JP4631252B2 - Method for decomposing a mixture of a molded body comprising a polylactic acid resin and a plant - Google Patents
Method for decomposing a mixture of a molded body comprising a polylactic acid resin and a plant Download PDFInfo
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- JP4631252B2 JP4631252B2 JP2003139898A JP2003139898A JP4631252B2 JP 4631252 B2 JP4631252 B2 JP 4631252B2 JP 2003139898 A JP2003139898 A JP 2003139898A JP 2003139898 A JP2003139898 A JP 2003139898A JP 4631252 B2 JP4631252 B2 JP 4631252B2
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- polylactic acid
- plant
- molded body
- net
- acid resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/105—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with enzymes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、生分解性樹脂組成物と植物の混合物の簡易な分解方法に関する。
【0002】
【従来の技術】
合成プラスチックは現代の社会生活において不可欠であるが、合成プラスチックの廃棄には焼却処理や埋め立て処理をする必要がある。焼却処理をした場合、地球温暖化の促進や、特定の種類のプラスチックは焼却時にダイオキシンの発生などの環境問題が懸念される。
【0003】
そこで、最近では生分解性樹脂組成物を使用して従来の合成プラスチックの代替に使用する試みがなされている。従来の合成プラスチックとほぼ同じ強度が得られる生分解性樹脂として、ポリ乳酸系樹脂があるが、ポリ乳酸系樹脂は分解が遅く土中などでは4〜5年と分解時間が長くかかってしまう問題点がある。
【0004】
例えば、特許文献1、2には、生分解性樹脂組成物のコンポスト化処理方法が開示されている。この方法は、生分解性樹脂組成物を細かく破砕しなければならないことに加え、生分解性樹脂組成物の含有量を抑えたり、有機性廃棄物を混合したりする必要があり、実施例を見れば明らかな通り、混合や破砕のために、一般的ではあるが大掛かりな混合装置が必要である。
【0005】
また、一般的な、プラスチックの分解方法として、特許文献3にハラタケ目菌類培養床を用いた分解方法が開示されている。例として、プラスチックがポリ乳酸であるものも挙げられ、さらに、尿素を栄養素として加えても良いことが開示されている。
【0006】
しかしながら、処理業者の場合には、温度を一定に保ったり、プラスチックを分解させるための菌を選択したりすることは可能であるが、一般家庭や、そのような装置がない場所での実施は現実的ではない。
【0007】
【特許文献1】
特開平9−249474号公報
【特許文献2】
特開平9−249475号公報
【特許文献3】
特開2002−348405号公報
【0008】
【発明が解決しようとする課題】
本発明の目的は、上記問題点を解消し、生分解性樹脂からなる成形体と植物の混合物に尿素を添加する事で、簡易に比較的短時間で生分解性樹脂から成る成形体を分解する方法を提供することにある。
【0009】
【課題を解決するための手段】
上記課題は、ポリ乳酸系樹脂からなる成形体と植物の混合物に尿素を添加することを特徴とする分解方法により解決する。
【0010】
【発明の実施の形態】
この方法に対する理解を助けるために考えられているメカニズムを説明する。
以下二段階のメカニズムが考えられている。
【0011】
分解の第一段階としては、ポリ乳酸系樹脂からなる成形体と植物の混合物の中で、植物部分が微生物による分解により発酵する工程である。この工程では、発酵によって、全体の温度が上昇する。その際尿素は発酵を助ける栄養分の役割を果たし、発酵を活発化させ、上昇した温度を長続きさせる効果がある。温度上昇は周囲の状況にも因るが、60〜80℃程度になる。上昇した温度は、発酵を助けると共に、後述する、ポリ乳酸系樹脂を分解させる第二段階を引き起こす。
【0012】
第二段階は、ポリ乳酸系樹脂が加水分解される工程である。ポリ乳酸系樹脂の分解は一般に、初め加水分解によって数百から数千の分子量まで分解された後に、微生物によって分解される。加水分解を進めるためには水分と温度が必要であり、特に分解温度はポリ乳酸系樹脂のガラス転移温度以上である事が必要である。本発明では、植物に含まれる水分と、発酵段階での温度によって、加水分解が引き起こされる。この際尿素は第一段階同様、温度上昇を長続きさせることで、加水分解を円滑に行うことに加えて、全体を若干アルカリ性にすることによって、さらにポリ乳酸系樹脂の加水分解を促進させる効果がある。60〜80℃という温度はポリ乳酸系樹脂を加水分解させるのに好適な温度である。
【0013】
ポリ乳酸系樹脂を分解させる時間は、できるだけ速い方が場所を取らず好ましく、1年以内に完全に分解させる事が好ましい。
【0014】
又、本発明の好ましい使用例としては、ポリ乳酸系樹脂からなる成形体を使用した後に、植物と成形体が混合し、分離することが困難なときに、植物と成形体を同時に処理する場合である。たとえば、農園芸や土木、漁業分野での使用が好ましい。
【0015】
次に各構成についてさらに詳しく述べる。
【0016】
本発明に用いられる尿素は、水に溶かして用いるとさらに好ましい。全体に、行き渡らせることが可能である上に、用いた水が、加水分解にも用いられるという効果もある。
【0017】
扱い易さの観点から、水に溶かして用いる際の濃度は2%以上50%以下が好ましい。
【0018】
本発明の方法に適用されるポリ乳酸系樹脂としては、L−乳酸単位またはD−乳酸単位を80%以上含有するポリ乳酸系樹脂により好ましく適用される。また、このポリ乳酸系樹脂は、融点が150℃以上であればいろいろな成形体で使用するのに、充分な強度を持つ成形体が可能であり好ましい。
【0019】
ポリ乳酸系樹脂からなる成形体としては、繊維からなるもの、シートからなるもの、押し出し成形体等どれでもよい。
【0020】
混合する植物は、農作物の収穫時に残った根や葉、蔦など特に規定はないが、乾いたものよりも、ある程度水分を含んだものが好ましい。すなわち、生分解性樹脂組成物の加水分解時に水分が必要とされるからである。
【0021】
又、分解途中で、かき混ぜたり、上下などを入れ替えたりすることがより好ましい。かき混ぜたり、上下を入れ替えたりする工程によって、均一になる上に、空気が入ることによって発酵が進み易くなる。
【0022】
この方法は以下の幾つかの観点から、特に農園芸用途に用いられる生分解性樹脂からなる成形体に適している。
【0023】
尿素は、一般的に、農薬に用いられる上、人などの哺乳動物の尿中にも含まれる。すなわち、農作業の現場に、尿素がごく一般的に存在することを意味している。また、尿素の添加方法として、動物の尿などを用いても構わない。
【0024】
また、農園芸分野では蔓と絡まったネットを廃棄するような状況が考えられる。例えば、長芋やきゅうりなどを栽培するにあたって、その蔓を支えて、誘引する誘引ネットを用いる。このネットは、収穫後に蔓と分別することができないため、根元から蔓の絡まった状態で切断して処理をする必要がある。
【0025】
この誘引ネットはこれまで、使いやすさや、強度の問題で、ポリプロピレンや、ポリエチレンの繊維から作られており、野焼き処理を余儀なくされていた。しかしながら、野焼き処理を禁止する条例が多くなってきており、焼却に高いコストがかかる現状がある。そこで、生分解性樹脂であるポリ乳酸系樹脂を用いた誘引ネットが開発され始めており、その誘引ネットを短期間で分解処分する必要性に迫られている。この場合には植物(蔓)と生分解性樹脂からなる成形体(ポリ乳酸系繊維)とが共存して、混合物となっているため、この場合に本発明の方法を用いるのは非常に効果的である。
【0026】
又、分解後に残った残物は堆肥として再度利用する事ができる。
【0027】
【実施例】
以下、実施例を挙げて本発明を説明するが、本発明はこの実施例に限定されない。
【0028】
[比較例1]
カネボウ製ポリ乳酸系樹脂(ラクトロン)からなる単糸繊度420dtexのモノフィラメントを3本撚り合わせたセットを更に3本撚り合わせて、計9本組のロープ状物とし、これを用いて高さ1.5m、幅100mの角目ネットを作成した。展帳ロープにも同じモノフィラメントを90本合わせたものを使用して、ネット上部の穴を通し、ネットを張り、5月に長芋を約25cm間隔で植え、10月に長芋を収穫した。
【0029】
10月に長芋を収穫した後、蔓が絡まった状態で、ネットを巻き取った。巻き取ったネットと蔓の束は約3mの直径になった。ネットの巻き取りは、尿素粉末をネット幅1mに対して約1g程度の割合になるように、蒔きながら行った。巻き取ったネットと蔓は、そのまま畑の隅に放置した。1ヶ月後のネットの状況を観察した。
【0031】
[実施例1]
尿素粉末の代わりに30重量%尿素水溶液用いる以外は比較例1と同様に行った。
【0032】
[比較例2]
尿素を蒔かずに処理する以外は比較例1と同様に行った。
【0033】
[比較例3]
比較例1と同じポリ乳酸からなるネットをロール状に巻き取って30重量%尿素水溶液をかけて、1ヶ月後のネットの状況を観察した。
【0034】
[比較例4]
比較例1と同じポリ乳酸からなるネットをロール状に巻き取り、3ヶ月後のネットの状況を観察した。
【0035】
ネットを構成しているポリ乳酸繊維の30%以上が消滅しており、残存部も軽く触ったらつぶれる程度分解していれば◎、消滅している部分が30%未満であるが、軽く引張ると切れる程度分解していれば○、軽く引張って切れない場合は×と判断した。
【0036】
【表1】
【0037】
実施例1は良好な分解性を示した。実施例1は、尿素を水に溶解して用いる事で分解を促進させ、特に良好であった。又残存物は、後に肥料として用いることもできた。
【0038】
比較例2は植物の発酵温度が充分に上がらず、ポリ乳酸繊維がほとんど分解していなかった。
【0039】
比較例3は植物の発酵がないためにポリ乳酸繊維は全く分解しなかった。
【0040】
比較例4は分解させる要素が何もなく、ポリ乳酸繊維は全く分解しなかった。
【0041】
この結果から、尿素を添加することにより、生分解性樹脂組成物の分解に効果があることが分かった。また、掘り返すことや、尿素を水に溶解して用いることの効果もあることが分かった。
【0042】
【発明の効果】
本発明により、生分解性樹脂組成物を簡易に遅くとも1年以内に分解することが可能となった。また、この方法は特に農業用途での使用に適しており、植物と生分解性樹脂を分けることなく一緒に分解することも可能となり、さらに残さは、肥料としても用いることができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a simple method for decomposing a mixture of a biodegradable resin composition and a plant.
[0002]
[Prior art]
Synthetic plastics are indispensable in modern social life, but it is necessary to incinerate or landfill the plastics for disposal. When incinerated, there are concerns about environmental issues such as promotion of global warming and the generation of dioxins when certain types of plastics are incinerated.
[0003]
Therefore, recently, an attempt has been made to use a biodegradable resin composition as a substitute for a conventional synthetic plastic. There is a polylactic acid resin as a biodegradable resin that can obtain almost the same strength as conventional synthetic plastics, but the degradation of polylactic acid resin is slow and takes 4-5 years in the soil. There is a point.
[0004]
For example, Patent Documents 1 and 2 disclose a method for composting a biodegradable resin composition. In this method, the biodegradable resin composition must be finely crushed, the content of the biodegradable resin composition must be suppressed, and organic waste must be mixed. As is apparent, a general but large-scale mixing device is required for mixing and crushing.
[0005]
Further, as a general plastic decomposition method, Patent Document 3 discloses a decomposition method using an agaric fungus culture bed. Examples include those in which the plastic is polylactic acid, and it is further disclosed that urea may be added as a nutrient.
[0006]
However, in the case of a processing contractor, it is possible to keep the temperature constant or select bacteria for decomposing plastic, but it is not possible to carry out in a general household or where there is no such device. Not realistic.
[0007]
[Patent Document 1]
Japanese Patent Laid-Open No. 9-249474 [Patent Document 2]
JP-A-9-249475 [Patent Document 3]
Japanese Patent Laid-Open No. 2002-348405
[Problems to be solved by the invention]
The object of the present invention is to solve the above-mentioned problems, and by adding urea to a mixture of a molded body made of a biodegradable resin and a plant, the molded body made of the biodegradable resin can be easily decomposed in a relatively short time. It is to provide a way to do.
[0009]
[Means for Solving the Problems]
The above-mentioned problem is solved by a decomposition method characterized by adding urea to a mixture of a molded body made of a polylactic acid resin and a plant.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Explain the mechanisms considered to help understand this method.
The following two-stage mechanism is considered.
[0011]
The first stage of decomposition is a process in which a plant part is fermented by decomposition by microorganisms in a mixture of a molded body made of polylactic acid resin and a plant. In this step, the overall temperature rises due to fermentation. At that time, urea plays a role of nutrients that assist fermentation, and has the effect of activating the fermentation and prolonging the elevated temperature. The temperature rise is about 60 to 80 ° C. although it depends on the surrounding conditions. The elevated temperature assists the fermentation and causes a second stage for decomposing the polylactic acid resin, which will be described later.
[0012]
The second stage is a process in which the polylactic acid resin is hydrolyzed. In general, polylactic acid-based resins are decomposed by microorganisms after first being hydrolyzed to several hundred to several thousand molecular weights. In order to proceed with hydrolysis, moisture and temperature are required, and in particular, the decomposition temperature needs to be equal to or higher than the glass transition temperature of the polylactic acid resin . In the present invention, hydrolysis is caused by the moisture contained in the plant and the temperature at the fermentation stage. At this time, as in the first stage, urea has the effect of further promoting the hydrolysis of the polylactic acid-based resin by making the whole slightly slightly alkaline in addition to performing the hydrolysis smoothly by continuing the temperature increase. is there. The temperature of 60 to 80 ° C. is a suitable temperature for hydrolyzing the polylactic acid resin .
[0013]
The time for decomposing the polylactic acid-based resin is preferably as fast as possible, and it is preferable that the polylactic acid-based resin be completely decomposed within one year.
[0014]
In addition, as a preferred use example of the present invention, when using a molded body made of polylactic acid resin , when the plant and the molded body are difficult to mix and separate, the plant and the molded body are treated at the same time. It is. For example, use in agriculture, horticulture, civil engineering, and fishery fields is preferable.
[0015]
Next, each configuration will be described in more detail.
[0016]
It is more preferable that the urea used in the present invention is dissolved in water. In addition to being able to spread throughout, the water used is also used for hydrolysis.
[0017]
From the viewpoint of ease of handling, the concentration when used by dissolving in water is preferably 2% to 50%.
[0018]
The Lupo polylactic acid-based resin is applied to the method of the present invention are preferably applied by the polylactic acid-based resin having an L- lactic acid unit or D- lactic acid units more than 80%. In addition, this polylactic acid resin is preferable because it can have a sufficient strength to be used in various molded products if the melting point is 150 ° C. or higher.
[0019]
The molded body made of a polylactic acid resin may be any one made of fibers, a sheet, or an extruded molded body.
[0020]
The plant to be mixed is not particularly limited in terms of roots, leaves, pods, etc. remaining at the time of crop harvesting, but preferably contains water to some extent rather than dry ones. That is, moisture is required at the time of hydrolysis of the biodegradable resin composition.
[0021]
Further, it is more preferable to stir or change the upper and lower sides during decomposition. In addition to being uniform by the step of stirring or changing the top and bottom, the fermentation is facilitated by the entry of air.
[0022]
This method is suitable for a molded body made of a biodegradable resin used for agricultural and horticultural applications from the following several viewpoints.
[0023]
Urea is generally used in agricultural chemicals and is also contained in the urine of mammals such as humans. That is, urea generally exists in the field of farm work. Animal urine or the like may be used as a method for adding urea.
[0024]
In the field of agriculture and horticulture, a situation where a net tangled with a vine is discarded can be considered. For example, when cultivating long bamboo shoots and cucumbers, an attracting net that supports and attracts the vines is used. Since this net cannot be separated from the vine after harvesting, it must be cut and processed with the vine tangled from the root.
[0025]
Up to now, this attracting net has been made from polypropylene and polyethylene fibers due to its ease of use and strength, and has been forced to be baked. However, the ordinance prohibiting the field burning process has increased, and there is a current situation that incineration is expensive. Therefore, an attracting net using a polylactic acid resin, which is a biodegradable resin, has begun to be developed, and there is an urgent need to disassemble the attracting net in a short period of time. In this case, the plant (vine) and the molded body (polylactic acid fiber) made of biodegradable resin coexist to form a mixture. In this case, it is very effective to use the method of the present invention. Is.
[0026]
The residue remaining after decomposition can be reused as compost.
[0027]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to this Example.
[0028]
[ Comparative Example 1 ]
A set of three twisted monofilaments made of Kanebo's polylactic acid resin (Lactron) with a single yarn fineness of 420 dtex is further twisted to form a total of nine ropes. A square net having a width of 5 m and a width of 100 m was created. We used 90 pieces of the same monofilament for the exhibition ropes, passed through the holes at the top of the net, stretched the net, planted long persimmons at intervals of about 25 cm in May, and harvested long persimmons in October .
[0029]
After harvesting the long bamboo shoots in October, he rolled up the net with the vines tangled. The wound net and vine bundles were about 3 meters in diameter. The winding of the net was performed while rolling the urea powder so that the ratio was about 1 g with respect to 1 m of the net width. The wound net and vine were left in the corner of the field. I observed the situation of the Internet one month later.
[0031]
[ Example 1 ]
The same procedure as in Comparative Example 1 was performed except that a 30 wt% aqueous urea solution was used instead of the urea powder.
[0032]
[ Comparative Example 2 ]
It carried out similarly to the comparative example 1 except having processed without urea.
[0033]
[ Comparative Example 3 ]
A net made of the same polylactic acid as in Comparative Example 1 was wound into a roll, and a 30% by weight urea aqueous solution was applied thereto, and the state of the net after one month was observed.
[0034]
[ Comparative Example 4 ]
A net made of the same polylactic acid as in Comparative Example 1 was wound into a roll, and the state of the net after 3 months was observed.
[0035]
If 30% or more of the polylactic acid fibers that make up the net have disappeared and the remaining part has decomposed to the extent that it can be crushed when touched lightly, the disappeared part is less than 30%. If it was broken to the extent that it could be broken, it was judged as “good”, and if it was not pulled easily, it was judged as “x”.
[0036]
[Table 1]
[0037]
Example 1 showed good degradability. In Example 1 , decomposition was accelerated by using urea dissolved in water, and it was particularly good. The residue could also be used later as fertilizer.
[0038]
In Comparative Example 2, the fermentation temperature of the plant was not sufficiently increased, and the polylactic acid fiber was hardly decomposed.
[0039]
In Comparative Example 3, there was no plant fermentation, so the polylactic acid fiber did not decompose at all.
[0040]
In Comparative Example 4, there was no element to be decomposed, and the polylactic acid fiber was not decomposed at all.
[0041]
From this result, it was found that the addition of urea is effective in decomposing the biodegradable resin composition. Moreover, it turned out that there is also an effect of digging up and using urea dissolved in water.
[0042]
【The invention's effect】
According to the present invention, the biodegradable resin composition can be easily decomposed within one year at the latest. In addition, this method is particularly suitable for use in agricultural applications, and it is possible to decompose the plant and the biodegradable resin together without separating them, and the residue can also be used as a fertilizer.
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JP2009091463A (en) * | 2007-10-09 | 2009-04-30 | Shimizu Corp | Volume reducing method for polylactic acid |
KR102557331B1 (en) * | 2020-02-19 | 2023-07-21 | 트리플더블유 리미티드 | Methods and systems for lactic acid production and polylactic acid recycling |
TWI823145B (en) * | 2021-09-14 | 2023-11-21 | 南亞塑膠工業股份有限公司 | Environmentally friendly polyester film and environmentally friendly polyester composition thereof |
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