JP2001348304A - Sanitary insect pest repellent and repellent active wax - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sanitary insect pest repellent having no problem of durability of the activity and gloss reduction of a floor wax when added to the floor wax. SOLUTION: The sanitary insect pest repellent and the wax, especially the floor wax comprise Copaiba oil and/or caryophyllene as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sanitary pest repellent and a sanitary pest repellent active wax containing copaiba oil and / or caryophyllene as an active ingredient, and more particularly to a sanitary pest repellent active floor wax.

[0002]

2. Description of the Related Art Today, when airtightness of houses has become a common sense, indoor pest contamination has been increasing. Particularly, kitchens of apartments and general houses, kitchens of restaurants, and kitchens are used. The introduction of sanitary pests, such as cockroaches, into equipment and raw material warehouses of food factories is unsanitary and unpleasant. Conventionally, organic phosphorus-based, carbamate-based or pyrethroid-based insecticides, which have been used for control of sanitary pests, have been used for a long time because they have excellent insecticidal activity and are inexpensive.

However, due to the toxicity of the drug, care must be taken when using it in places where people can easily touch it, such as houses, and in food factories. In such places, in addition to direct toxicity, chronic toxicity due to bioaccumulation in the food chain,
Repellent activity of safer chemicals derived from natural products than organic synthetic pesticides, which may lead to the emergence of drug-resistant pests or the spread of potential pests that can lead to a rapid ecological change It is preferable to use a repellent according to

[0004] Repellents are substances that repel harmful organisms by utilizing the negative chemotaxis of the chemotaxis of living organisms when they take a certain action. Repellents do not attack and kill animals, but prevent harmful behavior of humans by invading animals into human life while considering the coexistence of humans and animals and plants, and be harmless to humans and animals Is the basis.

[0005] The action mechanism of the repellent is that the active substance suppresses the stimulating nerve of the attractant necessary for the insect to be guided to the target substance, or that the information is confused by stimulating the sensilla unrelated to the attraction. It is believed that repellent activity appears.
In the latter case, it is likely that the nerves lose their functions because they stimulate different types of nerve cells simultaneously to cause information confusion.

[0006] Plant natural oils such as pine, hinoki and camphor are known as natural substances having repellent activity against sanitary pests. The repellent active components contained in these are terpenes, among which sesquiterbenes are particularly preferable. No. With respect to sesquiterpenes, repellent activity against cockroaches such as Elemol, β-Eudesmol, and β-Vetivon has been reported (JP-A-8-81306).

[0007] Since repellents have a lower insect repellent effect than insect repellents, it is necessary to keep the repellent effect as low as possible and to consider the persistence of the efficacy. If the repellent is added to the floor wax, it can be applied to the entire floor surface, and the wax can be expected to maintain its durability.

[0008] Although a floor wax containing an insect repellent added to a wax is commercially available, it is impossible to add a hydrophilic insect repellent active substance to an oily wax, and there is also a problem in sustainability. Further, when the insect repellent wax is applied to the floor, there are problems that the glossiness is lower than that of the wax alone, the commercial value as a floor wax is reduced, and the insect repellent active substance is expensive.

[0009]

Means for Solving the Problems As the inventors of the present invention examined plant essential oils containing a substance having a strong repellent activity, copaiba oil had an excellent repellent activity against sanitary pests, and the repellent activity was mainly that of copaiba oil. I knew it was due to the component, Caryophyllene.

The first aspect of the present invention is a sanitary pest repellent comprising copaiba oil and / or caryophyllene as an active ingredient, and the second aspect of the present invention is a copaiba which comprises adding these active ingredients to a wax, particularly a floor wax. It is a sanitary insect repellent active wax containing oil and / or caryophyllene as an active ingredient.

Copaiba oil Copaiba oil is copaiba balsam tree
(Copaifera L.) is an essential oil obtained by distilling copaiba balsam (copaiba balsam), which is a colorless fluid secretion (oleoresin) obtained by piercing the trunk of a legume plant to the pith. It is a colorless to pale yellow liquid with a unique aroma. Copaiba balsam tree is from the very hot northern part of South America, Brazil, Venezuela, Guyana, Suriname, Colombia, especially the basins of the Amazon and Orinoco rivers, with large trunks, smooth bark, and branches. There are many Takagi trees, some of which can reach a height of 30m. Oleoresin, produced by the stem of this plant, is a physiological byproduct and accumulates in the cavity of the decay caused by the degradation of the parenchyma cell wall and in many extinct vessels in the stem.
As it spreads and connects, more and more oleoresin accumulates. The pressure often causes the trees to make loud noises and tear. Indigenous people use it as an antibacterial agent.

Although oleoresin (copaiba balsam) is mainly composed of essential oils and resins, its composition and properties are not fixed,
Composition of Copaiba oil Sesquiterpenes, Caryop
Hyllene, humulene, copaene and the like are known.

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Its aroma is very pale, light woody and spicy (pepper-like), has a moderate persistence, and is well-harmonic with many fragrances and is used as a modulator of cosmetic fragrances. Flavors are bitter, irritating and tingling. Copaiba oil containing 50-70% β-caryophyllene is defined in the FDA standard (FDA number; 172-510). It is not known that copaiba oil can be used as a sanitary pest repellent.

Caryophyllene (4,1), which is the main component of copaiba oil
1,11-trimethyl-8-methylenebicyclo [7.2.
[0] undec-4-ene) is a sesquiterpene hydrocarbon widely present in nature, and is abundant in spice essential oils such as clove and nutmeg, but also present in citrus oils such as orange and lemon. COLORLESS LIQUID, insoluble in water, with woody aroma. α-Caryophyllene and γ-caryophyllene may coexist in addition to β-caryophyllene. Industrially, it is obtained as a by-product when eugenol is separated from clove leaf oil.
It is not known that caryophyllene can be used as a sanitary pest repellent.

[0015] Furthermore, the present inventors have added copaiba oil and / or caryophyllene to floor waxes to increase the glossiness and enhance the commercial value of floor waxes than waxes alone; // Caryophyllene is easily miscible with wax resins without the need for emulsifiers; the repellent effect of copaiba oil and / or caryophyllene is moderately retained by wax and lasts longer; less expensive than commercial insect repellent actives The present invention has been completed based on the finding that it is derived from natural products and has no concern about toxicity; it is an essential oil, but has an advantage that it does not matter the odor even as a floor wax.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The copaiba oil used in the present invention may be any copaiba oil that is commercially available as a perfume raw material for preparation. Caryophyllene is also available on the market. Caryophyllene, the main component of copaiba oil, can be used in the following description as well as copaiba oil.

Copaiba oil and caryophyllene can be used as repellents as they are, but they can be used as solid agents by adsorbing, mixing and impregnating them in a suitable carrier. Examples of carriers include, for example, alumina, attapulgite, silica, acid clay, kaolin, bentonite, activated carbon, wood flour, florite (calcium silicate),
Examples include granular aluminum oxide, zeolites, paper, cyclodextrin, starches, synthetic resins, or mixtures thereof.

In the sanitary pest repellent of the present invention, there are usually used additives for formulation such as emulsifier, spreading agent, suspending agent, dispersing agent and retaining agent (for example, polyvinylpyrrolidone).
(PVP), dipropylene glycol, 3-methoxy-3
-Methyl-1-butanol (trade name: Solfit), isoparaffin, triethyl citrate, hydrogenated limonene dimer, polymethyl acrylate or cellulose acetate), a transpiration regulator (for example, isoparaffin, solfit, diethylene glycol monoethyl ether or Dipropylene glycol), propellant (e.g., liquefied petroleum gas
(LPG), nitrogen gas, carbon dioxide gas, etc.), gelling agent, etc., and can be formulated into dosage forms such as oils, wettable powders, powders, tablets, sprays, plates, azole coatings, etc. . It can be formulated together with other insect repellents, repellents, insecticides, fungicides, fungicides, fragrances, coloring agents and the like.

It is not necessary to consider the toxicity of the copaiba oil in the repellent of the present invention. Therefore, the amount of copaiba oil may be appropriately determined depending on the dosage form, the method of use and the place of use, so as to exert the repellent effect. Although it is not particularly limited, when it is formulated as a repellent, it is preferably 0.1% to 5% in the formulation.
0%, more preferably 0.1% to 30%.

The copaiba oil, caryophyllene or repellent containing these of the present invention can be added to floor wax, furniture wax, automobile wax, paint, waterproofing agent, water repellent, leather retaining agent and the like. However, floor wax (floor polish) is particularly preferred. The floor wax may be any commercially available floor wax. Although an aqueous polymer type can be used, an oil-based or oil-soluble (lipophilic) wax type is preferable.

When added to wax (floor wax),
Copaiba oil and caryophyllene are waxes (floor waxes), although not particularly limited, in consideration of various circumstances.
Medium, preferably 0.05% to 30%, more preferably 0.1% to 10%.

Repellent activity test and glossiness test Repellent activity test Repellent activity test against German cockroaches 1) Test insect German cockroach (Blattella germanica Linnaeus) The body is light yellowish brown, and two black stripes are found on the back of the pectoralis chest. The male subgenitor plate is narrow and long, and the part cut off to the left is deep. The papillary tail is large on the left. The female upper anal plate is flat, triangular, with a wide dark brown portion at the base and a rounded end. Body length is 12mm inside and outside. It is a household pest commonly found in restaurants and buildings, and is distributed worldwide.

2) Test method for evaluating repellent activity A test sample was placed on the bottom of a circular plastic container having a diameter of 30 cm, and a container having an entrance covered with aluminum foil was covered with the test sample to form a shelter. Was kept at 25 ° C., the number of individuals outside the shelter after a certain period of time was counted, and% of the total number of individuals was calculated to obtain the repellent rate. This test utilizes the property that cockroaches favor corners, narrow places, dark places, and the like. The reason for using a circular container is to prevent cockroaches from collecting at the corners of the container.

3) Repellent activity sustaining test In the repelling activity sustaining test, the floor material coated with the floor wax was stored in a desiccator after completion of the test, and the repellent test was carried out by the above method at appropriate times.

4) Repellent activity of copaiba oil and its main component, caryophyllene Copaiba oil (Carpa) which is commercially available as a flavoring material for analytical preparation of copaiba oil by gas chromatography
A 0.1% hexane solution of yophyllene (containing about 50-70%) was subjected to gas chromatography. Column: HR-20M; 0.32 mm × 30 m; Column temperature: 40 ° C. to 220 ° C .; heating rate: 5 ° C./min Detector: FD The results are shown in FIG.

Separation of Caryophyllene from Copaiba Oil Column: BW-127ZH Developing solution: Hexane Fractions were separated into Fr.1 to Fr.3 while monitoring with thin layer chromatography while developing with hexane. Each fraction was subjected to gas chromatography again, and it was confirmed that the main component was in Fr. 1 (FIGS. 2 and 3). Fr.1 was purified by silica gel chromatography, obtaining an almost single peak (FIG. 4). This component was subjected to GCMS analysis.
(FIG. 5). m / z (M ⁺ ) is 204, indicating that the substance is a sesquiterpene hydrocarbon.

Caryophyll is a component of copaiba oil.
From the places where ene, humulene, copaene, etc. are known, identification by gas chromatography was performed using a known standard, caryophyllene. Since the retention time was consistent with that of the obtained sesquiterpene hydrocarbon, it was found that the main component of the used copaiba oil was caryophyllene.

5) Test for repellent activity of copaiba oil and caryophyllene Copaiba oil and caryophyllene were dissolved in ethanol to obtain a 0.1% ethanol solution, which was 5 cm × 5 c
m, and then dried at room temperature for 24 hours. Using this as a test sample, a repellent activity test after 24 hours was performed by the repellent activity test method described above. As a control, a filter paper impregnated with ethanol alone was dried for 24 hours before use. The data is shown in Table 1.

[0029] Table 1 copaiba oil and caryophyllene repellent activity test sample repellency of (%) copaiba oil 72 caryophyllene 93 Control 10

Considering that the repellency of caryophyllene was higher than that of copaiba oil, and considering the ratio of caryophyllene in copaiba oil, it can be concluded that the repellent activity of copaiba oil is due to caryophyllene.

6) Repellent activity test of floor wax containing copaiba oil Copaiba oil was added to floor wax (acrylic resin, trade name: Himac, manufactured by Suisho Yuka Kogyo Co., Ltd.) in an amount of 0.1, 2.0, respectively. After adding 7.0% and stirring until uniform, the mixture was applied to a 5 cm × 5 cm synthetic resin flooring,
After drying at room temperature for a period of time, the test sample was subjected to the above-described repellent activity test.

In the sense of comparison with copaiba oil, elemi oil is similarly 0.1%, 2.0% and 7.0% respectively.
Was added to perform a repellent activity test. The data is shown in Table 2.

Elemi oil is based on a resin such as Elemi of the family Orchidaceae. Essential oil is obtained by steam distillation of the resin (20 to 30%). Contains ingredients such as remycin, elemol (about 15%), α-d-ferrandrene, dipentene, and the like. A commercially available perfume raw material was used.

As the insect repellent wax, a commercially available product containing pyrethroid-based etoferon (manufactured by Fukubi Kogyo KK) was used.

[0035]

By adding copaiba oil and elemi oil, the floor wax showed a concentration-dependent repellent effect. The repellent effect was equal to or higher than that of insect repellent wax. 7) Persistence test of repellent activity Copaiba oil and Elemi oil were added to the floor wax at 0.1%, and a repellent activity test was performed every four days in the same manner as described above. Elemi oil contains elemol, which is already known as a sanitary pest repellent, is a resin composed of a high molecular compound called elemyresinoid, and since it is solid at normal temperature, it is presumed that it is preferable as an additive component of floor wax. Was. The data is shown in Table 3.

Table 3 Repellency of sustained repellency test Test wax repellency (%) After 4 days, after 8 days, after 12 days, after 16 days, after 20 days Floor wax only 18 20 0 10 6 + Copaiba oil 68 79 87 50 70 + Elemi oil 78 72 43 0 0 insect repellent wax 62 52 48 58 54

The floor wax to which copaiba oil was added did not lose its initial repellent activity until around 20 days, and showed repellent activity until around 30 days (data not shown). In contrast, Elemi oil had about half the repellent activity after 12 days, and was found to be inferior to copaiba oil as a repellent active for floor waxes that require persistence. This is presumed to be due to the difference in volatility of the repellent active ingredient in the oil.

2. Sustained repellent activity test against Agaricus blazei L. and L. japonicus 1) Insects to be tested Insects Lactobacillus brasiliensis reared on artificial feed
(Attagenus unicolorB _RAHM ) and Hirata _{Kokunutomodoki}
(Triborium confusum jacqueli D _AVAL ) adult individuals were used. Burdock beetles are pests that eat clothing and inhabit closets and closets. Hirata kokusutomodoki is one of the major pests of cereals such as rice and wheat, and is found in cereal storage, food factories, and home kitchens.

2) Test method for evaluation of duration of repellent activity 0.1% and 0.5% copaiba oil was mixed with acrylic floor wax, and stirred until uniform, followed by 5 cm.
X 5 cm applied to synthetic resin flooring, dried for 24 hours at room temperature, placed on the bottom of a 30 cm diameter circular plastic container,
A 500 ml beaker with an entrance covered with aluminum foil is placed over the test sample as a shelter, 20 German cockroaches are put in, and the number of individuals outside the shelter is measured after 24 hours at 25 ° C. % Was calculated and used as the repellent rate. After completion of the test, the applied flooring material was preserved in a desiccator, and a repellent activity persistence test was carried out by the above-described method as appropriate. A flooring agent to which only flooring wax was applied was used as a control. The data is shown in Table 4.

[Table 4] Sustained repellent activity test of the turtle beetle (A) and Pleurotus terrestris (B ) Repellent rate of test insect essential oil (%) Repellent rate (%) 4 days 8 days 12 days 16 days 20 days A 0.196 92 86 88 82 0.5 100 100 100 98 98 90 B 0.1 84 72 72 66 68 0.5 92 92 92 84 86 80

Results Both test insects were found to repel copaiba oil until about 20 days after application. In addition, the activity was higher in Himekatsuobushimushi (A) than in Hiratako-Kunostomodoki (B). Considering the wax effect, the amount of addition to the wax must be at least 0.5%.

II. Glossiness measurement test A sample was added to floor wax at 0.1%, applied to a resin flooring material, dried at room temperature for 24 hours, and then a glossmeter (GLOSSMETER JG JOHNSON CORPORATION) was used to evaluate the glossiness of the coated surface.
-100).

1) Test for glossiness of floor wax containing copaiba oil 0.1% copaiba oil or elemi oil was added to floor wax, applied to resin flooring, dried at room temperature for 24 hours, and then subjected to the above gloss. It was measured using a degree meter. As a control, a flooring material to which nothing was applied was used, and the ratio was expressed as a percentage of the glossiness of this flooring material alone. The data is shown in Table 5.

Table 5 Gloss test results (after 24 hours) Test wax essential oil concentration (%) Gloss ratio Floor wax only 5.4 + Copaiba oil 0.1 9.4 + Elemi oil 0.1 9.4 Insect repellent Wax 3.6

By adding copaiba oil or elemi oil, the glossiness, which is one component of the commercial value of floor wax, is far superior to floor wax alone and insect repellent wax.

2) Sustainability test of gloss One of the properties of the wax for flooring, which is required to be persistent as well as gloss. Copaiba oil and Elemi oil were added at 0.1% to the floor wax, and after 4 and 30 days, the gloss test was performed in the same manner as described above. The data is shown in Table 6.

[0048]

In both copaiba oil and eremi oil, the glossiness did not change after 30 days, and the glossiness was not reduced by the addition of the repellent active ingredient. It turned out that there was no problem in terms of the persistence of glossiness. In terms of practical use as a floor wax, its sustainability is extremely important. Copaiba oil was persistent in both repellent effect and glossiness, but Elemi oil was inferior to copaiba oil in persistence of repellent effect. For this reason, copaiba oil is more practical than elemi oil as a repellent active substance for floor wax.

[0050]

EXAMPLES In the following examples, various repellents can be produced using caryophyllene as an alternative to copaiba oil.

Example 1 Granular repellent 95% or more of caryophyllene was diluted with ethyl alcohol to 0.5%, and a retention agent (dipropylene glycol) 1.5.
g of attapulgite and mixed with 8 g of attapulgite, impregnated with 5% of karyophyllene as a final concentration, and then put into a non-woven fabric (two 3.5 cm × 11 cm cloths are laminated and bonded on three sides). Fill and close the bag.

Example 1 Granular repellent Retainer in copaiba oil 0.5% ethyl alcohol solution
1.5 g of (dipropylene glycol) were mixed and added to 8 g of attapulgite, and impregnated with 5% of copaiba oil as a final concentration, and the resultant was made of a nonwoven fabric (3.5 cm × 11 cm).
), And put it in a cylindrical bag.

Example 2 Gel-like repellent 2 g of carrageenan (natural polymer substance) was dissolved in water at 60 ° C., and when the temperature dropped to 40 ° C. or less, 2 g of copaiba oil and polyoxyethylene nonyl phenyl ether were added thereto.
(Ethylene oxyside added mole number) 10 to 20 (nonionic surfactant) 5 g (2 to 3 times the amount of copaiba oil) and a mixture thereof were poured into a mold for molding, cooled and molded. , About 100 g of gelling repellent.

Example 3 Packaging liquid repellent 5 g of copaiba oil and 95 g of dipropylene glycol
And filled in a liquid state in eight bags (3 cm × 3 cm) each coated with a polymer having a fragrance-permeable property.

Example 4 Cured resin repellent 5 g of copaiba oil was added to ultraviolet curable resin W-3 (trade name,
After mixing with 95 g of Mitsubishi Chemical Corporation and injecting into a mold, the resin is cured by irradiation with ultraviolet rays, molded, and formulated to give a product of 100 g.

Example 5 Oil-based gelling repellent Evaporation regulator (diethylene glycol monoethyl ether)
Add 50g of fatty acid soap and 3g of purified water to 50g,
The temperature is raised to 0 ° C., and when the fatty acid soap is dissolved, the temperature is lowered to 70 ° C., 5 g of copaiba oil is added, and after stirring, the mixture is poured into a mold and cooled and molded to produce an oily gelling repellent. .

Example 6 A plate in which EVA resin (manufactured by Mitsui DuPont, trade name, EVAFLEX) was molded was impregnated with a mixture of 2 g of copaiba oil and 2 g of a retention agent (Solfit), and about 10 g of repellent was obtained. Manufacture of a functional plate.

Example 7 Repellent Aerosol 2 g of copaiba oil, 2 g of triethyl citrate, 27 g of ethyl alcohol, and a propellant (liquefied petroleum gas (LPG)) 6
A mixture of 9 g is made and filled in a tin three-piece can to produce an aerosol product (coating agent).

Example 8 Repellent spray agent 5 g of copaiba oil, 10 g of ethyl alcohol and a retaining agent
(Dipropylene glycol) 10 g, and surfactant
(Polyoxyethylene alkyl ether) 5 g and a mixture of 70 g of water are put into a glass or molded container,
Manufactures non-gas type spray products.

Example 9 Wax for Repellent Active Bed Metal (zinc) crosslinked styrene acrylic copolymer emulsion (nonvolatile content 40%) 46.0%, high melting point synthetic wax emulsion (nonvolatile content 40%) 8.5%, alkali soluble 3.8% resin solution (30% non-volatile content), 2.0% plasticizer,
1.5% leveling agent (1% aqueous solution), 6.0% film forming aid,
30.2% of water, 1.0% of a preservative, and 1.0% of a defoamer are added with stirring while gradually mixing. After stirring for 5 hours,
After filtration through 200 mesh, copaiba oil is added (0.1% to 7% based on the wax), followed by stirring and mixing.

Example 10 Pest repellent for clothing A sublimable substance such as paradicrol benzol, naphthalene, camphor and the like is added with 0.1% to 10% of copaiba oil, and a tablet is produced by tableting.

Example 11 Pest repellent for clothing Flolite (calcium silicate) grains with copaiba oil 1
% To 10% impregnated.

[Brief description of the drawings]

FIG. 1 is a chart of gas chromatography of copaiba oil.

FIG. 2 is an analysis flow sheet of copaiba oil.

FIG. 3 is a development view of thin-layer chromatography of Fr. 1 to Fr.

FIG. 4 is a gas chromatography chart of Fr.

FIG. 5 is a chart of gas chromatography-mass spectrometry of Fr.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2B121 AA16 CA02 CC21 CC25 CC35 CC40 EA05 FA07 FA13 FA15 4H011 AC06 BA01 BB01 BB22 BC03 BC19 DA02 DA07 DA17 DA21 DB02 DB03 DD05 DD06 DF05 DG03 DG05 DH02 DH03 DH15

Claims (3)

[Claims] 1. A sanitary pest repellent comprising copaiba oil and / or caryophyllene as an active ingredient. 2. A sanitary pest repellent active wax containing copaiba oil and / or caryophyllene as an active ingredient. 3. The sanitary pest repellent active wax according to claim 2, wherein the wax is a floor wax.