JP2000153505A - Mothproof plywood, mothproofing agent for plywood and mothproof adhesive composition for plywood - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly safe and excellent mothproof effect by containing (2-methyl[1,1'-biphenyl]-3-yl)methyl=3-(2-chloro-3,3,3-trifluoro-1-pro penyl)-2,2- dimethyl cyclo propane carboxylate. SOLUTION: A mothproof plywood is obtained by containing (2-methyl[1,1'- biphenyl]-3-yl)methyl=3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2- dimethylcyclopropane carboxylate (hereafter, referred as a compound (I)). For the mothproof plywood, the compound (I) is a liquid composition, and veneers are stuck to each other by an adhesive composition containing that. An active ingradient concentration of the compound (I) in the liquid composition is generally 0.1-20 wt.%, and a blended amount of the liquid composition in the adhesive composition is preferably 0.05-5 wt.%. The adhesive of the adhesive composition comprises a urea series one, a melamine series one or the like, and a content of the compound (I) in the mothproof plywood is about 5-50 g/m2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insect repellent plywood, an insect repellent for plywood and an insect repellent adhesive composition, and more particularly to an insect repellent plywood which is highly safe and has an excellent insect repellent effect against Pleurotus quercivorus. For technology.

[0002]

2. Description of the Related Art Protecting precious timber resources from biological degradation and making them usable for a long period of time is important from the viewpoint of effective use of global resources and environmental conservation such as global warming. Insect repellents are used to protect them from biological degradation.

Insecticides for wood (especially insect repellents for termites)
Chlordane has been used as a chemical substance, but in 1986 it was specified as a specific chemical substance and its use has been banned. After that, various organic phosphorus compounds and boron compounds such as phoxime and fenitrothion were used as substitutes for chlordane, and were widely used as insect repellents especially for wood plywood.

[0004] However, the above-mentioned organophosphorus compounds such as phoxime and fenitrothion have high volatility, and in insect-proof plywood containing these, these volatile chemical substances (VOC) are generated due to heat insulation and airtightness of the building. Causes of failure are increasing. In particular, the fly bark beetle (L
In order to obtain a sufficient insect repellent effect against Yctus Brunneus, a large amount of these must be blended into the plywood, which further reduces the safety of the plywood. On the other hand, boron compounds have a low insect repellent effect, and cannot provide insect repellent plywood exhibiting a sufficient insect repellent effect.

[0005] Formalin used as an adhesive for wood plywood plays a part in the insect repellent effect (formalin itself shows insect repellent effect). Deterioration has recently become much more frequent. In addition, formalin has a high volatility like the above-mentioned organophosphorus compound, and the same safety problem as above has been pointed out.

[0006]

DISCLOSURE OF THE INVENTION In view of the circumstances described above, the present invention provides a highly safe insect repellent plywood having an excellent insect repellent effect, especially for a bark beetle, and a method for obtaining the insect repellent plywood. An object is to provide an insect repellent for plywood and an insect repellent adhesive composition for plywood.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, it has been found that a specific pyrethroid compound is effective in controlling insects on plywood, and in particular, has an excellent insect repellent effect on Pleurotus beetle. The present invention has been found, and the present invention has been completed based on the findings. That is, the present invention has the following features.

(1) (2-methyl [1,1′-biphenyl] -3-yl) methyl = 3- (2-chloro-3,3,3
Insect repellent plywood containing (3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate. (2) The insect plywood according to (1), further comprising an organic iodine-based wood preservative and / or a triazole-based wood preservative. (3) The organic iodine-based wood preservative is selected from 3-iodo-2-propynylbutylcarbamate, 3-bromo-2,3-diiodo-2-propenylethyl carbonate and parachlorophenyl-3-iodopropargylformal1 Insect repellent plywood according to the above (2), which is a kind or two or more kinds of compounds. (4) The triazole-based wood preservative is α- [2- (4-chlorophenyl) ethyl] -α (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, 1- [2- (2 ', 4'-dichlorophenyl) -4
-Propyl-1,3-dioxolan-2-yl-methyl] -1H-1,2,4-triazole, α- (4-chlorophenyl) -δ- (1-cyclopropylethyl)-
1H-1,2,4-triazole-1-ethanol and 1-[{2- (2,4-dichlorophenyl) -1,
3-dioxolan-2-yl {methyl] -1,2,4-
The insect repellent plywood according to the above (2) or (3), which is one or more compounds selected from triazoles. (5) (2-methyl [1,1′-biphenyl] -3-yl) methyl = 3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropane An insect repellent adhesive composition for plywood containing a carboxylate. (6) The insect repellent adhesive composition for plywood according to (5), further comprising an organic iodine-based wood preservative and / or a triazole-based wood preservative. (7) (2-methyl [1,1′-biphenyl] -3-yl) methyl = 3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropane An insect repellent for plywood containing a carboxylate as an active ingredient.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (2-methyl [1,1'-biphenyl] -3-yl) methyl = 3-
(2-Chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate (hereinafter also referred to as compound (I)) is represented by the following formula (I)
Is a pyrethroid-based compound having the following structure, and is known as a trade name “Bifenthrin”.

[0010]

Embedded image

The compound (I) exists in various optically active forms. In the present invention, any active isomer and a mixture thereof can be used.

Pyrethroid compounds have excellent insecticidal activity,
It is known that the compound (I) is used as a pesticide and has relatively low toxicity.
Was not known to show a high insecticidal efficacy against the bark beetle. In the present invention, by including the compound (I), an insect repellent plywood having a sufficient insect repellent effect and particularly exhibiting an excellent insect repellent effect against Pleurotus quercivorus can be obtained.

The insect-resistant plywood of the present invention can be obtained by laminating veneers with an adhesive composition containing the compound (I) (ie, the insect-resistant adhesive composition for plywood of the present invention).

The compound (I) is used in the form of a composition containing the compound (ie, the insect repellent for plywood of the present invention),
Usually, a liquid composition is prepared by dissolving or dispersing the compound in a suitable liquid carrier, and the liquid composition is mixed with a base adhesive to prepare the adhesive composition.

The liquid composition is, for example, an oil-type composition dissolved in a solvent such as kerosene, xylene, an isoparaffinic solvent, a solvent naphtha, a high-boiling aromatic solvent, or an interfacial composition. It is common to use an emulsion-type composition in which an activator is added to improve the compatibility with the adhesive. Here, as the surfactant, for example, alkyl naphthalene sulfonate (for example, trade name “Newcalgen BX-L” manufactured by Takemoto Yushi Co., Ltd.), 2
Anionic surfactants such as dialkyl sulfosuccinates (eg, Neocol SW-C, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), alkyl benzene sulfonates, various quaternary ammonium salts, and mixtures having mixed alkyl groups And cationic surfactants such as polyoxyethylene phenyl ether, polyoxyethylene octyl phenyl ether, and polyoxyalkylene styryl phenyl ether (for example, trade name “Newcalgen CP80 or CP120” manufactured by Takemoto Yushi Co., Ltd.). Nonionic surfactants are exemplified. The surfactant is generally 1 to 10% by weight based on the liquid composition,
It is desirable to mix them so as to be preferably 2 to 5% by weight. The concentration of the active ingredient of the compound (I) in the liquid composition is usually 0.1 to 20% by weight, preferably 1 to 10% by weight.

The amount of the liquid composition in the adhesive composition is such that the adhesiveness of the adhesive composition is not significantly reduced, that is, the adhesive strength of the plywood is not adversely affected. Is important, and from this viewpoint, the content is preferably 0.05 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the whole adhesive composition. The active ingredient concentration of the compound (I) in the adhesive composition is usually 0.00005 to 1% by weight, preferably 0.00.0% by weight.
It is suitably from 0.5 to 0.3% by weight.

As an adhesive serving as a base of the adhesive composition, a thermosetting resin adhesive capable of condensing with formaldehyde is suitable.
There are, but are not limited to, urea melamines. Other synthetic resin adhesives, for example, a vinyl acetate resin adhesive, an acrylic resin adhesive, an epoxy resin adhesive, and the like can also be used. Also, in the adhesive composition,
Pastes such as flour, other starches, carboxymethylcellulose (CMC) and other commonly used ingredients can be added.

The insect-control plywood of the present invention can be obtained by laminating veneers with an adhesive composition containing the compound (I) as described above. Plywood, mahogany plywood and the like can be mentioned. Of course, plywood made of veneer lumber made from various other trees is a target for insect control.

The content of the compound (I) (the amount of the active ingredient) in the insect-control plywood of the present invention may be a small amount of usually about 5 to 50 g / m ³ , preferably about 10 to 40 g / m ³ , and such a small amount is sufficient. Insect repellent effect can be obtained, and in particular, an excellent insect repellent effect can be obtained against the bark beetle. In particular, since the compound (I) hardly volatilizes or liberates in plywood, an insect-resistant plywood which is effective with a small amount and is extremely safe can be obtained.

According to the present invention, in the plywood, the liquid composition and the adhesive composition further contain an organic iodine-based preservative and / or a triazole-based preservative to obtain a plywood having a preservative property. Can be.

As the organic iodine preservative, for example, 3-
Iodo-2-propynylbutylcarbamate (Troy Chemical Corp.
portation, Inc. ), Product name "Troys
an Polyphase P-100 ", and is generically referred to as IPBC. ), 3-bromo-2,3-
Diiodo-2-propenylethyl carbonate (manufactured by Sankyo Co., Ltd., commercially available under the trade name "Sampras"); parachlorophenyl-3-iodopropargyl formal (manufactured by Nagase & Co., Ltd .; trade name "IF-1")
000 ". ), But are not limited to these.

As the triazole preservative, for example,
α- [2- (4-chlorophenyl) ethyl] -α (1,
1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (manufactured by Nippon Bayer Agrochem Co., Ltd. and commercially available under the trade name “tebuconazole”), 1- [2- (2 ′, 4'-dichlorophenyl)
-4-propyl-1,3-dioxolan-2-yl-methyl] -1H-1,2,4 triazole (commercially available from Novartis Agro Co., Ltd. under the trade name "propiconazole"), α- (4-chlorophenyl) -δ
-(1-cyclopropylethyl) -1H-1,2,4-
Triazole-1-ethanol (commercially available under the trade name “Ciproconazole” manufactured by DS Biotech Co., Ltd.), 1-[｛2- (2,4-dichlorophenyl) -1,3- Dioxolan-2-yl @ methyl] -1,2,4-triazole (manufactured by Janssen Co., Ltd. and commercially available under the trade name "azaconazole"), and the like, but are not limited thereto. .

These preservatives are usually used by being compounded in a liquid composition containing the compound (I) as an active ingredient. The preservative concentration in the liquid composition is usually 0.1
５０50% by weight, preferably 1-30% by weight is suitable. The preservative concentration in the adhesive composition is 0.00005-
2.5% by weight, preferably 0.005 to 0.9% by weight is suitable. By further blending such a preservative, the liquid composition and the adhesive composition can be further provided with a preservative effect in plywood.

In the insect repellent plywood of the present invention, the amount of the active ingredient of the organic iodine preservative and / or the triazole preservative is generally about 10 to 600 g / m ³ , preferably 30 to 600 g / m ^3.
About 400 g / m ³ is appropriate.

[0025]

The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples. In the following description, parts and% are expressed on a weight basis unless otherwise specified.

Preparation of preparation

Example 1 (2-methyl [1,1'-biphenyl] -3-yl) methyl = 3- (2-chloro-3,3,3-trifluoro-
1-propenyl) -2,2-dimethylcyclopropanecarboxylate (trade name “Bifenthrin”, manufactured by FMC Corporation)
25 parts, a mixture of polyoxyethylene alkyl allyl ether and alkylbenzene sulfonate as a surfactant (trade name "Sanimar H" manufactured by Nippon Emulsifier Co., Ltd.)
To 5 parts, and the remainder to 100 parts with white kerosene, and they were sufficiently mixed and dissolved to obtain a liquid composition.

Example 2 A liquid composition was obtained by mixing and dissolving in the same manner as in Example 1 except that 2.5 parts of bifenthrin was used.

Example 3 A liquid composition was obtained by mixing and dissolving in the same manner as in Example 1 except that 5 parts of bifenthrin was used.

Example 4 1.25 parts of bifenthrin and 3-iodo-2-propynylbutylcarbamate (manufactured by Troy Chemical Co., Ltd.
Product name "Troysan Polyphase P-10"
0 "), and the remaining amount is 1 with butyl diglycol.
The liquid composition was made to be 00 parts and sufficiently mixed and dissolved.

Comparative Example 1 "Tomigard PE-50" (trade name, manufactured by Yoshitomi Fine Chemical Co., Ltd., containing o, o-diethyl-o as an active ingredient)
-(Α-cyanobenzylideneamino) thiophosphate (emulsion containing 50% of phoxime) was used.

Comparative Example 2 "Tomigard PE-50" (trade name, manufactured by Yoshitomi Fine Chemical Co., Ltd.)
-(Α-cyanobenzylideneamino) thiophosphate (emulsion containing 50% of phoxim) was further diluted with white kerosene to obtain an emulsion containing 10% of phoxime.

Examples 5 to 8, Comparative Examples 3 to 5 Preparation of Adhesive Composition Example 1 was added to 100 parts of a urea / melamine resin (trade name "ML-131", manufactured by Honen Corporation).
1.8 parts of water and 5 parts of water are added and stirred for 10 minutes. Then, add 15 parts of flour and stir for another 5 minutes,
Thereafter, 1 part of ammonium chloride as a curing agent was added,
Example 5 consisting of a uniform pasty composition by stirring again for 5 minutes
Was obtained. Similarly, using the preparations of Examples 2 to 4 and the preparations of Comparative Examples 1 and 2, Example 6 was used.
Comparative Examples 5 and 8 were prepared, and the adhesive compositions of Comparative Examples 3 and 4 were prepared.
Was prepared.

Examples 9 to 12 and Comparative Examples 6 to 8 Production of plywood Single veneer of Red Lauan (300 mm long, 300 mm wide, 4 mm thick)
mm), a nutrient solution obtained by dissolving 150 g of malt extract and 30 g of peptone in 820 ml of water is injected in the same amount as the weight of the veneer. Thereafter, drying was performed in a dryer until the water content became about 5 to 12%. Using a single veneer of Red Lauan into which the above-mentioned nutrient solution was injected, the adhesive composition of Example 5 prepared above was applied on both sides at a rate of 17.5 g, and 35 g of both surfaces, and a single plate of the red Rawan was used to form a 3-ply plywood. 1.8mm thick on both sides of
Veneers were attached to both sides. Next, at room temperature for 20 minutes,
A pressure of 10 kg per square cm is applied,
A pressure of 10 kg / cm 2 was applied at 0 ° C. for 2 minutes and 55 seconds to produce the insect-control plywood of Example 9.

Similarly, using the adhesive compositions of Examples 6 to 8 and the adhesive compositions of Comparative Examples 3 to 5, Examples 10 to 12 were used.
And the plywoods of Comparative Examples 6 to 8 were produced.

Each of the plywoods of Examples 9 to 12 and Comparative Examples 6 to 8 was subjected to the following insect repellency test.

Insect repellency test The repellency of the insect repellent plywood against the leaf bark beetle was carried out in accordance with the Japan Wood Preservation Association Standard No. 8, "Testing method for insect repellency of wood insect repellent (2)". (Preparation of test specimen) There are three types of test specimens: a treated specimen prepared from the test treated plywood, a deterioration treated specimen, and an untreated specimen prepared from the test untreated plywood. 2. Eighteen plywood pieces of 80 mm in the fiber direction and 40 mm in a direction perpendicular to the fiber direction of the core of the matchboard are prepared from the plywood treated with the test and 9 pieces from the plywood not treated with the test. 3. Three pieces of plywood are stacked flatly and nails are driven into the four corners to form blocks, and a hole having a diameter of 24 mm is completely formed in the center of each block. 4. Three blocks prepared from the test-processed plywood and the test-unprocessed plywood were left at 25 ° C. and a relative humidity of 70 to 75% for one week or more to be treated and untreated, respectively. 5. The remaining three blocks made from the plywood were treated with nails driven into the four corners, and each plywood with a hole in the center was about 4
After accelerated deterioration for one month in a dryer at 0 ° C, nailed again to the original block at 25 ° C, relative humidity 7
A specimen left at 0% to 75% for one week or longer is used as a deterioration-treated test specimen. * The plywood of Comparative Example 8 is untreated plywood.

(Test) A filter paper was attached to one hole of the test piece with glue, and a glass ring having an inner diameter of 35 mm and a height of 40 mm was placed on the open portion with this surface facing down.
Forty-five males and females each were placed on a ring, a slide glass was placed on a ring, fixed with a rubber band, and reared at 25 to 27 ° C and a relative humidity of 70 to 75%. After the start of breeding, check for paralysis and life and death of the bark beetle every 24 hours and record it. After the observation was completed, the test body was crushed to confirm the number of surviving bark beetles. In the same manner, a repeated test was carried out, and the average of the results of the two tests was obtained to obtain the average number of insects.

(Evaluation of insect repellent efficacy) Evaluation of insect repellent efficacy was based on the performance standard of No. 10 wood insect repellent standard of the Wood Conservation Society of Japan. , The average number of worms of 5 or less was regarded as the acceptance criteria.

Table 1 below shows the results.

[0041]

[Table 1]

The plywoods of Examples 9 to 12 all had an average number of insects that produced the common bark beetle, No. 0, indicating that the above criterion for insect plywood was sufficiently satisfied. On the other hand, the plywoods of Comparative Examples 6 and 7 are insect-control plywoods using foxime as a conventional insect repellent, and the plywood of Comparative Example 6 having a foxime content (active ingredient content) of 400 g / cm ³ was used. Although the average number of insects satisfies the above acceptance criteria with 0 animals, the content of phoxime (the amount of active ingredient) is 8
In the plywood of Comparative Example 7 of 0 g / cm ³ , the average number of insects that produced the bark beetle, 9.5 or 10.0, did not satisfy the above-mentioned acceptance criteria, and the insect-controlling effect as an insect-control plywood was insufficient. That is, in the insect-control plywood of the present invention, the content of the insect-controlling agent (the amount of the active ingredient) in the conventional insect-control plywood is about 1/10 to 10%.
With a content of 1/40 (the amount of the active ingredient), a sufficient insect repellent effect can be obtained against the bark beetle.

[0043]

As is clear from the above description, according to the present invention, (2-methyl [1,1'-biphenyl]-
By including 3-yl) methyl = 3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate in plywood, a sufficient insect repellent effect is exhibited. In particular, an insect repellent plywood exhibiting an excellent insect repellent effect against Pleurotus quercivorus can be obtained. Also, in particular, (2-methyl [1,1′-biphenyl] -3-yl) methyl = 3- (2-chloro-3,3,3)
Since the content of (3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate is relatively small and a sufficient insect repelling effect can be obtained, the compound is hardly volatilized or released from wood, and Since the toxicity of the compound is low, an insect repellent plywood having extremely high safety can be obtained while having an excellent insect repellent effect.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 55/00 A01N 53/00 506A // A01N 25/34 508C

Claims (7)

[Claims] (1) (2-methyl [1,1′-biphenyl]
-3-yl) methyl = 3- (2-chloro-3,3,3-
Insect repellent plywood containing (trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate. 2. An organic iodine wood preservative and / or
2. The insect-proof plywood according to claim 1, further comprising a triazole-based wood preservative. 3. The organic iodine wood preservative is selected from 3-iodo-2-propynylbutyl carbamate, 3-bromo-2,3-diiodo-2-propenylethyl carbonate and parachlorophenyl-3-iodopropargyl formal. The insect repellent plywood according to claim 2, which is one or more compounds obtained. 4. The method of claim 1, wherein the triazole-based wood preservative is α- [2- (4-chlorophenyl) ethyl] -α (1,
1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, 1- [2- (2 ′, 4′-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl-methyl ]-
1H-1,2,4-triazole, α- (4-chlorophenyl) -δ- (1-cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol and 1-[｛2- (2 , 4-Dichlorophenyl) -1,3-dioxolan-2-yl {methyl]-
The insect-proof plywood according to claim 2 or 3, which is one or more compounds selected from 1,2,4-triazole. (5) (2-methyl [1,1′-biphenyl]
-3-yl) methyl = 3- (2-chloro-3,3,3-
Insect repellent adhesive composition for plywood containing (trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate. 6. An organic iodine wood preservative and / or
6. The insecticidal adhesive composition for plywood according to claim 5, further comprising a triazole-based wood preservative. 7. (2-Methyl [1,1′-biphenyl]
-3-yl) methyl = 3- (2-chloro-3,3,3-
An insect repellent for plywood, comprising (trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate as an active ingredient.