JPH0471044B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an insect repellent composition. Conventional technology It has been known that boron compounds such as boric acid and borax have insect repellent activity, but these compounds (1) have almost no volatility, and also have no insect repellent effect due to digestive poisoning of insects. (2) It spreads and elutes due to the presence of moisture, and its insect repellent activity gradually expires during the period of use. (3) It does not cause chemical reactions when used in combination with other insect repellents. The problem is that it is easy to cause problems, and it has not been widely put into practical use to date. Means for Solving the Problems In view of the current situation, the present inventor has solved all of the above-mentioned drawbacks (1) to (3) of boron compounds, and is able to exhibit insect repellent activity semi-permanently in practice. As a result of intensive research aimed at developing a drug, it has been discovered that the following specific reaction product can achieve the intended purpose of the present invention. The present invention was completed based on this knowledge. That is, the present invention provides (a) general formula HO(-R ¹ O)- _o H () [wherein R ¹ is a C _1-4 alkylene group that may have a side chain, and n is 1-100] Indicates an integer. ], general formula [In the formula, R ² is a C _1-10 alkylene group that may have a side chain or Indicates the group. Here, R ³ and R ⁴ represent a hydrogen atom or an alkyl group. ] Dicarboxylic acid or general formula represented by [In the formula, R ¹ , R ² and n are the same as above. ] The present invention relates to an insect repellent composition containing a reaction product of the oxycarboxylic acid represented by the following and (b) boric acids as an active ingredient. The above used as an active ingredient in the present invention
The reaction product of component (a) and component (b) is, for example, Minoru Nagakura: Journal of the Coloring Materials Association, 53, 678 (1980), Keiji Iwata: Nikkan Kogyo Shimbun, Polyurethane Resin, 51 (1982),
In addition, they are known compounds as described in the Encyclopedia of Chemistry, the Dictionary of Physics and Chemistry, etc., and any of these can be used in the present invention. In component (a), the diols represented by the general formula () include methylene glycol and each polymethylene glycol with a molecular weight of about 3000 or less, ethylene glycol and each polyethylene glycol with a molecular weight of about 4400 or less, propylene glycol, and Examples include polypropylene glycols with a molecular weight of about 5,800 or less, butylene glycol, and polybutylene glycols with a molecular weight of about 7,200 or less.Specifically, dicarboxylic acids represented by the general formula () include methylene-1,
1-diimino-dicarboxylic acid, hexamethylene-
1,6-diiminodicarboxylic acid, decamethylene-1,10-diiminodicarboxylic acid, tolylene-
2,4-diimino-dicarboxylic acid, tolylene-
Examples include 2,6-diimino-dicarboxylic acid, m-xylylene-2,4-diimino-dicarboxylic acid, m-xylylene-2,6-diimino-dicarboxylic acid, and oxycarboxylic acids represented by the general formula () Specifically, polyethylene glycol mono(hexamethylene-1,6-diimino-dicarboxylic acid) ester, polyethylene glycol mono(tolylene-2,4-diimino-dicarboxylic acid) ester, polypropylene glycol mono(m- xylylene-2,4-diimino-dicarboxylic acid) ester, butylene glycol-mono(methylene-1,1-diimino-dicarboxylic acid) ester, polybutylene glycol-mono(decamethylene-1,10-diimino-dicarboxylic acid) ester, Examples include methylene glycol mono(methylene-1,1-diimino-dicarboxylic acid) ester. In addition, the boric acids that are component (b) include, for example, boric acid, alkali metal salts of boric acid such as sodium salts and potassium salts, and alkyl esters of boric acid such as methyl ester, ethyl ester, propyl ester, and butyl ester (specifically, Trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, etc.), aryl esters such as phenyl ester, tolyl ester, xylyl ester of boric acid (specifically triphenyl borate, diphenyl borate chloride, tritolyl borate, ditolyl borate, etc.) , trixyl borate, dixyl borate chloride), and the like. Here, the boric acid may be any of orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octaboric acid. The amount of the reaction product of component (a) and component (b) in the composition of the present invention is not particularly limited, but is usually 5 to 100% by weight (hereinafter simply referred to as "%"). , preferably 15 to 100%. Furthermore, in the present invention, the above reaction product and various conventionally known insect repellents can also be used together. In this case, the former has a residual effect (i.e., the property that the insect repellent effect spreads to multiple insects when other insects eat the secretions of the insect that has eaten the reaction product), persistence, etc. This is preferable because it brings out the advantages of the latter, such as rapid action and improved initial effect.
Conventionally known insect repellents are not particularly limited and include, for example, pyrethrin, allethrin, phthalthrin, resmethrin, permethrin, phenothrin, flamethrin, 1-ethynyl-2-methyl-
2-pentenyl-2,2-dimethyl-3-(2'-
Methyl-1'-propenyl)-cyclopropane-1
-carboxylate, 1-ethynyl-2-methyl-2-pentenyl-2,2-dimethyl-3-
(2'-methoxycarbonyl-1'-propenyl)-cyclopropane-1-carboxylate, 1-ethynyl-2-methyl-2-pentenyl-2,2,
3,3,-Tetramethylcyclopropane-1-carboxylate, 1-ethynyl-2-methyl-2
-pentenyl-2,2-dimethyl-3-(2',
Pyrethroids such as 2'-dichlorovinyl)-cyclopropane-1-carboxylate, dimethyl-
2,2-dichlorovinyl phosphate, 2-isopropyl-4-methylpyrimidyl-6-diethylthiophosphate, O,O-diethyl-O-(3
-methyl-4-nitrophenyl) thiophosphate, O,O-diethyl-O-(3-oxo-2-
Organophosphorus such as phenyl-2H-pyridazin-6-yl)phosphothionate, propoxal, 1-
In addition to carbamate series such as naphthyl-N-methyl-carbamate, naphthalene, camphor, p-dichlorobenzene, safrole, isosafrole, cinnamic aldehyde, anisaldehyde, thymol, 2-hydroxyethyloctylsulfide, 1-hexanoyl Examples include piperidine, 1-hexanoyl-3-pipecoline, di(polychloroalkyl) ether, and synergists such as piperonyl butoxide, propyl isoime, piperonal dimethyl acetal, and N,N-dimethyltoluamide. , N,N-diethyltoluamide, butyrylacetanilide, ethylhexanediol, butylhydroxyanisole, dioctyl phthalate, didodecyl phthalate and other repellents, benzoic acids, sorbic acids, α-bromosinamoaldehyde, parachloromethylenol, thiophanate , triazine, danicol, imidazole, sodium trichlorphenol, benzimidazole, tetrachloroisophthalonitrile,
Antibacterial agents and antifungal agents such as 2-methoxycarbonylaminobenzimidazole can also be used in combination. The ratio of the conventional insect repellent to the above reaction product is not particularly limited and can be appropriately selected within a wide range, but usually the latter is 1 to 1000 parts by weight (hereinafter simply referred to as "parts") of the former. parts, preferably 20 to 200 parts. Furthermore, the composition of the present invention may optionally include fragrances and deodorants such as linalool, geraniol, letral, citronellal, cinnamo alcohol, limonene, cineol, vanillin, lilyal, plant extracts, rosephenone, BHT, tocopherol, Antioxidants such as triphenyl phosphite, butylated hydroxyanisole, distearyl thiodipropionate, phenyl diisodecyl phosphite, benzotriazole, tolyltriazole, 3-methyl-5-pyrazolone, benzotriazole-1-carboxylic acid, etc. rust inhibitor, ammonium phosphate, tricresyl phosphate,
Flame retardants such as triethyl phosphate and tetrabromobisphenol A, dimensional stabilizers such as polyethylene glycol (PEG) of various molecular weights, polypropylene glycol (PPG), and polyvinyl alcohol,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-
Dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, phenyl salicylate, P-
tert-butylphenyl salicylate, 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-ethylhexyl-2-cyano-3,
UV absorbers such as 3'-diphenyl acrylate,
Acetone, toluene, xylene, methanol, ethanol, propanol, butanol, ethyl acetate, butyl acetate, dimethyl ether, diethyl ether, n-hexane, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, methylene chloride, trichloroethylene, methyl cellosolve, ethyl cellosolve, ethylene acetate Solvents such as glycol monomethyl ester, acetic acid ethylene glycol monoether ester, and butyl cellosolve, and dispersants such as various surfactants such as polyoxyethylene, sorbitan, alkylaryl ether, and alkyl phosphoric acid may be added as appropriate. can. The amount of these various drugs to be blended varies depending on the purpose of use, etc., and cannot be generalized, but for example, the composition of the present invention may contain 1 to 95% (preferably 10 to 70%) of repellent, antibacterial agent, or antibacterial agent. Rust agent 0.05~10%
(preferably 0.1-5%), fragrance/deodorant from 0.05% to
20% (preferably 0.1-5%), antioxidant 0.1
~20% (preferably 0.5~5%), rust preventive from 0.1~
30% (preferably 1-25%), flame retardant 1-90%
(preferably 10-80%), dimensional stabilizer 10-95%
(preferably 20-90%), UV absorber 0.05-20%
% (preferably 0.1 to 5%), a solvent of 1 to 99% (preferably 10 to 99%), and a dispersant of 0.1 to 60% (preferably 0.5 to 30%). Further, when a pyrethroid insect repellent is used in combination, a synergist may be used, and the amount thereof is preferably about 1 to 30 times that of the pyrethroid insect repellent. There are no particular restrictions on the method of using the composition of the present invention, and it can be used in any commonly used manner. For example, the composition of the present invention may be applied to raw wood, laminated wood, plywood, bamboo, rattan,
Wood materials such as fiberboard, particle board, and cork, fibrous materials such as paper, cloth, felt, and glass wool, and building materials such as gypsum board, asbestos board, and concrete board, etc., by means of coating, dipping, and impregnation. Methods of containing, adhesives, adhesives, paints,
Examples include a method of mixing it into synthetic resin raw materials, a method of spraying it on the ceiling of a house, building, under the floor, tatami mats, rugs, soil, etc., and a method of placing it on the furniture of a house. Effects of the invention The reaction product of component (a) and component (b), which are the active ingredients of the present invention, is fast-acting compared to conventional boron compounds, and is less likely to cause chemical reactions with other insect repellents. Therefore, they can be used together, and even in the presence of moisture, they do not diffuse into water or elute, and their insect repellent activity does not decrease even after long-term use. Above (a)
Among the components, the compound of the general formula () or the reaction product of the compound of the general formula () and the boric acid as the component (b) also has the following advantages. That is, when the reaction product is heated to an appropriate temperature, the boric acids are dissociated and the isocyanate groups are activated. Therefore, the reaction product and PEC, PPG, and other polyols are mixed and heated. A urethane resin can be formed by this, and at this time, the liberated boric acids can be uniformly dispersed and immobilized in the resin. Therefore, by impregnating a wood material etc. with the above reaction product and the above polyols and performing heat treatment, it is possible to impart the two advantages of dimensional stability and insect repellency to the wood material. Furthermore, since the water resistance of the compound is significantly increased, it can be made particularly suitable for use in materials used outdoors or in humid environments. That is, when polyethylene glycol, polypropylene glycol, polyvinyl alcohol, etc. are normally contained in a wood material as a dimensional stabilizer, the hygroscopicity causes so-called "wetting" or "staining" on the surface of the material, but the reaction of the present invention By using the product, these drawbacks can be overcome, and furthermore, it can exhibit the advantages of imparting insect repellency and immobilizing boron compounds. The composition of the present invention exhibits an insecticidal effect mainly due to digestive poisoning of insects, and in addition to insect-proofing the wood material itself against woodworms, etc., it can also be used to prevent insects on clothing when applied to storage furniture and household appliances, and to protect human and human animals such as mites. It is effective against all kinds of pests such as pest control.
In addition, the above-mentioned general insect repellents can be used in combination to impart volatility and fast-acting properties, as well as antibacterial agents, insect repellents,
By using flame retardants, dimensional stabilizers, etc. in combination, we can provide products suitable for each field of use. In the above points, the composition of the present invention is considered to have very excellent properties, and can be widely used in various industries in the future. Examples Examples will be given below to further clarify the present invention. The reaction products of the present invention used in the following examples are as follows. Compound A...O=B-O(-CH ₂ CH ₂ O-) ₂₅ B=O Compound B...O=B-O-CH ₂ O-B=O Compound C...O=B-O(- CH ₂ CH ₂ CH ₂ CH ₂ O―)
₈₀ B=O Example 1 Only 100 parts of Compound A was used. Example 2 100 parts of Compound A and 2 parts of Asurin were used. Example 3 Only 100 parts of Compound B was used. Example 4 100 parts of compound B and 2 parts of allethrin were used. Example 5 Only 100 parts of Compound C was used. Example 6 100 parts of compound C and 2 parts of allethrin were used. Comparative Example 1 Only 2 parts of allethrin was used. Comparative Example 2 Only 100 parts of metaboric acid was used. Test 1 The compositions of Examples 1 to 6 and Comparative Examples 1 to 2 were
The composition was applied to both sides of a plywood board measuring mm x 300 mm x 300 mm at a rate of 5 g/m ² . The composition was used in the form of an aqueous solution or dispersion, and the solvent was evaporated after application. Next, each of these plywood boards was placed in a breeding box housing 50 adult male and female German cockroaches, and left for 2 days. The 50% start-up time and the mortality rate after 24 and 48 hours were determined. Next, 5 pieces of plywood were coated with each of the above compositions.
Year-round indoors (annual average temperature 20℃, average humidity 70%)
RH) and conducted the same test again. The results are shown in Table 1.

[Table] Example 7 Adding compound D to lauan material (18mm x 70mm x 480mm)
It was impregnated at a rate of 0.06 g/cm ² . This impregnation is 20%
This was carried out using an aqueous solution by a pressurization method (pressurized immersion at a liquid temperature of 45° C. and 5 kgf/cm ² for 5 hours). The obtained lauan material was dried at 50°C, further heat-treated at 75°C for 4 hours, and then cured at room temperature to obtain a lauan-impregnated material. Example 8 A lauan-impregnated material was obtained in the same manner as in Example 7 except that Compound E was used. Example 9 A lauan-impregnated material was obtained in the same manner as in Example 7 except that Compound F was used. Example 10 A lauan-impregnated material was obtained in the same manner as in Example 7 except that Compound G was used. Comparative Example 3 A lauan-impregnated material was obtained in the same manner as in Example 7 except that boric acid was used for impregnation with a 10% aqueous solution. Test 2 25 lauan impregnated materials of Examples 7 to 10 and Comparative Example 3
The sample was immersed in cold water at ℃ for 24 hours, and the dissolution rate of the impregnating agent was measured. A similar test was also conducted on the same material that had been left outdoors for five years. Quantification was performed by measuring boron content. The results are shown in Table 2. Test 3 15 lauan impregnated materials of Examples 7 to 10 and Comparative Example 3
The dimensions were mm x 40 mm x 80 mm, and it was installed in a 16 cm diameter chamber. Twenty larvae of the Japanese yellow beetle were placed in this chamber, and the mortality rate was determined after 24 hours and 48 hours. A similar test was conducted on materials left outdoors for 5 years. The results are shown in Table 2.

[Table] Example 11 100 parts of Compound H and 600 parts of PPG (molecular weight 700) were mixed, placed in a mold with an internal volume of 10 mm x 300 mm x 300 mm, and heated to 80°C to form a resin. Example 12 100 parts of Compound I and 800 parts of PPG (molecular weight 700) were mixed, placed in a mold with an internal volume of 10 mm x 300 mm x 300 mm, and heated to 80°C to form a resin. Example 13 100 parts of Compound J and 440 parts of PPG (molecular weight 700) were mixed, placed in a mold with an internal volume of 10 mm x 300 mm x 300 mm, and heated to 80°C to form a resin. Example 14 100 parts of Compound K and 300 parts of PPG (molecular weight 700) were mixed, placed in a mold with an internal volume of 10 mm x 300 mm x 300 mm, and heated to 80°C to form a resin. Comparative Example 4 A resin was prepared in the same manner as in Example 11, except that hexamethylene diisocyanate was used instead of Compound H. Test 4 Samples of Examples 11 to 14 and Comparative Example 4 were 1 mm thick.
It was cut into discs with a diameter of 11 cm, and each disc was placed in a chalet with an inner diameter of 11 cm. Add about 1 g of breeding powder (a mixture of wood flour and wheat flour, adjusted in advance so that there are about 100 woolly mites/g) inhabited by woolly mites in this sialet,
The number of dead insects was counted using a microscope after 24 and 48 hours. The results are shown in Table 3.

[Table] Example 15 Compound L 15 parts, PEG (molecular weight 2000) 85 parts and α
- A mixture of 0.1 part of bromosinamaldehyde was impregnated into paulownia laminated wood (7 mm x 450 mm x 1200 mm) at a rate of 0.04 g/cm ³ , dried at 50°C, and then heated to 80°C for 4 hours.
A paulownia impregnated material was obtained by heat treatment for a period of time. Comparative Example 5 A paulownia impregnated material was obtained in the same manner as in Example 15, except that PPG (molecular weight 700) was used instead of Compound L. Comparative Example 6 100 parts of boric acid and 0.1 part of α-bromosinamaldehyde
A paulownia impregnated material was obtained in the same manner as in Example 15 using a mixture of 1. Test 5 Each paulownia impregnated material of Example 15 and Comparative Examples 5 to 6 was 6 mm
The dimensions are 420mm x 1150mm, (45℃98%RH for 4 days,
The material was subjected to a dry/wet cycle test (45°C, 30% RH, 3 days)/cycle, and the amount of dimensional change was measured. The results are shown in Table 4.

[Table] Test 6 Each paulownia impregnated material of Example 15 and Comparative Examples 5 to 6 was
Each specimen had dimensions of 150 mm x 300 mm, and was placed in a breeding box containing 50 termites and left for 2 days. Table 5 shows the results of determining the insect mortality rates after 24 and 48 hours. In addition, each paulownia impregnated material was measured at the annual average room temperature.
A similar test was conducted on samples that had been left indoors at 20°C and 70% RH for 5 years.

【table】

Claims (1)

[Claims] 1 (a) General formula HO (-R ¹ O) - _o H () [In the formula, R ¹ is a C _1-4 alkylene group that may have a side chain, and n is 1-100 indicates an integer. ], general formula [In the formula, R ² is a C _1-10 alkylene group that may have a side chain or Indicates the group. Here, R ³ and R ⁴ represent a hydrogen atom or an alkyl group. ] Dicarboxylic acid or general formula represented by [In the formula, R ¹ , R ² and n are the same as above. ] An insect repellent composition comprising a reaction product of an oxycarboxylic acid represented by the following and (b) boric acids as an active ingredient. 2. The composition according to claim 1, wherein the boric acid is boric acid, an alkali metal salt of boric acid, an alkyl ester of boric acid, or an aryl ester of boric acid. 3 Claim 2 in which the boric acid is orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, or octaboric acid
Compositions as described in Section.