JP4578932B2 - Polylactic acid composite fiber - Google Patents
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本発明は、植物由来のポリ乳酸樹脂が単繊維内において接合されてなる複合繊維であって、優れた捲縮発現性能を有するポリ乳酸複合繊維に関するものである。 The present invention relates to a composite fiber obtained by bonding a plant-derived polylactic acid resin in a single fiber, and relates to a polylactic acid composite fiber having excellent crimp expression.
従来より、クッション材などの中綿用途などには、粘度や収縮率の異なるポリエチレンテレフタレートなどの２種類のポリエステルを並列的または偏心的に接合した複合繊維とし、延伸や熱処理によって捲縮を発現させた繊維が使用されている。 Conventionally, for batting applications such as cushioning materials, two types of polyesters such as polyethylene terephthalate with different viscosities and shrinkage rates are used as composite fibers joined in parallel or eccentrically, and crimps are expressed by stretching or heat treatment. Fiber is used.
合成繊維の中でも特にポリエステル繊維は、その優れた寸法安定性、耐候性、機械的特性、耐久性、さらにはリサイクル性等から、衣料、産業資材として不可欠のものとなっており、様々な分野、用途において広く使用されている。 Among synthetic fibers, especially polyester fibers are indispensable as clothing and industrial materials due to their excellent dimensional stability, weather resistance, mechanical properties, durability, and recyclability. Widely used in applications.
しかし、最近は、ポリエチレンテレフタレートなどの従来の合成樹脂が石油を原料としていることから、石油の枯渇を促進させる問題が生じるため、石油の枯渇を遅延する目的から、植物由来であるポリ乳酸樹脂が注目されるようになっている。 However, recently, since conventional synthetic resins such as polyethylene terephthalate are made from petroleum, there is a problem of accelerating the depletion of petroleum. Therefore, for the purpose of delaying the depletion of petroleum, a polylactic acid resin derived from plants is used. It is getting attention.
ポリ乳酸樹脂を使用した繊維として、特許文献１では、分子量や光学純度の異なる２種類のポリ乳酸を並列的または偏心的に接合し、捲縮が発現できるようにした複合繊維が提案されている。この発明においては、ポリ乳酸複合繊維は優れた捲縮発現性能を有するものであったが、２種類のポリ乳酸の分子量と光学純度が特定式の範囲を満足する必要があるため、分子量と光学純度を調整する工程が必要であった。そこで、さらに容易に得ることができ、かつ優れた捲縮発現性能を有するポリ乳酸繊維が要望されていた。
本発明は、上記の問題を解決し、ポリ乳酸樹脂からなり、比較的容易に得ることができ、優れた捲縮発現性能を有するポリ乳酸複合繊維を提供することを技術的な課題とするものである。 It is a technical object of the present invention to solve the above-mentioned problems and to provide a polylactic acid composite fiber made of a polylactic acid resin, which can be obtained relatively easily, and has excellent crimp expression performance. It is.
本発明者らは、上記課題を解決するために、鋭意検討を重ねた結果、本発明に到達した。 The inventors of the present invention have arrived at the present invention as a result of intensive studies in order to solve the above problems.
すなわち、本発明は、ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂとが単繊維内において接合されてなる複合繊維であって、ポリ乳酸樹脂Ｂはポリ乳酸樹脂Ｃとポリ乳酸樹脂Ｄとの混合物であり、ポリ乳酸樹脂Ｄはポリ乳酸樹脂Ｂ中の１０〜５０質量％含有されており、かつポリ乳酸樹脂Ａ、Ｃ、ＤはＬ−乳酸および／またはＤ−乳酸からなるものであって、下記条件（１）〜（３）を同時に満足することを特徴とするポリ乳酸複合繊維を要旨とするものである。
（１）ポリ乳酸樹脂Ａは、Ｌ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが98.0／2.0以上である。
（２）ポリ乳酸樹脂Ｃは、Ｌ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが98.0／2.0以上である。
（３）ポリ乳酸樹脂Ｄは、Ｌ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが90.0／10.0〜93.0／7.0である。
That is, the present invention is a composite fiber in which polylactic acid resin A and polylactic acid resin B are joined in a single fiber, and polylactic acid resin B is a mixture of polylactic acid resin C and polylactic acid resin D. The polylactic acid resin D is contained in the polylactic acid resin B in an amount of 10 to 50% by mass, and the polylactic acid resins A, C, and D are composed of L-lactic acid and / or D-lactic acid, and the following conditions are satisfied. The gist of the present invention is a polylactic acid composite fiber characterized by satisfying (1) to (3) at the same time.
(1) In the polylactic acid resin A, L / D or D / L, which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid, is 98.0 / 2.0 or more.
(2) In the polylactic acid resin C, L / D or D / L, which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid, is 98.0 / 2.0 or more.
(3) In the polylactic acid resin D, L / D or D / L, which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid, is 90.0 / 10.0 to 93.0 / 7.0.
本発明のポリ乳酸複合繊維は、優れた捲縮発現性能を有するものであり、比較的容易に得ることができるので、クッション材などの中綿用途、貼布材などの伸縮性不織布用途等をはじめ、様々な用途に好適に使用することが可能となる。 Since the polylactic acid composite fiber of the present invention has excellent crimp expression performance and can be obtained relatively easily, it is used for batting applications such as cushioning materials, stretchable nonwoven fabric applications such as patch materials, etc. , It can be suitably used for various applications.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のポリ乳酸複合繊維は、ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂが、単繊維内において接合されてなる複合繊維である。単繊維内において接合されている形態としては、捲縮発現性能を向上させるためには、並列的又は偏心的に接合されてなる複合繊維とすることが好ましい。つまり、並列的とは２成分が例えばサイドバイサイド型のように貼り合わされている形状であり、偏心的とは２成分が例えば芯鞘型に貼り合わされており、芯部と鞘部の中心点が一致せずにずれているものをいう。
そして、ポリ乳酸樹脂Ｂはポリ乳酸樹脂Ｃとポリ乳酸樹脂Ｄとの混合物である。
The polylactic acid conjugate fiber of the present invention is a conjugate fiber in which a polylactic acid resin A and a polylactic acid resin B are joined in a single fiber. As a form joined in the single fiber, in order to improve crimp expression performance, it is preferable to use a composite fiber joined in parallel or eccentrically. In other words, parallel means that the two components are bonded together like a side-by-side type, for example, and eccentric means that the two components are bonded together, such as a core-sheath type, so that the center points of the core and the sheath coincide. The one that has shifted without.
Polylactic acid resin B is a mixture of polylactic acid resin C and polylactic acid resin D.
本発明のポリ乳酸複合繊維におけるポリ乳酸樹脂Ａとポリ乳酸樹脂Ｃ、Ｄとは、ポリ乳酸及び／又はポリ乳酸を主体とする共重合物である。ポリ乳酸を製造するための乳酸としては、Ｄ体のみ、Ｌ体のみ、Ｄ体とＬ体の混合物のいずれでもよい。ポリ乳酸を主体とする共重合物としては、乳酸（Ｄ体のみ、Ｌ体のみ、Ｄ体とＬ体の混合物のいずれでもよい。）と、例えばε−カプロラクトン等の環状ラクトン類、α−ヒドロキシ酪酸、α−ヒドロキシイソ酪酸、α−ヒドロキシ吉草酸等のα−オキシ酸類、エチレングリコール、１，４−ブタンジオール等のグリコール類、コハク酸、セバシン酸等のジカルボン酸類から選ばれるモノマーの一種又は二種以上とを共重合したものが挙げられる。 The polylactic acid resin A and the polylactic acid resins C and D in the polylactic acid composite fiber of the present invention are polylactic acid and / or a copolymer mainly composed of polylactic acid. The lactic acid for producing polylactic acid may be only D-form, only L-form, or a mixture of D-form and L-form. Examples of the copolymer mainly composed of polylactic acid include lactic acid (D-form only, L-form alone, and a mixture of D-form and L-form), cyclic lactones such as ε-caprolactone, α-hydroxy, and the like. One or more monomers selected from butyric acid, α-hydroxyisobutyric acid, α-oxyacids such as α-hydroxyvaleric acid, glycols such as ethylene glycol and 1,4-butanediol, and dicarboxylic acids such as succinic acid and sebacic acid What copolymerized 2 or more types is mentioned.
本発明においては、ポリ乳酸樹脂Ａ、ポリ乳酸樹脂Ｃ、ポリ乳酸樹脂Ｄがそれぞれ以下の条件（１）〜（３）を満足し、ポリ乳酸樹脂Ｄがポリ乳酸樹脂Ｂ中の１０〜５０質量％含有されていることが必要である。 In the present invention, the polylactic acid resin A, the polylactic acid resin C, and the polylactic acid resin D satisfy the following conditions (1) to (3), respectively, and the polylactic acid resin D is 10 to 50 mass in the polylactic acid resin B. % Content is required.
これにより、ポリ乳酸樹脂Ａは低収縮成分となり、ポリ乳酸樹脂Ｃとポリ乳酸樹脂Ｄとの混合物であるポリ乳酸樹脂Ｂは、ポリ乳酸樹脂Ｃにポリ乳酸樹脂Ｄを混合させることにより、高収縮成分とすることができ、複合繊維を構成する２成分（ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂ）が収縮差を有することにより、優れた捲縮発現性能を有する繊維とすることができる。 Thereby, the polylactic acid resin A becomes a low shrinkage component, and the polylactic acid resin B, which is a mixture of the polylactic acid resin C and the polylactic acid resin D, is mixed with the polylactic acid resin D in the high degree of shrinkage. When the two components (polylactic acid resin A and polylactic acid resin B) constituting the composite fiber have a shrinkage difference, a fiber having excellent crimp development performance can be obtained.
まず、条件（１）として、ポリ乳酸樹脂Ａは、Ｌ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが98.0／2.0以上であり、中でも98.5／1.5以上が好ましく、さらには99.0／1.0以上が好ましい。Ｌ／Ｄ又はＤ／Ｌが98.0／2.0未満である場合、つまりＬ／Ｄ又はＤ／Ｌが97.0／3.0であったり、95.0／5.0というように、主体とするＬ−乳酸中のＤ−乳酸の含有割合や、主体とするＤ−乳酸中のＬ−乳酸の含有割合が多い場合、ポリ乳酸樹脂Ａの収縮が高くなり、高収縮成分であるポリ乳酸樹脂Ｂとの差が少なくなり、複合繊維は捲縮発現性に劣るものとなる。 First, as the condition (1), the polylactic acid resin A has L / D or D / L which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid is 98.0 / 2.0 or more, especially 98.5 / 1.5 or more. And more preferably 99.0 / 1.0 or more. When L / D or D / L is less than 98.0 / 2.0, that is, L / D or D / L is 97.0 / 3.0 or 95.0 / 5.0, D-lactic acid in L-lactic acid as a main component When the content ratio of L-lactic acid in the main D-lactic acid is large, the shrinkage of the polylactic acid resin A is increased, and the difference from the polylactic acid resin B, which is a highly shrinkable component, is reduced. The fiber is inferior in crimp expression.
次に、条件（２）として、ポリ乳酸樹脂Ｃは、Ｌ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが98.0／2.0以上であり、中でも98.5／1.5以上が好ましく、さらには99.0／1.0以上が好ましい。Ｌ／Ｄ又はＤ／Ｌが98.0／2.0未満である場合、つまりＬ／Ｄ又はＤ／Ｌが97.0／3.0であったり、95.0／5.0というように、主体とするＬ−乳酸中のＤ−乳酸の含有割合や、主体とするＤ−乳酸中のＬ−乳酸の含有割合が多い場合、ポリ乳酸樹脂Ｂの結晶性が低下し、延伸工程での融着等が発生しやすくなり、好ましくない。 Next, as the condition (2), the polylactic acid resin C has L / D or D / L which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid is 98.0 / 2.0 or more, and above all, 98.5 / 1.5 The above is preferable, and 99.0 / 1.0 or more is more preferable. When L / D or D / L is less than 98.0 / 2.0, that is, L / D or D / L is 97.0 / 3.0 or 95.0 / 5.0, D-lactic acid in L-lactic acid as a main component When the content ratio of L and the content ratio of L-lactic acid in the main D-lactic acid are large, the crystallinity of the polylactic acid resin B is lowered, and fusion and the like in the stretching process are likely to occur.
さらに条件（３）として、ポリ乳酸樹脂Ｄは、Ｌ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが90.0／10.0〜93.0／7.0である。Ｌ／Ｄ又はＤ／Ｌが90.0／10.0未満である場合、つまりＬ／Ｄ又はＤ／Ｌが89.0／11.0であったり、85.0／15.0というように、主体とするＬ−乳酸中のＤ−乳酸の含有割合や、主体とするＤ−乳酸中のＬ−乳酸の含有割合が多い場合、ポリ乳酸樹脂Ｂの結晶性が低下し、延伸工程での融着等が発生しやすくなり、好ましくない。 Furthermore, as the condition (3), in the polylactic acid resin D, L / D or D / L, which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid, is 90.0 / 10.0 to 93.0 / 7.0. When L / D or D / L is less than 90.0 / 10.0, that is, L / D or D / L is 89.0 / 11.0 or 85.0 / 15.0, D-lactic acid in the main L-lactic acid When the content ratio of L and the content ratio of L-lactic acid in the main D-lactic acid are large, the crystallinity of the polylactic acid resin B is lowered, and fusion and the like in the stretching process are likely to occur.
一方、Ｌ／Ｄ又はＤ／Ｌが93.0／7.0を超える場合、つまりＬ／Ｄ又はＤ／Ｌが95.0／5.0であったり、98.0／2.0というように、主体とするＬ−乳酸中のＤ−乳酸の含有割合や、主体とするＤ−乳酸中のＬ−乳酸の含有割合が少ない場合、ポリ乳酸樹脂Ｂの収縮が低くなり、低収縮成分であるポリ乳酸樹脂Ａとの差が少なくなり、捲縮発現性に劣るものとなる。 On the other hand, when L / D or D / L exceeds 93.0 / 7.0, that is, L / D or D / L is 95.0 / 5.0, or 98.0 / 2.0, D- in the main L-lactic acid. When the content ratio of lactic acid or the content ratio of L-lactic acid in the main D-lactic acid is small, the shrinkage of the polylactic acid resin B is low, and the difference from the polylactic acid resin A, which is a low shrinkage component, is small. It will be inferior to crimp expression.
そして、ポリ乳酸樹脂Ｄの含有量は、ポリ乳酸樹脂Ｂ中の１０〜５０質量％であり、中でも１５〜４５質量％が好ましく、さらには２５〜４０質量％とすることが好ましい。 And content of the polylactic acid resin D is 10-50 mass% in the polylactic acid resin B, 15-45 mass% is preferable especially, It is preferable to set it as 25-40 mass%.
上記したように、ポリ乳酸樹脂Ｃは主たる成分であるＬ−乳酸またはＤ−乳酸の比率が高く、低収縮成分であるが、ポリ乳酸樹脂Ｄは、主たる成分であるＬ−乳酸またはＤ−乳酸の比率が低く、高収縮成分である。このような高収縮成分であるポリ乳酸樹脂Ｄを１０〜５０質量％混合することによってポリ乳酸樹脂Ｂを高収縮成分とすることができ、ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂとの間に収縮差が生じ、延伸や熱処理により捲縮が発現する捲縮発現性能を有する繊維とすることができる。 As described above, the polylactic acid resin C has a high ratio of L-lactic acid or D-lactic acid, which is a main component, and is a low-shrinkage component, but the polylactic acid resin D is L-lactic acid or D-lactic acid, which is a main component. Is a high shrinkage component. By mixing 10 to 50% by mass of the polylactic acid resin D which is such a high shrinkage component, the polylactic acid resin B can be made a high shrinkage component, and shrinkage between the polylactic acid resin A and the polylactic acid resin B is achieved. A fiber having a crimping performance in which a difference occurs and crimps are expressed by stretching or heat treatment can be obtained.
ポリ乳酸樹脂Ｄの含有量がポリ乳酸樹脂Ｂ中の１０質量％未満であると、ポリ乳酸樹脂Ｂを高収縮成分とすることが困難となり、捲縮発現性能に劣るものとなる。一方、５０質量％を超えると、ポリ乳酸樹脂Ｂの結晶性が低下し、延伸工程での融着等が起こり、好ましくない。 When the content of the polylactic acid resin D is less than 10% by mass in the polylactic acid resin B, it becomes difficult to make the polylactic acid resin B a highly shrinkable component, and the crimping performance is inferior. On the other hand, if it exceeds 50% by mass, the crystallinity of the polylactic acid resin B is lowered, and fusion or the like occurs in the stretching step, which is not preferable.
また、本発明においては、捲縮発現性能を考慮して、ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂが粘度差を有することが好ましく、このため、ポリ乳酸樹脂Ａの数平均分子量を小さく、ポリ乳酸樹脂Ｂの数平均分子量を大きくすることが好ましい。ポリ乳酸樹脂Ｂの数平均分子量をポリ乳酸樹脂Ａより大きくするためには、中でも、ポリ乳酸樹脂Ｃ、Ｄの数平均分子量ともにポリ乳酸樹脂Ａより大きいことが好ましい。 In the present invention, it is preferable that the polylactic acid resin A and the polylactic acid resin B have a viscosity difference in consideration of the crimping performance, and therefore, the number average molecular weight of the polylactic acid resin A is small, It is preferable to increase the number average molecular weight of the resin B. In order to make the number average molecular weight of the polylactic acid resin B larger than that of the polylactic acid resin A, the number average molecular weights of the polylactic acid resins C and D are preferably larger than the polylactic acid resin A.
そして、ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂとの数平均分子量の差は、10000〜30000とすることが好ましい。
なお、ポリ乳酸樹脂Ｂの数平均分子量は、次式のようにして算出するものである。
〔ポリ乳酸樹脂Ｃの数平均分子量×ポリ乳酸樹脂Ｃのポリ乳酸樹脂Ｂ中の含有割合（質量％／１００）〕＋〔ポリ乳酸樹脂Ｄの数平均分子量×ポリ乳酸樹脂Ｄのポリ乳酸樹脂Ｂ中の含有割合（質量％／１００）〕
The difference in the number average molecular weight between the polylactic acid resin A and the polylactic acid resin B is preferably 10,000 to 30,000.
The number average molecular weight of the polylactic acid resin B is calculated as follows.
[Number average molecular weight of polylactic acid resin C × content ratio of polylactic acid resin C in polylactic acid resin B (mass% / 100)] + [Number average molecular weight of polylactic acid resin D × polylactic acid resin B of polylactic acid resin D Content ratio (mass% / 100)]
ポリ乳酸樹脂Ａの数平均分子量は５５０００〜７３０００とすることが好ましい。ポリ乳酸樹脂Ａの数平均分子量が５５０００未満であると、低粘度となるため、紡糸時に製糸性が悪化する傾向があり好ましくない。また、数平均分子量が７３０００より大きいと、ポリ乳酸樹脂Ｂとの粘度差が小さくなり、捲縮発現性が低下しやすくなるため好ましくない。 The number average molecular weight of the polylactic acid resin A is preferably 55000 to 73000. If the number average molecular weight of the polylactic acid resin A is less than 55,000, the viscosity becomes low, and therefore, the spinning property tends to deteriorate during spinning, which is not preferable. Moreover, when the number average molecular weight is larger than 73,000, the difference in viscosity from the polylactic acid resin B becomes small, and the crimp expression tends to be lowered, which is not preferable.
ポリ乳酸樹脂Ｃの数平均分子量は７８０００〜９５０００であることが好ましい。数平均分子量が７８０００未満であると、ポリ乳酸樹脂Ａとの粘度差が小さくなり、捲縮発現性が低下しやすくなるため好ましくない。また、数平均分子量が９５０００より大きいと、高粘度となるため、溶融押出が困難となる傾向があり好ましくない。 The number average molecular weight of the polylactic acid resin C is preferably 78000 to 95,000. If the number average molecular weight is less than 78000, the difference in viscosity from the polylactic acid resin A becomes small, and the crimp developability tends to decrease, such being undesirable. On the other hand, if the number average molecular weight is larger than 95,000, the viscosity becomes high, so that melt extrusion tends to be difficult.
ポリ乳酸樹脂Ｄの数平均分子量は６００００〜１１００００であることが好ましい。数平均分子量が６００００未満であると、ポリ乳酸樹脂Ｂとポリ乳酸樹脂Ａとの粘度差が小さくなり、捲縮発現性が低下しやすくなるため好ましくない。また、数平均分子量が１１００００より大きいと、ポリ乳酸樹脂Ｂが高粘度となり、溶融押出が困難となる傾向があり好ましくない。 The number average molecular weight of the polylactic acid resin D is preferably 60000-110,000. When the number average molecular weight is less than 60000, the difference in viscosity between the polylactic acid resin B and the polylactic acid resin A becomes small, and the crimp expression tends to be lowered, which is not preferable. On the other hand, when the number average molecular weight is larger than 110,000, the polylactic acid resin B has a high viscosity, and melt extrusion tends to be difficult.
また、本発明の複合繊維においては、本発明の効果を損なわない範囲であれば、ポリ乳酸樹脂の耐久性を高めることを目的として、ポリ乳酸樹脂に脂肪族アルコール、カルボジイミド化合物、オキサゾリン化合物、オキサジン化合物、エポキシ化合物などの末端封鎖剤を添加してもよい。 In the conjugate fiber of the present invention, an aliphatic alcohol, a carbodiimide compound, an oxazoline compound, an oxazine is added to the polylactic acid resin for the purpose of enhancing the durability of the polylactic acid resin, as long as the effects of the present invention are not impaired. You may add terminal blockers, such as a compound and an epoxy compound.
また、本発明のポリ乳酸樹脂には、可塑剤等の目的として、脂肪族ポリエステルや、脂肪族−芳香族ポリエステル、芳香族ポリエステル、ポリアミド、ポリオレフィンなどの他の樹脂を、本発明の目的を損なわない範囲（１０質量％以下程度）で混合してもよい。 In addition, the polylactic acid resin of the present invention may include other resins such as aliphatic polyesters, aliphatic-aromatic polyesters, aromatic polyesters, polyamides, and polyolefins for the purpose of plasticizers and the like. You may mix in the range which is not (about 10 mass% or less).
さらには、各種顔料、染料、撥水剤、吸水剤、難燃剤、安定剤、酸化防止剤、紫外線吸収剤、金属粒子、結晶核剤、滑剤、可塑剤、抗菌剤、香料その他の添加剤を混合していてもよい。 In addition, various pigments, dyes, water repellents, water absorbing agents, flame retardants, stabilizers, antioxidants, UV absorbers, metal particles, crystal nucleating agents, lubricants, plasticizers, antibacterial agents, perfumes and other additives It may be mixed.
次に、図面を用いて、本発明の複合繊維の形状について説明する。図１〜３は、本発明の複合繊維の好ましい形状の実施態様を示す単繊維の横断面模式図である。図において、ａはポリ乳酸樹脂Ａを、ｂはポリ乳酸樹脂Ｂを、ｃは中空部をそれぞれ示す。 Next, the shape of the conjugate fiber of the present invention will be described with reference to the drawings. 1 to 3 are schematic cross-sectional views of a single fiber showing an embodiment of a preferable shape of the conjugate fiber of the present invention. In the figure, a represents polylactic acid resin A, b represents polylactic acid resin B, and c represents a hollow portion.
前記したように、本発明においては、ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂが、単繊維内において接合されてなる複合繊維であって、自発捲縮性能を向上させるためには、並列的又は偏心的に接合されていることが好ましい。 As described above, in the present invention, the polylactic acid resin A and the polylactic acid resin B are composite fibers joined in a single fiber, and in order to improve the spontaneous crimping performance, parallel or eccentric It is preferable that they are joined together.
図１は並列的（サイドバイサイド型）に接合された例であり、図２は偏心的に接合された例（芯鞘型）であり、図３は並列的に接合された例であって中空部を有する例である。図３に示すように本発明の繊維においては、単繊維の横断面形状において中空部を有するものでもよい。 FIG. 1 is an example of joining in parallel (side-by-side type), FIG. 2 is an example of being joined eccentrically (core-sheath type), and FIG. 3 is an example of joining in parallel with a hollow portion. It is an example which has. As shown in FIG. 3, in the fiber of this invention, you may have a hollow part in the cross-sectional shape of a single fiber.
また、単繊維の横断面形状は、円形のみならず、長円形、ひょうたん形、多角形、多葉形、アルファベット形、その他各種の非円形（異形）、中空形などのいずれであってもよく、用途等に応じて任意に選択すればよい。 In addition, the cross-sectional shape of the single fiber is not limited to a circle, but may be any of an oval, a gourd, a polygon, a multi-leaf, an alphabet, various other non-circular shapes (an irregular shape), a hollow shape, and the like. Any selection may be made according to the application.
ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂとの複合比率（断面積比）は、特に限定されず、目的に応じて任意に選択すればよい。通常、複合比は１／１０〜１０／１の範囲、中でも１／５〜５／１の範囲が好ましく、さらには１／３〜３／１とすることが好ましい。 The composite ratio (cross-sectional area ratio) between the polylactic acid resin A and the polylactic acid resin B is not particularly limited, and may be arbitrarily selected according to the purpose. Usually, the composite ratio is preferably in the range of 1/10 to 10/1, more preferably in the range of 1/5 to 5/1, and more preferably 1/3 to 3/1.
また、本発明の繊維は長繊維、短繊維のいずれであってもよいが、短繊維とする場合には、繊維長は使用目的に応じて任意に選ばれるが、５〜８０ｍｍが好ましく、中でも２０〜７０ｍｍとすることが好ましい。 The fiber of the present invention may be either a long fiber or a short fiber. In the case of a short fiber, the fiber length is arbitrarily selected according to the purpose of use, but is preferably 5 to 80 mm. It is preferable to be 20 to 70 mm.
繊度も同様に使用目的に応じて任意に選ばれるが、通常、単糸繊度０．１〜５０デシテックス（ｄｔｅｘ）とすることが好ましく、中でも０．５〜３０ｄｔｅｘとすることが好ましい。 Similarly, the fineness is arbitrarily selected according to the purpose of use, but it is usually preferable to set the single yarn fineness to 0.1 to 50 dtex, and more preferably 0.5 to 30 dtex.
本発明のポリ乳酸複合繊維は捲縮発現性能を有するものであるが、中でも、短繊維とし、不織布などの繊維構造物にした後に捲縮を発現させる潜在捲縮繊維とすることが好ましい。 The polylactic acid composite fiber of the present invention has a crimp-expressing ability, and among them, it is preferable to use a short-cut fiber and a latent-crimped fiber that expresses crimp after forming a fiber structure such as a nonwoven fabric.
本発明のポリ乳酸複合繊維を潜在捲縮繊維とする場合は、製造工程中では捲縮を発現させず、得られた繊維を用いて布帛（織編物や不織布）とした後、熱処理を施すことにより捲縮を発現させることが好ましい。発現させる捲縮数は、使用用途に応じて任意に設定すればよいが、嵩高性や伸縮性を付与するためには、捲縮数が４０個／２５ｍｍ以上となることが好ましい。中でも伸縮性を付与するためには、捲縮数が５０〜１００個／２５ｍｍとすることが好ましい。 When the polylactic acid composite fiber of the present invention is a latent crimped fiber, the crimp is not expressed in the production process, and the resulting fiber is used to form a fabric (woven or knitted fabric or nonwoven fabric), followed by heat treatment. It is preferable to develop crimps. The number of crimps to be expressed may be arbitrarily set according to the intended use, but in order to impart bulkiness and stretchability, the number of crimps is preferably 40 pieces / 25 mm or more. Among these, in order to impart stretchability, the number of crimps is preferably 50 to 100 pieces / 25 mm.
捲縮数は、ポリ乳酸樹脂中のＬ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌや分子量、複合構造の偏心度合いや、延伸倍率、熱処理時の温度等によって適宜調整することができる。 The number of crimps is L / D or D / L, which is the content ratio (molar ratio) of L-lactic acid to D-lactic acid in the polylactic acid resin, molecular weight, degree of eccentricity of the composite structure, draw ratio, temperature during heat treatment It can be adjusted as appropriate.
また、本発明のポリ乳酸複合繊維は、布帛の作成工程中にネップや未開繊トラブルが発生しないようにするため、繊維の製造工程の最終工程において通常の押し込み式捲縮装置などにより、８〜２０個／２５ｍｍの機械捲縮を付与することが好ましい。 In addition, the polylactic acid composite fiber of the present invention can be used in the final step of the fiber production process by using an ordinary indentation crimping device or the like in order to prevent occurrence of nep and unopened troubles during the fabric production process. It is preferable to provide 20 crimps / 25 mm.
次に、本発明のポリ乳酸系自発捲縮繊維の製造方法について、一例を用いて説明する。
なお、ポリ乳酸樹脂Ｃとポリ乳酸樹脂Ｄを混合する方法は任意でよく、チップを適当な混合装置、たとえばＶ型ブレンダーやダブルコーン型ブレンダーなで混合するなどしてチップブレンドする方法、別々に溶融した後、エクストルーダーなどの駆動部を有する混練装置、またはスタティックミキサーなどの駆動部を有さない静的混練素子により混合してチップ化する方法、別々に溶融した後、エクストルーダーなどの駆動部を有する混練装置で混合した後、直接紡糸する方法などがある。
Next, the manufacturing method of the polylactic acid type spontaneous crimp fiber of this invention is demonstrated using an example.
In addition, the method of mixing the polylactic acid resin C and the polylactic acid resin D may be arbitrary, and the method of blending the chips by mixing the chips with an appropriate mixing device such as a V-type blender or a double cone type blender, separately. After melting, a kneading device having a driving unit such as an extruder, or a method of mixing with a static kneading element not having a driving unit such as a static mixer to form a chip, after separately melting, driving an extruder, etc. There is a method of directly spinning after mixing in a kneading apparatus having a part.
本発明の繊維は、両成分を通常使用される複合紡糸装置を用いて、複合紡糸することにより得ることができる。まず、ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂを並列的や偏心的に接合されるようにして紡糸し、紡糸した糸条を横吹付や環状吹付等の冷却装置を用いて冷却した後、油剤を付与する。続いて引き取りローラを介して未延伸糸として巻取機に巻取る。次に、巻取られた未延伸糸を周速の異なるローラ群間で延伸し、必要に応じて押し込み型の捲縮装置などで機械捲縮を付与した後に目的とする長さにカットする。
また、長繊維とする場合は、延伸後そのまま捲き取り、必要に応じて、撚糸、仮撚加工等の加工を行う。
The fiber of the present invention can be obtained by composite spinning of both components using a composite spinning apparatus usually used. First, polylactic acid resin A and polylactic acid resin B are spun so as to be joined in parallel or eccentrically, and the spun yarn is cooled using a cooling device such as horizontal spraying or annular spraying. Give. Subsequently, the unwound yarn is wound around a winder through a take-up roller. Next, the wound unstretched yarn is stretched between a group of rollers having different peripheral speeds, and if necessary, mechanically crimped by a push-type crimping device or the like, and then cut to a desired length.
Moreover, when making it into a long fiber, it winds as it is after extending | stretching, and processes, such as twisted yarn and false twisting, are performed as needed.
以下、実施例によって本発明を具体的に説明する。なお、実施例における特性値等の測定法及び評価は次の通りである。
（１）ポリ乳酸中のＬ−乳酸とＤ−乳酸の含有割合（Ｌ／Ｄ）
超純水と１Ｎの水酸化ナトリウムのメタノール溶液の等質量混合溶液を溶媒とし、高速液体クロマトグラフィー（ＨＰＬＣ）法により測定した。カラムにはｓｕｍｉｃｈｉｒａｌ ＯＡ６１００を使用し、ＵＶ吸収測定装置により検出した。
（２）数平均分子量
ポリ乳酸樹脂を１０ｍｇ／mｌの濃度になるように、クロロホルムに溶解して、クロロホルムを溶媒として、Gel Permeation Chromatography（ＧＰＣ）法により測定した。検出器は屈折率計を使用し、分子量の標準物質としてポリスチレンを使用した。
（３）単糸繊度（ｄｔｅｘ）
ＪＩＳ Ｌ−１０１５ ８．５．１（正量繊度）Ａ法により測定した。
（４）捲縮数
ＪＩＳ Ｌ１０１５ ８．１２．１のけん縮数に基づき測定した。
なお、熱処理後の捲縮数は、繊維を１２０℃で１５分間自由収縮可能な条件で熱処理することによって捲縮を発現させた後、測定した。
（５）紡糸性
２錘で６時間紡糸し、糸切れ回数が５回以下を○（合格）とし、糸切れ回数が５回を超えたものを×とした。
（６）融着の有無
延伸時に９０℃で緊張熱処理を行った際の単糸の融着の有無を目視にて判定し、以下のように２段階で評価した。
単糸の融着がない場合：○、単糸の融着がある場合：×
（７）伸張率
得られた不織布を幅５ｃｍに切断し、３０ｇ荷重時の長さＬ０と２４０ｇ荷重時の長さＬ１を測定し、次式より伸張率を算出した。
伸張率（％）＝〔（Ｌ１−Ｌ０）／Ｌ０〕×１００
本発明では８０％以上を合格とした。
Hereinafter, the present invention will be described specifically by way of examples. In addition, the measurement methods and evaluation of characteristic values and the like in the examples are as follows.
(1) Content ratio of L-lactic acid and D-lactic acid in polylactic acid (L / D)
It measured by the high performance liquid chromatography (HPLC) method by using the equal mass mixed solution of the ultrapure water and the methanol solution of 1N sodium hydroxide as a solvent. The column used was sumichiral OA6100, and was detected by a UV absorption measuring device.
(2) Number average molecular weight Polylactic acid resin was dissolved in chloroform so as to have a concentration of 10 mg / ml, and measurement was performed by Gel Permeation Chromatography (GPC) method using chloroform as a solvent. The detector used was a refractometer, and polystyrene was used as a molecular weight standard.
(3) Single yarn fineness (dtex)
It was measured by JIS L-1015 8.5.1 (positive fineness) A method.
(4) Number of crimps Measured based on the number of crimps of JIS L1015 8.12.1.
Note that the number of crimps after the heat treatment was measured after the fibers were heat-treated at 120 ° C. under conditions allowing free shrinkage for 15 minutes to develop crimps.
(5) Spinnability Spinning with 2 spindles for 6 hours, the number of yarn breaks of 5 or less was evaluated as ◯ (pass), and the number of yarn breaks exceeding 5 was evaluated as x.
(6) Presence / absence of fusion The presence / absence of fusion of single yarns when subjected to tension heat treatment at 90 ° C. during stretching was determined visually and evaluated in two stages as follows.
When there is no single yarn fusion: ○, when there is single yarn fusion: ×
(7) Elongation rate The obtained nonwoven fabric was cut into a width of 5 cm, the length L0 at 30 g load and the length L1 at 240 g load were measured, and the elongation rate was calculated from the following formula.
Elongation rate (%) = [(L1-L0) / L0] × 100
In the present invention, 80% or more was considered acceptable.
実施例１
ポリ乳酸樹脂Ａとして、Ｌ−乳酸を主体とするポリ乳酸樹脂であって、Ｌ／Ｄが98.6／1.4、数平均分子量６４３００であるものを用いた。ポリ乳酸樹脂Ｂとして、Ｌ−乳酸を主体とするポリ乳酸樹脂であって、Ｌ／Ｄが98.8／1.2、数平均分子量８３９２０であるポリ乳酸樹脂Ｃと、Ｌ−乳酸を主体とするポリ乳酸樹脂であって、Ｌ／Ｄが91.3／8.7、数平均分子量８５１１０であるポリ乳酸樹脂Ｄとの混合物であって、ポリ乳酸樹脂Ｄがポリ乳酸樹脂Ｂの３０質量％を占めるものを用いた。なお、ポリ乳酸樹脂Ｂは、ポリ乳酸樹脂Ｃ、Ｄをチップブレンドして得たものである。
ポリ乳酸樹脂Ａとポリ乳酸樹脂Ｂを複合紡糸装置に導入し、複合比１／１にて、図１に示すような並列型（サイドバイサイド型）となるようにして、孔数が７１３の紡糸口金より、吐出量４３０ｇ／分、２２０℃で複合紡糸した。紡糸した糸条を引取速度１１００ｍ／ｍｉｎで引き取り、未延伸糸を得た。この時、紡糸時の糸切れはなく、操業性は極めて良好であった。
得られた未延伸糸を集束して糸条束とし、延伸温度６０℃、延伸速度１００ｍ／ｍｉｎ、延伸倍率３．００倍で延伸した後、９０℃で緊張熱処理を行い、次いで、押し込み式捲縮装置で機械捲縮を付与した後、カット長５１ｍｍに切断して、繊度２．２ｄｔｅｘの短繊維を得た。
得られた短繊維をローラカードを用いて、速度２０ｍ／ｍｉｎで開繊してウエブを形成し、針密度１９２本／ｃｍ２でニードルパンチ処理を施した後、熱風通過式熱処理機を用い、１２０℃で２分間熱処理を施した。この熱処理により繊維の捲縮を発現させ、目付１５０ｇ／ｍ２の不織布を得た。
Example 1
As the polylactic acid resin A, a polylactic acid resin mainly composed of L-lactic acid having an L / D of 98.6 / 1.4 and a number average molecular weight of 64,300 was used. The polylactic acid resin B is a polylactic acid resin mainly composed of L-lactic acid and having a L / D of 98.8 / 1.2 and a number average molecular weight of 83920, and a polylactic acid resin mainly composed of L-lactic acid. A mixture of the polylactic acid resin D having an L / D of 91.3 / 8.7 and a number average molecular weight of 85110, wherein the polylactic acid resin D accounts for 30% by mass of the polylactic acid resin B was used. The polylactic acid resin B is obtained by chip blending polylactic acid resins C and D.
A polylactic acid resin A and a polylactic acid resin B are introduced into a composite spinning apparatus so that the composite ratio is 1/1, and a parallel type (side-by-side type) as shown in FIG. Thus, composite spinning was performed at 220 ° C. at a discharge rate of 430 g / min. The spun yarn was drawn at a take-up speed of 1100 m / min to obtain an undrawn yarn. At this time, there was no yarn breakage during spinning, and the operability was very good.
The obtained undrawn yarn is bundled into a yarn bundle, drawn at a drawing temperature of 60 ° C., a drawing speed of 100 m / min, and a draw ratio of 3.00 times, and then subjected to a tension heat treatment at 90 ° C. After applying mechanical crimping with a crimping device, it was cut into a cut length of 51 mm to obtain short fibers having a fineness of 2.2 dtex.
Using a roller card, the obtained short fibers were opened at a speed of 20 m / min to form a web, subjected to needle punching at a needle density of 192 needles / cm 2 , and then using a hot air passage type heat treatment machine, Heat treatment was performed at 120 ° C. for 2 minutes. By this heat treatment, the crimp of the fiber was expressed, and a nonwoven fabric having a basis weight of 150 g / m 2 was obtained.
実施例２〜４、比較例１〜３
ポリ乳酸樹脂Ｂ中のポリ乳酸樹脂Ｄの含有量を表１に示す値に変更した以外は実施例１と同様に行い、ポリ乳酸複合繊維（短繊維）と不織布を得た。
Examples 2-4, Comparative Examples 1-3
Except having changed the content of the polylactic acid resin D in the polylactic acid resin B into the value shown in Table 1, it carried out similarly to Example 1, and obtained the polylactic acid composite fiber (short fiber) and the nonwoven fabric.
比較例４
ポリ乳酸樹脂ＡのＬ／Ｄを表１に示す値に変更した以外は実施例１と同様に行い、ポリ乳酸複合繊維（短繊維）と不織布を得た。
Comparative Example 4
Except having changed L / D of polylactic acid resin A into the value shown in Table 1, it carried out similarly to Example 1, and obtained the polylactic acid composite fiber (short fiber) and the nonwoven fabric.
比較例５
ポリ乳酸樹脂ＣのＬ／Ｄを表１に示す値に変更した以外は実施例１と同様に行い、ポリ乳酸複合繊維（短繊維）と不織布を得た。
Comparative Example 5
Except having changed L / D of the polylactic acid resin C into the value shown in Table 1, it carried out similarly to Example 1 and obtained the polylactic acid composite fiber (short fiber) and the nonwoven fabric.
比較例６〜７
ポリ乳酸樹脂ＤのＬ／Ｄを表１に示す値に変更した以外は実施例１と同様に行い、ポリ乳酸複合繊維（短繊維）と不織布を得た。
Comparative Examples 6-7
Except having changed L / D of the polylactic acid resin D into the value shown in Table 1, it carried out similarly to Example 1, and obtained the polylactic acid composite fiber (short fiber) and the nonwoven fabric.
実施例１〜４、比較例１〜７で得られた繊維（短繊維）及び不織布の特性値等を表１に示す。 Table 1 shows the characteristic values of the fibers (short fibers) and nonwoven fabrics obtained in Examples 1 to 4 and Comparative Examples 1 to 7.
表１より、明らかなように、実施例１〜４の複合繊維は紡糸時の糸切れや延伸時に融着が生じることなく、操業性よく得ることができ、捲縮発現性も良好であり、これらの繊維から得られた不織布は伸張率も高いものであった。 一方、比較例１、２の複合繊維は、ポリ乳酸樹脂Ｂ中のポリ乳酸樹脂Ｄの含有量が少なかったため、捲縮発現性に劣るものであった。また、これらの複合繊維から得られた不織布は伸張率の低いものであった。比較例３の複合繊維は、ポリ乳酸樹脂Ｂ中のポリ乳酸樹脂Ｄの含有量が多すぎたため、ポリ乳酸樹脂Ｂの結晶性が低下し、延伸工程で融着が発生し、繊維を得ることができなかった。比較例４の複合繊維は、ポリ乳酸樹脂ＡのＬ／Ｄが98.0／2.0未満であったため、ポリ乳酸樹脂Ｂとの収縮差が小さくなり、捲縮発現性に劣るものであった。また、この複合繊維から得られた不織布は伸張率の低いものであった。比較例５の複合繊維は、ポリ乳酸樹脂ＣのＬ／Ｄが98.0／2.0未満であったため、ポリ乳酸樹脂Ｂの結晶性が低下し、延伸工程での融着が発生し、繊維を得ることができなかった。比較例６の複合繊維は、ポリ乳酸樹脂ＤのＬ／Ｄが93.0／7.0を超えるものであったため、ポリ乳酸樹脂Ｂの収縮性が低くなり、低収縮成分であるポリ乳酸樹脂Ａとの差が少なくなり、捲縮発現性に劣るものであった。また、この複合繊維から得られた不織布は伸張率の低いものであった。比較例７の複合繊維は、ポリ乳酸樹脂ＤのＬ／Ｄが90.0／10.0未満であったため、ポリ乳酸樹脂Ｂの結晶性が低下し、延伸工程での融着が発生し、繊維を得ることができなかった。 As can be seen from Table 1, the composite fibers of Examples 1 to 4 can be obtained with good operability without fusing at the time of spinning and stretching, and the crimp expression is also good. The nonwoven fabric obtained from these fibers had a high elongation rate. On the other hand, the composite fibers of Comparative Examples 1 and 2 were inferior in crimp expression because the content of the polylactic acid resin D in the polylactic acid resin B was small. Moreover, the nonwoven fabric obtained from these composite fibers had a low elongation rate. The composite fiber of Comparative Example 3 has too much content of polylactic acid resin D in polylactic acid resin B, so that the crystallinity of polylactic acid resin B is lowered and fusion occurs in the drawing process to obtain fibers. I could not. Since the composite fiber of Comparative Example 4 had a polylactic acid resin A having an L / D of less than 98.0 / 2.0, the shrinkage difference from the polylactic acid resin B was small, and the crimp expression was inferior. Moreover, the nonwoven fabric obtained from this composite fiber had a low elongation rate. Since the composite fiber of Comparative Example 5 has a polylactic acid resin C having an L / D of less than 98.0 / 2.0, the crystallinity of the polylactic acid resin B is lowered, and fusion occurs in the drawing process, thereby obtaining a fiber. I could not. In the composite fiber of Comparative Example 6, since the L / D of the polylactic acid resin D exceeded 93.0 / 7.0, the shrinkage of the polylactic acid resin B was lowered, and the difference from the polylactic acid resin A, which is a low shrinkage component, And the crimp expression was inferior. Moreover, the nonwoven fabric obtained from this composite fiber had a low elongation rate. In the composite fiber of Comparative Example 7, since the L / D of the polylactic acid resin D is less than 90.0 / 10.0, the crystallinity of the polylactic acid resin B is lowered, and fusion occurs in the drawing process, thereby obtaining a fiber. I could not.
Claims (1)
（１）ポリ乳酸樹脂Ａは、Ｌ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが98.0／2.0以上である。
（２）ポリ乳酸樹脂Ｃは、Ｌ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが98.0／2.0以上である。
（３）ポリ乳酸樹脂Ｄは、Ｌ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが90.0／10.0〜93.0／7.0である。 Polylactic acid resin A and polylactic acid resin B are composite fibers formed by bonding within a single fiber, polylactic acid resin B is a mixture of polylactic acid resin C and polylactic acid resin D, and polylactic acid resin D is The polylactic acid resins B are contained in an amount of 10 to 50% by mass in the polylactic acid resin B, and the polylactic acid resins A, C, and D are composed of L-lactic acid and / or D-lactic acid, and the following conditions (1) to (3 ), A polylactic acid composite fiber.
(1) In the polylactic acid resin A, L / D or D / L, which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid, is 98.0 / 2.0 or more.
(2) In the polylactic acid resin C, L / D or D / L, which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid, is 98.0 / 2.0 or more.
(3) In the polylactic acid resin D, L / D or D / L, which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid, is 90.0 / 10.0 to 93.0 / 7.0.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264913A (en) * | 1987-04-21 | 1988-11-01 | Bio Material Yunibaasu:Kk | Polylactic acid fiber |
| JPH1088425A (en) * | 1996-09-09 | 1998-04-07 | Shimadzu Corp | Self-crimpable conjugated fiber |
| JP2002227034A (en) * | 2001-01-29 | 2002-08-14 | Toray Ind Inc | Polylactic acid fiber structure having excellent black color development and method for producing the same |
| JP2003105629A (en) * | 2001-09-28 | 2003-04-09 | Unitika Ltd | Polylactic acid stereo complex fiber excellent in heat resistance and textile product using the same |
| JP2003306834A (en) * | 2002-04-17 | 2003-10-31 | Nippon Ester Co Ltd | Latently crimpable polylactic acid conjugated fiber |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264913A (en) * | 1987-04-21 | 1988-11-01 | Bio Material Yunibaasu:Kk | Polylactic acid fiber |
| JPH1088425A (en) * | 1996-09-09 | 1998-04-07 | Shimadzu Corp | Self-crimpable conjugated fiber |
| JP2002227034A (en) * | 2001-01-29 | 2002-08-14 | Toray Ind Inc | Polylactic acid fiber structure having excellent black color development and method for producing the same |
| JP2003105629A (en) * | 2001-09-28 | 2003-04-09 | Unitika Ltd | Polylactic acid stereo complex fiber excellent in heat resistance and textile product using the same |
| JP2003306834A (en) * | 2002-04-17 | 2003-10-31 | Nippon Ester Co Ltd | Latently crimpable polylactic acid conjugated fiber |
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