JP3391133B2 - Plasticized polylactic acid and its molded product - Google Patents
Plasticized polylactic acid and its molded productInfo
- Publication number
- JP3391133B2 JP3391133B2 JP01172495A JP1172495A JP3391133B2 JP 3391133 B2 JP3391133 B2 JP 3391133B2 JP 01172495 A JP01172495 A JP 01172495A JP 1172495 A JP1172495 A JP 1172495A JP 3391133 B2 JP3391133 B2 JP 3391133B2
- Authority
- JP
- Japan
- Prior art keywords
- plasticizer
- polylactic acid
- molecular weight
- polyalkylene ether
- acid
- 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 - Fee Related
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、可塑化された生分解性
ポリエステル組成物及びその成型品に関する。TECHNICAL FIELD The present invention relates to a plasticized biodegradable polyester composition and a molded article thereof.
【０００２】[0002]
【従来の技術】生分解性又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も有利で、更
に溶融成型性や耐熱性に優れるために最も期されてい
る。しかしポリ乳酸ホモポリマー（未変性品）は、結晶
性が高いために、硬くもろく、成型品が破損し易いとい
う問題点がある。また用途によっては、高い柔軟性が求
められる。このため、従来から第３成分を共重合した
り、混合して柔軟性の強化や、もろさの改善が図られて
いる。BACKGROUND OF THE INVENTION Polymers that are biodegradable or that decompose in the natural environment have attracted attention from the standpoint of environmental protection. In particular, polylactic acid is most advantageous because it is made of agricultural products as a raw material and is advantageous in terms of resources, and further has excellent melt moldability and heat resistance. However, since the polylactic acid homopolymer (unmodified product) has high crystallinity, it is hard and brittle, and the molded product is easily damaged. Further, depending on the application, high flexibility is required. Therefore, conventionally, the third component has been copolymerized or mixed to enhance flexibility and improve brittleness.
【０００３】[0003]
【発明が解決しようとする課題】しかし共重合法では結
晶性の低下に伴なう融点、耐熱性の低下という課題が生
じる。他方可塑剤の混合法では、可塑剤と母体であるポ
リ乳酸との親和性が低いため、可塑剤が表面に浸み出て
表面を汚したり、又成型品の透明性や光沢が損なわれる
という課題がある。However, in the copolymerization method, there is a problem that the melting point and heat resistance are lowered due to the decrease in crystallinity. On the other hand, in the plasticizer mixing method, the plasticizer and the matrix polylactic acid have a low affinity, so the plasticizer seeps out on the surface and stains the surface, and the transparency and gloss of the molded product are impaired. There are challenges.
【０００４】本発明の目的は、結晶性や耐熱性が過度に
損なわれることなく、優れた柔軟性、可撓性、透明性、
光沢を有し、しかも可塑剤の浸出による表面汚れの少な
い改良された新しいポリ乳酸組成物とその応用製品を提
供するにある。The object of the present invention is to obtain excellent flexibility, flexibility, transparency, and crystallinity and heat resistance without being excessively impaired.
It is an object of the present invention to provide an improved new polylactic acid composition having gloss and less surface stain due to leaching of a plasticizer, and its applied product.
【０００５】[0005]
【課題を解決するための手段】上記本発明の目的は、ポ
リ乳酸（Ａ）と、分子量2,000 以上のポリアルキレンエ
ーテル（Ｂ）とが、重量比（Ａ／Ｂ）99/1〜50/50 で共
重合された共重合ポリ乳酸（Ｃ）の中に、分子量2,000
以上（但し100,000より大きいものを除く）のポリアル
キレンエーテルを主成分とする可塑剤（Ｄ）を、重量比
（Ｄ／Ｃ）1/99〜50/50 の範囲で混合することによって
達成される。The above object of the present invention is to provide a polylactic acid (A) and a polyalkylene ether (B) having a molecular weight of 2,000 or more in a weight ratio (A / B) of 99/1 to 50/50. The molecular weight of 2,000 in the copolymerized polylactic acid (C)
It is achieved by mixing the above plasticizer (D) containing polyalkylene ether as a main component (excluding those larger than 100,000) in a weight ratio (D / C) of 1/99 to 50/50. .
【０００６】ここでポリ乳酸とは、ポリＬ−乳酸ホモポ
リマー、ポリＤ−乳酸ホモポリマー及びポリＬ／Ｄ−乳
酸共重合物を言う。ポリＬ／Ｄ−乳酸共重合物は、共重
合によって結晶性を低下させる目的で製造されることが
多く、共重合比率は任意であるが、結晶性と耐熱性を保
つ目的には、Ｄ体比率は７％以下及び９３％以上の範囲
が好ましく、特に５％以下及び９５％以上の範囲が良く
用いられる。Here, polylactic acid means a poly L-lactic acid homopolymer, a poly D-lactic acid homopolymer and a poly L / D-lactic acid copolymer. Poly L / D-lactic acid copolymers are often produced by copolymerization for the purpose of lowering crystallinity, and the copolymerization ratio is arbitrary, but for the purpose of maintaining crystallinity and heat resistance, D-form is used. The ratio is preferably 7% or less and 93% or more, and particularly preferably 5% or less and 95% or more.
【０００７】本発明組成物の母体（マトリクス）ポリマ
ーである共重合ポリ乳酸（Ｃ）の主成分は乳酸である。
すなわち、共重合ポリ乳酸（Ｃ）の構成成分中の乳酸由
来成分は、５０〜９９％であり、好ましくは６０〜９８
％、特に７０〜９７％のものが最も多く用いられる。The main component of the copolymerized polylactic acid (C) which is the matrix (matrix) polymer of the composition of the present invention is lactic acid.
That is, the lactic acid-derived component in the constituent components of the copolymerized polylactic acid (C) is 50 to 99%, preferably 60 to 98.
%, Especially 70 to 97% is most often used.
【０００８】本発明組成物の母体ポリマーである共重合
ポリ乳酸（Ｃ）の第２成分（Ｂ）は、分子量2,000 以上
のポリアルキレンエーテルである。ポリアルキレンエー
テルとしては、ポリエチレングリコール、ポリプロピレ
ングリコール、ポリブチレンエーテル、それらの共重合
物などが最も有用である。ポリアルキレンエーテルの分
子量は2,000 以上である必要があり、特に3,000 〜100,
000 程度のものが好ましい。分子量が小さすぎると共重
合物の分子量を大きくするのが困難となり、大きすぎる
と共重合の操作が困難になるからである。The second component (B) of the copolymerized polylactic acid (C) which is the base polymer of the composition of the present invention is a polyalkylene ether having a molecular weight of 2,000 or more. As the polyalkylene ether, polyethylene glycol, polypropylene glycol, polybutylene ether, and copolymers thereof are most useful. The molecular weight of the polyalkylene ether must be 2,000 or more, especially 3,000-100,
It is preferably about 000. This is because if the molecular weight is too small, it becomes difficult to increase the molecular weight of the copolymer, and if it is too large, the operation of copolymerization becomes difficult.
【０００９】共重合成分として用いるポリアルキレンエ
ーテルは、分子量や種類の異なるものを２種以上混用し
てもよく、１種のみ用いてもよい。混用すると、結晶性
が低下し、共重合物の可塑効果が高くなる。共重合ポリ
アルキレンエーテル、例えばポリエチレングリコールと
ポリプロピレングリコールのランダム又はブロック共重
合体を用いても、同様に可塑効果が高い。The polyalkylene ether used as the copolymerization component may be a mixture of two or more kinds having different molecular weights or kinds, or may be only one kind. When mixed, the crystallinity decreases and the plasticizing effect of the copolymer increases. Even if a copolymerized polyalkylene ether such as a random or block copolymer of polyethylene glycol and polypropylene glycol is used, the plasticizing effect is similarly high.
【００１０】共重合ポリ乳酸（Ｃ）中のポリアルキレン
エーテルの共重合比率は、１〜５０％であるが、特に２
〜４０％が好ましく、３〜３０％が最もよく用いられ
る。ポリアルキレンエーテルの共重合比率が高いほど可
塑剤（Ｄ）との親和性が高く、またポリマー自体の柔軟
性や耐衝撃性が高くなる傾向があるが、他方耐熱性や耐
久性が低下する傾向も認められ、目的、用途に応じて比
率を選べばよい。The copolymerization ratio of the polyalkylene ether in the copolymerized polylactic acid (C) is 1 to 50%, but especially 2
-40% is preferable, and 3-30% is the most used. The higher the copolymerization ratio of the polyalkylene ether, the higher the affinity with the plasticizer (D) and the higher the flexibility and impact resistance of the polymer itself, but the lower the heat resistance and durability tend to be. Is also recognized, and the ratio may be selected according to the purpose and application.
【００１１】本発明組成物の母体ポリマーである共重合
ポリ乳酸（Ｃ）は、主成分である乳酸、第２成分である
ポリアルキレンエーテルの他に、第３成分として少量の
（例えば３０％以下、特に２０％以下の）エステル結合
形成成分を含んでいてもよい。このような第３成分の例
としては、ヒドロキシブチルカルボン酸、グリコール酸
などのヒドロキシアルキルカルボン酸、カプロラクトン
やバレロラクトンなどのラクトン類、コハク酸、アジピ
ン酸、セバシン酸、テレフタル酸、イソフタル酸などの
ジカルボン酸、エチレングリコール、ブタンジオール、
ヘキサンジオールなどのジオール類、末端封鎖剤として
の炭素数２〜２０のモノカルボン酸又は／及びモノアル
コールなどがあげられる。The copolymerized polylactic acid (C), which is the base polymer of the composition of the present invention, contains a small amount (for example, 30% or less) as the third component in addition to lactic acid as the main component and polyalkylene ether as the second component. , Especially up to 20%). Examples of such third component include hydroxybutylcarboxylic acid, hydroxyalkylcarboxylic acid such as glycolic acid, lactones such as caprolactone and valerolactone, succinic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid and the like. Dicarboxylic acid, ethylene glycol, butanediol,
Examples thereof include diols such as hexanediol, and monocarboxylic acids having 2 to 20 carbon atoms and / or monoalcohols as terminal blocking agents.
【００１２】例えば、分子量5,000 程度以下の、比較的
分子量の小さいポリアルキレンエーテル（ジオール）を
共重合しようとすると、共重合物の分子量が上りにくい
傾向がある。しかし例えば、前もって分子量の小さいポ
リアルキレンエーテル（ジオール）とアジピン酸やテレ
フタル酸などのジカルボン酸とを縮合（エステル結合形
成）させて分子量を10,000〜100,000 程度まで高めてお
けば、乳酸成分と共重合して、容易に高分子量の共重合
物が得られる。For example, when trying to copolymerize a polyalkylene ether (diol) having a relatively small molecular weight of about 5,000 or less, the molecular weight of the copolymer tends to be difficult to increase. However, for example, if a polyalkylene ether (diol) with a small molecular weight is previously condensed with a dicarboxylic acid such as adipic acid or terephthalic acid (ester bond formation) to raise the molecular weight to about 10,000 to 100,000, it will be copolymerized with the lactic acid component. Thus, a high molecular weight copolymer can be easily obtained.
【００１３】可塑剤（Ｄ）の主成分はポリアルキレンエ
ーテルである。すなわち可塑剤（Ｄ）の構成成分中のポ
リアルキレンエーテルの重量比率は５０〜１００％であ
り、多くの場合６０〜９９％が好ましく用いられる。例
えば分子量2,000 のポリエチレングリコールの両末端の
水酸基をステアリン酸でエステル化（封鎖）したものの
ポリエチレンエーテルセグメントの重量比率は約７８％
であり、同様に酢酸で封鎖したもののポリエチレンエー
テルセグメントの比率は９５％である。The main component of the plasticizer (D) is polyalkylene ether. That is, the weight ratio of the polyalkylene ether in the constituent components of the plasticizer (D) is 50 to 100%, and in many cases 60 to 99% is preferably used. For example, polyethylene glycol having a molecular weight of 2,000 is prepared by esterifying (blocking) the hydroxyl groups at both ends with stearic acid, and the weight ratio of the polyethylene ether segment is about 78%.
Similarly, the proportion of polyethylene ether segment blocked with acetic acid is 95%.
【００１４】可塑剤（Ｄ）としては、未変性のポリアル
キレンエーテルも使用可能であるが、末端（水酸基、カ
ルボキシン基など）を封鎖し安定化したものがより好ま
しい。通常、ポリアルキレンエーテルの末端官能基は水
酸基の場合が多いが、これはモノカルボン酸、モノカル
ボン酸塩化物、モノカルボン酸無水物、モノイソシアネ
ート化合物などを反応させて封鎖出来る。封鎖用化合物
は、アルキル基、アルキルアリル基、アリル基その他の
基を持つものを用いることが出来るが、可塑効果や、離
型性、撥水性などの効果を持つ高級アルキル基やアルキ
ルアリル基を持つものが好ましく、特に炭素数８〜２０
のアルキル基をもつものが好ましい。As the plasticizer (D), an unmodified polyalkylene ether can be used, but it is more preferable that the terminal (hydroxyl group, carboxylic group, etc.) is blocked and stabilized. Usually, the terminal functional group of the polyalkylene ether is often a hydroxyl group, which can be blocked by reacting a monocarboxylic acid, a monocarboxylic acid chloride, a monocarboxylic acid anhydride, a monoisocyanate compound or the like. A compound having an alkyl group, an alkylallyl group, an allyl group or other groups can be used as the blocking compound, but a higher alkyl group or an alkylallyl group having a plasticizing effect, releasability, water repellency and the like can be used. It is preferable to have one, especially having 8 to 20 carbon atoms
Those having an alkyl group of are preferred.
【００１５】可塑剤を構成するポリアルキレンエーテル
としては、ポリエチレングリコール、ポリプロピレング
リコール、ポリブチレンエーテル及びそれらの共重合物
が好ましく用いられる。可塑剤の分子量は特に限定され
ないが、混合操作の容易性の見地からは、分子量2,000
〜300,000 程度、特に分子量5,000 〜200,000 のものが
好ましい。As the polyalkylene ether constituting the plasticizer, polyethylene glycol, polypropylene glycol, polybutylene ether and their copolymers are preferably used. The molecular weight of the plasticizer is not particularly limited, but from the viewpoint of ease of mixing operation, the molecular weight is 2,000.
It is preferably about 300 to 300,000, particularly preferably 5,000 to 200,000.
【００１６】一般に、ポリアルキレンエーテルは酸化や
分解され易い傾向がある。このため、ポリアルキレンエ
ーテルに対して、例えばヒンダートフェノールなどの酸
化防止剤や紫外線吸収剤を例えば0.01〜５％、特に0.05
〜２％程度混合することが望ましい。Generally, polyalkylene ethers tend to be easily oxidized and decomposed. Therefore, for example, an antioxidant such as hindered phenol or an ultraviolet absorber is added to the polyalkylene ether in an amount of 0.01 to 5%, particularly 0.05%.
It is desirable to mix them up to about 2%.
【００１７】可塑剤（Ｄ）の組成物中の混合率は、１〜
５０％であるが、２〜４０％が好ましく用いられ、３〜
３０％が最もよく用いられる。一般に混合率が大きいほ
ど可塑効果が高く、柔軟性が増大し、耐熱性が低下す
る。混合率は用途や目的によって選べばよい。共重合ポ
リ乳酸（Ｃ）中のポリアルキレンエーテルも可塑効果が
あるから、組成物全体の中の共重合成分（Ｂ）と可塑剤
（Ｄ）中のポリアルキレンエーテル成分の重量分率の合
計は２〜７０％、多くの場合５〜５０％、最も多くの場
合８〜４０％が好ましい。The mixing ratio of the plasticizer (D) in the composition is 1 to
Although it is 50%, 2 to 40% is preferably used, and 3 to
30% is most often used. Generally, the larger the mixing ratio, the higher the plasticizing effect, the greater the flexibility, and the lower the heat resistance. The mixing ratio may be selected depending on the application and purpose. Since the polyalkylene ether in the copolymerized polylactic acid (C) also has a plasticizing effect, the total weight fraction of the copolymerized component (B) and the polyalkylene ether component in the plasticizer (D) in the entire composition is 2-70%, often 5-50%, most often 8-40% is preferred.
【００１８】本発明組成物の特長は、母体ポリマー
（Ｃ）の共重合成分（Ｂ）と可塑剤（Ｄ）の親和性（混
和性、相溶性）が高いことである。両者の親和性が高い
ほど、柔軟性、可撓性、耐衝撃性、透明性、光沢などに
優れた成型品が得られる。両者の親和性は、母体ポリマ
ー（Ｃ）と可塑剤（Ｄ）が共にポリアルキレンエーテル
成分を持つことに由来する。この親和性は、両者が近似
性の極めて高い構成成分を有すると更に高くなり、同一
の構成成分を持つ場合に最も高い。従って、両者が同一
のポリアルキレンエーテルを構成成分として共有するこ
とが最も好ましい。勿論、同一とは同一構成単位（アル
キレンエーテル）を持つことであり、重合度は同一でな
くても良い。The feature of the composition of the present invention is that the copolymerization component (B) of the base polymer (C) and the plasticizer (D) have high affinity (miscibility, compatibility). The higher the affinity between them is, the more excellent the flexibility, the flexibility, the impact resistance, the transparency, the gloss, and the like of the molded product can be obtained. The affinity of both is derived from the fact that both the base polymer (C) and the plasticizer (D) have a polyalkylene ether component. This affinity is further increased when the both have extremely similar components, and is highest when they have the same components. Therefore, it is most preferable that both share the same polyalkylene ether as a constituent. Of course, the same means having the same constitutional unit (alkylene ether), and the degrees of polymerization may not be the same.
【００１９】可塑剤（Ｄ）は、多くの場合、母体である
共重合ポリ乳酸（Ｂ）の重合後、混合される。共重合ポ
リ乳酸（Ｂ）の重合原料や重合工程中に混合することも
不可能ではないが、エステル交換反応により母体ポリマ
ーと共重合したり、可塑剤が分解するのを防ぎ、所望の
混合率と可塑効果を正確に実現するには、母体ポリマー
の重合後、成型前又は成型工程で混合することが好まし
い。In many cases, the plasticizer (D) is mixed after the copolymerization polylactic acid (B) which is a base is polymerized. It is not impossible to mix the copolymerization polylactic acid (B) in the polymerization raw material or during the polymerization process, but it is possible to prevent the copolymerization with the base polymer by the transesterification reaction and the decomposition of the plasticizer, and to obtain a desired mixing ratio. In order to accurately realize the plasticizing effect, it is preferable to mix the base polymer after the polymerization and before the molding or in the molding step.
【００２０】混合方法は任意であるが、溶融状態や溶液
で機械的攪拌や静止混合器で混合してもよく、粉末状や
粒子状で混合して溶融又は溶解してもよい。本発明の組
成物は、母体ポリマー（Ｃ）と可塑剤との親和性が高
く、容易に均一に混合することが出来る。The mixing method is arbitrary, but the materials may be mixed in a molten state or a solution by mechanical stirring or a static mixer, or may be mixed in the form of powder or particles and melted or dissolved. The composition of the present invention has a high affinity for the base polymer (C) and the plasticizer and can be easily and uniformly mixed.
【００２１】本発明組成物中には、主成分である共重合
ポリ乳酸（Ｃ）と可塑剤（Ｄ）の他に、副次的に他の成
分を添加してもよい。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、着色材、各種無
機粒子、各種フィラー、撥水剤、親水剤、離型剤、可塑
剤、生理活性剤、防腐剤その他類似のものがあげられ
る。In the composition of the present invention, other components may be secondarily added in addition to the copolymerized polylactic acid (C) and the plasticizer (D) which are the main components. Examples of secondary additives include stabilizers, antioxidants, ultraviolet absorbers, pigments, colorants, various inorganic particles, various fillers, water repellents, hydrophilic agents, release agents, plasticizers, bioactive agents. , Preservatives and similar.
【００２２】[0022]
【作用】本発明によれば、母体ポリマー（Ｃ）の共重合
成分（Ｂ）と可塑剤（Ｄ）の親和性（混和性、相溶性）
が高いために、柔軟性、可撓性、耐衝撃性、透明性、光
沢などに優れた成型品が得られる。According to the present invention, the affinity (miscibility, compatibility) between the copolymerization component (B) of the base polymer (C) and the plasticizer (D).
Therefore, a molded product excellent in flexibility, flexibility, impact resistance, transparency and gloss can be obtained.
【００２３】[0023]
【実施例】以下の実施例で、％は特記しない限りすべて
重量分率で示す。ポリ乳酸及び共重合ポリ乳酸の分子量
は、試料のクロロホルム0.1 ％、溶液のＧＰＣ分析で分
子量５００以下を除く高分子物の分散の重量平均値であ
る。EXAMPLES In the following examples, all percentages are by weight unless otherwise specified. The molecular weight of polylactic acid and copolymerized polylactic acid is the weight average value of the dispersion of the polymer except for 0.1% chloroform of the sample and the molecular weight of 500 or less by GPC analysis of the solution.
【００２４】［実施例１］光学純度９９％以上のラクチ
ドに対し、直径0.05μｍの酸化チタン（結晶核剤）0.0
5、オクチル酸錫0.03％、共重合成分として両末端が水
酸基で分子量20,000のポリエチレングリコール６％を混
合し、２本のスクリュウが互いに噛み合う２軸連続混合
送液機で、窒素雰囲気中１８０℃、平均３０分間反応
（予備重合）させて平均分子量約10,000とした後、更に
重合触媒オクチル酸錫を0.1 ％添加し、互いに噛み合う
スクリュウ群と、互いに噛み合う長円形（２フライト
型）の攪拌素子群からなる２軸連続混練機を用い、１９
０℃で１５分間重合し、最終ベント孔より水分率１０pp
m 以下の溶融した可塑剤を供給し、更にケニックス社ス
タティックミキサー６０素子を組込んだ円筒を通過させ
て混合後、口金より押出し、水で冷却、固化、切断して
チップＣ１を得た。可塑剤は、両末端をステアリン酸で
封鎖した分子量20,000のポリエチレングリコールで、ヒ
ンダートフェノール系酸化防止剤チバガイギー社イルガ
ノックス1010を１％、トリエチレングリコール（固相重
合開始剤）１％を混合したものである。Example 1 For lactide having an optical purity of 99% or more, 0.05 μm diameter titanium oxide (crystal nucleating agent) 0.0
5, 0.03% tin octylate, 6% polyethylene glycol having a hydroxyl group at both ends and a molecular weight of 20,000 as a copolymerization component are mixed, and two screws are meshed with each other in a twin-screw continuous mixing and sending machine, 180 ° C in a nitrogen atmosphere, After reacting (preliminary polymerization) for an average of 30 minutes to an average molecular weight of about 10,000, 0.1% of tin octylate polymerization catalyst was further added, and screw groups that mesh with each other and elliptical (2-flight type) stirring element groups that mesh with each other Using a two-axis continuous kneader
Polymerize at 0 ° C for 15 minutes, water content is 10pp from final vent hole
A melted plasticizer of m or less was supplied, and the mixture was passed through a cylinder incorporating a static mixer 60 element manufactured by Kenix Co., Ltd., mixed, extruded from a die, cooled with water, solidified, and cut to obtain a chip C1. The plasticizer was polyethylene glycol having a molecular weight of 20,000 and capped with stearic acid at both ends, and 1% of hindered phenolic antioxidant Ciba Geigy Irganox 1010 and 1% of triethylene glycol (solid-state polymerization initiator) were mixed. It is a thing.
【００２５】チップＣ１を１２０℃、窒素中で１２時間
熱処理し、更に１６０℃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163,
000、残存モノマー（ラクチド）量は0.2 ％であった。The chip C1 is heat-treated in nitrogen at 120 ° C. for 12 hours, and further at 160 ° C. for 48 hours (solid-state polymerization).
Then, a chip C2 was obtained. The average molecular weight of the chip C2 is 163,
000, the amount of residual monomer (lactide) was 0.2%.
【００２６】チップＣ２を用い、２１０℃で射出成型し
て、Ｖ字型ノッチのついた衝撃試験片を作成した。同じ
くチップＣ２をスクリュウ押出機で２１０℃で溶融し、
Ｔ型口金のスリットより押出し、冷却固化後９０℃で縦
方向に3.3 倍、横方向に2.8倍延伸して、厚さ５０μｍ
のフィルムを得た。The chip C2 was injection molded at 210 ° C. to prepare an impact test piece having a V-shaped notch. Similarly, melt the chip C2 at 210 ° C with a screw extruder,
Extruded from the slit of T-type die, cooled and solidified, then stretched 3.3 times in the longitudinal direction and 2.8 times in the transverse direction at 90 ° C, and the thickness is 50 μm.
I got a film of.
【００２７】チップＣ２と同様にして、但し共重合成分
であるポリエチレングリコール及び可塑剤も加えず得た
ポリＬ−乳酸ホモポリマー（未変性品）をチップＣ３と
する。なお、チップＣ３には可塑剤は添加しなかった
が、固相重合開発始剤トリエチレングリコールは、ポリ
マーに対し0.05％添加した。チップＣ３の平均分子量は
155,000 であり、これを用いてチップＣ２と同様に衝撃
試験片及びフィルムを作成した。A poly L-lactic acid homopolymer (unmodified product) obtained in the same manner as in the chip C2, but without adding polyethylene glycol as a copolymerization component and a plasticizer, is used as a chip C3. Incidentally, no plasticizer was added to the chip C3, but 0.05% of the solid-phase polymerization development initiator triethylene glycol was added to the polymer. The average molecular weight of chip C3 is
It was 155,000, and an impact test piece and a film were prepared in the same manner as the chip C2.
【００２８】チップＣ２と同様にして、但し共重合成分
であるポリエチレングリコールは加えず、可塑剤は加え
て得たものをチップＣ４とする。チップＣ４の重合度は
153,000 で、これを用い同様に衝撃試験片及びフィルム
を作成した。The chip C4 was obtained in the same manner as the chip C2, except that the copolymerization component polyethylene glycol was not added and the plasticizer was added. The degree of polymerization of chip C4 is
At 153,000, impact test pieces and films were similarly prepared using this.
【００２９】チップＣ２と同様にして、但し可塑剤を用
いないでチップＣ５を得た。チップＣ５の平均分子量は
151,000 で、同様に衝撃試験片とフィルムを作成した。Chip C5 was obtained in the same manner as chip C2, but without the plasticizer. The average molecular weight of chip C5 is
At 151,000, impact test pieces and films were similarly prepared.
【００３０】チップＣ２と同様にして、但し可塑剤とし
てジオクチルフタレートを用いてチップＣ６を得た。チ
ップＣ６の平均分子量は151,000 であり、同様に試験片
とフィルムを作成した。Chip C6 was obtained in the same manner as chip C2, but using dioctyl phthalate as the plasticizer. The average molecular weight of Chip C6 was 151,000, and a test piece and a film were similarly prepared.
【００３１】チップＣ２〜Ｃ６から得た各衝撃試験片を
用い、衝撃強度を測定し、また各フィルムの透明性を肉
眼判定した。その結果を表１に示す。表１に見るよう
に、本発明組成物の衝撃強度及びフィルムの透明性は、
共に比較例よりも優れている。Impact strength was measured using each impact test piece obtained from the chips C2 to C6, and the transparency of each film was visually judged. The results are shown in Table 1. As seen in Table 1, the impact strength of the composition of the present invention and the transparency of the film are
Both are superior to the comparative example.
【表１】
［実施例２］実施例１のチップＣ２と同様にして、但し
ポリ乳酸への共重合成分（Ｂ）として、分子量3,000 の
ポリエチレングリコールとテレフタル酸の縮合物で分子
量約22,000、両末端が水酸基のものを用い、可塑剤とし
て同じく分子量3,000 のポリエチレングリコールとテレ
フタル酸の縮合物で分子量約22,000、両末端がステアリ
ン酸で封鎖されたものを５％添加したものをチップＣ６
とする。チップＣ６の平均分子量は161,000 で、それか
ら作成した試験片の衝撃強度は 4.6kg・cm／cm、フィル
ムの透明度もチップＣ２から得たフィルムと同程度で優
れていた。[Table 1] [Example 2] In the same manner as in the chip C2 of Example 1, except that as a copolymerization component (B) to polylactic acid, a condensate of polyethylene glycol having a molecular weight of 3,000 and terephthalic acid had a molecular weight of about 22,000 and hydroxyl groups at both ends. Chip C6 was prepared by adding 5% of a condensate of polyethylene glycol and terephthalic acid having the same molecular weight of 3,000 as the plasticizer and having a molecular weight of about 22,000 and both ends blocked with stearic acid.
And The average molecular weight of the chip C6 was 161,000, the impact strength of the test piece prepared therefrom was 4.6 kg · cm / cm, and the transparency of the film was as good as the film obtained from the chip C2.
【００３２】[0032]
【発明の効果】本発明によって、可塑剤と母体（マトリ
クス）ポリマーとの親和性の極めて高い組合せが容易に
実現可能となり、柔軟性、透明性、光沢などに優れるポ
リ乳酸成型品が得られる。更に、可塑剤と母体ポリマー
との親和性が高いために、成型品の加熱などによる可塑
剤の表面浸出による汚れその他のトラブルも改善され
る。 更に、可塑剤の構成成分であるポリアルキレンエ
ーテルとして、ポリエチレングリコール、ポリプロピレ
ングリコール又はそれらの共重合体を用いた場合、成型
品に制電性（帯電防止性）が付与され、静電気発生によ
るトラブルの防止に有効である。特に組成物中の上記ポ
リアルキレンエーテルの重量分率が５％以上でこの制電
効果が優れ、７％以上で最も優れる。According to the present invention, a combination of a plasticizer and a matrix (matrix) polymer having a very high affinity can be easily realized, and a polylactic acid molded article excellent in flexibility, transparency and gloss can be obtained. Further, since the plasticizer and the base polymer have a high affinity, stains and other troubles due to the surface leaching of the plasticizer due to heating of the molded product can be improved. Furthermore, when polyethylene glycol, polypropylene glycol or a copolymer thereof is used as the polyalkylene ether which is a constituent of the plasticizer, antistatic property (antistatic property) is imparted to the molded product and trouble due to static electricity is generated. It is effective in prevention. Particularly, when the weight fraction of the above polyalkylene ether in the composition is 5% or more, this antistatic effect is excellent, and when it is 7% or more, it is most excellent.
【００３３】また、高級アルキル基（炭素数８以上、特
に１０〜２０）を有する可塑剤を応用すれば、成型品の
撥水性が高まり、生分解性が低減し、分解速度をかなり
コントロールすることが出来る。同様に、可塑剤は離型
剤としても作用し、成型工程の効率向上にも有用であ
り、同じく成型品の表面摩擦係数を低減する効果もあ
り、滑らかな製品が得られる。Further, when a plasticizer having a higher alkyl group (having 8 or more carbon atoms, especially 10 to 20) is applied, the water repellency of the molded product is enhanced, the biodegradability is reduced, and the decomposition rate is considerably controlled. Can be done. Similarly, the plasticizer also acts as a mold release agent, is useful for improving the efficiency of the molding process, and also has the effect of reducing the surface friction coefficient of the molded product, so that a smooth product can be obtained.
【００３４】本発明に従って、可塑剤の種類や添加率を
大巾に変えることが出来、柔軟性、成型性、耐熱性など
を極めて広範に変えることが出来、変化に富む製品（成
型品）を得ることが出来る。According to the present invention, the type and the addition rate of the plasticizer can be widely changed, and the flexibility, moldability, heat resistance, etc. can be changed in a very wide range, and a product (molded product) that is rich in change can be obtained. You can get it.
【００３５】本発明組成物が好適である成型品の例とし
ては、繊維、編物、織物、不織布、紙、網、ロープ、フ
ィルム、シート、板、棒、各種容器、チューブ、各種部
品、その他各種の成型品があげられる。Examples of molded articles for which the composition of the present invention is suitable include fibers, knits, woven fabrics, non-woven fabrics, papers, nets, ropes, films, sheets, plates, rods, various containers, tubes, various parts, and various other types. Molded products can be mentioned.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 71:02） Ｃ０８Ｌ 71:02 (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 67/00 C08L 67/04 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 identification code FI C08L 71:02) C08L 71:02 (58) Fields investigated (Int.Cl. 7 , DB name) C08L 67/00 C08L 67 / 04
Claims (3)
ポリアルキレンエーテル（Ｂ）とが重量比（Ａ／Ｂ）99
/1〜50/50 で共重合された共重合ポリ乳酸（Ｃ）の中
に、分子量2,000 以上（但し100,000より大きいものを
除く）のポリアルキレンエーテルを主成分とする可塑剤
（Ｄ）が、重量比（Ｄ／Ｃ）1/99〜50/50 の範囲で混合
されていることを特徴とする、可塑化されたポリ乳酸組
成物。1. A weight ratio (A / B) 99 of polylactic acid (A) and polyalkylene ether (B) having a molecular weight of 2,000 or more.
In the copolymerized polylactic acid (C) copolymerized at / 1 to 50/50, a plasticizer (D) containing a polyalkylene ether having a molecular weight of 2,000 or more (excluding those larger than 100,000) as a main component is A plasticized polylactic acid composition, which is mixed in a weight ratio (D / C) of 1/99 to 50/50.
ングリコール、ポリプロピレングリコール、ポリブチレ
ンエーテル及びその共重合体の群より選ばれた１種又は
２種以上のものである請求項１記載の組成物 。2. The composition according to claim 1, wherein the polyalkylene ether is one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polybutylene ether and copolymers thereof.
成物よりなる繊維、編物、織物、不織布、フェルト、
紙、網、ロープ、フィルム、シート、板、チューブ、
棒、容器、各種部品又はその他の成型品。3. A fiber, a knitted fabric, a woven fabric, a non-woven fabric, a felt, which comprises the composition according to claim 1.
Paper, net, rope, film, sheet, board, tube,
Rods, containers, various parts or other molded products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01172495A JP3391133B2 (en) | 1995-01-27 | 1995-01-27 | Plasticized polylactic acid and its molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01172495A JP3391133B2 (en) | 1995-01-27 | 1995-01-27 | Plasticized polylactic acid and its molded product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08199052A JPH08199052A (en) | 1996-08-06 |
| JP3391133B2 true JP3391133B2 (en) | 2003-03-31 |
Family
ID=11785992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01172495A Expired - Fee Related JP3391133B2 (en) | 1995-01-27 | 1995-01-27 | Plasticized polylactic acid and its molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3391133B2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020035888A (en) | 1999-10-08 | 2002-05-15 | 쿼리, 안토니 | Vehicle mounted plastics drum for concrete mixing and methods of manufacture therof |
| EP1188781B1 (en) | 2000-03-22 | 2008-01-23 | Dainippon Ink And Chemicals, Inc. | Impact modifier and polyester composition containing the modifier |
| JP2002187964A (en) * | 2000-12-21 | 2002-07-05 | Toray Ind Inc | Polyester film for molding |
| JP2003082212A (en) * | 2001-09-13 | 2003-03-19 | Unitika Ltd | Biodegradable resin film |
| JP2003169967A (en) * | 2001-12-07 | 2003-06-17 | Asahi Kasei Corp | Fiber for hair of doll |
| EP1489121B1 (en) | 2002-03-26 | 2007-10-17 | Dainippon Ink And Chemicals, Inc. | Modifier for polylactic acid and polylactic acid composition containing the modifier |
| CN100395286C (en) | 2002-06-20 | 2008-06-18 | 东丽株式会社 | Polylactic acid base polymer composition molding thereof and film |
| JP3980446B2 (en) | 2002-08-13 | 2007-09-26 | 富士通株式会社 | Biodegradable resin composition, and filler and molded article for biodegradable resin composition |
| US7714077B2 (en) | 2003-07-07 | 2010-05-11 | Nof Corporation | Triblock copolymer, method for producing the same, and biocompatible material |
| JP5277531B2 (en) * | 2005-11-29 | 2013-08-28 | 東レ株式会社 | Resin composition and molded article comprising the same |
| MX2010013139A (en) | 2008-05-30 | 2011-03-04 | Kimberly Clark Worldwide Incorporated | Polylactic acid fibers. |
| JP5557435B2 (en) * | 2008-08-29 | 2014-07-23 | 株式会社Ａｄｅｋａ | Smoothing agent for solution casting process |
| JP6443432B2 (en) * | 2016-12-22 | 2018-12-26 | 大日本印刷株式会社 | Sealant film for packaging material, laminated film for packaging material, and packaging bag using plant-derived polyethylene |
| JP6439779B2 (en) * | 2016-12-22 | 2018-12-19 | 大日本印刷株式会社 | Sealant film for packaging material, laminated film for packaging material, and packaging bag using plant-derived polyethylene |
| JP2020012089A (en) * | 2018-07-20 | 2020-01-23 | シンコー技研株式会社 | Resin composition, resin molding, and method for producing resin composition |
-
1995
- 1995-01-27 JP JP01172495A patent/JP3391133B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08199052A (en) | 1996-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3391133B2 (en) | Plasticized polylactic acid and its molded product | |
| EP1881035B1 (en) | Biodegradable resin composition and molded article produced from the same | |
| CA1339026C (en) | Degradable thermoplastics from lactides | |
| WO1990001521A1 (en) | Degradable thermoplastic from lactides | |
| JP3666172B2 (en) | Naturally decomposable resin composition and molded product thereof | |
| EP2710076A1 (en) | Biologically degradable polymeric composition with high deformability | |
| JP3443603B2 (en) | Polylactic acid block copolymer composition, method for producing the same, and molded article | |
| JP3348752B2 (en) | Plasticized polylactic acid composition and molded article thereof | |
| US5352735A (en) | Polymer blends | |
| JPH08283557A (en) | Plasticized polylactic acid composition and its molded item | |
| JP3508678B2 (en) | Polylactic acid composition and molded article thereof | |
| JP2004359840A (en) | Resin composition, its molded product and disperse aid | |
| JP3729565B2 (en) | Method for producing polylactic acid composition | |
| JP3399130B2 (en) | Plasticized polylactic acid and its molded product | |
| JP3419127B2 (en) | Plasticized polylactic acid and its molded product | |
| JP3584579B2 (en) | Plasticized aliphatic polyester composition and molded article thereof | |
| JP3419575B2 (en) | Polylactic acid composition and molded product thereof | |
| JP3394347B2 (en) | Biodegradable polyester composition and molded article thereof | |
| JP2005126701A (en) | Molded product made from polylactic acid-based polymer composition | |
| JP3702410B2 (en) | Polylactic acid composition | |
| JP3471109B2 (en) | Polylactic acid copolymer and molded product thereof | |
| JP3350618B2 (en) | Polylactic acid copolymer and method for producing the same | |
| JP3608007B2 (en) | Decomposition accelerator | |
| JP3385329B2 (en) | Biodegradable polyester composition and molded article thereof | |
| Zhang et al. | The influence of epoxy functionalized acrylate particles on the properties of plasticized PLA blown films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080124 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090124 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090124 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100124 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110124 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110124 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120124 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130124 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130124 Year of fee payment: 10 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130124 Year of fee payment: 10 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130124 Year of fee payment: 10 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130124 Year of fee payment: 10 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130124 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140124 Year of fee payment: 11 |
|
| LAPS | Cancellation because of no payment of annual fees |