JP3077381B2 - Wood preservatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a wood preservative.

[0002]

BACKGROUND OF THE INVENTION Among wood preservatives, organic iodine compounds have been widely used, especially for surface treatment. However,
The compound has a problem that it is easily decomposed by light or heat and changes its color from pale yellow to yellowish brown.

[0003]

The inventors of the present invention have conducted intensive studies to develop a wood preservative having a high wood preservative power and having no discoloration due to heat or light, and as a result, have reached the present invention. That is, the present invention provides the following general formula 2

Embedded image [In the formula, R ¹ represents a methyl group, an ethyl group or a trifluoromethyl group, and R ² represents a methyl group, an ethyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom)
Or a hydrogen atom, R ³ represents a methyl group or an ethyl group, and X represents a methylene group or an oxygen atom. A wood preservative characterized by containing an amide derivative represented by the formula (1) as an active ingredient. The amide compound represented by the general formula (2) is disclosed in
It can be produced according to the description in JP-A-6472 or JP-A-2-131481. Examples of the compound represented by the general formula 2 used in the present invention are shown below. N- (1,1,3-trimethyl-2-oxa-4-indanyl) -5-chloro-1,3-dimethylpyrazole-
4-Carboxamide [Ia] N- (1,1,3-trimethyl-2-oxa-4-indanyl) -1,3,5-trimethylpyrazole-4-carboxyamide N- (1,1,3 -Trimethyl-2-oxa-4-indanyl) -1,3, -dimethylpyrazole-4-carboxylic acid amide N- (1,1,3-trimethyl-2-oxa-4-indanyl) -1-methyl-3 -Trifluoromethyl-pyrazole-4-carboxylic acid amide N- (1,1-dimethyl-2-oxa-3-ethyl-4
-Indanyl) -1,3,5-trimethylpyrazole-
4-carboxylic acid amide 1,3-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide [I
b] 1,5-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 1,3,5-trimethyl-N- (1,1,3-trimethylindan-4 -Yl) pyrazole-4-carboxamide 1,5-dimethyl-3-fluoro-N- (1,1,3-
Trimethylindan-4-yl) pyrazole-4-carboxamide 1,3-dimethyl-5-fluoro-N- (1,1,3-
Trimethylindan-4-yl) pyrazole-4-carboxamide 3-chloro-1,5-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 5-chloro-1,3 -Dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 5-bromo1,3-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole -4-Carboxamide 1,3-dimethyl-5-iodo-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 1-methyl-3-trifluoromethyl-N- (1, 1,
3-trimethylindan-4-yl) pyrazole-4-
Carboxamide 1-methyl-5-trifluoromethyl-N- (1,1,
3-trimethylindan-4-yl) pyrazole-4-
Carboxamide 3-fluoro-1-methyl-5-trifluoromethyl-
N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 5-fluoro-1-methyl-3-trifluoromethyl-
N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 3-chloro-1-methyl-5-trifluoromethyl-N
-(1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 5-chloro-1-methyl-3-trifluoromethyl-N
-(1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 5-bromo-1-methyl-3-trifluoromethyl-N
-(1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 5-iodo-1-methyl-3-trifluoromethyl-N
-(1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 1,3-dimethyl-5-trifluoromethyl-N-
(1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 1,5-dimethyl-3-trifluoromethyl-N-
(1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 3,5-bis (trifluoromethyl) -1-methyl-N
-(1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide

In applying the wood preservative of the present invention, the amide derivative represented by the general formula (2) may be used as it is without adding any other components, but usually, a solid carrier, a liquid carrier or a gaseous carrier is used. And, if necessary, surfactants and other formulation auxiliaries, and formulated into oils, emulsions, wettable powders, flowables such as suspensions in water and emulsions in water, powders, aerosols, etc. Used. These preparations contain, as an active ingredient, an amide derivative represented by the general formula (2) in a weight ratio of 0.01 to 95%, preferably 0.2 to 60%. Examples of solid carriers used in the formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.),
Fine powders or granular materials such as talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.); and liquid carriers such as water and alcohols. (Eg, glycols such as ethanol, isopropanol, 3-methyl-3-methoxybutanol, polyethylene glycol, and polypropylene glycol), ketones (eg, acetone, methyl ethyl ketone), and aromatic hydrocarbons (eg, benzene,
Toluene, xylene, alkylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, gas oil, etc.), esters (higher fatty acid esters such as ethyl acetate, butyl acetate, isopropyl myristate), 3-methyl- 3-methoxybutyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), Halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil and the like (these can be used as a mixture), and as a gaseous carrier, ie, a propellant Is, for example, freon gas, butanga , LPG (liquefied petroleum gas),
Examples include dimethyl ether and carbon dioxide. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. can give.
Examples of pharmaceutical auxiliaries such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol). , Polyvinylpyrrolidone, polyacrylic acids, etc.), and as a stabilizer, for example, PAP
(Isopropyl oxyphosphate), BHT (2,6-di-te
rt-butyl-4-methylphenol), BHA (2-te
a mixture of rt-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like. Flowable (suspension in water or emulsion in water)
Is generally 0.5 to 75% of the active ingredient compound.
15% dispersant, 0.1-10% suspension aid (e.g.,
Protective colloids and compounds that impart thixotropic properties),
In water containing 0-10% of suitable auxiliary agents (for example, antifoaming agent, rust inhibitor, stabilizer, spreading agent, penetration aid, antifreezing agent, antibacterial agent, fungicide, etc.) To be obtained. Instead of water, an oil in which the active ingredient compound hardly dissolves may be used as a suspension in oil. As the protective colloid, for example, gelanin, casein, gums, cellulose ether, polyvinyl alcohol and the like are used. Examples of the compound imparting thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid and the like. The preparation thus obtained is used as it is or diluted with water or the like. Also, other wood preservatives, insecticides, acaricides, termites (termite control agents),
It can be used simultaneously with or without mixing with fungicides and synergists. Examples of termicides used include chlorpyrifos, foxime, fenitrothion, fenobukab, permethrin, tralomethrin,
Cypermethrin, Deltamethrin, Cyfluthulin,
Fenvalate. Oils, powders, granules, aerosols and the like are applied as is, emulsions, wettable powders, flowables and the like are 0.01 to 10% by water, preferably 0.05 to 5%.
Dilute to% and apply. These application rates and application concentrations
In each case, the type of preparation, application time, application place, application method,
Varies depending on the type of wood rot fungus, degree of damage, etc.
It can be increased or decreased without affecting the above range. The wood preservative of the present invention is dipped,
Surface treatment such as spraying, application, etc. or pressure injection or vacuum injection is applied to wood (including bamboo) or the like, or by adding to plywood adhesive, especially applied to building materials. It can be used as an agent for controlling rot fungi. As wood to be controlled, for example, beech, cedar,
Japanese red pine and the like. Examples of the plywood adhesive include a phenol resin, a melamine resin, and a urea resin. Wood rot fungi that can be controlled by the wood preservative of the present invention include, for example, Coriolus versicolo
r), Squash (Tyromyces palustris), Namidae (Serpula lacrymans), Ginkgo (Paxillus pan)
uoides), Idtake (Coniophora puteana), Kikaiaratake (Gloeophyllum sepiarium), Chilimentake (Gloeo
phyllum trabeum), choke anamata (Antrodia xanth)
a), Matsuo-ji (Lentinus lepideus), Watag Salem (Antrodia sinuosa), Suehirotake (Schiozophyllum)
commune) and Hilotake (Pycnoporus coccineus). The wood preservative of the present invention is preferably used as a surface treatment agent for wood. In this case, usually, an oil agent is used as a formulation, and the oil agent is usually used in an amount of 50 to 200 per m ² of wood.
g, usually 0.1 to 1 per timber 1 m ² as an active ingredient amount
Use 0 g.

[0005]

The wood preservative of the present invention maintains its antiseptic effect compared to conventionally used organic iodine compounds having a slightly lower light resistance, has remarkably improved light resistance, and can be used under light irradiation conditions. A stable antiseptic effect can be obtained without worrying about discoloration.

[0006]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. First, formulation examples will be described. Formulation Example 1 Oil agent An oil agent was prepared by mixing 1 part of compound [Ia], 10 parts of 3-methyl-3-methoxybutanol (Solfit: manufactured by Kuraray Co., Ltd.) and 89 parts of kerosene. Formulation Example 2 Oil agent 0.5 part of the compound [Ib], 10 parts of 3-methyl-3-methoxybutanol (Solfit: manufactured by Kuraray Co., Ltd.) and 89.5 parts of kerosene were mixed to prepare an oil agent. Formulation Example 3 Oil 1 part of compound [Ia], 0.2 part of (3-phenoxyphenyl) methyl-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylate (generic name: permethrin), bis -1.5 parts of (2,3,3,3-tetrachloropropyl) ether (S-421), 10 parts of 3-methyl-3-methoxybutanol (Solfit: manufactured by Kuraray Co., Ltd.), and 87.3 parts of kerosene Thus, an oil agent was prepared. Formulation Example 4 Emulsion 2 parts of compound [Ia], 88 parts of xylene, Solpol SM
200 parts (made by Toho Chemical Co., Ltd.)
An emulsion was prepared.

Next, test examples will be described. The compounds used for comparison (all commercially available) are indicated by the compound symbols in Table 1.

[Table 1] Test Example 1 A 1% oil solution of the test compound was prepared according to Formulation Example 1. The oil was applied to a filter paper having a diameter of 5.5 cm at a concentration of 100 ml / m ² and air-dried. The filter paper thus prepared is
After being placed under light irradiation of 00 to 7000 lux for 5 minutes, the filter paper was taken out, and the degree of discoloration (coloring) of the filter paper surface was observed.
The degree of discoloration (coloring) was determined based on the following criteria. No discoloration (coloring)-slight discoloration (coloring) + Remarkable discoloration (coloring) ++ The results are shown in Table 2.

[Table 2] Test Example 2 A 1% w / v dimethyl sulfoxide solution of the test compound was prepared. A predetermined amount of the drug was mixed with a potato dextrose agar medium immediately after sterilization (using a wet heat sterilizer), poured into a 9 cm diameter petri dish, and allowed to stand at room temperature. After the medium was solidified, the mycelium was drawn out together with the medium from a pre-cultured microbial flora of Coriolus versicolor and Pleurotus versicolor with a 5 mm diameter cork borer, and inoculated into the center of the test medium. 4 after inoculation
On the day, the diameter of the bacterial flora spreading from the inoculation source was measured, and the growth inhibition rate of the bacteria was determined by the following equation. Growth inhibition rate (%) = {(diameter of microflora in control plot−diameter of microflora in test plot) / diameter of microbiota in control plot} × 100 The results are shown in Tables 3 and 4.

[Table 3] Growth inhibition rate against Kawatake mushroom

[Table 4] Growth inhibition rate against Japanese quail mushroom Test Example 3 An oil solution of a test compound was prepared according to Formulation Example 1, and tested according to a test method determined by the Japan Wood Preservation Association. The outline of the test is as follows. Beech and cedar wood pieces (thickness 5
(the surface of 40 mm × 20 mm, length of 40 mm and length of 40 × 20 mm) is sealed with epoxy resin and immersed in the above oil agent (absorbing amount of oil agent 110 ± 10 g / m ² surface area), then 20 days The specimen was air-dried. Specimen is 25 ± 3 ℃
Immersed in still water (water: wood chips = 10: 1 (volume ratio)) for 5 hours, and then volatilized at 40 ± 2 ° C. for 19 hours.
Repeated times. After the weathering operation, the test specimen was dried at 60 ± 2 ° C. for 48 hours, and then left in a desiccator for about 30 minutes to measure its weight W ₃ . (9 repetitions) After the bacteria were sterilized, the test samples were put into culture bottles in which rot fungi (Kawatake mushroom / beech, Japanese quail mushroom / cedar) were cultivated, and 26 ± 2 were added.
The cells were cultured for 8 weeks at 80 ° C. and 80% humidity. After 8 weeks, the test specimen was taken out of the culture bottle, and after removing mycelia and other deposits, dried at 60 ± 2 ° C. for 48 hours and left in a desiccator for about 30 minutes to measure its weight W ₄ .
The weight loss rate was calculated by the following equation. (W ₃ −W ₄ ) Weight loss rate (%) = ───────── × 100 W ₃ where W ₃ : Weight of wood piece before antibacterial operation W ₄ : Weight of wood piece after antibacterial operation It is shown in FIG.

[Table 5]

Continuation of the front page (56) References JP-A-5-194117 (JP, A) JP-A-62-96472 (JP, A) JP-A-2-131481 (JP, A) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) A01N 43/56

Claims (1)

(57) [Claims] 1. A compound represented by the general formula: [Wherein, R ¹ represents a methyl group, an ethyl group or a trifluoromethyl group, R ² represents a methyl group, an ethyl group, a halogen atom or a hydrogen atom, R ³ represents a methyl group or an ethyl group, and X represents Represents a methylene group or an oxygen atom. ] A wood preservative comprising an amide derivative represented by the formula (1) as an active ingredient.