JP2013006823A - Insect pest repellent for fiber product, and method for repelling insect pest - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insect pest repellent capable of producing a superior insect pest repelling effect on the skin when it is used for fiber products, and an insect pest repelling method using the repellent.SOLUTION: The insect pest repellent contains : (A) 0.01-20 mass% of repelling ingredient having a menthone skeleton ; (B) 0.01-20 mass% of at least one chosen from the compounds having tertiary amine, its neutralization product, and a quaternary ammonium group ; (C) 0.01-35 mass% of water-miscible solvent ; and (D) water.

Description

  The present invention relates to a pest repellent used by applying to textile products and a pest repellent method using the pest repellent.

Conventionally, mosquitoes have been repelled by applying a liquid repellent to the skin. As repellents for human bodies, those containing diet (diethyltoluamide) as an active ingredient are used. However, there are users who have restrictions and resistance to applying such repellents to the skin. For example, from the Ministry of Health, Labor and Welfare, if you want children (under 12 years of age) to use safety measures for drugs and quasi-drugs that contain diet, use them under the supervision of their parents, and for less than 6 months Instructions are given on the use of cautions not to use for infants, such as once a day for 6 months and under 2 years, 1 to 3 times a day for 2 years and under 12 years.
Therefore, in recent years, research and development have been conducted on naturally derived pest repellent components. For example, Patent Documents 1 to 3 disclose pest repellents containing a compound having a menthane skeleton such as p-menthane-3,8-diol as an active ingredient. Patent Document 4 discloses a pest repellent containing nerolidol and / or methyl undecyl ketone as an active ingredient.

However, although the repellents as described above have a high repellent effect on the part directly applied to the skin, a sufficient repellent effect cannot be obtained when there is uneven application. In addition, when sweating or entering the pool, the active ingredient flows and needs to be reapplied to the skin. In addition to diet, there are many users who are resistant to applying to skin even with other active ingredients.
In recent years, there are installation-type space repellents, but the place of installation is limited, although it has a repellent effect. Fan-type movable products are also commercially available, but they must be attached to the human body.

JP 60-199804 A JP-A-9-2910 JP-A-10-36201 JP 2009-132653 A

In view of the above, there is a need for a pest repellent technique that does not directly apply to the skin, takes less time for application, and provides a high pest repellent effect.
If a repellent as described above is applied to textile products such as clothes, curtains, and bedding to be worn, a repellent effect on the skin can be obtained, the problem of uneven application and repainting can be reduced. Especially in the case of clothing, it is only necessary to wear it, and the place where the effect is obtained is not limited. However, when a repellent such as diet that has been applied to the conventional skin is applied to the fiber product, a repellent effect cannot be obtained for a portion that is not in contact with the fiber product (for example, the skin exposed from the clothing).
The present invention has been made in view of the above circumstances, and an object thereof is to provide a pest repellent that exhibits a high pest repellent effect on the skin when applied to a textile product, and a pest repellent method using the pest repellent. And

As a result of intensive studies, the present inventors have applied a composition in which a specific repellent component and a specific cationic compound coexist in the presence of water and a water-miscible solvent to a textile product, thereby achieving a high pest repellent effect. And the repellent effect was found to last for a long time.
This invention is made | formed based on the said knowledge, and has the following aspects.
[1] (A) 0.01 to 20% by mass of a repellent having a menthane skeleton, and (B) at least one selected from a tertiary amine, a neutralized product thereof, and a compound having a quaternary ammonium group, 0.01 to A pest repellent for textiles, comprising 20% by mass, (C) 0.01 to 35% by mass of a water-miscible solvent, and (D) water.
[2] The pest repellent according to [1], wherein the component (B) contains a compound having a quaternary ammonium group.
[3] The pest repellent according to [1] or [2], wherein the component (A) is p-menthane-3,8-diol.
[4] The pest repellent according to any one of [1] to [3], wherein a mass ratio (A / B) of the component (A) to the component (B) is 0.01 to 20.
[5] The pest repellent according to any one of [1] to [4], further comprising (E) at least one selected from α-pinene, geraniol, citronellal, camphor, and linalool.
[6] The pest repellent according to any one of [1] to [5], further comprising (F) an ultraviolet absorber.
[7] A pest repellent method comprising attaching the pest repellent according to any one of [1] to [6] to a textile product.

  ADVANTAGE OF THE INVENTION According to this invention, the pest repellent which uses the pest repellent which exhibits the outstanding pest repellent effect with respect to skin by applying to a textile product, and the pest repellent method using this pest repellent can be provided.

  The pest repellent for textile products of the present invention (hereinafter referred to as the repellent of the present invention) contains the following component (A), component (B), component (C) and water (D).

[(A) component]
The component (A) is a repellent component having a menthane skeleton.
Menthane skeleton refers to a carbon skeleton of menthane (a saturated hydrocarbon in which one methyl group and one isopropyl group are bonded to two carbon atoms of a cyclohexane ring), and o-menthane represented by the following structural formula (a1) There are a skeleton, an m-menthane skeleton represented by the structural formula (a2), and a p-menthane skeleton represented by the structural formula (a3). In the menthane skeleton, part of the carbon-carbon bond may be a double bond.
As the component (A), those having a p-menthane skeleton are preferable.

The component (A) may be a hydrocarbon in which a hydrogen atom is bonded to a carbon atom constituting the menthane skeleton, or a hydrogen atom of the hydrocarbon substituted with a substituent. Examples of the substituent include a hydroxyl group, an etheric oxygen atom (—O—), an amino group, an alkyl group, a carboxylic acid group, an acyl group, an ester group, an amide group, and the like. Among these, those having a hydroxyl group as a substituent are preferable.
The component (A) can be appropriately selected from compounds known as compounds having a pest repellent action and having a menthane skeleton according to the pests to be repelled. Examples of the pest include flying pests such as mosquitoes, flies, flies and moths. Examples of mosquitoes include squids such as squid and chikaeka, aedes such as Aedes albopictus, chironomids and the like. The repellent of the present invention is particularly useful for mosquito repellent.
Specific examples of the component (A) include p-menthane, p-menthane-3,8-diol, l-menthol, eucalyptol, L-carvone, isimenton, d-limonene, α-terpineol, β-terpineol, γ. -Terpineol etc. are mentioned.
(A) As a component, since it uses for textiles, such as clothing, what is odorless and colorless is preferable. Of these, p-menthane-3,8-diol is preferred because it is odorless and colorless, has a high repellent effect, and is readily available. p-Mentane-3,8-diol can be obtained from Takasago Fragrance Co., Ltd.

The component (A) contained in the repellent of the present invention may be one type or two or more types.
In the repellent of this invention, content of (A) component is 0.01-20 mass% with respect to the total mass of a repellent. When it is 0.01% by mass or more, the repellent effect is excellent. The effect does not change greatly even if it exceeds 20% by mass. The content is preferably 0.1% by mass or more, and more preferably 1% by mass or more. Moreover, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable.

[Component (B)]
Component (B) is at least one selected from tertiary amines, neutralized products thereof, and compounds having a quaternary ammonium group. These compounds are common in that they contain a cationic group (a tertiary amino group or a quaternary ammonium group that may form a salt) that is positively charged in water in the molecule.
By containing (B) component, the sustainability of the repellent effect by (A) component improves. This is considered because (B) component volatilizes (A) component gradually from a fiber.
In particular, by using a compound having a quaternary ammonium group, the repelling effect of the component (A) can be further enhanced in addition to the above-described sustainability improving effect.

As the component (B), for example, a tertiary amine having one tertiary amino group in the molecule, a neutralized product thereof, a compound (B1) selected from the quaternized product, or a salt 3 may be formed. Examples thereof include a polymer compound having a plurality of secondary amino groups in the molecule, and a polymer compound (B2) selected from polymer compounds having a plurality of quaternary ammonium groups in the molecule.
As the tertiary amine in the compound (B1), at least 1 hydrocarbon group having 1 to 24 carbon atoms which may be separated by at least one linking group selected from an amide group, an ester group and an ether group is present in the molecule. Having a tertiary amine is preferred. The hydrocarbon group may be saturated or unsaturated and is preferably a chain.
Examples of the tertiary amine include compounds represented by the following general formula (b1), and more specifically, compounds represented by the following general formulas (b1-1) to (b1-8) Is mentioned.

［式中、Ｒ^１〜Ｒ^３はそれぞれ独立に、アミド基、エステル基およびエーテル基から選ばれる少なくとも１種の連結基で分断されていてもよい炭素数１〜２４の炭化水素基または炭素数１〜５のヒドロキシアルキル基を示し、Ｒ^１〜Ｒ^３のうち少なくとも１つは前記炭化水素基である。］

[Wherein, R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 24 carbon atoms or a carbon number optionally separated by at least one linking group selected from an amide group, an ester group and an ether group. 1 to 5 hydroxyalkyl groups, and at least one of R ^{1 to} R ³ is the hydrocarbon group. ]

［式中、Ｒ^１１およびＲ^１２はそれぞれ独立に炭素数１〜２４の炭化水素基である。Ｒ^１３〜Ｒ^２４はそれぞれ独立に炭素数１０〜２０の脂肪酸からカルボキシル基を除いた残基である。］

[Wherein, R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 24 carbon atoms. R ^{13 to} R ²⁴ are each independently a residue obtained by removing a carboxyl group from a fatty acid having 10 to 20 carbon atoms. ]

The compound represented by the general formula (b1-1) is generally obtained by reacting formaldehyde with hydrogen after further hydrogenation of a nitrile obtained by nitrifying it with ammonia using a fatty acid or its methyl ester as a starting material. Obtained by methylation.
The compound represented by the general formula (b1-2) or (b1-3) can be synthesized by a condensation reaction between a fatty acid having 10 to 20 carbon atoms or a methyl ester thereof and methyldiethanolamine.
The compound represented by the general formula (b1-4), (b1-5) or (b1-6) can be synthesized by a condensation reaction of a fatty acid having 10 to 20 carbon atoms or a methyl ester thereof with triethanolamine. it can.
The compound represented by the general formula (b1-7) or (b1-8) is obtained from an adduct of a fatty acid having 10 to 20 carbon atoms, N-methylethanolamine and acrylonitrile, according to “J. Org. Chem., 26, 3409 (1960) "can be synthesized by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by a known method.
The fatty acid having 10 to 20 carbon atoms may be a saturated fatty acid or an unsaturated fatty acid. The fatty acid may be a linear fatty acid or a branched fatty acid. Specific examples of the fatty acid include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, partially hydrogenated palm oil fatty acid, and partially hydrogenated beef tallow fatty acid.

The neutralized product in the compound (B1) can be obtained by neutralizing the tertiary amine with an acid.
The acid used for neutralization of the tertiary amine may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid.
Neutralization can be carried out by contacting a tertiary amine with an acid in the presence of water. For example, a premixed tertiary amine and acid may be dispersed in water, or the tertiary amine may be charged in liquid or solid form in an aqueous acid solution, or the tertiary amine and acid may be poured simultaneously into water. Also good.
The quaternized product in the compound (B1) is obtained by reacting the tertiary amine or a neutralized product thereof with a quaternizing agent, and has a quaternary ammonium group.
The quaternizing agent is a quaternizing agent by introducing a hydrocarbon group such as a methyl group into a tertiary nitrogen atom of a tertiary amine, and examples thereof include methyl chloride and dimethyl sulfate.

As the compound (B1), among them, a compound having a quaternary ammonium group, that is, a quaternized product of a tertiary amine is preferable. Examples of the quaternized product include monoalkyltrimethylammonium salts having 8 to 18 carbon atoms in the alkyl group, dialkyldimethylammonium salts having 4 to 10 carbon atoms in each alkyl group, and alkyls having 8 to 18 carbon atoms in the alkyl group. Preferred are benzyldimethylammonium salts, alkylpyridinium salts having 8 to 18 carbon atoms in the alkyl group, monoalkyltrimethylammonium salts having 8 to 18 carbon atoms in the alkyl group, and dialkyls having 4 to 10 carbon atoms in each alkyl group Dimethylammonium salts are more preferred, and stearyltrimethylammonium chloride and didecyldimethylammonium chloride are particularly preferred.
As the compound (B1), any one type may be used alone, or two or more types may be used in combination.

The polymer compound (B2) is selected from a polymer compound having a plurality of tertiary amino groups that may form a salt in the molecule and a polymer compound having a plurality of quaternary ammonium groups in the molecule.
“Polymer” in the polymer compound (B2) means that the weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000 to 6,000,000. The weight average molecular weight of the polymer compound (B2) is preferably 3,000 to 5,000,000, more preferably 5,000 to 4,000,000.
Specific examples of the polymer compound (B2) include cationized cellulose such as Leogard KGP (Lion), Daidol EC-004, Daidol HEC, Daidoru EC (Daido Kasei Kogyo), MERQUAT100 (Nalco), Adeka thioace PD- Polymers of dimethyldiallylammonium chloride such as 50 (Asahi Denka Kogyo), dimethyldiallylammonium chloride / acrylamide copolymers such as MERQUAT550 (Nalco), dimethyldiallylammonium chloride / acrylic acid copolymers such as MERQUAT280 (Nalco) , Imidazolinium chloride / vinyl pyrrolidone copolymer such as LUVIQUAT-FC905 (BASF), polyethyleneimine such as LUGALVAN-G15000 (BASF), POVAL CM318 (Kuraray) Cationized polyvinyl alcohol etc., the polymer derivatives of the natural system having an amino group such as chitosan, copolymers of vinyl monomers having diethylaminoethyl methacrylate and hydrophilic group such as ethylene oxide is added and the like.
Among these, cationized cellulose, a homopolymer of dimethyldiallylammonium chloride, and a copolymer of dimethyldiallylammonium chloride and other monomers are preferable.
As the polymer compound (B2), any one type may be used alone, or two or more types may be used in combination.

The component (B) contained in the repellent of the present invention may be one type or two or more types.
From the viewpoint of the effect of improving the sustainability of the repellent effect, the component (B) preferably contains at least the compound (B1), and preferably comprises the compound (B1).
In the repellent of this invention, content of (B) component is 0.01-20 mass% with respect to the total mass of a repellent. When it is 0.01% by mass or more, the repellent effect is excellent. The effect does not change greatly even if it exceeds 20% by mass. The content is preferably 0.1% by mass or more, and more preferably 1% by mass or more. Moreover, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable.
In this invention, it is preferable that mass ratio (A / B) of (A) component with respect to (B) component is 0.01-20. When A / B is within this range, both the repellent effect and its sustained effect are excellent. A / B is more preferably 10 or less, and even more preferably 5 or less. Further, A / B is more preferably 0.1 or more, and further preferably 1 or more.

[Component (C)]
Component (C) is a water-miscible solvent.
“Water-miscible solvent” means an organic solvent that forms a uniform solution when mixed with water.
As the component (C), at least one selected from glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and a compound represented by the following general formula (c1) is preferable. .
^{_{R 9 -O- (C 2 H 4}} O) y - (C 3 H 6 O) z -H ... (c1)
[Wherein, R ⁹ is an alkyl group or alkenyl group having 1 to 8 carbon atoms (preferably 2 to 6 carbon atoms), y and z are each an average addition mole number, and y is 0 to 20 (preferably 0 to 0). 10), z represents 0 to 5 (preferably 0 to 3). ]
Among these, ethanol, ethylene glycol, propylene glycol, butyl carbitol (also referred to as diethylene glycol monobutyl ether) and diethylene glycol monopropylene glycol monobutyl ether are preferable, and ethanol is more preferable from the viewpoint of stability, volatility, and odor.
The component (C) contained in the repellent of the present invention may be one type or two or more types.
In the repellent of this invention, content of (C) component is 0.01-35 mass% with respect to the total mass of a repellent. It is excellent in drying property as it is 0.01 mass% or more. It is excellent in odor as it is 35 mass% or less. The content is preferably 0.1% by mass or more, and more preferably 1% by mass or more. Moreover, 30 mass% or less is more preferable, and 20 mass% or less is further more preferable.

[(D) Water]
Examples of water include distilled water, ion exchange water, and tap water.
By blending water, the sustainability of the repellent effect tends to increase.
In the repellent of the present invention, the content of water is set according to the balance with the components (A) to (C) and is not particularly limited, but may be 50% by mass or more based on the total mass of the repellent. preferable. When it is 50% by mass or more, the effect of improving the sustainability of the repellent effect is sufficiently obtained.

[(E) component]
The repellent of the present invention may further contain (E) at least one selected from α-pinene, geraniol, citronellal, camphor, and linalool (hereinafter referred to as component (E)).
These (E) components are repellent components having a pest repellent effect, and the repellent effect is further improved when used in combination with the (A) component.
The component (E) contained in the repellent of the present invention may be one type or two or more types.
In the repellent of the present invention, the content of the component (E) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the repellent, considering the repellent effect. More preferably 1% by mass or more. Although the upper limit is not particularly limited, it is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the repellent, from the viewpoint that the effect does not change greatly even if the amount is increased, and the point of odor. 2 mass% or less is more preferable.

[(F) component]
The repellent of the present invention comprises (A) to (C) and (D) water, or (A) to (C), (E) and (D) in addition to water. It is preferable to contain an absorbent (hereinafter referred to as component (F)). The repellent effect of the repellent of the present invention against pests such as mosquitoes is particularly desired to be exhibited outdoors. By using the component (F) in combination, the repellent effect outdoors can be enhanced. Moreover, by using together (F) component, the quantity of the ultraviolet-ray which permeate | transmits textiles, such as clothing which is the original effect of (F) component, and acts on skin can also be reduced significantly.
Although the action mechanism in which the repellent effect in the outdoors is enhanced by the component (F) is not clarified, the component (A) of the present invention exhibits a repellent effect by gradually volatilizing from the fiber surface. When the amount of ultraviolet rays to the textile product increases, the volatility of the component (A) may increase due to the action of the component (F).

(F) As a component, well-known ultraviolet absorbers, such as an inorganic ultraviolet absorber and an organic ultraviolet absorber, can be used.
As an inorganic ultraviolet absorber, inorganic powders, such as a titanium oxide and a zinc oxide, are mentioned, for example.
Examples of the organic ultraviolet absorber include stilbene derivatives, benzophenone derivatives, benzotriazole derivatives, polyamide-2 derivatives, silicone derivatives, and the like.

  As a stilbene derivative used as an organic ultraviolet absorber, the compound represented by the following general formula (I), the compound represented by the following general formula (II), etc. are mentioned, for example.

（式中、Ｍは水素原子、アルカリ金属原子、アンモニウムイオン又はアミンから形成された陽イオンであり、Ｒ^１ａは置換されたアリール基であり、Ｒ^１ｂは水素原子、置換基を有していてもよいアリール基、モルホリノ基、アルキルアミノ基又はヒドロキシ基であり、ｎ_１及びｎ_２はそれぞれ独立的に０又は１である。）

(In the formula, M is a cation formed from a hydrogen atom, an alkali metal atom, an ammonium ion or an amine, R ^1a is a substituted aryl group, and R ^1b has a hydrogen atom and a substituent. An aryl group, a morpholino group, an alkylamino group or a hydroxy group, and n ₁ and n ₂ are each independently 0 or 1.)

（式中、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^２ｃ、Ｒ^２ｄはそれぞれ独立に、−ＮＲ^２ｅＲ^２ｆで示される基である。Ｒ^２ｅ、Ｒ^２ｆはそれぞれ独立に、水素原子、炭素数１〜３のアルキル基、炭素数１〜３のヒドロキシアルキル基もしくは置換基を有していてもよいアリール基であるか、又はＲ^２ｅとＲ^２ｆとがヘテロ原子を介して結合して複素環を形成しており、Ｍは前記と同じである。）

(In the formula, R ^2a , R ^2b , R ^2c and R ^2d are each independently a group represented by —NR ^2e R ^2f. R ^2e and R ^2f are each independently a hydrogen atom, a carbon number of 1 to 3. An alkyl group of 1 to 3, a hydroxyalkyl group having 1 to 3 carbon atoms or an aryl group which may have a substituent, or R ^2e and R ^2f are bonded via a hetero atom to form a heterocyclic ring. M is the same as above.)

  As the compound represented by the formula (II), a compound represented by the following general formula (III) or (IV) is particularly preferable.

（式中、Ｒ^３ａは水素原子又はヒドロキシ基であり、Ｘは−ＮＨ−Ｒ^３ｂ、−Ｏ−Ｒ^３ｂ又はモルホリノ基であり、Ｒ^３ｂはフェニル基又は炭素数１〜４のアルキル基であり、Ｙは−Ｃ（＝Ｏ）−ＮＲ^３ｃＲ^３ｄ、−ＳＯ_２−ＮＲ^３ｃＲ^３ｄ、−Ｃ（＝Ｏ）−ＮＨＲ^３ｂ又は−Ｃ（＝Ｏ）−ＯＭであり、Ｒ^３ｃ及びＲ^３ｄはそれぞれ独立に水素原子又は炭素数１〜４のアルキル基であり、Ｍは前記と同じである。）

(Wherein R ^3a is a hydrogen atom or a hydroxy group, X is —NH—R ^3b , —O—R ^3b or a morpholino group, and R ^3b is a phenyl group or an alkyl group having 1 to 4 carbon atoms. , Y is —C (═O) —NR ^3c R ^3d , —SO ₂ —NR ^3c R ^3d , —C (═O) —NHR ^3b or —C (═O) —OM, and R ^3c and R ^3d Are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and M is the same as described above.)

（式中、Ｒ^４ａは下記一般式（４ａ）で表される基であり、Ｒ^４ｂは−ＮＨ_２又は−Ｎ（ＣＨ_２ＣＨ_２ＯＨ）_２であり、Ｍは前記と同じである。）

(In the formula, R ^4a is a group represented by the following general formula (4a), R ^4b is —NH ₂ or —N (CH ₂ CH ₂ OH) ₂ , and M is the same as described above.)

（式中、Ｒ^４ｃは−ＮＲ^４ｄＲ^４ｅであり、Ｒ^４ｄ及びＲ^４ｅはそれぞれ独立に水素原子又はアルキル基である。）

(In the formula, R ^4c is —NR ^4d R ^4e , and R ^4d and R ^4e are each independently a hydrogen atom or an alkyl group.)

Specific examples of these stilbene derivatives include compounds described in Examples such as JP-A-10-87638, JP-A-10-81672, JP-A-9-3052.
A commercially available stilbene derivative can be used, for example, Tinosorb FD manufactured by Ciba Specialty Chemicals, Tinosorb FR manufactured by Ciba Specialty Chemicals, and the like.

  Examples of the benzophenone derivative used as the organic ultraviolet absorber include a compound represented by the following general formula (V), a homopolymer or a copolymer of a polymerizable vinyl monomer represented by the following general formula (VI), and the like. Can be mentioned. The copolymer may be a copolymer obtained by polymerizing two or more polymerizable vinyl monomers represented by the formula (VI), and at least one kind of the polymerizable vinyl monomer represented by the formula (VI). And other polymerizable vinyl monomers copolymerizable with the polymerizable vinyl monomer.

（式中、Ｒ^５ａ〜Ｒ^５ｊはそれぞれ独立に水素原子、アルキル基、アルケニル基、カルボキシル基、−ＯＲ’、ヒドロキシ基、ハロゲン原子、硫酸基、スルホン酸基又はアミノ基であり、Ｒ’はアルキル基又はアルケニル基である。）

Wherein R ^{5a to} R ^5j are each independently a hydrogen atom, an alkyl group, an alkenyl group, a carboxyl group, —OR ′, a hydroxy group, a halogen atom, a sulfuric acid group, a sulfonic acid group or an amino group, and R ′ is An alkyl group or an alkenyl group.)

（式中、Ｒ^６は水素原子またはメチル基であり、Ｌは−Ｏ−、−ＯＣＨ_２ＣＨ_２Ｏ−又は−ＯＣＨ_２ＣＨＣＨ_３Ｏ−である。）

(Wherein R ⁶ represents a hydrogen atom or a methyl group, and L represents —O—, —OCH ₂ CH ₂ O—, or —OCH ₂ CHCH ₃ O—).

  Commercially available benzophenone derivatives can be used, for example, SEESORB101S (Structural Formula V) manufactured by Sipro Kasei Co., Ltd., Sumisorb 130 (Structural Formula V) manufactured by Sumika Chemtex Co., Ltd. ULS-700 (Structural Formula VI) manufactured by the company can be used.

  Examples of the benzotriazole derivative used as the organic ultraviolet absorber include a homopolymer or a copolymer of a polymerizable vinyl monomer represented by the following general formula (VII). The copolymer may be a copolymer obtained by polymerizing two or more polymerizable vinyl monomers represented by the formula (VII), and is at least one kind of the polymerizable vinyl monomer represented by the formula (VII). And other polymerizable vinyl monomers copolymerizable with the polymerizable vinyl monomer.

（式中、Ｚは水素原子、ハロゲン原子又はメチル基であり、Ｒ^７ａは水素原子又は炭素数１〜６のアルキル基であり、Ｒ^７ｂは炭素数１〜６の直鎖又は分岐状のアルキレン基であり、Ｒ^７ｃは水素原子又はメチル基である。）

(In the formula, Z is a hydrogen atom, a halogen atom or a methyl group, R ^7a is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^7b is a linear or branched alkylene having 1 to 6 carbon atoms. And R ^7c is a hydrogen atom or a methyl group.)

  As the benzotriazole derivative, a commercially available product can be used, and examples thereof include ULS-1700 manufactured by Yushi Kogyo Co., Ltd., and NCI-905-20EM manufactured by Nikko Chemical Laboratory.

Examples of the polyamide-2 derivative used as the organic ultraviolet absorber include Solar GR8 manufactured by NALCO.
Examples of the silicone derivative used as the organic ultraviolet absorber include PARSOL SLX manufactured by DSM.

  Among the above, the component (F) is preferably an organic ultraviolet absorber because of its excellent outdoor repellency improving effect, and at least one selected from the group consisting of stilbene derivatives, benzophenone derivatives, and benzotriazole derivatives. Of these, benzophenone derivatives are preferred.

In addition, the component (F) is preferably water-dispersible or water-soluble because it has an excellent effect of improving the repellent effect outdoors. In particular, it is preferably water-soluble in order to uniformly act on the component (A).
Among the components (F) mentioned above, examples of the water-soluble (F) component soluble in water of 0.5% or more include SEESORB101S and SEESORB100 manufactured by Sipro Kasei Co., Ltd. Among them, SESORB101S having high water solubility is preferable.

The component (F) contained in the repellent of the present invention may be one type or two or more types.
In the repellent of the present invention, the content of the component (F) is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and more preferably 0.1 to 5% with respect to the total mass of the repellent. More preferred is mass%. The effect by mix | blending (F) component is fully acquired as it is 0.001 mass% or more. Even if blended in excess of 10% by mass, the effect does not change greatly. Therefore, it is preferably 10% by mass or less from the viewpoint of economy.

The repellent of this invention can contain other repellent components other than (A) component and (E) component for the purpose of improving a repellent effect further.
The other repellent component is not particularly limited as long as it has a pest repellent effect, and a naturally occurring component or a synthetic product may be used, but a naturally occurring component is preferable.
Examples of the other repellent component include the following.
Jasmon, dihydrojasmon, methyl jasmonate, methyl dihydrojasmonate, methyleugenol, isoeugenol, amyl salicylate, isoamyl salicylate, hexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, benzaldehyde, benzyl alcohol, 2-phenylethyl alcohol, 2-Phenoxyethanol, α-amyl cinnamaldehyde, cinnamon alcohol, cinnamaldehyde, ethyl cinnamate, propyl cinnamate, isopropyl cinnamate, cinnamyl acetate, amyl benzoate, isoamyl benzoate, hexyl benzoate, cis-3-hexenyl benzoate , Heptyl benzoate, octyl benzoate, farnesol, nerolidol, fetol, tetrahydrolinalol, bornyl acetate, mirceni Acetate, cedryl acetate, lavender acetate, citronellyl isobutyrate, terpinyl propionate, linalyl formate, citronellyl tigrate, nopyru acetate, vetiberyl acetate, rilal, citronellyloxyacetaldehyde, 2,6 , 10-trimethyl-9-undecanal, yonon, damascon, nootkatone, cedolyl methyl ether, citronellol, citral, β-pinene, citronellyl acetate, cinnamaldehyde, nonyl alcohol, thymol, eugenol, benzylformate, benzyl acetate, Benzylpropionate, benzylbutyrate, benzylvalerate, benzylcaproate, linalool, α-hexylcinnamic aldehyde, lemongrass oil, lavender oil, Range oil, Vetiver oil, Patchouli oil, Cananga oil, Clove oil, Cageput oil, Citronella oil, Nutmeg oil, Pepper oil, Sandalwood oil, Bulk oil, Gazine oil, Ginger oil, Campo oil, Cubeve oil, Conmint Oil, Anise oil, Lang oil, Cinnamon oil, Mace oil, Palomarosa oil, Fennel oil, Columnus oil, Times oil, Neem oil, Cinnamon leaf oil, Jasmine oil, Neroli oil, Peppermint oil, Bergamot oil, Geranium Oil, petitgren oil, lemon oil, eucalyptus oil, thyme oil, etc.
Among the above, some oils (oil) contain the component (A). When blending such oil, the content of the oil is the amount excluding the component (A), and the amount of the component (A) derived from the oil is included in the content of the component (A). .

[Other optional ingredients]
The repellent of this invention may contain other components other than the above in the range which does not impair the effect of this invention as needed. As the other components, components usually used for pest repellents and textile product treating agents can be blended, for example, nonionic surfactants, perfume compositions, silicone compounds, chelating agents, anti-staining agents. , Polymers, preservatives, antibacterial agents, repellents, extracts such as natural products, dispersants, dyes, antioxidants, thickeners, thickeners, pH adjusters and the like. Examples of the nonionic surfactant and the fragrance composition include those shown below.
The blending amount of these optional components is preferably 5% by mass or less and more preferably 1% by mass or less with respect to the total mass of the repellent.

(Nonionic surfactant)
As the nonionic surfactant, known ones can be used, for example, polyoxyethylene alkyl ether, polyoxyethylene fatty acid alkyl ester, polyoxyethylene alkylamine, alkyl polyglucoside, polyoxyethylene hydrogenated castor oil and the like. It is done. Among them, polyoxyethylene alkyl ether, polyoxyethylene fatty acid alkyl (C1-3) ester having an alkyl group or alkenyl group having 10 to 22 carbon atoms and an average addition mole number of oxyethylene group of 10 to 100 mol, , Polyoxyethylene alkylamine having an average addition mole number of oxyethylene group of 10 to 100 mole, alkyl polyglucoside having an alkyl group or alkenyl group having 8 to 18 carbon atoms, and an average addition mole number of oxyethylene group of 20 to 20 Hardened castor oil which is 100 moles is preferred, especially polyoxyethylene alkyl ether having an alkyl group having 10 to 14 carbon atoms and an average addition mole number of oxyethylene groups of 5 to 20 moles, an average addition mole of oxyethylene groups Hardened castor oil having a number of 30 to 50 mol is preferred.

(Fragrance)
Known fragrances can be used and are not particularly limited. Various documents such as “Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic fragrance chemistry and commercial knowledge", Motoichi Into, Chemical Industry Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower Oils". , Danute Lajaujis Anonis, Allured Pub. Co. (1993) and the like can be appropriately selected from the list of perfume ingredients.

The repellent of the present invention preferably has a pH of 3-8 at 25 ° C. When the pH is within this range, the fiber product is less damaged when the repellent of the present invention is applied to a fiber product such as clothing.
The repellent of this invention can be prepared by mixing the said (A) component, (B) component, (C) component and (D) water, and another component as needed.

The repellent of the present invention is applied to textile products for pest repellent.
By attaching the repellent of the present invention to a fiber product, the pest repellent effect is exhibited not only in the portion in contact with the fiber product but also in the vicinity thereof, and the effect lasts for a long time.
For example, when wearing a garment treated with the repellent of the present invention or covering a part of the skin with a cloth treated with the repellent of the present invention, not only the covered part but also the exposed part of the skin in the vicinity Is effective against insect pests.
These effects are that the (A) component adhering to the textile product exhibits a repellent effect by volatilization, and the (B) component suppresses rapid volatilization of the (A) component and improves its sustainability. It is thought that.

The amount of the repellent used in the present invention is preferably such that the amount of the component (A) per 100 cm ² of the textile product is 0.01 mg or more, and more preferably 0.1 mg or more in terms of the repellent effect.
Although an upper limit is not specifically limited, The quantity from which the quantity of (A) component per 100 cm < ² > of textiles becomes 40 mg or less is preferable, The quantity which becomes 30 mg or less is more preferable, The quantity which becomes 20 mg or less is preferable. The effect does not change greatly even if the blending amount is more than 40 mg. Moreover, there is a possibility that the clothes may be stained.

The method for attaching the repellent of the present invention to a textile product is not particularly limited. For example, a method in which a textile product is dipped in the repellent of the present invention and then air-dried, a method in which the repellent of the present invention is applied in a washing finishing process, the repellent of the present invention is stored in a spray container, and the textile product is And air drying after spraying.
In particular, from the viewpoint of simplicity that can be easily carried out at home, and economic efficiency that can be applied only to textile products that are desired to be used, there is a method in which the repellent of the present invention is stored in a spray container and sprayed onto the textile products and then air-dried. preferable.

Examples of the spray container include an aerosol spray container, a trigger spray container (direct pressure type or pressure accumulation type), a dispenser spray container, and the like.
Examples of the aerosol spray container include those described in JP-A-9-3441, JP-A-9-58765, and the like. Moreover, as a propellant used for an aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), a carbon dioxide gas, nitrogen gas, etc. are mentioned, These may be used independently and 2 or more types are mixed. May be used.
Examples of the trigger spray container include those described in JP-A-9-268473, JP-A-9-256272, JP-A-10-76196, and the like.
Examples of the dispenser spray container include those described in JP-A-9-256272.

  The amount of spray when the repellent of the present invention is stored in a spray container and sprayed onto the target textile is not particularly limited, but in terms of the repellent effect, 1 mass relative to the mass of the textile. % Or more, preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit is not particularly limited, but considering economy, it is preferably 100% by mass or less, more preferably 80% by mass or less, and further preferably 50% by mass or less, based on the mass of the fiber product.

The repellent of the present invention can be stored in a plastic container. Examples of the plastic container include a bottle container and a standing pouch for refilling.
Examples of the standing pouch include those described in JP-A No. 2000-72181. A standing pouch with a three-layer structure with a linear low-density polyethylene of 100 to 250 μm for the inner layer, a two-layer structure of stretched nylon of 15 to 30 μm for the outer layer, or an intermediate layer of 15 μm stretched nylon and an outer layer of 15 μm stretched nylon for storage stability From the viewpoint of sex.

The textile product to which the repellent of the present invention is applied is not particularly limited. For example, Y-shirts, T-shirts, polo shirts, blouses, chinos, suits, slacks, skirts, hats, socks, shoes and other clothing, tables Examples include cloth, place mats, curtains, bedding, and strollers.
The material of the target textile product is not particularly limited. For example, natural fibers such as cotton, wool and hemp, synthetic fibers such as polyester, nylon and acrylic, semi-synthetic fibers such as acetate, rayon, tencel and polynosic Examples thereof include recycled fibers and blended products, blended fabrics, blended products of these various fibers.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
The raw materials used in each example are shown below.
[Raw materials]
[(A) component]
p-Mentane-3,8-diol: manufactured by Takasago Incense.
[Component (B)]
Didecyldimethylammonium chloride: “Arcade 210” manufactured by Lion Akzo Corporation.
Stearyl trimethyl ammonium chloride: “Arcard T-800” manufactured by Lion Akzo Co., Ltd.
Trioctyl ammonium chloride: manufactured by Tokyo Chemical Industry Co., Ltd.
Dimethylaminopropylamide stearate: “Katinal MPAS-R” manufactured by Toho Chemical Co., Ltd.
Marcoat 100: “Marcoat 100” (dimethyldiallylammonium chloride polymer) manufactured by NALCO.
[Component (C)]
95% ethanol: manufactured by Nippon Synthetic Alcohol.
[(E) component]
Citronellal: manufactured by Tokyo Chemical Industry Co., Ltd.
[(F) component]
Hydroxymethoxybenzophenone sulfonic acid: “SEESORB101S” manufactured by Cypro Kasei Co., Ltd.

[Others]
Polyoxyethylene hydrogenated castor oil (40EO): “Brownon RCW-40” manufactured by Aoki Oil & Fat Co., Ltd., average added mole number of oxyethylene group 40.
Sodium lauryl sulfate: manufactured by Tokyo Chemical Industry Co., Ltd.
Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.
Sulfuric acid: manufactured by Mori Chemical Industry Co., Ltd.
Diet: Made by Nippon Seika Co., Ltd.

<Examples 1-12, Comparative Examples 1-7>
Each component was mixed so that it might become a composition shown in Tables 1-2, and the repellent was prepared.
In Tables 1 and 2, the unit of the blending amount is mass%, and the “balance” of purified water is an amount such that the total amount of the repellent is 100 mass%. The “trace amount” of sulfuric acid is derived from the sulfuric acid used for neutralization of dimethylaminopropylamide stearate. The “trace amount” of sodium hydroxide is such an amount that the repellent has a pH of 5 at 25 ° C., and was added to make the pH of Example 12 and Example 5 substantially the same.
The following evaluation was performed about the obtained repellent. The results are shown in Tables 1-2.

<1. Repelling effect>
[1-1. Pre-treatment of cotton for evaluation]
A cotton knitted fabric (Tanigami Shoten) is pretreated by treating it three times under the following conditions with a commercially available detergent “Top” (manufactured by Lion) using a two-tank washing machine (CW-C30A1-H manufactured by Mitsubishi Electric). Went.
Pretreatment conditions: 20 g / 30 L of detergent (standard use amount), 30 times the bath ratio, tap water at 45 ° C., 10 minutes of washing → 10 minutes of water rinsing twice.

[1-2. Preparation of evaluation sample]
A pretreated cotton knitted fabric (6 cm × 6 cm) was sewed on a supporter having a 6 cm × 12 cm hole, and used as an evaluation sample. The evaluation sample was attached to the arm, a work gloves were put on the hand, and there was no exposed portion except for a portion where the supporter had a hole (exposed portion).
When evaluating the repellent, 0.2 g of the repellent was sprayed on cotton knitted fabric sewn on the supporter using a dispenser pump spray (Style Guard, manufactured by Lion Corporation).

[1-3. Evaluation of repellent effect]
Indoors (summer season: room temperature 28 ° C), as a blank, put 10 female Aedes aegypti in a 30cm x 30cm x 30cm cocoon, and insert an arm wrapped with an evaluation sample not treated with repellent into the cocoon. The number (A) of Aedes albopictus moored in the exposed portion during 30 seconds was taken as the count.
Subsequently, an evaluation sample sprayed with repellent on cotton knitted material is wrapped around the arm immediately after spraying the repellent or after 3 hours from spraying, and the arm is inserted into the bag containing 10 human striped mosquito females as in the blank. Then, the number (B) of Aedes albopictus moored in the exposed part during 30 seconds was counted.
From the above values A and B, the repelling rate (%) was calculated according to the following formula immediately after spraying the repellent (immediately) and after 3 hours had elapsed since spraying (3 hr).
Repelling rate (%) = (B−A) / A × 100

[1-4. Evaluation of repellent effect outdoors]
For the repellents of Examples 5 and 12, the same evaluation as the evaluation of the repellent effect was performed outdoors on a sunny day (summer: outside air temperature 32 ° C.).

<2. Appearance immediately after production>
The appearance immediately after manufacture of the repellent was visually evaluated according to the following criteria.
○: Transparent.
X: Turbidity (not dissolved).

As shown in the above results, the repellents of Examples 1 to 12 had a repellent rate of 50% or more even after 3 hours, and were excellent in both the repellent effect and its sustainability.
Example 12 containing the component (F) had the same indoor repellent effect as Example 5, but the outdoor repellent effect was higher than that of Example 5.
On the other hand, Comparative Example 1 containing no component (B) had a high repellent rate immediately after 100%, but the repellent rate after 3 hours was as low as 40% and the sustainability was poor.
(A) The comparative example 2 which does not contain a component had a low repelling rate at the time immediately after.
Comparative Examples 3 and 4 in which polyoxyethylene hydrogenated castor oil or sodium lauryl sulfate is blended in place of the component (B), and Comparative Example 5 in which the blending amount of the component (C) exceeds 35% by mass, Was as high as 100%, but the group ratio after 3 hours was as low as 40% and the sustainability was poor.
The comparative example 6 which mix | blended monoethanolamine instead of (B) component had a low repellent rate at the time immediately after, and the external appearance immediately after manufacture was also bad.
The comparative example 7 which mix | blended diet instead of (A) component had a low repellent rate at the time immediately after.

Claims (7)

  (A) 0.01 to 20% by mass of repellent having a menthane skeleton, and (B) at least one kind selected from a tertiary amine, a neutralized product thereof, and a compound having a quaternary ammonium group 0.01 to 20% by mass And (C) 0.01-35 mass% of water miscible solvent, and (D) water, the insect repellent for textiles characterized by the above-mentioned.   The pest repellent according to claim 1, wherein the component (B) contains a compound having a quaternary ammonium group.   The pest repellent according to claim 1 or 2, wherein the component (A) is p-menthane-3,8-diol.   The pest repellent according to any one of claims 1 to 3, wherein a mass ratio (A / B) of the component (A) to the component (B) is 0.01 to 20.   The pest repellent according to any one of claims 1 to 4, further comprising (E) at least one selected from α-pinene, geraniol, citronellal, camphor, and linalool.   Furthermore, the pest repellent as described in any one of Claims 1-5 containing (F) ultraviolet absorber.   A pest repellent method comprising attaching the pest repellent according to any one of claims 1 to 6 to a textile product.