JPS62259584A - Fiber-or plastic-modified fermented, thermostable and acid-tolerant enzyme - Google Patents

Fiber-or plastic-modified fermented, thermostable and acid-tolerant enzyme

Info

Publication number
JPS62259584A
JPS62259584A JP61103136A JP10313686A JPS62259584A JP S62259584 A JPS62259584 A JP S62259584A JP 61103136 A JP61103136 A JP 61103136A JP 10313686 A JP10313686 A JP 10313686A JP S62259584 A JPS62259584 A JP S62259584A
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JP
Japan
Prior art keywords
plastic
fermentation
bacteria
stir
resistant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP61103136A
Other languages
Japanese (ja)
Other versions
JP2528096B2 (en
Inventor
Koji Fujimori
康次 藤森
Keiko Fujimori
藤森 啓子
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Individual
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Individual
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Priority to JP61103136A priority Critical patent/JP2528096B2/en
Publication of JPS62259584A publication Critical patent/JPS62259584A/en
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Expired - Lifetime legal-status Critical Current

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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Enzymes And Modification Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

PURPOSE:A thermostable and acid-tolerant enzyme consisting of the first phase liquid composition obtained by blending wood fibers, e.g. waste cellulose, etc., with edible vinegar and blending and stirring the resultant filtrate with a plastic raw material or material or fermentation solid material of the above-mentioned composition with a metal, etc. CONSTITUTION:A bound enzyme, having heat resistance and acid tolerance and obtained by blending, stirring and allowing wood fibers and edible vinegar liquid to stand at a temperature within the range where seedlings may be active, preferably ordinary temperature - <=60 deg.C to give a blend, filtering the blend, blending, stirring and fermenting the filtrate and a plastic raw material or material at a temperature where the seedling may be active to give a three- phase entrapped modified material, directly using a concentrate of the first phase liquid composition separated from the above-mentioned modified material or adding one or more selected from iron, zinc, aluminum, manganese, copper, chromium, cobalt, magnesium, silicon, fluorine, iodine, selenium, calcium carbonate, phosphorus and sulfur in an amount of preferably 1/2 based on the total amount to the above-mentioned concentrate and fermenting the concentrate.

Description

【発明の詳細な説明】 童−呆世叩片」 本発明は新規な酵素に関し、特に繊維及びプラスチック
変性物から発酵して得られた耐熱性・耐酸性酵素に関す
る。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel enzyme, and particularly to a heat-resistant and acid-resistant enzyme obtained by fermentation from modified fibers and plastics.

■−挟哲一 本発明者等は先に、製紙セルローズ系の廃棄資源、即ち
製紙資源、製紙廃棄物、紙、天然木破片、その他の木繊
維と食酢を混合し、そのろ過液をもってプラスチック原
料、プラスチック材料と撹拌し得られる電解性、イオン
変換性及び熱硬化性を有する繊維及びプラスチック変性
三相包括組成物について提案している(特願昭52−9
1.461号、特開昭54−26398号)。
■- Tetsuichi Han The inventors first mixed vinegar with cellulose-based papermaking waste resources, papermaking resources, papermaking waste, paper, natural wood fragments, and other wood fibers, and used the filtrate as a raw material for plastics. proposed a fiber and plastic modified three-phase comprehensive composition that has electrolytic properties, ion-converting properties, and thermosetting properties that can be obtained by stirring with a plastic material (Japanese Patent Application No. 1982-9).
1.461, JP-A-54-26398).

上記正相組成物の各相は上から順に見て第1相液相は電
解性を有し、錆等の剥離性を有する錆落剤他金属表面処
理剤等として、第2相はイオン交換性を有し、イオン交
換半透膜相として、また第3相液粘相は熱硬化性を有し
、接着剤、塗料等として、それぞれ有用な性質を有する
ものである。
The phases of the above-mentioned positive phase composition are viewed from top to bottom, and the first phase has electrolytic properties, the second phase is used as a rust remover and other metal surface treatment agents that have the ability to remove rust, etc., and the second phase is an ion exchanger. It has properties useful as an ion-exchange semipermeable membrane phase, and the third liquid-viscous phase has thermosetting properties and is useful as adhesives, paints, etc.

裏刷j ゛ しようとする」4立 本発明者等は、上記製紙セルローズ等の廃棄資源を活用
する該正相包括組成物について更に研究を深めていたが
該正相包括組成物の各相それぞれを、そのまま利用する
にはそれぞれ限界があることが分かり、更にこれらの有
効利用のための方式手段の解決が望まれていた。
The present inventors have been further deepening their research into the positive phase comprehensive composition that utilizes waste resources such as paper cellulose. It has been found that there are limitations to using these as they are, and it has been desired to find a method and means to utilize them more effectively.

刑題点を#決J−るための手段一 本発明者等は種々検討の結果上記第1相の液体組成物そ
のまま、又は該濃縮物に成る種の金属あるいは半金属物
質あるいは化合物を加えた後、発酵して得られる固体状
物質が種々の活性を有する耐熱性・耐酸性酵素と言うべ
きものであることを見出し、本発明に到達したものであ
る。
As a result of various studies, the inventors of the present invention used the liquid composition of the first phase as it was, or added a metal or metalloid substance or compound to form the concentrate. After that, it was discovered that the solid substance obtained by fermentation is what can be called a heat-resistant and acid-resistant enzyme having various activities, and this led to the present invention.

即ち、本発明は、木繊維と食酢液を混合撹拌、菌の活動
できる温度範囲で静置して得られる混合物をろ過、該ろ
過液とプラスチック原料、又はプラスチック材とを菌の
活動できる温度範囲で混和撹拌、醸成、静置して得られ
る三相抱括変性物より分離した第1相液体組成の濃縮液
そのまま、又は該濃縮物に、鉄、亜鉛、アルミニウム、
マンガン、銅、クロム、コバルト、マグネシウム、ケイ
素、フッ素、ヨウ素、セレン、炭酸カルシウム、リン及
び硫黄から成る群から選ばれた物質の1種以上を、好ま
しくは全体量の1/2倍以下添加、発酵させたものから
なる繊維、プラスチック変性発酵、耐熱性・耐酸性酵素
、該酵素の製造方法及び用途に関するものである。
That is, the present invention involves mixing and stirring wood fibers and a vinegar solution, filtering the resulting mixture by allowing it to stand in a temperature range where bacteria can be active, and mixing the filtrate and plastic raw materials or plastic materials within a temperature range where bacteria can be active. A concentrated solution of the first phase liquid composition separated from the three-phase encapsulated modified product obtained by mixing, stirring, fermentation, and standing still, or in the concentrate, iron, zinc, aluminum,
Adding one or more substances selected from the group consisting of manganese, copper, chromium, cobalt, magnesium, silicon, fluorine, iodine, selenium, calcium carbonate, phosphorus and sulfur, preferably not more than 1/2 times the total amount, The present invention relates to fermented fibers, plastic denatured fermentation, heat-resistant and acid-resistant enzymes, and methods for producing and using the enzymes.

本発明で用いられる第1相液体組成物を得るに当って、
製紙資源、製紙廃棄物等、その他の木繊維としては例え
ば以下のものが使用される。即ち、(イ)かっ色包装紙
、セメント用紙、 (ロ)新聞紙、段ボール (ハ)低級、高級印刷紙、グラビア紙 (ニ)木繊維 等である。(イ)(ロ)(ハ) (ニ)に含まれる組成
は、主に有機物としてαセルローズ、βセルローズ、ヘ
ミセルローズ、リグニン、抽出物、インキ等、無機物と
してS、P、Si、−AlO2゜C1、その他の金属等
であり前記中には製紙処理過程中に使用された物質の残
分も含まれており原形木質部、骨髄部、製紙用残分を主
体とする。食酢は、通常滅菌しであるが、ある程度の加
温等によって菌の活動が始まることがみとめられ、菌と
しては食酢中に存在する酢酸菌、メタン菌、枯草菌等が
、その例として挙げられる。
In obtaining the first phase liquid composition used in the present invention,
As other wood fibers such as paper resources and paper manufacturing waste, the following are used, for example. Namely, (a) brown wrapping paper, cement paper, (b) newspaper, cardboard, (c) low-grade and high-grade printing paper, gravure paper, and (d) wood fiber. The composition contained in (a), (b), (c), and (d) is mainly comprised of organic substances such as α-cellulose, β-cellulose, hemicellulose, lignin, extracts, and ink, and inorganic substances such as S, P, Si, and -AlO2゜. C1, other metals, etc., which also include the residues of substances used during the papermaking process, and are mainly composed of the original wood part, marrow part, and papermaking residues. Vinegar is usually sterilized, but it has been found that bacterial activity begins when heated to a certain degree, and examples of bacteria that exist in vinegar include acetic acid bacteria, methane bacteria, and Bacillus subtilis. .

本発明で利用するプラスチック原料、又はプラスチック
材は例えば以下のものが挙げられる。
Examples of the plastic raw materials or plastic materials used in the present invention include the following.

HCl、、CH2=CHCl、、C2H2゜CH,CH
O,CH,Coo)(、C2H4゜HOCH,−CHI
、OH,C,H50H,HCT(0゜フルフラール、イ
ソシアネート、メラミン、エポキシ化合物、アクリル化
合物、 HOOC−Ω−COOH。
HCl,,CH2=CHCl,,C2H2゜CH,CH
O, CH, Coo) (, C2H4゜HOCH, -CHI
, OH, C, H50H, HCT (0° furfural, isocyanate, melamine, epoxy compound, acrylic compound, HOOC-Ω-COOH.

HOOC(CH,)COOHなどプラスチック製造過程
の反応中間生成物及びウレタン樹脂、メラミン樹脂、ポ
リエステル樹脂、シリコーン樹脂等のthermose
tting  pJ、ast i c s、アクリル樹
脂、ポリメチルメタクリレート樹脂、ABS樹脂、ポリ
エチレン樹脂、ポリプロピレン樹脂、ナイロン等のt 
h s r moplastics等@ 本発明で用いられる第1相液体組成物は具体的には次の
ようにして製造される。
Reaction intermediate products in plastic manufacturing processes such as HOOC(CH,)COOH and thermoses of urethane resins, melamine resins, polyester resins, silicone resins, etc.
tting pJ, ast ic s, acrylic resin, polymethyl methacrylate resin, ABS resin, polyethylene resin, polypropylene resin, nylon, etc.
h s r moplastics, etc. @ The first phase liquid composition used in the present invention is specifically manufactured as follows.

先ず、廃棄セルローズ等の木繊維を食酢中に1=50以
内の重量比で混和し、撹拌し、静置した後、ろ過するこ
とによりプラスチック攻撃剤たるろ液を得る。この反応
時、特に静置に当っては温度は食酢中の菌の活動できる
温度であればどのような範囲でもよいが、一般に100
℃以下、特に常温〜60℃以下で行なうのが好ましく、
混和時間は混和により混合物がパルプ状(粥状)となる
まで行えばよいが、一般には3時間以上行うものとする
。このものをしばらく静置後、ろ過を行い、ろ液を得る
First, wood fibers such as waste cellulose are mixed in vinegar at a weight ratio within 1=50, stirred, allowed to stand, and then filtered to obtain a filtrate as a plastic attacking agent. During this reaction, especially when left to stand still, the temperature may be in any range as long as the bacteria in the vinegar can be active, but generally the temperature is 100°C.
It is preferable to carry out at a temperature of ℃ or less, especially room temperature to 60℃ or less,
The mixing time may be as long as the mixture becomes pulp-like (porridge-like), but the mixing time is generally 3 hours or more. After allowing this to stand for a while, it is filtered to obtain a filtrate.

該ろ液に、前記のポリエステル樹脂、ウレタン樹脂等の
プラスチック原料(モノマー、反応中間生成物等)、プ
ラスチック材を加え、数時間以上撹拌し、醸成すると三
相に分かれた液状物が得られる。この撹拌、醸成におけ
る温度は上記の場合と同様である。該三相は、上から順
に液状の第1相、イオン交換性を有する半透膜状液粘物
たる第2相、及び液粘相たる第3相である。該三相をそ
れぞれに分離する。
To the filtrate are added plastic raw materials (monomers, reaction intermediates, etc.) such as the polyester resin and urethane resin, and plastic materials, and when stirred and fermented for several hours or more, a liquid product separated into three phases is obtained. The temperature during this stirring and brewing is the same as in the above case. The three phases are, in order from the top, a liquid first phase, a semipermeable membrane-like liquid viscous phase having ion exchange properties as a second phase, and a liquid viscous third phase. The three phases are separated.

このようにして得られた第1相液体組成物は液量を1/
2以下、好ましくは175以下、更に好ましくは111
0程度にまで濃縮する。濃縮に当っては加熱するのが好
ましく、加熱はホットプレート等を用いて行い、煮沸さ
せるのが好ましいが、真空乾燥などの乾燥による濃縮で
も良く、加熱と乾燥の両者を併行して行うこともできる
The first phase liquid composition thus obtained has a liquid volume of 1/
2 or less, preferably 175 or less, more preferably 111
Concentrate to about 0. When concentrating, it is preferable to heat, and it is preferable to heat using a hot plate or the like and boil it, but it is also possible to concentrate by drying such as vacuum drying, and it is also possible to perform both heating and drying at the same time. can.

上記のようにして得られた第1相の濃縮液をそのまま用
いるか、又は該濃縮液に鉄、マグネシウム、亜鉛、アル
ミニウム、マンガン、銅、クロム、コバルト、フッ素、
ヨウ素、セレン、炭酸カルシウム、リン及び硫黄から成
る群から選ばれた物質の1種以上を、粉末等の形で濃縮
液の1/2倍量以上添加するが、この際、煮沸を続けな
がらの添加がより好ましい。
The first phase concentrate obtained as described above may be used as is, or the concentrate may contain iron, magnesium, zinc, aluminum, manganese, copper, chromium, cobalt, fluorine, etc.
One or more substances selected from the group consisting of iodine, selenium, calcium carbonate, phosphorus, and sulfur are added in the form of powder or the like at least 1/2 the amount of the concentrated liquid. Addition is more preferred.

上記濃縮液又は該濃縮液に上記金属等の添加物質を加え
たものを、浮卵器等を用い室温好ましくは35℃前後で
1週間以上発酵させる。このときに定期的に第1相液体
組成物の少量をかけることもできる。発酵がすむと最初
液状物であったものが全体に増殖しており、水分もとん
でベージュ色の固まりとなっている。これをかきとって
本発明の目的物を得る。得られた本発明の繊維、プラス
チック変性発酵、耐熱性・耐酸性酵素は以下のような物
性を有する。
The concentrated solution or the concentrated solution to which additives such as metals are added is fermented using an egg floater or the like at room temperature, preferably around 35° C., for one week or more. At this time, small amounts of the first phase liquid composition can also be applied periodically. Once fermentation is complete, what was initially a liquid substance has multiplied all over the place, and the water has disappeared, turning it into a beige solid. This is scraped off to obtain the object of the present invention. The obtained fibers, plastic modified fermentation, heat-resistant and acid-resistant enzymes of the present invention have the following physical properties.

旋光度、左旋光度10’〜12°、タン白質窒素量が硝
酸イオンの測定で0.56■/1であり、鉄−亜鉛酵素
は約4.35■/1、アルミニウム酵素は約1.61m
g/]、Al−Fe−8i酵素は約1.95■/]であ
り、結合酵素である。この酵素300℃まで作用し、塩
酸に対して耐酸性であり、耐溶媒である。相対群特異性
酵素は活性化に金属を必要とすることは既に知られてお
り(B、L、Vallee、J、E、O1smanコン
プレヘンシブバイオケミストリー(Co mprehe
nsive  Biochemistry) Vol、
、1.2. p186 (1964) ) 、この種の
酵素は活性に必要な金属が酵素蛋白と強固に結合して存
在するか、それともゆるく、透析などにより容易に除去
されるかにより、それぞれMetal  enzyme
とMetal−enzymecompiexとに区別さ
れている。現在金属を必要とする酵素(ヘム酵素は除く
)は200種近く知られており、Mn、Mo、Co、F
e、Ca。
Optical rotation, left optical rotation 10' to 12°, protein nitrogen content measured by nitrate ion is 0.56 ■/1, iron-zinc enzyme is approximately 4.35 ■/1, aluminum enzyme is approximately 1.61 m
g/], the Al-Fe-8i enzyme is about 1.95 g/], and is a conjugated enzyme. This enzyme works up to 300°C, is resistant to hydrochloric acid, and is resistant to solvents. It is already known that relatively group-specific enzymes require metals for activation (B.L., Vallee, J.E., Olsman, Comprehensive Biochemistry).
nsive Biochemistry) Vol.
, 1.2. (p186 (1964)), these types of enzymes are classified as metal enzymes depending on whether the metal required for activity is present tightly bound to the enzyme protein or is loose and easily removed by dialysis etc.
and Metal-enzymecompiex. Currently, nearly 200 types of enzymes (excluding heme enzymes) that require metals are known, including Mn, Mo, Co, and F.
e, Ca.

Mg、Cu、Zn等があり、ZnはFAD(第二基質に
関与するもの)を補欠分子族とする脱水素酵素に認めら
れ、又、7. nは種々加水分解酵素にも存在する。し
ばしば例に挙げられる糖化型α−Amylazeを分泌
する枯草菌はproteaseを分泌するが、Znを含
む金属酵素で、そのZnを可逆的に除去することができ
る。Znの変わりに他の金属を結合させた場合の活性は
金属の種類によって変わってくる。Cuは酸素を受容体
とする酸化酵素にのみに詔められ、FeはFADを補欠
分子族とする、脱水酵素となる。これら既存の酵素は以
下に示すような性質を有するが、本発明の酵素もこれに
類するものである。
There are Mg, Cu, Zn, etc., and Zn is found in dehydrogenases that have FAD (related to the second substrate) as a prosthetic group, and 7. n also exists in various hydrolytic enzymes. Bacillus subtilis, which secretes saccharified α-Amylase, which is often cited as an example, secretes protease, which can reversibly remove Zn using a metalloenzyme containing Zn. When other metals are bonded instead of Zn, the activity varies depending on the type of metal. Cu is used only as an oxidase that uses oxygen as an acceptor, and Fe acts as a dehydrase that uses FAD as a prosthetic group. These existing enzymes have the properties shown below, and the enzyme of the present invention is also similar to these.

上記プラスチック原料酸いはプラスチック材はいずれも
使用できるが第1相組成物及び後に使用する第3相組成
物として、好ましくは、ポリエステル、ポリウレタン、
フェノール樹脂、メラミン樹脂、エポキシ樹脂、アクリ
ル樹脂、ベークライト、ポリプロピレン、シリコーン等
が使用される。
Any of the above-mentioned plastic raw materials or plastic materials can be used, but preferably polyester, polyurethane,
Phenol resin, melamine resin, epoxy resin, acrylic resin, Bakelite, polypropylene, silicone, etc. are used.

該耐熱性・耐酸性酵素を上記繊維及びプラスチック変性
三相包括組織物から得られる第3相液粘和物に添加し、
種々の金属等の添加物を同様に添加して処理したところ
、その接着効力が大巾に増大することが、又ガラスコー
ティングしたところガラスの光透過性が向上することが
判明した。
Adding the heat-resistant and acid-resistant enzyme to the third phase liquid viscosity obtained from the fiber and plastic modified three-phase inclusive tissue,
It was found that when various additives such as metals were added and treated in the same manner, the adhesive efficacy was greatly increased, and when glass was coated, the light transmittance of the glass was improved.

接着力、ガラス光透過性向上剤の母体となる原料として
は前記第3相液粘相物に類するものはいずれも使用でき
るが第3相液粘和物が好ましい。
As the base material for the adhesive force and glass light transmittance improver, any material similar to the third phase liquid viscous substance can be used, but the third phase liquid viscous substance is preferable.

これらの接着剤は、例えば前記第3相液粘和物に金属粉
末等の添加剤を該液粘相100 gに対して、1g以上
添加し、10日前後保温静置発酵させ、ついで前記本発
明の耐熱性、耐酸性酵素を0.1g以上加え、希釈撹拌
することによって得られる。その際、接着剤の添加剤で
ある金属粉末は、接着すべき金属と同種の金属の粉末を
用いるのが好ましく、又接着性強化剤(酵素)に添加す
る添加剤(金属等)も同種のものが好ましく用いられる
。添加剤は、金属粉末としては、鉄、亜鉛、アルミニウ
ム、マンガン、銅、クロム、コバルト、マグネシウム、
けい素、炭酸カルシウム、酸化鉄等である。
These adhesives are prepared by, for example, adding 1 g or more of an additive such as a metal powder to the third phase liquid viscous material per 100 g of the liquid viscous phase, allowing it to stand and ferment at a temperature for about 10 days, and then adding it to the third phase liquid viscous material. It can be obtained by adding 0.1 g or more of the heat-resistant and acid-resistant enzyme of the invention and diluting and stirring. In this case, it is preferable to use powder of the same type of metal as the metal to be bonded as the metal powder that is an additive for the adhesive, and the additive (metal, etc.) added to the adhesive strength agent (enzyme) should also be of the same type as the metal to be bonded. is preferably used. Additives include metal powders such as iron, zinc, aluminum, manganese, copper, chromium, cobalt, magnesium,
These include silicon, calcium carbonate, and iron oxide.

又、ガラス透過性向上剤は同様にして該第3相液粘和物
に、Al粉末及び本発明の耐熱性、耐酸性酵素を添加処
理することによって得られる。この場合、酵素に添加す
る添加物質はAIがより好ましい。
Further, the glass permeability improver can be obtained in the same manner by adding Al powder and the heat-resistant and acid-resistant enzyme of the present invention to the third phase liquid viscosity. In this case, the additive substance added to the enzyme is more preferably AI.

上記第3相粘性組成物は、前記三和包括組成物のうちの
第3相に相当するものであり、食酢と繊維素とにより作
られたろ過液をプラスチック原料の至プラスチック材と
混和撹拌し静置後、濃度の高いものとして、製造容器内
の底部(第3相)に沈澱醸成するものである。
The third phase viscous composition corresponds to the third phase of the Sanwa comprehensive composition, and is made by mixing and stirring a filtrate made from vinegar and cellulose with a plastic material, which is a plastic raw material. After being allowed to stand still, a highly concentrated product is precipitated at the bottom (third phase) of the production container.

この組成物は原料プラスチックによりそれぞれ異なるが
例えば、フェノール樹脂変性物では、フェノールにホル
マリンが作用し、フェノールのオルト位置及びパラ位置
にメチロール化が起こり、これが縮重合して水を放出し
て高分子物質を作る。
This composition differs depending on the raw material plastic, but for example, in modified phenol resins, formalin acts on phenol, causing methylolization at the ortho and para positions of the phenol, which undergoes condensation and release of water, resulting in polymerization. create a substance.

ろ液中のアルデヒド類中にホルマリンとグルコン酸が含
まれており、ノボラック型とならず、ノボラック−鎖状
高分子形のフェノール変性物が出来るものと考えられる
。なお、ろ液中に酵素の含有。
Since formalin and gluconic acid are contained in the aldehydes in the filtrate, it is thought that novolak-type phenol-modified products are produced, rather than novolak-type chain polymers. In addition, the filtrate contains enzymes.

セルロース、ヘミセルロース、リグニンその他の含有の
為に、実際の反応は更に複雑になるものと考えられる。
It is believed that the actual reaction will be more complicated due to the inclusion of cellulose, hemicellulose, lignin, etc.

性能としては、ノボラック型フェノールより耐酸、耐熱
に勝り密着(金属等に対して)の非常に良いものが得ら
れる。又、ウレタン樹脂変性物は、製紙資源からのセル
ローズに基き、ろ液中の多量のセルローズ系窒素の存在
の為、アミド結合が生じ、変形し更にエステル化し、ア
ミドとの重縮合物が生成するものと考えられ、ろ過液中
の成分が複雑であるため、その反応は多岐にわたってい
る。3相粘液相を成形加工すると、混和プラスチックの
夫々が、2次元結合及び3次元結合の両方の性質を有す
る従来にない特殊なプラスチックに変性されたものとな
る。
In terms of performance, it has better acid resistance and heat resistance than novolac type phenol, and has very good adhesion (to metals, etc.). In addition, urethane resin modified products are based on cellulose from papermaking resources, and due to the presence of a large amount of cellulose nitrogen in the filtrate, amide bonds are generated, deformed, and further esterified to form polycondensates with amides. Since the components in the filtrate are complex, the reactions are diverse. When the three-phase viscous phase is molded, each of the mixed plastics is modified into an unprecedented special plastic that has both two-dimensional bonding and three-dimensional bonding properties.

本発明の該発酵固形物は他の添加剤と共に第3相液粘組
成物に添加されるが、該第3相組成物1000gに対し
て、0.2〜1.0 gの少量を添加することによりそ
の帯電防止性、耐電圧性、接着性特に金属類及びガラス
等の接着性を著しく向」ニさせることができる。又、ガ
ラスにおいては、その透明性をも向」ニさせることがで
きる。
The fermented solid of the present invention is added to the third phase liquid-viscous composition together with other additives, and is added in a small amount of 0.2 to 1.0 g per 1000 g of the third phase composition. As a result, its antistatic properties, voltage resistance, and adhesive properties, especially adhesive properties to metals, glass, etc., can be significantly improved. Furthermore, the transparency of glass can also be improved.

重刑 本発明の繊維、プラスチック変性発酵酵素はセルローズ
等廃棄資源及びプラスチックから変成された組成物から
極めて容易に製造でき、耐熱性、耐酸性にすぐれ、静電
気を帯びないものとすることができ、帯電防止剤、耐電
圧剤として有用な作用を有し、又、含有する金属をイオ
ン化して可溶状態と成す等の作用を有し、それらの金属
の接着性を増大させることができ、又ガラスの光透過性
を向上させる作用を有する。
The fiber and plastic-modified fermentation enzyme of the present invention can be extremely easily produced from a composition modified from waste resources such as cellulose and plastic, has excellent heat resistance and acid resistance, and is free from static electricity. It has a useful effect as an antistatic agent and a voltage-resistant agent, and also has the effect of ionizing the metals it contains to make them soluble, and can increase the adhesion of those metals. It has the effect of improving the light transmittance of glass.

実施例 次いで、本発明の実施例を挙げて本発明を具体的に説明
するが、本発明はこれに限定されるものではない。
EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

去*M1 食酢に粉砕した廃棄紙を加え、この混合物を3時間撹拌
してパルプ状(粥状)のものが得られたら、該粥状物を
約40℃において3日間寝かせた後、絞ってろ液を得る
。該ろ液は約40℃において再び3日間寝かせ、そこへ
ウレタンの原料たるグリコールを加え、3時間撹拌後3
日間寝かせて三相に分かれた変性物を得る。
*M1 Add crushed waste paper to vinegar and stir the mixture for 3 hours to obtain a pulp-like substance. Leave the porridge-like substance at about 40°C for 3 days, then squeeze it. Get the liquid. The filtrate was allowed to rest again at about 40°C for 3 days, and glycol, which is a raw material for urethane, was added thereto, and after stirring for 3 hours,
After aging for a day, a modified product separated into three phases is obtained.

該3相の内の第1相を傾斜法にて取り出し、5Qのガラ
ス容器内にいれ、ガス又はマントルヒーターを用いて9
8℃程度に加熱、煮沸させる。該操作を6時間行い液量
が115程度になったところで加熱をやめる。」二部操
作を数回くり返し115濃縮液100Qを得た。上記濃
縮液100Qを煮沸しながらZn粉末及びFe粉末を徐
々に加えた。
The first phase of the three phases is taken out by the decanting method, placed in a 5Q glass container, and heated to 90% using a gas or mantle heater.
Heat to around 8℃ and bring to a boil. This operation was continued for 6 hours, and heating was stopped when the liquid volume reached about 115 ml. The two-part operation was repeated several times to obtain 115 concentrate 100Q. While boiling the concentrated solution 100Q, Zn powder and Fe powder were gradually added.

このものを浮卵器内に入れ、35℃で10日間発酵させ
た。このとき濃縮液の表面は盛り上がって増殖しており
、濃縮液の水分はすっかりとんで、固形物となった。
This product was placed in an egg floater and fermented at 35°C for 10 days. At this time, the surface of the concentrated liquid was swollen and multiplied, and the water in the concentrated liquid was completely removed and it became a solid substance.

該発酵固形物をかきだしたところ、300gが得られた
。該固形物はベージュ色の固体固形物であり、分析した
ところ、耐熱性300〜900℃、HCIに対し耐酸性
であり、また耐溶媒性でもある。
When the fermented solid was scraped out, 300 g was obtained. The solid is a beige colored solid, and analysis shows that it has a heat resistance of 300-900°C, is acid resistant to HCI, and is also solvent resistant.

同様にして、添加物なしのものと、添加物としてFe−
Znの代わりに、A 1 、 F e −P 、 F 
e−Al−C−8i等を加えたものから、発酵固形物を
得た。
Similarly, one without additives and one with Fe-
Instead of Zn, A 1 , Fe −P , F
Fermented solids were obtained from the mixture to which e-Al-C-8i and the like were added.

これらの性状を第1表に示す。Their properties are shown in Table 1.

第1表 得られた発酵固形物は、添加物なしの場合、左旋光度1
0″〜12°、蛋白窒素量が、アンモニウムイオン0.
02mg/Q、リン酸イオン0゜05 m g / Q
、硝酸イオン0.56mg/ltであり、鉄−亜鉛酵素
では硝酸イオンが4.35mg/Q、アルミニウム酵素
では同1.61mg/12、Al−Fe−8i酵素では
同1.95mg/Qであった。本発明の発酵固形物の結
晶構造を示す450倍顕微鏡写真が第1図〜第4図であ
る。第1図は添加物なしの場合の酵素の結晶構造を示す
顕微鏡写真、第2図は添加物Zn−Feの場合の酵素の
結晶構造を示す顕微鏡写真、第3図は添加物F e −
A Iの場合の酵素の結晶構造を示す顕微鏡写真、第4
図は添加物Fe−AI−Zn−8i −Coの場合の酵
素の結晶構造を示す顕微鏡写真である。金属の結晶は例
えばZnは六角形、Feは円形、AIは円筒状であるが
、第2図、第3図及び第4図ではそれらの結晶はなくな
り、特有の結晶構造をなしている。なお第1−図は添加
物なしであるが、上記3相液粘和物に含有されている金
属の変性された結晶構造を有するものである。
Table 1 The fermented solid obtained without additives has a left optical rotation of 1
0″ to 12°, the amount of protein nitrogen is 0.
02 mg/Q, phosphate ion 0゜05 mg/Q
, nitrate ion was 0.56 mg/lt, nitrate ion was 4.35 mg/Q for the iron-zinc enzyme, 1.61 mg/12 for the aluminum enzyme, and 1.95 mg/Q for the Al-Fe-8i enzyme. Ta. FIGS. 1 to 4 are 450x microscopic photographs showing the crystal structure of the fermented solid of the present invention. Figure 1 is a photomicrograph showing the crystal structure of the enzyme without additives, Figure 2 is a photomicrograph showing the crystal structure of the enzyme with the additive Zn-Fe, and Figure 3 is the photomicrograph showing the crystal structure of the enzyme with the additive Fe-
Micrograph showing the crystal structure of the enzyme in the case of A I, No. 4
The figure is a micrograph showing the crystal structure of the enzyme in the case of the additive Fe-AI-Zn-8i-Co. Metal crystals are, for example, hexagonal for Zn, circular for Fe, and cylindrical for AI, but in FIGS. 2, 3, and 4, these crystals disappear and a unique crystal structure is formed. Although Figure 1 shows no additives, it has a modified crystal structure of the metal contained in the three-phase liquid viscosity.

以上のように本発明の上記生成物は蛋白質の一種であり
、又添加物の変性されたものであることが明らかであり
、一般に酵素が蛋白質を生成物とするものであり、生体
触媒であることから、本発明で得られた生成物は結合酵
素の一種であることがわかる。
As described above, it is clear that the above-mentioned product of the present invention is a type of protein, and is also a denatured product of additives. Generally, enzymes produce proteins as products, and are biocatalysts. This indicates that the product obtained in the present invention is a type of conjugated enzyme.

又、通常の酵素が最大活性温度が55℃前後であり、1
10℃程度でその活性を失うのに対して、本発明の前記
酵素は300℃位迄作用し、最大活性温度60〜250
℃であり、塩酸中で酵素の形を変化させながら塩酸の作
用をそこなうことなく作用し、活性pH3〜6、最大活
性pH4〜5である。
In addition, the maximum activity temperature of normal enzymes is around 55℃, and 1
Whereas it loses its activity at about 10°C, the enzyme of the present invention acts up to about 300°C and has a maximum activity temperature of 60 to 250°C.
℃, and acts without impairing the action of hydrochloric acid while changing the shape of the enzyme in hydrochloric acid, and has an active pH of 3 to 6 and a maximum active pH of 4 to 5.

次に、繊維及びプラスチック変性第3相液粘和物300
Qに下記金属粉末200gを加え、35℃以上に保温静
置し、10時間後に上記で得られた本発明の耐熱性、耐
酸性酵素を、6g以上加え、希釈撹拌することにより、
各種接着剤を製造した。
Next, fiber and plastic modified third phase liquid viscosity 300
Add 200 g of the following metal powder to Q, keep it warm at 35 ° C. or higher, and after 10 hours, add 6 g or more of the heat-resistant, acid-resistant enzyme of the present invention obtained above, and dilute and stir.
Manufactured various adhesives.

それらの接着効果を第2表に示す。Their adhesive effects are shown in Table 2.

第2表 傘接着面亀裂 又ガラス透過率向上剤は、同様にして得られた耐熱性、
耐酸性酵素を、前記と同様の第3相液粘和物100gに
第3表に示す金属粉末1.0 gを加えたものに添加し
、前記接着剤の場合と同様に処理することにより製造し
た。
The second umbrella adhesive surface crack or glass transmittance improver has heat resistance obtained in the same manner,
Manufactured by adding an acid-resistant enzyme to 100 g of the same third-phase liquid viscosity as described above and adding 1.0 g of the metal powder shown in Table 3, and treating the same as in the case of the adhesive. did.

このものをガラスにコーチングしたときのガラスの透過
率を第3表に示す。
Table 3 shows the transmittance of glass when coated with this material.

第  3  表 発明の効果 本発明はセルローズ系廃棄物の有効利用であって、繊維
、プラスチック変性物からの耐熱性・耐酸性を有する新
しい酵素であり、帯電防止、耐電圧の作用を有し、それ
らの向上を図ることができ、又金属のイオン化等の作用
を有し、接着性強化、或いはガラス透過性の向上等のす
ぐれた作用効果を有するものであり、粘弾性と硬化性を
向」ニさせることもでき、メッキ用プラスチック、プラ
スチック磁石、プリント基板、接着剤、ガラス光透過性
向上剤等、種々の用途が期待できる。又、その製造も極
めて操作が簡単であり、廃棄物の利用であるから安価に
製造でき、産業上極めて有用な発明であると言える。
Table 3 Effects of the Invention The present invention is a new enzyme that effectively utilizes cellulose-based waste and has heat resistance and acid resistance made from modified fibers and plastics, and has antistatic and withstand voltage effects. It also has the effect of ionizing metals, has excellent effects such as strengthening adhesion and improving glass permeability, and improves viscoelasticity and hardenability. It can be used in various applications such as plating plastics, plastic magnets, printed circuit boards, adhesives, and glass light transmittance improvers. In addition, it is extremely easy to manufacture, and since waste is used, it can be manufactured at low cost, making it an extremely useful invention industrially.

【図面の簡単な説明】[Brief explanation of drawings]

第1−図は、本発明の添加物なしの酵素の結晶構造を示
す顕微鏡写真、第2図は同じく添加物Zn。 Feの酵素の結晶構造を示す顕微鏡写真、第3図は同じ
く添加物F e v A lの酵素の結晶構造を示す顕
微鏡写真、第4図は同じく添加物Fe、A1.。 Zn、S:i、、Coの酵素の結晶構造を示す顕微鏡写
真である。
Fig. 1 is a photomicrograph showing the crystal structure of the enzyme of the present invention without additives, and Fig. 2 is also a photomicrograph showing the crystal structure of the enzyme without additives. FIG. 3 is a photomicrograph showing the crystal structure of the enzyme of Fe, FIG. 3 is a photomicrograph showing the crystal structure of the enzyme of the additive Fe, A1. . 1 is a micrograph showing the crystal structure of Zn, S:i, and Co enzymes.

Claims (6)

【特許請求の範囲】[Claims] (1)木繊維と食酢液を混合、撹拌、菌の活動できる温
度範囲で静置して得られる混合物をろ過、該ろ過液とプ
ラスチック原料又はプラスチック材とを菌の活動できる
温度範囲で混和撹拌、醸成、静置して得られる三相包括
変性物より分離した第1相液体組成物の濃縮物そのまま
、又は該濃縮物に、鉄、亜鉛、アルミニウム、マンガン
、銅、クロム、コバルト、マグネシウム、ケイ素、フッ
素、ヨウ素、セレン、炭酸カルシウム、リン及び硫黄か
ら成る群から選ばれた物質の1種以上を添加、発酵させ
たものから成る繊維、プラスチック変性発酵、耐熱性・
耐酸性酵素。
(1) Mix wood fibers and vinegar solution, stir, leave to stand at a temperature range where bacteria can be active, filter the resulting mixture, mix and stir the filtrate and plastic raw material or plastic material at a temperature range where bacteria can activate. The concentrate of the first phase liquid composition separated from the three-phase comprehensively modified product obtained by fermentation and standing still, or the concentrate contains iron, zinc, aluminum, manganese, copper, chromium, cobalt, magnesium, Fibers made by adding and fermenting one or more substances selected from the group consisting of silicon, fluorine, iodine, selenium, calcium carbonate, phosphorus and sulfur, plastic modified fermentation, heat resistant and
Acid-resistant enzyme.
(2)木繊維と食酢液を混合、撹拌、菌の活動できる温
度範囲で静置して得られる混合物をろ過、該ろ過液とプ
ラスチック原料またはプラスチック材とを菌の活動でき
る温度範囲で混和撹拌、醸成、静置して得られる三相包
括変性物より分離した第1相液体組成物を液量1/2以
下に濃縮し、該濃縮物そのまま、又は該濃縮物に、鉄、
亜鉛、アルミニウム、マンガン、銅、クロム、コバルト
、マグネシウム、ケイ素、フッ素、ヨウ素、セレン、炭
酸カルシウム、リン及び硫黄から成る群から選ばれた物
質の1種以上を添加し次いで発酵させることを特徴とす
る繊維、プラスチック変性発酵、耐熱性・耐酸性酵素の
製造方法。
(2) Mix wood fibers and vinegar solution, stir, let stand at a temperature range where bacteria can be active, filter the resulting mixture, mix and stir the filtrate and plastic raw material or plastic material at a temperature range where bacteria can activate. The first phase liquid composition separated from the three-phase comprehensively modified product obtained by fermentation and standing is concentrated to 1/2 or less of the liquid volume, and the concentrate is used as it is, or iron, iron,
It is characterized by adding one or more substances selected from the group consisting of zinc, aluminum, manganese, copper, chromium, cobalt, magnesium, silicon, fluorine, iodine, selenium, calcium carbonate, phosphorus and sulfur, and then fermenting. Methods for producing fibers, plastic denaturation fermentation, and heat- and acid-resistant enzymes.
(3)木繊維と食酢液を混合、撹拌、菌の活動できる温
度範囲で静置して得られる混合物をろ過、該ろ過液とプ
ラスチック原料またはプラスチック材とを菌の活動でき
る温度範囲で混和撹拌、醸成、静置して得られる三相包
括変性物より分離した第1相液体組成物の濃縮物を、発
酵させたものから成る繊維、プラスチック変性発酵、耐
熱性・耐酸性酵素からなる帯電防止剤。
(3) Mix wood fibers and vinegar solution, stir, let stand at a temperature range where bacteria can be active, filter the resulting mixture, mix and stir the filtrate and plastic raw material or plastic material at a temperature range where bacteria can activate. , a fiber made by fermenting a concentrate of the first phase liquid composition separated from a three-phase inclusive denatured product obtained by fermentation and standing, a plastic denatured fermentation product, and an antistatic product made of a heat-resistant/acid-resistant enzyme. agent.
(4)木繊維と食酢液を混合、撹拌、菌の活動できる温
度範囲で静置して得られる混合物をろ過、該ろ過液とプ
ラスチック原料またはプラスチック材とを菌の活動でき
る温度範囲で混和撹拌、醸成、静置して得られる三相包
括変性物より分離した第1組液体組成物の濃縮物を、発
酵させたものから成る繊維、プラスチック変性発酵、耐
熱性・耐酸性酵素からなる耐電圧剤。
(4) Mix the wood fibers and vinegar solution, stir, let stand at a temperature range where bacteria can be active, filter the resulting mixture, mix and stir the filtrate and plastic raw material or plastic material at a temperature range where bacteria can activate. , a fiber made by fermenting a concentrate of the first set of liquid compositions separated from a three-phase inclusive denatured product obtained by fermentation and standing, a plastic denatured fermentation product, and a withstand voltage made of a heat-resistant/acid-resistant enzyme. agent.
(5)木繊維と食酢液を混合、撹拌、菌の活動できる温
度範囲で静置して得られる混合物をろ過、該ろ過液とプ
ラスチック原料またはプラスチック材とを菌の活動でき
る温度範囲で混和撹拌、醸成、静置して得られる三相包
括変性物より分離した第1組液体組成物の該濃縮物に、
鉄、亜鉛、アルミニウム、マンガン、銅、クロム、コバ
ルト、マグネシウム、ケイ素、フッ素、ヨウ素、セレン
、炭酸カルシウム、リン及び硫黄から成る群から選ばれ
た物質の1種以上を添加発酵させたものから成る繊維、
プラスチック変性発酵、耐熱性・耐酸性酵素から成る接
着性強化剤。
(5) Mix wood fibers and vinegar solution, stir, let stand at a temperature range where bacteria can be active, filter the resulting mixture, mix and stir the filtrate and plastic raw material or plastic material at a temperature range where bacteria can activate. , to the concentrate of the first set of liquid compositions separated from the three-phase comprehensively modified product obtained by fermentation and standing,
Consists of fermentation with one or more substances selected from the group consisting of iron, zinc, aluminum, manganese, copper, chromium, cobalt, magnesium, silicon, fluorine, iodine, selenium, calcium carbonate, phosphorus, and sulfur. fiber,
Adhesive strength agent consisting of plastic modified fermentation, heat-resistant and acid-resistant enzymes.
(6)木繊維と食酢液を混合、撹拌、菌の活動できる温
度範囲で静置して得られる混合物をろ過、該ろ過液とプ
ラスチック原料またはプラスチック材とを菌の活動でき
る温度範囲で混和撹拌、醸成、静置して得られる三相包
括変性物より分離した第1組液体組成物の該濃縮物に、
鉄、亜鉛、アルミニウム、マンガン、銅、クロム、コバ
ルト、マグネシウム、ケイ素、フッ素、ヨウ素、セレン
、炭酸カルシウム、リン及び硫黄から成る群から選ばれ
た物質の1種以上を添加発酵させたものから成る繊維、
プラスチック変性発酵、耐熱性・耐酸性酵素から成るガ
ラス光透過性向上剤。
(6) Mix wood fibers and vinegar solution, stir, let stand at a temperature range where bacteria can be active, filter the resulting mixture, mix and stir the filtrate and plastic raw material or plastic material at a temperature range where bacteria can activate. , to the concentrate of the first set of liquid compositions separated from the three-phase comprehensively modified product obtained by fermentation and standing,
Consists of fermentation with one or more substances selected from the group consisting of iron, zinc, aluminum, manganese, copper, chromium, cobalt, magnesium, silicon, fluorine, iodine, selenium, calcium carbonate, phosphorus, and sulfur. fiber,
Glass light transmittance improver consisting of plastic denatured fermentation, heat-resistant and acid-resistant enzymes.
JP61103136A 1986-05-07 1986-05-07 Modified solids of fibers and plastics Expired - Lifetime JP2528096B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP61103136A JP2528096B2 (en) 1986-05-07 1986-05-07 Modified solids of fibers and plastics

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61103136A JP2528096B2 (en) 1986-05-07 1986-05-07 Modified solids of fibers and plastics

Publications (2)

Publication Number Publication Date
JPS62259584A true JPS62259584A (en) 1987-11-11
JP2528096B2 JP2528096B2 (en) 1996-08-28

Family

ID=14346112

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61103136A Expired - Lifetime JP2528096B2 (en) 1986-05-07 1986-05-07 Modified solids of fibers and plastics

Country Status (1)

Country Link
JP (1) JP2528096B2 (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5426398A (en) * 1977-08-01 1979-02-27 Kouji Fujimori Modified plastic substans by wood fiber * paper making material and waste paper material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5426398A (en) * 1977-08-01 1979-02-27 Kouji Fujimori Modified plastic substans by wood fiber * paper making material and waste paper material

Also Published As

Publication number Publication date
JP2528096B2 (en) 1996-08-28

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