カルボジイミド、ｐ−フェニレンビス（ｏ−トルイルカルボジイミド）、ｐ−フェニレンビス（シクロヘキシルカルボジイミド、ｐ−フェニレンンビス（ｐ−クロロフェニルカルボジイミド）、２，６，２’，６’−テトライソプロピルジフェニルカルボジイミド、ヘキサメチレンビス（シクロヘキシルカルボジイミド）、エチレンビス（フェニルカルボジイミド）、エチレンビス（シクロヘキシルカルボジイミド）、ビス（２，６−ジメチルフェニル）カルボジイミド、ビス（２，６−ジエチルフェニル）カルボジイミド、ビス（２−エチル−６−イソプロピルフェニル）カルボジイミド、ビス（２−ブチル−６−イソプロピルフェニル）カルボジイミド、ビス（２，６−ジイソプロピルフェニル）カルボジイミド、ビス（２，６−ジ−ｔ−ブチルフェニル）カルボジイミド、ビス（２，４，６−トリメチルフェニル）カルボジイミド、ビス（２，４，６−トリイソプロピルフェニル）カルボジイミド、ビス（２，４，６−トリブチルフェニル）カルボジイミド、ジ−β−ナフチルカルボシイミド、Ｎ−トリル−Ｎ’−シクロヘキシルカルボシイミド、Ｎ−トリル−Ｎ’−フェニルカルボシイミド等のモノまたはジカルボジイミド化合物が例示される。 Examples of the carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, octyldecylcarbodiimide, di-t-butylcarbodiimide, t-butylisopropylcarbodiimide, dibenzylcarbodiimide, N-octacarbodiimide, -N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, bis (p-nitrophenyl) carbodiimide, Bis (p-aminophenyl) carbodiimide, bis (p-hydroxyphenyl) carbodiimide, bis (p- Lorophenyl) carbodiimide, bis (o-chlorophenyl) carbodiimide, bis (o-ethylphenyl) carbodiimide, bis (p-ethylphenyl) carbodiimide bis (o-isopropylphenyl) carbodiimide, bis (p-isopropylphenyl) carbodiimide, bis (o -Isobutylphenyl) carbodiimide, bis (p-isobutylphenyl) carbodiimide, bis (2,5-dichlorophenyl) carbodiimide, p-phenylenebis (o-toluylcarbodiimide), p-phenylenebis (cyclohexylcarbodiimide, p-phenylenenebis ( p-chlorophenylcarbodiimide), 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, hexamethylenebis (cyclohexylcarbodiimide), Tylene bis (phenylcarbodiimide), ethylene bis (cyclohexylcarbodiimide), bis (2,6-dimethylphenyl) carbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2-ethyl-6-isopropylphenyl) carbodiimide, bis ( 2-butyl-6-isopropylphenyl) carbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, bis (2,6-di-t-butylphenyl) carbodiimide, bis (2,4,6-trimethylphenyl) carbodiimide, Bis (2,4,6-triisopropylphenyl) carbodiimide, bis (2,4,6-tributylphenyl) carbodiimide, di-β-naphthylcarboimide, N-tolyl-N′-cyclohexylcarbosiimide, N— Thrill Mono- or di-carbodiimide compounds such as N'- phenyl carbocyclylalkyl imide and the like.
なかでも反応性、安定性の観点からビス（２，６−ジイソプロピルフェニル）カーボジイミド、２，６，２’，６’−テトライソプロピルジフェニルカルボジイミドが好ましい。またこれらのうち工業的に入手可能なジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミドの使用も好適である。 Of these, bis (2,6-diisopropylphenyl) carbodiimide and 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide are preferred from the viewpoints of reactivity and stability. Of these, industrially available dicyclohexylcarbodiimide and diisopropylcarbodiimide are also suitable.
また、ポリ（１，６−シクロヘキサンカルボジイミド）、ポリ（４，４’−メチレンビスシクロヘキシルカルボジイミド）、ポリ（１，３−シクロヘキシレンカルボジイミド）、ポリ（１，４−シクロヘキシレンカルボジイミド）、ポリ（４，４’−ジフェニルメタンカルボジイミド）、ポリ（３，３’−ジメチル−４，４’−ジフェニルメタンカルボジイミド）、ポリ（ナフチレンカルボジイミド）、ポリ（ｐ−フェニレンカルボジイミド）、ポリ（ｍ−フェニレンカルボジイミド）、ポリ（ｐ−トリルカルボジイミド）、ポリ（ジイソプロピルカルボジイミド）、ポリ（メチルジソプロピルフェニレンカルボジイミド）、ポリ（トリエチルフェニレンカルボジイミド）等のポリカルボジイミド等が挙げられる。 Also, poly (1,6-cyclohexanecarbodiimide), poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4 , 4′-diphenylmethanecarbodiimide), poly (3,3′-dimethyl-4,4′-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly Examples thereof include polycarbodiimides such as (p-tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyldisopropylphenylenecarbodiimide), and poly (triethylphenylenecarbodiimide).
市販のポリカルボジイミド化合物としては例えば日清紡績株式会社より市販されている「カルボジライト」を用いることができ、具体的にはポリ乳酸樹脂改質剤として販売されている「カルボジライト」ＬＡ−１、あるいはポリエステル樹脂改質剤として販売されている「カルボジライト」ＨＭＶ−８ＣＡ等を例示することができる。 As the commercially available polycarbodiimide compound, for example, “Carbodilite” marketed by Nisshinbo Co., Ltd. can be used. Specifically, “Carbodilite” LA-1 sold as a polylactic acid resin modifier, or polyester “Carbodilite” HMV-8CA sold as a resin modifier can be exemplified.
カルボジイミド化合物は、従来公知の方法により製造することもできる。例えば触媒として有機リン化合物または有機金属化合物を使用して、有機イソシアネートを７０℃以上の温度で無溶媒あるいは不活性溶媒中で脱炭酸縮合反応に附することにより製造することができる。またポリカルボジイミド化合物は、従来公知のポリカルボジイミド化合物の製造法、例えば米国特許２９４１９５６号明細書、特公昭４７−３３２７９号公報、Ｊ．Ｏｒｇ．Ｃｈｅｍ．２８， ２０６９−２０７５（１９６３）、Ｃｈｅｍｉｃａｌ Ｒｅｖｉｅｗ １９８１，Ｖｏｌ．８１ Ｎｏ．４、ｐ６１９−６２１等により製造することができる。 A carbodiimide compound can also be manufactured by a conventionally well-known method. For example, it can be produced by subjecting an organic isocyanate to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of 70 ° C. or higher using an organic phosphorus compound or an organometallic compound as a catalyst. The polycarbodiimide compound may be a conventionally known method for producing a polycarbodiimide compound, for example, US Pat. No. 2,941,956, Japanese Examined Patent Publication No. 47-33279, J. Pat. Org. Chem. 28, 2069-2075 (1963), Chemical Review 1981, Vol. 81 no. 4, p619-621 and the like.
カルボキシル基末端封止剤の含有量は、ポリ乳酸組成物１００重量部当たり、好ましくは０．１〜５．０重量部、さらに好ましくは０．５〜２．０重量部である。かかる範囲のカルボキシル基末端封止剤を含有するポリ乳酸繊維は、１００℃の沸水中３０分間の処理後の分子量保持率が９５％以上となり、さらに好ましい繊維を得ることができる。 The content of the carboxyl group terminal blocking agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 2.0 parts by weight, per 100 parts by weight of the polylactic acid composition. A polylactic acid fiber containing a carboxyl group end-capping agent in such a range has a molecular weight retention of 95% or more after treatment for 30 minutes in boiling water at 100 ° C., and a more preferable fiber can be obtained.
また、例えば、下記式で表されるスルホン酸化合物をポリ乳酸組成物に含有するものは、アルカリ減量処理すると繊維表面に微細孔を形成することができ、繊細なドライ感を有した布帛が得られるので好ましい。 In addition, for example, those containing a sulfonic acid compound represented by the following formula in a polylactic acid composition can form fine pores on the fiber surface when subjected to alkali weight reduction treatment, and a fabric having a delicate dry feeling can be obtained. This is preferable.
式中、Ｒは炭素数３〜３０のアルキル基または炭素数７〜４０のアリール基もしくはアルキルアリール基、Ｍ1およびＭ2はアルカリ金属またはアルカリ土類金属、ｎは０〜２の整数を示す。 In the formula, R is an alkyl group having 3 to 30 carbon atoms, or an aryl group or alkylaryl group having 7 to 40 carbon atoms, M 1 and M 2 are alkali metals or alkaline earth metals, and n is an integer of 0 to 2. .
上記式において、Ｒがアルキル基またはアルキルアリール基であるときは、該アルキルは直鎖状でも分岐した側鎖を有していてもよい。特に減量後の微細孔形状の点からＲがアルキルアリール基であるアルキルアリールスルホン酸金属塩が好ましい。Ｍ1およびＭ2はナトリウム、カリウム、リチウム等のアルカリ属、またはカルシウム、マグネシウム等のアルカリ土類金属であり、なかでもナトリウム、カリウム、マグネシウムが好ましい。
かかるスルホン酸化合物の好ましい具体例としては、アルキルスルホン酸ナトリウム、スルホイソフタル酸ナトリウム等があげられる。
In the above formula, when R is an alkyl group or an alkylaryl group, the alkyl may be linear or have a branched side chain. In particular, an alkylaryl sulfonic acid metal salt in which R is an alkylaryl group is preferred from the viewpoint of the micropore shape after weight reduction. M 1 and M 2 are alkali metals such as sodium, potassium and lithium, or alkaline earth metals such as calcium and magnesium, among which sodium, potassium and magnesium are preferable.
Specific examples of such sulfonic acid compounds include sodium alkyl sulfonate and sodium sulfoisophthalate.
また、上記スルホン酸化合物は１種のみ単独で使用しても、また２種以上併用してもよい。その添加時期はポリ乳酸繊維を製造するにあたり、ポリ乳酸組成物を溶融紡糸の吐出が終了する以前の任意の段階で良く、たとえばポリ乳酸組成物中に添加配合しても、また合成終了後から溶融吐出紡糸するまでの間に添加してもよい。いずれにしても、添加後溶融状態で混合されるようにするのが好ましい。 Moreover, the said sulfonic acid compound may be used individually by 1 type, and may be used together 2 or more types. The polylactic acid composition may be added at any stage prior to the end of the melt spinning discharge. For example, the polylactic acid composition may be added and blended in the polylactic acid composition or after the synthesis is completed. It may be added before melt discharge spinning. In any case, it is preferable to mix in a molten state after addition.
次に、本発明の布帛を構成するマルチフィラメント糸は、糸長方向にマルチフィラメントとしての見掛けの太さ斑を有しており、その太部と細部との比が１．１以上（好ましくは１．２〜１．８）であることが肝要である。 Next, the multifilament yarn constituting the fabric of the present invention has an apparent thickness unevenness as a multifilament in the yarn length direction, and the ratio of the thick portion to the details is 1.1 or more (preferably It is important that it is 1.2 to 1.8).
ここで、見掛けの太細比は以下の方法により測定する。即ち、布帛を構成する糸条を、少なくとも１０ｃｍの長さに亘って電子顕微鏡を用いて観察し、その電子顕微鏡画面上もしくは写真上で、最も糸が膨らんだ部分（太部）の幅と最も糸が集束した部分（細部）の幅との比を求める。 Here, the apparent thickness ratio is measured by the following method. That is, the yarn constituting the fabric is observed with an electron microscope over a length of at least 10 cm, and on the electron microscope screen or photograph, the width of the most swollen part (thick part) and the most Find the ratio to the width of the part (detail) where the yarns converge.
上記の、太部と細部との比が１．１未満の場合は、充分なスパナイズ感と均一なナチュラル外観が発現しない。また、太部と細部との長さには特に限定はないが、太部の長さが１０〜５０ｍｍで、隣接する太部／細部の糸長比が１／０．５〜１／３０であることが好ましい。 When the ratio between the thick part and the detail is less than 1.1, sufficient spanization feeling and uniform natural appearance are not exhibited. The length between the thick part and the detail is not particularly limited, but the length of the thick part is 10 to 50 mm, and the adjacent thick part / detail has a yarn length ratio of 1 / 0.5 to 1/30. Preferably there is.
上記のマルチフィラメント糸は、例えば、マルチフィラメントを構成する各フィラメント間に、ランダムな繊度分布及びそれに起因する収縮分布を持たせることにより得ることができる。 The above-mentioned multifilament yarn can be obtained, for example, by giving a random fineness distribution and a shrinkage distribution resulting therefrom between the filaments constituting the multifilament.
この際の繊度分布は、１．１１〜４．４４ｄｔｅｘであることが好ましい。このような繊度分布を持たせることにより、各フィラメント間には沸水収縮率が３．０〜１５．０％のランダムな収縮斑が発現し、マルチフィラメントとしての見掛けの太さ斑が発現する。 In this case, the fineness distribution is preferably 1.11 to 4.44 dtex. By giving such a fineness distribution, random shrinkage spots with a boiling water shrinkage of 3.0 to 15.0% appear between the filaments, and apparent thickness spots as multifilaments appear.
また、上記のマルチフィラメント糸は、構成フィラメントがランダムな繊度分布を有しているので、太部と細部とが同一色に染色可能である。
ここで、同一色とは、形態差から太細の外観を認識することはできるが、染着差によりスラブ調の外観を呈するものではないということを意味する。
In the multifilament yarn, the constituent filaments have a random fineness distribution, so that the thick portion and the details can be dyed in the same color.
Here, the same color means that a thick and thin appearance can be recognized from a difference in form, but it does not exhibit a slab-like appearance due to a dyeing difference.
上記フィラメントは、丸断面であっても上述のナチュラル感、ドライ感を発現する事はできるが、三角（異型）断面の方が繊細なドライ感やスパナイズ外観を付与する面でより好ましい。また、吸汗・速乾といった快適性を発現させる場合にも三角（異型）断面の方が単繊維間の毛細管現象による水分の拡散性を発現しやすく好ましい。 Even if the filament has a round cross section, the above-mentioned natural feeling and dry feeling can be expressed, but a triangular (atypical) cross section is more preferable in terms of imparting a delicate dry feeling and a spanizing appearance. In addition, when expressing comfort such as sweat absorption and quick drying, a triangular (atypical) cross section is preferable because it tends to exhibit moisture diffusibility due to capillary action between single fibers.
上記のマルチフィラメント糸は、具体的には下記の方法により製造することができる。すなわち、前述のポリ乳酸組成物を加熱して紡糸口金から溶融吐出し、冷却固化した紡出糸条に油剤を付与し、インターレース付与装置でインターレースを付与した後、ポリエステルのガラス転移温度以下に設定した予熱ローラーおよび延伸ローラーを介して半延伸糸を一旦ワインダーに捲き取る。 Specifically, the multifilament yarn can be produced by the following method. That is, the above-mentioned polylactic acid composition is heated and melted and discharged from a spinneret, an oil agent is applied to the cooled and solidified spun yarn, interlace is applied by an interlace applying device, and then set to a glass transition temperature or less of the polyester. The semi-stretched yarn is once wound on a winder through the preheating roller and the stretching roller.
次いで、得られた半延伸糸を、延伸速度５００〜１５００ｍ／分で、８０〜１１０℃に加熱した予熱ローラーおよび１７０〜２２０℃に設定した非接触式ヒータを経て、１．１〜２．０倍の延伸倍率で延伸し、さらに必要に応じて１５０〜２００℃に設定した接触式または非接触式ヒーターを経て、０．８〜１．２倍の延伸倍率で熱セットを施す事により得られる。 Subsequently, the obtained semi-drawn yarn was passed through a preheating roller heated to 80 to 110 ° C. at a drawing speed of 500 to 1500 m / min and a non-contact heater set to 170 to 220 ° C., and then 1.1 to 2.0. It is obtained by stretching at a stretching ratio of 2 times, and further, through a contact type or non-contact heater set at 150 to 200 ° C. as necessary, and heat setting at a stretching ratio of 0.8 to 1.2 times. .
上記のマルチフィラメント糸を用いて布帛を製造するには、必要に応じて適度な撚りを施し、所望の組織に織編すればよい。また、得られた布帛は必要に応じてリラックス、熱セット、アルカリ減量処理を施すことにより、従来の織編物では表現できなかった、優れたナチュラルスパナイズ外観と、繊細なドライ感、さらにはフェミニンなシルエットが発現する。 In order to produce a fabric using the above-mentioned multifilament yarn, an appropriate twist may be applied as necessary and knitted into a desired structure. In addition, the obtained fabric is subjected to relaxation, heat setting, and alkali weight reduction treatment as necessary, so that it has an excellent natural spanish appearance, delicate dryness, and feminine that could not be expressed with conventional woven or knitted fabrics. A silhouette is expressed.
なお、本発明は、新規なスパナイズ感、均一色のナチュラル外観、繊細なドライ感を有する布帛の製造を意図しているので、複雑な組織に織成・編成するのは好ましくなく、平織もしくはその変化組織、綾織もしくはその変化組織、サテン織等に織編成するのが好ましい。また、本発明の布帛を構成するポリ乳酸繊維の該布帛中に占める割合は、必ずしも１００％である必要はないが、優れたスパナイズ外観とナチュラル感、ドライ感を得るためにはその割合が多いほど好ましい。 Since the present invention is intended to produce a fabric having a novel spanization feeling, a uniform natural appearance, and a delicate dry feeling, it is not preferable to weave and knitting into a complex structure. It is preferable to perform knitting into a change structure, a twill weave or its change structure, a satin weave, and the like. Further, the proportion of the polylactic acid fiber constituting the fabric of the present invention in the fabric does not necessarily need to be 100%, but the proportion is large in order to obtain an excellent spanize appearance, natural feeling and dry feeling. The more preferable.
さらに、上記のマルチフィラメント糸を構成するフィラメントの表面に凹凸を付与することにより水の接触角度を低下させ、さらには単繊維間の毛細管現象による水分の拡散性を利用することにより、布帛そのものに吸汗性（吸水性）を持たせることも可能である。 Furthermore, by providing irregularities on the surface of the filament constituting the above-mentioned multifilament yarn, the contact angle of water is lowered, and further by utilizing the diffusibility of moisture due to the capillary phenomenon between single fibers, the fabric itself It is also possible to impart sweat absorption (water absorption).
また、かかる布帛には、通常の染色加工が施されていることが好ましい。その際、染色処理の条件としては特に制限されず、通常の分散染料を用いた染色処理でよい。例えば、分散染料の他、均染剤、ｐＨ調整剤等を含んだ染料水溶液にて１００℃以上（好ましくは１００〜１４０℃）の温度で２０〜４０分間染色処理を行うとよい。染色に用いる染料としては、洗濯堅牢度が良好なアゾ系分散染料が好ましく例示されるが、特に限定されない。なかでも、後記の洗浄処理液中で容易に分解される分散染料として、ジエステル基を有する分散染料、アゾ系分散染料、中でもチアゾール型、チオフェン型が好ましく例示されるが、特に限定されない。さらに、アントラキノン系分散染料、ベンゾジフィラノン型分散染料、アルキルアミン基を有する分散染料なども挙げられる。 Moreover, it is preferable that normal dyeing | staining process is given to this fabric. In this case, the conditions for the dyeing process are not particularly limited, and a dyeing process using a normal disperse dye may be used. For example, the dyeing treatment may be performed at a temperature of 100 ° C. or higher (preferably 100 to 140 ° C.) for 20 to 40 minutes with a dye aqueous solution containing a leveling agent, a pH adjuster, etc. in addition to the disperse dye. The dye used for dyeing is preferably an azo-based disperse dye having good washing fastness, but is not particularly limited. Among these, disperse dyes that are easily decomposed in a cleaning treatment liquid described later are preferably disperse dyes having a diester group, azo disperse dyes, among which thiazole type and thiophene type, but are not particularly limited. Further examples include anthraquinone-based disperse dyes, benzodiphyranone-type disperse dyes, and disperse dyes having an alkylamine group.
次いで、かかる染色処理された布帛に還元洗浄処理を施すことが好ましい。その際、ｐＨ８〜２の還元浴中で還元洗浄処理する事が好ましい。ｐｈ８より大のアルカリ領域では、ポリ乳酸繊維が加水分解され、繊維強度が低下するおそれがある。 Next, it is preferable to perform a reduction cleaning process on the dyed fabric. At that time, it is preferable to perform a reduction cleaning treatment in a reducing bath having a pH of 8 to 2. In an alkaline region larger than ph8, the polylactic acid fiber may be hydrolyzed and the fiber strength may be reduced.
また、還元剤としては、錫系還元剤、ロンガリットＣ、ロンガリットＺ、塩化第１スズ、スルフィン系還元剤、ハイドロサルファイトなどが挙げられる。還元剤の使用濃度は、１〜１０ｇ／Ｌ、が好ましく、使用染料タイプ、染色濃度、還元浴温度によって濃度を選定すればよい。還元浴の処理温度は特に限定しないが、６０〜９８℃の範囲が好ましく、処理時間は１０〜４０分が好ましい。 Examples of the reducing agent include a tin-based reducing agent, Rongalite C, Rongalit Z, stannous chloride, a sulfine-based reducing agent, and hydrosulfite. The concentration of the reducing agent used is preferably 1 to 10 g / L, and the concentration may be selected according to the type of dye used, the dyeing concentration, and the reducing bath temperature. Although the processing temperature of a reducing bath is not specifically limited, The range of 60-98 degreeC is preferable, and the processing time is 10 to 40 minutes.
さらには、還元浴中での処理の際に、繊維膨潤剤として、一般に用いられるキャリヤー、例えばクロルベンゼン系キャリヤー、メチルナフタレン系キャリヤー、オルソフェニールフェノール系キャリヤー、芳香族エーテル系キャリヤー、芳香族エステル系キャリヤーなどを用いてもよい。この繊維膨潤剤としては、繊維に親和性があると考えられるポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレンアルキルフェノールエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアミンエーテル、ポリオキシエチレンアルキルベンジルアンモニウムクロライド、アルキルピコリニウムクロライドなどが挙げられるが、限定はされない。 Further, in the treatment in the reducing bath, as a fiber swelling agent, generally used carriers such as chlorobenzene carrier, methylnaphthalene carrier, orthophenylphenol carrier, aromatic ether carrier, aromatic ester A carrier or the like may be used. Examples of the fiber swelling agent include polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl amine, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl amine ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl amine, polyoxyethylene alkyl phenol ether, Examples include, but are not limited to, ethylene alkyl benzyl ammonium chloride and alkyl picolinium chloride.
なお、本発明の布帛には、常法の撥水加工、起毛加工、紫外線遮蔽あるいは抗菌剤、消臭剤、防虫剤、蓄光剤、再帰反射剤、マイナスイオン発生剤等の機能を付与する各種加工を付加適用してもよい。 The fabric of the present invention has various functions such as conventional water-repellent processing, raising processing, ultraviolet shielding or antibacterial agent, deodorant, insect repellent, phosphorescent agent, retroreflective agent, negative ion generator and the like. Processing may be additionally applied.
次に、本発明の衣料は、前記の布帛を用いてなる衣料である。かかる衣料には、婦人衣料、ファッション衣料、紳士衣料、スポーツ衣料、ニフォーム衣料、シャツ、ブルゾン、パンツ、コートなどが含まれる。かかる衣料は前記の布帛が含まれるので、ポリ乳酸繊維からなるにもかかわらず、スパナイズ感および均一色のナチュラル外観を呈する。 Next, the apparel of the present invention is apparel using the above-mentioned fabric. Such clothing includes women's clothing, fashion clothing, men's clothing, sports clothing, nifoam clothing, shirts, blousons, pants, coats, and the like. Since such a garment includes the above-described fabric, it has a feeling of spanization and a natural appearance with a uniform color despite being made of polylactic acid fiber.
以下、本発明を、実施例を用いて説明するが、本発明はこの実施例に限定されるものでははない。なお、実施例中の物性は下記の方法により測定した。 Hereinafter, although the present invention is explained using an example, the present invention is not limited to this example. In addition, the physical property in an Example was measured with the following method.
（１）重量平均分子量（Ｍｗ）
ポリマーの重量平均分子量はＧＰＣ（カラム温度４０℃、クロロホルム）により、ポリスチレン標準サンプルとの比較で求めた。
(1) Weight average molecular weight (Mw)
The weight average molecular weight of the polymer was determined by GPC (column temperature 40 ° C., chloroform) in comparison with a polystyrene standard sample.
（２）ステレオ化率（Ｓｃ化率）
理化学電気社製ＲＯＴＡ ＦＬＥＸ ＲＵ２００Ｂ型Ｘ線回折装置用いて透過法により、以下の条件でＸ線回折図形をイメージングプレートに記録した。得られたＸ線回折図形において赤道方向の回折強度プロファイルを求め、ここで２θ＝１２．０°、２０．７°、２４．０°付近に現れるステレオコンプレックス結晶に由来する各回折ピークの積分強度の総和ΣＩＳＣｉと、２θ＝１６．５°付近に現れるホモ結晶に由来する回折ピークの積分強度ＩＨＭから下式に従いステレオ化率（Ｓｃ化率）を求めた。尚、ΣＩＳＣｉならびにＩＨＭは図１に示すように、赤道方向の回折強度プロファイルにおいてバックグランドや非晶による散漫散乱を差し引くことによって見積もった。
Ｘ線源： Ｃｕ−Ｋα線（コンフォーカル ミラー）
出力： ４５ｋＶ×７０ｍＡ
スリット： １ｍｍΦ〜０．８ｍｍΦ
カメラ長： １２０ｍｍ
積算時間： １０分
サンプル： 長さ３ｃｍ、３５ｍｇ
Ｓｃ化率＝ΣＩＳＣｉ／（ΣＩＳＣｉ＋ＩＨＭ）×１００
ここで、ΣＩＳＣｉ＝ＩＳＣ１＋ＩＳＣ２＋ＩＳＣ３
ＩＳＣｉ（ｉ＝１〜３）はそれぞれ２θ＝１２．０°、２０．７°、
２４．０°付近の各回折ピークの積分強度
(2) Stereo conversion rate (Sc conversion rate)
An X-ray diffraction pattern was recorded on an imaging plate by the transmission method using a ROTA FLEX RU200B type X-ray diffractometer manufactured by RIKEN. In the obtained X-ray diffraction pattern, a diffraction intensity profile in the equator direction is obtained. Here, the integrated intensity of each diffraction peak derived from the stereocomplex crystal appearing in the vicinity of 2θ = 12.0 °, 20.7 °, and 24.0 °. Was obtained from the total intensity ΣI SCi and the integrated intensity I HM of the diffraction peak derived from the homocrystal appearing in the vicinity of 2θ = 16.5 ° in accordance with the following formula. Incidentally, as shown in FIG. 1, ΣI SCi and I HM were estimated by subtracting diffuse scattering due to background or amorphous in the diffraction intensity profile in the equator direction.
X-ray source: Cu-Kα ray (confocal mirror)
Output: 45kV x 70mA
Slit: 1mmΦ ~ 0.8mmΦ
Camera length: 120mm
Integration time: 10 minutes Sample: 3cm length, 35mg
Sc conversion rate = ΣI SCi / (ΣI SCi + I HM ) × 100
Here, ΣI SCi = I SC1 + I SC2 + I SC3
I SCi (i = 1 to 3) is 2θ = 12.0 °, 20.7 °,
Integrated intensity of each diffraction peak around 24.0 °
（３）融点、結晶融解ピーク、結晶融解開始温度、結晶融解エンタルピー測定：
ＴＡインストルメンツ製 ＴＡ−２９２０示差走査熱量測定計ＤＳＣを用いた。
測定は、試料１０ｍｇを窒素雰囲気下、昇温速度１０℃／分で室温から２６０℃まで昇温した。第一スキャンで、ホモ結晶融解ピーク、ホモ結晶融解（開始）温度、ホモ結晶融解エンタルピーおよびステレオコンプレックス結晶融解ピーク、ステレオコンプレックス結晶融解（開始）温度およびステレオコンプレックス結晶融解エンタルピーを求めた。
(3) Melting point, crystal melting peak, crystal melting start temperature, crystal melting enthalpy measurement:
TA-2920 differential scanning calorimeter DSC manufactured by TA Instruments was used.
In the measurement, 10 mg of a sample was heated from room temperature to 260 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the first scan, the homocrystal melting peak, homocrystal melting (starting) temperature, homocrystal melting enthalpy and stereocomplex crystal melting peak, stereocomplex crystal melting (starting) temperature and stereocomplex crystal melting enthalpy were determined.
（４）風合い評価
極めて良好（優）、良好（良）、不良（不可）の三段階にランク付けし、総合評価は、布帛の柔らかさ（柔軟性）も加味して官能判定した。
(4) Texture evaluation It was ranked in three stages of very good (excellent), good (good), and poor (impossible), and the overall evaluation was sensory-determined by taking into consideration the softness (flexibility) of the fabric.
（５）見掛けの太細比
布帛を構成する糸条を、１０ｃｍの長さに亘って電子顕微鏡を用いて観察し、その電子顕微鏡画面上もしくは写真上で、最も糸が膨らんだ部分（太部）の幅と最も糸が集束した部分（細部）の幅との比（太部の幅）／（細部の幅）を求めた。
(5) Apparent Thickness Ratio The yarn constituting the fabric was observed with an electron microscope over a length of 10 cm, and the most swollen portion (thick portion) on the electron microscope screen or photograph ) And the width of the portion where the yarn is most concentrated (detail) (thick portion width) / (detail width).
［製造例１］（ポリＬ−乳酸の製造）
Ｌラクチド（株式会社武蔵野化学研究所製、光学純度１００％）１００重量部に対し、オクチル酸スズを０．００５重量部加え、窒素雰囲気下、攪拌翼のついた反応機にて、１８０℃で２時間反応し、オクチル酸スズに対し１．２倍当量の燐酸を添加しその後、１３．３ｋＰａで残存するラクチドを除去し、チップ化し、ポリＬ−乳酸を得た。
得られたＬ−乳酸の重量平均分子量は１５万、ガラス転移点（Ｔｇ）６３℃、融点は１８０℃であった。
[Production Example 1] (Production of poly L-lactic acid)
To 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), 0.005 part by weight of octyltin is added, and the reaction is carried out at 180 ° C. in a nitrogen atmosphere in a reactor equipped with a stirring blade. After reacting for 2 hours, phosphoric acid equivalent to 1.2 times the amount of tin octylate was added, and then the remaining lactide was removed at 13.3 kPa to obtain chips to obtain poly L-lactic acid.
The obtained L-lactic acid had a weight average molecular weight of 150,000, a glass transition point (Tg) of 63 ° C., and a melting point of 180 ° C.
［製造例２］（ポリＤ−乳酸の製造）
Ｄラクチド（株式会社武蔵野化学研究所製、光学純度１００％）１００重量部に対し、オクチル酸スズを０．００５重量部加え、窒素雰囲気下、攪拌翼のついた反応機にて、１８０℃で２時間反応し、オクチル酸スズに対し１．２倍当量の燐酸を添加しその後、１３．３ｋＰａで残存するラクチドを除去し、チップ化し、ポリＤ−乳酸を得た 得られたポリＤ−乳酸の重量平均分子量は１５万、ガラス転移点（Ｔｇ）６３℃、融点は１８０℃であった。
[Production Example 2] (Production of poly-D-lactic acid)
To 100 parts by weight of D-lactide (manufactured by Musashino Chemical Laboratory, Inc., 100% optical purity), 0.005 part by weight of tin octylate was added, and the reactor was stirred at 180 ° C. with a stirring blade in a nitrogen atmosphere. After reacting for 2 hours, phosphoric acid equivalent to 1.2 times the amount of tin octylate was added, and then the remaining lactide was removed at 13.3 kPa to obtain chips. Poly D-lactic acid was obtained. The weight average molecular weight was 150,000, the glass transition point (Tg) was 63 ° C., and the melting point was 180 ° C.
［製造例３］（ステレオコンプレックスポリ乳酸樹脂の製造）
製造例１で得られたポリＬ−乳酸ならびに製造例２のポリＤ−乳酸を各５０重量部と、リン酸エステル金属塩（株式会社ＡＤＥＫＡ（旧：旭電化工業株式会社）製アデカスタブＮＡ−１１）０．５重量部を２３０℃で溶融混練し、ポリＬ−乳酸ならびにポリＤ‐乳酸の合計１００重量部あたりカルボジイミドとして日清紡（株）製カルボジライトＬＡ−１を０．７重量部、第一供給口より供給しシリンダー温度２３０℃で混練押出して、水槽中にストランドを取り、チップカッターにてチップ化してステレオコンプレックスポリ乳酸樹脂を得た。得られたステレオコンプレックスポリ乳酸樹脂のＭｗは１３．５万、融点（Ｔｍ）は２２４℃、ステレオ化率は１００％であった。
[Production Example 3] (Production of stereocomplex polylactic acid resin)
50 parts by weight of each of the poly L-lactic acid obtained in Production Example 1 and the poly D-lactic acid in Production Example 2, and phosphate metal salt (ADEKA (former: Asahi Denka Kogyo Co., Ltd.) ADK STAB NA-11) ) 0.5 parts by weight was melt-kneaded at 230 ° C., and 0.7 parts by weight of Nisshinbo Carbodilite LA-1 as the carbodiimide per 100 parts by weight of the total of poly L-lactic acid and poly D-lactic acid was supplied first. The mixture was supplied from the mouth and kneaded and extruded at a cylinder temperature of 230 ° C., and the strand was taken into a water tank and chipped with a chip cutter to obtain a stereocomplex polylactic acid resin. Mw of the obtained stereocomplex polylactic acid resin was 135,000, melting | fusing point (Tm) was 224 degreeC, and the stereoification rate was 100%.
［実施例１］
製造例３で得られたステレオコンプレックスポリ乳酸樹脂に、炭素数が７〜２０で平均炭素数が８であるアルキルスルホン酸ナトリウムを０．７５重量％含有させたステレオコンプレックスポリ乳酸樹脂を紡糸口金から溶融吐出し、該吐出糸条を冷却固化させた後に油剤を付与し、次いでインターレースを付与した後に２６００ｍ／分の速度で引取り、３０００ｍ／分の速度で半延伸し、巻き取った。
[Example 1]
A stereocomplex polylactic acid resin obtained by adding 0.75% by weight of sodium alkylsulfonate having 7 to 20 carbon atoms and an average carbon number of 8 to the stereocomplex polylactic acid resin obtained in Production Example 3 from a spinneret. After the melt was discharged and the discharged yarn was cooled and solidified, an oil agent was applied, and then an interlace was applied and then taken up at a speed of 2600 m / min, semi-stretched at a speed of 3000 m / min, and wound up.
得られた半延伸糸を、予熱ローラー温度９０℃、熱セットヒーター（非接触式）温度１９０℃、延伸倍率１．２倍、延伸速度８００ｍ／分で延伸した後、熱セットヒーター（接触式）温度１６７℃、延伸倍率０．９８倍で熱セットして巻き取り、１２０ｄｔｅｘ／３６フィラメントの糸条を得た。該糸条において、該融解ピーク温度（融点）が２２４℃であり、ステレオ化率１００％であった。 The semi-drawn yarn obtained was drawn at a preheating roller temperature of 90 ° C., a heat set heater (non-contact type) temperature of 190 ° C., a draw ratio of 1.2 times, and a drawing speed of 800 m / min, and then a heat set heater (contact type). Heat setting was performed at a temperature of 167 ° C. and a draw ratio of 0.98 times to wind up, and a 120 dtex / 36 filament yarn was obtained. In the yarn, the melting peak temperature (melting point) was 224 ° C., and the stereoification rate was 100%.
得られた糸条に１０００Ｔ／ｍの撚を付与したものを経糸及び緯糸に用い、経糸密度：７８本／２．５４ｃｍ、緯糸密度：６８本／２．５４ｃｍ、の規格にて平織り（ボイル）に織成した。次いで常法にしたがって精練、プレ熱セット、アルカリ減量加工（減量率１５％）、染色加工（温度１２０℃で２０分間）、ファイナル熱セットを施して仕上げた。 The obtained yarn with a twist of 1000 T / m is used for warp and weft. Plain weave (voile) according to the specifications of warp density: 78 / 2.54 cm and weft density: 68 / 2.54 cm. Was woven. Subsequently, scouring, pre-heat setting, alkali weight reduction processing (weight loss rate of 15%), dyeing processing (temperature of 120 ° C. for 20 minutes) and final heat setting were performed according to conventional methods.
得られた布帛を構成するマルチフィラメント糸の見掛けの太細比は１．５であり、布帛は均一に染色されていて、新規なスパナイズ感、ナチュラル外観、繊細なドライ感、フェミニンなシルエットといった高感性を呈し、且つ吸汗・速乾といった快適機能性にも優れたものであった。 The apparent thickness ratio of the multifilament yarn constituting the obtained fabric is 1.5, the fabric is uniformly dyed, and it has a high level of feeling such as a new spanish feeling, natural appearance, delicate dry feeling, and feminine silhouette. It exhibited sensibility and excellent comfort functionality such as sweat absorption and quick drying.
次いで、該布帛を用いて婦人衣料（ブラウス）を縫製したところ、該衣料は、新規なスパナイズ感、ナチュラル外観、繊細なドライ感、フェミニンなシルエットといった高感性を呈し、且つ吸汗・速乾といった快適機能性にも優れたものであった。 Next, when women's clothing (blouse) was sewn using the fabric, the clothing exhibited a high sensibility such as a novel spanning feeling, natural appearance, delicate dry feeling, feminine silhouette, and comfort such as sweat absorption and quick drying. It was also excellent in functionality.
［実施例２〜３、比較例１〜２］
実施例１において、半延伸糸の延伸倍率を種々変化させ、布帛を構成するマルチフィラメント糸の見掛けの太細比を表１に示す如く変更した以外は実施例と同様に実施した。
[Examples 2-3, Comparative Examples 1-2]
The same procedure as in Example 1 was performed except that the draw ratio of the half-drawn yarn was variously changed and the apparent thickness ratio of the multifilament yarn constituting the fabric was changed as shown in Table 1.
［比較例３］
実施例１において、ステレオコンプレックスポリ乳酸樹脂のかわりに製造例１で得られたポリＬ−乳酸を用いこと以外は実施例１と同様にした。
ポリ乳酸フィラメントの融点は１８０℃であった。得られた布帛は、染色の際の熱履歴で収縮して硬くなってしまい、スパナイズ感、ドライ感、ナチュラル感、外観全て不可であった。
[Comparative Example 3]
In Example 1, it carried out similarly to Example 1 except using the poly L-lactic acid obtained in manufacture example 1 instead of the stereocomplex polylactic acid resin.
The melting point of the polylactic acid filament was 180 ° C. The obtained fabric was shrunk and hardened by the heat history during dyeing, and all of the feeling of spanization, dryness, naturalness, and appearance were impossible.
［参考例１］
燐酸エステル金属塩として、アルミニウムビス（２，２’―メチレンビス（４，６−ジ第３ブチルフェニル）ホスフェート）ハイドロオキサイド（株式会社ＡＤＥＫＡ（旧：旭電化工業株式会社）製アデカスタブＮＡ−２１）を０．５重量部用いる以外は実施例１と同じ操作を行ったところ、紡糸の際に昇華物が激しく発生し、紡糸することが困難であった。
[Reference Example 1]
As a phosphoric acid ester metal salt, aluminum bis (2,2′-methylenebis (4,6-ditertiarybutylphenyl) phosphate) hydroxide (ADEKA STAB NA-21 manufactured by ADEKA Corporation (formerly Asahi Denka Kogyo Co., Ltd.)) When the same operation as in Example 1 was performed except that 0.5 part by weight was used, a sublimation product was vigorously generated during spinning, and it was difficult to perform spinning.
本発明によれば、スパナイズ感および均一色のナチュラル外観を呈するポリ乳酸布帛および該布帛を用いてなる衣料が提供され、その工業的価値は極めて大である。 ADVANTAGE OF THE INVENTION According to this invention, the polylactic acid cloth which exhibits a spanization feeling and the natural appearance of a uniform color, and the clothing using this cloth are provided, The industrial value is very large.
Claims (5)
前記マルチフィラメント糸が、（ｉ）ポリＬ−乳酸（Ａ成分）、（ｉｉ）ポリＤ―乳酸（Ｂ成分）および（ｉｉｉ）Ａ成分とＢ成分との合計１００重量部当たり０．０５〜５重量部の下記式（１）または（２）で表される燐酸エステル金属塩（Ｃ成分）を含有するポリ乳酸組成物から形成されることを特徴とするポリ乳酸布帛。
（見掛けの太細比の測定方法）
布帛を構成する糸条を、少なくとも１０ｃｍの長さに亘って電子顕微鏡を用いて観察し、その電子顕微鏡画面上もしくは写真上で、最も糸が膨らんだ部分（太部）の幅と最も糸が集束した部分（細部）の幅との比を求める。
The multifilament yarn is 0.05 to 5 per 100 parts by weight of (i) poly L-lactic acid (A component), (ii) poly D-lactic acid (B component) and (iii) A component and B component. A polylactic acid fabric formed from a polylactic acid composition containing parts by weight of a phosphoric acid ester metal salt (component C) represented by the following formula (1) or (2).
(Measurement method of apparent thickness ratio)
The yarn constituting the fabric is observed with an electron microscope over a length of at least 10 cm, and the width of the most swollen part (thick part) and the most thread are observed on the electron microscope screen or photograph. Find the ratio to the width of the focused part (detail).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011121380A1 (en) | 2011-12-19 | 2013-06-20 | Nextrusion Gmbh | Fabric used for e.g. filtration sieves, consists of yarns or threads containing polyethylene terephthalate, polyamides or polyolefin such as polyethylene or polypropylene and polylactide |
| CN112208159A (en) * | 2020-09-22 | 2021-01-12 | 石狮梵源服饰有限公司 | High-toughness fabric with good air permeability |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000226727A (en) * | 1999-02-08 | 2000-08-15 | Toray Ind Inc | Aliphatic polyester fiber having denier unevenness |
| JP2001329448A (en) * | 2000-05-18 | 2001-11-27 | Masako Oka | Uneven fabric and method for producing the same, uneven fiber product and method for producing the same |
| JP2002030208A (en) * | 2000-07-14 | 2002-01-31 | Toray Ind Inc | Polylactic acid resin composition and molded article |
| JP2003020520A (en) * | 2001-07-10 | 2003-01-24 | Toray Ind Inc | Aliphatic polyester thick and thin yarn and method for producing the same |
| JP2003129335A (en) * | 2001-10-24 | 2003-05-08 | Teijin Ltd | Method for manufacturing aliphatic polyester yarn with uneven thickness |
| WO2008029934A1 (en) * | 2006-09-04 | 2008-03-13 | Teijin Limited | Polylactic acid fiber and method for producing the same |
-
2008
- 2008-07-18 JP JP2008187105A patent/JP2010024576A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000226727A (en) * | 1999-02-08 | 2000-08-15 | Toray Ind Inc | Aliphatic polyester fiber having denier unevenness |
| JP2001329448A (en) * | 2000-05-18 | 2001-11-27 | Masako Oka | Uneven fabric and method for producing the same, uneven fiber product and method for producing the same |
| JP2002030208A (en) * | 2000-07-14 | 2002-01-31 | Toray Ind Inc | Polylactic acid resin composition and molded article |
| JP2003020520A (en) * | 2001-07-10 | 2003-01-24 | Toray Ind Inc | Aliphatic polyester thick and thin yarn and method for producing the same |
| JP2003129335A (en) * | 2001-10-24 | 2003-05-08 | Teijin Ltd | Method for manufacturing aliphatic polyester yarn with uneven thickness |
| WO2008029934A1 (en) * | 2006-09-04 | 2008-03-13 | Teijin Limited | Polylactic acid fiber and method for producing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011121380A1 (en) | 2011-12-19 | 2013-06-20 | Nextrusion Gmbh | Fabric used for e.g. filtration sieves, consists of yarns or threads containing polyethylene terephthalate, polyamides or polyolefin such as polyethylene or polypropylene and polylactide |
| CN112208159A (en) * | 2020-09-22 | 2021-01-12 | 石狮梵源服饰有限公司 | High-toughness fabric with good air permeability |
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