JP2003277215A - Antiseptic and insect-proofing agent for wood and woody material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiseptic and insect-proofing agent harmless to human body without causing environmental pollution for wood and the woody material. <P>SOLUTION: The antiseptic and insect-proofing agent is used for antiseptic and insect-proofing of the wood and the woody materials, and contains an effective amount of ingredient of a wood decomposed product prepared by decomposition of wood with a wood decomposing agent. A hydroxycarboxylic acid, a dicarboxylic acid, or an amino alcohol may be enumerated as the wood decomposing agent. The antiseptic and insect-proofing agent forms film on the wood by spreading it on the wood or infusing it in the wood to protect wood from erosion caused by fungi. Particularly, the agent exhibits excellent antiseptic effect against wood-rotting fungi, particularly against Tyromyces palustris and Trametes versicolor together with insect-proofing effect. Addition of a copper compound, a silver compound or a boron compound provides more effective insect-proofing effect. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antiseptic and insecticide for wood and wood materials, and more particularly to an antiseptic and insecticide obtained by chemically treating wood.

[0002]

2. Description of the Related Art Conventionally, wood preservatives and insecticides have been prepared by injecting a mixture of copper, chromium, an arsenic compound (hereinafter referred to as CCA) into wood by pressurization and depressurization. There was a method of expressing the antiseptic and insect repellent effect. This method requires a large-scale device for impregnating wood with a chemical, and it is necessary to dry the wood after the chemical is injected and before use. Also, when wood treated with CCA is incinerated at the time of disposal, the injected arsenic becomes toxic trimethylarsine or diarsenic trioxide, and is scattered into the atmosphere, and chromium becomes hexavalent chromium in charcoal. Remain and cause environmental pollution after disposal. That is, if there is even 1% of CCA-treated wood in the total waste, the waste becomes industrial waste containing harmful metals. Further, CCA wood has a drawback that it is rotted or damaged by ants, chrysanthemums, mosses and the like from cracks generated on the surface of the wood.

The copper alkylammonium compound is a chemical agent for preserving treatment containing copper and ammonia, but it is expensive and its fixing ability on wood is poor because the vapor pressure of ammonia is high. Repainting is necessary to some extent. In addition, there is a method of producing the effect by using a compound such as copper, boron, or fluorine alone or in a mixture, but any of these agents requires a large-scale depressurization in order to improve the fixing property to wood. A pressure injection device and a dryer that removes water and organic solvents are required, and there is concern about environmental pollution due to chemicals after disposal. It is also known to use organic nitrogen-containing compounds as preservatives, and amine salts and quaternary ammonium compounds are used for this purpose. However, these agents have poor fixability on wood and are not durable.

Further, pentachlorophenol and tetrachlorophenol are chemicals used for preserving solid wood, and it is easily expected from the structural formula that polychlorinated dibenzodioxins are generated. Creosote, which is a coal dry matter, is used for sleepers and housing base materials and has good permeability to wood, but it has poor anchoring property and is leached due to vibration, and the residual amount of creosote after use for 20 years is 10% or less. is there. In addition, creosote contains benzpyrene, which induces cancer in the process of metabolism. On the other hand, persimmon astringent, although used as a natural paint, has no weather resistance. In addition, a paint containing charcoal as a main component is expensive, and depending on the composition of the charcoal, the remaining wood component may attract termites and molds.

[0005]

In order to solve the above-mentioned various problems, the present inventors have conducted extensive studies and as a result, the wood component, which is a natural material, is used as a raw material and is harmless to the human body and does not cause environmental pollution. He found an antiseptic and insect repellent. That is, the present invention provides an antiseptic and insecticide for wood and wood materials, which contains a wood decomposition product obtained by decomposing wood with a wood decomposition agent as an active ingredient.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to embodiments. In the present invention, the wood scraps can be used as the raw wood as it is, but it is preferable that the raw wood is crushed (if necessary, polyvinyl chloride or the like is separated), and the crushed product is subjected to a pretreatment. The crushing is performed by, for example, impact crusher (hammer type, chain type), shear crusher, cutting type crusher, compression type crusher (roll type, conveyor type, screw type), stamp mill, ball mill, rod mill. It can be performed by a crusher or the like. The smaller the pulverized product is, the larger the surface area involved in the reaction is. Therefore, it is preferable that the pulverized product is such that it can pass through a sieve with 10 mm openings. Preferably 3m between eyes
m, more preferably a pulverized product that passes through a sieve having an opening of 1 mm.

The tree species used as the raw material wood of the present invention are not particularly limited, but for example, cous, pine, fir,
Spruce, larch, togasawara, hemlock, cypress, hiba,
Coniferous trees such as Neko and Japanese cedar, and boxwood, maple, beech, alder, cherry, oyster, horse chestnut, birch, birch, scabbard, red oak, Onigurumi, chestnut, shii, oak, oak, kunugi, kihada, harunire, zelkova, honoki,
Broad-leaved trees such as camphor tree, tabuki tree, cypress tree, vine, asada, doronoki tree, linden tree, dogwood tree, harpoon tree, millet, taro species, Inenju, Yamaguchi and the like. Examples of the wood material include particle board, fiber board, OSB, WB, strand board, softwood plywood, and hardwood plywood. Further, lignin, hemicellulose and the like are also included in the woody material of the present invention.

The hydroxycarboxylic acid which is one of the wood decomposing agents used in the present invention contains a saturated hydroxycarboxylic acid and an unsaturated hydroxycarboxylic acid. Examples of the saturated hydroxycarboxylic acid include glycolic acid, lactic acid, 2-hydroxybutyric acid, and 2-hydroxy-2.
-Methylpropanoic acid, 2-hydroxy-4-methylpentanoic acid, 2-ethyl-2-hydroxybutyric acid, 3-hydroxypropionic acid, 10-hydroxystearic acid,
3,3,3-Trichloro-2-hydroxypropionic acid, 2- (lactoyloxy) propionic acid, hydroxybenzoic acid, salicylic acid, 5-chlorosalicylic acid, 3,
5-dichlorosalicylic acid, 3-nitrosalicylic acid, 3,
5-dinitrosalicylic acid, methylsalicylic acid, thymotic acid, vanillic acid, isovanillic acid, hydroxyphenylacetic acid, 3- (o-hydroxyphenyl) propionic acid,
Examples thereof include mandelic acid, phenyllactic acid, 3-hydroxyphenylpropionic acid, 2-hydroxy-2,2-diphenylethanoic acid and the like. Examples of the unsaturated hydroxycarboxylic acid include hydroxycinnamic acid, 4
-Hydroxy-3-methoxycinnamic acid, 3-hydroxy-4-methoxycinnamic acid, 2-hydroxy-4-phenyl-3-butenoic acid, 4-allyl-2-hydroxy-6-
Methoxybenzoic acid, 2-hydroxy-6- (8,11-
Pentadecadienyl) benzoic acid, 12-hydroxy-9
-Octadecenoic acid and the like.

Another wood decomposing agent, dicarboxylic acids, includes saturated dicarboxylic acids and unsaturated dicarboxylic acids. Examples of the saturated dicarboxylic acid, for example, oxalic acid, malonic acid, succinic acid, chlorosuccinic acid, bromosuccinic acid,
Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid Acid, tetramethylsuccinic acid, phthalic acid, chlorophthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, tetrabromophthalic acid, chlorendic acid, phenylsuccinic acid Acid, o-
Examples include carboxyphenylacetic acid and o-phenylenediacetic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, chloromaleic acid, fumaric acid, chlorofumaric acid, citraconic acid, mesaconic acid, glutaconic acid, itaconic acid, allylmalonic acid, isopropylidenesuccinic acid, muconic acid, and the like. Can be mentioned.

Examples of other wood decomposing agents, amino alcohols, include 2-aminoethanol and 2-amino-
1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, diethanolamine, triethanol Amine,
Examples include tetraethanolamine and 2- (ethylamino) ethanol.

The weight ratio of the raw wood to the compound used as the wood decomposing agent is 1: 0.2 to 35, preferably 1: 0.
It is desirable to set it to 5-5. By changing this ratio, the molecular weight of the obtained wood decomposition product can be adjusted. Incidentally, when the amount of the wood decomposing agent is small, the molecular weight of the wood decomposing product becomes large, and when the amount of the wood degrading agent is large, the molecular weight of the wood decomposing product becomes small. From the viewpoint of processing cost, it is better to add less substance. However, in some cases, the wettability may not be reduced below a certain level. Moreover, since the ground wood is bulky, it may not be sufficiently immersed in the wood decomposing agent, and the surface of the ground wood may not get wet. However, if it does not get wet sufficiently, it is possible to wet and decompose the ground wood by adding the liquid (wood decomposition product) generated by decomposition to a new wood decomposition agent of the same type as that used for decomposition. it can. Further, it is possible to efficiently use the pulverized wood product effectively by separating the excess wood decomposing agent from the wood decomposition product.

In the present invention, a cellulose swelling agent may be used to decompose wood. Examples of the cellulose swelling agent include sodium nitrate-water system (sodium nitrate aqueous solution), ethylene carbonate, lactitol-water system (lactitol aqueous solution), dimethyl sulfoxide, dimethylformamide, N-methylmorpholine-
Examples thereof include N-oxide, N, N-dimethylacetamide-lithium chloride system (mixture of N, N-dimethylacetamide and lithium chloride), anisole, urea and water. These cellulose swelling agents act as a solubilizer and a swelling agent for lignin, hemicellulose, and cellulose, which are wood components, and accelerate the decomposition of the wood components. For example, anisole is believed to prevent insolubilization due to condensation of lignin at high temperatures.

On the other hand, in the present invention, a Lewis acid may be used as a reaction catalyst for accelerating the decomposition of wood components. Examples of such a Lewis acid include aluminum sulfate, boron trifluoride, aluminum trichloride, titanium tetrachloride, tin trichloride (a trace amount of water etc. is required as a cocatalyst),
Examples thereof include diethyl etherate.

The decomposition temperature of the wood in the present invention may be a relatively low temperature of about 100 ° C to 300 ° C. Preferably,
A decomposition temperature of 150 ° C. to 250 ° C. is desirable because the decomposition rate becomes faster. By the way, the decomposition temperature is 200 ℃ ~ 2
In the range of 80 ° C, 220 ° C had the highest decomposition rate.
When the decomposition temperature was higher than 220 ° C, the decomposition rate decreased. When the decomposition time was in the range of 1 to 5 hours, the decomposition rate was high in 1 to 2 hours, and the decomposition rate decreased after 2 hours. The wood chip: lactic acid bath ratio is 1:20, 1:10,
Experiments were carried out at 1: 5, 1: 3, 1: 2, but the decomposition rate was high up to 1: 5, and lower (1: 3 or 1: 2), the decomposition rate was low. This is because when the bath ratio is small, raw wood (chips)
Is not soaked in the wood decomposer. When the amount of aluminum sulfate added was 1 to 0.15%, 1% had the highest decomposition rate, and the decomposition rate also decreased as the amount of aluminum sulfate decreased.

The decomposition reaction in a nitrogen atmosphere is desirable because it can prevent coloring due to the oxidation reaction. Furthermore, when an antioxidant such as 2,6-di-t-butyl-4-methylphenol is added and decomposed, coloration can be prevented further. It is also possible to carry out the decomposition under atmospheric pressure or under pressure. Incidentally, when a low-boiling hydroxycarboxylic acid or the like is used, decomposition is carried out under pressure at a temperature above the boiling point.

The wood decomposition product thus obtained is used as an antiseptic and insecticide for wood and wood materials. The mode of use for wood and wood materials is not particularly limited.For example, a coating method for applying a brush to the surface of wood and wood materials, a flow coater method for applying the paint through a paint shower, or a vacuum impregnation device is used. The injection method by pressure reduction is mentioned.

As described above, it is possible to protect the wood from erosion of fungi by coating the surface of the wood with the antiseptic and insecticide to form a film on the surface of the wood, and by injecting the antiseptic and insecticide inside the wood. In particular, the antibacterial action, that is, the antiseptic action against the wood decay fungus, Pleurotus cornucopiae and Pleurotus cornucopiae, was extremely high. In addition, an insect repellent effect was also recognized.

On the other hand, since the antiseptic and insect repellent of the present invention is mainly composed of natural wood components, it is not toxic to the human body at the time of coating and processing, and does not easily volatilize during use and has good fixability.
In addition, it does not cause environmental pollution even when it is used up and turned into waste. Incidentally, L-lactic acid, which is one of the wood degrading agents, has an LD50 of 3.72 g / kg, and it causes almost no harm to the human body. Then, the wood decomposition product by L-lactic acid is cellulose, which is a constituent component of wood as described above.
Since it is composed of hemicellulose, lignin and L-lactic acid, the decomposition product itself has no toxicity.

The antiseptic and insect repellent of the present invention can be used alone, or other compounds may be added. If a copper compound, a silver compound, or a boron compound is added as such another compound, an extremely high insect repellent effect can be obtained. The form of these compounds may be acid, salt or other form.

The antiseptic and insecticide of the present invention can of course be used as a stock solution of the obtained wood decomposition product as it is, or may be diluted or dispersed in water or an organic solvent such as alcohol or acetone. Absent. The concentration of the decomposition product of wood in the diluent or dispersion is not particularly limited as long as it has an antiseptic and insecticidal effect on wood and wood materials. In addition, it is an antiseptic and insect repellent which is made by powdering the decomposition product of wood into a powder by vacuum drying, or an antiseptic and insect repellent made into granules or tablets by adding an appropriate filler or shape-retaining agent selected according to the use conditions. Even an agent can be provided to the market.

[0021]

EXAMPLES The present invention will now be described more specifically with reference to examples such as decomposition examples. In the following decomposition example, a raw material wood was placed in a portable reactor TVS-N2 type (cap bolt method, 200 mL) manufactured by Pressure Resistant Glass Industry Co., Ltd.
A wood decomposing agent and the like were charged and decomposed at a predetermined temperature for a predetermined time to obtain a wood decomposition product. The molecular weight of the liquid wood decomposition product that passed through the glass filter was measured by gel permeation chromatography (GPC) using a tetrahydrofuran solvent at 40 ° C. The wood decomposition product filtered after decomposition as described above was used as an antiseptic / insecticide in the examples described below.

Decomposition Examples 1 to 6, 9, 10, and 13 were used as raw wood for Japanese cedar (Cryptomeria japonica D.) produced in Wakayama Prefecture.
Don) thinned wood crushed product (trade name “Uglan” manufactured by Morishita Kikai Co., Ltd., sieve opening 0.25 to 2 mm, bulk specific gravity 0.17) is used. Also, decomposition example 1
˜5,7,8,11 to 15 represent examples of decomposition by “L-lactic acid”. As L-lactic acid, a reagent (purity 90%) manufactured by Wako Pure Chemical Industries, Ltd. was used.

(Decomposition Example 1) 5 g of crushed material of the above-mentioned cedar thinning material
50 g of L-lactic acid (an example of hydroxycarboxylic acid) was added thereto and decomposed at 220 ° C. for 2 hours to obtain a wood decomposition product. The decomposition rate at this time was 54.5%. The decomposition rate is
The solid content obtained at that time was filtered off, the solid content on the glass filter was washed successively with methanol, tetrahydrofuran, acetone, and water, and the insoluble matter remaining on the glass filter was dried under reduced pressure and weighed, and this weighed value was crushed. It was calculated by dividing by the weight of wood. The obtained decomposition product was analyzed by GPC. From the results of GPC analysis, peak 1 of wood degradation products
The average molecular weight was 154, the weight average molecular weight was 157, and the weight average molecular weight / number average molecular weight was 1.02. The peak 2 of the wood decomposition product is number average molecular weight = 239, weight average molecular weight = 240, weight average molecular weight / number average molecular weight = 1.
It was 01. The peak 3 of the wood decomposition product was number average molecular weight = 314, weight average molecular weight = 315, and weight average molecular weight / number average molecular weight = 1.00. Peak 4 of the wood decomposition product has a number average molecular weight of 674 and a weight average molecular weight of 9
23, the weight average molecular weight / number average molecular weight = 1.37. The liquid peaks are number average molecular weight = 232, weight average molecular weight = 424, weight average molecular weight / number average molecular weight = 1.
It was 83. In addition, the infrared absorption spectrum analysis of the wood decomposition products was also performed. From the infrared absorption spectrum obtained,
There is absorption of ester group at 1746 cm ^-1 , 1604c
m ^-1, 1509cm ^-1, there is absorption of phenyl groups at 1459cm ^-1, except absorption of ester groups was the same as the absorption spectrum of lignin. That is, it is understood that the wood decomposition product in this example was obtained by solvolysis (esterification) of the raw wood material with L-lactic acid.

(Decomposition Example 2) A wood decomposition product was obtained under the same conditions as in decomposition example 1 except that the decomposition reaction time was set to 1 hour.

(Decomposition example 3) The amount of crushed material of thinned cedar is 1 g.
Then, a wood decomposition product was obtained under the same conditions as in decomposition example 1 except that the amount of L-lactic acid was set to 20 g, and 2 g of 4-methylmorpholine-4-oxide (a cellulose swelling agent) was added for decomposition.

(Decomposition Example 4) The amount of crushed sugi thinned material is 1 g.
The amount of L-lactic acid was 20 g, 1 g of anisole (a cellulose swelling agent) was added, and the decomposition product was decomposed at 260 ° C. to obtain a wood decomposition product under the same conditions as in decomposition example 1.

(Decomposition Example 5) The amount of crushed sugi thinned material is 1 g
Then, a wood decomposition product was obtained under the same conditions as in decomposition example 1 except that the amount of L-lactic acid was 20 g, 5 g of ethylene carbonate (cellulose swelling agent) was added, and decomposition was carried out at 260 ° C. for 3 hours.

(Decomposition example 6) The amount of crushed sugi thinned material is 1 g
Then, using 20 g of monoethanolamine (an example of amino alcohol) instead of L-lactic acid, adding 1 g of dimethylformamide (a cellulose swelling agent), and decomposing at 250 ° C., under the same conditions as in Decomposition Example 1, wood A decomposition product was obtained.

(Decomposition Example 7) A wood decomposition product was obtained under the same reaction conditions as in decomposition example 2 except that 5 g of brown powder lignin was used as a raw material instead of the crushed sugi thinned material.

(Decomposition example 8) A wood decomposition product was obtained under the same reaction conditions as in decomposition example 2 except that 5 g of cypress crushed material was used as the raw material instead of the crushed product of cedar thinned wood.

Decomposition Example 9 Decomposition Example except that 60 wt% of citric acid (example of hydroxycarboxylic acid) was used instead of L-lactic acid based on the weight (5 g) of crushed cedar thinning material. A wood decomposition product was obtained under the same reaction conditions as in 2.

(Decomposition Example 10) Wood under the same conditions as in Decomposition Example 1 except that 20 g of adipic acid (an example of dicarboxylic acid) was used in place of L-lactic acid and the crushed material of thinned cedar wood was decomposed at 260 ° C. A decomposition product was obtained.

(Decomposition example 11) A wood decomposition product was obtained under the same reaction conditions as in decomposition example 2 except that 5 g of crushed ground product was used as a raw material instead of the crushed product of cedar thinned wood.

(Decomposition Example 12) Sugi thinned wood crushed product (5 g)
A wood decomposition product was obtained under the same reaction conditions as in decomposition example 2, except that 5 g of crushed hiba was used as the raw material instead of.

(Decomposition example 13) Weight of crushed sugi (5)
A decomposition product was obtained under the same reaction conditions as in decomposition example 2 except that 20% by weight of aluminum sulfate (Lewis acid) was added to L-lactic acid to cause decomposition.

(Decomposition Example 14) Sugi thinned wood crushed product (5 g)
Instead of using 5 g of lignin as a raw material instead of
A decomposition product was obtained under the same reaction conditions as in decomposition example 2.

(Decomposition Example 15) Sugi thinned wood crushed product (5 g)
A decomposition product was obtained under the same reaction conditions as in decomposition example 2 except that 5 g of cedar bark was used as a raw material instead of.

The following Examples 1 to 40 are the above decomposition examples 1 to
It is shown about "preservation test" by the wood decomposition product obtained in No. 10. In this "antiseptic test"
Glucose agar medium was used. The potato-glucose agar medium was prepared by adding 1000 mL of tap water to 200 g of potatoes that had been peeled and cut into square pieces, heated at 60 ° C. for 1 hour, and filtered with a cloth to give 20.0 g of glucose and 15.0 g of agar. Was added and autoclaved at 120 ° C. for 30 minutes. Hereinafter, this medium is abbreviated as PDA medium.
The test was carried out by inoculating 20 mL of PDA medium in a petri dish with wood-destroying fungi (Pleurotus cornucopiae, Pleurotus cornucopiae) in a sterile clean bench, and measuring the maximum length of mycelia after leaving it in a room at 28 ± 2 ° C for 7 days. did.

(Example 1) Pleurotus ostreatus is planted on a PDA medium containing 1% by volume of the wood decomposition product obtained in decomposition example 1,
The maximum length of the spread hyphae was measured. (Example 2) Pleurotus ostreatus was planted in a PDA medium containing 0.5% by volume of the wood decomposition product obtained in Decomposition Example 1, and the maximum length of the spread hyphae was measured. (Example 3) 1% by volume of the wood decomposition product obtained in decomposition example 1
Pleurotus cornucopiae was planted in the PDA medium containing the same, and the maximum length of the spread hyphae was measured. (Example 4) Pleurotus cornucopiae was planted in a PDA medium containing 0.5% by volume of the wood decomposition product obtained in Decomposition Example 1, and the maximum length of the spread hypha was measured.

(Example 5) Pleurotus ostreatus is planted in a PDA medium containing 1% by volume of the wood decomposition product obtained in decomposition example 2,
The maximum length of the spread hyphae was measured. (Example 6) Pleurotus ostreatus is planted in a PDA medium containing 0.5% by volume of the wood decomposition product obtained in Decomposition Example 2 and the maximum length of the spread hyphae is measured. (Example 7) 1% by volume of the wood decomposition product obtained in decomposition example 2
Pleurotus cornucopiae was planted in the PDA medium containing the same, and the maximum length of the spread hyphae was measured. (Example 8) Pleurotus cornucopiae was planted in a PDA medium containing 0.5% by volume of the wood decomposition product obtained in decomposition example 2, and the maximum length of the spread hypha was measured.

Example 9 Pleurotus ostreatus was planted in a PDA medium containing 1.0% by volume of the wood decomposition product obtained in decomposition example 3, and the maximum length of the spread hyphae was measured. (Example 10) The wood decomposition product obtained in decomposition example 3 was 0.5.
Pleurotus ostreatus was planted in a PDA medium containing volume% and the maximum length of the spread hyphae was measured. (Example 11) The wood decomposition product obtained in decomposition example 3 was 1.0
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured. (Example 12) The wood decomposition product obtained in decomposition example 3 was 0.5.
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured.

(Example 13) Pleurotus ostreatus was planted in a PDA medium containing 1.0% by volume of the wood decomposition product obtained in decomposition example 4, and the maximum length of the spread hyphae was measured. Example 14 The wood decomposition product obtained in decomposition example 4 was 0.5
Pleurotus ostreatus was planted in a PDA medium containing volume% and the maximum length of the spread hyphae was measured. (Example 15) The wood decomposition product obtained in decomposition example 4 was 1.0
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured. (Example 16) The wood decomposition product obtained in decomposition example 4 was 0.5.
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured.

(Example 17) Pleurotus ostreatus was planted in a PDA medium containing 1.0% by volume of the wood decomposition product obtained in decomposition example 5, and the maximum length of the spread hyphae was measured. (Example 18) The wood decomposition product obtained in decomposition example 5 was 0.5.
Pleurotus ostreatus was planted in a PDA medium containing volume% and the maximum length of the spread hyphae was measured. (Example 19) The wood decomposition product obtained in decomposition example 5 was 1.0
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured. (Example 20) The wood decomposition product obtained in decomposition example 5 was 0.5.
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured.

(Example 21) Pleurotus ostreatus was planted in a PDA medium containing 1.0% by volume of the wood decomposition product obtained in decomposition example 6, and the maximum length of the spread hyphae was measured. (Example 22) The wood decomposition product obtained in decomposition example 6 was 0.5
Pleurotus ostreatus was planted in a PDA medium containing volume% and the maximum length of the spread hyphae was measured. (Example 23) The wood decomposition product obtained in decomposition example 6 was 1.0
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured. (Example 24) The wood decomposition product obtained in decomposition example 6 was 0.5
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured.

(Example 25) Pleurotus ostreatus was planted in a PDA medium containing 1% by volume of the wood decomposition product obtained in decomposition example 7, and the maximum length of the spread hyphae was measured. (Example 26) The wood decomposition product obtained in decomposition example 7 was 0.5.
Pleurotus ostreatus was planted in a PDA medium containing volume% and the maximum length of the spread hyphae was measured. (Example 27) Kawatake mushrooms were planted in a PDA medium containing 1% by volume of the wood decomposition product obtained in Decomposition Example 7, and the maximum length of the spread hyphae was measured. (Example 28) The wood decomposition product obtained in decomposition example 7 was 0.5.
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured.

(Example 29) Pleurotus ostreatus was planted in a PDA medium containing 1.0% by volume of the wood decomposition product obtained in decomposition example 8, and the maximum length of the spread hyphae was measured. (Example 30) The wood decomposition product obtained in decomposition example 8 was 0.5
Pleurotus ostreatus was planted in a PDA medium containing volume% and the maximum length of the spread hyphae was measured. Example 31 The wood decomposition product obtained in decomposition example 8 was 1.0
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured. (Example 32) The wood decomposition product obtained in decomposition example 8 was 0.5
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured.

(Example 33) Pleurotus ostreatus was planted in a PDA medium containing 1.0% by volume of the wood degradation product obtained in Decomposition Example 9 and the maximum length of the spread hyphae was measured. (Example 34) The wood decomposition product obtained in decomposition example 9 was 0.5
Pleurotus ostreatus was planted in a PDA medium containing volume% and the maximum length of the spread hyphae was measured. (Example 35) The wood decomposition product obtained in decomposition example 9 was 1.0
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured. (Example 36) The wood decomposition product obtained in decomposition example 9 was 0.5
Pleurotus cornucopiae was planted in a PDA medium containing vol% and the maximum length of the spread hypha was measured.

(Example 37) Pleurotus ostreatus was planted in a PDA medium containing 1.0% by volume of the wood decomposition product obtained in decomposition example 10, and the maximum length of the spread hyphae was measured. (Example 38) The wood decomposition product obtained in decomposition example 10
Pleurotus ostreatus was planted in a PDA medium containing 5% by volume, and the maximum length of the spread hyphae was measured. (Example 39) The wood decomposition product obtained in decomposition example 10 was 1.
Pleurotus cornucopiae was planted in a PDA medium containing 0% by volume, and the maximum length of the spread hypha was measured. (Example 40) The wood decomposition product obtained in decomposition example 10
Pleurotus cornucopiae was planted in a PDA medium containing 5% by volume, and the maximum length of the spread hypha was measured.

Comparative Example 1 P containing no wood decomposition product
Pleurotus ostreatus was planted in a DA medium (blank), and the maximum length of the spread hypha was measured. (Comparative Example 2) Pleurotus cornucopiae was planted in a PDA medium (blank) containing no decomposition product of wood and the maximum length of the spread hypha was measured.

The results of the antiseptic tests obtained in Examples 1 to 40 and Comparative Examples 1 and 2 are shown in Tables 1 to 3 below.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

In Tables 1, 2 and 3, 4-MM-
4-OX is 4-methylmorpholine-4-oxide, EC
Indicates ethylene carbonate, MEA indicates monoethanolamine, DMF indicates dimethylformamide, OU indicates agaricus, and KW indicates agaricus. In addition, all the lactic acids described in the table indicate L-lactic acid. The same applies to the tables that follow.

As is clear from Tables 1, 2, and 3, as compared with Comparative Examples 1 and 2 (all blanks), Examples 1 to 40 all have an effect of suppressing the growth of mycelium against Pleurotus cornucopiae and Pleurotus cornucopiae. Presented. It was also observed that the increase in the amount of the decomposition product of wood increased the effect of suppressing the growth. Then, decomposition using lactic acid (Examples 1 to 1)
8), decomposition using lactic acid and anisole (Examples 13 to 1)
6), wood decomposition products obtained by decomposition using monoethanolamine and dimethylformamide (Examples 21 to 24) and decomposition using adipic acid (Examples 37 to 40) are all mycelial growth , And a high antiseptic effect was observed.

The "insect repellent test" is a filter paper (diameter 7 cm, thickness 0.02 mm) immersed in a wood decomposition product for 24 hours.
Was placed in a container containing 20 termites and 2 soldier ants for 8 days, and the number of surviving worker ants and soldier ants and the presence or absence of feeding damage on the filter paper were measured. Examples of such insect repellent tests are shown in Examples 41 to 51 below.

(Example 41) Wood decomposition product 1 obtained in decomposition example 2 per 100 parts by weight of filter paper (dry weight, the same applies hereinafter)
A filter paper with 30 parts by weight attached was used for the test. (Example 42) A filter paper having 180 parts by weight of the decomposition product of wood obtained in Decomposition Example 11 attached to 100 parts by weight of the filter paper was used for the test. (Example 43) A filter paper to which 130 parts by weight of the decomposition product of wood obtained in Decomposition Example 8 was attached to 100 parts by weight of the filter paper was used for the test. (Example 44) A filter paper having 100 parts by weight of the decomposition product of wood obtained in Decomposition Example 12 attached to 100 parts by weight of the filter paper was used for the test. (Example 45) A filter paper to which 130 parts by weight of the decomposition product of wood obtained in Decomposition Example 13 was attached to 100 parts by weight of the filter paper was used for the test. (Example 46) A filter paper having 137 parts by weight of the decomposition product of wood obtained in Decomposition Example 15 attached to 100 parts by weight of the filter paper was used for the test. (Example 47) A filter paper having 137 parts by weight of the decomposition product of wood obtained in Decomposition Example 14 adhered to 100 parts by weight of the filter paper was used for the test.

Example 48 A filter paper was used in which 131 parts by weight of a mixture of 10 parts by weight of copper chloride and 90 parts by weight of the decomposition product of wood obtained in Decomposition Example 11 was adhered to 100 parts by weight of the filter paper. (Example 49) A filter paper was used in which 131 parts by weight of a mixture of 10 parts by weight of copper sulfate and 90 parts by weight of the decomposition product of wood obtained in Decomposition Example 2 was adhered to 100 parts by weight of the filter paper. (Example 50) A filter paper was used in which 131 parts by weight of a mixture of 10 parts by weight of silver sulfate and 90 parts by weight of the decomposition product of wood obtained in Decomposition Example 2 was adhered to 100 parts by weight of the filter paper. (Example 51) A filter paper was used in which 131 parts by weight of a mixture of 10 parts by weight of boric acid and 90 parts by weight of the decomposition product of wood obtained in Decomposition Example 2 was attached to 100 parts by weight of the filter paper.

Comparative Example 3 A filter paper having 131 parts by weight of camphor attached to 100 parts by weight of filter paper was used for the test. (Comparative Example 4) An untreated filter paper was used as a blank in the test.

The above Examples 41 to 51 and Comparative Examples 3 and 4
The results of the insect repellent test obtained according to Table 1 are shown in Table 4 below.

[0061]

[Table 4]

As is clear from Table 4, the insect repellent effect was recognized in all of Examples 41 to 51 as compared with the untreated filter paper (Comparative Example 4). Among them, when a wood decomposition product and a copper compound, a silver compound, or a boron compound are used in combination (Examples 48 to 51), the insect repellent effect is extremely large,
It was superior to camphor (comparative example 3), which is a general insect repellent.

The following Examples 52 to 57 show the "penetration of wood" of decomposition products of wood. (Example 52) Wood decomposition product 100 m obtained in decomposition example 2
Put L in a 500 mL beaker and put the cedar sapwood (dimension: vertical 20
mm × width 20 mm × height 10 mm) is soaked in the decomposition product of wood so that the whole is soaked, and at room temperature (20 ° C.), 30
By decompressing (1 atm) for a minute, the wood decomposition product was injected into the cedar sapwood. After the injection, take out the cedar sapwood,
The weight increase rate (%) with respect to the weight of the cedar sapwood before the injection was calculated. (Example 53) 100 m of wood decomposition product obtained in decomposition example 3
A weight gain rate was obtained in the same manner as in Example 52 except that L was used. (Example 54) 100 m of wood decomposition product obtained in decomposition example 2
Put L in a 500-mL beaker and put the cedar sapwood (dimension: vertical 2
0 mm × width 20 mm × height 10 mm) was soaked as to immerse the whole body, and left as it was at room temperature (20 ° C.) for 24 hours. It was taken out after 24 hours, and the weight increase rate of the cedar sapwood before and after the immersion was calculated. (Example 55) 100 m of wood decomposition product obtained in decomposition example 3
A weight gain rate was obtained in the same manner as in Example 54 except that L was used. (Example 56) 100 m of wood decomposition product obtained in decomposition example 2
L is cedar sapwood (dimensions: vertical 20 mm × horizontal 20 mm × height 4
It was evenly applied to the surface of 5 mm) with a brush. Then, the weight increase rate of the cedar sapwood before and after coating was calculated. (Example 57) 100 m of wood decomposition product obtained in decomposition example 3
A weight gain rate was obtained in the same manner as in Example 56 except that L was used.

The results of the permeability test obtained in Examples 52 to 57 described above are shown in Table 5 below.

[0065]

[Table 5]

As is clear from Table 5, the decomposition products of wood can be penetrated into wood by any of the methods of injection under reduced pressure, immersion after immersion, and brush coating.
That is, a sufficient amount of the decomposition product of wood could be infiltrated into the wood even after being left standing after the immersion without using the reduced pressure injection after the immersion.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yuji Imamura             Gokasho, Uji City, Kyoto Prefecture Institute of Wood Science, Kyoto University             Inside the laboratory (72) Inventor Toshimitsu Hata             Gokasho, Uji City, Kyoto Prefecture Institute of Wood Science, Kyoto University             Inside the laboratory (72) Inventor Yu Nakai             Gokasho, Uji City, Kyoto Prefecture Institute of Wood Science, Kyoto University             Inside the laboratory F-term (reference) 4H011 AA01 AC03 BA01 BA06 BB18                       BB22 BC03 BC04 BC06 BC08                       BC10 DA13 DD03

Claims (3)

[Claims] 1. An antiseptic and insecticide for wood and wood materials, which contains, as an active ingredient, a wood decomposition product obtained by decomposing wood with a wood decomposition agent. 2. The wood decomposing agent is a hydroxycarboxylic acid,
The antiseptic insect repellent for wood and wood materials according to claim 1, which is any one compound selected from the group consisting of dicarboxylic acids and amino alcohols. 3. The antiseptic insect repellent for wood and wood materials according to claim 1 or 2, further comprising any one compound selected from the group consisting of a copper compound, a silver compound and a boron compound.