WO1997009338A1 - Process for producing water-soluble kraft lignin - Google Patents
Process for producing water-soluble kraft lignin Download PDFInfo
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- WO1997009338A1 WO1997009338A1 PCT/JP1995/001749 JP9501749W WO9709338A1 WO 1997009338 A1 WO1997009338 A1 WO 1997009338A1 JP 9501749 W JP9501749 W JP 9501749W WO 9709338 A1 WO9709338 A1 WO 9709338A1
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- lignin
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- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
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- the present invention relates to a water-soluble lignin which has an action such as macrophage activity as an anti-virus activity and an immune enhancing effect, and particularly to a water-soluble lignin having a small molecular weight which is easily absorbed from the intestinal tract even by oral administration.
- the present invention relates to a method for producing a modified lignin.
- AIDS is a viral disease that destroys the human body's immune system and causes death. It has spread very rapidly in countries around the world in recent years and has been in danger. Some of the phases have been developed and applied in clinical practice, and it has been pointed out that they also have various side effects.
- Lignin in the pulp production process by the Kraft method is separated from polysaccharides, mainly cellulose, which is the main component of pulp, as lignin, and is eluted and removed at night. Transport nights containing large amounts of craft lignin are concentrated and burned in boilers. Some of them are sprayed into hot air prior to combustion and isolated as powdered kraft lignin, which is used as an industrial raw material.
- Such kraft lignin has been conventionally made water-soluble by the introduction of a sulfomethyl group into an aromatic ring.
- a known force requires a high temperature in production, and the introduction rate of a water-soluble group is not so high.
- the problem of residual formalin used in manufacturing can also be an obstacle to its use as a drug. Disclosure of the invention
- the present invention provides a water-soluble denatured lignin isolated and purified from a conventional culture medium after Shitake mushrooms and lignosulfonate removed from sulphite pulp wastewater, as such an anti-AIDS virus and an immunostimulating agent.
- a water-soluble lignin having a low molecular weight that can be administered orally and having a very high anti-AIDS virus and immunostimulatory activity even at a low concentration can be obtained at low cost, easily and easily.
- An object of the present invention is to provide a production method for producing from lignin.
- Lactignin is composed of pulp by the kraft method iii. During the pulping by the Kraft method, the lignin in the wood material is severely cut by its main bond, the ether bond strength s, and its molecular weight is reduced to 350-4
- the water-soluble lignin obtained by carboxymethylation of kraft lignin has a high yield, a very high concentration at a low concentration, an anti-AIDS virus and an immunostimulatory activity, and a molecular weight of about 4
- the amount that can be absorbed from the intestinal tract and reach the tissues and cells containing the virus even after oral administration is small, and water-soluble denatured lignin or lignosulfonate isolated and purified from the culture medium after Shitake mushroom cultivation
- Water-soluble lignin having the same effect as that of ⁇ was able to be S3 ⁇ 4i.
- the degree of substitution of a water-soluble group, which is considered to play an important role in antiviral activity, that is, a carboxymethyl group is high and can be controlled according to the purpose.
- FIG. 1 is a schematic diagram of the effect of water-soluble lignin.
- Fig. 2 shows water-soluble sugarcane bagasse obtained by cultivating shiitake mushrooms, which is classified into water-soluble lignins that have a strong hydrophobicity and are further classified by molecular weight. It is. This was performed at 37 ° C in RPMI 1-1640 medium containing calo heat-inactivated FCS, penicillin and streptomycin with the addition of CD4 positive human T cell clones, HIV and water-soluble lignin. After culturing for days, the number of surviving cells was trended using the trypan blue staining method. A blank treated in the same manner without adding water-soluble lignin was used as a blank. This assay was also performed in Figures 3 to 5 below.
- Figure 3 shows lignosulfonic acid purified by removing the coexisting inorganic salts by concentrating the sulphite pulp effluent and dropping it in ethanol.
- the average molecular weight is about 35,000.
- FIG. 5 relates to the kraft lignin of the present invention, in which the kraft lignin obtained by concentrating the sulfate pulp night and injecting it with sulfuric acid is dissolved in dioxane and coexisted by dropping into ether.
- Figure 6 shows the addition of tritiated thymidine and water-soluble lignin to human bone marrow cell clones, culture at 37 ° C for 4 days, and measurement of the amount of tritium incorporated in DNA and release from tritium.
- 5 is a chart quantifying the DNA synthesis ability by performing the above steps.
- FIG. 7 is a chart showing the results obtained by adding water-soluble lignin to a commercially available reverse transcriptase, culturing at 37 ° C. for 4 days, and measuring the reversal activity by a conventional method.
- Soluble Clough Bok lignin present invention any not toxic to cells even in clear aqueous solution of 200 ⁇ g / m 1 As from Fig. 5, 1 2. 5 g / m 1 and Le, At very low concentrations, growth of AIDS is inhibited almost 100% at 90% t, 25 Mg / m 1.
- Isolation kraft lignin from the needle itt old or wide Wei goods are marketed are not subjected special purification processing power s, inorganic reagents used in the pulp, sugars and raw wood in partially eluted It also contains impurities other than lignin, such as the extracted components. In order to remove these impurities, about 10 times the amount of commercially available kraft lignin is used.
- the purified kraft lignin is collected by centrifugation, washed with fresh getyl ether and centrifuged to remove getyl ether. After repeating the washing with getyl ether, wash once with petroleum ether in the low boiling point category, and then mushroom at low temperature.
- the purified kraft lignin is made carboxymethyl and water-soluble by any of the following methods.
- carboxymethylated kraft lignin 2 is isolated from carboxymethylated kraft lignin 1 by freeze-drying.
- force Rubokishimechiru kraft lignin 1 only Fe Roh Ichire! 1 raw hydroxyl groups of the raw materials of kraft lignin is a force Rubokishimechiru of, location of the force Rubokishimechiru based on ⁇ about
- the craft lignin according to the present invention is used as an antiviral active agent and an immunopotentiator, and is expected to be used as a drug for chicken virus Newu Castle disease caused by retrovirus.
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Abstract
A process for producing water-soluble kraft lignin by refining and carboxymethylating kraft lignin obtained from wood, whereby it is possible to obtain a water-soluble lignin that has a potent antiviral activity even at a low concentration, is orally administrable, and has a low molecular weight and both anti-AIDS virus and immunopotentiating effects from isolated kraft lignin that is available readily at a low cost in a large quantity.
Description
明 細 書 水溶性クラフトリグニンの i方法 技術分野 Description i-method of water-soluble kraft lignin
本発明は、 抗ゥィルス活ϊ¾び免疫増強作用としてのマクロファージ活性ィ匕な どの作用力 tl忍されている水溶性化リグニンに関するものであり、 特に分子量が 小さく経口投与によっても腸管から吸収されやすい水溶性化リグニンの製造方法 に関するものである。 The present invention relates to a water-soluble lignin which has an action such as macrophage activity as an anti-virus activity and an immune enhancing effect, and particularly to a water-soluble lignin having a small molecular weight which is easily absorbed from the intestinal tract even by oral administration. The present invention relates to a method for producing a modified lignin.
エイズは、 人体の免疫機構を破壊し、 人を死に至らしめるウィルス疾患であ り、 近年世界各国に非常な勢いで広がり、 頃を危機に陥れている。 いくつかェ ィズの;?台 も開発され、 臨床に応用されている力、 それらはまた様々な副作用 を持つことも指摘されている。 AIDS is a viral disease that destroys the human body's immune system and causes death. It has spread very rapidly in countries around the world in recent years and has been in danger. Some of the phases have been developed and applied in clinical practice, and it has been pointed out that they also have various side effects.
近年、 シィタケ纖咅後の培地から単離さ il青製された水溶性の変性リグニン及 びサルフアイトパルプ排液から取り出されたリグノスルフォン酸がエイズゥィル スの増殖を抑え、 同時に免疫作用を増強すること力 s知られてきている。 In recent years, water-soluble denatured lignin isolated from the culture medium after Shitake mushroom fiber and lignosulphonic acid removed from the sulphite pulp wastewater suppress the growth of AIDS virus and simultaneously enhance the immunity. Force s has been known.
しカゝしな力 、 それらは分子量が大きく （シイタケ 咅後の培地から単離され 精製された水溶性の変性リグニン： 5 0万、 リグノスルフォン酸： 4万） 、 経口 投与では腸管から吸収されてウイルスのいる組»び細胞に到達することは極め て困難である。 エイズ患者の場合には、 二次 の危険性をなくすためには、 注 射は極力避けなければならない。 They have high molecular weight (water soluble denatured lignin isolated and purified from medium after Shiitake mushroom: 500,000, lignosulfonic acid: 40,000), and are absorbed from the intestinal tract by oral administration It is extremely difficult to reach tissues and cells containing viruses. In the case of AIDS patients, injections should be avoided as much as possible to eliminate secondary risks.
このため経口投与でも腸管から吸収されてウイルスのいる組織及び細胞に至 IJ達 しうる 量が小さく、 しかもシィタケ纖咅後の培地から単離され精製された水 溶性の変性リグニンやリグノスルフォン酸と同様な効果をもつ水溶性リグニンの 現出が望まれている。 リグニンは、 セルロース及びその他の他糖類と共に木材の細胞壁を構成する主
要成分の一つであり、 芳香族重合化合物である。 木材は言うまでもなく製 «業 において製紙用パルプの主要原料である。 製紙用パルプは木材を化学的に又は機 械的に処理して製造されるが、 主力は化学的に処理して得られる化学パルプであ る。 ィ匕学パルプ製造法にはクラフト法とサルフアイト法がある力 s我が国において も又世界的にみても前者の生 が圧倒的に多い。 For this reason, even when administered orally, the amount that can be absorbed from the intestinal tract and reach the tissues and cells containing the virus to IJ is small, and in addition to water-soluble denatured lignin or lignosulfonate isolated and purified from the medium after Shitake mushroom fiber. The emergence of water-soluble lignin having the same effect is desired. Lignin, together with cellulose and other sugars, is the main constituent of the cell wall of wood. One of the key components, it is an aromatic polymer compound. Wood is, of course, the main raw material for paper pulp in the manufacturing industry. Paper pulp is manufactured by chemically or mechanically processing wood, but the mainstay is chemical pulp obtained by chemically processing wood. Also worldwide also the former raw is overwhelmingly large to see in a force s Japan to I匕学pulp production process where there is a craft method and Sarufuaito method.
我が国においては、 サルファイト法パルプ化は減衰の一途をたどり、 その術夜 力 >ら得られる水溶性リグニンであるリグノスルフォン酸はその肝量が大きいと いう禾翻上の欠点だけでなく、 原料の入手も困難になることも予想される。 これに対してクラフ卜法パルプ化からのクラフトリグニンは原料の入手という 点は問題がない。 ちなみに、 平成 5年度我力堀でクラフト法によって製造された 製紙用パルプは約 9 0 0万トンにおよぶ。 In Japan, sulfite pulping continues to decline, and lignosulfonic acid, which is a water-soluble lignin that can be obtained at night, has not only the disadvantage of conversion to large amounts of liver but also the disadvantage of raw materials. It is also expected that it will be difficult to obtain. On the other hand, there is no problem in obtaining raw materials for kraft lignin from the pulping process. By the way, the papermaking pulp manufactured by the craft method at Agarikibori in FY1993 amounted to about 900,000 tons.
クラフト法によるパルプ製造過程でォ 才中のリグニンは、 クラフ卜リグニンと してパルプの主成分であるセルロースを主とする多糖類から分離され、 夜中に 溶出除去される。 クラフトリグニンを多量に含む搬夜は濃縮されボイラーで燃焼 される。 その一部は燃焼に先立って熱風中に噴霧され粉末状のクラフトリグニン として単離され工業原料として利用されている。 Lignin in the pulp production process by the Kraft method is separated from polysaccharides, mainly cellulose, which is the main component of pulp, as lignin, and is eluted and removed at night. Transport nights containing large amounts of craft lignin are concentrated and burned in boilers. Some of them are sprayed into hot air prior to combustion and isolated as powdered kraft lignin, which is used as an industrial raw material.
かかるクラフトリグニンの水溶性化は従来芳香環へのスルフォメチル基の導入 による方法力 s知られている力 製造にあたっては高温を 要とし、 水溶性基の導 入率もそれほど高くない。 カロえて製造に用いたホルマリンの残留の問題も医薬品 としての利用上障害となりうる。 発明の開示 Such kraft lignin has been conventionally made water-soluble by the introduction of a sulfomethyl group into an aromatic ring. A known force requires a high temperature in production, and the introduction rate of a water-soluble group is not so high. The problem of residual formalin used in manufacturing can also be an obstacle to its use as a drug. Disclosure of the invention
本発明は、 このような抗エイズウイルス及び免疫 活剤としての、 従来のシィ タケ ¾t咅後の培地から単離され精製された水溶性の変性リグニン及びサルフアイ トパルプ排液から取り出されたリグノスルフォン酸の^^こ鑑み、 経口投与可能 な低分子量であり、 且つ低濃度においても極めて高レヽ抗エイズゥィルス及び免疫 賦活能を有する水溶性リグニンを、 安価で容易にしかも^ ¾に入手できる単離ク ラフトリグニンから製造する製造方法を提供しようとするものである。 The present invention provides a water-soluble denatured lignin isolated and purified from a conventional culture medium after Shitake mushrooms and lignosulfonate removed from sulphite pulp wastewater, as such an anti-AIDS virus and an immunostimulating agent. In view of the above, a water-soluble lignin having a low molecular weight that can be administered orally and having a very high anti-AIDS virus and immunostimulatory activity even at a low concentration can be obtained at low cost, easily and easily. An object of the present invention is to provide a production method for producing from lignin.
その要旨とするところは、 木材から得られるクラフトリグニンを精製した後、
これをカルボキシメチル化して水溶性クラフトリグニンを製造することを特徴と する水溶 1生クラフトリグニンの製造方法である。 The point is that after purifying kraft lignin obtained from wood, This is a method for producing water-soluble single raw kraft lignin, which comprises carboxymethylating this to produce water-soluble kraft lignin.
ここに木材とは針^！拼才または広翁耕才の両者を含み、 またラクトリグニンは l己のとおりクラフト法によるパルプ iii 程で分离胜成されるものである。 木 材細 中のリグニンは、 クラフト法によるパルプ化中に、 その主要な結合であ るエーテル結合力 s切断されて著しく低 化され、 その分子量は、 3 5 0 0 - 4 Wood is a needle here! Lactignin is composed of pulp by the kraft method iii. During the pulping by the Kraft method, the lignin in the wood material is severely cut by its main bond, the ether bond strength s, and its molecular weight is reduced to 350-4
5 0 0といわれている。 同時に他の方法で単離されたリグニンに比べて多量の フエノ一ル性水酸基を有し、 ィ匕学的に活性に富んでいる。 It is said to be 500. At the same time, it has a large amount of phenolic hydroxyl groups as compared with lignin isolated by other methods, and is rich in activity.
本発明により、 クラフトリグニンをカルボキシメチル化して得られた水溶性リ グニンは、 収量が多く、 力つ低濃度で極めて高レ、抗エイズウイルス及び免疫賦活 能を有し、 更にその分子量は約 4 0 0 0であり、 経口投与でも腸管から吸収され てウイルスのいる組織及び細胞に到達しうる 量が小さく、 しかもシィタケ栽 培後の培地から単離され精製された水溶性の変性リグニンやリグノスルフオン酸 と同様な効果をもつ水溶性リグニンを S¾iすることができたものである。 更に、 抗ウィルス活性に重要な役割を果していると考えられる水溶性基、 すなわちカル ボキシメチル基の置換度は高く、 目的に応じて制御することが出来る。 図面の簡単な説明 According to the present invention, the water-soluble lignin obtained by carboxymethylation of kraft lignin has a high yield, a very high concentration at a low concentration, an anti-AIDS virus and an immunostimulatory activity, and a molecular weight of about 4 The amount that can be absorbed from the intestinal tract and reach the tissues and cells containing the virus even after oral administration is small, and water-soluble denatured lignin or lignosulfonate isolated and purified from the culture medium after Shitake mushroom cultivation Water-soluble lignin having the same effect as that of と was able to be S¾i. Furthermore, the degree of substitution of a water-soluble group, which is considered to play an important role in antiviral activity, that is, a carboxymethyl group, is high and can be controlled according to the purpose. BRIEF DESCRIPTION OF THE FIGURES
図 1は、 水可溶性リグニンの効果の模式図である。 FIG. 1 is a schematic diagram of the effect of water-soluble lignin.
図 2は、 シィタケを培養したシュガーケーンバガスを水抽出し、 その疎水性の 強い区分をとり、 さらに分子量で分別した水可溶性リグニンに関するものであ り、 平均分子量が約 5 0万禾號の区分である。 これを、 カロ熱不活性化 F C S、 ぺ ニシリンおよびストレプトマイシンを含む R PM 1 - 1 6 4 0培地で、 C D 4陽 性ヒト T細胞クローン、 H I Vおよび水可溶性リグニンを加えて 3 7 °Cで 4日間 培養し、 生存する細胞数をトリパン .ブル一染色法を用いて趨した。 水可溶性 リグニンを加えずに同様に処理したものをブランクとした。 この定量法は以下図 3ないし図 5でも^された。 Fig. 2 shows water-soluble sugarcane bagasse obtained by cultivating shiitake mushrooms, which is classified into water-soluble lignins that have a strong hydrophobicity and are further classified by molecular weight. It is. This was performed at 37 ° C in RPMI 1-1640 medium containing calo heat-inactivated FCS, penicillin and streptomycin with the addition of CD4 positive human T cell clones, HIV and water-soluble lignin. After culturing for days, the number of surviving cells was trended using the trypan blue staining method. A blank treated in the same manner without adding water-soluble lignin was used as a blank. This assay was also performed in Figures 3 to 5 below.
図 3は、 サルファイトパルプ排液を濃縮し、 エタノール中に滴下することに よって、 共存する無機塩を除き精製したリグノスルフォン酸に関するものであ
り、 平均分子量は約 35000である。 Figure 3 shows lignosulfonic acid purified by removing the coexisting inorganic salts by concentrating the sulphite pulp effluent and dropping it in ethanol. The average molecular weight is about 35,000.
図 4は、 ブナ木粉を希硫酸で加水分解して糖を除いた後、 残渣を酸素圧 5 k g/m2で 1モルの苛性ソーダ水溶液を用いて 170 °C、 1時間処理して得ら れた酸素アルカリ処理リグニンに関するものであり、 平均分子量は約 1 5000 である。 4, after removal of sugars by hydrolysis of beech wood flour with dilute sulfuric acid, the residue oxygen pressure 5 kg / m 2 using a 1 molar aqueous solution of caustic soda 170 ° C, 1 hour to obtain et al The average molecular weight is about 15,000.
図 5は、 本発明のクラフトリグニンに関するものであり、 スルフェートパルプ 撒夜を濃縮し、 硫酸で酸注にすることによって ¾ させたクラフトリグニンを、 ジォキサンに溶解し、 エーテルに滴下して共存する無機塩を除き精製したもの を、 カルボキシメチル化して水可溶としたものに関し、 平均分子量は約 5000である。 FIG. 5 relates to the kraft lignin of the present invention, in which the kraft lignin obtained by concentrating the sulfate pulp night and injecting it with sulfuric acid is dissolved in dioxane and coexisted by dropping into ether. The average molecular weight of the purified product, excluding inorganic salts, was carboxymethylated and made water-soluble.
図 6は、 ヒト骨髄細胞クローンに卜リチウム化したチミジンおよび水可溶性リ グニンを加えて 37°Cで 4日間培養し、 DN A中に取り込まれたトリチウムの量 をトリチウムから出る放^^を測定することによって、 DNA合成能を定量した 図表である。 Figure 6 shows the addition of tritiated thymidine and water-soluble lignin to human bone marrow cell clones, culture at 37 ° C for 4 days, and measurement of the amount of tritium incorporated in DNA and release from tritium. 5 is a chart quantifying the DNA synthesis ability by performing the above steps.
図 7は、 市販の逆転写酵素に水可溶性リグニンを加えて 37°Cで 4日間培養 し、 常法により逆転 活性を測定した図表である。 FIG. 7 is a chart showing the results obtained by adding water-soluble lignin to a commercially available reverse transcriptase, culturing at 37 ° C. for 4 days, and measuring the reversal activity by a conventional method.
本発明の水溶性クラフ卜リグニンは、 図 5から明らかなように 200 μ g/ m 1の水溶液であっても細胞に対して何ら毒性を示さず、 1 2. 5 g/m 1と レ、う極めて低い濃度でエイズゥィルスの増殖を 90% t, 25 M g/m 1では ほぼ 100%阻害する。 Soluble Clough Bok lignin present invention, any not toxic to cells even in clear aqueous solution of 200 μ g / m 1 As from Fig. 5, 1 2. 5 g / m 1 and Le, At very low concentrations, growth of AIDS is inhibited almost 100% at 90% t, 25 Mg / m 1.
これに対して、 図 2ないし 4の試料は、 いずれも 200 g/m 1では細胞に 対して毒性を示さなレ、が、 1 2. 5 g/m 1及び 25 μ g/m 1の濃度でのェ ィズゥィルスの増殖 ISih率は、 図 2のシィタケ鍵咅培地から調整された水溶性リ グニン （分子量約 50万） ではそれぞれ 40%及び 80%、 また図 3のリグノス ルフォン酸 （分子量約 4万） は、 それぞれ 60%及び 90%であって、 図 4の酸 素アルカリ処理リグニンは、 それぞれ 70%及び 85%であって、 本発明によつ て i¾ された水溶性クラフトリグニンは、 の水溶性リグニンに比較して優れ た性質を有している。
発明を実施するための最良の形態 In contrast, all of the samples in Figs. 2 to 4 show no toxicity to cells at 200 g / m1, but at concentrations of 12.5 g / m1 and 25 μg / m1. The ISih ratio of water-soluble lignin (molecular weight of about 500,000) prepared from Shitake mushroom medium shown in Fig. 2 was 40% and 80%, respectively, and the lignosulfuric acid (molecular weight of about 4 Are 60% and 90%, respectively, the alknin-treated lignin of FIG. 4 is 70% and 85%, respectively, and the water-soluble kraft lignin obtained according to the present invention is: It has superior properties compared to water-soluble lignin. BEST MODE FOR CARRYING OUT THE INVENTION
市販されている針 itt才または広魏財からの単離クラフトリグニンは、 特別 な精製処理力 s施されておらず、 パルプ に用いられた無機試薬、 部分的に溶出 された糖類及び原料木材中の抽出成分などリグニン以外の不純物も含まれてい る。 これらの不純物を除去するため、 市販単離クラフトリグニンを約 1 0倍量Isolation kraft lignin from the needle itt old or wide Wei goods are marketed are not subjected special purification processing power s, inorganic reagents used in the pulp, sugars and raw wood in partially eluted It also contains impurities other than lignin, such as the extracted components. In order to remove these impurities, about 10 times the amount of commercially available kraft lignin is used.
(容量/ ) の 9 0 %含水ジォキサンに溶解し、 生じた不純物の をろ過し て除き、 ろ液を更に約 1 0倍量 （容量 Z容量） のジェチルェ一テル中に激しく撹 拌しながらゆっくりと滴下する。 として した精製クラフトリグニンを遠 心分離によって集め、 新しいジェチルエーテルで洗浄し、 遠心分離によってジェ チルエーテルを除く。 ジェチルエーテルでの洗浄をもう一度繰り返した後、 低沸 点区分の石油エーテルで一度洗浄し、 低温で草 桑する。 この精製クラフト リグニンを次のいずれかの方法でカルボキシメチルイヒし水溶性ィヒする。 (Volume / volume) in 90% aqueous dioxane, and the resulting impurities were removed by filtration. The filtrate was further slowly stirred with vigorous stirring into about a 10-fold volume (volume Z volume) of getyl ether. And dripping. The purified kraft lignin is collected by centrifugation, washed with fresh getyl ether and centrifuged to remove getyl ether. After repeating the washing with getyl ether, wash once with petroleum ether in the low boiling point category, and then mushroom at low temperature. The purified kraft lignin is made carboxymethyl and water-soluble by any of the following methods.
( 1 ) 充分草 桑した精製クラフトリグニン 1部を 2 0部の 2モル苛性ソーダに溶 力 、 溶液を撤半しながら 5 5 °Cに加熱する。 この溶液に固体のモノクロ口酢酸 1部を撹拌しながら 3 0分かけて徐々に加え、 更に 2時間 5 5 °Cで加熱を続け る。 反応後 2モル塩酸で中和し、 目の細かい透析膜、 例えばスぺクトラボア 一 3 (スぺクトラル 'メジカル工業社製、 限界ノ 量 3 5 0 0 ) を使って透析し て無MS応試薬を除去し、 力ルポキシメチルイヒクラフトリグニン 1を凍結乾燥に よって単離する。 (1) Sufficient grass One part of the refined kraft lignin is dissolved in 20 parts of 2 molar caustic soda, and the solution is heated to 55 ° C while removing the solution. To this solution, gradually add 1 part of solid monochrome acetic acid over 30 minutes while stirring, and continue heating at 55 ° C for 2 hours. After the reaction, neutralize with 2 molar hydrochloric acid, dialyze using a fine-dialysis membrane, for example, Spectra Laboratories 13 (Spectral 'Medical Industry Co., Ltd., limited volume: 3500), and use MS-free reagents. And lypoxymethyl ichkraft lignin 1 is isolated by lyophilization.
( 2 ) 充分乾燥した精製クラフトリグニン 1部を 2 0部の 4モル苛性ソーダに分 散し、 懸濁液を撤半しながら 5 5 °Cに加熱する。 この懸濁液に固体のモノクロ口 酢酸 1部を撹拌しながら 3 0分かけて徐々に加え、 更に 2時間 5 5 °Cで加熱を続 ける。 反応後 2モル塩酸で中和し、 目の細かい透析膜、 例えばスぺクトラボア —3 (スぺクトラル'メジカル工業社製、 限界 ^量 3 5 0 0 ) を使って透析し て無機反応試薬を除去し、 カルボキシメチル化クラフトリグニン 1よりカルボキ シメチル基の置換度力稿い力ルボキシメチル化クラフトリグニン 2を凍結乾燥に よって単離する。
力ルボキシメチル化クラフトリグニン 1では、 原料のクラフトリグニンのフェ ノ一レ!1生水酸基だけが力ルボキシメチル化され、 力ルボキシメチル基の置^^約(2) Disperse 1 part of purified kraft lignin that has been sufficiently dried in 20 parts of 4 molar caustic soda, and heat to 55 ° C while removing the suspension. To this suspension, gradually add 1 part of solid monochrome acetic acid over 30 minutes while stirring, and continue heating at 55 ° C for 2 hours. After the reaction, the reaction mixture is neutralized with 2M hydrochloric acid, dialyzed using a fine-dialysis membrane, for example, Spectropore-3 (manufactured by Spectral's Medical Industrial Co., Ltd., limited amount: 3500), and the inorganic reaction reagent is removed. After removal, carboxymethylated kraft lignin 2 is isolated from carboxymethylated kraft lignin 1 by freeze-drying. In force Rubokishimechiru kraft lignin 1, only Fe Roh Ichire! 1 raw hydroxyl groups of the raw materials of kraft lignin is a force Rubokishimechiru of, location of the force Rubokishimechiru based on ^^ about
0. 4 5である力 カルボキシメチル化クラフトリグニン 2では、 アルコール个生 水酸基の一部もカルボキシメチルイ匕され、 カルボキシメチル基の置換度は約 0. 7まで上昇する。 上の利用可能性 In the carboxymethylated kraft lignin 2 which is 0.45, a part of the hydroxyl group of the alcohol is also carboxymethylated, and the degree of substitution of the carboxymethyl group increases to about 0.7. Availability on
本発明に係るクラフ卜リグニンは、 抗ゥィルス活性剤及び免疫増強剤として利 用され、 さらにレトロビールスに起因する鶏の二ュウーキャッスル病の薬剤とし ての利用力項月待される。
The craft lignin according to the present invention is used as an antiviral active agent and an immunopotentiator, and is expected to be used as a drug for chicken virus Newu Castle disease caused by retrovirus.
Claims
1 . クラフト法により木材から得られるクラフトリグニンを精製した後、 これを カルボキシメチルイ匕して水溶性クラフトリグニンを得ることを樹敷とするクラフ トリグニンの 3i方法 1. After purifying kraft lignin obtained from wood by the kraft method, carboxymethyl ligne is used to obtain water-soluble kraft lignin.
2 . カルボキシメチルイ匕することによる基の置^^が 0. 4 5であることを稱教 とする請求項 1の水溶'注クラフトリグニンの ii方法 2. The water-soluble kraft lignin ii method according to claim 1, wherein it is said that the substitution of the carboxymethyl group is 0.45.
3. カルボキシメチルイ匕することによる基の置 ¾^が 0. 7であることを特徴と する請求項 1の水溶性クラフトリグニンの i¾i方法 3. The i¾i method for water-soluble kraft lignin according to claim 1, wherein the substitution of carboxymethyl group is 0.7.
4. 精製したクラフトリグニンを苛性ソーダに溶かしまたは分散させ、 その溶液 または懸濁液にモノクロ口酢酸を加えて所定時間加熱し、 醒中和した後、 透析 膜で透析を行うことを翔数とする請求項 1の水溶性クラフトリグニンの製造方法
4. Dissolve or disperse the purified kraft lignin in caustic soda, add monochloroacetic acid to the solution or suspension, heat for a predetermined time, awake neutralize, and dialyze with a dialysis membrane. A method for producing the water-soluble kraft lignin according to claim 1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP1995/001749 WO1997009338A1 (en) | 1995-09-01 | 1995-09-01 | Process for producing water-soluble kraft lignin |
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/JP1995/001749 WO1997009338A1 (en) | 1995-09-01 | 1995-09-01 | Process for producing water-soluble kraft lignin |
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| PCT/JP1995/001749 WO1997009338A1 (en) | 1995-09-01 | 1995-09-01 | Process for producing water-soluble kraft lignin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006202607A (en) * | 2005-01-20 | 2006-08-03 | Furukawa Co Ltd | Anode additive for lead-acid battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05294981A (en) * | 1992-04-14 | 1993-11-09 | Mokushitsu Shinsozai Gijutsu Kenkyu Kumiai | Production of carboxyalkylated lignin derivative |
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1995
- 1995-09-01 WO PCT/JP1995/001749 patent/WO1997009338A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05294981A (en) * | 1992-04-14 | 1993-11-09 | Mokushitsu Shinsozai Gijutsu Kenkyu Kumiai | Production of carboxyalkylated lignin derivative |
Non-Patent Citations (5)
| Title |
|---|
| HOLZFORSCHUNG, Vol. 42, No. 5, (1988), ROBERT BREZNY et al., "Mild Coagulation of Aqueous Suspensions of Kraft Lignin and its Derivatives", pp. 335-336. * |
| HOLZFORSCHUNG, Vol. 42, No. 6 (1988), ROBERT BRENZNY et al., "The Ion-Exchanging Lignin Derivatives Prepared by Mannich Reaction with Amino Acids", pp. 369-373. * |
| HOLZFORSCHUNG, Vol. 47, No. 4 (1993), RAJESH K. JAIN et al., "Lignin Derivatives. II. Functional Ethers", pp. 325-332. * |
| TAPPI, J., Vol. 73, No. 6 (1990), ROBERT BRENZNY et al., "Specific Ion-Exchangers Based on Lignins and their Characterization by Silicon-29 NMR Spectroscopy", pp. 199-204. * |
| WOOD SCI. TECHNOL., Vol. 14, No. 1, (1980), W. LANGE et al., "The Carboxymethylation of Organosolv and Kraft Lignins", pp. 1-7. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006202607A (en) * | 2005-01-20 | 2006-08-03 | Furukawa Co Ltd | Anode additive for lead-acid battery |
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