TWI704259B - 纖維之用途 - Google Patents
纖維之用途 Download PDFInfo
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- TWI704259B TWI704259B TW105107410A TW105107410A TWI704259B TW I704259 B TWI704259 B TW I704259B TW 105107410 A TW105107410 A TW 105107410A TW 105107410 A TW105107410 A TW 105107410A TW I704259 B TWI704259 B TW I704259B
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- TW
- Taiwan
- Prior art keywords
- fiber
- antibacterial
- polyacetal copolymer
- polyacetal
- group
- Prior art date
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- 239000000835 fiber Substances 0.000 title claims abstract description 159
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 147
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- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 36
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 claims abstract description 16
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- 239000011347 resin Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 8
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- AQWKGXFXWCQPDB-UHFFFAOYSA-N trimethoxy(methoxymethoxy)methane Chemical compound COCOC(OC)(OC)OC AQWKGXFXWCQPDB-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
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Abstract
本發明提供即使不添加抗菌劑亦具有優異抗菌性，且即使重複洗滌抗菌性亦持續之抗菌用纖維。
一種抗菌纖維，其係於表面具有含有氧伸烷基之聚縮醛共聚物(X)之纖維，聚縮醛共聚物(X)中之氧伸烷基之莫耳量相對於氧亞甲基之莫耳量與氧伸烷基之莫耳量之合計值為0.2~5mol%。
Description
本發明係有關表面具有聚縮醛共聚物之抗菌用纖維。且有關使用前述抗菌用纖維之不織布、編物、織物、毛氈及織片(web)。進而，有關使用前述不織布之過濾器、使用自前述之編物、織物、毛氈及織片所成之群中選出之任1種以上之衣料、寢具或室內裝飾配件。
聚縮醛為機械物性、耐熱性、耐藥品性、電性特性優異之工程塑膠，已廣泛利用於電機、汽車、機械、建材等領域。且，亦由於成形加工容易，故亦利用作為纖維、不織布、過濾器(例如參考專利文獻1~3)。
另一方面，伴隨社會之發展，而對於塑膠除了要求上述物性以外，亦要求對細菌之耐性(抗菌性)。然而，塑膠由於具有作為介電材料及電絕緣材料之性質，故容易吸附空氣中之塵埃及細菌，且具有若溫度及濕度條件一致，則細菌易於其表面增殖之性質。細菌之增殖成為外觀惡化、惡臭之發生原因，且亦成為接觸者之污染原因。例如，已知莫拉菌(Moraxella)為洗滌後之衣類所發
生之具有抹布般臭味之4-甲基-3-己烯酸之發生原因。
作為改善塑膠抗菌性之方法，已知有於塑膠中混練2-(4-噻唑基)-苯并咪唑(噻苯達唑(thiabendazole))等之有機系抗菌劑、或含有銀、銅、鋅離子等之金屬離子之物質等之無機系抗菌劑之方法，或將前述有機系抗菌劑或無機系抗菌劑塗佈於塑膠成形體表面之方法(例如參考專利文獻4、5)。
亦提案有對聚縮醛改善抗菌性之方法。例如專利文獻4揭示於聚縮醛中熔融混練苯甲酸鋅、硫酸鋅、氧化鋅等之含有金屬離子之惡質的樹脂組成物。且專利文獻5揭示於聚縮醛中熔融混練聚-β-丙胺酸聚合物與無機系抗菌劑沸石之樹脂組成物。進而專利文獻6揭示於聚縮醛中熔融混練琥珀酸二甲酯‧1-(2-羥基乙基)-4-羥基-2,2,6,6-四甲基哌啶聚縮合物等之特定受阻胺系物質之樹脂組成物。
[專利文獻1]日本特開2008-163505號公報
[專利文獻2]日本特開2004-360146號公報
[專利文獻3]日本特開2005-13829號公報
[專利文獻4]日本特開平5-230325號公報
[專利文獻5]日本特開平9-291193號公報
[專利文獻6]日本特開平10-265585號公報
然而，有機系抗菌劑大多情況於外觀、耐熱性、安全性(例如致癌性或異位性)、樹脂親和性等之方面具有問題。例如前述噻苯達唑由於即使與塑膠混合亦非常易於滲出，故無法期待持續之抗菌效果(抗菌性)。且已知因滲出而使成形品表面成為吹附白粉之狀態，而有表面發黏等之問題。進而，於安全性方面亦已知有致癌性。且，有機系抗菌劑與塑膠材料熔融混練時亦有易於因熱而分解之課題(例如參考專利文獻4)。
另一方面，使用無機系抗菌劑時，為了賦予抗菌效果而有必要對塑膠多量添加(例如1~2重量%)，且由於因摩擦等引起自塑膠之脫落故持續效果差，有因與水或溶劑接觸而溶出等之課題。
本發明之目的在於提供具有優異抗菌性，即使重複洗滌，抗菌性亦持續之抗菌用纖維。且，目的在於提供使用前述抗菌用纖維之抗菌性優異之不織布、編物、織物、毛氈及織片。進而，目的在於提供使用前述不織布之過濾器、使用自前述之編物、織物、毛氈及織片所成之群中選出之任1種以上之衣料、寢具或室內裝飾配件。
本發明人針對上述課題積極檢討之結果，發現於表面具有含有特定量之氧伸烷基之聚縮醛共聚物之纖維具有優異之抗菌性，且即使重複洗滌，抗菌性亦持續，因而完成本發明。
亦即本發明係以下者。
(1)一種抗菌用纖維，其係於表面具有含有氧亞甲基與以下述通式(1)表示之氧伸烷基之聚縮醛共聚物(X)之纖維，聚縮醛共聚物(X)中之氧伸烷基之莫耳量相對於氧亞甲基之莫耳量與氧伸烷基之莫耳量之合計值為0.2~5mol%，
(式中，R0及R0’可相同亦可不同，分別選自氫原子、碳數1~8之烷基、具有碳數1~8之烷基之有機基、苯基、及具有苯基之有機基，m為2~6之整數)。
(2)如(1)之抗菌用纖維，其中前述聚縮醛共聚物(X)之取向度為60%以上。
(3)如(1)或(2)之抗菌用纖維，其中表面具有前述聚縮醛共聚物(X)之纖維係聚縮醛共聚物(X)之單層纖維。
(4)如(1)或(2)之抗菌用纖維，其中表面具有前述聚縮醛共聚物(X)之纖維係以聚縮醛共聚物(X)被覆由熱可塑性樹脂所成之纖維之多層纖維。
(5)如(1)或(2)之抗菌用纖維，其中表面具有前述聚縮醛共聚物(X)之纖維係於由熱可塑性樹脂所成之纖維之表面上具有聚縮醛共聚物(X)之複合纖維。
(6)如(4)或(5)之抗菌用纖維，其中前述熱可塑性樹脂係自聚縮醛均聚物、聚縮醛共聚物(X)以外之聚縮醛共聚物、聚烯烴樹脂、聚乳酸樹脂、尼龍樹脂、聚酯樹脂、聚乙烯樹脂、及該等之彈性體中選出之1種或2種以上。
(7)一種不織布，係使用如(1)至(6)中任一項之抗菌用纖維。
(8)一種過濾器，係使用如(7)之不織布。
(9)一種編物，係使用如(1)至(6)中任一項之抗菌用纖維。
(10)一種織物，係使用如(1)至(6)中任一項之抗菌用纖維。
(11)一種毛氈，係使用如(1)至(6)中任一項之抗菌用纖維。
(12)一種織片，係使用如(1)至(6)中任一項之抗菌用纖維。
(13)一種衣料，係使用自如(9)~(12)之編物、織物、毛氈及織片所成之群中選出之任一種以上。
(14)一種寢具，係使用自如(9)~(12)之編物、織物、毛氈及織片所成之群中選出之任一種以上。
(15)一種室內裝飾配件，係使用自如(9)~(12)
之編物、織物、毛氈及織片所成之群中選出之任一種以上。
依據本發明，可提供具有優異抗菌性，即使重複洗滌，抗菌性亦持續之抗菌用纖維。且，本發明之抗菌用纖維可加工為抗菌性優異之不織布、編物、織物、毛氈及織片，而可提供使用其之抗菌性優異之過濾器、衣料、寢具及室內裝飾配件。
以下針對本發明詳細說明。本發明係一種抗菌用纖維，其係於表面具有含有氧亞甲基與以後述通式(1)表示之氧伸烷基之聚縮醛共聚物(X)之纖維，聚縮醛共聚物(X)中之氧伸烷基之莫耳量相對於氧亞甲基之莫耳量與氧伸烷基之莫耳量之合計值為0.2~5mol%。亦即本發明之抗菌用纖維之特徵係於纖維表面具有聚縮醛共聚物(X)，該聚縮醛共聚物(X)之以後述通式(1)表示之氧伸烷基相對於氧亞甲基之莫耳量與氧伸烷基之莫耳量之合計值為0.2~5mol%。
本發明之抗菌用纖維係於表面具有前述聚縮醛共聚物(X)之纖維。表面具有聚縮醛共聚物(X)之
纖維形態並未特別限制，但較好為[A]聚縮醛共聚物(X)之單層纖維形態，[B]以聚縮醛共聚物(X)被覆由熱可塑性樹脂所成之纖維之多層纖維之形態，[C]於由熱可塑性樹脂所成之纖維之表面上具有聚縮醛共聚物(X)之複合纖維之形態。
上述之[A]聚縮醛共聚物(X)之單層纖維形態係由聚縮醛共聚物(X)所成之纖維。單層纖維可藉由熔融紡絲聚縮醛共聚物(X)所得，並根據需要進而延伸加工而得。
上述之[B]以聚縮醛共聚物(X)被覆由熱可塑性樹脂所成之纖維之多層纖維之形態中之芯部分，可使用由熱可塑性樹脂所成之纖維。前述熱可塑性樹脂之種類並未特別限制，但舉例為例如聚縮醛均聚物、聚縮醛共聚物(X)以外之聚縮醛共聚物(例如以通式(1)表示之氧伸烷基之含量相對於氧亞甲基之莫耳量與氧伸烷基之莫耳量之合計值超過5mol%之聚縮醛共聚物)、聚烯烴樹脂、聚乳酸樹脂、尼龍樹脂、聚酯樹脂、聚乙烯樹脂、及該等之彈性體等。該等熱可塑性樹脂可單獨使用1種或層合或相溶2種以上而使用。又，本發明中所謂「被覆」意指對於芯纖維之纖維方向平行的表面的全部或一部分被覆之形態。表面被覆之比例並未特別限制，比例越高抗菌性越優異故較好。
此種多層纖維可藉由使聚縮醛共聚物(X)與上述之熱可塑性樹脂熔融紡絲而得，並根據需要進而延伸
加工而得。所得之多層纖維形態係成為芯纖維的由熱可塑性樹脂所成之纖維周圍之全部或一部分被覆有聚縮醛共聚物(X)之芯鞘構造。
上述之[C]於由熱可塑性樹脂所成之纖維之表面上具有聚縮醛共聚物(X)之複合纖維之形態中之熱可塑性樹脂種類並未特別限制，可使用與上述之多層纖維之形態中之熱可塑性樹脂相同者。該等熱可塑性樹脂可單獨使用1種或層合或相溶2種以上而使用。
於由熱可塑性樹脂所成之纖維之表面上具有聚縮醛共聚物(X)之複合纖維可藉由使聚縮醛共聚物(X)與上述之熱可塑性樹脂之混合物熔融紡絲而得，並根據需要進而延伸加工而得。所得之複合纖維形態可為以聚縮醛共聚物(X)與熱可塑性樹脂成為相溶狀態之聚合物分子等級露出於纖維表面之狀態，亦可為成為海島構造或源自其之分散狀態於纖維表面露出聚縮醛共聚物(X)之狀態，亦可以如並排方式使聚縮醛共聚物(X)與熱可塑性樹脂露出表面之狀態。前述複合纖維表面之聚縮醛共聚物(X)之露出比例並未特別限制，但比例越高抗菌性越優異故較好。
本發明之抗菌用纖維中之聚縮醛共聚物(X)之取向度並未特別限制，但較好為60%以上，更好為70%以上，特佳為80%以上。此係因為聚縮醛共聚物(X)之取向度越高抗菌性越優異。且，如後述之聚縮醛共聚物(X)之抗菌性與共聚物之氧伸烷基含量有關，有氧伸烷
基含量越多聚縮醛共聚物(X)之抗菌性變低之傾向。然而，由於氧伸烷基含量多的聚縮醛共聚物(X)具有取向度對抗菌性之影響大之特徵，故氧伸烷基含量多的聚縮醛共聚物(X)中，取向度越高抗菌性越優異。聚縮醛共聚物(X)之取向度藉由使熔融紡絲之纖維延伸加工而有效率地提高。
抗菌用纖維之取向度可如本說明書實施例所述般使用廣角X射線繞射裝置求得。
本發明之抗菌用纖維之單纖度由於係根據用途之容許值亦不同故未特別限定，作為過濾器使用時由於必須減小對流體之壓力損失同時提高過濾精度，故較好為10dtex(單位：分特克斯)以下。
本發明之抗菌用纖維根據JIS L 1902(纖維製品之抗菌性試驗方法及抗菌效果)之抗菌性試驗所得之靜菌活性值，於作為食物中毒之原因菌而已知之金黃色葡萄球菌時，通常為2.2以上，較好為2.4以上，特佳為2.7以上。該數值係滿足一般社團法人纖維評價技術協議會所定出之抗菌防臭加工之認證者。又，本發明之抗菌用纖維具有金黃色葡萄球菌之殺菌活性值亦優異之特徵。進而與於聚縮醛纖維中混練抗菌性物質所得之抗菌用纖維相比，具有即使重複洗滌抗菌性亦持續之優異特徵。
本發明之抗菌用纖維對於成為惡臭原因之莫拉菌亦顯示高的靜菌活性值。莫拉菌中之靜菌活性值通常為1.8以上，較好為2.0以上，特佳為2.2以上。且本發
明之抗菌用纖維具有對莫拉菌亦顯示優異殺菌活性之特徵。進而與於聚縮醛纖維中混練抗菌性物質所得之抗菌用纖維相比，具有即使重複洗滌抗菌性亦持續之優異特徵。
本發明之抗菌用纖維可依據以往習知之纖維之製造方法製造。例如可使聚縮醛共聚物(X)之顆粒熔融紡絲而製造。此時，基於可提高上述之取向度之方面，較好使熔融紡絲之纖維進一步延伸加工。延伸加工條件亦可藉以往習知方法、條件進行。延伸倍率基於取向度之觀點較好為3倍以上。延伸倍率之上限並非以取向度方面被限定者，但基於生產時之安定性(防止斷絲)或防止過度纖絲化之方面而言為15倍。又，熔融紡絲、延伸加工之裝置可使用以往習知之裝置進行。
存在於本發明之抗菌用纖維表面之聚縮醛共聚物(X)除了分子中之氧亞甲基(-CH2-O-)以外，具有以下述通式(1)表示之構造之氧伸烷基。
式中，R0及R0’可相同亦可不同，分別選自氫原子、碳數1~8之烷基、具有碳數1~8之烷基之有機基、苯基、
及具有苯基之有機基。且m為2~6之整數。較好R0及R0’可相同亦可不同，分別選自氫原子、碳數1~4之烷基、碳數1~4之烷氧基、苯基及苄基，m為2~4之整數。更好R0及R0’選自氫原子及碳數1~4之烷基，m為2。
作為前述碳數1~8之烷基舉例為例如甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、己基、環己基等。且作為上述具有碳數1~8之烷基之有機基，舉例為例如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基等。作為前述具有苯基之有機基舉例為苄基、苯乙基等。
作為上述之氧伸烷基較好為氧伸乙基、氧伸丙基及氧伸丁基，特佳為氧伸乙基。
上述之氧伸烷基於聚縮醛共聚物(X)中，可為1種或含2種以上。亦即本發明之聚縮醛共聚物(X)不僅為2元共聚物，亦包含多元共聚物。
且本發明之聚縮醛共聚物(X)亦可為進而具有氧亞甲基、氧伸烷基以外之嵌段構造之聚縮醛共聚物，或者亦可為分子內進而具有分支構造之聚縮醛共聚物。作為該等聚縮醛共聚物舉例為例如藉由將分子末端或分子中具有如羥基之具有活性氫之官能基的熱可塑性樹脂或共聚物作為鏈轉移劑使用而得之末端導入有前述鏈轉移劑之構造之聚縮醛共聚物、在主鏈中含有如聚乙烯甲醛之具有共聚合反應性之環狀甲醛部位之化合物存在下進行聚合反應而得之聚縮醛共聚物。
本發明之聚縮醛共聚物(X)可為使用如縮水
甘油醚之環氧化合物或烯丙醚等作為單體而製造者，亦包含於聚縮醛共聚物中具有源自該等化合物之構造者。
一般聚縮醛共聚物中之氧伸烷基含量(氧伸烷基之莫耳量)相對於氧亞甲基之莫耳量與氧伸烷基之莫耳量之合計值為0.01~20mol%之廣範圍，但本發明之聚縮醛共聚物(X)中之氧伸烷基含量(氧伸烷基之莫耳量)相對於氧亞甲基之莫耳量與氧伸烷基之莫耳量之合計值通常為0.2~5mol%，較好為0.2~3.0mol%，更好為0.2~2.0mol%，特佳為0.2~1.0mol%。前述氧伸烷基之含量若為0.2mol%以上、5mol%以下，則抗菌性優異，表示抗菌性之靜菌活性值高，即使重複進行洗滌，靜菌活性值亦不降低。且前述氧伸烷基之含量若為0.2mol%以上、3.0mol%以下，則抗菌性更優異，表示抗菌性之靜菌活性值更高，即使重複進行洗滌，靜菌活性值亦更不降低。
本發明之聚縮醛共聚物(X)可單獨使用1種，亦可組合2種以上之氧伸烷基種類不同之聚縮醛共聚物，亦可組合2種以上之氧伸烷基含量不同之聚縮醛共聚物。組合2種以上之氧伸烷基種類或氧伸烷基含量不同之聚縮醛共聚物時，該等聚縮醛共聚物可為相溶狀態，亦可為海島構造或源自其之分散狀態，亦可為如並排之狀態。
本發明之聚縮醛共聚物(X)遵照ISO1133之MVR(Melt Volume Rate，熔融體積率)較好為100cm3/10分鐘以下。MVR值越大於熔融紡絲中越適於獲得細纖維，但只要為100cm3/10分鐘以下，則可獲得機械
物性(尤其韌性)優異之纖維。
本發明之聚縮醛共聚物(X)之製造方法為任意，只要藉由以往習知之方法製造即可。例如作為以氧亞甲基、碳數2以上4以下之氧伸烷基作為構成單位之聚縮醛樹脂之製造方法，可藉由使甲醛之3聚物(三氧環己烷)或4聚物(四氧環辛烷)等之氧亞甲基之環狀縮醛、與環氧乙烷、1,3-二氧雜環戊烷、1,3,6-三氧雜環辛烷、1,3-二氧雜環庚烷等之含碳數2以上4以下之氧伸烷基之環狀縮醛共聚合而製造。其中，作為本發明之聚縮醛共聚物(X)，較好為三氧環己烷或四氧環辛烷等之環狀縮醛、與環氧乙烷或1,3-二氧雜環戊烷之共聚物，其中特佳為三氧環己烷與1,3-二氧雜環戊烷之共聚物。
例如本發明之聚縮醛共聚物(X)可藉由使用聚合觸媒，使氧亞甲基之環狀縮醛與單體的含有碳數2以上4以下之氧伸烷基之環狀縮醛塊狀聚合之方法獲得。為了使聚合觸媒及聚合成長末端失活處理，亦可根據需要使用反應停止劑。且，為了調節聚縮醛共聚物之分子量，亦可根據需要使用分子量調節劑。本發明之聚縮醛共聚物(X)之製造中可使用之聚合觸媒、反應停止劑、分子量調節劑之種類或量，只要不阻礙本發明效果，則未特別限定，可適當使用以往習知之任意聚合觸媒、反應停止劑、分子量調節劑。
前述聚合觸媒並未特別限制，但舉例為例如三氟化硼、四氯化錫、四氯化鈦、五氯化磷、五氟化磷、五氟化砷、及五氟化銻等之路易士酸、以及該等路易士酸之錯化合物或鹽化合物。且亦舉例為三氟甲烷磺酸、過氯酸等之質子酸；過氯酸與低級脂肪族醇之酯等之質子酸之酯；過氯酸與低級脂肪族羧酸之混合酸酐等之質子酸之酸酐等。此外，舉例為三乙基氧鎓六氟磷酸鹽、三苯基甲基六氟砷酸鹽、乙醯基六氟硼酸鹽、雜聚酸或其酸性鹽、異聚酸或其酸性鹽、全氟烷基磺酸或其酸性鹽等。其中，較好包含三氟化硼之化合物，特佳為與醚類之配位錯合物的三氟化硼二乙醚化物、三氟化硼二丁基醚化物。
前述聚合觸媒之使用量並未特別限制，但對於三氧環己烷與單體的合計總莫耳1mol，通常為1.0×10-8~2.0×10-3mol，較好為5.0×10-8~8.0×10-4mol，特佳為5.0×10-8~1.0×10-4mol。
作為前述反應停止劑並未特別限制，但舉例為例如三價之有機磷化合物、胺化合物、鹼金屬或鹼土類金屬之氫氧化物。該等反應停止劑可單獨使用1種，或可組合2種以上使用。其中，較好為三價有機磷化合物、三級胺、受阻胺。
前述反應停止劑之使用量若為可使聚合觸媒失活之充分量，則無特別限制，作為對於聚合觸媒之莫耳比，通常為1.0×10-1~1.0×101之範圍。
作為前述分子量調節劑並未特別限制，舉例
為例如甲縮醛、甲氧基甲縮醛、二甲氧基甲縮醛、三甲氧基甲縮醛、氧亞甲基二-正-丁基醚等。其中較好為甲縮醛。該等分子量調節劑之使用量係根據成為目標之分子量適當決定。通常，對於全部單體於0~0.1質量%之範圍調整添加量。
且，實施本發明時，本發明之聚縮醛共聚物(X)中，在不損及本來目的之範圍內，可添加由受阻酚化合物、受阻胺化合物、胺基取代之三嗪化合物、磷系安定劑、鹼金屬及鹼土金屬類之氫氧化物、脂肪酸鹽、無機酸鹽或烷氧化物所成之群所示之含金屬化合物。以下，本說明書中，上述之「受阻酚化合物、受阻胺化合物、胺基取代之三嗪化合物、磷系安定劑、鹼金屬及鹼土金屬類之氫氧化物、脂肪酸鹽、無機酸鹽或烷氧化物所成之群所示之含金屬化合物」有時稱為「任意成分」。作為該等任意成分可使用以往習知者。
又，實施本發明時，本發明之聚縮醛共聚物(X)中，在不損及本來目的之範圍內，除上述之任意成分以外，亦可根據需要適當添加安定劑、核化劑、脫模劑、填充劑、顏料、染料、滑劑、可塑劑、抗靜電劑、油劑、集束劑、紫外線吸收劑、難燃劑、難燃助劑、抗黴劑、抗病毒劑等之各種添加劑、其他樹脂、彈性體等。以下，本說明書中，上述「安定劑、核化劑、脫模劑、填充
劑、顏料、染料、滑劑、可塑劑、抗靜電劑、油劑、集束劑、紫外線吸收劑、難燃劑、難燃助劑、抗黴劑、抗病毒劑等之各種添加劑、其他樹脂、彈性體等」有時稱為「其他成分」。作為填充劑，舉例為玻璃纖維、玻璃片、玻璃珠、矽灰石、雲母、滑石、氮化硼、碳酸鈣、高嶺土、二氧化矽、黏土、石綿、氧化矽、矽藻土、石墨、二硫化鉬等之礦物質填充劑及玻璃纖維、研磨纖維、鈦酸鉀纖維、硼纖維等之無機纖維，以及碳纖維、以芳醯胺纖維為代表之有機纖維、鈦酸鉀晶鬚，以及碳黑、顏料等。
上述任意成分或其他成分添加於聚縮醛共聚物(X)之方法並未特別限制，例如使上述之聚縮醛共聚物(X)與根據需要添加之任意成分及/或其他成分以任意順序混合、混練而製造。混合‧混練之溫度、壓力等之條件只要根據以往習知之聚縮醛共聚物之製造方法適當選擇即可。例如，混練只要在聚縮醛共聚物之熔融溫度以上進行即可，通常較好在180℃以上260℃以下進行。聚縮醛共聚物之製造裝置亦未特別限制，可使用過去以來該種聚縮醛共聚物之製造所用之混合、混練裝置等。又，上述任意成分或其他成分亦可另外、混合、浸透、吸附、附著於含有聚縮醛共聚物(X)之纖維上。
本發明之抗菌用纖維可根據用途加工成不織布、織物、編物、毛氈、織片等之形態。用以活用抗菌劑之特佳
形態為由不織布所成之過濾器。該等不織布、織物、編物、毛氈、織片亦具有與本發明之抗菌用纖維同等之抗菌性，具有即使重複洗滌，抗菌性亦持續之優異特徵。且，與以往之具有有機系抗菌劑或無機系抗菌劑之抗菌用纖維相比，並無加工時之耐熱性或變色等之問題，安全性優異，故可較好地使用於廣範圍用途。尤其，本發明之不織布可較好地使用作為過濾器。該過濾器亦具有與本發明之抗菌用纖維同等之抗菌性，具有即使重複洗滌，抗菌性亦持續之優異特徵。且本發明之織物、編物、毛氈、織片可較好地使用於內衣、襯衫、運動衣、圍裙、襪子、長筒襪、緊身衣褲、連褲襪、日本式短布襪、穿日式服裝品、領帶、手帕、圍巾、帽子、手套、口罩、尿片等之衣料，枕套、毛巾毯、床單、被胎等之寢具，窗簾、地毯、墊子、地毯、壁掛、壁紙、桌布、絨面毛毯等之室內裝飾配件，毛巾、抹布、掃把、拖把、絨毛玩具填充物等之雜貨等。該等衣料、寢具、室內裝飾配件及雜貨亦具有與本發明之抗菌用纖維同等之抗菌性，具有即使重複洗滌，抗菌性亦持續之優異特徵。
又，使用本發明之抗菌用纖維加工成不織布、織物、編物、毛氈、織片等之形態時，可僅用本發明之抗菌用纖維加工，但亦可與尼龍、聚酯、聚胺基甲酸酯等之合成纖維、木綿或絹絲等之天然纖維、碳纖維、玻璃纖維等複合，作成合撚絲、包芯紗、辮繩，加工為不織布、織物、編物、毛氈、織片等之形態，亦可與尼龍或聚
酯、聚胺基甲酸酯等之合成纖維、木綿或絹絲等之天然纖維、碳纖維、玻璃纖維混纖、混紡，加工為不織布、織物、編物、毛氈、織片等之形態。且，本發明之抗菌用纖維或根據用途加工成織物、編物等之形態中，藉由進一步進行染色或各種修飾加工(防皺、防污、難燃、防蟲、防黴、防臭、吸濕、防水、上光、抗毛球等)，可賦予抗菌性以外之機能。
本發明之具有抗菌性之不織布之製造方法並未特別限制，可使用過去習知之乾式法、濕式法、紡黏法、熔融吹塑法等。此時較好藉由使纖維彼此充分結合且絡合而抑制纖維脫落。作為此等方法，舉例為熱熔法、化學熔法、針刺法、無紡法(水流絡合法)、縫編法、蒸氣噴射法等，其中熱熔法可達成充分結合故較佳。
又，藉由對於支撐由上述不織布所成之過濾器之框架構件亦使用聚縮醛共聚物(X)，可成為抗菌性、回收性優異之製品。
以下針對本發明顯示實施例、比較例，關於其實施形態與效果具體說明，但本發明絕非限定於該等例。
實施例及比較例所用之聚縮醛共聚物如下。又，聚縮
醛共聚物(X)中之氧伸乙基之含量(氧伸乙基之莫耳量)係對於氧亞甲基之莫耳量與氧伸乙基之莫耳量之合計值之值。
POM-1：氧伸乙基含量為0.4mol%，MVR為8之聚縮醛共聚物。
POM-2：氧伸乙基含量為1.6mol%，MVR為8之聚縮醛共聚物。
POM-3：氧伸乙基含量為3.0mol%，MVR為8之聚縮醛共聚物。
POM-4：氧伸乙基含量為4.7mol%，MVR為8之聚縮醛共聚物。
POM-5：氧伸乙基含量為5.7mol%，MVR為8之聚縮醛共聚物。
PLA(聚乳酸樹脂)：直接使用UNITIKA股份有限公司製TERRAMAC(註冊商標)TE2000。
PET(聚對苯二甲酸乙二酯樹脂)：直接使用單纖度2dtex之多纖絲。
聚縮醛共聚物之MVR(cm3/10分鐘)係根據ISO1133測定。
將實施例及比較例所用之聚縮醛共聚物溶解於六氟異丙醇(d2)，製作NMR測定試料，針對該測定試料測定NMR光譜，測定聚縮醛共聚物中之氧伸乙基含量。
纖維之纖度[dtex(分特克斯)]係使用光學顯微鏡測定單纖維之纖徑，設為密度1.40g/cm3算出纖度，將測定根數50根之平均值作為纖維之纖度。
使用廣角X射線繞射裝置(島津製作所股份有限公司製DP-D1)，以CuKα(使用Ni過濾器)作為線源進行測定(輸出45KV，40mA)。取向度(fc)係自針對於2θ=22.2°附近觀察之(100)面，於圓周方向掃描而得之繞射強度之分佈曲線(方位角分佈曲線)之半值寬FWHM(°)，使用下述式(1)求得。
[數1]fc(%)=((180°-FWHM)/180°)×100 式(1)
將汽缸、噴嘴部之溫度加溫至200℃，自具備48個直徑0.6mm之孔之噴嘴以1.2kg/h之速度，噴出熔融樹脂。又，芯鞘複合纖維時，自噴嘴之噴出速度對芯成分之
樹脂、鞘成分之樹脂均設為0.6kg/h。此時，拉伸速度固定於100m/分鐘，連續採取未延伸纖維，所得未延伸纖維持續導入加熱延伸步驟，以輥溫度120~140℃進行延伸處理，作成纖維試料。
對上述延伸纖維實施捲縮處理後，切成51mm長。以梳棉機(京和機材作所股份有限公司製)將其作成織片，以針刺裝置(大和機工股份有限公司製)交絡作成針刺不織布。
依據JIS L 1902(纖維製品之抗菌性試驗方法及抗菌效果)，藉由定量試驗(菌液吸收法)進行評價。將標準棉布之纖維試料、實施例或比較例之纖維試料(以下稱為測定試料)各0.4g饋入個別小瓶中，接種0.2ml之試驗菌液，在37±2℃培養18±1小時後，添加含0.2%非離子界面活性劑之生理食鹽水20ml，自試料洗出菌，洗出液中之菌數藉由混釋平板培養法(菌落法)測定，依據下述式(2)算出靜菌活性值。靜菌活性值之數值越大，抗菌性越優異。且對於金黃色葡萄球菌之靜菌活性值若為2.2以上，則相當於一般社團法人纖維評價技術協議會認證之SEK標記(藍色：抗菌防臭加工)。且，依據下述式
(3)算出殺菌活性值。殺菌活性值越大，抗菌性越優異，若大於0，則意指於抗菌性試驗之前後菌減少。
[數2]靜菌活性值={log(標準棉布中之培養後生菌數)-log(標準棉布中之剛接種後生菌數)}-{log(測定試料中之培養後生菌數)-log(測定試料之剛接種後生菌數)} 式(2)
[數3]殺菌活性值=log(標準棉布中之剛接種後生菌數)-log(測定試料中之培養後生菌數) 式(3)
洗滌10次後之靜菌活性保持率與殺菌活性保持率如下般求得。洗滌方法係依據JIS L 0217之103號，洗劑係使用JAFET標準配合洗劑。進行10次重複洗滌處理後，進行與上述同樣之抗菌性試驗，依據下述式(4)，算出洗滌10次後之靜菌活性保持率[單位：%]。且依據下述式(5)，算出洗滌10次後之殺菌活性保持率[單位：%]。兩者均數值越接近100%，抗菌性越優異。
[數4]靜菌活性保持率(%)=(10次洗滌處理後之靜菌活性值/洗滌處理前之靜菌活性值)×100 式(4)
[數5]殺菌活性保持率(%)=(10次洗滌處理後之殺菌活性值/洗滌處理前之殺菌活性值)×100 式(5)
上述靜菌活性值、殺菌活性值及洗滌10次後之靜菌
活性保持率、殺菌活性保持率係針對金黃色葡萄球菌與莫拉菌進行測定。
表1中顯示氧伸乙基含量在特定範圍內之聚縮醛共聚物之單層纖維、氧伸乙基含量在特定範圍內之聚縮醛共聚物之多層纖維、氧伸乙基含量在特定範圍內之聚縮醛共聚物與PLA之多層纖維之實施例、以及聚酯纖維、氧伸乙基含量多於特定範圍之聚縮醛共聚物單層纖維之比較例。
針對各例，顯示聚縮醛共聚物中之氧伸乙基含量、單纖度、取向度與上述之抗菌性試驗中之培養後之靜菌數(單位：個)、抗菌性試驗前後之增加比、靜菌活性值、洗滌10次後之靜菌活性保持率、殺菌活性值、洗滌10次後之殺菌活性保持率。
由實施例1~6及比較例1、2，可知聚縮醛共聚物中之氧伸乙基含量若為0.2~5mol%，則靜菌活性值、殺菌活性值、洗滌後之殺菌活性保持率優異。又，由實施例4~6可知，纖維中之聚縮醛共聚物之取向度若高，則靜菌活性值、殺菌活性值、洗滌後之殺菌活性保持率更優異。
Claims (11)
- 一種纖維作為抗菌用纖維之用途，其特徵為該纖維對金黃色葡萄球菌及莫拉菌具有抗菌性，該纖維係於表面具有含有氧亞甲基與以下述通式(1)表示之氧伸烷基之聚縮醛共聚物(X)，且聚縮醛共聚物(X)中之氧伸烷基之莫耳量相對於氧亞甲基之莫耳量與氧伸烷基之莫耳量之合計值為0.2~5mol%；
- 如請求項1之纖維作為抗菌用纖維之用途，其中前述聚縮醛共聚物(X)之取向度為60%以上。
- 如請求項1之纖維作為抗菌用纖維之用途，其中前述表面具有聚縮醛共聚物(X)之纖維係聚縮醛共聚物(X)之單層纖維。
- 如請求項1之纖維作為抗菌用纖維之用途，其中前述表面具有聚縮醛共聚物(X)之纖維係以聚縮醛共聚物(X)被覆由熱可塑性樹脂所成之纖維之多層纖維。
- 如請求項1之纖維作為抗菌用纖維之用途，其中前述表面具有聚縮醛共聚物(X)之纖維係於由熱可塑性樹脂所成之纖維之表面上具有聚縮醛共聚物(X)之複合纖維。
- 如請求項4之作為抗菌用纖維之用途，其中前述熱可塑性樹脂係自聚縮醛均聚物、聚縮醛共聚物(X)以外之聚縮醛共聚物、聚烯烴樹脂、聚乳酸樹脂、尼龍樹脂、聚酯樹脂、聚乙烯樹脂、及該等之彈性體中選出之1種或2種以上。
- 如請求項5之纖維作為抗菌用纖維之用途，其中前述熱可塑性樹脂係自聚縮醛均聚物、聚縮醛共聚物(X)以外之聚縮醛共聚物、聚烯烴樹脂、聚乳酸樹脂、尼龍樹脂、聚酯樹脂、聚乙烯樹脂、及該等之彈性體中選出之1種或2種以上。
- 如請求項1至7中任一項之纖維作為抗菌用纖維之用途，其係使用於表面具有聚縮醛共聚物(X)之纖維來作成不織布。
- 如請求項8之纖維作為抗菌用纖維之用途，其係使用前述不織布來作成過濾器。
- 如請求項1至7中任一項之纖維作為抗菌用纖維之用途，其係使用於表面具有聚縮醛共聚物(X)之纖維來作成選自由編物、織物、毛氈及織片所成群之任一種。
- 如請求項10之纖維作為抗菌用纖維之用途，其係使用前述選自由編物、織物、毛氈及織片所成群之任一種以上來作成衣料、寢具或室內裝飾配件。
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| EP3270720B1 (en) * | 2015-03-20 | 2019-01-02 | Defente, Ruggiero | Differentiated lymph drainage garment |
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| MY189735A (en) | 2015-09-18 | 2022-02-28 | Mitsubishi Gas Chemical Co | Cloth having excellent contact cold sensation and colorfastness |
| WO2017047460A1 (ja) * | 2015-09-18 | 2017-03-23 | 三菱瓦斯化学株式会社 | 接触冷感用繊維及びそれを用いた繊維製品 |
| US11441242B2 (en) | 2017-07-14 | 2022-09-13 | Mitsubishi Gas Chemical Company, Inc. | Method for manufacturing polyacetal fiber |
| TWI776002B (zh) | 2017-12-28 | 2022-09-01 | 日商三菱瓦斯化學股份有限公司 | 色差校正用光學樹脂材料及光學元件 |
| US11452959B2 (en) * | 2018-11-30 | 2022-09-27 | Hollingsworth & Vose Company | Filter media having a fine pore size distribution |
| JP7229800B2 (ja) * | 2019-02-07 | 2023-02-28 | 旭化成株式会社 | ポリアセタール樹脂組成物 |
| JP7595935B2 (ja) * | 2021-05-21 | 2024-12-09 | 株式会社プレジール | 抗菌性織物 |
| CN117166113B (zh) * | 2023-09-06 | 2024-12-03 | 山西妙睡宝睡眠科技有限公司 | 一种抗菌亲肤面料 |
| US20260013575A1 (en) * | 2024-07-10 | 2026-01-15 | Drymax Technologies, Inc. | Anti-slip sock or shoe cover with antimicrobial action |
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| KR20170129156A (ko) | 2017-11-24 |
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