JPH0347102A - Alkaline phenolic resin adhesive for termite-preventive plywood production - Google Patents

Abstract

PURPOSE:To provide the title adhesive capable of giving plywoods excellent in both stability and bond strength, comprising a water-based alkaline phenolic resin adhesive and a lubricant which is prepared by dissolving an organophosphorus insecticide and/or pyrethrin-based insecticide in a water- insoluble organic solvent so as to effect a specified concentration. CONSTITUTION:The objective adhesive comprising (A) a lubricant-type termite preventive prepared by dissolving (1) an organophosphorus insecticide (pref. phoxim) and/or a pyrethrin-based insecticide (pref. permethrin) in (2) a water- insoluble organic solvent with a solubility to water of <=1.0 (pref. <=0.1) at 25 deg.C so as to effect a concentration 5-30wt.% and (B) a water-based alkaline phenolic resin adhesive with a pH pref. 10-13 curable at 120-150 deg.C. The present adhesive is such that said insecticide (s) can be stably retained even under hot pressing conditions at which plywoods are produced and termite-preventive plywoods excellent in bond strength can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an alkaline phenolic resin adhesive for producing termite-proof plywood.

Traditionally, plywood is made of lauan, abyton, Kabul, beech,
It is manufactured by bonding veneers of Chinese wood, Douglas fir, etc. with a urea-based, melamine-based, or phenol thread-ring wood adhesive, and then heating and pressurizing this.

Conventionally, methods for imparting termite-proofing properties to such plywood include mixing a termite-proofing agent into the adhesive used, forming a veneer into plywood and then applying a termite-proofing agent to the surface of the plywood, or Methods such as pressurized injection and applying anti-termite treatment to the veneer are known. Among these methods, the first method involves applying an adhesive mixed with termiticide to the veneer in advance;
This veneer is laminated, bonded together, cold pressed, left to stand, and then heated under pressure to produce plywood, which is another method that requires an anti-termite treatment process in addition to the conventional plywood manufacturing process. It has superior productivity and the quality of the plywood obtained is also superior.

On the other hand, conventionally, for example, organochlorine insecticides such as dieldrin, aldrin, and chlordane, CCA agents (copper, chromium,
Inorganic fixing type compounds such as arsenic agents) and CFK agents (8, fluorine, chromium agents) are known as termiticides. but,
These termiticides are not only toxic to humans and animals, but also pose a risk of causing environmental pollution.
Its use is prohibited or restricted. for example,
Although organochlorine termiticides such as dieldrin, aldrin, and chlordane have excellent termitproofing properties, they are highly toxic to humans and livestock, and are difficult to decompose and accumulate, so there are concerns about environmental pollution. In Japan, its use is prohibited as a specified chemical substance.

Therefore, in recent years, organophosphorus insecticides such as phoxim and chlorpyrifos, and carbamate insecticides such as propoxa and bassa, which have relatively low toxicity and are less likely to cause environmental pollution, have been used.

For example, in JP-A-60-56906, along with phoxim, 1,1,1,2,6,7,7.7 is listed as a synergist.
An oil-based termiticide containing octachloro-4-oxaheptane as an essential component is disclosed. In addition, adhesives for producing termite-proof plywood are already known, for example, in Japanese Patent Application Laid-Open No. 16402/1982, N-cyclohexyl-N-methoxy-2, which is known as a wood preservative, is , 5-dimethyl-3-furancarboxamide and the synergist described above are mixed into a phenolic resin adhesive, and a phenolic resin adhesive for producing termite-proof plywood is disclosed.

In general, termiticides are required to have a long termiticidal effect and be safe for humans and livestock. The above-mentioned organophosphorus insecticides and carbamate insecticides have excellent anticidal efficacy, but on the other hand, they are easily decomposed by light or heat, so they lack sustainability of efficacy over a long period of time.

Therefore, some proposals have been made to use pyrethrin insecticides as termiticides. Although pyrethrin has low toxicity to humans and livestock, it has poor long-lasting anticide effect. Synthetic pyrethrins such as allethrin and resmethrin similarly have poor long-lasting anticidal efficacy.

Furthermore, the above-mentioned merin-based and pyrethrin-based insecticides are
When this is mixed into an adhesive and used to manufacture laminated boards, when a urea-based or melamine-based adhesive is used as the adhesive, no deterioration such as decomposition of the insecticide is observed, but water-based alkaline phenol resin adhesive In the case of adhesives, the insecticide often reacts with the alkali in the adhesive and deteriorates, reducing its anti-termite effect.

Therefore, the present inventors conducted extensive research in order to obtain a stable termiticide that can be used in conjunction with a water-based alkaline phenolic resin adhesive in the production of plywood. An oil-based termiticide prepared by dissolving an organophosphorus insecticide or a pyrethrin insecticide in a water-insoluble organic solvent at a predetermined concentration has high stability even when used with an aqueous alkaline phenolic resin adhesive. At the same time, the inventors discovered that a plywood having excellent adhesive strength could be provided, leading to the present invention.

Therefore, an object of the present invention is to provide an alkaline phenolic resin adhesive for producing termite-proof plywood.

In order to achieve this goal, the phenolic resin adhesive for producing termite-proof plywood according to the present invention comprises: (a) at least one insecticide selected from the group consisting of organophosphorus insecticides and pyrethrin insecticides in a water-insoluble manner; It is characterized by comprising an oil agent dissolved in an organic solvent in a range of 5 to 30% by weight, and (2) an aqueous alkaline phenolic resin adhesive.

Examples of the organophosphorus insecticide used in the present invention include phoxim, fenitrothion, pyridafenthione, chlorbilifos, tetrachlorvinphos, isoxathion, isofenphos, prothiophos, viraclofos, diazinon, and the like. Also,
Examples of pyrethrin insecticides include allethrin, resmethrin, phthalthrin, permethrin (3-(2,2-dichloroethynyl L-2,2-dimethylcyclopropanecarboxylic acid (3-phenoxyphenyl) methyl ester),
Dibermethrin, Decamethrin, Dihalomethrin, Tralomethrin, Cyfluthrin (3-(2,2-dichloroethynyl)-2,2-dimethylcyclopropanecarboxylic acid cyano(4-fluoro-3-phenoxyphenyl) methyl ester), Flusulinate, Fluparinate, Cyclo Proswan, fenvalerate, etofenbrox, etc. can be mentioned.

In the present invention, phoxim is particularly preferred among the above-mentioned organophosphorus insecticides, and permethrin is particularly preferred among the above-mentioned pyrethroid insecticides.

The oil type termiticide used in the present invention is obtained by dissolving the above-mentioned insecticide in a water-insoluble organic solvent at a predetermined concentration. The water-insoluble organic solvent used in the present invention has a solubility in water of 1.0 at 25°C.
% or less, preferably 0.1% or less. Such organic solvents include aliphatic hydrocarbons, aromatic hydrocarbons,
Alicyclic hydrocarbons, organic carboxylic acid esters, etc. are used. These organic solvents may be used alone or as a mixture of two or more. .

The phenolic resin adhesive for producing termite-proof plywood according to the present invention is as follows:
It can be obtained by mixing the above-mentioned oil type termiticide and an aqueous alkaline phenolic resin adhesive.

The phenolic resin adhesive for producing termite-proof plywood according to the present invention is as follows:
In addition to the above-mentioned oil type termiticide, various additives may be contained as necessary. Such additives include:
For example, tris(N-nitroso-N-cyclohexylazeniumdioxyaluminum, N-cyclohexyl-
N-methoxy-2,5-dimethylfuran-3-carboxamide, 1-((2-(2,4-dichlorophenyl)
-1,3dioxolan-2-yl]-methyl)-IH-
2,2,4-triazole, 4-chlorophenyl-3-
Iodopropargyl formal, 3-bromo-2゜3-short-2-propenylethyl carbonate, N-(dichlorofluoromethylthio)-N,N-7-dimethyl-
Wood preservatives such as N-phenylsulfamide, wood fungicides such as thiabendazole (TB-Z), repellents, efficacy enhancers, stabilizers such as antioxidants and ultraviolet absorbers, emulsifiers, alkyd resins, acrylics. Resins such as resins, colorants, thickeners, deodorants, fragrances, etc. can be used as necessary.

According to the present invention, the insecticide is contained in an oil-type termiticide in a range of 5 to 30% by weight.

The insecticide content in this oil type termiticide is 5% by weight.
If the amount is less than that, it is necessary to mix a large amount of termite-proofing agent into the adhesive in order to manufacture termite-proof plywood, which reduces the adhesive strength of the resulting plywood.

If the insecticide is mixed neat into the aqueous alkaline phenolic resin adhesive, the insecticide will degrade due to the high pH value of the adhesive, as described above.

However, when the insecticide is included in the water-based adhesive in the form of an oil, the insecticide is protected from direct contact with the water-based adhesive and thus escapes degradation.

However, the amount of insecticide is 30% in oil type termiticides.
, the insecticide degrades due to insufficient protection from the water-based adhesive.

In the present invention, the aqueous alkaline phenol resin may be any water-soluble resin obtained by reacting phenol and formaldehyde in the presence of an alkaline catalyst. Desirable results can be obtained when a material that is cured by heating to 120 to 150°C is used.

The blending ratio of the oil-type termiticide in the alkaline phenolic resin adhesive for producing termite-proof plywood of the present invention varies depending on the type of adhesive, but is usually 0.5 to 20% by weight, preferably 1 to 10% by weight. %.

In the production of termite-proof plywood, the oil-type termite-proofing agent is mixed with an alkaline phenolic resin adhesive at a ratio such that the insecticide is 100 to 1500 g, preferably 300 to 1200 g per plywood. and applied.

The amount of oil type termiticide applied is 100g per rrr of plywood.
If the amount is less than 1,500g, it will not be possible to obtain plywood with sufficient termite-proofing properties.On the other hand, if the amount applied exceeds 1,500g, depending on the adhesive used, it will be difficult to obtain plywood with sufficient anti-termite properties. As described above, according to the phenolic resin adhesive for producing termite-proof plywood according to the present invention, even in the presence of an aqueous alkaline adhesive, organophosphorus insecticides and pyrethrin insecticides can be removed under the pressurized and heated conditions under which plywood is manufactured. The agent is stably retained, making it possible to produce termite-proof plywood with excellent adhesive strength.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.

The aromatic petroleum solvent used below was Tsurpets 150 (
Manufactured by Exxon, aromatic base 198.7%, specific gravity 0.89,
The solubility in water at boiling point 188-209°C325°C is 300 ppm or less), and the aliphatic petroleum solvent is
Exxon Solvent Nu7 (manufactured by Exxon, aromatic content 1
9%, specific gravity 0.81, boiling point 202-265°C, solubility in water at 125°C 3001)I)II+). In addition, in the following, parts indicate parts by weight.

Example 1 20 parts of phoxim was dissolved in 80 parts of an aromatic petroleum solvent to prepare a 20% phoxim oil solution.

Example 2 25 parts of phoxime was dissolved in 75 parts of a mixed solvent of an aliphatic petroleum solvent and an aromatic petroleum solvent (mixing ratio 70/30),
Phoxim 25% oil was prepared by iM.

Example 3 Phoxim 15% oil solution was amHed by dissolving 15 parts of Phoxim in 85 parts of aromatic petroleum solvent.

Example 4 15 parts of phoxim and 3 parts of a nonylphenol-ethylene oxide adduct (Emulgen 909 manufactured by Kao, 9 moles of ethylene oxide added, HL B 12.4) were dissolved in 82 parts of an aromatic petroleum solvent to form phoxim 15. % oil solution was prepared.

Comparative Example 1 25 parts of phoxime, 3 parts of styrylphenol-ethylene oxide adduct (Emulgen A-60 manufactured by Kao ■, number of moles of ethylene oxide added: 13, HLB 12.8, the same applies hereinafter), and 3 parts of calcium dodecylbenzenesulfonate.
25 parts of phoxim was mixed with 69 parts of aromatic petroleum solvent.
% emulsion was prepared.

Comparative Example 2 A 50% phoxim emulsion was prepared by mixing 50 parts of phoxim, 3 parts of a styrylphenol-ethylene oxide adduct, and 3 parts of calcium dodecylbenzenesulfonate with 44 parts of an aromatic petroleum solvent.

Comparative Example 3 A 10% phoxim emulsion was prepared by mixing 10 parts of phoxim, 3 parts of a styrylphenol-ethylene oxide adduct, and 3 parts of calcium dodecylbenzenesulfonate with 84 parts of an aromatic petroleum solvent.

Test Example 1 Alkaline phenol resin with pH 10.7 (Daichi Shinko ■
100 parts of Deianolia), 7 parts of wheat flour, 4 parts of the enhancer, and a predetermined amount of the termiticide in the form of an oil or emulsion obtained in the above Examples and Comparative Examples were thoroughly stirred and mixed.
A phenolic resin adhesive for producing termite-proof plywood having a pH of 10.5 was prepared.

Apply 350g/rd of this adhesive to both sides of one lauan veneer.
After coating at a ratio of 1-3-1, 3-brie plywood with a thickness of 1-3-1 was cold pressed at a pressure of 10 kg/c+fl for 30 minutes, and then hot pressed at a temperature of 135°C and a pressure of 10 kg/cJ for 200 seconds. . According to these conditions, the phoxim content of the plywood was 1 kg/rrr.

Table 1 shows the results of measuring the phoxim recovery rate and the shear strength of structural plywood according to Japanese Agricultural Standards for each of the plywoods produced as described above.

As previously mentioned, aqueous alkaline phenolic resins generally have a high pH, so when the pesticide is mixed with such adhesives, the pesticide decomposes. However, in the phenolic resin adhesive for producing termite-proof plywood according to the present invention,
The insecticide is contained in the adhesive in the form of an oil solution dissolved in a water-insoluble organic solvent, and since the insecticide is protected from the water-based adhesive, its decomposition is suppressed. Therefore,
The phoxim recovery rate is an index of the termite-proofing effect of plywood; the lower the phoxim decomposition rate, the higher the phoxim recovery rate, and thus the greater the termite-proofing effect of plywood.

As is clear from the results shown in Table 1, when using the adhesive containing the oil-type termiticide according to the present invention, it is possible to obtain plywood with a high recovery rate of phoxim and high adhesive strength.

Example 5 A 10% permethrin oil solution was prepared by dissolving 10 parts of permethrin in 90 parts of an aromatic petroleum solvent.

Example 6 5 parts of permethrin and 15 parts of phoxim were mixed in a mixed solvent of an aliphatic petroleum solvent and an aromatic petroleum solvent (mixing ratio 70/10).
A 20% insecticide oil solution was prepared by dissolving 80 parts of the insecticide.

Test Example 2 100 parts of an alkaline phenol resin with a pH of 10.7 (PR-51341 manufactured by Sumitomo Durez Field), 8 parts of wheat flour, 4 parts of enhancer, 7 parts of water, and each oil type obtained in Example 5 or 6 above. Thoroughly stir and mix 6.9 parts of termiticide,
A phenolic resin adhesive for producing termite-proof plywood of lllo.5 was prepared.

Apply this adhesive to one piece of Ceraya veneer (30cm x 30cm
After applying 38 g to both sides of 1.8 ttm (thickness), this was used as a core material to stack three layers together with two Ceraya veneers, and the pressure was 10 kg/cffl and the temperature was 30°C.
Cold pressure for minutes, then pressure 8kg/cJ, temperature 120℃
3-ply plywood was manufactured by hot pressing for 270 seconds.

A sample of 2 Cl1 x 2 cm was taken from the obtained plywood, crushed to make wood powder, and mixed with 100 m of methanol.
1 and subjected to shaking extraction for 2 hours. The amount of insecticide in the obtained extract was determined by high performance liquid chromatography. The results are shown in Table 2. In addition, the results of measuring the shear strength of structural plywood according to the Japanese Agricultural Standards are also included in the second report.
Shown in the table.

As is clear from the results shown in Table 2, when using the adhesive containing the oil-based termiticide according to the present invention, it is possible to obtain plywood with a high recovery rate of insecticide and high adhesive strength. .

Claims (4)

[Claims] (1) (a) An oil agent prepared by dissolving at least one insecticide selected from the group consisting of organophosphorus insecticides and pyrethrin insecticides in a water-insoluble organic solvent in a range of 5 to 30% by weight. , (2) An alkaline phenolic resin adhesive for producing termite-proof plywood, characterized by comprising an aqueous alkaline phenolic resin adhesive. (2) The alkaline phenolic resin adhesive for producing termite-proof plywood according to claim 1, wherein the organophosphorus insecticide is phoxim. (3) The alkaline phenolic resin adhesive for producing termite-proof plywood according to claim 1, wherein the pyrethrin insecticide is permethrin. (4) Water-based alkaline phenolic resin adhesive is 10 to 1
The alkaline phenolic resin adhesive for producing termite-proof plywood according to claim 1, characterized in that it has a pH of 3 and hardens at a temperature of 120 to 150°C.