JPH0778006B2 - Gel type insect repellent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a gel-type insect repellent capable of exterminating clothing pests for a long period of time by gradually evaporating a room temperature volatile insecticide. Is.

[Conventional technology]

Conventionally, sublimable solid agents such as paradichlorobenzene, naphthalene, camphor have been used as insect repellents for clothing. Since these themselves gradually sublimate at room temperature and atmospheric pressure, the residual drug efficacy state and the end point thereof can be recognized in the size and disappearance state in the granular, tablet, and ball-shaped dosage forms. However, these solid insect repellents have a problem in that they have an offensive odor and safety (toxicity) with respect to paradichlorobenzene and naphthalene, while they have a problem that they have a low insecticidal effect with respect to camphor.

As a solution to such a problem, in recent years, liquid insecticides and insect repellents that are volatile at room temperature, such as pyrethroid insecticide Empenthrin, have attracted attention in recent years, and many products using this have been released. It is connected. For example, JP-A-59-15940 discloses a method in which an insect-repellent mat in which paper or plastic is impregnated with highly safe Epensulin without odor is enclosed in a plastic case or laminated paper or non-woven fabric interior paper. ing.

[Problems to be solved by the invention]

The liquid insecticides which are volatile at room temperature and typified by the above-mentioned empensulin have high efficacy and are sufficiently satisfactory as compared with the above-mentioned sublimable solid insecticides. However, on the other hand,
Compared to the fact that the end point is clearly indicated by the disappearance of the sublimable insect repellent, the liquid drug such as the above-mentioned empensulin is generally used as a dosage form which is impregnated and held in an impregnated body because of its properties. Even at the end of the effect, the impregnated body such as paper or plastic remains in its original shape and does not cause any change in appearance, and it is difficult to clearly recognize the end point of use.

For this reason, in general, a method of notifying the user of the end-of-drug effect by printing the scheduled end-of-date or affixing a printed sticker on these products after confirming the effective period of the drug in advance, etc. Has been adopted. However, such a method does not accurately display the actual efficacy of the drug, and although the volatilization rate of the drug is considerably different in the hot season of summer and the cold season of winter, for example, it is replaced after a certain period of time. It is about to do. For this reason, the drug in the impregnated body disappears and it continues to be used even though it is ineffective, or conversely, it is discarded even though the drug remains sufficiently and is effective. And there is a problem that the effective period obtained when actually used does not match.

Therefore, the object of the present invention is to eliminate the above-mentioned drawbacks,
It has no offensive odor and exhibits stable insecticidal effect over a long period of time, and there is almost no residue after the completion of volatilization of the drug.
Therefore, it is to provide a gel-type insect repellent whose end point can be clearly identified.

[Means for solving problems]

In order to achieve the above-mentioned object, the gel-type insect repellent of the present invention is (A) a liquid insecticide having room temperature volatility, (B) N-acyl amino acid ester, N-acyl amino acid amide and N-acyl amino acid amine. It is formed by gelling from a composition containing an N-acyl amino acid derivative-based gelling agent selected from salts and (C) a hydrocarbon-based solvent.

[Operation and Mode of Invention]

A method of gelling and solidifying a volatile drug is used, for example, in the field of deodorant air fresheners, and as a gelling agent for such solid air fresheners, agar, carrageenan, locust bean gum, xanthan gum are generally used. Are used (for example, JP-A-49-12046 and JP-A-53-503).
(See Japanese Patent Publication No. 46). However, since such a gel fragrance type is water-based, it has a very high volatility and volatilizes in a short period of time, so it is not suitable as a insect repellent for clothing that should be continuously volatilized for a long period of time. Is. As a gelling agent, there is also a water gelling agent (for example, Sumika Gel N-100 manufactured by Sumitomo Chemical Co., Ltd.), but a large amount of a surfactant is used when making an insecticidal drug such as empensulin water-soluble. It does not gel because it is necessary.

The present inventors have earnestly studied in order to obtain a gel type insect repellent using a liquid insect repellent which is vaporizable at room temperature, and as a result, the N-acyl amino acid derivative-based gelling agent (s) conventionally used for solidifying oil ( (See Japanese Patent Publication No. 51-42079), and when a hydrocarbon solvent is used, gelation occurs well, and the volatile acid of the above insecticide is stable over a long period of time. I found it. On the other hand, when a solvent other than the above hydrocarbon-based solvent, for example, a highly polar solvent such as ketones and alcohols is used, gelation does not occur, and when an ester such as diethyl phthalate is used, The amount of decrease in the composition is extremely small, that is, the volatilization is extremely slow because the gel is hard, and it takes about 1400 to 2400 days (about 46 to 77 months) until the volatilization of the gel-type insect repellent is completed, which is quite sufficient. It cannot exert the effective insecticidal effect.

Therefore, the present invention provides a gel-type insect repellent that can stably exert a sufficient insecticidal effect over a long period of time, and leaves almost no residue after the completion of the vaporization of the drug, and thus the end point can be clearly discriminated. In order to achieve the above object, it is essential to select and use the N-acyl amino acid derivative-based gelling agent as a gelling agent to be used with a liquid insecticide having room temperature volatility and a hydrocarbon-based solvent as a solvent. It is a configuration requirement.

The insecticide used in the present invention has a volatility at room temperature, for example, (R, S) -1-ethynyl-2-methylpent-2-enyl (1R) -cis, transcrisanthemate (hereinafter, Referred to as empensulin), 1-ethynyl-2-methyl-2-pentenyl-2,2-dimethyl-
3- (2 ', 2'-dichlorovinyl) -cyclopropane-
1-carboxylate, 1-ethynyl-2-methyl-2
-Pentenyl-2,2,3,3-tetramethylcyclopropanecarboxylate, 3-allyl-2-methylcyclopent-2-en-4-one-1-yl-2,2,3,3-tetramethyl Pyrethroid insecticides such as cyclopropanecarboxylate (hereinafter referred to as teraresulin), 5- (2-propargyl) -3-furylmethylchrysanthate (generic name flamethrin), room temperature volatile insecticides such as dichlorvos, phthalic acid Dimethyl, diethyl phthalate, dibutyl phthalate, diethyl fumarate, N, N-diethyl-m-
Insect repellents such as toluamide, repellents, insect fragrances such as ethyl benzoate, safrole, isosaflor, eugenol, citronellol, anethole, l-carvone, cinnamic aldehyde, insect repellents such as benzaldehyde, and the like. The above insect repellent agents can be used alone or in combination of two or more kinds. Particularly preferred agents are the above-mentioned empensulins in terms of insecticidal efficacy and volatility.
Terrarethlin and Dichlorvos.

The three types of N used as a gelling agent in the present invention
Among N-acyl amino acid derivatives, N-acyl amino acid ester and N-acyl amino acid amide include, for example, N-acyl amino acid and alcohol or amine which are heated or reacted in the presence or absence of an acid catalyst respectively, or an amino acid ester. Alternatively, it can also be obtained by N-acylating an amino acid amide with an acylating agent such as a fatty acid halide. Further, the N-acyl amino acid amine salt can be easily obtained by neutralizing the N-acyl amino acid with an amine.

The amino acid of the N-acyl amino acid derivative is α
Various amino acids such as −, β-, and ω-amino acids are used, and particularly glycine, α-alanine, β-alanine, valine, serine, methionine, phenylalanine, 3,4-
Dioxyphenylalanine, aspartic acid, glutamic acid, lysine, ornithine, arginine, histidine,
ε-aminocaproic acid or the like is used. In addition, it may be a mixture of amino acids, such as soybean, fish meat, yeast,
A hydrolyzate of a protein of algae, a residual amino acid in the amino acid production waste liquid, or the like can also be used.

Further, the N-acyl group in the N-acyl amino acid derivative is a linear or branched saturated or unsaturated aliphatic or aromatic acyl group or alicyclic acyl group having 1 to 30 carbon atoms, preferably 2 to 18 carbon atoms. It may be any group, especially a caproyl group, a capryloyl group, a lauroyl group, a myristoyl group, a stearoyl group and the like or a mixture thereof.

As the alcohol used for esterification, straight chain and branched saturated or unsaturated aliphatic or aromatic alcohols or alicyclic alcohols having 1 to 30 carbon atoms, preferably 8 to 18 carbon atoms are used, for example, octyl alcohol, Examples thereof include lauryl alcohol, cetyl alcohol, isostearyl alcohol, stearyl alcohol, benzyl alcohol and cyclohexanol.

The amine used for the amidation and amine salt includes ammonia and saturated and unsaturated linear and branched primary and secondary amines having 2 to 60 carbon atoms, preferably 2 to 18 carbon atoms, mono- and dialcohol amines (for example, Mono- and diethanolamines), aromatic amines, cycloaliphatic amines and tertiary amines in amine salts, trialcoholamines (eg triethanolamine) are used, eg butylamine,
Examples include octylamine, laurylamine, isostearylamine, stearylamine, benzylamine and cyclohexylamine.

As such gelling agents, various ones are commercially available, for example, "oil gelling agent GP-1" manufactured by Ajinomoto Co., Inc., "Gelol D" manufactured by Shin Nippon Rika Co., Ltd. The above-mentioned "GP-1" is preferable in that it gels at a low concentration.

In the present invention, a hydrocarbon solvent is used as the solvent, and for example, aliphatic or aromatic hydrocarbons such as kerosene, liquid paraffin, benzene and toluene can be used. In the case of a paraffin-based hydrocarbon, the smaller the carbon number is, the faster the volatilization is, and the stable volatilization is difficult over a long period of time. Therefore, it is preferable to use the one having 13 to 16 carbon atoms.
By using a paraffin hydrocarbon having a carbon number in this range as a solvent, it is possible to continuously volatilize for about 4 to 7 months. If a kerosene-based solvent is used, it can be volatilized continuously for about 6 months.

The gel-type insect repellent of the present invention is appropriately mixed with the respective components in an amount of 0.01 to 5 parts by weight of a gelling agent and 10 to 50 parts by weight of a hydrocarbon solvent per 1 part by weight of the insecticide.

Further, the gel-type insect repellent of the present invention is prepared by adding a predetermined amount of a gelling agent to the hydrocarbon-based solvent to obtain a melting temperature or higher (about 70 to 150
It can be easily produced as a gel-like product by heating and dissolving at 0 ° C.), then adding a predetermined amount of the liquid insecticide and then allowing to stand and cool.

The gel-type insect repellent of the present invention can be appropriately blended with a colorant, a fragrance, etc., if necessary, and a color or scent can be added to enhance the commercial value.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 A gelling agent was added to 20 parts by weight of a solvent deotomizole (C _13-16 fraction).
GP-1 (manufactured by Ajinomoto Co., Inc., N-lauroyl-L-glutamic acid-α, γ-di-n-butyramide) (0.01 part by weight) was added and dissolved by heating, and then this was added to 1 part by weight of empensulin. (Diameter 85 mm), and allowed to cool.

After cooling, the gel-like insect repellent in the gelled dish was allowed to stand at room temperature in an open state, and its weight decrease and the change with time of the remaining amount of the active ingredient (empensulin) were measured. The results are shown in Table-1.

As is clear from the above results, it can be seen that the gel type insect repellent of the present invention volatilizes at a substantially constant rate for about 6 months. In addition, after evaporation (after 6 months), the film was a hard thin film.

Application Example 1 One piece of the gel-type insect repellent prepared in the above Example 1 was placed in a Western dance (about 750 liters), and 10 meshes of squid larvae and wool muslin cloth (2 cm x 2 cm) were put in the Western dance. The ball was set and the damage of the muslin cloth was observed. The results are shown in Table-2.

The feeding damage inhibition rate was calculated by the following formula.

From the above results, it is understood that the gel type insect repellent of the present invention can exert a sufficiently high insect repellent effect over a long period (6 months).

Examples 2 to 10 and Comparative Examples 1 and 2 A solution having the composition shown in Table 3 was prepared, poured into a sheare (diameter 85 mm) and allowed to cool to obtain a gel insect repellent. This was placed under the condition of 25 to 30 ° C. and volatilized. The results are also shown in Table-3.

As is clear from the above results, gelation does not occur when a solvent (ketone, alcohol) other than the hydrocarbon solvent is used.

〔The invention's effect〕

As described above, the gel-type insect repellent of the present invention uses a liquid insect repellent at room temperature that is excellent in insecticidal effect, uses an N-acylamino acid derivative-based gelling agent as a gelling agent, and a hydrocarbon-based agent as a solvent. As the solvent is selected and used,
It can be easily molded into a gel, has no offensive odor, is highly safe, and can exhibit a stable and high insecticidal effect over a long period of time. Furthermore, since almost no residue remains after the end of the volatilization of the drug, the end point of use can be clearly discriminated.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area A01N 57/12 B

Claims (3)

[Claims] 1. An N-acyl amino acid derivative system selected from (A) a liquid insecticide having room temperature volatility and (B) an N-acyl amino acid ester, an N-acyl amino acid amide and an N-acyl amino acid amine salt. A gel-type insect repellent obtained by gelling a composition containing a gelling agent and (C) a hydrocarbon solvent. 2. An insecticide is (R, S) -1-ethynyl-
2-Methylpent-2-enyl (1R) -cis, trans-chrysanthemate, 3-allyl-2-methylcyclopent-2-en-4-one-1-yl-2,2,3,3-tetra The insect repellent according to claim 1, which is one kind or two or more kinds selected from the group consisting of methylcyclopropanecarboxylate and dichlorvos. 3. The insect repellent according to claim 1 or 2, wherein the solvent is an aliphatic hydrocarbon solvent.