JPH0222202A - Insect repellent formulations and materials - Google Patents

Abstract

PURPOSE:To obtain the title insecticidal formulation and insecticidal material preventing fall off of microcapsule stably binding with a base material and reserving, and thus making possible to preserve an evasion effect in a long time of period, by making gradually releasing microcapsule including diethyltoluamide and PVA. CONSTITUTION:A gradually releasing microcapsule of melamine resin, etc., including 1-100g/m<2> diethyltoluamide (N,N-diethyl-m-toluamide) is dispersed using polyvinyl alcohol as a binder and an insecticidal formulation is prepared, then said formulation is held by base material such as paper, woven cloth, nonwoven cloth, synthetic resin film or wood to afford an insecticidal material. Said insecticidal formulation, etc., is useful for evading harmful insects such as cockroach or acarid. Besides, said insecticidal formulation and insecticidal material is able to suppress evaporation of the drug and preserve from surrounding environment, further able to prevent fall off of microcapsule by working such as bending, scratching or cutting.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an insect repellent formulation and an insect repellent material for repelling pests such as cockroaches and mites.

More specifically, the present invention relates to an insect repellent formulation and an insect repellent material using sustained-release microcapsules containing N,N-diethyl-m-toluamide (hereinafter referred to as diethyl toluamide), which is an insect repellent compound.

[Prior Art] More than 1.8 million species of insects are known, and among these there is a group called sanitary pests that directly or indirectly have a negative impact on human life.

The following are the main sanitary pests:

In addition to causing severe itching, redness, and swelling when bitten, sharks transmit infectious diseases such as Japanese encephalitis, dengue fever, yellow fever, malaria, and filariasis; adult female sharks bite humans and livestock violently and can transmit infectious diseases. Certain gnats, flies, and gnats;
Cockroaches that spread infectious disease bacteria such as Vibrio cholerae, Salmonella typhi, and Shigella, as well as pathogenic bacteria such as Mycobacterium tuberculosis; Chiggers that cause Tsutsugamushi disease; Dust mites that vigorously suck the blood of humans and livestock and can cause allergies. In addition, sanitary pests include clothing pests such as burrs and carp moths, fleas, flies, and ants.

As a method for exterminating these sanitary pests, spraying of insecticides, use of aerosols containing insecticides as active ingredients, fumigants, etc. are generally carried out. However, the use of high-concentration insecticides is expected to have harmful effects on the human body, and pests may re-invade after the insecticide's effectiveness disappears over a certain period of time, and continuous use of insecticides may cause pests to There are problems such as developing drug resistance, making insecticides ineffective, and requiring die-off treatment.

As a way to avoid these problems, research has been conducted on repellents for sanitary pests, and many repellent substances,
For example, diethyltoluamide, N-butylacetanilide, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1°3-propanediol, propylmanplate, etc. were found.

Methods for applying repellents include insect repellent materials such as insect repellent paper, insect repellent sheets, and insect repellent tape; dissolve repellent ingredients such as diethyltoluamide in a suitable solvent or latex to carpet pile yarn, base fabric, backing material, etc. Avoid dust mites, etc. by applying, impregnating, mixing, etc. with repellent; make insect-proof furniture and cupboards by impregnating the ceilings of wardrobes, side panels, drawers, and cupboard members with repellents.

Among them, insect repellent materials have been widely used since they are easy to use, such as cutting and laying, but the molds are either paper impregnated with insecticide or repellent, or sheet-like materials with insecticides on one side. Generally, they are coated with a repellent or a repellent. However, considering the impact on living organisms, using insect repellent paper or insect repellent sheets containing insecticides, especially organophosphorus insecticides, inside residences is problematic in terms of safety for humans and pets. is more preferable.

However, conventional repellents have the following drawbacks.

That is, it is desirable for the repellent to have a certain degree of vapor pressure and for the active ingredient to gradually volatilize; if the volatilization is too large, the repellent effective period will be shortened, and if the volatilization is too small, the repellent effect will not be expressed.

In addition, with the above-mentioned repellent molds (for example, sheets impregnated with repellent), it is difficult to control the volatilization rate, and the environmental factors of the place where the insect repellent paper or sheet is installed, For example, there is a problem in that the effective period is greatly affected by sunlight, temperature, moisture, etc., and it has been difficult to stably maintain the repellent effect.

Among these repellents, conventional repellents have a wide range of targets,
Diethyltoluamide is said to be the most ideal because it is highly safe and has an odor that humans do not dislike, but like the various repellents mentioned above, it has the disadvantage of poor long-term durability. Ta.

[Problems to be Solved by the Invention] As a result of intensive studies to achieve long-term sustainability of the repellent effect, the present inventors previously disclosed in Japanese Patent Application No. 1118 B2-24390 that the core material is made of diethyltoluamide, We also proposed a sustained-release microencapsulated insect repellent formulation whose wall material is made of microcapsules with sustained-release properties.

With this insect repellent formulation, the volatilization of medicinal efficacy can be freely adjusted and minimized to the necessary minimum, and compared to the raw material diethyltoluamide, it can provide repellent effects against various pests for an extremely long period of time. However, there was a problem in that the holding power (binding power) of the insect repellent formulation applied to the substrate etc. was weak.

That is, for example, in the case of insect repellent paper, insect repellent sheets, insect repellent carpets, etc., the microcapsules fall off during folding or cutting operations, and in the case of insect repellent furniture, etc., there is a problem that the insect repellent falls off due to mechanical contact.

Therefore, the object of the present invention is to control the volatilization of the drug by microcapsulating diethyltoluamide, to protect it from the surrounding environment, and to stably bind and hold the microcapsules to the base material, so that the microcapsules can be folded and ,
An object of the present invention is to provide an insect repellent formulation and an insect repellent material that can prevent microcapsules from falling off from a base material due to operations such as scratching or cutting, and can maintain a long-term repellent effect.

[Means for Solving the Problems] As a result of intensive research in order to solve the problems, the present inventors have developed microcapsules that have diethyltoluamide as a core material and whose wall material has sustained release properties. The present invention has been completed based on the discovery that the above-mentioned problems can be solved by binding and holding polyvinyl alcohol to a base material as a binder.

That is, the present invention provides: 1) an insect repellent formulation characterized by containing sustained-release microcapsules containing N,N-diethyl-m-toluamide and polyvinyl alcohol; 2) sustained-release microcapsules containing polyvinyl alcohol; The insect repellent preparation of 1) above, characterized in that it is dispersed in an aqueous solution. , 05-1:
1) The insect repellent preparation according to 1) or 2) above, 4) sustained-release microcapsules containing N,N-diethyl-m-toluamide are held on a base material by polyvinyl alcohol. An insect repellent material characterized by: 5) sustained-release microcapsules of N,N-diethyl-m-
The insect repellent material according to 4) above, characterized in that the toluamide content is 1 to 100 g/rd; 6) the base material is made of a material selected from paper, woven fabric, nonwoven fabric, synthetic resin film, and wood; The present invention relates to the insect repellent material according to feature 4) or 5) above.

[Function] In the present invention, by microcapsulating diethyltoluamide, volatilization of the drug is controlled, and it is protected from the surrounding environment, and the microcapsules are stably bound and retained on wood using polyvinyl alcohol. This prevents the microcapsules from falling off from the base material due to operations such as bending, scratching, and cutting, making it possible to maintain the repellent effect over a long period of time.

As specifically disclosed in Japanese Patent Application No. 62-24390, the sustained-release microcapsules containing diethyltoluamide according to the present invention have a core material made of diethyltoluamide and a wall material having sustained-release properties. It is something.

As a method for microencapsulation, interfacial polymerization method, rn-si, which is widely known in microcapsule production technology, is used.
tu method, phase separation method, submerged curing coating method (orifice method),
Submerged drying method, spraying/granulation method, etc. can be used, but interfacial polymerization method and rn-srtu method are especially preferred because they enable effective and economical microencapsulation of diethyltoluamide. Useful.

As the wall material, any material can be used as long as it has sustained release properties for diethyltoluamide, but in particular polyamide resin, polyester resin, polyurea resin,
Preferred are polyurethane resins, urea resins, guanamine resins, melamine resins, and composite materials thereof.

There is no particular limitation on the preferred ratio of the core material to the wall material, but in consideration of economic efficiency, the microcapsule wall material in the present invention must sufficiently retain the liquid diethyltoluamide contained therein and protect the contained material. Therefore, the preferred weight ratio of core material and wall material is 1:1.
~1:Q,01, more preferably 1:0.3~
1:0.03.

In the present invention, polyvinyl alcohol is used together with the sustained-release microcapsules as a binder for binding and holding the microcapsules to a substrate.

The properties required of the binder include being able to uniformly disperse the microcapsules therein, having high adhesiveness to prevent the microcapsules from falling off from the substrate, and having high adhesion properties to prevent the microcapsules containing diethyltoluamide from being dispersed. It is necessary that the effect on radioactivity is small.

It is unsuitable to use an oil-soluble binder dissolved in an organic solvent as such a binder, since this will cause the diethyltoluamide in the sustained-release microcapsules to be rapidly eluted out of the capsules.

Therefore, it is desirable to use a binder that is water-soluble or can be dispersed in water, but even if such a binder is compatible with diethyltoluamide, the diethyltoluamide will be eluted outside the capsule. , unsuitable as a binder.

In general, even if it is water-soluble, from the viewpoint of environmental resistance, it is desirable that the coated and dried material is not easily soluble.

As a result of intensive studies on binders from this point of view, it was discovered that polyvinyl alcohol, which is a water-soluble polymer, satisfies the above requirements.

In the present invention, by using polyvinyl alcohol as a binder, the surface properties of the substrate, especially the surface properties of paper, such as smoothness, abrasion resistance, oil resistance, are improved,
The long-term sustainability of the repellent effect is maintained.

In the present invention, polyvinyl alcohol has a degree of polymerization,
Regardless of the degree of saponification, conventionally known ones can be used without particular limitation.

In the present invention, there are no particular restrictions on the blending ratio and amount of sustained-release microcapsules containing diethyltoluamide and polyvinyl alcohol used as a binder, but for example, the On the other hand, if long-term repellency is required, the amount of diethyltoluamide should be 1 to 100 g/TIt1.
Preferably, the content is 3 to 25 g/m, and the solid content of sustained-release microcapsules: solid content of binder is 1:o. 05-1:1, preferably 1:
The ratio is preferably 0.1 to 1:0.6.

If the amount of binder is less than this ratio, the binding force will be weak and it will be difficult to stably hold the microcapsules on the substrate, while if the amount of microcapsules or binder is more than this, it will be economically disadvantageous.

In the present invention, the insect repellent formulation containing the above microcapsules and a binder is preferably used as a coating liquid in which the microcapsules are dispersed in an aqueous binder solution. At this time, the solid content of the binder aqueous solution in which the microcapsules are dispersed is 5 to 50%, preferably 10 to 30%.
%.

In the present invention, the coating solution described above is coated or impregnated onto various base materials such as paper, woven fabric, non-woven fabric, synthetic resin film, wood, etc. to produce insect repellent materials such as insect repellent paper, insect repellent sheet, insect repellent tape, and insect repellent cloth. A container that can form the coating solution,
It is possible to apply insect repellent treatment to furniture such as cupboards and wardrobe boxes, carpets, futon bars, sheets, etc. by coating or impregnating them with the insect repellent.

Furthermore, using the base material coated or impregnated with the above coating liquid, it is possible to manufacture molded products such as furniture such as dressers, cupboards, wardrobe boxes, carpets, futon bars, sheets, etc., and this manufacturing process Sometimes insect repellent formulations do not fall off.

Further, the insect repellent preparation may contain a flavoring agent, a coloring material, and the like.

[Example] The present invention will be described in more detail with reference to Examples below, but the present invention is not particularly limited thereto.

In the following description, "parts" and "%" expressing blending ratios are based on weight unless otherwise specified.

[Preparation of test microcapsules]

3% aqueous solution of pH 4.5 prepared by dissolving styrene-maleic anhydride resin with a small amount of sodium hydroxide 2
00 parts, add 135 parts of diethyltoluamide, and use an ultra homogenizer to reduce the particle size of the emulsion to 10 parts.
It was emulsified to give μ.

8.1 parts of melamine and 6.8 parts of a 37% formaldehyde aqueous solution were added to 65 parts of water, adjusted to pH 9.5 with a 20% aqueous sodium hydroxide solution, heated at 80° C. for 15 minutes, and then added to the emulsion.

This was stirred for 2 hours at a liquid temperature of 75°C to obtain a dispersion of sustained-release microcapsules with melamine walls encapsulating diethyltoluamide.

The solid content in the dispersion was about 36%, and the active ingredient was about 32%.

[Test binder]

As the water-soluble binder according to the present invention, the following (A), (
Commercially available polyvinyl alcohol shown in B) was used.

In addition, the water-soluble binder shown below (C) and the following (
The water-dispersible binder shown in D) was used as a comparative binder.

Binder A: Polyvinyl alcohol manufactured by Unitika (I) (product name VP-240G>) Binder B: Polyvinyl alcohol manufactured by Nippon Gosei ■ (product name Gosenol NH-18) Binder C: Polyvinyl methyl ether manufactured by Sanko Chemical Industry ■ (product name PV)
M-30W>Binder D; 5BR (styrene-butadiene rubber) latex manufactured by Asahi Kasei ■ (product name L-187)
6> Example 1 Test binders (A) and (B) were added to the test microcapsules obtained as described above at a solid content of 10 and 20% (W/W>) based on the solid content of the microcapsules. Each was added as follows.

This was applied to kraft paper using a wire bar so that the ratio was 69/min in terms of diethyltoluamide.
Dry for 3 minutes at
Ta.

Comparative Example 1 Insect-proof papers (O) to (R) in Table 1 were obtained in the same manner as in Example 1 except that the test binders were (C) and (D>).

In addition, as a comparative control with no binder added, the test microcapsules were coated with a wire bar at a concentration of 6 g/Trt in terms of diethyltoluamide, and 6 g/Trt was applied after coating.
C for 3 minutes to obtain additive-free insect repellent paper shown in Table 1.

Table 1 Example 2 The binding property between the insect repellent paper base material and the microcapsules prepared in Example 1 was evaluated by folding the insect repellent paper several times and determining whether the microcapsules fell off from the coated surface. Microcapsules on paper were observed using an electron microscope. The evaluation results are shown in Table 2.

The degree of microcapsules falling off from the coated surface in the table is as follows: (-): Not falling off at all, (+): Only a small portion falling off, (++): Falling off from several places on the coated surface. Boss.

Comparative Example 2 Example 2 except that the insect repellent paper prepared in Comparative Example 1 was used.
In the same manner as above, the binding property between the substrate and the microcapsules was evaluated, and the microcapsules on the insect repellent paper were observed using an electron microscope. The evaluation results are shown in Table 2.

As is clear from Table 2, the insect repellent papers (A) to (1) using the binder of the present invention exhibit strong binding properties without causing microcapsules to fall off from the base material, and The microcapsules maintained their spherical shape without being particularly crushed.

In contrast, with additive-free insect repellent paper shown as a comparison, although the microcapsules on the base material maintain their spherical shape, the binding between the base material and the microcapsules is weak, and the microcapsules often fall off. It was seen.

In addition, insect repellent paper (e) using a binder outside the scope of the present invention
~(ri) has relatively good adhesion to the base material, but the microcapsules on the base material have a crushed shape and exhibit a long-lasting repellent effect as if they were connected multiple times. There was nothing I could do.

Table 2 Example 3 Using the insect repellent papers (A) to (1) prepared in Example 1, the insect repellent papers (A) to (1) were left in a constant temperature and humidity room at 23°C and 165% RH, and the diethyl The residual amount of toluamide was measured. The results are shown in Table 3 as the residual rate for the 5 coated amounts.

Comparative Example 3 Residual amount of diethyltoluamide after 1 month and 3 months in the same manner as in Example 3 except that insect repellent papers (O) to (R) prepared in Comparative Example 1 and additive-free insect repellent paper were used. was measured. The results are shown in Table 3.

As a separate comparison, diethyltoluamide raw material was diluted with ethanol and coated on high-quality paper at a rate of 6 y/m in terms of diethyltoluamide raw material. The results of the test are shown in Table 3.

As is clear from Table 3, the active ingredients of the insect repellent papers (O) to (RI) using binders outside the scope of the present invention and the original coated paper were all rapidly lost, whereas Insect-proof papers (A) to (1) using binders had the same high retention of active ingredients as additive-free paper.

Table 3 Example 4: Test of repellent effect on mites Using the insect repellent papers (A) to (E) prepared in Example 1, the repellent effect on the woolly mites and the mites was examined.

First, each of the insect repellent papers (A) to (1) was cut into 7 x 7 cm pieces, and the cut papers were placed in a hollow vat placed in a chamber at 25°C and 190% RH.

Next, powdered feed with a moisture content of 15% was applied to the surface of each insect repellent cut paper for 2 hours. A small amount of culture medium in which a large number of mites were propagated was placed between these insect-proof cut papers.

To evaluate the repellent effect, 1 day, 1 month, 3 months, and 6 months after the tick inoculation, black rasher paper cut into 5 x 5 cm pieces was placed one by one on the cut insect repellent paper, and 3 hours later, the ticks were observed. This was done by counting the number of live mites. The results are shown in Table 4.

Comparative Example 4 The same procedures as in Example 4 were carried out, except that the insect repellent papers (O) to (R) prepared in Comparative Example 1 and the additive-free insect repellent paper and the bulk-coated paper prepared in Comparative Example 3 were used, respectively. We investigated the repellent effect of insect repellent paper on woolly mites and mites. The results are shown in Table 4.

As is clear from Table 4, all of the insect repellent papers using the binder according to the present invention exhibited a high repellent effect against mites.

Example 5 A sample binder (A> and (
B) was added to the microcapsules at a solid content of 5% and 15% (W/W>), respectively.

This was applied to synthetic paper (manufactured by Tamako Yuka Synthetic Paper Co., Ltd., Yupo #130 (trade name)) at a rate of 5 and 10 g in terms of diethyltoluamide.
/Trt with a wire bar, and after application 1
The sheets were dried at 05° C. for 2 minutes to obtain insect repellent sheets (k) to (ri) shown in Table 5.

The binding properties between the base material of these insect repellent sheets and the microcapsules were evaluated by loosening the insect repellent sheets by hand and checking whether the microcapsules fell off from the coated surface. Observed. The evaluation results are shown in Table 6.

The degree of microcapsules falling off from the coated surface in the table is as follows: (-): Not falling off at all, (10): Only a small part of the capsules falling off, (10): Falling off from several places on the coated surface. shows.

Comparative Example 5 Insect-proof sheets (J) to (N) in Table 5 were obtained in the same manner as in Example 5 except that the test binders were (C) and (D>).

In addition, as a comparative control with no binder added, test microcapsules were used at 5 and 10 g in terms of diethyltoluamide.
/7Ff and dried to obtain insect repellent sheets shown in Table 5 as 1 Additive-free-5'' and ``Additive-free-10J''.

The binding properties between the base material of these insect repellent sheets and the microcapsules were evaluated in the same manner as in Example 5, and the microcapsules on the insect repellent sheets were observed using an electron microscope. The evaluation results are shown in Table 6.

As is clear from Table 6, the insect repellent sheets of (k) to (b) using the binder according to the present invention exhibit strong binding properties without the microcapsules falling off from the base material, and
The microcapsules on the base material were not particularly crushed and maintained their spherical shape.

In contrast, additive-free-57-3 shown as a comparison control
In the case of the insect repellent sheets prepared with No.1 and Additive-10, the microcapsules on the substrate maintained their spherical shape, but the binding between the substrate and the microcapsules was weak, and some of the microcapsules were observed to fall off.

In addition, although the insect repellent sheets (J) to (N) using binders outside the scope of the present invention have relatively good binding properties with the base material, the microcapsules on the base material have a crushed shape. However, the repellent effect could not be maintained over a long period of time.

Table 6 Example 6; Repellent effect test against German cockroach Insect repellent sheet exemplified in Table 5 prepared in Example 5;
A repellent effect test on German cockroaches was conducted using (C), (C) and (R).

The repellent effect test against the German cockroach was conducted as follows, and the evaluation results are summarized in Table 7.

First, using each of the above insect repellent sheets, make a 2 x 10 x 7 cm rectangular box with the coated side of the insect repellent sheet inside, and make a 1 cm wide hole in one place on the 2 x 7 cm side of this box. I opened it.

Next, a large vat was prepared, and one box each obtained from the above-mentioned insect repellent sheet and one box not treated with the chemical (control) were arranged on the vat.

After preparing a total of 4 similar bats, heat them at 23°C.
Leave it standing in a constant temperature and humidity room at 65% RH, and 1 day after coating.
After 1 month, 4 months and 6 months, a total of 100 adult German cockroaches (50 male and female) were placed in each pad. The repellent effect was evaluated by counting.

Comparative Example 6 The insect repellent sheets prepared in Comparative Example 5 (T), (G), (D) and (N), and the additive-free insect repellent sheet 10 were used; diluted with ethanol to give 10g in terms of diethyltoluamide raw material.
The repellent effect of each insect repellent sheet on German cockroaches was investigated in the same manner as in Example 6, except that the insect repellent sheets prepared by applying the coating at a concentration of 10 J/m were used as the original coating-10J. The results are shown in Table 7.

As is clear from Table 7, the insect repellent sheets (C), (C), (C) and (Y) using the binder according to the present invention have a long-lasting repellent effect similar to the additive-free sheets. did.

However, the insect repellent sheets and bulk-coated sheets of (T), (G), (D), and (N) using binders outside the scope of the present invention lost their repellent effects early.

Example 7 A sample binder (A> and (
B) was added to the solid content of microcapsules at a solid content of 10% (W/W), and this was added to a cardboard using diethyltoluamide @ Feng at a rate of 10 g/lrt.
After coating and drying, it was molded into a costume box to obtain an insect-proof costume box.

This costume box was a must because it has a long-lasting repellent effect.

Example 8 A sample binder (A> and (
B) was added to the solid content of the microcapsules at a solid content of 15% (W/W>), and this was applied to the surface of the synthetic paper with the release paper attached. Ta.

This insect repellent tape had an excellent long-term repellent effect.

Example 9 The primary base of carpet material (polypropylene) has a surface of 2
FJO was added with sample binders (A) and (B) so that the ratio of
I painted it in stripes across the width for 15 minutes.

After weaving polypropylene pile yarn into this primary base fabric, a secondary base fabric (jute) was adhered to create an insect-proof carpet.

This insect repellent carpet had an excellent long-lasting repellent effect.

Example 10 10% solid content (based on microcapsule solid content)
W/W> test binders (A> and (B)) were added, and acrylic pile yarn was impregnated with this.

After drying, this pile yarn was fixed to the primary base fabric, and then a secondary base fabric was adhered thereon to create an insect-proof carbera.

This insect repellent carpet had an excellent long-lasting repellent effect.

[Effects of the Invention] As explained above, in the present invention, diethyltoluamide controls the volatilization of the drug, protects it from the surrounding environment, and stabilizes the microcapsules on the base material using polyvinyl alcohol. By binding and holding the microcapsules to the base material, it is now possible to provide an insect repellent formulation that has a long-lasting repellent effect and prevents the microcapsules from falling off from the base material due to operations such as bending, scratching, and cutting.

In addition, this insect repellent formulation can be used in a wide range of fields,
By using this, it is possible to easily perform insect repellent treatment with excellent long-lasting repellent effects on various base materials, and it is also possible to provide insect repellent materials and molded products with excellent long-lasting repellent effects. became.

Claims (1)

[Scope of Claims] 1) An insect repellent formulation comprising sustained release microcapsules containing N,N-diethyl-m-toluamide and polyvinyl alcohol. 2) The insect repellent preparation according to claim 1, characterized in that sustained-release microcapsules are dispersed in an aqueous polyvinyl alcohol solution. 3) The content ratio of sustained-release microcapsules and polyvinyl alcohol is 1:0.05 to 1 in terms of solid content of sustained-release microcapsules:polyvinyl alcohol.
The insect repellent formulation according to claim 1 or 2, characterized in that: 4) An insect repellent material comprising sustained release microcapsules containing N,N-diethyl-m-toluamide held on a base material by polyvinyl alcohol. 5) Sustained-release microcapsules of N,N-diethyl-m-
The insect repellent material according to claim 4, characterized in that the toluamide content is 1 to 100 g/m^2. 6) The insect repellent material according to claim 4 or 5, wherein the base material is made of a material selected from paper, woven fabric, nonwoven fabric, synthetic resin film, and wood.