JP4405765B2 - Indoor acaricide - Google Patents

Description

  The present invention relates to an acaricide for indoor mites.

As a method for controlling ticks, the most common method is to use an insect repellent. However, in recent years, safety problems of drugs that have been used as insect repellents have been particularly pointed out, and those with less toxicity are required.
As compounds for controlling mites other than insect repellents, it is known that alkyl esters of aliphatic or aromatic carboxylic acids have mite repellent activity (see Patent Documents 1 and 2). In addition, among aliphatic dibasic acid dialkyl esters, dialkyl esters of dibasic acids having 4 to 8 carbon atoms are reported to be excellent as mite repellents for textile products and mite-preventing agents for resin kneading agents. (See Patent Documents 3 and 4).

JP-A-4-108171 JP-A-6-25971 JP-A-8-92010 Japanese Patent Laid-Open No. 9-3241

  However, in particular, regarding the compounds described in Patent Documents 3 and 4, there is no mention of the difference in the mite control effect depending on the carbon number of the alkyl group. Further, in the examples, although mite control effects on di-n-octyl adipate, di-n-butyl sebacate, and di-2-ethylhexyl azelate have been confirmed, the alkyl group of each of the above compounds Confirmation of the mite control effect using a compound having a different carbon number is not performed, and the results are not shown.

  On the other hand, in recent years, the use of organic solvent-based preparations has a tendency to be restricted due to environmental problems and the like, and especially during fiber processing, the organic solvent is volatilized by heating. There is a need for an aqueous agent that uses water instead of a solvent. Further, among these aqueous preparations, there is a need for a preparation having a low skin irritation and a surfactant having a low skin irritation.

  Accordingly, the object of the present invention is to provide an indoor mite control agent containing a drug having low toxicity and a tick control property, and it is particularly preferable that the amount of skin irritation is low and the amount used is reduced. An object of the present invention is to provide an indoor mite control agent containing a drug having a low toxicity and a tick control property, which can be used as an aqueous agent together with a surface active agent.

This invention solved the said subject by using the indoor mite control agent which contains diethyl sebacate and / or diisopropyl sebacate as an active ingredient.
The indoor mite control agent may contain the active ingredient and the polyoxyethylene addition type nonionic surfactant, and the water content may be 50% by weight or more.
Furthermore, the mixing ratio (weight ratio) of the above active ingredient and the surfactant may be 2.0 or less in terms of surfactant / active ingredient.

  According to this invention, since a predetermined chemical | medical agent is used, the indoor mite control agent containing the chemical | medical agent with low toxicity and a tick control property can be provided.

  In addition, since a predetermined chemical is used, it is difficult to volatilize even when exposed to high temperatures, so that a tick control effect can be maintained even after high temperature treatment such as drying and resin kneading.

  In addition, by using a predetermined surfactant in combination, it can be used as an aqueous agent, and the water content can be increased, and the amount of surfactant used with respect to the amount of the predetermined agent used is suppressed. can do. Thereby, skin irritation can be further reduced and it can be used as an aqueous agent with less stickiness.

The present invention will be described in more detail.
The indoor mite control agent concerning this invention is a chemical | medical agent containing diethyl sebacate and / or diisopropyl sebacate as an active ingredient.

  As an active ingredient of a tick control drug, since diethyl sebacate and diisopropyl sebacate are used, toxicity is low, and as shown in the examples described later, compared to dimethyl sebacate and dibutyl sebacate, tick repellent effect, Tick control effect such as acaricidal effect was high.

  Moreover, as said active ingredient, when exposed to high temperature of 150 degreeC, it is preferable to hold the repellent rate by a tick repellent test 80% or more compared with the repellent rate before making it high temperature, and hold 85% or more. Is more preferable. If it is less than 80%, a large amount of active ingredient is volatilized when exposed to a high temperature, for example, when kneaded into a molten resin at about 200 to 300 ° C., so that the mite control effect by resin kneading tends to be greatly reduced. .

  In the case of using an aqueous medium such as water or a mixed solvent of water and a water-soluble organic solvent as a medium for the indoor mite control agent, a surfactant is used to disperse the active ingredient. Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.

  Examples of the anionic surfactant include fatty acid soaps, polyoxyethylene (hereinafter abbreviated as “POE”) carboxylates such as alkyl ether carboxylates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and sulfosuccinic acids. Examples thereof include salts, sulfonates such as POE alkylsulfosuccinic acid, sulfates such as alkyl sulfates and POE alkyl allyl ether sulfates, and phosphate esters such as POE alkyl allyl ether phosphates.

Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, and benzalkonium chloride salts.
Examples of the zwitterionic surfactant include carboxybetaine.

  Examples of the nonionic surfactant include POE alkyl ether, POE alkyl polycyclic ether, POE polycyclic phenyl ether, POE addition type ethers such as POE lanolin derivative, POE glycerin fatty acid ester, POE castor oil ether, POE hydrogenated castor oil POE addition type ester ethers such as ether and POE sorbitan fatty acid ester, esters such as POE fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, and sucrose fatty acid ester.

Among these, POE addition type non-ion as a surfactant having high emulsification stability with a small amount of surfactant, less skin irritation, and excellent safety with respect to the active ingredient of the above-mentioned mite control agent. A surfactant is preferred. Further, among these POE addition type nonionic surfactants, POE polycyclic phenyl ether, POE castor oil ether, POE hydrogenated castor oil ether, POE sorbitan fatty acid ester and the like are particularly preferable.
The above surfactants, particularly POE addition type nonionic surfactants, may be used alone or in combination of two or more.

  The addition amount of the surfactant, particularly the POE addition type nonionic surfactant, to the active ingredient of the above-mentioned tick-controlling agent is the surfactant / weight ratio of the active ingredient and the surfactant. The active ingredient is preferably 2.0 or less, and preferably 0.6 or less. When the mixing ratio exceeds 2.0, the solubilizing power of the active ingredient is increased and the stability of the preparation is increased. However, the compound is covered with a surfactant and the efficacy is reduced, and skin irritation occurs. It tends to be sticky after spraying and tends to adhere to dirt. Further, the lower limit of the mixing ratio is preferably 0.1, and preferably 0.2. If it is less than 0.1, the active ingredient is separated, the dispersibility is lowered, and the preparation stability tends to deteriorate.

  When using an aqueous medium such as water or a mixed solvent of water and a water-soluble organic solvent as a medium for the indoor mite control agent, that is, when the obtained indoor mite control agent is an aqueous agent, The water content is preferably 50% by weight or more, and preferably 80% by weight or more. If it is less than 50% by weight, the ratio of the organic solvent is increased, which may cause stickiness and may be unfavorable for health.

  In the indoor mite control agent according to the present invention, if necessary, in addition to the above active ingredients and surfactants, solvents, fragrances, coloring agents, preservatives, other acaricides, insecticides, water-soluble A polymer or the like may be added. For example, when the solvent is added, the dispersibility of the active ingredient may increase.

  Examples of the solvent include ethanol, phenoxyethanol, propylene glycol, 1,3-butylene glycol, sorbitol and the like.

  As the indoor mite control agent according to the present invention, a dispersion liquid (hereinafter simply referred to as “liquid preparation”) composed of the above-mentioned active ingredients, surfactants and other additives may be used as an emulsion as it is. Alternatively, it may be mixed with a solid carrier, liquid carrier, gaseous carrier, film-forming agent, or other formulation adjuvants, and formulated into an emulsion, powder, granule, oil, aerosol or the like. Handling becomes easy by formulating.

  The content ratio of the active ingredient in the liquid preparation or the preparation is preferably 0.1 to 20% by weight, and preferably 1 to 10% by weight. When the amount is less than 0.1% by weight, it tends to be difficult to sufficiently exert the mite control effect. On the other hand, when it is more than 20% by weight, the amount of the drug is increased, the cost is increased, and stickiness is caused. In addition, when the amount of liquid preparation or preparation used is small, it is difficult to perform uniform application or the like, resulting in unevenness of the active ingredient, and the efficacy tends to vary.

  The solid carrier is not particularly limited, and examples thereof include bentonite, diatomaceous earth, and zeolite. Examples of the liquid carrier include water, ethanol, isopropanol, ethylene glycol, carbon tetrachloride and the like. Furthermore, examples of the gaseous carrier include liquefied natural gas (LPG) and dimethyl ether.

  The method of using the above liquid preparation or preparation is not particularly limited, and in the case of general household use, it can be used after being sprayed. Moreover, when impregnating a fiber and using it for fibers, it can be used by directly spraying the above liquid preparation or liquid preparation of the preparation onto the fiber, or impregnating it in a tank and then drying it. Examples of the drying conditions include a method of air drying at room temperature, a method of drying by heating with a dryer or the like. When heating, the conditions are preferably about 110 to 150 ° C. and about 3 to 6 minutes. When the temperature is lower than 110 ° C., drying takes time, and production efficiency tends to decrease. On the other hand, when it is higher than 150 ° C., volatilization due to entrainment with the heat of the drug and the solvent vapor increases, which causes a decrease in efficacy.

In the above case, the spray amount or impregnation amount of the active ingredient, 0.01 to 0.5 g / ^{m 3} C., is 0.03 to 0.3 g / ^{m 3} preferred. If it is less than 0.01 g / m ³ , sufficient mite control ability may not be exhibited. On the other hand, although it may be more than 0.5 g / m ³ , 0.5 g / m ³ is sufficient for the amount of the active ingredient used because the mite control ability is hardly improved.

  Furthermore, examples of usage of the above active ingredients, liquid preparations, preparations and the like include kneading methods in which the above active ingredients, liquid preparations, preparations and the like are kneaded into a resin. Examples of this resin include polyolefin resins such as polyethylene and polypropylene, styrene resins such as polystyrene resins and ABS resins, polyvinyl resins such as vinyl acetate, vinyl chloride, and methyl methacrylate, polyamide resins, polyester resins, and polyether resins. And thermoplastic resins such as polycarbonate resin and polyurethane resin. Among these, polyester resins, polyamide resins, polyolefin resins and the like are preferable.

  Specific examples of what can be obtained by this kneading method include films, fiber products, synthetic resin cotton, and molded products.

  When the kneading method is employed, the kneading amount of the active ingredient to the resin is preferably 2% by weight or less, and more preferably 1% by weight or less. Although it may be more than 2% by weight, 2% by weight is sufficient for the amount of the active ingredient used because it is difficult to improve mite control ability. On the other hand, the lower limit of the kneading amount is preferably 0.01% by weight, more preferably 0.1% by weight. If it is less than 0.01% by weight, sufficient mite control ability may not be exhibited.

  When spraying the above liquid preparations or preparations, impregnating fibers, or kneading into resins, antibacterial agents, fungicides and other insecticides, antioxidants, UV absorbers, dispersion An agent, lubricant, deodorant and the like can be used in combination.

Hereinafter, the present invention will be described in more detail with reference to examples. First, the evaluation method will be described.
<Tick repellent test>
The tick repellent test was evaluated by the invasion prevention method (designated by the Mite Prevention Products Association). That is, the drug-impregnated cloth prepared in each of the following experimental examples and comparative examples was laid in a petri dish, and food was placed in the center. Then, 1100 ticks (yander leopard mite) were placed around the petri dish, and the number of ticks reaching the food in the center of the petri dish was counted.
The number of mites that reach the food in the center of the petri dish when using a cloth that has not been sprayed with the prescribed drug is a, and the number of mites that reach the food in the center of the petri dish when the cloth impregnated with the drug is b. The repelling rate was calculated from the following formula.
Repelling rate (%) = (a−b) / a × 100
When this repelling rate is 50% or more, the invasion prevention method (designated method of anti-tick processing product council) stipulates that it has an excellent repelling effect.

<Micidal test>
The miticide effect was evaluated by the forced filter paper contact method (clip method). Specifically, the filter paper impregnated with a 5 × 10 cm drug is folded in half, and 10 ticks (yake leopard mites) are placed and 3 sides are clipped. After 72 hours, the number of mite deaths was counted, and the tick kill rate was calculated.

<Stability test>
After the preparation solutions prepared in each experimental example and comparative example were manufactured, they were left for one day, and the liquid separation state was visually observed. The results were evaluated according to the following criteria.
○: Emulsification was stable.
X: Layer separation occurred.

(Experimental example 1)
Diethyl sebacate was dissolved in acetone, sprayed uniformly onto 100% cotton cloth (gold width 100 g / m ² ) so as to be 40 mg / m ^2, and air-dried at room temperature for 3 hours to prepare a drug-impregnated cloth. The tick repellency test was conducted using this drug-impregnated cloth. The results are shown in Table 1.

(Experimental example 2)
A tick repellency test was conducted in the same manner as in Experimental Example 1 except that diisopropyl sebacate was used instead of diethyl sebacate. The results are shown in Table 1.

(Comparative Example 1)
A tick repellency test was conducted in the same manner as in Experimental Example 1 except that dimethyl sebacate was used instead of diethyl sebacate. The results are shown in Table 1.

(Comparative Example 2)
A tick repellency test was conducted in the same manner as in Experimental Example 1 except that dibutyl sebacate was used instead of diethyl sebacate. The results are shown in Table 1.

(Experimental example 3)
Diethyl sebacate was dissolved in acetone, sprayed uniformly on 100% cotton cloth (gold width 100 g / m ² ) so as to be 80 mg / m ^2, and air-dried at room temperature for 6 hours. And it was made to dry for 5 minutes or 15 minutes at 150 degreeC, and the chemical | medical agent impregnation cloth was produced. The tick repellency test was conducted using this drug-impregnated cloth. The results are shown in Table 2.

(Experimental example 4)
A tick repellency test was conducted in the same manner as in Experimental Example 3 except that diisopropyl sebacate was used instead of diethyl sebacate. The results are shown in Table 2.

(Comparative Example 3)
A tick repellency test was conducted in the same manner as in Experimental Example 3 except that dimethyl sebacate was used instead of diethyl sebacate. The results are shown in Table 2.

(Comparative Example 4)
A tick repellency test was conducted in the same manner as in Experimental Example 3 except that dibutyl sebacate was used instead of diethyl sebacate. The results are shown in Table 2.

(Experimental example 5)
To a polypropylene resin (Sumitomo Mitsui Polyolefin Co., Ltd .: Grade J105-P), diethyl sebacate was added in an amount of 0.1% by weight or 0.5% by weight, kneaded at 220 ° C., and an extruder. Thus, a film having a thickness of 0.5 mm was produced. The above-mentioned mite repellent test was conducted using this film. The results are shown in Table 3.

(Experimental example 6)
A tick repellency test was conducted in the same manner as in Experimental Example 5 except that diisopropyl sebacate was used instead of diethyl sebacate. The results are shown in Table 3.

(Comparative Example 5)
A tick repellency test was conducted in the same manner as in Experimental Example 5 except that dimethyl sebacate was used instead of diethyl sebacate. The results are shown in Table 3.

(Comparative Example 6)
A tick repellent test was conducted in the same manner as in Experimental Example 5 except that dibutyl sebacate was used instead of diethyl sebacate. The results are shown in Table 3.

(Experimental example 7)
Diethyl sebacate was dissolved in acetone, spray-coated uniformly on a filter paper (5 × 10 cm) to 200 mg / m ^2, and air-dried at room temperature for 3 hours. And the said mite killing test was done using this. The results are shown in Table 4.

(Experimental example 8)
An acaricidal test was conducted in the same manner as in Experimental Example 7 except that diisopropyl sebacate was used instead of diethyl sebacate. The results are shown in Table 4.

(Comparative Example 7)
An acaricidal test was conducted in the same manner as in Experimental Example 7, except that dimethyl sebacate was used instead of diethyl sebacate. The results are shown in Table 4.

(Comparative Example 8)
An acaricidal test was conducted in the same manner as in Experimental Example 7 except that dibutyl sebacate was used instead of diethyl sebacate. The results are shown in Table 4.

(Experimental example 9)
7 g of POE hydrogenated castor oil ether (manufactured by Nippon Emulsifier Co., Ltd .: trade name TP9511, ethylene oxide 20 mol / liter added) is dissolved and stirred with 5 g of diethyl sebacate at 40 ° C., and then 88 g of ion-exchanged water is added and stirred. Thus, a preparation solution was obtained. And the stability test was done using this formulation solution.
In addition, the obtained preparation solution was uniformly spray-coated on 100% cotton cloth (gold width 100 g / m ² ) so that the amount of the active ingredient was 80 mg / m ² and air-dried at room temperature for 6 hours. The mite repellency test was conducted. The results are shown in Table 5.

(Experimental example 10)
A stability test and a tick repellency test were conducted in the same manner as in Experimental Example 9 except that POE polycyclic phenyl ether (manufactured by Nippon Emulsifier Co., Ltd .: trade name New Coal 2607) was used instead of POE hydrogenated castor oil ether. It was. The results are shown in Table 5.

(Experimental example 11)
A stability test and a tick repellency test were performed in the same manner as in Experimental Example 9 except that diisopropyl sebacate was used instead of diethyl sebacate. The results are shown in Table 5.

(Experimental example 12)
A stability test and a tick repellency test were conducted in the same manner as in Experimental Example 9 except that sorbitan oleate (manufactured by Nippon Emulsifier Co., Ltd .: trade name New Coal 80) was used instead of POE hydrogenated castor oil ether. The results are shown in Table 5.

(Experimental example 13)
A stability test and a tick repellent test were performed in the same manner as in Experimental Example 9 except that sucrose laurate (trade name: LWA1695 manufactured by Mitsubishi Chemical Foods Co., Ltd.) was used instead of POE hydrogenated castor oil ether. The results are shown in Table 5.

(Experimental example 14)
A stability test and a tick repellent test were performed in the same manner as in Experimental Example 9 except that polyglycerin stearate (manufactured by Mitsubishi Chemical Foods, Inc .: trade name DS13W) was used instead of POE hydrogenated castor oil ether. . The results are shown in Table 5.

(Experimental example 15)
A stability test and a tick repellent test were conducted in the same manner as in Experimental Example 9 except that a dialkyl succinate sulfonic acid sodium salt (manufactured by Nippon Emulsifier Co., Ltd .: trade name New Coal 291PG) was used instead of POE hydrogenated castor oil ether. Went. The results are shown in Table 5.

[Results of Example 5]
Experimental Examples 9 to 15 all had a sufficient mite repellent rate, but in Experimental Examples 12 to 15, the stability test was poor and layer separation occurred.

Claims (3)

  An indoor mite control agent containing diethyl sebacate and / or diisopropyl sebacate as an active ingredient.   The indoor mite control agent according to claim 1, comprising an aqueous agent containing the active ingredient and a polyoxyethylene addition type nonionic surfactant and having a water content of 50% by weight or more.   The indoor acaricide according to claim 2, wherein a mixing ratio (weight ratio) between the active ingredient and the surfactant is 2.0 or less in terms of surfactant / active ingredient.