JP4929564B2 - Biodegradable tubular molded product - Google Patents
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Abstract
Description
本発明は生分解性管状成形品に関するものであり、ワンウェイで使用されるストローに関する。 The present invention relates to a biodegradable tubular molded article, about the stroke over which is used in one way.
従来より、例えばストローやチューブなどの管状成形品には、石油由来のポリエチレン系、ポリスチレン系またはポリプロピレン系などの樹脂が多く用いられている（例えば、特許文献１参照。）。これら管状成形品のうちワンウェイで使用されるものは、使用後に廃棄され、埋め立てまたは焼却により処理されることが通常である。 Conventionally, for example, petroleum-derived polyethylene-based, polystyrene-based, or polypropylene-based resins are often used for tubular molded articles such as straws and tubes (for example, see Patent Document 1). Of these tubular molded articles, those used in one way are usually discarded after use and processed by landfill or incineration.
ところが、石油由来の樹脂を埋め立てた場合は、分解されることなく半永久的にその姿をとどめ、また焼却する場合は、燃焼発熱量が高く、二酸化炭素の排出量も多く、環境への負荷が高くなる。そのため、例えば滑石（タルク）を混入し、素材の強度と剛性を保ちつつ、原材料の使用量を減らすことにより焼却時の発熱が抑止できるようにした飲料用ストロー（例えば、特許文献２参照。）や、自然分解するため埋め立てられる環境負荷の低い素材、例えば澱粉を主原料とした通孔を有するストローなどのような管（例えば、特許文献３参照。）などが提案されている。 However, when petroleum-derived resin is reclaimed, it remains semipermanently without being decomposed, and when it is incinerated, it generates a high amount of combustion heat, emits a large amount of carbon dioxide, and has an environmental impact. Get higher. Therefore, for example, talc is mixed to maintain the strength and rigidity of the raw material and reduce the amount of raw material used so that the heat generated during incineration can be suppressed (see, for example, Patent Document 2). In addition, a material having a low environmental load that is buried for natural decomposition, for example, a tube such as a straw having a through hole made of starch as a main raw material (see, for example, Patent Document 3) has been proposed.
一方近年では、特許文献３に記載された澱粉の他にも、コンポスト化（好気性発酵）・バイオガス化（嫌気性発酵）が可能な、バイオマス由来の素材が多く見出されている。例えばポリ乳酸もその一つである（例えば、特許文献４参照。）。 On the other hand, in addition to the starch described in Patent Document 3, many biomass-derived materials that can be composted (aerobic fermentation) / biogasified (anaerobic fermentation) have been found. For example, polylactic acid is one of them (for example, see Patent Document 4).
しかしながら、上記特許文献２に記載された飲料ストローは、埋め立て処理しようにも、生分解性を有するものではなく、結局のところ焼却処理せざるを得ない。また、特許文献３に記載された通孔を有する管は、澱粉を練って製造したものであり、ストローなどに用いた場合、使用時の曲げに弱く、ひび割れや破損などを生じやすいうえ、使用時の口当たりも良いものではない。一方、ポリ乳酸を用いて、例えばストローなどを製造した場合も、ポリ乳酸１００重量％の樹脂は硬く衝撃に弱いため、製造時のカッティングや使用時の曲げなどにより、ひび割れや破損などを生じやすいことが判明した。 However, the beverage straw described in the above-mentioned Patent Document 2 is not biodegradable even if it is landfilled, and eventually must be incinerated. In addition, the tube having a through hole described in Patent Document 3 is manufactured by kneading starch, and when used in a straw or the like, it is vulnerable to bending during use and is likely to be cracked or damaged. The taste of time is not good either. On the other hand, even when a straw or the like is produced using polylactic acid, for example, the resin of 100% by weight of polylactic acid is hard and vulnerable to impact, so that it is liable to be cracked or damaged by cutting during production or bending during use. It has been found.
そこで本発明者らは、上記課題に鑑みて、ポリ乳酸を主成分とし、例えばストローやチューブなどの管状成形品として、製造や使用に耐えうるものを鋭意研究した結果、特定のポリエステル重合体を混ぜ合わせることにより実現できることを見出し、本発明を完成した。 Therefore, in view of the above problems, the present inventors have conducted research on what can withstand production and use as a tubular molded product such as a straw or a tube, for example, based on polylactic acid. The present invention has been completed by finding out that it can be realized by mixing.
すなわち本発明の目的は、環境への負荷が少なく、コンポスト化・バイオガス化が可能であり、曲げ・衝撃に強く、食品用途への使用も可能な生分解性ストローを提供することにある。 That is, an object of the present invention is to provide a biodegradable straw that has little impact on the environment, can be composted and biogasified, is resistant to bending and impact, and can be used for food applications.
上述の目的を達成するため、本発明による生分解性ストローは、ポリ乳酸が９０重量％以下と、脂肪族ポリエステルおよび脂肪族−芳香族ポリエステルが合計１０重量％以上とからなることを特徴としている。 In order to achieve the above-described object, the biodegradable straw according to the present invention is characterized by comprising polylactic acid of 90 % by weight or less and aliphatic polyester and aliphatic-aromatic polyester of 10 % by weight or more in total. .
さらに、脂肪族ポリエステルは、ポリブチレンサクシネートまたはポリブチレンサクシネート・アジペートであることが好ましい。また、脂肪族−芳香族ポリエステルは、ポリブチレンアジペート・テレフタレートであることが好ましい。 Further, the aliphatic polyester is preferably polybutylene succinate or polybutylene succinate adipate. The aliphatic-aromatic polyester is preferably polybutylene adipate terephthalate.
そして、本発明のストローとしては、ポリ乳酸が９０重量％以下と、脂肪族ポリエステルおよび脂肪族−芳香族ポリエステルが合計１０重量％以上とからなる混練物（ただし、ケイ酸マグネシウムを含むものを除く）を、管状に押出成形し、冷却工程を経て、所定の長さにカットする製造方法により得ることが好適である。 And as a straw of the present invention, a kneaded product comprising polylactic acid of 90 % by weight or less and a total of aliphatic polyester and aliphatic-aromatic polyester of 10 % by weight or more (excluding those containing magnesium silicate) ) Is preferably obtained by a manufacturing method in which a tube is extruded and cut into a predetermined length through a cooling step.
以上のように、本発明によれば、環境への負荷が少なく、コンポスト化・バイオガス化が可能であり、曲げ・衝撃に強く、食品用途への使用も可能な生分解性ストローを提供できる。 As described above, according to the present invention, it is possible to provide a biodegradable straw that has low environmental impact, can be composted and biogasified, is resistant to bending and impact, and can be used for food applications. .
特に、押出成形によりストローを得るときは、製造時のカッティングや使用時の曲げなどによっても、ひび割れや破損などを起こすことがない。また使用時にストローを噛んだ場合に割れることもなく、さらに口当たりも良い。 In particular, when a straw is obtained by extrusion, cracking or breakage does not occur due to cutting during manufacture or bending during use. Moreover, when a straw is bitten at the time of use, it does not break and is even better.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のポリ乳酸は、従来公知の方法で合成することができる。具体的には、乳酸からの直接重合、または乳酸環状二量体ラクチドの開環重合によって合成することができる。開環重合では、より高分子量のものを得ることができる。 The polylactic acid of the present invention can be synthesized by a conventionally known method. Specifically, it can be synthesized by direct polymerization from lactic acid or ring-opening polymerization of lactic acid cyclic dimer lactide. In the ring-opening polymerization, a higher molecular weight can be obtained.
直接重合を行なう場合、Ｌ−乳酸、Ｄ−乳酸、ＤＬ−乳酸、またはこれらの混合物のいずれの乳酸を用いても良い。また、開環重合を行なう場合においても、Ｌ−ラクチド、Ｄ−ラクチド、ＤＬ−ラクチド、メソ−ラクチドまたはこれらの混合物のいずれのラクチドを用いても良い。 When direct polymerization is performed, any lactic acid of L-lactic acid, D-lactic acid, DL-lactic acid, or a mixture thereof may be used. Also, in the case of carrying out ring-opening polymerization, any lactide of L-lactide, D-lactide, DL-lactide, meso-lactide or a mixture thereof may be used.
この重合反応に用いる触媒は特に限定されるものではないが、公知の乳酸重合用触媒を用いることができる。触媒の使用量は、一般にラクチド１００重量部に対して０．００１〜５重量部程度である。 Although the catalyst used for this polymerization reaction is not particularly limited, a known catalyst for lactic acid polymerization can be used. The amount of the catalyst used is generally about 0.001 to 5 parts by weight with respect to 100 parts by weight of lactide.
重合反応は、上記触媒の存在下、触媒種によっても異なるが通常１００〜２００℃の温度で行うことができる。 The polymerization reaction can be usually performed at a temperature of 100 to 200 ° C. in the presence of the catalyst, although it varies depending on the catalyst type.
本発明に使用する乳酸ポリマーは、Ｌ−乳酸単位、Ｄ−乳酸単位の構成モル比Ｌ／Ｄは１００／０〜０／１００のいずれであってもよい。また、Ｌ−乳酸とＤ−乳酸のブロック共重合体、ランダム共重合体、または混合物でもよい。 The lactic acid polymer used in the present invention may have a constituent molar ratio L / D of L-lactic acid units and D-lactic acid units of 100/0 to 0/100. Further, a block copolymer, a random copolymer, or a mixture of L-lactic acid and D-lactic acid may be used.
本発明の脂肪族ポリエステルとは、生分解性を有するものであり、ポリ乳酸を含まないものである。脂肪族ポリエステルは、脂肪族二価アルコールと脂肪族ジカルボン酸を重合して得られるもの、環状ラクトン類を開環重合したもの、合成系のもの、菌体内で生合成されるもの等があげられるが、脂肪族二価アルコールと脂肪族ジカルボン酸を重合して得られるものが最適である。 The aliphatic polyester of the present invention is biodegradable and does not contain polylactic acid. Aliphatic polyesters include those obtained by polymerizing aliphatic dihydric alcohols and aliphatic dicarboxylic acids, those obtained by ring-opening polymerization of cyclic lactones, those synthesized, and those biosynthesized in bacterial cells. However, those obtained by polymerizing an aliphatic dihydric alcohol and an aliphatic dicarboxylic acid are optimal.
上記脂肪族二価アルコールと脂肪族ジカルボン酸を重合して得られる脂肪族ポリエステ
ルは、脂肪族二価アルコールであるエチレングリコール、ブタンジオール、１．３プロパンジオール、ヘキサンジオール及びオクタンジオールなどから少なくとも１種類と、脂肪族ジカルボン酸であるコハク酸、アジピン酸、セバシン酸及びドデカン二酸等から少なくとも１種類とを選択し、重合して得られる。さらに、アジペート共重合化して得られるものも良い。そのような具体例として、コハク酸、ブタンジオールおよびエチレングリコールから得られるポリブチレンサクシネートまたはポリブチレンサクシネート・アジペート等があげられる。
The aliphatic polyester obtained by polymerizing the aliphatic dihydric alcohol and the aliphatic dicarboxylic acid is at least 1 from the aliphatic dihydric alcohols such as ethylene glycol, butanediol, 1.3 propanediol, hexanediol, and octanediol. It is obtained by polymerizing by selecting at least one type from succinic acid, adipic acid, sebacic acid, dodecanedioic acid and the like which are aliphatic dicarboxylic acids. Furthermore, what is obtained by adipate copolymerization is also good. Specific examples thereof include polybutylene succinate or polybutylene succinate adipate obtained from succinic acid, butanediol and ethylene glycol.
また、本発明の脂肪族−芳香族ポリエステルとは、生分解性を有するものであり、ポリ乳酸を含まないものである。脂肪族−芳香族ポリエステルは、脂肪族ポリエステルに、適量の芳香族成分（例えば、芳香族ジカルボン酸など）を共重合して得られる。そのような具体例として、ポリブチレンアジペート・テレフタレート等があげられる。 The aliphatic-aromatic polyester of the present invention is biodegradable and does not contain polylactic acid. The aliphatic-aromatic polyester is obtained by copolymerizing an aliphatic polyester with an appropriate amount of an aromatic component (for example, aromatic dicarboxylic acid). Specific examples thereof include polybutylene adipate and terephthalate.
本願発明の生分解性ストローにおいては、曲げ・衝撃により強くするには、ポリ乳酸を９０重量％以下とし、上記脂肪族ポリエステルおよび脂肪族−芳香族ポリエステルの合計を１０重量％以上とする。なお、脂肪族ポリエステルおよび脂肪族−芳香族ポリエステルは、その比率を特に限定するものではない。 In the biodegradable straw of the present invention, the stronger the bending-impact, polylactic acid and 90 wt% or less, the aliphatic polyester and aliphatic - you the total of the aromatic polyester and 10 wt% or more . The ratio of the aliphatic polyester and the aliphatic-aromatic polyester is not particularly limited.
本発明の生分解性ストローを得るには、まず、ポリ乳酸、脂肪族ポリエステルおよび脂肪族−芳香族ポリエステルの適宜量を溶融状態で混合させるが、その方法は通常の公知の方法が可能である。例えば、それぞれペレット化したポリ乳酸、脂肪族ポリエステルおよび脂肪族−芳香族ポリエステルを混合し、単軸又は二軸混練機等で溶融混合する方法でも可能である。そして、得られた溶融状態の混練物を、公知の押出成形機を用いて、管状に押出成形し、冷却工程を経て、所定の長さにカットする。 In order to obtain the biodegradable straw of the present invention, first, appropriate amounts of polylactic acid, aliphatic polyester and aliphatic-aromatic polyester are mixed in a molten state, and the method can be a commonly known method. . For example, a method of mixing pelletized polylactic acid, aliphatic polyester, and aliphatic-aromatic polyester and melt-mixing them with a single-screw or twin-screw kneader or the like is also possible. Then, the obtained kneaded material in a molten state is extruded into a tubular shape using a known extruder and cut into a predetermined length through a cooling step.
以下、本発明を実施例及び比較例を例示することにより具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example illustrate this invention concretely, this invention is not limited at all by these Examples.
＜生分解性管状成形品の製造＞
Ｌ−ラクチド９８重量％、Ｄ−ラクチド２重量％と、オクチル酸スズを重合触媒として用いてポリ乳酸樹脂を得た。このポリ乳酸樹脂と、脂肪族ポリエステルとしてのポリブチレンサクシネート・アジペート（昭和高分子（株）製ビオノーレ＃３０００）および脂肪族−芳香族ポリエステルとしてのポリブチレンアジペート・テレフタレート（ＢＡＳＦ社製エコフレックス）を表１に示す割合で、単軸の混練機で溶融混練し、得られた溶融混練物を、チューブ状サーキュラーのダイで、直径５ｍｍ、肉厚０．２ｍｍの管状に押出成形し、長さ２０ｃｍにカットして、ストローを得た。
<Manufacture of biodegradable tubular molded products>
A polylactic acid resin was obtained using 98% by weight of L-lactide, 2% by weight of D-lactide and tin octylate as a polymerization catalyst. This polylactic acid resin, polybutylene succinate adipate as an aliphatic polyester (Bionole # 3000 manufactured by Showa Polymer Co., Ltd.) and polybutylene adipate terephthalate as an aliphatic-aromatic polyester (Ecoflex manufactured by BASF) Were melt-kneaded with a single-screw kneader at the ratio shown in Table 1, and the obtained melt-kneaded product was extruded into a tubular tube having a diameter of 5 mm and a wall thickness of 0.2 mm with a tubular circular die. Cut to 20 cm to obtain a straw.
＜生分解性管状成形品の評価方法＞
（１）切断による割れ評価
得られたストローの先端から１０ｍｍの位置を、汎用のはさみを用いて、ストロー１０本をカットした。切断によってストローの切断部分に割れを生じた本数に応じて次の基準で判定した。
・割れた本数０〜２本：判定 ○
・割れた本数３〜４本：判定 △
・割れた本数５本〜 ：判定 ×
<Method for evaluating biodegradable tubular molded article>
(1) Crack evaluation by cutting Ten straws were cut at 10 mm from the end of the obtained straw using general-purpose scissors. Judgment was made according to the following criteria according to the number of cracks in the cut portion of the straw.
-Number of cracks 0-2: Judgment ○
-Number of cracks 3-4: Judgment △
・ The number of cracks is 5 or more: Judgment ×
（２）衝撃による割れ評価
得られたストローをシャルピー衝撃試験機を用いて、ストロー１０本に対し、衝撃試験を行った。衝撃によるストローの割れの本数に応じて上記同様の基準で判定した。
(2) Crack evaluation by impact Using the Charpy impact tester, the obtained straw was subjected to an impact test on 10 straws. The determination was made according to the same criteria as described above according to the number of straw cracks caused by impact.
（３）噛み込みによる割れ評価
得られたストローを銜え、奥歯で５回噛むことを１０本に対しそれぞれ行った。噛み込みによるストローの割れの本数に応じて上記同様の基準で判定した。
(3) Evaluation of cracking due to biting Ten of the obtained straws were gripped and chewed five times with the back teeth. The determination was made according to the same criteria as above according to the number of straw cracks caused by biting.
＜実施例１、比較例１〜３＞
上記ポリ乳酸樹脂と、ポリブチレンサクシネート・アジペートおよびポリブチレンアジペート・テレフタレートの構成比を変えて得られたストローの評価結果を表１に示す。
<Example 1 , Comparative Examples 1-3 >
Table 1 shows the evaluation results of the straws obtained by changing the constituent ratios of the polylactic acid resin, polybutylene succinate adipate, and polybutylene adipate terephthalate.
表１の比較例１から明らかなように、ポリ乳酸１００％のものは、切断や衝撃による割れが多く、また噛み込みによる割れもみられ、ストローとしての実用性が得られない。 As is clear from Comparative Example 1 in Table 1, 100% polylactic acid has many cracks due to cutting and impact, and cracks due to biting are also observed, so that practicality as a straw cannot be obtained.
そして、比較例２および比較例３から明らかなように、脂肪族ポリエステルであるポリブチレンサクシネート・アジペートまたは脂肪族−芳香族ポリエステルであるポリブチレンアジペート・テレフタレートを５重量％以上含むストローは、噛み込みによる割れがみられず、ストローとして使用するうえの実用性が有ることが分かる。 As is apparent from Comparative Example 2 and Comparative Example 3 , a straw containing 5% by weight or more of polybutylene succinate adipate which is an aliphatic polyester or polybutylene adipate terephthalate which is an aliphatic-aromatic polyester is bitten. It can be seen that there is no practical cracking due to the use of a straw.
また、実施例１から明らかなように、脂肪族ポリエステルであるポリブチレンサクシネート・アジペートおよび脂肪族−芳香族ポリエステルであるポリブチレンアジペート・テレフタレートをともに用いることで、噛み込みによる割れとともに切断や衝撃による割れもみられず、ストローとして使用するうえの実用性があり、さらに製造時（例えば押出成形後の切断時）の実用性もより向上することが分かる。 As is clear from Example 1, polybutylene succinate adipate and aliphatic aliphatic polyester - that have use both polybutylene adipate terephthalate aromatic polyester, Ya cut with cracks due to biting It can be seen that there is no cracking due to impact, there is practicality in use as a straw, and further practicality at the time of production (for example, at the time of cutting after extrusion molding) is further improved.
以上のように、本実施例のストローは、製造時のカッティングや使用時の曲げなどによっても、ひび割れや破損などを起こすことがない。また使用時にストローを噛んだ場合に割れることもなく、さらに口当たりも良い。 As described above, the straw of this embodiment does not cause cracking or breakage due to cutting during manufacture or bending during use. Moreover, when a straw is bitten at the time of use, it does not break and is even better.
本発明の生分解性管状成形品は、ストローとして広く利用することができる。 The biodegradable tubular molded article of the present invention can be widely used as a straw.
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| US11865855B2 (en) | 2018-12-18 | 2024-01-09 | SOCIéTé BIC | Lead casing for pencil, and pencil thereof for writing, drawing, marking, plotting, and coloring |
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|---|---|---|---|---|
| JP5393566B2 (en) * | 2010-03-30 | 2014-01-22 | 富士ケミカル株式会社 | Tubular molded product |
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| JP3508678B2 (en) * | 1995-03-09 | 2004-03-22 | トヨタ自動車株式会社 | Polylactic acid composition and molded article thereof |
| JP3662152B2 (en) * | 1999-11-19 | 2005-06-22 | 三菱樹脂株式会社 | Biodegradable shrink tube |
| JP3510218B2 (en) * | 2001-05-02 | 2004-03-22 | ユニチカ株式会社 | Polylactic acid based film and method for producing the same |
| JP2003286354A (en) * | 2002-01-28 | 2003-10-10 | Asahi Kasei Corp | Biodegradable oriented film |
| JP4223245B2 (en) * | 2002-08-07 | 2009-02-12 | ユニチカ株式会社 | Biodegradable polyester resin composition, method for producing the same, and foam and molded product obtained therefrom |
| US7138439B2 (en) * | 2004-02-27 | 2006-11-21 | Biocorp North America, Inc. | Biodegradable compounds including poly(lactic acid) polymer compositions and products |
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| US11865855B2 (en) | 2018-12-18 | 2024-01-09 | SOCIéTé BIC | Lead casing for pencil, and pencil thereof for writing, drawing, marking, plotting, and coloring |
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