JPH10265508A - Treatment of porous article and composition for treating porous article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart antimicrobial property, antiseptic property, bactericidal properties, etc., to a porous article by polymerizing an organic compound having a specific group in a structural part and/or on the surface of the porous article by a polymerization catalyst in the presence of a boron-containing organic compound. SOLUTION: An organic compound having CH2 =CH-, -CH=CH-, CH2 =C (CH3 )-, CH2 =N-, -CH=N-, NH=CH-, NH=N- and/or -N=N- in the structural part (e.g. acrylic acid), a boron-containing compound [e.g. boric acid (salt)] and a polymerization catalyst are simultaneously or continuously impregnated into and/or applied to a porous article (e.g. a metal sintered compact or wood) and the organic compound is polymerized in the presence of a boron-containing compound to fix the resultant polymer in the porous article or on the surface of the porous article. When an organic compound having both of the above structural part and a structural part of the formula -CHR-CHR-, -CHR-CH2 - CHR-, etc., (R is OH or NH2 ) in the structural part is used, the boron-containing compound can further efficiently be fixed in the porous article.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a porous article.
CH ₂ = CH- and / or _{-CH = CH -, CH 2 =} C (CH 3) -, CH
₂ = N-, -CH = N-, NH = CH-, NH = N-, -N = N-, a compound having a structural portion in the presence of a boron-containing compound is polymerized by a polymerization catalyst. The present invention relates to a method for treating a porous article, a composition used in the method, and a treated porous article obtained by the method.

More specifically, the present invention relates to an organic compound having an aromatic group having an OH group and / or an OCH ₃ group or an NH ₂ group as a substituent in a structural part, and furthermore, —CHR—CH
R - and / or _{-CHR-CH 2 -CHR -, -} O-CH 2 -CH 2 -O
_{-, - NH-CH 2 -CH} 2 -NH -, - CH 2 -CH (CH 2 R) - [ wherein R is
An organic compound having an OH group or an NH ₂ group] in a structural part thereof, together with a boron-containing compound and a metal or a metal complex such as a metal enzyme, is impregnated into a porous article by coating or pressurizing and / or depressurizing the metal, Alternatively, a method for treating a porous article for immobilizing a boron-containing compound by performing polymerization using a metal complex such as a metal enzyme as a catalyst,
And a composition used in the treatment method, and further, antibacterial property, antiseptic property, bactericidal property, insect repellent property, insecticidal property, antiviral property, biorepellent property, dimensional stability, crack prevention property, difficult to obtain, obtained by the method. Flammability, adhesion, strength, abrasion resistance, weather resistance, rust prevention, sustained release of chemicals, coloring, deodorization, deoxidation, humidity control, water absorption, water repellency, surface smoothness, formaldehyde absorption sex,
The present invention relates to a processed product of a porous article having a drug leaching prevention property or an inorganic compound migration prevention property to a wood surface.

[0003]

2. Description of the Related Art Conventionally, copper, zinc, nickel, arsenic, and the like have been used for imparting antibacterial and insect repellent properties to porous articles such as wood.
Alternatively, addition of a salt of fluorine or the like is performed. However, the use of these substances in large amounts has caused problems on the environment and toxicity to the human body. On the other hand, boron-containing compounds such as boric acid and borax have higher safety than the above-mentioned compounds, and are resistant to emergence of resistant bacteria, colorless and odorless, against termites, mites, cockroaches, and the like. It has advantages such as insecticidal properties and has been used in various fields for many years.

However, boron-containing compounds and wood,
Due to low reactivity with porous articles such as fibers, the boron-containing compound is easily eluted by rainwater or the like from the treated product in which the boron-containing compound is impregnated or applied to the porous article,
As a result, there is a disadvantage that the preservative and insect repellent effects are reduced. Therefore, in order to suppress the elution and leaching of boron,
A method in which ethylene glycol is used together with boron as a liquid carrier (Japanese Patent Publication No. 1-34762), a method in which boron and a quaternary ammonium compound are used together (Japanese Patent Publication No. 3-74602, Japanese Patent Publication No. 523163, Japanese Patent Application Laid-Open No. 9-1508), boron And a method of using a volatile basic compound together (Japanese Unexamined Patent Publication No.
808) has been implemented, but the problems remain: suppression of metal corrosion when a large amount of quaternary ammonium compounds are used, and reduction of the effects on the human body and environment due to the use of volatile basic compounds and heavy metals in large amounts. In addition, since the boron-containing compound is not fixed together with the essentially water-insoluble or poorly water-soluble compound, it has been desired to develop a boron fixing method having a higher leaching-inhibiting effect.

[0005] Conventionally, attempts have been made to inject a treatment liquid containing an acrylic oligomer and boric acid into wood, and to carry out a polymerization reaction by heating at 180 ° C for 3 hours to fix boric acid in the wood. (Japanese Wood Research Society North Sea Degree Chapter Lectures No.
No. 27, 63 (1995)). However, polymerization at lower temperatures,
There has been a demand for a simpler and more effective boric acid fixing method by using boric acid at a higher concentration and improving the boric acid fixing rate.

[0006] Conventionally, various enzyme utilization methods using metal enzymes such as laccase, polyphenol oxidase and peroxidase produced by basidiomycetes and incomplete fungi as oxidation catalysts or polymerization catalysts have been disclosed in WO87-2939 and JP-A-Hei.
5-117591, JP-A-6-316874, JP-A-6-287516, JP-A-7-
126354, JP-A-7-126377, WO95-1426, WO96-3546, or Journal of Biotechnology, 13 , 229-241, 1990. However, these enzyme utilization methods are those that use the polymerization reaction by the enzyme as an adhesive, a coating agent, a waterproofing agent, or those that are used for dyeing, and those that are used to obtain the polymer compound itself. Methods for simultaneously imparting antibacterial properties and insect repellency to the obtained porous article, and methods for using boric acid, which is an inexpensive and safe antibacterial and insect repellent, and a method for suppressing leaching of boric acid are shown. However, methods for preserving and controlling insects such as fibers, wood, and wood products obtained by these methods have been left as problems. Conventionally, attempts have been made to obtain an adhesive effect by enzymatically oxidizing a phenolic compound, a lignocellulosic substance, or a phenolic polysaccharide, and to use this in the production of fiberboard, plywood, and the like (EP433258). , US4432921, WO96-03546). However, these technologies are aimed at industrial use and application using a lacquer-like reaction as an adhesive action, and the treatment and treatment of wood itself, especially in the preservative wood industry, has not been advanced, and moreover, Methods for preserving and controlling insects on porous articles obtained by these methods have been left as problems.

[0007]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide CH ₂ = CH- and / or -CH = CH-, CH ₂ = C (CH ₃ ).
_{-, CH 2 = N -,} - CH = N-, NH = CH -, NH = N -, - N = N -
An object of the present invention is to provide a method for polymerizing an organic compound having a structural portion of the above with a polymerization catalyst and fixing a boron-containing compound in a porous article using the reaction product. Another object of the present invention is to provide an organic compound having an aromatic group having an OH group and / or an OCH ₃ group or an NH ₂ group as a substituent in a structural part, such as CH ₂ CHCH— and / or —CH = CH −. , CH ₂ = C (CH ₃ )
_{-, CH 2 = N -,} - CH = N-, NH = CH -, NH = N -, - N = N -
Antibacterial, antiseptic, bactericidal, insecticidal, insecticidal, antiviral, including a step of polymerizing an organic compound having a structural part with a polymerization catalyst and contacting the reaction product with a boron-containing compound in a porous article. Properties, biological repellency, dimensional stability,
Anti-cracking, flame-retardant, adhesive, strength, abrasion-resistant, weather-resistant, rust-proof, sustained-release of drugs, coloring, deodorizing, deoxidizing, moisture-controlling, water-absorbing, water-repellent, surface It is an object of the present invention to provide a method, a treating agent, or a treated product for a porous article having an effect of imparting smoothness, formaldehyde absorption, drug leaching prevention, or inorganic compound migration prevention to a wood surface.

[0008]

Means for Solving the Problems The present inventors fix a boron-containing compound, which is an inexpensive and highly safe antibacterial and insect repellent agent, in a porous article such as wood, and have a long-term effective antibacterial property.
Antiseptic, bactericidal, insect repellent, insecticidal, antiviral, biorepellent, dimensional stability, crack resistance, flame retardancy, adhesion, strength, abrasion resistance, weather resistance, rust resistance , Drug sustained release,
Coloring, deodorant, deoxygenation, humidity control, water absorption, water repellency, surface smoothness, formaldehyde absorption, drug leaching prevention,
In addition, diligent research was conducted to develop a method for imparting or improving the property of preventing the transfer of the inorganic compound to the wood surface. As a result, CH ₂ = CH- and / or -CH = CH
_{-, CH 2 = C (CH} 3) -, CH 2 = N -, - CH = N-, NH = CH -, NH
= N-, -N = N- an organic compound having a structural part, in particular,
The porous article is impregnated or coated with an organic compound having an aromatic group having an OH group and / or an OCH ₃ group or an NH ₂ group as a substituent together with a polymerization catalyst, and a polymerization reaction is performed in the porous article. The inventors have found that the object of the present invention can be achieved by bringing the reaction product into contact with a boron-containing compound in a porous article, and have completed the present invention.

That is, the present invention utilizes oxygen (air) or hydrogen peroxide as an oxidizing agent to make CH ₂ = CH- and / or -CH = CH-, CH ₂ = C (CH ₃ )-, CH ₂ = N−, −CH = N−,
NH = CH -, NH = N -, - N = N - an organic compound having a structural part, in particular, organic having OH groups and / or OCH ₃ group, an aromatic having NH ₂ groups as a substituent structural part The compound is oxidatively polymerized, and a boron-containing compound is brought into contact with the compound to fix boron. The oxidative polymerization catalyst is a metal catalyst such as an enzyme having a polyphenol oxidizing action, and it is surprising that such a catalyst catalyzes the oxidation reaction and the polymerization reaction in an environment where the oxygen supply rate inside the porous article is low. It should be. In particular, the impregnating treatment including the decompression operation as a part of the treatment step is extremely effective as an operation for increasing the injection amount of the treatment liquid into the porous article that is difficult to impregnate. However, the concentration of dissolved oxygen in the processing solution and the processed product that has undergone the decompression operation is low, which is disadvantageous for a catalytic reaction using oxygen as an oxidizing agent. However, surprisingly, it has been found that even in a processed product of a porous article that has been subjected to a decompression operation, a catalytic oxidation reaction and a polymerization reaction in the inside proceed. As an operation for increasing the injection amount of the treatment liquid into porous articles that are difficult to impregnate, the pressure injection method is also extremely effective, but it is known that many enzymes are unstable to the pressure treatment. Have been. However, surprisingly, polyphenol oxidase as an oxidation catalyst maintains its catalytic activity even after pressure injection treatment, and furthermore, in an environment where the oxygen supply rate inside the porous article is low, the oxidation reaction, It has been found that it catalyzes the reaction.

Further, -CHR-CHR- and / or -CHR-
_{CH 2 -CHR -, - O-} CH 2 -CH 2 -O -, - NH-CH 2 -CH 2 -NH -,
The coexistence of an organic compound having —CH ₂ —CH (CH ₂ R) — [R is an OH group or an NH ₂ group] in the structural part further improves the fixability of the boron-containing compound and regulates the sustained release. Have been found possible, and the present invention has been completed. Further still, the boron fixing method of the present invention, a conventionally used fragrance, deodorant, rust inhibitor, flame retardant, antibacterial, antiseptic, bactericide, insect repellent, antiviral, or By combining the addition of various agents such as biological repellents, these agents are also efficiently fixed at the same time as boron immobilization,
Finding that a synergistic porous article treatment effect can be obtained,
The present invention has been completed as being more useful.

That is, the present invention provides the following. [1] CH ₂ = CH-, -CH = CH-, CH ₂ = C (CH ₃ )-, -CH ₂ =
N-, -CH = N-, NH = CH-, NH = N-, and / or -N = N
The porous article is impregnated and / or coated with an organic compound having a-in the structural part, a boron-containing compound, and a polymerization catalyst simultaneously or before and after, and the organic compound is made porous by the polymerization catalyst in the presence of the boron-containing compound. A method for treating a porous article, comprising polymerizing in the article and / or on the surface of the porous article. [2] CH ₂ = CH-, -CH = CH-, CH ₂ = C (CH ₃ )-, -CH ₂ =
N-, -CH = N-, NH = CH-, NH = N-, and / or -N = N
-Impregnating and / or coating a porous article with a composition containing an organic compound having a-in its structural part, a boron-containing compound, and a polymerization catalyst, and subjecting the organic compound to a porous article with a polymerization catalyst in the presence of the boron-containing compound A method for treating a porous article, comprising polymerizing in and / or on the surface of the porous article. [3] Application of boron-containing compound to porous article and / or
Alternatively, as a pre-treatment or post-treatment for impregnation, CH ₂ = CH−, −
_{CH = CH -, CH 2 =} C (CH 3) -, - CH 2 = N -, - CH = N-, NH = C
Using a composition containing an organic compound having a structural part of H-, NH = N-, and / or -N = N-, and polymerizing the organic compound in a porous article and / or using a polymerization catalyst. A method for treating a porous article, comprising polymerizing on the article surface.

[4] The organic compound described above, wherein the organic compound has an aromatic ring having a OH group, an OCH ₃ group, and / or an NH ₂ group as a substituent in a structural part thereof. 3] The method for treating a porous article according to any one of [1] to [3]. [5] The organic compound further comprises -CHR-CHR-, -CHR-CH
_{2 -CHR -, - O-CH} 2 -CH 2 -O -, - NH-CH 2 -CH 2 -NH -, and / or _{-CH 2 -CH (CH 2 R)} - [ wherein R is or OH groups NH
_The method for treating a porous article according to any one of the above items [1] to [4], wherein the organic compound has an organic compound having [ ₂ groups] in a structural portion. [6] an organic compound having an OH group, an NH ₂ group, and / or an aromatic compound having an unsaturated side chain as a substituent, and a vinyl ester, a vinyl ether, a methacryl The method for treating a porous article according to the above [5], which is an organic compound produced through a reaction with an acid ester, allyl ether, allyl alcohol, and / or allylamine.

[7] An organic compound in which an aromatic compound having, as a substituent, an OH group, an NH ₂ group, and / or a compound obtained by protecting the same, and polyvinyl alcohol, polyethylene glycol, polyallylamine, polyethyleneimine and / or The method for treating a porous article according to the above [5], which is an organic compound produced through a reaction with a derivative. [8] The method for treating a porous article according to any one of [1] to [7], wherein the polymerization catalyst is a metal salt or complex. [9] The method for treating a porous article according to [8], wherein the metal is a transition element or at least one metal selected from zinc and aluminum. [10] The method for treating a porous article according to the above [8] or [9], wherein the complex is a metalloenzyme.

[11] The method for treating a porous article according to [10], wherein the metal enzyme is catechol oxidase, laccase, polyphenol oxidase, ascorbate oxidase, bilirubin oxidase, or peroxidase. [12] The method for treating a porous article according to any one of [1] to [10], wherein the boron-containing compound is a borate. [13] -CHR-CHR -, - CHR-CH 2 -CHR -, - O-CH 2 -
CH ₂ —O—, —NH—CH ₂ —CH ₂ —NH—, and / or —CH ₂ —CH
The porous article according to any one of [1] to [12], further including an organic compound having (CH ₂ R)-[the R is an OH group or an NH ₂ group] in a structural part. Processing method. [14] Also includes at least one agent selected from fragrances, deodorants, rust inhibitors, flame retardants, antibacterial agents, preservatives, bactericides, insect repellents, antiviral agents, and biological repellents. The method for treating a porous article according to any one of the above [1] to [13].

[15] The chemical is copper, arsenic, zinc, chromium, nickel, aluminum, molybdenum, magnesium, titanium, cobalt, palladium, tin, lead, iron,
The method for treating a porous article according to the above [14], wherein the porous article is a solution or a fine powder of at least one metal selected from antimony, zirconium or silver, a metal salt, a metal compound or a metal complex. [16] The method for treating a porous article according to the above [14], wherein the drug is a quaternary ammonium compound. [17] The method for treating a porous article according to the above [14], wherein the drug is an aromatic compound or a cyclic compound having one or more substituents selected from an OH group, an amino group, a halogen, and a nitro group. [18] The method for treating a porous article according to [14], wherein the drug is a plant-derived extract, an extract component, or a synthetic compound having a structure equivalent to that of the plant extract component. [19] the aforementioned [18], wherein the drug is hinokitiol;
A method for treating a porous article according to the above.

[20] The above-mentioned [2] to [2], wherein the composition is prepared as a high-concentration solution for dilution at the time of use, or as a powder or a granulated powder for dissolution at the time of use. [19] The method for treating a porous article according to any of [19]. [21] The method for treating a porous article according to any one of [1] to [20], wherein the impregnation is performed by applying pressure and / or reduced pressure. [22] The method for treating a porous article according to [21], wherein the pressure is applied at 1 to 20 atm. [23] A polymerization reaction temperature of 0 to 200 ° C., preferably 5 to 200 ° C.
The method for treating a porous article according to any one of [1] to [22], wherein the temperature is 120 ° C, more preferably 10 to 80 ° C. [24] The porous article may be a metal sintered body, a cast product, an alloy, a die-cast product, a ceramic, a brick, a concrete, a wood, a piece of wood, a wood powder, a wood processing material, a fir shell, a rush, a straw, a bamboo material, a leather, a cloth, The method for treating a porous article according to any one of the above [1] to [23], which is a nonwoven fabric, fiber, activated carbon, or a synthetic resin foam. [25] antibacterial, antiseptic, bactericidal, insect repellent, insecticidal,
Antiviral, biological repellency, dimensional stability, crack resistance,
Flame retardancy, adhesion, strength, abrasion resistance, weather resistance, rust prevention, drug sustained release, coloring, deodorant, deoxidizing, humidity control, water absorption,
The above-mentioned [1] to [1] to, which have an effect of imparting water repellency, surface smoothness, formaldehyde absorption, drug leaching prevention, or inorganic compound migration prevention to wood surfaces.
The method for treating a porous article according to any one of [24].

[26] A method for producing a treated porous article, comprising using the method according to any one of [1] to [25]. _{[27] CH 2 = CH -} , - CH = CH -, CH 2 = C (CH 3) -, - CH
₂ = N-, -CH = N-, NH = CH-, NH = N-, and / or-
A composition for treating a porous article, comprising an organic compound having a structure of N = N-, a boron-containing compound, and a polymerization catalyst. [28] The organic compound is an OH group, an OCH ₃ group, and / or
The composition for treating a porous article according to the above [27], which is an organic compound having an aromatic ring having an NH ₂ group as a substituent in a structural part. [29] The organic compound further comprises -CHR-CHR-, -CHR-
_{CH 2 -CHR -, - O-} CH 2 -CH 2 -O -, - NH-CH 2 -CH 2 -NH -,
And / or _{-CH 2 -CH (CH 2 R)} - [ wherein R is or OH groups
The composition for treating a porous article according to the above [27] or [28], which is an organic compound having [NH ₂ group] in a structural part.

[30] The organic compound is an OH group, an NH ₂ group,
And / or an aromatic compound having a protected one thereof as a substituent and further having an unsaturated side chain as a substituent, a vinyl ester, a vinyl ether, a methacrylic ester, an allyl ether, an allyl alcohol, and / or
Alternatively, the composition for treating a porous article according to the above [29], which is an organic compound produced through a reaction with allylamine. [31] An organic compound having an OH group, an NH ₂ group, and / or an aromatic compound having a protected one as a substituent and polyvinyl alcohol, polyethylene glycol, polyallylamine, polyethyleneimine and / or a derivative thereof The composition for treating a porous article according to the above [29], which is an organic compound produced through a reaction.

[32] The composition for treating a porous article according to any one of [27] to [31], wherein the polymerization catalyst is a metal salt or complex. [33] The above-mentioned [32], wherein the metal is a transition element or at least one metal selected from zinc and aluminum.
The composition for treating a porous article according to the above. [34] The composition for treating a porous article according to the above [32] or [33], wherein the complex is a metalloenzyme. [35] The composition for treating a porous article according to the above [34], wherein the metal enzyme is catechol oxidase, laccase, polyphenol oxidase, ascorbate oxidase, bilirubin oxidase, or peroxidase. [36] The composition for treating a porous article according to any of [27] to [35], wherein the boron-containing compound is a borate. [37] -CHR-CHR -, - CHR-CH 2 -CHR -, - O-CH 2 -
CH ₂ —O—, —NH—CH ₂ —CH ₂ —NH—, and / or —CH ₂ —CH
The porous article treatment according to any one of the above [27] to [36], further comprising an organic compound having (CH ₂ R)-[the R is an OH group or an NH ₂ group] in a structural part. Composition.

[38] At least one agent selected from fragrances, deodorants, rust inhibitors, flame retardants, antibacterial agents, preservatives, bactericides, insect repellents, antiviral agents, and biological repellents The composition for treating a porous article according to any one of the above [27] to [37], comprising: [39] The agent is at least one selected from copper, arsenic, zinc, chromium, nickel, aluminum, molybdenum, magnesium, titanium, cobalt, palladium, tin, lead, iron, antimony, zirconium and silver.
The composition for treating a porous article according to the above [38], which is a solution or a fine powder of a kind of metal, metal salt, metal compound or metal complex. [40] The composition for treating a porous article according to the above [38], wherein the drug is a quaternary ammonium compound. [41] The composition for treating a porous article according to the above [38], wherein the drug is an aromatic compound or a cyclic compound having one or more substituents selected from an OH group, an amino group, a halogen, and a nitro group. [42] The composition for treating a porous article according to [38], wherein the drug is a plant-derived extract, an extract component, or a synthetic compound having a structure equivalent to that of the plant extract component.

[43] The composition for treating a porous article according to the above [42], wherein the drug is hinokitiol. [44] As a highly concentrated solution for dilution at the time of use,
Or [2] prepared as a powder for dissolving or granulated powder at the time of use.
7] The composition for treating a porous article according to any one of [43]. [45] antibacterial, antiseptic, bactericidal, insect repellent, insecticidal,
Antiviral, biological repellency, dimensional stability, crack resistance,
Flame retardancy, adhesion, strength, abrasion resistance, weather resistance, rust prevention, drug sustained release, coloring, deodorant, deoxidizing, humidity control, water absorption,
[27] The above-mentioned [27], which has an effect of imparting water repellency, surface smoothness, formaldehyde absorption, drug leaching prevention, or inorganic compound migration prevention to the wood surface.
-The composition for treating a porous article according to any one of [44].

Hereinafter, the present invention will be described in detail. [Boron-containing compound] In the present invention, the boron-containing compound used by coating or impregnating the porous article is a boron-containing compound such as boric acid (orthoboric acid), metaboric acid, tetraboric acid, octaboric acid, and the like. Other metal salts such as alkali metal salts of copper, copper borofluoride, copper tetrafluoroborate, copper silicofluoride, antimony fluoride, or complexes, but when considering safety to the human body and the environment, boric acid (Orthoboric acid), boron-containing compounds such as metaboric acid, tetraboric acid, and octaboric acid, and alkali metal salts thereof are particularly desirable.

As the compound to be added to form a complex, many conventionally known compounds can be used. For example, pyrocatechol, gallic acid, hinokitiol, catechin, pyrogallol, o-phenylenediamine and the like can be used. Phenolic compounds or aromatic amine compounds,
Ethane-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane-
Phosphonic acids such as 1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-
2,3,4-tricarboxylic acid, phosphonocarboxylic acids such as α-methylphosphonosuccinic acid, aspartic acid, glutamic acid, glycine, amino acids or amino acid analogs such as 2-aminoisobutyric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, Aminopolyacetic acid such as diethylenetriaminepentaacetic acid, polyacrylic acid, polyitaconic acid, polymaleic acid, maleic anhydride copolymer, polymer electrolytes such as carboxymethylcellulose, non-dissociated polymers such as polyethylene glycol, polyethylene oxide and polyvinyl alcohol, benzene poly Organic acids such as carboxylic acid, oxalic acid, malic acid, diglycolic acid, succinic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, gluconic acid, citric acid, lactic acid, tartaric acid, sucrose, lactose, pentae Carboxymethylated products such as thritol, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, triethylenetetramine, propanolamine, pentaethylenehexamine, polyethyleneimine, triisopropanolamine, triazacyclononane And organic substances such as triazacyclododecane, starch, urea, chitosan, and ξ-polylysine.

[Polymerization Catalyst] In the present invention, a catalyst used for the purpose of conducting a polymerization reaction by coating or impregnating a porous article is CH ₂ = CH- and / or -CH = CH-, CH ₂ = C ( CH
_{3) -, CH 2 = N} -, - CH = N-, NH = CH -, NH = N -, - N = N
- an organic compound having a structural part, in particular, OH groups and / or OCH ₃ group, if the oxidation reaction of organic compounds having an aromatic a structural part having as a substituent a NH ₂ group those catalysts, can accelerate Any substance can be used, but as specific examples of the catalyst, the above-mentioned substances mentioned as compounds added to form the boron-containing complex, and other phosphonic acids, phosphonocarboxylic acids, amino acids or amino acids Analogues, aminopolyacetic acid, polyelectrolyte, non-dissociated polymer, organic acid, carboxymethylated compound, organic alkali agent, organic substance and manganese, iron, cobalt, nickel,
Examples include complexes and salts with metals such as copper, zinc, molybdenum, palladium, silver, tin, and aluminum. Other specific examples of the metal complex include 1,4,7-triazacyclononane and its N-methyl derivative, dicarboxylic acids such as adipic acid and tartaric acid, organic alkali agents such as ethylenediamine, phthalocyanine and hydrophilic compounds thereof. Complex with a metal ion such as manganese, iron, cobalt, or copper. The oxidizing agent is air (oxygen), hydrogen peroxide,
Although an organic peracid compound can be used, it is more desirable to use a polymerization catalyst that can use air (oxygen) as an oxidizing agent for inexpensive and easy treatment of a porous article.

In addition, metal enzymes which are naturally occurring metal complex catalysts can also be used for the purpose of the present invention. Examples of such enzymes include polyphenol oxidases such as catechol oxidase, laccase, polyphenol oxidase, ascorbate oxidase, or bilirubin oxidase produced by microorganisms, such as fungi or bacteria, or produced by plants. Since these enzymes can catalyze an oxidation reaction and a polymerization reaction using air (oxygen) as an oxidizing agent, they are particularly useful for carrying out the porous article treatment of the present invention at low cost.

The polymerization reaction by enzymatic oxidation can also be carried out by using an enzyme having a peroxidase effect such as peroxidase, lignin peroxidase, manganese peroxidase or catalase derived from microorganisms or plants and hydrogen peroxide. The method of adding and supplying hydrogen peroxide is a method of directly adding a hydrogen peroxide solution,
Instead of hydrogen peroxide, there is a method using a hydrogen peroxide precursor such as perborate or percarbonate, or a method using an oxidase capable of producing hydrogen peroxide and its substrate. In the case where both hydrogen peroxide or a hydrogen peroxide precursor and an enzyme having a peroxidase action are added to the raw material for the polymerization reaction, the oxidation reaction and the polymerization reaction proceed immediately. Therefore, in order to impregnate the treatment liquid into the interior of the porous article, it is desirable to mix these enzymes and the oxidizing agent immediately before use to suppress the polymerization reaction before coating or impregnation. A specific method for that is to use a mixture of a substance having a peroxidase action and an oxidase capable of producing hydrogen peroxide. Since hydrogen peroxide is not generated unless oxidase is generated by using dissolved oxygen, the oxidation reaction and the polymerization reaction by peroxidase hardly proceed. Therefore, the object of the present invention can also be achieved by a mixture of such an enzyme having a peroxidase action, an oxidase capable of producing hydrogen peroxide, and an oxidase substrate.

Examples of such oxidases capable of producing 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 the like. There are ureate oxidase, xanthine oxidase, cholesterol oxidase and the like, and particularly preferable are glucose oxidase and alcohol oxidase.

When it is desired to carry out the oxidation reaction and the polymerization reaction with the metal enzyme used in the present invention at a higher speed, those having an oxidizing action at an alkaline pH are more desirable. Those on the alkaline side of 7.5 or more are desirable. Specifically, it is desirable that such an enzyme has an optimum reaction pH on the alkaline side of pH 7.5 or more in activity measurement using syringaldazine. In addition, the oxidase capable of producing hydrogen peroxide used in the present invention preferably has an optimum reaction pH on the alkaline side at pH 7.5 or higher for efficient reaction. The activity of polyphenol oxidase using air (oxygen) as an oxidizing agent was measured at 20 ° C at 20 ppm syringaldazin (syri
ngaldazine) and 100 mM Tris-HCl buffer or potassium phosphate buffer in an aqueous solution at an optimum reaction pH, and measuring the absorbance at 525 nm. The amount of activity for oxidizing 1 μmol of syringaldazine per minute is 1 unit (hereinafter abbreviated as U).
Defined. The oxidation activity of the enzyme having peroxidase activity was measured at 20 ° C in an aqueous solution containing 20 ppm syringaldazine, 20 ppm hydrogen peroxide, and 100 mM Tris-HCl buffer or potassium phosphate buffer. The reaction was carried out at an optimum reaction pH and the absorbance at 525 nm was measured. And
The activity of oxidizing 1 μmol of syringaldazine per minute was defined as 1 unit (hereinafter abbreviated as U). In addition, the activity of oxidase capable of producing hydrogen peroxide was measured at 20 ° C. by using 1 to 100 mM of an oxidase substrate,
20ppm syringaldazine, 1U / ml
In an aqueous solution containing peroxidase and 100 mM Tris-HCl buffer or potassium phosphate buffer,
The reaction was performed at the optimum reaction pH, and the absorbance at 525 nm was measured. The amount of activity for oxidizing 1 μmol of syringaldazine per minute was defined as 1 unit (hereinafter abbreviated as U).

Examples of microorganisms producing the enzymes used for the purpose of the present invention include the following. As fungi, Aspergillus ( Aspergillus ) and Botrytium ( Botryt ) belonging to the subphylum Subuterus ( Deuteromycotina )
is), Myrothecium (Myrothecium), Emuberishia (Embellisia), Doreshurera (Dreschlera), Penicillium (Penicillium), Pesutarochia (Pestaloti
a), Rhizoctonia (Rhizoctonia), Trichoderma (T
ricoderma), Asuromaisesu (Arthromyces), Humicula (Humicola), Vel tee Ssireum (Verticil
lum), Urokurajiumu (Ulocladium), Cal Dario Mrs. (Caldariomyces), Sutirubera (Stilbella
), Sagenomella ( Sagenomella ), Stachyridium ( S
tachylidium ), preferably Aspergillus nidulans , Botrytis cinerea , Myrosecesium loridum ( My
rothecium roridum , Milosesium velcaria ( M
yrothecium verrucaria ), myrothesium prestoni ( Myrothecium prestonii ), myrothesium leukotricum ( Myrothecium leucotrichum ),
Ali (Embellisia alli), Doreshurera-Harodesu (Dreschlera halodes), Penicillium sclerotinia Oram (Penicillium sclerotiorum), Penicillium
Yanchinerumu (Penicillium janthinellum), Pesutarochia-Parumaramu (Pestalotia palmarum), Rhizoctonia Puratikora (Rhizoctonia praticola), Rhizoctonia solani (Rhizoctonia solani), Trichoderma Reshii (Tricoderma resii), Trichoderma viride (Tricoderma viride), Asuromaisesu-Ramosasu ( Arthromycesramosus , Humicola insolens , Verticillum dahlie , Verticillum alboatrum , Ulocladium chartarum , Caldarios ario Calmygosmario ario・Stilbella annulata , Stilbella bulbicola , Stilbella erythrocephal
a ), Stilbella flavesens
scens , Stilbella flavipes
pes ), Stilbella ther
mophila ), Stillbera sp. ( Stilbella sp.
), Sagenomella viride , Sagenomella sp. ( Sagenomella sp. ), Stachylidium bicolor , Stachylidium theobromae , Stachylidium sp. ( Stachylidium sp. ).

Of these, particularly preferred is Myrothecium verrucaria SD3001 ( Myrothecium verruc)
aria SD3001) (Institute of Biotechnology, Industrial Technology Research Institute)
FERMP-14955, transferred to the International Depositary and assigned accession number FERM BP-5520), Myrothecium vercaria IFO6113 ( Myrothecium verruc
aria IFO 6113), or myrocesium loridum S
D3002 ( Myrothecium roridum SD3002) (deposited with the National Institute of Bioscience and Human Technology, FERM P-15255, transferred to an international deposit, and given accession number FERM BP-5523).

Other preferred fungi include Pleu belonging to the subdivision Basidiomycotina.
rotus ), Lentinus , Schizophyllum , Armillariella
), Flammulina , Agaricu
s), Coprinus (Coprinus), Phanerochaete (Phane
rochaete), Furebia (Phlebia), hygromycin Roman-flops cis (Hygrophoropsis), Renchitesu (Lenzites),
Melanoleuca , foliota
a), Sutereumu (Stereumu), Polyporus (Polyporus
), Poriporerusu (Polyporellus), Kurushiburumu (C
rucibulum), Mikuroporasu (Microporus), Fomitopushisu (Fomitopsis), Pikunoporasu (Pycnoporus),
Collybia , Trametes , Coriolus , Daedaleopsi
s), Rijidoporasu (Rigidoporus), Fomesu (Fomes
), Ganoderma (Ganoderma), Torakideruma (Trach
Yderma), Himenokaete (Hymenochaete), Inonotasu (Inonotus), Pusachirera (Psathyrella) can be mentioned, preferably among these are Ploy Lotus Korunukopie (Pleurotus cornucopiae), Ploy Lotus
Osutoreatasu (Pleurotus osteratus), Rentinasu edodes (Lentinus edodes), Schizophyllum commune (Schizophyllum commune), Almira Riera-Merea (Armillariella mellea), Furamurina-Berutipesu (Flammulina velutipes), Agarikasu-bisporus (Agaricusbisporus), Coprinus Komatasu ( Coprinus comatus ), Coprinus cinereus ( Copr
inus cinereus), Coprinus Konguregatasu (Copr
inus congregatus), Coprinus replica Tirith (Co
prinus plicatilis ), Coprinus macrolithus ( Co
prinus macrorhizus), Phanerochaete chrysosporium (Phanerochaete chrysosporium), Furebia-radiata (Phlebia radiata), hygromycin Roman-flops cis aurantiacus mosquito (Hygrophoropsis aurantiaca),
Renchitesu-Betsurina (Lenzites betulina), Meranoroika-Berurushipesu (Melanoleuca verrucipes), Foriota-nameko (Pholiota nameko), Sutereumu -
Hirusutamu (Stereumu hirsutum), Polyporus, Sukuamosasu (Polyporus squamosus), Polyporus, Pinshitasu (Polyporus pinsitus), Poriporerusu badius (Polyporellus badius), Kurushiburumu-Raebe (Crucibulum laeve), Mikuroporasu Hula Berri folder Miss (Microporus flabelliformis), Fomitopushisu・ Piconola ( Fomitopsis pinicola ), Pycnopora ・
Koshineusu (Pycnoporus coccineus), Koribia-Aserubata (Collybia acervata), Koribia-Makyurata (Collybia maculata), Trametes orientalis (Trametes orientalis), Trametes Virosa (Trametes villosa), Coriolus Verushikora (Coriolus versicolor), Coriolus Hirusutasu (Coriolus hirsutus), Dedareopushisu-Torikora (Daedaleopsis tricolor), Rijidoporasu-Zonarisu (Rigidoporus zonalis), Fomesu-follower Mentha Prius (Fomes fomentarius), Ganoderma lucidum (Ga
noderm a lucidum ), Trachyderma tsunodae ( Trachy
derma tsunodae , Hymenokaete rubiginosa ( Hyme)
nochaete rubiginosa ), Inonotas Mikadoi ( Inon
otus mikadoi , Psathyre multissima ( Psathyre)
lla multissima ), Psachirella pirriformis ( Ps
athyrella piluliformis ). Other preferred fungi other than the incomplete mycoplasma and the basidiomycota are
Podospora ( Podo ) belonging to the subphylum Ascomycotina ( Ascomycotina )
Spora), Neurospora (Neurospora), Monoshiriumu (Monocillium), Fusarium (Fusarium), Mucor belonging to Zygomycetes subdivision (Zygomycotina) (Mucor), Rhizopus (Rhizopus), preferably, Podosupora-Anserina (Podospora anserina), Neurospora, crassa (Neurospora crassa), Monoshiriumu Indy cam (Monocillium indicum), Fusarium oxysporum (Fusarium oxysporum), Mucor Hiemarisu (Mu
cor hiemalis ), Rhizopus niglicans ( Rhizopus n
igricans ).

[0032] Some preferred bacteria, Azosupiriumu (Azospirillum), preferably Azosupiriumu-Ripoferamu (Azospirillum lipoferum), or, activator flea Seta-less eyes (Actinomycetales), for example, Streptomyces (Streptomyces), preferably Streptomyces Anchibio Ticas ( Streptomyces antibioti
cus ), Streptomyces sphaeroides ( Streptom)
yces spheroides ), Streptomyces thermoviolaceus , or
Aerobacter , preferably a strain belonging to Aerobacter aerogenes is included.

[0033] Other preferred bacteria, Bacillus alkalophilus (Bacillus alcalophilus), Bacillus amyloliquefaciens (Bacillus amyloliquefacien
s), Bacillus brevis (Bacillus brevis), Bacillus Famasu (Bacillusfirmus), Bacillus licheniformis (Bacillus licheniformis), Bacillus subtilis (Bacillus subtilis), Bacillus Natto (Bacillus natto), Bacillus pumilus (Bacillus p
umilus ), Bacillus sphae
ricus ), Bacillus stearothermophilus ( Bacill)
us stearothermophilus ), preferably Bacillus licheniformis . Some preferred plants containing the enzymes used in the present invention include Acerpseudoplatanum , Dioscorea ( Dios )
corea ), okra ( Abelmoschus ), guava ( Psidium )
), Sunflowers ( Helianthus ), potatoes, apples,
Including pumpkin, cucumber, wheat, soy, alfalfa, horseradish.

[Preparation of metalloenzyme] The metalloenzyme used in the present invention can be obtained by culturing the above-mentioned microorganisms, for example, fungal or bacterial strains and mutants thereof, and also by using genetically engineered bacteria. It is also possible. That is,
A DNA having a replication origin for replicating a vector in a host organism, together with a DNA sequence encoding the enzyme protein, an appropriate promoter having an enzyme expression function in the host organism, and an operator and terminator DNA sequence.
A host cell transformed with the expression vector inserted into the vector, or D encoding the enzyme protein
Appropriate promoter having NA sequence and enzyme expression function in host organism, operator, terminator DNA
A host cell transformed by incorporating it into the host cell DNA together with the sequence is cultured under conditions capable of expressing the enzyme protein, and further produced by a method of recovering the enzyme protein from the medium.

In order to obtain a DNA fragment encoding the metalloenzyme protein of the present invention, a cDNA or genomic library from the aforementioned microorganism, for example, a strain belonging to fungi or bacteria, is used as an isolation source, and the enzyme of the present invention is obtained. Identify the target DNA fragment using an oligonucleotide synthesized based on the amino acid sequence of the protein as a probe, or select a clone that expresses the activity as an oxidase, or select a protein that reacts with an antibody against the enzyme protein. It can be performed by a conventional method such as selecting a clone to be produced.

The metalloenzyme protein according to the present invention can also be prepared by extracting from the above-mentioned plant-derived seeds, fruits, leaves and the like. For culturing strains belonging to fungi or bacteria and mutants thereof for obtaining the metalloenzyme used in 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 the case of culturing, the metal at the active center of the metalloenzyme is used as a metal salt in an amount of 0.00
It is desirable to add at a concentration of 1 mM to 10 mM, preferably 0.01 mM to 1 mM.

When the metalloenzyme protein of the present invention is secreted outside the fungal or bacterial cells, it can be recovered from the culture medium by a well-known method. This recovery procedure includes:
It includes a series of procedures in which cells are separated from a medium by centrifugation, filtration, or membrane separation, and chromatography is performed by, for example, ion exchange chromatography. Further, membrane concentration using an ultrafiltration membrane is also effective. When the enzyme protein accumulates in fungal or bacterial cells or is present in plant tissues, it can be recovered from the cell tissues or plant tissues by a well-known method. This recovery procedure includes a series of procedures of mechanical disruption of tissue by homogenization, separation and extraction of an enzyme protein solution by centrifugation or filtration, and membrane separation, and then, for example, chromatography by ion exchange chromatography or the like. Also,
Membrane concentration using an ultrafiltration membrane is also effective.

[Raw Materials for Polymerization Reaction] CH ₂ CHCH— and / or —CHCHCH—, CH ₂ CC (CH ₃ ) to be polymerized in the present invention.
_{-, CH 2 = N -,} - CH = N-, NH = CH -, NH = N -, - N = N -
In the organic compound having a structural portion of, particularly, an organic compound having an aromatic group having an OH group and / or an OCH ₃ group or an NH ₂ group as a substituent, the catalyst used in the present invention is oxidized or polymerized. Any compound that can be used can be used.

Specific examples of such organic compounds include allyl alcohol, acrylic acid, allylamine, allyl acetate, allyl acetoacetate, N-allylaniline,
-Allylanisole, allyl chloride, diallyl ether,
Allyl glycidyl ether, 3-allyloxy-1,2-
Propanediol, O-allylhydroxylamine, allylisocyanate, methacrylic acid, methacrylamide, methacrylonitrile, allyl methacrylate, trimethallyl isocyanurate, 2-allyl-6-methoxyphenol, 4-allyl-2-methoxyphenol, 2
-Allyl-6-methylphenol, 4-allyl-1,2
-Dimethoxybenzene, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 2-allylphenol,
Allyl urea, thiocinamine, triacryl formal,
Triallyl isocyanurate, triallyl cyanurate, tris (acryloxyethyl) isocyanurate,
p-vinylphenol, vinyl acetate, vinyl propionate, 4-vinylanisole, vinyl benzoate, 4-vinylbenzoic acid, N-vinylcaprolactam, crotonic acid,
Vinyl crotonate, vinyl chloride, 4,4'-diaminostilbene, 2-vinylpyridine, 4-vinylpyridine,
Vinyl sulfate, ethylene glycol vinyl ether, ethylene glycol divinyl ether, 1-allyloxy-2
-Propanol, 2-propenylphenol, 4-propenylphenol, 4-propenylanisole, 2-methoxy-4- (1-propenyl) phenol, 2-ethoxy-4- (1-propenyl) phenol, 2-methoxy-5 (1-propenyl) phenol, 2-ethoxy-5- (1-propenyl) phenol, 2-methoxy-
6- (1-propenyl) phenol, 2-ethoxy-6
-(1-propenyl) phenol, pentaerythritol monoacrylic acid, pentaerythritol diacrylic acid, pentaerythritol diacrylate monostearic acid, pentaerythritol triacrylic acid, pentaethritol tetraacrylic acid, pentaerythritol monoallyl ether, penta Erythritol diallyl ether, pentaerythritol diallyl ether monostearic acid, pentaerythritol triallyl ether, pentaethritol tetraallyl ether, pentaerythritol monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, trimethylol ethane monoacrylic acid, trimethylol Ethane diacrylic acid, trimethylol ethane triacrylic acid, trime Trimethylolethane monoallyl ether, trimethylolethane diallyl ether, trimethylolethane diallyl ether, trimethylolethane monovinyl ether, trimethylolethane divinyl ether, trimethylolethane trivinyl ether,
Trimethylolpropane monoacrylic acid, trimethylolpropane diacrylic acid, trimethylolpropane triacrylic acid, trimethylolpropane ethoxylate triacrylic acid, trimethylolpropane propoxylate triacrylic acid, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether,
Trimethylolpropane triallyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinylether, dimethylolpropionate monoallyl ether, dimethylolpropionate diallyl ether, dimethylolpropionate monovinylether, dimethylolpropion Acid divinyl ether, poly (ethylene glycol) methacrylate, poly (ethylene glycol) dimethacrylate, poly (ethylene glycol) vinyl ether, poly (ethylene glycol) divinyl ether, poly (ethylene glycol) phenyl ether acrylate, poly (ethylene glycol) 4-
Nonylphenyl ether acrylate, diallylamine, 2,2'-diallylbisphenol A, 2,2'-
Diallyl biphenyl, diallyl dimethyl ammonium,
Diallyloxyacetic acid, diallylphthalic acid, diallylmaleic acid, diallylsuccinic acid, N, N'-diallyltartaryl diamide, 1,3-diallylurea, triallylamine, triallyl trimesate, cinnamic acid, cinnamaldehyde, cinnamonitrile, Compounds such as cinnamyl alcohol and cinnamyl acetate and compounds obtained by derivatizing these compounds are exemplified.

Further, an organic compound having an aromatic group having an OH group and / or an OCH ₃ group or an NH ₂ group as a substituent in a porous part can efficiently polymerize a porous article and fix a boron-containing compound. Specific examples of such organic compounds are lignin, ligninsulfonic acid, humic acid, nitrohumic acid, tannin, catechin, gallic acid, 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, vanillyl alcohol, o-ba Lyl alcohol, isovanillyl alcohol, vanillylamine, vanillin azine, 4-hydroxy-3-methoxybenzonitrile, syringic acid, sinapyr alcohol, sinapinic acid, sinapine aldehyde, homovanilla acid, homovanillyl alcohol, homovanilonitrile, hesperidin , Chlorogenic acid, hinokitiol, pyrocatechol, hydroquinone, tert-butylhydroquinone, phenylhydroquinone, trimethylhydroquinone, pyrogallol, lauryl gallate,
Octyl gallate, 3,4-dihydroxybenzoic acid,
1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 6,7-dihydroxy-2-naphthalenesulfonic acid, anthralobin, alizarin, quinizarin, o-phenylenediamine, p-phenylenediamine, 3,4-diaminobenzophenone, o-anisidine, p-anisidine, o-aminophenol, p-aminophenol, 1,2-diaminoanthraquinone, 1,
Examples include compounds such as 4-diaminoanthraquinone and compounds obtained by derivatizing these.

In particular, the above-mentioned lignin, ligninsulfonic acid, and salts thereof, or acetic acid ester, propionic acid ester, carboxymethyl ether, 2-hydroxyethyl ether, 2-acetoxyethyl ether or 2-acetoxyethyl ether -Hydroxypropyl etherified derivatives and those obtained by hydrolyzing them are highly safe substances derived from natural products, and are extremely useful as the polymerization reaction raw material of the present invention. Also, unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid, unsaturated alcohols such as oleyl alcohol, unsaturated alkyls such as squalene, and higher unsaturated aliphatic substances such as tung oil, linseed oil and other drying oils. Useful as a highly safe substance.

In addition to these compounds, if the catalyst used in the present invention is a substance capable of accelerating oxidation, it can be used as a raw material for an oxidation reaction or a polymer reaction. Specific examples of such compounds include ascorbic acid, isoascorbic acid,
Quercetin, rutin, guaiacol, ABTS (2,
2'-azobis (3-ethylbenzothiazoline-6-sulfonic acid)), bilirubin, o-hydroxybenzoic acid,
p-hydroxybenzoic acid, 4-methoxyphenol, biphenol, 4,4'-ethylenedianiline, methylhydroquinone, ethylhydroquinone, 1-hydroxybenzotriazole, 6-hydroxy-2,4,5-triaminopyrimidine, 4, 5,6-triaminopyrimidine, 2,3-dihydroxypyridazine, 3,6-dihydroxypyridazine, 2,3-dihydroxypyridine, 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) -L
-Alanine, 2-amino-3-hydroxypyridine, 3
-Amino-2-methoxydibenzofuran, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4
-Dimethoxyaniline, 2 ', 5'-dimethoxyacetophenone, 3', 4'-dimethoxyacetophenone,
1,4-dimethoxybenzene, veratrol, 2,3-
Dimethoxy benzoic acid, 2,5-dimethoxy benzoic acid, veratrulic acid, veratraldehyde, veratrylamine, homoveraturic acid, homoveratrylamine, homoveratronitrile, 3,4-dimethoxycinnamic acid, 3,4-dimethoxy Cinnamonitrile, 2,3-dimethoxyphenol, 3,4-dimethoxyphenol, 3,4-dimethoxybenzyl alcohol, 3,4-dimethoxyphenethylamine, 3,4-dimethoxystyrene, (3,4-dimethoxyphenyl) acetic acid, (3,4-dimethoxyphenyl) acetonitrile, (3,4-dimethoxyphenyl)
Acetone, 3- (3,4-dimethoxyphenyl) propionic acid, 3- (3,4-dimethoxyphenyl) propanol, 4- (3,4-dimethoxyphenyl) butyric acid,
(3,4-dimethoxyphenyl) propanol, 2-methoxy-4-propphenylphenol, 2-methoxy-
5-methylaniline, 2-methoxy-5-nitroaniline, 4-methoxy-2-nitroaniline, 3-methoxysalicylic acid, acetylsalicylic acid, methyl salicylate,
Ethyl salicylate, 3-methylcatechol, 4-methylcatechol, methylgallate, propylgallate, 3,
4,5-trimethoxyaniline, 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 and various azo dyes.

Further, CH ₂ = CH- and / or -CH = CH
_{-, CH 2 = C (CH} 3) -, - CH 2 = N -, - CH = N-, NH = CH -,
NH = N-, -N = N- and a structural part represented by -CHR-CHR-
And / or _{-CHR-CH 2 -CHR -, -} O-CH 2 -CH 2 -O -,
An organic compound having both a structural part represented by —NH—CH ₂ —CH ₂ —NH—, —CH ₂ —CH (CH ₂ R) — [the above R is an OH group or an NH ₂ group] is used. This makes it possible to more efficiently fix the boron-containing compound in the porous article. Specific examples of such organic compounds include polyoxyethylene allyl glycidyl nonyl phenyl ether,
Polyoxyethylene propenyl glycidyl nonyl phenyl ether, polyoxy ethylene nonyl propenyl phenyl ether, polyoxy ethylene nonyl allyl phenyl ether, 3-polyoxy ethylene-1,2-dihydroxy phenyl ether, 5-polyoxy ethylene
Examples thereof include 3,4-dihydroxycarboxyphenyl ether, those in which the ends of polyoxyethylene chains are sulfated or phosphorylated, and those in which these polyoxyethylene chains are partly polyethyleneimine. These polymerization reaction raw materials are OH
Group or NH ₂ group, a compound having a carbonyl group as a substituent, using a mineral acid or alkali as a catalyst,
It is produced efficiently by performing ring-opening addition polymerization of ethylene oxide or ethylene imine.

Further, an aromatic structural portion having an OH group and / or an OCH ₃ group or an NH ₂ group as a substituent, and —CHR—CHR —
And / or _{-CHR-CH 2 -CHR -, -} O-CH 2 -CH 2 -O -,
_{-NH-CH 2 -CH 2 -NH -} , - CH 2 -CH (CH 2 R) - preparation of [said R is an OH group or NH ₂ group] organic compound having both a structural part of the structural portion represented by Include ethyl-3,4-dihydroxycinnamic acid, 3-hydroxy-4-methoxycinnamic acid, 3,4-dihydroxycinnamic acid, sinapir alcohol, sinapinic acid, chlorogenic acid, and 3,4-dimethoxystyrene , 3,4-dimethoxycinnamic acid, 2-allyl-
Compounds having an OH group and / or an NH ₂ group as a substituent, such as 6-methoxyphenol, 4-allyl-2-methoxyphenol, and 4-allyl-1,2-dimethoxybenzene, can be used.

When a compound having an OH group and / or NH ₂ group as a substituent on an aromatic ring is used for producing an organic compound intended for use in the present invention, such a compound may be oxidized by air or a required radical may be used. When inhibiting the polymerization reaction, these OH groups and / or NH ₂ groups,
Acetalize with acetone, cyclic carbonate with phosgene or diphenyl carbonate, or add methyl, ethyl, acetyl, tert-butyl, tert-butoxycarbonyl, silyl, and trimethylsilyl groups. And an OH group and / or NH
₂ group is protected, after synthesis and purification for organic compounds acquisition purposes, OH groups and / or NH protecting group by elimination
It is also possible to return to _two . As disclosed in the present invention, an aromatic structural part having an OH group and / or an OCH ₃ group and an NH ₂ group as a substituent, -CHR-CHR- and / or -CHR-CH
_{2 -CHR -, - O-CH} 2 -CH 2 -O -, - NH-CH 2 -CH 2 -NH -, -
The production of an organic compound having both a structural part represented by CH ₂ —CH (CH ₂ R) — [the R is an OH group or an NH ₂ group] in the structural part is performed by using an OH group and / or an NH ₂ group, or Having an aromatic compound having an unsaturated side chain as a substituent, a vinyl ester such as vinyl acetate or vinyl propionate, and / or
Vinyl ethers such as poly (ethylene glycol) vinyl ether and poly (ethylene glycol) divinyl ether, poly (ethylene glycol) methacrylate, poly (ethylene glycol) dimethacrylate, poly (ethylene glycol) phenyl ether acrylate, poly (ethylene glycol) 4-nonyl Methacrylic acid esters such as phenyl ether acrylate, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, trimethylolethane monoallyl ether, trimethylolpropane monoallyl ether,
It is carried out by polymerizing allyl ether such as trimethylolpropane diallyl ether, monoallyl ether dimethylolpropionate, diallyl ether dimethylolpropionate, allyl alcohol, allylamine and the like.

When a vinyl ester is used in the production, it is preferable to complete saponification or partial saponification after polymerization to obtain a polyol compound. The polymerization method, gas phase polymerization, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, granular polymerization that can be used usually can be used, the polymerization initiation method, a method using a thermally decomposable initiator, A method using a redox catalyst, a method using electromagnetic waves such as ultraviolet rays and γ-rays, and cationic polymerization and anionic polymerization can be performed.

Further, an aromatic structural part having an OH group and / or an OCH ₃ group or an NH ₂ group as a substituent, and —CHR—CHR —
And / or _{-CHR-CH 2 -CHR -, -} O-CH 2 -CH 2 -O -,
_{-NH-CH 2 -CH 2 -NH -} , - CH 2 -CH (CH 2 R) - preparation of [said R is an OH group or NH ₂ group] organic compound having both a structural part of the structural portion represented by Is an OH group and / or NH ₂
The reaction is also carried out by reacting an aromatic compound having a group or a protected group thereof as a substituent with polyvinyl alcohol and / or polyethylene glycol, polyallylamine, polyethyleneimine or a derivative thereof. In addition, poly-N-vinylacetamide and poly-N-vinylformamide can also be used for producing the organic compound used in the present invention.

The production of the above-mentioned organic compound used in the present invention is carried out by, for example, vanillin, o-vanillin, 3,4-dihydroxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,4-dimethoxycinnamaldehyde, A compound having an aldehyde group as a substituent, such as -hydroxy-3-methoxycinnamaldehyde, 3-hydroxy-4-methoxycinnamaldehyde, or sinapinaldehyde, and -CHR-CHR- and / or -CHR-
_{CH 2 -CHR -, - O-} CH 2 -CH 2 -O -, - NH-CH 2 -CH 2 -NH -,
Forming a Schiff base with an amino group of an organic compound having —CH ₂ —CH (CH ₂ R) — [the R is an OH group or an NH ₂ group] in a structural part, or forming an acetal bond with an OH group It is implemented by having Polyallylamine or polyethyleneimine is particularly useful as the organic compound having an amino group, and polyvinyl alcohol or partially saponified polyvinyl acetate is particularly useful as the organic compound having an OH group used in such a production method. Further, the carboxylic acid or carboxylic acid anhydride, acyl chloride compound and -CHR-CHR - and / or -CHR-CH ₂ -CH
_{R -, - O-CH 2} -CH 2 -O -, - NH-CH 2 -CH 2 -NH -, - CH 2 -C
It is also produced by forming an ester with a hydroxyl group of an organic compound having H (CH ₂ R)-[R is an OH group or an NH ₂ group] in the structural part. In the production of the organic compound used in the present invention, specifically, acryloyl chloride is added to an aromatic compound having a plurality of OH groups and / or NH ₂ groups, and this is further added to -CHR-CHR- as well as/
Or _{-CHR-CH 2 -CHR -, -} O-CH 2 -CH 2 -O -, - NH-C
It is also carried out by reacting with an amino group of an organic compound having H ₂ —CH ₂ —NH—, —CH ₂ —CH (CH ₂ R) — [R is an OH group or an NH ₂ group] in a structural part. .

Compounds having a plurality of OH groups and / or OCH ₃ groups and NH ₂ groups, in particular, OH groups and / or OCH ₃ groups,
In aromatic compounds having a plurality of NH ₂ groups as adjacent substituents, some of these functional groups may be subjected to cyclic carbonation with acetal, phosgene or diphenyl carbonate with acetone, or methyl groups. , Ethyl group, acetyl group, tert-butyl group, tert-
By protecting the butoxycarbonyl group and silyl group by addition, etc., and further performing ring-opening addition polymerization of ethylene oxide or ethyleneimine, and then removing the protecting group,
It is possible to produce a polymerization reaction raw material having higher reactivity.

In addition, -CHR-CH such as polyethylene glycol, polyethylene oxide, polyvinyl alcohol, etc.
R - and / or _{-CHR-CH 2 -CHR -, -} O-CH 2 -CH 2 -O
_{-, - NH-CH 2 -CH} 2 -NH -, - CH 2 -CH (CH 2 R) - [ wherein R is
An OH group or an NH ₂ group] in the structural portion thereof with epichlorohydrin using a catalyst such as trimethylamine to form a glycidyl ether derivative, which is further converted to gallic acid, tannin, o-coumaric acid, p- −
Coumaric acid, ferulic acid, 3-hydroxy-4-methoxycinnamic acid, vanilla acid, syringic acid, sinapinic acid, homovanilla acid, chlorogenic acid, 3,4-dihydroxybenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid Acid, methyl-4-hydroxy-3-methoxybenzoic acid,
2,5-dihydroxybenzoic acid, 2,3-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, veratric acid,
3,4-dimethoxycinnamic acid, (3,4-dimethoxyphenyl) acetic acid, 3- (3,4-dimethoxyphenyl) propionic acid, 4- (3,4-dimethoxyphenyl) butyric acid, 3-methoxysalicylic acid, , 5-dihydroxy-
OH and / or OCH ₃ groups, such as 2-naphthoic acid, NH
By reacting a compound having _two groups on the aromatic ring as a substituent and having a carboxyl group, -CHR-CHR
- and / or _{-CHR-CH 2 -CHR -, -} O-CH 2 -CH 2 -O
—, —NH—CH ₂ —CH ₂ —NH—, —CH ₂ —CH (CH ₂ R) — [where R is an OH group or NH ₂ group], and an OH group and / or OCH ₃ It is possible to produce a compound in which an aromatic structural portion having a group or NH ₂ group as a substituent is constituted via an ester bond. Further, an aromatic structural part having an OH group and / or an OCH ₃ group or an NH ₂ group as a substituent, —CHR—CHR— and / or —CHR—CH ₂ —CHR—, —O—CH ₂ —CH ₂ -O −, −
NH-CH ₂ —CH ₂ —NH—, —CH ₂ —CH (CH ₂ R) — [the R is an OH group or an NH ₂ group]. Examples are OH groups and / or OCH ₃
Group, a compound having an aromatic structure portion having an NH ₂ group as a substituent and a polysaccharide structure portion.Examples of the polysaccharide structure that can be used in such a compound include arabinose, galactose, and galacturon as units constituting the polysaccharide. Examples include acids, glucuronic acid, rhamnose, fucose, apiose, mannose, mannooctulosonic acid, xyloseaceric acid, heptulosaric acid, and the like, and compounds including methylated and deoxylated derivatives thereof.

In the present invention, by using these compounds as a raw material for the polymerization reaction, dimensional stability, crack prevention,
It is possible to simultaneously improve humidity control, water absorption, water repellency, surface smoothness, etc., and these active ingredients are oxidized,
The present invention is extremely useful because it is firmly fixed in a porous article by a polymerization reaction.

Further, when a polymerization reaction is carried out in a porous article according to the present invention, a quinone compound which is polymerized by the same reaction route may be allowed to coexist. Examples of such quinone compounds are benzoquinone derivatives, naphthoquinone derivatives, anthraquinone derivatives, and more specifically, anthraquinone-2-sulfonic acid, anthraquinone-1,5-disulfonic acid, anthraquinone-2, 6-disulfonic acid, anthraquinone-2-carboxylic acid, 1-aminoanthraquinone, 2-aminoanthraquinone, anthralphine, aminonaphthoquinone, 1,8-dihydroxyanthraquinone, camphoquinone, dehydroascorbic acid, 2-hydroxy-1 , 4-naphthoquinone, isatin, 5-nitroisatin, and various anthraquinone dyes.

[0053] In order to adjust the fixed rate in the porous article of the other additives] boron-containing compounds, in the present invention, -CHR-CHR - and / or -CHR-CH ₂ -CHR -, -
_{O-CH 2 -CH 2 -O -} , - NH-CH 2 -CH 2 -NH -, - CH 2 -CH (CH 2 R)
An organic compound having-[the above R is an OH group or an NH ₂ group] in the structural part can be used by adding it to the treatment liquid. Specific examples of such compounds include glycerin, diglycerin, propylene glycol, tartaric acid, starch, dextrin, gelatin, chitosan, carboxymethylcellulose, glucose, sucrose, lactose, pentaerythritol, gluconic acid, ethylenediamine, ethanolamine, Diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, triethylenetetramine, propanolamine, pentaethylenehexamine, triisopropanolamine, polyethylene glycol, polyvinyl alcohol, polyethyleneimine, polyallylamine, polyglycerin, polypropylene glycol, etc. And its derivatives. In the case of a polyallylamine derivative as a specific example of the derivative, poly- (N-allylurea),
Examples include polyallylsulfamic acid, phosphonic acid and formalin adducts, formic acid and formalin adducts. The concentration of such an organic compound used in the present invention in the treatment solution is 0.001 to 20%, preferably 0.01 to 10%.

Further, for the purpose of increasing the effect of the treatment of the porous article of the present invention and for effectively utilizing the drug fixing ability and the drug sustained release ability of the compound polymerized inside the porous article, a fragrance and a deodorant are used. Treatment with various agents known as agents, rust inhibitors, flame retardants, antibacterial agents, preservatives, bactericides, insect repellents, antiviral agents, and biological repellents is the pretreatment of the porous article treatment of the present invention. , Can be used as simultaneous processing or post-processing. Usable drugs include not only water-soluble or fat-soluble drugs but also O / O by adding dispersants or surfactants.
Those that form a W-type or W / O-type emulsion and those that disperse in a solution as fine powder can also be used.

Examples of the surfactant used for this purpose include 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 single or multiple components of propylene oxide and butylene oxide are added, alkyl sulfonates, amide sulfonates, dialkyl sulfosuccinates, α-olefins, vinylidene type It has an aliphatic sulfonate such as an olefin and an internal olefin sulfonate, an aromatic sulfonate such as a linear or branched alkylbenzene sulfonate, a linear or branched alkyl or alkenyl group. Alkyl or alkenyl ether carboxylate or amide to which one or more components of ethylene oxide, propylene oxide and butylene oxide are added, α
-Sulfo fatty acid salts or esters, amino acid surfactants, alkyl or alkenyl acid phosphates, phosphate ester surfactants such as alkyl or alkenyl phosphates, sulfonic acid amphoteric surfactants, betaine amphoteric surfactants Alkyl or alkenyl ethers or alcohols having a straight or branched chain alkyl or alkenyl group and having one or more of ethylene oxide, propylene oxide and butylene oxide added thereto, alcohols, straight or branched chain alkyl groups Or having an alkenyl group, ethylene oxide,
Polyoxyethylene alkyl phenyl ether to which one or more components of propylene oxide and butylene oxide are added, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid glycerin monoester, alkyl or alkenylamine oxide, tetra Alkyl ammonium salt type cationic surfactants and the like can be mentioned.

As the dispersant, many conventionally known dispersants can be used. In particular, lignin, ligninsulfonic acid or ligninsulfonate is a raw material for an oxidation reaction and a polymerization reaction. However, since these substances themselves have a drug dispersing action, they are extremely useful for the purpose of the present invention. When the drug is a fine powder, powders having various sizes can be used depending on the purpose. For example, when impregnating wood, 5 μm is used.
m or less, preferably 0.5 μm or less, more preferably 0.1
It is desirable to use a fine powder having a diameter of less than μm.

In order to enhance the antibacterial, antiseptic, bactericidal, insecticidal, antiviral, or biological repellency effects of the porous article treatment of the present invention, the porous article treatment of the present invention can be enhanced. Examples of agents used as pre-treatment, simultaneous treatment, or post-treatment include copper, arsenic, zinc, chromium, nickel, aluminum, molybdenum, magnesium, titanium, cobalt, palladium, tin, lead, iron,
Antimony, at least one metal or metal salt selected from zirconium or silver, a metal compound, a metal complex, solution or fine powder and the like, more specifically, the anion moiety is F ^-, Cl ^-, Br ^{- _{, I -, NO 3 -,}} BO
_{^{3 3-, PO 4 3-, SO}} 4 2-, metal salts consisting of CO ₃ ^2-, etc., naphthenic acid, compound with a carboxylic acid or sulfamic acid and metal ions such as oleic acid, metal oxides, metal oxides Examples include an ion, a metal complex, and a complex thereof. In addition, calcium bromide, sodium bromide, magnesium bromide, potassium bromide, sodium iodide, sodium fluoride, potassium fluoride, sodium sulfide, potassium sulfide, potassium selenate, and the like can also be used.

The concentration of the metal, metal salt, metal oxide, metal oxide ion, metal complex, or complex thereof in the treatment solution used in the present invention depends on the strength of the physiological activity of the metal. It is desirable to adjust according to the purpose of the treatment, but usually 0.01 to 500 mM, preferably 0.1
~ 200 mM. In addition, organic drugs such as pyrethroid drugs, conazole drugs, and insect hormones and derivatives thereof can also be used.

Further, in the present invention, for the purpose of adjusting the fixing rate of the boron-containing compound in the porous article, and improving the antibacterial property, the preservative property, the bactericidal property, the insect repellent property, the antiviral property, and the biological repellency. , may be used by adding a quaternary ammonium compound in the treatment liquid, in particular, C _n H _{2n + 1} or _{C n H 2n-1 (n} = 1~22), C n H 2n-3 ( n =
1 to 22), quaternary ammonium having a hydrocarbon represented by C _n H _2n-5 (n = 1 to 22) as a substituent, quaternary ammonium having an aromatic compound as a substituent, and a hydrophilic polymer. Hydrochloride or sulfate such as quaternary ammonium contained in the substituent may be used, and conventionally used DDAC (didecyldimethylammonium chloride) may be used, but those having an unsaturated structure moiety in the substituent are more preferable. desirable. The concentration of such a quaternary ammonium compound used in the present invention in the treatment solution is 0.001 to 50%, preferably 0.01 to 20%.

Further, rust inhibitors, antibacterial agents, preservatives, bactericides,
OH as an insect repellent, antiviral, or biological repellent
An aromatic compound or a cyclic compound having one or more substituents selected from a group, an amino group, a halogen, and a nitro group can be used. Specific examples of such compounds include o-phenylphenol, 1-naphthol,
2-naphthol-o-chlorophenol, 2,4-dinitrophenol, 4,6-dinitro-o-cresol,
Pentachlorophenol, 2,3,5-trichlorophenol, 2,4,6-trichlorophenol, monochloronaphthalene, trichloronaphthalene, tetrachloronaphthalene, 2,4,5-trichlorophenyllaurate monochloronaphthalene, chloronitrophenol, chloro Nitrotoluene, 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, and chlorinated terpenes.

Also, thiofamate methyl, dasban,
Organic phosphorus compounds such as diazinon, fluorine substances such as sodium fluoride, potassium fluoride, sodium silicofluoride, magnesium silicofluoride, cyclodiene compounds such as chlordane, dieldrin, aldrin, heptachlor, carbamates such as bigon, dimethylene and sevin Compounds, nitroso compounds such as N-nitroso-N-cyclohexylhydroxylamine, pyrethroid compounds, conazole compounds, benzoic acid, p-hydroxybenzoic acid, p-hydroxybenzoic acid methyl, ethyl, propyl, butyl, isobutyl, Esters such as isopropyl, butylhydroxyanisole, and butylhydroxytoluene. The concentration of the aromatic compound or the cyclic compound used in the present invention in the treatment solution is preferably adjusted according to the strength of the physiological activity possessed by these compounds and the purpose of the treatment, and the solubility.
-20%, preferably 0.05-5%.

Further, fragrances, deodorants, rust inhibitors, antibacterial agents,
Preservatives, bactericides, insect repellents, antivirals, or biological repellents, plant-derived extracts, extractable components, or synthetic compounds having a structure equivalent to that of the plant extractable components are also used in the porous article treatment of the present invention. It can be used as pre-processing, simultaneous processing, or post-processing. Specific examples of such plants are cypress, trees such as Aomori Hiba, herbs, mustard, wasabi, iriomote thistle rhizome, or yaeyama palm root and the like. , An extract or an extracted component can be obtained.

Specific examples of plant-derived components or compounds having a structure equivalent to the plant-derived components include tropolone such as hinokitiol, 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; Examples include naphthalene derivatives such as 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. Among these compounds, hinokitiol is particularly useful in terms of human / environmental safety, antibacterial efficacy and the like.

The concentration of such an extract derived from a plant, an extract component, or a compound having a structure equivalent to that of a plant extract component used in the present invention in a treatment solution is 0.001 to 50.
%, Preferably 0.01 to 10%. When these additives form a complex or a salt with a metal ion,
It is possible to use various metal complexes or salts for the purpose of improving the fixing property of the additive in the porous article, antibacterial property, antiseptic property, bactericidal property, insect repellent property, antiviral property, or biological repellency. I can do it. The metals that can be used are, specifically,
Copper, arsenic, zinc, chromium, nickel, aluminum, molybdenum, magnesium, titanium, cobalt, palladium, tin, lead, iron, antimony, zirconium, silver,
Magnesium, calcium, strontium, barium, sodium and potassium. For example, the above-mentioned hinokitiol can be used as a complex or salt of a metal such as copper, arsenic, zinc, chromium, nickel, titanium, and silver, so that the action of a metal can be added to the action of hinokitiol. Particularly useful for purposes. Many azo compounds conventionally known as polymerization initiators can be used as a polymerization reaction raw material and / or a polymerization initiator by being added to the treatment liquid for a porous article of the present invention. Specific examples of such compounds include 4,4′-
Azobis (4-cyanovaleric acid), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,
2'-azobisisobutyronitrile, 2,2'-azobis (2-methylpropionamidine), 2,2'-azobis (2-methylbutyronitrile), 2- (carbamoylazo) isobutyronitrile , 2,2'-azobis (2-
Amidinopropane), 2,2'-azobis [2- (2-
Amidonitrile compounds or azoamidine compounds such as imidazolin-2-yl) propane], azoamide compounds such as 2,2′-azobis (isobutylamide),
Alkyl azo compounds such as 2,2'-azobis (2-methylpropane) are exemplified. When using these azo compounds in the present invention, first, the oxidation reaction at normal temperature, the polymerization reaction proceeds to reduce the dissolved oxygen concentration in the reaction solution impregnated in the porous article, By heating the porous article and accelerating the polymerization reaction by the azo compound,
The polymerization reaction can be used more effectively. The concentration of the azo compound in the treatment liquid used in the present invention is preferably adjusted according to the solubility of the azo compound and the concentration and type of the polymerization reaction raw material used at the same time. Preferably it is 0.001 to 1%.

[Polymer Article Processing Method and Use Thereof] The polymerization reaction raw material and the polymerization catalyst of the present invention are used as metal sintered bodies, cast products, alloys, die-cast products, ceramics, bricks, concrete, wood, wood chips, wood flour, woody materials. Processing materials, fir shells, rushes,
It impregnates porous articles such as straw, bamboo, leather, cloth, non-woven cloth, fiber, activated carbon, or synthetic resin foam, and performs oxidation reaction and polymerization reaction in these porous articles, and comes into contact with boron-containing compounds. By doing so, the resulting polymer material is firmly fixed in the porous article, and at the same time, a matrix containing the boron-containing compound is formed in the porous article, so that the leaching action of rainwater and the like is prevented. More stable boron-containing porous articles can be manufactured, and the present invention is extremely useful. In particular, if the porous articles are wood, wood chips, wood flour, woodwork, fir hulls, rush, straw, bamboo, the lignin already contained in these porous articles and impregnated according to the present invention. As a result of oxidation and polymerization of both of the polymerization reaction raw materials, the resulting polymer is more firmly fixed, and the effect of fixing the boron-containing compound is further improved, so that the present invention is extremely useful.

In the present invention, boron-containing compounds such as boric acid (orthoboric acid), metaboric acid, tetraboric acid and octaboric acid, which are used by being coated or impregnated on a porous article, and alkali metal salts thereof, and others. The concentration of a boron-containing compound such as a metal salt or a complex in the treatment liquid is 0.01 to 50%, preferably 0.1 to 20%.

In the case where a polymerization reaction raw material and a polymerization catalyst are impregnated in the presence of a boron-containing compound and an oxidation reaction and a polymerization reaction are performed in a porous article, gelation or solidification occurs in the state of the treatment liquid before impregnation. Instead, it is desirable that gelation and solidification proceed when the treatment liquid is dried and concentrated in the porous article after impregnation. The concentration of the raw material for the polymerization reaction in the treatment liquid is 0.01 to 80%, preferably 0.1 to 30%. Also,
The reaction temperature is 0 to 200 ° C, preferably 5 to 120 ° C, more preferably 10 to 80 ° C. By the method for treating a porous article of the present invention, it is possible to carry out a polymerization reaction at a lower temperature as compared with the conventional temperature conditions for producing a thermosetting resin, to save energy due to heating, to simplify treatment equipment, The present invention has many advantages, such as improved safety during processing, and is extremely useful.

Furthermore, the pH of the reaction is 2 to 13, preferably 7
~ 12, more preferably 7.5 ~ 10, pH as needed
It is desirable to use a compound having a buffering capacity. When the catalyst is a metal enzyme, the concentration of the catalyst used is 1 to 10,000 U / liter, preferably 10 to 2000 U / liter, as the concentration of the oxidizing activity. The catalyst concentration is preferably adjusted depending on the catalytic activity per weight and the purpose of processing the porous article. That is, when it is desired to achieve a rapid oxidation reaction and polymerization, the reaction may be performed at a high active concentration. On the other hand, if the reaction is carried out at a low active concentration, a mild oxidation reaction and a polymerization reaction proceed, and a more uniform composite of a polymer and a porous article can be obtained. Stopping the reaction at the time of reaching a suitable degree of polymerization is carried out by shutting off the supply of oxygen by coating on the surface of the porous article or wrapping with a film, etc., especially when the polymerization catalyst is a metal enzyme, NaOH. _{, NH 3, Na 2 CO 3} , impregnation of alkali or alkali salts, such as CaCO _3, hydrochloric acid, carried out by heat treatment sulfate, impregnation of acid such as nitric acid, impregnation of the known enzyme inhibitor, 100 ° C., such as 15 minutes it can.

As a post-treatment of the application or impregnation of the boron-containing compound, an oxidation reaction and a polymerization reaction treatment in the porous article are carried out, so that the boron-containing compound and the drug added simultaneously with the boron-containing compound are porous. The transfer to the porous article surface can be effectively prevented, and the method for treating a porous article of the present invention is extremely useful. Conversely, by performing an oxidation reaction and a polymerization reaction treatment in the porous article, and then applying or impregnating the boron-containing compound, the boron-containing compound and the agent added simultaneously with the boron-containing compound are removed. A treated surface layer containing a high concentration can be formed on the surface of a porous article, and the method for treating a porous article of the present invention is extremely useful.

For the purpose of the present invention, in order to increase the impregnation amount of the processing solution into the porous article, it is desirable to adjust the size and amount of the insoluble solid component in the processing solution. Is more important when it is a lignin-based raw material such as lignin, ligninsulfonic acid, ligninsulfonate, a derivative thereof, or a product obtained by hydrolyzing them. That is, in the state where lignin or lignin sulfonic acid is generated from the process of alkaline cooking pulp or sulfite pulp, it contains various water-insoluble solid components. Depending on the type of the article, the purpose of the impregnation treatment, and the economics involved in the removal, it is desirable to carry out by various centrifugation, filtration, or standing. For example, for the purpose of performing pressure injection treatment on wood, the diameter or long diameter in the pulp waste liquid is 1 μm or more, preferably 0.5 μm or more.
It is desirable to remove water-insoluble solid components having a size of at least 0.1 μm, more preferably at least 0.1 μm, by filtration. In addition, the lignin-based raw material may be desalted and desugared by ultrafiltration, or a lower-molecular-weight fraction having a molecular weight of 50,000 to 100,000 or less to further enhance impregnation. It is possible. Desaccharification can also be performed by a microorganism such as yeast.

It is known that lignin is originally contained in wood core material in a large amount, thereby increasing the resistance to rot fungi and termites. Therefore, as the polymerization reaction raw material of the present invention, in particular, using such a lignin-based raw material,
When this is used as a wood preservative, the treatment method of the present invention is an effective method for industrially treating all woods by using a method of protecting natural wood from rot fungi and termites. To be able to implement,
The polymer inhibits the invasion of rot fungi by sealing the voids in the wood, and further enables the antiseptic and termiticidal effects to be further improved by effectively utilizing the boron-containing compound, and the present invention is extremely useful. is there.

Further, the present invention enables effective treatment of a porous article containing no or a small amount of a polymerization reaction raw material such as lignin, and the polymerization reaction mainly proceeds inside the porous article. A large amount of a treatment liquid can be easily impregnated with a treatment liquid having a relatively low molecular weight, that is, a treatment liquid having a relatively low viscosity, and the present invention is extremely useful.

The pressurization and / or depressurization performed for the purpose of the present invention is to inject a sufficient amount of the treatment liquid into various kinds of porous articles which are difficult to impregnate with the treatment liquid, and to obtain a necessary treatment effect. It is extremely important for you. The pressurization operation is carried out at an atmospheric pressure of 1 to 20 atm, more desirably 3 to 15 atm, but higher pressures can be applied if the catalytic activity is not lost. The depressurizing operation can be performed at any pressure up to the vacuum pressure. However, for effective treatment of a porous article that is difficult to impregnate, a depressurizing pressure in the range of 100 to 760 mmHg is desirable. In addition, it is more preferable that the depressurizing operation is a pre-evacuation method in which the pressure is reduced before the treatment liquid is added to the porous article. It is also effective to combine these pressurizing operations and depressurizing operations in order to impregnate the treatment liquid in a larger amount in the porous article.

When the porous article is made of 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) ), Double vacuum method (double vacuum method),
OscillatingPressure Method and a method combining these operations can be applied. Also, the insizing method can be applied to increase the impregnation amount. It is also effective to carry out compression treatment using a roller or the like, microwave heating, freezing treatment, steaming treatment, steam treatment, or heat treatment as a pretreatment of the porous article that is difficult to impregnate.

Further, a method of impregnating the porous article with the treatment liquid and then performing a decompression treatment to recover a part of the treatment liquid outside the porous article, and a polymerization reaction inside the treated porous article are not required. Before proceeding sufficiently, the porous article is washed with water or the like to remove unpolymerized substances, so that the degree of maintaining the porous property can be easily adjusted. Such a retained porous material, the treated material has a humidity adjusting ability, a water retaining ability, an adsorption ability, an ion exchange ability,
The present invention is extremely useful because it can be used for various applications utilizing such capabilities. In addition, a porous article having various composite properties can be produced by further impregnating a drug, a polymer, and a prepolymer into a treated product having a porous property, and the present invention is extremely useful. is there.

The imparting or improving of formaldehyde absorption by the porous article treatment of the present invention can be carried out by the sealing ability by the porous article treatment of the present invention. In order to further improve the formaldehyde absorption, This can be achieved by using a compound containing an amino group in the processing solution. Also, it is known that polyphenol substances such as catechin deodorize such as by reacting with malodorous substances such as methyl mercaptan, trimethylamine, ammonia, and tobacco odor. Useful for use. Since the reaction with such a gaseous substance proceeds more efficiently as the surface area of the reaction field is larger, an article having a high formaldehyde absorbing effect and a high deodorizing effect can be manufactured by using the porous article treatment method of the present invention. . The oxidation catalytic activity of the substance used in the present invention as a polymerization catalyst can also be used as a catalyst for a deodorizing reaction, and the present invention is extremely useful. In addition, by using activated carbon as the porous article of the present invention, in addition to the deodorizing properties of the activated carbon itself, the reactivity of the polyphenol compound and amine compound added to the treatment liquid and fixed can be used for deodorizing. The present invention is extremely useful.

The imparting or improving of the flame retardancy by the treatment of the porous article of the present invention can be carried out by adding a flame retardant to the treatment liquid, and many conventionally known flame retardants can be used. For example, Na, K, Mg, Ca, Ba, Al, Zn, Cu,
Phosphate, hydrogen phosphate, sulfate, hydrogen sulfate, carbonate, borate, silicate, nitrate having elements such as Mn, Ni, Si, Sn, Pb, Zr, and Sb in the cation portion , Fluoride,
Chlorides, bromides, hydroxides and the like, specifically, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, antimony trioxide, barium metaborate, tin oxide, red phosphorus, ammonium phosphate . In particular, borate is used as the main component of the treatment agent of the present invention, and is highly useful. Also, in the digestion process of the pulp mill where lignin sulfonic acid is produced,
As a result of mainly using calcium sulfite or magnesium sulfite, the resulting ligninsulfonic acid contains fine powders such as calcium carbonate, calcium hydroxide, magnesium carbonate, and magnesium hydroxide. Therefore, when ligninsulfonic acid is used as a raw material for the polymerization reaction of the present invention, these fine powders can be effectively used as a flame retardant, and the present invention is extremely useful.

The coloring by the porous article treatment of the present invention is represented by o
A dye or dye precursor, such as phenylenediamine, p-phenylenediamine, catechol, gallic acid, and quercetin, on which the polymerization catalyst of the present invention can act; By selecting an object to be colored and adding it to the treatment liquid, the formation of a colored substance in the wood and / or the conversion of the colored substance and a polyphenol compound such as lignin already contained in the wood into the wood. As a result of performing the composite polymerization, the wood is strongly dyed and colored. Further, as a polymerization reaction raw material of the present invention, in particular, by using lignin, lignin sulfonic acid, lignin sulfonic acid salt, or a derivative thereof for wood treatment, the difference in color tone and chromaticity between the core and sapwood portions of wood. Therefore, the present invention is extremely useful because it is possible to obtain a wood having a more uniform and natural texture coloring. The moisture control, water absorption, water repellency, and surface smoothness imparted or improved by the porous article treatment of the present invention can be achieved by using a hydrophilic substance or a hydrophobic substance as the porous article treatment composition. Alternatively, it can be adjusted by the addition amount and the mixing ratio at the time of preparing the treatment liquid. That is, when the polymerization reaction raw material, polymerization catalyst, additive agent, and the like are more hydrophobic substances, by preparing a processing solution using a petroleum fraction such as kerosene, an emulsifier, and / or an organic solvent, It is possible to impart strong water repellency to the processed porous article. Conversely, when the polymerization reaction raw material, polymerization catalyst, additive agent, and the like are more hydrophilic substances, by preparing a treatment liquid as an aqueous solution or an emulsion, water treatment is imparted to the processed porous article. It is possible.

The treating agent for a porous article of the present invention can be prepared as a single agent by mixing the above composition as a powder or a granulated powder. Granulation is shaping for suppressing dust generation, and can be specifically achieved by granulation operations such as malm granulation, extrusion granulation, fluidized granulation, and centrifugal fluidized granulation. In this case, in order to improve the storage stability of the polymerization catalyst in the treating agent, it is also effective to granulate the polymerization catalyst together with a stabilizer separately from other treating agent components. Further, the treatment agent for the porous article of the present invention can be prepared by any method of a high-concentration solution premised on performing 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 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. Also,
It is more desirable to suppress oxidation by degassing or the like during production of the treatment agent. When preparing the treating agent for the porous article of the present invention, the polymerization catalyst may be prepared separately from the other treating agent components, and may be mixed and used immediately before use.

[0080]

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: Obtaining a metalloenzyme To obtain a metalloenzyme used as a polymerization catalyst in the present invention, 0.5% glucose, 0.1% NaNO ₃ , 1.34% Na ₂ HP
_{O 4 · 12H 2 O, 0.3} % KH 2 PO 4, 0.1% NaCl, 0.2% peptone, 20 ppm yeast _{extract, 0.01% MgSO 4 · 7H 2} O, 0.1mM
Add 10% NaOH to a 3 liter medium consisting of CuSO ₄
A culture vessel containing a medium having a pH of 8 was inoculated with Myrothecium verrucaria SD3001 (Accession No. FERMBP-5520) and cultured at 28 ° C. for 3 days with shaking. After culturing, 2.5 liters of culture broth was removed by centrifugation at 4 ° C. Next, a part of this culture broth was transferred to a minitan filter packet (CAT. NO .:
It was concentrated as a fraction having a molecular weight of 10,000 or more by a minitan ultrafiltration system (Millipore) using PTGC0MP04 (Millipore). This is further added to 200 ppm NH ₄ HCO ₃
After dialysis, the lyophilized product was freeze-dried to obtain the target metal enzyme as a crude product. The polyphenol oxidase activity of this metalloenzyme preparation was 10 U / mg.

Example 2 Preparation of Polymerization Reaction Raw Material In a 500 ml three-necked flask, 60 g of 4-allyl-1,2-dimethoxybenzene, 100 g of chloroform and 80 g of iodotrimethylsilane were mixed, and the mixture was heated at 50 ° C. The mixture was heated for 60 hours under a nitrogen atmosphere while refluxing on a hot water bath, and further dried under reduced pressure by an evaporator. 150 g of acetone and 42 g of anhydrous magnesium sulfate were added to the precipitate thus obtained, and concentrated sulfuric acid was added dropwise and heated for 40 hours while refluxing on a 55 ° C. water bath, and then 10% (W / W V) Na
OH (methanol solution) was added for neutralization, followed by drying under reduced pressure using an evaporator. 100 g of methanol was added to the obtained fraction, which was filtered and acetalized with 4-allyl 1,2-dihydroxybenzene. A methanol solution of the protected product was obtained.

Next, in a 500-ml three-necked flask, 20 g of the methanol solution obtained above, 150 g of vinyl acetate and 200 g of methanol were mixed, and nitrogen gas was blown thereinto to perform nitrogen substitution. Increase the temperature to 60 while stirring
° C. Further, 0.5 g of 2,2 was used as a polymerization initiator.
A solution prepared by dissolving 2′-azobis (isobutyronitrile) in 30 g of methanol was added, and the whole was gradually heated to 50 ° C. After about 6 hours, 0.2 g of dinitrobenzene was added to carry out the polymerization operation. finished. Next, heating was performed for 2 hours while methanol was added dropwise, and the obtained fraction was poured into water.
After heating at 80 ° C., the precipitate was dried. Next, 5 liters of methanol, 100 ml of 10% (W / V) NaOH (methanol solution) and 25% (W / V) CH ₃ ONa (methanol solution) were added to the precipitate.
Was added, and the mixture was heated at 40 ° C. for 5 hours, and the resulting precipitate was collected and further dried under reduced pressure by an evaporator.
100 ml of 0.2N NaOH aqueous solution substituted with nitrogen is added thereto, heated at 80 ° C. for 2 hours under a nitrogen atmosphere, neutralized with sulfuric acid, desalted with an ion exchange resin, and further dried to obtain the desired product. A polymerization reaction raw material was obtained.

The polymerization reaction raw material thus obtained is a compound that is water-soluble and undergoes air oxidation at an alkaline pH (pH 10). The GFC column (Shodex PROTEIN KW) equilibrated with 1% NaCl at a flow rate of 1 ml / min -802.5, 2 stations)
(Gel Filtration Chromatography) analysis by HPLC using HPLC and UV detector revealed a number average molecular weight of about 1
Since it had an absorption at a wavelength of 260 nm to 300 nm, it was presumed that it was a polyvinyl alcohol derivative having a 3,4-dihydroxyphenyl group in the structural part. Further, under the same GFC conditions as above, fractions having a molecular weight of 5,000 or more were collected, concentrated by drying under reduced pressure, and analyzed by infrared spectroscopy. An absorption characteristic of a 1,4-dihydroxyphenyl structure was observed at a position of 1289 cm ^-1 (derived from a phenolic hydroxyl group). In addition, 4-allyl-1,2-dimethoxybenzene and iodotrimethylsilane were obtained from Aldrich Chemical Company, and 2,2'-azobis (isobutyronitrile) was obtained from Wako Pure Chemical Industries, Ltd.

Example 3 Production of Raw Materials for Polymerization In a 500 ml three-necked flask, 70 g of methanol, 60 g of vinyl acetate, and 1 g of 4-allyl-2-methoxyphenol were mixed, and nitrogen gas was blown into the mixture. The displacement was made and the temperature was then raised to about 62 ° C. with stirring and reflux. Further, 0.2 g of 2,2 ′ was used as a polymerization initiator.
Azobis (isobutyronitrile) in 5 ml of methanol is added and after about 6 hours 0.1 g of 2,2
A solution prepared by dissolving 2'-azobis (isobutyronitrile) in 3 ml of methanol was added thereto, and further heated at about 62 ° C for 6 hours. Next, heating was carried out for 2 while adding methanol dropwise.
After 3 hours, methanol was added to the obtained fraction, and 3 liters of methanol was added to the mixture. The mixture was stirred at room temperature, and 37.5 ml of a 40% aqueous sodium hydroxide solution was added over 30 minutes. After the operation, the precipitate was collected, washed with 1 liter of methanol three times, and dried to obtain a light yellow target polymerization reaction material.

The polymerization reaction raw material thus obtained is a compound having water solubility and subject to air oxidation at an alkaline pH (pH 10). The GFC analysis by the same method as in Example 2 shows that the number average molecular weight is about 8,000 and the wavelength is Since it has an absorption at 260 nm to 300 nm, it was inferred to be a polyvinyl alcohol derivative having a 4-hydroxy-3-methoxyphenyl group in the structural part. Under the same GFC conditions as above, fractions having a molecular weight of 2,000 or more were collected, concentrated by drying under reduced pressure, and analyzed by infrared spectroscopy. As a result, the 4-hydroxy-3-methoxyphenyl structure was characterized. Absorption was observed at the position of 1269 cm ^-1 . In addition, 4-allyl-2
-Methoxyphenol was obtained from Wako Pure Chemical Industries, Ltd.

Example 4 Production of Polymerization Reaction Raw Material In a 300 ml flask, 50 g of pyrogallol was dissolved in 100 g of diethyl ether, and 23 g of acetone and 50 g of anhydrous magnesium sulfate were further added. here,
While stirring, 2.5 ml of concentrated sulfuric acid was added over 2 minutes, and the mixture was stirred at room temperature for 24 hours with the mouth of the flask sealed, to obtain a filtrate, and further 10% sodium hydroxide (methanol solution). Was added thereto with stirring to neutralize, and the filtrate was dried under reduced pressure by an evaporator to obtain a syrup-like fraction. 100 g of ethyl acetate and 50 ml of ion-exchanged water were added thereto, and the ethyl acetate layer was separated and collected, dried under reduced pressure by an evaporator, and added with 50 g of chloroform.
A chloroform solution of the protected acetal of pyrogallol was obtained.

Next, in a 500 ml three-necked flask, 40 g of the chloroform solution obtained above and 60 g of allyl chloride were mixed, and 40 g of triethylamine was added dropwise while refluxing on a 60 ° C. water bath. The mixture was further heated for 10 hours, dried under reduced pressure by an evaporator, and 100 g of methanol was added to the obtained fraction to obtain a methanol solution of a protected acetal of 2,3-dihydroxyphenylallyl ether. .

Next, in a 500 ml three-necked flask, 10 g of the methanol solution obtained above, 150 g of vinyl acetate, and 200 g of methanol were mixed, and nitrogen gas was blown thereinto to perform nitrogen substitution. Increase the temperature to 60 while stirring
° C. Further, 0.5 g of 2,2 was used as a polymerization initiator.
A solution prepared by dissolving 2′-azobis (isobutyronitrile) in 30 g of methanol was added, and the whole was gradually heated to 50 ° C., and after about 6 hours, 0.2 g of dinitrobenzene was added to carry out polymerization. Finished. Next, heating was performed for 2 hours while methanol was added dropwise, and the obtained fraction was thrown into water.
After further heating at 80 ° C., the precipitate was dried. Next, 5 liters of methanol, 100 ml of 10% (W / V) NaOH (methanol solution) and 5 ml of 25% (W / V) CH ₃ ONa (methanol solution) were added to the precipitate, and the mixture was added at 40 ° C. for 5 hours. The resulting precipitate was collected, dried under reduced pressure by an evaporator, and 100 ml of a 0.2 N NaOH aqueous solution purged with nitrogen was added thereto.
The mixture was heated at 80 ° C. for 2 hours under a nitrogen atmosphere, neutralized with sulfuric acid, desalted with an ion-exchange resin, and dried to obtain a desired polymerization reaction material.

The polymerization reaction raw material thus obtained is a compound having water solubility and undergoing air oxidation at an alkaline pH (pH 10). Since it has an absorption in the range of 250 nm to 280 nm, it was inferred to be a polyvinyl alcohol derivative having a 2,3-dihydroxyphenyl group in the structural part. Allyl chloride and pyrogallol were obtained from Wako Pure Chemical Industries, Ltd.

Example 5: Preparation of raw material for polymerization reaction 8.5 g of pyrogallol was added to a 200 ml eggplant flask containing 10 g of triethylamine and 50 g of diethyl ether, and 5.8 g of acryloyl chloride was added thereto with stirring for 2 hours. And dropped. Next, drying under reduced pressure by an evaporator was performed, and 80 ml of ion-exchanged water was added to the obtained fraction, followed by purging with nitrogen and heating at 70 ° C. for 1 hour. Next, 25 g of polyethyleneimine (average molecular weight 600 to 800
) And 100 ml of 20% (W / V) methanol in a 500 ml flask, the pH was adjusted to 10 with NaOH and sulfuric acid, and the atmosphere was replaced with nitrogen for 1 hour. The pyrogallol ester solution was added slowly over 2 hours at room temperature.

Next, concentration under reduced pressure by an evaporator,
The solid was obtained by drying with a freeze dryer, and 200 ml of ion-exchanged water was added thereto to form an aqueous solution. The aqueous solution was subjected to desalting treatment with an ion-exchange resin, and further concentrated under reduced pressure to obtain a desired raw material for a polymerization reaction. The polymerization reaction raw material thus obtained is a compound that is water-soluble and undergoes air oxidation at an alkaline pH (pH 10). In the same GFC analysis as in Example 2, the substance eluted to a molecular weight of about 1,000 shows a wavelength Since it has an absorption at 270 nm, it was inferred to be a polyethyleneimine derivative having a 2,3-dihydroxyphenyl group in the structural part. In addition, polyethyleneimine (average molecular weight of 600 to
800) was obtained from Aldrich Chemical Company.

Example 6: Preparation of polymerization reaction raw material 8.5 g of pyrogallol was added to a 200 ml eggplant flask containing 10 g of triethylamine and 50 g of diethyl ether, and 5.8 g of acryloyl chloride was added thereto with stirring for 2 hours. And dropped. Next, drying under reduced pressure by an evaporator was performed, and 80 ml of ion-exchanged water was added to the obtained fraction, followed by purging with nitrogen and heating at 70 ° C. for 1 hour. Next, 25 g of polyallylamine hydrochloride (average molecular weight 8,550)
~ 11,000) and 50 containing 100 ml of 20% (W / V) methanol
In a 0 ml flask, adjust the pH to 10 using NaOH and sulfuric acid.
After performing nitrogen replacement for 1 hour, the above pyrogallol acrylate solution was gradually added at room temperature over 2 hours with stirring to obtain a viscous liquid.

Next, concentration under reduced pressure using an evaporator, washing with acetonitrile, and concentration under reduced pressure again using an evaporator were performed, and 200 ml of ion-exchanged water was added thereto to form an aqueous solution. Thus, the desired raw material for the polymerization reaction was obtained. The polymerization reaction raw material thus obtained is a compound having water solubility and undergoing air oxidation at an alkaline pH (pH 10).
According to the GFC analysis similar to that described above, the substance eluted at a molecular weight of about 10,000 was assumed to be a polyallylamine derivative having a 2,3-dihydroxyphenyl group in the structural part because it had an absorption at a wavelength of 270 nm. GF similar to the above
Under C conditions, fractions with a molecular weight of 5,000 or more were collected, concentrated by vacuum drying, and analyzed by infrared spectroscopy.
Absorption characteristic of the 2,3-dihydroxyphenyl structure, not observed in polyallylamine, was observed. In addition, polyallylamine hydrochloride (average molecular weight 8,55-11,0
00) was obtained from Aldrich Chemical Company.

Example 7: Preparation of raw material for polymerization reaction To 25 g of polyethyleneimine (average molecular weight: 600 to 800),
0.2 ml of 3,4-dihydroxybenzaldehyde in 20 ml
Add the solution dissolved in ethanol and mix well.
The mixture was kept at room temperature for 2 hours, and the filtrate was concentrated under reduced pressure to obtain a desired polymerization reaction raw material. The polymerization reaction raw material thus obtained is a compound that is water-soluble and undergoes air oxidation at an alkaline pH (pH 10). In the same GFC analysis as in Example 2, the substance eluted to a molecular weight of about 1,000 shows a wavelength Since it has absorption at 270 nm, it was inferred to be a polyethyleneimine derivative having a 3,4-dihydroxyphenyl group in the structural part. In addition, 3,4-dihydroxybenzaldehyde was obtained from Aldrich Chemical Company.

Example 8: Production of raw material for polymerization reaction Polyallylamine hydrochloride (average molecular weight: 8,500 to 11,000)
After 25 g of an aqueous solution, treated with an ion exchange resin and desalted, concentrated under reduced pressure by an evaporator on a 50 ° C. water bath,
A viscous solution was obtained, and 0.2 g of 3,4-dihydroxybenzaldehyde dissolved in 20 ml of ethanol was added thereto, mixed well, left at room temperature for 2 hours, and the filtrate was concentrated under reduced pressure. A polymerization reaction raw material was obtained. The polymerization reaction raw material thus obtained is a compound having water solubility and undergoing air oxidation at an alkaline pH (pH 10), and a substance eluted to a molecular weight of about 10,000 by GFC analysis as in Example 2
It was presumed to be a polyallylamine derivative having a 3,4-dihydroxyphenyl group in the structural part due to absorption at a wavelength of 270 nm. Further, under the same GFC conditions as above, fractions having a molecular weight of 5,000 or more were collected, concentrated by drying under reduced pressure, and analyzed by infrared spectroscopy. As a result, no polyallylamine was observed. Absorption characteristic of -dihydroxyphenyl structure was observed at 1284 cm ^-1 (derived from phenolic hydroxyl group).

Example 9: Production of polymerization reaction raw material In a 200 ml eggplant flask containing 50 g of polyethyleneimine (average molecular weight: 600 to 800) under a nitrogen atmosphere, 9.4 g of pyrogallol and 16 ml of ion-exchanged water were added. While stirring, 5.5 g of glyoxylic acid was added dropwise over 30 minutes, followed by stirring at room temperature for 40 hours. This is neutralized with concentrated sulfuric acid, and then dried under reduced pressure by an evaporator, and 200 ml of ion-exchanged water is added thereto to form an aqueous solution. Obtained. The polymerization reaction raw material thus obtained is a compound having water solubility and undergoing air oxidation at an alkaline pH (pH 10).
Since the substance eluted at a molecular weight of about 1,000 has an absorption at a wavelength of 270 nm, it was presumed that the substance was a polyethyleneimine derivative having pyrogallol in the structural part.

Example 10: Preparation of raw material for polymerization reaction 10 g of polyallylamine hydrochloride (average molecular weight of 8,500 to 1
1.9 g of pyrogallol and 4 ml of ion-exchanged water were added to an eggplant flask under a nitrogen atmosphere of 100 ml containing 1,000), and 1.1 g of glyoxylic acid was added dropwise with stirring over 20 minutes, followed by 40 hours at room temperature. Was stirred. This is neutralized with concentrated sulfuric acid, and then dried under reduced pressure by an evaporator, and 50 ml of ion-exchanged water is added thereto to form an aqueous solution. Obtained. The polymerization reaction raw material thus obtained is a compound that is water-soluble and undergoes air oxidation at an alkaline pH (pH 10).
In the C analysis, substances eluted at a molecular weight of about 10,000
Since it has an absorption at 0 nm, it was presumed to be a polyallylamine derivative having a polyphenol in its structural part.

Example 11: Wood treatment An aqueous solution containing 1% of the polymerization raw material obtained in Examples 2 to 10, 0.6% of boric acid, and 2% of commercially available ligninsulfonic acid was prepared, and the pH was adjusted to 10N sodium hydroxide. The solution was adjusted to 8.4 with an aqueous solution and concentrated sulfuric acid, and the metal enzyme preparation described in Example 1 (lyophilized product having a polyphenol oxidase activity of 12 U / mg) or commercially available bilirubin oxidase (lyophilized product) was further added as a polymerization catalyst. ) (Obtained from Sigma)
Was added at a concentration of 30 ppm to prepare a reaction solution for wood treatment, and a piece of cedar wood (2 cm × 2 cm × 1 cm, 2 cm × 2 c
m, sapwood). The vacuum impregnation operation is performed after immersing the cedar wood pieces in the treatment solution.
The reduced pressure at 700 mmHg was applied for 30 minutes, and the immersion was performed at normal pressure for 30 minutes. By this vacuum impregnation operation, a sufficient amount of the processing solution (2.3 to 3.2 g
Was confirmed by measuring the weight of wood chips before and after the impregnation operation.

Further, the impregnated wood pieces were placed in a constant temperature room at 28 ° C. for 5 days, dried, oxidized and polymerized, and then dried at 60 ° C. for 48 hours. Next, 40 ml of ion-exchanged water was added to each piece of wood, and the rotor was rotated using a magnetic stirrer while the piece of wood was submerged under water, and stirred at 25 ± 2 ° C. for 8 hours, A leaching operation was performed. Then, for the water (leaching solution) after the leaching operation, complex formation using quinalizarin (obtained from Wako Pure Chemical Industries, Ltd.) and the absorbance at 620 nm were measured to calculate the leaching amount of boric acid, The amount of leaching was compared with the amount of boric acid injected during the impregnation treatment as 100%. As a result, it was shown that boric acid can be effectively injected into wood and leaching can be suppressed by the treatment method of the present invention. As a control, detailed results are shown in Table 1, together with the results when no polymerization catalyst was present.

[0101]

[Table 1]

Example 12: Wood treatment 1% of the polymerization reaction raw material obtained in Example 8 and 1% of pyrogallol were used.
%, And an aqueous solution containing boric acid at 0.6% was prepared. Various chemicals were further added thereto, the pH was adjusted to 8.5 with a 10N aqueous sodium hydroxide solution or concentrated sulfuric acid, and further described in Example 1 as a polymerization catalyst. Of metal enzyme preparation (lyophilized product with polyphenol oxidase activity of 12 U / mg)
At a concentration of pm, a reaction solution for wood treatment was prepared. When using a low water-soluble drug, the reaction solution for wood treatment before the addition of the polymerization catalyst was heated to 60 to 90 ° C., and the drug was suspended, dispersed or dissolved by a vortex mixer. Thereafter, the mixture was cooled to 25 ° C., and then a polymerization catalyst was added to prepare a reaction liquid for wood treatment. Then, in the same manner as in Example 11, cedar wood chips were subjected to vacuum impregnation, drying and polymerizing reactions, drying, and leaching. 2-naphtho
l, complex formation and absorption analysis using Aldrich Chemical Company or quinalizarin (obtained from Wako Pure Chemical Industries, Ltd.), separation / identification / quantification using HPLC or gas chromatography, or atomic absorption analysis. By doing so, the leaching amount of the drug was calculated. Then, the amount of boric acid and chemicals injected during the impregnation process is reduced to 100
% And the amount of leaching was compared. As a result, it was shown that the wood treatment method of the present invention enables effective drug injection and fixation. Detailed results are shown in Table 2. Copper sulfate, antimine trichloride, and zirconium acetate were obtained from Wako Pure Chemical Industries, Ltd. as 2,4,6-tribromophenol,
Hinokitiol was obtained from Tokyo Chemical Industry Co., Ltd. (1R)-
(+)-Α-pinene was obtained from Aldrich Chemical Company.

[0103]

[Table 2]

Example 13 Synthesis of Polymerization Catalyst and Wood Treatment To 15 ml of a 10% aqueous solution of sodium L-tartrate dihydrate,
15 ml of an aqueous solution containing 0.8 g of cobalt chloride hexahydrate was added to obtain an aqueous solution of a cobalt tartaric acid complex. Next, 2 g of L
-Tartaric acid, 600 ml of diethyl ether and 2.1 g of allyl chloride were mixed, 2.7 g of triethylamine was added dropwise with further stirring, and the mixture was further stirred for 10 hours. Next, concentration under reduced pressure by an evaporator was performed to obtain an allylated derivative of tartaric acid. Next, 3% of the above-mentioned allylated derivative of tartaric acid, 1% pyrogallol, 0.3% boric acid, 1.8%
10N sodium hydroxide was added to 30 ml of an aqueous solution containing copper sulphate pentahydrate to adjust the pH to 9.5. The reaction solution was prepared in the same manner as in Example 11;
After leaching, the amount of boric acid injected during the impregnation
When the amount of leaching was calculated assuming 100%, the leaching amount was 24%. As a control, when no polymerization catalyst is present,
The leaching amount was 85%, and it was shown that the treatment method of the present invention enables effective injection of boric acid into wood and suppression of leaching.

Example 14: Wood treatment 1% of the polymerization reaction raw material obtained in Examples 6 and 7 and boric acid were used.
An aqueous solution containing 0.6% and 2% of commercially available lignin sulfonic acid was prepared, and the pH was adjusted with a 10N aqueous sodium hydroxide solution and concentrated sulfuric acid to 8.
4, and the metal enzyme preparation described in Example 1 (lyophilized product having a polyphenol oxidase activity of 12 U / mg) was added thereto at a concentration of 30 ppm as a polymerization catalyst, and the reaction for wood treatment was carried out. Prepare a liquid and use a piece of cedar wood (2cm x 2cm
× 1 cm, 2 cm × 2 cm on the wood opening, sapwood) were subjected to reduced pressure and pressure impregnation. For the decompression and pressurization operation, immerse the cedar wood chips in the treatment liquid, depressurize at 650 to 700 mmHg for 30 minutes, return to normal pressure, and pressurize at 10 atm for 1 hour. I went in. The wood pieces after the impregnation treatment were subjected to the same drying / polymerization reaction, drying and leaching treatment as described in Example 11, and the amount of leaching was compared with the amount of boric acid injected during the impregnation treatment being 100%. As a result, it was shown that the treatment method of the present invention enables effective treatment of wood by decompression and pressurization. Detailed results are shown in Table 3.

[0106]

[Table 3]

Example 15: Antibacterial test of treated wood The cedar wood chips which were subjected to vacuum impregnation, drying / polymerization reaction, drying and leaching in Examples 11 and 12 were No. 1 and No. 1.
3, 5, 7, 29, 30, 34 pieces of wood,
Drying for 16 hours, adding 40 ml of ion-exchanged water to each piece of wood, rotating the rotor using a magnetic stirrer with the wood piece submerged under water, and stirring for 8 hours at 25 ± 2 ° C The leaching operation was repeated twice. The thus obtained wood pieces subjected to the leaching operation a total of three times were placed in a dryer at 60 ° C. for 48 hours, and further placed in a desiccator for 30 minutes to be sufficiently dried, and the weight before the antibacterial operation was measured.

For an antibacterial test, first, a 500 ml plastic container was used for an incubator, and 4% glucose, 1.5%
% Malt extract, 0.3% peptone, 100ml containing 2% agar
Agar medium (pH 6.5) was inoculated with rot fungi, Tyromyces palustris FEPRI 0507 or Kawatake mushroom ( Coriolus versicolor ) FEPRI 1030,
Culture was performed at 26 ° C. for one week. A wood piece of heat-resistant plastic having a thickness of about 1 mm was placed on the culture obtained in this manner, and the wood piece that had been subjected to the above-mentioned three leaching operations and drying was directly sterilized with Kawatake mushrooms and sterilized with Japanese quail mushrooms. An antibacterial test operation was carried out by placing the piece on top of it with the tip side down and placing it at 26 ° C. for 9 weeks. After the antibacterial test operation is completed, remove the wood pieces from the incubator and remove the mycelium on the surface sufficiently.
After air-drying for a period of time, the sample was sufficiently dried using a drier and a desiccator in the same manner as described above, and the weight was measured. as a result,
It was shown that antibacterial properties can be imparted by the wood treatment method of the present invention. Detailed results are shown in Table 4.

[0109]

[Table 4]

Example 16: Termite resistance test on treated wood Nos. 1, 3, obtained by performing vacuum impregnation, drying / polymerization, drying and leaching in the same manner as described in Examples 11 and 12. Five,
Cedar wood chips equivalent to 7, 29, 30, 34 are placed in a dryer at 60 ° C.
The sample was placed in a desiccator for 48 hours and then placed in a desiccator for 30 minutes to be sufficiently dried, and the dry weight was measured. These pieces of wood were placed on soil about 50 cm around the termite nest and left for 2 months, after which the termite-controlling effect was observed. And furthermore, sufficiently remove the surface soil and the like, and after air-drying for about 24 hours, measure the weight after sufficiently drying using a dryer and a desiccator in the same manner as described above, and compare with the weight before installation, The weight loss rate was calculated. As a result, it was shown that the wood treatment method of the present invention can impart termite resistance. Detailed results are shown in Table 5.

[0111]

[Table 5]

Example 17: Iron Corrosion Test of Treated Wood A reaction liquid for wood treatment having the same composition as that of the case of preparing the cedar wood pieces Nos. 1, 4 and 5 described in Example 11 was prepared. 2
cm × 2 cm × 4.5 cm, 2 cm × 2 cm sapwood, sapwood), the same vacuum impregnation treatment, drying / polymerization reaction, drying and leaching treatment as described in Example 11 were carried out. Drying, leaching and drying operations were carried out in the same manner as described to obtain a treated wood piece which had been subjected to a total of 5 leaching operations. However, in the leaching operation, 180 ml of ion exchange was used for each piece of wood. Next, using this piece of wood, according to the iron corrosion test method described in JIS A 9201, and examined the corrosiveness to iron round nails, the iron humus ratio was 0.2, in order of No. 1, 4, 5 equivalent wood pieces, 0.2, It was 1.2, 1.9, indicating that it is useful as a wood treatment agent.

Example 18: Control of sustained-release property 1% of the polymerization reaction raw material obtained in Example 8 and 0.6% of boric acid were used.
% Aqueous solution containing 2% of commercially available ligninsulfonic acid (pH 8.4
) And polyethylene glycol (number average molecular weight 1,500, obtained from Aldrich Chemical Company) and 0.2% of polyethylene glycol (from Aldrich Chemical Company) were added thereto, and those with no addition were prepared. 12 U
/ mg of a freeze-dried product having a polyphenol oxidase activity) at a concentration of 30 ppm to prepare a reaction solution for wood treatment.
Polymerization reaction was carried out in 5 pieces of each reaction solution.
200 ml of ion-exchanged water was added to the wood piece, and the wood piece was submerged under the surface of the water. The rotor was rotated using a magnetic stirrer, and the mixture was stirred at 25 ± 2 ° C. By sampling and concentrating and measuring the amount of boric acid, the change in the amount of boric acid leached was examined. As a result, it was shown that by adding polyethylene glycol, the leaching rate and leaching amount of boric acid were increased, and it was possible to control the sustained release of boric acid and its concentration. Table 6 shows detailed results
It was shown to.

[0114]

[Table 6]

Example 19: Rice straw treated product 50 ml of a wood treatment reaction liquid having the same composition as that of the case of preparing the cedar wood piece No. 7 described in Example 11 was prepared, and sufficiently dried rice straw was added thereto. 5 g cut into 2 cm length was added and stirred, and this was mixed with two plastic nets (mesh about 4 mm).
And placed in a constant temperature / humidity incubator at 28 ° C. and a relative humidity of 80% for 7 days to allow the enzyme polymerization reaction to proceed. As a result, a lightweight and antibacterial plate material could be obtained.

Example 20: Deodorant A wood treatment reaction solution having the same composition as that of the case of preparing the cedar wood piece No. 7 described in Example 11 was prepared, and this reaction solution was further added with (+)-catechin.H _After adding 0.2% of ₂ O, cedar wood chips (2 × 0.5 × 0.5 cm, 2 × 0.5 cm at the tip, sapwood)
Then, the same vacuum impregnation treatment and drying / polymerization reaction as described in Example 11 were performed. Next, put this piece of wood in a 10 ml test container, and further add 10% methyl mercaptan and 50%
An aqueous solution of methanol (30 μl) was added to the inner wall of the test container so as not to come into direct contact with the wood chips, and allowed to stand at 37 ° C. for 30 minutes. Then, the head space of the container was extracted using a syringe, the concentration of methyl mercaptan was analyzed by gas chromatography, the ratio to the concentration in the absence of wood chips was determined, and the deodorization rate was calculated by subtracting this value from 1. .
Gas chromatography uses SUPELCOWAX 10 30
m (0.25 mm ID, 0.25 μm df) and N ₂ (1 ml
/ min), column temperature 60 ° C, inlet temperature 200 ° C,
This was performed using FID. As a result, 95% of the above treated wood chips
Deodorization rate. In addition, when an untreated wood piece was used as a control, the deodorization rate was 35%. Thus, the treated product of the present invention was shown to have an effective deodorizing effect.

Example 21: Agent for treating porous articles 10 mg of the metal enzyme preparation (lyophilized product) described in Example 1, 3 g of boric acid, and 10 g of commercially available lignin sulfonic acid powder were added to Example 2 or 5, 6, 5 g of the polymerization reaction raw materials described in 7 and 8 were added and mixed sufficiently using a mortar. Further, when a 5% aqueous solution was prepared using this powder, the pH was 8.0.
If necessary, a small amount of sodium carbonate powder was added so as to be 9.0, and the mixture was sufficiently mixed to obtain a powdery porous article treating agent. Next, this powdery treatment agent was kept at 40 ° C. for 2 weeks, and 4 g of the powder was dissolved in 100 ml of ion-exchanged water to prepare a solution for treating porous articles. Using this solution, cedar wood chips were subjected to vacuum impregnation treatment, drying and polymerizing reaction, and leaching treatment in the same manner as in Example 11, and the amount of boric acid injected during the impregnation treatment was set to 100% and the leaching amounts were compared. did.
As a result, it was shown that the treatment agent of the present invention can effectively treat wood. Detailed results are shown in Table 7.

[0118]

[Table 7]

Also, 4 g of the powdery treating agent obtained in the same manner as above was dissolved in 12 ml of ion-exchanged water to obtain a solution-like treating agent for a porous article. Next, this solution-form treatment agent was transferred to a 20 ml screw cap / test tube, and kept sealed at 40 ° C. for 2 weeks.
, And further diluted 9-fold with ion-exchanged water to prepare a solution for treating porous articles. Using this solution, cedar wood chips were subjected to vacuum impregnation treatment, drying and polymerizing reaction, and leaching treatment in the same manner as in Example 11, and the amount of boric acid injected during the impregnation treatment was set to 100%, and the amount of leaching was compared. did. As a result, it was shown that the treatment agent of the present invention can effectively treat wood. Detailed results are shown in Table 8.

[0120]

[Table 8]

[0121]

According to the method for treating a porous article of the present invention,
Effective fixation of boron in porous articles, antibacterial, antiseptic, bactericidal, insect repellent, insecticidal, antiviral, biorepellent, dimensional stability, crack resistance, flame retardant , Adhesiveness, strength, abrasion resistance, weather resistance, rust prevention, sustained drug release, coloring, deodorization, deoxidation, humidity control, water absorption, water repellency, surface smoothness, formaldehyde absorption, A porous article having a drug leaching prevention property or an inorganic compound migration prevention property to a wood surface can be efficiently obtained. The composition for treating the inside of a porous article of the present invention is particularly effective when using the method for treating a porous article of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B27K 3/52 BBA B27K 3/52 BBAA C08G 73/00 C08G 73/00

Claims (45)

[Claims] 1. A _{CH 2 = CH -, - CH} = CH -, CH 2 = C (CH 3) -,
_{-CH 2 = N -, - CH} = N-, NH = CH -, NH = N-, and / or -N = N - an organic compound having the structural part, the boron-containing compound, and a polymerization catalyst at the same time or phase Impregnating and / or applying to the porous article before and after, the organic compound,
A method for treating a porous article, comprising polymerizing in a porous article and / or on a porous article surface with a polymerization catalyst in the presence of a boron-containing compound. 2. A _{CH 2 = CH -, - CH} = CH -, CH 2 = C (CH 3) -,
_{-CH 2 = N -, - CH} = N-, NH = CH -, NH = N-, and / or -N = N - an organic compound having the structural part, the boron-containing compounds, and compositions containing a polymerization catalyst Impregnating and / or coating the product on a porous article, and polymerizing the organic compound in the porous article and / or on the surface of the porous article by a polymerization catalyst in the presence of a boron-containing compound. Processing method. 3. As a pre-treatment or post-treatment of applying and / or impregnating a boron-containing compound to a porous article, CH ₂ CHCH
-, - CH = CH -, CH 2 = C (CH 3) -, - CH 2 = N -, - CH = N
-, NH = CH-, NH = N-, and / or -N = N- using a composition containing an organic compound having a structural part and a polymerization catalyst, the organic compound in a porous article by a polymerization catalyst and A method for treating a porous article, comprising polymerizing on the surface of the porous article. 4. The organic compound according to claim 1, wherein the organic compound has an aromatic ring having a OH group, an OCH ₃ group, and / or an NH ₂ group as a substituent in a structural part thereof. A method for treating a porous article according to any one of the above. 5. The organic compound further comprises -CHR-CHR-,-
_{CHR-CH 2 -CHR -, -} O-CH 2 -CH 2 -O -, - NH-CH 2 -CH 2 -NH
- and / or _{-CH 2 -CH (CH 2 R)} - [ wherein R is an OH group or NH ₂ group] to any one of the preceding claims, characterized in that an organic compound having a structural part of the A method for treating a porous article according to the above. 6. An aromatic compound having, as a substituent, an OH group, an NH ₂ group, and / or a compound obtained by protecting the OH group or NH ₂ group, and an aromatic compound having an unsaturated side chain as a substituent; , Methacrylate,
The method for treating a porous article according to claim 5, wherein the organic compound is an organic compound produced through a reaction with allyl ether, allyl alcohol, and / or allylamine. 7. An aromatic compound in which an organic compound has an OH group, an NH ₂ group, and / or a protected one thereof as a substituent, and polyvinyl alcohol, polyethylene glycol, polyallylamine, polyethyleneimine and / or a derivative thereof. 6. The method for treating a porous article according to claim 5, wherein the organic compound is an organic compound produced through a reaction with a porous article. 8. The method for treating a porous article according to claim 1, wherein the polymerization catalyst is a metal salt or complex. 9. The metal according to claim 8, wherein the metal is a transition element or at least one metal selected from zinc and aluminum.
A method for treating a porous article according to the above. 10. The method for treating a porous article according to claim 8, wherein the complex is a metalloenzyme. 11. The method according to claim 11, wherein the metalloenzyme is catechol oxidase,
The method for treating a porous article according to claim 10, which is laccase, polyphenol oxidase, ascorbate oxidase, bilirubin oxidase, or peroxidase. 12. The method for treating a porous article according to claim 1, wherein the boron-containing compound is a borate. 13. -CHR-CHR -, - CHR- CH 2 -CHR -, -
_{O-CH 2 -CH 2 -O -} , - NH-CH 2 -CH 2 -NH -, and / or -
_{CH 2 -CH (CH 2 R)} - porous article according to any of claims 1 to 12, [the R is an OH group or NH ₂ group], further comprising an organic compound having a structural part of the Processing method. 14. A fragrance, a deodorant, a rust inhibitor, a flame retardant,
The porous article according to any one of claims 1 to 13, further comprising at least one drug selected from an antimicrobial agent, a preservative, a bactericide, an insect repellent, an antiviral agent, and a biological repellent. Processing method. 15. The drug is at least one metal selected from copper, arsenic, zinc, chromium, nickel, aluminum, molybdenum, magnesium, titanium, cobalt, palladium, tin, lead, iron, antimony, zirconium or silver; The method for treating a porous article according to claim 14, which is a solution or a fine powder of a metal salt, a metal compound, or a metal complex. 16. The method for treating a porous article according to claim 14, wherein the drug is a quaternary ammonium compound. 17. The method according to claim 14, wherein the drug is an OH group, an amino group, a halogen,
The method for treating a porous article according to claim 14, which is an aromatic compound or a cyclic compound having one or more substituents selected from nitro groups. 18. The method for treating a porous article according to claim 14, wherein the drug is a plant-derived extract, an extract component, or a compound having a structure equivalent to that of the plant extract component. 19. The method for treating a porous article according to claim 18, wherein the drug is hinokitiol. 20. The composition according to claim 2, wherein the composition is prepared as a highly concentrated 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. A method for treating a porous article according to any one of the above. 21. The method for treating a porous article according to claim 1, wherein the impregnation is performed by applying pressure and / or reducing pressure. 22. The method for treating a porous article according to claim 21, wherein the pressurization is performed at 1 to 20 atm. 23. The porous article according to claim 1, wherein the polymerization reaction temperature is 0 to 200 ° C., preferably 5 to 120 ° C., more preferably 10 to 80 ° C. Processing method. 24. The porous article is made of a sintered metal, a cast, an alloy, a die-cast product, a ceramic, a brick, a concrete, a wood, a piece of wood, a wood powder, a wood-processed material, a fir shell, a rush,
24. The method for treating a porous article according to any one of claims 1 to 23, which is a foam of straw, bamboo, leather, cloth, non-woven cloth, fiber, activated carbon, or synthetic resin. 25. Antibacterial property, antiseptic property, bactericidal property, insect repellent property, insecticidal property, antiviral property, biological repellency, dimensional stability, crack resistance, flame retardancy, adhesion, strength, abrasion resistance, Weather resistance, rust prevention, drug sustained release, coloring, deodorant, deoxygenation, humidity control, water absorption, water repellency, surface smoothness, formaldehyde absorption,
The method for treating a porous article according to any one of claims 1 to 24, which has an effect of imparting a drug leaching prevention property or an inorganic compound migration prevention property to a wood surface. 26. A method for producing a treated porous article, comprising using the method according to claim 1. Description: 27. CH ₂ = CH-, -CH = CH-, CH ₂ = C (CH ₃ )
_{-, - CH 2 = N -} , - CH = N-, NH = CH -, NH = N-, and /
A composition for treating a porous article, comprising: an organic compound having -N = N- in a structural part; a boron-containing compound; and a polymerization catalyst. 28. The organic compound, wherein the organic compound is an OH group, an OCH ₃ group, and / or
28. The composition for treating a porous article according to claim 27, wherein the composition is an organic compound having an aromatic ring having an NH ₂ group as a substituent in a structural part. 29. The organic compound further comprises -CHR-CHR-,
_{-CHR-CH 2 -CHR -, -} O-CH 2 -CH 2 -O -, - NH-CH 2 -CH 2 -N
H -, and / or _{-CH 2 -CH (CH 2 R)} - [ wherein R is an OH group or NH ₂ group] according to claim 27 or 28, characterized in that an organic compound having a structural part of the A composition for treating a porous article. 30. The organic compound, wherein the organic compound is an OH group, an NH ₂ group, and / or
Or reaction of an aromatic compound having a protected one thereof as a substituent and further having an unsaturated side chain as a substituent with vinyl ester, vinyl ether, methacrylic ester, allyl ether, allyl alcohol, and / or allylamine 30. The composition for treating a porous article according to claim 29, wherein the composition is an organic compound produced through the following. 31. The organic compound, wherein the organic compound is an OH group, an NH ₂ group, and / or
Or an aromatic compound having a substituent protected by a substituent, polyvinyl alcohol, polyethylene glycol, polyallylamine, polyethyleneimine and / or
30. The composition for treating a porous article according to claim 29, wherein the composition is an organic compound produced through a reaction with a derivative thereof. 32. The composition for treating a porous article according to claim 27, wherein the polymerization catalyst is a metal salt or complex. 33. The composition for treating a porous article according to claim 32, wherein the metal is a transition element or at least one metal selected from zinc and aluminum. 34. The composition for treating a porous article according to claim 32, wherein the complex is a metalloenzyme. 35. The metal enzyme is catechol oxidase,
35. The composition for treating a porous article according to claim 34, which is laccase, polyphenol oxidase, ascorbate oxidase, bilirubin oxidase, or peroxidase. 36. The composition for treating a porous article according to claim 27, wherein the boron-containing compound is a borate. 37. -CHR-CHR -, - CHR- CH 2 -CHR -, -
_{O-CH 2 -CH 2 -O -} , - NH-CH 2 -CH 2 -NH -, and / or -
_{CH 2 -CH (CH 2 R)} - porous article according to any of claims 27 to 36 in which [said R is an OH group or NH ₂ group], further comprising an organic compound having a structural part of the Processing composition. 38. A fragrance, a deodorant, a rust inhibitor, a flame retardant,
The porous article treatment according to any one of claims 27 to 37, comprising at least one drug selected from an antimicrobial agent, a preservative, a bactericide, an insect repellent, an antiviral agent, and a biological repellent. Composition. 39. The drug is at least one metal selected from copper, arsenic, zinc, chromium, nickel, aluminum, molybdenum, magnesium, titanium, cobalt, palladium, tin, lead, iron, antimony, zirconium and silver; 39. The composition for treating a porous article according to claim 38, which is a solution or a fine powder of a metal salt, a metal compound, or a metal complex. 40. The composition for treating a porous article according to claim 38, wherein the drug is a quaternary ammonium compound. 41. The drug is an OH group, an amino group, a halogen,
39. The composition for treating a porous article according to claim 38, which is an aromatic compound or a cyclic compound having one or more substituents selected from nitro groups. 42. The composition for treating a porous article according to claim 38, wherein the drug is a plant-derived extract, an extract component, or a compound having a structure equivalent to that of the plant extract component. 43. The composition for treating a porous article according to claim 42, wherein the drug is hinokitiol. 44. The method according to claim 27, 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. A composition for treating a porous article. 45. Antibacterial property, antiseptic property, bactericidal property, insect repellent property, insecticidal property, antiviral property, biological repellency, dimensional stability, crack prevention property, flame retardancy, adhesion, strength, abrasion resistance, Weather resistance, rust prevention, drug sustained release, coloring, deodorant, deoxygenation, humidity control, water absorption, water repellency, surface smoothness, formaldehyde absorption,
The composition for treating a porous article according to any one of claims 27 to 44, which has an effect of imparting a drug leaching prevention property or an inorganic compound migration prevention property to a wood surface.