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WO1998032871A1 - Procede pour la polymerisation de composes phenoliques ou similaires et utilisation de ce procede - Google Patents

Procede pour la polymerisation de composes phenoliques ou similaires et utilisation de ce procede Download PDF

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Publication number
WO1998032871A1
WO1998032871A1 PCT/JP1998/000172 JP9800172W WO9832871A1 WO 1998032871 A1 WO1998032871 A1 WO 1998032871A1 JP 9800172 W JP9800172 W JP 9800172W WO 9832871 A1 WO9832871 A1 WO 9832871A1
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WIPO (PCT)
Prior art keywords
compound
acid
reaction
wood
treatment
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PCT/JP1998/000172
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English (en)
Japanese (ja)
Inventor
Takashi Echigo
Tadashi Yoneda
Hirobumi Aoki
Ritsuko Ohno
Original Assignee
Showa Denko K.K.
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Filing date
Publication date
Application filed by Showa Denko K.K. filed Critical Showa Denko K.K.
Priority to AU54974/98A priority Critical patent/AU5497498A/en
Priority to HU0800628A priority patent/HU229841B1/hu
Publication of WO1998032871A1 publication Critical patent/WO1998032871A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/14—Ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D197/00—Coating compositions based on lignin-containing materials
    • C09D197/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J197/00—Adhesives based on lignin-containing materials
    • C09J197/005—Lignin

Definitions

  • the present invention relates to a method for utilizing a novel polyphenol oxidase having an optimum reaction pH on the side of the reaction force.
  • the present invention relates to a novel polyphenol oxidase having an optimum reaction pH on the side of pH 8 near phenol, a phenol compound, an alkoxyl group-containing aromatic compound, a halogenated phenol compound, and a quinone compound. Or a method of polymerizing these compounds by acting on an aromatic amine compound, and rapidly converting a phenolic compound, an alkoxyl group-containing aromatic compound, a halogenated phenolic compound, a quinone compound or an aromatic amine compound into a polymer. Thickeners, stabilizers, flocculants, emulsifiers, dispersants, water retention agents, humidifiers, antioxidants, adhesives, dyes, paints, paints, etc.
  • compositions such as antibacterial agents, virus infection inhibitors, biofouling inhibitors, biological repellents, insecticides, insect repellents, cataplasms, ink bases, concrete admixtures, wood treatment agents, etc., and these various compositions Methods, soil treatment methods, and even metal sintered compacts, metal products, alloys, die-cast products, ceramics, bricks, concrete, wood, wood-based processed materials, fir, rush, straw, bamboo, or synthetic resin
  • the present invention relates to a method for treating a porous article such as a foam.
  • polyphenol oxidase As natural products having polyphenol in the structural part, plant pigments and lignins such as flavonoids, xanthones, and melanin are known, and polyphenol oxidase has an oxidizing effect on these natural products.
  • polyphenol oxidase can be used as a reaction substrate even for dichlorophenol and trichloromouth phenol, for which toxicity is a problem. Therefore, polyphenol oxidase is also useful in treating wastewater containing these natural and non-natural products.
  • the conventional enzyme has an optimal reaction pH from acidic pH to neutral pH, and it is practically difficult to use it in an alkaline pH range, which is a factor in the industrial use of polyphenol oxidase. This was a factor that narrowed the range of use.
  • phenolic compounds and the like can be polymerized using enzymes such as laccase-polyphenoloxidase produced by basidiomycetes and incomplete fungi (Journal of Biotechnology, 13, 229). -241, 1990, etc.).
  • laccase-polyphenoloxidase produced by fungi has an optimal reaction pH in the acidic region, in order to catalyze the polymerization reaction using these enzymes, it is necessary to convert the reaction from acidic to acidic. The reaction had to be carried out in the neutral pH range, and the rate of the polymerization reaction was not high enough.
  • Wood also consists of a first stage in which derivatized lignin is added to wood to prevent microbial corrosion, and a second stage in which a weakly acidic aqueous solution containing metal ions is impregnated in order to make the lignin water-insoluble.
  • An impregnation method has been tried in JP-A-61-268729. However, in this method, the solubility of the complex of the lignin derivative and the metal ion in water is reduced, but the lignin derivative itself is not fixed as a water-insoluble substance. In addition, two types of processing agents must be switched and used.
  • thermosetting resin for the purpose of modifying physical properties, imparting strength, manufacturing aggregates, imparting antibacterial properties and insect repellency, etc.
  • sintered bodies such as bricks, wood, wood chips, wood flour, fiber, paper, or A method of impregnating or applying a thermosetting resin or the like to a porous article such as pulp has been implemented.
  • unreacted formaldehyde is contained in the thermosetting resin, there is concern about the effect on the human body, and the use of a compound that does not contain formaldehyde has been required.
  • heating at 80 to 200 ° C. is required for curing the thermosetting resin, there is a disadvantage that a special heating facility and energy for heating are required.
  • An object of the present invention is to provide a novel enzyme-catalyzed method for polymerizing a phenol compound, an alkoxyl group-containing aromatic compound, a halogenated phenol compound, a quinone compound, or an aromatic amine compound. is there.
  • Another problem to be solved by the present invention is to reduce the practical enzymatic oxidation in the pH range by using polyphenol oxidase having an optimal reaction pH on the side of the enzyme. Achieved and expanded applications of polyphenoloxidase It is to contribute greatly. Disclosure of the invention
  • the present inventors have diligently searched for a wide range of microorganisms for extracellular products that catalyze the oxidation of polyphenolic substances at alkaline pH, and have found that the imperfect fungi spp.Stilbella and Sagenomella spp. Alternatively, the present inventors have found that a strain belonging to the genus Stachylidium produces an objective enzyme having an optimum reaction pH on the alkaline side near pH 8 outside the cells, thereby completing the present invention. .
  • the present inventors use these enzymes in an alkaline region, particularly in an alkaline region having a pH of 8 or more, to obtain a phenol compound, an alkoxyl group-containing aromatic compound, a halogenated phenol compound, a quinone compound, The present inventors have found that it is possible to efficiently achieve the polymerization of an aromatic amine compound, and have completed the present invention.
  • the present inventors have developed a long-term effective strength, abrasion resistance, weather resistance, weather resistance, flame retardancy, antibacterial, antiseptic, bactericidal, insect repellent, insecticidal, antiviral, Bio-repellent, adhesive, sustained-release of drug, coloring, dimensional stability, anti-cracking, deodorant, deoxidizing, humidity-controlling, water-absorbing, water-repellent, surface smoothness, bio-affinity, ion exchange
  • intensive research has been conducted. went.
  • the polyphenol oxidase and the phenol compound, the alkoxyl group-containing aromatic compound, the halogenated phenol compound, the quinone compound, or the aromatic amine compound of the present invention, and the unsaturated compound and / or the drug are porous. It has been found that the object of the present invention can be achieved by impregnating or impregnating an article by applying pressure and / or depressurization, and performing a polymerization reaction in a porous article, thereby completing the present invention. .
  • the present invention provides a polyphenol utilizing oxygen (air) as an oxidizing agent.
  • oxygen air
  • oxidase is used, it is surprising that such an enzyme or enzyme system catalyzes an oxidation reaction or a polymerization reaction in an environment with a low oxygen supply rate inside a porous article.
  • impregnation which includes a decompression operation as part of the treatment process, is extremely effective as an operation for increasing the injection amount of the treatment liquid into porous articles that are difficult to impregnate.
  • the concentration of dissolved oxygen in the processing solution and the processed product that has undergone the depressurization operation is low, which is disadvantageous for a catalytic reaction using oxygen as an oxidizing agent.
  • the pressure injection method is also very effective as an operation to increase the injection amount of the processing solution into porous articles that are difficult to impregnate, but many enzymes are unstable to the pressure treatment.
  • many enzymes are unstable to the pressure treatment.
  • the polyphenol oxidase of the present invention maintains its catalytic activity even after the pressure injection treatment, and furthermore, in a low oxygen supply rate environment inside the porous article, the oxidation reaction, It has been found that it catalyzes the molecular reaction.
  • the purpose is to increase the treatment effect of the porous article, and to fix the drug with a phenolic compound, an alkoxyl group-containing aromatic compound, a halogenated phenol compound, a quinone compound, or an aromatic amine compound polymerized inside the porous article.
  • a phenolic compound an alkoxyl group-containing aromatic compound, a halogenated phenol compound, a quinone compound, or an aromatic amine compound polymerized inside the porous article.
  • Various fragrances, deodorants, antioxidants, flame retardants, antibacterials, preservatives, bactericides, insect repellents, antivirals We conducted intensive research on a treatment method using a biorepellent.
  • the polymerization reaction using the polyphenol oxidase of the present invention generally involves the immobilization or slowing down of many drugs including drugs that are thought to cause enzyme reaction inhibition or enzyme inactivation. They found that they could be released and completed the present invention.
  • the present invention provides a method for polymerizing a phenolic compound or the like, a method for producing a compound having an increased molecular weight, an agent (composition) for various applications utilizing the polymerizing method, a method for producing the same, and a method for soil treatment , Porous article processing method, processed material And a method for manufacturing the same.
  • molecular weight the molecular weight measured by gel filtration chromatography (GFC) analysis is in the range of about 33,000 to 76,000;
  • Isoelectric point isoelectric point measured by isoelectric focusing is in the range of about 5.9 to 7.0;
  • a method for polymerizing a phenol compound, an alkoxyl group-containing aromatic compound, a halogenated phenol compound, a quinone compound, or an aromatic amine compound which comprises reacting a polyphenol oxidase having the formula:
  • molecular weight the molecular weight measured by GFC analysis is in the range of about 33,000 to 76,000;
  • Isoelectric point isoelectric point measured by isoelectric focusing is in the range of about 5.9 to 7.0;
  • a compound having an increased molecular weight characterized in that a polyphenol oxidase having the formula (1) is reacted with a phenol compound, an alkoxy group-containing aromatic compound, a halogenated phenol compound, a quinone compound, or an aromatic amine compound to form a polymer, thereby increasing the molecular weight. Manufacturing method.
  • Optimum reaction pH has an optimum reaction pH around pH 8.2 to 8.5;
  • molecular weight measured by GFC analysis is in the range of about 33,000 to 76,000;
  • Isoelectric point isoelectric point measured by isoelectric focusing is in the range of about 5.9 to 7.0;
  • molecular weight measured by GFC analysis is in the range of about 33,000 to 76,000;
  • Isoelectric point isoelectric point measured by isoelectric focusing is in the range of about 5.9 to 7.0;
  • a polyphenol oxidase having a phenolic compound, Silyl group-containing aromatic compound, halogenated phenol compound, quinone compound, or aromatic amine compound, and fragrance, deodorant, fire retardant, flame retardant, antibacterial, antiseptic, bactericide, insect repellent A method for producing a compound having an increased molecular weight, which comprises reacting a mixture with at least one drug selected from a drug, an antiviral agent, and a biorepellent to carry out a polymerization reaction.
  • a thickener, a stabilizer, a flocculant, an emulsifier, and a dispersion characterized by using the method for producing a compound having an increased molecular weight according to any one of the above [6] to [19].
  • Agents water retention agents, humidity control agents, antioxidants, adhesives, dyes, paints, fire retardants, flame retardants, oil recovery agents, soil modifiers, seed spray topsoil stabilizers, deodorants, deodorants Odorant, pesticide spreading agent, oxygen absorber, preservative, bactericide, antibacterial agent, virus infection inhibitor, biofouling inhibitor, biological repellent, insecticide, insect repellent, packing agent, ink base, A method for producing a concrete admixture or a wood treating agent.
  • a soil treatment method wherein a reaction for performing the production method according to any one of [6] to [19] is performed in soil.
  • the porous article is a metal sintered body, manufactured article, alloy, die cast article, ceramitas, brick, concrete, wood, wood processing material, fir, rush, straw, bamboo material, or synthetic resin foam Any of the above [22] to [24] A method for treating a porous article according to any of the preceding claims.
  • a strength, abrasion resistance, weather resistance, weather resistance, flame retardancy, antibacterial property, and antiseptic characterized by using the treatment method according to any one of the above [22] to [25].
  • FIG. 1 is a graph showing the relationship between the relative pH and the reaction pH of polyphenol oxidase produced by Stillella sp. SD3101 (Stilbella SD3101).
  • FIG. 2 is a graph showing the relationship between the reaction pH and the relative activity of polyphenol oxidase produced by Sagenomera 'SP. SD3102 (SaRenomella sp. SD3102) SD3102.
  • FIG. 3 is a graph showing the relationship between the reaction pH and the relative activity of polyphenol oxidase produced by Stachylidium sp. SD3103 (Stachylidium sp. SD3103) SD3103.
  • Figure 4 shows the temperature and phase of polyphenoloxidase produced by SD3101. It is a graph which shows the relationship with activity.
  • FIG. 5 is a graph showing the relationship between the temperature and the relative activity of polyphenol oxidase produced by SD3102.
  • FIG. 6 is a graph showing the relationship between the temperature and the relative activity of polyphenol oxidase produced by SD3103.
  • FIG. 7 is a graph showing the temperature stability of polyphenol oxidase produced by SD3101.
  • FIG. 8 is a graph showing the temperature stability of polyphenol oxidase produced by SD3102.
  • FIG. 9 is a graph showing the temperature stability of polyphenol oxidase produced by SD3103.
  • FIG. 10 is a graph showing the pH stability (relation between treatment pH and residual activity) of polyphenoloxidase.
  • FIG. 11 is a graph showing the relationship between the reaction pH and the relative activity of a polyphenol oxidase mixture. Detailed description
  • Stilbella sp. (Stilbella sp.) Stilbella sp. force to be mentioned force s preferably Sutirubera 's p. SD 3 1 01 (Stilbella sp.
  • strains belonging to the genus Sagenomella used to obtain the polyphenoloxidase used in the present invention include Sagenomella viride and Sagenomella sp. (Sagenomella sp.) SDS lOS (Sagenomella sp.SD3102) (Ministry of International Trade and Industry, Tsukuba-Higashi 1-3-1-3, Ibaraki, Japan on January 28, 1996) FERM P-15964 was deposited with the National Institute of Bioscience and Biotechnology, and transferred to the international deposit on January 8, 1998 as FERM BP-6220.)
  • strains belonging to the genus Stachylidium used to obtain the polyphenoloxidase used in the present invention include strains belonging to the genus Stachylidium 'Stachylidium bicolor', Stachylidium theobromae (Stachylidium theobromae), and Stachylidium 'Slipium sp. ) Is preferred.
  • Stachylidium's p. SD 3103 Stachylidium sp. SD3103
  • a filamentous fungus that forms chain conidia without forming a bunch (cinema) and forms elliptical to lemon-shaped small conidia with a major axis of 2 to 4 im is used as a seedling of Salagenoma sp. Sagenomella sp.SD3102), and a filamentous fungus that forms a dark brown to black viscous colony and has a rotile spore pattern and a fibrous spore, but does not form a spore locus. It was named SD3103 (Stachylidium sp. SD3103).
  • the polyphenol oxidase used in the present invention can be obtained by culturing a strain belonging to the genus Stilbella or the genus Sagenomella, belonging to the genus Stachylidium and a mutant thereof, It is also possible to prepare using bacteria. That is, the DNA encoding the polyphenol oxidase, together with an appropriate promoter, an operator, and a terminator DNA having an enzyme expression function in the host organism, together with a DNA, serves as an origin of replication for replicating the vector in the host organism.
  • Host cells transformed by integration into host cell DNA together with DNA are cultured under conditions that allow polyphenol oxidase to be expressed, and polyphenol oxidase is also recovered from the culture medium.
  • the polyphenol oxidase of the present invention based on the knowledge about the amino acid sequence of the polyphenol oxidase obtained based on the DNA sequence encoding the polyphenol oxidase, based on the conventional acidic side It may be produced by a protein engineering technique for modifying the DNA of polyphenol oxidase having an optimum reaction pH.
  • a DNA fragment encoding the polyphenol oxidase of the present invention for example, cDNA or a genomic library from the strain of the present invention is separated.
  • the method can be carried out by a conventional method, such as selecting a clone that expresses a catalytic activity, or selecting a clone that produces a protein that reacts with the antibody against the polyphenoloxidase.
  • a commonly used synthetic medium or a nutrient medium containing an organic carbon source and an organic nitrogen source can be used.
  • C u 2 + O.OOlmM from 1 Omm ion as the metal salt preferred properly is preferably added at a concentration of 1 mM from 0. OlmM.
  • the culture temperature is 10 to 60 ° C, preferably 20 to 40 ° C.
  • An appropriate culture time is 20 hours to 250 hours, preferably 50 hours to 150 hours.
  • the secreted polyphenol oxidase can be recovered from the medium by a known method. This recovery procedure includes a series of procedures in which cells are separated from the medium by centrifugation, filtration, or membrane separation, and chromatography is performed, for example, by ion exchange chromatography. Also, membrane concentration using an ultrafiltration membrane is effective.
  • the polyphenol oxidase used in the present invention has the following properties. (1) Action: oxidizes polyphenol;
  • molecular weight the molecular weight measured by gel filtration chromatography (GFC) analysis is in the range of about 33,000 to 76,000;
  • Isoelectric point The isoelectric point measured by isoelectric focusing is in the range of about 5.9 to 7.0.
  • polyphenol oxidases used in the present invention include the following. 1 Polyphenol oxide derived from Stilbella sp. (Stilbella sp.) SD3101 (accession number FERM BP-6219):
  • Optimum reaction pH has an optimum reaction pH around pH 8.2;
  • Isoelectric point The isoelectric point measured by isoelectric focusing is about 6.6.
  • Isoelectric point The isoelectric point measured by isoelectric focusing is about 5.9.
  • Isoelectric point The isoelectric point measured by isoelectric focusing is about 7.0.
  • polyphenol oxidases can perform the oxidation reaction in a wide pH range of 5 to 11, but are preferably pH 6 to 10, more preferably pH 7 to 9, and have an optimum pH around pH 8, It has the advantage of catalyzing the oxidation reaction from alkaline to alkaline (Figs. 1 to 3).
  • the optimal temperature for a 10-minute reaction at pH 8 is around 50 ° C (Figs. 4 to 6), and furthermore, after a 30-minute heat treatment at various temperatures.
  • the activity showed approximately 100% residual activity in the range of 50 ° C. or less (FIGS. 7 to 9).
  • various The remaining activity after treatment at 30 ° C. for 30 minutes in a buffer at pH was stable over a wide range of pH (FIG. 10).
  • the polyphenol oxidase according to the present invention in combination with a conventional enzyme having an optimal reaction pH on the acidic side.
  • a conventionally known polyphenol oxidase having an optimum reaction pH on the acidic side in combination with the polyphenol oxidase of the present invention, a wide pH range from acidic to alkaline can be obtained.
  • a polyphenol oxidase reaction can be performed.
  • the mixing ratio of the activity of the polyphenol oxidase having the optimal reaction pH on the acidic side to the activity of the polyphenol oxidase according to the present invention is preferably 1:10 to 10: 1, more preferably 1: 3 to 3: 1.
  • the polyphenol oxidase according to the present invention is also useful for achieving a polyphenol oxidase reaction in a wide pH range.
  • the activity of the polyphenol oxidation activity was measured at 25 ° C in an aqueous solution containing 20 ppm syringaldazine and 100 mM potassium phosphate buffer solution ( ⁇ 8.2). This was performed by measuring the absorbance at 525 nm.
  • the amount of activity that oxidizes 1 // mo1 of syringal dazine per minute was defined as 1 unit (Unit; hereinafter, abbreviated as U).
  • the phenolic compound, alkoxyl group-containing aromatic compound, halogenated phenol compound, quinone compound, or aromatic amine compound to be polymerized in the present invention is any compound as long as the enzyme used in the present invention can be oxidized. Can also be used.
  • Such compounds include lignin, ligninsulfonic acid, humic acid, nitrohumic acid, tannin, catechin, Gallic acid, urushiol, hesperidin, chlorogenic acid, hinokitiol, pyrocatechol, hydroquinone, O-coumaric acid, p-coumaric acid, coniferyl alcohol, coniferyl aldehyde, 3,4-dihydroxybenzoic acid, tert-butyl high Droquinone, phenylhydridoquinone, trimethinole hydroquinone, 3,4-dihydroxycinnamic acid, ethyl-3,4-dihydroxycinnamic acid, pyrogallol, 4-hydroxydroxycinnaminoleanolecone, la perylgallate, octylgallate, syringic acid Sinapyr alcohol, Sinapic acid, Sinapine aldehyde, Homovanilla
  • any substance that can oxidize the enzyme used in the present invention can be used as a raw material of a polymerized substance or as a catalyst for a polymerization reaction.
  • examples of such compounds are 2,2 '.- azobis (3-ethylbenzothiazoline-16-sulphonic acid) (ABTS), pyrirubin, isoascorbic acid, quercetin, rutin, guaiacol, 4-methoxyphenol, biphenol , 4, A'-Ethylenedianiline, Methylhydroquinone, Ethylhydroquinone, o-Hydroxybenzoic acid, p-Hydroxybenzoic acid, 1-Hydroxybenzotriazole, 6-Hydroxy-1,2,4, 5—Triaminopyrimidine, 4, 5, 6—Triaminopyrimidine, 2,3-Dihydroxypyridazine, 3, 6—Dihydroxypyridazine, 2,3-
  • a plurality of these compounds can be used in combination for the purpose of adjusting the physical properties of the polymerized product.
  • a quinone compound which is polymerized by a similar reaction route may be allowed to coexist.
  • quinone compounds include anthraquinone 1-2-sulfonic acid, anthraquinone 1-1,5-disnoroleic acid, anthraquinone 1-2,6-disulfonic acid, anthraquinone-2-carboxylic acid, 1-aminoanthra Quinone, 2-aminoaminosuraquinone, anthralphine, aminonaphthoquinone, 1,8-dihydroxylaquinone, camphoquinone, dehydroascorbic acid, 2-hydroxy-1,4-naphthoquinone, isatin, 5-nitroisatin And various anthraquinone dyes.
  • unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid
  • unsaturated alcohols such as oleyl alcohol
  • unsaturated alkyls such as squalene
  • dryness such as tung oil, linseed oil, and castor oil Oxidation and polymerization can be performed simultaneously with the enzymatic reaction by coexisting a substance to be auto-oxidized such as oil.
  • novel polyphenol oxidase having an optimum reaction pH in the alkaline pH range include, for example, fuynol compounds, alkoxyl-containing aromatic compounds, halogenated phenol compounds, quinone compounds, and aromatic amines.
  • a polymerization reaction of a compound In the production of the phenolic compound, the alkoxyl group-containing aromatic compound, the halogenated phenolic compound, the quinone compound, or the aromatic amine compound having an increased molecular weight by the polymerization reaction of the present invention, the concentration of these compounds is 0.01 to 0.1%. It is 90% by weight, preferably 1 to 80% by weight.
  • the reaction temperature is 0 to 100 ° C, preferably 0 to 70 ° C.
  • the pH of the reaction is 5-11, preferably 6-10, more preferably 7-9.
  • the enzyme activity concentration used is 1 to 10,000 UZ liter, preferably 10 to 2000 U / L. It is desirable to adjust the enzyme activity concentration according to the purpose. That is, when it is desired to achieve rapid polymerization and gelation or solidification, the reaction may be performed at a high active concentration. On the other hand, the reaction was performed at a low activity concentration. For example, a moderate polymerization reaction proceeds, and a more uniform solution of the polymerization product can be obtained as a liquid substance. When the reaction is further continued, a gentle gelation reaction proceeds throughout the reaction solution.
  • thermal solubility is a useful property when used in applications such as dispersants, adhesives, and paints. Also, by adding hot water or the like after heat dissolution and dispersing and dissolving, it is possible to obtain a compound having a very high molecular weight as a solution.
  • metal sintered bodies manufactured articles, alloys, die cast articles, ceramics, bricks, concrete, wood, woodwork, fir, rush, straw, bamboo, synthetic resin foam, etc.
  • polyphenol oxidase is impregnated with both a phenol compound, an aromatic compound containing an alkoxyl group, a halogenated phenol compound, a quinone compound, or an aromatic amine compound, and a polymerization reaction is performed in the porous article.
  • the treatment liquid before the impregnation does not gel or solidify, and the gelation and solidification proceed when the treatment liquid is dried and concentrated in the porous article after the impregnation.
  • the concentration of the phenol compound, the alkoxyl group-containing aromatic compound, the halogenated phenol compound, the quinone compound or the aromatic amine compound in the treatment solution is 0.01 to 50% by weight. /. Preferably, it is 0.1 to 30% by weight.
  • the reaction temperature is 0 to 100 ° C, preferably 10 to 70 ° C.
  • the pH of the reaction is between 5 and 11, preferably between 6 and 10, more preferably between 7 and 9.
  • the enzyme activity concentration to be used is:! To 10,000 U / liter, preferably 1 O to 2000 U / liter.
  • N a OH, NH 3, Na 2 C_ ⁇ 3 Impregnation of alkali or alkali salts, such as C a CO 3, hydrochloric acid, sulfuric acid, impregnation of an acid such as nitric, impregnation of known enzyme inhibitors, heat treatment such as 1 0 0 ° C, 1 5 minutes, Oh Rui porous It can be implemented by coating the surface of the product with oxygen and shutting off the oxygen supply by packaging with film.
  • polyphenol oxidase and a phenol compound, an aromatic compound containing an alkoxyl group, a halogenated phenol compound, a quinone compound, or an aromatic amine compound, and an unsaturated compound Fatty acids, unsaturated alcohols, unsaturated alkyl compounds, and unsaturated compounds such as drying oils are polymerized together to form phenolic compounds by enzymatic or automatic oxidation, aromatic compounds containing alkoxyl groups, halogenated phenols
  • the polymerization reaction of the compound, the quinone compound, or the aromatic amine compound and the polymerization reaction based on the autoxidation of the unsaturated compound are simultaneously performed, so that a stronger composite can be obtained.
  • the concentration of the unsaturated compound used for such purpose in the treatment solution is 0.001 to 60% by weight, preferably 0.01 to 40% by weight.
  • polyphenol oxidase is impregnated into a porous article by pressurizing and / or depressurizing, and is already contained in a porous article, such as a polyphenol compound such as lignin already contained in wood.
  • a porous article such as a polyphenol compound such as lignin already contained in wood.
  • the porous article is wood, the workability in the drying step after the wood impregnation treatment can be improved by polymerizing the polyphenol compound, aromatic amine compound, etc.
  • the product does not contain or contains a substance on which polyphenoloxidase acts.
  • Effective treatment of porous articles with less
  • a treatment liquid having a relatively low molecular weight of the reaction solution composition that is, a treatment liquid having a relatively low viscosity is used.
  • a large amount of the processing solution can be easily impregnated.
  • the pressurization or depressurization performed for the purpose of the present invention is extremely important in injecting a sufficient amount of the processing liquid into various types of porous articles that are difficult to impregnate with the processing liquid, and to obtain a necessary processing effect. is there.
  • the pressurization operation is performed at atmospheric pressure (1 atm) to 20 atm, more preferably at 3 to 15 atm, but if the enzyme activity is not lost, higher pressure is applied. It is also possible.
  • the decompression operation can be performed at any pressure up to the vacuum pressure.However, for effective treatment of porous materials that are difficult to impregnate, a pressure in the range of 100 to 76 OmmHg is required. It is desirable to reduce the pressure.
  • the depressurizing operation be performed by evacuation before depressurizing before adding the processing liquid to the porous article.
  • the depressurizing operation be performed by evacuation before depressurizing before adding the processing liquid to the porous article.
  • it is also effective to carry out a combination of these pressure operation and pressure operation.
  • porous article When the porous article is wood, various commonly used pressurizing and depressurizing methods can be used, specifically, a packed cell method (Vesel method), a semi-empty cell method (Lowry method), and a double vacuum method.
  • the method double vacuum method
  • the pressure change method Oscillating Pressure Method
  • the insizing method can be applied to increase the impregnation amount.
  • compression treatment using rollers microwave heating, freezing treatment, steaming treatment, steam treatment, or heat treatment It is also effective to perform processing.
  • lignin is contained abundantly in wood core material, thereby increasing the resistance to rot fungi and termites. Therefore, when the phenol compound, the alkoxyl group-containing aromatic compound, the halogenated phenol compound, the quinone compound, or the aromatic amine compound of the present invention is lignin or a lignin derivative, and is used as a wood preservative, INDUSTRIAL APPLICABILITY
  • the treatment method of the present invention enables a method for protecting against rot fungi and termites, which are essentially carried out on natural living wood, to be efficiently implemented as an industrial treatment method for all types of wood. .
  • Lignin, or ligninsulfonic acid or ligninsulfonate contains various water-insoluble solid components as produced from the process of cooking pulp or sulfite pulp. Therefore, when the porous article is impregnated with polyphenoloxidase and lignin or ligninsulfonic acid or ligninsulfonate, and the polymerization reaction is performed in the porous article, the porous article is used for the purpose of the present invention. In order to increase the amount of the treatment liquid impregnated in the quality article, it is desirable to remove the water-insoluble solid components in these pulp waste liquids.
  • the removal treatment is performed by a method such as centrifugation, filtration, and standing according to the type of the porous article to be impregnated, the purpose of the impregnation treatment, and the economics involved in the removal.
  • the diameter or major diameter in the waste pulp ⁇ ⁇ or more preferably 0.5 m or more, more preferably 0.1 // m or more
  • Desaccharification can also be performed by a microorganism such as yeast.
  • the lignin derivative used for the purpose of the present invention may be lignin or lignin sulfonic acid, in addition to lignin sulfonic acid, acetic esterification, propionate esterification, carboxymethyl etherification, 2-hydroxylesteryl esterification, 2-acetoxityl etherified or 2-hydroxypropyl etherified, and lignin or lignin derivatives thereof Can be used. Also, mixtures thereof can be used.
  • phenol compounds alkoxyl group-containing aromatic compounds, halogenated phenol compounds, quinone compounds and aromatic amine compounds used in the present invention
  • Natural products or natural product derivatives such as gallic acid, urushiol, hesperidin, and hinokitiol are highly useful because of their high safety to the environment and the human body.
  • the porous article It is also effective to apply or impregnate a drug to the porous article as a pre-treatment or post-treatment of the polymerization reaction treatment in the porous article.
  • the first step of applying or impregnating the drug on the porous article for the purpose of sealing the drug inside the porous article, and in particular, preventing the migration of the inorganic compound to the surface of the porous article, and polyphenol.
  • Impregnating a porous article with oxidase and both a phenolic compound, an aromatic compound containing an alkoxyl group, a halogenated funinol compound, a quinone compound, or an aromatic amine compound under pressure and Z or under reduced pressure A porous article treatment method performed in two steps is useful.
  • both polyphenoloxidase and a phenolic compound, an alkoxyl group-containing aromatic compound, a halogenated phenolic compound, a quinone compound, or an aromatic amine compound are pressurized and / or depressurized to form a porous article.
  • the first stage of impregnation and the use of the interaction of the drug with a phenolic compound, an aromatic compound containing an alkoxyl group, a fluorinated halogenated compound, a quinone compound, or an aromatic amine compound to put the drug inside the porous article
  • a porous article treatment method that is performed through a second step of applying or impregnating a porous article with a drug is also useful for effective drug treatment.
  • the present invention in combination with pre-treatment or post-treatment as compared to a case where a porous article is simply impregnated with a phenol compound, an alkoxyl group-containing aromatic compound, a halogenated phenol compound, a quinone compound, or an aromatic amine compound.
  • a phenol compound, an alkoxy group-containing aromatic compound, a halogenated phenol compound, a quinone compound Since the aromatic amine compound is polymerized and fixed in the porous article by the enzyme-catalyzed reaction, the drug can be more firmly fixed.
  • a method of performing a decompression treatment to recover a part of the treatment liquid outside the porous article, and a sufficient polymerization reaction inside the treated porous article is washed with water or the like to remove unpolymerized substances, so that the degree of maintaining the porous property can be easily adjusted.
  • the treated material that has maintained and adjusted such porosity retains the ability to adjust humidity, water retention, adsorption, and ion exchange, and can be used in a variety of applications that utilize these capabilities. is there.
  • a porous article having various composite properties can be manufactured by further impregnating the treated material with the retained porous property with a drug, a polymer, or a prepolymer.
  • Usable chemicals include not only water-soluble chemicals, but also those that form OZW-type or W / O-type emulsions by the addition of dispersants or surfactants, or as fine powders in aqueous solutions. Dispersing ones are also available.
  • Surfactants used for such purposes include, for example, linear or branched alkyl or alkenyl sulfates, amide sulfates, linear or branched alkyl or alkenyl groups, ethylene oxide, Aliphatic sulfates such as alkyl or alkenyl ether sulfates to which one or more of propylene oxide and butylene oxide have been added, alkyl sulfonates, amide sulfonates, dialkyl sulfosuccinates, phosphorates Aliphatic sulfonates such as fin, vinylidene type olefin and ⁇ part olefin sulfonate, aromatic sulfonates such as linear or branched alkylbenzene sulfonic acid, linear or branched alkyl group or Alkyl or alkenyl ether carboxylate or amide having a alkenyl group, to which one or more of ethylene oxide, propylene oxide and
  • Amino acid type surfactants alkyl or alkenyl acid phosphates, phosphate ester surfactants such as alkyl or alkenyl phosphates, sulfonic acid amphoteric surfactants, betaine amphoteric surfactants, linear or branched A chain alkyl or alkenyl group Having an alkyl or alkenyl ether or alcohol to which one or more of ethylene oxide, propylene oxide and butylene oxide are added, a linear or branched alkyl or alkenyl group, and ethylene oxide Polyoxyethylene alkyl phenyl ether to which one or more of propylene oxide and butylene oxide are added, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid glycerin monoester, Examples thereof include an alkyl or alkenyl amine oxide, a tetraalkyl ammonium salt type cationic surfactant, and the
  • ligninsulfonic acid is particularly a raw material for the polymerization reaction of polyphenoloxidase.
  • these substances themselves have a drug dispersing action, they are useful for the purpose of the present invention.
  • Copper, arsenic, zinc, chromium, nickel, aluminum, molybdenum, magnesium as the above agents used for the purpose of the present invention, as antibacterial agents, preservatives, bactericides, insect repellents, antiviral agents, or biological repellents
  • a solution or fine powder of a silver metal salt, a metal compound, or a metal complex can be used.
  • the anion moiety is F -, CI -, B r -, N 0 3, BO -, P_ ⁇ 3 -, S 2 -, metal salts consisting of C CK 2, etc., naphthenic acid, Orein acid And the like, a compound of a carboxylic acid or a sulfamic acid and a metal ion, a metal oxide, a metal oxide ion, or a complex thereof.
  • calcium bromide, sodium bromide, magnesium bromide, potassium bromide, sodium iodide, sodium fluoride, potassium fluoride, sodium potassium fluoride, magnesium fluoride, sodium sulfide, potassium sulfide, selenium Acid reames can also be used.
  • phenolic compounds such as pyrocatechol, gallic acid, hinokitionore, catechin, pyrogallol, o-phenylenediamine, 2-aminophenol or aromatic amine compounds, ethane-1,1-diphosphonic acid and derivatives thereof, ethanehydroxyl Phosphonic acids such as 1,1,2-triphosphonic acid, 1,2-dicanoleboxyl-1,2-diphosphonic acid and methanehydroxyphosphonic acid, 2-phosphonobutane 1,2-dicanolevonic acid, and 1-phosphonobutane 12 2,3,4-Tricarboxylic acid, phosphonocarboxylic acid such as ct-methylphosphonosuccinic acid, amino acid such as aspartic acid, glutamic acid, glycine, 2-aminoisobutyric acid or amino acid analog, tri-triacetic acid, ethylenediamine Tetraacetic acid, diethylenetriamine
  • the above hinokitiol can be used as various metal complexes or salts. Specific examples include complexes with copper, arsenic, zinc, chromium, nickel, aluminum, molybdenum, magnesium, calcium, barium, iron or silver, or sodium salts.
  • a complex with copper, arsenic, zinc, chromium, nickel or silver can be used for the purpose of the present invention since a metal can be added to the physiological action of hinokitiol, such as antibacterial action.
  • a powder composed of metal fine particles of various sizes can be used depending on the purpose.
  • a powder composed of fine particles having a diameter of 0.1 m or less can be used.
  • the treatment of the porous article with a metal salt, a metal compound, or a metal complex can be performed by any of the pretreatment, post-treatment, and simultaneous treatment of the porous article with polyphenoloxidase.
  • the solubility under the enzyme reaction conditions, the presence or absence of aggregation and sedimentation when mixed with the treating agent, the purpose of the treatment, etc., in various methods or in various combinations. can be.
  • the concentration of the metal salt, metal compound, or metal complex in the treatment solution is preferably adjusted according to the strength of the physiological activity of the metal used and the purpose of the treatment.
  • copper, arsenic acid, or zinc In this case, it is usually 0.01 to 50 OmM, preferably 0.1 to 20 OmM.
  • solutions or fine powders of boron salts, boron compounds, or boron-containing complexes can be used as flame retardants, antibacterial agents, preservatives, bactericides, insect repellents, antiviral agents, or biological repellents. Specific examples include boric acid, borax, and copper borofluoride.
  • pyrethroid drugs, conazole drugs, insect hormone drugs and the like can also be used as the drug of the present invention. By imparting and improving the sustained-release property of these volatile drugs to the porous article according to the present invention, the efficacy can be maintained for a longer period.
  • fragrance, deodorant, antibacterial, antibacterial, antiseptic, bactericide, insect repellent, antibacterial As a virus agent or a biological repellent a plant-derived extract, an extract component, or a compound having a structure equivalent to that of a plant extract component
  • a plant-derived extract, an extract component, or a compound having a structure equivalent to that of a plant extract component can be used.
  • Specific examples of such plants include trees such as hinoki and Aomori hiba, herbs, radish, rust, bamboo, iriomote thistle rhizome, or yaeyama palm root.These plants are crushed, squeezed, Extracts and extractable components can be obtained by boiling or steam distillation.
  • plant-derived components or compounds having a structure equivalent to that of plant extracts include tropolones such as hinoki chionore, hyibinene,] 3-binene, camphor, menthol nore, limonene, Bonneol, ⁇ -tenorebinene, ⁇ -terbinene, mono-tenore pines such as pineo-pinole, tenorepinene 4-monoole, mono-enoles such as sineo-no-ole, sesquiterpenes such as ⁇ -casinole and t-murol, catechin, tanji
  • polyphenols such as butane, naphthalene derivatives such as 2,3,5-trimethylnaphthalene, long-chain aliphatic alcohols such as citronellol, aldehydes such as cinnamaldehyde, citral, perillaaldehyde, and arylisothiocyanate.
  • the porous article is made of wood, wood-processed material, wood chips, wood flour. , Fir, rush, straw, bamboo, fiber, paper, or pulp, and the raw material for the polymerization reaction on which polyphenoloxidase acts is lignin or lignin derivatives.
  • a plant-derived component in addition to the action of sealing the voids in the porous article by the polymer, a plant-derived extract, an extract component, or a compound having an equivalent structure, and a porous article or a reaction raw material thereof By interacting with, it is possible to obtain desirable effects such as leaching resistance and sustained release of the drug.
  • the processed products of porous articles produced by combining these natural products have high safety to the environment and the human body, and are biocompatible, so they can be used in various fields. It is. It also has one or more substituents selected from hydroxyl, amino, halogen, and nitro groups as antibacterial agents, antibacterial agents, preservatives, bactericides, insect repellents, antiviral agents, or biological repellents.
  • Aromatic compounds or cyclic compounds can be used. These aromatic compounds are also desirable in terms of the leaching resistance of the drug and the sustained release, based on the same principle as in the case of the above-mentioned plant-derived extract, extract component, or compound having a structure equivalent to the plant extract component. The effect can be obtained.
  • aromatic compounds or cyclic compounds having one or more substituents selected from a hydroxyl group, an amino group, a halogen, and a nitro group include o-phenylphenol, 1-naphthol, and 2-naphthol.
  • organophosphorus compounds such as thiofamate methyl, dasban, diazinon, cyclogen compounds such as chlordane, dieldrin, aldrin, heptachlor, carbamate compounds such as bigon, dimethylene, sevin, etc., and N-nitroso-N-cyclo Nitroso compounds such as xylhydroxylamine, dehydroacetic acid, and sonolevic acid can also be used for the purpose of the present invention as antibacterial agents, preservatives, bactericides, insect repellents, antiviral agents, or biological repellents.
  • the dimensional stability, crack prevention, humidity control, water absorbency, water repellency, and surface smoothness imparted or improved by the porous article treatment of the present invention are based on the hydrophilicity or hydrophobicity of the polymer generated in the porous article. This is achieved by adjusting For example, a polymerized product of lignin sulfonic acid is polymerized into a hydrophilic polymer gel in a porous article, but other treating agent components such as unsaturated fatty acids, unsaturated alcohols, unsaturated alkyl compounds, Hydrophobicity can be improved by using an unsaturated compound such as oil in combination.
  • an aromatic compound having a saturated or unsaturated alkyl side chain having 1 to 22 carbon atoms as a substituent in addition to a hydroxyl group is a main component to be polymerized by polyphenoloxidase. Hydrophobicity can also be improved by using it or adding it to lignin or lignin derivatives.
  • a phenol compound having a substituent having polyoxyethylene or polyethyleneimine as a structural part an aromatic compound containing an alkoxyl group, a halogenated phenol compound, a quinone compound, or an aromatic compound
  • an aromatic amine compound as a main component to be polymerized by polyphenoloxidase, or by adding it to a lignin / lignin derivative, the water retention of the porous article after the treatment can be improved.
  • dimensional stability and crack prevention can be imparted or improved.
  • a phenol compound such as lignin or a lignin derivative, an aromatic compound containing an alkoxyl group, a halogenated phenol compound, a quinone compound, or an aromatic amine compound
  • Addition of oxyethylene, polyethyleneimine, or an aromatic compound having a substituent having a saturated or unsaturated alkyl chain having 1 to 22 carbon atoms as a structural part to modify the physical properties of the polymer Can be used as an agent.
  • Aromatic compounds having a substituent having polyoxyethylene or polyethyleneimine as a structural part include ethylene oxide in aromatic compounds having a hydroxyl, amino, carboxyl or the like as a structural part.
  • Vaniri O-vanillin, 3,4-dihydroxybenzanolaldehyde, benzanolaldehyde, 2-phenylpropionaldehyde, or other aldehyde groups on the aromatic ring or on the aromatic ring It can also be obtained by allowing polyethyleneimine to act on an aromatic compound having a part of the structure of the substituent to generate a Schiff base.
  • the imparting or improving of the ion exchange property by the treatment of the porous article of the present invention can be achieved by adjusting the anionic property or cationic property of the polymerized product generated in the porous article.
  • polymerized ligninsulfonic acid since polymerized ligninsulfonic acid has cation exchange ability, it can be used for plant-based porous articles such as wood, wood-processed materials, wood chips, wood flour, fir, rush, straw, bamboo, fiber, paper, and pulp. It is possible to improve the cation exchange capacity.
  • An aromatic compound having an amino group such as aminoaminosuraquinone, 1,4-diaminoanthraquinone, a quaternary ammonium salt, polyallylamine, or an aromatic compound having a substituent having a polyethylenimine as a structural part is ligated.
  • the addition or improvement of formaldehyde absorption by the porous article treatment of the present invention can be performed by the sealing ability of the porous article treatment of the present invention. Further, the formaldehyde absorption can be further improved by performing the treatment for imparting or improving the anion exchange ability described above, and reacting the formaldehyde with the amino group in the treating agent.
  • polyphenol substances such as catechin or oxides of polyphenol substances deodorize by reacting with malodorous substances such as methyl mercaptan, trimethylamine, ammonia, and tobacco odor. It is useful for deodorizing purposes. The reaction with such a gaseous substance proceeds more efficiently as the surface area of the reaction field is larger. By using it, it is possible to manufacture an article having a high deodorizing effect.
  • flame retardants can be used as the chemical for imparting or improving the flame retardancy by treating the porous article of the present invention.
  • Na, K, Mg, C a , Ba, Al, Zn, Cu, Mn, Ni, Si, Sn, Pb, etc. in the cation part phosphate, hydrogen phosphate, sulfate, sulfate water Salts, carbonates, borates, silicates, nitrates, fluorides, chlorides, bromides, hydroxides, and the like.
  • aluminum hydroxide, magnesium hydroxide, zirconium hydroxide examples include antimony trioxide, barium metaborate, tin oxide, red phosphorus, and ammonium phosphate.
  • the digestion process in the pulp mill is mainly used.
  • the resulting lignin sulfonic acid contains fine powders such as calcium carbonate, calcium hydroxide, magnesium carbonate, or magnesium hydroxide.
  • porous article processing of the present invention for example, manufacturing containers from biodegradable natural materials such as wood chips, wood flour, fir, rush, straw, bamboo, fiber, paper, and pulp Can be. It is desirable to adjust the humidity control, water absorption, water repellency, surface smoothness, biocompatibility, and ion exchange properties of these containers according to the purpose. Further, since the present invention utilizes an enzymatic polymerization method, it is highly safe for the human body and the environment, and the manufactured container can be used in a wide range of fields. It is particularly useful in the field where biodegradability is required in soil, compost, and the like. Even if it is transplanted to the ground as it is, the container will gradually biodegrade, reducing the labor required for transplantation.
  • biodegradable natural materials such as wood chips, wood flour, fir, rush, straw, bamboo, fiber, paper, and pulp Can be. It is desirable to adjust the humidity control, water absorption, water repellency, surface smoothness, biocompatibility, and ion exchange properties
  • the coloring by the treatment of the porous article of the present invention may be performed by polyphenol such as o-phenylenediamine, p-phenylenediamine, catechol, gallic acid, and quercetin.
  • polyphenol such as o-phenylenediamine, p-phenylenediamine, catechol, gallic acid, and quercetin.
  • a dye or dye precursor capable of acting on oxidase and polyphenol oxidase on wood to produce a colored substance in wood, or a colored substance and a polyphenol compound such as lignin already contained in wood Is made into a composite polymer in wood, and the wood is strongly dyed and colored.
  • many polyphenol oxidases bleach lignin, which is a coloring substance in wood
  • the wood dyeing and coloring treatment of the present invention is carried out enzymatically.
  • the bleaching and dyeing / coloring treatments can be performed simultaneously, the process is shortened and the color tone is improved, which is extremely useful.
  • polyphenoloxidase and lignin or lignin derivatives such as ligninsulfonic acid and ligninsulfonate for wood processing, the difference in color tone and chromaticity between the core and sapwood of wood is reduced. Thus, wood having a more uniform and natural texture can be obtained.
  • the polyphenol oxidase of the present invention is added to concrete together with a phenol compound, an alkoxyl group-containing aromatic compound, a halogenated phenol compound, a quinone compound, or an aromatic amine compound, and these compounds are polymerized in the concrete. It is possible to improve slump loss, improve concrete strength, and control rust on reinforcing steel by lowering oxygen concentration in concrete.
  • the polyphenol oxidase of the present invention is added to the soil together with a phenol compound, an alkoxyl group-containing aromatic compound, a halogenated funol compound, a quinone compound, or an aromatic amine compound, and these compounds are added in the soil. Maintaining and improving the aggregate structure of the soil, improving water retention, improving the sustained release of antibacterial agents or virus infection inhibitors, improving seed spraying topsoil stability, and improving plant support by molecularization
  • the effect of polymer compound spraying such as improving the ability to suppress dust generation, improving the ability to prevent soil, sediment, and gravel from collapsing due to wind and rain on ridges and slopes, and improving the fixation of sediment and gravel before laying asphalt Is obtained.
  • the present invention it is possible to suppress the viscosity of the spray liquid by setting the polymerization reaction not to be sufficiently advanced at the time of spraying. Handling can be made easier and the penetration of the spray liquid into the underground can be improved.Furthermore, the high molecular weight reaction on the soil surface after spraying makes the spray surface sticky Can be suppressed.
  • the treatment agent for the porous article of the present invention may be a composition such as polyphenol oxidase, a phenol compound, an aromatic compound containing an alkoxyl group, a halogenated phenol compound, a quinone compound, an aromatic amine compound, an unsaturated compound, and a drug.
  • a pH adjuster, a dye, a polymer compound, a specific gravity adjuster, a solid, and the like can be further included.
  • an enzyme having a polyphenol oxidizing action is used as an oxidation catalyst, and oxygen in the air can be used as an oxidizing agent, which means that the present invention can be applied to a wide range of applications. Enable.
  • oxygen in the air can be used as an oxidizing agent, which means that the present invention can be applied to a wide range of applications. Enable.
  • peroxidase and hydrogen peroxide, or an oxidase capable of generating hydrogen peroxide instead of hydrogen peroxide and its substrate are added to the reaction solution, and the reaction of the present invention in which oxygen is used as an oxidizing agent, and hydrogen peroxide is used as an oxidizing agent It is also possible to make the reaction proceed simultaneously.
  • the treating agent for a porous article of the present invention can be prepared as a single agent by mixing the above composition as a powder or a granulated powder.
  • Granulation is a shaping performed for the purpose of suppressing dust generation, or for the convenience of use depending on the preservability of the treatment agent or the purpose of use, and specifically, granulation of granules and pressing. It can be performed by a granulation operation such as dispensing granulation, fluidized granulation, and centrifugal fluidized granulation. In this case, it is also effective to granulate the enzyme together with the enzyme stabilizer separately from the other treating agent components in order to improve the storage stability of the polyphenol oxidase in the treating agent.
  • the treatment agent for the porous article of the present invention can be prepared by either a high-concentration solution premised on dilution at the time of use or a solution having a concentration that can be used without dilution.
  • seal the container containing the treatment agent when storing the treatment agent It is desirable to avoid contact.
  • a phenolic compound or an aromatic amine compound, and further, a polyphenol oxidase are prepared separately from other treating agent components, and mixed immediately before use. It is also possible to use.
  • the oxidizing agent that can be used in the present invention, air, oxygen, ozone, hydrogen peroxide, a hydrogen peroxide precursor, a peracid precursor, or a peracid can be used alone or in combination.
  • the hydrogen peroxide precursor dissolves in water to form peroxyl ions.
  • Such substances include monohydrate or tetrahydrate perborates, percarbonates, perborates, sodium perpyrophosphate, perbenzoic acid, urea hydrogen peroxide reactants, melamine hydrogen peroxide reactions And peroxyhydrate, particularly preferred are perborate and percarbonate.
  • a hydrogen peroxide generation system using oxidase and its substrate can be used as a hydrogen peroxide precursor.
  • oxidases examples include glucose oxidase, alcohol oxidase, glycerol oxidase, amine oxidase, amino acid oxidase, D-amino acid oxidase, arylino real oxidase, aldehyde deoxidase, galactose oxidase.
  • sorbose oxidase peroxidase, xanthine oxidase, cholesterol rhone oxidase and the like, and particularly preferable are glucose oxidase and alcohol oxidase.
  • the peracid precursor is an organic compound having a reactive acyl group or a carboxylic acid ester, a carboxylic acid anhydride, or an acetate.
  • a substance includes tetraacetylethylenediamine (TAED), Tetraaceti z lemethyleneshimine (TAMDA), tetraacetylglycoluril (TAGU), diacetyldioxohexahydro-triazine (DADHT), xenonanol Sodium sulfonate (sodium nonanoyloxybenzene sulfonate; SNOB S), sodium i sononanoyloxybenzene sulfonate (IS ONOB S), succinic anhydride, benzoic anhydride, phthalic anhydride, There are glucose pentaacetate (glucose pentaacetate; PAG) and xylose tetraacetate, and TAED and SNOBS are particularly
  • the peracids include, for example, diperoxydodecanedioic acid (DPDDA), diperoxyisophthalic acid, magnesium monoperoxydiophthalate, and magnesium monohydrate. It is a non-amidoperoxyadipic acid (NAPAA).
  • DPDDA diperoxydodecanedioic acid
  • NAPAA non-amidoperoxyadipic acid
  • Flavonoid, xanthone, melanin and other plant pigments and lignin are known as natural products having polyphenol in the structural part, and polyphenol oxidase has an oxidizing effect on these natural products.
  • Polyphenol oxidase can also be used as a reaction substrate for halogen-substituted phenols (AOX), such as phenol or trichlorophenol, for which toxicity is a problem. Therefore, for example, the polyphenol oxidase of the present invention is also useful for treating wastewater containing these natural products and non-natural products.
  • AOX halogen-substituted phenols
  • the culture broth was removed by centrifugation at 4 ° C.
  • the culture broth that had been sterilized was concentrated as a fraction with a molecular weight of 10,000 or more by a minitan ultrafiltration system (Millipore) using a minitan filter packet (CAT.N0: PTGC0MP04, manufactured by Millipore). did.
  • N a 2 ⁇ 0 4 ⁇ 1 2 ⁇ 2 0 (1.34%), ⁇ 2 ⁇ 0 4 (0.3%), N a C l equilibrated with (0.1%) was Jeffrey chill aminoethyl cellulose (DEAE) -Cellulofine A- 800m (raw Chemical Industry Co., Ltd.)
  • DEAE Jeffrey chill aminoethyl cellulose
  • the concentrated culture broth described in Example 1 was applied to the top of the column (06 Omm, 330 cc) in the space above the column, and a buffer of the same composition as that used for equilibration.
  • the column was washed with 400 mH.
  • Example 4 Culture and concentration, crude purification
  • Example 5 Measurement of isoelectric point
  • the activity staining and isoelectric point were measured by isoelectric focusing using an oral Tofoa 'system (BIO-RAD3 ⁇ 4i3 ⁇ 4). pH 2.5 to 5) (Sigma)
  • the activity of the gel plate after the electrophoresis was performed using 50 ppm of syringaldorezine and 10 OmM. It was immersed in an aqueous solution containing a potassium phosphate buffer solution (pH 8.2), and observed by observing the red-purple band resulting from the reaction with polyphenol oxidase.
  • Stilbella sp. (Stilbella sp.) SD3101 (Accession number FERM BP-6219), Sagenomella sp. (Sagenomella sp.) SD3102 (Accession number FERM BP-6220) ), Stachylidium 's p. (Stachylidium sp.) SD3103 (Accession No.FERM BP-6221) has isoelectric points of 6.6 ⁇ 0.5, 5.9 ⁇ 0.5 and 7.0 ⁇ 0.5, respectively. there were.
  • Example 6 Substrate specificity
  • the molecular weight was measured using gel filtration chromatography (GFC). Na 2 HP0 4 'l 2H 2 0 (1.34%), KH 2 P 0 4 (0.3%), GFC column equilibrated at a flow rate of 1.0 m 1 / min by Na C l (1%) ( Shodex PROTEIN KW- 802.5 , Two columns) and an HP detector using a UV detector (280 nm), the crude polyphenol oxidase described in Examples 2 to 4 was analyzed, fractionated, and assayed for polyphenol oxidase. The activity peaks were eluted at the molecular weights of 76,000 ⁇ 5000, 33,000 ⁇ 5000, and 55,000 ⁇ 5000, respectively.
  • Example 8 Cultivation and crude purification in a 5-liter flask
  • Example 10 Polymerization reaction
  • Lignin sulfonic acid sodium salt obtained from Aldrich Chemical Company, Inc.
  • 30% (W / V) as polyphenoloxidase
  • Stilbella's sp. sp. Prepare 1 ml of a reaction solution containing a freeze-dried product obtained from SD3101 (Accession number FE thigh BP-6219) at an active concentration of 300 UZ liter, and react in a glass test tube.
  • the reaction was carried out by shaking at 100 rpm at a temperature of 30 ° C.
  • the pH of the reaction solution was adjusted to 8.2 with a small amount of sulfuric acid.
  • the color tone of the reaction solution became deep, and after 8 hours, remarkable progress of polymerization was observed, and after 20 hours, most of the reaction solution was solidified.
  • SD3 102 (Accession number FERM BP-6220) or stachyridium sp.
  • lignin (alkali) obtained from nacalai tesque
  • ligninsulfonic acid obtained from nacalai tesque
  • W / V the concentration of ligninsulfonic acid
  • polyphenol oxidase 300 U / liter and pH 8.5
  • the sample for molecular weight analysis was sampled from the reaction solution, subjected to a heat treatment at about 100 ° C. for 15 minutes in a water bath to stop the reaction, and analyzed by HP LC. Analysis by HP LC was performed using 5 OmM phosphoric acid as eluent. Buffer (pH 7.0) or 0. ImM sodium sulfate aqueous solution, a differential refractive index detector (Shodex RI, manufactured by Showa Denko KK) was used as the detector, and Shodex PROTEIN KW-802.5 (Showa This was performed by GFC using a combination of Shodex PROTEIN KW802.5 and Shodex OHpak SB-804HQ (manufactured by Showa Denko KK).
  • Reaction containing 30% (W / V) ligninsulfonic acid sodium salt and commercially available polyphenol oxidase (derived from Rigidoporus zonalis, obtained from TaKaRa Co., Ltd.) as polyphenol oxidase at an active concentration of 300 UZL 1 ml of the liquid was prepared, and the reaction was carried out in a glass test tube by shaking at a reaction temperature of 30 ° C. and 100 rpm.
  • the commercially available polyphenol oxidase used here was shown to be an acidic enzyme having an optimal reaction pH of pH 6 to 7 in the activity measurement using syringaldazine, so that it was used in the polymerization reaction.
  • SD 3102 (Accession No. FERM BP-6220) or stachyridium sp.
  • FERM BP-6219 was added at an activity concentration of 2 OUZ liters, and immediately the cedar wood chips (3 The pressure was reduced at 650 to 700 mmHg for 30 minutes with the cmX 3 cmX lcm and the kiguchi surface 3 cmX 3 cm) submerged, and the sample was left at normal pressure for 15 minutes while immersed. Thereafter, a piece of wood was taken out, the solution on the surface was wiped off, and left at 24 ° C. for 2 days to allow drying and enzymatic reaction to proceed.
  • a reaction solution for the treatment was prepared, and the cedar wood pieces (3 cm ⁇ 3 cm ⁇ 2 cm, 3 cm ⁇ 3 cm on the tip) were subjected to vacuum impregnation.
  • the pH was adjusted with sodium hydroxide or sulfuric acid.
  • the vacuum impregnation operation was performed by a simple method in which cedar wood pieces were immersed in the treatment solution, then reduced at 65-70 OmmHg for 1 hour, and then kept at normal pressure for 30 minutes while immersed. It was confirmed by measurement of the weight of the wood chips before and after the impregnation operation that a sufficient amount of the treatment liquid (10 to 14 g) had been injected by this vacuum impregnation operation.
  • the impregnated wood pieces were placed in a constant temperature room at 28 ° C for 5 days, and after drying and high-molecularization reaction, 20 Oml of water was added to each wood piece and the wood piece was submerged under the water surface
  • the leaching operation was performed by rotating the rotor using a magnetic stirrer and stirring at 25 ⁇ 3 ° C for 8 hours. Then, by measuring the absorbance at 280 nm of the water (leaching solution) after the leaching operation, the leaching amount of ligninsulfonic acid can be determined.
  • Pyridylazo) -2-naphthol abbreviated as PAN.
  • the leaching amount of the drug was calculated by performing complex formation and absorption analysis using Aldrich (Chemical) Company).
  • a reaction solution for wood treatment containing 300 U / liter, and 5% (W / V) of sodium ligninsulfonate and various chemicals was prepared, and a cedar wood chip was prepared in the same manner as in Example 13. Vacuum impregnation treatment, drying and polymerization reaction, and leaching treatment were performed.
  • lignin sulfonic acid aqueous solution is
  • a treatment liquid was prepared by adding a freeze-dried product of luoxidase.
  • the leaching amount of ligninsulfonic acid, and PAN or quinalizarin was calculated by complexation and absorption spectroscopy using HPLC, or separation, identification, quantification, or atomic absorption analysis using HPLC or gas chromatography. If the drug used has an absorbance at 280 nm, calculate the absorbance at 280 nm of the drug whose concentration was measured by the above method, and calculate the absorbance at 280 nm of the leached solution. The concentration of lignin sulfonic acid was calculated by dividing the influence component.
  • (+) - Power catechin & Eta 2 ⁇ , tannic acid, Ariru isothiocyanate Xia sulphonate from Company have Aldori pitch-Kemikano, copper carbonate (copper (II) carbonate monohydrate), copper sulfate, Zinc, nickel chloride, boric acid, and silver sulfate were obtained from Wako Pure Chemical Industries, Ltd., and hinokitiol and 1,3,5-tritalirololbenzene were obtained from Tokyo Chemical Industry Co., Ltd., respectively.
  • Example 8 As the polyphenol oxidase system, the Sagenomera sp. Described in Example 8 was used.
  • Stilbella sp. (Stilbella sp.) SD3 101 (Accession No. FERM BP-6219) described in Example 8 (300 liters of polyphenol oxidase (lyophilized product)) and 5% of ligninsulfonic acid sodium salt (W / V), and a wood treatment reaction solution containing 2000 ppm of tung oil was prepared.
  • the cedar wood chips were subjected to vacuum impregnation treatment, drying, polymerization reaction, and leaching treatment. The amounts of lignin sulfonic acid and drug injected were set at 100%, and the leached amounts were compared. As a result, a further improvement in drug fixability was observed. Details JP9
  • the leaching amount was calculated based on the amount of lignin sulfonic acid injected during the impregnation treatment as 100%, and as a result of the progress of the polymerization reaction inside the wood, the leaching amount of lignin sulfonic acid was determined.
  • the leaching amount of lignin sulfonic acid was determined.
  • Example 18 Wood treatment
  • Stilbella sp. (Stilbella sp.) SD31O1 (received A reaction solution for wood treatment containing polyphenoloxidase (freeze-dried product) derived from Deposit No. FERM BP-6219) containing 3 OUZ liter and ligninsulfonic acid sodium salt at 2% (W / V) was prepared. In the same manner as in 18, the cedar wood chips were subjected to pressure reduction and pressure impregnation, drying, and polymerization reaction. The pH of the reaction solution was adjusted to 8.5.
  • an aqueous solution containing 0.4% (W / V) polyethyleneimine (Aldrich 'Chemical Co., Ltd., average molecular weight 700) and 0.02M copper sulfate was prepared.
  • the same impregnation treatment under reduced pressure and pressure was performed to perform the second impregnation operation.
  • the same leaching treatment as in Example 13 was performed, and the amount of leaching was calculated with the amount of copper ions injected at the time of impregnation as 100%.
  • the leaching amount was only 1.5%. It was shown that the polymerization and fixation of ligninsulfonic acid inside the wood and the formation of a complex of ligninsulfuric acid, copper ions and polyethyleneimine caused the copper ion to be firmly fixed in the wood.
  • Example 3 Stilbella sp. (Stilbella sp.) SD3101 (accession number FERM BP-6219) derived polyfunoxoxidase (lyophilized product) was collected at 300 U / liter and sodium ligninsulfonate.
  • a reaction solution containing 10% (W / V) of a lithium salt was applied to the piece of wood, and placed in a constant temperature and humidity incubator at 28 ° C and a relative humidity of 80% for 3 days to allow the enzyme polymerization reaction to proceed.
  • the resulting wood chips prevented the copper complex from migrating to the wood surface and had a more natural brown surface color.
  • Example 20 Wood treatment
  • Stilbella sp. Described in Example 8 (Stilbella sp.) SD31 01 (Accession No. FERM BP-6219) derived from polyfunoxoxidase (lyophilized product) in 300 UZ liter and ligninsulfonic acid sodium salt in 5% (W / V), and a tree containing 0.5% of p-phenylenediamine dihydrochloride (Kanto Chemical Co., Ltd.) A reaction solution for wood treatment was prepared, and depressurization was carried out on a piece of cedar wood (3 cm x 3 cm x 10 cm, 3 cm x 3 cm at the tip end) partially containing a core material.
  • Example 21 Antibacterial test of processed wood
  • agar medium containing glucose (4%), 1.5% malt extract, 0.3% peptone and 2% agar ( pH 6.5) was inoculated with the rot fungus Tyromyces palustris FEPRI 0507 or the viper mushroom (Coriolus versicolor) FEPRI 1030 (both obtained from the Ministry of Agriculture, Forestry and Fisheries, Forestry Research Institute) at 26 ° C and 1 ° C.
  • a week of culture was performed.
  • the leached wood chips obtained in Example 18 were directly sterilized with agaric mushrooms and sterilized with a heat-resistant plastic having a thickness of about 1 mm with mushroom mushrooms.
  • Example 18 The dry weight of the leached wood chips obtained in Example 18 was measured in the same manner as in Example 21, and these were placed on soil about 40 cm around the termite nest. After standing for months, the effect of termites was observed. The soil on the surface was sufficiently removed, and the dry weight was measured in the same manner as in Example 21. The weight loss was calculated by comparing the dry weight with the weight before installation. As a result, it was shown that the wood treatment method of the present invention can impart termite resistance. Table 8 shows the detailed results. '
  • Stilbella sp. (Stilbella sp.) SD3101 (accession number FERM BP-6219) -derived polyphenoloxidase (lyophilized product 12 mg) described in Example 8 and ligninsulfonic acid sodium salt powder ( To 10 g), various drugs were further added and mixed well using a mortar. Furthermore, when a 5% aqueous solution is prepared using this powder, a small amount of sodium carbonate powder is added as necessary so that the pH is 8.0 to 9.0, and the mixture is thoroughly mixed to obtain a powdery porous material. A quality article treating agent was obtained.
  • the powdered treatment agent is left in a glass container at room temperature for 2 weeks, and the powder (5 g) is dissolved in ion-exchanged water (lOOml) to form a porous article.
  • a solution for processing was prepared. Using this solution, the cedar wood chips were subjected to depressurization and pressure impregnation, drying and polymerizing reaction, and leaching as in Example 13, and the amounts of ligninsulfonic acid and chemicals injected during the impregnation were determined. The leaching amount was compared at 100%. As a result, it was shown that the porous article can be effectively treated by the powdery treating agent. Table 9 shows the detailed results.
  • the powdery treating agent (6 g) obtained in the same manner as above was dissolved in ion-exchanged water (12 ml) to obtain a solution-like porous article treating agent.
  • this solution processing The agent was transferred to a 20 ml screw cap test tube, left at room temperature for 2 weeks in a sealed state, and further diluted 10 times with ion-exchanged water to prepare a solution for treating porous articles.
  • the cedar wood chips were subjected to depressurization and pressure impregnation, drying, polymerization reaction, and leaching as in Example 13, and the amounts of ligninsulfonic acid and chemicals injected during the impregnation were determined. The amount of leaching was compared with 100%. As a result, it was shown that the porous article can be effectively treated even with the solution treating agent. Table 10 shows the detailed results.
  • an efficient polymerization reaction of a phenol compound, an alkoxy group-containing aromatic compound, a halogenated phenol compound, a quinone compound, or an aromatic amine compound is achieved.
  • a thickener a stabilizer, a step of polymerizing a phenol compound, an alkoxyl group-containing aromatic compound, a halogenated phenol compound, a quinone compound, or an aromatic amine compound, Flocculant, emulsifier, dispersant, water retention agent, antioxidant, adhesive, concrete admixture, dye, Paints, oil recovery agents, soil modifiers, seed spraying topsoil stabilizers, sealants, deodorants, deodorants, pesticide spreading agents, bactericides, antibacterial agents, virus infection inhibitors, biofouling inhibitors, organisms
  • An efficient method for producing repellents, insecticides, cataplasms, ink bases and wood treatments is provided.
  • polyphenol oxidase of the present invention an effective method for wood treatment, concrete treatment, soil treatment and the like is provided.

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Abstract

Cette invention se rapporte à un procédé servant à polymériser des composés phénoliques ou similaires avec une polyphénol-oxydase ayant un pH de réaction optimal du côté alcalin; à des compositions préparées à l'aide de ce procédé, telles qu'un épaississant, un stabilisant, un coagulant, un émulsifiant, un dispersant, un agent rétenteur d'eau, un agent de conditionnement d'humidité, un anti-oxydant, un adhésif, un colorant, un agent d'enrobage, un agent antirouille, un agent inhifuge, un agent de récupération du pétrole, un conditionneur de sol, un stabilisant pour un sol à la surface duquel on a pulvérisé des semences, un désodorisant, un déodorant, un agent d'épandage de produits chimiques à usage dans l'agriculture, un désoxydant, un conservant, un désinfectant, un agent antimicrobien, un inhibiteur d'infections virales, un inhibiteur de dépôt de micro-organismes, un agent répulseur de micro-organismes, un insecticide, un insectifuge, un cataplasme, une base d'encre, un mélange pour béton, et un agent de traitement du bois; à des procédés pour préparer de telles compositions; à un procédé de traitement des sols; à un procédé de traitement d'articles poreux; et un article poreux ainsi traité ainsi qu'un procédé pour le préparer.
PCT/JP1998/000172 1997-01-22 1998-01-19 Procede pour la polymerisation de composes phenoliques ou similaires et utilisation de ce procede WO1998032871A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000072694A1 (fr) * 1999-05-28 2000-12-07 Meiji Seika Kaisha Ltd. Procede d'amelioration des caracteristiques gustatives d'une masse de cacao et ses produits de transformation
KR100389585B1 (ko) * 2000-09-02 2003-06-27 최용환 폴리페놀 성분이 함유된 산화방지제의 제조방법
CN112266651A (zh) * 2020-10-23 2021-01-26 四川上愚生物科技有限公司 丙烯基苯酚类化合物在制备浅色生漆中的应用、浅色生漆及其制备方法
CN112957899A (zh) * 2021-03-08 2021-06-15 北京环卫集团环卫服务有限公司 一种除臭剂及其制备方法和应用

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JPS63502079A (ja) * 1985-11-13 1988-08-18 エンジモル・インターナショナル・インク フェノール樹脂、現像シート、記録材料及びフェノール樹脂の調製方法
JPH05117591A (ja) * 1991-10-29 1993-05-14 Honsyu Kagaku Kogyo Kk コーテイング組成物
JPH06287516A (ja) * 1993-03-31 1994-10-11 Rengo Co Ltd 合成漆塗料
JPH07126354A (ja) * 1993-10-29 1995-05-16 Sumitomo Metal Mining Co Ltd 高分子量フェノール樹脂およびその酵素触媒による合成方法
JPH07126377A (ja) * 1993-10-29 1995-05-16 Sumitomo Metal Mining Co Ltd フェノール類とアニリン類からなる共重合体及びその製造方法

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JPS63502079A (ja) * 1985-11-13 1988-08-18 エンジモル・インターナショナル・インク フェノール樹脂、現像シート、記録材料及びフェノール樹脂の調製方法
JPH05117591A (ja) * 1991-10-29 1993-05-14 Honsyu Kagaku Kogyo Kk コーテイング組成物
JPH06287516A (ja) * 1993-03-31 1994-10-11 Rengo Co Ltd 合成漆塗料
JPH07126354A (ja) * 1993-10-29 1995-05-16 Sumitomo Metal Mining Co Ltd 高分子量フェノール樹脂およびその酵素触媒による合成方法
JPH07126377A (ja) * 1993-10-29 1995-05-16 Sumitomo Metal Mining Co Ltd フェノール類とアニリン類からなる共重合体及びその製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000072694A1 (fr) * 1999-05-28 2000-12-07 Meiji Seika Kaisha Ltd. Procede d'amelioration des caracteristiques gustatives d'une masse de cacao et ses produits de transformation
KR100389585B1 (ko) * 2000-09-02 2003-06-27 최용환 폴리페놀 성분이 함유된 산화방지제의 제조방법
CN112266651A (zh) * 2020-10-23 2021-01-26 四川上愚生物科技有限公司 丙烯基苯酚类化合物在制备浅色生漆中的应用、浅色生漆及其制备方法
CN112266651B (zh) * 2020-10-23 2022-11-18 四川上愚生物科技有限公司 丙烯基苯酚类化合物在制备浅色生漆中的应用、浅色生漆及其制备方法
CN112957899A (zh) * 2021-03-08 2021-06-15 北京环卫集团环卫服务有限公司 一种除臭剂及其制备方法和应用

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