JP2011012028A - Rosemary oil extract, cockroach repellent containing the rosemary oil extract and method of obtaining rosemary oil extract - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a repellent having a sufficient repellent effect against cockroaches and durability.SOLUTION: A rosemary oil extract having a repellent effect against cockroaches obtained by purifying rosemary oil by chromatography is obtained by eluting rosemary oil from the column in which the rosemary oil is adsorbed on an adsorbent with the use of hexane or a hexane-diethyl ether mixed solvent as a developing solvent and thereafter eluting the residue with the use of diethyl ether and ethyl acetate as developing solvents, respectively. The cockroach repellent contains the rosemary oil extract.

Description

  The present invention relates to a cockroach repellent containing a specific fraction component which is an extract of rosemary oil, and a method for obtaining the extract of rosemary oil.

  Conventionally, in order to repel sanitary pests such as cockroaches, diets and pyrethroid insecticides have been used. However, in recent years, there has been a tendency to have a feeling of resistance to using such ingredients in places where humans can easily touch or where food is present.

  Thus, repellents using safer ingredients derived from natural products have been studied, and for example, pests are repelled using essential oils collected from plants. Specifically, a method for attaching a pest repellent footband containing plant essential oil to a human foot and a satellite pest repellent device using a sanitary pest repellent containing a plant essential oil belonging to the family Labiatae have been proposed ( For example, see Patent Documents 1 and 2). For such pest repellents, for example, plant essential oils such as lavender oil, peppermint oil, and basil oil can be used.

JP 2004-51564 A JP 2003-164248 A

However, plant essential oils have high safety but have insufficient repellent effects, and have the disadvantage of lack of sustainability. Therefore, in order to obtain a sufficient repellent effect, it is necessary to use a large amount, and there are problems in practical use such as difficulty in obtaining and high cost.
Therefore, an object of the present invention is to provide a plant essential oil and a cockroach repellent that have a sufficient repellent effect even if it is not used in a large amount with respect to cockroaches, can reduce costs, and are durable.

  As a result of intensive studies, the present inventors have found that, among the fraction components of rosemary oil, specific fraction components have a high repellent effect on cockroaches and have a high sustainability, and thus complete the present invention. It came.

That is, the present invention is achieved by the following (1) to (3).
(1) An extract obtained by purifying rosemary oil by chromatography,
After eluting from a column adsorbed with rosemary oil on the adsorbent using hexane or hexane / diethyl ether mixed solvent as the developing solvent, the residue is repelled against cockroaches eluted with diethyl ether and ethyl acetate as the developing solvent, respectively. Has an extract of rosemary oil.
(2) A cockroach repellent containing the rosemary oil extract of (1) above.
(3) Chromatography from a column in which rosemary oil is adsorbed on an adsorbent,
(A) a step of eluting the first fraction component using hexane as a developing solvent;
(B) From the residue obtained by collecting the first fraction component, the second fraction component using a mixed solvent of hexane: hexane / diethyl ether mixed solvent (hexane: diethyl ether (4: 1)) = 1: 1 as a developing solvent. Elution step,
(C) a step of eluting the third fraction component from the residue obtained by collecting the second fraction component using a mixed solvent of hexane: diethyl ether = 1: 1 as a developing solvent;
(D) a step of eluting the fourth fraction component from the residue obtained by collecting the third fraction component using a mixed solvent of hexane: diethyl ether = 1: 4 as a developing solvent;
(E) eluting the fifth fraction component from the residue obtained by collecting the fourth fraction component using diethyl ether as a developing solvent;
(F) Collecting the fifth fraction component and the sixth fraction component from the residue obtained by collecting the fifth fraction component in a step of eluting the sixth fraction component using ethyl acetate as a developing solvent, and repelling cockroaches A method for obtaining an extract of rosemary oil having an action.

  Since the fifth fraction component and the sixth fraction component, which are extracts obtained by elution of diethyl ether and ethyl acetate from the rosemary oil of the present invention as developing solvents, contain purified repellent components, this rose The cockroach repellent of the present invention comprising an extract of mary oil as an active ingredient has a high repellent effect on cockroaches and has a high sustainability, so that the amount used can also be suppressed. In addition, since it is highly safe for the human body, it can be applied to various places, and can be used especially in places where people are easily touched or where food is present.

It is a gas chromatogram of the 1st fraction component of rosemary oil. It is a gas chromatogram of the 2nd fraction component of rosemary oil. It is a gas chromatogram of the 3rd fraction component of rosemary oil. It is a gas chromatogram of the 4th fraction component of rosemary oil. It is a gas chromatogram of the 5th fraction component of rosemary oil. It is a gas chromatogram of the 6th fraction component of rosemary oil. It is a figure for demonstrating the experimental apparatus used in Example 2, 3. FIG.

  Hereinafter, the present invention will be described in detail. The extract of rosemary oil according to the present invention is an extract obtained by purifying rosemary oil by chromatography.

  Rosemary (scientific name: Rosmarinus officinalis) is an evergreen shrub of the family Lamiaceae widely distributed in countries of the Mediterranean coast. Rosemary oil is an essential oil collected by distilling leaves and flowers of rosemary. It is liquid. Examples of the rosemary oil that can be used in the present invention include rosemary cineole, rosemary berbenone, rosemary camphor and the like.

  Rosemary oil can be fractionated by adsorption column chromatography, liquid chromatography, or gas chromatography using an adsorbent such as silica gel, alumina, glass beads, polymer resin, or diatomaceous earth. In the present invention, it is preferable to use adsorption column chromatography using silica gel because the operation is simple and a large amount of sample can be processed.

  When using adsorption column chromatography, it is preferable to use a developing solvent in order from a low polarity and to elute in multiple steps. This is because, by gradually increasing the polarity of the solvent, it is possible to sequentially elute high polar substances from low polar substances. Examples of the developing solvent include hexane, diethyl ether, ethyl acetate, and the like. These solvents can be mixed, and the polarity of the developing solvent can be changed depending on the mixing ratio.

  In the present invention, from a column in which rosemary oil is adsorbed to an adsorbent, components other than repellent components are separated by elution using hexane or a hexane / diethyl ether mixed solvent as a developing solvent. Ethyl is eluted as a developing solvent, and the repellent components are purified and concentrated.

  Specifically, first, the first fraction component is eluted from the rosemary oil adsorbed on an adsorbent such as silica gel using hexane as a developing solvent using chromatography. Next, the residue obtained by collecting the first fraction component is subjected to chromatography using a mixed solvent of hexane: hexane / diethyl ether (hexane: diethyl ether (4: 1)) = 1: 1 as a developing solvent. Elute the second fraction component. Subsequently, the residue obtained by collecting the second fraction component is subjected to chromatography using a mixed solvent of hexane: diethyl ether = 1: 1 as a developing solvent to elute the third fraction component. Then, the residue obtained by collecting the third fraction component is subjected to chromatography using a mixed solvent of hexane: diethyl ether = 1: 4 as a developing solvent to elute the fourth fraction component. It is considered that the aromatic component, antioxidant component and deodorizing component of rosemary oil are purified, concentrated and eluted from the first fraction component to the fourth fraction component.

  Thereafter, the residue obtained by collecting the fourth fraction component is subjected to chromatography using diethyl ether as a developing solvent to elute the fifth fraction component. Then, the residue obtained by collecting the fifth fraction component is subjected to chromatography using ethyl acetate as a developing solvent to elute the sixth fraction component.

  In the step of obtaining the fourth fraction component from the step of obtaining the first fraction component, which is an elution step using a mixed solvent of hexane and hexane / diethyl ether, by eluting sequentially from components that are easily soluble in a low polarity solvent. It separates fragrance components and antioxidant components. The developing solvent gradually increases in polarity by increasing the proportion of diethyl ether in order. In addition, elution using hexane, hexane / diethyl ether mixed solvent may be performed in any number of steps.

  The fifth fraction component and the sixth fraction component collected by the above method contain a cockroach repellent component purified and concentrated. These fraction components may be used as they are as the elution stock solution, but may be used after being concentrated and dried by an appropriate method, or may be used after being dissolved in an appropriate solvent. Examples of the solvent include acetone, ethanol, methanol, paraffin, and the like.

  The cockroach repellent of the present invention is obtained by separating rosemary oil from hexane and hexane / diethyl ether mixed solvent by the above method, and then extracting at least an extract eluted with diethyl ether and ethyl acetate as developing solvents, respectively. One is an active ingredient. The cockroach repellent of the present invention can be used as various preparations, for example, as a liquid, a gel, a sol, a granule, a granule, a spray, a sheet, etc., using a carrier such as a liquid or a solid. What is necessary is just to formulate. By installing these preparations in the target space, the repellent component is naturally volatilized or directly sprayed on the target space, and the repellent component is spread throughout the target space using air movement and convection in the target space. Like that. In addition, the cockroach repellent may be attached to at least a part of the body of the cockroach, or may be attached to the entire body surface / leg.

The rosemary oil extract, which is an active ingredient, may be selected in its blending amount and usage amount so as to be an effective amount suitable for these preparations. For example, when used as a liquid, the active ingredient is preferably contained in an amount of 0.01% by mass or more, more preferably 0.1 to 30% by mass in the liquid. When used as a gel, the active ingredient is preferably contained in an amount of 0.1% by mass or more, more preferably 0.5 to 30% by mass in the gel. When used as a granule, the active ingredient is preferably contained in an amount of 0.1% by mass or more, and more preferably 0.5 to 30% by mass. By making the extract of the rosemary oil within the above range, a sufficient repelling effect of cockroaches can be obtained and the sustainability can be enhanced.
The effective air concentration of the active ingredient is preferably 0.1 μg / L to 1000 μg / L, more preferably 1 μg / L to 100 μg / L. For example, in the living room, the active ingredient naturally spreads throughout the room due to movement of the occupant, movement of air generated by opening / closing of doors and windows, or convection.

  In addition, the cockroach repellent of the present invention can be blended with other components as necessary, as long as the effect is not impaired. For example, 1 type (s) or 2 or more types chosen from a coloring agent, a ultraviolet absorber, antiseptic | preservative, a pH adjuster, antioxidant, a fragrance | flavor, essential oil, etc. can be mix | blended.

  Examples of the colorant include legal dyes such as Blue No. 1, Green No. 202 and Purple No. 201, and natural dyes such as riboflavin, perilla and chlorophyll.

  Examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, and benzotriazole-based compounds such as 2- (2′-hydroxy-5′-methylphenyl) enzotriazole.

  Examples of the preservative include phenoxyethanol, benzyl alcohol, and parabens.

  Examples of the pH adjuster include citric acid, phosphoric acid, sodium carbonate and the like.

  The cockroach repellent of the present invention can be applied to various cockroaches, for example, German cockroach, black cockroach, American cockroach, Great cockroach, Great cockroach, etc. .

  Hereinafter, although the cockroach repellent of this invention is demonstrated in detail from an Example, this invention is not restrict | limited at all by these examples.

Example 1
<Rosemary oil fraction>
Fractionation was performed using silica gel chromatography.
Absorbent cotton was packed into the liquid outlet of a glass column for chromatography (inner diameter 50 mm × length 500 mm) for diameter reduction toward the liquid outlet. After pouring an appropriate amount of hexane into the column, sea sand was packed into the reduced diameter portion.
An appropriate amount of hexane was put into a beaker containing 200 g of silica gel (trade name: silica gel 60 (spherical, particle size 63 to 210 μm), manufactured by Kanto Chemical Co., Inc.) and stirred. This was slowly poured into the column, and it was confirmed that silica gel was tightly packed in the column while flowing hexane.
When hexane was dripped from the lower surface position of the silica gel layer, 10 g of rosemary oil (trade name: ROSEMARY OIL, MATIERES PREMIERES ESSENTIELLES) was poured to adsorb the rosemary oil onto the silica gel.

After confirming that all the rosemary oil had soaked into the silica gel, the first to sixth fraction components were eluted and fractionated using the following developing solvent (flow rate: 40 to 50 mL / min).
(Developing solvent)
First fraction: 300 mL of hexane
Second fraction: hexane 300 mL + hexane: diethyl ether = 4: 1 300 mL
Third fraction: hexane: diethyl ether = 1: 1 300 mL
Fourth fraction: hexane: diethyl ether = 1: 4 300 mL
Fifth fraction: diethyl ether 300mL
6th fraction: 300 mL ethyl acetate

With respect to the collected first fraction component to sixth fraction component, the component composition was analyzed by gas chromatography. The analysis conditions are as follows. The analysis results are shown in FIGS.
(Analysis conditions for gas chromatography)
Gas chromatograph apparatus: GC-14B (trade name, manufactured by Shimadzu Corporation)
Column: PEG-20M (trade name, manufactured by GL Science Co., Ltd.)
Carrier: 10% Uniport HP (trade name, manufactured by GL Science Co., Ltd.)
Column size: 3.2mmφ × 2m
Column temperature: 70 ° C. (1 min) → 8 ° C./min→210° C. (5 min)
Injection temperature (Injection temperature): 240 ° C
Detection temperature: 240 ° C
Carrier gas: Nitrogen: 50 mL / min, Hydrogen: 60 mL / min

  As shown in FIGS. 1 to 6, the gas chromatograms of the fifth fraction component shown in FIG. 5 and the sixth fraction component shown in FIG. 6 show similar peaks around a retention time of 10 minutes. I found out. This shows that the repellent component was isolated from other active ingredients by the method of the present invention.

(Example 2)
<Repellent experiment: Black-eye cockroach>
As shown in FIG. 7, 0.8 L-bottom cylindrical plastic cups 1 to 4 having bottoms were installed at the four corners of the cage 10 having a width of 100 cm, a length of 100 cm, and a height of 25 cm. In the plastic cup, an opening 5 having a length of 1 cm and a width of 4 cm was formed on a side surface by cutting away from the side in contact with the floor of the cage 10.
10 μg of the first fraction component of rosemary oil obtained in Example 1 was dropped onto 10 mm long × 10 mm wide × 2 mm thick pulp paper, covered with aluminum foil, and 10 holes were made with a worm needle to make a first sample. Was made. The same process was performed for the second fraction component to the sixth fraction component to prepare second to sixth samples.

The first specimen S was placed in the cup 1 and cup 3 to be treated, and food 6 and water 7 were placed in the approximate center of the cage 10, and 25 males and 25 females of black cockroaches were released in the cage 10. . In addition, the cup 2 and the cup 4 are untreated sections.
The first sample S was moved from the treated area to the untreated area every day, and the number of cockroaches fixed in the treated area and the untreated area was counted every day, and the repelling rate (%) was calculated by the following formula. . The same operation was performed for the second to sixth samples. The test was performed twice for each sample, and the average value of the results is shown in Table 1.
Repelling rate (%) = (number of fixings in the non-treated area−number of fixings in the processing area) / number of fixings in the non-processing area × 100

(Example 3)
<Repellent experiment: German cockroach>
A repelling experiment was conducted on German cockroaches in the same manner as in Example 2 except that the cage 10 having a width of 50 cm, a length of 50 cm, and a height of 25 cm was used. The test was conducted with 30 male and female cockroaches. The results are shown in Table 2.

  From the results of Tables 1 and 2, it can be seen that the fifth sample and the sixth sample have a higher repellent effect and longer duration than the first to fourth samples. From this, it was found that the fifth fraction component and the sixth fraction component fractionated by the method of the present invention were excellent in the repellent effect against cockroaches.

  Subsequently, formulation examples (formulation examples 1 to 8) of cockroach repellents using the extract of rosemary oil according to the present invention are shown. In the preparation examples, the fifth fraction component and the sixth fraction component of rosemary oil are extracts obtained by purifying rosemary oil with diethyl ether and ethyl acetate by the method of Example 1, respectively.

<Formulation Example 1: Solution>
Rosemary oil 5th fraction component 1.0g
Polyethylene hydrogenated castor oil 2.0g
Ethanol 1.0g
Total balance of ion water 100.0 g

<Formulation Example 2: Solution>
Rosemary oil 6th fraction component 1.0g
Polyethylene hydrogenated castor oil 2.0g
Ethanol 1.0g
Total balance of ion water 100.0 g

<Formulation Example 3: Gel Agent>
Rosemary oil 5th fraction component 5.0g
0.8g polyethylene hardened castor oil
Ethanol 1.0g
Carrageenan 2.0g
Concentrated glycerin 0.5g
Green 3 0.1g
Total balance of ion water 100.0 g

<Formulation Example 4: Gel Agent>
Rosemary oil 6th fraction component 5.0g
0.8g polyethylene hardened castor oil
Ethanol 1.0g
Carrageenan 2.0g
Concentrated glycerin 0.5g
Green 3 0.1g
Total balance of ion water 100.0 g

<Formulation Example 5: Granule>
Rosemary oil 5th fraction component 5.0g
Silica anhydride 2.0g
BHT 0.001g
Heavy calcium carbonate balance total 100.0 g

<Formulation Example 6: Granule>
Rosemary oil 6th fraction component 5.0g
Silica anhydride 2.0g
BHT 0.001g
Heavy calcium carbonate balance total 100.0 g

<Formulation Example 7: Aerosol>
[Undiluted solution]
Rosemary oil 5th fraction component 5.0g
Neothiozol 100.0 mL [propellant]
DME (dimethyl ether) 90.0mL
LPG (liquefied petroleum gas) 110.0mL
Total 300.0mL

<Formulation Example 7: Aerosol>
[Undiluted solution]
Rosemary oil 6th fraction component 5.0g
Neothiozol 100.0 mL [propellant]
DME (dimethyl ether) 90.0mL
LPG (liquefied petroleum gas) 110.0mL
Total 300.0mL

  The cockroach repellent of the present invention has a high repellent effect on cockroaches and a high persistence. And since it does not contain a substance that is harmful to the human body, it can be used safely even in places where it is easy for humans to touch or where food is present.

1-4 Cup 5 Opening 6 Feed 7 Water 10 Cage S Specimen

Claims (3)

An extract obtained by chromatographic purification of rosemary oil,
After eluting from a column adsorbed with rosemary oil on the adsorbent using hexane or hexane / diethyl ether mixed solvent as the developing solvent, the residue is repelled against cockroaches eluted with diethyl ether and ethyl acetate as the developing solvent, respectively. Has an extract of rosemary oil.   A cockroach repellent containing the extract of rosemary oil of claim 1. From the column where rosemary oil is adsorbed to the adsorbent, by chromatography,
(A) a step of eluting the first fraction component using hexane as a developing solvent;
(B) From the residue obtained by collecting the first fraction component, the second fraction component using a mixed solvent of hexane: hexane / diethyl ether mixed solvent (hexane: diethyl ether (4: 1)) = 1: 1 as a developing solvent. Elution step,
(C) a step of eluting the third fraction component from the residue obtained by collecting the second fraction component using a mixed solvent of hexane: diethyl ether = 1: 1 as a developing solvent;
(D) a step of eluting the fourth fraction component from the residue obtained by collecting the third fraction component using a mixed solvent of hexane: diethyl ether = 1: 4 as a developing solvent;
(E) eluting the fifth fraction component from the residue obtained by collecting the fourth fraction component using diethyl ether as a developing solvent;
(F) Collecting the fifth fraction component and the sixth fraction component from the residue obtained by collecting the fifth fraction component in a step of eluting the sixth fraction component using ethyl acetate as a developing solvent, and repelling cockroaches A method for obtaining an extract of rosemary oil having an action.

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