JP2009144258A - Direct drawn polylactic acid fiber and method for producing the same - Google Patents
Direct drawn polylactic acid fiber and method for producing the same Download PDFInfo
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- JP2009144258A JP2009144258A JP2007319547A JP2007319547A JP2009144258A JP 2009144258 A JP2009144258 A JP 2009144258A JP 2007319547 A JP2007319547 A JP 2007319547A JP 2007319547 A JP2007319547 A JP 2007319547A JP 2009144258 A JP2009144258 A JP 2009144258A
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- lactic acid
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- 239000000835 fiber Substances 0.000 title claims abstract description 93
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 33
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims abstract description 45
- 229940022769 d- lactic acid Drugs 0.000 claims abstract description 39
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract description 38
- 229930182843 D-Lactic acid Natural products 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 238000004804 winding Methods 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims description 53
- 230000008018 melting Effects 0.000 claims description 53
- 238000005259 measurement Methods 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001340 alkali metals Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000004736 wide-angle X-ray diffraction Methods 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000002270 phosphoric acid ester group Chemical group 0.000 claims 1
- 150000003014 phosphoric acid esters Chemical class 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 description 50
- -1 phosphate ester Chemical class 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 19
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 230000004927 fusion Effects 0.000 description 8
- 238000010409 ironing Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000004310 lactic acid Substances 0.000 description 6
- 235000014655 lactic acid Nutrition 0.000 description 6
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000002074 melt spinning Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 229920002988 biodegradable polymer Polymers 0.000 description 4
- 239000004621 biodegradable polymer Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920001577 copolymer Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000009940 knitting Methods 0.000 description 3
- 239000000463 material Substances 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
- 239000002245 particle Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 239000004753 textile 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
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-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
- 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
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 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
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization 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
- 230000007547 defect Effects 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
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- 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
- 230000007062 hydrolysis Effects 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 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
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- 229960000380 propiolactone Drugs 0.000 description 2
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- 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
- 239000002759 woven fabric Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- KZGROEDUAFPSGN-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphate Chemical compound CC(C)(C)C1=CC=C(OP(O)(O)=O)C(C(C)(C)C)=C1 KZGROEDUAFPSGN-UHFFFAOYSA-N 0.000 description 1
- QMXGHCBQHAQFHX-UHFFFAOYSA-N 2,4-ditert-butylphenol;sodium Chemical compound [Na].CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 QMXGHCBQHAQFHX-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- 101000979912 Homo sapiens Sphingomyelin phosphodiesterase 2 Proteins 0.000 description 1
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- JAKYSQPCKJGHDB-UHFFFAOYSA-N ethyl(oxo)tin Chemical compound CC[Sn]=O JAKYSQPCKJGHDB-UHFFFAOYSA-N 0.000 description 1
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
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Images
Abstract
Description
本発明は、ポリ乳酸からなり、実用的強度、耐熱性、低熱収縮性を有し、未延伸糸の経時による物性変化管理が必要でない直接延伸法によって得られた繊維およびその製造方法に関する。また、本発明は該繊維からなる繊維製品に関する。 The present invention relates to a fiber made of polylactic acid, having a practical strength, heat resistance, and low heat shrinkage, and a fiber obtained by a direct drawing method that does not require management of changes in physical properties of undrawn yarn over time, and a method for producing the same. The present invention also relates to a fiber product comprising the fiber.
近年、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、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、ポリ乳酸が知られている。これらは溶融成形が可能であり、汎用性ポリマーとしても期待されている。これらの中でポリ乳酸は、ポリ乳酸の原料である乳酸あるいはラクチドが、天然物から製造することができるので、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つつある。ポリ乳酸のような生分解性ポリマーは透明性が高く、強靭であるが、水の存在下では容易に加水分解され、廃棄後には環境を汚染することなく分解するので、環境負荷の少ない汎用ポリマーとして期待されている。 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. As biodegradable polymers, polyhydroxybutyrate, polycaprolactone, aliphatic polyester, and polylactic acid are known. These can be melt-molded and are expected as versatile polymers. Among these, polylactic acid is a raw material for polylactic acid, and since lactic acid or lactide can be produced from natural products, we are considering using it as a general-purpose polymer that is not only a biodegradable polymer but also a global environment. It is being done. Biodegradable polymers such as polylactic acid are highly transparent and tough, but they are easily hydrolyzed in the presence of water and decompose without polluting the environment after disposal. As expected.
ポリ乳酸の融点は１５０〜１７０℃の範囲にあり、衣料用繊維として使用する場合、アイロン可能な温度が低温に限られてしまう。また、産業用繊維として使用する場合、製造温度が１５０℃程度の高温に晒されるゴム資材や樹脂コート布巾には適さないなどの問題もあった。 The melting point of polylactic acid is in the range of 150 to 170 ° C., and when used as clothing fibers, the ironable temperature is limited to low temperatures. In addition, when used as an industrial fiber, there is a problem that the manufacturing temperature is not suitable for rubber materials and resin-coated cloths that are exposed to a high temperature of about 150 ° C.
一方、Ｌ−乳酸単位のみからなるポリＬ−乳酸（以下、ＰＬＬＡと略称することがある。）とＤ−乳酸単位のみからなるポリＤ−乳酸（以下、ＰＤＬＡと略称することがある。）を溶液あるいは溶融状態で混合することにより、ステレオコンプレックスポリ乳酸が形成されることが知られている（非特許文献１）。このステレオコンプレックスポリ乳酸は、ＰＬＬＡやＰＤＬＡに比べて、高融点で、高結晶性を示すことが知られている。ステレオコンプレックスポリ乳酸を用いた繊維についても種々の検討がなされている。 On the other hand, poly L-lactic acid (hereinafter sometimes abbreviated as PLLA) consisting only of L-lactic acid units and poly D-lactic acid (hereinafter sometimes abbreviated as PDLA) consisting only of D-lactic acid units. It is known that stereocomplex polylactic acid is formed by mixing in a solution or in a molten state (Non-patent Document 1). This stereocomplex polylactic acid is known to have a higher melting point and higher crystallinity than PLLA and PDLA. Various studies have also been made on fibers using stereocomplex polylactic acid.
例えば、特許文献１には、ポリ−Ｌ−乳酸とポリ−Ｄ−乳酸を等モル量含む組成物を溶融紡糸したステレオコンプレックスポリ乳酸繊維が開示されている。得られた繊維の強度は０．５ｃＮ／ｄｔｅｘ程度で実用に供するには強度は充分ではない。 For example, Patent Document 1 discloses a stereocomplex polylactic acid fiber obtained by melt spinning a composition containing equimolar amounts of poly-L-lactic acid and poly-D-lactic acid. The strength of the obtained fiber is about 0.5 cN / dtex, and the strength is not sufficient for practical use.
また非特許文献２には、溶融紡糸によりステレオコンプレックスポリ乳酸繊維を得ることが記載されている。この文献には、ポリＬ−乳酸とポリＤ−乳酸との溶融ブレンド物を溶融紡糸した未延伸糸を熱処理することでステレオコンプレックス繊維を得ることが記載されているが、熱処理時に繊維内部の分子配向が緩和してしまい、得られる繊維の強度は２．３ｃＮ／ｄＴｅｘにとどまっている。 Non-Patent Document 2 describes that a stereocomplex polylactic acid fiber is obtained by melt spinning. This document describes that a stereocomplex fiber is obtained by heat-treating an undrawn yarn obtained by melt-spinning a melt blend of poly-L-lactic acid and poly-D-lactic acid. The orientation is relaxed, and the strength of the resulting fiber remains at 2.3 cN / dTex.
このように従来のステレオコンプレックスの形成方法は、ポリＬ−乳酸とポリＤ−乳酸のブレンド物を紡糸して得られる非晶性未延伸糸を延伸、熱処理するものである。即ち従来技術では、ステレオコンプレックスを十分成長させるためには、ポリＬ−乳酸或いはポリＤ−乳酸の単独結晶の融点以上の温度で熱処理することが効率的であるとの理念のもと、熱処理を単独結晶の融点より高い温度で実施するものが主流であった。たしかに、ステレオコンプレックス生成にこの高温熱処理は有効であったが、しかし、高温で熱処理すると糸の部分融解が発生し、糸が粗硬化したり低強度化したりする問題があった。 Thus, the conventional method for forming a stereocomplex involves stretching and heat-treating an amorphous undrawn yarn obtained by spinning a blend of poly L-lactic acid and poly D-lactic acid. That is, in the prior art, in order to sufficiently grow the stereocomplex, it is effective to perform the heat treatment at a temperature equal to or higher than the melting point of the single crystal of poly L-lactic acid or poly D-lactic acid. The mainstream was one carried out at a temperature higher than the melting point of the single crystal. Certainly, this high-temperature heat treatment was effective for the formation of a stereocomplex, but there was a problem that when the heat treatment was performed at a high temperature, the yarn partially melted, and the yarn was coarsely cured or reduced in strength.
この問題に対し、特許文献２には、紡糸線上でポリ乳酸の溶融体から一気にステレオコンプレックスの形成する方法が提案されている。例えば紡糸速度４０００ｍ／分の高速で紡糸し、広角Ｘ線回折法（ＸＲＤ）測定よるステレオ化率が１０〜３５％の結晶化未延伸糸を１．４〜２．３倍の延伸を行うことで、糸の部分融着を改善することが提案されている。しかし、この方法を実施するためには、３０００ｍ／分程度の紡速では不十分で、５０００ｍ／分以上の紡速で紡糸するための特殊な紡糸設備が必要である。また、この提案における耐熱性の評価は、繊維の筒編に１７０℃アイロンをあて編地の破れ、粗硬化といった激しい変化をみるものであり、衣料用繊維における衣料の縮みについてはなんら検討されておらず、耐熱性についての検討は不十分である。このように、ステレオ化率が０％の未延伸糸から、高いステレオ化率を有し、強度および耐熱収縮性に優れた繊維を製造する技術は完成されていないのが現状である。 In order to solve this problem, Patent Document 2 proposes a method of forming a stereocomplex at once from a melt of polylactic acid on a spinning line. For example, spinning is performed at a spinning speed of 4000 m / min, and a crystallized undrawn yarn having a stereoization ratio of 10 to 35% as measured by wide angle X-ray diffraction (XRD) is stretched by 1.4 to 2.3 times. It has been proposed to improve the partial fusion of the yarn. However, in order to carry out this method, a spinning speed of about 3000 m / min is insufficient, and a special spinning facility for spinning at a spinning speed of 5000 m / min or more is necessary. In addition, the evaluation of heat resistance in this proposal shows a drastic change such as breaking the fabric by applying a 170 ° C iron to the fiber knitting of the fiber and rough hardening. However, the study on heat resistance is insufficient. Thus, the present condition is that the technique which manufactures the fiber which has a high stereoization rate and was excellent in intensity | strength and heat-resistant shrinkage from the undrawn yarn whose stereoization rate is 0% is not completed.
また特許文献３には、紡糸ドラフト≧５０、引き取り速度≧３００ｍ／分で溶融紡糸した未延伸糸をいったん巻き取ったあと延伸を行うか、または巻き取ることなく２．８倍延伸を行い、１２０〜１８０℃で熱処理することによりポリ乳酸ホモ結晶と１９０℃以上のステレオコンプレックス結晶の２つのピークを有する２００℃の耐熱性を有する繊維が提案されている。 Patent Document 3 discloses that an undrawn yarn melt-spun at a spinning draft ≧ 50 and take-up speed ≧ 300 m / min is once wound and then stretched or stretched 2.8 times without being wound. A fiber having heat resistance of 200 ° C. having two peaks of polylactic acid homocrystal and 190 ° C. or higher stereocomplex crystal by heat treatment at ˜180 ° C. has been proposed.
更に特許文献４には、ポリＬ−乳酸、ポリＤ−乳酸のブレンド物を溶融紡糸・延伸・熱セットしステレオコンプレックスを形成させ、ＤＳＣ測定でのステレオコンプレックス結晶の結晶融解に起因する吸熱量と、ホモポリＬ−乳酸、ホモポリＤ−乳酸単独結晶の結晶融解に起因する吸熱量との比が１０以上となる技術が提案されているが、２種類以上の結晶形態が混在している状態である上、未延伸状態での結晶・非晶などの構造については示されておらず、製糸する技術としては不十分である。 Furthermore, in Patent Document 4, a poly-L-lactic acid and poly-D-lactic acid blend is melt-spun, stretched, and heat-set to form a stereo complex, and the endothermic amount resulting from crystal melting of the stereo complex crystal in DSC measurement In addition, a technique has been proposed in which the ratio of the endothermic amount resulting from crystal melting of homopoly L-lactic acid or homopoly D-lactic acid single crystal is 10 or more, but two or more crystal forms are mixed. In addition, the structure such as crystal / amorphous in an unstretched state is not shown, and it is insufficient as a technique for spinning.
特許文献５には、ステレオコンプレックスポリ乳酸からなる仮撚加工糸が提案されている。この提案も特許文献３、４と同様、ＤＳＣ測定でポリ乳酸ホモ結晶とステレオコンプレックス結晶の２種類以上の結晶融解ピークを有する繊維である。
特許文献３〜５の技術に共通する課題として、複数の種類の結晶が混在する構造となっているため、口金からの吐出後、冷却固化・細化の段階および延伸・熱セットの段階で、複数の構造の結晶の存在が均一な繊維形成を阻害し、毛羽や糸切れ、あるいは染斑や繊度斑不良といった繊維品質不良の原因になる という問題があった。 As a problem common to the techniques of Patent Documents 3 to 5, since it has a structure in which a plurality of types of crystals are mixed, after discharging from the die, at the stage of cooling solidification / thinning and at the stage of stretching / heat setting, There existed a problem that the presence of crystals having a plurality of structures hindered the formation of uniform fibers, leading to fiber quality defects such as fuzz, yarn breakage, dye spots and fineness defects.
一方、ＤＳＣ測定でステレオコンプレックス結晶の単一融解ピークを示すポリ乳酸を得るために、特許文献６には燐酸エステル金属塩をポリＬ−乳酸、ポリＤ−乳酸に含有させる方法が提案されているが、繊維のように高速で引き取りながら成形する際の技術手段については示されていない。 On the other hand, in order to obtain polylactic acid showing a single melting peak of a stereocomplex crystal by DSC measurement, Patent Document 6 proposes a method of containing a phosphate metal salt in poly L-lactic acid and poly D-lactic acid. However, it does not show technical means for forming while taking up at a high speed like fibers.
本発明の目的は、ポリ乳酸からなり、強度、耐熱性、耐熱収縮性に優れた繊維を提供することにあり、該繊維からなる繊維製品を提供することにある。また、生産性の高い直接延伸法により高いステレオ化率を有し、強度および耐熱収縮性に優れた繊維を製造する技術に関する。 An object of the present invention is to provide a fiber made of polylactic acid and having excellent strength, heat resistance and heat shrinkage resistance, and to provide a fiber product comprising the fiber. Further, the present invention relates to a technique for producing a fiber having a high stereoization ratio by a highly productive direct stretching method and excellent in strength and heat shrinkage resistance.
本発明者らは、ポリＬ−乳酸（Ａ成分）とポリＤ−乳酸（Ｂ成分）とを、溶融紡糸する際に、燐酸エステル金属塩（Ｃ成分）を存在させると、８００ｍ／ｍｉｎ以下の巻き取り速度領域において実質的に非晶のステレオコンプレックスからなる未延伸糸が得られることを見出し、該未延伸糸を一旦巻き取ることなく３．５倍以上で延伸した直接延伸法により得られた延伸糸はポリＬ−乳酸とポリＤ―乳酸に起因する低温度の融解ピークは観測されないこと、更に延伸糸を高温で熱処理してもポリ乳酸の部分融解が見られないことを見出し、本発明を完成した。 When the present inventors have melt-spun poly L-lactic acid (component A) and poly D-lactic acid (component B) and a phosphate ester metal salt (component C) is present, it is 800 m / min or less. It was found that an undrawn yarn consisting of a substantially amorphous stereocomplex was obtained in the winding speed region, and was obtained by a direct drawing method in which the undrawn yarn was drawn at a ratio of 3.5 times or more without being wound once. In the drawn yarn, it was found that the melting peak at low temperature due to poly L-lactic acid and poly D-lactic acid was not observed, and that the partial melting of polylactic acid was not observed even when the drawn yarn was heat-treated at high temperature. Was completed.
即ち本発明によれば
重量平均分子量５万〜３０万のポリＬ−乳酸（Ａ成分）と重量平均分子量５万〜３０万のポリＤ―乳酸（Ｂ成分）からなる強度３．０ｃN／ｄｔｅｘ以上、伸度３０％以上のポリ乳酸繊維の製造方法であって、下記式（１）及び／又は（２）で表される燐酸エステル金属塩（Ｃ成分）をＡ成分とＢ成分との合計１００重量部当たり０．０５〜５重量部含有する組成物とし紡糸延伸を一旦巻き取ることなく直接延伸法により行うポリ乳酸繊維の製造方法。
That is, according to the present invention, a strength of 3.0 cN / dtex or more comprising poly L-lactic acid (component A) having a weight average molecular weight of 50,000 to 300,000 and poly D-lactic acid (component B) having a weight average molecular weight of 50,000 to 300,000. , A method for producing a polylactic acid fiber having an elongation of 30% or more, wherein a phosphate ester metal salt (C component) represented by the following formula (1) and / or (2) is added to a total of 100 A components and B components: A method for producing polylactic acid fiber, which comprises a composition containing 0.05 to 5 parts by weight per part by weight and is directly drawn by a drawing method without winding up the yarn.
本発明の方法により、生産性の高い直接延伸法により高いステレオ化率を有し、強度および耐熱収縮性に優れたポリ乳酸繊維を製造することができる。 By the method of the present invention, it is possible to produce a polylactic acid fiber having a high stereogenicity by a direct stretching method with high productivity and excellent in strength and heat shrinkage resistance.
以下本発明について説明をする。
〈繊維の製造方法〉
（ポリ−Ｌ−乳酸：Ａ成分）
ポリＬ―乳酸は、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、乳酸以外の共重合単位がある。Ｄ−乳酸単位および乳酸以外の共重合単位は、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。
The present invention will be described below.
<Production method of fiber>
(Poly-L-lactic acid: A component)
Poly L-lactic acid mainly consists of L-lactic acid units. The L-lactic acid unit is a repeating unit derived from L-lactic acid. The poly L-lactic acid 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 copolymer units other than lactic acid. The D-lactic acid unit and the copolymer unit other than lactic acid are preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.
共重合単位としては、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である。 Copolymerized units include glycolic acid, caprolactone, butyrolactone, hydroxycarboxylic acids such as 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, It is a unit 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出来るからである。
ポリＬ−乳酸は、重量平均分子量が、好ましくは５万〜３０万、より好ましくは１４万〜２５万である。
The poly L-lactic acid preferably has crystallinity. The melting point is preferably 150 to 190 ° C, more preferably 160 to 190 ° C. This is because, if these conditions are satisfied, a stereocomplex crystal having a high melting point can be formed and the crystallinity can be increased.
The poly L-lactic acid preferably has a weight average molecular weight of 50,000 to 300,000, more preferably 140,000 to 250,000.
（ポリ−Ｄ−乳酸：Ｂ成分）
ポリＤ―乳酸は、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、乳酸以外の共重合単位がある。Ｌ−乳酸単位および乳酸以外の共重合単位は、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。
(Poly-D-lactic acid: B component)
Poly D-lactic acid mainly consists of 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%, still more preferably 98 to 100 mol% of D-lactic acid units. Other repeating units include L-lactic acid units and copolymerized units other than lactic acid. The L-lactic acid unit and the copolymer unit other than lactic acid are preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.
共重合単位としては、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である。 Copolymerized units include glycolic acid, caprolactone, butyrolactone, hydroxycarboxylic acids such as 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, It is a unit 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出来るからである。
ポリＤ−乳酸は、重量平均分子量が、好ましくは５万〜３０万、より好ましくは１４万〜２５万である。
The poly D-lactic acid preferably has crystallinity. The melting point is preferably 150 to 190 ° C, more preferably 160 to 190 ° C. This is because, if these conditions are satisfied, a stereocomplex crystal having a high melting point can be formed and the crystallinity can be increased.
Poly D-lactic acid has a weight average molecular weight of preferably 50,000 to 300,000, more preferably 140,000 to 250,000.
ポリＬ―乳酸またはポリＤ―乳酸は、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出来る。 Poly-L-lactic acid or poly-D-lactic acid can be produced by a method of directly dehydrating condensation of L-lactic acid or D-lactic acid, or by subjecting L-lactic acid or D-lactic acid to dehydration cyclization to form lactide and then ring-opening polymerization. It can be manufactured by a method. 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 include calcium compounds and lanthanide compounds.
ポリＬ−乳酸およびポリＤ−乳酸は、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。 For poly L-lactic acid and poly D-lactic acid, it is preferable that the polymerization catalyst used in the polymerization is washed away with a solvent 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。
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.
ポリＬ−乳酸およびポリＤ−乳酸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 and poly D-lactic acid 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.
（燐酸エステル金属塩：Ｃ成分）
燐酸エステル金属塩（Ｃ成分）として、好ましくは下記式（１）または（２）で表される化合物が挙げられる。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。
(Phosphate metal salt: C component)
As the phosphoric acid ester metal salt (component C), a compound represented by the following formula (1) or (2) is preferably exemplified. 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), R1 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 R1 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. .
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、ｔｅｔ−ブチル基、アミル基、ｔｅｔ−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、ｔｅｔ−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、ｔｅｔ−デシル基、ウンデシル基、ドデシル基、ｔｅｔ−ドデシル基などが挙げられる。 R2 and R3 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, tet-butyl group, amyl group, tet-amyl group, hexyl group, heptyl group, octyl group, iso-octyl group, tet-octyl group, 2-ethylhexyl group, nonyl group, iso-nonyl group, decyl group, iso-decyl group, tet-decyl group, An undecyl group, a dodecyl group, a tet-dodecyl group, etc. are mentioned.
Ｍ１は、Ｎａ、Ｋ、Ｌｉなどのアルカリ金属原子、Ｍｇ、Ｃａ等のアルカリ土類金属原子、亜鉛原子またはアルミニウム原子を表す。ｐは１または２を表し、ｑはＭ１がアルカリ金属原子、アルカリ土類金属原子、亜鉛原子のときは０を、Ｍ１がアルミニウム原子のときは１または２を表す。 M1 represents an alkali metal atom such as Na, K or Li, an alkaline earth metal atom such as Mg or Ca, a zinc atom or an aluminum atom. p represents 1 or 2, q represents 0 when M1 is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M1 is an aluminum atom.
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ｔｅｔ−ブチル基のものが挙げられる。 Preferable examples of the phosphoric acid ester metal salt represented by the formula (1) include those in which R1 is a hydrogen atom, and R2 and R3 are both tet-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、ｔｅｔ−ブチル基、アミル基、ｔｅｔ−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、ｔｅｔ−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、ｔｅｔ−デシル基、ウンデシル基、ドデシル基、ｔｅｔ−ドデシル基などが挙げられる。 In Formula (2), R4, R5, and R6 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, tet-butyl group, amyl group, tet-amyl group, hexyl group, heptyl group, octyl group, iso-octyl group, tet-octyl group, 2-ethylhexyl group, nonyl group, iso-nonyl group, decyl group, iso-decyl group, tet-decyl group, An undecyl group, a dodecyl group, a tet-dodecyl group, etc. are mentioned.
Ｍ２は、Ｎａ、Ｋ、Ｌｉなどのアルカリ金属原子、Ｍｇ、Ｃａ等のアルカリ土類金属原子、亜鉛原子またはアルミニウム原子を表す。ｐは１または２を表し、ｑはＭ２がアルカリ金属原子、アルカリ土類金属原子、亜鉛原子のときは０を、Ｍ２がアルミニウム原子のときは１または２を表す。 M2 represents an alkali metal atom such as Na, K or Li, an alkaline earth metal atom such as Mg or Ca, a zinc atom or an aluminum atom. p represents 1 or 2, q represents 0 when M2 is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M2 is an aluminum atom.
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、例えばＲ４、Ｒ６がメチル基、Ｒ５がｔｅｔ−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、旭電化（株）製の商品名、アデカスタブＮＡ−１０、ＮＡ−１１、ＮＡ−２１、ＮＡ−３０、ＮＡ−３５などが挙げられる。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。 Preferred examples of the phosphoric acid ester metal salt represented by the formula (2) include, for example, those in which R4 and R6 are methyl groups and R5 is a tet-butyl group. Examples of the phosphoric acid ester metal salt include trade names manufactured by Asahi Denka Co., Ltd., ADK STAB NA-10, NA-11, NA-21, NA-30, NA-35 and the like. The phosphoric acid ester metal salt can be synthesized by a known method.
燐酸エステル金属塩は、平均粒径が好ましくは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 average particle size of the phosphoric acid ester metal salt is preferably 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.
（組成物）
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０．０５〜５重量部、好ましくは０．０５〜４重量部、より好ましくは０．１〜３重量部である。０．０５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。
(Composition)
The content of the phosphoric acid ester metal salt (component C) is 0.05 to 5 parts by weight, preferably 0.05 per 100 parts by weight in total of poly L-lactic acid (component A) and poly D-lactic acid (component B). -4 parts by weight, more preferably 0.1-3 parts by weight. If the amount is less than 0.05 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。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 composition thus obtained can be melt-mixed and transferred to the spinning device as it is or via a metering pump. 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.
組成物は、２６０℃において溶融させた場合の重量平均分子量の低下が２０％以下であるのが好ましい。高温での分子量低下が激しいと、紡糸が困難になるばかりでなく、得られた糸の物性が低下し好ましくない。 The composition preferably has a decrease in weight average molecular weight of 20% or less when melted at 260 ° C. When the molecular weight is drastically reduced at high temperatures, spinning is not only difficult, but physical properties of the obtained yarn are lowered, which is not preferable.
また組成物は、水分率が１００ｐｐｍ以下であることが好ましい。水分率が高いとポリＬ―乳酸成分とポリＤ―乳酸成分の加水分解が促進され、分子量が著しく低下し、紡糸が困難になるばかりでなく、得られた糸の物性が低下し、好ましくない。 The composition preferably has a moisture content of 100 ppm or less. When the moisture content is high, hydrolysis of the poly-L-lactic acid component and the poly-D-lactic acid component is promoted, the molecular weight is remarkably lowered, and not only spinning becomes difficult, but physical properties of the obtained yarn are lowered, which is not preferable. .
また、組成物中の残留ラクチド量は４００ｐｐｍ以下が好ましい。ラクチド法によって得られるポリ乳酸中のラクチドは溶融紡糸時に気化して糸斑の原因になることがあるため、ラクチド量を４００ｐｐｍ以下に抑えることが良好な糸を得る目的からすると好ましい。 Further, the amount of residual lactide in the composition is preferably 400 ppm or less. Since lactide in the polylactic acid obtained by the lactide method may vaporize during melt spinning and cause yarn unevenness, it is preferable for the purpose of obtaining a good yarn to suppress the lactide amount to 400 ppm or less.
組成物は、エクストルーダー型やプレッシャーメルター型の溶融押出し機で溶融された後、ギアポンプにより計量され、パック内で濾過された後、口金に設けられたノズルからモノフィラメンント、マルチフィラメント等として吐出され紡糸される。口金の形状、口金数は特に制限されるものではなく、円形、異形、中実、中空等のいずれも採用することができる。吐出ポリマーは６０〜１５０ｃｍの保温領域を通過した後、冷却風により冷却固化された後、オイリングにより集束され巻き取られる。 The composition is melted by an extruder type or pressure melter type melt extruder, measured by a gear pump, filtered in a pack, and then discharged as a monofilament, multifilament, etc. from a nozzle provided on the base. And spun. The shape of the base and the number of the bases are not particularly limited, and any of circular, irregular, solid, hollow and the like can be adopted. The discharged polymer passes through a heat-retaining region of 60 to 150 cm, is cooled and solidified by cooling air, and then is focused and wound by oiling.
第１引き取りローラーの速度を８００ｍ／ｍｉｎ以下とし第２引き取りローラーでの一段延伸倍率が３．５倍以上で延伸することが重要である。第１引き取りローラーの速度を８００ｍ／ｍｉｎ以下として延伸前の未延伸状態にて広角Ｘ線回折法の測定で実質的に非晶性であることとし、その未延伸糸を３．５倍以上の倍率で延伸することにより強度３．０ｃＮ／ｄＴｅｘ以上及び伸度３０％以上を達成できる。更に好ましくは第３引き取りローターにて１．２倍以上の延伸を行い全倍率を４．２倍以上とすることでより高い強度の繊維を得ることができる。しかし、延伸倍率が高すぎると繊維が失透し白化するため、繊維の強度が低下するため全倍率は５．０倍以下が好ましい。第１引き取りローラーの延伸前余熱温度は、好ましくは５０〜１００℃、より好ましくは６０〜９０℃である。第２引き取りローラー以降の延伸熱セット温度は１００〜２００℃、好ましくは１００〜１６０℃で行う。 It is important that the speed of the first take-up roller is 800 m / min or less, and the second take-up roller is stretched at a one-stage draw ratio of 3.5 times or more. The speed of the first take-up roller is set to 800 m / min or less, and the non-stretched yarn is determined to be substantially amorphous as measured by the wide-angle X-ray diffraction method in an unstretched state before stretching. By stretching at a magnification, a strength of 3.0 cN / dTex or more and an elongation of 30% or more can be achieved. More preferably, a fiber having higher strength can be obtained by stretching 1.2 times or more with a third take-up rotor and setting the total magnification to 4.2 times or more. However, if the draw ratio is too high, the fiber is devitrified and whitened, so that the strength of the fiber is lowered. Therefore, the total magnification is preferably 5.0 times or less. The preheating temperature of the first take-up roller before stretching is preferably 50 to 100 ° C, more preferably 60 to 90 ° C. The stretching heat setting temperature after the second take-up roller is 100 to 200 ° C, preferably 100 to 160 ° C.
得られた延伸糸には、低温結晶融解相（Ａ）は実質的に全く観察されず、高温結晶融解相（Ｂ）の単一融解ピークのみが見られる。また、延伸糸の高温結晶融解相（Ｂ）の融解開始温度は好ましくは１９０℃以上、より好ましくは２００℃以上である。加えて、延伸糸の広角Ｘ線回折測定によるステレオコンプレックス結晶回折ピークの積分強度よりもとめたステレオ化率（Ｓｃ率）は９０％以上と高い水準にあり耐熱収縮性および耐アイロン性に優れ、強度３．０ｃＮ／ｄＴｅｘ以上の繊維を得ることができる。 In the obtained drawn yarn, substantially no low-temperature crystal melt phase (A) is observed, and only a single melt peak of the high-temperature crystal melt phase (B) is observed. Moreover, the melting start temperature of the high-temperature crystal melting phase (B) of the drawn yarn is preferably 190 ° C. or higher, more preferably 200 ° C. or higher. In addition, the stereoization rate (Sc rate) obtained from the integrated intensity of the stereocomplex crystal diffraction peak measured by wide-angle X-ray diffraction measurement of the drawn yarn is at a high level of 90% or more, and has excellent heat shrinkage resistance and iron resistance, A fiber of 3.0 cN / dTex or more can be obtained.
ステレオコンプレックス結晶を形成してなるポリ乳酸においては、構成成分、組成比、並びにステレオコンプレックスの形成条件に応じて、通常は、低温結晶融解相（Ａ）と高温結晶融解相（Ｂ）の少なくとも２つの吸熱ピークを示すことが知られている。 In polylactic acid obtained by forming a stereocomplex crystal, at least two of a low-temperature crystal melt phase (A) and a high-temperature crystal melt phase (B) are usually used depending on the component, composition ratio, and stereocomplex formation conditions. It is known to show two endothermic peaks.
又示差走査熱量計（ＤＳＣ）測定を行った際に、低温結晶融解相（Ａ）と高温結晶融解相（Ｂ）の少なくとも２つの吸熱ピークを示すことはなく、実質的にステレオコンプレックス結晶の単一融解ピークを示すことを特徴とする。又融解ピーク温度は１９５℃以上であることを特徴とする。即ち直接延伸法により第一引き取りローラーで引き取られた時点の未延伸糸は、非晶性のステレオコンプレックスを形成しているが、低温結晶相を形成可能なポリＬ−乳酸相及び／又はポリＤ−乳酸相を含有していないものと推定される。 Further, when the differential scanning calorimeter (DSC) measurement is performed, at least two endothermic peaks of the low-temperature crystal melting phase (A) and the high-temperature crystal melting phase (B) are not shown, and the stereocomplex crystal is substantially single. It is characterized by showing one melting peak. The melting peak temperature is 195 ° C. or higher. That is, the undrawn yarn at the time of being drawn by the first take-up roller by the direct drawing method forms an amorphous stereocomplex, but a poly L-lactic acid phase and / or poly D capable of forming a low-temperature crystalline phase. -Presumed to contain no lactic acid phase.
これらの特徴は、繊維が燐酸エステル金属塩（Ｃ成分）を含有していることに起因し、従来全く予想されなかった有用な特性であり、これが直接延伸法においても高いステレオ化率を有し、強度及び耐熱収縮性に優れた繊維が製造可能になった理由と推定する。 These characteristics are useful properties that have never been expected in the past due to the fact that the fiber contains a phosphoric acid ester metal salt (component C), which has a high stereo ratio even in the direct drawing method. This is presumed to be the reason why a fiber excellent in strength and heat shrinkability can be produced.
本発明において延伸糸も、低温結晶融解相（Ａ）は実質的に全く観察されず、高温結晶融解相（Ｂ）の単一融解ピークのみが見られる。これらの特徴は、繊維が燐酸エステル金属塩（Ｃ成分）を含有していることに起因し、従来まったく予想されなかった有用な特性である。なお、燐酸エステル金属塩（Ｃ成分）を含有しない通常の未延伸糸では示差走査熱量計（ＤＳＣ）測定を行った際に、ポリＬ−乳酸、ポリＤ−乳酸の単独結晶、ステレオコンプレックス結晶の二本の融解ピークが観測される。 In the present invention, in the drawn yarn, substantially no low-temperature crystal melt phase (A) is observed, and only a single melt peak of the high-temperature crystal melt phase (B) is observed. These characteristics are useful properties that have never been expected in the past due to the fact that the fiber contains a phosphoric acid ester metal salt (component C). In a normal undrawn yarn containing no phosphate ester metal salt (component C), when differential scanning calorimetry (DSC) measurement was performed, poly L-lactic acid, poly D-lactic acid single crystal, stereocomplex crystal Two melting peaks are observed.
延伸糸は、ポリＬ−乳酸またはポリＤ−乳酸の低温結晶融解相を有していないので、ポリＬ−乳酸またはポリＤ−乳酸の結晶融点以上の温度で、熱処理してもポリＬ−乳酸またはポリＤ−乳酸の単独結晶の部分融解の熱融着、破断を示さず、単独結晶の融点より高い１７０℃以上、例えば１９０℃で熱処理することができる。この結果、高いステレオ化率を示し、強度および耐熱性に優れた繊維を得ることができる。この繊維は、耐熱性に優れるので製造時における熱融着などのトラブルも少なく、耐熱収縮性にも優れる。 Since the drawn yarn does not have a low-temperature crystal melting phase of poly L-lactic acid or poly D-lactic acid, the poly L-lactic acid can be subjected to heat treatment at a temperature higher than the crystalline melting point of poly L-lactic acid or poly D-lactic acid. Alternatively, it can be heat-treated at 170 ° C. or higher, for example, 190 ° C., higher than the melting point of the single crystal without showing thermal fusion or fracture of partial melting of the single crystal of poly D-lactic acid. As a result, it is possible to obtain a fiber that exhibits a high stereo ratio and is excellent in strength and heat resistance. Since this fiber is excellent in heat resistance, there are few troubles such as heat fusion during production, and it is excellent in heat shrinkage.
また、直接延伸法による最も大きな利点は、紡糸および延伸の２工程にておこなう場合での未延伸糸の経時物性変化を管理しなくてもよいという点である。紡糸および延伸の２工程にておこなう場合は未延伸糸を温度２５℃、湿度６０％の環境下で保管した場合、３日が経過した時点で未延伸糸の強力が５０％以上低下し、該当未延伸糸では延伸工程での断糸し工程通過性が著しく低下する結果となった。 In addition, the greatest advantage of the direct drawing method is that it is not necessary to manage the physical property change of the undrawn yarn over time in two steps of spinning and drawing. When performing the spinning and drawing in two steps, when the undrawn yarn is stored in an environment at a temperature of 25 ° C. and a humidity of 60%, the strength of the undrawn yarn is reduced by 50% or more when 3 days have passed. With undrawn yarn, the yarn was cut in the drawing process, resulting in a marked decrease in process passability.
本発明の繊維は、Ａ成分、Ｂ成分およびＣ成分を含有する組成物からなり、強度が３．０ｃＮ／ｄｔｅｘ以上より好ましくは３．５ｃＮ／ｄｔｅｘ以上で、伸度が３０％以上の繊維である。強度の上限は高いほど好ましいが実際は４．５ｃＮ／ｄｔｅｘ程度となる。衣料用および産業用として使用するにあたり、３．０ｃＮ／ｄｔｅｘ以上の強度を有している繊維は実用面での使用範囲が広く好ましい。 The fiber of the present invention comprises a composition containing an A component, a B component and a C component, and is a fiber having a strength of 3.0 cN / dtex or more, more preferably 3.5 cN / dtex or more, and an elongation of 30% or more. is there. The higher the upper limit of the strength, the better, but in practice it is about 4.5 cN / dtex. When used for apparel and industrial use, fibers having a strength of 3.0 cN / dtex or more have a wide range of practical use and are preferred.
本発明の繊維の伸度は、好ましくは３０％以上、より好ましくは３３％以上である。衣料用および産業用として使用するにあたり、３０％以上の伸度を有している繊維は実用面での使用範囲が広く好ましい。 The elongation of the fiber of the present invention is preferably 30% or more, more preferably 33% or more. When used for apparel and industry, fibers having an elongation of 30% or more are preferred because of their wide practical use range.
本発明の繊維は、１５０℃における熱収縮率が好ましくは３〜２０％、より好ましくは３〜１５％、さらに好ましくは３〜１０％である。熱収縮率が大きいと繊維製品がアイロン掛けをはじめ、高温に晒されたとき、収縮して小さくなり実用に耐えなくなる問題が発生する。
本発明の繊維のステレオ化率は９０％以上、好ましくは９０〜１００％、より好ましくは９５〜１００％、さらに好ましくは９８〜１００％である。
The fiber of the present invention has a heat shrinkage rate at 150 ° C. of preferably 3 to 20%, more preferably 3 to 15%, and still more preferably 3 to 10%. If the heat shrinkage rate is large, the textile product shrinks and becomes smaller when it is exposed to high temperatures, such as ironing, and becomes unusable.
The stereoification rate of the fiber of the present invention is 90% or more, preferably 90 to 100%, more preferably 95 to 100%, and still more preferably 98 to 100%.
本発明の繊維は、示差走査熱量計（ＤＳＣ）測定において、実質的に単一の融解ピークを有し、該融解ピーク温度が１９５℃以上であり、広角Ｘ線回折法（ＸＲＤ）測定によるステレオ化率が９０％以上である。こうした特性から本発明の繊維は、後述の評価法で１７０℃で耐アイロン性を有する。 The fiber of the present invention has a substantially single melting peak in differential scanning calorimetry (DSC) measurement, the melting peak temperature is 195 ° C. or higher, and stereo by wide-angle X-ray diffraction (XRD) measurement. The conversion rate is 90% or more. From these characteristics, the fiber of the present invention has iron resistance at 170 ° C. according to the evaluation method described later.
本発明の繊維は、仮撚加工、機械捲縮加工、押し込み捲縮加工などの糸加工用の原糸とすることもできる。また長繊維、短繊維および短繊維を使用した紡績糸とすることもできる。本発明の繊維は、ステレオ化率が高く、強度、耐熱性および耐熱収縮性に優れるので、織物、編物、不織布、カップのような成形品などの様々な繊維製品とすることができる。即ち、本発明は、本発明の繊維を含有する繊維製品を包含する。 The fiber of the present invention can also be used as a raw yarn for yarn processing such as false twisting, mechanical crimping, and indentation crimping. Moreover, it can also be set as the spun yarn using a long fiber, a short fiber, and a short fiber. Since the fiber of the present invention has a high stereo ratio and is excellent in strength, heat resistance and heat shrinkage resistance, it can be made into various fiber products such as woven fabrics, knitted fabrics, non-woven fabrics, and molded products such as cups. That is, this invention includes the textiles containing the fiber of this invention.
具体的には、シャツ、ブルゾン、パンツ、コートといった衣料用途、カップ、パッド、靴表皮、中敷等の衣料資材用途、カーテン、カーペット、マット、家具等のインテリア用途、ベルト、ネット、ロープ、重布、袋類、フェルト、フィルター、スレーキ、ティーバッグ等の産業資材および一般資材用途、車両内装用途にも好適に使用することができる。 Specifically, apparel such as shirts, blousons, pants, coats, apparel materials such as cups, pads, shoe skins and insoles, interior uses such as curtains, carpets, mats, furniture, belts, nets, ropes, heavy It can also be suitably used for industrial materials such as cloth, bags, felts, filters, sleeks, tea bags, etc., general materials and vehicle interiors.
本発明の繊維は、ポリＬ−乳酸またはポリＤ−乳酸の単独結晶相を持たない。そのため本発明の繊維からなる繊維製品にアイロン掛けを行っても、繊維の一部が軟化し、融解、収縮するという恐れが無い。本発明の繊維製品は、布質や風合いおよび寸法をアイロン掛けにより損ねることがないため、高温での使用が想定される産業用途への展開が期待できる。 The fiber of the present invention does not have a single crystal phase of poly L-lactic acid or poly D-lactic acid. Therefore, even if ironing is performed on the fiber product made of the fiber of the present invention, there is no fear that a part of the fiber is softened, melted and contracted. Since the textile product of the present invention does not impair the fabric quality, texture, and dimensions by ironing, it can be expected to be used in industrial applications that are expected to be used at high temperatures.
以下、本発明を実施例によりさらに具体的に説明するが、本発明は、これらの実施例に何等限定を受けるものではない。また実施例中における各値は下記の方法で求めた。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Moreover, each value in an Example was calculated | required with the following method.
（１）還元粘度：
ポリマー０．１２ｇを１０ｍＬのテトラクロロエタン／フェノール（容量比１／１）に溶解し、３５℃における還元粘度（ｍＬ／ｇ）を測定した。
(1) Reduced viscosity:
0.12 g of the polymer was dissolved in 10 mL of tetrachloroethane / phenol (volume ratio 1/1), and the reduced viscosity (mL / g) at 35 ° C. was measured.
（２）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。
(2) 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.
（３）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、以下条件でＸ線回折図形（図１参照）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
(3) Stereo ratio (Sc ratio)
An X-ray diffraction pattern (see FIG. 1) was recorded on an imaging plate by the transmission method using a ROTA FLEX RU200B type X-ray diffractometer manufactured by RIKEN, under the following conditions. 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 °. Of the diffraction peak and the integrated intensity IHM of the diffraction peak derived from the homocrystal appearing in the vicinity of 2θ = 16.5 °, the stereo ratio (Sc conversion ratio) was determined. As shown in FIG. 1, ΣISCi and IHM 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 = ΣISCi / (ΣISCi + IHM) × 100
Where ΣISCi = ISC1 + ISC2 + ISC3
ISCi (i = 1 to 3) is 2θ = 12.0 °, 20.7 °, respectively.
Integrated intensity of each diffraction peak around 24.0 °
（４）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。
(4) 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.
（５）強度、伸度
（株）オリエンテック社製“テンシロン”引っ張り試験機にて試料長２５ｃｍ、引張速度３０ｃｍ／分の条件で測定した。
(5) Strength and elongation Measured with a “Tensilon” tensile tester manufactured by Orientec Co., Ltd. under the conditions of a sample length of 25 cm and a tensile speed of 30 cm / min.
（６）耐アイロン性
テストする繊維にて１０ｃｍ角の布巾を作成し表面温度１７０℃に調整したアイロンで
３０秒アイロン掛けを行い、布巾形状、寸法、風合いの変化より耐熱性を判定した。判定は以下の基準で行った。
合格： ○ 単糸の融着もなく処理前の布巾の形状、寸法、風合いを良好に保つ。
不合格：× 単糸の融着あるいは処理前の布巾の熱変形、ごわごわした風合いへの変化がみられた。
(6) Ironing resistance A 10 cm square cloth was made from the fiber to be tested and ironed for 30 seconds with an iron adjusted to a surface temperature of 170 ° C., and the heat resistance was determined from changes in the cloth width, dimensions and texture. The determination was made according to the following criteria.
Pass: ○ Keeps the shape, dimensions and texture of the cloth before treatment without fusing single yarn.
FAIL: X Single yarn was fused, heat deformation of the cloth before treatment, or change to a stiff texture.
（７）１５０℃での熱収縮率の測定
ＪＩＳ Ｌ−１０１３ ８．１８．２項ａ）に準じて測定した。
(7) Measurement of thermal shrinkage at 150 ° C. Measurement was performed according to JIS L-1013 8.18.2 a).
［製造例１：ポリマーＡ１の製造］
光学純度９９．８％のＬ−ラクチド（株式会社武蔵野化学研究所）１００重量部を重合容器に加え、系内を窒素置換した後、ステアリルアルコール０．２重量部、触媒としてオクチル酸スズ０．０５重量部を加え、１９０℃、２時間、重合を行い、ポリマーを製造した。このポリマーを７％５Ｎ塩酸のアセトン溶液で洗浄し、触媒を除去し、ポリマーＡ１を得た。得られたポリマーＡ１の還元粘度は２．９２（ｍＬ／ｇ）、重量平均分子量は１９万であった。融点（Ｔｍ）は１６８℃であった。結晶化点（Ｔｃ）は１２２℃であった。
[Production Example 1: Production of polymer A1]
After adding 100 parts by weight of L-lactide having an optical purity of 99.8% (Musashino Chemical Laboratory Co., Ltd.) to the polymerization vessel and replacing the inside of the system with nitrogen, 0.2 part by weight of stearyl alcohol and 0. 05 parts by weight was added, and polymerization was carried out at 190 ° C. for 2 hours to produce a polymer. This polymer was washed with an acetone solution of 7% 5N hydrochloric acid to remove the catalyst to obtain a polymer A1. The resulting polymer A1 had a reduced viscosity of 2.92 (mL / g) and a weight average molecular weight of 190,000. The melting point (Tm) was 168 ° C. The crystallization point (Tc) was 122 ° C.
（製造例２：ポリマーＡ２の製造）
光学純度９９．８％のＤ−ラクチド（株式会社武蔵野化学研究所）１００重量部を重合容器に加え、系内を窒素置換した後、ステアリルアルコール０．２重量部、触媒としてオクチル酸スズ０．０５重量部を加え、１９０℃、２時間、重合を行い、ポリマーを製造した。このポリマーを７％５Ｎ塩酸のアセトン溶液で洗浄し、触媒を除去し、ポリマーＡ２を得た。得られたポリマーＡ２の還元粘度は２．６５（ｍＬ／ｇ）、重量平均分子量は２０万であった。融点（Ｔｍ）は１７６℃であった。結晶化点（Ｔｃ）は１３９℃であった。
(Production Example 2: Production of polymer A2)
After adding 100 parts by weight of D-lactide having an optical purity of 99.8% (Musashino Chemical Laboratory Co., Ltd.) to the polymerization vessel and replacing the inside of the system with nitrogen, 0.2 parts by weight of stearyl alcohol and 0.1% of tin octylate as a catalyst were added. 05 parts by weight was added, and polymerization was carried out at 190 ° C. for 2 hours to produce a polymer. This polymer was washed with an acetone solution of 7% 5N hydrochloric acid to remove the catalyst to obtain a polymer A2. The obtained polymer A2 had a reduced viscosity of 2.65 (mL / g) and a weight average molecular weight of 200,000. The melting point (Tm) was 176 ° C. The crystallization point (Tc) was 139 ° C.
［実施例１］
ポリマーＡ１およびポリマーＡ２のチップを作成し、ポリマーＡ１／ポリマーＡ２＝５０／５０（重量比）の割合でＶ型ブレンダーを使用してチップブレンドした後、１１０℃で５時間減圧乾燥した。このチップ１００重量部に、燐酸２，２―メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェノール）ナトリウム塩（平均粒径５μｍ）０．５重量部添加し、２軸ルーダー付溶融紡糸機を用い２３５℃で溶融し、吐出孔を３６個有した口金から吐出させ、紡糸筒により冷却した後、油剤を付加して、第１引き取りローラーの速度を４００ｍ／ｍｉｎ、温度を８５℃とし第２引き取りローラーでの延伸倍率が４．５倍、熱処理温度を１４０℃で行い、８４ｄｔｅｘ／３６ｆｉｌの繊維として巻き取った。得られた繊維は、示差走査熱量計（ＤＳＣ）測定において、ポリＬ−乳酸およびポリＤ―乳酸からなるステレオコンプレックス結晶の単一融解ピークを示し、融点が２２４℃であった。また、広角Ｘ線回折測定でのＳｃ化率１００％、繊維の強度３．４ｃＮ／ｄｔｅｘ、伸度３５％、１５０℃熱収縮率１２％であった。得られた繊維を筒編にして、１７０℃でアイロン掛けテストをおこなったところ、破れ、穴あき、融着、粗硬化、寸法変化などはみられず、判定は良好であった。結果を表１に示す。
[Example 1]
Chips of polymer A1 and polymer A2 were prepared, chip blended using a V-type blender at a ratio of polymer A1 / polymer A2 = 50/50 (weight ratio), and then dried under reduced pressure at 110 ° C. for 5 hours. 0.5 parts by weight of 2,2-methylenebis (4,6-di-tert-butylphenol) sodium salt (average particle size: 5 μm) phosphate was added to 100 parts by weight of this chip, and 235 using a melt spinning machine with a twin screw rudder. After melting at ℃, discharged from a nozzle having 36 discharge holes, cooled by a spinning cylinder, oil was added, the speed of the first take-up roller was 400 m / min, the temperature was 85 ° C., and the second take-up roller The draw ratio at 4.5 was 4.5 times, the heat treatment temperature was 140 ° C., and wound up as 84 dtex / 36 fil fiber. The obtained fiber showed a single melting peak of a stereocomplex crystal composed of poly L-lactic acid and poly D-lactic acid in a differential scanning calorimeter (DSC) measurement, and the melting point was 224 ° C. In addition, the Sc conversion rate was 100%, the fiber strength was 3.4 cN / dtex, the elongation was 35%, and the 150 ° C. heat shrinkage rate was 12% as measured by wide-angle X-ray diffraction. When the obtained fiber was made into a cylindrical knitting and subjected to an ironing test at 170 ° C., no tearing, perforation, fusion, rough hardening, dimensional change or the like was observed, and the determination was good. The results are shown in Table 1.
［実施例２］
燐酸エステル金属塩として、アルミニウム２，２―メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニルホスフェート）ハイドロオキサイドを用いたこと以外は実施例１と同様に実施して８４ｄｔｅｘ／３６ｆｉｌの繊維として巻き取った。得られた繊維は、示差走査熱量計（ＤＳＣ）測定において、ポリＬ−乳酸およびポリＤ―乳酸からなるステレオコンプレックス結晶の単一融解ピークを示し、融点が２２４℃であった。また、広角Ｘ線回折測定でのＳｃ化率１００％、繊維の強度３．３ｃＮ／ｄｔｅｘ、伸度３５％、１５０℃熱収縮率１２％であった。得られた繊維を筒網にして、１７０℃でアイロン掛けテストをおこなったところ、破れ、穴あき、融着、粗硬化、寸法変化などはみられず、判定は良好であった。結果を表１に示す。
[Example 2]
This was carried out in the same manner as in Example 1 except that aluminum 2,2-methylenebis (4,6-di-tert-butylphenyl phosphate) hydroxide was used as the phosphoric acid ester metal salt. It was. The obtained fiber showed a single melting peak of a stereocomplex crystal composed of poly L-lactic acid and poly D-lactic acid in a differential scanning calorimeter (DSC) measurement, and the melting point was 224 ° C. In addition, the Sc conversion rate was 100%, the fiber strength was 3.3 cN / dtex, the elongation was 35%, and the 150 ° C. heat shrinkage rate was 12% as measured by wide-angle X-ray diffraction. When the obtained fiber was made into a tubular net and an ironing test was performed at 170 ° C., no breakage, perforation, fusion, rough hardening, dimensional change, etc. were observed, and the determination was good. The results are shown in Table 1.
［実施例３］
第１引き取りローラーの速度を３５０ｍ／ｍｉｎ、温度を８５℃とし第２引き取りローラーでの１段延伸倍率が４．０倍、第３引き取りローラーでの２段延伸倍率が１．２倍、全倍率が４．８倍、熱処理温度を１４０℃で行なった以外は実施例１と同様にして８４ｄｔｅｘ／３６ｆｉｌの繊維として巻き取った。得られた繊維は、示差走査熱量計（ＤＳＣ）測定において、ポリＬ−乳酸およびポリＤ―乳酸からなるステレオコンプレックス結晶の単一融解ピークを示し、融点が２２４℃であった。また、広角Ｘ線回折測定でのＳｃ化率１００％、繊維の強度３．８ｃＮ／ｄｔｅｘ、伸度３１％、１５０℃熱収縮率１０％であった。得られた繊維を筒網にして、１７０℃でアイロン掛けテストをおこなったところ、破れ、穴あき、融着、粗硬化、寸法変化などはみられず、判定は良好であった。結果を表１に示す。
[Example 3]
The speed of the first take-up roller is 350 m / min, the temperature is 85 ° C., the first-stage draw ratio at the second take-up roller is 4.0 times, the second-stage draw ratio at the third take-up roller is 1.2 times, and the total magnification Was 4.8 times and wound at a heat treatment temperature of 140 ° C. in the same manner as in Example 1 as 84 dtex / 36 fil. The obtained fiber showed a single melting peak of a stereocomplex crystal composed of poly L-lactic acid and poly D-lactic acid in a differential scanning calorimeter (DSC) measurement, and the melting point was 224 ° C. In addition, the Sc conversion rate was 100%, the fiber strength was 3.8 cN / dtex, the elongation was 31%, and the heat shrinkage rate at 150 ° C. was 10% as measured by wide-angle X-ray diffraction. When the obtained fiber was made into a tubular net and an ironing test was performed at 170 ° C., no breakage, perforation, fusion, rough hardening, dimensional change, etc. were observed, and the determination was good. The results are shown in Table 1.
［実施例４］
第１引き取りローラーの速度を７００ｍ／ｍｉｎ、温度を８５℃とし第２引き取りローラーでの１段延伸倍率が３．５倍、第３引き取りローラーでの２段延伸倍率が１．２倍、全倍率が４．２倍、熱処理温度を１４０℃で行なった以外は実施例１と同様にして８４ｄｔｅｘ／３６ｆｉｌの繊維として巻き取った。得られた繊維は、示差走査熱量計（ＤＳＣ）測定において、ポリＬ−乳酸およびポリＤ―乳酸からなるステレオコンプレックス結晶の単一融解ピークを示し、融点が２２４℃であった。また、広角Ｘ線回折測定でのＳｃ化率１００％、繊維の強度３．６ｃＮ／ｄｔｅｘ、伸度３３％、１５０℃熱収縮率１０％であった。得られた繊維を筒網にして、１７０℃でアイロン掛けテストをおこなったところ、破れ、穴あき、融着、粗硬化、寸法変化などはみられず、判定は良好であった。結果を表１に示す。
[Example 4]
The speed of the first take-up roller is 700 m / min, the temperature is 85 ° C., the one-stage draw ratio at the second take-up roller is 3.5 times, the two-stage draw ratio at the third take-up roller is 1.2 times, and the total magnification Was 4.2 times and wound at a heat treatment temperature of 140 ° C. in the same manner as in Example 1 as 84 dtex / 36 fil. The obtained fiber showed a single melting peak of a stereocomplex crystal composed of poly L-lactic acid and poly D-lactic acid in a differential scanning calorimeter (DSC) measurement, and the melting point was 224 ° C. Further, the Sc conversion rate was 100%, the fiber strength was 3.6 cN / dtex, the elongation was 33%, and the 150 ° C. heat shrinkage rate was 10% as measured by wide-angle X-ray diffraction. When the obtained fiber was made into a tubular net and an ironing test was performed at 170 ° C., no breakage, perforation, fusion, rough hardening, dimensional change, etc. were observed, and the determination was good. The results are shown in Table 1.
［比較例１］
第１引き取りローラーの速度を１０００ｍ／ｍｉｎ、温度を８５℃とし第２引き取りローラーでの延伸倍率が３．３倍、熱処理温度を１４０℃で行なった以外は実施例１と同様にして８４ｄｔｅｘ／３６ｆｉｌの繊維として巻き取った。得られた繊維は、示差走査熱量計（ＤＳＣ）測定において、ポリＬ−乳酸およびポリＤ―乳酸からなるステレオコンプレックス結晶の単一融解ピークを示し、融点が２２４℃であった。また、広角Ｘ線回折測定でのＳｃ化率１００％であったが、繊維の強度２．２ｃＮ／ｄｔｅｘ、伸度２２％と十分な強度及び伸度を得ることができず、巻き取られた繊維にも単糸切れが目立った。
[Comparative Example 1]
84 dtex / 36 fill in the same manner as in Example 1 except that the speed of the first take-up roller was 1000 m / min, the temperature was 85 ° C., the draw ratio of the second take-up roller was 3.3 times, and the heat treatment temperature was 140 ° C. Rolled up as a fiber. The obtained fiber showed a single melting peak of a stereocomplex crystal composed of poly L-lactic acid and poly D-lactic acid in a differential scanning calorimeter (DSC) measurement, and the melting point was 224 ° C. Further, although the Sc conversion rate was 100% in wide-angle X-ray diffraction measurement, the fiber strength was 2.2 cN / dtex, the elongation was 22%, and sufficient strength and elongation could not be obtained, and the fiber was wound. Single fiber breakage was also noticeable in the fibers.
［比較例２］
燐酸エステル金属塩を使用しないことした以外は実施例１と同じ操作を行った。本例では、ステレオコンプレックス結晶の比率が低く、ポリＬ−乳酸、ポリＤ−乳酸の結晶相が混在しているため、延伸後熱処理温度１４０℃ではポリＬ−乳酸、ポリＤ−乳酸の結晶相融解に起因する単糸融着、断糸が顕著となり正常に捲取不可能であり、製織編以降を実施できなかった。結果を表１に示す。
[Comparative Example 2]
The same operation as in Example 1 was performed except that the phosphoric acid ester metal salt was not used. In this example, since the ratio of stereocomplex crystals is low and the crystal phase of poly L-lactic acid and poly D-lactic acid is mixed, the crystal phase of poly L-lactic acid and poly D-lactic acid at a heat treatment temperature of 140 ° C. after stretching. Single yarn fusion and breakage due to melting became prominent and it was not possible to cut normally, and weaving and subsequent knitting could not be performed. The results are shown in Table 1.
本発明の繊維は、ステレオ化率が高く、強度、耐熱性および耐収縮性に優れるので、織物、編物、不織布、カップのような成形品などの様々な繊維製品とすることができる。 Since the fiber of the present invention has a high stereo ratio and is excellent in strength, heat resistance and shrinkage resistance, it can be made into various fiber products such as woven fabrics, knitted fabrics, nonwoven fabrics, and molded products such as cups.
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