JP2003001704A - Biodegradable film - Google Patents
Biodegradable filmInfo
- Publication number
- JP2003001704A JP2003001704A JP2001194152A JP2001194152A JP2003001704A JP 2003001704 A JP2003001704 A JP 2003001704A JP 2001194152 A JP2001194152 A JP 2001194152A JP 2001194152 A JP2001194152 A JP 2001194152A JP 2003001704 A JP2003001704 A JP 2003001704A
- Authority
- JP
- Japan
- Prior art keywords
- aliphatic
- dicarboxylic acid
- resin
- weight
- diol
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Bag Frames (AREA)
- Wrappers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は特定の生分解性樹脂を配
合した組成物を用いることにより、インフレーション成
形機によるフイルム化に優れ、生分解性を有する農業用
マルチフイルムやゴミ袋などとして有用な生分解性フイ
ルムに関する。INDUSTRIAL APPLICABILITY The present invention is excellent in film formation by an inflation molding machine by using a composition containing a specific biodegradable resin, and is useful as a biodegradable agricultural multi-film or garbage bag. Biodegradable film.
【０００２】[0002]
【従来の技術】従来、生分解性樹脂として各種の樹脂が
開発され、それぞれの用途に使用されるようになってき
た。2. Description of the Related Art Conventionally, various resins have been developed as biodegradable resins and have been used for their respective purposes.
【０００３】インフレーション成形機によりフイルム成
形できる生分解性樹脂として、脂肪族ポリエステル系樹
脂が知られている。しかしながら、成形されたフイルム
の柔軟性が不十分で、用途によっては使用に制限があっ
た。Aliphatic polyester resins are known as biodegradable resins that can be film-formed by an inflation molding machine. However, the flexibility of the formed film was insufficient, and its use was limited depending on the application.
【０００４】[0004]
【発明が解決しようとする課題】その他の生分解性樹脂
は、溶融粘度が低いためインフレーション成形機により
フイルム成形できるものは少なく、Ｔダイ押出方式でキ
ャスティングロールによる急冷によってフイルム成形し
ているが現状である。Other biodegradable resins have a low melt viscosity, so that few of them can be formed into a film by an inflation molding machine. Currently, the film is formed by quenching with a casting roll in the T-die extrusion method. Is.
【０００５】そこで本発明の目的は、各種の生分解性樹
脂を組み合わせることにより、インフレーション成形機
によりフイルム成形でき、生分解性を損なわず、フイル
ムの耐候性および柔軟性に優れたフイルムを提供するこ
とにある。Therefore, an object of the present invention is to provide a film which can be formed into a film by an inflation molding machine by combining various biodegradable resins, does not impair biodegradability, and has excellent weather resistance and flexibility of the film. Especially.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するた
め、本発明に係る生分解性フイルムは、脂肪族ジカルボ
ン酸および芳香族ジカルボン酸よりなるジカルボン酸成
分と、脂肪族ジオールからなるジオール成分とを縮合し
てなる脂肪族芳香族ポリエステルを多官能イソシアネー
トで高分子化した融点１０５〜１１５℃の脂肪族芳香族
ポリエステル系樹脂２０〜８２重量％と、脂肪族ジカル
ボン酸よりなるジカルボン酸成分と、脂肪族ジオールか
らなるジオール成分とを縮合してなる脂肪族ポリエステ
ルを多官能イソシアネートで高分子化した融点１１０〜
１２０℃の脂肪族ポリエステル系樹脂（Ａ）１８〜８０
重量％を配合した生分解性樹脂組成物をインフレーショ
ン成形機によりフイルム化したことを特徴とするもので
ある。To achieve the above object, the biodegradable film according to the present invention comprises a dicarboxylic acid component composed of an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a diol component composed of an aliphatic diol. 20 to 82% by weight of an aliphatic aromatic polyester-based resin having a melting point of 105 to 115 ° C. obtained by polymerizing an aliphatic aromatic polyester obtained by condensing a polyfunctional isocyanate with a dicarboxylic acid component composed of an aliphatic dicarboxylic acid, Melting point 110 to which an aliphatic polyester obtained by condensing a diol component composed of an aliphatic diol is polymerized with a polyfunctional isocyanate.
Aliphatic polyester resin (A) 18 to 80 at 120 ° C
It is characterized in that the biodegradable resin composition containing the weight% is formed into a film by an inflation molding machine.
【０００７】また、本発明に係る生分解性フイルムは、
脂肪族ジカルボン酸および芳香族ジカルボン酸よりなる
ジカルボン酸成分と、脂肪族ジオールからなるジオール
成分とを縮合してなる脂肪族芳香族ポリエステルを多官
能イソシアネートで高分子化した融点１０５〜１１５℃
の脂肪族芳香族ポリエステル系樹脂２０〜８０重量％
と、脂肪族ジカルボン酸よりなるジカルボン酸成分と、
脂肪族ジオールからなるジオール成分とを縮合してなる
脂肪族ポリエステルを多官能イソシアネートで高分子化
した融点１１０〜１２０℃の脂肪族ポリエステル系樹脂
（Ａ）および脂肪族ジカルボン酸よりなるジカルボン酸
成分と、脂肪族ジオールからなるジオール成分とを縮合
してなる脂肪族ポリエステルを多官能イソシアネートで
高分子化した融点９０〜１００℃の脂肪族ポリエステル
系樹脂（Ｂ）の配合割合を（Ａ）／（Ｂ）＝１／３〜５
／１の範囲で合計量２０〜８０重量％を配合し、かつ、
（Ａ）の配合量を少なくとも１８重量％である生分解性
樹脂組成物をインフレーション成形機によりフイルム化
したことを特徴とするものである。Further, the biodegradable film according to the present invention is
Melting point 105-115 ° C. obtained by polymerizing an aliphatic aromatic polyester obtained by condensing a dicarboxylic acid component composed of an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid and a diol component composed of an aliphatic diol with a polyfunctional isocyanate.
20-80% by weight of aliphatic aromatic polyester resin
And a dicarboxylic acid component consisting of an aliphatic dicarboxylic acid,
A dicarboxylic acid component composed of an aliphatic polyester resin (A) having a melting point of 110 to 120 ° C. obtained by polymerizing an aliphatic polyester obtained by condensing a diol component composed of an aliphatic diol with a polyfunctional isocyanate, and an aliphatic dicarboxylic acid; The blending ratio of the aliphatic polyester resin (B) having a melting point of 90 to 100 ° C. obtained by polymerizing an aliphatic polyester obtained by condensing a diol component composed of an aliphatic diol with a polyfunctional isocyanate is (A) / (B ) = 1 / 3-5
In the range of / 1, a total amount of 20 to 80% by weight is blended, and
A biodegradable resin composition containing at least 18% by weight of (A) is formed into a film by an inflation molding machine.
【０００８】上記の脂肪族芳香族ポリエステル系樹脂の
配合割合が、２０重量％未満であると柔軟性が乏しくな
り、また上記の脂肪族ポリエステル系樹脂（Ａ）の配合
割合が、１８重量％未満であるとインフレーション成形
時のバブル安定性に劣るようになり、厚み精度が悪化す
る。さらに、脂肪族芳香族ポリエステル系樹脂と脂肪族
ポリエステル系樹脂（Ａ）からなる生分解性樹脂組成物
に、上記の脂肪族ポリエステル系樹脂（Ｂ）を適量配合
することにより、フイルムの生分解性が向上するが、配
合量が多くなり過ぎるとインフレーション成形時のバブ
ル安定性に劣るので好ましくない。If the blending ratio of the above aliphatic aromatic polyester resin is less than 20% by weight, the flexibility becomes poor, and the blending ratio of the above aliphatic polyester resin (A) is less than 18% by weight. If so, the bubble stability at the time of inflation molding becomes poor, and the thickness accuracy deteriorates. Furthermore, the biodegradability of the film can be improved by adding an appropriate amount of the above aliphatic polyester resin (B) to the biodegradable resin composition consisting of the aliphatic aromatic polyester resin and the aliphatic polyester resin (A). However, if the blending amount is too large, the bubble stability during inflation molding is deteriorated, which is not preferable.
【０００９】上記の脂肪族芳香族ポリエステル系樹脂と
しては、アジピン酸とテレフタル酸からなるジカルボン
酸成分と、１，４−ブタンジオールからなるジオール成
分とを縮合してなる脂肪族芳香族ポリエステルを多官能
イソシアネートで高分子化した樹脂が好ましい。また、
脂肪族ポリエステル系樹脂（Ａ）としては、コハク酸か
らなるジカルボン酸成分と、１，４−ブタンジオールか
らなるジオール成分とを縮合してなる脂肪族ポリエステ
ルを多官能イソシアネートで高分子化した樹脂が好まし
くい。脂肪族ポリエステル系樹脂（Ｂ）は、コハク酸と
アジピン酸からなるジカルボン酸成分と、１，４−ブタ
ンジオールからなるジオール成分とを縮合してなる脂肪
族ポリエステルを多官能イソシアネートで高分子化した
樹脂が好ましい。上記の脂肪族芳香族ポリエステル系樹
脂や脂肪族ポリエステル系樹脂（Ａ）または（Ｂ）に用
いることができるその他のジカルボン酸成分としては、
アジピン酸、セバシン酸、イタコン酸等の脂肪族ジカル
ボン酸が挙げられ、その他のジオール成分としては、
２，３−ブタンジオール、１，３−ブタンジオール、
１，４−ペンタンジオール、１，５ペンタンジオール
−、２，４−ペンタンジオール、１，６−ヘキサンジオ
ール、ネオペンチルグリコール、エチレングリコール、
ジエチレングリコール等の脂肪族ジオールが挙げられ
る。As the above-mentioned aliphatic aromatic polyester resin, there are many aliphatic aromatic polyesters obtained by condensing a dicarboxylic acid component consisting of adipic acid and terephthalic acid and a diol component consisting of 1,4-butanediol. A resin polymerized with a functional isocyanate is preferable. Also,
The aliphatic polyester-based resin (A) is a resin obtained by polymerizing an aliphatic polyester obtained by condensing a dicarboxylic acid component composed of succinic acid and a diol component composed of 1,4-butanediol with a polyfunctional isocyanate. I like it. The aliphatic polyester-based resin (B) is obtained by polymerizing an aliphatic polyester obtained by condensing a dicarboxylic acid component composed of succinic acid and adipic acid and a diol component composed of 1,4-butanediol with a polyfunctional isocyanate. Resins are preferred. Other dicarboxylic acid components that can be used in the above aliphatic aromatic polyester resin or aliphatic polyester resin (A) or (B) include
Aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and itaconic acid are listed, and other diol components include:
2,3-butanediol, 1,3-butanediol,
1,4-pentanediol, 1,5 pentanediol-, 2,4-pentanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol,
Aliphatic diols such as diethylene glycol may be mentioned.
【００１０】上記の生分解性樹脂組成物において、脂肪
族芳香族ポリエステル系樹脂の配合割合は３０〜７０重
量％、好ましくは３０〜６０重量％の範囲で、脂肪族ポ
リエステル系樹脂（Ａ）の配合割合は１８〜５０重量
％、好ましくは２０〜４０重量％の範囲で、脂肪族ポリ
エステル系樹脂（Ｂ）の配合割合は１０〜５５重量％、
好ましくは１５〜５０重量％の範囲のものが、成形性、
生分解性、柔軟性などのバランスが良いフイルムとな
る。In the above biodegradable resin composition, the proportion of the aliphatic aromatic polyester resin is 30 to 70% by weight, preferably 30 to 60% by weight. The blending ratio is 18 to 50% by weight, preferably 20 to 40% by weight, and the blending ratio of the aliphatic polyester resin (B) is 10 to 55% by weight,
The range of 15 to 50% by weight is preferable for moldability,
The film has a good balance of biodegradability and flexibility.
【００１１】また、生分解性樹脂組成物において配合さ
れるその他の生分解性樹脂としては、ポリ乳酸系樹脂、
ポリカプロラクトン系樹脂、ポリエステルカーボネート
系樹脂、ポリエステルアミド系樹脂、ポリヒドロキシブ
チレート（ＰＨＢ）またはポリヒドロキシバリレート
（ＰＨＶ）もしくはその共重合体（ＰＨＶＢ）などが挙
げられる。これらのその他の生分解性樹脂の配合量は、
２０重量％以下、好ましくは２〜１５重量％の範囲であ
る。Further, other biodegradable resins to be blended in the biodegradable resin composition include polylactic acid resins,
Examples thereof include polycaprolactone-based resin, polyester carbonate-based resin, polyesteramide-based resin, polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV) or a copolymer thereof (PHVB). The blending amount of these other biodegradable resins is
The amount is 20% by weight or less, preferably 2 to 15% by weight.
【００１２】本発明において、各種充填剤を添加するこ
とが好ましい。例えば、炭酸カルシウム、珪酸カルシウ
ム、パーライト、アルミナ、ゼオライト、セピオライ
ト、蛭石、活性白土、カオリン、タルク、ハイドロタル
サイト、ベントナイト、ケイソウ土、活性炭等の無機粉
末や公知の有機粉末が挙げられる。これらの粉末の粒径
は、平均粒径３０μｍ以下が好ましく、より好ましくは
１０μｍ以下である。In the present invention, it is preferable to add various fillers. Examples thereof include inorganic powders such as calcium carbonate, calcium silicate, perlite, alumina, zeolite, sepiolite, vermiculite, activated clay, kaolin, talc, hydrotalcite, bentonite, diatomaceous earth, and activated carbon, and known organic powders. The average particle size of these powders is preferably 30 μm or less, more preferably 10 μm or less.
【００１３】これらの脂肪族芳香族ポリエステル系樹脂
の具体例としては、ＢＡＳＦ社製の「エコフレックス」
（１，４−ブタンジオールとアジピン酸およびテレフタ
ル酸からなる脂肪族芳香族ポリエステルを多官能イソシ
アネートで高分子化した脂肪族芳香族ポリエステル系樹
脂、融点：約１１０℃）を挙げることができ、脂肪族ポ
リエステル系樹脂（Ａ）の具体例としては、昭和高分子
社製の「ビオノーレ＃１００１」（１，４−ブタンジオ
ールとコハク酸からなる脂肪族ポリエステルを多官能イ
ソシアネートで高分子化した脂肪族ポリエステル系樹
脂、融点：約１１４℃）、「ビオノーレ＃１０２０」
（同上、融点：約１１５℃）を、脂肪族ポリエステル系
樹脂（Ｂ）の具体例としては、「ビオノーレ＃３００
１」（１，４−ブタンジオールとコハク酸およびアジピ
ン酸からなる脂肪族ポリエステルを多官能イソシアネー
トで高分子化した脂肪族ポリエステル系樹脂、融点：約
９４℃）、「ビオノーレ＃３０２０」（同上、融点：約
９５℃）を挙げることができる。Specific examples of these aliphatic aromatic polyester resins include "Ecoflex" manufactured by BASF.
(Aliphatic aromatic polyester resin obtained by polymerizing an aliphatic aromatic polyester consisting of 1,4-butanediol and adipic acid and terephthalic acid with a polyfunctional isocyanate, melting point: about 110 ° C.) Specific examples of the group polyester resin (A) include "Bionole # 1001" manufactured by Showa High Polymer Co., Ltd. (an aliphatic polyester obtained by polymerizing an aliphatic polyester composed of 1,4-butanediol and succinic acid with a polyfunctional isocyanate). Polyester resin, melting point: approx. 114 ° C), "Bionore # 1020"
(Same as above, melting point: about 115 ° C.) is a specific example of the aliphatic polyester-based resin (B).
1 "(aliphatic polyester resin obtained by polymerizing an aliphatic polyester composed of 1,4-butanediol and succinic acid and adipic acid with a polyfunctional isocyanate, melting point: about 94 ° C)," Bionole # 3020 "(same as above, Melting point: about 95 ° C.).
【００１４】[0014]
【実施例】以下、本発明の実施例を挙げるが、本発明は
かかる実施例によって何ら限定されるものではない。ま
た、次の評価項目により評価した。EXAMPLES Examples of the present invention will be given below, but the present invention is not limited to these examples. In addition, the following evaluation items were used for evaluation.
【００１５】（成形性）ダイ径３００ｍｍのインフレー
ション成形機により厚さ２０μｍ、折り径２７５０ｍｍ
のフイルムを成形し、次の基準で評価した。
◎：ダイ出口からのバブルが非常に安定している。
○：ダイ出口からのバブルが安定している。
△：ダイ出口からのバブルが不安定で、厚みの調整が不
可能。
×：溶融粘度が小さく、成形困難。(Moldability) Using an inflation molding machine with a die diameter of 300 mm, the thickness is 20 μm and the folding diameter is 2750 mm.
The film was molded and evaluated according to the following criteria. ⊚: Bubbles from the die exit are very stable. ○: Bubbles from the die exit are stable. Δ: Bubbles from the die exit are unstable, and the thickness cannot be adjusted. X: Melt viscosity is small and molding is difficult.
【００１６】（耐候性）サンシャイン・ウェザーメータ
（スガ試験機社製）に資料のフイルムを入れた後、劣化
して破壊までの時間を測定した。
◎：４００時間以上
○：３００時間以上、４００時間未満
△：２００時間以上、３００時間未満
×：２００時間未満、(Weather resistance) After putting the film of the sample into a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), the time until deterioration and destruction was measured. ◎: 400 hours or more ○: 300 hours or more, less than 400 hours Δ: 200 hours or more, less than 300 hours ×: less than 200 hours,
【００１７】（生分解性）
１．サンプルの作成
（１）作成したフイルムを６ｃｍ四方に切り取りサンプ
ルとし、その重量を測定する。ここで、暴露面積（４ｃ
ｍ四方）当たりの重量を計算し、これをサンプルの初期
重量とする。
（２）適当な厚さのアルミ板を６ｃｍ四方に切り取り、
この中央部の４ｃｍ四方を切り抜いてアルミ枠を作成す
る。
（３）このアルミ枠２対でサンプルを挟むことができる
ように、アルミ枠２対のそれぞれの片面に両面テープを
張りつける。
（４）この両面テープ付きの２対のアルミ枠の重量を測
定する。
（５）サンプルをアルミ枠で挟んだ状態の試験サンプル
を生分解性の試験に用いる。
２．堆肥の調整
（１）適当な大きさ（深さ５ｃｍ以上）の密閉できる容
器を用意する。
（２）堆肥は、市販の堆肥に水分を補給して用いる。水
の補給量は、加えた水が底に溜まらない状態で、かつ、
指で摘んだときに僅かに水がしみ出てくる程度の状態を
標準とする。
３．生分解性の試験方法
（１）生分解性の試験は、標準状態の堆肥中で行う。容
器中の堆肥の表面から約３ｃｍ位の深さに試験サンプル
をセットする。
（２）試験サンプルをセットした後、容器を蓋で密閉し
て５８℃のオーブンに入れ、生分解性試験をスタートす
る。
（３）生分解性試験中はできれば１日１度は蓋を開い
て、初期の堆肥の水分状態を維持するために水を適時、
霧吹き等で加える。
（４）生分解性の状態は、適時試験サンプルを取り出
し、水洗して表面の水分を取った後、重量変化を測定す
る。
（５）サンプルの重量変化において、初期重量対してサ
ンプルの重量減が８０％以上となった日数を生分解性の
日数として次の基準で評価した。
◎：４０日未満
○：４０日以上、６０日未満
△：６０日以上、８０日未満
×：８０日以上(Biodegradability) 1. Preparation of sample (1) The prepared film is cut into a sample of 6 cm square, and the sample is weighed. Here, the exposed area (4c
Calculate the weight per m square) and use this as the initial weight of the sample. (2) Cut an aluminum plate of appropriate thickness into a 6 cm square,
An aluminum frame is created by cutting out the 4 cm square in the central portion. (3) A double-sided tape is attached to one surface of each of the two pairs of aluminum frames so that the sample can be sandwiched between the two pairs of aluminum frames. (4) The weight of the two pairs of aluminum frames with the double-sided tape is measured. (5) A test sample in which the sample is sandwiched between aluminum frames is used for the biodegradability test. 2. Preparation of compost (1) Prepare an airtight container of appropriate size (depth of 5 cm or more). (2) As the compost, commercially available compost is supplemented with water before use. The amount of water supply is such that the added water does not accumulate at the bottom, and
The standard condition is that a small amount of water seeps out when picked with your finger. 3. Biodegradability test method (1) The biodegradability test is performed in standard compost. The test sample is set at a depth of about 3 cm from the surface of the compost in the container. (2) After setting the test sample, the container is sealed with a lid and placed in an oven at 58 ° C. to start the biodegradability test. (3) During the biodegradability test, if possible, open the lid once a day, and add water in a timely manner to maintain the initial moisture condition of the compost,
Add by spraying. (4) For the state of biodegradability, a test sample is taken out at appropriate times, washed with water to remove water on the surface, and then the weight change is measured. (5) In the change in weight of the sample, the number of days when the weight loss of the sample was 80% or more relative to the initial weight was evaluated as the number of days of biodegradability based on the following criteria. ◎: Less than 40 days ○: 40 days or more, less than 60 days △: 60 days or more, less than 80 days ×: 80 days or more
【００１８】（柔軟性）資料のフイルムの縦方向（押出
方向）および横方向（押出方向と直角方向）の引張弾性
率をそれぞれ測定し、その平均値を次の基準で評価し
た。
◎：３０ｋｇ／ｍｍ2 未満
○：３０ｋｇ／ｍｍ2 以上、５０ｋｇ／ｍｍ2 未満
△：５０ｋｇ／ｍｍ2 以上、７０ｋｇ／ｍｍ2 未満
×：７０ｋｇ／ｍｍ2 以上(Flexibility) Tensile elastic moduli in the longitudinal direction (extrusion direction) and the transverse direction (direction perpendicular to the extrusion direction) of the film of the material were measured, and the average value thereof was evaluated according to the following criteria. ◎: Less than 30 kg / mm 2 ○: 30 kg / mm 2 or more, less than 50 kg / mm 2 △: 50 kg / mm 2 or more, less than 70 kg / mm 2 ×: 70 kg / mm 2 or more
【００１９】実施例１
脂肪族芳香族ポリエステル系樹脂「エコフレックス」
（ＢＡＳＦ社製）３０重量部、脂肪族ポリエステル系樹
脂（Ａ）「ビオノーレ＃１００１」（昭和高分子社製）
７０重量部を混合し、ダイ径３００ｍｍのインフレーシ
ョン成形機により厚さ２０μｍ、折り径２７５０ｍｍの
フイルムを成形した。フイルムの評価を表１に示す。Example 1 Aliphatic aromatic polyester resin "Ecoflex"
(Manufactured by BASF) 30 parts by weight, aliphatic polyester resin (A) "Bionore # 1001" (manufactured by Showa High Polymer Co., Ltd.)
70 parts by weight were mixed, and a film having a thickness of 20 μm and a folding diameter of 2750 mm was molded by an inflation molding machine having a die diameter of 300 mm. The evaluation of the film is shown in Table 1.
【００２０】実施例２
脂肪族芳香族ポリエステル系樹脂「エコフレックス」
（ＢＡＳＦ社製）７０重量部、脂肪族ポリエステル系樹
脂（Ａ）「ビオノーレ＃１００１」（昭和高分子社製）
３０重量部を混合し、ダイ径３００ｍｍのインフレーシ
ョン成形機により厚さ２０μｍ、折り径２７５０ｍｍの
フイルムを成形した。フイルムの評価を表１に示す。Example 2 Aliphatic Aromatic Polyester Resin "Ecoflex"
(BASF) 70 parts by weight, aliphatic polyester resin (A) "Bionore # 1001" (Showa High Polymer)
30 parts by weight were mixed, and a film having a thickness of 20 μm and a folding diameter of 2750 mm was molded by an inflation molding machine having a die diameter of 300 mm. The evaluation of the film is shown in Table 1.
【００２１】実施例３
脂肪族芳香族ポリエステル系樹脂「エコフレックス」５
０重量部、脂肪族ポリエステル系樹脂（Ａ）「ビオノー
レ＃１００１」３０重量部および脂肪族ポリエステル系
樹脂（Ｂ）「ビオノーレ＃３００１」（昭和高分子社
製）２０重量部を混合し、ダイ径３００ｍｍのインフレ
ーション成形機により厚さ２０μｍ、折り径２７５０ｍ
ｍのフイルムを成形した。フイルムの評価を表１に示
す。Example 3 Aliphatic Aromatic Polyester Resin "Ecoflex" 5
0 parts by weight, 30 parts by weight of aliphatic polyester-based resin (A) "Bionore # 1001" and 20 parts by weight of aliphatic polyester-based resin (B) "bionore # 3001" (manufactured by Showa Polymer Co., Ltd.) were mixed, and the die diameter was mixed. 20mm thick, folding diameter 2750m by 300mm inflation molding machine
m film was formed. The evaluation of the film is shown in Table 1.
【００２２】実施例４
脂肪族芳香族ポリエステル系樹脂「エコフレックス」３
０重量部、脂肪族ポリエステル系樹脂（Ａ）「ビオノー
レ＃１００１」２０重量部および脂肪族ポリエステル系
樹脂（Ｂ）「ビオノーレ＃３００１」（昭和高分子社
製）５０重量部を混合し、ダイ径３００ｍｍのインフレ
ーション成形機により厚さ２０μｍ、折り径２７５０ｍ
ｍのフイルムを成形した。フイルムの評価を表１に示
す。Example 4 Aliphatic Aromatic Polyester Resin "Ecoflex" 3
0 parts by weight, 20 parts by weight of aliphatic polyester-based resin (A) "Bionore # 1001" and 50 parts by weight of aliphatic polyester-based resin (B) "Bionore # 3001" (manufactured by Showa Polymer Co., Ltd.) were mixed, and the die diameter 20mm thick, folding diameter 2750m by 300mm inflation molding machine
m film was formed. The evaluation of the film is shown in Table 1.
【００２３】実施例５
脂肪族芳香族ポリエステル系樹脂「エコフレックス」６
０重量部、脂肪族ポリエステル系樹脂（Ａ）「ビオノー
レ＃１００１」２０重量部および脂肪族ポリエステル系
樹脂（Ｂ）「ビオノーレ＃３００１」（昭和高分子社
製）２０重量部を混合し、ダイ径３００ｍｍのインフレ
ーション成形機により厚さ２０μｍ、折り径２７５０ｍ
ｍのフイルムを成形した。フイルムの評価を表１に示
す。Example 5 Aliphatic Aromatic Polyester Resin "Ecoflex" 6
0 parts by weight, 20 parts by weight of aliphatic polyester-based resin (A) "Bionore # 1001" and 20 parts by weight of aliphatic polyester-based resin (B) "Bionore # 3001" (manufactured by Showa High Polymer Co., Ltd.) were mixed, and the die diameter was mixed. 20mm thick, folding diameter 2750m by 300mm inflation molding machine
m film was formed. The evaluation of the film is shown in Table 1.
【００２４】実施例６
脂肪族芳香族ポリエステル系樹脂「エコフレックス」４
０重量部、脂肪族ポリエステル系樹脂（Ａ）「ビオノー
レ＃１００１」３０重量部、脂肪族ポリエステル系樹脂
（Ｂ）「ビオノーレ＃３００１」（昭和高分子社製）２
０重量部およびポリカプロラクトン系樹脂「セルグリー
ン」（ダイセル社製）１０重量部を混合し、ダイ径３０
０ｍｍのインフレーション成形機により厚さ２０μｍ、
折り径２７５０ｍｍのフイルムを成形した。フイルムの
評価を表１に示す。Example 6 Aliphatic Aromatic Polyester Resin "Ecoflex" 4
0 parts by weight, 30 parts by weight of aliphatic polyester resin (A) "Bionore # 1001", aliphatic polyester resin (B) "Bionore # 3001" (manufactured by Showa High Polymer Co., Ltd.) 2
A die diameter of 30 was obtained by mixing 0 part by weight and 10 parts by weight of a polycaprolactone-based resin "Cell Green" (manufactured by Daicel).
20μm thickness by 0mm inflation molding machine,
A film having a folding diameter of 2750 mm was formed. The evaluation of the film is shown in Table 1.
【００２５】実施例７
脂肪族芳香族ポリエステル系樹脂「エコフレックス」５
０重量部、脂肪族ポリエステル系樹脂（Ａ）「ビオノー
レ＃１００１」２０重量部、脂肪族ポリエステル系樹脂
（Ｂ）「ビオノーレ＃３００１」（昭和高分子社製）２
０重量部およびポリ乳酸系樹脂「ラクティ９０３０」
（島津製作所社製、Ｄ体４％含有）１０重量部を混合
し、ダイ径３００ｍｍのインフレーション成形機により
厚さ２０μｍ、折り径２７５０ｍｍのフイルムを成形し
た。フイルムの評価を表１に示す。Example 7 Aliphatic Aromatic Polyester Resin "Ecoflex" 5
0 parts by weight, 20 parts by weight of aliphatic polyester-based resin (A) "Bionore # 1001", aliphatic polyester-based resin (B) "Bionore # 3001" (manufactured by Showa High Polymer Co., Ltd.) 2
0 parts by weight and polylactic acid-based resin "Lacty 9030"
10 parts by weight (manufactured by Shimadzu Corporation, containing 4% of D body) were mixed, and a film having a thickness of 20 μm and a folding diameter of 2750 mm was molded by an inflation molding machine having a die diameter of 300 mm. The evaluation of the film is shown in Table 1.
【００２６】比較例１
脂肪族芳香族ポリエステル系樹脂「エコフレックス」９
０重量部、脂肪族ポリエステル系樹脂（Ａ）「ビオノー
レ＃１００１」１０重量部を混合し、ダイ径３００ｍｍ
のインフレーション成形機により厚さ２０μｍ、折り径
２７５０ｍｍのフイルムを成形した。フイルムの評価を
表１に示す。Comparative Example 1 Aliphatic Aromatic Polyester Resin "Ecoflex" 9
0 parts by weight and 10 parts by weight of aliphatic polyester resin (A) "Bionole # 1001" are mixed, and the die diameter is 300 mm.
A film having a thickness of 20 μm and a folding diameter of 2750 mm was formed by the above inflation molding machine. The evaluation of the film is shown in Table 1.
【００２７】比較例２
脂肪族芳香族ポリエステル系樹脂「エコフレックス」７
０重量部および脂肪族ポリエステル系樹脂（Ｂ）「ビオ
ノーレ＃３００１」（昭和高分子社製）３０重量部を混
合し、ダイ径３００ｍｍのインフレーション成形機によ
り厚さ２０μｍ、折り径２７５０ｍｍのフイルムを成形
した。フイルムの評価を表１に示す。Comparative Example 2 Aliphatic Aromatic Polyester Resin "Ecoflex" 7
30 parts by weight of 0 parts by weight and aliphatic polyester resin (B) "Bionole # 3001" (manufactured by Showa High Polymer Co., Ltd.) are mixed, and a film having a thickness of 20 µm and a folding diameter of 2750 mm is formed by an inflation molding machine having a die diameter of 300 mm. did. The evaluation of the film is shown in Table 1.
【００２８】比較例３
脂肪族芳香族ポリエステル系樹脂「エコフレックス」７
０重量部およびポリカプロラクトン系樹脂「セルグリー
ン」（ダイセル社製）３０重量部を混合し、ダイ径３０
０ｍｍのインフレーション成形機により厚さ２０μｍ、
折り径２７５０ｍｍのフイルムを成形した。フイルムの
評価を表１に示す。Comparative Example 3 Aliphatic Aromatic Polyester Resin "Ecoflex" 7
Mixing 0 part by weight and 30 parts by weight of polycaprolactone-based resin "CELL GREEN" (manufactured by Daicel) to obtain a die diameter of 30
20μm thickness by 0mm inflation molding machine,
A film having a folding diameter of 2750 mm was formed. The evaluation of the film is shown in Table 1.
【００２９】比較例４
脂肪族芳香族ポリエステル系樹脂「エコフレックス」７
０重量部およびポリ乳酸系樹脂「ラクティ９０３０」
（島津製作所社製、Ｄ体４モル％含有）３０重量部を混
合し、ダイ径３００ｍｍのインフレーション成形機によ
り厚さ２０μｍ、折り径２７５０ｍｍのフイルムを成形
した。フイルムの評価を表１に示す。Comparative Example 4 Aliphatic Aromatic Polyester Resin "Ecoflex" 7
0 parts by weight and polylactic acid-based resin "Lacty 9030"
30 parts by weight (manufactured by Shimadzu Corporation, containing 4 mol% of D-form) were mixed, and a film having a thickness of 20 μm and a folding diameter of 2750 mm was molded by an inflation molding machine having a die diameter of 300 mm. The evaluation of the film is shown in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明によれば、特定の生分解性樹脂を
組み合わせることにより、インフレーション成形機によ
るフイルム成形ができ、生分解性を損なわず、耐候性や
柔軟性に優れ、特に農業用マルチフイルムとして有用な
生分解性フイルムを提供することができる。INDUSTRIAL APPLICABILITY According to the present invention, by combining a specific biodegradable resin, a film can be formed by an inflation molding machine, the biodegradability is not impaired, and the weather resistance and flexibility are excellent. A biodegradable film useful as a film can be provided.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 75/06 Ｃ０８Ｌ 75/06 ４Ｊ０３４ // Ｂ６５Ｄ 30/02 Ｂ６５Ｄ 30/02 Ｂ２９Ｋ 67:00 Ｂ２９Ｋ 67:00 Ｂ２９Ｌ 7:00 Ｂ２９Ｌ 7:00 (72)発明者 橋本 英明 東京都中央区京橋１丁目18番１号 シーア イ化成株式会社内 (72)発明者 中山 英隆 東京都中央区京橋１丁目18番１号 シーア イ化成株式会社内 Ｆターム(参考） 3E064 BA54 EA22 EA30 FA01 3E086 AB01 AD01 BA02 BA15 BB90 CA40 4F071 AA43 AA53 AF52 AF53 AH01 AH04 AH05 BA01 BB06 BB09 BC01 4F210 AA24J AA24K AA31J AG01 AH54 AR06 QA01 QG01 QK01 QK12 4J002 CF182 CF192 CG042 CK031 CL082 FD01 GA01 GG01 GG02 4J034 BA03 BA07 DC02 DC12 DC35 DC37 DE01 DF01 DF16 DF20 DF21 DF22 HA01 HA06 QC01 QD04 RA01 RA06 Front page continuation (51) Int.Cl. 7 identification code FI theme code (reference) C08L 75/06 C08L 75/06 4J034 // B65D 30/02 B65D 30/02 B29K 67:00 B29K 67:00 B29L 7: 00 B29L 7:00 (72) Inventor Hideaki Hashimoto 1-18-1 Kyobashi, Chuo-ku, Tokyo Shiai Kasei Co., Ltd. (72) Inventor Hidetaka Nakayama 1-1-18 Kyobashi, Chuo-ku, Tokyo Shiai Kasei In-house F-term (reference) 3E064 BA54 EA22 EA30 FA01 3E086 AB01 AD01 BA02 BA15 BB90 CA40 4F071 AA43 AA53 AF52 AF53 AH01 AH04 AH05 BA01 BB06 BB09 BC01 4F210 AA24J AQ24 Q02K01Q02K01Q02Q01QH12 AR01 QH2 AR01 QH12 AR01 QH12 AR01 QH12 AR01 QH12 AR02 GA01 GG01 GG02 4J034 BA03 BA07 DC02 DC12 DC35 DC37 DE01 DF01 DF16 DF20 DF21 DF22 HA01 HA06 QC01 QD04 RA01 RA06
Claims (7)
ボン酸よりなるジカルボン酸成分と、脂肪族ジオールか
らなるジオール成分とを縮合してなる脂肪族芳香族ポリ
エステルを多官能イソシアネートで高分子化した融点１
０５〜１１５℃の脂肪族芳香族ポリエステル系樹脂２０
〜８２重量％と、脂肪族ジカルボン酸よりなるジカルボ
ン酸成分と、脂肪族ジオールからなるジオール成分とを
縮合してなる脂肪族ポリエステルを多官能イソシアネー
トで高分子化した融点１１０〜１２０℃の脂肪族ポリエ
ステル系樹脂（Ａ）１８〜８０重量％を配合した生分解
性樹脂組成物をインフレーション成形機によりフイルム
化したことを特徴とする生分解性フイルム。1. A melting point 1 obtained by polymerizing an aliphatic aromatic polyester obtained by condensing a dicarboxylic acid component composed of an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid and a diol component composed of an aliphatic diol with a polyfunctional isocyanate.
Aliphatic aromatic polyester-based resin 20 having a temperature of 05 to 115 ° C
To 82% by weight, a dicarboxylic acid component consisting of an aliphatic dicarboxylic acid, and a diol component consisting of an aliphatic diol are condensed to polymerize an aliphatic polyester with a polyfunctional isocyanate. A biodegradable film comprising a biodegradable resin composition containing 18 to 80% by weight of a polyester resin (A) formed into a film by an inflation molding machine.
ボン酸よりなるジカルボン酸成分と、脂肪族ジオールか
らなるジオール成分とを縮合してなる脂肪族芳香族ポリ
エステルを多官能イソシアネートで高分子化した融点１
０５〜１１５℃の脂肪族芳香族ポリエステル系樹脂２０
〜８０重量％と、脂肪族ジカルボン酸よりなるジカルボ
ン酸成分と、脂肪族ジオールからなるジオール成分とを
縮合してなる脂肪族ポリエステルを多官能イソシアネー
トで高分子化した融点１１０〜１２０℃の脂肪族ポリエ
ステル系樹脂（Ａ）および脂肪族ジカルボン酸よりなる
ジカルボン酸成分と、脂肪族ジオールからなるジオール
成分とを縮合してなる脂肪族ポリエステルを多官能イソ
シアネートで高分子化した融点９０〜１００℃の脂肪族
ポリエステル系樹脂（Ｂ）の配合割合を（Ａ）／（Ｂ）
＝１／３〜９／１の範囲で合計量２０〜８０重量％を配
合し、かつ、（Ａ）の配合量を少なくとも１８重量％で
ある生分解性樹脂組成物をインフレーション成形機によ
りフイルム化したことを特徴とする生分解性フイルム。2. A melting point 1 obtained by polymerizing an aliphatic aromatic polyester obtained by condensing a dicarboxylic acid component composed of an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid and a diol component composed of an aliphatic diol with a polyfunctional isocyanate.
Aliphatic aromatic polyester-based resin 20 having a temperature of 05 to 115 ° C
To 80% by weight, a dicarboxylic acid component consisting of an aliphatic dicarboxylic acid, and a diol component consisting of an aliphatic diol are condensed to polymerize an aliphatic polyester with a polyfunctional isocyanate. Fat having a melting point of 90 to 100 ° C. obtained by polymerizing an aliphatic polyester obtained by condensing a dicarboxylic acid component composed of a polyester resin (A) and an aliphatic dicarboxylic acid and a diol component composed of an aliphatic diol with a polyfunctional isocyanate. The blending ratio of the group polyester resin (B) is (A) / (B)
= 1/3 to 9/1 in a total amount of 20 to 80% by weight, and the biodegradable resin composition containing (A) in an amount of at least 18% by weight is formed into a film by an inflation molding machine. A biodegradable film characterized in that
は、アジピン酸とテレフタル酸からなるジカルボン酸成
分と、１，４−ブタンジオールからなるジオール成分を
縮合してなる脂肪族芳香族ポリエステルを多官能イソシ
アネートで高分子化した樹脂であることを特徴とする請
求項１または２に記載の生分解性フイルム。3. The above aliphatic aromatic polyester-based resin contains a large amount of an aliphatic aromatic polyester obtained by condensing a dicarboxylic acid component composed of adipic acid and terephthalic acid and a diol component composed of 1,4-butanediol. The biodegradable film according to claim 1 or 2, which is a resin polymerized with a functional isocyanate.
は、コハク酸からなるジカルボン酸成分と、１，４−ブ
タンジオールからなるジオール成分とを縮合してなる脂
肪族ポリエステルを多官能イソシアネートで高分子化し
た樹脂であることを特徴とする請求項１または２に記載
の生分解性フイルム。4. The aliphatic polyester resin (A) as described above.
Is a resin obtained by polymerizing an aliphatic polyester obtained by condensing a dicarboxylic acid component composed of succinic acid and a diol component composed of 1,4-butanediol with a polyfunctional isocyanate. Alternatively, the biodegradable film according to item 2.
は、コハク酸とアジピン酸からなるジカルボン酸成分
と、１，４−ブタンジオールからなるジオール成分とを
縮合してなる脂肪族ポリエステルを多官能イソシアネー
トで高分子化した樹脂であることを特徴とする請求項２
に記載の生分解性フイルム。5. The above aliphatic polyester resin (B)
Is a resin obtained by polymerizing an aliphatic polyester obtained by condensing a dicarboxylic acid component composed of succinic acid and adipic acid and a diol component composed of 1,4-butanediol with a polyfunctional isocyanate. Claim 2
The biodegradable film described in 1.
３０〜７０重量％、脂肪族ポリエステル系樹脂（Ａ）１
８〜５０重量％および脂肪族ポリエステル系樹脂（Ｂ）
１０〜５５重量％を配合した生分解性樹脂組成物である
ことを特徴とする請求項２に記載の生分解性フイルム。6. The aliphatic aromatic polyester resin 30 to 70% by weight, the aliphatic polyester resin (A) 1
8 to 50% by weight and aliphatic polyester resin (B)
The biodegradable film according to claim 2, which is a biodegradable resin composition containing 10 to 55% by weight.
樹脂、ポリカプロラクトン系樹脂などのその他の生分解
性を０〜２０重量％配合したことを特徴とする請求項
１、２および６のいずれかに記載の生分解性フイルム。7. The biodegradable resin composition is blended with 0 to 20% by weight of other biodegradable resin such as polylactic acid resin and polycaprolactone resin. The biodegradable film according to any one of 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001194152A JP3710726B2 (en) | 2001-06-27 | 2001-06-27 | Biodegradable film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001194152A JP3710726B2 (en) | 2001-06-27 | 2001-06-27 | Biodegradable film |
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| Publication Number | Publication Date |
|---|---|
| JP2003001704A true JP2003001704A (en) | 2003-01-08 |
| JP3710726B2 JP3710726B2 (en) | 2005-10-26 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001194152A Expired - Lifetime JP3710726B2 (en) | 2001-06-27 | 2001-06-27 | Biodegradable film |
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| Country | Link |
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| JP (1) | JP3710726B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007515545A (en) * | 2003-12-22 | 2007-06-14 | イーストマン ケミカル カンパニー | Polyester composition |
| WO2014064983A1 (en) * | 2012-10-23 | 2014-05-01 | 三菱樹脂アグリドリーム株式会社 | Aliphatic polyester resin composition and biodegradable film |
| JP2016106171A (en) * | 2011-02-02 | 2016-06-16 | 三菱化学株式会社 | Polyester resin composition, film by molding the resin composition and bag by molding the film |
-
2001
- 2001-06-27 JP JP2001194152A patent/JP3710726B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007515545A (en) * | 2003-12-22 | 2007-06-14 | イーストマン ケミカル カンパニー | Polyester composition |
| JP2016106171A (en) * | 2011-02-02 | 2016-06-16 | 三菱化学株式会社 | Polyester resin composition, film by molding the resin composition and bag by molding the film |
| WO2014064983A1 (en) * | 2012-10-23 | 2014-05-01 | 三菱樹脂アグリドリーム株式会社 | Aliphatic polyester resin composition and biodegradable film |
| CN104540895A (en) * | 2012-10-23 | 2015-04-22 | 三菱树脂农业梦想株式会社 | Aliphatic polyester resin composition and biodegradable film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3710726B2 (en) | 2005-10-26 |
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