WO1999013716A1 - Antibiotic preparations and use of the same - Google Patents

Abstract

Antibiotic preparations for imparting antibiotic properties to articles, which contain hinokitiol and phenol compounds and/or aromatic amine compounds; a method for processing articles which comprises applying the antibiotic preparations onto the articles such as porous ones and/or impregnating the articles therewith to effect an oxidation reaction and/or a reaction of elevating the molecular weight; resultant processed products having antibiotic properties thus imparted; and a process for producing the same. Thus, hinokitiol can be efficiently fixed and processed porous articles excellent in the capability of sustaining hinokitiol can be obtained.

Description

 Description Antibiotics and their uses

 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

Conventionally, hinokitiol has been used in various treatment agents that utilize antibiotics such as antibacterial, antiseptic, bactericidal, insect repellent, insecticidal, antiviral, and biorepellent properties. However, because 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. Although 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. It has been desired to suppress the odor by increasing the fixing property of hinokitiol. In order to suppress odor, a method of including in cyclodextrin and a method of converting it into an esterified derivative have been conventionally carried out. However, development of a simpler method of suppressing odor of hinokitiol has been desired. Conventionally, hinokitiol and metal salts or complexes are sterilized, antibacterial, and antibacterial. A method utilizing a compound having an antibiotic property such as viral property is disclosed in

6-279271, JP-A-7-53369 (U.S. Patent No. 5,696,169), JP-A-7-69873, JP-A-7-138155 (European Patent 728,478), No. 173053 and JP-A-8-259439. These prior arts show that hinokitiol is capable of suppressing sublimation, suppressing metal corrosion, increasing antibiotic properties, and improving ultraviolet stability. However, when these prior art drugs are used as treating agents for imparting long-term antibiotic properties, a stronger hinokitiol-fixing ability is required. In particular, when treating articles such as wood that are difficult to impregnate with a treating agent solution, in order to impregnate a sufficient amount of treating agent, 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. Further, after the impregnation treatment of the article, it is desired that 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. .

 In addition, when a drug prepared by a method of forming a salt or complex of hinokitiol and a metal using a metal having toxicity to living organisms is used for article treatment, and when the treated article is used in a living environment, Although effective antibiotic properties due to toxicity can be expected, there is a risk that harmful metals will elute due to the adhesion of water and contaminate the living environment. Therefore, higher metal fixation properties have been sought for drugs containing salts or complexes of hinokitiol and metals.

 In addition, when a salt or complex of hinokitiol and a metal is used, problems such as toxicity and coloring of the metal ion and precipitation of the metal salt remain. It has been desired to develop a method for fixing hinokitiol that does not use a coloring or toxic metal salt.

Conventionally, 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. However, since 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.

 In addition, various chemicals are used as wood preservatives to improve the antibiotic properties of wood against rot fungi and termites.However, the injected chemicals are leached out by rainwater, etc. It is difficult to apply the compound, or there is concern about the use of highly toxic compounds and their leaching, which may cause environmental problems and affect the human body.They have low leaching properties and long-term wood preservation effects. There was a need for a wood treatment method that is easy to handle and that is safe for the environment and the human body. In addition, for the purpose of suppressing volatile organic compounds and simplifying the treatment equipment, a treatment method using a water-soluble drug is particularly useful, but the conventional water-soluble drug does not have sufficient fixation of a medicinal component. Therefore, development of a wood preservative that is a water-soluble drug and has excellent sticking properties has been desired.

 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). However, in the method using an enzyme, the processing temperature for oxidation and / or polymerization is limited, and it takes time to complete the reaction. For this reason, there has been a demand for a method for shortening the processing time of a porous article or the like. Purpose of the invention

 Accordingly, 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. Summary of the Invention

 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. As a result, using 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.

 That is, 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, 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.

 That is, the present invention provides the following antibiotics, an article processing method using the same, and a method for producing a processed product.

 (1) An antibiotic, comprising hinokitiol, a phenolic compound and a Z or aromatic amine compound.

(2) The phenolic compound and the Z or aromatic amine compound undergo a oxidation reaction and / or a high molecular weight reaction to form a conjugate with hinokitiol. Or the compound forming a complex.

(3) The antibiotic agent according to (2) above, wherein the phenolic compound and the Z or aromatic amine compound are low molecular weight compounds that are oxidized and / or polymerized at a temperature of 0 to 200 ° C. under oxidizing conditions.

(4) The antibiotic agent according to the above (3), wherein the low molecular weight compound is at least one compound selected from pyrogallol, pyrocatechol, hydroquinone, gallic acid or tannic acid, or a derivative thereof.

 (5) The antibiotic agent according to the above item 2, wherein the phenolic compound and the Z or aromatic amine compound are compounds that are oxidized and / or increased in molecular weight in the presence of a polyphenol oxidation catalyst.

 (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 antibiotic agent according to the above 5, which is a compound.

(7) The antibiotic agent according to the above (6), wherein the lignin derivative is ligninsulfonic acid or ligninsulfonic acid salt.

 (8) The antibiotic agent according to any one of the above (5) to (7), comprising a polyphenol oxidation catalyst.

 (9) The antibiotic agent according to the above (8), wherein the polyphenol oxidation catalyst is potassium hydroxide, laccase, polyphenoloxidase, ascorbate oxidase, bilirubinoxidase, or peroxidase.

 (10) The antibiotic agent according to any one of the above (1) to (9), further comprising a metal compound.

(1 1) 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. The antibiotic agent according to the above 10, which is a compound containing the metal element of the above.

 (12) The antibiotic agent according to any one of (1) to (11) above, further comprising a boron compound.

 (13) The antibiotic agent according to the above (12), wherein the boron compound is a borate. (14) It further contains at least one agent selected from fragrances, deodorants, fire retardants, flame retardants, antibacterials, preservatives, bactericides, insect repellents, antivirals, and biological repellents 14. The antibiotic agent according to any one of 1 to 13 above.

 (15) The antibiotic agent according to any one of the above (1) to (14), which is a high-concentration solution, powder or granule.

 (16) 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.

 (17) The article processing method according to (16), wherein the article is a porous article.

 (18) Porous articles made of sintered metal, manufactured products, alloys, die-cast products, ceramics, bricks, concrete, wood, wood chips, wood flour, wood products, fir, lancho, straw, bamboo, charcoal, fiber, 18. The article processing method according to the above item 17, wherein the article is a processed fiber product or a synthetic resin foam.

(19) The article processing method according to any of the above (16) to (18), comprising a step of holding the article under reduced pressure before impregnation and / or pressurizing the article during impregnation to promote the impregnation of the solution into the article. .

(20) The article processing method as described in (19) above, wherein the pressurization is performed at 1 to 20 atm.

(21) The article treating method according to any one of the above (16) to (20), further comprising a step of performing an oxidation reaction and / or a high molecular weight reaction of the applied or impregnated antibiotic.

(22) Accelerate oxidation reaction and no- or high-molecular-weight reaction by heating 23. The article processing method according to any one of the above 16 to 21.

(23) The article processing method according to any one of the above (16) to (22), wherein the oxidation reaction and / or the high-molecular-weight reaction are accelerated by a polyphenol oxidation catalyst.

(24) An article obtained by the processing method according to any one of (16) to (23).

 (25) A method for producing a treated article, comprising a treatment step according to any one of the above items (16) to (23).

(26) 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.

 (27) Antibiotics containing hinokitiol are applied to porous articles and

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.

(28) The process for producing a treated porous article according to the above (26) or (27), wherein the oxidation reaction and / or the high-molecular-weight reaction are performed using a polyphenol oxidation catalyst.

(29) The porous article according to the above item 28, wherein the polyphenol oxidation catalyst is potassium hydroxide, laccase, polyphenoloxidase, ascorbate oxidase, bilirubinoxidase, or peroxidase. Manufacturing method of processed material.

(30) A method for producing a treated porous article, wherein the antibiotic according to any one of the above (26) to (29) contains a metal compound.

(31) 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 porous article treatment according to the item 30, which is a compound containing at least one metal element selected from barium. Method of manufacturing a product.

 (32) The method according to any one of the above (26) to (31), wherein the porous article is a plant-derived porous article.

 (33) The above-mentioned item (32), wherein the plant-derived porous article is wood, a piece of wood, wood flour, a processed wood product, a fir, a rush, a straw, a bamboo material, a plant fiber, or a processed plant fiber product. Manufacturing method.

 (34) A processed article obtained by the production method according to any one of (25) to (33). Detailed description

 Hereinafter, the present invention will be described in detail.

 [Hinokitiol]

 The hinokitiol used in the present invention has the following formula:

で示される構造を有する化合物であり、 フエノール性化合物および/また は芳香族ァミン化合物とともに、 または、 さらにポリフエノール酸化触媒 とともに用いて酸化および/または高分子量化することにより、 被処理物 に高収率で固定させることが可能であることが確認された。 なお、 ここで 高分子量化とは、 前記フエノ一ル性化合物および Zもしくは芳香族ァミン 化合物の酸化体もしくはラジカル体の結合による二量体以上の重合体の形 成の他に、 これらの物質に対するヒノキチオールもしくはヒノキチオール の酸化体との付加反応物の形成、 あるいはこれらの物質の金属を介しての 錯体形成等による分子量の増加を含む。 ヒノキチオールは、 天然材料、 例えば、 ヒノキやヒバ等の樹木から慣用 の方法により抽出し、 結晶として得ることができるが、 他の天然物から誘 導したり、 合成品を用いてもよい。

A compound having a structure represented by the formula: oxidized and / or increased in molecular weight with a phenolic compound and / or an aromatic amine compound or further with a polyphenol oxidation catalyst to obtain a high yield on a treatment object. It was confirmed that it was possible to fix at a rate. Here, 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. However, hinokitiol may be derived from another natural product or a synthetic product may be used.

 Although 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 compound and aromatic amine compound]

 In the present invention, 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. In particular, 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. Further, 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. In the present specification, 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. Specific examples include 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, Hesperidin, Chlorogen Acid, hinokitiol, pyrocatechol, hydroquinone, tert-butylhydroquinone, phenylhydroquinone, trimethylhydroquinone, pyrogallol, lauryl gallate, octyl gallate, 3,4-dihydroxybenzoic acid, 1,2-dihydroxynaphthalene, 2,3-dihydroxy Naphthylene, 6,7-dihydroxy-12-naphthalenesulfonic acid, anthralobin, alizarin, quinizarin, o-phenylenediamine, p-phenylenediamine, 3,4 diaminobenzophenone, o_anisidine, p-anisidine, o-aminophenol, p-aminophenol, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone and other compounds This is a compound derived from

 All of these compounds can be used together with the enzymes described below.Especially, 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. In addition, lignin or a derivative thereof requires a catalyst, but can be particularly preferably used for the purpose of the present invention.

As the lignin derivative, ligninsulfonic acid or ligninsulfonate obtained from the pulp industry can be particularly preferably used. When 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. In particular, when impregnating wood by pressurization and / or depressurization, in order to increase the amount of impregnation of the processing solution into the wood, the water-insoluble solid component removal treatment must be performed. It is desirable to carry out by centrifugation, filtration, or standing. For example, when pressure injection treatment is performed for the production of preservative wood for base, 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. Lignin or lignin or lignin sulfonic acid derivative hydrolyzed, or lignin sulfonic acid partially desulfonated It is possible. Also, a mixture of these can be used. In addition, 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. Alternatively, 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.

In addition to these compounds, 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-dihydroxypyridin, methyl_4-hydroxy-3-methoxybenzoic acid, 4,5- Diamino 6-hydroxy-2-mercaptopyrimidine, 2,3-diaminopyridine, 2,5-dihydroxy 1,4-benzoquinone, 2,5-dihydroxybenzoic acid, 3,4-dihydroxy_3-cyclobutene-1,2-dione, 3- (3,4-dihydroxyphenyl) 1-L-alanine, 2- Amino — 3-hydroxypyridine, 3-amino-1-methoxydibenzofuran, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, 2 ', 5'-dimethoxyacetof Enone, 3 ', 4'-dimethoxyacetophenone, 1,4-dimethoxybenzene, verato-mouth, 2,3-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, veratolic acid, veratraldehyde, veratrylamine , Homoberatoric acid, Homoberatorilamine, Homoberatoronitrile, 3,4-Dimethoxycinnamic acid, 3,4-Dimethoxycinnamonitrile, 2,3-Dimethoxyphenol, 3,4-dimethoxyphenol, 3,4-dimethoxybenzyl alcohol, 3,4-dimethoxyphenethylamine, 3,4-dimethoxystyrene, (3,4-dimethoxyphenyl) acetic acid, (3,4-dimethoxy) Phenyl) acetonitrile, (3,4-dimethoxyphenyl) acetone, 3- (3,4-dimethoxyphenyl) propionic acid, 3- (3,4-dimethoxyphenyl) propanol, 4- (3,4— Dimethoxyphenyl) butyric acid, 3- (3,4-dimethoxyphenyl) propanol, 2-methoxy-1- 4-methyl Rufenol, 2-methoxy-5-methylaniline, 2-methoxy-5-nitroaniline, 4-methoxy-2-nitronitroaniline, 3-methoxysalicylic acid, acetylsalicylic acid, methyl salicylate, methyl ethyl salicylate, 3 — Methylcatechol, 4-methylcatechol, methylgallate, propylgallate, 3,4,5-trimethoxyaniline, 3,4,5-trimethoxyphenol, trobolone, purprogalin, salicylaldoxime, 3-amino-5, 6,7,8-tetrahydro-12-naphthol, 1,5-dihydroxynaphthylene, 3,5-dihydroxy-12-naphthoic acid, 4-hydroxy_1-naphthalenesulfonic acid, purpurin, 2, 3-dihydro-9,10-dihydroxy-1,4-anthracenedione, various azo dyes, and their compounds Which is a derivative. The concentration of these compounds used in the present invention in the liquid at the time of article treatment is 0.0001 to 80% by weight, preferably 0.001 to 20% by weight.

Further, when the phenolic compound and / or the aromatic amine compound is subjected to oxidation treatment and Z or high molecular weight treatment according to the present invention, a quinone compound which is oxidized and Z or polymerized by the same reaction route is allowed to coexist. Can also. Examples of such quinone compounds are: 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 α-ascorbic acid, 2-hydroxy-1,4-naphthoquinone, isatin, 5-12 troisatin, various types Anthraquinone dye. In addition, unsaturated fatty acids such as oleic acid and linoleic acid, unsaturated alcohols such as oleyl alcohol, unsaturated alkyls such as squalene, and auto-oxidizing substances such as tung oil and linseed oil are used. It is also possible to carry out air oxidation and polymerization together with a phenolic compound and a Ζ or aromatic amine compound. In the liquid at the time of article processing of these compounds used in the present invention The concentration is from 0.0001 to 80% by weight, preferably from 0.001 to 20% by weight. In addition, for the purpose of adjusting the physical properties, color tone, hinokitiol fixation property, and the like of the oxidation reaction product and Z or the reaction product for increasing the molecular weight, a plurality of the compounds described above can be used in combination.

 [Metal compound]

 In the present invention, 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_,

C 1 _, Br 1, factory, N 0 _3- , B 0 ₃ ³ _, P 0 ₄ ^{3 _} , P ₂ 0 ₇ ⁴ ", S〇 ₄ ^2- , S〇 ₃ ² —, SC N_, C〇 ₃ ^2_, 〇 ^2_, 〇_H_, B ₄ 0 ₇ ^2_, B (〇_H) ₄ one, BF ₄ ^_, or naphthenic acid, Orein acid, stearic acid, octanoic acid, sebacic acid, acetic acid, formic acid, benzoic acid Examples of such compounds include compounds with anionic acids, such as, for example, organic acids, complexes thereof, and hydrates.Antibiotics by pressurizing and Z or depressurizing porous articles such as wood When the agent is impregnated, it is desirable to use a combination of a metal compound and a phenolic compound and / or an aromatic amine compound that do not generate a water-insoluble component in the treating agent. 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.

Further, a complex of the above-mentioned metal element cationized with an organic compound or an ionic group can be used. As the organic compound added to form a complex with a metal, many conventionally known compounds can be used. For example, pyrocatechol, gallic acid, catechin, pyrogallol, o_phenylenediamine, 2- 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 α-methylphosphonosuccinic acid Amino acids or amino acids such as carboxylic acid, aspartic acid, glutamic acid, glycine, and 2-aminoisobutyric acid Polyacids such as amino acid analogs, aminopolyacetic acid such as nitric triacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid; polyacrylic acid, polyitaconic acid, polymaleic acid, maleic anhydride copolymer, and carboxymethylcellulose; Non-dissociated polymers such as polyethylene glycol, polyethylene oxide, and polyvinyl alcohol; benzenepolycarboxylic acid, oxalic acid, malic acid, diglycolic acid, succinic acid, oxydisuccinic acid, and propyloxymethyloxysuccinic acid; Organic acids such as dalconic acid, cunic acid, lactic acid, tartaric acid, etc., sucrose, lactose, carboxymethylated compounds such as pentaerythritol, ethylenediamine, ethanolamine, jetanolamine, triethanolamine, Ν —Methylje Yuno Organic alkaline agents such as luamine, polyethyleneethylamine, triethylenetetramine, propanolamine, pentaethylenehexamine, polyethyleneimine, triisopropanolamine, triazacyclononane, triazacyclododecane, starch, Organic compounds such as urea, chitosan, and polylysine can be mentioned. Further, the above-mentioned metal compound or metal fine powder can also be used for the purpose of the present invention. For such fine powders, 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. For example, in the case of zirconium, copper, zinc, or aluminum, it is usually 0.01 mM to 2.5M, preferably 0.1 LMM to 0.5M.

 [Polyphenol oxidation catalyst]

 In the antibiotic of the present invention, 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. Examples of such a polyphenol oxidation catalyst include metal ions, metal complexes, and natural enzymes.

Among the metal complexes, artificial enzymes that mimic oxidoreductases are useful for obtaining effective catalytic effects with lower concentrations of metal ions. Specific examples of such 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. In addition, 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. Examples of oxidases that can generate such hydrogen peroxide include glucose oxidase, alcohol oxidase, glycerol oxidase, amine oxidase, amino acid oxidase, and D-amino acid oxidase. , Aryl alcohol oxidase, aldehyde oxidase, galactose oxidase, sorbose oxidase, peroxidase, xanthine oxidase, cholesterol oxidase, etc., and glucose oxidase is particularly preferred. It is alcoholic alcohol.

 Examples of 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, Rhizoctonia praticola) , Rhizoctonia solani, Trichoderma 'Resii', Tricoderma viride, f-Sulomyces' Arthromyces ramosus', Hyumicora 'sol solis sulens, Humicolica insulens Verticillum dahlie), Verticillum 'Varopoatrum Verticill who alboatrum), Perocladium' Calyreta rem Ulocladium chartarum, Cardariomyces' Fumago Caldariomyces fumago, Stilla var. 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. Among them, particularly preferred is 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. Or transferred to the International Depository under the International Depository No.-5520.) Or 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. Other preferred fungi include Pleotus tus Ple tus), Lentinas Lenti, SchizophyUuin, Almiliariella Armillariella, Flamlulina (Flammulina), Agaricus Agaricus), Kosana, belonging to the basidiomycete subclass Basidiomycotina. Phanerochaete,, Phlebia, Phlebia, Hygrophoropsis, Lentites, ^ Melanoleic iMelanoleuca, Pholiota Pholiota, Stereumi Stereumii), Polyporus Pofyporus, Microporus, Microporus, Polyporus, Microporus Pycnoporus, Pycnoporus, Corlybi), Trametes, Trametes, Coriolus, Daedaleopsis, Rigidoporus, Fomes, Fomes, Gano Luma Ganode awakening,, Trachyderma, Hymenochaete), Inonosu Unonotus "), Psathyrella (Psathyrella), and among them, preferably Peloirotus" Evening Pleurotus osteratus), Lenti eggplant, Lenti dish edodes), Schizophyllum 'communes (Schizophyllum commune), Almira Riella' Melea ArmiUarieIla mellea), Flamlulina veltis Flammulina velutipes), Sword Rika's' Hisporus Agaricus bisporus), Cophrinas comas tau (Coprinus cinereus), Coprinus, Congregatus

(Coprinus congregatus), Coff Unas plicatiis), Coprinus macrorhizus, Phanerochaete chrysosporium, Flebia radia radi h ata ata ata ata ata (ata) Tia sword (Hygrophoropsis aurantiaca), Lentias' Hellina

(Lenzites betulina), Melano Roy's' Me noleuca verrucipes), Folio Evening 'Nameko PhoHota nameko), Sterewam' Hirstum (Stereu thigh hirsutum), Polyporus squamosas

(Polyporus squamosus), small and small hus pinontas, Polyporus pinsitus), Polyporellus 'Podius Polyporellus badius), Crucibulum laeve (Crucibulum laeve), Microporus' Flavelli folliformis)

(Fomitopsis pmicola), Pycnos fuscus' Conneus (Pycnoporus coccineus), Kolybia aselvata Collybia acervata, Kolybia maquila evening (Collybia maculata), Trametes orientalis

(Trametes onentalis), Tofume r ス s 'Norosa (Trametes villosa), Coriolus versicolor, Coriolus versicolor), Coriolus' Hills suis (Coriolus hirsutus), Dedalepsis

, Daedaleopsis tricolor), Lintidophorus zonalis, Fomes 'Fomes fomentarius, Ganoderma lucidum), Trachiderma'

(Trachyderma tsunodae), Hime no Kaete 'Rubiginosa

(Hymenochaete rubiginosa), Inonotus, Inonotus ikadoi), Psathyrella. Psathyrella multissima), and a strain belonging to Psathyrella piluliformis).

 Other preferred fungi other than the phylum Incomplete Mycota and the Basidiomycota include Podosbora Podospora and Neurospora belonging to Ascomycotina.

(Neurospora), monosilium (Moiwcillium), Fusarium (Fusarium), zygomycetes (Zygomycotina) belonging to Mucor (Mucor), Rhizopus (Mhizopus, preferably Podosbora 'Anselina, Podospora ansenna) 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.

 Other preferred bacteria are Bacillus alcalophilus, Bacillus amyloliquefaciens, Bacillus brevis, Bacillus firmus, Bacillus licheniformis

(Bacillus licheniformis), Non narus' Sonanaris Bacillus subtihs), Bacillus natto B _ac m _us natto), 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.

 In order to obtain a DNA fragment encoding the enzyme protein of the present invention, 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.

 In addition, as 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. . In addition, it is desirable to add 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. .

 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. When 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.

 With respect to the activity of the polyphenol oxidation catalyst, when the activity of oxidizing 1 zmol of the phenolic compound and the Z or aromatic amine compound per minute is defined as 1 unit (hereinafter abbreviated as U), the present invention relates to: When the polyphenol oxidation catalyst is used for treating articles, the oxidation activity concentration of the polyphenol oxidation catalyst is 1 to 100,000 U /, preferably 10 to 5, ooouzrc.

 [Boron-containing compound]

In the present invention, 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. Of 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. The concentration of such a boron-containing 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 50% by weight.

 [Porous articles]

 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. In the impregnating treatment, a favorable effect of increasing the amount of the treatment agent fixed inside the article can be obtained. Examples of such 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. In particular, when 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, Since 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

 [Other drugs]

 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.

Examples of such agents are plant-derived extracts, extracted components, or compounds having a structure equivalent to that of plant-extracted components. Specifically, 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. Specific examples of plant-derived extracts or compounds having a structure equivalent to that of plant extracts include tropolones such as] 3-drabulin, α-binene, β-pinene, camphor, menthol, limonene, Monoterpenes such as porneol, α-terpinene, terbinene, terpineol, terpinene-41-ol, cineole, sesquiterpenes such as α-casino and t-murol, catechin, tannin, etc. Polyphenols, naphthalene derivatives such as 2,3,5-trimethylnaphthalene, long-chain aliphatic alcohols such as citronellol, and aldehydes such as cinnamaldehyde, citral, and perilla aldehyde. Wood vinegar obtained by steaming trees can also be used. By adding these natural compounds as medicines and using 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.

Other 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. Specific examples of such compounds include o-phenylphenol, 1-naphthol, 2-naphthol-o-chlorophenol, 2,4-dinitrophenol, 4,6-dinitro-o-cresol, and pentachlorophenol. Enol, 2,3,5_Trichloro mouth phenol, 2,4,6-Tricyclo mouth phenol, Monochloronaphthalene, Triclo mouth naphthalene, Tetraclo mouth naphthylene, 2,4,5-Triclo mouth phenyllaurate Monochrome mouth naf Yuren, chloronitrophenol, chloronitrotolue Benzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 2,4,6-tribromophenol, 4-bromo-2,5-dichlorophenol , Bromo-o-phenylphenate, 4-chlorophenyl-3_-proppropylformal, creosote oil, chlorinated terpene, p-hydroxybenzoic acid, p-hydroxybenzoic acid methyl, ethyl, Esters such as propyl, butylhydroxyanisole, butylhydroxytoluenebutyl, isoptyl, and isopropyl. The concentration of such a compound used in the present invention in a liquid at the time of article treatment is from 0.001 to 50% by weight, preferably from 0.01 to 10% by weight.

 Other 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. By using these compounds together with the antibiotic of the present invention, it is possible to adjust physical properties such as water solubility and water repellency of the treatment liquid or treated article. The 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.

Many conventionally known flame retardants can be added to the article treating agent of the present invention. For example, 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. In particular, when ligninsulfonic acid is used as the phenolic compound or the aromatic amine compound of the present invention, 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. 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.

In addition to these agents, various commonly used fungicides, insecticides, or insect repellents can be added to the article treating agent of the present invention for use. Specific examples of 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, fluconazole, triconazole derivatives such as fluconazole 'cis, ciproconazole, di Sulfonamides such as lorofluanid (epalene), trifluanid (methyl repalene), cyclofluanide, folpet, fluorofluorpet, carbendazim, benomyl, feveryl thiazol, thiabendazol, or salts thereof Benzoimidazoles, thiocyanonemethylthiobenzothiazole, thiocyanates such as methylenebisthiocyanate, C11-C14-14-alkyl-2,6-dimethylmorpholine homologs (tridemorph), (Earth) —cis—4— [3- (t_butylphenyl) _2-methylpropyl porphyr] 1,2,6-dimethylmorpholine (fenpropimorph, farimo Morpholine derivatives, such as 3-fluoro-2-propyl-1-n-butyl carbamate, 3-propyl 2-n-propyl-n-hexylcarbamate, 3--1-r-Δ-norohillirenk j Rireno main Ichiboku, 3- ® ¹ ~~ - 2 - Puropirufue two le carbamate, p- black port phenyl one 3-tio one Dopuro Pagiruhorumaru, 3 _ bromo _ 2, 3 _ job one de _ 2- Pro Organic compounds such as penylethyl carbonate (Sampras), 1-[(jodomethyl) sulfonyl] _4-methylbenzene (Amical), organic bromo derivatives such as bronopol, N_methylisothiazoline_3-one, 5-chloro-N-methylisothiazoline-3-one, 4,5-dichloro-N-octylisothiazoline-3-one, N-octylisothiazoline-3-one (octylinone Isothiazolines such as cyclopentene isothiazoline, etc., 1-hydroxy-12-pyridinethione (or its sodium salt, iron salt, manganese salt, zinc salt, etc.), tetrachloro-4-methylsulfonyl Pyridines such as pyridine, sodium or zinc salts of dialkyldithiocarbamates, dialkyldithiolbamates such as tetramethyldiuramdisulfide (TMT D), 2,4,5,6-tetrachloroisophthalonitrile Microbial agents having an active halogen atom, such as nitriles such as Cl_Ac, MCA, Tecuma, Bronopol, and Blumidox, benzothiazoles such as 2-mercaptobenzothiazoles and dazomet Kind, chlordane, dill-drin, aldrin, hep Cyclogens such as chlor; nitrosos such as N-ditroso-N-cyclohexylhydroxylamine; quinolines such as 8-hydroxyquinoline; benzyl alcohol mono (poly) hemifolmar, oxazolidine, hexahydro-s— Formaldehyde-generating substances such as triazine, N-methylol chloroacetamide, tris_N- (cyclohexyldiazenidiomdoxine) tributyltin or potassium salt, bis- (N-cyclohexyl) diazideゥ Moudioxin copper or aluminum. Also, insecticides usable in the present invention Specific examples of chemicals, insecticidal components, insect repellents, or insect repellents 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, BPMC, 2- (1-methylpropyl) phenylmethylcarbamate , Butacarboxime, butoxycarpoxime, levulinyl, carbafuran, carbosulfan, cloetocarb, isoprocarb, methomyl, oxamil, pirimicarb, promecarb, propoxul, thidicarb, bigon, dimethylene, sevin, etc. , Bioresmethrin, cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, α-cyano-3-phenyl-2-meth 1,2-benzyl-2-methyl-2- (2-chloro-2-trifluoromethylvinyl) cyclopropane _ 1 _propane carboxylate, fenpropatrine, fenfluthrin, fenvalerate, flucitrinate, flumutrin, fluvaline Pyrethroids such as permethrin, permethrin, etofenprox, and resmethrin; 1— (6_black mouth—3-pyridinyl—methyl) -1,4,5-dihydro ——— nitro-1 一 —imidazole—2— Ditrominos such as amide (imidacloprid) and nitromethylenes.

Insect hormone or IGR (insect growth regulator) and its induction 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. Further, in the present invention, drug fixation, adjustment of sustained release, and for the purpose of improving antibiotic properties, may be used by adding a quaternary Anmoniumu compound treating agent, specifically, C _n H _{2n +1} (n = l-22), C _n H _2n —! a quaternary ammonium having a hydrocarbon represented by (n = 2 to 22), C _n H _2n - ₃ (n = 4 to 22) or C _n H _2n — ₅ (n = 6 to 22) as a substituent, Quaternary ammonium containing an aromatic compound as a substituent, quaternary ammonium containing a hydrophilic polymer as a substituent, or a hydrochloride, sulfate, carbonate, phosphate or borate thereof. . Conventionally used DDAC (didecyldimethylammonium chloride) can also be used, but those having an unsaturated structure moiety in the substituent are particularly desirable. The 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.

 In addition, 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.

Further, the antibiotics of the present invention or the compounds used in addition thereto 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, α- Aliphatic sulfonates such as olefins, vinylidene-type olefins, and internal olefins; aromatic sulfonates such as linear or branched alkylbenzene sulfonates; linear or branched alkyl sulfonates; Having a kill group or an alkenyl group, ethylene oxide, Alkyl or alkenyl ether carboxylate or amide, α-sulfo fatty acid salt or ester, amino acid type surfactant, alkyl or alkenyl acid phosphoric acid to which propylene oxide or butylene oxide is added alone or in combination. 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. In addition, many conventionally known dispersants can be used, and particularly, 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. If 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.

 Further, if necessary, 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.

 [Formulation]

 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.Specifically, granulation and extrusion Granulation, fluidized granulation, centrifugal fluidized granulation and the like can be achieved by any granulation operation according to the purpose. In this case, in order to improve the storage stability of the polyphenol oxidation catalyst in the treating agent, it is effective to granulate the catalyst together with the stabilizer separately from other treating agent components. Further, 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. In this case, in order to prevent the treatment agent composition from being oxidized before use, it is desirable to seal the container containing the treatment agent during storage of the treatment agent to avoid contact with the outside air. Further, it is more desirable to suppress the oxidation by using nitrogen gas or inert gas or degassing during the production of the treating agent. When the antibiotic of the present invention is prepared, 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.

 [Processing method]

When processing articles using the antibiotics of the present invention, brushes, rollers, etc. Application, spraying, spraying with an aerosol, etc., or impregnation is performed. In particular, in the impregnation operation, 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 In the case of 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.

In addition, after the treatment liquid is impregnated into 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. Before proceeding, 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. In addition, 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. When 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. Also, 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. In addition, after such treatment, 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.

At this time, a method of applying pressure to the processed product to suppress volatilization of hinokitiol, and applying physical pressure to the processed product to adhere the structure of the porous article to the strength Also, a method of improving hinokitiol retention is also useful. Oxidation treatment and

During the Z or high molecular weight treatment, and after the completion of the oxidation reaction and the Z or high molecular weight reaction, 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. In addition, by performing 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. When 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. However, when 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.

 [Other]

 When the antibiotic of the present invention containing a phenolic compound and / or an aromatic amine compound is used in the field of building materials, 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.

In order to further increase the effects of the oxidation reaction and the Z or high molecular weight reaction in the porous article, 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.

 In addition, by suppressing the oxidation reaction and the Z or high molecular weight reaction in the antibiotic before treatment, 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. In particular, if a substance such as lignin or flaponoid that can act as a catalyst having a polyphenol oxidizing action already exists and is immobilized in the porous article, it becomes phenolic by the catalytic action in the porous article. As a result of reacting with the compound and / or the aromatic amine compound, and further with hinokitiol to increase the molecular weight, the hinokitiol and the phenolic compound and / or the aromatic amine compound are more firmly immobilized in the porous article. Therefore, the present invention is extremely useful.

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. Moreover, positive Rifueno Ichiru oxidation catalyst, the case is an enzyme having Porifueno Ichiru _{oxidation, N a OH, NH 3,} N a 2 C_〇 _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.

Also, in many treatment methods conventionally performed, and in which leaching of the treatment agent component is a problem, treatment using the antibiotic of the present invention as post-treatment, pre-treatment, or simultaneous treatment of such treatment By carrying out the above, it is possible to enhance the fixability of easily leached components contained in the conventional treating agent. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, typical examples of the present invention will be shown and described in more detail. However, these are merely examples, and the present invention is not limited to these. In the following examples,% represents% by weight unless otherwise specified.

 In the present invention, 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. Alternatively, 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. Then, the activity of oxidizing 1 / mo 1 of syringaldazine per minute was defined as 1 unit (hereinafter abbreviated as U). Reference Example 1: Acquisition of polyphenol oxidase

To obtain the enzyme used as Porifueno Ichiru oxidation catalyst, 0.5% Dar courses and 0. 1% N a N_〇 _{3, 1. 34% N a 2} HPO 4 '1 2 H 2 〇, 0.3% KH ₂ P0 _{4, 0.1% N a C 1} , 0.2% peptone, 20 p pm yeast _{extract, 0.01% Mg S 0 4 ·} 7 H 2 0, 0. ImM Cu S0 4 1 3 liters of medium composed of 0% N A_〇 Inoculate the culture tank containing H-added to pH 8 with Myrothecium verrucaria SD 300 1 (Accession number FERM BP-5520) and shake at 28 ° C for 3 days Culture was performed. After the cultivation, 2.5 liters of the culture broth was removed by centrifugation at 4 ° C.

Next, a portion of the culture broth was subjected to fractionation with a molecular weight of 10,000 or more using a minitan ultrafiltration system (Millipore) using Minitan 'filter packet (CAT. NO .: PTGC0MP04, manufactured by Millipore). And concentrated. This was further dialyzed against 200 ppm of NH4HCO3, and then freeze-dried to obtain a target enzyme as a crude product. Polyphenol of this enzyme preparation Oxidase activity was 1 OU / mg. Example 1: Preparation of antibiotic, impregnation, leaching, and preservative test

 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. At the final stage of the preparation, 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. Next, using the prepared aqueous solution of the antibiotic, 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.

Furthermore, the impregnated wood pieces were placed in a constant temperature room at 28 ° C for 5 days to dry and react. In order to examine the stickiness of hinokitiol, etc., on the treated wood pieces obtained in this way, first, 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. Next, in order to calculate the remaining amount of hinokitiol, 8 ml of 5 OmM EDTA was added to each leached wood piece, and the mixture was stirred for 2 hours, and then 8 ml of ethanol was added thereto. The hinokitiol inside the wood chip was extracted and recovered by stirring for 16 hours. The obtained extract was analyzed by HPLC (High Performance Liquid Chromatography) to measure the concentration of extracted hinokitiol, and the amount of hinokitiol injected in the impregnation treatment was set to 100%. The residual ratio of hinokitiol present in the tandem was calculated. In order to calculate the amount of copper remaining, 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.

Furthermore, 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. . Next, 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). . After the antibacterial operation, 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. Then, the rate of decrease in the weight of wood chips due to the action of wood rot fungi was calculated. As a result, it was shown that the treatment method of the present invention can provide effective antibacterial properties. Table 1 shows the detailed results. Antimicrobial composition residual rate (%)

 Weight loss rate Hinokiti Pyroga Polyphenols Hinokiti (%) Copper pH Copper

 All Lonole sulfuric acid

 Oxidation catalyst All

Agent A Yes No No No 8.4 20 14.1 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 Without With / Without 8. 4 92 83 1. With 4 Agent H With With With With With / Without 8.4 95 94 0.9

 Control (unprocessed wood pieces) 29.5

Example 2: Preparation of antibiotic, impregnation, leaching, and preservative test

 In the same manner as in Example 1, 10 mg of hinokitiol, 1.5 g of pyrogallol, and 4 mg of the polyphenol oxidation catalyst described in Reference Example 1 in 20 mL of water were added with various metal salts. The solution was added at a concentration of O mM, adjusted to pH 8.2 using 2NNa〇H, and an aqueous antibiotic solution was prepared.

 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. As a result, it was shown that the antibiotics of the present invention can effectively fix hinokitiol and can impart effective antibacterial properties.

The detailed results are shown in Table 2. Metal salt used Residual rate (%) Weight reduction rate

 (%) Agent I Copper hydroxide (Π) 93 ND * agent J Copper oxalate (Π) 92 ND * agent Copper borofluoride (Π) 85 ND * agent zirconium carbonate ammonium 89 2.9 agent M iron sulfate (Π) 7) Hydrate 92 ND * agent N Nickel chloride (Π) · Hexahydrate 90 1.0 agent〇 Zinc chloride 83 1.5 agent P Aluminum chloride (m) · Hexahydrate 88 2.8 agent Q Sodium aluminum sulfate · 12 Hydrate 88 3.8

ND *; not performed Example 3: Preparation of antibiotics

 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.

 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. As a result, it was shown that the antibiotics of the present invention can effectively fix hinokitiol and can impart effective antibacterial properties.

Table 3 shows these detailed results. Table 3

実施例 4 ：抗生物剤の調製、 含浸処理、 溶脱処理、 および防腐性試験

Example 4: Preparation of antibiotic, impregnation, leaching, and preservative test

 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.

 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. As a result, it was shown that the antibiotics of the present invention can effectively fix hinokitiol and can impart effective antibacterial properties.

Also, 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. As a result, when a low molecular weight phenolic compound is used (agents W to X), it is possible to maintain the hinokitiol residual ratio at a sufficient level even under the above-mentioned accelerated conditions. Indicated.

 Table 4 shows these detailed results.

 Table 4

 ND *; not performed Example 5: Preparation of antibiotics

 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〇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.

 Table 5 shows these detailed results.

ND *; not implemented Example 6: Preparation of antibiotics, impregnation, and leaching

 10 mg of hinokitiol, 1.26 g of pyrogallol, and 2.5 g of copper sulfate (II) pentahydrate are mixed in 20 Om1 of water, and the hinokitiol is completely dissolved by heating in a 50 ° C water bath and stirring well. Then, 40 U of commercially available bilirubinoxidase (a product derived from Milosecium vuelcaria, obtained from SI GMA) or polyphenoloxidase (a product derived from Rigidoboras zonalis, obtained from TAKARA) is added as a polyphenol oxidation catalyst. The pH was adjusted using 2N NaOH to prepare a treating agent aqueous solution. Next, using the prepared aqueous antibiotic solution, the same impregnation treatment, leaching treatment and hinokitiol residual ratio as in Example 1 were performed. As a result, it was shown that hinokitiol can be immobilized more effectively by the antibacterial agent of the present invention. The detailed results are shown in Table 6.

 Table 6

実施例 7 ：抗生物剤による物品処理

Example 7: Article treatment with antibiotics

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. As a result, when the agent A, the agent H, or the agent V was used, the residual ratio of hinokitiol was 33%, 95%, and 96%, respectively. It has been shown that the production of noktiol-containing articles is possible. Example 8: Article treatment with antibiotics and termite control test

 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. Next, these pieces of wood were placed together with untreated wood pieces on the soil around the nests of the termites, and after standing for 3 months, the condition of the wood pieces was observed. As a result, no damage was observed on the untreated wood pieces and the wood pieces treated with the agent A, but no damage was observed on the wood pieces treated with the agent H, the agent U, or the agent V. It was shown that termite control could be provided. Example 9: Preparation of treatment agent

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. As a result, 91% of hinokitiol remained, indicating that the powdery treating agent of the present invention allowed effective hinokitiol fixation and production of hinokitiol-containing articles. Although the cypress odor was found in the powdered treatment agent, the hinoki odor was completely confirmed in the treated solution and the processed product. Did not.

 In addition, 1 O mg of hinokitiol, 1.5 g of pyrogallol, 2.5 g of copper sulfate (Π) pentahydrate, 1.5 g of anhydrous sodium carbonate, and 0.8 g of monoethanolamine were added to ion-exchanged water. After dissolving, 4 mg of the polyphenol oxidation catalyst described in Reference Example 1 was added thereto and mixed well to obtain a solution-type concentrating agent having a total volume of 2 O ml. Next, transfer 14 ml of this treating agent to a 15 ml 1-cap screw cap test tube, leave it sealed at 40 ° C for 2 weeks, and then 10 times with ion-exchanged water. To prepare a solution for wood treatment. Using this solution, the same impregnation treatment, leaching treatment, and measurement of hinokitiol residual ratio as in Example 1 were performed. As a result, 90% of hinokitiol remained, indicating that the solution-type concentrating agent of the present invention enabled effective fixation of hinokitiol and production of hinokitiol-containing articles. Industrial applicability

 By treating the articles using the treatment agent of the present invention, 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. Further, the treatment method of the present invention is particularly effective in imparting useful effects such as antibiotic properties to porous articles such as wood. Furthermore, according to the method of the present invention, the processing temperature can be increased to shorten the processing time.

Claims

The scope of the claims 1. An antibiotic agent comprising hinokitiol, a phenolic compound and a Z or aromatic amine compound. 2. The antibiotic according to claim 1, wherein the phenolic compound and / or the aromatic amamine compound is a compound which forms a conjugate or a complex with hinokitiol through an oxidation reaction and a reaction for increasing the molecular weight. Agent. 3. Claim 2 wherein the phenolic compound and / or aromatic amine compound is a low molecular weight compound that oxidizes and Z or has a high molecular weight under the oxidation conditions at a temperature of 0 to 200 ° C. Antibiotics as described. 4. The antimicrobial agent according to claim 3, wherein the low molecular weight compound is at least one compound selected from pyrogallol, pyrocatechol, quinone hydrate, gallic acid or tannic acid or a derivative thereof. 5. The antibiotic agent according to claim 2, wherein the phenolic compound and the Z or aromatic amine compound are compounds that oxidize and / or increase the molecular weight in the presence of a polyphenol oxidation catalyst. 6. At least one compound selected from pyrogallol, pyrocatechol, hydroquinone, gallic acid, tannic acid, lignin, or a derivative thereof, wherein the compound that oxidizes and / or increases its molecular weight in the presence of a polyphenol oxidation catalyst is used. 6. The antibiotic agent according to claim 5, which is: 7. The antibiotic agent according to claim 6, wherein the lignin derivative is lignin sulfonic acid or a lignin sulfonic acid salt. 8. The antibiotic agent according to any one of claims 5 to 7, which comprises a polyphenol oxidation catalyst. 9. The antibiotic agent according to claim 8, wherein the polyphenol oxidation catalyst is potassium hydroxide, laccase, polyphenoloxidase, ascorbic acidoxidase, pyrilrubinoxidase, or peroxidase. . 10. The antibiotic agent according to any one of claims 1 to 9, further comprising a metal compound. 1 1. Metal compounds from zirconium, titanium, vanadium, chromium, molybdenum, manganese, iron, cobalt, nickel, palladium, copper, silver, zinc, cadmium, aluminum, tin, lead, antimony, calcium, magnesium, or barium The antibiotic according to claim 10, which is a compound containing at least one selected metal element. 12. The antibiotic agent according to any one of claims 1 to 11, further comprising a boron compound. 3. The antibiotic agent according to claim 12, wherein the boron compound is a borate. 14. It further contains at least one drug selected from fragrances, deodorants, fire retardants, flame retardants, antibacterials, preservatives, bactericides, insect repellents, antivirals, and biological repellents. The antibiotic according to any one of claims 1 to 13, wherein 15 5. Claims 1 to 14 which are high concentration solution, powder or granule Antibiotic described in any of the above. 16. A method for treating an article, which comprises applying and / or impregnating an article as it is, or as a solution, with the antibiotic agent according to any one of claims 1 to 15. 17. The article processing method according to claim 16, wherein the article is a porous article. 1 8. Porous articles are made of metal sintered products, structures, alloys, die-cast products, ceramics, bricks, concrete, wood, wood chips, wood flour, wood products, fir, rush, straw, bamboo, charcoal, textile, The article processing method according to claim 17, which is a processed fiber product or a synthetic resin foam. 19. The method of any one of claims 16 to 18 including the step of maintaining the article under reduced pressure prior to impregnation, and applying a pressure during Z or impregnation to promote impregnation of the solution into the article. Article processing method. 20. The article processing method according to claim 19, wherein the pressurization is performed at 1 to 20 atm. 21. The article processing method according to any one of claims 16 to 20, further comprising a step of performing an oxidation reaction and / or a high molecular weight reaction of the applied or impregnated antibiotic. 22. The article processing method according to any one of claims 16 to 21, wherein the oxidation reaction and the reaction for increasing the molecular weight or the molecular weight are accelerated by heating. 23. The article processing method according to any one of claims 16 to 22, wherein the oxidation reaction and the Z or high molecular weight reaction are accelerated by a polyphenol oxidation catalyst. 24. An article obtained by the processing method according to any one of claims 16 to 23. 25. A method for producing a processed article, comprising a processing step according to the method according to any one of claims 16 to 23. 26. A method for producing a treated porous article, which comprises applying and / or impregnating an antibiotic containing hinokitiol to a porous article and performing an oxidation reaction. 27. A method for producing a processed porous article, comprising applying and / or impregnating a porous article with an antibiotic containing hinokitiol to carry out an oxidation reaction and / or a high molecular weight reaction. 28. The process for producing a treated porous article according to claim 26 or 27, wherein the oxidation reaction and the Z or high molecular weight reaction are carried out using a polyphenol oxidation catalyst. 29. The process for producing a treated porous material according to claim 28, wherein the polyphenol oxidation catalyst is catechol oxidase, laccase, polyphenol oxidase, ascorbate oxidase, pyrilvin oxidase, or peroxidase. Method. 30. The antimicrobial agent according to any one of claims 26 to 29 is a metal compound. A method for producing a treated porous article, comprising: 3 1. Metal compounds from zirconium, titanium, vanadium, chromium, molybdenum, manganese, iron, cobalt, nickel, palladium, copper, silver, zinc, cadmium, aluminum, tin, lead, antimony, calcium, magnesium, or barium The method for producing a treated porous article according to claim 30, which is a compound containing at least one selected metal element. 32. The method according to any one of claims 26 to 31, wherein the porous article is a plant-derived porous article. 3 3. Claims characterized in that the plant-derived porous article is wood, wood chips, wood flour, processed wood, fir, rush, straw, bamboo, plant fiber, or processed plant fiber. The production method described in 1. 34. A processed article obtained by the production method according to any one of claims 25 to 33.