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CN102066627A - 多层复合纤维 - Google Patents

多层复合纤维 Download PDF

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CN102066627A
CN102066627A CN2009801195381A CN200980119538A CN102066627A CN 102066627 A CN102066627 A CN 102066627A CN 2009801195381 A CN2009801195381 A CN 2009801195381A CN 200980119538 A CN200980119538 A CN 200980119538A CN 102066627 A CN102066627 A CN 102066627A
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resin
composite fiber
polyacetal
multilayer composite
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CN102066627B (zh
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冈村显
长井聪
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Mitsubishi Gas Chemical Co Inc
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Abstract

本发明的目的是提供一种使用了主要由不依赖于石油的原料即甲醇衍生的、环境负荷低的材料聚缩醛的新型多层复合纤维，进而提供一种通过将其热粘合而使其结合的无纺布。根据本发明，可提供一种含有以聚乳酸作为主要成分的树脂和以聚缩醛作为主要成分的树脂，且各种成分均形成沿纤维轴方向连续的层的多层复合纤维以及将该纤维热粘合而得到的无纺布。

Description

多层复合纤维
技术领域
本发明涉及一种以聚乳酸作为主要成分的树脂作成芯，将与其具有特定的熔点差的以聚缩醛作为主要成分的树脂作成鞘而成的复合纤维，进而涉及将其通过热粘合加工而成的无纺布。
背景技术
近年来，为了对应对于地球规模的环境问题，防止工业废弃物污染环境，而使用生物降解性(微生物降解性、或自然降解性)的原材料受到注目。进而，最近强烈要求应对伴随地球资源的枯竭、温室化的CO2排出量的自主规制中，由不是源自石油而是源自天然物构成的原材料、或焚烧处理时需要的热量和产生的CO2量少的原材料正受到注目。
以往，已知在具有脂肪族酯结构的聚合物中具有生物降解性，作为代表的是利用微生物生产的聚-3-羟基丁酸酯(PHB)、作为合成高分子的聚己内酯(PCL)、琥珀酸和丁二醇作为主要成分的聚丁二酸丁二醇酯(PBS)或聚丁二酸/己二酸-丁二醇酯(PBSA)、聚酯碳酸酯、以及以利用发酵生产的L-乳酸和/或D-乳酸作为主要原料的聚乳酸(PLA)等。其中，作为由源自天然物的物质构成的原材料，可列举出如PLA。
具有这些脂肪族酯结构的聚合物除了PLA，通常是具有聚乙烯类似的物性的成形性和生物降解性良好的聚合物。但是，在要求刚性的领域和要求拉伸强度的领域中不具有充分的强度。为了改善刚性，可通过滑石等填充材料和纳米复合材料(nanocomposite)化技术而进行改善，但还有流动性降低等问题，期望进行该改良。另外，对于PLA强烈要求提高耐热性和韧性。
迄今为止，发现了几个以生物降解性原材料制作芯鞘复合纤维，且作为用于热粘合类型的无纺布的原棉的研究。例如，专利文献1、2中公开了作为热塑性的生物降解纤维，芯部、或鞘部使用熔点不同的生物降解性聚合物。另外，专利文献3公开了芯部使用高熔点的L-聚乳酸、鞘部使用L和D-聚乳酸的共聚物。专利文献4公开了将芯鞘成分的至少1个成分作为生物降解性聚合物的复合纤维，特点是其熔点差为20～80℃，且各成分的熔点分布是尖锐的。进而专利文献5中公开有由对聚乳酸被覆其他的热塑性树脂所形成的复合纤维而得到的内装材料。
专利文献1：日本特开平7-133511号
专利文献2：日本特开平8-260320号
专利文献3：日本专利3355026号
专利文献4：日本特开2006-97148号
专利文献5：日本特开2008-57095号
发明内容
发明要解决的问题
然而，实质上由于鞘成分使用生物降解聚合物，因使用环境而容易受到生物降解成为问题，有由水解导致的强度降低的担心。另外，通过使用低熔点的生物降解性聚合物、进一步使用热塑性树脂，从而加工性稳定，但相反有粘接点的耐热性降低的担心。本发明的目的是提供脂肪族醚型、或者脂肪族醚为主要成分的、主要使用由不依赖于石油原料的甲醇衍生且认为环境负荷低的材料的聚缩醛中具有特定的熔点的物质的新型多层复合纤维，进而通过将其进行热粘合而使其结合而成的无纺布。
用于解决问题的方案
本发明人等为解决前述课题精心进行了研究，结果是实质上通过以聚乳酸作为主要成分的树脂作成芯，以特定的聚缩醛作为主要成分的树脂作成鞘，克服了上述问题，并完成了本发明。
本发明包括以下的方案。
(1)一种多层复合纤维，其是含有以聚乳酸作为主要成分的树脂和以聚缩醛作为主要成分的树脂，且各种成分均形成沿纤维轴方向连续的层的多层复合纤维，所述以聚缩醛作为主要成分的树脂的熔点相对于所述以聚乳酸作为主要成分的树脂的熔点低10～20℃；
(2)根据上述(1)所述的多层复合纤维，其中，将所述以聚乳酸作为主要成分的树脂作成芯，将所述以聚缩醛作为主要成分的树脂作成鞘；
(3)根据上述(1)或(2)所述的多层复合纤维，其中，所述聚缩醛为100重量份的三聚甲醛与5～20重量份的1种或者2种以上的环状缩甲醛和/或环状醚的共聚物；
(4)一种无纺布，其通过将上述(1)～(3)任一项所述的多层复合纤维热粘合而得到；
(5)一种无纺布，其通过在上述(1)～(3)任一项所述的多层复合纤维中配合含有以聚乳酸作为主要成分的树脂和/或以聚缩醛作为主要成分的树脂的纤维，并热粘合而得到。
聚缩醛与脂肪族聚酯的亲和性良好，尤其是通过在熔融状态使其接触可以得到比较高的界面粘接强度。本发明中，鞘成分中尤其与脂肪族聚酯成分亲和性高，而且选择可通过热粘合而进行无纺布加工的聚缩醛是重要的。优选以聚缩醛作为主要成分的树脂的熔点相对于以聚乳酸作为主要成分的树脂的熔点低10～20℃。由此，不使用其他的热熔纤维而实现稳定的热粘合加工的同时，通过在聚乳酸的表面形成聚缩醛层，可赋予适当的耐水解性、耐化学药品性、耐摩擦磨耗性等新的特点。在使用以往的热熔纤维的热粘合中，有其耐水解性、耐化学药品性存在问题的情况，本发明中由于聚缩醛兼具了热粘合层，所以不会产生那样的问题。可以使用热熔纤维，但有聚缩醛与其他的树脂缺乏粘接性的缺点，其使用极受限制。
发明的效果
根据本发明，通过使用含有以聚乳酸作为主要成分的树脂和以聚缩醛作为主要成分的树脂的多层复合纤维，可以得到粘接强度、以及耐化学药品性优异的热粘合性无纺布。
具体实施方式
以下对本发明进行详细说明。
本发明是含有以聚乳酸作为主要成分的树脂和以聚缩醛作为主要成分的树脂，且各种成分均形成沿纤维轴方向连续的层的多层复合纤维，所述以聚缩醛作为主要成分的树脂的熔点，相对于所述以聚乳酸作为主要成分的树脂的熔点低10～20℃。
本发明中的聚乳酸(PLA)是指仅L-乳酸、仅D-乳酸、L-乳酸和D-乳酸的混合物中的任何一种作为主要构成成分的聚合物、或者其混合物，但也可以含有除了乳酸以外的其他的共聚成分。作为其他的单体单元，可列举ε-己内酯等环状内酯类、α-羟基异丁酸、α-羟基异戊酸等的α-含氧酸类、乙二醇、丙二醇、1，4-丁二醇等二醇化合物、琥珀酸、草酸、己二酸、癸二酸等二羧酸。其中，优选二醇类和环状内酯类。
作为PLA的聚合方法，可以使用已知的聚合方法，可例示来自乳酸的直接聚合法、通过丙交酯的开环聚合法等。开环聚合法是将L-丙交酯、进而共聚成分(共聚单体、或低聚物)在催化剂存在下开环聚合，根据需要再次沉淀精制而得到。
PLA的分子量和分子量分布没有特别的限制，数均分子量优选1万以上，更优选5万以上。
PLA的熔点没有特别限制，优选为160℃以上，更优选为165℃以上。
本发明的聚缩醛可列举通常市售的均聚物和/或共聚物，本发明中，优选100重量份的三聚甲醛与5.0～30重量份(更优选5～20重量份)的1种或者2种以上的环状缩甲醛和/或环状醚的共聚物。
作为共聚物中的氧化烯单元，优选氧化乙烯单元、氧化丙烯单元等。该氧化烯单元的含量为5～30重量％，更优选5～20重量％。
少于5重量％时，则熔点变高，有时无法得到与聚乳酸的熔点差。相反超过30重量％时，则熔点过低，因此有时耐热性、进而耐化学药品性受损。
作为本发明的聚缩醛，可列举例如，含有由甲醛或其三聚物(三聚甲醛)、以及，其四聚物(四聚甲醛)、环氧乙烷、环氧氯丙烷、1，3-二氧戊环、1，3-二氧七环、1，3，5-三氧七环、甘醇缩甲醛、二甘醇缩甲醛等的由碳原子数2～8的环状醚制造的含有氧化烯单元结构的共聚物。本发明中所说的共聚物不仅包含2元共聚物，也包含多元共聚物，例如，优选使用通过使缩水甘油醚类共聚而在主链中导入支链、交联结构的物质。进而还可以广泛使用具有氧化乙烯单元、除氧化丙烯单元以外的嵌段结构的嵌段共聚物、或者接枝聚合物等。
本发明中，所述以聚缩醛作为主要成分的树脂的熔点，相对于所述以聚乳酸作为主要成分的树脂的熔点优选低10～100℃，更优选低10～20℃。通过前述以聚缩醛作为主要成分的树脂的熔点相对于前述以聚乳酸作为主要成分的树脂的熔点低10～100℃，从而前述以聚缩醛作为主要成分的树脂和前述以聚乳酸作为主要成分的树脂的粘接性良好，故优选。
另外，本发明使用的聚乳酸、聚缩醛在不损害本发明的本来的目的范围内可以添加公知的添加剂和/或填充剂。作为添加剂，可列举结晶成核剂、抗氧化剂、增塑剂、消色剂、发泡剂、润滑剂、脱模剂、抗静电剂、紫外线吸收剂、光稳定剂、热稳定剂、除臭剂、阻燃剂、滑动剂、香料、抗菌剂等。另外，填充剂可列举玻璃纤维、滑石、云母、碳酸钙、钛酸钾、晶须等。进而，也可以加入颜料、染料来实现所希望的颜色。另外，还可以加入酯交换催化剂、各种单体、偶联剂、末端处理剂、其他的树脂、木粉、淀粉等来进行改性。
本发明是以聚乳酸作为主要成分的树脂和以聚缩醛作为主要成分的树脂的各种成分均形成沿纤维轴方向连续的层的多层复合纤维，作为形成沿纤维轴方向连续的层方法，可列举使用如成为一根纤维那样的喷嘴对二种以上的原料聚合物进行纺丝的方法，将这样得到的纤维称为复合纤维。其中有贴合各原料聚合物的双金属型和一方聚合物用其他的聚合物包围的芯鞘型，还可以得到将这些进一步拓展的所谓的多芯、花瓣、多层这样的结构。
作为得到本发明的芯鞘复合纤维的方法，通过以往公知的熔融纺丝得到。作为芯鞘复合纤维的结构，可以是多个以芯成分存在，也可以采用异形截面。另外，还可以是芯成分的一部存在于纤维表面。
本发明的聚乳酸系复合纤维可作为复丝或者单丝直接使用、或者制成短纤维(staple)状后，例如用作纺织丝。不仅仅限于这些纤维，还可以添加包含含有以聚乳酸作为主要成分的树脂和/或以聚缩醛作为主要成分的树脂的纤维热塑性树脂组合物的纤维，进行2次加工。
作为2次加工主要列举无纺布，对于加工方法同样适用公知的方法。优选使用纺粘(spunbond)法、针刺法(needle punch)、熔体流动法等，期望最终发挥芯鞘的特点以使纤维间进行热粘合。本发明不限于无纺布，也可以加工成织物、编织物、编带、花边、网等。进而，通过将纤维间进行热粘合，另外通过与含有聚缩醛和聚乳酸为代表的脂肪族聚酯热塑性树脂组合物的各种成形品进行热粘合而使其高度复合化的物质也包含在本发明中。
实施例
以下列举实施例对本发明进一步具体的说明，本发明只要不超过其要旨，不限于以下示出的具体例子。
<实施例1、比较例1>
实施例和比较例中使用的材料、熔点的测定法、以及粘接方法、卷缩处理的方法和是否符合基准示于以下。材料使用表1记载的物质。表2记载的结构中芯鞘成分的比率设为50wt％，进行熔融纺丝纤维后，进行4倍拉伸得到5dtex的纤度。使用这些多层复合纤维，进行了以下的试验。结果记载于表2中。
<熔点的测定>
以10℃/分钟的速度，从30℃升温到210℃，通过差示扫描量热法(DSC)测定溶融峰温度。
<粘接方法>
将实施例、比较例记载的多层复合纤维切成10cm长度以交叉方式配置在铁板上，并用另外一个铁板夹持。利用预先加热到表1记载的温度的油压式热压装置，在规定的时间加热、加压的条件下实施了热粘合。处理后，目视确认交叉位置的粘接状态。
<耐溶剂性>
将通过粘接试验得到的无纺布浸渍到丙酮中一昼夜，目视确认由丙酮带来的膨胀状态的粘接状态。
<纤维轴方向的连续的层的确认>
是否聚乳酸和聚缩醛的各种成分均形成沿纤维轴方向连续的层的判断是切断纤维，且用目视确认截面。能够确认实施例1中上述各种成分均形成沿纤维轴方向连续的层。
表1
Figure BPA00001259489300081
上述聚缩醛(1)和聚缩醛(2)的化学结构式如下。
[-CH2O-]n[-CH2CH2O-]m
上述聚缩醛(1)和聚缩醛(2)的[-CH2CH2O-]含量各自不同，聚缩醛(1)有7％、聚缩醛(2)有10％。
表2
  实施例1  比较例1
  芯   PLA  PLA
  鞘   POM-1  POM-2
  粘接成分   -  -
  与芯的熔点差(℃)   15  5
  粘接试验(℃)   160  170
  粘接状况   良好  x芯鞘同时熔融
  丙酮浸渍试验   良好  -
通过使用含有以聚乳酸作为主要成分的树脂和以具有特定的熔点差的聚缩醛作为主要成分的树脂的多层复合纤维，可以得到粘结强度、以及耐化学药品性优异的热粘合性无纺布。

Claims (5)

1.一种多层复合纤维，其是含有以聚乳酸作为主要成分的树脂和以聚缩醛作为主要成分的树脂，且各种成分均形成沿纤维轴方向连续的层的多层复合纤维，所述以聚缩醛作为主要成分的树脂的熔点相对于所述以聚乳酸作为主要成分的树脂的熔点低10～20℃。
2.根据权利要求1所述的多层复合纤维，其中，将所述以聚乳酸作为主要成分的树脂作成芯，将所述以聚缩醛作为主要成分的树脂作成鞘。
3.根据权利要求1或2所述的多层复合纤维，其中，所述聚缩醛为100重量份的三聚甲醛与5～20重量份的1种或者2种以上的环状缩甲醛和/或环状醚的共聚物。
4.一种无纺布，其通过将权利要求1～3任一项所述的多层复合纤维热粘合而得到。
5.一种无纺布，其通过在权利要求1～3任一项所述的多层复合纤维中配合含有以聚乳酸作为主要成分的树脂和/或以聚缩醛作为主要成分的树脂的纤维，并热粘合而得到。
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