JP2005179258A - Insect repellent composition against termite and/or wood borer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop an insect repellent composition against termites and wood borers. <P>SOLUTION: A composition containing a nonhalogen monophenyl ether is used as the insect repellent composition against termites and/or wood borers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an insect repellent for termites or (and) bark beetles

  Various wood preservatives are known in order to control wood pests such as termites and oyster beetles, and to prevent contamination by wood-rotting fungi such as giant crabs and id bamboo. As the active ingredient, various compounds having insect repellent action, wood preservative action, bactericidal action, fungicidal action and the like are known. However, these conventionally known wood preservatives have a high impact on safety and the environment for human livestock, and may destroy natural ecosystems. Common insecticides are used as control agents for wood pests such as termites and larvae. For example, according to the Japan Wood Preservation Association's “Wood Preservation Guidelines” (October 1994), organic phosphorus systems include peroxiline, oxime, chlorhopyris, pyridafenthion, tetrachlorbinphos, fenitrothion, propentanephos, pyrethroids, Tralomethrin, allethrin, pyrethroid-like compounds: silafluophene, entofenblox, carbamate-based proboxur, bassa, tridian-based tripropylisocyanurate, naphthalene-based monochloronaphthalene, tar-based creosote oil, chlorinated dialkyl Octachlorodipropyl ether (S-421) as ether addition system, imidacloprid as chloronicotinyl system, 4-chlorophenyl-3 as organic iodine system -Iodobrovaquil formal (1F-1000), 3-ethoxycarbyloxy-1-bromo-1,2-iodopropene (Samplus), 3-iodo-2 -upyrobenthylbutyl carbamate (Troysan), Examples of the naphthenic acid metal salt type include naphthenic copper and naphthenic zinc, and examples of the hydroxylamine type include N-nitrone-cyclohexylhydroxylamine aluminum (xylazane AL).

  Most of these compounds have relatively low toxicity, but some organophosphorus and carbamate insecticides have a cholinesterase activity inhibitory action on the human body, and many pyrethroid insecticides have high fish toxicity. However, it is difficult to say that it is safe enough from the viewpoint of environmental pollution, and there are voices that question its use. Further, among phenolic compounds, it is known to use lignin, lignin sulfonic acid, lignin sulfonate, and the like in combination with one or more specific compounds as antiseptic and insect repellents (Japanese Patent Laid-Open No. 2003). -160402).

  However, the specific compound used as the antiseptic and insect repellent is a combination of at least one alkylene glycol quaternary ammonium compound.

However, in the above-mentioned preservatives and insecticides, lignin, lignin sulfonic acid, lignin sulfonate, etc. must be used in combination with the other two kinds of specific compounds described above, and are used alone as an antifungal or insecticidal effect. The case is not supposed at all.
In general, halogen-based pesticides such as silafluophene (Japanese Patent Laid-Open No. 2003-63902) are widely used as chemicals for controlling white ants, but in recent years there is concern about their strong toxic effects on the human body.

Therefore, recently, there has been a demand for a pest control agent that is highly safe for human livestock and is environmentally friendly.
Therefore, a termite control agent containing an extract of seeds of the ginger family plant Aframomum melegueta as an active ingredient. (Japanese Patent Laid-Open No. 9-194318) 1,2-β-acetoxy-flatoxin, a homologue of 1,2-β-acetoxy-flatoxin, which is a novel fratoxin derivative extracted and produced from Wiskstromia retusa A. Gray And a cyclic flatoxin to which a benzoyl group is added, and a termite control agent, a termicide, an insecticide, and a bactericidal agent containing flatoxin and these novel flatoxin derivatives as active ingredients. (JP-A-7-48378) A novel cinnamic acid amide derivative isolated from the seed extract of Xylopia aethiopica, a method for producing the same, and a termite control agent comprising the compound as an active ingredient. (JP-A-6-16609) Further, JP-A-3-41011 discloses a control agent containing an extract of neem's organic solvent or water-containing solvent as an active ingredient as a highly safe termite control agent, Furthermore, JP-A-6-329514 discloses the use of a component extracted or exuded from plants such as Moringa or Mala as a pest control agent. It was not an effective solution.

  The present invention has been made in view of the above problems, and has activities such as feeding inhibition, repellent, and insecticidal activity against wood pests, is highly safe for human livestock, is environmentally friendly, and wood and the like. It aims at providing the wood pest control agent which does not have a possibility of coloring.

  The present inventor has been extensively engaged in research on insect repellents, and in this research, the development of termite or (and) bark beetle repellents has been studied. And in this research, it has been found that non-halogen monophenyl ethers, among phenolic compounds, exhibit insecticidal action extremely effectively against termites or (and) bark beetles, either alone or in combination of two or more. It was.

  As a result of intensive studies on the effects of various drugs on termites and / or bark beetles, the present inventors have found that specific drugs prevent woody feeding behavior of termites and bark beetles, and have completed the present invention. . That is, the present invention is solved by using non-halogen monophenyl ether as an active ingredient of an insect repellent for termites and / or bark beetles.

  The composition of the present invention exhibits extremely excellent insect repellent action against termites and / or bark beetles.

The composition for insect repellent of the present invention may contain other components as long as the non-halogen monophenyl ether is contained as an active ingredient.
The insect repellent composition of the present invention is a non-halogen monophenyl ether mixed with various carriers such as water, water-based resin, organic solvent, clay, talc, diatomaceous earth, calcium carbonate, sodium sulfate, and optionally a surfactant. It can be used together with other wood preservatives, antifungal agents, insecticides, flameproofing agents, water repellents and the like. Other antifungal agents include (a) halogenated phenols, (b) imidazoles, (c) phthalimides, (d) thiazoles such as 2- (4-thiocyanomethylthio) benzothiazole, 2- n-octyl-4-isothiazolin-3-one, 2-mercaptobenzothiazole, (e) phenol ether, (f) organotin, (g) iodo, (g) organocopper, (g) pyridine (E) Sulfone and the like. Examples of other insect repellents include (a) organochlorine, (b) organophosphorus, (c) carbamate, (d) pyrethroid, and flame retardants such as phosphorus compounds, heavy metal compounds, halogen compounds, and water repellents. In this case, natural wax, paraffin wax, silicon water repellent, fluorine water repellent and the like can be added and used, but the present invention is not necessarily limited to the above compounds.

  The insect repellent composition of the present invention can be used in various dosage forms, and can be used in various forms such as oils, emulsions, suspensions, pastes, moisture agents, powders and the like according to the purpose of use. A) Addition to oil-based paints, oil-based adhesives, oil-based adhesives, etc. as oil agents, and b) Emulsion resins, water-soluble resins, aqueous metalworking oils, emulsion adhesives, waxes, emulsions as emulsions, suspensions, and water solvents Add to paints, water-soluble paints, water-based adhesives, water-based adhesives, color dispersions, thickeners, glues, sizing agents, circulating water for cooling, white water for papermaking, coating colors, wet pulp, wood chips, etc. C) As a powder, it can be used by adding to wall materials, particle boards, hard boards and the like.

  The insect repellent composition in the present invention includes an insecticidal and insect repellent composition, and the insect repellent composition includes a repellent composition.

  In the insect repellent composition of the present invention, a composition containing a non-halogen phenoxy ether as an active ingredient is used.

Preferred examples of the non-halogen phenoxy ether used at this time include the following compounds.
The non-halogen monophenyl ether is vanillin, ethyl vanillin, vanillin alkylene acetal vanillic acid, ethyl vanillate, vanillin propylene glycol acetal, vanillyl alcohol, vanillyl methyl ether, vanillyl ethyl ether, vanillyl propyl ether, vanillyl Butyl ether, Vanillyl amyl ether, Vanillyl isoamyl ether, Vanillyl hexyl ether, Vanillyl allyl ether, Vanillyl cyclopentyl ether, Vanillyl cyclohexyl ether, Vanillyl tetrahydrofuruhyl ether, Vanillyl 3-hydroxy-2-butyl ether, Vanillyl 4 -Hydroxy-1-butyl ether, vanillyl 3-hydroxy-1-propyl ether, vanillyl 3-hydroxy-1-butyl ether, vanillyl 2-hydroxy-1-propyl Ether, vanillylethoxyethyl ether, methoxyaniline, methoxyphenol, 2-methoxy-5-methyl-benzenamine, ethoxyphenol, ethoxyaniline, ethylphenyl ether, ethylene glycol monophenyl ether, phenoxyethyl acrylate, phenoxyacetic acid, 1, At least one or more selected from the group consisting of 2-dimethoxybenzene, alkylphenol ethoxylate, and 3,4-dimethoxybenzaldehyde are preferable. Among them, vanillin, vanillyl butyl ether, vanillyl methyl ether, vanillyl ethyl ether, vanillyl are preferable. Propyl ether, methoxyphenol, ethoxyphenol, ethylene glycol monophenyl ether, and 1,2-dimethoxybenzene are particularly preferred.

  The content of the non-halogen phenoxy ether of the active ingredient of the present invention is 0.01 to 80% by weight, preferably 0.5 to 30% by weight. In addition, the mixing ratio with the above-mentioned other additive components is 0.01 to 100 parts, preferably 0.01 to 10 parts, with respect to 1 part by weight of the non-halogen phenoxy ether. The preventive composition of the present invention is an object to be eaten by termites or (and) bark beetles, such as woody materials (wood, boards, pillars), cellulose products (papers, etc.), planted trees, concrete, covered electric wires, foam insulation. What is necessary is just to adhere to materials (urethane resin, polystyrene resin) by arbitrary methods, such as immersion, spraying, application | coating, scouring, and injection | pouring. The adhesion amount is 400-50000 ppm as non-halogen phenoxy ether, preferably 1000-10,000 ppm.

  The composition for prevention according to the present invention can prevent feeding damage of termites or (and) bark beetles over a long period of time, for example, by performing treatments such as application to healthy wood, immersion, and injection. It has a preventive effect that it can be used, and by using a mixture of a fast-acting and non-residual insect repellent as described above for a place where a termite or (and) bark beetle has already been damaged, for example, A long-term preventive effect can be achieved after removing termites or (and) bark beetles. In addition, the present inhibitor is an excellent inhibitor that can be used safely compared to conventional drugs because it has no elution from treated products or soil persistence, and there is no problem such as residual harmful metals after incineration. Furthermore, since the inhibitor of the present invention has an effect of suppressing the growth of wood decaying fungi (bactericidal), it is also useful as a preservative (protective agent) for wood and the like.

  The inorganic porous fine particles used in the present invention include inorganic porous fine particles with strong capsule strength developed by the present inventors (Japanese Patent Publication No. 57-055554) (trade names: God Ball B-6C, A-11C, B- 16C, B-25C, E-6C, D-11C, E-16C, E-2C, etc., manufactured by Suzuki Yushi Kogyo Co., Ltd.), in addition, Nipsil series or Laponite series (trade name, (Made by Nippon Silica Industry Co., Ltd.), Aerosil 50, 90G, 130, 200, 200FAD, 300, R202, R812R, OX50, MOX170, etc. (trade name, made by Nippon Aerosil Co., Ltd.), Cylicia 250, 256, 310, 320, 430 530, 730, 770, etc. (trade name, manufactured by Fuji Silysia Chemical Co., Ltd.), Smectite SWN, SAN, STN, SEN, SPN, etc. (trade name, manufactured by Coop Chemical Co., Ltd.), talc, kaolin, activated clay, diatomaceous earth Perlite, bentonite and the like can also be used. Inorganic porous fine particles (Japanese Patent Publication No. 57-0555454) are particularly suitable. Inorganic porous fine particles (Japanese Examined Patent Publication No. 57-055454) are not affected by the structure of the porous structure by heating. Therefore, even in products that require a heating process for commercialization, insect repellent for termites or (and) bark beetles is used. It has an excellent advantage that the activity can be maintained.

  Inorganic porous fine particles suitable for the present invention (Japanese Examined Patent Publication No. 57-055454) include a method for carrying a repellent active compound in the production process of inorganic porous fine particles, and a method for carrying a repellent active compound after the production of inorganic porous fine particles. There is a way.

  The method of carrying the repellent active compound after the production of the inorganic porous fine particles first is carried out by using an organic solvent in an aqueous solution of an inorganic compound (compound A: for example, an inorganic compound such as an alkali metal silicate or carbonate). And a water-in-oil emulsion (emulsion) with a surfactant and an inorganic compound capable of forming an insoluble precipitate with the inorganic compound (compound B: for example, alkaline earth metal halide, inorganic acid or After mixing with an aqueous solution of an organic acid or the like, a precipitation reaction is caused at the water droplet interface to form an inorganic shell, and then a by-product or a surfactant is removed to have a hollow portion or a hollow portion. Non-hollow inorganic porous fine particles having no carbon dioxide are obtained (see Japanese Patent Publication No. 05-009133, Japanese Patent Publication No. 57-0555454, etc.).

  In order to carry the repellent active compound during the production process, the repellent active compound may be first dispersed in an aqueous solution of an inorganic compound. The inorganic porous fine particles are impregnated with a repellent active compound.

  Examples of the organic porous fine particles include cyclodextrins, porous nylon fine particles, porous acrylic fine particles, and porous polyethylene fine particles.

By carrying the termite which is a repellent active composition or the insect repellent for bark beetles on the porous fine particles, the effect can be sustained for a long time, and the sustained-release repellent active fine particles can be obtained.
As the organic polymer fine particles used in the present invention, fine particles composed of various organic polymers are used, but a typical one is an organic gel, and the organic gel is not particularly limited. Any substance that crosslinks may be used, and any substance that can cause gelation from a liquid state is usable. More specifically, the crosslinking method may be any of covalent bond, ionic bond, and intermolecular force bond, or a substance that causes gelation due to entanglement. That is, the form is not particularly limited as long as it is a solidified substance by gelling or forming a film to be included.

Crosslinking by a covalent bond forms a gel using a monomer, a crosslinking agent, an initiator, and the like, and the monomer used at that time is not particularly limited as long as it performs normal radical polymerization. For example, acrylamide, methacrylamide, N-vinylpyrodon, N-vinylacetamide, N-vinylformamide, acrylic acid, methacrylic acid, styrene, P-styrene sulfonic acid, vinyl sulfonic acid, 2-methacryloyloxyethyl sulfonic acid, 3 -Methacryloyloxy-2-hydroxypropylsulfonic acid, allylsulfonic acid, methacrylsulfonic acid, and ammonium and alkali metal salts of these acids, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, 2-vinylpyridine and 4-vinylpyridine Quaternized products of hydrochloric acid, nitric acid, dimethyl sulfate, diethyl sulfate or ethyl chloride, 2hydroxyethyl methacrylate, 2hydroxyethyl acrylate, 2acrylamido-2-methylpropanesulfonic acid, Can be exemplified by these copolymers.
Examples of the crosslinking agent having two or more polymerizable functional groups include ethylene glycol, propylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, polyglycerin, N, N′-methylenebisacrylamide, N, N-methylene-bis-N vinylacetamide, N, N-butylene-bis-N vinylacetamide, tolylene diisocyanate, hexamethylene diisocyanate, allylated starch, allylated cellulose, diallyl phthalate, tetraallyloxyethane, pentaerythridine Examples include stall triallyl ether, trimethylolpropane triallyl ether, diethylene glycol diallyl ether, triallyl trimellitate and the like.
The initiator is not particularly limited, and an initiator suitable for gelation may be selected. Examples thereof include hydrogen peroxide, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate. Azo initiators such as 2,2'-azobis (2-midinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride, 2,2'-azobis { 2-Methyl-N- [1,1, -bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4'-dimethylvaleronitrile), and the like. Hydrogen peroxide or persulfate can also be used as a redox initiator in combination with a reducing substance such as sulfite or L-ascorbic acid or an amine salt.

Crosslinking by ionic bonding is, for example, a substance obtained by gelling a polymer electrolyte having a cation or anion such as an ammonium salt or a carboxyl group with a polyvalent ionic substance such as calcium.
Crosslinking by intermolecular force is common in natural polymers, such as starch, galactomannan, nitrocellulose, methylcellulose, hydroxypropylmethylcellulose, pectic acid, alginic acid, agar, carrageenan, protechoglycan, glycoprotein, gelatin, actin, tube Examples include phosphorus, hemoglobin S, insulin, fibrin, ovalbumin, serum albumin, myosin, collagen, polypeptide, and the like. Examples of synthetic polymers include polyvinyl alcohol.

  The solvent used for the gelation is not particularly limited, and a solvent suitable for the gelation may be selected. For example, water, alcohol, acetone, tetrahydrofuran, dimethylformamide, diethyl ether, n-pentane, n- Examples include hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and the like.

  In order to form a film around the droplet, a normal microencapsulation method such as an interfacial polymerization method or an in-situ polymerization method is used. In order to perform the microencapsulation method by the interfacial polymerization method, a polyvalent isocyanate (for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, Range isocyanate, toluene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl diisocyanate), polyvalent carboxylic acid chlorides (eg sebacic acid dichloride, adipic acid dichloride, azelaic acid dichloride, terephthalic acid The microcapsule film-forming raw material such as dichloride, trimesic acid dichloride), polyvalent sulfonyl chloride (for example, benzenesulfonyl dichloride) is added, and it is necessary to submerge the suspension droplets in water. Add water-soluble film-forming materials such as polyhydric alcohols (eg, ethylene glycol, butanediol, hexanediol) and polyamines (eg, ethylenediamine, hexamethylenediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, piperazine). Keep it. The film forming reaction is usually carried out in the temperature range of 0 to 80 ° C., preferably 40 to 80 ° C., for about 0.5 to 48 hours, and a catalyst can be used to promote the reaction. In this way, films of polyurethane, polyurea, polyamide, polyester, polysulfonate, polysulfonamide and the like are formed.

  In order to perform microencapsulation by in-situ polymerization, water-soluble prepolymers such as aminoplast, urea formalin condensate, and melamine formalin condensate are previously added to the water in which the suspension droplets are dispersed. Under stirring, it can be carried out usually by heating within a range of 40 to 80 ° C. and holding for about 0.5 to 48 hours.

  The microencapsulated repellent slurry thus produced can be used as a repellent as it is, but is usually an aqueous suspension to which a thickener, antifreeze, preservative, specific gravity regulator and the like are added. Used as an agent. As thickeners, natural polysaccharides such as xanthan gum, rhamzan gum, locust bean gum, carrageenan, and welant gum, synthetic polymers such as sodium polyacrylate, semi-synthetic polymers such as carboxymethylcellulose, aluminum magnesium silicate, smectite, bentonite, Examples thereof include mineral powders such as hectorite and dry silica, and alumina sol. Examples of the antifreezing agent include propylene glycol. Examples of the preservative include p-hydroxybenzoic acid ester and salicylic acid derivative. Specific gravity regulators include water-soluble salts such as sodium sulfate and water-soluble fertilizers such as urea. Moreover, it can also be used as a powdery preparation by a technique such as spray drying.

  Some gel base materials used in the gel of the present invention are mainly composed of oligomers and monomers having unsaturated bonds that can be cured by light energy.

  Examples of the oligomer used as the gel substrate include polyester acrylate, epoxy acrylate, urethane acrylate, alkyd resin acrylate, and spiraline resin acrylate.

  Moreover, as a monomer, a monofunctional, bifunctional, and polyfunctional monomer can be used. For example, monofunctional monomers include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl. Acrylate, tetrahydrofurfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, and bifunctional monomers include hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol Propylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypentylate neopentylglycol Diacrylate, neopentyl glycol adipate diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, etc., and polyfunctional monomers include trimethylolpropane triacrylate, propionate dipentaerythritol triacrylate, propionate diacrylate. Pentaerythritol tetraacrylate, dipentaerythritol propacrylate, dipentaerythritol hexaacrylate, triacrylate of trimethylolpropane ethylene oxide adduct, triacrylate of trimethylolpropane ethylene oxide or propylene oxide adduct, 1,3-dioxane pen Hexaacrylate of pentanol acrylate, dipentaerythritol ε-caprolactone adduct And the like.

  The mixing ratio of the oligomer and the monomer is not particularly limited, but generally, when there are many oligomers, the viscosity in an uncured state increases, and bubbles are difficult to escape when filled into a container, resulting in poor workability. Moreover, the shrinkage rate at the time of hardening becomes large, and the gel base material is easily removed from the container.

Moreover, when there are many monomers, it will become too soft and the volatilization of the termite or (and) bark beetle repellent composition will become quick, and it will become hard to harden | cure.

  Therefore, the ratio of oligomer to monomer should be adjusted according to the type of oligomer and monomer, taking into account the fluidity of the uncured gel base material, workability, container material, shape, fragrance volatilization time, etc. . In general, it is appropriate that the ratio of oligomer: monomer is 5:95 to 70:30, more preferably about 10:90 to 50:50.

  In addition, a photopolymerization initiator or a photosensitizer is blended in the gel base material mainly composed of these oligomers and monomers so that they can be polymerized by light energy and gelled.

Examples of photopolymerization initiators or photosensitizers include benzyl dimethyl ketal, benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether, benzoin methyl ether, 1-phenyl 1,2-propanedione-2- (o- Ethoxycarbonyl) oxime, 2,2-dimethoxy-2-phenylacetophenone, hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, p-chlorobenzophenone, chloro Examples include thioxanthone, isopropylthioxanthone, 2-methylthioxanthone, triethanolamine, and diethylethanolamine.

  The blending amount of these photopolymerization initiators or photosensitizers is usually about 3% by weight with respect to the gel substrate.

  By carrying non-halogen monophenyl ether, which is a repellent active compound, in organic polymer fine particles, the effect can be sustained for a long time, and sustained-release repellent active fine particles can be obtained.

  In the present invention, in preparing an adhesive / pressure-sensitive adhesive or ink containing sustained-release repellent active organic polymer fine particles, the fine particles can be prevented from settling and used as a uniform particle dispersion.

  The fine particle dispersion at this time contains water or an organic solvent + an anti-settling agent in addition to the fine particles. Since the fine particle dispersion disperses fine particles carrying a repellent active compound having a high specific gravity in an organic solvent or an aqueous emulsion, it is highly desirable to use an anti-settling agent. As the anti-settling agent, proteins, polysaccharides, various synthetic resins, acrylic acid polymers, and inorganic substances can be used.

For example, as described in JP-A-53-84881, JP-A-53-84882, JP-A-60-28819, and JP-A-60-216838, microfilms using urea formaldehyde resin or melamine formaldehyde resin as a film material are used. As described in JP-A-61-40188, the radical weight of a monomer component consisting of an unsaturated double bond (for example, acrylonitrile, acrylamide, acrylate ester, N, N-methylenebisacrylamide as a cross-linking agent, etc.) Examples thereof include microcapsules using a combined material as a film material.
Examples of the hydrophobic organic solvent used in the present invention include aromatic hydrocarbons such as toluene and xylene, and hydrocarbons such as hexane, n-heptane and mineral spirit, and these solvents can be used alone or in combination. Some may be mixed with water.
The composition ratio of the microcapsule composition of the present invention is generally used in the range of 2 to 30 parts by weight of a hydrophobic substance (non-halogen monophenyl ether, etc.) and 30 to 100 parts by weight of an organic solvent in 100 parts by weight of the microcapsule. To do.

  The microcapsule composition of the present invention is obtained by mixing and dissolving a hydrophobic substance (non-halogen monophenyl ether) in a hydrophobic organic solvent, adding a microcapsule solution, and removing water from the system by azeotropic dehydration. .

  Printing inks and paints can be produced by using an adhesive, a protective material, a still as a buffer material, and the like as necessary in the microcapsule composition of the present invention.

Adhesives include natural resins and modified natural resins such as shellac, rosin, hydrogenated rosin, rosin ester, maleic acid modified rosin, etc., or synthetic resins such as petroleum resin, nitrified cotton, ethylene-malein Examples thereof include acid resins, styrene-maleic acid resins, modified alkyd resins, phenol resins, ethylene-vinyl acetate polymers, vinyl chloride vinyl acetate polymers, acrylic resins, and synthetic rubbers.
Stilts include cellulose powder, starch produced from raw materials such as wheat, corn, potato, sweet potato, tapioca, oxidized starch obtained from these and oxidizing agents, esterified starch represented by acetylated starch, etherified starch, aldehyde Examples thereof include starch derivatives such as starch, starch particles such as modified starch, stilts for preventing contamination such as particles of talc, calcium carbonate and polystyrene resin. In addition, if necessary, a pigment, a thickener, a wax, etc. may be added for the reason of improving ink / paint physical properties.

  Printing ink containing a microcapsule composition prepared by the above combination produces a partially coated printing paper by spot printing of microcapsules by a printing method such as flexographic printing, screen printing, and gravure printing. It becomes possible to do.

Method for producing organic fine particle dispersion (precipitating agent: acrylic acid polymer)
0.1 to 5.0 parts by weight, preferably 0.1 to 0.4 parts by weight of the acrylic polymer is mixed with 100 parts by weight of water or an organic solvent to prepare an antisettling solution (1). About 1.0 to 5.0 parts by weight, preferably 2.5 to 3.5 parts by weight of a surfactant as a solubilizing agent per non-halogen monophenyl ether and 1 part by weight of the repellent solution. Mix well to make the repellent solution (2).

  Add about 50-200 parts by weight of organic polymer fine particles to 100 parts by weight of the repellent liquid (2) in a vacuum high-speed stirrer, add 100 parts by weight of the repellent liquid and mix well, and reduce the pressure to about 10 torr. After 10 minutes, gently return to normal pressure. This operation is repeated 1 to 10 times to obtain repellent liquid (2) supported fine particles, MC (3) (that is, repellent active sustained-release organic polymer fine particles). The obtained MC (3) is gently added to the anti-settling agent solution (1) and mixed and dispersed well. Next, an appropriate amount of sodium hydroxide is added to adjust the pH to 6.5 to 7.5 to obtain a fine particle dispersion.

Production method of fine particle dispersion (anti-settling agent: protein)
About 0.1 to 15.0 parts by weight of sodium caseinate as an anti-settling agent with respect to the total weight of the fine particle dispersion, preferably about 1.0 to 7.0 parts by weight, more preferably about 3.0 to 5. Using 0 parts by weight, the anti-settling agent solution (1) is prepared in the same manner as described above to obtain a fine particle dispersion.

Manufacturing method of fine particle dispersion (Precipitating agent: Inorganic substance)
For example, about 0.1 to 15 parts by weight of bentonite as an anti-settling agent, preferably about 3.5 to 10.5 parts by weight, more preferably about 6.5 to 8.5 parts by weight with respect to the total weight of the fine particle dispersion. In the same manner as above, an anti-settling agent solution (1) is prepared to obtain a fine particle dispersion.

  In the present invention, in preparing an adhesive / pressure-sensitive adhesive or ink containing sustained-release repellent active inorganic fine particles, a uniform particle dispersion is used to prevent sedimentation of the sustained-release repellent active inorganic fine particles. Can do.

Production method of inorganic fine particle dispersion The inorganic fine particle dispersion contains water or an organic solvent and an anti-settling agent in addition to the inorganic porous fine particles. The fine particle dispersion disperses inorganic porous fine particles (for example, inorganic porous fine particles having true specific gravity of 2.1, which contains silica), which carry a repellent active compound having a high specific gravity in an organic solvent or an aqueous emulsion. is required. Proteins, polysaccharides, synthetic resins, acrylic acid polymers, and inorganic substances can be used as anti-settling agents. The repellent active compound is supported in the production process of inorganic porous fine particles (Japanese Examined Patent Publication No. 57-055554). In the method, for example, a repellent active compound is dispersed in an aqueous solution containing alkali metal silicate (compound A) such as sodium silicate and having a concentration of 0.3 mol / liter to saturation. Next, the solubility in water is preferably 5% or less. After mixing with an organic solvent in which a surfactant such as sorbitan monostearate is dissolved, for example, toluene, a W / O emulsion is obtained, and then water insoluble with Compound I Aqueous solution (concentration 0.05 mol / liter to saturated concentration, preferably 0.1 to 2 mol / liter) of an alkaline earth metal halide (compound B) such as calcium chloride capable of forming a precipitate (ie wall material) Is mixed with the above W / O type emulsion in a proportion of chemical equivalent or more with respect to the former with respect to 100 parts by weight of the former, and thus, porous fine particles of spherical inorganic wall containing the repellent active compound (repellent active compound) -Calcium silicate) is obtained.

  The compound B used in the production of the inorganic porous fine particles is water-soluble and does not adversely affect the repellent compound, and the compound that reacts with the compound A to form a water-insoluble precipitate depends on the type of the compound I. Is selected as follows. That is, when an alkali metal silicate such as sodium or potassium is used as compound I, (1) an alkaline earth metal halide such as calcium, barium or magnesium, such as chloride or bromide Can be used to obtain inorganic porous fine particles such as calcium silicate, barium silicate, magnesium silicate and the like. In addition, (2) inorganic porous fine particles of silica can be obtained using sulfuric acid, hydrochloric acid or the like.

  The combination of compound A and compound B can be reversed, and when compound I uses a halide of an alkaline earth metal such as calcium, barium or magnesium, such as chloride or bromide. As the compound II, alkali metal carbonates or bicarbonates such as sodium and potassium can be advantageously used. By these reactions, inorganic porous fine particles such as calcium carbonate, barium carbonate, and magnesium carbonate are obtained.

  Preferred are porous fine particles of silica (anhydrous silicic acid), calcium carbonate, barium carbonate, magnesium carbonate, more preferably silica, calcium silicate.

  As a second method, after the inorganic porous fine particles are first manufactured, the method of supporting the repellent compound is the method described above. First, after forming the inorganic porous fine particles without dispersing the repellent compound, the inorganic porous fine particles are formed. Non-halogenated monophenyl ether (1.0 kg) is added to fine particles (1.5 kg), mixed well, reduced to 10 torr, allowed to stand for 10 minutes, and then gently returned to normal pressure. As a result, non-halogen monophenyl ether-carrying inorganic porous fine particles can be obtained. This method can also be used for other inorganic porous fine particles such as talc, kaolin, activated clay, diatomaceous earth, perlite, bentonite and the like.

The inorganic porous fine particles have the following characteristics including hollow and non-hollow. That is, the particle size is 0.05 to 25 μm, the surface average pore diameter is 2 to 30 nm, the specific surface area is 10 to 1000 m ² / g, and the bulk density is 0.1 to 0.8 g / cm ³ . For hollow inorganic porous fine particles, liquid pest repellent or pest repellent dissolved or dispersed in a solvent can be encapsulated in 100 to 180 ml / 100 g. For non-hollow inorganic porous fine particles, The pest repellent dissolved or dispersed in 50 to 175 ml / 100 g can be impregnated.

  The acrylic acid polymer used as an anti-settling agent for the porous fine particles contained in the fine particle dispersion is also called polyacrylic acid, which is a polymer of two or more acrylic acids, and in particular, a cross-linked acrylic acid polymer is used. it can. Specific examples of the acrylic acid polymer are Junron series (PW-110, PW-150 (Nippon Pure Chemicals Co., Ltd.), Carbopol series (907, 910, Showa Denko Co., Ltd.)), etc. (See JP-A-9-77605) The content of the acrylic acid polymer in the drug dispersion is 0.0001 to 6% by weight, preferably 0.01 to 0.5% by weight. Is desirable.

  In order to neutralize the acrylic acid polymer with respect to the acrylic acid polymer, an alkali agent is added and mixed with the acrylic acid polymer to increase the viscosity to make it insoluble or sparingly soluble in water. Specific examples of the alkali salt include sodium hydroxide, potassium hydroxide, aqueous ammonia and morpholine (see JP-A-9-77605).

  The content of the alkali salt is an amount necessary for neutralizing the acrylic acid polymer and adjusting the pH to 5.0 to 9.0, preferably pH 6.5 to 7.5. Depending on the content of the type acrylic acid polymer, 0.0001 to 20% by weight, preferably 0.01 to 0.5% by weight, is desirable.

  As the protein as an anti-settling agent, water-soluble gelatin or the like is used, and examples include water-insoluble casein, casein sodium, and gluten. Polysaccharides can be used alone or derivatives thereof, including water-soluble gum arabic, gellan gum, xanthan gum, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, psyllium seed gum, and water-insoluble methyl cellulose. , Ethyl cellulose, cellulose acetate, curdlan and the like. Furthermore, water-soluble polyvinyl alcohol, polyvinyl pyrrolidone, etc. are used in a synthetic resin. 0.1-20.0, preferably 1.0-10.0, more preferably 3.0-8.0 is used with respect to 100 parts by weight of the fine particle dispersion.

  Examples of inorganic substances as anti-settling agents include kaolin, sericite, glazed clay, mica, synthetic mica, hydrophobized synthetic mica, bentonite, hydrophobized bentonite, and other clay minerals that coagulate card houses and card packs. Fine silica and ultrafine alumina can be mentioned. 0.1 to 20.0, preferably 5.0 to 12.0, more preferably 8.0 to 9.0 is used with respect to 100 parts by weight of the fine particle dispersion.

  Water or an organic solvent used in the fine particle dispersion and a mixture thereof are liquids that can disperse the sustained-release repellent active inorganic porous fine particles. As the organic solvent, alcohols, ethers such as diethyl ether, ketones such as acetone, etc. , Esters such as petroleum ether and ethyl acetate, and aromatics such as toluene can be used, but are not particularly limited.

  An appropriate amount of this fine particle dispersion is added to the constituents of the pressure-sensitive adhesive and applied to the tape base to obtain a repellent active compound-containing pressure-sensitive adhesive. In addition, an appropriate amount of the fine particle dispersion is added to the constituents of the ink / paint to make an ink / paint containing the repellent active composition.

  The fine particle dispersion of the present invention is added to a known or commonly used label (tack) or packaging tape, a solvent used for a tape such as a masking tape or an aqueous type adhesive, or an adhesive for a multilayer film. Use repellent active compound-containing adhesives and adhesives.

  The fine particle dispersion of the present invention can be added to a commonly used pressure-sensitive adhesive. The pressure-sensitive adhesive / adhesive usually used may contain natural rosin (pine ani) mainly composed of acrylic resin. The fine particle dispersion of the present invention is added to these known commonly used pressure-sensitive adhesives / adhesives in an amount of 0.01 to 30% by weight, more preferably 0.1 to 10% by weight, based on the total weight of the pressure-sensitive adhesives / adhesives. Most preferably, 3-5% by weight is added.

  The repellent active compound-containing pressure-sensitive adhesive / adhesive can be spread on a holding material usually used in this field, and includes the following, but is not limited thereto. Exhibitions on paper (quality paper, Miracote, art, recycled paper, foil, synthetic paper, thermal paper, Japanese paper), films (PP, PET, OPP, etc., for laminates / PET, OPP, etc.), synthetic paper, synthetic paper and foil It is made to hold and is manufactured as a sheet label (tack). It is spread and held on kraft paper / Japanese paper / synthetic paper, cloth / nonwoven fabric, film (PP / PET / OPP, etc.) and manufactured as packing tape and masking tape. In addition, the wound protective tape can be produced by spreading on cloth / nonwoven fabric, paper / synthetic paper / synthetic fiber paper, film or the like. As an adhesive, it can also be used for a synthetic film (such as hot melt bonding) and a multilayer film. Furthermore, water-dispersed adhesives (acrylic / synthetic rubber, etc.), α-cyanoacrylate adhesives (α-cyanoacrylate), and synthetic rubber adhesives (chloroprene / nitrile rubber / synthetic rubber / SBR) Latex, recycled rubber, etc.), vinyl acetate, ABS resin solvent adhesive (ABS, vinyl acetate, vinyl chloride / vinyl acetate, etc.), α-olefin resin wood adhesive (α-olefin, modified epoxy, etc.), copolymer resin Emulsion installation agent (ethylene / vinyl acetate / vinyl acetate resin emulsion wood adhesive (vinyl acetate), water-based polymer-isocyanate wood adhesive, phenol resin wood adhesive (phenol / phenol / melamine, etc.), resilcinol resin Wood adhesive (resylcinol / resylcinol / phenol, etc.), urea / melamine resin Used in plywood, etc. by blending with agents (Yurea / Melamine ・ Yurea ・ Yurea / Melamine / Phenol etc.) In manufacturing these products, repellent active composition can be released from the adhesive / adhesive agent. At least one surface of the holding material may be breathable.

  The normally used ink or (and) paint containing the fine particle dispersion of the present invention is not particularly limited as long as it is an ink or (and) paint usually used in this field. These inks and / or paints are mainly acrylic resin-based, and are solvent-based or water-based (emulsion). For example, water-based ink (emulsion type) used for flexo, pre-slot, gravure, silk, surface coating, etc., oil-based ink (solvent type) used for flexo, gravure, silk, offset, UV processing / surface coating, etc. There are paints. Furthermore, it can be added to a dispersant having a water repellent effect. Further, it may be an ink based on a protein or a vegetable ink based on a fatty oil such as soybean oil or (and) a paint.

  The fine particle dispersion of the present invention is added to these known and commonly used compositions in an amount of 0.01 to 30% by weight, more preferably 0.1 to 10% by weight, based on the total weight of the ink or (and) the paint. Most preferably, 3-5% by weight is added.

  The composition for insect repellent of the present invention acts extremely effectively against termites or (and) bark beetles and is an excellent insect repellent. It is almost odorless and easy to use.

Production of dispersion (A) Weight%
Vanillyl alcohol 3
Sodium polyacrylate 0.5
Purified water
100

Production of dispersion (B) Weight%
Ethyl vanillate 2
Sodium alginate 1
Polyoxyethylene sorbitan monolaurate 2
Sodium metaphosphate 2
Purified water
100
It carried out like the above by said composition.

Production of dispersion (C) Weight%
Ethoxyaniline 4
Methyl cellulose 1
Polyoxyethylene alkyl ether 1
Polyglycerin fatty acid ester 1
Potassium metaphosphate 1
Polyvinylpyrrolidone 3
Purified water
100
It carried out like the above by said composition.

Production of Dispersion (D) Weight%
Phenoxyacetic acid 5
Zinc pyrithione 5
Aromatic carboxylic acid dialkyl ester 25
Hydrophobic mica 10
Toluene appropriate amount
100

Production of dispersion (E) Weight%
Vanillin 5
Polyoxyethylene alkyl ether 1
Ethyl acetate appropriate amount
100

Method for producing repellent active adhesive 3% by weight of the dispersion prepared in Example 1 was added to the acrylic resin adhesive of 50% aqueous emulsion solution in the ratio of acrylic resin 95 and natural rosin (pine ani) 5; By mixing well, an insecticide repellent active adhesive for termites or (and) bark beetles was produced.

Method for producing repellent active adhesive 3% by weight of the dispersion prepared in Example 2 was added to the acrylic resin adhesive of 50% aqueous emulsion solution with a ratio of acrylic resin 95 and natural rosin (pine ani) 5; By mixing well, an insecticide repellent active adhesive for termites or (and) bark beetles was produced.

Method for producing repellent active adhesive 3% by weight of the dispersion prepared in Example 3 was added to the acrylic resin adhesive of 50% aqueous emulsion solution with a ratio of acrylic resin 95 and natural rosin (pine ani) 5; By mixing well, an insecticide repellent active adhesive for termites or (and) bark beetles was produced.

Method for producing repellent active adhesive 3% by weight of the dispersion prepared in Example 4 was added to the acrylic resin adhesive of 50% aqueous emulsion solution with a ratio of acrylic resin 95 and natural rosin (pine ani) 5; By mixing well, an insecticide repellent active adhesive for termites or (and) bark beetles was produced.

Method for producing repellent active adhesive 3% by weight of the dispersion prepared in Example 5 was added to the acrylic resin adhesive in a 50% aqueous emulsion solution with a ratio of acrylic resin 95 and natural rosin (pine ani) 5; By mixing well, an insecticide repellent active adhesive for termites or (and) bark beetles was produced.

Manufacture of repellent active water-based flexo ink
Pigment (red) 20
Acrylic resin (main component) 30
Water 49
Diethanolamine 1
A repellent active flexo ink was produced by adding 5% by weight or 10% by weight of the dispersion (A) produced in Example 1 to the aqueous flexo ink obtained by mixing the above components.

Manufacture of repellent active flexo clear ink
Acrylic resin (main component) 40
Water 60
A repellent active flexoclear ink was produced by adding 5% by weight or 10% by weight of the dispersion (B) produced in Example 2 to the aqueous flexoclear ink obtained by mixing the above components.

Manufacture of repellent active Prislo ink
Pigment (blue) 20
Acrylic resin (main component) 20
Ethylene glycol 20
Glycols 20
Humino alcohols 5
Ethyl alcohol 12
Other auxiliaries 3
A repellent active Prislo ink was produced by adding 5% by weight or 10% by weight of the dispersion (C) produced in Example 3 to the Prislo ink obtained by mixing the above components.

Manufacture of oil-based flexographic inks by weight
Pigment 20
Polyamide resin 15
Toluene 35
Methyl ethyl ketone 10
Isopropyl alcohol 20
A repellent active oil-based flexo ink was prepared by adding 5% by weight or 10% by weight of the dispersion (D) prepared in Example 4 to the oil-based flexo ink obtained by mixing the above components.

Production of UV ink for overprinting Weight%
Epoxy acrylate (oligomer) 50
1,6-hexanediol diacrylate 8
Trimethylolpropane triacrylate 30
2-Hydroxy-2-methylpropiophenone 6
2,2-Dimethoxy-2-phenylacetophenone 4
Wax 1
Diethanolamine 1
A repellent active oil-based flexographic ink was prepared by adding 5% by weight or 10% by weight of vanillyl alcohol to the dispersion (E) prepared in Example 5 to the UV ink for overprinting obtained by mixing the above components. .

Manufacture of repellent active paint Weight%
Vinegar-ethylene-acrylic resin (main component) 20
Aomori Hiba Oil 30
Water 50
A repellent active paint was prepared by adding 5% by weight or 10% by weight of ethylene glycol monophenyl ether to the above components.

Example 1 of production of fine particles
100 g of vanillyl alcohol was added to a mixed solution of 100 g of phenylxylylethane and 100 g of diisodecyl adipate and pulverized with a bead mill to obtain a suspension having a solid content concentration of about 31% by weight. To this, 25 g of Sumidur L-75 was added to 500 g of water containing 30 g of gum arabic and 20 g of ethylene glycol. K. The mixture was stirred at room temperature with an auto homomixer (a homogenizer manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain fine droplets. Next, by stirring at 60 ° C. for 24 hours, a slurry in which diniconazole suspended in a mixed liquid of phenylxylylethane and diisodecyl adipate was microencapsulated with a polyurethane film was obtained. To this slurry, 175 g of water containing 1 g of xanthan gum and 5 g of aluminum magnesium silicate was added to obtain a 10% by weight vanillyl alcohol capsule composition.

Fine particle production example 2
50 g of ethyl vanillate was added to 200 g of phenylxylylethane and pulverized with a bead mill to obtain a suspension having a solid concentration of about 19% by weight. To this, 10 g of Sumidur L-75 was added to 500 g of water containing 30 g of gum arabic and 20 g of ethylene glycol. K. The mixture was stirred at room temperature with an auto homomixer to obtain fine droplets. Next, by stirring at 60 ° C. for 24 hours, a slurry in which bromobutide suspended in phenylxylylethane was microencapsulated with a polyurethane film was obtained. To this slurry, 240 g of water containing 1 g of xanthan gum and 5 g of aluminum magnesium silicate was added to obtain a 5 wt% ethyl vanillate capsule composition.

Production Example 3 of Fine Particle
100 g of ethoxyaniline was added to a mixed solution of 100 g of phenylxylylethane and 100 g of diisodecyl adipate, and pulverized with a bead mill to obtain a suspension having a solid content concentration of about 31% by weight. To this, 25 g of Sumidur L-75 was added to 490 g of water containing 30 g of gum arabic. K. The mixture was stirred at room temperature with an auto homomixer to obtain fine droplets. Next, by stirring at 60 ° C. for 24 hours, a slurry was obtained in which diniconazole suspended in a mixed liquid of phenylxylylethane and diisodecyl adipate was microencapsulated with a polyurea film. To this slurry, 185 g of water containing 1 g of xanthan gum and 5 g of aluminum magnesium silicate was added to obtain a 10 wt% ethoxyaniline composition.

Production Example 4 of Fine Particle
100 g of phenoxyacetic acid was added to 200 g of diisodecyl adipate and finely pulverized with a bead mill to obtain a suspension having a solid concentration of about 30% by weight. To this, 25 g of Sumidur L-75 was added to 325 g of water containing 30 g of gum arabic and 20 g of ethylene glycol. K. The mixture was stirred at room temperature with an auto homomixer to obtain fine droplets. Next, by stirring at 60 ° C. for 24 hours, a slurry in which procymidone suspended in diisodecyl adipate was microencapsulated with a polyurethane film was obtained. To this slurry, 350 g of water containing 1 g of xanthan gum and 5 g of aluminum magnesium silicate was added to obtain a 10 wt% phenoxyacetic acid capsule composition.

Fine particle production example 5
100 g of vanillin was added to a mixed solution of 150 g of phenylxylylethane and 50 g of diisodecyl adipate and pulverized with a bead mill to obtain a suspension having a solid content concentration of about 32% by weight. To this, 50 g of Sumidur L-75 was added to 530 g of water containing 30 g of gum arabic and 30 g of ethylene glycol. K. The mixture was stirred at room temperature with an auto homomixer to obtain fine droplets. Next, by stirring at 60 ° C. for 24 hours, a slurry in which copaiba oil suspended in a mixed solution of phenylxylylethane and diisodecyl adipate was microencapsulated with a polyurethane film was obtained. To this slurry, 120 g of water containing 1 g of xanthan gum and 5 g of aluminum magnesium silicate was added to obtain a 10% by weight vanillin composition.

Fine particle production example 6
To a mixed solution of 100 g of phenylxylylethane and 100 g of diisodecyl adipate, 80 g of vanillin and 20 g of vanillyl butyl ether were added and pulverized with a bead mill to obtain a suspension having a solid content concentration of about 30% by weight. To this, 25 g of Sumidur L-75 was added to 500 g of water containing 15 g of polyvinyl alcohol and 20 g of ethylene glycol. K. The mixture was stirred at room temperature with an auto homomixer to obtain fine droplets. Next, by stirring at 60 ° C. for 24 hours, a slurry in which procymidone suspended in a mixed liquid of phenylxylylethane and diisodecyl adipate was microencapsulated with a polyurethane film was obtained. To this slurry, 175 g of water containing 1 g of xanthan gum and 5 g of aluminum magnesium silicate was added to obtain a 10% by weight vanillin and vanillyl butyl ether capsule composition.

Fine particle production example 7
120 parts of a 5% aqueous solution of acrylic acid, acrylonitrile, 2-acrylamido-2-methylpropanesulfonic acid copolymer was adjusted to 4.0 with 10% NaOH aqueous solution, and 50 parts of ethyl vanillin was added thereto, and emulsified with a homomixer. After that, 24 parts of a methylated methylolmelamine aqueous solution (80% by weight of non-volatiles) (Mitsui Toatsu Chemical “Euramin T-30”) was added, and the mixture was kept at 80 ° C. for 2 hours with stirring to produce microcapsules having an average particle size of 5.0 μ A liquid was obtained.

Fine particle production example 8
Trade name) 63 parts of methoxyphenol, 8.11 parts of Araldite 6060 (trade name) as epoxy resin, 0.97 parts of Versamine K-11 (trade name) as ketimine, and 399 of accelerator 399 (trade name) Mixed with 0.20 parts. This mixture was emulsified in 130 parts of a solution of 3% aqueous Tamol L / Vinol 523 (both trade names) (95: 5) as an emulsifier. The slurry was heated to 75 ° C. for 4 hours to produce microcapsules.
The obtained product confirmed that spherical microcapsules were formed by an electron microscope, and the average particle size was about 5 microns.

Fine particle production example 9
A microcapsule was produced in the same manner as in Example 1 except that 6.87 parts of Araldite 3336 (trade name) as epoxy resin and 2.20 parts of Versamine K-11 (trade name) as ketimine were used. Various tests were conducted in the same manner as in Example 1, and it was confirmed that spherical microcapsules were formed with an average particle diameter of about 6 microns.

Fine particle production example 10
After the temperature of an aqueous solution of 20 g of sodium hydroxide was raised to 80 ° C., 100 g of a styrene maleic anhydride copolymer (Script Set 520; manufactured by Monsanto) was added and mixed with stirring for 2 hours, and the pH of the styrene maleic anhydride copolymer was 5 Prepare a 5% by weight aqueous solution.

  In 150 g of the preparation solution, 200 g of a dispersion of 25 wt% methoxyaniline suspended silicon KF-96 is dispersed, and a styrene maleic anhydride copolymer hydrolyzate is adsorbed around the suspension.

In the solution obtained above, 9.9 g of melamine is dispersed and stirred well.
The solution obtained above was heated to 70 ° C., 25 wt% glutaraldehyde was divided into 5 portions, 25.7 g was added every 30 minutes, and methylolated melamine and styrene-maleic acid were mixed around the core material. The polymer is reacted to coat the core material.

Fine particle production example 11
An aqueous solution is prepared in the same manner as in [Example 26].

  In the solution obtained above, 12.8 g of melamine and 5.7 g of resorcin are dispersed / dissolved and stirred well.

  The solution obtained above was heated to 70 ° C., 25 wt% glutaraldehyde was divided into 3 portions, 27.2 g was added every 40 minutes, methylolated melamine and phenol resin around the core material, and The core material is coated by reacting the styrene maleic acid copolymer.

Fine particle production example 12
In a stirring and mixing container equipped with a heating device, 150 parts of a 3% aqueous solution of polyvinyl alcohol (trade name: PVA-117, manufactured by Kuraray Co., Ltd.) was added to obtain an aqueous medium for capsule production. Separately, 100 parts of vanillyl hexyl ether, 5 parts of polymethylene polyphenyl isocyanate (trade name: Millionate MR400, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-isocyanatoethyl-2,6-diisocyanate hexaate (trade name: T -100, manufactured by Toray Industries, Inc.) A solution obtained by dissolving 2 parts was used as a capsule core substance, and dispersed in the above-mentioned aqueous medium for capsule preparation at 10000 rpm for 1 minute using a TK homomixer.

  1 part of diethylenetriamine was added to this emulsified dispersion, and the mixture was stirred at room temperature for 30 minutes, and then the temperature of the system was raised to 70 ° C. and reacted for 3 hours while continuing stirring. The temperature was lowered to room temperature to prepare a microcapsule composed of a polyurea resin / polyurethane resin wall film having an average particle diameter of 5.7 μm and an average film thickness of 0.16 μm.

Fine particle production example 13
An oligomer, a monomer, a photopolymerization initiator, a non-halogen monophenyl ether, an ultraviolet absorber, a light stabilizer and a dye were blended according to Table 1. In addition, the substance of each compounding agent shown by Table 1 is as follows.

Oligomer A: Epoxy acrylate B: Polyester acrylate C: Urethane acrylate D: Alkyd resin acrylate
Monomer E: 2-ethylhexyl acrylate F: diethylene glycol diacrylate G: dipentaerythritol hexaacrylate
Photopolymerization initiator H: benzyl dimethyl ketal I: 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-2-phenylacetophenone UV absorber L: 2,4-dihydroxybenzophenone M: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole
Light stabilizer N: 4-hydroxy-2,2,6,6-tetramethylpiperidine O: di (2,2,6,6-tetramethylpiperidin-4-yl) -sebacic acid ester
Dye P: Anthraquinone dye (blue) (0.5% butanol solution) Q: Azo dye (red) (0.5% butanol solution)
After thoroughly mixing each substance shown in Table 1, it is filled to a transparent glass container with a diameter of 7 cm and a depth of 2 cm to a depth of 1 cm, and cured by irradiating with a high-pressure mercury lamp to obtain colored insect repellent fine particles. It was.

Preparation of sustained-release inorganic porous fine particles supporting ethoxyaniline Dissolve 15 g of ethoxyaniline with 5 g of polyoxyethylene (n = 9) higher alcohol nonionic surfactant (Leocor SC-90 manufactured by Lion Corporation). The mixture is mixed in 50 ml of a sodium silicate aqueous solution (5M), and emulsified for 3 minutes at a stirring speed of 10,000 rpm or more using a homogenizer or the like to form an O / W type (oil-in-water type) emulsion. This emulsion was mixed with 100 ml of toluene in which 5 g of sorbitan monooleate (Leodol SP-O10 manufactured by Kao Co., Ltd.) was dissolved, and emulsified for 5 minutes at a speed of 10,000 revolutions per minute using a homogenizer. An emulsion is formed. This emulsion is poured into a stirring 3 mol / liter ammonium sulfate aqueous solution, and stirring is continued for 1 hour to form silica containing ethoxyaniline. After silica formation, the reaction solution is filtered, 20 ml of water is added and filtered, and further 20 ml of ethanol is added and filtered to obtain 30 g of inorganic porous fine particles carrying ethoxyaniline.

Production of repellent active compound-supported sustained release inorganic porous fine particles by supporting ethoxyaniline on already prepared sustained release inorganic porous fine particles First, inorganic porous fine particles (Godball Silica B-6C, manufactured by Suzuki Oil & Fat Co., Ltd.) ) Set 100 g in the vacuum chamber, close the leak valve and the introduction valve and open the exhaust valve, and reduce the pressure in the vacuum chamber to 1.0 × 10 ⁻² torr. Next, the exhaust valve is closed to finish exhausting the vacuum chamber, and the introduction valve is opened. At this time, since the inside of the tank containing 100 g of ethoxyaniline is at atmospheric pressure, ethoxyaniline is introduced into the vacuum chamber due to the pressure difference. Since the void portion of the God Ball is also in a reduced pressure state due to the exhaust in the vacuum chamber, the repellent active compound introduced into the vacuum chamber penetrates into the void portion of the God Ball. Subsequently, the leak valve is opened to return the vacuum chamber to atmospheric pressure, and then the excess ethoxyaniline solution is separated by filtration or the like to obtain 200 g of inorganic porous fine particles enclosing ethoxyaniline.

Production of sustained-release organic porous microparticles carrying vanillyl methyl ether 0.2 part of vanillylmethyl with respect to 1 part of cyclodextrin (trade name; Dexy Pearl K-100, manufactured by Shimizu Minato Sugar Co., Ltd.) Ether was added, and another 1 part of water was added and stirred with a homogenizer for 30 minutes. Thereafter, hot air drying was performed at 60 ° C. for about 3 hours, and vanillyl methyl ether was included to obtain a repellent active compound-supported cyclodextrin.

Production of fine particle dispersion (F) Weight%
God Ball Silica Fine Particle 15
Sodium polyacrylate 0.5
Hinokitiol 5
Vanillyl butyl ether 15
Calcium propionate 3
Purified water
100

In 50 ml of sodium silicate aqueous solution (5M) in which 15 g of vanillyl butyl ether and 5 g of hinokitiol were dissolved in 5 g of polyoxyethylene (n = 9) higher alcohol nonionic surfactant (Leocol SC-90 Lion Co., Ltd.) And then emulsified with a homogenizer or the like at a stirring speed of 10,000 rpm or more for 3 minutes to form an O / W type (oil-in-water type) emulsion. This emulsion was dissolved in 5 g of sorbitan monooleate (Leodol SP-O10 manufactured by Kao Corporation), mixed with 100 ml of toluene, emulsified with a homogenizer at a speed of 10,000 revolutions per minute for 5 minutes, and O / W / O type An emulsion is formed. This emulsion is poured into a stirring 3 mol / liter ammonium sulfate aqueous solution, and stirring is continued for 1 hour to form silica containing vanillyl butyl ether. After the formation of silica, the reaction solution is filtered, 20 ml of water is added and filtered, and further 20 ml of ethanol is added and filtered to obtain 30 g of godball silica fine particles carrying vanillyl butyl ether.
Add silica fine particles containing the drug to purified water in which 0.5 g of sodium polyacrylate and 3.5 g of calcium propionate are dissolved in advance, and uniformly disperse using a homogenizer or propeller stirrer to obtain 100 g of a dispersion. .

Production of fine particle dispersion (G) Weight%
God Ball B-6C 20
Hiba oil extract 3
Ethyl phenyl ether 3
Zinc pyrithione 5
Aromatic carboxylic acid dialkyl ester 25
Hydrophobic mica 10
Toluene appropriate amount
100
First, 3 g of ethyl phenyl ether, 3 g of Hiba oil extract and 5 g of zinc pyrithione are encapsulated in 20 g of God Ball B-6C as follows. Silicic acid in which 3 g of ethyl phenyl ether, 3 g of Hiba oil extract, 5 g of zinc pyrithione and 5 g of polyoxyethylene (n = 9) higher alcohol-based nonionic surfactant (Leocor SC-90 Lion Co., Ltd.) were dissolved It is mixed in 67 ml of an aqueous sodium solution (5M) and emulsified for 3 minutes at a stirring speed of 10,000 rpm or more using a homogenizer or the like to form an O / W type (oil-in-water type) emulsion. This emulsion was mixed with 100 ml of toluene in which 5 g of sorbitan monooleate (Leodol SP-O10 manufactured by Kao Co., Ltd.) was dissolved, and emulsified for 5 minutes at a speed of 10,000 revolutions per minute using a homogenizer. An emulsion is formed. This emulsion is poured into a 3 mol / liter ammonium sulfate aqueous solution while stirring, and stirring is continued for 1 hour to form silica carrying ethylphenyl ether. After the formation of silica, the reaction solution is filtered, 20 ml of water is added and filtered, and further 20 ml of ethanol is added and filtered to obtain 56 g of inorganic porous fine particles carrying ethylphenyl ether.

  31 g of B-6C carrying a drug was added to 34 g of toluene in which 10 g of hydrophobized mica and 25 g of aromatic carboxylic acid dialkyl ester had been dispersed in advance, and the mixture was stirred for 30 minutes at 5000 rpm using a homogenizer, and 100 g of dispersion was obtained. Is obtained.

Production of fine particle dispersion (H) Weight%
God Ball B-25C 15
Carboxymethylcellulose 1
Hinokitiol 5
Ethylene glycol monophenyl ether 10
Calcium propionate 3
Purified water
100
It carried out like Example 34 using said composition. However, the pH was not adjusted.

Production of fine particle dispersion (I) Weight%
God Ball E-16C 15
Carboxymethylcellulose 1
Hinokitiol 5
1,2-dimethoxybenzene 10
Alkylphenol ethoxylate 1
Calcium propionate 3
Purified water
100
It carried out like Example 4 by said composition.

Production of fine particle dispersion (J) Weight%
Siricia 250 15
Carboxymethylcellulose 1
Hinokitiol 5
Ethoxyphenol 10
Methoxyphenol 3
Calcium propionate 3
Purified water
100
It carried out like Example 34 by said composition.

Production of fine particle dispersion (K) Weight%
Nipsil E220A 15
Carboxymethylcellulose 1
Hinokitiol 5
Vanillyl ethyl ether 10
Ethylene glycol monophenyl ether 5
Calcium propionate 3
Purified water
100
It carried out like Example 18 using said composition.

  3% by weight of the fine particle dispersion (B) obtained in Example 34 was added to the rubber-based adhesive and mixed well to prepare a sanitary pest repellent active adhesive.

Repellent active adhesive 3% by weight of the fine particle dispersion prepared in Example 33 was added to the acrylic resin adhesive of a 50% aqueous emulsion solution in a ratio of acrylic resin 95 and natural rosin (pine ani) 5. A hygienic pest repellent active adhesive was produced by mixing.

Repellent active adhesive 3% by weight of the fine particle dispersion prepared in Example 34 was added to the acrylic resin adhesive in a 50% aqueous emulsion solution with a ratio of acrylic resin 95 and natural rosin (Matsuyani) 5. A hygienic pest repellent active adhesive was produced by mixing.

Repellent active adhesive 3% by weight of the fine particle dispersion prepared in Example 35 was added to the acrylic resin adhesive in a 50% aqueous emulsion solution with a ratio of acrylic resin 95 and natural rosin (Matsuyani) 5. A hygienic pest repellent active adhesive was produced by mixing.

Repellent active adhesive 3% by weight of the fine particle dispersion prepared in Example 36 was added to the acrylic resin adhesive in a 50% aqueous emulsion solution with a ratio of acrylic resin 95 and natural rosin (pine ani) 5 A hygienic pest repellent active adhesive was produced by mixing.

Repellent active adhesive 3% by weight of the fine particle dispersion prepared in Example 37 was added to the acrylic resin adhesive in a 50% aqueous emulsion solution with a ratio of acrylic resin 95 and natural rosin (Matsuyani) 5. A hygienic pest repellent active adhesive was produced by mixing.

Repellent active adhesive 3% by weight of the fine particle dispersion prepared in Example 38 was added to the acrylic resin adhesive in a 50% aqueous emulsion solution with a ratio of acrylic resin 95 and natural rosin (pine ani) 5. A hygienic pest repellent active adhesive was produced by mixing.

Manufacture of repellent active aqueous flexo ink Pigment (red) 20
Acrylic resin (main component) 30
Water 49
Diethanolamine 1
A repellent active flexo ink was produced by adding 5% by weight or 10% by weight of the fine particle dispersion (F) produced in Example 33 to the aqueous flexo ink obtained by mixing the above components.

Manufacture of repellent active flexo clear ink
Acrylic resin (main component) 40
Water 60
A repellent active flexoclear ink was produced by adding 5% by weight or 10% by weight of the fine particle dispersion (G) produced in Example 34 to the aqueous flexoclear ink obtained by mixing the above components.

Manufacturing of Prislo ink Weight%
Pigment (blue) 20
Acrylic resin (main component) 20
Ethylene glycol 20
Glycols 20
Humino alcohols 5
Ethyl alcohol 12
Other auxiliaries 3
A repellent active Prislo ink was produced by adding 5% by weight or 10% by weight of the fine particle dispersion (H) produced in Example 35 to the Prislo ink obtained by mixing the above components.

Manufacture of oil-based flexographic inks by weight
Pigment 20
Polyamide resin 15
Toluene 35
Methyl ethyl ketone 10
Isopropyl alcohol 20
The repellent active oil-based flexo ink was prepared by adding 5% by weight or 10% by weight of the fine particle dispersion (I) prepared in Example 36 to the oil-based flexo ink obtained by mixing the above components.

<Manufacture of termite agent for xylem>
-Aomori Hiba Oil 6.0 parts-Hinokitiol 0.1 part-Vanillin 3.0 parts-Polyoxyethylene castor oil 2.0 parts-Silica microcapsule 5.0 parts-Purified water 83.9 parts The above ingredients were mixed to produce a termite-proof termite agent for xylem.
As Comparative Example 1, 3.0 parts of copaiba oil was added to the above components in place of vanillin to produce a termite-proofing agent for xylem containing no vanillin.

Comparative Example 1

<Manufacture of termite agent for xylem>
・ Aomori Hiba Oil 6.0 parts ・ Hinokitiol 0.1 part ・ Copaiba Oil 3.0 parts ・ Polyoxyethylene Castor Oil 2.0 parts ・ Silica Microcapsule 5.0 parts ・ Purified Water 83.9 parts

<Manufacture of termite agent for soil>
-Yoshino cypress oil 8.0 parts-Ethyl phenyl ether 1.0 part-Palm oil fatty acid sorbitan 2.0 parts-Silica microcapsule 4.0 parts-Purified water 85.0 parts The above ingredients were mixed to prepare a termite-proofing agent for soil.

<Manufacture of xylem insecticide for xylem>
・ Aomori Hiba Oil 5.0 parts ・ 1,2-Dimethoxybenzene 1.0 part ・ Sucrose fatty acid ester
(Myristic acid scroll) 2.0 parts ・ Silica microcapsule 5.0 parts ・ Purified water 87.0 parts The above ingredients were mixed to prepare a xylem insecticide for xylem.

Test example 1

Kibe synthesis test <(1) Test wood piece>
(B) Wood pieces to be used for the test are normal black pine or red pine sapwood with 10 annual rings.
(B) Wood pieces are dried for 24 hours in a constant temperature oven of 60 ± 2 ℃.
<(2) Specimen>
(B) The test specimens shall be two crops: a treated specimen obtained by treating a piece of wood with a specified concentration sample and an untreated specimen that is not treated with the sample. Furthermore, after the sample is treated, the treated specimens are divided into those that have been subjected to the weathering operation specified in (2) (d) below and those that are not.
(B) The number of test specimens shall be five for each of the treated specimen subjected to weathering operation, the treated specimen not subjected to weathering operation, and the untreated specimen.
(C) After applying a specified concentration sample at a rate of 110 ± 10 g / m ² using a brush on a piece of wood,
After standing at room temperature for 20 days or more, it is divided into 2 groups: 5 with and without weathering.
(D) The weathering operation repeats the wetting operation and the volatilization operation 10 times alternately.

  Wetting operation: After immersing the sample-treated wood pieces for weathering operation in room temperature at room temperature for 30 seconds. Place it in a desiccator with water on the bottom and leave it in a temperature-controlled room at 26 ± 2 ° C for 4 o'clock.

Volatilization operation: The sample-treated wood piece that has been wetted is immediately left in a circulating hot air incubator at a temperature of 40 ± 2 ° C for 20 hours.
(E) Sample treated wood pieces that were subjected to weathering operations, sample treated wood pieces that were not subjected to weathering operations, and untreated wood pieces were dried at a temperature of 60 ± 2 ° C for 48 hours and left in a desiccator for about 30 minutes. The mass (W1) is weighed to 0.01 g and used as a test specimen.
<(3) Rearing container>
As a breeding container, a piece of acrylic resin cylinder with a diameter of 8 cm and a length of 6 cm is used, which is made of hard gypsum hardened to a thickness of about 5 mm, and then wet cotton is scattered to a thickness of about 2 cm in advance. Place 10-15 pieces in a lidded container.

            Note (4) Add 130-150 ml of water to 100 g of absorbent cotton.

Note (5) Make a small hole in the lid for ventilation.
<(4) Rearing>
(Ii) Place the test specimens or untreated specimens one by one on the hard stone plaster in the breeding container made in the previous section, and place them one by one from the nest at random. Throw out 150 craft ants and 15 soldier ants.
(B) Keep the lidded container in a dark place at a temperature of 28 ± 2 ° C for 21 days.
The test results are calculated as follows.
(A) After 21 days, remove the specimen from the container, carefully remove the deposits on the specimen surface, dry at a temperature of 60 ± 2 ° C for 48 hours, leave it in a desiccator for about 30 minutes, and weigh to 0.01 g. To determine the mass (W2).
(B) Record the number of termite ants killed.
Moreover, it calculates with the following formulas.
Mass reduction rate (%) = (W1-W2) / W1 × 100
Mortality rate (%) = dead insect count / 150 x 100
Table 1 shows the results of the xylem comprehensive test using the samples prepared in Examples 1 to 16 and 33 to 50.

耐候操作あり、耐候操作なしのいずれの場合においても質量減少率は無処理試験体と比較して大幅に減少したことより、各試料は防蟻性に優れていることが判明した。一方、比較例１において、非ハロゲン系モノフェニルエーテルの代わりにコパイバ油を用いた防蟻剤については、重量減少率が比較的高かったことより、防蟻性が低いことが判明した。以上のことより、非ハロゲン系モノフェニルエーテルを含まない防蟻剤については、防蟻性が低いことが明らかとなった。

In both cases with and without weathering operation, the mass reduction rate was significantly reduced compared to the untreated specimen, indicating that each sample had excellent ant protection. On the other hand, in Comparative Example 1, it was found that the termite-proofing agent using copaiba oil instead of the non-halogenated monophenyl ether had a low rate of termite-proofing because the weight reduction rate was relatively high. From the above, it has been clarified that the termite-proofing agent containing no non-halogen monophenyl ether has a low termite-proofing property.

Test example 2

Soil treatment test <Test method>
・ The sandy loam that has passed through a 20-mesh sieve and dried to a constant weight at a temperature of 60 ± 2 ° C is treated as untreated dry soil.
・ Add 3.0 g of the sample to be tested to 12.0 g of untreated dry soil, mix well, and leave it in the room for 3 weeks.
・ The soil to be treated is divided into those with and without the weather resistance specified below.
・ Weather resistance operation is as follows.

Volatilization operation: The test soil is left in a 40 ± 2 ° C incubator for 4 weeks.
・ Add water until each unit of the test-treated soil without weathering operation and the test-treated soil with weathering operation reaches 15.0 g, and mix well.
・ Use untreated dry soil 12.0g and water 3.0g as test untreated soil.
・ The test container consists of two glass cylinders with an inner diameter of about 5 cm and a height of about 12 cm, and a glass tube with an inner diameter of about 1.5 cm and a length of about 10 cm at a location about 2 cm from the bottom (transparent part excluding the rubbing part at both ends) Are 5cm long and are graduated every 5mm).
・ About 60 g of untreated soil adjusted to a water content of about 25% is placed in one of the glass cylinders of a test container that has been previously sterilized by drying, and about 3 g of red pine fragments are placed on the other side. Fill the center transparent part of the glass tube with the test soil specified in (5) and (6), respectively, and connect it to the glass cylinder.
・ Put 200 termite ants and 20 soldier ants from the nest into a glass cylinder containing untreated soil.
・ Leave the test container in a temperature-controlled room at 28 ± 2 ℃ and humidity of 70% or more for 3 weeks.
・ Repeat the test 3 times for each test concentration.
<Result>
・ After 3 weeks, observe the progress of the clogging in the test soil for each test container, and obtain the degree of perforation of the test soil according to the following criteria.

  Perforation degree 0: No perforation in the test soil is observed.

Drilling degree 1: Drilling distance less than 1cm Drilling degree 2: Drilling distance less than 2cm Drilling degree 3: Drilling distance less than 3cm Drilling degree 4: Drilling distance less than 4cm Drilling degree 5: Drilling distance of 4cm or more ・ The total number of input termites is within the test period If deemed dead, record the time or days required.
Table 2 shows the results of the soil treatment test using the sample prepared in Example 51.

耐候操作あり、耐候操作なしのいずれの場合においても処理土壌については穿 孔が全く見られなかったことより、試料は防蟻性に優れていることが判明した。

In all cases with and without weathering operation, no holes were observed in the treated soil, indicating that the sample had excellent ant-proofing properties.

Test example 3

<Kibe insect repellent test>
Test method ・ From the larvae approximately 60 days after laying eggs, 60 healthy animals with a body length of 2 to 3 mm (body weight 3 to 5 mg) are selected as test insects. A 50 × 50 mm piece of wood is made from a 4 mm thick veneer with Lauan sapwood as a test piece. A nutrient solution (150 g of malt extract and 30 g of peptone dissolved in 820 ml of water) is injected into this piece of wood under reduced pressure. The injection amount is about 100% of the mass of the piece of wood. The wood pieces that have been injected with the nutrient solution are dried for about 24 hours at 40 to 50 ° C. with an air dryer to measure the mass to 0.01 g.
・ There are two types of specimens: treated specimens and untreated specimens.
・ Treat wood pieces under reduced pressure and weigh up to 0.01g. The injection amount is about 100% of the mass of the wood piece, and the absorption amount and absorption rate of the insect repellent are obtained from the following formula.

Insect repellent absorption (g) = (mass after injection-mass before injection) x concentration (%) x 1/100
Insecticide absorption rate (%) = insecticide absorption (g) / mass before injection (g) x 100
-After leaving the treated wood pieces for 14 days at room temperature, volatilize for 30 days in a 40 ° C incubator. Furthermore, a specimen to be treated for 7 days or more at 25 ° C. and a relative humidity of 70 to 75% is used as a treated specimen. The number of test specimens shall be 5 each.
・ Make three holes each with a diameter of 2 to 2.5 mm and a depth of 15 mm on both sides of the specimen.
・ Put one test insect into each hole, and after capping the glass, put 5 specimens in one breeding bottle and raise them at about 25 ℃ and relative humidity of 70-75%.
• After 21 days have passed since all specimens have been raised, observe with a soft X-ray device and continue until the adults have almost completely escaped from the untreated specimen.
・ After the observation is completed, the treated specimens are crushed to confirm the life and death of the test insects, and the average mortality rate is calculated according to the following formula. The results are shown in Table 3.

Average death rate (%) = total number of dead insects / 30 (total number of test insects) x 100
Table 3 shows the results of the xylem treatment test using the sample prepared in Example 52.

処理試験体中のヒラタキクイムシは全て死亡していたことより、試料は防キクイムシ性に優れていることが判明した。

Since all the larvae of the treated specimens had died, it was found that the sample was excellent in the resistance to bark beetles.

Test example 4

Cockroach repellent test of white ant agent A cockroach repellent test was conducted on the dispersion containing vanillin in Example 50 and the dispersion containing copaiba oil instead of vanillin.

Test Method A “sample paper” in the shape of a circle having a diameter of 10 cm is placed in a container having a diameter of 30 cm. About 0.1 g of each dispersion is applied to the sample paper. A plastic cylindrical container with an intrusion port covered with aluminum foil was placed over the sample. Thirty adult German cockroaches were released in the container, and left for 24 hours at room temperature of 25 degrees to examine the number of cockroaches on the paper. The control treatment group (where the sample paper was installed) and the control non-treatment group Calculate the (blank) repellent rate (%). The test is performed twice under the same conditions and the average of each is presented. Covering the plastic container utilizes the property that the cockroach prefers a dark place and therefore enters a light-shielded plastic container placed in a 30 cm diameter container left under bright conditions.
Table 4 shows the test results after 24 hours.

バニリンを含有している分散液のゴキブリに対する忌避活性は極めて低いことが分かった。以上の結果より、非ハロゲン系モノフェニルエーテルを含む分散液は白蟻、キクイムシ以外には忌避効果を有さない事が明らかとなった。

It was found that the dispersion containing vanillin has very low repellent activity against cockroaches. From the above results, it was revealed that the dispersion containing non-halogen monophenyl ether has no repellent effect other than white ants and bark beetles.

Claims (13)

  Termite and / or insect repellent composition containing non-halogen monophenyl ether   The non-halogen monophenyl ether is vanillin, ethyl vanillin, vanillin alkylene acetal vanillic acid, ethyl vanillate, vanillin propylene glycol acetal, vanillyl alcohol, vanillyl methyl ether, vanillyl ethyl ether, vanillyl propyl ether, vanillyl Butyl ether, Vanillyl amyl ether, Vanillyl isoamyl ether, Vanillyl hexyl ether, Vanillyl allyl ether, Vanillyl cyclopentyl ether, Vanillyl cyclohexyl ether, Vanillyl tetrahydrofuruhyl ether, Vanillyl 3-hydroxy-2-butyl ether, Vanillyl 4 -Hydroxy-1-butyl ether, vanillyl 3-hydroxy-1-propyl ether, vanillyl 3-hydroxy-1-butyl ether, vanillyl 2-hydroxy-1-propyl Ether, vanillylethoxyethyl ether, methoxyaniline, methoxyphenol, 2-methoxy-5-methylbenzeneamine, ethoxyphenol, ethoxyaniline, ethylphenyl ether, ethylene glycol monophenyl ether, phenoxyethyl acrylate, phenoxyacetic acid, 1, The termite or / and bark beetle composition according to claim 1, comprising at least one or more selected from the group of 2-dimethoxybenzene, alkylphenol ethoxylate, and 3,4-dimethoxybenzaldehyde. Organic polymer fine particles or (and) inorganic fine particles carrying the termite or (and) bark beetle insect repellent composition according to claim 1 or 2. A dispersion comprising the termite or (and) bark beetle insect repellent composition according to claim 1 or 2. A fine particle dispersion comprising organic polymer fine particles or (and) inorganic fine particles carrying the termite or (and) bark beetle insect repellent composition according to claim 3. A fine particle dispersion, wherein the fine particle dispersion further comprises an anti-settling agent. A termite or (and) bark beetle insect repellent active adhesive / pressure-sensitive adhesive comprising the termite or (and) bark beetle insect repellent composition according to claim 1 or 2. A termite or (and) insect repellent repellent active adhesive / pressure-sensitive adhesive comprising organic polymer fine particles or (and) inorganic fine particles carrying the termite or (and) bark beetle insect repellent composition according to claim 3. An insect repellent repellent active adhesive / adhesive for termites or (and) bark beetles, comprising the termite or (and) bark beetle insect repellent dispersion according to any one of claims 4 to 6. An adhesive / pressure-sensitive adhesive product using the adhesive / pressure-sensitive adhesive according to any one of claims 7 to 9. An insect repellent repellent active ink or paint for termites or (and) bark beetles comprising the termite or (and) bark beetle insect repellent composition according to claim 1 or (and). A termite or (and) bark beetle insect repellent active ink or paint comprising the organic polymer fine particles or (and) inorganic fine particles carrying the termite or (and) bark beetle insect repellent composition according to claim 3. An insect repellent repellent active ink or paint for termites or (and) bark beetles comprising the termite or (and) bark beetle insect repellent dispersion according to any one of claims 4 to 6.