WO1999013716A1 - Preparations antibiotiques et leur utilisation - Google Patents

Preparations antibiotiques et leur utilisation Download PDF

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Publication number
WO1999013716A1
WO1999013716A1 PCT/JP1998/003759 JP9803759W WO9913716A1 WO 1999013716 A1 WO1999013716 A1 WO 1999013716A1 JP 9803759 W JP9803759 W JP 9803759W WO 9913716 A1 WO9913716 A1 WO 9913716A1
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WIPO (PCT)
Prior art keywords
article
compound
antibiotic
acid
hinokitiol
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PCT/JP1998/003759
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English (en)
Japanese (ja)
Inventor
Hirobumi Aoki
Keijitsu Tanaka
Takashi Echigo
Original Assignee
Showa Denko K.K.
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Application filed by Showa Denko K.K. filed Critical Showa Denko K.K.
Priority to AU87501/98A priority Critical patent/AU8750198A/en
Publication of WO1999013716A1 publication Critical patent/WO1999013716A1/fr

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    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/38—Aromatic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/50—Mixtures of different organic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K9/00—Chemical or physical treatment of reed, straw, or similar material

Definitions

  • the present invention relates to an antibiotic agent containing hinokitiol (also known as 4-isopropyltrobolone or] 3-tuyaprisin). More specifically, the present invention relates to an antioxidant containing hinokitiol, a phenolic compound and a Z or aromatic amine compound, which is applied to and / or impregnated into an article such as a porous article, and is used for oxidation.
  • the present invention relates to a method for treating an article by carrying out a reaction and a Z or high molecular weight reaction, a composition used in the treatment method, and a treated substance obtained by the method and having antibiotic properties. Background art
  • hinokitiol has been used in various treatment agents that utilize antibiotics such as antibacterial, antiseptic, bactericidal, insect repellent, insecticidal, antiviral, and biorepellent properties.
  • antibiotics such as antibacterial, antiseptic, bactericidal, insect repellent, insecticidal, antiviral, and biorepellent properties.
  • hinokitiol has volatilization and sublimation properties, when articles are treated with hinokitiol-containing chemicals, the concentration of hinokitiol in the treated product decreases rapidly, and the period during which antibiotic action is exhibited is an inorganic antibacterial period. There is a drawback that it is shorter than the agent.
  • the unique odor of hinokitiol is favorable to those who like wooden buildings, it is important to use hinokitiol for various purposes in a wider living environment.
  • a water-insoluble hinokitiol metal salt or hinokitiol metal in the state of the treating agent solution is required. It is desirable not to form a complex.
  • the hinokitiol metal salt or the hinokitiol metal complex be changed from the treated article to a state in which the hinokitiol metal complex or the hinokitiol metal complex is not eluted by rainwater or the like.
  • the development of a method for imparting such contradictory properties to the treatment agent was required to make the antibiotic properties of hinokitiol more effective for a long period of time and to expand the field of use of hinokitiol as an antibiotic agent. .
  • JP-A 64-38203 wood preservatives using Hiba oil and insect repellents, and A colorant using a reaction product of a roboron salt and a metal salt is disclosed in JP-A 64-38203.
  • hiba oil is extracted from natural hiba wood by steam distillation, it is expensive and its supply is unstable, and it is effective to use compounds that can be supplied cheaper and more stably by artificial synthesis.
  • the development of new biocides was required.
  • the present applicant discloses a method for treating a porous article, comprising an enzyme having a polyphenol oxidizing action and a phenolic compound and / or an aromatic amine compound, and oxidizing and / or polymerizing the latter by the action of the former. And a composition for use therein (JP-A-9-322784 and JP-A-9-142386).
  • a composition for use therein JP-A-9-322784 and JP-A-9-142386.
  • an object of the present invention is to provide a hinokitiol-fixing drug utilizing a phenolic compound and a Z or aromatic amine compound, a method for treating an article with such a drug, or a processed product.
  • Another object of the present invention is to provide an oxidative reaction of a drug containing hinokitiol and A method for producing a treated porous article having excellent hinokitiol retention capacity by increasing the molecular weight or increasing the molecular weight, or a treated porous article obtained by such a method, and a treatment method with a reduced treatment time It is to provide.
  • the present inventors have developed a hinokitiol-containing hinokitiol that improves the shortcomings of hinokitiol, which is an antibiotic with excellent environmental and human safety, such as volatility, volatilization, or leaching, and has a long-lasting antibiotic effect. We worked diligently to develop antibiotics.
  • hinokitiol and a phenolic compound and a Z or aromatic amine compound simultaneously as a drug component, or performing an oxidation reaction and / or a high molecular weight reaction when using a drug containing hinokitiol, or
  • the present inventors have found that the effect of immobilizing hinokitiol can be improved by carrying out a combination of these methods, and further by using a metal compound in combination, thereby completing the present invention.
  • the present invention relates to the use of the antibacterial agent of the present invention when applied to an article and Z or impregnated with the product, the product of an oxidation reaction product of hinokitiol, a polyphenol compound and a no or aromatic amine compound,
  • the product of an oxidation reaction product of hinokitiol, a polyphenol compound and a no or aromatic amine compound By forming a polymerization reaction product and further a complex of these compounds and a metal compound, and thereby firmly fixing hinokitiol on the surface or inside of the article, defects such as volatility or leaching of hinokitiol are improved, Furthermore, it was completed based on the finding that the adhesion of the used metal was significantly improved.
  • the present invention provides the following antibiotics, an article processing method using the same, and a method for producing a processed product.
  • An antibiotic comprising hinokitiol, a phenolic compound and a Z or aromatic amine compound.
  • the low molecular weight compound is at least one compound selected from pyrogallol, pyrocatechol, hydroquinone, gallic acid or tannic acid, or a derivative thereof.
  • (6) at least one compound selected from pyrogallol, pyrocatechol, hydroquinone, gallic acid, tannic acid, lignin, or a derivative thereof, wherein the compound that is oxidized and / or increased in molecular weight in the presence of a polyphenol oxidation catalyst is 6.
  • the metal compound is zirconium, titanium, vanadium, chromium, molybdenum, manganese, iron, cobalt, nickel, palladium, copper, silver, zinc, cadmium, aluminum, tin, lead, antimony, calcium, magnesium, or At least one selected from barium 11.
  • a method for treating an article which comprises applying and / or impregnating an article as it is, or as a solution, with the antibiotic of any one of the above 1 to 15 as it is.
  • a process for producing a treated porous article comprising applying an hinokitiol-containing antibiotic to a porous article and Z or impregnating the same, followed by an oxidation reaction.
  • a method for producing a treated porous article comprising performing Z or impregnation, and performing an oxidation reaction and / or a high molecular weight reaction.
  • the metal compound is zirconium, titanium, vanadium, chromium, molybdenum, manganese, iron, cobalt, nickel, palladium, copper, silver, zinc, cadmium, aluminum, tin, lead, antimony, calcium, magnesium, or 30.
  • the hinokitiol used in the present invention has the following formula:
  • the term "high molecular weight” refers to not only the formation of a dimer or higher polymer by bonding the phenolic compound and the oxidized or radical form of the Z or aromatic amine compound, but also to these substances. Includes the formation of addition products with hinokitiol or oxidized forms of hinokitiol, or increases in molecular weight due to complex formation of these substances via metals.
  • Hinokitiol can be extracted as a crystal by extracting it from a natural material, for example, a tree such as cypress or cypress, by a conventional method.
  • hinokitiol may be derived from another natural product or a synthetic product may be used.
  • the amount of hinokitiol used in the present invention depends on the purpose of treatment, it is usually sufficient that the concentration of the hinokitiol in the liquid when formulated into a treatment object is 5 ppm or more. Below this, it is difficult to exert the antibiotic effect of hinokitiol. Preferably, about 25 to 5000 ppm is used.
  • phenolic compounds and aromatic amine compounds that are oxidized and Z or made into a high molecular weight by using hinokitiol or hinokitiol with a polyphenol oxidation catalyst include air, oxygen, hydrogen peroxide, and hydrogen peroxide precursor.
  • Any compound that can be oxidized or oxidatively polymerized by the above oxidizing agent can be used.
  • compounds having a plurality of hydroxyl groups or amino groups in the ortho or para position on the aromatic ring can be suitably used for the purpose of the present invention.
  • a compound having a substituent having an aryl structure in addition to a hydroxyl group or an amino group in an ortho- or para-position on the aromatic ring can also be suitably used for the purpose of the present invention.
  • Such phenolic compounds and aromatic amine compounds include low molecular weight compounds and high molecular compounds.
  • the “low molecular weight phenolic compound and / or aromatic amine compound” includes a phenolic compound containing preferably 1 to 5, more preferably 1 to 3, benzene nuclei.
  • nitrohumic acid tannin, force techin, gallic acid, lignin, urushiol, 4-hydroxycinnamyl alcohol, o-coumaric acid, p-coumaric acid, coniferyl alcohol, coniferyl aldehyde, ferulic acid , Ethyl-3,4-dihydroxycinnamic acid, 3-hydroxy-4-methoxycinnamic acid, 3,4-dihydroxycinnamic acid, 3-hydroxy-4-methoxycinnamaldehyde, vanillin, o-vanillin, vanilla acid, vanillin Lil alcohol, o_ vanillyl alcohol, Isovanillyl alcohol, Vanillylamine, Vanillinazine, 4-Hydroxy-3-methoxybenzonitrile, Syringic acid, Sinapyr alcohol, Sinapinic acid, Sinapinaldehyde, Homovanilla acid, Homovanillyl alcohol, Homovanilonitrile, Hesperi
  • low-molecular-weight phenolic compounds and / or aromatic amine compounds can be oxidized and / or increased in molecular weight without using enzymes. It was found that As such low molecular weight compounds, low molecular weight phenolic compounds such as pyrocatechol, hydroquinone, pyrogallol, gallic acid and tannic acid are suitable.
  • lignin or a derivative thereof requires a catalyst, but can be particularly preferably used for the purpose of the present invention.
  • ligninsulfonic acid or ligninsulfonate obtained from the pulp industry can be particularly preferably used.
  • lignin, ligninsulfonic acid, or ligninsulfonate obtained as a waste liquid in the pulp industry is used as the phenolic compound of the present invention, it is desirable to remove water-insoluble solid components as necessary.
  • the water-insoluble solid component removal treatment must be performed. It is desirable to carry out by centrifugation, filtration, or standing.
  • the diameter or major diameter in the pulp waste liquid is 1 m or more, preferably 0.5 m or more, more preferably 0.lim or more. It is desirable to remove the water-insoluble solid component by filtration. It is also possible to use those that have been desalted and desugared by ultrafiltration, or lower molecular fractions with a molecular weight of less than 0.5000 to 100,000 to further enhance impregnation. It is.
  • 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 acid esterification, propionic acid esterification, carboxymethyl etherification, 2-hydroxyethyl etheration, 2-acetoxyl ether, 2-hydroxypropyl ether, or alkylated with alkyl halide, cross-linked with formalin, epoxy compounds, isocyanate compounds, aryl compounds, etc.
  • a catechol derivative having a saturated or unsaturated alkyl side chain having 1 to 22 carbon atoms as a substituent in addition to the H group or NH 2 group is used as a main component to be oxidized and increased in molecular weight.
  • it can be used in addition to other phenolic compounds and Z or aromatic amine compounds.
  • the concentration of the phenolic compound and the Z or aromatic amine compound used for the purpose of the present invention in the liquid at the time of article processing is from 0.0001% by weight to 99% by weight, preferably from 0.001% to 99% by weight. 60% by weight.
  • any substance capable of oxidizing the polyphenol oxidation catalyst used in the present invention can be used as a raw material for an oxidation reaction and / or a high molecular weight reaction or as a polymerization initiator.
  • examples of such compounds are ABTS (2,2'-azobis (3-ethylbenzothiazoline-6-sulphonic acid)), pyrirubin, ascorbic acid, isoascorbic acid, quercetin, rutin, guaiacol, o-hydroxybenzoic acid, p-hydroxy Benzoic acid, 4-methoxyphenol, biphenol, 4,4'-ethylenediline, methylhydroquinone, ethylhydroquinone, 1-hydroxybenzotriazole, 6-hydroxy-1,2,4,5-triaminopyrimidine , 4,5,6-triaminopyrimidine, 2,3-dihydroxypyridazine, 3,6-dihydroxypyridazine, 2,3-dihydroxy
  • quinone compounds examples include: anthraquinone-2-sulphonic acid, anthraquinone-l, 5-disulfonic acid, anthraquinone-l, 6-disulphonic acid, anthraquinone- 2-capronic acid, 1-aminoanthra Quinone, 2-aminoaminosuraquinone, anthralphine, aminonaphthoquinone, 1,8-dihydroxyanthraquinone, camphoquinone, aldehyde ⁇ -ascorbic acid, 2-hydroxy-1,4-naphthoquinone, isatin, 5-12 migraineatin, various types Anthraquinone dye.
  • unsaturated fatty acids such as oleic acid and linoleic acid
  • unsaturated alcohols such as oleyl alcohol
  • unsaturated alkyls such as squalene
  • auto-oxidizing substances such as tung oil and linseed oil
  • concentration is from 0.0001 to 80% by weight, preferably from 0.001 to 20% by weight.
  • a plurality of the compounds described above can be used in combination.
  • metal compounds used for the purpose of suppressing the volatility, volatility, and leaching of hinokitiol are zirconium, titanium, vanadium, chromium, molybdenum, manganese, iron, cobalt, nickel, palladium, copper, silver, A compound containing at least one metal element selected from zinc, cadmium, aluminum, tin, lead, antimony, calcium, magnesium, and barium.Zirconium, titanium, vanadium, chromium, molybdenum, manganese, iron Those containing, cobalt, nickel, palladium, copper, silver, zinc, aluminum, or tin can be particularly preferably used. Specifically, these metal elements are cationized, F_,
  • Examples include phenolic compounds and pyrogamines as Z or aromatic amine compounds. If zirconium acetate, zirconium carbonate, zirconium ammonium carbonate, molybdenum chloride, manganese sulfate, iron chloride, iron sulfate, nickel chloride, copper chloride, copper sulfate, copper carbonate, copper hydroxide, copper hydroxide, copper naphthenate, Chloride Examples include lead, zinc sulfate, aluminum chloride, aluminum sulfate, and aluminum sulfate.
  • a complex of the above-mentioned metal element cationized with an organic compound or an ionic group can be used.
  • organic compound added to form a complex with a metal many conventionally known compounds can be used.
  • many conventionally known compounds can be used.
  • a phenolic compound such as an aminophenol or an aromatic amide compound, ethane-1,1-diphosphonic acid and its derivative, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1, Phosphonic acids such as 2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-1,2,3,4-tricarboxylic acid, and ⁇ -methylphosphonosuccinic acid Amino acids or amino acids such as carboxylic acid, aspartic acid, glutamic acid,
  • the above-mentioned metal compound or metal fine powder can also be used for the purpose of the present invention.
  • powders composed of fine particles of various sizes can be used according to the purpose.For example, when impregnating wood, the average particle size is 5 / m or less, preferably Q. or less. More preferably, a powder composed of fine particles having a particle size of 0.1 / im or less can be suitably used.
  • the concentration of these metal compounds or metal powders used in the present invention in the liquid at the time of article processing is preferably adjusted according to the solubility, the antibiotic property of the metal used, the purpose of the processing, etc.
  • concentration of these metal compounds or metal powders used in the present invention in the liquid at the time of article processing is preferably adjusted according to the solubility, the antibiotic property of the metal used, the purpose of the processing, etc.
  • zirconium, copper, zinc, or aluminum it is usually 0.01 mM to 2.5M, preferably 0.1 LMM to 0.5M.
  • hinokitiol can be fixed without using a polyphenol oxidation catalyst, particularly when a low-molecular-weight phenolic compound is contained, but also when a low-molecular-weight phenolic compound is used, Even when other phenolic compounds and aromatic or aromatic amine compounds are used, it is preferable to include a catalyst for accelerating the oxidation and Z or high molecular weight of these compounds.
  • a polyphenol oxidation catalyst include metal ions, metal complexes, and natural enzymes.
  • artificial enzymes that mimic oxidoreductases are useful for obtaining effective catalytic effects with lower concentrations of metal ions.
  • human enzymes include cyclic nitrogen-containing compounds such as triazacyclononane and triazacyclododecane and N-methylated derivatives thereof, phthalocyanine or porphyrin and derivatives thereof having a hydrophilic substituent. is there.
  • polyphenol oxidase can be widely used as long as it has a polyphenol oxidizing action.Since these have high safety as a catalyst for natural products, they can be suitably used for the purpose of the present invention. is there.
  • Examples of such enzymes include catechol oxidases, laccases, polyphenols produced by microorganisms, such as fungi or bacteria, or produced by plants.
  • Examples include polyphenol oxidases such as oxidase, ascorbate oxidase, and pyrylrubin oxidase. Particularly, when it is desired to carry out the oxidation reaction and the oxidative polymerization reaction at a high speed, those having a polyphenol oxidizing action at an alkaline pH are more preferable.
  • Oxidation by enzymatic oxidation and Z or high molecular weight reaction can also be carried out by using hydrogen peroxide and an enzyme having a peroxidase action such as microorganism- or plant-derived peroxidase, lignin peroxidase, manganese peroxidase, etc. It is feasible.
  • the method of adding and supplying hydrogen peroxide is a method of directly adding a hydrogen peroxide solution, a method of using a hydrogen peroxide precursor such as perborate or a perponate instead of hydrogen peroxide, or a method of peroxidation.
  • There is a method using oxidase and its substrate that can generate hydrogen and various methods can be used depending on the treatment purpose and treatment method.
  • oxidases that can generate such hydrogen peroxide include glucose oxidase, alcohol oxidase, glycerol oxidase, amine oxidase, amino acid oxidase, and D-amino acid oxidase.
  • microorganisms that produce polyphenol oxidase used for the purpose of the present invention include the following.
  • Fungi include Aspergillus Aspergillus ⁇ , Potritis Botrytis, Myrothecium, Embellisia, Dreschlera, Penicillium Pestalotia, Rhizoctonia, Tricoderma, Arthromyces, Humicola, Verticillum, Perocladium (Ulocladium), Caldariomyces, Stilbella, Sagenomella, Stachylidium, preferably Aspergillus nidulans, Pot U ice Myrothecium verridcaria, Myrothecium verridcaria, Myrothecium verridcaria, Myrothecium prestonii, Myrothecium humorium Embellisia alii), Dreschlera halodes), Penicillium sclerotiorum Penicillium sclerotioruni), Penicillium 'Penicillium janthinellum), Pesrum stialotia, Palma (Phikov, Rhizoct
  • Stilbella erithrocephala Stilbella Gavescens, Stilbella avipes, Stilla thermophila, Stilbella thermophila, Stilbella sp., Sagenomella viride), Sagenomella sp., Sachnomella sp., Stachylidium bicolor, Stachylidium theobromae, Fungus on Yusenjirijimu 'sp. (Stachylidium sp.) Including strains.
  • Cesium verrucaria SD3001 Myrothecium verrucaria SD3001 (Ministry of International Trade and Industry of Japan, Institute of Biotechnology, Industrial Technology Research Institute (Address: Tsukuba East, Ibaraki, Japan 1) (Chome No. 1-3), deposited as P-14955 on May 29, 1995 and accession number FERM BP on April 24, 1996 based on the Budapest Treaty.
  • Myrothecium 'Kuchi-Ridum SD 3002 Myrothecium roridum SD3002 (Japan Institute of Biotechnology and Industrial Technology, Ministry of International Trade and Industry, Japan (Address: Ibaraki, Japan) Deposited at Tsukuba East 1-Chome 1-3-3) on October 26, 1995 as P-15255, and based on the Budapest Treaty April 24, 1996 Has been transferred to the International Depositary under the accession number FERM BP-5523.
  • fungi include Pleotus tus Ple tus), Lentinas Lenti, SchizophyUuin, Almiliariella Armillariella, Flamlulina (Flammulina), Agaricus Agaricus), Kosana, belonging to the basidiomycete subclass Basidiomycotina.
  • fungi other than the phylum Incomplete Mycota and the Basidiomycota include Podosbora Podospora and Neurospora belonging to Ascomycotina.
  • Neurospora Neurospora crassa, Monosilium 'onocillium indicum', Fusarium 'Fusarium oxysporu', Mucor hiemalis, Rhizopus ricinos, Rhizopus ric It is.
  • Some preferred bacteria include AzospirUlum, Azospirillum lipoferum, or Actino zero etales, such as Streptomyces, and preferably Streptomyces antipio Ticas (Streptomyces antibioticus), Streptomyces spheroides, Streptomyces thermoviolaceus ⁇ Streptomyces thermoviolaceus, and also [/ Aerobacter aerogenes, preferably Aerobactei, The strain to which it belongs is included.
  • Streptomyces and preferably Streptomyces antipio Ticas (Streptomyces antibioticus), Streptomyces spheroides, Streptomyces thermoviolaceus ⁇ Streptomyces thermoviolaceus, and also [/ Aerobacter aerogenes, preferably Aerobactei, The strain to which it belongs is included.
  • Bacillus alcalophilus Bacillus amyloliquefaciens, Bacillus brevis, Bacillus firmus, Bacillus licheniformis
  • Bacillus licheniformis Bacillus licheniformis
  • Non narus' Sonanaris Bacillus subtihs Bacillus natto B ac m us natto
  • Bacillus pumilus Bacillus pumilus Bacillus pumilus
  • Bacillus sphaericus Bacillus stearothermophilus, preferably Bacillus licheuiformis.
  • Some preferred plants that contain the enzymes used in the present invention include sycamore, Acerpseudopla tan umno, Diamcorea (Dioscorea), Okfu iAbelmoschus), Guava Psidium), Sunflower (Melianthus, Jasium, apple, Includes kapotiya, kiuri, wheat, soybeans, alfalpha, and horseradish.
  • the polyphenol oxidase used in the present invention can be obtained by culturing the aforementioned microorganisms, for example, strains belonging to fungi or bacteria and mutants thereof, and can also be prepared using genetically engineered bacteria. is there. That is, a DNA sequence encoding the enzyme protein is used to replicate a vector in a host organism together with an appropriate promoter having an enzyme expression function in the host organism, an operator, and a DNA sequence. A host cell transformed using an expression vector inserted into a DNA vector having the replication origin of the above, or a DNA sequence encoding the above-mentioned enzyme protein is converted into an appropriate promoter having an enzyme expression function in a host organism. The host cells transformed by integration into the host cell DNA together with the DNA sequence of the overnight, the operator, the evening, and the minerals are cultured under conditions that allow expression of the enzyme protein. Is also produced by a method of recovering from the medium.
  • cDNA or a genomic library from the microorganisms described above, for example, fungal or bacterial strains, is used as an isolation source. Identify the target DNA fragment using the oligonucleotide synthesized based on the amino acid sequence as a probe, select a clone that expresses the activity as an oxidase, or produce a protein that reacts with an antibody against the enzyme protein Once a clone is selected, it can be done in a conventional manner.
  • the enzyme protein according to the present invention may be a seed, fruit, or leaf derived from the plant. It can also be prepared by extraction from any source.
  • a culture of fungi or bacteria belonging to fungi or bacteria and a mutant thereof for obtaining the enzyme protein according to the present invention a commonly used synthetic medium or a nutrient medium containing an organic carbon source and an organic nitrogen source can be used.
  • a metal ion which is contained in the active center of the target enzyme protein, to the medium as a metal salt at a concentration of 0.001 to 1 mM, preferably 0.1 to 1 mM as a metal salt during the culture. .
  • the polyphenol oxidase of the present invention When the polyphenol oxidase of the present invention is secreted outside the fungal or bacterial cells, it can be recovered from the medium by a well-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 enzyme protein accumulates in fungal or bacterial cells or is present in plant tissues, it can be recovered from cell tissues or plant tissues by well-known methods.
  • This recovery procedure includes a series of steps of mechanical disruption of tissue by homogenization, separation and extraction of an enzyme protein solution by centrifugation or filtration, and membrane separation, and chromatography, for example, by ion exchange chromatography. Also, membrane concentration using an ultrafiltration membrane is effective.
  • the present invention relates to:
  • the oxidation activity concentration of the polyphenol oxidation catalyst is 1 to 100,000 U /, preferably 10 to 5, ooouzrc.
  • the boron-containing compound used for the purpose of increasing the antibiotic properties of hinokitiol is, specifically, boric acid (orthoboric acid), diboric acid, metaboric acid, tetraboric acid, pentaboric acid, octaboric acid, or the like.
  • boric acid (orthoboric acid), diboric acid, metaboric acid, tetraboric acid, pentaboric acid, octaboric acid, or the like are boron-containing compounds, And their alkali metal salts, copper borofluoride, copper tetra'fluoroborate, etc., but when considering safety to the human body and the environment, boric acid (orthoboric acid), metaboric acid, tetraboric acid, Particularly preferred are boron-containing compounds such as octaboric acid, and alkali metal salts thereof.
  • concentration of such a boron-containing compound used in the present invention in a liquid at the time of article processing is
  • the treating agent of the present invention can be used as a treating agent for surface treatment and Z or internal treatment of various articles, and in particular, when used for articles having porous properties, it can be used in a coating treatment.
  • a favorable effect of increasing the amount of the treatment agent fixed inside the article can be obtained.
  • porous articles are: sintered metal, manufactured products, alloys, die-cast products, ceramics, bricks, concrete, wood, wood chips, wood flour, wood products, fir, rush, straw, bamboo, charcoal, fiber , Textile processed goods, synthetic resin foam.
  • the porous article is a plant-derived porous article, such as wood, wood chips, wood flour, processed wood, fir, rush, straw, bamboo, plant fiber, or processed plant fiber
  • natural porous phenol compounds such as lignin-based compounds and flaponoid-based compounds are already contained in the porous material, these compounds can be oxidized and / or polymerized by using the treatment method of the present invention. It can be effectively used as a raw material for
  • fragrances for the purpose of further enhancing the action of the antibiotic of the present invention or at the same time imparting various article processing effects, fragrances, deodorants, antioxidants, flame retardants, antibacterial agents, preservatives Further, an agent selected from a fungicide, an insect repellent, an antiviral agent, and a biological repellent can be further contained.
  • Such agents are plant-derived extracts, extracted components, or compounds having a structure equivalent to that of plant-extracted components.
  • Hinoki and Aomori Plant extracts and extractables obtained by treating plants such as bamboo trees, bamboo, herbs, radish, horseradish, iromote thistle rhizomes, or yae palm roots by crushing, pressing, boiling, or steam distillation. Is mentioned.
  • plant-derived extracts or compounds having a structure equivalent to that of plant extracts include tropolones such as] 3-drabulin, ⁇ -binene, ⁇ -pinene, camphor, menthol, limonene, Monoterpenes such as porneol, ⁇ -terpinene, terbinene, terpineol, terpinene-41-ol, cineole, sesquiterpenes such as ⁇ -casino and t-murol, catechin, tannin, etc.
  • tropolones such as] 3-drabulin, ⁇ -binene, ⁇ -pinene, camphor, menthol, limonene, Monoterpenes such as porneol, ⁇ -terpinene, terbinene, terpineol, terpinene-41-ol, cineole, sesquiterpenes such as ⁇ -casino and t-murol, catechin, tannin, etc
  • naphthalene derivatives such as 2,3,5-trimethylnaphthalene
  • long-chain aliphatic alcohols such as citronellol
  • aldehydes such as cinnamaldehyde, citral, and perilla aldehyde.
  • Wood vinegar obtained by steaming trees can also be used.
  • plant-derived compounds such as lignin or rhidanine derivatives as raw materials for oxidation and / or polymerization reactions, it is possible to manufacture processed articles with high environmental and human safety. It is possible.
  • the concentration of the plant-derived extract, the extract component, or the compound having the same structure as that of the plant extract component used in the present invention in the liquid at the time of article treatment is 0.001 to 80% by weight. It is preferably 0.01 to 20% by weight.
  • agents that can be used in the present invention are aromatic compounds or cyclic compounds having, as substituents, OH groups, amino groups, halogens, nitro groups, methyl groups, methoxy groups and the like.
  • aromatic compounds or cyclic compounds having, as substituents, OH groups, amino groups, halogens, nitro groups, methyl groups, methoxy groups and the like.
  • Specific examples of such compounds include o-phenylphenol, 1-naphthol, 2-naphthol-o-chlorophenol, 2,4-dinitrophenol, 4,6-dinitro-o-cresol, and pentachlorophenol.
  • agents that can be used in the present invention include unsaturated fatty acids such as oleic acid and linoleic acid, unsaturated alcohols such as oleyl alcohol, unsaturated alkyls such as squalene, and drying oils such as tung oil, linseed oil, and castor oil. And catechol derivatives having an unsaturated side chain such as urushiol.
  • concentration of such a compound used in the present invention in a liquid at the time of article treatment is 0.01 to 90% by weight, preferably 0.1 to 50% by weight.
  • phosphates having elements such as Na, K, Mg, Ca, Ba, A and Zn, Cu, Mn, Ni, Si, Sn, and Pb in the cation portion phosphates having elements such as Na, K, Mg, Ca, Ba, A and Zn, Cu, Mn, Ni, Si, Sn, and Pb in the cation portion, , Hydrogen phosphate, sulfate, hydrogen sulfate, carbonate, borate, silicate, nitrate, fluoride, chloride, bromide, hydroxide, etc.
  • Examples include aluminum, magnesium hydroxide, zirconium hydroxide, antimony trioxide, barium metaborate, tin oxide, red phosphorus, and ammonium phosphate.
  • the digestion process in the pulp mill is mainly performed by calcium sulfite or magnesium sulfite. Since it is carried out by gnesium, lignin sulfonic acid containing calcium carbonate, calcium hydroxide, magnesium carbonate or magnesium hydroxide is added to the cooking liquor by adding a carbonate such as sodium carbonate or an alkali such as sodium hydroxide. Obtainable.
  • ligninsulfonic acid By treating the article of the present invention using ligninsulfonic acid, it is possible to effectively use these calcium salts or magnesium salts as a flame retardant.
  • the concentration of these flame retardants used in the present invention in the liquid at the time of article processing is 0.01 to 90% by weight, preferably:! ⁇ 50% by weight.
  • bactericides or bactericidal components include azaconazole, etaconazole, propiconazole, bromoconazole, diphenoconazole, itraconazole, furtriahole, microbuilnil, fenenamil, Penconazole, tetraconazole, hexaconazole, tebuconazole, imibenconazole, flusilazol, ribavirin, triamiphos, isazophos, triazofos, ididinphos, fluotrimazole, triazimehon, triazimenol, diclobutra Zole, diconazole, diconazole M, bitertanol, epoxyconazole, triticonazole, methconazole, ipconazole, fluconazo
  • insecticides usable in the present invention include fluorine-based substances such as sodium fluoride, potassium fluoride, sodium gay fluoride, and magnesium fluoride, thiofamethomethyl, dasban, diazinon, etc.
  • Organophosphorus compounds azinophos-ethyl, azinophos-methyl, 1- (4-chlorophenyl) -4-1 (O-ethyl, S-propyl) phosphoryloxyvirazol (TIA-230), Mouth pyrifos, tetraclorobinphos, kumafos, dementen-S-methyl, diazinone, dichlorpos, dimethoet, etoprofos, etrimfoss, funitrothion, pyridafenthion, heptenofos, parathion, parathion-methyl, propethamphos, phopetamphos, phopetamphos —Ethyl, Pirimiphos—Methyl, Profenophos, Protiforth, Sulfophos, Triazofos, Phosphoric acid esters such as Torchlorlfon, Ardicarb, Benyokab, BP
  • Insect hormone or IGR insect growth regulator
  • the body can also be used.
  • These fungicides, insecticides, or insect repellents can be used alone or in combination.
  • the concentration of such a bactericide, insecticide, or insect repellent used in the present invention in a liquid at the time of article processing should be adjusted according to the strength of the physiological activity possessed by these agents, the purpose of the treatment, and the solubility. However, it is 0.0001 to 20% by weight, preferably 0.001 to 5% by weight.
  • DDAC diidecyldimethylammonium chloride
  • concentration of such a quaternary ammonium compound used in the present invention in a liquid at the time of article processing is 0.001 to 50% by weight, preferably 0.01 to 20% by weight.
  • inorganic compounds having strong antibiotic properties can also be used by adding them to the treating agent of the present invention.
  • examples of such compounds include arsenic, antimony, selenium, bromine, iodine, fluorine, iodide, and the like.
  • Compounds containing nitrate ions more specifically, arsenous acid, antimony chloride, antimony trioxide, potassium selenate, calcium bromide, sodium bromide, magnesium bromide, potassium bromide, zinc bromide, Examples include sodium iodide, zinc iodide, sodium fluoride, potassium fluoride, antimony fluoride, gay copper fluoride, sodium sulfide, potassium sulfide, and zirconium nitrate.
  • the concentration of such a compound used in the present invention in a liquid at the time of article processing is 0.01 to 200 mM, preferably 0.1 to: L0 OmM.
  • antibiotics of the present invention When the water solubility is low, a method of forming an OZW type or W / O type emulsion by adding a dispersant or a surfactant is useful.
  • 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 propylene oxide and butylene oxide are added alone or in combination with a plurality of components, alkyl sulfonates, amido sulfonates, dialkyl sulfosuccinates, ⁇ - Aliphatic sulfonates such as olefins, vinylidene-type olefins, and internal olefins; aromatic sulfonates such as
  • Phosphate ester surfactants such as ester, alkyl or alkenyl phosphate, sulfonic acid type amphoteric surfactant, betaine type amphoteric surfactant, having linear or branched alkyl or alkenyl group, ethylene Having an alkyl or alkenyl ether or alcohol to which one or more of oxide, propylene oxide and butylene oxide are added, a linear or branched alkyl group or an alkenyl group, and ethylene oxide, propylene oxide Polyoxyethylene alkylphenyl ether, to which one or more components of oxide and butyl oxide are added, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid dalycerin monoester, alkyl or alkenyl Amine oxide, tetraalkylammonium salt type cationic surfactant and the like.
  • lignin, Lignin sulfonic acid or lignin sulfonic acid salt is not only a raw material for an oxidation reaction and a polymerization reaction, but also because these substances themselves have a drug dispersing action, they are extremely useful for the purpose of the present invention.
  • the drug is a fine powder
  • powders of various sizes can be used depending on the purpose.However, when pressure injection into wood is performed, the average particle size is 5 m or less, preferably 0.5. It is preferable to use a fine powder having a particle size of not more than 0.1 m / m, more preferably not more than 0.1 m.
  • a pH adjuster a dye, a pigment, a thickener, a polymer compound, a solid, and the like can be added to the treatment agent of the present invention for use.
  • the antibiotic agent 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 convenience of use depending on the preservability of the treatment agent and the purpose of use.
  • granulation and extrusion Granulation, fluidized granulation, centrifugal fluidized granulation and the like can be achieved by any granulation operation according to the purpose.
  • it is effective to granulate the catalyst together with the stabilizer separately from other treating agent components.
  • the antibiotic of the present invention can be prepared by any method of a high-concentration solution premised on dilution at the time of use, or a concentrated solution that can be used without dilution.
  • a phenolic compound and a Z or aromatic amine compound, and further a polyphenol oxidation catalyst are prepared separately from other treating agent components, and mixed immediately before use. It can also be used.
  • the treated articles are metal sintered compacts, manufactured products, alloys, die-cast products, ceramics, bricks, concrete, wood, wood chips, wood flour, wood products, fir, rush, straw, bamboo, charcoal, plant fiber
  • a porous article such as a fiber, a processed fiber product, a processed fiber product, a synthetic resin foam, and the like, it is extremely useful for fixing a sufficient amount of a hinokitiol-containing antibiotic to the article.
  • the impregnation operation can be performed simply by immersing the article in a treating agent solution.However, in order to inject a sufficient amount of the treating solution into various types of porous articles that are difficult to impregnate, Pressurizing and / or depressurizing operations are very useful.
  • the pressurization operation is performed at atmospheric pressure of 1 to 20 atm, more preferably 3 to 15 atm, but the activity of the polyphenol oxidation catalyst, especially polyphenol oxidase, is not lost. Then it is possible to apply more pressure.
  • the depressurization operation can be performed at any pressure up to the vacuum pressure, but for effective treatment of porous articles that are difficult to impregnate, a pressure in the range of 100 to 76 OmmHg is required.
  • Reduced pressure is desirable. It is more preferable that the pressure reducing operation be performed by a pre-evacuation method in which the pressure is reduced before adding the treatment liquid to the porous article. It is also effective to combine these pressurizing and depressurizing operations in order to impregnate the treatment liquid in a larger amount in the porous article.
  • a pressure reduction treatment is performed to recover a part of the treatment liquid outside the porous article, and the polymerization reaction inside the treated porous article is sufficiently performed.
  • the porous article is washed with water or the like to remove the unpolymerized substance, so that the degree of maintaining the porous property can be easily adjusted.
  • the treated material whose porosity is maintained or adjusted retains the humidity adjustment capacity, water retention capacity, adsorption capacity, and ion exchange capacity, and can be used for various applications that utilize such capacity. It is.
  • a porous article having various composite properties can be manufactured by further impregnating a drug, a polymer, and a prepolymer into a processed material having a maintained porous property.
  • the porous article is wood, various commonly used pressurizing and / or depressurizing treatment methods can be used. Specifically, the packed cell method (Vesel method), the semi-empty cell method (Lowry method), and the empty method Cell method (Leuping method), Double vacuum method (Double vacuum method), Pressurization / Decompression method (Oscillating Pressure Method), Pulsation pressure method (Pulsation Pressure Method), Constant pressure method (Constant Pressure Method), Low speed fluctuation A pressure method (Slow Pressure Change Method) and a method combining these operations are applicable.
  • an insizing method can be applied to increase the impregnation amount. It is also effective to perform a compression treatment using a roller or the like, a microwave heating, a freezing treatment, a steaming treatment, a steam treatment, or a heat treatment as a pretreatment of the porous article which is difficult to impregnate.
  • the application and / or impregnation using the antibiotic of the present invention is carried out at 0 to 150 ° C, preferably at 10 to 80 ° C.
  • the treated material is further allowed to stand in the air or oxygen gas, and gradually dried, and then subjected to oxidation and / or polymerization to increase the molecular weight, thereby further strengthening the treatment.
  • Hinokitiol can be immobilized.
  • the oxidation reaction and / or the polymerization reaction is carried out at a temperature of 0 to 200 ° C, more preferably 10 to 100 ° C. More specifically, when porifenol oxidase is used in an antibiotic, a temperature condition of 10 to 70 ° C. is preferable. When polyphenol oxidase is not used, the temperature is preferably from 10 to 200 ° C, more preferably from 20 to 150 ° C. In general, the higher the temperature, the higher the reaction rate, but the temperature conditions are limited to the extent that the enzyme is not inactivated by the antibiotic containing the enzyme. As mentioned above, when a low molecular weight phenolic compound is used, it is possible to use an antibiotic that does not add an enzyme, so that treatment at a higher temperature reduces the time required to complete the reaction. It is possible to do so.
  • a method of using both pressure and heat treatments is useful for increasing the strength of the processed material and the adhesion of hinokitiol. is there. It is also effective to further coat the surface of the finished product and seal the hinokitiol-containing drug.
  • the oxidation treatment and the Z or high molecular weight treatment on the treated article, it is possible to further firmly fix the treating agent component.
  • the pH of the antibiotic of the present invention can be adjusted in any pH range as long as the desired oxidation reaction and / or reaction for increasing the molecular weight proceeds.
  • a polyphenol oxidation catalyst is not used, or when a metal complex / artificial enzyme is used, the reaction generally proceeds more rapidly at the pH on the side of the reaction force.
  • polyphenol oxidase is used as a catalyst, the increase in the autoxidation rate in the alkaline pH range and the change in the pH-dependent enzyme reaction rate are comprehensively determined, and the It is desirable to adjust the pH to a range where the oxidation reaction and the Z or high molecular weight reaction proceed more efficiently.
  • the treated product contains a phenolic compound having an antioxidant property and a phenolic or aromatic amine compound. Due to the presence of the compound, the treated product according to the present invention has an effect of suppressing the corrosion even when a corrosive component such as an iron nail comes into contact. Therefore, the treatment of the present invention is also useful for maintaining the strength of the construct.
  • the polyphenol oxidation catalyst and the phenolic compound and the phenolic or aromatic amine compound are pressurized and pressurized and pressurized or pressurized or depressurized. Do not contain substances that can act as polyphenol oxidation catalyst by impregnating in porous articles and performing oxidation reaction and / or high molecular weight reaction in porous articles Effective treatment of porous articles with low strength or low content is possible.
  • the high molecular weight reaction can proceed mainly inside the porous article. That is, a large amount of a processing solution can be easily impregnated into a porous article by using a processing agent having a relatively low molecular weight of a constituent material of the reaction solution composition, that is, a relatively low viscosity, and furthermore, impregnation.
  • the subsequent oxidation reaction and / or high molecular weight reaction enables effective fixation of the treating agent component.
  • the reaction is stopped when the appropriate oxidation and / or high molecular weight progresses on the surface or inside of the treated article, due to acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, organic acid, etc. Impregnation, or by shutting off the oxygen supply by coating the surface of the porous article with a coating film.
  • positive Rifueno Ichiru oxidation catalyst the case is an enzyme having Porifueno Ichiru oxidation, N a OH, NH 3, N a 2 C_ ⁇ 3, alkali or alkaline such as C a C 0 3
  • the reaction can also be effectively stopped by impregnation with a neutral salt, impregnation with a known enzyme inhibitor, or heat treatment at 100 ° C for 15 minutes.
  • the measurement of the polyphenol oxidizing activity of the enzyme protein having a polyphenol oxidizing action was performed at 25 ° C. at 20 ppm of syringaldazine and 10 OmM of Tris_HC 1 buffer.
  • the reaction was performed at an optimal reaction pH in an aqueous solution containing potassium phosphate buffer, and the absorbance at 525 nm was measured.
  • the activity of oxidizing 1 / mo 1 of syringaldazine per minute was defined as 1 unit (hereinafter abbreviated as U).
  • Antibiotics were prepared containing 10 mg of hinokitiol, 1.26 g of pyrogallol, 2.5 g of copper sulfate (II) pentahydrate, and 4 mg of the polyphenol oxidation catalyst described in Reference Example 1 in 20 Om1 of water in various combinations.
  • In the preparation in order to completely dissolve hinokitiol, heating in a water bath at 50 ° C and sufficient stirring were performed.
  • a polyphenol oxidation catalyst was added and the pH was adjusted.
  • the pH was adjusted to 8.4 using pI ⁇ 2N NaOH.However, in the case of an agent that did not contain pyrogallol and contained copper sulfate, the pH was not adjusted because the copper compound precipitated when NaOH was added. Was.
  • impregnation treatment was applied to cedar wood chips (3 cm x 3 cm x 0.5 cm, 3 cm x 3 cm on the wood front, sapwood). The impregnation operation was performed by immersing the cedar wood pieces in the treatment solution, reducing the pressure at 650 to 700 mmHg for 30 minutes, and then leaving the immersed pieces at normal pressure for 30 minutes. It was confirmed by the measurement of the weight of the wood pieces before and after the impregnation operation that a sufficient amount of the treatment solution (3.3 to 3.9 g amount) was injected by this impregnation operation.
  • the impregnated wood pieces were placed in a constant temperature room at 28 ° C for 5 days to dry and react.
  • the treated wood pieces were dried in a dryer at 60 ° C for 16 hours, and 4 Om 1 of water was added to each wood piece. Water was stirred using magnetics under the condition that a piece of wood was submerged under the water surface, and leaching operation was performed by stirring at 25 ⁇ 3 ° C for 8 hours. These drying and leaching operations were repeated five times, and finally, the treated wood pieces were dried in a dryer at 60 ° C for 16 hours to obtain leached wood pieces.
  • the leaching solution after a total of 5 leaching operations was evaluated using PAN (l- (2-Pyridylazo) -2-napht oL obtained from Aldrich Chemical Company) and EDTA (ethylenediamine
  • the concentration of copper injected in the impregnation process was set to 100%, and the residual rate of copper present in the wood chips was calculated after five leaching operations with the amount of copper injected being 100%. did.
  • the measurement of hinokitiol concentration by HPLC was performed using Shodex RSpak DS-613 (40 ° C) as a column and 60% acetonitrile and 0.05% phosphoric acid (flow rate 1.5 ml / min) as eluents. The measurement was performed by measuring the absorbance at 254 nm. As a result, it was shown that hinokitiol and copper can be effectively fixed by the antibiotics of the present invention.
  • the wood chips that had been subjected to the same impregnation and leaching treatments as described above were placed in a dryer at 60 ° C for 48 hours, then placed in a dessicator for 30 minutes, and dried sufficiently to measure the dry weight.
  • antibacterial tests of these wood chips were performed using HS A 9201 (performance standards of wood preservatives and test method 1991) using Tromyces palustris FEPRI 0507 (obtained from Forest Research Institute, Ministry of Agriculture, Forestry and Fisheries). .
  • remove the wood chips from the culture bottle sufficiently remove the mycelium on the surface of the wood chips, air-dry for about 24 hours, and then dry thoroughly using a drier and desiccator as described above, and measure the weight.
  • Agent B Yes No No Yes 8.4 33 9.4 Agent c Yes Yes No No 8.4 31 10.3
  • Agent D Yes Yes No Yes 8.4 35 9 4 Agent E With / Without With / Without 4.3 15 59 3.1 With Agent F With / Without With With / Without 4.3 28 72 2.2 With Agent G With With With With / Without 8. 4 92 83 1. With 4 Agent H With With With With With / Without 8.4 95 94 0.9
  • Example 1 using the prepared aqueous antibiotic solution, the same impregnation treatment, leaching treatment and hinokitiol residual ratio as in Example 1 were performed. Some of the wood pieces subjected to the same impregnation and leaching treatments were subjected to the same preservative test (measurement of the weight loss rate of the wood pieces) as in Example 1. As a result, it was shown that the antibiotics of the present invention can effectively fix hinokitiol and can impart effective antibacterial properties.
  • Example 1 As in Example 1, an aqueous solution containing 10 to 20 mg of hinokitiol, 1 to 10 mM of pyrogallol, and 1 to 1 OmM of aluminum chloride in 200 ml of water was prepared, and adjusted to pH 8.2 with 2N NaOH. An aqueous solution of the antibiotic was prepared.
  • Example 1 using the prepared aqueous antibiotic solution, the same impregnation treatment, leaching treatment and hinokitiol residual ratio as in Example 1 were performed. Some of the wood pieces subjected to the same impregnation and leaching treatments were subjected to the same preservative test (measurement of the weight loss rate of the wood pieces) as in Example 1. As a result, it was shown that the antibiotics of the present invention can effectively fix hinokitiol and can impart effective antibacterial properties.
  • Example 1 As in Example 1, an aqueous solution containing 1 O mg of hinokitiol, 2.5 g of copper sulfate (II) pentahydrate, 4 mg of the polyphenol oxidation catalyst described in Reference Example 1 in water 20 Om1 Various phenolic compounds and Z or aromatic amine compounds were added thereto, and the pH was adjusted to 8.4 with 2N NaOH to prepare an aqueous solution of the antibiotic.
  • Example 1 using the prepared aqueous antibiotic solution, the same impregnation treatment, leaching treatment and hinokitiol residual ratio as in Example 1 were performed. Some of the wood pieces subjected to the same impregnation and leaching treatments were subjected to the same preservative test (measurement of the weight loss rate of the wood pieces) as in Example 1. As a result, it was shown that the antibiotics of the present invention can effectively fix hinokitiol and can impart effective antibacterial properties.
  • an aqueous antibiotic solution was prepared in the same manner as in the above example except that the polyphenol oxidation catalyst was not added, and the conditions after the impregnation treatment were replaced with oxygen gas in Example 1 instead of holding at 28 ° C for 5 days.
  • Leaching treatment was performed in the same manner as in Example 1, except that the heating and acceleration treatment was performed in a pressure vessel pressurized to 2 atm at 125 ° C for 2 hours and then at 60 ° C for 16 hours. The hinokitiol residual ratio was measured. Further, of the wood pieces subjected to the same impregnation treatment and leaching treatment, some of the wood pieces were subjected to the same preservative test (measurement of the weight loss rate of the wood pieces) as in Example 1.
  • Example 1 As in Example 1, in an aqueous solution containing 10 mg of hinokitiol, 1.5 g of pyrogallol, 2.5 g of copper (II) sulfate ⁇ pentahydrate, 4 mg of the polyphenol oxidation catalyst described in Reference Example 1 in 200 ml of water Then, various drugs were added, and the pH was adjusted to 8.2 with 2N Na ⁇ H to prepare an antibiotic solution. Next, using the prepared aqueous antibiotic solution, the same impregnation treatment, leaching treatment and hinokitiol residual ratio as in Example 1 were performed. Some of the wood pieces subjected to the same impregnation and leaching treatments were subjected to the same preservative test (measurement of the weight loss rate of the wood pieces) as in Example 1.
  • Example 1 Using a crushed piece of commercially available perforated brick (about 9 cm x about 5 cm x about 3 cm), add 1 Oml of Agent A, Agent H, or Agent V described in Example 1 or 4, One of them (approximately 9 to 111 pieces was applied to about 5 (: 111). Next, the brick pieces were placed in a constant temperature room at 28 ° C for 5 days, and were dried and reacted. The leaching operation was performed by adding 50 Oml of water and immersing in still water for 5 hours, and the water (leaching solution) after the leaching operation was analyzed using HP LC in the same manner as in Example 1.
  • agent A Using agent A, agent H, agent U, or agent V prepared in Example 1, 3 or 4, on a piece of cedar wood (1 cm x 1 cm x 2 cm, 1 cm x 1 cm on the wood front, sapwood) The same impregnation, drying and reaction as in Example 1 were performed. Then, add 3 Oml of water to each piece of wood, stir the water using a magnetic mixer with the piece of wood submerged under the water, and stir for 8 hours at 25 ⁇ 3 ° C. The leaching operation of removing the wood chips and drying in a dryer at 60 ° C for 16 hours was repeatedly performed, and a total of 10 leaching operations were performed.
  • Hinokitiol (10 mg), pyrogallol (1.5 g), copper sulfate (II) ⁇ pentahydrate (2.5 g), and anhydrous sodium carbonate (2.9 g) were thoroughly mixed in a mortar. Further, 4 mg of the polyphenol oxidation catalyst described in Reference Example 1 was added thereto and mixed well to obtain a powdery treating agent. Next, after keeping this powdery treatment agent sealed in a glass container for 2 weeks at 40 ° C, 4 g of the powder was dissolved in 11 Oml of ion-exchanged water and used for wood treatment. Was prepared. Using this solution, the same impregnation treatment, leaching treatment and residual hinokitiol measurement as in Example 1 were performed.
  • the hinokitiol-containing articles having improved usefulness such as antibacterial properties which are effective for long-term, are improved in terms of the volatility, volatility or leaching property of hinokitiol.
  • the treatment method of the present invention is particularly effective in imparting useful effects such as antibiotic properties to porous articles such as wood.
  • the processing temperature can be increased to shorten the processing time.

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  • Agronomy & Crop Science (AREA)
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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne des préparations antibiotiques, destinées à conférer des propriétés antibiotiques à des articles renfermant des composés au phénol et au hinokitiol, et/ou des composés d'amines aromatiques. L'invention concerne également un procédé de traitement de ces articles, ce procédé consistant à appliquer lesdites préparations antibiotiques sur ces articles, par exemple des matériaux poreux, et/ou à imprégner ces articles de ces préparations antibiotiques, afin d'obtenir une réaction d'oxydation et/ou une réaction provoquant une hausse de la masse moléculaire. L'invention concerne enfin les produits aux propriétés antibiotiques obtenus grâce à un tel traitement, ainsi qu'un procédé de fabrication de ces produits. Cette invention permet donc de fixer efficacement le hinokitiol et de fabriquer des matériaux poreux présentant une excellente capacité de rétention du hinokitiol.
PCT/JP1998/003759 1997-09-16 1998-08-25 Preparations antibiotiques et leur utilisation WO1999013716A1 (fr)

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AU87501/98A AU8750198A (en) 1997-09-16 1998-08-25 Antibiotic preparations and use of the same

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JP9/250971 1997-09-16

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JP2010534675A (ja) * 2007-07-24 2010-11-11 マローネ バイオ イノベーションズ，インコーポレイテッド 植物除草剤としてのヒノキチオール
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KR101167069B1 (ko) * 2010-01-14 2012-07-27 전진바이오팜 주식회사 천연물질로 이루어진 야생동물 기피제 조성물

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JPH0347118A (ja) * 1989-04-14 1991-02-28 Sangi:Kk ハイドロキシアパタイト抗菌剤及びその製造法
JPH09175916A (ja) * 1995-12-25 1997-07-08 Mitsubishi Gas Chem Co Inc 木材防腐剤

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006111599A (ja) * 2004-10-18 2006-04-27 Kansai Paint Co Ltd 防腐剤
JP2006111600A (ja) * 2004-10-18 2006-04-27 Kansai Paint Co Ltd 防蟻剤
JP2010534675A (ja) * 2007-07-24 2010-11-11 マローネ バイオ イノベーションズ，インコーポレイテッド 植物除草剤としてのヒノキチオール
KR101167068B1 (ko) * 2009-11-27 2012-07-27 전진바이오팜 주식회사 설치류 기피제 조성물
KR101167069B1 (ko) * 2010-01-14 2012-07-27 전진바이오팜 주식회사 천연물질로 이루어진 야생동물 기피제 조성물

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