JP2005041969A - Antioxidant for resin - Google Patents
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- JP2005041969A JP2005041969A JP2003202229A JP2003202229A JP2005041969A JP 2005041969 A JP2005041969 A JP 2005041969A JP 2003202229 A JP2003202229 A JP 2003202229A JP 2003202229 A JP2003202229 A JP 2003202229A JP 2005041969 A JP2005041969 A JP 2005041969A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、樹脂に添加された際にその酸化防止性を高める、植物由来のリグニンからなる酸化防止剤に関する。
【０００２】
【従来の技術】
樹脂は、光や熱の作用によってひび割れが生じたり、着色等の劣化が生ずる。これは空気中の酸素やオゾンによる自動酸化によるものであり、ラジカル連鎖機構で進行し、樹脂を構成する高分子の主鎖の切断、橋かけ、側鎖の切断に起因している。このような樹脂の酸化を抑制するため、従来より酸化防止剤が用いられている。
【０００３】
上記のように、樹脂の酸化は酸素のラジカルに起因するものであるから、酸化防止剤としてはラジカル消去特性を有する化合物が用いられており、フェノール系酸化防止剤（例えば２，６−ジ−ｔ−ブチル−４−メチル、ＢＨＴ）が代表的なものである。しかしながら、従来一般に用いられている酸化防止剤は石油資源を原料としているため、化石資源の枯渇やその燃焼に伴うＣＯ２の増加による地球温暖化の課題がある。
【０００４】
ところで、近年、様々な環境問題から、石油資源を原料とする樹脂に代えて、植物資源を原料とする植物由来の樹脂が環境に負荷を与えない材料として注目されている（例えば、特許文献１参照）。このような植物由来の樹脂においても、使用中には酸化を防止することが必要とされるが、上記のように従来の酸化防止剤は石油資源を原料とするものであり、天然材料を原料とする酸化防止剤が求められている。
【０００５】
【特許文献１】
特開２０００−２９０５１５号公報
【０００６】
【発明が解決しようとする課題】
本発明は、天然材料である植物を原料とし、樹脂に対して酸化防止効果を奏する物質を提供することを目的とする。
【０００７】
【課題を解決するための手段】
上記課題を解決するために本発明によれば、植物から抽出してなるリグニンからなる樹脂用酸化防止剤が提供される。このリグニンは好ましくは疎水性リグニンであり、さらに好ましくは、植物を木材腐朽菌により処理してリグニンとセルロースに分解させ、アルコールによりリグニンを抽出し、このアルコール溶液に酸性溶液を添加してリグニンを沈殿させ、分離することにより得られるものである。
【０００８】
さらに本発明によれば、植物を木材腐朽菌により処理してリグニンとセルロースに分解させ、アルコールによりリグニンを抽出し、このアルコール溶液に酸性溶液を添加してリグニンを沈殿させ、分離することを含む、上記酸化防止剤の製造方法が提供される。
【０００９】
【発明の実施の形態】
リグニンはセルロース及びヘミセルロースと共に植物体の主要成分であり、植物性資源としてはセルロースに次ぐ保有量を有する材料であるが、現在のところあまり有効活用されていない。本発明者は、このリグニンについて検討の結果、樹脂に対して従来の石油資源を原料とする酸化防止剤と同等もしくはそれ以上の酸化防止効果を奏することを見出した。
【００１０】
本発明においてリグニンとしては、植物より得られる各種のリグニンを用いることができ、具体的には木材チップを酢酸及び塩酸を用いて高温蒸煮することにより得られる酢酸リグニン、高圧の飽和水蒸気で処理し、瞬時に圧力を開放することにより得られる爆砕リグニン、水酸化ナトリウムと硫酸ナトリウムの混合水溶液を蒸解液として高温で木材チップを蒸解することにより得られるクラフトリグニン、木粉を中性又は弱アルカリ性の亜硫酸水溶液で高温で蒸解することにより得られるリグニンスルホン酸、木粉から有機溶剤によって抽出することにより得られるオルガノソルブリグニン等が例示される。
【００１１】
これらのリグニンは親水性リグニンと疎水性リグニンに分類することができるが、本発明においては疎水性リグニン、具体的にはオルガノソルブリグニン、特にエタノリシスにより得られるエタノリシスリグニンを用いることが好ましい。
【００１２】
上記のように木材からリグニンを取り出すため、従来は強酸又は強アルカリと共に加熱処理する手法が用いられているが、これらの薬品は環境負荷が高く、また高エネルギーを与えて処理されるため、環境に優しい手法とは言いがたい。そこで、本発明では、より環境に優しいリグニンからなる酸化防止剤の製造方法を見出した。
【００１３】
この方法においては、まず植物を木材腐朽菌により処理してリグニンとセルロースに分解させる。植物としては制限はなく、例えばブナ、カバ等の広葉樹、スプルース、ヒノキ、スギ等の針葉樹を用いることができる。木材腐朽菌としても特に制限はなく、例えば白色腐朽菌（例えば、Ｃｅｒｉｐｏｒｉｏｐｓｉｓ ｓｕｂｖｅｒｍｉｓｐｏｒａ、Ｄｉｃｈｏｍｉｔｕｓ ｓｑｕａｌｅｎｓ、Ｃｏｒｉｏｌｕｓ ｖｅｒｓｉｃｏｌｏｒ、Ｐｌｅｕｒｏｔｕｓ ｏｓｔｒｅａｔｕｓ）及び褐色腐朽菌（例えば、Ｇｌｏｅｐｈｙｌｌｕｍ ｔｒａｂｅｕｍ、Ｔｙｒｏｍｙｃｅｓ ｐａｌｕｓｔｒｉｓ）を用いることができる。この木材腐朽菌による分解処理工程の条件は、用いる木材腐朽菌及び植物材料によって適宜決定することができ、例えば木粉に蒸留水を加え、ここに十分量の木材腐朽菌を入れ、必要に応じてグルコース、ペプトン、コーンスティープリカー等の栄養素やミネラル分を添加し、４〜１２週間菌培養を行う。
【００１４】
こうして植物を分解処理した後、２０〜１００％のアルコール水溶液、好ましくは５０〜７０％のエタノール水溶液を加え、例えば２００℃にて１２０分間抽出処理することによりリグニンを抽出する。木材腐朽菌によって分離されたリグニンはアルコール中に溶解し、一方セルロース等の他の成分はそのまま残存しているため、濾過によって濾液を分離し、この濾液を濃縮した後、再びアルコールを添加し、希酸水溶液を添加し、リグニンを沈殿させる。この工程において糖が分離され、最後に遠心分離によって沈殿を分離することにより、最終生成物が得られる。
【００１５】
上記のように、樹脂の酸化劣化は、熱や紫外線によってラジカルが発生し、このラジカルにより樹脂を構成する分子の連鎖的な分子切断がおこるためであると考えられている。本発明のリグニンからなる酸化防止剤は、従来用いられている酸化防止剤と同様に、この発生したラジカルを捕捉し消去することにより樹脂の酸化を有効に防止する。
【００１６】
本発明の酸化防止剤は各種樹脂の酸化防止に有効であるが、特に植物資源を原料とする植物由来樹脂に用いることが好ましい。それは、リグニン自体が植物を原料とするものであり、植物由来樹脂に添加すればすべてが植物由来となり、より環境への負荷が小さくなると考えられるからである。この植物由来樹脂としては、例えばポリ乳酸、ポリヒドロキシアルカノエート等が挙げられる。樹脂への本発明の酸化防止剤の添加量は、樹脂の種類や酸化防止剤としてのリグニンの種類によっても異なるが、一般に樹脂の質量に対して０．０１〜３０ｗｔ％の範囲で用いることが好ましい。
【００１７】
【実施例】
木材腐朽菌によるリグニンの調製
グルコース・ペプトン寒天培地で白色腐朽菌（ヒラタケ）を４〜５日間、２８℃で培養した。この寒天プレートからコルクボーラー（直径９ｍｍ）でペレットを４個打ち抜いた。三角フラスコにブナ木粉５ｇと蒸留水５ｍＬを添加し、１２１℃で２０分間オートクレーブして得た滅菌培地に、このペレット４個を植菌した。２８℃で４週間静置培養後、１２１℃、２０分間オートクレーブして菌の生育を止めた。次いで三角フラスコ３本分の培養物（１５ｇ）をステンレス製のオートクレーブに移し、ここに６０％エタノール９０ｇを加え、２００℃において１２０分間エタノリシル反応を行った。これを濾過し、濾液をロータリーエバポレーターにより濃縮し、５０％エタノールを１００ｍＬ加え、この溶液に希塩酸６００ｍＬを加えた。すると沈殿が発生し、この沈殿を遠心分離により集め、凍結乾燥することにより本発明のリグニンを得た。収率は４．１％であった。
【００１８】
酸化防止効果の評価
酸化防止効果はＤＰＰＨ法により評価した。ＤＰＰＨ（１，１−ジフェニル−２−ピクリルヒドラジル）の溶液は液中で安定的にラジカルを発生し紫色を呈し、その際５１９ｎｍ付近に吸光特性を示す。ここにラジカル消去作用を有する溶液が混入されると紫色が消え、無色透明となる。この現象を利用し、酸化防止剤としてのリグニンを投入し、５１９ｎｍ付近の吸光度の経時的変化を観察することによってラジカル消去性、すなわち酸化防止性の評価を行う。
【００１９】
リグニンとして、市販親水性リグニン（日本製紙製パールレックスＮＰ、サンプル１）、市販疎水性リグニン（アルドリッチ製オルガノソルブリグニン、サンプル２）、及び上記の木材腐朽菌を用いて製造したリグニン（サンプル３）を用い、これらの０．７１ｇ／Ｌ溶液（溶媒：アセトン又は水）０．１ｍＬを、吸光度測定容器中のＤＰＰＨの１ｍＭエタノール溶液０．１８ｍＬ＋エタノール０．７２ｍＬの溶液に入れ、混合後直ちに吸光度測定機にセットし、３０秒後の５１９ｎｍにおける吸光度を測定した。また、対照として従来の酸化防止剤（ＢＨＴ）を同じ濃度で用い、吸光度を測定した。酸化防止剤を全く添加しなかった際の吸光度に対し、酸化防止剤を添加した場合の吸光度の低下率をラジカル消去率とし、図１に示す。
【００２０】
図１の結果から明らかなように、リグニンは現在一般に用いられている酸化防止剤であるＢＨＴと同等もしくはそれ以上のラジカル消去効果を示し、特に疎水性リグニン及び木材腐朽菌を用いて得られたリグニンは非常に優れたラジカル消去効果を示した。
【００２１】
【発明の効果】
本発明のリグニンからなる酸化防止剤は、樹脂に対して従来の石油資源を原料とする酸化防止剤と同等もしくはそれ以上の酸化防止効果を奏し、かつそれ自体が植物由来であるため、植物由来樹脂用の酸化防止剤として特に好ましい。さらに、本発明による酸化防止剤の製造方法は、環境負荷物質を用いることがなく、かつ菌処理による省エネルギー化により、より環境に優しい手法である。
【図面の簡単な説明】
【図１】本発明の酸化防止剤及び従来の酸化防止剤のラジカル消去率の評価結果を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antioxidant comprising a plant-derived lignin that enhances its antioxidant properties when added to a resin.
[0002]
[Prior art]
The resin is cracked or deteriorated by coloring or the like due to the action of light or heat. This is due to auto-oxidation by oxygen or ozone in the air, and proceeds by a radical chain mechanism, and is caused by cleavage of the main chain, crosslinking, and side chain of the polymer constituting the resin. In order to suppress such oxidation of the resin, an antioxidant is conventionally used.
[0003]
As described above, since the oxidation of the resin is caused by oxygen radicals, compounds having radical scavenging properties are used as antioxidants, and phenolic antioxidants (for example, 2,6-di-) are used. t-Butyl-4-methyl, BHT) is representative. However, since the antioxidants generally used in the past use petroleum resources as a raw material, there is a problem of global warming due to depletion of fossil resources and an increase in CO 2 due to the combustion thereof.
[0004]
By the way, in recent years, due to various environmental problems, plant-derived resins using plant resources as raw materials instead of resins using petroleum resources as raw materials have attracted attention as materials that do not give an environmental load (for example, Patent Document 1). reference). Even in such plant-derived resins, it is necessary to prevent oxidation during use. However, as described above, conventional antioxidants are made from petroleum resources, and natural materials are used as raw materials. There is a need for antioxidants.
[0005]
[Patent Document 1]
Japanese Patent Laid-Open No. 2000-290515 [0006]
[Problems to be solved by the invention]
An object of this invention is to provide the substance which has the antioxidant effect with respect to resin, using the plant which is a natural material as a raw material.
[0007]
[Means for Solving the Problems]
In order to solve the above problems, according to the present invention, there is provided an antioxidant for resin comprising lignin extracted from a plant. The lignin is preferably a hydrophobic lignin, and more preferably, the plant is treated with wood-rotting fungi to decompose it into lignin and cellulose, the lignin is extracted with alcohol, and an acidic solution is added to the alcohol solution to add the lignin. It is obtained by precipitating and separating.
[0008]
Furthermore, according to the present invention, the plant is treated with wood rot fungi to decompose into lignin and cellulose, the lignin is extracted with alcohol, an acidic solution is added to the alcohol solution to precipitate and separate the lignin. A method for producing the antioxidant is provided.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Lignin is a major component of plants together with cellulose and hemicellulose, and is a material having the second largest amount after plant cellulose as a vegetable resource, but it is not so effectively utilized at present. As a result of studying this lignin, the present inventor has found that the resin exhibits an antioxidant effect equivalent to or higher than that of a conventional antioxidant made from petroleum resources.
[0010]
As the lignin in the present invention, various lignins obtained from plants can be used. Specifically, lignin acetate obtained by high-temperature steaming wood chips with acetic acid and hydrochloric acid, and treated with high-pressure saturated steam. Explosive lignin obtained by instantly releasing pressure, Kraft lignin obtained by cooking wood chips at high temperature using a mixed aqueous solution of sodium hydroxide and sodium sulfate as a cooking solution, neutral or weak alkaline Examples thereof include lignin sulfonic acid obtained by cooking at a high temperature with a sulfurous acid aqueous solution, organosolv lignin obtained by extraction from wood flour with an organic solvent, and the like.
[0011]
These lignins can be classified into hydrophilic lignins and hydrophobic lignins. In the present invention, it is preferable to use hydrophobic lignins, specifically organosolv lignins, particularly ethanolysis lignin obtained by ethanolysis.
[0012]
In order to extract lignin from wood as described above, conventionally, a method of heat treatment with a strong acid or strong alkali has been used. However, these chemicals have a high environmental impact and are treated with high energy. It is hard to say that it is a gentle approach. Therefore, the present invention has found a method for producing an antioxidant comprising lignin that is more environmentally friendly.
[0013]
In this method, the plant is first treated with wood-rotting fungi and decomposed into lignin and cellulose. There is no restriction | limiting as a plant, For example, conifers, such as a broad-leaved tree, such as a beech and a hippopotamus, a spruce, a cypress, and a cedar can be used. The wood-rotting fungus is not particularly limited, and for example, white-rotting fungi (for example, Ceriporiopsis subvermisspora, Dichomitus squalens, Coriolus versicolor, Pleurotus ostratus) and brown-roting fungi (for example, Gloetropylum, Gloetropylum, and Gloetropylum) can be used. The conditions of the decomposition treatment process with this wood-rotting fungus can be determined as appropriate depending on the wood-rotting fungus used and the plant material. For example, distilled water is added to the wood flour, and a sufficient amount of wood-rotting fungus is added here. Add nutrients and minerals such as glucose, peptone, corn steep liquor, etc., and culture the bacteria for 4 to 12 weeks.
[0014]
After decomposing the plant in this manner, 20 to 100% alcohol aqueous solution, preferably 50 to 70% ethanol aqueous solution is added, and lignin is extracted by, for example, extraction treatment at 200 ° C. for 120 minutes. The lignin separated by the wood-rotting fungi dissolves in the alcohol, while other components such as cellulose remain as they are, so the filtrate is separated by filtration, the filtrate is concentrated, and then the alcohol is added again. A dilute aqueous acid solution is added to precipitate the lignin. In this step, the sugar is separated and finally the precipitate is separated by centrifugation to obtain the final product.
[0015]
As described above, the oxidative degradation of the resin is considered to be caused by the generation of radicals by heat or ultraviolet rays, and the chain molecular cleavage of the molecules constituting the resin by the radicals. The antioxidant comprising lignin of the present invention effectively prevents oxidation of the resin by capturing and eliminating the generated radicals, as in the case of conventionally used antioxidants.
[0016]
The antioxidant of the present invention is effective for preventing various resins from being oxidized, but it is particularly preferable to use it for plant-derived resins using plant resources as raw materials. This is because lignin itself is derived from a plant, and if added to a plant-derived resin, everything is derived from a plant, and it is considered that the burden on the environment is further reduced. Examples of the plant-derived resin include polylactic acid and polyhydroxyalkanoate. The amount of addition of the antioxidant of the present invention to the resin varies depending on the type of resin and the type of lignin as an antioxidant, but it is generally used in the range of 0.01 to 30 wt% with respect to the mass of the resin. preferable.
[0017]
【Example】
Preparation of lignin by wood-rotting fungi White-rotting fungi (oyster mushrooms) were cultured at 28 ° C. for 4-5 days on glucose peptone agar medium. Four pellets were punched from this agar plate with a cork borer (diameter 9 mm). Four pellets were inoculated into a sterile medium obtained by adding 5 g of beech wood powder and 5 mL of distilled water to an Erlenmeyer flask and autoclaving at 121 ° C. for 20 minutes. After stationary culture at 28 ° C. for 4 weeks, autoclaving at 121 ° C. for 20 minutes stopped the growth of the bacteria. Next, the culture (15 g) for the three Erlenmeyer flasks was transferred to a stainless steel autoclave, and 90 g of 60% ethanol was added thereto, and an ethanolic reaction was performed at 200 ° C. for 120 minutes. This was filtered, the filtrate was concentrated by a rotary evaporator, 100 mL of 50% ethanol was added, and 600 mL of diluted hydrochloric acid was added to this solution. Then, a precipitate was generated, and this precipitate was collected by centrifugation and lyophilized to obtain the lignin of the present invention. The yield was 4.1%.
[0018]
Evaluation of antioxidant effect The antioxidant effect was evaluated by the DPPH method. A solution of DPPH (1,1-diphenyl-2-picrylhydrazyl) stably generates radicals in the liquid and exhibits a purple color. In this case, the solution exhibits light absorption characteristics near 519 nm. When a solution having a radical scavenging action is mixed here, the purple color disappears and becomes colorless and transparent. Utilizing this phenomenon, lignin as an antioxidant is added, and the radical scavenging property, that is, the antioxidant property is evaluated by observing the change in absorbance around 519 nm with time.
[0019]
Commercially available hydrophilic lignin (Nippon Paper Pearl Rex NP, sample 1), commercially available hydrophobic lignin (Aldrich organosolv lignin, sample 2), and lignin produced using the above-mentioned wood-rotting fungi (sample 3) Then, 0.1 mL of these 0.71 g / L solutions (solvent: acetone or water) are put into a solution of 1 mM ethanol solution of DPPH 0.18 mL + 0.72 mL ethanol in an absorbance measurement container, and the absorbance is measured immediately after mixing. The absorbance at 519 nm after 30 seconds was measured. Further, as a control, a conventional antioxidant (BHT) was used at the same concentration, and the absorbance was measured. FIG. 1 shows the rate of decrease in absorbance when an antioxidant is added to the absorbance when no antioxidant is added, as the radical scavenging rate.
[0020]
As is clear from the results of FIG. 1, lignin exhibits radical scavenging effect equivalent to or better than BHT, which is an antioxidant generally used at present, and is particularly obtained using hydrophobic lignin and wood decay fungi. Lignin showed a very good radical scavenging effect.
[0021]
【The invention's effect】
The antioxidant comprising the lignin of the present invention has an antioxidant effect equivalent to or higher than that of a conventional petroleum resource-based antioxidant for the resin, and is itself derived from a plant. Particularly preferred as an antioxidant for resins. Furthermore, the method for producing an antioxidant according to the present invention is a more environmentally friendly method by using no environmentally hazardous substances and saving energy by treating bacteria.
[Brief description of the drawings]
FIG. 1 is a graph showing evaluation results of radical scavenging rates of an antioxidant of the present invention and a conventional antioxidant.
Claims (4)
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| JP2003202229A JP2005041969A (en) | 2003-07-28 | 2003-07-28 | Antioxidant for resin |
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| JP2003202229A JP2005041969A (en) | 2003-07-28 | 2003-07-28 | Antioxidant for resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010254611A (en) * | 2009-04-24 | 2010-11-11 | Dainichiseika Color & Chem Mfg Co Ltd | Antioxidant, cosmetic composition and method for producing antioxidant |
| JP2011219716A (en) * | 2010-02-10 | 2011-11-04 | Hitachi Chem Co Ltd | Antibacterial resin composition |
| JP2014015579A (en) * | 2012-07-11 | 2014-01-30 | Idemitsu Kosan Co Ltd | Thermoplastic resin composition |
| WO2018079640A1 (en) * | 2016-10-27 | 2018-05-03 | 東レ株式会社 | Food discoloration inhibitor |
| JP2020533436A (en) * | 2017-09-07 | 2020-11-19 | レンマティックス, インコーポレイテッドRenmatix, Inc. | Polymer antioxidant stabilizer |
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2003
- 2003-07-28 JP JP2003202229A patent/JP2005041969A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010254611A (en) * | 2009-04-24 | 2010-11-11 | Dainichiseika Color & Chem Mfg Co Ltd | Antioxidant, cosmetic composition and method for producing antioxidant |
| JP2011219716A (en) * | 2010-02-10 | 2011-11-04 | Hitachi Chem Co Ltd | Antibacterial resin composition |
| JP2014015579A (en) * | 2012-07-11 | 2014-01-30 | Idemitsu Kosan Co Ltd | Thermoplastic resin composition |
| WO2018079640A1 (en) * | 2016-10-27 | 2018-05-03 | 東レ株式会社 | Food discoloration inhibitor |
| JP6354914B1 (en) * | 2016-10-27 | 2018-07-11 | 東レ株式会社 | Anti-fading agent for food |
| US11096395B2 (en) | 2016-10-27 | 2021-08-24 | Toray Industries, Inc. | Food discoloration inhibitor |
| JP2020533436A (en) * | 2017-09-07 | 2020-11-19 | レンマティックス, インコーポレイテッドRenmatix, Inc. | Polymer antioxidant stabilizer |
| US11873384B2 (en) | 2017-09-07 | 2024-01-16 | Renmatix, Inc. | Antioxidant stabilizer in polymers |
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