JP6887796B2 - Biodegradable film with tear propagation resistance - Google Patents
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Description
本発明は生分解性フィルムに関し、例えば農業用のハウスやマルチフィルム等に用いられる生分解性フィルムに関する。 The present invention relates to a biodegradable film, for example, a biodegradable film used for an agricultural house, a mulch film, or the like.
従来、野菜などの栽培において生産性を向上させるために、土壌の温度を一定に保ち、農作物の育成を促進したり、雑草の発生を抑制したりする農業用マルチフィルムが農業資材として広く用いられている。
ここで、前記農業用マルチフィルムは、使用後回収し、廃棄処理する必要がある。しかし、農業は使用する土地も広いことが多く、回収は重労働となっている。
Conventionally, in order to improve productivity in the cultivation of vegetables, agricultural multi-films that keep the soil temperature constant, promote the growth of crops, and suppress the growth of weeds have been widely used as agricultural materials. ing.
Here, the agricultural mulch film needs to be collected after use and disposed of. However, agriculture often uses a large amount of land, and recovery is a heavy labor.
上記問題を解決する手段として、生分解性フィルムがある。該生分解性フィルムは、使用後、土壌にすき込むことによって、土中にて分解される。この為、重労働とされている前記回収作業などを省略でき、農作業の負担を減らすことができる。 There is a biodegradable film as a means for solving the above problem. After use, the biodegradable film is decomposed in the soil by being plowed into the soil. Therefore, the above-mentioned collection work, which is regarded as heavy labor, can be omitted, and the burden of agricultural work can be reduced.
前記生分解性フィルムとしては、例えばポリエステル系樹脂等がよく使用されている。しかし、生分解性フィルムとして用いられる前記ポリエステル系樹脂からなるフィルムは、もしフィルム上のいずれかの箇所にでも傷を有している場合、引っ張り等の力が加わると、前記傷から裂け目が広がりやすいことが問題となっている。例えばマルチフィルムとして展張する際等には、主にトラクター等でフィルムを引っ張り出しながら田畑に敷いていくが、石等の突起物でフィルムが傷ついた際等、前記トラクターの引っ張り出す力によって一気に裂け目が広がり、綺麗に展張し難いなどの問題が生じていた。
該課題を解決する生分解性フィルムとして、例えば特許文献１に開示されている生分解性ポリエステルフィルムがある。
As the biodegradable film, for example, a polyester resin or the like is often used. However, if the film made of the polyester resin used as a biodegradable film has scratches at any part on the film, when a force such as pulling is applied, the tears widen from the scratches. The problem is that it is easy. For example, when spreading as a mulch film, the film is mainly pulled out by a tractor and laid in the field, but when the film is damaged by protrusions such as stones, the pulling force of the tractor causes a rift at once. Spread, and there were problems such as difficulty in spreading it neatly.
As a biodegradable film that solves this problem, for example, there is a biodegradable polyester film disclosed in Patent Document 1.
上記特許文献１では、少なくとも、脂肪族及び芳香族ジカルボン酸と脂肪族ジヒドロキシ化合物を基礎とする生分解性ポリエステルと、ポリヒドロキシアルカノエートに、炭酸カルシウム、滑石を含有する生分解性ポリエステルフィルムが開示されており、引裂伝播性の改善を計っている。しかし、該技術においては、炭酸カルシウムといった無機粒子の分散性が悪く、混合中に凝集が起こり易い。結果として、製造されたフィルムには該炭酸カルシウムが凝集している箇所が点在し、良好に分散されていないため、展張の際の張力によって該箇所からフィルムが破れ易くなるといった問題があった。また、添加した炭酸カルシウムが凝集して点在、すなわち良好に分散していないため、結果として傷ついた際の裂け目の伝播の改善が十分ではなかった。 Patent Document 1 discloses at least a biodegradable polyester based on an aliphatic or aromatic dicarboxylic acid and an aliphatic dihydroxy compound, and a biodegradable polyester film containing calcium carbonate and talc in polyhydroxyalkanoate. It has been designed to improve tear propagation. However, in this technique, the dispersibility of inorganic particles such as calcium carbonate is poor, and aggregation tends to occur during mixing. As a result, the produced film is dotted with places where the calcium carbonate is agglomerated and is not well dispersed, so that there is a problem that the film is easily torn from the places due to the tension at the time of stretching. .. In addition, the added calcium carbonate was aggregated and scattered, that is, it was not well dispersed, and as a result, the improvement of the propagation of the crevice when injured was not sufficient.
本発明はかかる課題を解決し、設置作業時等に破れ難く、たとえ傷が付いても該傷が裂け目として伝播し難い、すなわち傷が広がり難い生分解性フィルムを提供することである。 The present invention solves this problem and provides a biodegradable film that is hard to tear during installation work and the like, and even if it is scratched, the scratch is hard to propagate as a crevice, that is, the scratch is hard to spread.
かかる課題に対し、鋭意検討した結果、生分解性フィルム中に炭酸カルシウムを良好に分散させることで引裂伝播強度を向上させる点に着目し、本発明に至った。 As a result of diligent studies on such a problem, the present invention has been made by paying attention to the point that the tear propagation strength is improved by satisfactorily dispersing calcium carbonate in the biodegradable film.
すなわち、本発明は、（１）炭酸カルシウム微粒子と生分解性樹脂とを含有してなる生分解性フィルムであり、前記生分解性樹脂は、ポリブチレンアジペートテレフタレート（ＰＢＡＴ）、ポリブチレンサクシネートアジペート（ＰＢＳＡ）、ポリブチレンサクシネート（ＰＢＳ）から選ばれる少なくとも１種類以上である。
また、前記炭酸カルシウムは、表面に官能基を有する微粒子で、平均粒径が８０ｎｍ以上２００ｎｍ以下であり、前記生分解性フィルムを構成する組成物１００重量％に対し、２０重量％以上含有されていることを特徴とする耐引裂伝播性を有する生分解性フィルム。
（２）前記請求項１に記載の生分解性フィルムであって、厚みが１０μｍ以上１００μｍ以下であることを特徴とする農業用マルチフィルム。
That is, the present invention is (1) a biodegradable film containing (1) calcium carbonate fine particles and a biodegradable resin, and the biodegradable resin is polybutylene adipate terephthalate (PBAT) or polybutylene succinate adipate. (PBSA), at least one selected from polybutylene succinate (PBS).
Further, the calcium carbonate is fine particles having a functional group on the surface, has an average particle size of 80 nm or more and 200 nm or less, and is contained in an amount of 20% by weight or more with respect to 100% by weight of the composition constituting the biodegradable film. A biodegradable film having tear propagation resistance, which is characterized by being present.
(2) The biodegradable film according to claim 1, wherein the thickness is 10 μm or more and 100 μm or less.
本発明によれば、フィルム中に炭酸カルシウムを良好に分散させることができ、展張中の緊張力による破れの発生を良好に抑制でき、且つ仮に展張中等に土壌中の石等による引っ掻き傷等が付いたとしても該傷から裂け目が伝播してフィルムが裂けてしまうといった問題を解消できる。 According to the present invention, calcium carbonate can be satisfactorily dispersed in the film, the occurrence of tearing due to tension during expansion can be satisfactorily suppressed, and scratches or the like caused by stones or the like in the soil can be tentatively suppressed during expansion. Even if it is attached, the problem that the crevice propagates from the scratch and the film is torn can be solved.
以下、本発明の生分解性フィルムについて図と併せて詳細に説明するが、該説明は本発明を何ら限定するものではない。
なお、各図中の（ａ）は端部が傷付いたフィルムであり、（ｂ）は（ａ）に示す矢印方向の力が加わった際のフィルムの引裂き挙動を示している。
Hereinafter, the biodegradable film of the present invention will be described in detail with reference to the drawings, but the description does not limit the present invention in any way.
In each figure, (a) is a film whose edges are damaged, and (b) shows the tearing behavior of the film when a force in the direction of the arrow shown in (a) is applied.
［生分解性樹脂］
本発明の生分解性フィルムは、生分解性樹脂を主成分としてなる。生分解性樹脂は、詳しくは、ポリブチレンアジペートテレフタレート（ＰＢＡＴ）、ポリブチレンサクシネートアジペート（ＰＢＳＡ）、ポリブチレンサクシネート（ＰＢＳ）から選ばれる少なくとも１種類以上である。
なお、ＰＢＡＴはＢＡＳＦ製「エコフレックス」、ＰＢＳ及びＰＢＳＡは昭和電工株式会社製「ビオノーレ」や三菱化学株式会社製「ＧＳ Ｐｌａ」等が挙げられる。
[Biodegradable resin]
The biodegradable film of the present invention contains a biodegradable resin as a main component. The biodegradable resin is, in particular, at least one selected from polybutylene adipate terephthalate (PBAT), polybutylene succinate adipate (PBSA), and polybutylene succinate (PBS).
Examples of PBAT include "Ecoflex" manufactured by BASF, and examples of PBS and PBSA include "Bionore" manufactured by Showa Denko Corporation and "GS Pla" manufactured by Mitsubishi Chemical Corporation.
また、好ましい樹脂組成としては、ポリブチレンテレフタレート（ＰＢＡＴ）、ポリブチレンサクシネート（ＰＢＳ）、ポリブチレンサクシネートアジペート（ＰＢＳＡ）等の混合物が好ましく、その混合比率としては、ＰＢＡＴは２０〜８０質量％、ＰＢＳは０〜６０質量％、ＰＢＳＡは０〜６０質量％であることが好ましい。
なお、本発明の効果を損ねない範囲で他の生分解性樹脂や添加剤等を含んでもよい。
Further, as a preferable resin composition, a mixture of polybutylene terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA) and the like is preferable, and the mixing ratio thereof is 20 to 80% by mass of PBAT. , PBS is preferably 0 to 60% by mass, and PBSA is preferably 0 to 60% by mass.
In addition, other biodegradable resins, additives and the like may be contained as long as the effects of the present invention are not impaired.
［炭酸カルシウム］
炭酸カルシウムは、引裂き伝播性を抑制するために添加させるものである。
前記炭酸カルシウムは、表面修飾が施され、表面に官能基を有する粒子であり、レーザー解析法によって導き出される平均粒径が８０〜２００ｎｍである。
前記表面修飾は、例えばパルミトレイン酸、パルミチン酸、リノレン酸、ステアリン酸、オレイン酸等の飽和又は不飽和脂肪酸によって表面処理することによって形成され、粒子の分散性を向上させる。
また、前記平均粒径が８０ｎｍ未満の場合、前記表面処理を施していても、粒子間のファンデルワールス力が大きすぎ、結果として、部分的に炭酸カルシウムの分散状態が悪化して凝集体が生じる箇所が発生し、該箇所から裂け等の傷が発生し易い。一方、２００ｎｍを超える場合、フィルムの厚みが薄い場合にはフィルム表面の平滑性が失われ易く、また、製膜時に穴あきなどの不良が発生しやすくなるおそれがある。
[Calcium carbonate]
Calcium carbonate is added to suppress tear propagation.
The calcium carbonate is a particle having a surface modification and having a functional group on the surface, and has an average particle size of 80 to 200 nm derived by a laser analysis method.
The surface modification is formed by surface treatment with saturated or unsaturated fatty acids such as palmitoleic acid, palmitic acid, linolenic acid, stearic acid, and oleic acid, and improves the dispersibility of the particles.
Further, when the average particle size is less than 80 nm, the van der Waals force between the particles is too large even if the surface treatment is applied, and as a result, the dispersed state of calcium carbonate is partially deteriorated and aggregates are formed. Occurrence occurs, and scratches such as tears are likely to occur from the location. On the other hand, if it exceeds 200 nm, the smoothness of the film surface is likely to be lost if the film is thin, and defects such as holes are likely to occur during film formation.
更に、前記炭酸カルシウムの含有量は、前記生分解性フィルムを構成する組成物１００重量％に対し、少なくとも２０重量％以上である。
前記含有量が２０重量％未満の場合、フィルム中の炭酸カルシウムの分散密度が足りず、耐引裂伝播性を得られにくい。また、４０重量％を超える場合、樹脂に対する無機物の量が多くなり、引張物性が低下するおそれがあるため、炭酸カルシウムの含有量は生分解性フィルムを構成する組成物１００重量％に対し、２０〜４０重量％とすることが好ましい。
Further, the content of the calcium carbonate is at least 20% by weight or more with respect to 100% by weight of the composition constituting the biodegradable film.
When the content is less than 20% by weight, the dispersion density of calcium carbonate in the film is insufficient, and it is difficult to obtain tear propagation resistance. On the other hand, if it exceeds 40% by weight, the amount of the inorganic substance with respect to the resin may increase and the tensile physical characteristics may decrease. Therefore, the content of calcium carbonate is 20 with respect to 100% by weight of the composition constituting the biodegradable film. It is preferably ~ 40% by weight.
本発明の生分解性フィルムは、緊張力による傷が生じ難く、また、傷が付いても該傷が伝播し難いため、農業用マルチフィルムとして好適に使用できる。農業用マルチフィルムとする場合、１０μｍ以上１００μｍ以下の厚みとすることが好ましい。厚みが１０μｍ未満の場合、ハンドリング性が低下するおそれがあり、一方、１００μｍを超える場合、分解期間が長くなりすぎるおそれがある。 The biodegradable film of the present invention is less likely to be scratched by tension, and even if it is scratched, the scratches are less likely to propagate, so that it can be suitably used as an agricultural mulch film. In the case of an agricultural mulch film, the thickness is preferably 10 μm or more and 100 μm or less. If the thickness is less than 10 μm, the handleability may be deteriorated, while if it exceeds 100 μm, the decomposition period may be too long.
また、本発明の効果を損なわない範囲で、通常、生分解性フィルムに用いられている添加剤を混合することができる。例えば、紫外線吸収剤、顔料、滑剤、可塑剤等が挙げられる。 In addition, additives usually used for biodegradable films can be mixed as long as the effects of the present invention are not impaired. For example, ultraviolet absorbers, pigments, lubricants, plasticizers and the like can be mentioned.
本発明のフィルムの製造方法としては、インフレーション成形等の溶融押出成形や、カレンダー成形等の従来公知の方法が用いられる。尚、本発明の生分解性フィルムを、農業用マルチフィルムとして用いる場合、成形性の観点からインフレーション成形が好ましい。 As a method for producing a film of the present invention, conventionally known methods such as melt extrusion molding such as inflation molding and calendar molding are used. When the biodegradable film of the present invention is used as an agricultural mulch film, inflation molding is preferable from the viewpoint of moldability.
各実施例について、表に記載の配合比の組成物を、Ｔダイ押出機を用いて厚み２０μｍの生分解性フィルムを製膜し、外観、製膜性、引裂き物性を評価した。
［試料］
ＰＢＡＴ：ＢＡＳＦ製 Ｅｃｏｆｌｅｘ Ｆｂｌｅｎｄ Ｃ１２００
ＰＢＳ：三菱化学株式会社製 ＡＺ９１ＴＮ
ＰＢＳＡ：三菱化学株式会社製 ＡＤ９２ＷＮ
For each example, a biodegradable film having a thickness of 20 μm was formed from the composition of the compounding ratio shown in the table using a T-die extruder, and the appearance, film-forming property, and tearing physical property were evaluated.
[sample]
PBAT: BASF Ecoflex Fblend C1200
PBS: AZ91TN manufactured by Mitsubishi Chemical Corporation
PBSA: AD92WN manufactured by Mitsubishi Chemical Corporation
［外観］
製膜したフィルムを、透過台を用いて目視で確認し、異物数を測定し、以下の基準で評価した。
○：０．５ｍｍ２以上の異物が１０個未満／ｍ２
△：０．５ｍｍ２以上の異物が１０個以上／ｍ２、２０個未満／ｍ２
×：異物が全面に発生し、良好な製膜が不可能
［製膜性］
以下の基準で評価した。
○：樹脂単体と同様に製膜可能
△：製膜できるが、安定化が困難
×：製膜できない
［引裂き物性］
＜引裂き性＞
手でＭＤ方向へ引裂いて感触を確認した。
○：引裂き時に抵抗を感じ、一直線に裂け目が伝播しなかった
×：一直線に裂け目が伝播した
＜エルメンドルフ＞
縦７６ｍｍ、横６３ｍｍの試料を用意し、ＭＤ方向又はＴＤ方向中央に２０ｍｍの切れ込みを入れ、エルメンドルフにて引裂き強度を確認し、以下の基準で評価した。
〔ＭＤ方向〕
○：１００Ｎ以上
×：１００Ｎ未満
[appearance]
The formed film was visually confirmed using a transmission table, the number of foreign substances was measured, and the film was evaluated according to the following criteria.
◯: 0.5 mm 2 or more foreign substances less than 10 / m 2
Δ: 0.5 mm 2 or more foreign substances 10 or more / m 2 , less than 20 / m 2
X: Foreign matter is generated on the entire surface, and good film formation is impossible [Film formation property]
Evaluation was made based on the following criteria.
◯: Can form a film in the same way as a single resin △: Can form a film, but is difficult to stabilize ×: Cannot form a film [Tear physical characteristics]
<Tearability>
The feel was confirmed by tearing it in the MD direction by hand.
○: I felt resistance when tearing, and the rift did not propagate in a straight line ×: The rift propagated in a straight line <Elmendorf>
A sample having a length of 76 mm and a width of 63 mm was prepared, a notch of 20 mm was made in the center of the MD direction or the TD direction, the tear strength was confirmed by Elmendorf, and the sample was evaluated according to the following criteria.
[MD direction]
◯: 100N or more ×: less than 100N
本発明の生分解性フィルムは、炭酸カルシウムが良好に分散しており、炭酸カルシウムの凝集が少なく、緊張力に対する裂けの発生を良好に抑制できる。また、炭酸カルシウムが良好に分散していることで、傷が発生しても、該傷から裂け目が伝播し難い生分解性フィルムを得られる。 In the biodegradable film of the present invention, calcium carbonate is well dispersed, calcium carbonate is less agglomerated, and the occurrence of tearing due to tension can be satisfactorily suppressed. In addition, since calcium carbonate is well dispersed, a biodegradable film can be obtained in which tears are less likely to propagate from the scratches even if scratches occur.
１：生分解性フィルム
２：傷
３：裂け目
1: Biodegradable film 2: Scratch 3: Rip
Claims (2)
前記生分解性樹脂は、ポリブチレンアジペートテレフタレート（ＰＢＡＴ）、ポリブチレンサクシネートアジペート（ＰＢＳＡ）、ポリブチレンサクシネート（ＰＢＳ）から選ばれる少なくとも１種類以上であり、
前記炭酸カルシウム微粒子は、飽和又は不飽和脂肪酸によって表面処理されたもので、かつ平均粒径が８０ｎｍ以上２００ｎｍ以下であり、
前記生分解性フィルムを構成する組成物１００重量％に対し、２０重量％以上含有されていることを特徴とする耐引裂伝播性を有する生分解性フィルム。 A biodegradable film containing fine particles of calcium carbonate and a biodegradable resin.
The biodegradable resin is at least one selected from polybutylene adipate terephthalate (PBAT), polybutylene succinate adipate (PBSA), and polybutylene succinate (PBS).
The calcium carbonate fine particles are surface-treated with saturated or unsaturated fatty acids and have an average particle size of 80 nm or more and 200 nm or less .
A biodegradable film having tear propagation resistance, which is contained in an amount of 20% by weight or more based on 100% by weight of the composition constituting the biodegradable film.
The biodegradable film according to claim 1, wherein the thickness is 10 μm or more and 100 μm or less.
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| CN107556716B (en) * | 2017-08-22 | 2019-10-18 | 界首市天鸿新材料股份有限公司 | A kind of production technology of bioerodible film |
| CN109553934A (en) * | 2018-10-25 | 2019-04-02 | 南京五瑞生物降解新材料研究院有限公司 | Using the PBS/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation |
| JP6802242B2 (en) * | 2018-11-26 | 2020-12-16 | Ｗｍ株式会社 | Method for producing biodegradable resin composition |
| CN112251002A (en) * | 2020-09-11 | 2021-01-22 | 新疆蓝山屯河降解材料有限公司 | PBS (Poly Butylene succinate) degradable packaging material with excellent toughness and temperature resistance and preparation method thereof |
| JP6916571B1 (en) | 2021-03-25 | 2021-08-11 | 株式会社Ｔｂｍ | Resin composition and molded product |
| WO2024117626A1 (en) * | 2022-11-29 | 2024-06-06 | 에스케이티비엠지오스톤 주식회사 | Biodegradable resin composition and biodegradable molded product comprising same |
| KR20240079911A (en) * | 2022-11-29 | 2024-06-05 | 에스케이티비엠지오스톤 주식회사 | Biodegradable resin composition biodegradable molded article comprising same |
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