JP3315968B2 - Method for producing biodegradable biaxially stretched film - Google Patents
Method for producing biodegradable biaxially stretched filmInfo
- Publication number
- JP3315968B2 JP3315968B2 JP2000086097A JP2000086097A JP3315968B2 JP 3315968 B2 JP3315968 B2 JP 3315968B2 JP 2000086097 A JP2000086097 A JP 2000086097A JP 2000086097 A JP2000086097 A JP 2000086097A JP 3315968 B2 JP3315968 B2 JP 3315968B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- biodegradable
- film
- biaxially stretched
- stretched 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.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 31
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 20
- 229920000229 biodegradable polyester Polymers 0.000 claims description 18
- 239000004622 biodegradable polyester Substances 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 6
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical group OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 claims description 4
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical compound CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 claims 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims 1
- 229920001610 polycaprolactone Polymers 0.000 description 8
- 239000004632 polycaprolactone Substances 0.000 description 8
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical group OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000061 acid fraction Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical group CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 241000252867 Cupriavidus metallidurans Species 0.000 description 1
- 229920006257 Heat-shrinkable film Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000218 poly(hydroxyvalerate) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリヒドロキシ酪
酸（３−ヒドロキシブチレート単位と４−ヒドロキシブ
チレート単位からなる生分解性ポリエステル共重合体を
除く。）、ポリヒドロキシ吉草酸、および３-ヒドロキ
シ酪酸と３-ヒドロキシ吉草酸の共重合体から選ばれた
少なくとも１以上の微生物分解性を有するポリエステル
系ポリマーから成り、かつ優れた強度を有する微生物分
解性２軸延伸フィルム（以下「生分解性２軸延伸フィル
ム」と称す）の製造方法に関する。The present invention relates to polyhydroxybutyric acid (3-hydroxybutyrate unit and 4-hydroxybutyrate unit).
A biodegradable polyester copolymer consisting of
except. ) , A biodegradable polymer having at least one biodegradable polyester polymer selected from polyhydroxyvaleric acid and a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, and having excellent strength. The present invention relates to a method for producing a biaxially stretched film (hereinafter referred to as “biodegradable biaxially stretched film”).
【０００２】[0002]
【従来の技術】従来より、微生物分解性が必要とされる
フィルム用途、例えば農業用フィルム、生ごみ包装用袋
などとしては、優れた生分解性を有するポリヒドロキシ
酪酸（３−ヒドロキシブチレート単位と４−ヒドロキシ
ブチレート単位からなる生分解性ポリエステル共重合体
を除く。）、ポリヒドロキシ吉草酸、および３−ヒドロ
キシ酪酸と３−ヒドロキシ吉草酸の共重合体からなる群
より選ばれた１以上の微生物分解性ポリエステル系ポリ
マー（Ａ）からなる生分解性フィルムを使用することが
提案されている。2. Description of the Related Art Hitherto, polyhydroxybutyric acid (3-hydroxybutyrate unit ) having excellent biodegradability has been used for film applications requiring biodegradability, such as agricultural films and garbage packaging bags. And 4-hydroxy
Biodegradable polyester copolymer consisting of butyrate units
except for. ) , A biodegradable film comprising one or more biodegradable polyester-based polymers (A) selected from the group consisting of polyhydroxyvaleric acid and a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid. It has been proposed.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、かかる
ポリヒドロキシ酪酸（３−ヒドロキシブチレート単位と
４−ヒドロキシブチレート単位からなる生分解性ポリエ
ステル共重合体を除く。）、ポリヒドロキシ吉草酸、お
よび３−ヒドロキシ酪酸と３−ヒドロキシ吉草酸の共重
合体などの微生物分解性ポリエステル系ポリマー（Ａ）
は、融点が高いが、結晶性が高いため脆く、該ポリマー
（Ａ）からなるフィルムは、その強度が、例えば引張強
度が３００ｋｇ／ｃｍ2以下と弱く、生分解性フィルム
としては実用上問題があり、その用途が限定されてい
た。However, such polyhydroxybutyric acid (3-hydroxybutyrate unit and
Biodegradable polyether consisting of 4-hydroxybutyrate units
Excluding steal copolymer. ) , Biodegradable polyester polymers such as polyhydroxyvaleric acid and copolymers of 3-hydroxybutyric acid and 3-hydroxyvaleric acid (A)
Has a high melting point but is brittle due to its high crystallinity, and the film made of the polymer (A) has a weak strength, for example, a tensile strength of 300 kg / cm 2 or less, and poses a practical problem as a biodegradable film. And its use was limited.
【０００４】一般的にフィルムなどの強度を向上させる
方法としては、フィルムを少なくとも一方向に延伸する
ことが知られている。しかしながら、該微生物分解性ポ
リエステル系ポリマーからなるフィルムは結晶性が高く
脆いなどのために延伸し難い傾向があり実用化されてい
ない。It is generally known that a film is stretched in at least one direction as a method for improving the strength of the film or the like. However, a film made of the biodegradable polyester-based polymer has a high crystallinity and is brittle, and thus tends to be difficult to be stretched.
【０００５】本発明は、前記のような状況を鑑みなされ
たものであり、本発明の目的は、ポリヒドロキシ酪酸
（３−ヒドロキシブチレート単位と４−ヒドロキシブチ
レート単位からなる生分解性ポリエステル共重合体を除
く。）、ポリヒドロキシ吉草酸、および３−ヒドロキシ
酪酸と３−ヒドロキシ吉草酸の共重合体などの微生物分
解性ポリエステル系ポリマー（Ａ）が有する脆さを改善
し、該ポリマー（Ａ）からなるフィルムに延伸性を付与
することにより、強度が強い実用性ある生分解性２軸延
伸フィルムを提供することにある。The present invention has been made in view of the above situation, and an object of the present invention is to provide polyhydroxybutyric acid.
(3-hydroxybutyrate unit and 4-hydroxybutyrate
Excluding biodegradable polyester copolymer
Good. ), Polyhydroxy valerate, and 3-microbial degradation polyester polymers such as hydroxybutyrate and copolymers of 3-hydroxy valeric acid (A) to improve the brittleness possessed by, the film made of the polymer (A) An object of the present invention is to provide a practically biodegradable biaxially stretched film having high strength and imparting stretchability.
【０００６】[0006]
【課題を解決するための手段】前記課題を解決する手段
として、本発明は、ポリヒドロキシ酪酸（３−ヒドロキ
シブチレート単位と４−ヒドロキシブチレート単位から
なる生分解性ポリエステル共重合体を除く。）、ポリヒ
ドロキシ吉草酸、および３−ヒドロキシ酪酸と３−ヒド
ロキシ吉草酸の共重合体から選ばれた少なくとも１以上
の微生物分解性ポリエステル系ポリマー（Ａ）と、ポリ
カプロラクトン（Ｂ）との混合物を押出機より溶融押出
し、５０〜１５０℃で縦方向および横方向に各々少なく
とも１．５倍以上１０倍以下に延伸することを特徴とす
る。As a means for solving the above-mentioned problems, the present invention provides polyhydroxybutyric acid (3 -hydroxy).
From sibutyrate unit and 4-hydroxybutyrate unit
Excluding biodegradable polyester copolymers. At least one biodegradable polyester polymer (A) selected from polyhydroxyvaleric acid and a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid ;
The mixture with caprolactone (B) is melt-extruded from an extruder, and stretched at 50 to 150 ° C. at least 1.5 times to 10 times in the longitudinal and transverse directions, respectively.
【０００７】[0007]
【０００８】又、本発明は、縦方向および横方向の引張
破断強度が共に少なくとも５３０ｋｇ／ｃｍ2ある微生
物分解性２軸延伸フィルムの製造方法であることを特徴
とする。[0008] The present invention is also directed to a method for producing a biodegradable biaxially stretched film having both tensile strength in the machine direction and transverse tensile strength of at least 530 kg / cm 2 .
【０００９】さらに、本発明は、縦方向および横方向の
引張破断強度が共に少なくとも５３０ｋｇ／ｃｍ2ある
微生物分解性２軸延伸フィルムであることを特徴とす
る。Further, the present invention is characterized in that the film is a biodegradable biaxially stretched film having both a tensile strength in a longitudinal direction and a tensile strength in a transverse direction of at least 530 kg / cm 2 .
【００１０】[0010]
【発明の実施の形態】本発明に関わるポリヒドロキシ酪
酸（３−ヒドロキシブチレート単位と４−ヒドロキシブ
チレート単位からなる生分解性ポリエステル共重合体を
除く。）、ポリヒドロキシ吉草酸、および３−ヒドロキ
シ酪酸と３−ヒドロキシ吉草酸の共重合体とは、例えば
水素細菌Ａｌｃａｌｉｇｅｎｅｓ ｅｕｔｒｏｐｈｕｓ
などの微生物によって生物合成されるポリヒドロキシ酪
酸、ポリヒドロキシ吉草酸、および３−ヒドロキシ酪酸
と３−ヒドロキシ吉草酸の共重合体から選ばれた微生物
分解性ポリエステル系ポリマー（Ａ）を例示でき、その
数平均分子量が１万〜１００万、好ましくは１万〜２０
万程度、融点が１４０〜１８０℃のものが用いられる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Polyhydroxybutyric acid (3-hydroxybutyrate unit and 4-hydroxybutyrate)
A biodegradable polyester copolymer consisting of
except. ) , Polyhydroxyvaleric acid, and a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid include, for example, hydrogen bacterium Alcaligenes eutrophus.
Biodegradable polyester-based polymers (A) selected from polyhydroxybutyric acid, polyhydroxyvaleric acid, and copolymers of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, which are biosynthesized by microorganisms such as Number average molecular weight is 10,000 to 1,000,000, preferably 10,000 to 20
Those having a melting point of about 140 to 180 ° C. are used.
【００１１】尚、３−ヒドロキシ酪酸と３−ヒドロキシ
吉草酸の共重合体の場合、３−ヒドロキシ吉草酸の分率
が５〜２０モル％のものが好ましいものとして例示でき
るが、特に制限はない。In the case of a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, a copolymer having a fraction of 3-hydroxyvaleric acid of 5 to 20 mol% can be exemplified as a preferable one, but there is no particular limitation. .
【００１２】本発明にかかる前記微生物分解性ポリエス
テル系ポリマー（Ａ）と混合される前記以外の生分解性
を有する熱可塑性ポリマー（Ｂ）としては、具体的に
は、ポリカプロラクトンが例示できる。The biodegradable thermoplastic polymer (B) to be mixed with the biodegradable polyester polymer (A) according to the present invention specifically includes polycaprolactone.
【００１３】この際、融点が前記の微生物分解性ポリエ
ステル系ポリマー（Ａ）と略同等もしくは低いことが好
ましく、とくに、ポリカプロラクトンが好ましいものと
して例示できる。ポリカプロラクトンとしては、環状モ
ノマーであるε−カプロラクトンの開環重合により得ら
れる脂肪族ポリエステルのポリカプロラクトンを例示で
きる。かかるポリカプロラクトンは、数平均分子量が
１,０００〜１２０,０００のポリマーを例示できる。In this case, the melting point is preferably substantially the same as or lower than that of the above-mentioned biodegradable polyester-based polymer (A), and polycaprolactone is particularly preferred. Examples of polycaprolactone include aliphatic polyester polycaprolactone obtained by ring-opening polymerization of ε-caprolactone, which is a cyclic monomer. Examples of such polycaprolactone include polymers having a number average molecular weight of 1,000 to 120,000.
【００１４】本発明に係るポリヒドロキシ酪酸（３−ヒ
ドロキシブチレート単位と４−ヒドロキシブチレート単
位からなる生分解性ポリエステル共重合体を除く。）、
ポリヒドロキシ吉草酸、および３−ヒドロキシ酪酸と３
−ヒドロキシ吉草酸の共重合体から選ばれた１以上の微
生物分解性ポリエステル系ポリマー（Ａ）と、ポリカプ
ロラクトン（Ｂ）との混合物は押出機より溶融押出し、
成膜後、縦方向および横方向に延伸される。延伸される
ことにより、本発明にかかわる生分解性フィルムの強度
が向上する。The polyhydroxybutyric acid according to the present invention (3-H
Droxybutyrate unit and 4-hydroxybutyrate unit
Excluding biodegradable polyester copolymers consisting of ) ,
Polyhydroxyvaleric acid, and 3-hydroxybutyric acid and 3
- one or more microbial degradation polyester polymer selected from a copolymer of hydroxy valeric acid (A), Porikapu
The mixture with lolactone (B) is melt extruded from an extruder,
After film formation, the film is stretched in the vertical and horizontal directions. By stretching, the strength of the biodegradable film according to the present invention is improved.
【００１５】延伸倍率は、縦方向および横方向に少なく
とも１．５倍以上１０倍以下、好ましくは各々３．５倍
以上１０倍以下にするのがよい。１．５倍未満では、強
度向上が不十分であり、未延伸部分が残る傾向にある。
また、１０倍を超えると、延伸時に破れる頻度が増加し
成膜性が低下する傾向がある。The stretching ratio is at least 1.5 times and not more than 10 times in the longitudinal and transverse directions, preferably 3.5 times and 10 times, respectively. If it is less than 1.5 times, the strength is not sufficiently improved, and unstretched portions tend to remain.
On the other hand, when it exceeds 10 times, the frequency of tearing during stretching increases, and the film-forming properties tend to decrease.
【００１６】延伸温度としては、具体的には、延伸温度
は５０〜１５０゜Ｃが好ましい。Specifically, the stretching temperature is preferably from 50 to 150 ° C.
【００１７】延伸温度が５０゜Ｃ未満では延伸負荷が大
きく、延伸し難い傾向があり、延伸温度が１５０゜Ｃを
超えると、延伸の場合溶融する傾向がある。If the stretching temperature is less than 50 ° C., the stretching load is large and stretching tends to be difficult, and if the stretching temperature exceeds 150 ° C., there is a tendency to melt in the case of stretching.
【００１８】更に、本発明に係る生分解性２軸延伸フィ
ルムには、必要に応じて、延伸後、適宜な公知の装置、
方法で熱固定しても良い。具体的には、逐次２軸延伸の
場合は、縦延伸、横延伸に引き続き、横延伸温度よりも
高い温度で幅方向に数％弛緩しながら熱固定する方法を
例示できるが、特に制限はなく、熱固定しなくてもよ
い。この際、熱固定しない場合は、熱収縮性フィルムと
して使用できる。Further, if necessary, the biodegradable biaxially stretched film according to the present invention may be appropriately stretched after stretching.
It may be heat-set by a method. Specifically, in the case of sequential biaxial stretching, a method in which, after longitudinal stretching and transverse stretching, heat fixing is performed at a temperature higher than the transverse stretching temperature while relaxing several% in the width direction, but there is no particular limitation. It is not necessary to heat-fix. At this time, when not heat-fixed, it can be used as a heat-shrinkable film.
【００１９】本発明にかかる生分解性２軸延伸フィルム
の厚さは、特に制限はなく、生分解時間、用途などによ
って適宜選択すればよく、一般的には、１０〜２００μ
ｍが例示できる。The thickness of the biodegradable biaxially stretched film according to the present invention is not particularly limited, and may be appropriately selected depending on the biodegradation time, application, and the like.
m can be exemplified.
【００２０】前記のようにして製造された生分解性２軸
延伸フィルムは、縦方向および横方向の引張破断強度が
共に少なくとも５３０ｋｇ／ｃｍ2あり、脆さが改善さ
れているため、実用性あるものとなり、さまざまな用途
に使用できる。The biodegradable biaxially stretched film produced as described above has tensile breaking strength in both the longitudinal and transverse directions of at least 530 kg / cm 2, and has improved brittleness, so that it is practical. It can be used for various purposes.
【００２１】例えば、生ごみ用ごみ袋、買い物袋、衛生
用品、ラミネート用フィルム、食品用トレイ、園芸用
（例えば、ポット用シート）、農業用シート、カード用
シートなどを例示できるが、特に制限はない。For example, garbage bags for garbage, shopping bags, sanitary articles, laminating films, food trays, horticultural (eg, pot sheets), agricultural sheets, card sheets, and the like can be exemplified, with particular limitations. There is no.
【００２２】本発明に係る生分解性２軸延伸フィルム
は、印刷性、ラミネート、コーティング性などを向上さ
せるために表面処理を行なってもよい。表面処理の方法
としてはコロナ放電処理、プラズマ処理、火炎処理、溶
媒処理などが例示できる。これらの中ではフィルム製造
過程の巻取り工程前に容易に実施でき、使用簡便さの点
からコロナ放電処理が好ましいが特に制限はない。The biodegradable biaxially stretched film according to the present invention may be subjected to a surface treatment in order to improve printability, lamination, coating properties and the like. Examples of the surface treatment method include corona discharge treatment, plasma treatment, flame treatment, and solvent treatment. Among these, a corona discharge treatment is preferred from the viewpoint of simplicity of use, which can be easily carried out before the winding step in the film production process, but is not particularly limited.
【００２３】[0023]
【実施例】以下実施例に基づき本発明を説明する。但
し、本発明にかかる生分解性２軸延伸フィルムは後記実
施例に限定されるものではない。本発明の実施例におい
て各検査項目の測定は以下の方法により行なった。The present invention will be described below with reference to examples. However, the biodegradable biaxially stretched film according to the present invention is not limited to the examples described later. In the examples of the present invention, measurement of each inspection item was performed by the following method.
【００２４】［引張破断強度］：ＪＩＳ Ｋ−６７３２
号に準じて測定評価した。 ［延伸性］：縦方向にロール加熱延伸後横方向にテンタ
ーで延伸をする逐次２軸延伸を行ない評価した。○・・
・延伸良好、×・・・延伸不可（未延伸、破断などが発
生）[Tensile breaking strength]: JIS K-6732
No. was measured and evaluated according to No. [Stretchability]: Evaluation was performed by sequentially performing biaxial stretching in which the film was stretched by a tenter in the transverse direction after the roll heating stretching in the longitudinal direction. ○ ・ ・
・ Stretching is good, ×: Stretching is not possible (unstretched, broken, etc.)
【００２５】実施例１〜３ ３−ヒドロキシ吉草酸の分率が１２モル％の３−ヒドロ
キシ酪酸と３−ヒドロキシ吉草酸の共重合体と、数平均
分子量７０,０００のポリカプロラクトンとを表１で示
した割合でブレンドした。この混合物を、シリンダー温
度１７０℃、ダイス温度１７０゜Ｃに設定した４０φ押
出機に供給し、溶融混練し押出して厚さ３００μｍの原
反フィルムを得た。引き続いて、ロール温度５５℃で縦
方向に表１に示す倍率でロール加熱延伸後、雰囲気温度
５５℃のテンターで横方向に表１に示す倍率で延伸し、
厚さ２０μｍの生分解性２軸延伸フィルムを得た。得ら
れた生分解性２軸延伸フィルムの延伸性、引張破断強度
を表１に示した。Examples 1 to 3 Copolymers of 3-hydroxybutyric acid and 3-hydroxyvaleric acid having a 3-hydroxyvaleric acid fraction of 12 mol% and polycaprolactone having a number average molecular weight of 70,000 are shown in Table 1. Were blended at the ratios indicated by. This mixture was supplied to a 40φ extruder set at a cylinder temperature of 170 ° C. and a die temperature of 170 ° C., melt-kneaded and extruded to obtain a 300 μm thick raw film. Subsequently, the film was roll-heat-stretched at a roll temperature of 55 ° C. in the longitudinal direction at a magnification shown in Table 1, and then stretched horizontally in a tenter at an ambient temperature of 55 ° C. at a magnification shown in Table 1.
A biodegradable biaxially stretched film having a thickness of 20 μm was obtained. Table 1 shows the stretchability and tensile strength at break of the obtained biodegradable biaxially stretched film.
【００２６】比較例１〜３ ３−ヒドロキシ吉草酸の分率が１２モル％の３−ヒドロ
キシ酪酸と３−ヒドロキシ吉草酸の共重合体と、数平均
分子量７０,０００のポリカプロラクトンとを表１に示
した割合でブレンドした。この混合物を、シリンダー温
度１７０℃、ダイス温度１７０℃に設定した４０φ押出
機に供給し、溶融混練し押出して未延伸フィルムを得
た。得られた未延伸生分解性フィルムの引張破断強度を
表１に示した。Comparative Examples 1-3 Copolymers of 3-hydroxybutyric acid and 3-hydroxyvaleric acid having a 3-hydroxyvaleric acid fraction of 12 mol% and polycaprolactone having a number average molecular weight of 70,000 are shown in Table 1. Were blended in the proportions shown in Table 1. This mixture was supplied to a 40φ extruder set at a cylinder temperature of 170 ° C. and a die temperature of 170 ° C., melt-kneaded and extruded to obtain an unstretched film. Table 1 shows the tensile breaking strength of the obtained unstretched biodegradable film.
【００２７】[0027]
【表１】 [Table 1]
【００２８】表１から明かなように、延伸することによ
り引張破断強度が大幅に向上し極めて優れた強度を有す
る生分解性２軸延伸フィルムが得られる。As is clear from Table 1, the tensile strength at break is greatly improved by stretching, and a biodegradable biaxially stretched film having extremely excellent strength can be obtained.
【００２９】[0029]
【発明の効果】本発明によるポリヒドロキシ酪酸（３−
ヒドロキシブチレート単位と４−ヒドロキシブチレート
単位からなる生分解性ポリエステル共重合体を除
く。）、ポリヒドロキシ吉草酸、および３−ヒドロキシ
酪酸と３−ヒドロキシ吉草酸の共重合体から選ばれた少
なくとも１以上の微生物分解性ポリエステル系ポリマー
（Ａ）と、ポリカプロラクトン（Ｂ）との混合物からな
る生分解性２軸延伸フィルムは、十分な強度を有し、更
に、本発明の生分解性２軸延伸フィルムはその使用目的
が完了した後、廃棄物として地中に埋設されたり、河川
や海に投棄されても、自然環境下で短期間に分解される
ので、環境汚染の恐れもなく好適に使用される。According to the present invention, polyhydroxybutyric acid (3-
Hydroxybutyrate unit and 4-hydroxybutyrate
Excluding biodegradable polyester copolymer
Good. ) , A mixture of at least one biodegradable polyester polymer (A) selected from polyhydroxyvaleric acid and a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, and polycaprolactone (B). The biodegradable biaxially stretched film has sufficient strength, and the biodegradable biaxially stretched film of the present invention is buried in the ground as waste after completion of its intended use, Even if discarded in the sea, it is decomposed in a short period of time in the natural environment, so that it is suitably used without fear of environmental pollution.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B29C 55/00 - 55/30 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 7 , DB name) B29C 55/00-55/30
Claims (3)
チレート単位と４−ヒドロキシブチレート単位からなる
生分解性ポリエステル共重合体を除く。）、ポリヒドロ
キシ吉草酸、３−ヒドロキシ酪酸と３−ヒドロキシ吉草
酸の共重合体から選ばれた少なくとも１以上の微生物分
解性ポリエステル系ポリマー（Ａ）と、ポリカプロラク
トン（Ｂ）との混合物を押出機より溶融押出し、５０〜
１５０℃で縦方向および横方向に各々少なくとも１．５
倍以上１０倍以下に延伸することを特徴とする微生物分
解性２軸延伸フィルムの製造方法。A polyhydroxybutyric acid (3-hydroxybutyrate)
Consists of a thylate unit and a 4-hydroxybutyrate unit
Excludes biodegradable polyester copolymer. At least one biodegradable polyester polymer (A) selected from polyhydroxyvaleric acid, copolymers of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, and polycaprolactic acid
The mixture with ton (B) is melt-extruded from an extruder,
At least 1.5 each in the machine and transverse directions at 150 ° C.
A method for producing a biodegradable biaxially stretched film, characterized in that the film is stretched by a factor of 10 to 10 times.
に少なくとも５３０ｋｇ／ｃｍ２ある請求項１記載の微
生物分解性２軸延伸フィルムの製造方法。2. The method for producing a biodegradable biaxially stretched film according to claim 1, wherein both the tensile strength in the machine direction and the tensile strength in the transverse direction are at least 530 kg / cm 2 .
微生物分解性２軸延伸フィルム。3. A biaxially stretched biodegradable film produced by the production method according to claim 1 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000086097A JP3315968B2 (en) | 1995-11-07 | 2000-03-27 | Method for producing biodegradable biaxially stretched film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000086097A JP3315968B2 (en) | 1995-11-07 | 2000-03-27 | Method for producing biodegradable biaxially stretched film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31469595A Division JPH09132701A (en) | 1995-11-07 | 1995-11-07 | Microorganism-decomposable film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000289104A JP2000289104A (en) | 2000-10-17 |
| JP3315968B2 true JP3315968B2 (en) | 2002-08-19 |
Family
ID=18602315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000086097A Expired - Fee Related JP3315968B2 (en) | 1995-11-07 | 2000-03-27 | Method for producing biodegradable biaxially stretched film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3315968B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003311825A (en) * | 2002-04-25 | 2003-11-06 | Inst Of Physical & Chemical Res | High strength film comprising polyhydroxyalkane and manufacturing method therefor |
-
2000
- 2000-03-27 JP JP2000086097A patent/JP3315968B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000289104A (en) | 2000-10-17 |
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