JP5565971B2 - Polymer alloy comprising polylactic acid resin and polyethylene terephthalate resin and method for producing the same - Google Patents
Polymer alloy comprising polylactic acid resin and polyethylene terephthalate resin and method for producing the same Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims description 125
- 229920005989 resin Polymers 0.000 title claims description 125
- 239000000956 alloy Substances 0.000 title claims description 104
- 229910045601 alloy Inorganic materials 0.000 title claims description 104
- 229920000642 polymer Polymers 0.000 title claims description 93
- 229920000747 poly(lactic acid) Polymers 0.000 title claims description 75
- 239000004626 polylactic acid Substances 0.000 title claims description 75
- -1 polyethylene terephthalate Polymers 0.000 title claims description 57
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims description 54
- 239000005020 polyethylene terephthalate Substances 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000835 fiber Substances 0.000 claims description 69
- 238000004898 kneading Methods 0.000 claims description 31
- 125000003700 epoxy group Chemical group 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 238000002074 melt spinning Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 229920006243 acrylic copolymer Polymers 0.000 claims description 7
- 238000002844 melting Methods 0.000 description 26
- 230000008018 melting Effects 0.000 description 26
- 239000002994 raw material Substances 0.000 description 12
- 238000009987 spinning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001225 polyester resin Polymers 0.000 description 7
- 239000004645 polyester resin Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920005692 JONCRYL® Polymers 0.000 description 5
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- 238000012545 processing Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000012770 industrial material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229920006381 polylactic acid film Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Artificial Filaments (AREA)
Description
本発明は、ポリ乳酸樹脂とポリエチレンテレフタレート樹脂からなるポリマーアロイおよびその製造方法に関するものであり、さらに詳しくは、ポリ乳酸樹脂とポリエチレンテレフタレート樹脂とのポリマーアロイにおいて、ポリ乳酸樹脂をナノレベルで分散させたことで、繊維への優れた加工性を持つポリマーアロイおよび該ポリマーアロイからなる繊維、ならびに、それらの製造方法に関するものである。 The present invention relates to a polymer alloy comprising a polylactic acid resin and a polyethylene terephthalate resin and a method for producing the same, and more specifically, in a polymer alloy of a polylactic acid resin and a polyethylene terephthalate resin, the polylactic acid resin is dispersed at the nano level. Therefore, the present invention relates to a polymer alloy having excellent processability to fibers, a fiber made of the polymer alloy, and a method for producing them.
ポリ乳酸は植物由来の樹脂であり、生分解性であるため環境への負荷は小さい。しかし、一般的なポリ乳酸樹脂は硬質の樹脂であるため、繊維にする場合、ポリ乳酸樹脂単成分では加工性は良いとは言えず、繊維となった場合でも、耐熱性、繊維強度、耐光性が低いという問題がある。 Polylactic acid is a plant-derived resin and is biodegradable, so the load on the environment is small. However, since general polylactic acid resin is a hard resin, when it is made into a fiber, it cannot be said that the processability is good with a single component of polylactic acid resin, and even when it becomes a fiber, heat resistance, fiber strength, light resistance There is a problem that the nature is low.
一方、ポリエチレンテレフタレートやポリブチレンテレフタレートに代表されるポリエステル樹脂は、高い融点と結晶化度を持ち、吸水率や熱膨張係数が低く、優れた寸法安定性を示す樹脂である。このポリエステル樹脂を溶融紡糸して得られるポリエステル繊維は、力学特性や寸法安定性に優れるため、衣料用途のみならず、インテリア、車両内装、産業資材等として幅広く利用されている。 On the other hand, polyester resins represented by polyethylene terephthalate and polybutylene terephthalate are resins having a high melting point and crystallinity, a low water absorption rate and a low coefficient of thermal expansion, and excellent dimensional stability. Polyester fibers obtained by melt spinning this polyester resin are excellent in mechanical properties and dimensional stability, and thus are widely used not only for clothing but also for interiors, vehicle interiors, industrial materials, and the like.
ポリ乳酸樹脂の繊維への加工性を改善する方法として、製糸性に優れるポリエステル樹脂と混合しブレンドする方法がある。しかし、従来のポリマーブレンド繊維の技術は、そのほとんどが紡糸機のチップホッパー中でのドライブレンドであり、ブレンド斑の発生や経時によるブレンド比の変動のため、紡糸性が悪く、大量生産に耐えうるものではなかった。 As a method for improving the processability of the polylactic acid resin into fibers, there is a method of mixing and blending with a polyester resin having excellent yarn-making properties. However, most of the conventional polymer blend fiber technologies are dry blending in the tip hopper of a spinning machine. Due to the occurrence of blending spots and blend ratio fluctuations over time, the spinnability is poor and can withstand mass production. It wasn't good.
一方、二軸押出機などを用いて混練し、ポリマーアロイを得る例もあるが、この場合には、混練時の温度や剪断力などによって、混合されたポリマー間での化学反応などの相互作用があり、混練条件によりポリマーアロイの品質に大きな差が生じることがある。そのため、単純に二軸押出機で混練しても、耐熱性の劣化した部分が発生し、熱劣化物が異物として振る舞い糸切れを誘発させることで、生産性を著しく低下させてしまう場合がある。このため、紡糸という特異な成形加工に適した耐熱性の良いポリマーアロイを得ることが非常に難しく、繊維の分野ではポリマーアロイの利用が進んでいないのが現状である。 On the other hand, there is an example in which a polymer alloy is obtained by kneading using a twin screw extruder or the like, but in this case, an interaction such as a chemical reaction between the mixed polymers due to temperature or shearing force during kneading. There may be a large difference in the quality of the polymer alloy depending on the kneading conditions. Therefore, even if simply kneading with a twin-screw extruder, a part with deteriorated heat resistance is generated, and the thermally deteriorated material behaves as a foreign substance, and may cause a thread breakage, thereby significantly reducing productivity. . For this reason, it is very difficult to obtain a polymer alloy having good heat resistance suitable for a specific molding process called spinning, and the present situation is that the use of polymer alloys is not progressing in the field of fibers.
耐熱性が良く紡糸性に優れたポリマーアロイの製造方法として、特許文献１記載の技術がある。この公知技術によると、ナノファイバーを得る目的で、少量成分の易溶解性ポリマー（ポリ乳酸、親水基を共重合したポリオレフィン）と、多量成分の難溶解性ポリマー（ポリエステル、結晶性ポリオレフィン）とのアロイ化を行っている。難溶解性ポリマーであるポリエステルとしては、溶融混練時や溶融紡糸時にポリ乳酸や共重合ポリオレフィンの熱分解を抑制し紡糸性を向上させるべく、融点が２２５〜２３５℃の範囲にあるポリエステル樹脂であるポリトリメチレンテレフタレートあるいはポリブチレンテレフタレートを用い、易溶解性ポリマーと溶融混練してポリマーアロイを得ている。 As a method for producing a polymer alloy having good heat resistance and excellent spinnability, there is a technique described in Patent Document 1. According to this known technique, for the purpose of obtaining nanofibers, a small amount of easily soluble polymer (polylactic acid, polyolefin copolymerized with hydrophilic groups) and a large amount of hardly soluble polymer (polyester, crystalline polyolefin) Alloying is in progress. The polyester, which is a hardly soluble polymer, is a polyester resin having a melting point in the range of 225 to 235 ° C. in order to suppress the thermal decomposition of polylactic acid or copolymerized polyolefin during melt kneading or melt spinning and to improve the spinnability. A polymer alloy is obtained by using polytrimethylene terephthalate or polybutylene terephthalate and melt-kneading with an easily soluble polymer.
そのため、特許文献１記載のポリマーアロイは、優れた繊維加工性を有するものの、ポリ乳酸の熱分解の問題から、融点の低い比較的高価なポリエステル樹脂を使用しなければならず、ポリマーの耐熱性や価格の点で課題がある。 Therefore, although the polymer alloy described in Patent Document 1 has excellent fiber processability, from the problem of thermal decomposition of polylactic acid, a relatively expensive polyester resin having a low melting point must be used. There is a problem in terms of price.
本発明は上記の事情に鑑みてなされたものであり、融点が高いポリエチレンテレフタレート樹脂に、ポリ乳酸樹脂をナノレベルで分散させることで、耐熱性と繊維への加工性に優れ環境への負荷も小さいポリマーアロイおよびそのアロイからなる繊維を提供することを課題とするものである。 The present invention has been made in view of the above circumstances, and by dispersing a polylactic acid resin at a nano level in a polyethylene terephthalate resin having a high melting point, it has excellent heat resistance and processability to fibers and has an environmental burden. An object of the present invention is to provide a small polymer alloy and a fiber made of the alloy.
前記課題を解決するために、本発明者らは、繊維加工性に優れたポリエチレンテレフタレート樹脂とポリ乳酸樹脂のポリマーアロイおよびその製造方法を確立すべく鋭意研究した結果、ポリエチレンテレフタレート樹脂とポリ乳酸樹脂を溶融混練する際に、エポキシ基を有する架橋剤を添加することにより、ポリエチレンテレフタレート樹脂の耐熱性や伸度等の糸特性を損なうことなく、繊維への加工性に優れるポリマーアロイが得られることを見出した。 In order to solve the above-mentioned problems, the present inventors have intensively studied to establish a polymer alloy of polyethylene terephthalate resin and polylactic acid resin excellent in fiber processability and a method for producing the same, and as a result, polyethylene terephthalate resin and polylactic acid resin When melt-kneading, an epoxy group-containing cross-linking agent is added, so that a polymer alloy having excellent processability into fibers can be obtained without impairing yarn properties such as heat resistance and elongation of the polyethylene terephthalate resin. I found.
すなわち、本発明は以下の通りである。 That is, the present invention is as follows.
（１）ポリエチレンテレフタレート６０〜９５重量％、ポリ乳酸５〜４０重量％からなる樹脂成分１００重量部に、エポキシ基を有する架橋剤０．１〜５．０重量部が配合されてなるポリマーアロイであって、ポリエチレンテレフタレートが海、ポリ乳酸が島の海島構造状にポリ乳酸が微分散していることを特徴とするポリマーアロイ。
（２）島の平均直径が１０ｎｍ〜１０００ｎｍである上記（１）に記載のポリマーアロイ。
（３）エポキシ基を有する架橋剤がスチレン・アクリル系共重合物である上記（１）または（２）に記載のポリマーアロイ。
（４）上記（１）〜（３）いずれか記載のポリマーアロイからなるポリマーアロイ繊維。
（５）上記（１）〜（３）いずれか記載のポリマーアロイの製造方法であって、ポリエチレンテレフタレート６０〜９５重量％、ポリ乳酸５〜４０重量％からなる樹脂成分１００重量部と、エポキシ基を有する架橋剤０．１〜５．０重量部とをドライブレンドし、ブレンドした材料を、二軸押出機を使用し、スクリュー回転数２００〜５００ｒｐｍの条件下で溶融混練することを特徴とするポリマーアロイの製造方法。
（６）上記（１）〜（３）いずれか記載のポリマーアロイのチップを溶融紡糸する工程を含む、ポリマーアロイ繊維の製造方法。
（７）上記（５）に記載の方法でポリマーアロイを製造し、そのポリマーアロイのチップを溶融紡糸する工程を含むことを特徴とするポリマーアロイ繊維の製造方法。
(1) A polymer alloy in which 0.1 to 5.0 parts by weight of a crosslinking agent having an epoxy group is blended with 100 parts by weight of a resin component comprising 60 to 95% by weight of polyethylene terephthalate and 5 to 40% by weight of polylactic acid. A polymer alloy in which polylactic acid is finely dispersed in a sea-island structure in which polyethylene terephthalate is sea and polylactic acid is island .
(2) The polymer alloy according to (1) above, wherein the average diameter of the islands is 10 nm to 1000 nm.
(3) The polymer alloy according to the above (1) or (2), wherein the crosslinking agent having an epoxy group is a styrene / acrylic copolymer.
(4) A polymer alloy fiber comprising the polymer alloy according to any one of (1) to (3) above.
(5) A method for producing a polymer alloy according to any one of (1) to (3 ) above, wherein 100 parts by weight of a resin component comprising 60 to 95% by weight of polyethylene terephthalate and 5 to 40% by weight of polylactic acid, and an epoxy group 0.1 to 5.0 parts by weight of a cross-linking agent having a dry blend, and the blended material is melt-kneaded using a twin screw extruder at a screw rotation speed of 200 to 500 rpm. A method for producing a polymer alloy.
(6) A method for producing a polymer alloy fiber, comprising a step of melt spinning the polymer alloy chip according to any one of (1) to (3) above.
(7) A method for producing a polymer alloy fiber, comprising a step of producing a polymer alloy by the method described in (5 ) above and melt-spinning the polymer alloy chip.
以上説明したように、本発明のポリマーアロイは、分解温度の低いポリ乳酸樹脂を混合しても、耐熱性、繊維の伸度および繊維への加工性に優れるものである。また、得られるポリマーアロイ繊維は繊維物性に優れ、低コストという利点を有するものである。
本発明のポリマーアロイ製造方法によれば、耐熱性および繊維加工性に優れ、環境負荷の小さいポリマーアロイを、低コストで効率よく製造することができる。
As described above, the polymer alloy of the present invention is excellent in heat resistance, fiber elongation and processability to fibers even when a polylactic acid resin having a low decomposition temperature is mixed. Further, the polymer alloy fiber obtained has excellent fiber properties and has the advantage of low cost.
According to the method for producing a polymer alloy of the present invention, a polymer alloy having excellent heat resistance and fiber processability and having a small environmental load can be produced efficiently at a low cost.
次に本発明の最も好ましい実施の形態を説明する。本発明のポリマーアロイにおいて、ポリエチレンテレフタレート樹脂の比率は、多いほど、繊維加工性、繊維強度、耐熱性が良くなるが、環境負荷を考慮すると、６０〜９５重量％が好ましい。さらに好ましくは、７０〜９０重量％である。ポリ乳酸樹脂は５〜４０重量％が好ましく、さらに好ましくは１０〜３０重量％である。 Next, the most preferred embodiment of the present invention will be described. In the polymer alloy of the present invention, the greater the ratio of the polyethylene terephthalate resin, the better the fiber workability, fiber strength, and heat resistance, but 60 to 95% by weight is preferable in consideration of environmental load. More preferably, it is 70 to 90% by weight. The polylactic acid resin is preferably 5 to 40% by weight, more preferably 10 to 30% by weight.
本発明のポリマーアロイは、ポリエチレンテレフタレート樹脂中にポリ乳酸樹脂が微分散していることが好ましく、ポリエチレンテレフタレート樹脂の比率が６０重量％未満になると、ポリエチレンテレフタレート樹脂が海でポリ乳酸樹脂が島の海島構造状にポリ乳酸樹脂が微分散しにくくなるため、ポリマーアロイの繊維加工性が低下し、糸切れが多発するようになる。また、本発明のポリマーアロイの構造とは逆に、ポリ乳酸樹脂が海でポリエチレンテレフタレート樹脂が島の海島構造状に、ポリエステル樹脂を微分散したポリマーアロイにした場合は、海成分であるポリ乳酸樹脂の熱分解を抑制しなければならないため、高融点（融点２４０℃以上）のポリエチレンテレフタレート樹脂を使用することは困難となる。 In the polymer alloy of the present invention, it is preferable that the polylactic acid resin is finely dispersed in the polyethylene terephthalate resin. When the ratio of the polyethylene terephthalate resin is less than 60% by weight, the polyethylene terephthalate resin is the sea and the polylactic acid resin is the island. Since the polylactic acid resin is less likely to be finely dispersed in the sea-island structure, the fiber processability of the polymer alloy is lowered, and thread breakage frequently occurs. Contrary to the structure of the polymer alloy of the present invention, when the polylactic acid resin is a sea and the polyethylene terephthalate resin is a sea-island structure of an island and the polymer alloy is a finely dispersed polyester resin, the polylactic acid is a sea component. Since the thermal decomposition of the resin must be suppressed, it becomes difficult to use a polyethylene terephthalate resin having a high melting point (melting point of 240 ° C. or higher).
ポリエチレンテレフタレート樹脂とポリ乳酸樹脂を溶融混合する際には、エポキシ基を有する架橋剤を添加するのがよい。こうして溶融混練を行うと、架橋剤中のエポキシ基がポリ乳酸やポリエチレンテレフタレートの末端に結合することでグラフト化や架橋反応が起こり、ポリ乳酸が加水分解して低粘度化するのを防止できるとともに、ポリエチレンテレフタレート樹脂とポリ乳酸樹脂の相溶化を促進させることができる。 When melt-mixing the polyethylene terephthalate resin and the polylactic acid resin, it is preferable to add a crosslinking agent having an epoxy group. When melt-kneading is carried out in this way, the epoxy group in the crosslinking agent is bonded to the terminal of polylactic acid or polyethylene terephthalate to cause grafting or crosslinking reaction, and it is possible to prevent polylactic acid from hydrolyzing to lower the viscosity. The compatibilization of the polyethylene terephthalate resin and the polylactic acid resin can be promoted.
エポキシ基を有する架橋剤は、ポリエチレンテレフタレート樹脂とポリ乳酸樹脂からなる樹脂成分１００重量部に対し、０．１〜５．０重量部、より好ましくは０．１〜１．０重量部配合する。配合物を溶融混練することによって、ポリエチレンテレフタレート樹脂とポリ乳酸樹脂の相溶性が良くなり、海成分がポリエチレンテレフタレート樹脂で島成分がポリ乳酸樹脂である海島構造状のポリマーアロイとなる。エポキシ基を有する架橋剤は、０．１重量部未満の場合は、両樹脂の相溶性が不良になる傾向があり、配合量を増やすことにより相溶性が良好になるが、５．０重量部を超える場合は樹脂粘度が高くなり過ぎることで、ポリ乳酸樹脂の分散性が不良になる、あるいは加工性が低下するといった傾向が見られるようになる。 The crosslinking agent having an epoxy group is blended in an amount of 0.1 to 5.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of a resin component composed of a polyethylene terephthalate resin and a polylactic acid resin. By melt-kneading the blend, the compatibility between the polyethylene terephthalate resin and the polylactic acid resin is improved, and a sea-island structure polymer alloy in which the sea component is a polyethylene terephthalate resin and the island component is a polylactic acid resin is obtained. When the crosslinking agent having an epoxy group is less than 0.1 parts by weight, the compatibility of both resins tends to be poor, and the compatibility is improved by increasing the blending amount, but 5.0 parts by weight. In the case where it exceeds 1, the resin viscosity becomes too high, so that the dispersibility of the polylactic acid resin becomes poor or the processability tends to be lowered.
エポキシ基を有する架橋剤は、特に限定されるものではないが、エポキシ基を有するアクリル系またはスチレン系の樹脂が好ましい。市販品としては、例えば、ＢＡＳＦジャパン社製「ＪＯＮＣＲＹＬ」（エポキシ基を有するスチレン・アクリル系共重合物）、東亜合成社製「ＡＲＵＦＯＮ ＵＧ」（エポキシ基を有するアクリル系樹脂）等が挙げられる。 The crosslinking agent having an epoxy group is not particularly limited, but an acrylic or styrene resin having an epoxy group is preferable. Examples of commercially available products include “JONCRYL” (styrene-acrylic copolymer having an epoxy group) manufactured by BASF Japan, “ARUFON UG” (acrylic resin having an epoxy group) manufactured by Toagosei Co., Ltd., and the like.
本発明に使用される海成分のポリエチレンテレフタレート樹脂は、加工性、価格の観点より好ましい材料であり、バージンあるいは再生用の樹脂、例えばポリエチレンテレフタレートのフィルム屑や市場回収ペットボトル等を挙げることができる。 The sea component polyethylene terephthalate resin used in the present invention is a preferable material from the viewpoints of processability and cost, and examples thereof include virgin or resin for recycling, such as polyethylene terephthalate film scraps and market recovery PET bottles. .
上記のポリエチレンテレフタレート樹脂は、チップ状、フレーク状、粉末状などであってよく、形態の制限はないが、ポリ乳酸樹脂と均一に混合するためには、ポリ乳酸樹脂と同じ形態、同程度のサイズのものが好ましい。 The polyethylene terephthalate resin may be in the form of chips, flakes, powders, etc., and there is no limitation on the form, but in order to mix uniformly with the polylactic acid resin, the same form as the polylactic acid resin, the same degree Sizes are preferred.
ポリエチレンテレフタレート樹脂は、その粘度が溶融混練前の固有粘度（ＩＶ）で０．５８以上のものが好ましいが、溶融混練時の粘度低下を考慮しつつ繊維加工性を向上させるためには、０．６３〜０．６７の範囲のものがより好ましい。固有粘度が０．５８以上であれば、溶融混練時に多少の粘度低下が生じてもポリエチレンテレフタレート樹脂本来の特性を損なうことがない。固有粘度が０．６７以下であれば、繊維加工性を低下させることがない。 The polyethylene terephthalate resin preferably has an intrinsic viscosity (IV) of 0.58 or more before melt kneading, but in order to improve the fiber workability while considering the decrease in viscosity at the time of melt kneading, it is preferable that The thing of the range of 63-0.67 is more preferable. If the intrinsic viscosity is 0.58 or more, the original characteristics of the polyethylene terephthalate resin will not be impaired even if the viscosity is lowered somewhat during melt-kneading. If the intrinsic viscosity is 0.67 or less, the fiber processability is not lowered.
本発明に使用される島成分のポリ乳酸樹脂としては、融点が１５０℃以上、特に融点が１７０℃±１０℃のポリ乳酸樹脂が好ましく、原料の形態はバージンまたはポリ乳酸フィルム屑等のリサイクル品のいずれでもよい。 The polylactic acid resin of the island component used in the present invention is preferably a polylactic acid resin having a melting point of 150 ° C. or higher, particularly a melting point of 170 ° C. ± 10 ° C., and the form of the raw material is a recycled product such as virgin or polylactic acid film waste Either of these may be used.
ポリ乳酸樹脂の溶融粘度は特に制限はないが、溶融混練時の粘度低下と繊維加工性を向上させるため、ポリ乳酸樹脂の溶融混練前の溶融粘度は、２００〜５００Ｐａ・ｓ（条件：２２０℃、５．９ＭＰａ）の範囲であることが好ましい。 The melt viscosity of the polylactic acid resin is not particularly limited, but the melt viscosity before melt kneading of the polylactic acid resin is 200 to 500 Pa · s (condition: 220 ° C.) in order to improve the viscosity reduction and fiber processability during melt kneading. 5.9 MPa).
本発明ではポリエチレンテレフタレート樹脂とポリ乳酸樹脂の相溶性が重要であるが、これはＤＳＣ（示差走査熱量計）で評価することができる。ポリエチレンテレフタレート樹脂とポリ乳酸樹脂を、相溶化剤であるエポキシ基を有する架橋剤を添加せずに溶融混練して得たポリマー組成物について、ＤＳＣ測定を行うと、１７０℃付近と２５０℃付近に吸熱ピークが観察され、これらの吸熱ピークは、それぞれポリ乳酸樹脂の吸熱ピークならびにポリエチレンテレフタレート樹脂の吸熱ピークに合致する。一方、上記の相溶化剤を添加して溶融混練して得られたポリマーアロイについて、ＤＳＣ測定を行うと、２５０℃付近に吸熱ピークが観察されるのみで、１７０℃付近の吸熱ピークは消失する。したがって、相溶化剤を添加して溶融混練した場合には、ポリエチレンテレフタレート樹脂とポリ乳酸樹脂がアロイ化していることが示唆される。 In the present invention, the compatibility between the polyethylene terephthalate resin and the polylactic acid resin is important, and this can be evaluated by DSC (differential scanning calorimeter). When a polymer composition obtained by melting and kneading a polyethylene terephthalate resin and a polylactic acid resin without adding a cross-linking agent having an epoxy group as a compatibilizing agent was subjected to DSC measurement, Endothermic peaks are observed, and these endothermic peaks coincide with the endothermic peaks of the polylactic acid resin and the polyethylene terephthalate resin, respectively. On the other hand, when a DSC measurement is performed on a polymer alloy obtained by melt-kneading the above compatibilizer, only an endothermic peak is observed near 250 ° C., and the endothermic peak near 170 ° C. disappears. . Therefore, when a compatibilizing agent is added and melt-kneaded, it is suggested that the polyethylene terephthalate resin and the polylactic acid resin are alloyed.
また、本発明のポリエチレンテレフタレート樹脂とポリ乳酸樹脂のポリマーアロイは、ポリエチレンテレフタレートが海で、ポリ乳酸が島の海島構造状にポリ乳酸が微分散していることが好ましいが、ここで島成分のポリ乳酸は、平均直径１０ｎｍ〜１０００ｎｍで微分散させることが好ましく、さらには繊維加工性および繊維物性を向上させるためには、５００ｎｍ以下で微分散させることが好ましい。ポリ乳酸の島の平均直径が大きすぎると、島であるポリ乳酸が異物となり、糸加工時に糸切れが多発しやすくなる傾向があり、最終製品での耐久性が得られにくい傾向となる。 In the polymer alloy of the polyethylene terephthalate resin and polylactic acid resin of the present invention, polyethylene terephthalate is preferably sea, and polylactic acid is preferably finely dispersed in an island-island structure. The polylactic acid is preferably finely dispersed with an average diameter of 10 nm to 1000 nm, and further preferably finely dispersed at 500 nm or less in order to improve fiber processability and fiber properties. If the average diameter of the polylactic acid islands is too large, the polylactic acid that is the islands becomes a foreign substance, and yarn breakage tends to occur frequently during yarn processing, and the durability in the final product tends to be difficult to obtain.
ポリマーアロイからなるポリマーアロイ繊維の場合は、繊維方向に垂直な断面に現れる島の平均直径が１０〜５００ｎｍであることが好ましい。 In the case of a polymer alloy fiber made of a polymer alloy, it is preferable that an average diameter of islands appearing in a cross section perpendicular to the fiber direction is 10 to 500 nm.
島の平均直径は、樹脂チップまたは繊維の断面（繊維方向に垂直な断面）の走査型電子顕微鏡写真を、画像処理ソフトを用いて処理し、個々の島についての画像処理から得られた面積から、島の形状を円として、その直径を求め、得られた個々の直径から、数平均値として平均直径を求めることができる。 The average island diameter is calculated from the area obtained from image processing of individual islands by processing a scanning electron micrograph of a cross section of a resin chip or fiber (cross section perpendicular to the fiber direction) using image processing software. The diameter of the island can be determined as a circle, and the average diameter can be calculated as a number average value from the obtained individual diameters.
本発明のポリマーアロイならびにポリマーアロイ繊維を製造する製造方法には制限はないが、例えば次のようにして得ることができる。 Although there is no restriction | limiting in the manufacturing method which manufactures the polymer alloy and polymer alloy fiber of this invention, For example, it can obtain as follows.
図１には、本発明に係るポリマーアロイおよびポリマーアロイ繊維の製造方法のフローチャートを示す。ここでは、供給する樹脂および架橋剤の供給方法が重要である。ポリエチレンテレフタレート樹脂、ポリ乳酸樹脂およびエポキシ基を有する架橋剤を、個々に計量し（工程１、２）、タンブラー等でブレンドする（工程３）。次に、ブレンドした材料を、供給量を調整できる供給装置に投入し、二軸混練押出機で溶融混練を行い、同時にベント口より脱水する（工程４、５）。樹脂と架橋剤をブレンドせずに二軸押出機などの混練装置に投入した場合は、ブレンド比が変動しやすくなるため、紡糸性が悪く、糸切れしやすくなる。 In FIG. 1, the flowchart of the manufacturing method of the polymer alloy and polymer alloy fiber based on this invention is shown. Here, the resin to be supplied and the method for supplying the crosslinking agent are important. A polyethylene terephthalate resin, a polylactic acid resin, and a crosslinking agent having an epoxy group are individually weighed (steps 1 and 2) and blended with a tumbler or the like (step 3). Next, the blended material is put into a supply device capable of adjusting the supply amount, melt kneaded with a twin-screw kneading extruder, and dehydrated from the vent port at the same time (steps 4 and 5). When the resin and the cross-linking agent are not blended and charged into a kneading apparatus such as a twin-screw extruder, the blend ratio is likely to fluctuate, so that the spinnability is poor and yarn breakage tends to occur.
こうして、溶融混練され、ストランド状または板状に押し出された樹脂を冷却した後、所定の長さにカットしてアロイチップを得る（工程６、７）。次に、得られたチップを溶融紡糸して繊維化する（工程８）。 Thus, after the resin melt-kneaded and extruded into a strand shape or a plate shape is cooled, it is cut into a predetermined length to obtain alloy chips (steps 6 and 7). Next, the obtained chip is melt-spun and fiberized (step 8).
溶融混練する場合においては、ポリエステル樹脂で多く生産されているポリエチレンテレフタレート（融点２５５℃付近のもの）を使用した場合、混合するポリ乳酸樹脂は２５０℃以上で熱分解することが多いため、架橋反応を短時間でかつ均一に行うためには、スクリューが高速で回転する二軸混練押出機を用いて溶融混練を行うことが好ましい。 In the case of melt kneading, when poly (ethylene terephthalate) (polyethylene terephthalate having a melting point of around 255 ° C.), which is often produced from polyester resin, is used, the polylactic acid resin to be mixed is often thermally decomposed at 250 ° C. In order to carry out the process uniformly in a short time, it is preferable to carry out melt kneading using a twin-screw kneading extruder in which the screw rotates at high speed.
図２は二軸混練押出機を用いた製造例であり、ポリエチレンテレフタレート樹脂、ポリ乳酸樹脂およびエポキシ基を有する架橋剤を混合した材料を、原料供給装置（１１）よりホッパー（１２）を介して二軸混練押出機（１３）内に投入し、スクリュー（１４）を高速回転させながら樹脂を溶融混練し（この間、ベント口（１５）から水蒸気を排出する）、押し出した樹脂を水槽（１６）で冷却した後、ペレタイザー（１７）でカットしてアロイチップを得る。 FIG. 2 shows an example of production using a twin-screw kneading extruder, in which a material obtained by mixing a polyethylene terephthalate resin, a polylactic acid resin, and a crosslinking agent having an epoxy group is fed from a raw material supply device (11) through a hopper (12). The resin is put into a twin-screw kneading extruder (13) and melted and kneaded while rotating the screw (14) at a high speed (while water vapor is discharged from the vent port (15)), and the extruded resin is put into the water tank (16). After cooling, the alloy chip is obtained by cutting with a pelletizer (17).
また、溶融混練時においては、押出温度、スクリュー回転数、ブレンドした材料の供給量の調整が重要である。押出温度が高い場合は、島成分のポリ乳酸樹脂の分散は良くなるが、分解が抑制できなくなる。スクリュー回転数は高回転であるほど熱履歴が抑えられ、ポリ乳酸樹脂の熱分解が抑制できるが、樹脂の溶解不足による煎断発熱がおき押出温度の制御が困難になる。ブレンドした材料供給量は多い方が生産コストを削減できるが、樹脂の混練性が低下する。したがって、押出条件としては、押出温度２７５〜２９０℃の範囲で、スクリューを２００〜５００ｒｐｍ、好ましくは３００〜４００ｒｐｍの高速回転に設定し、ブレンドした材料を低供給量で押出しすることが好ましい。 Further, at the time of melt kneading, it is important to adjust the extrusion temperature, the screw rotation speed, and the supply amount of the blended material. When the extrusion temperature is high, the dispersion of the polylactic acid resin of the island component is improved, but the decomposition cannot be suppressed. The higher the screw rotation speed, the more the heat history is suppressed, and the thermal decomposition of the polylactic acid resin can be suppressed. However, the heat of decoction due to insufficient dissolution of the resin occurs and the control of the extrusion temperature becomes difficult. A larger amount of blended material can reduce the production cost, but the resin kneadability decreases. Therefore, as extrusion conditions, it is preferable to set the screw at a high speed of 200 to 500 rpm, preferably 300 to 400 rpm, and to extrude the blended material at a low supply amount in the range of the extrusion temperature of 275 to 290 ° C.
本発明のポリマーアロイのチップを、溶融紡糸工程を含む公知の方法にて繊維化することにより、本発明のポリマーアロイ繊維を製造できる。図３に、溶融紡糸装置を用いてポリマーアロイ繊維を製造する例を示す。溶融紡糸機原料供給装置（１８）に供給したポリマーアロイチップを、溶融紡糸機ホッパー（１９）を介して溶融紡糸押出機（２０）に投入し、溶融したポリマーを、ポリマー管（２４）および紡糸ノズル（２１）から押出した後、オイリングロール（２５）、引取りロール（２２）を通して、未延伸採取缶（２３）に収容する。溶融紡糸の際に、着色剤、難燃剤、抗菌剤を混合して繊維化を行ってもよい。 The polymer alloy fiber of the present invention can be produced by fiberizing the polymer alloy chip of the present invention by a known method including a melt spinning step. FIG. 3 shows an example of producing a polymer alloy fiber using a melt spinning apparatus. The polymer alloy chip supplied to the melt spinning machine raw material supply device (18) is charged into the melt spinning extruder (20) via the melt spinning machine hopper (19), and the molten polymer is fed into the polymer tube (24) and the spinning. After extruding from the nozzle (21), it passes through an oiling roll (25) and a take-up roll (22) and is accommodated in an unstretched collection can (23). At the time of melt spinning, a coloring agent, a flame retardant, and an antibacterial agent may be mixed and fiberized.
引取りロールで引き取った未延伸糸を延伸する場合は、通常のポリエステル繊維の延伸条件を採用することができ、未延伸糸を一旦巻取り、未延伸採取缶に収容した後に、改めて延伸工程を経て延伸糸を得る方法により、ポリマーアロイ繊維を得ることができる。あるいは、紡糸した後、巻取りをせずに直接延伸を行う方法でも構わない。 When stretching unstretched yarn taken up by a take-up roll, normal polyester fiber stretching conditions can be adopted.After unwinding the unstretched yarn and storing it in an unstretched collection can, the stretching process is performed again. A polymer alloy fiber can be obtained by a method of obtaining a drawn yarn through the process. Alternatively, it may be a method of directly stretching without spinning after spinning.
また、本発明のポリマーアロイを繊維化してポリマーアロイ繊維を得た後、得られた繊維表面に撥水処理、親水処理等の表面処理を行ってもよい。 Moreover, after polymerizing the polymer alloy of the present invention to obtain a polymer alloy fiber, the resulting fiber surface may be subjected to a surface treatment such as a water repellent treatment or a hydrophilic treatment.
本発明のポリマーアロイ繊維の断面形状は、特に限定されるものではなく、Ｙ断面、中空糸などの異形断面であってもよい。また、その繊維形態は、長繊維、短繊維（ステープル）等の任意の形態を採ることができる。 The cross-sectional shape of the polymer alloy fiber of the present invention is not particularly limited, and may be an irregular cross section such as a Y cross section or a hollow fiber. Moreover, the fiber form can take arbitrary forms, such as a long fiber and a short fiber (staple).
本発明のポリマーアロイ繊維は、各種衣料品や衣料資材、カーペット等のインテリア材、フィルター等の産業用資材、車両用内装材等の各種用途の繊維製品に好適に用いることができる。 The polymer alloy fiber of the present invention can be suitably used for various clothing products, clothing materials, interior materials such as carpets, industrial materials such as filters, and textile products for various uses such as vehicle interior materials.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。特に言及しない限り、「％」は「重量％」、「部」は「重量部」である。なお、実施例中の評価は以下の方法に従った。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by weight” and “parts” means “parts by weight”. The evaluation in the examples followed the following method.
［繊維物性値］
ＪＩＳ Ｌ１０１５：２０１０「化学繊維ステープル試験方法」に示される標準時試験条件にて、強度、伸度を求めた。
[Fiber property values]
Strength and elongation were determined under the standard time test conditions shown in JIS L1015: 2010 “Chemical Fiber Staple Test Method”.
［融点］
アロイチップを１０ｍｇ±０．５ｍｇでサンプリングし、ＤＳＣ（示差走査熱量計）にて吸熱ピークを測定し、ピークトップに相当する温度を融点とした。
[Melting point]
The alloy chip was sampled at 10 mg ± 0.5 mg, the endothermic peak was measured with DSC (differential scanning calorimeter), and the temperature corresponding to the peak top was taken as the melting point.
［固有粘度］
アロイチップを１２５ｍｇ±０．５ｍｇでサンプリングし、溶剤としてオルトクロロフェノール２５ｍｌを用いて、１００℃、３０分間溶解し、２５℃の恒温水槽にて１５分間放置後、オストワルド粘度計にて固有粘度を測定した。
[Intrinsic viscosity]
Sample the alloy chip at 125mg ± 0.5mg, dissolve in orthochlorophenol 25ml as a solvent, dissolve at 100 ° C for 30 minutes, leave it in a constant temperature water bath at 25 ° C for 15 minutes, and then determine the intrinsic viscosity with an Ostwald viscometer. It was measured.
［電子顕微鏡観察］
アロイチップを繊維化したものを超薄切りにし、クロロホルムにてポリ乳酸樹脂だけを抽出した後、走査型電子顕微鏡で観察した。繊維化する前のアロイチップも同様の方法で観察した。
[Electron microscope observation]
The fiber made of alloy chips was cut into ultra-thin slices, and only the polylactic acid resin was extracted with chloroform, and then observed with a scanning electron microscope. The alloy chip before fiberization was also observed by the same method.
［島であるポリ乳酸の平均直径］
ポリマーアロイ繊維の繊維方向に垂直な断面の走査型電子顕微鏡写真を、画像処理ソフトを用いて処理し、得られた面積から、島の形状を円として、その直径を求め、得られた個々の直径から、数平均値として平均直径を求めた。
[Average diameter of polylactic acid in the island]
Scanning electron micrographs of the cross section perpendicular to the fiber direction of the polymer alloy fibers were processed using image processing software. From the obtained area, the shape of the island was taken as a circle, and the diameter was determined. From the diameter, the average diameter was determined as a number average value.
（実施例１）
ポリエチレンテレフタレート（ＰＥＴ）樹脂（固有粘度０．６１、融点２５３℃）７５％と、ポリ乳酸（ＰＬＡ）樹脂（溶融粘度３００Ｐａ・ｓ）２５％、および、樹脂合計重量１００部に対し０．５部のエポキシ基を有するスチレン・アクリル系共重合物（ＢＡＳＦジャパン(株)製の商品名ＪＯＮＣＲＹＬ）を、個々に計量し、タンブラーで１０分間ブレンドした。次に、原料供給装置にブレンドした原料を投入し、吐出量２００ｋｇ／ｈｒの流量で二軸混練押出機のホッパーに樹脂を供給した。５０ｍｍ同方向回転の多段ベント式二軸混練押出機をホッパー側から１６０℃〜２８５℃の設定温度にし、スクリュー回転数４００ｒｐｍで溶融混練を行った。その後、二軸混練押出機より吐出した樹脂を水槽にて冷却固化し、ペレタイザーでカットし、アロイチップを得た。
Example 1
Polyethylene terephthalate (PET) resin (intrinsic viscosity 0.61, melting point 253 ° C.) 75%, polylactic acid (PLA) resin (melt viscosity 300 Pa · s) 25%, and 0.5 parts for 100 parts total resin weight The styrene-acrylic copolymer having the epoxy group (trade name JONCRYL manufactured by BASF Japan Ltd.) was weighed individually and blended with a tumbler for 10 minutes. Next, the blended raw materials were charged into the raw material supply device, and the resin was supplied to the hopper of the twin-screw kneading extruder at a discharge rate of 200 kg / hr. A multistage vent type twin-screw kneading extruder of 50 mm rotating in the same direction was set to a set temperature of 160 ° C. to 285 ° C. from the hopper side, and melt kneading was performed at a screw rotation speed of 400 rpm. Thereafter, the resin discharged from the twin-screw kneading extruder was cooled and solidified in a water tank and cut with a pelletizer to obtain an alloy chip.
得られたアロイチップの断面を走査型電子顕微鏡で観察した結果、直径５０〜１０００ｎｍの島状の多数のポリ乳酸が分散していた。得られたアロイチップについて固有粘度、融点を測定した。その結果を表１に示す。 As a result of observing the cross section of the obtained alloy chip with a scanning electron microscope, a large number of island-shaped polylactic acids having a diameter of 50 to 1000 nm were dispersed. The intrinsic viscosity and melting point of the obtained alloy chip were measured. The results are shown in Table 1.
次に、図３に示す装置を用いて、上記で得られたアロイチップが９９．６％、二酸化チタンが０．４％の配合比率になるように、それぞれの原料供給装置に投入し、紡糸口金から溶融吐出した後、冷却固化せしめ、糸表面に給油しながら引取りロールで引取り、ドラム状パッケージで巻き上げた。その後、得られた未延伸糸を延伸温度８０℃、熱セット温度１４０℃、延伸倍率４．０倍で延伸熱セットし、繊度６．６ｄｔｅｘ、強度２．０ｃＮ／ｄｔｅｘ、伸度６５％での延伸糸を得た。ポリマーアロイ繊維における、ポリ乳酸の島の平均直径は２００ｎｍであった。巻き上げ時に糸切れはなく、安定して紡糸延伸できた。得られた繊維についての測定結果を、同じく表１に示す。 Next, using the apparatus shown in FIG. 3, the alloy chips obtained above were put into the raw material supply apparatuses so that the blending ratio was 99.6% and titanium dioxide was 0.4%. After being melted and discharged from the die, it was cooled and solidified, taken up with a take-up roll while supplying oil to the yarn surface, and wound up with a drum-shaped package. Thereafter, the obtained undrawn yarn was drawn and heat-set at a drawing temperature of 80 ° C., a heat setting temperature of 140 ° C. and a draw ratio of 4.0 times, and the fineness was 6.6 dtex, the strength was 2.0 cN / dtex, and the elongation was 65%. A drawn yarn was obtained. The average diameter of the polylactic acid island in the polymer alloy fiber was 200 nm. There was no yarn breakage at the time of winding, and the yarn could be stably spun and drawn. The measurement results for the obtained fibers are also shown in Table 1.
（実施例２）
ポリエチレンテレフタレート樹脂（固有粘度０．６１、融点２５３℃）７０％と、ポリ乳酸樹脂（溶融粘度３００Ｐａ・ｓ）３０％、および、樹脂合計重量１００部に対し０．５部のエポキシ基を有するスチレン・アクリル系共重合物（ＢＡＳＦジャパン(株)製の商品名ＪＯＮＣＲＹＬ）を、個々に計量し、実施例１と同条件にてアロイチップを得た。得られたアロイチップについて固有粘度、融点を測定した。その結果を表１に示す。
(Example 2)
Polystyrene terephthalate resin (inherent viscosity 0.61, melting point 253 ° C.) 70%, polylactic acid resin (melt viscosity 300 Pa · s) 30%, and styrene having 0.5 parts of epoxy groups with respect to 100 parts of total resin weight An acrylic copolymer (trade name JONCRYL manufactured by BASF Japan Ltd.) was weighed individually, and an alloy chip was obtained under the same conditions as in Example 1. The intrinsic viscosity and melting point of the obtained alloy chip were measured. The results are shown in Table 1.
（実施例３）
ポリエチレンテレフタレート樹脂（固有粘度０．６１、融点２５３℃）７５％と、ポリ乳酸樹脂（溶融粘度３００Ｐａ・ｓ）２５％、および、樹脂合計重量１００部に対し１．０部のエポキシ基を有するスチレン・アクリル系共重合物（ＢＡＳＦジャパン(株)製の商品名ＪＯＮＣＲＹＬ）を、個々に計量し、実施例１と同条件にてアロイチップを得た。得られたアロイチップについて固有粘度、融点を測定した。その結果を表１に示す。
(Example 3)
Polystyrene terephthalate resin (intrinsic viscosity 0.61, melting point 253 ° C.) 75%, polylactic acid resin (melt viscosity 300 Pa · s) 25%, and styrene having 1.0 part of epoxy group with respect to 100 parts of total resin weight An acrylic copolymer (trade name JONCRYL manufactured by BASF Japan Ltd.) was weighed individually, and an alloy chip was obtained under the same conditions as in Example 1. The intrinsic viscosity and melting point of the obtained alloy chip were measured. The results are shown in Table 1.
（比較例１）
ポリエチレンテレフタレート樹脂（固有粘度０．６１、融点２５３℃）７５％と、ポリ乳酸樹脂（溶融粘度３００Ｐａ・ｓ）２５％を、個々に計量し、タンブラーで１０分間ブレンドした。次に、原料供給装置にブレンドした原料を投入し、実施例１と同条件にてアロイチップを得た。得られたアロイチップについて固有粘度、融点を測定した。その結果を表１に示す。
次に、図３に示す装置を用いて、上記で得られたアロイチップが９９．６％、二酸化チタンが０．４％の配合比率になるように、それぞれの原料供給装置に投入し、実施例１と同条件で、紡糸、延伸することにより繊度６．６ｄｔｅｘのポリマーアロイ繊維を得た。ただし、巻き取り時に糸切れが頻発したため、安定して紡糸延伸できなかった。
(Comparative Example 1)
Polyethylene terephthalate resin (inherent viscosity 0.61, melting point 253 ° C.) 75% and polylactic acid resin (melt viscosity 300 Pa · s) 25% were individually weighed and blended for 10 minutes with a tumbler. Next, the blended raw materials were charged into the raw material supply apparatus, and alloy chips were obtained under the same conditions as in Example 1. The intrinsic viscosity and melting point of the obtained alloy chip were measured. The results are shown in Table 1.
Next, using the apparatus shown in FIG. 3, the alloy chips obtained above were put into each raw material supply apparatus so that the blending ratio was 99.6% and titanium dioxide was 0.4%. A polymer alloy fiber having a fineness of 6.6 dtex was obtained by spinning and drawing under the same conditions as in Example 1. However, since yarn breakage occurred frequently during winding, the spinning and stretching could not be stably performed.
（比較例２）
ポリエチレンテレフタレート樹脂（固有粘度０．６１、融点２５３℃）５０％と、ポリ乳酸樹脂（溶融粘度３００Ｐａ・ｓ）５０％、および、樹脂合計重量１００部に対し０．５部のエポキシ基を有するスチレン・アクリル系共重合物（ＢＡＳＦジャパン(株)製の商品名ＪＯＮＣＲＹＬ）を、個々に計量し、実施例１と同条件にてアロイチップを得た。得られたアロイチップについて固有粘度、融点を測定した。その結果を表１に示す。
(Comparative Example 2)
Polystyrene terephthalate resin (inherent viscosity 0.61, melting point 253 ° C.) 50%, polylactic acid resin (melt viscosity 300 Pa · s) 50%, and styrene having 0.5 parts of epoxy groups with respect to 100 parts of total resin weight An acrylic copolymer (trade name JONCRYL manufactured by BASF Japan Ltd.) was weighed individually, and an alloy chip was obtained under the same conditions as in Example 1. The intrinsic viscosity and melting point of the obtained alloy chip were measured. The results are shown in Table 1.
（比較例３）
ポリエチレンテレフタレート樹脂（固有粘度０．６１、融点２５３℃）９９．６％と二酸化チタン０．４％の配合比率にして、それぞれの原料供給装置に投入し、実施例１と同条件で、繊度６．６ｄｔｅｘ、強度３．６ｃＮ／ｄｔｅｘ、伸度５５％のセミダル延伸糸を得た。巻き取り時に糸切れはなく、安定して紡糸延伸できた。
(Comparative Example 3)
Polyethylene terephthalate resin (intrinsic viscosity 0.61, melting point 253 ° C.) 99.6% and titanium dioxide 0.4% were mixed in each raw material supply device, and under the same conditions as in Example 1, fineness 6 A semi-dull drawn yarn having a strength of 3.6 dtex, a strength of 3.6 cN / dtex, and an elongation of 55% was obtained. There was no yarn breakage at the time of winding, and the yarn could be stably spun and drawn.
また、実施例１および比較例１で得たポリマーアロイ繊維について、走査型電子顕微鏡による繊維断面の写真を、図４および図５に示す。 Moreover, about the polymer alloy fiber obtained in Example 1 and Comparative Example 1, the photograph of the fiber cross section by a scanning electron microscope is shown in FIG. 4 and FIG.
表１より、ポリエチレンテレフタレート樹脂とポリ乳酸樹脂からなる樹脂混合物に、エポキシ基を有するスチレン・アクリル系共重合物が配合されてなるポリマーアロイ（実施例１〜３）は、融点が高い耐熱性に優れる樹脂であることが分る。図４より、ポリ乳酸を溶解させた後のポリマーアロイ繊維断面に空洞が見られないことより、ポリ乳酸樹脂のポリエチレンテレフタレート樹脂中への分散性が非常に優れていることが分る。また、エポキシ基を有するスチレン・アクリル系共重合物の添加量を変更することで、ポリマーアロイの固有粘度の調整も可能である。 From Table 1, the polymer alloy (Examples 1 to 3) in which a styrene / acrylic copolymer having an epoxy group is blended with a resin mixture composed of a polyethylene terephthalate resin and a polylactic acid resin has high heat resistance. It turns out that it is an excellent resin. From FIG. 4, it can be seen that the dispersibility of the polylactic acid resin in the polyethylene terephthalate resin is very excellent because no cavity is seen in the cross section of the polymer alloy fiber after the polylactic acid is dissolved. Moreover, the intrinsic viscosity of the polymer alloy can be adjusted by changing the amount of the styrene / acrylic copolymer having an epoxy group.
一方、添加剤（エポキシ基を有するスチレン・アクリル系共重合物）が配合されていないポリマーアロイ（比較例１）は、ポリ乳酸樹脂の融点とポリエチレンテレフタレート樹脂の融点を示す２つのピークが出現した。図５より、ポリ乳酸を溶解させた後のポリマーアロイ繊維断面には、多数の空洞が不均一な状態で存在し、直径２〜３μｍの大きな空洞も存在したことより、ポリ乳酸樹脂がポリエチレンテレフタレート樹脂中に均一に微分散しておらず、ポリ乳酸樹脂が異物となることで糸切れが多発したものと考察される。 On the other hand, in the polymer alloy (Comparative Example 1) in which the additive (styrene-acrylic copolymer having an epoxy group) is not blended, two peaks indicating the melting point of the polylactic acid resin and the melting point of the polyethylene terephthalate resin appeared. . FIG. 5 shows that the polyalloy resin is made of polyethylene terephthalate because a large number of cavities exist in a non-uniform state and large cavities having a diameter of 2 to 3 μm are present in the cross section of the polymer alloy fiber after the polylactic acid is dissolved. It is considered that the yarn breakage frequently occurs because the polylactic acid resin is not a fine dispersion evenly in the resin and the polylactic acid resin becomes a foreign substance.
ポリエチレンテレフタレート樹脂に対するポリ乳酸樹脂の比率を高めたポリマーアロイ（比較例２）は、添加剤を実施例１と同量添加しても、ポリ乳酸樹脂の融点とポリエチレンテレフタレート樹脂の融点を示す２つのピークが出現し、ポリ乳酸樹脂をポリエチレンテレフタレート樹脂中に均一に微分散させることができなかった。 A polymer alloy (Comparative Example 2) having an increased ratio of polylactic acid resin to polyethylene terephthalate resin has two melting points of polylactic acid resin and polyethylene terephthalate resin even when the same amount of additive is added as in Example 1. A peak appeared, and the polylactic acid resin could not be finely dispersed uniformly in the polyethylene terephthalate resin.
本発明のポリマーアロイは、従来のポリマーアロイに比べて耐熱性、生産性、コスト、環境負荷の面で優れているため、ポリエチレンテレフタレート樹脂が用いられる各種用途の他、環境対応が必要な各種用途に用いることができる。 The polymer alloy of the present invention is superior in heat resistance, productivity, cost, and environmental load compared to conventional polymer alloys, so various applications in which polyethylene terephthalate resin is used and various applications that require environmental measures Can be used.
本発明のポリマーアロイ繊維は、長繊維または短繊維（ステープル）にした後、公知の繊維加工処理を施すことで、衣料用、インテリア、車両内装、産業資材等、種々用途に幅広く利用できる。 The polymer alloy fiber of the present invention can be widely used in various applications such as clothing, interiors, vehicle interiors, industrial materials, etc., by making long fibers or short fibers (staples) and then performing known fiber processing.
１１：原料供給装置
１２：ホッパー
１３：二軸混練押出機
１４：スクリュー
１５：ベント口
１６：水槽
１７：ペレタイザー
１８：溶融紡糸機原料供給装置
１９：溶融紡糸機ホッパー
２０：溶融紡糸押出機
２１：紡糸ノズル
２２：引取りロール
２３：未延伸採取缶
２４：ポリマー管
２５：オイリングロール
11: Raw material supply device 12: Hopper 13: Biaxial kneading extruder 14: Screw 15: Vent port 16: Water tank 17: Pelletizer 18: Melt spinning machine Raw material supply device 19: Melt spinning machine hopper 20: Melt spinning extruder 21: Spinning nozzle 22: take-up roll 23: unstretched collection can 24: polymer tube 25: oiling roll
Claims (7)
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| JP2011114710A JP5565971B2 (en) | 2011-05-23 | 2011-05-23 | Polymer alloy comprising polylactic acid resin and polyethylene terephthalate resin and method for producing the same |
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