JPS6169431A - Stretching method of poly(beta-hydroxybutyric acid) molded product - Google Patents
Stretching method of poly(beta-hydroxybutyric acid) molded productInfo
- Publication number
- JPS6169431A JPS6169431A JP19183484A JP19183484A JPS6169431A JP S6169431 A JPS6169431 A JP S6169431A JP 19183484 A JP19183484 A JP 19183484A JP 19183484 A JP19183484 A JP 19183484A JP S6169431 A JPS6169431 A JP S6169431A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- preform
- melting point
- molded product
- hydroxybutyric 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.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【発明の詳細な説明】
a)技術分野
本発明はポリ(β−ヒドロキシ醋酸)及び/又はその共
重合体よりなる成形物の延伸方法に関する。DETAILED DESCRIPTION OF THE INVENTION a) Technical Field The present invention relates to a method for stretching a molded product made of poly(β-hydroxyacetic acid) and/or a copolymer thereof.
b)従来技術
ポリ(β−ヒドロキシ酪酸)及び/又はその共重合体(
以下これらを総称してPH8と略称することがある)は
、例えばE tlrODean ChelRicalN
ews June 28.1982.17頁に示される
如く微生物分解性等を有し、圧電性を示す等特異な性質
を呈する重合体として種々の用途が11il持される。b) Prior art poly(β-hydroxybutyric acid) and/or copolymers thereof (
Hereinafter, these may be collectively referred to as PH8), for example, E tlrODean ChelRicalN
As shown in EWS June 28, 1982, page 17, it has various uses as a polymer exhibiting unique properties such as microbial degradability and piezoelectricity.
また、これらの重合体は石油化学で製造されず、微生物
を用いて製造される点で、今後の石油不足を考えると有
用な高分子材料となることが推定される。Furthermore, since these polymers are not produced through petrochemistry but are produced using microorganisms, they are expected to be useful polymeric materials considering future petroleum shortages.
ところが、PHBは特開昭58−82723号公報にも
示される如く通常の合成重合体に適用される溶融成形、
湿式成形等の成形法を用いて成形したものを、延伸して
物性を改良しようとしても、通常の方法では困難である
。例えば成形物を加圧圧延した後に延伸すると言った如
き特殊な方法が必要であるとされている。However, as shown in JP-A No. 58-82723, PHB is a melt-molding method applied to ordinary synthetic polymers.
Even if it is attempted to improve the physical properties of a product formed using a molding method such as wet molding by stretching it, it is difficult to do so using normal methods. For example, a special method is considered necessary, such as stretching the molded product after pressure rolling.
C)解決手段
本発明者らはかかる特殊な方法ではなく、通常の延伸方
法で延伸すべく検討を重ねた結果、成形物を一度特定の
温度に加熱した後特定期間冷却して延伸すれば、通常の
延伸方法で延伸が可能であることを見出し、本発明に到
ったものである。C) Solution The inventors of the present invention have repeatedly investigated the possibility of stretching using a normal stretching method rather than using such a special method. The inventors have discovered that stretching is possible using a normal stretching method, and have arrived at the present invention.
d)発朗の構成
本発明はβ−ヒドロキシ醋酸を主たる構成成分とする重
合体よりなる成形物を延伸するに際し、該成形物をその
融点未満の温度で且つ融点より40℃以上低くない温度
に加熱し、次いで100℃以下の温度に1〜120秒間
保持した後1.2倍以上に延伸することを特徴とするポ
リ(β−ヒドロキシ酪酸)成形物の延伸方法である。d) Structure of Hatsuro When stretching a molded product made of a polymer whose main component is β-hydroxyacetic acid, the molded product is heated to a temperature below its melting point and not lower than the melting point by 40°C or more. This is a method for stretching a poly(β-hydroxybutyric acid) molded product, which is characterized by heating, then holding at a temperature of 100° C. or lower for 1 to 120 seconds, and then stretching 1.2 times or more.
本発明で言うPHBは例えば特開昭57−150393
号公報、特開昭58−69224号公報等に示される如
き重合体又は共重合体である。つまり微生物により産出
される−0− G H+ CR3+CH2−G O−の
繰返し単位を有するもの、又はこれに−〇−0RI R
2そCR3R” −)n Co−(nはO又は整、・
数であり・Ro・Ro・Ro・Ro番よ炭化水素
基・ハロ又はヒドロキシ−置換炭化水素基、ヒドロキシ
基、ハロゲン原子、水素原子から選ばれる)を共重合し
たものであり、この共重合割合は通常50モル%未満で
ある。The PHB referred to in the present invention is, for example, JP-A No. 57-150393.
These are polymers or copolymers as shown in Japanese Patent Application Laid-open No. 58-69224 and the like. In other words, those having -0-G H+ CR3+CH2-G O- repeating units produced by microorganisms, or -0-0RI R
2soCR3R"-)n Co-(n is O or regular, ・
It is a copolymerized product selected from Ro, Ro, Ro, Ro number, hydrocarbon group, halo or hydroxy-substituted hydrocarbon group, hydroxy group, halogen atom, hydrogen atom), and this copolymerization ratio is usually less than 50 mol%.
本発明においてはかかるPH8を予備成形物とした後延
伸する。この予備成形物の製造法は如何なる方法でもよ
く、例えば溶融成形法、湿式成形法、乾式成形法等が用
いられる。但し、溶融成形法を用いた場合、得られた予
備成形物は結晶化している必要がある。結晶化していな
い予備成形物は本発明を実施する際、変形したり、破断
したりするので好ましくない。In the present invention, such PH8 is made into a preform and then stretched. Any method may be used to produce this preform, such as a melt molding method, a wet molding method, a dry molding method, etc. However, when the melt molding method is used, the obtained preform must be crystallized. Uncrystallized preforms are not preferred because they deform or break during the practice of the present invention.
かかる予備成形物を本発明においては融点未満の温度で
且つ融点より40℃以上低くない温度、好ましくは(融
点−5℃)〜(融点−30℃)の温度に加熱した後10
0℃以下、好ましくは70℃以下O℃以上に冷却して1
〜120秒、好ましくは5〜60秒保った後1.2倍以
上、好ましくは1.5倍以上、更に好ましくは2倍以上
に延伸する。この加熱時間、加熱温度は共重合量、予備
成形物の形状等で異なるが、予備テストにより適宜窓め
ることが望ましい。また、冷却温度1時間についても同
様である。In the present invention, such a preform is heated to a temperature below the melting point and not more than 40°C below the melting point, preferably at a temperature of (melting point -5°C) to (melting point -30°C), and then heated for 10 minutes.
Cool to 0°C or lower, preferably 70°C or lower, and cool to 1°C or higher.
After holding for 120 seconds, preferably 5 to 60 seconds, it is stretched 1.2 times or more, preferably 1.5 times or more, more preferably 2 times or more. The heating time and heating temperature vary depending on the amount of copolymerization, the shape of the preform, etc., but it is desirable to adjust the heating time and temperature appropriately by preliminary tests. The same applies to the cooling temperature for 1 hour.
加熱温度が融点以上では当然溶融し、融点より40℃以
上低い温度では延伸倍率を上げることができず好ましく
ない。また、冷W温度が高すぎたり冷却時間が短いと、
いわゆるフロー延伸が起り、強度を上げることができな
い。冷却時間があまりに長ずざると延伸倍率が上がらな
くなる。If the heating temperature is higher than the melting point, it will naturally melt, and if the heating temperature is 40° C. or more lower than the melting point, the stretching ratio cannot be increased, which is not preferable. Also, if the cold W temperature is too high or the cooling time is short,
So-called flow stretching occurs and strength cannot be increased. If the cooling time is not too long, the stretching ratio will not increase.
加熱は通常定長下で行なうが、1.5倍未満の延伸を伴
いながら行ってもよい。冷却も通常は無緊張状態で行な
う。Heating is usually carried out under a constant length, but may be carried out with stretching less than 1.5 times. Cooling is also normally performed under no tension.
熱処理後冷却した予備成形物を延伸するのは、通常の延
伸方法で行えばよく、この際の温度は通常室温〜100
℃である。The preform cooled after heat treatment may be stretched by a normal stretching method, and the temperature at this time is usually room temperature to 100°C.
It is ℃.
e)実施例
実施例1
グルコース上でアルカリゲネス・オイトロファス突然変
異株(A 1caiaenes eutrophus
mut’ant)S 801/C5(N G I
811599)の好気培養によって製造されたβ−ヒド
ロキシ酪酸・重合体を水性セル懸濁液から1.2−ジク
ロルエタンで抽出し、メタノール/水溶液に添加して沈
澱させ、メタノール洗滌し、乾燥したものを190℃で
プレス成形して厚み0.2mのフィルム状予備成形物を
得た。e) Examples Example 1 Alcaiaenes eutrophus mutant strain (A1caiaenes eutrophus
mut'ant) S 801/C5 (NG I
β-Hydroxybutyric acid polymer produced by aerobic cultivation of 811599) was extracted from an aqueous cell suspension with 1,2-dichloroethane, precipitated by addition to a methanol/water solution, washed with methanol, and dried. was press-molded at 190°C to obtain a film-like preform with a thickness of 0.2 m.
この予備成形物を室温で1日放置した後、′160℃の
シリコンオイル中で定長で5秒熱処理し、次いで25℃
の空気中に10秒保った後そのまま8倍に一軸延伸した
。得られたものは190M P aの強度があった。ま
た、このものの融点は20℃/分の昇温速度で示差熱分
析した結果174℃であった。。After this preform was left at room temperature for one day, it was heat treated in silicone oil at 160°C for 5 seconds, and then at 25°C.
After being kept in air for 10 seconds, it was uniaxially stretched 8 times as it was. The resulting material had a strength of 190 MPa. Further, the melting point of this product was 174°C as a result of differential thermal analysis at a heating rate of 20°C/min. .
比較例1
実施例1の予備成形物を室温で1日放置後そのまま延伸
しようとしたが1.1倍にしか延伸できず、強度は25
MPaであった。また、130℃で5秒間熱処理しても
1.3倍にしか延伸できず強度は31MPaであった。Comparative Example 1 An attempt was made to stretch the preform of Example 1 after leaving it at room temperature for one day, but it could only be stretched 1.1 times, and the strength was 25.
It was MPa. Further, even when heat treated at 130° C. for 5 seconds, the stretching was only 1.3 times, and the strength was 31 MPa.
比較例2
実施例1の熱処理後直ちに8倍に延伸しようとしたが切
断して延伸できなかった。Comparative Example 2 Immediately after the heat treatment in Example 1, an attempt was made to stretch the film 8 times, but the film was cut and could not be stretched.
実施例2,3
実施例1においてグルコースのかわりにグルコース/プ
ロピオン酸混合物を用いることにより得たβ−ヒドロキ
シ古草酸・共重合ポリβ−ヒドロキシ酪酸を用いた結果
を表に示す。Examples 2 and 3 The results of using the β-hydroxy archaic acid/copolymerized polyβ-hydroxybutyric acid obtained by using the glucose/propionic acid mixture in place of glucose in Example 1 are shown in the table.
(以下余白)
実施例4
実施例1のポリマーを190℃で溶融し、1#ll11
径のノズルから押出して1日数デした糸及びクロロホル
ムに溶解し、ガラス板上に流延して自然乾燥して得たフ
ィルムについて実施例1と同様に熱処理、冷却、延伸し
た結果溶融押出した糸の強度は+50MPa、流延フィ
ルムの強度は+30M P aを示した。(Left below) Example 4 The polymer of Example 1 was melted at 190°C, and 1#ll11
Thread extruded from a nozzle with a diameter of about 100 mm and dried for several days, and a film obtained by dissolving it in chloroform, casting it on a glass plate and drying naturally, were heat treated, cooled, and stretched in the same manner as in Example 1, resulting in a melt-extruded thread. The strength of the cast film was +50 MPa, and the strength of the cast film was +30 MPa.
特許出願人 帝 人 株 式 会 社ど)。Patent applicant: Teijin Kaisha Ltd.).
/、:\
代 理 人 弁理士 前 1) 純 博1
1...j1...l:\、:゛・ し/、:\ Representative Patent Attorney 1) Jun Hiroshi 1
1. .. .. j1. .. .. l:\、:゛・ し
Claims (1)
体よりなる成形物を延伸するに際し、該成形物をその融
点未満の温度で且つ融点より40℃以上低くない温度に
加熱し、次いで100℃以下の温度に1〜120秒間保
持した後1.2倍以上に延伸することを特徴とするポリ
(β−ヒドロキシ酪酸)成形物の延伸方法。(1) When stretching a molded product made of a polymer whose main constituent is β-hydroxybutyric acid, the molded product is heated to a temperature below its melting point and no lower than 40°C below the melting point, and then heated to 100°C. A method for stretching poly(β-hydroxybutyric acid) molded articles, which comprises holding the following temperature for 1 to 120 seconds and then stretching 1.2 times or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19183484A JPS6169431A (en) | 1984-09-14 | 1984-09-14 | Stretching method of poly(beta-hydroxybutyric acid) molded product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19183484A JPS6169431A (en) | 1984-09-14 | 1984-09-14 | Stretching method of poly(beta-hydroxybutyric acid) molded product |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6169431A true JPS6169431A (en) | 1986-04-10 |
JPH0263056B2 JPH0263056B2 (en) | 1990-12-27 |
Family
ID=16281291
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19183484A Granted JPS6169431A (en) | 1984-09-14 | 1984-09-14 | Stretching method of poly(beta-hydroxybutyric acid) molded product |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6169431A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5191037A (en) * | 1991-04-11 | 1993-03-02 | Yoshiharu Doi | Biodegradable polymeric composition |
EP0544701A1 (en) * | 1990-07-16 | 1993-06-09 | E.I. Du Pont De Nemours And Company | Polyhydroxy acid films |
WO1994028048A1 (en) * | 1993-06-02 | 1994-12-08 | Zeneca Limited | Processing of polyesters |
WO1994028049A1 (en) * | 1993-06-02 | 1994-12-08 | Zeneca Limited | Processing of polyesters |
WO1994028047A1 (en) * | 1993-06-02 | 1994-12-08 | Zeneca Limited | Processing of polyesters |
EP0736563A1 (en) * | 1995-04-07 | 1996-10-09 | SAFTA S.p.A. | Process for the manufacture of totally bio-decomposable films with high mechanical characteristics and relevant products and applications |
WO1997022459A1 (en) * | 1995-12-21 | 1997-06-26 | Monsanto Company | Oriented polyester |
US5874040A (en) * | 1993-06-02 | 1999-02-23 | Monsanto Company | Processing of polyesters |
WO2005120808A1 (en) * | 2004-06-09 | 2005-12-22 | Novamont S.P.A. | Process for the production of biodegradable films having improved mechanical properties |
-
1984
- 1984-09-14 JP JP19183484A patent/JPS6169431A/en active Granted
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0544701A1 (en) * | 1990-07-16 | 1993-06-09 | E.I. Du Pont De Nemours And Company | Polyhydroxy acid films |
US5191037A (en) * | 1991-04-11 | 1993-03-02 | Yoshiharu Doi | Biodegradable polymeric composition |
WO1994028048A1 (en) * | 1993-06-02 | 1994-12-08 | Zeneca Limited | Processing of polyesters |
WO1994028049A1 (en) * | 1993-06-02 | 1994-12-08 | Zeneca Limited | Processing of polyesters |
WO1994028047A1 (en) * | 1993-06-02 | 1994-12-08 | Zeneca Limited | Processing of polyesters |
US5789536A (en) * | 1993-06-02 | 1998-08-04 | Monsanto Company | Process of polyesters |
US5874040A (en) * | 1993-06-02 | 1999-02-23 | Monsanto Company | Processing of polyesters |
EP0736563A1 (en) * | 1995-04-07 | 1996-10-09 | SAFTA S.p.A. | Process for the manufacture of totally bio-decomposable films with high mechanical characteristics and relevant products and applications |
WO1997022459A1 (en) * | 1995-12-21 | 1997-06-26 | Monsanto Company | Oriented polyester |
WO2005120808A1 (en) * | 2004-06-09 | 2005-12-22 | Novamont S.P.A. | Process for the production of biodegradable films having improved mechanical properties |
Also Published As
Publication number | Publication date |
---|---|
JPH0263056B2 (en) | 1990-12-27 |
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