JP2009046411A - Insect proof dye - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insect proof dye comprising an ingredient derived from an alkaloid having antimicrobial properties as an active ingredient and having high safety and excellent fastness. <P>SOLUTION: The insect proof dye is selected from the group represented by general formula (I) or general formula (II) (wherein, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>, R<SP>7</SP>and R<SP>8</SP>represent each independently H, OH, a methyl, a methoxy or an acetoxy or represent a methylenedioxy; and X represents a methyl, a methoxy or a trifluoromethyl). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an insect repellent dye containing an alkaloid derivative imparted with antibacterial properties or a salt thereof.

In order to protect clothing such as silk and wool from pest damage, the following three methods are known.
1) Apply an insect repellent containing a volatile insect repellent to clothing.
2) An insect repellent component is contained in the fiber constituting the clothing.
3) Use a dye having insecticidal or repellent properties.
Among these, volatile insect repellent components used in the method 1) include empentrin, profluthrin and the like, and many insect repellents have been put into practical use. In addition, for example, silafluophene is useful for the method 2) (Patent Document 1).

On the other hand, in recent years, there has been a need for clothes that have natural fibers dyed with natural materials against the background of increasing consumer preference for nature and cleanliness, and have antibacterial and deodorizing effects using natural materials. An antibacterial cloth using dyed berberine (Patent Document 2) or matrine extracted from Clara root (Patent Document 3) is disclosed. However, these have no insect repellent effect and do not satisfy the requirement 3).

By the way, the present inventors tried to develop a pest control agent derived from natural chemical substances such as terpenes and alkaloids, and studied the components contained in extracts such as Takenigusa (Macleaya cordata), which is a poppy family plant. . In the process, it has been found that certain alkaloid derivatives or salts bring about a high lethal action as sanitary pests and agricultural pest control agents, particularly mosquitoes and fly larvae, and patents have already been filed (Patent Documents 4 and 5). However, the development of the above 3) intended for use as insect repellent dyes has not been studied.
Japanese Patent No. 2739223 Japanese Examined Patent Publication No. 6-33259 JP-A-6-183926 Japanese Patent Application No. 2006-75502 Japanese Patent Application No. 2006-221923

It is an object of the present invention to provide an insect repellent dye having an antibacterial property and an alkaloid-derived component as an active ingredient and having high safety and excellent fastness.

In order to solve the above-mentioned problems, the present inventors have conducted an intensive study on extracts of the poppy family, Takelegusa (Macleaya cordata) and the like, and based on protopins and allocryptopins represented by the following general formula (I): Alkaloid derivatives or salts having a skeleton, and sanguinarine or chelerythrine represented by the general formula (II) and alkaloid derivatives or salts having them as a basic skeleton exhibit a high feeding inhibitory effect or repellent effect against clothing pests, It was found that the antibacterial property was excellent, and the present invention was completed.

（Ｉ）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴はおのおの独立して水素原子、水酸基、メチル基、メトキシ基、アセトキシ基を示すか、もしくはＲ¹、Ｒ²及び／又はＲ³、Ｒ⁴は一緒になってメチレンジオキシ基を示す。また、Xはメチル基、メトキシ基又はトリフルオロメチル基を示す。）又は一般式（II）

（II）

（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸はおのおの独立して水素原子、水酸基、メチル基、メトキシ基、アセトキシ基を示すか、もしくはＲ⁵、Ｒ⁶及び／又はＲ⁷、Ｒ⁸は一緒になってメチレンジオキシ基を示す。また、Xはメチル基、メトキシ基又はトリフルオロメチル基を示す。）で示される群から選ばれる一種又は二種以上の化合物を含有する防虫染料。
（２）アルカロイド誘導体又はそれらの塩が、プロトピン（Ｒ¹、Ｒ²及びＲ³、Ｒ⁴が一緒になってメチレンジオキシ基、Xがメチル基）又はその塩である（１）記載の防虫染料。
（３）アルカロイド誘導体又はそれらの塩が、アロクリプトピン（Ｒ¹、Ｒ²が一緒になってメチレンジオキシ基、Ｒ³及びＲ⁴がメトキシ基、Xがメチル基）又はその塩である（１）記載の防虫染料。
（４）アルカロイド誘導体又はそれらの塩が、サンギナリン（Ｒ⁵、Ｒ⁶及びＲ⁷、Ｒ⁸が一緒になってメチレンジオキシ基、Xがメチル基）である（１）記載の防虫染料。
（５）アルカロイド誘導体又はそれらの塩が、ケレリスリン（Ｒ⁵、Ｒ⁶が一緒になってメチレンジオキシ基、Ｒ⁷及びＲ⁸がメトキシ基、Xがメチル基）である（１）記載の防虫染料。
（６）アルカロイド誘導体又はそれらの塩が、タケニグサ由来物である（１）乃至（５）のいずれか記載の防虫染料。 That is, the present invention adopts the following configuration.
(1) Alkaloid derivatives having antibacterial properties or salts thereof having the general formula (I)

(I)

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group or an acetoxy group, or R ¹ , R ² and / or R ³ , R ⁴ together represents a methylenedioxy group, and X represents a methyl group, a methoxy group or a trifluoromethyl group.) Or the general formula (II)

(II)

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group or an acetoxy group, or R ⁵ , R ⁶ and / or R ⁷ , R ⁸ represents a methylenedioxy group together, and X represents a methyl group, a methoxy group or a trifluoromethyl group.) Insect repellents containing one or more compounds selected from the group represented by .
(2) The insect repellent according to (1), wherein the alkaloid derivative or a salt thereof is protopine (R ¹ , R ² and R ³ , R ⁴ are taken together to form a methylenedioxy group, X is a methyl group) or a salt thereof dye.
(3) Alkaloid derivatives or salts thereof are allocryptopine (R ¹ and R ² together, methylenedioxy group, R ³ and R ⁴ are methoxy groups, X is a methyl group) or a salt thereof ( 1) Insect repellent dyes.
(4) The insect repellent dye according to (1), wherein the alkaloid derivative or a salt thereof is sanguinarine (R ⁵ , R ⁶ and R ⁷ , R ⁸ are taken together to form a methylenedioxy group, and X is a methyl group).
(5) The insect repellent according to (1), wherein the alkaloid derivative or a salt thereof is chelerythrine (R ⁵ and R ⁶ together represent a methylenedioxy group, R ⁷ and R ⁸ are a methoxy group, and X is a methyl group). dye.
(6) The insect repellent dye according to any one of (1) to (5), wherein the alkaloid derivative or a salt thereof is derived from a bamboo rush.

The insect repellent dye of the present invention is extremely practical because the alkaloid-derived substance as an active ingredient exhibits a high anti-feeding or repellent effect against clothing pests and is also excellent in antibacterial properties.

（Ｉ）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴はおのおの独立して水素原子、水酸基、メチル基、メトキシ基、アセトキシ基を示すか、もしくはＲ¹、Ｒ²及び／又はＲ³、Ｒ⁴は一緒になってメチレンジオキシ基を示す。また、Xはメチル基、メトキシ基又はトリフルオロメチル基を示す。）又は一般式（II）

（II）

（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸はおのおの独立して水素原子、水酸基、メチル基、メトキシ基、アセトキシ基を示すか、もしくはＲ⁵、Ｒ⁶及び／又はＲ⁷、Ｒ⁸は一緒になってメチレンジオキシ基を示す。また、Xはメチル基、メトキシ基又はトリフルオロメチル基を示す。）で示されるアルカロイド誘導体又はそれらの塩からなる群から選ばれる少なくとも一種を使用する。 The pest control agent of the present invention has the general formula (I) as an active ingredient.

(I)

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group or an acetoxy group, or R ¹ , R ² and / or R ³ , R ⁴ together represents a methylenedioxy group, and X represents a methyl group, a methoxy group or a trifluoromethyl group.) Or the general formula (II)

(II)

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group or an acetoxy group, or R ⁵ , R ⁶ and / or R ⁷ , R ⁸ represents a methylenedioxy group together, and X represents a methyl group, a methoxy group or a trifluoromethyl group.) And at least one selected from the group consisting of alkaloid derivatives or salts thereof To do.

Among these compounds, protopine (R ¹ , R ² and R ³ , R ⁴ together form a methylenedioxy group), allocryptopine (R ¹ , R ² together form methylenedioxy) Group, R ³ and R ⁴ are methoxy groups), sanguinarine (R ⁵ , R ⁶ and R ⁷ , R ⁸ together methylenedioxy group, X is a methyl group), or chelerythrine (R ⁵ , R ⁶ is a methylenedioxy group, R ⁷ and R ⁸ are methoxy groups, and X is a methyl group), which is an alkaloid peculiar to poppy plants and is particularly useful.

Protopine, alocryptopine, sanguinarine or chelerythrine can be obtained from the living body of dried bamboo shoots or dried products, such as water, methanol, ethanol, isopropanol, acetone, acetic acid and other hydrophilic solvents, and toluene, diethyl ether, ethyl acetate, methylene chloride, chloroform, etc. It can be obtained by extraction at room temperature or about the boiling point of the solvent using a lipophilic solvent or a mixed solvent thereof. It can also be extracted by supercritical extraction with carbon dioxide. These extracted substances may be used as they are, but those extracted by adsorption purification using ion exchange resin, silica gel, activated carbon, column chromatography, recrystallization, etc. can also be used.

In the present invention, protopine, allocryptin, sanguinarine or chelerythrine and their derivatives may be either natural extracts or chemical compounds. And they should be used as salts with inorganic acids (eg carbonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, etc.) and organic acids (formic acid, acetic acid, propionic acid, butyric acid, fatty acid, cinnamic acid, benzenesulfonic acid, coalic acid, etc.) Is also possible.

When used as an insect repellent, the alkaloid represented by the general formula (I) or the general formula (II) or a salt thereof is water, alcohols (for example, methyl alcohol, ethyl alcohol, n-propyl alcohol) if necessary. , Isopropyl alcohol, ethylene glycol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers (eg, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), liquid solvents, and further emulsification, dispersion, stabilization, etc. Depending on the purpose, surfactants, water-soluble polymers, antioxidants and the like can be used as auxiliaries.

Moreover, it is common to use a mordant at the time of dyeing. The mordant is not particularly limited, and examples thereof include tannin and aluminum acetate.
The alkaloid derivatives and salts thereof used in the present invention exhibit high fastness because the base contained in the chemical structure is strongly bonded to the phenolic hydroxyl group constituting the tyrosine residue of silk or wool fiber.

Specific examples of clothing pests targeted by the insect-repellent dyes of the present invention include, for example, moths, moths, cutlet worms, scallops, blemis, etc., and Bacillus cereus, Escherichia coli. It exhibits high antibacterial properties against bacteria such as Pseudomonas aeruginosa and Trichophyton mentagrophytes.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

About 3 kg of bamboo shoot leaf and stem methanol extracts were filtered and concentrated with an evaporator to obtain an extract. Moreover, protopine, allocryptopine, sanguinarine and chelerythrine were isolated as active ingredients by various chromatographies and recrystallization. These extracts and each isolated component were dissolved in ethanol at a predetermined concentration to obtain an insect repellent dye of the present invention.

[Preparation of dyed fabric]
A 5% dose of alkaloid derivative hydrochloride was dissolved in 10% ethanol aqueous solution at a dissolution ratio of 1: 200 per 10 g of silk cloth. This was added to the dyeing machine and stirred well, and the silk cloth from which the paste was removed was put into this, and the stirring was continued gently for 30 minutes with hot water of 35 to 85 ° C. Next, a silk cloth dyed in a 3% aqueous solution of aluminum acetate as a mordant was soaked for 30 minutes for the purpose of enhancing fastness to washing and washing. This was taken out, washed with water for 1 minute, and naturally dried indoors. This water washing and drying cycle was repeated 10 times. The yellow color hardly faded and was confirmed to be excellent in fastness, and then subjected to the following performance test.

[Insect repellent test of dyed cloth]
Cut the test dyed cloth to 4.5cm x 4.5cm, put it in a petri dish with a diameter of 7.5cm and a depth of 1.5cm, along with 10 moths or swordworm larvae, cover it and cover it with a darkness of 25 ± 1 ° C I saved it in the place. The insecticidal efficacy was evaluated by observing the feeding damage of the dyed fabric after 1 week and 2 weeks, respectively. The evaluation results are shown in Table 1 based on the following criteria.
-: No damage, +: Small trace of damage, ++: Small damage,
++++: Significant food damage.

As a result of the test, it was confirmed that the insect repellant dye of the present invention in which the bamboo rush extract and each isolated component were dissolved in ethanol at a predetermined concentration showed an excellent feeding inhibitory effect against clothing pests.

[Antimicrobial test of dyed fabric]
The antibacterial activity of the test dyed fabric against bacteria and filamentous fungi was evaluated by the halo test method, and the antibacterial fabric was evaluated by measuring the diameter of the inhibition circle. The test results are shown in Table 2.

・試験菌1；Bacillus cereus NBRC3002, ブイヨン寒天培地。
・試験菌2；Escherichia coli NIHJ, ブイヨン寒天培地。
・試験菌3；Psedomonas aeruginosa ATCC27853, ブイヨン寒天培地。
・試験菌4；Trichophyton mentagrophytes IFO5975, サブロー寒天培地。

Test bacteria 1; Bacillus cereus NBRC3002, bouillon agar medium.
Test bacteria 2; Escherichia coli NIHJ, bouillon agar medium.
Test bacteria 3; Psedomonas aeruginosa ATCC27853, bouillon agar medium.
Test bacteria 4; Trichophyton mentagrophytes IFO5975, Sabouraud agar medium.

As a result of the test, it was shown that the dyed fabric obtained by the present invention has high antibacterial properties and there is no fear of discoloration even after long-term storage.

Claims (6)

An alkaloid derivative having antibacterial properties or a salt thereof, which has the general formula (I)

(I)

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group or an acetoxy group, or R ¹ , R ² and / or R ³ , R ⁴ together represents a methylenedioxy group, and X represents a methyl group, a methoxy group or a trifluoromethyl group.) Or the general formula (II)

(II)

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group or an acetoxy group, or R ⁵ , R ⁶ and / or R ⁷ , R ⁸ represents a methylenedioxy group together, and X represents a methyl group, a methoxy group or a trifluoromethyl group.) And contains one or more compounds selected from the group represented by Insect repellent dye. 2. The alkaloid derivative or a salt thereof is protopine (R ¹ , R ² and R ³ , R ^{4 taken} together are methylenedioxy group, X is a methyl group) or a salt thereof. Insect repellent dye. The alkaloid derivative or a salt thereof is allocryptopine (R ¹ and R ² together are a methylenedioxy group, R ³ and R ⁴ are a methoxy group, X is a methyl group) or a salt thereof The insect repellent dye according to claim 1. 2. The insect repellent dye according to claim 1, wherein the alkaloid derivative or a salt thereof is sanguinarine (R ⁵ , R ⁶ and R ⁷ , R ^{8 taken} together are a methylenedioxy group and X is a methyl group). . 2. The alkaloid derivative or a salt thereof is chelerythrine (R ⁵ and R ⁶ together are a methylenedioxy group, R ⁷ and R ⁸ are a methoxy group, and X is a methyl group). Insect repellent dye. The insect repellent dye according to any one of claims 1 to 5, wherein the alkaloid derivative or a salt thereof is derived from a bamboo rush.