JPH08176331A - Polylactic acid porous film and production thereof - Google Patents
Polylactic acid porous film and production thereofInfo
- Publication number
- JPH08176331A JPH08176331A JP32585394A JP32585394A JPH08176331A JP H08176331 A JPH08176331 A JP H08176331A JP 32585394 A JP32585394 A JP 32585394A JP 32585394 A JP32585394 A JP 32585394A JP H08176331 A JPH08176331 A JP H08176331A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polylactic acid
- lactic acid
- stretching
- porous film
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリ乳酸多孔質フイル
ム及びその製造方法に関する。FIELD OF THE INVENTION The present invention relates to a polylactic acid porous film and a method for producing the same.
【０００２】[0002]
【従来の技術】ポリエチレン、ポリプロピレン等のポリ
オレフイン系樹脂に非相溶性物質を配合してフイルム化
した後、延伸して多孔質フイルムとする方法が知られて
いる。このような多孔質フイルムは医療材料、衛生材
料、包装材料等の種々の分野で使い捨ての用途に使用さ
れている。しかしながら、このようなフイルムは自然環
境中で分解されないため、現在大きな社会問題となって
いる。2. Description of the Related Art There is known a method in which a polyolefin resin such as polyethylene or polypropylene is mixed with an incompatible substance to form a film, which is then stretched to form a porous film. Such a porous film is used for disposable applications in various fields such as medical materials, sanitary materials and packaging materials. However, since such a film is not decomposed in the natural environment, it is currently a big social problem.
【０００３】自然環境中で分解される材料からなる多孔
質フイルムは特開平５−２４７２４５号公報に提案され
ているが、フイルムを多孔質化させるために充填剤が添
加されるが、この充填剤がフイルム中に残留するという
問題があり、充填剤の種類によってはかかる多孔質フイ
ルムを医療用、衛生用等に用いることができないという
問題点がある。A porous film made of a material that is decomposed in a natural environment is proposed in Japanese Patent Laid-Open No. 247245/1993. A filler is added to make the film porous. Remains in the film, and there is a problem that such a porous film cannot be used for medical purposes, hygiene purposes, etc. depending on the type of filler.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上述した如
き問題点を有さず、自然環境中で生分解性を有し、且つ
充填剤等の残留成分のないポリ乳酸多孔質フイルム及び
その製造方法を提供することを目的としている。The present invention does not have the above-mentioned problems, is biodegradable in a natural environment, and has no residual component such as a filler, and a polylactic acid porous film thereof. It is intended to provide a manufacturing method.
【０００５】[0005]
【課題を解決するための手段】即ち、本発明は、光学活
性なポリ乳酸からなり、フイルム中に微細孔を１０〜６
０体積％有するポリ乳酸多孔質フイルム、及び次の工程
を含むポリ乳酸多孔質フイルムの製造方法にある。 （１）光学活性なポリ乳酸を未延伸のフイルムにする工
程 （２）該未延伸フイルムを９０℃以下の温度で、少なく
とも一方向に初期長の５倍以上に延伸する工程That is, the present invention is composed of optically active polylactic acid and has 10 to 6 fine pores in the film.
A polylactic acid porous film having 0% by volume and a method for producing a polylactic acid porous film including the following steps. (1) A step of converting optically active polylactic acid into an unstretched film (2) A step of stretching the unstretched film at a temperature of 90 ° C. or lower in at least one direction at least 5 times the initial length
【０００６】本発明で用いられる光学活性なポリ乳酸
は、光学活性なエナンチオマーであるＬ−乳酸又はＤ−
乳酸の単位を９０モル％以上含有するポリ乳酸をいい、
ＤＳＣ等の測定により明瞭な融点を有する結晶性重合体
である。The optically active polylactic acid used in the present invention is L-lactic acid or D-lactic acid which is an optically active enantiomer.
Polylactic acid containing 90 mol% or more of lactic acid units,
It is a crystalline polymer having a clear melting point as measured by DSC or the like.
【０００７】なお、本発明のフイルムとしての性能を損
なわない範囲であれば、少量の他の共重合性成分が共重
合されていてもよい。好ましい他の共重合性成分の具体
例としては、例えばグリコール酸、３−ヒドロキシ酪
酸、４−ヒドロキシ酪酸、４−ヒドロキシ吉草酸等が挙
げられる。これらの共重合性成分は、乳酸と直接脱水重
縮合により合成してもよく、又、乳酸の環状二量体であ
るラクチドとグリコリド、ε−カプロラクトン等の環状
エステルとの開環重合により合成したものでもよい。Incidentally, a small amount of another copolymerizable component may be copolymerized as long as the performance of the film of the present invention is not impaired. Specific examples of preferable other copolymerizable components include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, and 4-hydroxyvaleric acid. These copolymerizable components may be synthesized by direct dehydration polycondensation with lactic acid, or by ring-opening polymerization of lactide, which is a cyclic dimer of lactic acid, and a cyclic ester such as glycolide or ε-caprolactone. It may be one.
【０００８】本発明で用いられる光学活性なポリ乳酸
は、公知の任意の方法により合成される。例えば、乳酸
を不活性気体中又は減圧下で直接脱水してポリ乳酸とす
る直接重合法や、乳酸を環状二量体とした後に開環重合
してポリ乳酸とする方法等が挙げられる。これらの反応
の際に適宜触媒を用いて反応の速度を上げたりすること
もできる。The optically active polylactic acid used in the present invention is synthesized by any known method. For example, a direct polymerization method of directly dehydrating lactic acid in an inert gas or under reduced pressure to obtain polylactic acid, a method of converting lactic acid into a cyclic dimer and then ring-opening polymerization to obtain polylactic acid, and the like can be mentioned. During these reactions, a catalyst may be appropriately used to increase the reaction rate.
【０００９】本発明で用いられるポリ乳酸の分子量は、
得られるフイルムの機械的強度の観点から重量平均分子
量で２万以上であるものが好ましい。The molecular weight of the polylactic acid used in the present invention is
From the viewpoint of mechanical strength of the obtained film, a film having a weight average molecular weight of 20,000 or more is preferable.
【００１０】本発明のポリ乳酸多孔質フイルムは、多孔
質構造が形成され、フイルム中に微細孔を空孔率で１０
〜６０体積％有するものである。微細孔が１０体積％未
満では、フイルムの自然環境中での分解速度が遅く、
又、通気性や透湿性が低いために医療用途や衛生用途に
適しにくい面がある。又、微細孔が６０体積％を超える
と、フイルムの機械的物性が著しく低下する傾向となる
ため好ましくない。In the polylactic acid porous film of the present invention, a porous structure is formed and fine pores are formed in the film with a porosity of 10 or less.
-60% by volume. If the fine pores are less than 10% by volume, the decomposition rate of the film in the natural environment is slow,
In addition, since it has low air permeability and moisture permeability, it is not suitable for medical and hygiene applications. On the other hand, if the fine pores exceed 60% by volume, the mechanical properties of the film tend to be remarkably deteriorated, which is not preferable.
【００１１】本発明におけるポリ乳酸多孔質フイルムを
製造するには、少なくとも（１）光学活性なポリ乳酸を
未延伸のフイルムにする工程、（２）かかるポリ乳酸の
未延伸フイルムを９０℃以下の温度で少なくとも一方向
に初期長の５倍以上に延伸する工程を含むことが必要で
ある。In order to produce the polylactic acid porous film of the present invention, at least (1) the step of converting the optically active polylactic acid into an unstretched film, (2) the unstretched film of the polylactic acid at 90 ° C. or lower. It is necessary to include a step of stretching at least 5 times the initial length in at least one direction at a temperature.
【００１２】（１）の工程においては、光学活性なポリ
乳酸をフイルム化する公知の任意の方法を用いることが
できる。例えば、光学活性なポリ乳酸を加熱溶融して、
押出機の先端に取り付けたＴダイから押し出して未延伸
のフイルムとする方法、光学活性なポリ乳酸を溶媒中に
溶解した溶液を平滑なガラス基板上にキャストして、そ
の後溶媒を蒸発させて未延伸のフイルムとする方法、さ
らには光学活性なポリ乳酸を溶媒中に溶解した溶液を平
滑なガラス基板上にキャストした後、これを非溶媒中に
浸漬して溶媒を除去し未延伸のフイルムとする方法等が
用いられる。用いるＴダイ等の形状、サイズ等は目的と
する多孔質フイルムの使用目的に応じて適宜選択すれば
よく、特に限定されるものではない。In the step (1), any known method for film-forming optically active polylactic acid can be used. For example, by heating and melting optically active polylactic acid,
A method in which an unstretched film is extruded from a T-die attached to the tip of an extruder, a solution of optically active polylactic acid dissolved in a solvent is cast on a smooth glass substrate, and then the solvent is evaporated to obtain an unstretched film. A method of stretching film, further cast a solution of optically active polylactic acid dissolved in a solvent on a smooth glass substrate, and then dipping it in a non-solvent to remove the solvent and unstretched film. And the like are used. The shape and size of the T-die used may be appropriately selected according to the intended use of the porous film, and is not particularly limited.
【００１３】このようにして製造された光学活性なポリ
乳酸からなる未延伸フイルムは、必要に応じてアニール
することにより結晶状態を制御した後、次の延伸工程に
供される。（２）の延伸工程においては、この未延伸フ
イルムを９０℃以下の温度で少なくとも一方向に初期長
の５倍以上に延伸する。The unstretched film made of the optically active polylactic acid produced as described above is annealed as needed to control the crystalline state and then subjected to the subsequent stretching step. In the stretching step (2), this unstretched film is stretched at a temperature of 90 ° C. or lower in at least one direction at least 5 times the initial length.
【００１４】延伸処理は一定のサイズのフイルムをバッ
チで延伸する方法や連続したフイルムを連続的に延伸す
る方法のいずれの方法によってもよい。又、一軸延伸、
逐次二軸延伸、同時二軸延伸等いずれの方法で行っても
よく、少なくとも一方向に初期長の５倍以上に延伸する
ことが重要である。さらに又、延伸は一段で行ってもよ
く、温度、延伸倍率、変形速度等を変えて多段方式で行
ってもよい。例えば、室温以下の温度で一軸冷延伸を行
った後、９０℃以下の温度で同一方向に総延伸倍率が初
期長の５倍以上となるように延伸する等の任意の延伸方
式を採用してよい。The stretching treatment may be carried out by any of a method of stretching a film of a certain size in a batch and a method of continuously stretching a continuous film. Also, uniaxial stretching,
Any method such as sequential biaxial stretching or simultaneous biaxial stretching may be used, and it is important to stretch at least 5 times the initial length in at least one direction. Furthermore, the stretching may be carried out in a single stage, or may be carried out in a multistage system by changing the temperature, the stretching ratio, the deformation speed and the like. For example, an arbitrary stretching method such as uniaxial cold stretching at a temperature of room temperature or lower and then stretching at a temperature of 90 ° C. or lower so that the total stretching ratio is 5 times or more of the initial length is adopted. Good.
【００１５】延伸温度は９０℃以下の温度である必要が
あり、延伸温度が９０℃を超えると、延伸フイルム中に
微細孔が形成されにくく多孔質構造となりにくい。又、
延伸倍率は少なくとも一方向に初期長の５倍以上である
ことが必要であり、延伸倍率が５倍未満では、延伸フイ
ルム中の微細孔の形成が不十分であり、１０体積％以上
の空孔率を有するフイルムを得ることが困難となる。The stretching temperature needs to be 90 ° C. or lower, and when the stretching temperature is higher than 90 ° C., it is difficult to form fine pores in the stretched film and it is difficult to form a porous structure. or,
The draw ratio must be at least 5 times the initial length in at least one direction. If the draw ratio is less than 5 times, the formation of fine pores in the stretched film is insufficient, and the void volume of 10% by volume or more. It becomes difficult to obtain a film having a high rate.
【００１６】本発明の実施に際しては、目的に応じて適
宜（２）の延伸工程の後で延伸したフイルムを緊張下で
熱処理を行ってもよい。In carrying out the present invention, the stretched film may be heat-treated under tension after the stretching step (2) depending on the purpose.
【００１７】本発明における上記（１）及び（２）の工
程の実施は、各々バッチで行ってもよいが、これらの工
程を連続させて行ってもよい。The above steps (1) and (2) in the present invention may be carried out in batches, but these steps may be carried out continuously.
【００１８】本発明においては、上記（１）及び（２）
の工程を含む製造方法により、ポリ乳酸フイルム中に微
細孔を１０〜６０体積％有する多孔質化された構造を形
成することができる。In the present invention, the above (1) and (2)
According to the production method including the step of (1), it is possible to form a porous structure having 10 to 60% by volume of fine pores in the polylactic acid film.
【００１９】本発明によるポリ乳酸多孔質フイルムは、
その使用目的に応じて、そのままの状態で用いたり、又
は任意の形態に加工して用いることができる。The polylactic acid porous film according to the present invention comprises:
Depending on the purpose of use, it can be used as it is, or can be used after being processed into an arbitrary form.
【００２０】[0020]
【実施例】以下、本発明を実施例によりさらに詳しく説
明するが、これらに限定されるものではない。The present invention will be described in more detail with reference to the following examples, but the invention is not limited thereto.
【００２１】実施例１ 重量平均分子量が４５０，０００であるポリＬ−乳酸を
クロロホルムに溶解し、その溶液をガラス基板上にキャ
ストした。この後、クロロホルムを蒸発させて未延伸の
ポリＬ−乳酸フイルムを作成した。Example 1 Poly L-lactic acid having a weight average molecular weight of 450,000 was dissolved in chloroform, and the solution was cast on a glass substrate. Then, chloroform was evaporated to prepare an unstretched poly L-lactic acid film.
【００２２】しかる後、かかる未延伸フイルムをガラス
基板から剥離し、剥離したフイルムを窒素雰囲気下７０
℃で８倍に一軸延伸し、次いで７５℃で２分間緊張下で
定長熱処理を行った。Thereafter, the unstretched film was peeled from the glass substrate, and the peeled film was removed in a nitrogen atmosphere 70
It was uniaxially stretched at 8 ° C. to 8 times, and then subjected to constant length heat treatment at 75 ° C. for 2 minutes under tension.
【００２３】得られた一軸延伸フイルムは膜厚１２．５
μｍであり、延伸方向の強度は３７．５ｋｇ／ｍｍ2、
伸度３３．５％であり、又、この延伸フイルムは微細孔
を有する多孔質構造を形成しており、空孔率が４３．５
体積％であった。The uniaxially stretched film thus obtained has a film thickness of 12.5.
μm, the strength in the stretching direction is 37.5 kg / mm 2 ,
The elongation is 33.5%, and the stretched film has a porous structure having fine pores and has a porosity of 43.5%.
% By volume.
【００２４】実施例２ 実施例１で得た未延伸フイルムを窒素雰囲気下９０℃で
１０倍に一軸延伸し、次いで９５℃で２分間緊張下で定
長熱処理を行った。Example 2 The unstretched film obtained in Example 1 was uniaxially stretched 10 times at 90 ° C. in a nitrogen atmosphere, and then subjected to a fixed length heat treatment at 95 ° C. for 2 minutes under tension.
【００２５】得られた一軸延伸フイルムは膜厚９．８μ
ｍであり、延伸方向の強度は３１．５ｋｇ／ｍｍ2、伸
度３８．５％であり、又、この延伸フイルムは微細孔を
有する多孔質構造を形成しており、空孔率が５７．８体
積％であった。The uniaxially stretched film thus obtained has a film thickness of 9.8 μm.
m, the strength in the stretching direction was 31.5 kg / mm 2 , the elongation was 38.5%, and the stretched film had a porous structure with fine pores and a porosity of 57. It was 8% by volume.
【００２６】実施例３ 重量平均分子量が２２４，０００、融点１７８℃のポリ
Ｌ−乳酸を１９０℃でＴダイより溶融押出して未延伸フ
イルムとした。Example 3 Poly L-lactic acid having a weight average molecular weight of 224,000 and a melting point of 178 ° C. was melt extruded from a T die at 190 ° C. to obtain an unstretched film.
【００２７】しかる後、かかる未延伸フイルムを８０℃
で５倍に一軸延伸し、次いで９０℃で緊張下で定長熱処
理を行った。Thereafter, the unstretched film was heated to 80 ° C.
Was uniaxially stretched to 5 times and then subjected to constant length heat treatment at 90 ° C. under tension.
【００２８】得られた一軸延伸フイルムは膜厚２５．３
μｍであり、延伸方向の強度は３１．５ｋｇ／ｍｍ2、
伸度２８．５％であり、又、この延伸フイルムは微細孔
を有する多孔質構造を形成しており、空孔率が２３．８
体積％であった。The obtained uniaxially stretched film has a film thickness of 25.3.
μm, the strength in the stretching direction is 31.5 kg / mm 2 ,
The elongation is 28.5%, and the stretched film has a porous structure having fine pores and has a porosity of 23.8.
% By volume.
【００２９】比較例１ 実施例３において、未延伸フイルムを１００℃で一軸延
伸した以外は実施例３と同様にして延伸フイルムを得
た。得られた延伸フイルムは、微細孔がなく非多孔質で
あった。Comparative Example 1 A stretched film was obtained in the same manner as in Example 3 except that the unstretched film was uniaxially stretched at 100 ° C. The stretched film obtained was non-porous with no fine pores.
【００３０】比較例２ 実施例３において、未延伸フイルムを９０℃で３倍に一
軸延伸した以外は実施例３と同様にして延伸フイルムを
得た。得られた延伸フイルムは、不十分な多孔質であ
り、空孔率３．２体積％であった。Comparative Example 2 A stretched film was obtained in the same manner as in Example 3, except that the unstretched film was uniaxially stretched at 90 ° C. by 3 times. The obtained stretched film was insufficiently porous and had a porosity of 3.2% by volume.
【００３１】実施例４ 実施例１で得た未延伸フイルムを１１０℃で２４時間ア
ニールした後、２０℃で１．１倍に一軸冷延伸し、次い
で９０℃で同一方向に総延伸倍率８倍となるように延伸
し、次いで９５℃で緊張下で定長熱処理を行った。Example 4 The unstretched film obtained in Example 1 was annealed at 110 ° C. for 24 hours, uniaxially cold stretched at 20 ° C. to 1.1 times, and then at 90 ° C. in the same direction at a total stretching ratio of 8 times. The film was stretched so as to have the following length, and then subjected to constant length heat treatment at 95 ° C. under tension.
【００３２】得られた一軸延伸フイルムは膜厚１１．９
μｍであり、延伸方向の強度は２８．０ｋｇ／ｍｍ2、
伸度２５．１％であり、又、この延伸フイルムは微細孔
を有する多孔質構造を形成しており、空孔率が４１．３
体積％であった。The resulting uniaxially stretched film has a film thickness of 11.9.
μm, the strength in the stretching direction is 28.0 kg / mm 2 ,
The elongation is 25.1%, and the stretched film has a porous structure having fine pores and has a porosity of 41.3%.
% By volume.
【００３３】実施例５ 実施例１で得た未延伸フイルムを１１０℃で３時間アニ
ールした後、９０℃で縦、横それぞれ２倍に二軸延伸
し、さらに９０℃で縦方向に３倍に一軸延伸し、次いで
９５℃で緊張下で定長熱処理を行った。Example 5 The unstretched film obtained in Example 1 was annealed at 110 ° C. for 3 hours, then biaxially stretched at 90 ° C. in the longitudinal and transverse directions, and further at 90 ° C. in the longitudinal direction. It was uniaxially stretched and then subjected to constant length heat treatment at 95 ° C. under tension.
【００３４】得られた多段延伸フイルムは膜厚１３．３
μｍであり、縦方向の強度は２９．４ｋｇ／ｍｍ2、伸
度２１．３％であり、又、この多段延伸フイルムは微細
孔を有する多孔質構造を形成しており、空孔率が３１．
９体積％であった。The obtained multi-stage stretched film has a film thickness of 13.3.
μm, the strength in the machine direction is 29.4 kg / mm 2 , the elongation is 21.3%, and the multi-stage stretched film has a porous structure having fine pores and has a porosity of 31. ．
It was 9% by volume.
【００３５】[0035]
【発明の効果】本発明によるポリ乳酸多孔質フイルム
は、実質的にポリ乳酸のみからなるため、自然環境中で
の生分解性を有し、又、充填剤等の残留成分もなく、空
孔率で１０〜６０体積％の微細孔を有するため、医療材
料や衛生材料等の用途に好適なものである。EFFECT OF THE INVENTION The polylactic acid porous film according to the present invention is substantially composed of only polylactic acid, and therefore has biodegradability in a natural environment and has no residual components such as fillers and voids. Since it has fine pores of 10 to 60% by volume, it is suitable for applications such as medical materials and sanitary materials.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｌ 7:00 Ｃ０８Ｌ 67:04 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location B29L 7:00 C08L 67:04
Claims (3)
中に微細孔を１０〜６０体積％有するポリ乳酸多孔質フ
イルム。1. A polylactic acid porous film comprising optically active polylactic acid and having 10 to 60% by volume of fine pores in the film.
上、又はＤ−乳酸単位が９０モル％以上であることを特
徴とする請求項１記載のポリ乳酸多孔質フイルム。2. The polylactic acid porous film according to claim 1, wherein the polylactic acid has an L-lactic acid unit content of 90 mol% or more, or a D-lactic acid unit content of 90 mol% or more.
の製造方法。 （１）光学活性なポリ乳酸を未延伸のフイルムにする工
程 （２）該未延伸フイルムを９０℃以下の温度で、少なく
とも一方向に初期長の５倍以上に延伸する工程3. A method for producing a polylactic acid porous film, which comprises the steps of: (1) A step of converting optically active polylactic acid into an unstretched film (2) A step of stretching the unstretched film at a temperature of 90 ° C. or lower in at least one direction at least 5 times the initial length
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32585394A JPH08176331A (en) | 1994-12-27 | 1994-12-27 | Polylactic acid porous film and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32585394A JPH08176331A (en) | 1994-12-27 | 1994-12-27 | Polylactic acid porous film and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08176331A true JPH08176331A (en) | 1996-07-09 |
Family
ID=18181356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32585394A Pending JPH08176331A (en) | 1994-12-27 | 1994-12-27 | Polylactic acid porous film and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08176331A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6600008B1 (en) | 1998-07-22 | 2003-07-29 | Toyo Boseki Kabushiki Kaisha | Aliphatic polyester film and gas barrier film |
| CN102791465A (en) * | 2010-03-30 | 2012-11-21 | 尤妮佳股份有限公司 | Film having moisture permeability and water-proof properties, and process for production thereof |
| CN109575538A (en) * | 2017-09-29 | 2019-04-05 | 东丽先端材料研究开发（中国）有限公司 | A kind of micro- porous orientation polylactic acid film |
-
1994
- 1994-12-27 JP JP32585394A patent/JPH08176331A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6600008B1 (en) | 1998-07-22 | 2003-07-29 | Toyo Boseki Kabushiki Kaisha | Aliphatic polyester film and gas barrier film |
| US6649732B2 (en) | 1998-07-22 | 2003-11-18 | Toyo Boseki Kabushiki Kaisha | Aliphatic polyester film and gas barrier film |
| CN102791465A (en) * | 2010-03-30 | 2012-11-21 | 尤妮佳股份有限公司 | Film having moisture permeability and water-proof properties, and process for production thereof |
| CN109575538A (en) * | 2017-09-29 | 2019-04-05 | 东丽先端材料研究开发（中国）有限公司 | A kind of micro- porous orientation polylactic acid film |
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