JP2020183496A - Method of preparing highly biodegradable material - Google Patents
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本発明は高度生分解性材料の調製方法に関し、生物化学工学の分野に属する。 The present invention relates to a method for preparing highly biodegradable materials and belongs to the field of biochemical engineering.
ここ２０年間、生分解性プラスチックは急速な発展を遂げており、そのなかでもポリ乳酸（Ｐｏｌｙｌａｃｔｉｃ ａｃｉｄ、以下ＰＬＡと称する）やポリブチレンアジペートテレフタレート（Ｐｏｌｙｂｕｔｙｌｅｎｅａｄｉｐａｔｅ−ｃｏ−ｔｅｒｅｐｈｔｈａｌａｔｅ、以下ＰＢＡＴと称する）のような生分解性と加工性に優れた環境に優しい材料が注目を集めている。 In the last 20 years, biodegradable plastics have undergone rapid development, such as polylactic acid (hereinafter referred to as PLA) and polybutylene adipate-co-terephthalate (hereinafter referred to as PBAT). Environmentally friendly materials with excellent biodegradability and workability are attracting attention.
ＰＬＡは脂肪族ポリエステルであり、その合成原料である乳酸は従来の石油原料を使わず、実質的に生物学的発酵によって調製することができ、優れた生体適合性と高い強度を有し、日用品および生物医学分野において幅広く使われている。脂肪族ポリエステルを用いた易分解性樹脂組成物が、例えば特許文献１に記載されている。 PLA is an aliphatic polyester, and its synthetic raw material, lactic acid, can be prepared substantially by biological fermentation without using conventional petroleum raw materials, has excellent biocompatibility and high strength, and is a daily necessities. And widely used in the field of biomedicine. An easily decomposable resin composition using an aliphatic polyester is described in, for example, Patent Document 1.
しかし、ＰＬＡは、強度が高いが、靭性が低く、耐衝撃性および耐引裂性が劣り、そのうえ５０℃以上の温度に耐えられないため、ＰＬＡの使用範囲がある程度制限されている。一方、ＰＢＡＴは２価アルコールと二塩基酸が重合してなる脂肪族−芳香族コポリエステルであり、柔軟性および成膜性に優れているが、強度が低く、ヤング率が低いため、ＰＢＡＴの普及および使用もある程度制限されている。したがって、多くの研究者はＰＬＡとＰＢＡＴをブレンド材料に調製したが、ブレンドの過程における両者の相溶性が悪く、様々なプラスチックの調製工程の要求を満たすことができず、そのうえ耐熱性が低く、コストが高い問題点があった。
本発明は、上記の問題点を改善するためになされたものであり、高度生分解性材料の調製方法を提供することを目的とし、本発明によって調製される高度生分解性材料は、性能が優れて、耐熱性がよく、コストが低く、ブロー成形、射出成形、ホットプレス成形、真空成形、押出成形などの様々な成形工程に使用でき、且つ１８０日以内に実質的に生分解して堆肥として使用することができる。
However, although PLA has high strength, it has low toughness, is inferior in impact resistance and tear resistance, and cannot withstand temperatures of 50 ° C. or higher, so that the range of use of PLA is limited to some extent. On the other hand, PBAT is an aliphatic-aromatic copolyester obtained by polymerizing a dihydric alcohol and a dibasic acid, and is excellent in flexibility and film forming property, but has low strength and a low Young's modulus. Dissemination and use are also limited to some extent. Therefore, many researchers have prepared PLA and PBAT as blending materials, but the compatibility between them in the blending process is poor, they cannot meet the requirements of various plastic preparation processes, and the heat resistance is low. There was a problem that the cost was high.
The present invention has been made to improve the above-mentioned problems, and an object of the present invention is to provide a method for preparing a highly biodegradable material. The highly biodegradable material prepared by the present invention has high performance. Excellent, good heat resistance, low cost, can be used in various molding processes such as blow molding, injection molding, hot press molding, vacuum forming, extrusion molding, and can be substantially biodegraded within 180 days to compost. Can be used as.
上記の目的を達成するための本発明は、高度生分解性材料の調製方法であって、変性ＰＬＡ３０〜８０重量部、ＰＢＡＴ３０〜８０重量部、変性超微細タルク粉末（ｍｏｄｉｆｉｅｄ Ｕｌｔｒａｆｉｎｅ Ｔａｌｃ Ｐｏｗｄｅｒ）５〜２５重量部、モノステアリン（Ｍｏｎｏｓｔｅａｒｉｎ）１〜５重量部、エチレンビスステアリン酸アミド（Ｅｔｈｙｌｅｎｅ Ｂｉｓ Ｓｔｅａｒａｍｉｄｅ、以下ＥＢＳと称する）０〜２重量部、Ｎ，Ｎ’−エチレンビスオレイン酸アミド（Ｎ，Ｎ−ｅｔｈｙｌｅｎｅｂｉｓｏｌｅａｍｉｄｅ、以下ＥＢＯと称する）０〜２重量部、クエン酸トリブチル（Ｔｒｉｂｕｔｙｌ Ｃｉｔｒａｔｅ）０〜３重量部、ポリエチレンワックス（Ｐｏｌｙｅｔｈｙｌｅｎｅ ｗａｘ）０〜３重量部、可塑化澱粉（Ｐｌａｓｔｉｃｉｚｅｄ ｓｔａｒｃｈ）０〜２５重量部、炭酸カルシウム（Ｃａｌｃｉｕｍ ｃａｒｂｏｎａｔｅ）０〜１０重量部、二酸化チタン（Ｔｉｔａｎｉｕｍ ｄｉｏｘｉｄｅ）０．１〜２重量部、ステアリン酸（Ｓｔｅａｒｉｃ ａｃｉｄ）１〜５重量部、グリセロール（Ｇｌｙｃｅｒｏｌ）０〜１５重量部、エポキシ化大豆油（Ｅｐｏｘｉｄｉｚｅｄ ｓｏｙｂｅａｎ ｏｉｌ）０〜３重量部、およびチタネートカップリング剤（Ｉｓｏｐｒｏｐｙｌ ｄｉｏｌｅｉｃ（ｄｉｏｃｔｙｌｐｈｏｓｐｈａｔｅ）ｔｉｔａｎａｔｅ）０〜２重量部の原料から調製されることを特徴とする。 The present invention for achieving the above object is a method for preparing a highly biodegradable material, which comprises 30 to 80 parts by weight of modified PLA, 30 to 80 parts by weight of PBAT, and modified ultrafine starch powder 5 to 5. 25 parts by weight, 1 to 5 parts by weight of monostarin, 0 to 2 parts by weight of Ethylene Bis stearic acid (hereinafter referred to as EBS), N, N'-ethylenebisoleic acid amide (N, N). −Ethylene bisoleamide, hereinafter referred to as EBO) 0 to 2 parts by weight, tributyl citrate 0 to 3 parts by weight, polyethylene wax (Polyethylene wax) 0 to 3 parts by weight, plasticized starch (Plasticized starch) 0 to 25 weight Parts, 0 to 10 parts by weight of calcium carbonate, 0.1 to 2 parts by weight of titanium dioxide, 1 to 5 parts by weight of stearic acid, 0 to 15 parts by weight of glycerol, It is characterized by being prepared from 0 to 3 parts by weight of epoxidized soybean oil and 0 to 2 parts by weight of a titanate coupling agent (dioctylphosphate) titantate.
また、上記の高度生分解性材料の調製方法において、変性ＰＬＡは、ＰＬＡ樹脂を１００重量部とした場合、ジグリシジルエーテル（Ｄｉｇｌｙｃｉｄｙｌ ｅｔｈｅｒ）が０．２〜２重量部、オキサゾリン系多官能モノマー（Ｐｏｌｙｆｕｎｃｔｉｏｎａｌ ｍｏｎｏｍｅｒ ｏｆ ｏｘａｚｏｌｉｎｅ）が０．１〜４重量部、トリフェニルホスフィン（Ｔｒｉｐｈｅｎｙｌｐｈｏｓｐｈｉｎｅ）が０．０５〜０．２重量部、酸化防止剤（Ａｎｔｉｏｘｉｄａｎｔ）が０．１〜１重量部、造核剤（Ｎｕｃｌｅａｔｉｎｇ ａｇｅｎｔ）が０．１〜１重量部であり、これらを高速混合機で十分に混合した後、１４０〜１６０℃の造粒温度で、二軸スクリュー押出機で造粒して得ることを特徴とする。 Further, in the above method for preparing a highly biodegradable material, when the PLA resin is 100 parts by weight, the modified PLA contains 0.2 to 2 parts by weight of diglycidyl ether and an oxazoline-based polyfunctional monomer (exazoline-based polyfunctional monomer). Polylactic monster of oxazole is 0.1 to 4 parts by weight, Triphenylphosfine is 0.05 to 0.2 parts by weight, Antioxidant is 0.1 to 1 part by weight, and nucleating agent (nucleating agent). Nucleating agent) is 0.1 to 1 part by weight, and these are sufficiently mixed with a high-speed mixer and then granulated with a twin-screw screw extruder at a granulation temperature of 140 to 160 ° C. And.
また、上記の高度生分解性材料の調製方法において、オキサゾリン系多官能モノマーは、２，２’−（１，４−フェニレン）オキサゾリン（２，２’−（１，４−ｐｈｅｎｙｌｅｎｅ）ｏｘａｚｏｌｉｎｅ）、２，２’−（１，３−フェニレン）ジオキサゾリン（２，２’−（１，３−ｐｈｅｎｙｌｅｎｅ）ｄｉｏｘａｚｏｌｉｎｅ）、２，２’−（１，２−フェニレン）ジオキサゾリン（２，２’−（１，２−ｐｈｅｎｙｌｅｎｅ）ｄｉｏｘａｚｏｌｉｎｅ）、２，２’−ビス（２−オキサゾリン）（２，２’−ｂｉｓ（２−ｏｘａｚｏｌｉｎｅ））、２，２’−ビス（５−メチルオキサゾリン）（２，２’−ｂｉｓ（５−ｍｅｔｈｙｌ ｏｘａｚｏｌｉｎｅ））、２，２’ −メチレン−ビス（５−メチルオキサゾリン）（２，２’−ｍｅｔｈｙｌｅｎｅ−ｂｉｓ（５ｍｅｔｈｙｌ ｏｘａｚｏｌｉｎｅ））、２，２’ −イソプロピレン−ビス（４−フェニル−２−オキサゾリン）（２，２’−ｉｓｏｐｒｏｐｙｌｅｎｅ−ｂｉｓ（４−ｐｈｅｎｙｌ−２−ｏｘａｚｏｌｉｎｅ））、２，２’ −イソプロピレン−ビス（３−フェニル−２−オキサゾリン）（ ２，２’−ｉｓｏｐｒｏｐｙｌｅｎｅ−ｂｉｓ（３−ｐｈｅｎｙｌ−２−ｏｘａｚｏｌｉｎｅ））、および２，２’−イソプロピレン−ビス（２−フェニル−２−オキサゾリン）（ ２，２’−ｉｓｏｐｒｏｐｙｌｅｎｅ−ｂｉｓ（２−ｐｈｅｎｙｌ−２−ｏｘａｚｏｌｉｎｅ））から選択される少なくとも１種であることを特徴とする。 Further, in the above method for preparing a highly biodegradable material, the oxazoline-based polyfunctional monomer is 2,2'-(1,4-phenylene) oxazoline (2,2'-(1,4-phenylene) oxazoline). 2,2'-(1,3-phenylene) dioxazoline (2,2'-(1,3-phenylene) dioxazoline), 2,2'-(1,2-phenylene) dioxazoline (2,2'- (1,2-phenylene) dioxazoline), 2,2'-bis (2-oxazoline) (2,2'-bis (2-oxazoline)), 2,2'-bis (5-methyloxazoline) (2, 2'-bis (5-methyl oxazoline), 2,2'-methylene-bis (5-methyloxazoline) (2,2'-methylene-bis (5methyl oxazoline)), 2,2'-isopropylene-bis (4-Phenyl-2-oxazoline) (2,2'-isopropyrene-bis (4-phenyl-2-oxazoline)), 2,2'-isopropylene-bis (3-phenyl-2-oxazoline) (2, 2'-isopropylene-bis (3-phenyl-2-oxazoline), and 2,2'-isopropylene-bis (2-phenyl-2-oxazoline) (2,2'-isopropylene-bis (2-phenyl-) It is characterized in that it is at least one selected from 2-oxazoline)).
また、上記の高度生分解性材料の調製方法において、酸化防止剤は、酸化防止剤ＩＲＧＡＮＯＸ１３３０（ＢＡＳＦ社製）であることを特徴とする。 Further, in the above method for preparing a highly biodegradable material, the antioxidant is an antioxidant IRGANOX1330 (manufactured by BASF).
また、上記の高度生分解性材料の調製方法において、造核剤は、セバシン酸ジ安息香酸ヒドラジド（Ｄｉｂｅｎｚｏｙｌｈｙｄｒａｚｉｄｅ ｓｅｂａｃａｔｅ）であることを特徴とする。 Further, in the above-mentioned method for preparing a highly biodegradable material, the nucleating agent is hydrazide sebacate dibenzoic acid (Dibenzoylhydrazide sebacate).
また、上記の高度生分解性材料の調製方法において、変性超微細タルク粉末は、３０００〜６０００メッシュの超微細タルク粉末１００部を高速混合機に入れて１００℃の温度で２０分間脱水した後に、水分を測定して０．０１％以下に抑え、脱水した材料にアセチルクエン酸トリブチル０．３〜１部およびＫＨ５６０ １〜５部を加え、２０分間低速で撹拌してから、さらに１０分間高速混合（）して得ることを特徴とする。 Further, in the above method for preparing a highly biodegradable material, the modified ultrafine talc powder is prepared by placing 100 parts of ultrafine talc powder of 3000 to 6000 mesh in a high-speed mixer and dehydrating at a temperature of 100 ° C. for 20 minutes. Measure the water content to keep it below 0.01%, add 0.3 to 1 part of tributyl acetylcitrate and 1 to 5 parts of KH560 to the dehydrated material, stir at low speed for 20 minutes, and then mix at high speed for another 10 minutes. It is characterized by being obtained by ().
また、上記の高度生分解性材料の調製方法において、可塑化澱粉は、澱粉１００部を高速混合機に入れて８０〜１００℃の温度で２０〜３０分間高速攪拌してから、グリセロール２０〜３０部と無水マレイン酸２〜３部を加え、さらに２０〜３０分間高速混合して得ることを特徴とする。 Further, in the above method for preparing a highly biodegradable material, for plasticized starch, 100 parts of starch is placed in a high-speed mixer and stirred at a temperature of 80 to 100 ° C. for 20 to 30 minutes, and then glycerol 20 to 30 is obtained. It is characterized by adding 2 to 3 parts of maleic anhydride and further mixing at high speed for 20 to 30 minutes.
また、上記の高度生分解性材料の調製方法において、（１）変性ＰＬＡを調製するステップと、（２）変性超微細タルク粉末を調製するステップと、（３）可塑化澱粉を調製するステップと、（４）変性ＰＬＡ３０〜８０重量部、ＰＢＡＴ３０〜８０重量部、変性超微細タルク粉末５〜２５重量部、モノステアリン１〜５重量部、ＥＢＳ０〜２重量部、ＥＢＯ０〜２重量部、クエン酸トリブチル０〜３重量部、ポリエチレンワックス０〜３重量部、可塑化澱粉０〜２５重量部、炭酸カルシウム０〜１０部、二酸化チタン０．１〜２重量部、ステアリン酸１〜５重量部、グリセロール０〜１５重量部、エポキシ化大豆油０〜３重量部、およびチタネートカップリング剤０〜２重量部を高速混合機に投入し、８０〜１００℃の温度で強く均一に攪拌して、プレミックスを得るステップと、（５）プレミックスをさらに二軸スクリュー押出機の供給口から投入し、二軸スクリュー押出機の各段の温度を１４０〜１７５℃に制御して、溶融押出し、空気冷却およびペレット化して、ブロー成形、射出成形、ホットプレス成形、真空成形、押出成形などの成形工程に使用できる高度生分解性材料を得るステップと、含むことを特徴とする。 Further, in the above method for preparing a highly biodegradable material, there are (1) a step of preparing a modified PLA, (2) a step of preparing a modified ultrafine talc powder, and (3) a step of preparing a plasticized starch. , (4) Modified PLA 30 to 80 parts by weight, PBAT 30 to 80 parts by weight, Modified ultrafine talc powder 5 to 25 parts by weight, Monostea 1 to 5 parts by weight, EBS 0 to 2 parts by weight, EBO 0 to 2 parts by weight, Citric acid 0 to 3 parts by weight of tributyl, 0 to 3 parts by weight of polyethylene wax, 0 to 25 parts by weight of plasticized starch, 0 to 10 parts of calcium carbonate, 0.1 to 2 parts by weight of titanium dioxide, 1 to 5 parts by weight of stearate, glycerol. Add 0 to 15 parts by weight, 0 to 3 parts by weight of epoxidized soybean oil, and 0 to 2 parts by weight of the titanate coupling agent into a high-speed mixer, stir strongly and uniformly at a temperature of 80 to 100 ° C., and premix. And (5) the premix is further charged from the supply port of the twin screw extruder, and the temperature of each stage of the twin screw extruder is controlled to 140 to 175 ° C., melt extrusion, air cooling and It is characterized by including a step of pelletizing to obtain a highly biodegradable material that can be used in molding processes such as blow molding, injection molding, hot press molding, vacuum molding and extrusion molding.
本発明の調製方法によれば、性能が優れて、耐熱性がよく、コストが低く、ブロー成形、射出成形、ホットプレス成形、真空成形、押出成形などの様々な成形工程に使用でき、且つ１８０日以内に実質的に生分解して堆肥として使用することができる高度生分解性材料を得ることができる。 According to the preparation method of the present invention, it has excellent performance, good heat resistance, low cost, can be used in various molding processes such as blow molding, injection molding, hot press molding, vacuum forming, extrusion molding, and 180. It is possible to obtain a highly biodegradable material that can be substantially biodegraded within a day and used as a compost.
以下、実施例に基づいて本発明についてさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail based on Examples.
（実施例１）変性ＰＬＡの調製
ＰＬＡ１０００ｇ、ジグリシジルエーテル２ｇ、２，２’−（１，３−フェニレン）ジオキサゾリン１ｇ、トリフェニルホスフィン０．５ｇ、酸化防止剤ＩＲＧＡＮＯＸ１３３０（ＢＡＳＦ社製）１ｇ、セバシン酸ジ安息香酸ヒドラジド１ｇを高速混合機（一例として約１４００ｒｐｍ、本明細書中で同様）で十分に混合した後、１４０〜１６０℃の造粒温度で、二軸スクリュー押出機で造粒して変性ＰＬＡを得る。得られた変性ＰＬＡは以下の実施例に使用可能である。
(Example 1) Preparation of modified PLA 1000 g of PLA, 2 g of diglycidyl ether, 1 g of 2,2'-(1,3-phenylene) dioxazoline, 0.5 g of triphenylphosphine, 1 g of antioxidant IRGANOX1330 (manufactured by BASF), After sufficiently mixing 1 g of dibenzoic acid hydrazide sebacic acid with a high-speed mixer (for example, about 1400 rpm, the same applies herein), granulate with a twin-screw screw extruder at a granulation temperature of 140 to 160 ° C. To obtain modified PLA. The obtained modified PLA can be used in the following examples.
（実施例２）変性超微細タルク粉末の調製
５０００メッシュの超微細タルク粉末１０００ｇを高速混合機に入れて１００℃の温度で２０分間脱水した後に、水分を測定して０．０１％以下に抑え、脱水した材料にアセチルクエン酸トリブチル５ｇおよびＫＨ５６０ １０ｇを加え、２０分間低速（一例として約７００ｒｐｍ、本明細書中で同様）で撹拌してから、さらに１０分間高速混合（一例として約１４００ｒｐｍ、本明細書中で同様）して変性超微細タルク粉末を得る。得られた変性超微細タルク粉末は以下の実施例に使用可能である。
(Example 2) Preparation of modified ultrafine talc powder After putting 1000 g of 5000 mesh ultrafine talc powder in a high-speed mixer and dehydrating at a temperature of 100 ° C. for 20 minutes, the water content is measured and suppressed to 0.01% or less. , 5 g of tributyl acetylcitrate and 10 g of KH560 were added to the dehydrated material, stirred at low speed for 20 minutes (about 700 rpm as an example, the same in the present specification), and then mixed at high speed for another 10 minutes (about 1400 rpm as an example). The same applies in the specification) to obtain a modified ultrafine talc powder. The obtained modified ultrafine talc powder can be used in the following examples.
（実施例３）可塑化澱粉の調製
澱粉１０００ｇを高速混合機に入れて８０〜１００℃の温度で２０〜３０分間高速撹拌（一例として約１４００ｒｐｍ、本明細書中で同様）してから、グリセロール２５０ｇと無水マレイン酸２０ｇを加え、さらに２０〜３０分間高速撹拌して可塑化澱粉を得る。得られた可塑化澱粉は以下の実施例に使用可能である。
(Example 3) Preparation of plasticized starch 1000 g of starch is placed in a high-speed mixer and stirred at high speed for 20 to 30 minutes at a temperature of 80 to 100 ° C. (for example, about 1400 rpm, the same in the present specification), and then glycerol. 250 g and 20 g of maleic anhydride are added, and the mixture is further stirred at high speed for 20 to 30 minutes to obtain plasticized starch. The obtained plasticized starch can be used in the following examples.
（実施例４）高度生分解性薄膜の調製
変性ＰＬＡ８００ｇ、ＰＢＡＴ８００ｇ、変性超微細タルク粉末２５０ｇ、モノステアリン５０ｇ、ＥＢＳ１０ｇ、ＥＢＯ５ｇ、クエン酸トリブチル１５ｇ、ポリエチレンワックス１０ｇ、可塑化澱粉２００ｇ、二酸化チタン１ｇ、ステアリン酸１０ｇ、エポキシ化大豆油１５ｇ、およびチタネートカップリング剤１０ｇを高速混合機に投入し、８０〜１００℃の温度で強く均一に攪拌して、プレミックスを得る。プレミックスをさらに二軸スクリュー押出機の供給口から投入し、溶融押出し、空気冷却およびペレット化して、インフレーションフィルム用のペレットを得る。押出ペレット化の条件としては、二軸スクリュー押出機の各段の温度を１４０〜１７５℃に制御する。インフレーションフィルム用のペレットはさらにインフレーションフィルム成形機でインフレーションフィルム成形して、高度生分解性薄膜を得る。インフレーションフィルム成形温度は１３５〜１５５℃である。
(Example 4) Preparation of highly biodegradable thin film Modified PLA 800 g, PBAT 800 g, modified ultrafine talc powder 250 g, monostearic acid 50 g, EBS 10 g, EBO 5 g, tributyl citrate 15 g, polyethylene wax 10 g, plasticized starch 200 g, titanium dioxide 1 g, 10 g of stearic acid, 15 g of epoxidized soybean oil, and 10 g of titanate coupling agent are put into a high-speed mixer and stirred strongly and uniformly at a temperature of 80 to 100 ° C. to obtain a premix. The premix is further fed through the supply port of the twin screw extruder, melt extruded, air cooled and pelletized to obtain pellets for an inflation film. As a condition for extrusion pelletization, the temperature of each stage of the twin-screw extruder is controlled to 140 to 175 ° C. The pellets for the inflation film are further molded by the inflation film forming machine to obtain a highly biodegradable thin film. The inflation film molding temperature is 135 to 155 ° C.
（実施例５）高度生分解性シートの調製
変性ＰＬＡ６００ｇ、ＰＢＡＴ３００ｇ、変性超微細タルク粉末５０ｇ、モノステアリン２０ｇ、クエン酸トリブチル１５ｇ、ポリエチレンワックス２５ｇ、可塑化澱粉２００ｇ、炭酸カルシウム１００ｇ、二酸化チタン２０ｇ、ステアリン酸３０ｇ、エポキシ化大豆油２０ｇ、およびチタネートカップリング剤１０ｇを高速混合機に投入し、８０〜１００℃の温度で強く均一に攪拌して、プレミックスを得る。プレミックスをさらに二軸スクリュー押出機の供給口から投入し、溶融押出し、空気冷却およびペレット化して、シート材用のペレットを得る。押出ペレット化の条件としては、二軸スクリュー押出機の各段の温度を１４０〜１７５℃に制御する。シート材用のペレットはさらに二軸スクリューシートマシンでシート成形して、高度生分解性シートを得る。得られた高度生分解性シートは真空成型製品に使用可能である。
(Example 5) Preparation of highly biodegradable sheet Modified PLA 600 g, PBAT 300 g, modified ultrafine talc powder 50 g, monostearic acid 20 g, tributyl citrate 15 g, polyethylene wax 25 g, plasticized starch 200 g, calcium carbonate 100 g, titanium dioxide 20 g, 30 g of stearic acid, 20 g of epoxidized soybean oil, and 10 g of titanate coupling agent are put into a high-speed mixer and stirred strongly and uniformly at a temperature of 80 to 100 ° C. to obtain a premix. The premix is further charged from the supply port of the twin-screw extruder, melt-extruded, air-cooled and pelletized to obtain pellets for sheet material. As a condition for extrusion pelletization, the temperature of each stage of the twin-screw extruder is controlled to 140 to 175 ° C. The pellets for the sheet material are further sheet-molded with a twin-screw sheet machine to obtain a highly biodegradable sheet. The obtained highly biodegradable sheet can be used for vacuum forming products.
（実施例６）高度生分解性射出成形材料の調製
変性ＰＬＡ１６００ｇ、ＰＢＡＴ１２００ｇ、変性超微細タルク粉末３００ｇ、モノステアリン５０ｇ、クエン酸トリブチル２０ｇ、ポリエチレンワックス６０ｇ、炭酸カルシウム２００ｇ、二酸化チタン２０ｇ、ステアリン酸４０ｇ、およびエポキシ化大豆油２０ｇを高速混合機に投入し、８０〜１００℃の温度で強く均一に攪拌して、プレミックスを得る。プレミックスをさらに二軸スクリュー押出機の供給口から投入し、溶融押出し、空気冷却およびペレット化して、射出成形用のペレットを得る。押出ペレット化の条件としては、二軸スクリュー押出機の各段の温度を１４０〜１７５℃に制御する。得られたペレットは様々な高度生分解性製品の射出成形に使用可能である。
(Example 6) Preparation of highly biodegradable injection molding material Modified PLA 1600 g, PBAT 1200 g, modified ultrafine talc powder 300 g, monostea 50 g, tributyl citrate 20 g, polyethylene wax 60 g, calcium carbonate 200 g, titanium dioxide 20 g, stearic acid 40 g , And 20 g of denaturated soybean oil are put into a high speed mixer and stirred strongly and uniformly at a temperature of 80-100 ° C. to obtain a premix. The premix is further fed through the supply port of the twin screw extruder and melt extruded, air cooled and pelletized to obtain pellets for injection molding. As a condition for extrusion pelletization, the temperature of each stage of the twin-screw extruder is controlled to 140 to 175 ° C. The resulting pellets can be used for injection molding of various highly biodegradable products.
（実施例７）高度生分解性飲料ストローの調製
変性ＰＬＡ８００ｇ、ＰＢＡＴ１６００ｇ、変性超微細タルク粉末４００ｇ、モノステアリン５０ｇ、クエン酸トリブチル１５ｇ、ポリエチレンワックス１０ｇ、二酸化チタン１ｇ、ステアリン酸１０ｇ、およびエポキシ化大豆油１５ｇを高速混合機に投入し、８０〜１００℃の温度で強く均一に攪拌して、プレミックスを得る。プレミックスをさらに二軸スクリュー押出機の供給口から投入し、溶融押出し、空気冷却およびペレット化して、飲料ストロー調製用のペレットを得る。押出ペレット化の条件としては、二軸スクリュー押出機の各段の温度を１４０〜１７５℃に制御する。飲料ストロー調製用のペレットはさらにストロー押出機でストロー成形して、高度生分解性飲料ストローを得る。
(Example 7) Preparation of highly biodegradable beverage straw 800 g of modified PLA, 1600 g of PBAT, 400 g of modified ultrafine talc powder, 50 g of monostearate, 15 g of tributyl citrate, 10 g of polyethylene wax, 1 g of titanium dioxide, 10 g of stearic acid, and large epoxidation. 15 g of soybean oil is put into a high-speed mixer and stirred strongly and uniformly at a temperature of 80 to 100 ° C. to obtain a premix. The premix is further fed through the supply port of the twin screw extruder and melt extruded, air cooled and pelletized to obtain pellets for the preparation of beverage straws. As a condition for extrusion pelletization, the temperature of each stage of the twin-screw extruder is controlled to 140 to 175 ° C. The pellets for preparing beverage straws are further straw-molded with a straw extruder to obtain highly biodegradable beverage straws.
本発明の調製方法によって得られる高度生分解性材料は、ブロー成形、射出成形、ホットプレス成形、真空成形、押出成形などの様々な成形工程に使用可能である。 The highly biodegradable material obtained by the preparation method of the present invention can be used in various molding steps such as blow molding, injection molding, hot press molding, vacuum forming and extrusion molding.
上記の目的を達成するための本発明は、高度生分解性材料の調製方法であって、変性ＰＬＡ３０〜８０重量部、ＰＢＡＴ３０〜８０重量部、変性超微細タルク粉末（ｍｏｄｉｆｉｅｄ Ｕｌｔｒａｆｉｎｅ Ｔａｌｃ Ｐｏｗｄｅｒ）５〜２５重量部、モノステアリン（Ｍｏｎｏｓｔｅａｒｉｎ）１〜５重量部、エチレンビスステアリン酸アミド（Ｅｔｈｙｌｅｎｅ Ｂｉｓ Ｓｔｅａｒａｍｉｄｅ、以下ＥＢＳと称する）０〜２重量部、Ｎ，Ｎ’−エチレンビスオレイン酸アミド（Ｎ，Ｎ−ｅｔｈｙｌｅｎｅｂｉｓｏｌｅａｍｉｄｅ、以下ＥＢＯと称する）０〜２重量部、クエン酸トリブチル（Ｔｒｉｂｕｔｙｌ Ｃｉｔｒａｔｅ）０〜３重量部、ポリエチレンワックス（Ｐｏｌｙｅｔｈｙｌｅｎｅ ｗａｘ）０〜３重量部、可塑化澱粉（Ｐｌａｓｔｉｃｉｚｅｄ ｓｔａｒｃｈ）０〜２５重量部、炭酸カルシウム（Ｃａｌｃｉｕｍ ｃａｒｂｏｎａｔｅ）０〜１０重量部、二酸化チタン（Ｔｉｔａｎｉｕｍ ｄｉｏｘｉｄｅ）０．１〜２重量部、ステアリン酸（Ｓｔｅａｒｉｃ ａｃｉｄ）１〜５重量部、グリセロール（Ｇｌｙｃｅｒｏｌ）０〜１５重量部、エポキシ化大豆油（Ｅｐｏｘｉｄｉｚｅｄ ｓｏｙｂｅａｎ ｏｉｌ）０〜３重量部、およびチタネートカップリング剤（Ｉｓｏｐｒｏｐｙｌ ｄｉｏｌｅｉｃ（ｄｉｏｃｔｙｌｐｈｏｓｐｈａｔｅ）ｔｉｔａｎａｔｅ）０〜２重量部の原料から調製され、
前記変性超微細タルク粉末は、３０００〜６０００メッシュの超微細タルク粉末１００重量部を高速混合機に入れて１００℃の温度で２０分間脱水した後に、水分を測定して０．０１％以下に抑え、脱水した材料にアセチルクエン酸トリブチル０．３〜１重量部およびＫＨ５６０ １〜５重量部を加え、２０分間低速撹拌してから、さらに１０分間高速混合して得ることを特徴とする。
また、本発明に係る他の高度生分解性材料の調製方法は、変性ポリ乳酸３０〜８０重量部、ポリブチレンアジペートテレフタレート３０〜８０重量部、変性超微細タルク粉末５〜２５重量部、モノステアリン１〜５重量部、エチレンビスステアリン酸アミド０〜２重量部、Ｎ，Ｎ’−エチレンビスオレイン酸アミド０〜２重量部、クエン酸トリブチル０〜３重量部、ポリエチレンワックス０〜３重量部、可塑化澱粉０〜２５重量部、炭酸カルシウム０〜１０重量部、二酸化チタン０．１〜２重量部、ステアリン酸１〜５重量部、グリセロール０〜１５重量部、エポキシ化大豆油０〜３重量部、およびチタネートカップリング剤０〜２重量部の原料から調製され、２５重量部までの前記可塑化澱粉を含み、前記可塑化澱粉は、澱粉１００重量部を高速混合機に入れて８０〜１００℃の温度で２０〜３０分間高速攪拌してから、グリセロール２０〜３０重量部と無水マレイン酸２〜３重量部を加え、さらに２０〜３０分間高速混合して得ることを特徴とする。
The present invention for achieving the above object is a method for preparing a highly biodegradable material, which comprises 30 to 80 parts by weight of modified PLA, 30 to 80 parts by weight of PBAT, and modified ultrafine talc powder (modified Ultrafine Tarc Powerer) 5 to 5. 25 parts by weight, 1 to 5 parts by weight of monostearin, 0 to 2 parts by weight of polyethylene bisstearamide (hereinafter referred to as EBS), N, N'-ethylenebisoleic acid amide (N, N). −Ethylene bisoleamide, hereinafter referred to as EBO) 0 to 2 parts by weight, tributyl citrate 0 to 3 parts by weight, polyethylene wax (Polyethylene wax) 0 to 3 parts by weight, plasticized starch (Plasticized starch) 0 to 25 parts by weight. Parts, 0 to 10 parts by weight of calcium carbonate, 0.1 to 2 parts by weight of titanium dioxide, 1 to 5 parts by weight of stearic acid, 0 to 15 parts by weight of glycerol, Prepared from 0 to 3 parts by weight of epoxidized soybean oil and 0 to 2 parts by weight of a titanate coupling agent (isopolyethylene (dioctylphosphate) titantate) .
In the modified ultrafine talc powder, 100 parts by weight of ultrafine talc powder of 3000 to 6000 mesh is placed in a high-speed mixer and dehydrated at a temperature of 100 ° C. for 20 minutes, and then the water content is measured and suppressed to 0.01% or less. , 0.3 to 1 part by weight of tributyl acetylcitrate and 1 to 5 parts by weight of KH560 are added to the dehydrated material, and the mixture is stirred at low speed for 20 minutes and then mixed at high speed for 10 minutes .
In addition, other methods for preparing highly biodegradable materials according to the present invention include 30 to 80 parts by weight of modified polylactic acid, 30 to 80 parts by weight of polybutylene adipate terephthalate, 5 to 25 parts by weight of modified ultrafine starch powder, and monostearic acid. 1-5 parts by weight, ethylene bisstearic acid amide 0 to 2 parts by weight, N, N'-ethylene bisoleic acid amide 0 to 2 parts by weight, tributyl citrate 0 to 3 parts by weight, polyethylene wax 0 to 3 parts by weight, 0 to 25 parts by weight of plasticized starch, 0 to 10 parts by weight of calcium carbonate, 0.1 to 2 parts by weight of titanium dioxide, 1 to 5 parts by weight of stearic acid, 0 to 15 parts by weight of glycerol, 0 to 3 parts by weight of epoxidized soybean oil. 80 to 100 parts of the plasticized starch prepared from 0 to 2 parts by weight of the titanate coupling agent and up to 25 parts by weight of the plasticized starch, with 100 parts by weight of the starch placed in a high speed mixer. After stirring at high speed for 20 to 30 minutes at a temperature of ° C., 20 to 30 parts by weight of glycerol and 2 to 3 parts by weight of maleic anhydride are added, and the mixture is further mixed at high speed for 20 to 30 minutes .
また、上記の高度生分解性材料の調製方法において、酸化防止剤は、酸化防止剤ＩＲＧＡＮＯＸ（登録商標）１３３０（ＢＡＳＦ社製）であることを特徴とする。 Further, in the above method for preparing a highly biodegradable material, the antioxidant is an antioxidant IRGANOX (registered trademark) 1330 (manufactured by BASF).
また、上記の高度生分解性材料の調製方法において、（１）変性ＰＬＡを調製するステップと、（２）変性超微細タルク粉末を調製するステップと、（３）可塑化澱粉を調製するステップと、（４）変性ＰＬＡ３０〜８０重量部、ＰＢＡＴ３０〜８０重量部、変性超微細タルク粉末５〜２５重量部、モノステアリン１〜５重量部、ＥＢＳ０〜２重量部、ＥＢＯ０〜２重量部、クエン酸トリブチル０〜３重量部、ポリエチレンワックス０〜３重量部、可塑化澱粉０〜２５重量部、炭酸カルシウム０〜１０重量部、二酸化チタン０．１〜２重量部、ステアリン酸１〜５重量部、グリセロール０〜１５重量部、エポキシ化大豆油０〜３重量部、およびチタネートカップリング剤０〜２重量部を高速混合機に投入し、８０〜１００℃の温度で強く均一に攪拌して、プレミックスを得るステップと、（５）プレミックスをさらに二軸スクリュー押出機の供給口から投入し、二軸スクリュー押出機の各段の温度を１４０〜１７５℃に制御して、溶融押出し、空気冷却およびペレット化して、ブロー成形、射出成形、ホットプレス成形、真空成形、および押出成形から選択したいずれかを含む成形工程に使用できる高度生分解性材料を得るステップと、
を含み、
前記変性超微細タルク粉末は、３０００〜６０００メッシュの超微細タルク粉末１００重量部を高速混合機に入れて１００℃の温度で２０分間脱水した後に、水分を測定して０．０１％以下に抑え、脱水した材料にアセチルクエン酸トリブチル０．３〜１重量部およびＫＨ５６０ １〜５重量部を加え、２０分間低速撹拌してから、さらに１０分間高速混合して調製し、
２５重量部までの前記可塑化澱粉を含み、前記可塑化澱粉は、澱粉１００重量部を高速混合機に入れて８０〜１００℃の温度で２０〜３０分間高速攪拌してから、グリセロール２０〜３０重量部と無水マレイン酸２〜３重量部を加え、さらに２０〜３０分間高速混合して得ることを特徴とする。
Further, in the above method for preparing a highly biodegradable material, there are (1) a step of preparing a modified PLA, (2) a step of preparing a modified ultrafine talc powder, and (3) a step of preparing a plasticized starch. , (4) Modified PLA 30 to 80 parts by weight, PBAT 30 to 80 parts by weight, Modified ultrafine starch powder 5 to 25 parts by weight, Monostea 1 to 5 parts by weight, EBS 0 to 2 parts by weight, EBO 0 to 2 parts by weight, Citric acid tributyl 0-3 parts by weight, 0-3 parts by weight of polyethylene wax, 0-25 parts by weight of plasticized starch, 0-10 parts by weight of calcium carbonate, 0.1 to 2 parts by weight titanium dioxide, 1 to 5 parts by weight of stearic acid, 0 to 15 parts by weight of glycerol, 0 to 3 parts by weight of epoxidized soybean oil, and 0 to 2 parts by weight of the titanate coupling agent are put into a high-speed mixer, and the mixture is strongly and uniformly stirred at a temperature of 80 to 100 ° C. The step of obtaining the mix and (5) the premix is further charged from the supply port of the twin-screw extruder, the temperature of each stage of the twin-screw extruder is controlled to 140 to 175 ° C., melt extrusion, and air cooling. And pelleting to obtain a highly biodegradable material that can be used in molding processes, including one of the choices of blow molding, injection molding, hot press molding, vacuum molding, and extrusion.
Including
In the modified ultrafine talc powder, 100 parts by weight of ultrafine talc powder of 3000 to 6000 mesh is placed in a high-speed mixer and dehydrated at a temperature of 100 ° C. for 20 minutes, and then the water content is measured and suppressed to 0.01% or less. , 0.3 to 1 part by weight of tributyl acetylcitrate and 1 to 5 parts by weight of KH560 were added to the dehydrated material, and the mixture was stirred at low speed for 20 minutes and then mixed at high speed for another 10 minutes to prepare.
Containing up to 25 parts by weight of the plasticized starch, the plasticized starch is prepared by placing 100 parts by weight of starch in a high-speed mixer and stirring at a temperature of 80 to 100 ° C. for 20 to 30 minutes, and then glycerol 20 to 30. It is characterized by adding 2 to 3 parts by weight of maleic anhydride and 2 to 3 parts by weight and further mixing at high speed for 20 to 30 minutes .
（実施例１）変性ＰＬＡの調製
ＰＬＡ１０００ｇ、ジグリシジルエーテル２ｇ、２，２’−（１，３−フェニレン）ジオキサゾリン１ｇ、トリフェニルホスフィン０．５ｇ、酸化防止剤ＩＲＧＡＮＯＸ（登録商標）１３３０（ＢＡＳＦ社製）１ｇ、セバシン酸ジ安息香酸ヒドラジド１ｇを高速混合機（一例として約１４００ｒｐｍ、本明細書中で同様）で十分に混合した後、１４０〜１６０℃の造粒温度で、二軸スクリュー押出機で造粒して変性ＰＬＡを得る。得られた変性ＰＬＡは以下の実施例に使用可能である。
(Example 1) Preparation of modified PLA 1000 g of PLA, 2 g of diglycidyl ether, 1 g of 2,2'-(1,3-phenylene) dioxazoline, 0.5 g of triphenylphosphine, antioxidant IRGANOX (registered trademark) 1330 (BASF ) 1 g of dibenzoic acid hydrazide sevacinate (manufactured by the same company) is sufficiently mixed with a high-speed mixer (for example, about 1400 rpm, the same applies herein), and then a twin-screw screw extrusion is performed at a granulation temperature of 140 to 160 ° C. Granulate with a machine to obtain modified PLA. The obtained modified PLA can be used in the following examples.
Claims (8)
（１）前記変性ポリ乳酸を調製するステップと、
（２）前記変性超微細タルク粉末を調製するステップと、
（３）可塑化澱粉を調製するステップと、
（４）前記変性ポリ乳酸３０〜８０重量部、ポリブチレンアジペートテレフタレート３０〜８０重量部、変性超微細タルク粉末５〜２５重量部、モノステアリン１〜５重量部、エチレンビスステアリン酸アミド０〜２重量部、Ｎ，Ｎ’−エチレンビスオレイン酸アミド０〜２重量部、クエン酸トリブチル０〜３重量部、ポリエチレンワックス０〜３重量部、可塑化澱粉０〜２５重量部、炭酸カルシウム０〜１０部、二酸化チタン０．１〜２重量部、ステアリン酸１〜５重量部、グリセロール０〜１５重量部、エポキシ化大豆油０〜３重量部、およびチタネートカップリング剤０〜２重量部を高速混合機に投入し、８０〜１００℃の温度で強く均一に攪拌して、プレミックスを得るステップと、
（５）プレミックスをさらに二軸スクリュー押出機の供給口から投入し、二軸スクリュー押出機の各段の温度を１４０〜１７５℃に制御して、溶融押出し、空気冷却およびペレット化して、ブロー成形、射出成形、ホットプレス成形、真空成形、押出成形などの成形工程に使用できる高度生分解性材料を得るステップと、
を含むことを特徴とする高度生分解性材料の調製方法。 In the method for preparing a highly biodegradable material according to claim 1,
(1) The step of preparing the modified polylactic acid and
(2) The step of preparing the modified ultrafine talc powder and
(3) Steps to prepare plasticized starch and
(4) 30 to 80 parts by weight of the modified polylactic acid, 30 to 80 parts by weight of polybutylene adipate terephthalate, 5 to 25 parts by weight of modified ultrafine talc powder, 1 to 5 parts by weight of monostearic acid, 0 to 2 parts by weight of ethylene bisstearic acid. By weight, N, N'-ethylenebisoleic acid amide 0 to 2 parts by weight, tributyl citrate 0 to 3 parts by weight, polyethylene wax 0 to 3 parts by weight, plasticized starch 0 to 25 parts by weight, calcium carbonate 0 to 10 parts by weight High-speed mixing of 0.1 to 2 parts by weight of titanium dioxide, 1 to 5 parts by weight of stearic acid, 0 to 15 parts by weight of glycerol, 0 to 3 parts by weight of epoxidized soybean oil, and 0 to 2 parts by weight of titanate coupling agent. The step of putting it in a machine and stirring it strongly and uniformly at a temperature of 80 to 100 ° C. to obtain a premix,
(5) The premix is further charged from the supply port of the twin-screw extruder, the temperature of each stage of the twin-screw extruder is controlled to 140 to 175 ° C., melt extrusion, air cooling and pelletization are performed, and blown. Steps to obtain highly biodegradable materials that can be used in molding processes such as molding, injection molding, hot press molding, vacuum molding, extrusion molding,
A method for preparing a highly biodegradable material, which comprises.
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