JP3471109B2 - Polylactic acid copolymer and molded product thereof - Google Patents
Polylactic acid copolymer and molded product thereofInfo
- Publication number
- JP3471109B2 JP3471109B2 JP04799095A JP4799095A JP3471109B2 JP 3471109 B2 JP3471109 B2 JP 3471109B2 JP 04799095 A JP04799095 A JP 04799095A JP 4799095 A JP4799095 A JP 4799095A JP 3471109 B2 JP3471109 B2 JP 3471109B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polylactic acid
- oxide
- glycol
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Woven Fabrics (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、繊維、フィルム及びそ
の他の成型品に適する可塑化されたポリ乳酸共重合体及
びその成型品に関する。FIELD OF THE INVENTION The present invention relates to a plasticized polylactic acid copolymer suitable for fibers, films and other molded articles and molded articles thereof.
【0002】[0002]
【従来の技術及び課題】生分解性または自然環境下で分
解するポリマーが、環境保護の見地から注目されてい
る。特にポリ乳酸は、農産物を原料とするため資源的に
有利で、又、溶融成型性や耐熱性にも優れているために
最も期待されている。しかし、未変性品であるポリ乳酸
ホモポリマーは、結晶性が高いため、硬く脆く、成型品
が破損し易いことから、耐衝撃性や強靭性についての改
良が求められている。また、用途によっては、例えばフ
ィルム用や成型品用の一部には、高い柔軟性や生分解性
が必要とされている。2. Description of the Related Art Polymers that are biodegradable or decompose in a natural environment have been attracting attention from the viewpoint of environmental protection. In particular, polylactic acid is most expected because it is resource-friendly because it uses agricultural products as raw materials, and it is also excellent in melt moldability and heat resistance. However, since the polylactic acid homopolymer, which is an unmodified product, has high crystallinity, it is hard and brittle, and the molded product is easily damaged. Therefore, improvement in impact resistance and toughness is required. Further, depending on the application, for example, a part for a film or a molded product is required to have high flexibility and biodegradability.
【0003】本発明は係る結晶性を抑制し、目的や用途
に応じた耐衝撃性、強靭性、柔軟性、生分解性等に調節
することが可能で、しかもコスト的に有利な新規ポリ乳
酸共重合体を提供するものである。The present invention is a novel polylactic acid which suppresses the crystallinity and can be adjusted to have impact resistance, toughness, flexibility, biodegradability, etc. according to the purpose and application, and which is cost-effective. It is intended to provide a copolymer.
【0004】[0004]
【課題を解決するための手段及び作用】上述の課題を解
決するため、本発明のポリ乳酸共重合体は、乳酸と、脂
肪族及び/又は芳香族ジカルボン酸と、両末端に水酸基
を有する重合度10以下(但し、重合度3以下を除く)
のオリゴアルキレンオキシドとの共重合組成物であっ
て、その乳酸成分の重量比率が50%以上であることを
特徴とする。In order to solve the above-mentioned problems, the polylactic acid copolymer of the present invention comprises lactic acid, an aliphatic and / or aromatic dicarboxylic acid, and a polymer having hydroxyl groups at both ends. Degree 10 or less (excluding polymerization degree 3 or less)
Of oligoalkylene oxide, wherein the weight ratio of the lactic acid component is 50% or more.
【0005】乳酸にはL−乳酸とD−乳酸があり、これ
らを重合してポリL−乳酸、ポリD−乳酸、及びポリL
/D−共重合乳酸を得る。本発明に係る共重合物は、こ
れらの乳酸又はポリ乳酸に、脂肪族又は/及び芳香族ジ
カルボン酸と、両末端に水酸基を有するアルキレンオキ
シドのオリゴマーとを共重合したものである。Lactic acid includes L-lactic acid and D-lactic acid, which are polymerized to produce poly L-lactic acid, poly D-lactic acid, and poly L-lactic acid.
/ D-copolymerized lactic acid is obtained. The copolymer according to the present invention is obtained by copolymerizing these lactic acid or polylactic acid with an aliphatic or / and aromatic dicarboxylic acid and an alkylene oxide oligomer having hydroxyl groups at both ends.
【0006】ポリ乳酸と共重合させるものとして、アル
キレンオキシドのポリマー、例えばポリエチレンオキシ
ド(グリコール)や、ポリプロピレンオキシド(グリコ
ール)はよく知られている。しかし、これらは不安定な
物質であり、これから得られる成型品は耐熱性や耐光性
に劣る。また、ガラス転移温度を低下させる傾向があ
り、耐熱性を要求される用途には不向きであった。Alkylene oxide polymers such as polyethylene oxide (glycol) and polypropylene oxide (glycol) are well known as copolymers with polylactic acid. However, these are unstable substances, and the molded products obtained from them are inferior in heat resistance and light resistance. Further, it tends to lower the glass transition temperature and is not suitable for applications requiring heat resistance.
【0007】本発明のような、アルキレンオキシドのオ
リゴマー、例えば重合度10以下のもので特に分子量3
00未満のものとポリ乳酸との共重合体は知られていな
い。たとえ、アルキレンオキシドのオリゴマー、即ちオ
リゴアルキレンオキシド(グリコール)をポリ乳酸と共
重合させようとしても、高分子量の共重合体が得られ
ず、その実用性は殆どない。しかし、本件発明者は、鋭
意検討の結果、両末端が水酸基のオリゴアルキレンオキ
シドとジカルボン酸とをほぼ等モルとなるように組み合
わせてポリ乳酸と共重合させることにより、改良された
広範な特性を有する高分子量ポリ乳酸共重合体が得られ
ることを見出だし、本発明を完成した。Alkylene oxide oligomers such as those of the present invention, for example, those having a degree of polymerization of 10 or less and particularly having a molecular weight of 3
A copolymer of less than 00 and polylactic acid is not known. Even if an alkylene oxide oligomer, that is, an oligoalkylene oxide (glycol) is to be copolymerized with polylactic acid, a high molecular weight copolymer cannot be obtained, and its practicality is hardly achieved. However, the present inventor, as a result of diligent studies, obtained a wide range of improved properties by combining an oligoalkylene oxide having hydroxyl groups at both ends and a dicarboxylic acid in such a manner that they are approximately equimolar and copolymerized with polylactic acid. It was found that a high molecular weight polylactic acid copolymer having the above can be obtained, and the present invention was completed.
【0008】本発明の目的に適うオリゴアルキレンオキ
シドは重合度10以下(但し、重合度3以下を除く)の
もので、例えば、オリゴエチレンオキシド、オリゴプロ
ピレンオキシド、オリゴブチレンオキシド、及びこれら
の共重合物(例えば、オリゴエチレン/プロピレンオキ
シド、オリゴエチレン/ブチレンオキシド等)が挙げら
れる。The oligoalkylene oxide suitable for the purpose of the present invention has a degree of polymerization of 10 or less (excluding the degree of polymerization of 3 or less) , and examples thereof include oligoethylene oxide, oligopropylene oxide, oligobutylene oxide, and copolymers thereof. (For example, oligoethylene / propylene oxide, oligoethylene / butylene oxide and the like).
【0009】ここでいう共重合オリゴマーの重合度と
は、1分子を形成する構成単位のモル数で表しており、
例えば、エチレンオキシド1モルとプロピレンオキシド
(グリコール)1モルからなるものは重合度2であり、
エチレンオキシド2モルとプロピレンオキシド(グリコ
ール)1モルからなるものは重合度3である。The degree of polymerization of the copolymerization oligomer referred to herein is represented by the number of moles of constitutional units forming one molecule,
For example, one consisting of 1 mol of ethylene oxide and 1 mol of propylene oxide (glycol) has a degree of polymerization of 2,
A polymer composed of 2 mol of ethylene oxide and 1 mol of propylene oxide (glycol) has a degree of polymerization of 3.
【0010】エチレンオキシドの2量体、即ちジエチレ
ングリコールは、エチレングリコールに1モルのエチレ
ンオキシドを付加反応させれば得られ、2モル付加すれ
ば3量体、即ちトリエチレングリコールが得られる。同
様にプロピレングリコールにエチレンオキシドを付加し
たり、エチレングリコールにプロピレンオキシドを付加
することによって、オリゴエチレン/プロピレンオキシ
ド(グリコール)共重合オリゴマーを得ることができ
る。同様にブタンジオールやヘキサンジオールにエチレ
ンオキシドやプロピレンオキシドを付加することによっ
て種々の共重合オリゴマーを得ることができ、本発明に
適用することができる。A dimer of ethylene oxide, that is, diethylene glycol, can be obtained by adding 1 mol of ethylene oxide to ethylene glycol, and a trimer, ie, triethylene glycol can be obtained by adding 2 mol of ethylene oxide. Similarly, an oligoethylene / propylene oxide (glycol) copolymerized oligomer can be obtained by adding ethylene oxide to propylene glycol or propylene oxide to ethylene glycol. Similarly, various copolymerized oligomers can be obtained by adding ethylene oxide or propylene oxide to butanediol or hexanediol and can be applied to the present invention.
【0011】このように、グリコール類にエチレンオキ
シドやプロピレンオキシドを付加することによって、容
易かつ安価に本発明に好適なオリゴマーを得ることがで
きる。しかし、一般にこうした付加反応は必ずしも均一
に行われるとは限らず、得られる反応生成物は重合度の
異なるものの混合物となる。こうした混合オリゴマー
は、末端水酸基量を調査し、それとほぼ等モルのジカル
ボン酸を反応させれば高分子量のポリエステルを得るこ
とができる。また、蒸留や限外濾過等の方法を用いてこ
の混合物を分離し、高純度のオリゴマーを得た後にジカ
ルボン酸と反応させることもできる。Thus, by adding ethylene oxide or propylene oxide to glycols, oligomers suitable for the present invention can be obtained easily and inexpensively. However, in general, such an addition reaction is not always carried out uniformly, and the obtained reaction product is a mixture having different degrees of polymerization. In such a mixed oligomer, a high molecular weight polyester can be obtained by investigating the amount of terminal hydroxyl group and reacting it with an approximately equimolar amount of dicarboxylic acid. It is also possible to separate this mixture using a method such as distillation or ultrafiltration to obtain a highly pure oligomer, and then to react it with a dicarboxylic acid.
【0012】オリゴアルキレンオキシド(グリコール)
と組み合わせるジカルボン酸は、脂肪族でも芳香族でも
よく、両者を併用してもよい。脂肪族ジカルボン酸とし
ては、コハク酸、アジピン酸、セバシン酸、デカンジカ
ルボン酸、ドデカンジカルボン酸など、炭素数4〜20
のジカルボン酸が好適である。芳香族ジカルボン酸とし
ては、(オルソ)フタル酸、イソフタル酸、5−スルホ
イソフタル酸及びその金属(Na,K等)塩、テレフタ
ル酸、ナフタレンジカルボン酸などが好適であり、ジフ
ェニル基を有するものも有用である。Oligoalkylene oxide (glycol)
The dicarboxylic acid to be combined with may be aliphatic or aromatic, and both may be used in combination. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid and the like, having 4 to 20 carbon atoms.
The dicarboxylic acids of are preferred. As the aromatic dicarboxylic acid, (ortho) phthalic acid, isophthalic acid, 5-sulfoisophthalic acid and its metal (Na, K etc.) salts, terephthalic acid, naphthalenedicarboxylic acid and the like are preferable, and those having a diphenyl group are also preferable. It is useful.
【0013】一般に、芳香族を有するジカルボン酸と、
オリゴアルキレンオキシド(グリコール)とから得られ
るポリエステルエーテルは、脂肪族ジカルボン酸成分を
用いたものに比べて、融点やガラス転移点が高い傾向が
あり、ポリ乳酸と共重合することにより、耐熱性の優れ
た共重合物が得られる。しかし、このポリエステルエー
テルの融点が高すぎると、ポリ乳酸との溶融共重合が困
難となり、また、得られる共重合物の溶融成型性が劣っ
てしまう。従って、芳香族ジカルボン酸を用いる場合
は、それとオリゴアルキレンオキシド(グリコール)と
から得られるポリエステルエーテルの融点に注意し、例
えば、融点200℃以下、特に180℃以下、最も好ま
しくは170℃以下となるよう成分を調節することが望
ましい。このポリエステルエーテルの融点を低下させる
ことは、オリゴアルキレンオキシド(グリコール)の鎖
長の長いものを使うことや、脂肪族ジカルボン酸を併用
(混用)することにより、極めて容易に実現できる。同
様にイソフタル酸のような対称性の低い化合物を用いる
と、結晶性が低下し、融点が低下する。逆にテレフタル
酸のような対称性の高いものや、ナフタレン核のように
分子量の大きい成分を持つものを用いると、融点や耐熱
性が高くなる。Generally, a dicarboxylic acid having an aromatic group,
Polyester ethers obtained from oligoalkylene oxides (glycols) tend to have higher melting points and glass transition points than those using aliphatic dicarboxylic acid components. An excellent copolymer is obtained. However, if the melting point of this polyester ether is too high, melt copolymerization with polylactic acid becomes difficult, and the melt moldability of the obtained copolymer becomes poor. Therefore, when an aromatic dicarboxylic acid is used, pay attention to the melting point of the polyester ether obtained from the aromatic dicarboxylic acid and the oligoalkylene oxide (glycol). For example, the melting point is 200 ° C or lower, particularly 180 ° C or lower, and most preferably 170 ° C or lower. It is desirable to adjust the ingredients. Reducing the melting point of this polyester ether can be extremely easily realized by using an oligoalkylene oxide (glycol) having a long chain length or by using (mixing) an aliphatic dicarboxylic acid together. Similarly, when a compound having low symmetry such as isophthalic acid is used, crystallinity is lowered and melting point is lowered. On the other hand, when a highly symmetric compound such as terephthalic acid or a compound having a large molecular weight component such as a naphthalene nucleus is used, the melting point and heat resistance are increased.
【0014】ポリ乳酸(又は乳酸)と、脂肪族又は/及
び芳香族ジカルボン酸とオリゴアルキレンオキシド(グ
リコール)とからなるポリエステルエーテルとの共重合
は、容易に行うことがきる。例えば、前記ジカルボン酸
とグリコールとをほぼ等モルで重合し、末端に水酸基を
有するポリエステルエーテルを得た後、このポリエステ
ルエーテルの末端水酸基を重合開始点として、乳酸の環
状2量体であるラクチドの開環重合を行うことにより、
ポリ乳酸セグメント(ブロックA)とポリエステルエー
テル(ブロックB)とのブロック共重合体が得られる。
ポリエステルエーテルの1つの末端が水酸基である場合
には、A・B型のブロック共重合体が得られ、両末端が
水酸基である場合には、A・B・A型のブロック共重合
体が得られる。The copolymerization of polylactic acid (or lactic acid) with a polyester ether composed of an aliphatic or / and aromatic dicarboxylic acid and an oligoalkylene oxide (glycol) can be easily carried out. For example, the above-mentioned dicarboxylic acid and glycol are polymerized in substantially equimolar amounts to obtain a polyester ether having a hydroxyl group at the terminal, and then the terminal hydroxyl group of this polyester ether is used as a polymerization initiation point to obtain a lactide which is a cyclic dimer of lactic acid. By performing ring-opening polymerization,
A block copolymer of a polylactic acid segment (block A) and a polyester ether (block B) is obtained.
When one end of the polyester ether is a hydroxyl group, an A / B type block copolymer is obtained, and when both ends are a hydroxyl group, an A / B / A type block copolymer is obtained. To be
【0015】ポリエステルエーテルの末端基は、オリゴ
アルキレンオキシド(グリコール)とジカルボン酸を等
モルとすれば、一方が水酸基で他方がカルボキシル基と
なる。オリゴアルキレンオキシドを若干過剰にすれば、
ポリエステルエーテルの両末端基が水酸基となる。例え
ば、ジカルボン酸100モルに対し、オリゴアルキレン
オキシド(グリコール)101モルを完全に反応させれ
ば、重合度約101のポリエステルエーテルが得られ
る。即ち、ジカルボン酸成分とグリコール成分とのモル
比を調節することにより、ポリエステルエーテルの分子
量と末端基を制御することができる。単官能性化合物、
例えばモノアルコール又はモノカルボン酸を少量重量系
に添加すれば、重合停止剤としてはたらき、末端が封鎖
されたポリエステルエーテルが得られる。勿論、ラクチ
ドとの共重合のためにはポリエステルエーテルの少なく
とも一方の末端が水酸基である必要があり、重合停止剤
はモノアルコールに限られ、モノカルボン酸は用いな
い。If the oligoalkylene oxide (glycol) and dicarboxylic acid are equimolar, one end group of the polyester ether will be a hydroxyl group and the other will be a carboxyl group. With a slight excess of oligoalkylene oxide,
Both terminal groups of the polyester ether become hydroxyl groups. For example, by completely reacting 101 mol of oligoalkylene oxide (glycol) with 100 mol of dicarboxylic acid, a polyester ether having a degree of polymerization of about 101 can be obtained. That is, the molecular weight and end groups of the polyester ether can be controlled by adjusting the molar ratio of the dicarboxylic acid component and the glycol component. Monofunctional compound,
For example, when a small amount of monoalcohol or monocarboxylic acid is added, it functions as a polymerization terminator and a polyester ether having a blocked end is obtained. Of course, for copolymerization with lactide, it is necessary that at least one end of the polyester ether has a hydroxyl group, the polymerization terminator is limited to monoalcohol, and monocarboxylic acid is not used.
【0016】このようにして、ジカルボン酸とオリゴア
ルキレンオキシド(グリコール)とからなるポリエステ
ルエーテルとラクチドとを反応(重合)させることによ
り、容易にブロック共重合物を得ることができる。ブロ
ック共重合物は、主成分であるポリ乳酸の結晶性や融点
をあまり低下させることなく、強靭性、可塑性、柔軟
性、染色性、ガラス転移点等を改良することができ、本
発明の目的に特に好ましい。他方、ランダム共重合物
は、乳酸、ジカルボン酸、オリゴアルキレンオキシド
(グリコール)をカルボキシル基と水酸基とをほぼ等モ
ルになるように調合して、溶剤中又は溶融状態で脱水縮
合すれば得ることができる。このランダム共重合物は結
晶性が低く、共重合比率が大きい場合は非晶性となり、
耐熱性には劣るが強靭性、可塑性、柔軟性を改良できる
ので、耐熱性をそれほど必要としない用途には利用でき
る。In this way, a block copolymer can be easily obtained by reacting (polymerizing) a polyester ether composed of a dicarboxylic acid and an oligoalkylene oxide (glycol) with a lactide. The block copolymer can improve toughness, plasticity, flexibility, dyeability, glass transition point, etc., without significantly lowering the crystallinity or melting point of polylactic acid, which is the main component, and the object of the present invention. Is particularly preferred. On the other hand, the random copolymer can be obtained by preparing lactic acid, dicarboxylic acid and oligoalkylene oxide (glycol) so that the carboxyl group and the hydroxyl group are almost equimolar and dehydrating and condensing in a solvent or in a molten state. it can. This random copolymer has low crystallinity and becomes amorphous when the copolymerization ratio is high,
Although it is inferior in heat resistance, it can be improved in toughness, plasticity and flexibility, so it can be used in applications where heat resistance is not required so much.
【0017】本発明のポリ乳酸共重合体の分子量は、強
度や加工性等の実用的見地から、ある程度大きい必要が
ある。繊維、フィルム及び多くの成型品用には、分子量
は5万以上が必要であり、7万〜50万が好ましく、1
0万〜30万が最も多く用いられる。このような高分子
量のブロック共重合物を得るには、ジカルボン酸とオリ
ゴアルキレンオキシド(グリコール)とからなるポリエ
ステルエーテルの分子量がある程度大きいことが必要で
ある。このポリエステルエーテルの分子量が小さいと、
共重合比率(重合分率)を大きくして改質効果を十分に
得て、しかも高分子量のブロック共重合物を得ることが
困難である。この見地からは、前記ポリエステルエーテ
ル(ブロックB)の分子量は5千以上が好ましく、8千
以上が特に好ましく、1万〜10万が最も広く使われ
る。即ち、このような高分子量のポリエステルエーテル
を用意し、それとラクチドとをブロック共重合させれば
優れたポリ乳酸共重合体が得られる。The molecular weight of the polylactic acid copolymer of the present invention needs to be large to some extent from the practical viewpoint of strength and processability. For fibers, films and many molded products, a molecular weight of 50,000 or more is required, preferably 70,000 to 500,000, and 1
Most commonly used is from 0,000 to 300,000. In order to obtain such a high molecular weight block copolymer, it is necessary that the polyester ether composed of a dicarboxylic acid and an oligoalkylene oxide (glycol) has a relatively high molecular weight. If the molecular weight of this polyester ether is small,
It is difficult to obtain a sufficient modifying effect by increasing the copolymerization ratio (polymerization fraction) and obtain a high molecular weight block copolymer. From this point of view, the molecular weight of the polyester ether (block B) is preferably 5,000 or more, particularly preferably 8,000 or more, most preferably 10,000 to 100,000. That is, an excellent polylactic acid copolymer can be obtained by preparing such a high molecular weight polyester ether and block-copolymerizing it with lactide.
【0018】本発明の共重合物において、主成分である
ポリ乳酸又はポリ乳酸セグメント(ブロックA)は十分
に結晶性が高く、成型品に高い耐熱性を与える。一方、
共重合成分である、ジカルボン酸とオリゴアルキレンオ
キシド(グリコール)とから得られるポリエステルエー
テルセグメント(ブロックB)は、耐衝撃性や柔軟性な
どの見地から非晶質であることが好ましい。そのために
は、ポリエステルエーテルセグメントを構成するジカル
ボン酸とグリコールとを夫々一種にせずに、その一方又
は双方が二種以上のものを用いたもの(ある種の共重合
物)であることが好ましい。例えば、グリコール成分と
して、ジエチレングリコールとトリエチレングリコール
との混用、ジエチレングリコールとトリプロピレングリ
コールとの混用、エチレンオキシドとプロピレングリコ
ールとの共重合オリゴマーの使用などが有用である。同
様にアジピン酸とセバシン酸、アジピン酸とテレフタル
酸又はイソフタル酸との混用、アジピン酸とナフタレン
ジカルボン酸との混用なども有用である。In the copolymer of the present invention, the main component, polylactic acid or polylactic acid segment (block A), has sufficiently high crystallinity and gives a molded product high heat resistance. on the other hand,
The polyester ether segment (block B) obtained from a dicarboxylic acid and an oligoalkylene oxide (glycol), which is a copolymer component, is preferably amorphous from the viewpoint of impact resistance and flexibility. For that purpose, it is preferable that one or both of dicarboxylic acids and glycols constituting the polyester ether segment are not used alone but one or both of them are used (a certain kind of copolymer). For example, as a glycol component, it is useful to mix diethylene glycol and triethylene glycol, mix diethylene glycol and tripropylene glycol, and use a copolymer oligomer of ethylene oxide and propylene glycol. Similarly, mixing adipic acid and sebacic acid, mixing adipic acid and terephthalic acid or isophthalic acid, mixing adipic acid and naphthalenedicarboxylic acid, and the like are also useful.
【0019】本発明の共重合物において、ジカルボン酸
とオリゴアルキレンオキシドとからなる共重合成分の共
重合比率(共重合物中の重合分率)が大きい程、得られ
るポリ乳酸共重合体が強く変性される。従って、目的・
用途に応じて好適な共重合比率を選択すればよいが、多
くの場合、共重合比率は2〜40%、特に3〜30%の
範囲が用いられ、5〜20%が最も広く用いられる。In the copolymer of the present invention, the larger the copolymerization ratio of the copolymerization component composed of dicarboxylic acid and oligoalkylene oxide (polymerization fraction in the copolymer), the stronger the polylactic acid copolymer obtained. Be denatured. Therefore, the purpose
A suitable copolymerization ratio may be selected according to the application, but in many cases, the copolymerization ratio is in the range of 2 to 40%, particularly 3 to 30%, and 5 to 20% is most widely used.
【0020】本発明の共重合物において、主要な成分は
乳酸、脂肪族及び/又は芳香族ジカルボン酸、オ
リゴアルキレンオキシド(グリコール)の3つである。
しかし、これら以外の成分、例えば、炭素数2〜20の
脂肪族グリコールなどを副次的に加えてもよい。但し、
グリコール成分中の主たるもの(50重量%以上)はオ
リゴアルキレンオキシドである。The main components in the copolymer of the present invention are lactic acid, aliphatic and / or aromatic dicarboxylic acid, and oligoalkylene oxide (glycol).
However, a component other than these, such as an aliphatic glycol having 2 to 20 carbon atoms, may be added as a secondary component. However,
The main component (50% by weight or more) in the glycol component is oligoalkylene oxide.
【0021】同様に本発明の共重合物には、副次的添加
剤を加えて色々な改質を行うことができる。副次的添加
剤の例としては、安定剤、酸化防止剤、紫外線吸収剤、
顔料、着色剤、各種無機粒子、各種フィラー、揮発剤、
親水剤、制電剤、離型剤、可塑剤、生理活性物質、防腐
剤、香料、抗菌剤、発泡剤、その他の類似のものが挙げ
られる。Similarly, the copolymer of the present invention can be modified in various ways by adding a secondary additive. Examples of secondary additives include stabilizers, antioxidants, UV absorbers,
Pigments, colorants, various inorganic particles, various fillers, volatilizers,
Examples include hydrophilic agents, antistatic agents, release agents, plasticizers, physiologically active substances, preservatives, fragrances, antibacterial agents, foaming agents, and the like.
【0022】本発明及び以下の実施例において、部、%
は特記しない限り、重量比、重量分率で示している。乳
酸を主成分とする重合体の分子量は、試料のクロロホル
ム0.1%溶液のGPC分析で、ポリスチレン換算で分
子量500以下を除く高分子物の分散の重量平均値であ
る。In the present invention and the following examples, parts,%
Unless otherwise specified, weight ratios and weight fractions are shown. The molecular weight of the polymer containing lactic acid as the main component is the weight average value of the dispersion of the polymer excluding the molecular weight of 500 or less in terms of polystyrene by GPC analysis of a 0.1% chloroform solution of the sample.
【0023】[0023]
【実施例】ジエチレングリコール、トリエチレングリコ
ール、及びアジピン酸を、モル比50/50/98で混合し、混
合物に対しチタン酸テトラブチルエステルを0.05%添加
し、220 ℃、窒素中で撹拌下2時間反応させ、更に減圧
して1Torrで2時間反応させて、高粘度の水飴状のポリ
エステルエーテルP1を得た。P1は両末端が水酸基で
分子量約18,000である。[Example] Diethylene glycol, triethylene glycol, and adipic acid were mixed at a molar ratio of 50/50/98, and 0.05% of tetrabutyl titanate was added to the mixture, and the mixture was stirred at 220 ° C in nitrogen for 2 hours. The reaction was carried out, and the pressure was further reduced and the reaction was carried out at 1 Torr for 2 hours to obtain a high-viscosity starch syrup-like polyester ether P1. P1 has hydroxyl groups at both ends and has a molecular weight of about 18,000.
【0024】光学純度99%以上のL−ラクチド93部に対
し、ポリエステルエーテルP1を7部溶融混合し、全重
合系に対しオクチル酸錫0.03%、チバガイギー社イルガ
ノックス1010(酸化防止剤)0.5 %及び直径0.05μmの
酸化チタン粒子(結晶核剤)0.1 %を混合し、2本のス
クリューが噛み合う連続溶融混合機で窒素雰囲気中180
℃で平均30分間混合・反応させ、続いてオクチル酸錫を
0.1%混合し、互いに噛み合うスクリュー群と互いに噛
み合う長円形(2フライト型)の撹拌素子群からなる2
軸混練機を用い、190 ℃で17分間重合した後、口金より
押出し、水で冷却固化し、切断して、ポリ乳酸共重合体
チップC1を得た。7 parts of polyester ether P1 was melt-mixed with 93 parts of L-lactide having an optical purity of 99% or more, tin octylate 0.03%, and Ciba Geigy Irganox 1010 (antioxidant) 0.5% based on the total polymerization system. And 0.1% of titanium oxide particles (crystal nucleating agent) with a diameter of 0.05 μm are mixed, and the mixture is melted with two screws in a continuous melt mixer.
Mix and react for an average of 30 minutes at ℃, then tin octylate
Mixing 0.1%, consisting of screw groups that mesh with each other and oval (2-flight type) stirring element groups that mesh with each other 2
Polymerization was carried out at 190 ° C. for 17 minutes using a shaft kneader, then extruded from a die, cooled and solidified with water, and cut to obtain a polylactic acid copolymer chip C1.
【0025】チップC1を 120℃、圧力1.5kg/cm2 の窒
素中で12時間処理し、更に 160℃、常圧で48時間熱処理
(固相重合)して、チップC2を得た。チップC2の平
均分子量は181,000 、残存モノマー(ラクチド)は 0.2
%であった。Chip C1 was treated in nitrogen at 120 ° C. and a pressure of 1.5 kg / cm 2 for 12 hours, and then heat-treated (solid phase polymerization) at 160 ° C. and normal pressure for 48 hours to obtain chip C2. Chip C2 has an average molecular weight of 181,000 and residual monomer (lactide) of 0.2
%Met.
【0026】チップC2と略同様にして、但し、ポリエ
ステルエーテルとしてジエチレングリコールとイソフタ
ル酸とを重合させて得た、両末端が水酸基で分子量約1
6,000、融点約130 ℃のものを7%共重合させて得た分
子量183,000 のポリ乳酸共重合体のチップをC3とす
る。一方比較のためにポリエステルエーテルを共重合さ
せずに得た分子量183,000 のポリL−乳酸(ホモポリマ
ー)のチップをC4とする。 チップC2〜C4を用
い、射出成型してV字形ノッチのついた試験片を作成
し、夫々衝撃強度を測定した。使用したチップとそれか
ら得られた試験片の衝撃強度を表1に示す。表1に見る
ように、本発明のチップC2,C3から得られる成型品
は、比較例に比べて衝撃強度が高く、耐衝撃性に優れて
いる。Approximately the same as the chip C2, except that diethylene glycol as a polyester ether was polymerized with isophthalic acid.
A chip of polylactic acid copolymer having a molecular weight of 183,000 obtained by copolymerizing 7% of 6,000 and a melting point of about 130 ° C is designated as C3. On the other hand, for comparison, a chip of poly L-lactic acid (homopolymer) having a molecular weight of 183,000 obtained without copolymerizing polyester ether is designated as C4. Using chips C2 to C4, injection molding was performed to prepare test pieces with V-shaped notches, and the impact strengths were measured. Table 1 shows the impact strength of the chips used and the test pieces obtained therefrom. As seen in Table 1, the molded products obtained from the chips C2 and C3 of the present invention have higher impact strength and superior impact resistance as compared with the comparative examples.
【0027】[0027]
【表1】 [Table 1]
【0028】[0028]
【発明の効果】本発明によれば、内部可塑化されて耐衝
撃性や柔軟性等が改良された新規なポリ乳酸共重合体
が、容易且つ低コストで得ることができる。共重合成分
であるオリゴアルキレンオキシドと脂肪族又は/及び芳
香族ジカルボン酸から得られるポリエステルエーテルの
重量比率を調節することにより、広範な耐衝撃性や柔軟
性を持つ重合体が得られ、種々の用途に応用できる。According to the present invention, a novel polylactic acid copolymer which is internally plasticized and has improved impact resistance and flexibility can be obtained easily and at low cost. By adjusting the weight ratio of the oligoalkylene oxide as the copolymerization component and the polyester ether obtained from the aliphatic or / and aromatic dicarboxylic acid, a polymer having a wide range of impact resistance and flexibility can be obtained. It can be applied to various purposes.
【0029】更に本発明の共重合体は、多くの可塑剤に
対して親和性が高く、例えば脂肪族又は/及び芳香族ジ
カルボン酸成分を有する可塑剤、特に本発明共重合成分
と同じジカルボン酸成分やグリコール成分を有する低分
子型又は高分子型可塑剤に対して高い親和性を有し、容
易且つ均一に混合可能で、透明性、柔軟性、耐衝撃性に
優れた組成物を得ることができ、広範且つ変化に富む用
途に適用することができる。Furthermore, the copolymer of the present invention has a high affinity for many plasticizers, for example, a plasticizer having an aliphatic or / and aromatic dicarboxylic acid component, particularly the same dicarboxylic acid as the copolymerization component of the present invention. To obtain a composition having a high affinity for a low molecular weight type or high molecular weight type plasticizer having a component or a glycol component, capable of being mixed easily and uniformly, and having excellent transparency, flexibility and impact resistance. Therefore, it can be applied to a wide variety of applications.
【0030】更に、オリゴアルキレンオキシドやジカル
ボン酸の共重合による結晶性の低下に伴い、生分解性や
自然崩壊性が高められる傾向が認められ、未変性ポリ乳
酸(ホモポリマー)では分解速度が遅すぎる用途に好適
である。生分解性を高める目的のためには、脂肪族ジカ
ルボン酸を用いたものが好ましい。一般にポリアルキレ
ンオキシドも生分解性ではあるが、本発明に用いるアル
キレンオキシドのオリゴマーは、特に分解性に優れてい
る。又、一般にポリアルキレンオキシドは、加熱、紫外
線などにより酸化され易く、安定性に劣る傾向がある
が、本発明に用いるオリゴマー(オリゴアルキレンオキ
シド)は、ポリマーに比べて安定性に優れ、信頼性の高
い成型品を得ることができる。Further, it is recognized that the biodegradability and the spontaneous disintegration tend to be increased with the decrease in crystallinity due to the copolymerization of oligoalkylene oxide and dicarboxylic acid, and the decomposition rate of unmodified polylactic acid (homopolymer) is slow. Suitable for too many uses. For the purpose of enhancing biodegradability, those using an aliphatic dicarboxylic acid are preferable. Generally, polyalkylene oxide is also biodegradable, but the alkylene oxide oligomer used in the present invention is particularly excellent in degradability. In general, polyalkylene oxides are apt to be oxidized by heating, ultraviolet rays, etc. and tend to be inferior in stability, but the oligomer (oligoalkylene oxide) used in the present invention is superior in stability and reliability to the polymer. Highly molded products can be obtained.
【0031】本発明共重合物及び本発明共重合物に可塑
剤を配合した組成物は、広範な特性を有するように改良
することが可能で、成型品すなわち、繊維、編物、織
物、不織布、紙、フェルト、網、ロープ、フィルム、シ
−ト、板、棒、チューブ、各種容器、各種部品、その他
の各種の成型品等の各々の用途に応じて、最適な特性に
改良して、好適に利用することができる。The copolymer of the present invention and the composition in which the plasticizer is added to the copolymer of the present invention can be improved so as to have a wide range of properties. Molded products, that is, fibers, knits, woven fabrics, non-woven fabrics, Suitable for paper, felt, net, rope, film, sheet, plate, rod, tube, various containers, various parts, various molded products, etc. Can be used for.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小林 正和 京都市中京区西ノ京桑原町1番地 株式 会社 島津製作所 三条工場内 (56)参考文献 特開 平7−233245(JP,A) 特開 平7−173266(JP,A) 特開 平8−165339(JP,A) (58)調査した分野(Int.Cl.7,DB名) C08G 63/00 - 63/91 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masakazu Kobayashi Masakazu Kobayashi, No. 1, Kuwahara-cho, Nishinokyo, Nakagyo-ku, Kyoto Shimadzu Corporation Sanjo Factory (56) Reference JP-A-7-233245 (JP, A) JP-A-7- 173266 (JP, A) JP-A-8-165339 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C08G 63/00-63/91
Claims (7)
ボン酸と、両末端に水酸基を有する重合度10以下(但
し、重合度3以下を除く)のオリゴアルキレンオキシド
との共重合物であって、該乳酸成分の重量比率が50%
以上であることを特徴とするポリ乳酸共重合体。1. A lactic acid, an aliphatic and / or aromatic dicarboxylic acid, and a polymerization degree of 10 or less having hydroxyl groups at both ends (however,
Of the lactic acid component is 50% by weight.
The polylactic acid copolymer is characterized by the above.
0のものである請求項1記載のポリ乳酸共重合体。2. The aliphatic dicarboxylic acid has 4 to 2 carbon atoms.
The polylactic acid copolymer according to claim 1, which is 0.
フタル酸、5−スルホイソフタル酸及びその金属塩、テ
レフタル酸、ナフタレンジカルボン酸より選ばれた少な
くとも1種のものである請求項1〜2のいずれかに記載
のポリ乳酸共重合体。3. The aromatic dicarboxylic acid is at least one selected from phthalic acid, isophthalic acid, 5-sulfoisophthalic acid and metal salts thereof, terephthalic acid, and naphthalenedicarboxylic acid . The polylactic acid copolymer according to any one of claims.
オキシド、プロピレンオキシド、ブチレンオキシドのオ
リゴマー又はそれらの共重合オリゴマ−で、分子量が3
00未満のものである請求項1〜3のいずれかに記載の
ポリ乳酸共重合体。4. The oligoalkylene oxide is an oligomer of ethylene oxide, propylene oxide, butylene oxide or a copolymerization oligomer thereof, and has a molecular weight of 3
The polylactic acid copolymer according to any one of claims 1 to 3 , which is less than 00.
る請求項1〜4のいずれかに記載のポリ乳酸共重合体。5. The polylactic acid copolymer according to claim 1, wherein the weight ratio of the lactic acid component is 70 to 97%.
脂肪族及び/又は芳香族ジカルボン酸成分とオリゴアル
キレンオキシド(グリコール)成分とのポリエステルエ
ーテルセグメント(ブロックB)とを有するブロック共
重合体である請求項1〜5のいずれかに記載のポリ乳酸
共重合体。6. A polylactic acid segment (block A),
A polylactic acid copolymer according to any one of claims 1 to 5 , which is a block copolymer having a polyester ether segment (block B) of an aliphatic and / or aromatic dicarboxylic acid component and an oligoalkylene oxide (glycol) component. Polymer.
酸共重合体からなる成型品。7. A molded article comprising the polylactic acid copolymer according to any one of claims 1 to 6.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04799095A JP3471109B2 (en) | 1995-03-08 | 1995-03-08 | Polylactic acid copolymer and molded product thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04799095A JP3471109B2 (en) | 1995-03-08 | 1995-03-08 | Polylactic acid copolymer and molded product thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH08245775A JPH08245775A (en) | 1996-09-24 |
JP3471109B2 true JP3471109B2 (en) | 2003-11-25 |
Family
ID=12790768
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP04799095A Expired - Lifetime JP3471109B2 (en) | 1995-03-08 | 1995-03-08 | Polylactic acid copolymer and molded product thereof |
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JP (1) | JP3471109B2 (en) |
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---|---|---|---|---|
KR100428687B1 (en) * | 2001-09-10 | 2004-04-30 | 주식회사 이래화학 | Biodegradable polyester resin composition which has superior tear strength |
JP5297632B2 (en) * | 2006-11-17 | 2013-09-25 | 独立行政法人国立循環器病研究センター | Blood coagulation inhibiting material, coating material using the same, and biological indwelling member |
CN107299414B (en) * | 2017-07-05 | 2019-11-29 | 浙江理工大学 | High molecular weight dextrorotation polylactic acid-low molecular weight l-lactic acid blended fiber preparation method and product |
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1995
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