JPH11320674A - Method for stretching process of aliphatic polyester sheet - Google Patents
Method for stretching process of aliphatic polyester sheetInfo
- Publication number
- JPH11320674A JPH11320674A JP2797699A JP2797699A JPH11320674A JP H11320674 A JPH11320674 A JP H11320674A JP 2797699 A JP2797699 A JP 2797699A JP 2797699 A JP2797699 A JP 2797699A JP H11320674 A JPH11320674 A JP H11320674A
- Authority
- JP
- Japan
- Prior art keywords
- plla
- polylactic acid
- pcl
- poly
- caprolactone
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、成形が可能な脂肪
族ポリエステル系で使用後に、土壌中、水中で、分解可
能な新規な生分解性ポリエステルシートの延伸加工方法
に関するものである。さらに詳しくは、本発明は、例え
ば、農業、畜産、漁業用分野で使用されるシートや文
具、日用品に好適に利用できる新規な生分解性ポリエス
テルシートの延伸加工方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for stretching a biodegradable polyester sheet which can be decomposed in soil or water after being used in a moldable aliphatic polyester system. More specifically, the present invention relates to a novel method for stretching a biodegradable polyester sheet that can be suitably used for, for example, sheets, stationery, and daily necessities used in the fields of agriculture, livestock, and fisheries.
【０００２】[0002]
【従来の技術】生分解性とは、材料が土壌中、又は、海
水、淡水などの水中で微生物や酵素によって分解され、
低分子になる現象である。従来から、脂肪族ポリエステ
ルの一部は生分解性を示すことが知られており、ポリ乳
酸、ポリ（ε−カプロラクトン）は、この現象が顕著で
ある。ポリ乳酸にポリ（ε−カプロラクトン）をブレン
ドすることで、柔軟性や耐衝撃性を付与することができ
る。しかしながら、強度や弾性率を向上させるために
は、高融点成分であるポリ乳酸の分子鎖を配向させる必
要がある。通常の延伸加工法をポリ乳酸とポリ（ε−カ
プロラクトン）のブレンドに適用し、均一な延伸を行う
には、比較的厚みの薄いフィルム状のものである必要が
あった。このために、延伸後のフィルムの厚さに制限が
あり、力学的性質も満足な状況とはいえない状況にあ
る。2. Description of the Related Art Biodegradability means that a material is decomposed by microorganisms or enzymes in soil or in water such as seawater or freshwater.
This is the phenomenon of becoming low molecular. Hitherto, it has been known that some aliphatic polyesters exhibit biodegradability, and this phenomenon is remarkable in polylactic acid and poly (ε-caprolactone). By blending poly (ε-caprolactone) with polylactic acid, flexibility and impact resistance can be imparted. However, in order to improve strength and elastic modulus, it is necessary to orient the molecular chains of polylactic acid, which is a high melting point component. In order to apply a normal stretching method to a blend of polylactic acid and poly (ε-caprolactone) and perform uniform stretching, the film had to be relatively thin and film-shaped. For this reason, the thickness of the film after stretching is limited, and the mechanical properties are not satisfactory.
【０００３】[0003]
【発明が解決しようとする課題】本発明の課題は、ポリ
乳酸とポリ（ε−カプロラクトン）のブレンドからな
り、生分解性を示し、かつ、厚みのあるシート状成形物
に高融点成分であるポリ乳酸の分子鎖配向を付与するた
めの延伸方法を提供することである。An object of the present invention is to provide a biodegradable and thick sheet-like molded product comprising a blend of polylactic acid and poly (ε-caprolactone) and having a high melting point component. An object of the present invention is to provide a stretching method for imparting the molecular chain orientation of polylactic acid.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意検討した結果、本発明を完成するに至
った。即ち、本発明によれば、ポリ乳酸とポリ（ε−カ
プロラクトン）を主成分とする高分子ブレンド組成物か
らなるシートを、下式（１）の温度Ｔｓ（℃）に加熱し
た一対のロールの間隙から引き抜いて、一軸方向に３倍
以上の延伸比を与える高配向延伸加工方法が提供され
る。 [Tg(PLLA) × W(PLLA) + ｛Tm (PCL)−40｝×W(PCL)]/1
00 ＜ Ts ≦ [{Tm(PLLA) - 80｝× W(PLLA) + ｛Tm (PCL)−30｝×W
(PCL)]/100 （１） ［但し、Ｔｇ（ＰＬＬＡ）はポリ乳
酸のガラス転移温度（℃）であり、Ｗ（ＰＬＬＡ）はポ
リ乳酸の重量％、Ｔｍ（ＰＣＬ）はポリ（ε−カプロラ
クトン）の融点（℃）、Ｗ（ＰＣＬ）はポリ（ε−カプ
ロラクトン）の重量％、Ｔｍ（ＰＬＬＡ）はポリ乳酸の
融点である］Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, according to the present invention, a sheet made of a polymer blend composition containing polylactic acid and poly (ε-caprolactone) as main components is heated to a temperature Ts (° C.) of the following formula (1). There is provided a highly oriented stretching method of drawing from a gap to give a stretching ratio of 3 times or more in a uniaxial direction. [Tg (PLLA) × W (PLLA) + ｛Tm (PCL) −40｝ × W (PCL)] / 1
00 <Ts ≤ [(Tm (PLLA)-80｝ × W (PLLA) + ｛Tm (PCL) −30｝ × W
(PCL)] / 100 (1) [where Tg (PLLA) is the glass transition temperature (° C.) of polylactic acid, W (PLLA) is the weight% of polylactic acid, and Tm (PCL) is poly (ε-caprolactone). ), W (PCL) is the weight% of poly (ε-caprolactone), and Tm (PLLA) is the melting point of polylactic acid.]
【０００５】[0005]
【発明の実施の形態】本発明の方法においては、ポリ乳
酸とポリ（ε−カプロラクトン）を主成分とする高分子
ブレンド組成物からなるシートを被処理原料として用い
る。この場合、前記高分子ブレンド組成物としては、ポ
リ乳酸とポリ（ε−カプロラクトン）をあらかじめドラ
イブレンドした後、二軸押出機を用いて、溶融混練する
ことで得られるポリ乳酸とポリ（ε−カプロラクトン）
を主成分とする高分子ブレンド組成物であって、該ポリ
乳酸の含有量が２５〜１００重量％未満、好ましくは５
０〜１００重量％未満の範囲、であるものの使用が好ま
しい。本発明の高配向性延伸加工方法においては、前記
高分子ブレンド組成物シートを一対のロールの間隙から
引き抜いて、一軸方向に３倍以上の延伸比を与え、高融
点成分であるポリ乳酸の分子鎖を高度に配向させるが、
この場合、そのロール引き抜き方法それ自体はポリエチ
レン等の高分子の延伸に適用され、公知の方法である
（たとえば特開昭５９−２２０３２９）。また、ポリ乳
酸とポリ（ε−カプロラクトン）が、生分解性を示すこ
とは公知である。しかしながら、本発明者等の知る限
り、ロール引き抜き法を脂肪族ポリエステルの延伸加工
ブレンド組成物に適用した報告はなされておらず、勿論
それにより得られるブレンド成形物に適用した報告もな
されていない。ポリ乳酸とポリ（ε−カプロラクトン）
を主成分とする高分子ブレンド組成物からなるシートを
本発明による温度条件に加熱した一対のロールの間隙か
ら引き抜いて、一軸方向に３倍以上の延伸比を与え、高
融点成分のポリ乳酸の分子鎖を高度に配向させる延伸加
工方法は本発明者らによって初めて見い出されたもので
ある。次に添付図面によって、本発明方法を説明する。
図１は、本発明の実施態様を示すローラ部分であって、
シート３をローラ１の内部に取り付けたヒータで所定の
温度に加熱した一対のロ−ラ１，１の間から張力を加え
て引き抜き、目的のシート４を得る。このローラの間隙
は調節可能であり、種々の厚さのシートを得ることがで
きる。本発明では、ポリ乳酸には、そのＬ−体、Ｄ−体
及びＤＬ−体が包含されるが、本発明の場合、Ｌ−体を
７０〜１００重量％含有するもの、又は、Ｄ−体を７０
〜１００重量％含有するもの、好ましくは、ポリ（Ｌ−
乳酸）の使用が好ましい。ＤＬ−体の含有量が高いと結
晶性の低下が生じるのであまり好ましいものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the method of the present invention, a sheet composed of a polymer blend composition containing polylactic acid and poly (ε-caprolactone) as main components is used as a raw material to be treated. In this case, as the polymer blend composition, polylactic acid and poly (ε-caprolactone) are dry-blended in advance, and then melt-kneaded using a twin-screw extruder to obtain polylactic acid and poly (ε-caprolactone). Caprolactone)
A polymer blend composition comprising, as a main component, a polylactic acid having a content of 25 to less than 100% by weight, preferably 5 to 100% by weight.
It is preferred to use those in the range of 0 to less than 100% by weight. In the highly oriented stretching method of the present invention, the polymer blend composition sheet is pulled out from a gap between a pair of rolls to give a stretching ratio of 3 times or more in one axis direction, and the molecular weight of polylactic acid as a high melting point component is increased. Highly oriented chains,
In this case, the roll drawing method itself is applied to stretching of a polymer such as polyethylene and is a known method (for example, JP-A-59-220329). It is known that polylactic acid and poly (ε-caprolactone) exhibit biodegradability. However, to the knowledge of the present inventors, there have been no reports that the roll drawing method has been applied to a stretch blend composition of an aliphatic polyester, and, of course, no report has been made that the roll drawing method has been applied to a blend molded product obtained thereby. Polylactic acid and poly (ε-caprolactone)
A sheet made of a polymer blend composition containing as a main component is drawn out from a gap between a pair of rolls heated to a temperature condition according to the present invention, and a stretching ratio of 3 times or more is provided in a uniaxial direction, and polylactic acid of a high melting point component is obtained. A stretching method for highly orienting molecular chains has been found for the first time by the present inventors. Next, the method of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a roller portion showing an embodiment of the present invention,
The sheet 3 is pulled out by applying tension between a pair of rollers 1 and 1 heated to a predetermined temperature by a heater mounted inside the roller 1 to obtain a target sheet 4. The gap between the rollers is adjustable so that sheets of various thicknesses can be obtained. In the present invention, the polylactic acid includes its L-form, D-form and DL-form. In the present invention, the polylactic acid contains 70 to 100% by weight of the L-form, or the D-form. 70
To 100% by weight, preferably poly (L-
(Lactic acid) is preferred. If the content of the DL-form is high, the crystallinity is reduced, so that it is not so preferable.
【０００６】本発明の生分解性高分子組成物を成形する
には、ポリ乳酸とポリ（ε−カプロラクトン）をあらか
じめドライブレンドしたのち、二軸押出機を用いて、溶
融混練することで得られるポリＬラクチドとポリ（ε−
カプロラクトン）を主成分とする高分子ブレンド組成物
であって、ポリＬラクチドの含有量が２５重量％から１
００重量％未満の範囲、好ましくは、５０重量％から１
００重量％未満の範囲の組成物を、ポリＬ乳酸の融点
（Ｔｍ）である１７４℃以上の温度、好ましくは、１９
０℃から２５０℃の範囲で溶融混練したのち、押出成形
する。これによりシート状の成形物を得ることができ
る。こうして得られたシートを延伸加工後に希望するシ
ート厚みにロール間隙を設定したロールの間から引き抜
くことにより、一軸方向に３倍以上の延伸比を与える。
これにより、高融点成分のポリ乳酸の分子鎖の配向した
シートを得ることができる。シートの一軸方向に与える
延伸比は３倍以上、好ましくは４倍以上である。その上
限値は、通常、６倍程度である。[0006] The biodegradable polymer composition of the present invention can be obtained by dry-blending polylactic acid and poly (ε-caprolactone) in advance, and then melt-kneading using a twin-screw extruder. Poly L lactide and poly (ε-
Caprolactone) as a main component, wherein the content of poly-L-lactide is from 25% by weight to 1%.
Less than 00% by weight, preferably from 50% to 1% by weight.
A composition having a melting point (Tm) of poly-L-lactic acid of 174 ° C. or more, preferably 19
After melt-kneading in the range of 0 ° C to 250 ° C, extrusion molding is performed. Thereby, a sheet-like molded product can be obtained. The sheet thus obtained is drawn out from between the rolls having a roll gap set to a desired sheet thickness after the drawing process, thereby giving a stretch ratio of 3 times or more in the uniaxial direction.
As a result, a sheet in which the molecular chains of the polylactic acid having a high melting point are oriented can be obtained. The stretching ratio given in the uniaxial direction of the sheet is 3 times or more, preferably 4 times or more. The upper limit is usually about six times.
【０００７】[0007]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail with reference to examples.
【０００８】実施例１ 原料のポリ乳酸として、島津製作所製ラクティ１０１２
を用いた。このものの融点（ＤＳＣのピーク温度）は１
７４℃で、ガラス転移温度は６８℃であった。また、ポ
リ（ε−カプロラクトン）として、ＵＣＣ社製ＴＯＮＥ
Ｐ７８７を用いた。このものの融点（ＤＳＣのピーク
温度）は６４℃で、ガラス転移温度は−６２℃であっ
た。両者を真空下で２４時間以上乾燥したのち、室温度
でポリ乳酸９０重量％とポリ（ε−カプロラクトン）１
０重量％の割合でドライブレンドした。この混合物を二
軸押出機内で温度２０５℃に加熱溶融、混練したのち、
幅６０ｍｍ、隙間１．０５ｍｍのＴダイからシート状に
押出し、水中で冷却後に巻き取った。こうして得られた
厚さ約１ｍｍのシートを所定の温度（６８℃）に加熱し
た外径１２０ｍｍ、幅１５０ｍｍの一対のクロムメッキ
した鋼製ローラを用い、ロールの間隙から引き出して延
伸加工したところ、表面状態の良好なシートを得ること
ができた。Example 1 As a raw material polylactic acid, Lacty 1012 manufactured by Shimadzu Corporation was used.
Was used. Its melting point (peak temperature of DSC) is 1
At 74 ° C, the glass transition temperature was 68 ° C. In addition, as poly (ε-caprolactone), TONE manufactured by UCC
P787 was used. Its melting point (DSC peak temperature) was 64 ° C and its glass transition temperature was -62 ° C. After drying both under vacuum for 24 hours or more, 90% by weight of polylactic acid and poly (ε-caprolactone)
Dry blending was performed at a ratio of 0% by weight. This mixture was heated and melted at a temperature of 205 ° C. in a twin-screw extruder and kneaded.
It was extruded into a sheet form from a T-die having a width of 60 mm and a gap of 1.05 mm, and was wound up after cooling in water. Using a pair of chrome-plated steel rollers having an outer diameter of 120 mm and a width of 150 mm heated to a predetermined temperature (68 ° C.), the sheet having a thickness of about 1 mm thus obtained was drawn out from the gap between the rolls and stretched. A sheet having a good surface condition could be obtained.
【０００９】実施例２ 実施例１において、ポリ乳酸とポリ（ε−カプロラクト
ン）の組成比を変えた組成物から得られたシートをロー
ル間隙から引き抜いて延伸加工した際のロールの温度Ｔ
ｓ、延伸比、及び得られたシートに付与されたポリ乳酸
成分の分子配向性を表１に示す。Example 2 In Example 1, a sheet obtained from a composition in which the composition ratio of polylactic acid and poly (ε-caprolactone) was changed was pulled out from a gap between the rolls and stretched to obtain a roll temperature T.
Table 1 shows s, the stretching ratio, and the molecular orientation of the polylactic acid component applied to the obtained sheet.
【００１０】[0010]
【表１】 [Table 1]
【００１１】[0011]
【発明の効果】本発明のポリ乳酸とポリ（ε−カプロラ
クトン）を主成分とする高分子ブレンド組成物からなる
シートは、フィルム状に比べて厚さが大きいにもかかわ
らず、均一な分子鎖の配向を示し、延伸後の表面も平滑
であり、高い強度を示す。本発明の延伸加工方法が厚み
の大きいシートの延伸に適用でき、かつ、良好な延伸シ
ートを与えることができる理由は、ロール温度の範囲を
適切に選ぶことによって、ロールの間隙から引き出され
変形したブレンドのシートが高度に分子鎖配向すること
により、破断や流動することなく、平滑な表面を有する
シート形状を維持できることにある。本発明によって延
伸加工してシート成形物は、弾性率、強度が高く、例え
ば、農業、漁業用分野での、生分解性を必要とする部
品、部材等に好適に利用できる。また、玩具や、日用品
に好適に利用できる。The sheet comprising the polymer blend composition comprising polylactic acid and poly (ε-caprolactone) as the main components of the present invention has a uniform molecular chain despite its thickness being larger than that of a film. And the surface after stretching is smooth and shows high strength. The reason why the stretching method of the present invention can be applied to stretching of a sheet having a large thickness, and that a good stretched sheet can be obtained is that by appropriately selecting the range of the roll temperature, the sheet is drawn from the gap between the rolls and deformed. An object of the present invention is to maintain a shape of a sheet having a smooth surface without breaking or flowing due to a highly oriented molecular chain of a sheet of the blend. The sheet molded product obtained by stretching according to the present invention has a high elastic modulus and high strength, and can be suitably used, for example, for parts and members that require biodegradability in the agricultural and fishery fields. Further, it can be suitably used for toys and daily necessities.
【図１】本発明に用いるロール引き抜き延伸加工装置の
構造を示す断面図。FIG. 1 is a sectional view showing the structure of a roll drawing and stretching apparatus used in the present invention.
１ ローラ ２ 加熱ヒーター ３ 原料シート ４ 引き抜いて延伸加工したシート DESCRIPTION OF SYMBOLS 1 Roller 2 Heater 3 Material sheet 4 Sheet drawn and drawn
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ２９Ｌ 7:00 (72)発明者 レオン テベイク 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI B29L 7:00 (72) Inventor Leon Tebei 1-1-1 Higashi, Tsukuba-shi, Ibaraki Pref.
Claims (4)
を主成分とする高分子ブレンド組成物からなるシート
を、下式（１）の温度Ｔｓ（℃）に加熱した一対のロー
ルの間隙から引き抜いて、一軸方向に３倍以上の延伸比
を与えることを特徴とする高配向延伸加工方法。 [Tg(PLLA) × W(PLLA) + ｛Tm (PCL)−40｝×W(PCL)]/1
00 ＜ Ts ≦ [{Tm(PLLA) - 80｝× W(PLLA) + ｛Tm (PCL)−30｝×W
(PCL)]/100 （１） ［但し、Ｔｇ（ＰＬＬＡ）はポリ乳
酸のガラス転移温度（℃）であり、Ｗ（ＰＬＬＡ）はポ
リ乳酸の重量％、Ｔｍ（ＰＣＬ）はポリ（ε−カプロラ
クトン）の融点（℃）、Ｗ（ＰＣＬ）はポリ（ε−カプ
ロラクトン）の重量％、Ｔｍ（ＰＬＬＡ）はポリ乳酸の
融点である］1. Polylactic acid and poly (ε-caprolactone)
A sheet composed of a polymer blend composition containing as a main component is drawn out from a gap between a pair of rolls heated to a temperature Ts (° C.) of the following formula (1) to give a stretch ratio of three times or more in a uniaxial direction. A highly oriented stretching method. [Tg (PLLA) × W (PLLA) + ｛Tm (PCL) −40｝ × W (PCL)] / 1
00 <Ts ≤ [(Tm (PLLA)-80｝ × W (PLLA) + ｛Tm (PCL) −30｝ × W
(PCL)] / 100 (1) [where Tg (PLLA) is the glass transition temperature (° C.) of polylactic acid, W (PLLA) is the weight% of polylactic acid, and Tm (PCL) is poly (ε-caprolactone). ), W (PCL) is the weight% of poly (ε-caprolactone), and Tm (PLLA) is the melting point of polylactic acid.]
１００重量％含有することを特徴とする請求項１の高配
向延伸加工方法。2. The polylactic acid according to claim 1, wherein the poly (lactic acid) is 70 to
2. The highly oriented stretching method according to claim 1, wherein the content is 100% by weight.
１００重量％含有することを特徴とする請求項１の高配
向延伸加工方法。3. The polylactic acid has a poly (D-lactic acid) content of 70 to
2. The highly oriented stretching method according to claim 1, wherein the content is 100% by weight.
ポリ（ε−カプロラクトン）をあらかじめドライブレン
ドしたのち、二軸押出機を用いて、溶融混練することで
得られるポリ乳酸とポリ（ε−カプロラクトン）を主成
分とする高分子ブレンド組成物であることを特徴とする
請求項１記載の高配向延伸加工方法。4. A polylactic acid and poly (ε) obtained by dry blending polylactic acid and poly (ε-caprolactone) in advance and then melt-kneading the mixture using a twin screw extruder. 2. The method according to claim 1, which is a polymer blend composition containing (caprolactone) as a main component. 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2797699A JP2990277B2 (en) | 1998-03-19 | 1999-02-04 | Stretching method of aliphatic polyester sheet |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-69628 | 1998-03-19 | ||
| JP10069628 | 1998-03-19 | ||
| JP2797699A JP2990277B2 (en) | 1998-03-19 | 1999-02-04 | Stretching method of aliphatic polyester sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11320674A true JPH11320674A (en) | 1999-11-24 |
| JP2990277B2 JP2990277B2 (en) | 1999-12-13 |
Family
ID=26365990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2797699A Expired - Lifetime JP2990277B2 (en) | 1998-03-19 | 1999-02-04 | Stretching method of aliphatic polyester sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2990277B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006098115A1 (en) * | 2005-03-15 | 2006-09-21 | Sekisui Chemical Co., Ltd. | Process for production of stretched thermoplastic polyester resin sheet and laminated molded article |
| JP2008238499A (en) * | 2007-03-27 | 2008-10-09 | Sekisui Chem Co Ltd | Manufacturing method of drawn and stretched thermoplastic resin sheet |
| JP2008302544A (en) * | 2007-06-06 | 2008-12-18 | Sekisui Chem Co Ltd | Stretched thermoplastic polyester resin sheet and its manufacturing method |
| WO2012018238A2 (en) * | 2010-08-06 | 2012-02-09 | Skc Co., Ltd. | Biodegradable oriented polyester film and preparation method thereof |
| JP2012514070A (en) * | 2008-12-24 | 2012-06-21 | ランクホルスト ピュール コンポシテ ビー．ブイ． | Polylactic acid products and uses thereof |
| KR101327890B1 (en) * | 2010-08-06 | 2013-11-11 | 에스케이씨 주식회사 | Biodegradable polyester film and preparation method thereof |
| CN105150510A (en) * | 2015-07-08 | 2015-12-16 | 内蒙古农业大学 | Fully-degradable polycaprolactone film and production method and application thereof |
| CN108192304A (en) * | 2017-12-28 | 2018-06-22 | 广东工业大学 | A kind of polylactic acid film and a kind of preparation method of polylactic acid film |
-
1999
- 1999-02-04 JP JP2797699A patent/JP2990277B2/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006098115A1 (en) * | 2005-03-15 | 2006-09-21 | Sekisui Chemical Co., Ltd. | Process for production of stretched thermoplastic polyester resin sheet and laminated molded article |
| US8617445B2 (en) | 2005-03-15 | 2013-12-31 | Sekisui Chemical Co., Ltd. | Process for producing oriented thermoplastic polyester resin sheet, and laminate-molded body |
| JP2008238499A (en) * | 2007-03-27 | 2008-10-09 | Sekisui Chem Co Ltd | Manufacturing method of drawn and stretched thermoplastic resin sheet |
| JP2008302544A (en) * | 2007-06-06 | 2008-12-18 | Sekisui Chem Co Ltd | Stretched thermoplastic polyester resin sheet and its manufacturing method |
| JP2012514070A (en) * | 2008-12-24 | 2012-06-21 | ランクホルスト ピュール コンポシテ ビー．ブイ． | Polylactic acid products and uses thereof |
| US9440393B2 (en) | 2008-12-24 | 2016-09-13 | Lankhorst Pure Composites B.V. | Polylactic acid products and their use |
| WO2012018238A2 (en) * | 2010-08-06 | 2012-02-09 | Skc Co., Ltd. | Biodegradable oriented polyester film and preparation method thereof |
| WO2012018238A3 (en) * | 2010-08-06 | 2012-04-26 | Skc Co., Ltd. | Biodegradable oriented polyester film and preparation method thereof |
| KR101214473B1 (en) | 2010-08-06 | 2012-12-24 | 에스케이씨 주식회사 | Biodegradable polyester oriented film and preparation method thereof |
| KR101327890B1 (en) * | 2010-08-06 | 2013-11-11 | 에스케이씨 주식회사 | Biodegradable polyester film and preparation method thereof |
| CN105150510A (en) * | 2015-07-08 | 2015-12-16 | 内蒙古农业大学 | Fully-degradable polycaprolactone film and production method and application thereof |
| CN108192304A (en) * | 2017-12-28 | 2018-06-22 | 广东工业大学 | A kind of polylactic acid film and a kind of preparation method of polylactic acid film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2990277B2 (en) | 1999-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100515274B1 (en) | Biodegradable film and process for producing the same | |
| TWI572645B (en) | Porous film | |
| TW201241083A (en) | Polylactic acid based film | |
| JP4611214B2 (en) | Biodegradable resin composition | |
| JP3330712B2 (en) | Method for producing polylactic acid-based film | |
| JP2990277B2 (en) | Stretching method of aliphatic polyester sheet | |
| DE4300420A1 (en) | Poly:lactide(s) with increased flexibility, suitable for film prodn. | |
| JP2990278B2 (en) | Stretching method of aliphatic polyester sheet | |
| WO2021241712A1 (en) | Biodegradable resin composition and biodegradable resin molded articles | |
| JPH07205278A (en) | Production of stretched film of polylactic acid polymer | |
| JPH08198955A (en) | Oriented polylactic acid film and sheet and their production | |
| WO2014156952A1 (en) | Film | |
| JPH10147653A (en) | Biodegradable oriented film | |
| JP2003119367A (en) | Polylactic acid-based heat-shrinkable film | |
| JPH09272794A (en) | Biodegradable film | |
| CN116656094A (en) | Degradable polymer composition and preparation method thereof | |
| JP2972913B2 (en) | Shape memory method and shape restoration method for biodegradable shape memory polymer molded article | |
| JP2015083661A (en) | Porous film and manufacturing method therefor | |
| JP2005154524A (en) | Aliphatic polyester resin composition and film | |
| JP2005139395A (en) | Mulching film | |
| JP3490241B2 (en) | Degradable films or sheets, molded articles made of these, and methods for decomposing them | |
| JP3619055B2 (en) | Biodegradable packing band and manufacturing method thereof | |
| US20220411595A1 (en) | Biodegradable Compositions and Products Produced Therefrom | |
| JPH1180524A (en) | Biodegradable mulching film | |
| JP3623053B2 (en) | Biodegradable resin molding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |