JPH0466682B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a wood preservative that has excellent permeability into wood and exhibits excellent antiseptic, termite, and insect repellent properties over a long period of time. ``Conventional technology'' In recent years, Japan's demand for lumber has increased significantly, leading to the depletion of domestic forest resources.With the increase in imported materials with poor durability, such as South Sea lumber, damage from biological organisms such as termites and wood beetles has increased. It is increasing. Additionally, changes in construction methods are creating an environment where wood is more likely to rot and termite damage occurs. Traditionally, various wood preservatives have been used to protect wood from biological deterioration. For example, termite and insect repellent ingredients include organochlorine insecticides such as deirdrin, aldrin, DDT, lindane, heptachlor, and chlordane, CCA agents (copper, chromium, and arsenic agents), and CFK agents (copper, futsuso, and chromium agents).
Inorganic fixation type compounds such as these have been mainly used. These compounds cause odor, rash, irritation,
It has problems in terms of toxicity to humans and livestock, and environmental pollution. For example, although deirdrin has excellent ant and insect repellent properties, it is highly toxic to humans and livestock, and due to its accumulation and persistent properties, it has been designated as a specified chemical substance and its use has been prohibited in Japan. Chlordane is highly toxic to humans and livestock, and is highly accumulative and difficult to decompose, causing serious environmental pollution. In addition, CCA agents and CFK agents contain toxic heavy metals, which pose problems in terms of toxicity to humans and livestock and environmental pollution.
In addition, as preservative ingredients, creosote oil, PF agents (phenol/fluorine), CCA agents, chlornaphthalene, organotin compounds, naphthenic acid metal salts, phenolic compounds, etc. have been used, but all of them have odor and Rash, irritation, toxicity to the human body,
It has drawbacks in terms of environmental pollution, etc. ``Problems to be solved by the invention'' Due to the above-mentioned circumstances, it is necessary to develop a wood preservative that has excellent wood preservation performance over a long period of time, is highly safe for humans and livestock, and is free from environmental pollution. This poses a serious and urgent challenge to those skilled in the art. Many organophosphorus insecticides and carbamate insecticides exhibit excellent insecticidal efficacy, and are expected to be used as insect repellent and termite repellent ingredients in wood preservatives that are highly safe for humans and livestock and cause little environmental pollution. However, these compounds generally tend to be easily decomposed by light, heat, water, microorganisms, etc., and if a solution of these compounds is simply applied to the surface of the wood, it will be decomposed in a relatively short period of time. It is inferior to organic chlorine compounds in terms of long-term efficacy required for preservatives. Even though these active ingredients are relatively easy to decompose, if they can penetrate into the interior of the wood, they will be less susceptible to light, heat, water, etc., and decomposition will be considerably suppressed, allowing their effects to last longer. However, solutions of organic components in organic solvents are surprisingly difficult to penetrate into the interior of wood. Furthermore, if the organic component is solid at room temperature, i.e., has a melting point or softening point of 30°C or higher, the organic component will disappear even if the solution is applied from the surface of the wood or the wood is immersed in the solution. It does not penetrate deep into the wood. This is thought to be because the solution becomes concentrated before penetrating into the interior of the wood, and some of the organic components become solid and precipitate on the surface layer of the wood. For example, 2-isopropoxyphenyl-N-methylcarbamate, which is a type of carbamate-based insecticidal ingredient, is safe for humans and livestock and shows excellent insecticidal effects, but when the solution is applied to the surface of wood. If you use it alone, the active ingredients will not penetrate into the wood, and the organic components on the wood surface will lose their effectiveness in a few weeks. "Means for Solving the Problem" The present inventors discovered that although the method is highly safe for humans and animals and has little risk of environmental pollution, it has not been used much in the past and has a long-lasting effect. Even if we use insecticides and sterilizers, which were thought to be completely unusable due to the We discovered that by adding specific additives and formulating a wood preservative that is superior to conventional wood preservatives,
The invention has been completed. That is, the present invention provides (a) a melting point or softening point of 30°C;
The above insecticidal/sterilizing ingredients, (b) liquid aromatic compound with a boiling point of 290°C or higher, (c) ethylene glycol monoether or polyethylene glycol monoether [hereinafter referred to as (poly)ethylene glycol monoether], and (d) alkyd modification. drying oil (e)
A composition dissolved in a solvent, in which the content of the component (a) is 0.01 to 10.0% by weight, the sum of the content of the component (b) and the content of the component (c) is 1 to 50% by weight, and the content of the component (d) is 1 to 50% by weight. is 0 to 30% by weight, the content of component (e) is 10 to 95% by weight, and the weight ratio of component (b) to component (c) is 5:95 to 95:5. When the wood preservative of the present invention is applied to wood,
It easily penetrates deep and exhibits wood preservation effects over a long period of time without volatilization or leaching. Insecticidal and fungicidal ingredients that can be used in the present invention include any ingredients that have a melting point or softening point of 30°C or higher and are soluble in organic solvents, especially petroleum-based solvents. good. Typical insecticidal ingredients used in the present invention include the following. Organophosphorus O,S-dimethyl-N-acetylphosphoroamidothioate (acephate) O,O-diethyl-3,5,6-trichlor-
2-Pyridyl-phosphorothioate (chlorpyrifos) O,O-diethyl-2,3-dihydro-3-oxo-2-phenyl-6-pyridazinylphosphorothioate (pyridafenthion) O,O-diethyl-2-chloro -(α-cyanobenzylideneamino)phosphorothioate (chromefoxime) O,O-dimethyl-2-chloro-1(2,4,
5-Trichlorophenyl) vinyl phosphate (tetrachlorvinphos) O,O-dimethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate (chlorpyrifosmethyl) Carbamate series O-Sec-butylphenyl methylcarbamate ( BassaU) 1-naphthylmethylcarbamate (SevinU)
) O-isopropoxyphenyl methyl carbamate (propoxor) m-toluyl methyl carbamate (tumaside) Pyrethroids α-cyano-3-phenoxybenzyl (1RS)
cis,3-(2,2-dibromvinyl)-2,2-
Dimethylcyclopropane-1-carboxylate (decamethrin) 5-benzyl-3-furyl-methyl (1RS) cis, trans, chrysanthemate (resmethrin) Typical bactericidal ingredients used in the present invention are as follows. I can give you something. N-cyclohexyl-N-methoxy-2,5-
Dimethylfuran-3-carboxamide (flumethociclotux) Metal salt of N-nitroso-N-cyclohexylhydroxylamine (metal salt of NCH) N,N-dimethyl-N'-(dichlorofluoromethylthio)-N'-phene Nilsulfamide (dichlorofluanide) 2,4,6-tribromophenol Zinc naphthenate Diiodomethyl 4-methylphenylsulfone 2,3,5,6-tetrachloroisophthalonitrile Insecticidal ingredients used in the present invention, The ratio of each bactericidal component to the wood preservative is 0.01~
10.0% by weight, preferably 0.1-5.0% by weight, more preferably 0.3-3.5% by weight. The liquid aromatic compound with a boiling point of 290°C or higher and (poly)ethylene glycol monoether used in the present invention cooperate with each other to penetrate the active ingredient into the wood, preventing volatilization and leaching of the active ingredient, It works to maintain its effectiveness for a long time. This liquid aromatic compound with a boiling point of 290℃ or higher is
Petroleum fraction, catalytic cracking oil fraction, or synthetic oil with a boiling point of 290°C or higher and liquid at room temperature. Its components include polyalkylbenzenes such as monoalkylbenzenes, dialkylbenzenes, trialkylbenzenes, and tetraalkylbenzenes,
It contains indene derivatives, monoalkylnaphthalenes, dialkylnaphthalenes, phenylxylylnaphthalenes, alkyl diphenyls, diphenyl ethers, etc. singly or in combination. The (poly)ethylene glycol ether used in the present invention is preferably in liquid form with a boiling point of 200°C or higher;
For example, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, etc. have a molecular weight of about 140~
About 400 things can be mentioned. The usage ratio (weight ratio) of the aromatic compound and (poly)ethylene glycol monoether is 5:95 to 95:5, preferably
25:75-75:25. The proportion of these penetration aids used in the total wood preservative is 1 to 50% by weight, preferably 3 to 30% by weight. It is also possible to add an alkyd-modified drying oil to the composition of the present invention to more reliably fix the active ingredient inside the wood, prevent the used active ingredient from leaching out, and fully exhibit its effectiveness. This alkyd-modified drying oil is prepared by dissolving 50 parts of the alkyd-modified drying oil in 50 parts of a mineral spirit with a boiling point of 50 to 200°C, a flash point of 40°C, and 15% aromatic content. Those having a viscosity of 200 to 15,000 cps at °C and an oil length of 30 to 70% are preferably used. The proportion of this alkyd-modified drying oil used is preferably 30% or less based on the total weight of the wood preservative.
~10%. Sunflower oil as a drying oil,
Soybean oil, tall oil, linseed oil, etc. are used. This alkyd-modified drying oil combines drying oils with polybasic acids (e.g. phthalic anhydride) and polyhydric alcohols (e.g.
It can be obtained by mixing and dissolving alkyd resin raw materials (glycerin), reacting at 100 to 220°C while removing generated water, and finishing the reaction under reduced pressure if necessary. If necessary, this may be adjusted to a solution by adding a predetermined amount of solvent. Examples of the solvent used in the present invention include aliphatic hydrocarbons such as kerosene, isoparaffin, white spirit, aliphatic petroleum naphtha, hexane, and heptane, and alicyclic hydrocarbons such as naphthene and aromatic hydrocarbons. Examples include solvent naphtha, aliphatic/aromatic mixed hydrocarbons such as mineral spirits, halogenated hydrocarbons such as dichlorobenzene and trichloroethane, and alcoholic solvents such as isopropanol and 3-methoxy-1. -Butanol, 3-methyl-3-methoxybutanol, 2-t-butoxyethanol, etc. are used as ketone solvents, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are used as ester solvents, and ethyl acetate, butyl acetate, diethyl phthalate are used as ester solvents. etc. can be mentioned. These solvents are used in the wood preservative in an amount of 10 to 95% by weight, preferably 30 to 90% by weight. In addition, wood preservatives, stabilizers such as antioxidants and ultraviolet absorbers, colorants, rust preventives, and the like can also be added. The final viscosity of the composition at 25℃ is 15~
200cps is good. To apply the wood preservative of the present invention to wood etc., apply it. Methods conventionally applied to oil-based or oil-soluble chemicals, such as spraying, dipping, injection, scattering, and mixing, can be used as they are. ``Effects of the present invention'' The wood preservative of the present invention can easily penetrate deep into the wood with insecticidal and fungicidal ingredients that conventionally could not be used as wood preservatives because they could not penetrate deeply into the wood. Since the wood can be penetrated and fixed, the wood preservation effect can be maintained for a long period of time. Example 1 O,O-diethyl-O-(α-cyanobenzylideneamino)phosphorothioate 1.0 part 2-isopropoxyphenyl-N-methylcarbamate 0.5 part Aluminum salt of N-nitroso-N-cyclohexylhydroxylamine 0.5 part N- Cyclohexyl-N-methoxy-2,5-
Dimethylfuran-3-carboxamide 0.5 parts 100% aromatic solvent with a boiling point of 290-305℃
10 parts Alkyd modified soybean oil (oil length 66, viscosity of 50% mineral spirits solution 1070 cps) 5 parts Petroleum solvent (boiling point 203-260°C, aromatic content 21
%) 72.5 parts diethylene glycol monobutyl ether 10 parts The ingredients were mixed according to the above formulation and stirred at 30°C for 1 hour to completely dissolve the ingredients to prepare a uniform wood preservative solution. Example 2 O,O-diethyl-O-(α-cyanobenzylideneamino)phosphorothioate 1.0 part 2-isopropoxyphenyl-N-methylcarbamate 0.5 part Aluminum salt of N-nitroso-N-cyclohexylhydroxylamine 0.5 part N- Cyclohexyl-N-methoxy-2,5-
Dimethylfuran-3-carboxamide 0.5 parts 100% aromatic solvent with a boiling point of 290-305℃
10 parts petroleum solvent (boiling point 203-260℃, aromatic content 21
%) 77.5 parts diethylene glycol monobutyl ether 10 parts Each component was mixed according to the above formulation and stirred at 25°C for 30 minutes to completely dissolve it, to prepare a homogeneous wood preservative solution. Comparative Example 1 O,O-diethyl-O-(α-cyanobenzylideneamino)phosphorothioate 1.0 part 2-isopropoxyphenyl-N-methylcarbamate 0.5 part N-nitroso-N-cyclohexyl-hydroxylamine aluminum salt 0.5 part N -cyclohexyl-N-methoxy-2,5-
Dimethylfuran-3-carboxamide 0.5 parts Alkyd modified soybean oil (oil length 66, viscosity _Ua 1070cps)
5 parts petroleum solvent (boiling point 203-260℃, aromatic content 21
%) 82.5 parts Cyclohexanol 10 parts The ingredients were mixed according to the above formulation and stirred at 25°C for 30 minutes to completely dissolve, thereby preparing a homogeneous wood preservative solution. a Mineral spirit 50% solution (25°C) Comparative example 2 O,O-diethyl-O(α-cyanobenzylideneamino)phosphorothioate 1.0 part 2-isopropoxyphenyl-N-methylcarbamate 0.5 part N-nitroso-N- Aluminum salt of cyclohexylamine 0.5 part N-cyclohexyl-N-methoxy-2,5-
Dimethylfuran-3-carboxamide 0.5 parts Diethylene glycol monobutyl ether 10 parts Alkyd modified soybean oil (oil length 66, viscosity 1070 cps)
5 parts petroleum solvent (boiling point 203-260℃, aromatic content 21
%) 82.5 parts The ingredients were mixed according to the above formulation and stirred at 25°C for 30 minutes to completely dissolve the ingredients and prepare a homogeneous wood preservative solution. Comparative Example 3 O,O-diethyl-O-(α-cyanobenzylideneamino)phosphorothioate 1.0 part 2-isopropoxy-phenyl-N-methylcarbamate 0.5 part Aluminum salt of N-nitroso-N-cyclohexylamine 0.5 part N-cyclohexyl -N-methoxy-2,5-
Dimethylfuran-3-carboxamide 0.5 parts Alkyd modified soybean oil (oil length 66, viscosity 1070cs)
5 parts Solvent with boiling point 290-305℃, 100% aromatic compounds
10 parts petroleum solvent (boiling point 203-260℃, aromatic content 21
%) 82.5 parts The ingredients were mixed according to the above formulation and stirred at 25°C for 30 minutes to completely dissolve the ingredients to prepare a homogeneous solution. Test Example 1 Using the wood preservatives prepared in Examples 1 and 2 and Comparative Examples 1 to 3, an anti-termite efficacy test was conducted in accordance with Japan Wood Preservation Association Standard No. 11. A preservative efficacy test was conducted. The results are shown in Table 1.

[Table] Test Example 2 Using the wood preservatives of Examples 1 and 2 and Comparative Examples 1 to 3, a three-year field test was conducted at Fukiagehama, Kagoshima Prefecture, in accordance with the Japan Wood Preservation Association Standard No. 11. Table 2 shows the results of testing the anti-termite efficacy and antiseptic efficacy. In both of the treated test specimens of Examples 1 and 2, no feeding damage caused by termites or damage caused by wood-decaying fungi was observed. On the other hand, in Comparative Examples 1 to 3, damage from house termites and wood-decaying fungi was observed in all of the treated specimens, and in the untreated specimens, they suffered significant feeding damage three months after the start of the test, with a weight loss rate of 70%. Some of them reached this point and did not retain their original shape. This result shows that the wood preservative of the present invention has excellent performance.

【table】

【table】

Claims (1)

[Claims] 1 (a) Insecticidal/sterilizing ingredients with a melting point or softening point of 30°C or higher, (b) Liquid aromatic compound with a boiling point of 290°C or higher,
A composition in which (c) ethylene glycol monoether or polyethylene glycol monoether and (d) alkyd-modified drying oil are dissolved in (e) a solvent, the content of component (a) in the composition being 0.01 to 10.0% by weight. ,
(b) The sum of component content and (c) component content is 1 to 50% by weight, (d)
The component content is 0 to 30% by weight, the component (e) content is 10 to 95% by weight, and the weight ratio of component (b) to component (c) is 5:95 to 95:
5. Wood preservative.