JPH11165303A - Timber treating agent and method for treating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a timber treating agent constituted as one agent by improving a storage stability to efficiently obtain a metallic ion fixed timber, and a method for treating. SOLUTION: The timber treating agent comprises a metallic salt, a phenolic compound, a thiosulfate or a thiocyanate, and further an organic alkalifying agent. The method for treating a timber comprises the steps of impregnating the timber with the agent, and fixing metal into the timber. A method for manufacturing a timber or a woody material metal treated by using the method for treating. And, the timber or woody material metal treated is obtained by the manufacturing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wood treating agent utilizing the antibiotic action of a metal salt and a wood treating method using the same. More specifically, the present invention is characterized in that a wood treating agent configured as one agent containing a metal salt, a phenolic compound, and a thiosulfate or thiocyanic acid, and impregnating wood with the treating agent. The present invention relates to a method for treating wood, and a processed wood product obtained by the method.

[0002]

2. Description of the Related Art Metal salts are useful as wood treating agents because they have antibacterial, bactericidal, antiseptic, insecticidal, antiviral, biological repellent and other antibiotic and coloring effects. When a metal salt is used as a wood treating agent, it is important to increase the permeability and fixation of the metal salt to wood. As such a method, Harima et al. Impregnate wood with ferulic acid together with a copper salt ("Treatment of wood with ferulic acid and ferulic acid derivatives" Proceedings of the 47th Annual Meeting of the Japan Wood Science Society (1997) pp.566 -567). This is because after introducing a metal salt into wood using ferulic acid similar in structure to lignin that constitutes wood as a carrier, a redox reaction using ferulic acid as a reducing agent and copper ions as an oxidizing agent proceeds, This is to deposit metallic copper therein. Similar injection experiments have been attempted for gallic acid, cinnamic acid, and benzoic acid derivatives in addition to ferulic acid.

[0003] However, wood treatment chemicals that use a redox reaction to improve the adhesion of metal salts to wood are
When prepared as a single agent by mixing all of these components,
There is a problem that a redox reaction that should proceed in wood proceeds during storage to produce a water-insoluble metal or metal compound. These insolubles block the voids in the wood surface and inside the wood when impregnating the wood with the drug, which reduces the amount of drug injected into the wood and reduces the effects of preservatives, termites, coloring, etc. on the wood. The amount of metal required to provide the wood cannot be introduced into the wood. An effective method for avoiding such problems is a method in which a compound such as ferulic acid and a metal ion such as copper ion are separately stored, and these are mixed immediately before use (the above-described method such as seeding is also used in this method). Is adopted.). However, since the conventional wood treatment agent almost adopts a single agent formulation, the use of such a two-agent treatment agent requires modification or expansion of the conventional treatment equipment.
In addition, there is a complication in use such that the metal salt must be dissolved at the time of use and mixed at an appropriate mixing ratio. For this reason, there has been a need for the development of a wood treating agent containing a metal salt as an active ingredient, which has excellent storage stability as one agent, has excellent permeability to wood, and is excellent in fixation in wood.

[0004]

Accordingly, an object of the present invention is to provide a wood treating agent containing a metal ion such as copper ion and a phenolic compound which undergoes an oxidation-reduction reaction with the metal ion. It is an object of the present invention to provide a treating agent having a storage stability as above.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have prepared various additives for obtaining a wood treating agent containing metal ions such as ferulic acid and copper ions and having improved storage stability as one agent. We conducted intensive research on the combination.
As a result, by using thiosulfate or thiocyanate, and further by using a specific organic alkalizing agent in combination, a wood treating agent having significantly improved storage stability while maintaining the metal fixing effect is prepared. They have found that this is possible and have completed the present invention. Furthermore, it is more easily oxidized than ferulic acid, so that its storage stability is remarkably low. As a result, pyrocatechol, hydroquinone, and pyrogallol, which were conventionally difficult to use with one agent coexisting with metal ions, were difficult. Also, phenolic compounds such as gallic acid and tannic acid and their derivatives can be stably prepared as a single agent together with thiosulfate or thiocyanate, together with metal ions that are susceptible to reduction, such as copper ions and silver ions. The inventors have found that the present invention can be preserved and completed the present invention.

That is, the present invention provides the following wood treating agent, a wood treating method using the same, a metal-containing wood / wood material, and a method for producing the same. [1] A wood treating agent comprising a metal salt, a phenolic compound, and a thiosulfate or thiocyanate. [2] The wood treating agent according to the above 1, further comprising an organic alkalizing agent. [3] The wood treating agent according to the above item 2, wherein the organic alkalizing agent is at least one compound selected from ethanolamine, diethanolamine, triethanolamine and ethylenediamine. [4] The above 1 wherein the metal salt is a copper compound or a silver compound.
A wood treating agent according to any one of claims 1 to 3.

[5] The method according to any one of [1] to [4], wherein the phenolic compound is at least one compound selected from pyrocatechol, hydroquinone, pyrogallol, gallic acid, tannic acid, ferulic acid, and derivatives thereof. Wood treatment agent. [6] The phenolic compound is added to 1 mole of the metal salt.
0.1 to 2 mol, 0.05% of thiosulfate or thiocyanate
The wood treating agent according to any one of the above 1 to 5, which contains the organic alkalizing agent in a ratio of 0 to 1 mol and 0 to 4 mol. [7] The wood treating agent according to any one of the above items 1 to 6, further comprising a polyphenol oxidation catalyst. [8] The wood treating agent according to any one of the above items 1 to 7, which is prepared as a high-concentration solution for dilution at the time of use, or as a powder or a granulated powder to be dissolved at the time of use. [9] A method for treating wood, comprising impregnating wood with the wood treating agent according to any one of the above items 1 to 8, and fixing the metal to the wood. [10] A method for producing a metal-containing treated wood or woody material, comprising using the wood treatment method according to 9 above. [11] A metal-containing wood or wood material obtained by the production method according to the above item 10.

[0008]

(I) Wood treatment agent The wood treatment agent of the present invention comprises a metal salt, a phenolic compound,
And a thiosulfate or thiocyanate as an essential component, and more preferably an organic alkalizing agent and other components. Wood treatment agent of the present invention, antibacterial, bactericidal, preservative,
Wood is given properties such as insect repellency, antiviral properties, biological repellency, and coloring, but other properties can be given by selecting additional components. Hereinafter, each component will be described in detail.

[Metal salt] As the metal salt used in the wood treating agent of the present invention, any metal compound can be used as long as it contains a metal ion that can be reduced by a phenolic compound. A metal salt containing a smaller metal ion as a component can be particularly preferably used. Examples of such metal ions include copper ions or silver ions. Examples of the ^{anion, F -, Cl -, Br} -, I -, NO 3 -, BO 3 3-, P
_{^{O 4 3-, P 2 O 7}} 4-, SO 4 2-, SO 3 2-, S 2 O 3 2-, SC
N ⁻ , CO ₃ ²⁻ , O ²⁻ , OH ⁻ , B ₄ O ₇ ²⁻ , B (O
H) Inorganic ions such as ₄ ^- and BF ₄ ^- and organic ions such as naphthenic acid, oleic acid, stearic acid, octanoic acid, acetic acid, formic acid, benzoic acid, citric acid, lactic acid and tartaric acid. The metal salt as referred to in the present invention may be a complex of a metal ion and an anion, and includes a complex and a hydrate. Among these metal salts, compounds having high solubility such as copper sulfate and silver chloride are preferable. When solubilization is performed using an organic alkalizing agent described later, a metal salt containing copper ion or silver ion and thiosulfate ion (S ₂ O ₃ ²⁻ ) or thiocyanate ion (SCN ⁻ ion) is used. As a metal salt component having excellent storage stability and metal fixability, it can be particularly suitably used in the present invention.

[Phenolic compound] The phenolic compound used as an essential component in the wood treating agent of the present invention includes:
The compound is not particularly limited as long as it has a function of reducing metal ions. By using such a phenolic compound, metal ions can be reduced in wood to precipitate and fix the metal. The phenolic compound has an effect of solubilizing the above-mentioned metal salt, and polyphenol has an effect of promoting the introduction of the metal salt into wood.

Specific examples of such phenolic compounds include pyrocatechol, hydroquinone, pyrogallol, gallic acid, tannic acid, ferulic acid, catechin, urushiol, 4-hydroxycinnamyl alcohol, o-coumaric acid, p-coumaric acid, coniferyl alcohol, coniferyl aldehyde, ethyl-3,4-
Dihydroxycinnamic acid, 3-hydroxy-4-methoxycinnamic acid, 3,4-dihydroxycinnamic acid, 3-hydroxy-4-methoxycinnamaldehyde, vanillin, o
-Vanillin, vanillic acid, vanillyl alcohol, o-vanillyl alcohol, isovanillyl alcohol, vanillylamine, vanillinazine, 4-hydroxy-3-methoxybenzonitrile, syringic acid, sinapyr alcohol,
Sinapic acid, sinapine aldehyde, homovanillic acid, homovanillyl alcohol, homovanilonitrile, hesperidin, chlorogenic acid, hinokitiol, tert-butylhydroquinone, phenylhydroquinone, trimethylhydroquinone, lauryl gallate, octyl gallate,
3,4-dihydroxybenzoic acid, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 6,7
-Dihydroxy-2-naphthalenesulfonic acid, nitrohumic acid, ascorbic acid, lignin, and derivatives of these compounds. Of these compounds, in particular, pyrocatechol, hydroquinone, pyrogallol,
Gallic acid, tannic acid and ferulic acid can be suitably used.

Further, compounds having a lower metal ion reducing property than these compounds can also be used as the phenolic compound of the present invention. Specific examples of such phenolic compounds include quercetin, rutin, o-hydroxybenzoic acid, p-hydroxybenzoic acid, guaiacol, 4-methoxyphenol, biphenol, bisphenol A, 3,5,3 ', 5' -Tetrahydroxymethylbisphenol A, methylhydroquinone, ethylhydroquinone, 1-hydroxybenzotriazole, 6-hydroxy-2,4,5-triaminopyrimidine, 2,3-dihydroxypyridazine, 3,6-dihydroxypyridazine, 2,3 -Dihydroxypyridine, methyl-4-hydroxy-3-methoxybenzoic acid, 4,5
-Diamino-6-hydroxy-2-mercaptopyrimidine, 2,5-dihydroxy-1,4-benzoquinone,
2,5-dihydroxybenzoic acid, 3- (3,4-dihydroxyphenyl) -L-alanine, 2-amino-3-hydroxypyridine, 2,3-dimethoxyphenol,
3,4-dimethoxyphenol, 2-methoxy-4-methylphenol, acetylsalicylic acid, methyl salicylate, ethyl salicylate, 3-methylcatechol, 4-methylcatechol, methylgallate, propylgallate,
3,4,5-trimethoxyphenol, tropolone, purprogalin, salicylaldoxime, 3-amino-
5,6,7,8-tetrahydro-2-naphthol, 1,
5-dihydroxynaphthalene, 3,5-dihydroxy-
2-naphthoic acid, 4-hydroxy-1-naphthalenesulfonic acid, purpurin, 2,3-dihydro-9,10-dihydroxy-1,4-anthracenedione, ligninsulfonic acid and the like. In order for the metal fixation reaction to proceed sufficiently in wood treated with a wood treatment chemical using a compound having a low metal ion reducing property, it is more desirable to perform heat treatment after impregnation.

[0013] Compounds obtained by derivatizing these phenolic compounds can also be used as phenolic compounds in the wood treating agent of the present invention. As a specific method for derivatization, acetic acid esterification, propionate esterification, carboxymethyl etherification, 2-hydroxyethyl etherification, 2-acetoxyethyl etherification, 2-hydroxypropyl etherification, Alkylation using alkyl halide, etc., hydroxymethylation with formalin, cross-linking with formalin, epoxy compound, isocyanate compound, allyl compound, acetone, etc., cross-linking reaction with other phenolic compounds, sulfone with neutral sulfite solution, etc. Having a polyoxyethylene chain, a saturated or unsaturated alkyl chain having 1 to 22 carbon atoms, hydroxymethyl, polyol, polyamine, allyl, epoxy, or aryl in the structural part. The introduction of groups, or include hydrolysis. Further, compounds obtained by combining these derivatizations and mixtures of the compounds obtained by performing these derivatizations can also be used.

The amount of the phenolic compound added to the wood treating agent is determined according to the reducing power of the phenolic compound and the content of phenolic hydroxyl groups involved in the reduction reaction in the phenolic compound. By adjusting the amount of the phenolic compound relative to the metal salt, it is possible to adjust the degree of progress of the oxidation-reduction reaction in wood. For example, when a relatively low-molecular and highly reducing phenolic compound such as pyrocatechol, hydroquinone, pyrogallol, gallic acid, tannic acid, and ferulic acid is used as the phenolic compound, one mole of the metal salt is used. It is desirable to mix the phenolic compound with the phenolic compound in a ratio of 0.1 to 2 mol. In addition, when using a high molecular compound such as lignin and lignin sulfonic acid, or a relatively high molecular compound obtained by derivatizing a phenolic compound,
Estimate the number of moles of hydroxyl groups contained in these compounds,
It is desirable that the hydroxyl groups are mixed so as to have a ratio of 0.1 to 2 mol per 1 mol of the metal salt. In any case, if the addition amount is too small, the effect of fixing the metal is not sufficiently exhibited. Excessive use does not improve the effect and adversely affects storage stability.

[Thiosulfate or thiocyanate] In the wood treating agent of the present invention, it is important to add a thiosulfate or thiocyanate together with a metal salt and a phenolic compound. By adding a thiosulfate or a thiocyanate, even when a metal salt and a phenolic compound coexist in one agent, it is possible to stably store the metal salt and the phenolic compound. That is, the redox reaction between the metal salt and the phenolic compound during storage is significantly suppressed by the action of the thiosulfate (or thiocyanate). Specific examples of the thiosulfate or thiocyanate used in the wood treating agent of the present invention are thiosulfate ions or thiocyanate ions, and salts composed of alkali metal ions or alkaline earth metal ions. , Sodium thiosulfate and potassium thiosulfate are preferably used.

The amount of thiosulfate or thiocyanate to be added to the wood treating agent is determined according to the amounts (concentrations) and types of metal salts and phenolic compounds. By adjusting the amount of thiosulfate or thiocyanate to be added, it is possible to adjust the degree of storage stability of the prepared wood treatment chemical. For example, when it is desired to achieve storage stability under conditions of about one month under an accelerated test environment of 40 ° C. for one year at room temperature, it is desirable to mix at a ratio of 0.05 mol or more with respect to 1 mol of the metal salt. . If the amount is too small, the effect of stabilizing components such as metal salts cannot be sufficiently exhibited.
When used in excess, decomposition products of thiosulfate or thiocyanate itself tend to precipitate. In addition, since thiosulfate or thiocyanate is corrosive to iron, the content is generally 1 mol or less. It is desirable to adjust in consideration of the degree of non-corrosiveness of iron required according to the place and mode of use of the treated wood.

[Organic alkalinizing agent] In the wood treating agent of the present invention, the metal ion is solubilized by the phenolic compound. Reduce usage,
For the purpose of preparing wood treatment chemicals at lower cost, and to adjust the pH of wood treatment chemicals from neutral to alkaline,
An organic alkalizing agent can be added for use. The organic alkalizing agent used in the present invention is preferably a basic organic compound which forms a salt or a complex with a metal ion, and is preferably an amine or imine having one or more hydroxyl groups in the molecule, or a A compound having two or more amino groups or imino groups (hydrogen atoms in these groups may be substituted).

Specific examples of the organic alkalizing agent having such properties include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, N-ethylethanolamine and N-ethylethanolamine. , N-diethylethanolamine, N-butylethanolamine, N, N-dibutylethanolamine, 3-amino-1-propanol, 2-
(Ethylamino) -ethanol, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, triethanolamine ethoxylate, bicine, propanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, 3-amino-1,
2-propanediol, 2-amino-1,3-propanediol, 2,3-diamino-1-propanol, 1,
3-diamino-2-propanol, 2-amino-2-propanol, 1- [N, N-bis (2-hydroxyethyl) amino] -2-propanol, ethylenediamine,
N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N-ethylethylenediamine,
N, N'-bis (2-hydroxyethyl) ethylenediamine, diaminopropane, triethylenetetramine, pentaethylenehexamine, polyethyleneimine, polyallylamine, triazacyclononane, triazacyclododecane, etc., and especially ethanolamine ,
Diethanolamine, triethanolamine, ethylenediamine, and mixtures thereof are preferably used.

The amount of the organic alkalizing agent added depends on the metal ion solubilizing ability of the phenolic compound used, the amount of the phenolic compound, the amount of the thiosulfate (or thiocyanate), the water solubility of the metal compound, and the like. adjust. In order to simultaneously improve the storage stability and fix the metal ions in the treated wood, it is desirable to use the metal salt in a range of 4 mol or less per mol of the metal salt.

[Other Components] (a) Polyphenol oxidation catalyst In order to sufficiently fix metal ions in wood, the oxidation reaction and / or the high molecular weight reaction of a phenol compound are performed using a polyphenol oxidation catalyst. It is particularly preferred to accelerate. Examples of such polyphenol oxidation catalysts include metal complexes, natural enzymes, and the like. Among the metal complexes, an artificial enzyme that mimics an oxidoreductase can obtain an effective catalytic effect by using a lower concentration of the metal complex, and is useful for the purpose of the present invention. Specific examples of such an artificial enzyme include cyclic nitrogen-containing compounds such as triazacyclononane and triazacyclododecane, N-methylated derivatives thereof, phthalocyanine or porphyrin, and derivatives having a hydrophilic substituent.

The polyphenol oxidase, which is a natural enzyme, can be widely used as long as it has a polyphenol oxidation catalytic activity. Examples of such enzymes include:
Produced by a microorganism, such as a fungus or bacterium,
Alternatively, polyphenol oxidases such as catechol oxidase, laccase, polyphenol oxidase, ascorbate oxidase, and bilirubin oxidase produced by plants can be used. Since these already exist in the natural world, they have little effect on the environment and can be particularly suitably used for the purpose of the present invention. In particular, when it is desired to carry out the oxidation reaction and / or the polymerization reaction at a high speed, those having a polyphenol oxidizing action in an alkaline pH range are more preferable.

The oxidation reaction and / or polymerization reaction by enzymatic oxidation can also be carried out by using an enzyme having a peroxidase function such as peroxidase, lignin peroxidase, manganese peroxidase or the like derived from microorganisms or plants and hydrogen peroxide. The addition and supply of hydrogen peroxide are carried out by directly adding a hydrogen peroxide solution, using a hydrogen peroxide precursor such as perborate or percarbonate instead of hydrogen peroxide, or an oxidase capable of producing hydrogen peroxide and its oxidase. There is a method using a substrate, which can be carried out in various ways depending on the processing purpose and processing method. Examples of oxidases that can generate such hydrogen peroxide include glucose oxidase, alcohol oxidase, glycerol oxidase, amine oxidase, amino acid oxidase, D-amino acid oxidase, allyl alcohol oxidase, aldehyde oxidase, galactose oxidase, sorbose oxidase, and urea. There are rate oxidase, xanthine oxidase, cholesterol oxidase and the like, and particularly preferable are glucose oxidase and alcohol oxidase. Regarding the activity of the polyphenol oxidation catalyst,
When the amount of activity for oxidizing 1 μmol of a phenolic compound and / or an aromatic amine compound per minute is defined as 1 unit (hereinafter abbreviated as U), the polyphenol oxidation catalyst of the present invention is used for wood treatment. The oxidation activity concentration of the polyphenol oxidation catalyst is 1 to 100,000 U / l,
Preferably it is 10-5,000 U / l.

(B) Chelating agent Further, for the purpose of promoting the introduction of metal ions into wood,
Chelating agents other than the above-mentioned organic alkalizing agents can also be used in addition to the wood treating agent of the present invention. Specific examples of such chelating agents include ethane-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,
Phosphonic acids such as 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3 , 4-tricarboxylic acid, phosphonocarboxylic acids such as α-methylphosphonosuccinic acid, amino acids such as aspartic acid, glutamic acid, glycine, 2-aminoisobutyric acid, β-alanine or amino acid analogs, iminodiacetic acid, nitrilotriacetic acid, Aminopolyacetic acid such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, polyacrylic acid, polyitaconic acid, polymaleic acid, maleic anhydride copolymer, polymer electrolytes such as carboxymethylcellulose, benzene polycarboxylic acid, oxalic acid, malic acid, diglycol Acid, succinic acid, oxy Organic acids such as disuccinic acid, carboxymethyloxysuccinic acid, gluconic acid, citric acid, lactic acid, and tartaric acid; and organic compounds such as urea, chitosan, and polylysine.

(C) Other additives Antibacterial properties such as antibacterial properties, bactericidal properties, antiseptic properties, insect repellency, antiviral properties, biological repellency, weather resistance, and fire resistance of the treated wood products produced by the present invention. Fragrance, deodorant, rust inhibitor, antibacterial agent, bactericide, etc., for the purpose of further enhancing the wood treatment effect such as resistance, abrasion resistance and coloring, or at the same time imparting various wood treatment effects Known agents such as preservatives, insect repellents, antiviral agents, biological repellents, and water repellents can be further included in the wood treatment agent used in the present invention.

Examples of such agents are plant-derived extracts, extract components, or synthetic compounds having a structure equivalent to that of plant extracts. Specifically, plants such as cypress, trees such as Aomori Hiba, herbs, mustard, wasabi, bamboo, iriomote thistle rhizome, or yaeyama palm root are crushed,
Examples include plant extracts and extractable components obtained by treatment such as pressing, boiling, or steam distillation. Specific examples of plant-derived extract components or synthetic compounds having a structure equivalent to the plant extract component include hinokitiol, tropolone such as β-drabrin, α-pinene, β-pinene, camphor, menthol, limonene, borneol Monoterpenes such as α-terpinene, γ-terpinene, α-terpineol, terpinen-4-ol and cineol;
sesquiterpenes such as α-casinole and t-murol, polyphenols such as catechin and tannin, 2,
Examples thereof include naphthalene derivatives such as 3,5-trimethylnaphthalene, long-chain aliphatic alcohols such as citronellol, and aldehydes such as cinnamaldehyde, citral, and perilaldehyde. Wood vinegar obtained by steaming trees can also be used. By using a combination of these natural physiologically active substances and the high metal fixation by the wood treating agent of the present invention, treated wood having high safety to the environment and the human body can be produced.
The concentration of the plant-derived extract used in the present invention, the extract component, or the compound having a structure equivalent to that of the plant extract component in the wood treatment solution is 0.001-1.
0% by weight, preferably 0.01 to 1% by weight.

Other agents that can be used in the present invention are O
An aromatic compound or a cyclic compound having an H group, an amino group, a halogen, a nitro group, a methyl group, a methoxy group, or the like as a substituent. Specific examples of such compounds include o-phenylphenol, 1-naphthol, 2-naphthol-o-chlorophenol, 2,4-dinitrophenol, 4,6-dinitro-o-cresol, pentachlorophenol, 3,5-trichlorophenol, 2,4,6-trichlorophenol, monochloronaphthalene, trichloronaphthalene, tetrachloronaphthalene, 2,4,5-trichlorophenyllaurate monochloronaphthalene, chloronitrophenol, chloronitrotoluene, 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-iodopropargyl formal, creosote oil, chlorinated terpene, p-hydroxybenzoic acid, methyl, ethyl, propyl p-hydroxybenzoic acid, Esters such as butylhydroxyanisole, butylhydroxytoluenebutyl, isobutyl, and isopropyl are exemplified. The concentration of such compounds used in the present invention in the solution during wood treatment is as follows:
It is 0.001 to 5% by weight, preferably 0.01 to 1% by weight.

Other agents usable 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 tung oil, linseed oil, castor oil and the like. It is an autoxidizable compound such as a drying oil or a catechol derivative having an unsaturated side chain such as urushiol. By using these compounds together with the chemicals for treating wood of the present invention, it is possible to adjust physical properties such as water solubility and water repellency of the treatment liquid or treated wood. The concentration of such compounds used in the present invention in the solution at the time of wood 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 wood treating agent of the present invention. For example, N
a, K, Mg, Ca, Ba, Al, Zn, Cu, Mn,
A phosphate, a hydrogen phosphate, a sulfate, a hydrogen sulfate having an element such as Ni, Si, Sn, or Pb in a cation portion;
Carbonates, borates, silicates, nitrates, fluorides, chlorides, bromides, hydroxides, and the like, specifically,
Examples thereof include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, antimony trioxide, barium metaborate, tin oxide, red phosphorus, and ammonium phosphate. The concentration of these flame retardants used in the present invention in the solution at the time of wood treatment is 0.01 to 90% by weight, preferably 1 to 50% by weight.

Inorganic compounds having strong antibiotic properties can also be used by adding them to the treatment agent of the present invention. Examples of such compounds include boron, arsenic, antimony, selenium, bromine and iodine. , Fluorine, sulfur ions, compounds containing nitrate ions, more specifically,
Boron compounds such as boric acid, borate, borax, and fluoroboronate, fluosilicate, arsenous acid, antimony chloride, antimony trioxide, potassium selenate, calcium bromide, sodium bromide, and bromide Magnesium, potassium bromide, zinc bromide, sodium iodide, zinc iodide, sodium fluoride, potassium fluoride, antimony fluoride, sodium silicate fluoride, magnesium silicate fluoride, sodium sulfide, potassium sulfide, zirconium nitrate, etc. . The concentration of such a compound used in the present invention in a solution at the time of wood treatment is 0.01 to 500 mM, preferably 0.1 to 100 mM.

Further, in the present invention, for the purpose of adjusting the fixability and sustained release of metal, metal compound, and / or metal ion and other drugs, and improving the antibiotic properties,
A quaternary ammonium compound can be used by adding it to the treatment agent. _{Specifically, C n H 2 n + 1} (n = 1~22) , or _{C n H 2n-1 (n} = 2~22), C n H 2n-3 (n = 4~
22), a quaternary ammonium having a hydrocarbon represented by C _n H _2n-5 (n = 6 to 22) as a substituent, a quaternary ammonium containing an aromatic compound as a substituent, and a substituent comprising a hydrophilic polymer. Hydrochloride or sulfate, such as quaternary ammonium, can be used, and conventionally used didecyldimethylammonium chloride (DDAC) can also be used, but those having an unsaturated structural moiety as a substituent are more preferable. The concentration of such a quaternary ammonium compound used in the present invention in a solution during wood treatment is 0.001 to 50% by weight, preferably 0.01 to 20% by weight.

In addition to these agents, various commonly used fungicides, insecticides, or insect repellents can be used by adding them to the wood treatment agent of the present invention. In particular,
Triazole derivatives, sulfonamides, benzimidazoles, thiocyanates, morpholine derivatives, organic iodine compounds, organic bromo derivatives, isothiazolines, benzisothiazolines, pyridines, dialkyldithiocarbamates, nitriles, benzthiazoles, cyclodienes, Examples include nitrosos, quinolines, microbial agents having an active halogen atom, and bactericides or bactericidal components belonging to formaldehyde-generating substances.
In addition, insecticides, insecticidal components, insect repellents, or insect repellents belonging to organophosphorus compounds, phosphates, carbamates, pyrethroids, nitroimino, nitromethylenes, etc. are also added to the wood treatment agent of the present invention. It can be used.

Insect hormones or IGR (insect growth regulator) and derivatives thereof 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 solution at the time of wood treatment is preferably adjusted according to the strength of physiological activity possessed by these agents, solubility, and the like. 0.
0001-20% by weight, preferably 0.001-5% by weight.

Further, when the compound used in addition to the wood treating agent used in the present invention has a low water solubility, the addition of a dispersing agent or a surfactant allows O / O
A method of forming a W-type or W / O-type emulsion is useful. As the surfactant used for such purposes, many commonly used surfactants can be used, and specifically, sulfates having a linear or branched alkyl or alkenyl structure portion, aliphatic sulfonates , Aromatic sulfonates, amide sulfates, ether carboxylates,
Examples include compounds such as amides, esters, ethers, alcohols, phosphates, phenyl ethers, and higher fatty acid alkanolamides, and compounds to which one or more of ethylene oxide, propylene oxide, and butylene oxide are added. In addition, amino acid type surfactant, sulfonic acid type amphoteric surfactant, betaine type amphoteric surfactant, amine oxide, sucrose fatty acid ester, fatty acid glycerin monoester,
A tetraalkylammonium salt type cationic surfactant can also be used.

When the drug is a fine powder, powders of various sizes can be used depending on the purpose.
5 μm or less, preferably 0.5 μm or less, more preferably
It is desirable to use a fine powder having a diameter of 0.1 μm or less.
Further, in the present invention, for the purpose of accelerating the oxidation and / or oxidative polymerization of the phenolic compound contained in the wood treatment chemical, a redox reaction such as catechol oxidase, laccase, polyphenol oxidase, ascorbate oxidase, bilirubin oxidase, peroxidase, etc. It is also possible to add a catalyst for use. Further, as an oxidizing agent for oxidizing the phenolic compound, oxygen, ozone, hydrogen peroxide, a hydrogen peroxide precursor, a peracid precursor or a peracid can be used alone or in combination. is there. Among these oxidizing agents, the operation of intentionally adding oxygen to wood during curing and drying of the treated wood includes catechol oxidase, laccase,
It is particularly useful when polyphenol oxidase, ascorbate oxidase, and bilirubin oxidase are used in combination. The method for accelerating the oxidation and / or oxidative polymerization of phenolic compounds by using hydrogen peroxide or a hydrogen peroxide precursor at the time of treating wood or curing and drying treated wood is particularly effective when combined with peroxidase. Useful.

Further, if necessary, p such as an organic acid may be further added.
H regulators, natural or synthetic dyes, pigments, thickeners, high molecular compounds, solids, and the like can be added to the treatment agent of the present invention.

[Dosage form] The wood treating agent of the present invention comprises the above-mentioned metal salt, phenolic compound, thiosulfate or thiocyanate and other components (particularly organic alkalizing agent).
Are uniformly mixed in the above ratio to obtain one agent. The concentration of the active ingredient in the drug is not particularly limited as long as it can be adjusted, and is determined according to the mode of use. Usually, when the metal salt concentration during wood treatment is in the range of 0.1 to 5.0 mol / L. Good. Therefore, the wood treating agent of the present invention may be in the form of either a high-concentration solution on the premise of dilution at the time of use or a solution having a concentration that can be used without dilution. In this case, in order to prevent the phenolic compound as a treating agent component from being air-oxidized before use, it is desirable to seal the container containing the treating agent during storage of the treating agent to avoid contact with the outside air. In addition, it is desirable to suppress the oxidation by producing the treating agent in a nitrogen gas or inert gas atmosphere or by performing a degassing treatment.

Further, the wood treating agent of the present invention may be used by mixing each component as it is or at a high concentration to form a powder or granular agent, which is dissolved in a solvent at the time of use. Granulation is
It is a shaping method performed for the purpose of suppressing dust generation and improving the preservability of drugs and the convenience of use, and specifically, Malm granulation, extrusion granulation, flow granulation, centrifugal flow granulation, etc. including. In the present invention, any granulation operation can be adopted according to the purpose. The solvent and the solvent at the time of dilution may be any substance that can sufficiently dissolve the pharmaceutical composition of the present invention. Examples of such materials include water, dichloromethane, and the like. Although the treating agent of the present invention can provide excellent storage stability regardless of pH, from the viewpoint of the progress of the metal fixing reaction and the effect on the strength of treated wood, the treating agent of pH 2 at the time of wood treatment is used.
~ 12, more preferably pH 3 ~ 11.

(II) Wood Treatment Method The treatment of wood according to the present invention is carried out by impregnating wood with the above-mentioned treating agent solution. The impregnation operation can be performed by a simple method of immersing the article in the treating agent solution.For wood that can be easily impregnated, the impregnation operation can also be performed by application using a brush or a roller, spraying, or spraying using an aerosol. However, as an impregnating operation for injecting a sufficient amount of treatment liquid into wood of a type that is difficult to impregnate, a pressurizing and / or depressurizing operation is extremely useful. The pressurizing operation is performed by applying pressure from the outside of the wood at atmospheric pressure (1 atm) to 30 atm, more preferably 3 to 15 atm, in a state where the wood is in contact with the treatment chemical solution. The decompression operation can be performed at any pressure up to the vacuum pressure, but for effective treatment of hard-to-impregnated wood, decompression in the range of 100 to 760 mmHg is desirable. For the depressurizing operation, it is more preferable to perform a pre-evacuation method in which the depressurizing is performed before the wood and the processing liquid come into contact with each other. It is also effective to combine these pressurizing and depressurizing operations in order to impregnate the wood with the treatment liquid in a larger amount.

Further, after impregnating the wood with the treatment liquid, decompression treatment is performed, and a part of the treatment liquid is collected outside the wood, and the metal fixing reaction inside the treated wood proceeds sufficiently. Before the cleaning, the wood is washed with water or the like to remove the non-adhered matter, so that the degree of maintaining the porosity can be easily adjusted. Wood with such porosity maintained or adjusted retains humidity adjustment ability, water retention ability, adsorption capacity, ion exchange ability, surface texture as wood, and various properties utilizing such ability and texture It can be used for applications. In addition, the porous retained wood can be further impregnated with chemicals, polymers, and prepolymers to produce wood treatment articles having various combined properties.

Various methods commonly used for pressurizing and / or depressurizing wood can be used, and specifically, a packed cell method (Vesel method), a semi-empty cell method (Lowry method), and an empty cell method Cell method (Leuping method), Double vacuum method (Double vacuum method), Pressurization / decompression alternate method (Osci
llating Pressure Method), Pulsation Pr
essure Method), Constant Pressure Meth
od), Slow Pressure Change Metho
d) and a method combining these operations are applicable. Also, the insizing method can be applied to increase the impregnation amount. It is also effective to carry out 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 wood that is difficult to impregnate.

In the wood treatment method of the present invention, the operation of impregnating the wood with the treating agent is carried out at 0 to 150 ° C., preferably 10 to 150 ° C.
Performed at 00 ° C. In addition, after such treatment, the cured product is further subjected to an oxidative reaction and / or an oxidative polymerization reaction of the phenolic compound while leaving the treated product in the air or oxygen gas and gradually drying it. It is possible to more firmly fix metal ions. In addition, by performing heating during curing, it is possible to more efficiently fix metal ions. The heating at the time of curing is performed at a temperature of 20 to 300C, more preferably 40 to 150C. When wood is treated with a treating agent containing a polyphenol oxidation catalyst, the catalytic ability of the polyphenol oxidation catalyst is effectively exhibited by 20 to 6%.
It is desirable to heat to a temperature of 0 ° C.

It is also useful to apply pressure to the treated product during curing to make the wood structure adhere to the metal to further improve the metal ion retention and wood strength. It is also effective to further coat the surface of the wood that has been subjected to these treatments and seal the components such as the treatment chemical composition and metal ions.

Further, it is effective to carry out the method of the present invention in combination with a treatment with a conventional treating agent. In particular, when a conventional treating agent contains a drug component that forms a complex with a metal ion, leaching is performed by using the wood treatment of the present invention as a post-treatment, a pre-treatment, or a simultaneous treatment according to the conventional method. It is possible to increase the sticking property of the component which is easy to perform.

(III) Treated Wood and Method for Producing the Same Woods to which the method of the present invention can be applied include plate materials and log materials obtained by mechanically processing wood. Therefore, according to the present invention, it is possible to produce treated wood such as various kinds of plates and logs that have been subjected to metal-containing treatment. Wood that can be treated according to the present invention also includes various woody materials. Examples of such woody materials include wood products such as laminated wood, laminated veneer, plywood, particle board, fiber board, and raw materials thereof. Therefore, according to the present invention, it is possible to produce such various woody materials that have been subjected to a metal-containing treatment.

The wood material produced by using the adhesive (wood processed product such as glued wood) may be impregnated after the completion of the processing operation such as gluing, but the wood material processing operation may be performed. It is useful to incorporate the treatment method of the present invention as one step. This makes it possible to impregnate the wood with a sufficient amount of the treatment agent. For example, when manufacturing glued laminated timber,
First, the wood treatment method of the present invention is carried out, and thereafter, a vertical glue, stripping, applying an adhesive, and performing compression and curing to produce a laminated material impregnated with a sufficient amount of the treatment agent. It becomes possible. The processed wood product of the present invention maintains the properties required for the manufacture of processed wood products such as workability and adhesiveness.By adopting such a method, it has the same strength as a conventional processed product, In addition, it is possible to manufacture a processed wood product that is uniformly treated with chemicals.

The treated wood according to the present invention contains a phenolic compound having an antioxidant property and an organic alkalizing agent having an anticorrosive property. Since it has the effect of suppressing corrosion, it is also useful for maintaining the strength of the structure. further,
Phenolic compounds such as lignin and flavonoids are originally contained in wood, but these phenolic compounds originally present in wood are involved in the oxidation-reduction reaction between the phenolic compound in the treating agent and metal ions. By the addition, a complexed metal and a metal complex are generated, and the metal ions impregnated in the wood are fixed very firmly in the wood.

[0047]

The present invention will be described more specifically below with reference to typical examples. However, these are merely examples, and the present invention is not limited to only these. Example 1 Preparation and Storage Stability Test of Wood Treatment Concentrate Distilled water and sodium hydroxide were added to 37.5 g of copper (II) sulfate pentahydrate, 18.9 g of pyrogallol, and 4.7 g of anhydrous sodium thiosulfate. A solution having a pH of 9 was prepared, and distilled water was further added to adjust the total amount to 75 ml, thereby obtaining a concentrate for a wood treatment agent (concentrate A). As a control, a solution prepared by removing only sodium thiosulfate from the above composition was similarly prepared (concentrated solution A _c ).

A storage stability test was performed using the concentrated solutions of these wood treating agents. Storage stability test is 50ml concentrate
Was transferred to a 100 ml glass container and sealed.
This was carried out by allowing the solution to stand in a 0 ° C. incubator, observing the concentrated solution 1 to 4 weeks later, and measuring the copper ion concentration in the solution portion of the concentrated supernatant solution. Quantification of copper ions is determined by PAN
Complexation using 1- (2-Pyridylazo) -2-naphthol, obtained from Aldrich Chemical Company and absorption spectroscopy. As a result, in the concentrated solution containing no sodium thiosulfate as a control, a large amount of precipitate was formed two weeks after storage, and the copper ion concentration in the concentrated solution supernatant was 34% of that in the concentrated solution preparation.
On the other hand, the concentration of the concentrated solution to which sodium thiosulfate was added did not change even after 4 weeks, and the concentration of copper ions in the supernatant showed a very high value of 93% at the time of preparing the concentrated solution. It was shown that the wood treating agent of the present invention significantly improved the storage stability.

Example 2: Preparation of concentrate for wood treatment and
Storage stability test Copper (II) sulfate pentahydrate 37.5 g, pyrogallol 3.8 g, anhydrous sodium thiosulfate 4.7 g, and ethanolamine
Distilled water and boric acid were added to 9.2 g to prepare a solution having a pH of 9, and distilled water was further added to adjust the total volume to 75 ml, thereby obtaining a wood processing concentrate (concentrated solution B). As a control, a solution prepared by removing only sodium thiosulfate from the above composition was prepared in the same manner (concentrated solution B _c ). A storage stability test was performed in the same manner as in Example 1 using these wood treating agent concentrates.
As a result, in the concentrate containing no sodium thiosulfate as a control, a large amount of precipitate was formed three weeks after storage, and the concentration of copper ions in the supernatant of the concentrate was reduced to 45% of that at the time of preparing the concentrate. On the other hand, in the concentrated solution to which sodium thiosulfate was added, the state of the solution did not change even after 4 weeks, and the concentration of copper ions in the supernatant showed a very high value of 97% at the time of preparing the concentrated solution. It was shown that the storage stability of the agent was significantly improved.

Example 3 Obtaining Polyphenol Oxidase In order to obtain an enzyme used as a polyphenol oxidation catalyst, 0.5% by weight of glucose and 0.1% by weight of NaN were used.
O _3, 1.34 _{wt% Na 2 HPO 4 · 12H 2} O, 0.3 wt%
KH ₂ PO ₄ , 0.1% by weight NaCl, 0.2% by weight peptone,
20ppm yeast extract, 0.01% MgSO ₄ · 7H
1 liter in a 3 liter medium consisting of ₂ O, 0.1 mM CuSO ₄
In a culture tank containing 0% NaOH to adjust the pH to 8, add Myrothecium verruc.
aria ) SD3001 (deposited with the National Institute of Bioscience and Human-Technology, National Institute of Advanced Industrial Science and Technology as FERM P-14955, transferred to an international deposit and given accession number FERM BP-5520), and inoculated at 28 ° C. for 3 days. Was shake-cultured. After culture, 4
2.5 liters of the culture broth which had been sterilized was obtained by centrifugation at ℃. Next, the culture broth was concentrated as a fraction having a molecular weight of 10,000 or more by a minitan ultrafiltration system (manufactured by Millipore) using a minitan filter packet (CAT. NO .: PTGC0MP04, manufactured by Millipore). This was further dialyzed against 200 ppm NH ₄ HCO ₃ and then freeze-dried to obtain a target enzyme as a crude product. 550 using enzymatic reaction with syringaldazine as substrate
The polyphenol oxidase activity of this enzyme preparation determined by absorbance measurement in nm was 10 U / mg.

Example 4: Preparation of wood processing concentrate and
Storage stability test Lignin sulfonic acid (obtained from Aldrich Chemical Company) 7.5 g, copper (II) sulfate pentahydrate 37.5 g, anhydrous sodium thiosulfate 4.7 g, and ethanolamine
Distilled water and boric acid were added to 9.2 g to prepare a pH 9 solution, distilled water was added until the total amount of the prepared drug became 75 ml, and the polyphenol oxidase obtained in Example 3 was further added to 600 U (freeze-dried product). 60 mg) to obtain a wood treating agent concentrate (concentrated liquid C). As a control, a solution in which only sodium thiosulfate was removed from the above composition was similarly prepared (concentrated solution C _c ). A storage stability test was performed in the same manner as in Example 1 using these wood treating agent concentrates. as a result,
In the control concentrate containing no sodium thiosulfate, a large amount of precipitate was formed two weeks after storage, and the concentration of copper ions in the supernatant of the concentrate was reduced to 68% of that in the preparation of the concentrate. Even after 4 weeks, the concentrated solution containing sodium sulfate did not change in the state of the solution, and the copper ion concentration in the supernatant showed a very high value of 99% at the time of the preparation of the concentrated solution. Significantly improved stability was shown.

Example 5 Preparation of a Wood Treatment Concentrate and
Storage stability test A concentrate was prepared in the same manner as in Example 1, except that 2.4 g of sodium thiocyanate was used instead of 4.7 g of anhydrous sodium thiosulfate used in the preparation of the concentrate for the wood treating agent in Example 1. It was prepared (Concentrate D), and the same storage stability test as in Example 1 was performed using this concentrate. Even after 4 weeks from storage, there was no change in the state of the concentrate D, and the copper ion concentration in the supernatant showed a very high value of 89% at the time of the preparation of the concentrate, and the storage stability of the wood treatment agent of the present invention was remarkably high. It has been shown to be improved.

Example 6 Preparation of a Wood Treatment Concentrate and
Storage stability test In Example 1, silver (I) chloride (II) 2 was used instead of copper (II) sulfate pentahydrate (37.5 g) used in preparing the wood processing agent concentrate.
A concentrate was prepared in exactly the same manner as in Example 1 except that 1.5 g was used (concentrate E). As a control, a solution in which only sodium thiosulfate was removed from this composition was similarly prepared (concentrated solution E _c ). Using these wood treating agent concentrates, a storage stability test was conducted in the same manner as in Example 1. As a result, in the concentrate containing no sodium thiosulfate as a control, a large amount of precipitate was formed two weeks after storage, and the silver ion concentration in the supernatant of the concentrate was reduced to 18% of that in the preparation of the concentrate. On the other hand,
The concentrated solution to which sodium thiosulfate was added had no change in the state of the solution even after 4 weeks, and the silver ion concentration in the supernatant showed a very high value of 85% at the time of preparing the concentrated solution. It was shown that the storage stability was significantly improved.

Example 7: Preparation of concentrate for wood treatment and
Storage stability test In place of pyrogallol used in the preparation of the wood treatment agent concentrate in Example 1, 16.5 g of pyrocatechol, 16.5 g of hydroquinone, 28.2 g of gallic acid monohydrate, 30.0 g of tannic acid, or Ferula Concentrating agents were prepared in exactly the same manner as in Example 1 except that 29.1 g of the acid was used (concentrated solutions F to J). As a control, a solution in which only sodium thiosulfate was removed from this composition was prepared in the same manner (concentrate F _c ~
_Jc ). Using these wood treating agent concentrates, a storage stability test was conducted in the same manner as in Example 1. As a result, it was shown that the storage stability of the wood treating agent to which thiosulfate was added according to the present invention was remarkably improved when any phenolic compound was used. Storage stability test period,
Table 1 shows detailed results of the copper ion concentration of the supernatant at the time when the test period had elapsed (the ratio when the concentration of the concentrated solution was taken as 100%).

[0055]

[Table 1]

Example 8: Manufacture of treated wood and gold content
Genus leaching test The wood treating agent concentrates (concentrates A to E) prepared in Examples 1, 2, 4 to 6 and having undergone the storage stability test were diluted with water to 3
Dilute 0-fold to an aqueous solution of wood treatment agent (treatment agent solution A ~
E) was prepared, and a cedar wood chip (2) was prepared using this treating agent solution.
cm × 2cm × 1cm, Kiguchi 2cm × 2cm, Sapwood)
Was impregnated. The impregnation operation is performed by immersing the cedar wood pieces in the treatment liquid, applying a reduced pressure of 650 to 700 mmHg for 30 minutes, and further immersing the cedar wood pieces at normal pressure for 30 minutes.
We went by putting for minutes. By this impregnation operation, it was confirmed that a sufficient amount of the treating agent solution (3.0 to 3.4 g amount) had been injected by measuring the weight of wood chips before and after the impregnation operation.
Furthermore, the wood pieces (wood pieces A to E) that have been subjected to the impregnation treatment are heated at 30 ° C.
For 5 days, and further at room temperature (about 24 ° C.) for 2 weeks to carry out the reaction, drying and curing. In order to examine the sticking property of the metal to the treated wood piece thus obtained, first, the treated wood piece was dried in a dryer at 60 ° C. for 16 hours, and 40 ml of water was added to each wood piece. The water was stirred using a magnetic stirrer and a rotor in a state of sinking, and the leaching operation was performed by stirring at 25 ± 3 ° C. for 8 hours.

The aqueous solution containing the leached metal obtained by the leaching operation was subjected to ICAP-575II manufactured by Nippon Jarrell Ash.
The amount of eluted metal ions was analyzed by high-frequency plasma emission spectroscopy (ICP method) using, and the amount of metal remaining in the wood chips was calculated with the amount of impregnated metal as 100%. As a control, concentrates A _c , B _c , C _c and E _c (solutions having the same composition as concentrates A, B, C and E except that they do not contain sodium thiosulfate or sodium thiocyanate, ) Is similarly diluted, and the same impregnation treatment is carried out to obtain wood pieces A _c , B _c , C _c and E _c
And a leaching test was performed on these test pieces in the same manner as described above. As a result, the wood pieces (wood pieces A to E) treated with the treating agent solution containing sodium thiosulfate or sodium thiocyanate were converted into the wood pieces (wood pieces A _c to 〜) treated with the treating agent solution containing no sodium thiosulfate or sodium thiocyanate. indicate the E _c) substantially equal to the metal sticking property was confirmed. The detailed results are shown in Table 2. Note that control for wood D is wood A _c. D
In the control column (D _c ), the result for the wood piece A _c is repeatedly shown.

[0058]

[Table 2]

[0059]

According to the wood treating agent of the present invention, a thiosulfate or a thiocyanate is used as a wood treating agent containing a phenolic compound and a metal ion. Nevertheless, the stability as a single agent is remarkably improved, and the oxidation-reduction reaction between the phenolic compound and the metal ion in the wood proceeds favorably. For this reason, the use of the treatment agent of the present invention makes it possible to carry out wood treatment with a large amount of metal introduced and good metal fixation by simple operations using conventional wood treatment equipment. Further, in the wood according to the treatment method of the present invention, the metal is retained as fine precipitates or a complex with the wood structure, so that the effect of imparting antibiotic properties and the like is stably maintained over a long period of time.

Claims (11)

[Claims] 1. A wood treating agent comprising a metal salt, a phenolic compound, and a thiosulfate or thiocyanate. 2. The wood treating agent according to claim 1, further comprising an organic alkalizing agent. 3. The organic alkalizing agent is ethanolamine,
The wood treating agent according to claim 2, which is at least one compound selected from diethanolamine, triethanolamine and ethylenediamine. 4. The wood treating agent according to claim 1, wherein the metal salt is a copper compound or a silver compound. 5. The phenolic compound is pyrocatechol,
The wood treating agent according to any one of claims 1 to 4, which is at least one compound selected from hydroquinone, pyrogallol, gallic acid, tannic acid, ferulic acid, and derivatives thereof. 6. A phenolic compound is used in an amount of 0.1 to 2 mol, and a thiosulfate or a thiocyanate is used per 1 mol of the metal salt.
The wood treating agent according to any one of claims 1 to 5, comprising 0.05 to 1 mol of the organic alkalizing agent in a ratio of 0 to 4 mol. 7. The wood treating agent according to claim 1, further comprising a polyphenol oxidation catalyst. 8. The wood treating agent according to claim 1, which is prepared as a high-concentration solution to be diluted at the time of use, or as a powder or a granulated powder to be dissolved at the time of use. 9. A method for treating wood, comprising impregnating the wood with the wood treating agent according to claim 1 to fix the metal in the wood. 10. A method for producing a metal-containing wood or woody material, comprising using the wood treatment method according to claim 9. 11. A metal-treated wood or woody material obtained by the production method according to claim 10.