JP2025003295A - Oil-in-water pest repellent composition - Google Patents

Abstract

To provide an oil-in-water type pest insect repellent composition that delivers a pleasant sensation upon application to the skin, offers excellent stability during long-term storage, and sustainedly exhibits excellent repellency against pests, particularly flying pests.SOLUTION: The present invention relates to an oil-in-water type pest insect repellent composition that contains components (A) to (E). (A) 13-50 mass% of at least one non-volatile liquid oily component selected from silicone oils, ester oils, ether oils, hydrocarbon oils, aliphatic alcohols and polyhydric alcohols; (B) 0.5-35 mass% of hydrophilic inorganic particles which have a volume-based median particle diameter of 1-40 μm and include silica particles and/or silicate mineral particles; (C) 0.1-3 mass% of one or more selected from polyether-modified silicones, polyglycerin-modified silicones, branched polyglycerol-modified silicones, alkyl glyceryl ether-modified silicones and carboxyl-modified silicones, which are liquid at 25°C; (D) 0.05-3 mass% of a thickening agent; and (E) 30-86.35 mass% of water. The viscosity of component (A) at 23°C, as measured using a B type rotary viscometer, is 1-400 mPa s. The silicone oil for component (A) does not include component (C).SELECTED DRAWING: None

Description

The present invention relates to an oil-in-water type pest repellent composition.

Pests, for example, flying pests such as mosquitoes and flies, are a cause of infectious diseases and dermatitis by transmitting pathogens to animals such as humans. In particular, some mosquitoes are insects that are extremely harmful from the viewpoint of hygiene because they transmit pathogens such as dengue fever, Zika fever, yellow fever, encephalitis, and malaria.
In order to protect oneself from such flying pests, for example, Patent Document 1 describes an oil-in-water pest repellent composition and an oil-in-water pest retention-inhibiting composition, which are intended to provide an oil-in-water pest repellent composition that has an excellent long-lasting repellent effect against pests, particularly flying pests, is safe, has a good feel when applied to the skin, and is also excellent in long-term storage stability, and contains (A) 13% by mass or more and 50% by mass or less of one or more non-volatile liquid oily components selected from the group consisting of silicone oils, ester oils, ether oils, hydrocarbon oils, aliphatic alcohols, and polyhydric alcohols, each having a surface tension of 40 mN/m or less at 25° C. and a viscosity of 400 mPa·s or less at 23° C. as measured by a B-type rotational viscometer, (B) 0.5% by mass or more and 35% by mass or less of hydrophobic particles having a volume median particle size of 0.1 μm or more and 40 μm or less, and (C) 30% by mass or more and 86.5% by mass or less of water.

JP 2020-109075 A

The oil-in-water pest repellent composition described in Patent Document 1 has a good feel when applied to the skin and has good long-term storage stability. However, the inventors' studies have revealed that there is room for further improvement in the sustained repellent effect.
The present invention relates to an oil-in-water pest repellent composition which has a good feel when applied to the skin, is excellent in long-term storage stability, and further has an excellent sustained repellent effect against pests, particularly flying pests; a method for producing the oil-in-water pest repellent composition; and a method for repelling pests.

As a result of intensive research, the inventors have found that the above-mentioned problems can be solved by an oil-in-water type pest repellent composition containing a specific non-volatile liquid oily component, hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a specific volume median particle size, a specific modified silicone that is liquid at 25°C, a thickener, and water in predetermined amounts.
That is, the present invention provides the following [1] to [4].
[1] An oil-in-water type pest repellent composition comprising the following components (A) to (E):
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C).
[2] A method for producing an oil-in-water pest repellent composition, comprising the step of mixing a mixture containing the following components (B), (C), and (E) with a mixture containing the following components (A) and (D):
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less; (C) one or more substances selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.; (D) a thickener; and (E) water, provided that the viscosity of component (A) at 23° C. as measured with a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C). In addition, in the oil-in-water type pest repellent composition, the content of component (A) is 13 mass% or more and 50 mass% or less, the content of component (B) is 0.5 mass% or more and 35 mass% or less, the content of component (C) is 0.1 mass% or more and 3 mass% or less, the content of component (D) is 0.05 mass% or more and 3 mass% or less, and the content of component (E) is 30 mass% or more and 86.35 mass% or less.
[3] A method for repelling pests, comprising applying an oil-in-water pest repellent composition containing the following components (A) to (E) to the surface of human skin:
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C).
[4] A method for repelling pests, comprising attaching an oil-in-water pest repellent composition containing the following components (A) to (E) to the legs of a pest to prevent the pest from remaining on human skin:
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C).

The present invention provides an oil-in-water pest repellent composition that has a good feel when applied to the skin, excellent long-term storage stability, and excellent long-lasting repellent effect against pests, particularly flying pests, as well as a method for producing the oil-in-water pest repellent composition and a method for repelling pests.

The following describes preferred embodiments of the present invention. In this specification, the range "X to Y" means "X or more and Y or less." In this specification, the upper and lower limits of the numerical ranges can be combined in any way.

[Pest repellent composition]
The pest repellent composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") is an oil-in-water type composition containing the following components (A) to (E).
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C).

The composition of the present invention is an oil-in-water type composition that contains specific amounts of components (A) to (E), has a good feel when applied to the skin, has excellent long-term storage stability, and has a long-lasting repellent effect against pests, particularly flying pests.

In the present invention, the "repellent effect against pests" includes the effect of pests immediately leaving the target object without remaining thereon even when they come into contact with the target object (retention inhibitory effect), and may further include one or more of keeping pests away from the target object and exterminating pests.
The composition of the present invention at least exerts an effect of repelling pests, by preventing pests such as mosquitoes from remaining on the spot and immediately leaving the site even if the pests land on the object to which the composition is applied or attached. Specifically, the composition exerts a retention inhibition effect of preventing pests such as mosquitoes from remaining in a specific area on the skin surface for a time to insert their stingers, specifically, for one second or more, after landing on the skin of an animal such as a human. Such an effect is safe and does not cause side effects such as rough skin.
In the present invention, the "long-lasting repellent effect against pests" means that the repellent effect continues even after time has passed after the composition of the present invention is applied to an object. In the following description, the long-lasting repellent effect, particularly against flying pests, in the present invention will be simply referred to as the "long-lasting repellent effect."

The composition of the present invention contains component (A) one or more non-volatile liquid oily components selected from silicone oils, ester oils, ether oils, hydrocarbon oils, aliphatic alcohols, and polyhydric alcohols, component (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less, component (C) one or more types of silicones that are liquid at 25° C. and are selected from polyether-modified silicones, polyglycerin-modified silicones, branched polyglycerol-modified silicones, alkyl glyceryl ether-modified silicones, and carboxy-modified silicones, component (D) a thickener, and component (E) water, each in a specific amount.
The composition of the present invention has a good feel when applied to the skin, is excellent in long-term storage stability, and further has an excellent and sustained repellent effect against pests, particularly flying pests. The reason for this is not clear, but is thought to be as follows.
Flying pests such as mosquitoes have the property of avoiding landing on a surface where their legs become wet in order to avoid the gravitational force generated from the landing surface when their legs become wet. When flying pests land on a skin surface to which component (A) has been applied or attached, their legs become wet, and it is believed that they avoid the gravitational force generated from the landing surface and fly away without staying at the landing point. In addition, a part of component (C) in the composition is adsorbed to component (B), thereby improving the pleasant feel of component (B) on the skin, and a part of component (C) is mixed with component (A), thereby imparting thixotropy to component (A), so that component (A) does not drip due to gravity and spreads wet on the legs when an external force is applied by the landing of flying pests. As a result, when the composition is applied to the skin surface, the composition is maintained in a uniformly applied state on the skin surface for a long time, providing a pleasant feel and improving the sustained repellent effect. Furthermore, it is believed that the composition of the present invention also has excellent long-term storage stability due to the inclusion of a specific amount of component (D) and other factors.
In the present invention, landing refers to a flying pest such as a mosquito contacting an object for less than one second, whereas stationary refers to a flying pest such as a mosquito remaining in contact with an object for one second or more.

<Component (A): Non-volatile Liquid Oily Component>
Component (A) contained in the composition of the present invention is one or more non-volatile liquid oily components selected from (a) silicone oil, (b) ester oil, (c) ether oil, (d) hydrocarbon oil, (e) aliphatic alcohol, and (f) polyhydric alcohol.
However, the silicone oil of component (A) does not contain component (C).

From the viewpoints of facilitating application to the skin and improving the sustained repellent effect, component (A) is preferably liquid at 25°C, more preferably liquid at 20°C, even more preferably liquid at 15°C, and even more preferably liquid at 10°C.
The term "liquid" in the liquid oil component means that the viscosity at 23° C. measured with a Brookfield type rotational viscometer is 120,000 mPa·s or less.
From the viewpoint of improving the sustained repellent effect, component (A) is preferably a water-insoluble or slightly water-soluble component, and specifically, the amount of solubility thereof in 100 g of water at 20° C. is preferably 1 g or less, more preferably 0.5 g or less, even more preferably 0.1 g or less, and even more preferably essentially 0 g.

The liquid oily component of component (A) used in the present invention is a non-volatile liquid oily component from the viewpoint of improving the repellency duration effect. Here, the non-volatile liquid oily component in the present invention refers to a liquid oily component whose volatilization rate after drying at 25°C for 60 minutes under 1 atmosphere is 50% or less, and preferably refers to a liquid oily component whose volatilization rate after drying at 25°C for 120 minutes under 1 atmosphere is 50% or less. The volatilization rate is evaluated according to the German test standard DIN53249, and specifically, is performed according to the following steps 1 to 4.
1. Measure the weight (P(g)) of a round filter paper with a diameter of 150 mm.
2. Using a pipette, a 0.3 g sample of component (A) is dropped onto a round filter paper, and immediately thereafter the weight (W ₀ (g)) of the filter paper is measured.
3. In a ventilated environment, measure the weight of the filter paper at 25° C. at 5-minute intervals using a gravimetric measurement accurate to about 0.001 g. The weight of the filter paper measured 60 minutes after the measurement in 2 is defined as W ₆₀ (g).
4. The value calculated using the formula {((W ₀ - P) - (W ₆₀ - P))/(W ₀ - P)} x 100 is the volatility rate (%).
The lower the volatility rate, the longer the liquid oily component will remain on the skin when applied, resulting in a longer lasting repellent effect.
When two or more kinds of liquid oily components are used, the volatility of the liquid oily components means the volatility of the mixture of two or more kinds of liquid oily components. Therefore, as long as the volatility of the mixture is within the above range, liquid oily components having a volatility of more than 50% after drying at 25°C for 60 minutes under 1 atmospheric pressure may be used in combination.

From the viewpoint of availability, the surface tension of component (A) at 25°C is preferably 15 mN/m or more, more preferably 17 mN/m or more, and from the viewpoint of improving the sustained repellent effect, it is preferably 40 mN/m or less, more preferably 30 mN/m or less, even more preferably 28 mN/m or less, still more preferably 25 mN/m or less, still more preferably 23 mN/m or less, and still more preferably 21 mN/m or less. When two or more liquid oily components with different surface tensions are used, the surface tension means the surface tension of a mixture of these liquid oily components.
The viscosity of component (A) at 23°C as measured with a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, more preferably 300 mPa·s or less, even more preferably 210 mPa·s or less, still more preferably 100 mPa·s or less, still more preferably 60 mPa·s or less, still more preferably 40 mPa·s or less, and still more preferably 30 mPa·s or less. When two or more liquid oily components with different viscosities are used, the viscosity means the viscosity of a mixture of these liquid oily components.
The viscosity of component (A) at 23°C as measured by a B-type rotational viscometer is preferably not less than the above-mentioned lower limit from the viewpoint of suppressing volatility and improving the sustained repellent effect, and is preferably not more than the above-mentioned upper limit from the viewpoint of ensuring long-term storage stability.
The surface tension of component (A) and the viscosity at 23° C. as measured by a Brookfield type rotational viscometer are measured by the method described in the Examples.

(a) Silicone Oil As the silicone oil, from the viewpoint of improving the sustained repellent effect, one or more types selected from dimethylpolysiloxane (dimethicone), dimethiconol (dimethylpolysiloxane having a hydroxy group at the terminal), methylphenylpolysiloxane, and modified silicone are preferable.
Examples of modified silicones include amino-modified silicones (dimethylpolysiloxanes having amino groups), amino derivative silicones, fatty acid-modified silicones, alcohol-modified silicones, aliphatic alcohol-modified silicones, epoxy-modified silicones, fluorine-modified silicones, and alkyl-modified silicones.

Among the silicone oils, from the viewpoint of improving the sustained repellent effect and improving the feel when applied to the skin, one or more selected from dimethylpolysiloxane, dimethiconol, methylphenylpolysiloxane, and modified silicone are preferred, one or more selected from dimethylpolysiloxane and dimethiconol are more preferred, and dimethylpolysiloxane is even more preferred.

The dimethylpolysiloxane may be one or more selected from linear dimethylpolysiloxane and cyclic dimethylpolysiloxane. Of these, linear dimethylpolysiloxane is more preferred from the viewpoint of improving the sustained repellent effect.
Commercially available examples of linear dimethylpolysiloxanes include the KF-96 series from Shin-Etsu Chemical Co., Ltd., the SH200C series from Dow Corning Toray Co., Ltd., "2-1184 Fluid," and "Silsoft DML,""Element14 PDMS 5-JC,""Element14 PDMS 10-JC," and "Element14 PDMS 20-JC" from Momentive Performance Materials.

(b) Ester Oil As the ester oil, from the viewpoint of improving the repellent effect, an ester oil represented by any one of the following general formulas (1) to (3) and a dialkyl carbonate compound represented by the following general formula (4) are preferred.

R ¹ -COO-R ² (1)
In the general formula (1), R ¹ represents a linear or branched alkyl group having 7 to 23 carbon atoms, which may be substituted with a hydroxyl group, or an aromatic hydrocarbon group having 6 to 24 carbon atoms. R ² represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms.
When ^R1 is an alkyl group, from the viewpoint of improving the repellent effect, the number of carbon atoms is preferably 7 or more, more preferably 9 or more, and from the viewpoint of improving the feel when applied to the skin, Preferably, R ^{1 is 21 or less, more preferably 17 or less. When R 1} is an aromatic hydrocarbon group, the number of carbon atoms is preferably 8 or more, more preferably 10 or more, from the viewpoint of improving the repellent effect. From the viewpoint of providing a good feel when applied to the skin, the molecular weight is preferably 22 or less, and more preferably 20 or less.
From the viewpoint of providing a good feel when applied to the skin, ^R2 is preferably a linear or branched alkyl or alkenyl group having 20 or less carbon atoms, more preferably 18 or less carbon atoms. From the viewpoint of improving the feel when applied to the skin, it is preferable that at least one of R ¹ and R ² is a branched alkyl group.

The ester oils represented by the general formula (1) include myristyl 2-ethylhexanoate, cetyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, isodecyl octanoate, isocetyl octanoate, isononyl isononanoate, isotridecyl isononanoate, cetearyl isononanoate, octyl propylheptanoate, methyl laurate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, isocetyl palmitate, stearyl oleate, ethylhexyl oleate, isocetyl palmitate, ethylhexyl oleate, isocetyl ole ... Examples of the esters include one or more selected from 2-ethylhexyl phosphate, isocetyl stearate, isotridecyl stearate, isopropyl isostearate, octyl isostearate, isocetyl isostearate, isostearyl isostearate, 2-ethylhexyl hydroxystearate, methyl oleate, oleyl oleate, isobutyl oleate, oleyl erucate, alkyl benzoate (alkyl carbon number 12 to 15), and diethylhexyl naphthalenedicarboxylate.

(R ³ O)-CH ₂ CH (OR ⁴ )-CH ₂ (OR ⁵ ) (2)
In the general formula (2), R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a group represented by the following general formula (2-1), and all of them cannot be hydrogen atoms. .
-CO-R ⁶ (2-1)
(In the formula, ^R6 represents an alkyl or alkenyl group having 7 to 23 carbon atoms, preferably 17 or less, which may be substituted with a hydroxyl group.)
The ester oil represented by the general formula (2) may be one or more selected from glyceryl tri-2-ethylhexanoate and glyceryl tricaprylate. These include jojoba oil, olive oil, sunflower oil, soybean oil, and peanut oil. , rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, thistle oil, evening primrose oil, macadamia nut oil, corn germ oil, and avocado oil may also be used. .

R ⁷ O-(AO)m-COR ⁸ (3)
In the general formula (3), ^R7 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, ^R8 represents an alkyl or alkenyl group having 1 to 23 carbon atoms, AO represents an aromatic hydrocarbon group having 2 or more carbon atoms, 4 or less alkyleneoxy groups, and m represents the average number of moles added of 1 to 50.
^R7 preferably has 6 or more carbon atoms from the viewpoint of improving the repellent effect, and preferably has 12 or less carbon atoms, more preferably 10 or less carbon atoms from the viewpoint of improving the feel when applied to the skin. and more preferably a benzyl group.
R ⁸ preferably has 7 or more carbon atoms, more preferably 11 or more carbon atoms, from the viewpoint of improving the repellent effect, and preferably has 21 or less carbon atoms, from the viewpoint of improving the feel when applied to the skin. , more preferably an alkyl group having 15 or less.
From the viewpoint of improving the repellent effect and improving the feel on the skin when applied, m is preferably 1. It is preferably from 1 to 5 inclusive.
Examples of the ester oil represented by the general formula (3) include an ester of a propylene oxide 3-mol adduct of benzyl alcohol and myristic acid ("Crodamol STS" manufactured by Croda), an ester of a propylene oxide 3-mol adduct of benzyl alcohol and 2-ethyl Examples of the hexanoic acid ester include one or more selected from hexanoic acid esters (Croda "Crodamol SFX").

R ⁹ -O-(CH ₂ CH ₂ O)v-CO-(OCH ₂ CH ₂ )w-OR ¹⁰ (4)
In formula (4), R ⁹ and R ¹⁰ each independently represent an alkyl or alkenyl group having 6 to 22 carbon atoms; v and w each independently represent 0 or an average integer of 1 to 50. The number of moles added is indicated.
R ⁹ and R ¹⁰ each preferably have 8 or more carbon atoms from the viewpoint of improving the repellent effect, and preferably have 18 or less carbon atoms from the viewpoint of improving the feel when applied to the skin, and more preferably The alkyl group is 12 or less.
From the viewpoint of providing a good feel when applied to the skin, v and w are preferably 0 or a number between 1 and 5, and more preferably 0.
Examples of the dialkyl carbonate compound represented by the general formula (4) include dioctyl carbonate ("Cetyolic Acid CC" manufactured by Cognis Co., Ltd.).

Examples of ester oils other than those mentioned above include esters of polyvalent carboxylic acids and alcohols, and esters of polyhydric alcohols other than glycerin and fatty acids.
Specific examples thereof include one or more selected from diisopropyl dimerate, diisopropyl adipate, diethoxyethyl succinate, 2-ethylhexyl succinate, propanediol dicaprate, neopentyl glycol dicaprate, neopentyl glycol di-2-ethylhexanoate, etc. Among these, from the viewpoint of improving the sustained repellent effect, esters of neopentyl glycol and fatty acids are preferred, and one or more selected from neopentyl glycol dicaprate and neopentyl glycol di-2-ethylhexanoate are more preferred.
Of the above (b) ester oils, at least one selected from the ester oils represented by the general formula (1) and esters of neopentyl glycol and fatty acids are preferred.

(c) Ether Oil As the ether oil, from the viewpoint of improving the repellent effect, a dialkyl ether compound represented by the following general formula (5) or a polyoxyalkylene alkyl ether compound represented by the following general formula (6) is preferable.

R ¹¹ -O-R ¹² (5)
In the general formula (5), R ¹¹ and R ¹² each independently represent a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, or an aromatic hydrocarbon group having 6 to 24 carbon atoms. Shows.
R ¹¹ and R ¹² are preferably alkyl groups from the viewpoint of improving the repellent effect, and the number of carbon atoms is preferably 8 or more from the viewpoint of improving the repellent effect. From the viewpoint of improving the feel when applied, the molecular weight is preferably 18 or less, more preferably 16 or less, and further preferably 12 or less.
Examples of the dialkyl ether compound represented by the general formula (5) include dihexyl ether, dioctyl ether ("Cetyl OE" by Cognis), dicaprylyl ether, cetyl-1,3-dimethylbutyl ether ("ASE-166K" by Kao Corporation), and the like. " ) etc.

R ¹³ -O-(PO)r(EO)s-H (6)
In the general formula (6), R ¹³ represents an alkyl group or an alkenyl group having 6 to 22 carbon atoms, PO represents a propyleneoxy group, and EO represents an ethyleneoxy group. represents the average number of moles added, and s represents the average number of moles added of from 0 to 10. When s is not 0, the addition form of PO and EO may be random or block.
The number of carbon atoms in R ¹³ is preferably 8 or more from the viewpoint of improving the repellent effect and is preferably 20 or less, more preferably 18 or less, from the viewpoint of improving the feel when applied to the skin. , and more preferably 12 or less.
The average number of moles added, r, is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, from the viewpoint of improving the repellent effect, and from the viewpoint of improving the feel when applied to the skin. From the viewpoint of providing a good feel when applied to the skin, the average number of moles added s is preferably 5 or less, more preferably 1 or less, and even more preferably 1 or less. is 0.
Examples of the polyoxyalkylene alkyl ether compound represented by the general formula (6) include polypropylene glycol, polyoxypropylene octyl ether, polyoxypropylene decyl ether, and the like, each of which has an average added mole number r of propyleneoxy groups of 3 or more and 10 or less. and polyoxypropylene lauryl ether.
Among the above (c) ether oils, the ether oil represented by the general formula (5) is preferred from the viewpoint of improving the sustained repellent effect.

(d) Hydrocarbon Oils Examples of the hydrocarbon oils include liquid paraffin, liquid isoparaffin, squalane, isohexadecane, isoeicosane, hydrogenated polyisobutene, light liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomers, and cycloparaffin.
Among these, from the viewpoint of improving the sustained repellent effect and from the viewpoint of providing a good feel when applied to the skin, one or more selected from liquid paraffin, liquid isoparaffin, and squalane are preferred.

(e) Aliphatic Alcohols Examples of the aliphatic alcohol include monohydric chain or cyclic aliphatic alcohols, and from the viewpoint of improving the repellent duration effect, monohydric chain aliphatic alcohols are preferred. The number of carbon atoms in the aliphatic alcohol is preferably 14 or more, more preferably 18 or more, from the viewpoint of improving the repellent duration effect, and is preferably 28 or less, more preferably 24 or less, and even more preferably 22 or less, from the viewpoint of improving the feel when applied to the skin.
The aliphatic alcohol may be either straight-chain or branched, and may be either saturated or unsaturated. From the viewpoint of improving the sustained repellent effect and of providing a good feel when applied to the skin, a branched-chain aliphatic saturated alcohol is preferred.
Examples of the straight chain aliphatic alcohols include oleyl alcohol, and examples of the branched chain aliphatic saturated alcohols include butyl octanol, butyl decanol, hexyl decanol, and octyldodecanol.
Among these, from the viewpoint of improving the sustained repellent effect and from the viewpoint of providing a good feel when applied to the skin, branched chain aliphatic saturated alcohols are preferred, and one or more selected from hexyldecanol and octyldodecanol are preferred.

(f) Polyhydric Alcohols Examples of polyhydric alcohols include aliphatic alcohols having 2 or more carbon atoms, aromatic alcohols, and sugar alcohols having 4 or more carbon atoms, and may be either saturated or unsaturated. From the viewpoint of providing a good feel when applied to the skin, one or more types selected from aliphatic alcohols having 2 to 10 carbon atoms, aromatic alcohols, and sugar alcohols having 4 to 10 carbon atoms are preferred.
Among the polyhydric alcohols, examples of aliphatic alcohols having 2 or more carbon atoms include dihydric alcohols such as ethylene glycol, propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,2-pentanediol, 1,2-hexanediol, diethylene glycol, dipropylene glycol, and hexylene glycol.
Examples of the sugar alcohol include sorbitol, erythritol, pentaerythritol, xylitol, and mannitol.

Among the liquid oily components, from the viewpoint of improving the repellent effect, one or more selected from (a) silicone oil, (b) ester oil, (c) ether oil, and (d) hydrocarbon oil are preferred, one or more selected from (a) silicone oil, (b) ester oil, and (d) hydrocarbon oil are more preferred, one or more selected from (a) silicone oil and (b) ester oil are even more preferred, and (a) silicone oil is even more preferred. Among (a) silicone oil, from the viewpoint of improving the repellent effect, one or more selected from dimethylpolysiloxane, dimethiconol, methylphenylpolysiloxane, and modified silicone are preferred, one or more selected from dimethylpolysiloxane and dimethiconol are more preferred, dimethylpolysiloxane is even more preferred, and linear dimethylpolysiloxane is even more preferred.

(Content of component (A))
The content of component (A) in the composition of the present invention is 13% by mass or more, preferably 18% by mass or more, more preferably 25% by mass or more, from the viewpoint of improving the repellent effect. Also, from the viewpoint of improving the feel when applied to the skin and ensuring the long-term storage stability of the composition, it is 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less. The content of component (A) in the composition of the present invention is 13 to 50% by mass, preferably 18 to 40% by mass, more preferably 25 to 35% by mass.

<Component (B): Hydrophilic inorganic particles>
The composition of the present invention contains, as component (B), silica particles and/or silicate mineral particles, and contains hydrophilic inorganic particles having a volume median particle size of 1 μm or more and 40 μm or less. By containing component (B), the repellent effect of component (A) is improved and the composition feels good when applied to the skin.

In this specification, the term "hydrophilic inorganic particles" refers to inorganic particles having a surface wetting tension of 70 mN/m or more at 23°C.
By using hydrophilic inorganic particles having a specific particle size as the particles of component (B), the repellent effect is improved and a composition having a good feel when applied to the skin is obtained. From the viewpoint of improving the repellent effect and improving the feel when applied to the skin, the component (B) used in the composition of the present invention preferably has a wetting tension at 23°C of 70 mN/m or more, more preferably 73 mN/m or more. The upper limit can be, for example, 100 mN/m or less, and may be 95 mN/m or less. The wetting tension of the particle surface can be measured by the method described in the Examples.

Component (B) contains silica particles and/or silicate mineral particles.
From the viewpoint of providing a good feel when applied to the skin, the silicate mineral particles preferably contain at least one type selected from talc particles, mica particles, sericite particles, smectite particles, montmorillonite particles, bentonite particles, and kaolin particles, and more preferably contain at least one type selected from talc particles and mica particles.
From the viewpoint of providing a good feel when applied to the skin, component (B) preferably contains one or more types of particles selected from silica particles, talc particles, and mica particles, more preferably contains silica particles, and even more preferably contains porous silica particles.

Examples of the shape of component (B) include spherical, plate-like, flat, flaky, irregular, etc. Among these, from the viewpoint of providing a good feel when applied to the skin, spherical or flat shapes are more preferable.
More specifically, when component (B) is silica particles, it is more preferable that the particles are spherical, and when component (B) is silicate mineral particles, it is more preferable that the particles are flat.

From the viewpoint of providing a good feel when applied to the skin, the volume median particle size (D50) of component (B) is 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and 40 μm or less, preferably 30 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, and even more preferably 12 μm or less.

(Content of component (B))
The content of component (B) in the composition of the present invention is 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, from the viewpoint of improving the feel when applied to the skin and ensuring long-term storage stability. Also, from the viewpoint of improving the sustained repellent effect, it is 35% by mass or less, preferably 27% by mass or less, more preferably 16% by mass or less, and even more preferably 8% by mass or less. The content of component (B) in the composition of the present invention is 0.5 to 35% by mass, preferably 1 to 27% by mass, more preferably 2 to 16% by mass, and even more preferably 4 to 8% by mass.
In addition, from the viewpoint of improving the sustained repellent effect and of providing a good feel when applied to the skin, the total content of silica particles and silicate mineral particles in component (B) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and is 100% by mass or less, preferably 100% by mass.

<Component (C): Modified Silicone>
The composition of the present invention contains, as component (C), one or more modified silicones selected from polyether-modified silicones, polyglycerin-modified silicones, branched polyglycerol-modified silicones, alkyl glyceryl ether-modified silicones, and carboxy-modified silicones, which are liquid at 25° C. The term "liquid at 25° C." refers to a state in which the silicone has fluidity in a bulk state under an atmospheric pressure and at 25° C. Specifically, the term "liquid at 25° C." refers to a viscosity of 120,000 mPa·s or less measured at 25° C. using a Brookfield viscometer according to JIS Z8803:v2011 "Method for measuring viscosity of liquids."
In the composition of the present invention, a part of component (C) is adsorbed to component (B) via hydrogen bonds or the like to cover a part or all of component (B), thereby improving the sustained repellent effect of component (A) and providing a good feel when the composition is applied to the skin. From the viewpoint of improving the sustained repellent effect and providing a good feel when applied to the skin, the amount of component (C) adsorbed to component (B) in the composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 4% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 6% by mass or less.

Polyether-modified silicone has a structure in which the side chain and/or terminal hydrocarbon groups of silicone oil are substituted with polyether groups.
The polyether group of the polyether-modified silicone is preferably a polyethyleneoxy group, a polypropyleneoxy group, or a polyalkyleneoxy group in which an ethyleneoxy group (EO) and a propyleneoxy group (trimethyleneoxy group or propane-1,2-diyloxy group; PO) are added in a block or random manner, and more preferably a polyethyleneoxy group. As the polyether-modified silicone, a compound in which a polyether group is grafted onto a silicone main chain, a compound in which silicone and a polyether group are bonded in a block form, etc. can be used.

From the viewpoint of providing a good feel when the composition is applied to the skin, the HLB (hydrophilic-lipophilic balance) of the polyether-modified silicone is preferably 1.0 or more, more preferably 2.0 or more, even more preferably 2.5 or more, and is preferably 20.0 or less, more preferably 18.0 or less, even more preferably 16.0 or less, still more preferably 15.5 or less, even more preferably 15.0 or less.
Here, the HLB value is a value indicating the affinity of the polyether-modified silicone to water and oil, and can be calculated by the Griffin method using the following formula:
HLB = 20 x [(sum of molecular weights of hydrophilic groups contained in polyether-modified silicone)/(molecular weight of polyether-modified silicone)]
Examples of the hydrophilic group include a hydroxy group and an ethyleneoxy group.

From the viewpoint of providing a good feel when the composition is applied to the skin, the viscosity of the polyether-modified silicone at 25°C is preferably 50 mPa·s or more, more preferably 75 mPa·s or more, and even more preferably 100 mPa·s or more, and may be 120,000 or less, 10,000 or less, 4,500 mPa·s or less, 4,000 mPa·s or less, or 3,500 mPa·s or less. The above viscosity can be measured at 25°C using a Brookfield viscometer based on JIS Z8803:2011 "Method for measuring viscosity of liquids".

Specific examples of polyether-modified silicones include PEG-3 dimethicone, PEG-9 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-11 methyl ether dimethicone, PEG-12 dimethicone, PEG/PPG-20/22 butyl ether dimethicone, PEG-32 methyl ether dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-10 tris(trimethylsiloxy)silylethyl dimethicone, PEG/PPG-19/19 dimethicone, cetyl PEG/PPG-10/1 dimethicone, PEG/PPG-30/10 dimethicone, and linear polyether-modified silicones in which dimethyl silicone units and polyether units are alternately copolymerized.
Examples of commercially available polyether-modified silicones include the KF series (e.g., KF-6004, KF-6011, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6028, KF-6038, KF-6043, KF-6048) manufactured by Shin-Etsu Chemical Co., Ltd., and the DOWSIL series (BY25-337, BY25-339, SH3775M, FZ-2203, ES-5300 Formulation Aid) manufactured by Dow Chemical Japan Ltd.

Polyglycerin-modified silicone refers to silicone having a monovalent polyglyceryl group in the structure, and examples thereof include polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, etc. Here, in this specification, branched polyglycerol-modified silicone is excluded from polyglycerin-modified silicone.
Commercially available polyglycerin-modified silicone products include, for example, the KF series (for example, KF-6100, KF-6104, KF-6106, and KF-6105) manufactured by Shin-Etsu Chemical Co., Ltd.

From the viewpoint of providing a good feel when the composition is applied to the skin, the viscosity of the polyglycerin-modified silicone at 25°C is preferably 500 mPa·s or more, more preferably 1,000 mPa·s or more, even more preferably 2,000 mPa·s or more, and even more preferably 3,000 mPa·s or more, and is preferably 20,000 mPa·s or less, more preferably 10,000 mPa·s or less, and even more preferably 5,000 mPa·s or less. The above viscosity can be measured at 25°C using a Brookfield viscometer based on JIS Z8803:2011 "Method for measuring viscosity of liquids".

An example of a branched polyglycerol-modified silicone is a compound having a structure in which a branched polyglycerol chain is bonded to both ends of a dimethylpolysiloxane via a linking group containing an oxyphenylene group, as shown in the following formula (1).

(In formula (1), R ¹² each independently represents a branched polyglycerol chain, and m represents an integer of 0 to 10,000.)

In formula (1), the bonding mode between the oxygen atom in the phenylene group portion and the trimethylene group (-C ₃ H ₆ -) is not particularly limited, and may be any of the ortho, meta, and para positions. m represents an integer of 0 to 10,000, and preferably 1 to 300. R ¹² represents a branched polyglycerol chain, which is composed of glycerol units represented by the following structural formulas (2) to (5), has at least one glycerol unit having a branched structure represented by structural formula (2), and is terminated by a glycerol unit represented by structural formula (5). The average total number of bonds of the glycerol units in the branched polyglycerol chain is 3 to 200, and preferably 3 to 30.

From the viewpoint of providing a good feel when the composition is applied to the skin, the viscosity of the branched polyglycerol-modified silicone at 25°C is preferably 10,000 mPa·s or more, more preferably 15,000 mPa·s or more, and preferably 500,000 mPa·s or less, more preferably 300,000 mPa·s or less, and even more preferably 150,000 mPa·s or less. The above viscosity can be measured at 25°C using a Brookfield viscometer based on JIS Z8803:2011 "Method for measuring viscosity of liquids".

The branched polyglycerol-modified silicone represented by formula (1) can be produced, for example, by the method described in JP 2004-339244 A, in which 2,3-epoxy-1-propanol is added to a modified silicone having phenyl groups substituted with hydroxy groups at both ends, in the presence of an acidic or basic catalyst, and graft polymerization is carried out, or by other commonly known methods.
In addition, examples of commercially available branched polyglycerol-modified silicones include SOFCARE GS-G (manufactured by Kao Corporation).

Examples of alkyl glyceryl ether modified silicones include those represented by the following formula (6).

[In formula (6), Q represents a divalent hydrocarbon group having 3 to 20 carbon atoms; R ¹ to R ⁹ may be the same or different and represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 32 carbon atoms, or a phenyl group; R ¹⁰ and R ¹¹ may be the same or different and represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 32 carbon atoms, and multiple R ^10s and R ^11s in the same molecule may be different from each other; p represents a number from 1 to 500, and q represents a number from 1 to 50. It is preferable that p and q represent numbers such that the content of alkyl glyceryl ether groups [-Q-OCH ₂ -CH(OR ¹⁰ )-CH ₂ (OR ¹¹ )] in the molecule is 1% by mass or more and 50% by mass or less.]

In formula (6), the divalent hydrocarbon group having 3 to 20 carbon atoms represented by Q is preferably a straight-chain or branched-chain alkylene group having 3 to 20 carbon atoms. More specifically, examples of such straight-chain alkylene groups include trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, and octadecamethylene; and branched-chain alkylene groups such as propylene, 2-methyltrimethylene, 2-methyltetramethylene, 2-methylpentamethylene, and 3-methylpentamethylene.

In the definition of R ¹ to R ¹¹ , examples of the linear or branched hydrocarbon group having 1 to 32 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, doeicosyl, tetraeicosyl, hexaeicosyl, octaeicosyl, and triacontyl; and branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, neopentyl, 1-ethylpropyl, and 1-heptyldecyl. In the present specification, R ¹ to R ⁹ are preferably linear or branched alkyl groups having 1 to 25 carbon atoms (which may be partially hydrogen atoms), and more preferably linear or branched alkyl groups having 1 to 22 carbon atoms (which may be partially hydrogen atoms). In addition, R ¹⁰ and R ¹¹ are preferably hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and more preferably hydrogen atoms.

Furthermore, p and q are preferably numbers that result in the content of alkyl glyceryl ether groups [-Q-OCH ₂ -CH(OR ¹⁰ )-CH ₂ (OR ¹¹ )] of 1 mass % or more and 50 mass % or less, more preferably numbers that result in 5 mass % or more and 40 mass % or less, and even more preferably numbers that result in 10 mass % or more and 30 mass % or less. Specifically, from the standpoint of ease of availability of the organopolysiloxane used as a raw material and operability during production, p is in the range of 1 to 500, preferably 10 to 30, and q is in the range of 1 to 50, preferably 1 to 30.

From the viewpoint of providing a good feel when the composition is applied to the skin, the viscosity of the alkyl glyceryl ether modified silicone at 25°C is preferably 1,000 mPa·s or more, more preferably 2,000 mPa·s or more, even more preferably 3,000 mPa·s or more, and preferably 20,000 mPa·s or less, more preferably 15,000 mPa·s or less, even more preferably 10,000 mPa·s or less. The above viscosity can be measured at 25°C using a Brookfield viscometer based on JIS Z8803:2011 "Method for measuring viscosity of liquids".

Such alkyl glyceryl ether-modified silicones can be produced by reacting an organohydrogenpolysiloxane having at least one silicon-hydrogen bond with the corresponding alkenyl glyceryl ether according to the methods described in JP-A-4-134013 and JP-A-2005-194523.
Furthermore, examples of commercially available alkyl glyceryl ether modified silicones include SI-UGE and SOFCARE RS-U (both manufactured by Kao Corporation).

Examples of the carboxy-modified silicone include compounds having a structure in which a carboxy group is bonded to the side chain and/or end of a silicone oil. The main chain of the silicone oil and the carboxy group may be bonded via a linking group. Specific examples of the carboxy-modified silicone include carboxydecyl dimethicone, carboxydecyl trisiloxane, and biscarboxydecyl dimethicone.
From the viewpoint of providing a good feel when the composition is applied to the skin, the viscosity of the carboxy-modified silicone at 25° C. is preferably 500 mPa·s or more, more preferably 1,000 mPa·s or more, even more preferably 1,500 mPa·s or more, and is preferably 3,500 mPa·s or less, more preferably 3,000 mPa·s or less, even more preferably 2,500 mPa·s or less. The above viscosity can be measured at 25° C. using a Brookfield viscometer based on JIS Z8803:2011 "Method for measuring viscosity of liquids."
The carboxy-modified silicone may be either a synthetic product or a commercially available product.
Examples of commercially available carboxy-modified silicones include X-22-3701E, X-22-3710, and X-22-162C manufactured by Shin-Etsu Chemical Co., Ltd., and DOWSIL BY 16-880 Fluid and DOWSIL ES-5800 Formulation Aid manufactured by Dow Chemical Japan, Ltd.

These modified silicones may be used alone or in combination of two or more, and it is preferable to use two types in combination.

(Content of component (C))
The content of component (C) in the composition of the present invention is 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.4% by mass or more, from the viewpoint of improving the repellent effect and improving the feel when applied to the skin, and is 3% by mass or less, preferably 2.3% by mass or less, more preferably 1.6% by mass or less, and even more preferably 1.0% by mass or less, from the viewpoint of ensuring long-term storage stability. The content of component (C) in the composition of the present invention is 0.1 to 3% by mass, preferably 0.2 to 2.3% by mass, more preferably 0.3 to 1.6% by mass, and even more preferably 0.4 to 1.0% by mass.

In the composition of the present invention, the mass ratio of component (B) to component (A) [(B)/(A)] is preferably 0.02 or more, more preferably 0.06 or more, and even more preferably 0.1 or more, from the viewpoint of providing a good feel when applied to the skin and ensuring long-term storage stability, and is preferably 0.7 or less, more preferably 0.5 or less, and even more preferably 0.3 or less, from the viewpoint of improving the sustained repellent effect.

In addition, in the composition of the present invention, the mass ratio of component (C) to component (A) [(C)/(A)] is preferably 0.005 or more, more preferably 0.01 or more, and even more preferably 0.015 or more, from the viewpoint of improving the sustained repellent effect and ensuring long-term storage stability, and is preferably 0.1 or less, more preferably 0.08 or less, and even more preferably 0.04 or less, from the viewpoint of providing a good feel when applied to the skin.

In the composition of the present invention, the mass ratio of component (C) to component (B) [(C)/(B)] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.07 or more, and even more preferably 0.1 or more, from the viewpoint of improving the sustained repellent effect, and is preferably 0.9 or less, more preferably 0.7 or less, even more preferably 0.5 or less, and even more preferably 0.3 or less, from the viewpoint of improving the feel when applied to the skin and ensuring long-term storage stability.

<Component (D): Thickener>
The composition of the present invention contains a thickener as component (D). From the viewpoint of improving the repellent effect by adjusting the fluidity after application to the skin, from the viewpoint of ensuring excellent application to the skin by dispersing or dissolving each component well, and from the viewpoint of ensuring the long-term storage stability of the composition, the thickener is preferably one having a moderate emulsifying ability (i.e., surface activity). In the present invention, the agent having emulsifying ability and thickening effect is a thickener. Specifically, the component (D) may be a water-soluble cationic polymer, anionic polymer, nonionic polymer, and amphoteric or dipolar polymer.

Specific examples of cationic polymers include hydroxyethyl cellulose having an O-[2-hydroxy-3-(trimethylammonio)propyl] chloride group (polyquaternium-10), vinylpyrrolidone-dimethylaminomethylethyl methacrylate copolymer diethyl sulfate (polyquaternium-11), and methylvinylimidazolium chloride-vinylpyrrolidone copolymer.

Specific examples of anionic polymers include carboxyvinyl polymer, carboxymethylcellulose, carrageenan, xanthan gum, polystyrene sulfonate, agar, ghatti gum, karaya gum, pectin, alginate salt, acrylic acid/alkyl methacrylate copolymer, (sodium acrylate/sodium acryloyldimethyltaurate) copolymer, polyacrylamide, (ammonium acryloyldimethyltaurate/vinylpyrrolidone) copolymer, (acrylates/alkyl acrylate (C10-C30)) crosspolymer, (ammonium acryloyldimethyltaurate/beheneth-25 methacrylate) crosspolymer, (hydroxyethyl acrylate/sodium acryloyldimethyltaurate) copolymer, (acrylamide/ammonium acrylate) copolymer, (sodium acrylate/acryloyldimethyltaurate/dimethylacrylamide) crosspolymer, polyacrylate-13, polyacrylate crosspolymer-6, alkali metal salts of poly(acrylic acid), and hyaluronic acid or its alkali metal salts.

Specific examples of nonionic polymers include cellulose ethers (hydroxybutyl methylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose stearoxy ether, etc.), propylene glycol alginate, poly(ethylene oxide), polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl guar gum, locust bean gum, amylose, hydroxyethyl amylose, starch and starch derivatives, and mixtures thereof.

Specific examples of amphoteric or dipolar polymers include octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, polyquaternium-47, polyquaternium-43, etc.

The component (D) can be used alone or in combination of two or more types, and it is preferable to use a combination of two or more types.
From the viewpoint of improving the durability of the pest repellent effect by adjusting the fluidity after application to the skin, from the viewpoint of ensuring excellent application to the skin by well dispersing or dissolving each component, and from the viewpoint of ensuring long-term storage stability of the composition, component (D) is preferably one or more selected from anionic polymers and nonionic polymers, preferably one or more selected from carboxyvinyl polymers, acrylic acid/alkyl methacrylate copolymers, (sodium acrylate/sodium acryloyldimethyltaurate) copolymers, (ammonium acryloyldimethyltaurate/beheneth-25 methacrylate) crosspolymers, hydroxypropyl methylcellulose stearoxy ether, and (acrylates/alkyl acrylate (C10-C30)) crosspolymers, more preferably one or more selected from (ammonium acryloyldimethyltaurate/beheneth-25 methacrylate) crosspolymers, hydroxypropyl methylcellulose stearoxy ether, and (acrylates/alkyl acrylate (C10-C30)) crosspolymers.
Examples of commercially available products of component (D) include "CARBOPOL 980", "CARBOPOL 981", "CARBOPOL 1342", "CARBOPOL ETD2020", "PEMULEN TR-1", and "PEMULEN TR-2" from Lubrizol Advanced Materials, "Aculyn 22" from Dow Chemical Company, "Aristoflex AVC", "Aristoflex HMB", and "Aristoflex Velvet" from Clariant Iberica Production S.A., and "Sangelose 60L" from Daido Kasei Kogyo Co., Ltd. The thickener can also be blended as a dispersion dispersed in a dispersion medium.

From the viewpoint of obtaining the above-mentioned effects, the content of component (D) in the composition of the present invention is 0.05 mass% or more, preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and from the same viewpoint, preferably 3 mass% or less, more preferably 2 mass% or less, even more preferably 1.5 mass% or less. The content of component (D) in the composition of the present invention is 0.05 to 3 mass%, preferably 0.1 to 2 mass%, more preferably 0.2 to 1.5 mass%.
When the composition of the present invention contains a thickener having surface-active properties, the content of other surfactants is preferably 1.5% by mass or less, and more preferably 1% by mass or less.

<Component (E): Water>
The composition of the present invention contains water as component (E). The content of component (E) in the composition is 30% by mass or more from the viewpoint of making it an oil-in-water composition, and is preferably 32% by mass or more, more preferably 36% by mass or more, and even more preferably 40% by mass or more from the viewpoint of improving the feel when applied to the skin. In addition, from the viewpoint of improving the repellent sustaining effect and from the viewpoint of improving the feel when applied to the skin, it is 86.35% by mass or less, preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. The specific range of the content of component (E) in the composition is 30 to 86.35% by mass, preferably 32 to 80% by mass, more preferably 36 to 75% by mass, and even more preferably 40 to 70% by mass.

(Surfactant)
The composition of the present invention may further contain a surfactant in order to make it an oil-in-water composition. As the surfactant, any of known surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. may be used. These may be used alone or in combination of two or more kinds.
When the composition of the present invention contains a surfactant, the content of the surfactant in the composition of the present invention is, from the viewpoint of forming an oil-in-water composition, preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and even more preferably 0.1 mass % or more, and from the same viewpoint, is preferably 5 mass % or less, more preferably 3 mass % or less, and even more preferably 1 mass % or less.

<Other ingredients>
The composition of the present invention may contain other components than those mentioned above, such as medicinal or physiologically active components, such as organic solvents, preservatives, colorants, moisturizers, fragrances, pH adjusters, vitamins, blood circulation promoters, active oxygen scavengers, anti-inflammatory agents, skin whitening agents, bactericides, etc., within the scope of not impairing the effects of the invention. Each of these components may also be used for other purposes, and for example, a fragrance may be used as a bactericide.

The components (A) to (E) contained in the composition of the present invention and the components that the composition of the present invention may contain may be used alone or in combination of two or more.

It is preferable that the composition of the present invention contains component (A) as an active ingredient for pest repellency and does not contain any other effective amount of pest repellent, from the viewpoint of preventing allergies and rough skin in the user.
The composition of the present invention has a sustained repellent effect even if it does not contain an effective amount of an existing pest repellent described later. In other words, even if the composition of the present invention contains a pest repellent other than component (A) in an amount less than the lower limit of the effective amount, as long as the retention-inhibiting effect of the present invention is expressed, that is, the retention-inhibiting effect of the present invention is expressed, in which the pest does not remain in place even if it lands. In other words, the composition of the present invention does not need to substantially contain a pest repellent other than component (A).

Here, "not containing an effective amount of" a pest repellent other than component (A) generally means that the content of existing pest repellents other than component (A) in the composition of the present invention is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, still more preferably 4% by mass or less, still more preferably 3% by mass or less, and even more preferably 1% by mass or less.
The effective amount of an existing pest repellent can be determined by referring to, for example, the minimum effective amount published by the manufacturer of each repellent product.
More specifically, the effective amount of DEET: N,N-diethyltoluamide, which is an existing pest repellent described later, is 4% by mass or more, preferably 10% by mass or more, the effective amount of icaridin: 1-methylpropyl-2-(2-hydroxyethyl)-1-piperidinecarboxylate is 4% by mass or more, the effective amount of IR3535: 3-(acetylbutyl)aminopropionic acid ethyl ester is 4% by mass or more, and the effective amount of citronella oil is 10% by mass or more.

The effective amount of an existing pest repellent can also be measured by the repellency evaluation test described below.
(Repellency evaluation test)
100 mated female mosquitoes (Aedes albopictus) are placed in a plastic cage (30 x 30 x 30 cm: BugDorm-1 cage) surrounded by mesh. An arm is inserted into a Qualatech Super Long Glove (50 cm) (AS ONE Corporation, Catalog number: 3-6432-02) with a rectangular cut of 10 cm length x 3 cm width. To activate the mosquitoes, the arm is blown into the cage for 5 seconds. In a state where nothing is applied to the exposed part from the cut, the arm is inserted into the cage under conditions of 27°C and relative humidity (RH) 60%, and it is confirmed that the mosquito lands on two exposed parts of the skin within 2 minutes and remains there for 1 second or more. If the mosquito does not remain there for 1 second or more, a new mosquito is prepared. Hereinafter, a stay of 1 second or more is simply referred to as a stay. The test of the evaluation sample, which is a solution of the pest repellent, is carried out by adjusting the concentration with ethanol so that the evaluation sample can be applied to the exposed skin part (10 cm x 3 cm) at 3.3 mg/ ^cm2 . The liquid with the adjusted concentration is placed on the exposed part using a pipette, and spread over the entire exposed skin part. The solution is then left to stand for 3 minutes, and the test is started.
The test is performed by inserting the arm coated with the evaluation sample into the cage for 2 minutes and counting the number of times the arm stays there. The test is terminated when the arm stays there twice in total, and the arm is inserted for 2 minutes every 30 minutes until the end of the test. If the second stay occurs at 30 minutes, the duration of the repellent effect is determined to be 0 minutes, and if the second stay occurs at 60 minutes, the duration of the repellent effect is determined to be 30 minutes. The test is performed on three subjects, and the average duration of the repellent effect is calculated.
In this test, the concentration of a pest repellent that shows an average duration of repellent effect of 2 hours or more can be regarded as the effective concentration (effective amount) of that pest repellent.
Furthermore, from the viewpoint of safety and of having a sustained repellent effect even without containing an effective amount of an existing pest repellent, it is preferable that the composition of the present invention does not substantially contain any pest repellent other than component (A). The content of pest repellent other than component (A) in the composition of the present invention is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and even more preferably substantially 0% by mass.

Examples of existing pest repellents other than component (A) include known pest repellent compounds such as DEET, icaridin, dimethyl phthalate, 2-ethyl-1,3-hexanediol, p-menthane-3,8-diol, carane-3,4-diol, di-n-butyl succinate, hydroxyanisole, rotenone, 3-(acetylbutyl)aminopropionic acid ethyl ester, citronellol, eucalyptol, α-pinene, geraniol, citronellal, camphor, linalool, and 2-undecanone, as well as repellent essential oils such as citronella oil and lemongrass oil. "Repellent essential oil" refers to essential oils (essential oils) that have a pest repellent effect and are obtained by extracting, distilling, or squeezing components contained in plants.

From the viewpoint of environmental compatibility, it is preferable that the composition of the present invention does not substantially contain organic particles having a wet tension of 70 mN/m or less. "Substantially does not contain organic particles having a wet tension of 70 mN/m or less" means that the content of the organic particles in the composition of the present invention is less than 1.0 mass%, preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and even more preferably 0 mass%.

There are no particular limitations on the pests that the composition of the present invention can repel, but it is more effective against flying pests.
"Flying pests" refer to pests that approach humans and other animals while flying and suck blood from their skin, pests that transmit pathogenic bacteria while flying without sucking blood, and pests that cause discomfort to humans by flying themselves.
Specific examples of flying pests include mosquitoes such as Culex pipiens quinquefasciatus, Culex tritaeniorhynchus, Culex pipiens molestus, and Culex quinquefasciatus; mosquitoes such as Aedes aegypti, Aedes albopictus, Anopheles sinensis, Aedes togoi, Anopheles gambiae, and Anopheles stephensis; midges such as Chironomidae and Chironomidae akamusi; black flies such as Juniperus quinquefasciatus, Juniperus quinquefasciatus, and Juniperus acutus; house flies, Musca domestica, and Musca domestica. Flies such as house flies, little house flies, black flies, flesh flies, seed flies, onion flies, fruit flies, Drosophila melanogaster, moth flies, Chichewa flies, and stable flies; horse flies such as black flies, horse flies, deer flies, and spotted flies; midges such as Tokunaga black midge, Oshima midge, and chicken midge; and bees such as Japanese yellow hornets, Japanese paper wasps, and honeybees.
The composition of the present invention is particularly effective in providing a long-lasting repellent effect against mosquitoes, particularly Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus, Aedes aegypti, and Aedes albopictus.

[Method of manufacturing pest repellent composition]
The composition of the present invention can be obtained by mixing components (A) to (E).
As long as an oil-in-water mixture is obtained, the order of mixing the components (A) to (E) is not particularly limited. For example, from the viewpoint of adsorbing at least a part of the component (C) onto the surface of the component (B), it is preferable to have a step of mixing a mixture containing the components (B), (C), and (E) (hereinafter referred to as "mixture (1)") with a mixture containing the components (A) and (D) (hereinafter referred to as "mixture (2)").
The mixture (1) can be obtained by a step of mixing the components (B), (C), and (E). The order of mixing the components (B), (C), and (E) is not particularly limited, but it is preferable to mix the components (B) and (E) and then mix the components (B) and (E) with the component (C). From the viewpoint of uniformly adsorbing the component (C) on the surface of the component (B), it is more preferable to mix the components (B) and (E) and then mix the components (B) and (E) with the component (C) dissolved in a solvent.
As the solvent, a mixed solvent of water and an organic solvent can be used. The organic solvent is not particularly limited, but for example, an alcohol such as methanol, ethanol, 1-propanol, or 2-propanol can be used. Among the alcohols, at least one selected from ethanol and 2-propanol is more preferable, and ethanol is even more preferable.
From the viewpoint of uniformly mixing the components (B), (C), and (E), the concentration of the organic solvent in the mixed solvent is preferably 70 V/V % or more, more preferably 80 V/V % or more, even more preferably 90 V/V % or more, and is preferably 99 V/V % or less, more preferably 98 V/V % or less.

The temperature when mixing components (B), (C), and (E) is preferably 5° C. or higher, more preferably 10° C. or higher, from the viewpoint of efficiently adsorbing component (C) into component (B), and is preferably 70° C. or lower, more preferably 50° C. or lower, from the viewpoint of suppressing evaporation of the solvent.
The mixing time of components (B), (C), and (E) is preferably 20 minutes or more, more preferably 30 minutes or more, from the viewpoint of allowing component (C) to be sufficiently adsorbed by component (B), and is preferably 3 hours or less, more preferably 2 hours or less, from the viewpoint of production efficiency.

The mixture (2) can be obtained by a step of mixing the component (A) and the component (D).
The temperature when mixing components (A) and (D) is preferably 5° C. or higher, more preferably 10° C. or higher, from the viewpoint of uniformly mixing components (A) and (D), and is preferably 70° C. or lower, more preferably 50° C. or lower.
The mixing time of components (A) and (D) is preferably 20 minutes or more, more preferably 30 minutes or more, from the viewpoint of uniformly mixing components (A) and (D), and is preferably 3 hours or less, more preferably 2 hours or less.

The temperature when mixing mixture (1) and mixture (2) is preferably 5° C. or higher, more preferably 10° C. or higher, from the viewpoint of uniformly dispersing the oil phase in the aqueous phase, and is preferably 70° C. or lower, more preferably 50° C. or lower.
In addition, the mixing time of mixture (1) and mixture (2) is preferably 1 minute or more, more preferably 2 minutes or more, from the viewpoint of uniformly dispersing the oil phase in the aqueous phase, and is preferably 15 minutes or less, more preferably 10 minutes or less.

The rotation speed of the stirring device used to mix mixture (1) and mixture (2) is preferably 3,000 rpm or more, more preferably 4,000 rpm or more, and preferably 20,000 rpm or less, more preferably 15,000 rpm or less, from the viewpoint of uniformly dispersing the oil phase in the aqueous phase.

A known stirring device can be used in the process of mixing components (B), (C), and (E), the process of mixing components (A) and (D), and the process of mixing mixture (1) and mixture (2).

[Methods of repelling pests]
The method for repelling pests of the present invention is carried out by applying the pest repellent composition of the present invention to the surface of human skin.
Another method for repelling pests according to the present invention is to prevent pests, particularly flying pests, from remaining on human skin by attaching the pest repellent composition of the present invention to the legs of the pests, particularly flying pests. Hereinafter, these methods are collectively referred to as the "method of the present invention."

Here, "applying to the skin surface" includes not only directly applying the composition to the skin surface with the hands or the like, but also attaching the composition to the skin surface by spraying or the like.
The amount of the composition applied to the skin surface is preferably 0.1 mg or more, more preferably 0.2 mg or more, and even more preferably 0.25 mg or more ^per 1 ^cm2 from the viewpoint of improving the sustained repellent effect. The upper limit of the application amount is preferably 10 mg or less, more preferably 8 mg or less, and even more preferably 5 mg or less per 1 cm2 from the viewpoint of suppressing stickiness and economic efficiency.

In relation to the above-mentioned embodiment, the present invention further discloses the following embodiments.
＜1＞
An oil-in-water type pest repellent composition comprising the following components (A) to (E):
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C).
＜2＞
The oil-in-water pest repellent composition according to <1>, wherein the component (A) is one or more oils selected from silicone oils, ester oils, and hydrocarbon oils.
＜3＞
The oil-in-water pest repellent composition according to <1> or <2>, wherein the mass ratio of component (B) to component (A) [(B)/(A)] is 0.02 or more and 0.7 or less.
＜4＞
<1> to <3>, wherein the mass ratio of the component (C) to the component (A) [(C)/(A)] is 0.005 or more and 0.1 or less.
＜5＞
The oil-in-water pest repellent composition according to any one of <1> to <4>, wherein the volume median particle diameter of component (B) is 2 μm or more, preferably 3 μm or more, and 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 12 μm or less.
＜6＞
The oil-in-water pest repellent composition according to any one of <1> to <5>, wherein the content of component (B) is 1 mass% or more, preferably 2 mass% or more, more preferably 4 mass% or more, and is 27 mass% or less, preferably 16 mass% or less, more preferably 8 mass% or less.
＜７＞
The oil-in-water pest repellent composition according to any one of <1> to <6>, wherein the content of component (C) is 0.2 mass% or more, preferably 0.3 mass% or more, more preferably 0.4 mass% or more, and 2.3 mass% or less, preferably 1.6 mass% or less, more preferably 1.0 mass% or less.
＜8＞
The oil-in-water pest repellent composition according to any one of <1> to <7>, wherein the mass ratio of the component (C) to the component (B) [(C)/(B)] is 0.01 or more and 0.9 or less, preferably 0.05 or more, more preferably 0.07 or more, even more preferably 0.1 or more, and is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.3 or less.

＜9＞
A method for producing an oil-in-water type pest repellent composition, comprising the step of mixing a mixture containing the following components (B), (C), and (E) with a mixture containing the following components (A) and (D):
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less; (C) one or more substances selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.; (D) a thickener; and (E) water, provided that the viscosity of component (A) at 23° C. as measured with a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C).
In addition, in the oil-in-water type pest repellent composition, the content of component (A) is 13 mass% or more and 50 mass% or less, the content of component (B) is 0.5 mass% or more and 35 mass% or less, the content of component (C) is 0.1 mass% or more and 3 mass% or less, the content of component (D) is 0.05 mass% or more and 3 mass% or less, and the content of component (E) is 30 mass% or more and 86.35 mass% or less.
＜10＞
The method for producing an oil-in-water pest repellent composition according to <9>, wherein the component (A) is one or more oils selected from the group consisting of silicone oils, ester oils, and hydrocarbon oils.
<11>
The method for producing an oil-in-water pest repellent composition according to <9> or <10>, wherein the mass ratio of component (B) to component (A) [(B)/(A)] is 0.02 or more and 0.7 or less.
＜12＞
The method for producing an oil-in-water pest repellent composition according to any one of <9> to <11>, wherein the mass ratio of the component (C) to the component (A) [(C)/(A)] is 0.005 or more and 0.1 or less.
＜13＞
The method for producing an oil-in-water pest repellent composition according to any one of <9> to <12>, wherein the volume median particle diameter of component (B) is 2 μm or more, preferably 3 μm or more, and 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 12 μm or less.
＜14＞
The method for producing an oil-in-water pest repellent composition according to any one of <9> to <13>, wherein the content of component (B) is 1 mass% or more, preferably 2 mass% or more, more preferably 4 mass% or more, and is 27 mass% or less, preferably 16 mass% or less, more preferably 8 mass% or less.
＜15＞
The method for producing an oil-in-water type pest repellent composition according to any one of <9> to <14>, wherein the content of component (C) is 0.2 mass% or more, preferably 0.3 mass% or more, more preferably 0.4 mass% or more, and is 2.3 mass% or less, preferably 1.6 mass% or less, more preferably 1.0 mass% or less.
＜16＞
The method for producing an oil-in-water pest repellent composition according to any one of <9> to <15>, wherein the mass ratio of the component (C) to the component (B) [(C)/(B)] is 0.01 or more and 0.9 or less, preferably 0.05 or more, more preferably 0.07 or more, even more preferably 0.1 or more, and is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.3 or less.

＜１７＞
A method for repelling pests, comprising applying an oil-in-water type pest repellent composition containing the following components (A) to (E) to the surface of human skin:
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C).
＜18＞
The method for repelling pests according to <17>, wherein the component (A) is one or more oils selected from silicone oils, ester oils, and hydrocarbon oils.
＜19＞
The method for repelling pests according to <17> or <18>, wherein the mass ratio of the component (B) to the component (A) [(B)/(A)] is 0.02 or more and 0.7 or less.
＜20＞
The method for repelling a pest according to any one of <17> to <19>, wherein the mass ratio of the component (C) to the component (A) [(C)/(A)] is 0.005 or more and 0.1 or less.
＜21＞
The method for repelling a pest according to any one of <17> to <20>, wherein the volume median particle size of component (B) is 2 μm or more, preferably 3 μm or more, and 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 12 μm or less.
＜22＞
The method for repelling a pest according to any one of <17> to <21>, wherein the content of component (B) is 1 mass% or more, preferably 2 mass% or more, more preferably 4 mass% or more, and is 27 mass% or less, preferably 16 mass% or less, more preferably 8 mass% or less.
＜23＞
The method for repelling insects according to any one of <17> to <22>, wherein the content of component (C) is 0.2% by mass or more, preferably 0.3% by mass or more, more preferably 0.4% by mass or more, and is 2.3% by mass or less, preferably 1.6% by mass or less, more preferably 1.0% by mass or less.
＜24＞
The method for repelling a pest according to any one of <17> to <23>, wherein the mass ratio of the component (C) to the component (B) [(C)/(B)] is 0.01 or more and 0.9 or less, preferably 0.05 or more, more preferably 0.07 or more, even more preferably 0.1 or more, and is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.3 or less.

＜25＞
A method for repelling pests, which prevents pests from remaining on human skin by attaching an oil-in-water pest repellent composition containing the following components (A) to (E) to the legs of the pests:
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C).
＜26＞
The method for repelling pests according to <25>, wherein the component (A) is one or more oils selected from silicone oils, ester oils, and hydrocarbon oils.
＜27＞
The method for repelling pests according to <25> or <26>, wherein the mass ratio of the component (B) to the component (A) [(B)/(A)] is 0.02 or more and 0.7 or less.
＜28＞
The method for repelling a pest according to any one of <25> to <27>, wherein a mass ratio of the component (C) to the component (A) [(C)/(A)] is 0.005 or more and 0.1 or less.
＜29＞
The method for repelling a pest according to any one of <25> to <28>, wherein the volume median particle size of component (B) is 2 μm or more, preferably 3 μm or more, and 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 12 μm or less.
＜30＞
The method for repelling a pest according to any one of <25> to <29>, wherein the content of component (B) is 1 mass% or more, preferably 2 mass% or more, more preferably 4 mass% or more, and is 27 mass% or less, preferably 16 mass% or less, more preferably 8 mass% or less.
＜31＞
The method for repelling a pest according to any one of <25> to <30>, wherein the content of component (C) is 0.2% by mass or more, preferably 0.3% by mass or more, more preferably 0.4% by mass or more, and is 2.3% by mass or less, preferably 1.6% by mass or less, more preferably 1.0% by mass or less.
＜32＞
The method for repelling a pest according to any one of <25> to <31>, wherein the mass ratio of the component (C) to the component (B) [(C)/(B)] is 0.01 or more and 0.9 or less, preferably 0.05 or more, more preferably 0.07 or more, even more preferably 0.1 or more, and is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.3 or less.

The present invention will be described below with reference to examples, but the present invention is not limited to the scope of the examples. In the examples, various measurements and evaluations were performed by the following methods.

(Surface tension of liquid oily component)
The surface tension of the liquid oily component is measured in an environment of 25° C. by the Wilhelmy method using a platinum plate, using an automatic surface tensiometer "Tensiometer K100" (KRUSS).

(Viscosity of Liquid Oily Component)
A Viscometer TVB-10 manufactured by Toki Sangyo Co., Ltd. was used as a B-type rotational viscometer according to JIS K7117-1:1999. The viscosity values of the components to be measured vary greatly for each sample, so it is difficult to accurately measure all of them under one set of measurement conditions. Therefore, measurements were performed using two types of rotors. The viscosity was first measured using rotor M2 at a rotation speed of 12 rpm in a 23°C environment. At this time, components with a viscosity of 2500 mPa·s or more were measured again at a rotation speed of 6 rpm to obtain the viscosity value.
On the other hand, the components having a viscosity of 20 mPa·s or less were measured again using an L adapter, which is a rotor for low viscosity, at a rotation speed of 30 rpm in a 23° C. environment to obtain viscosity values.

(Wetting tension of particle surface)
The measurement was carried out as follows using a mixture for wetting tension testing manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
0.2 mL of the mixture for wetting tension test No. 70 (surface tension 70 mN/m) was weighed into a container in an environment of 23° C. Then, 0.01 g of particles to be measured was gently poured into the mixture.
Thirty seconds after the particles were added, it was visually confirmed whether the particles were wetted by the mixed liquid, and if the particles were wetted by the mixed liquid No. 70 (surface tension 70 mN/m), it was determined that the wetting tension of the particle surface was 70 mN/m or more. If the particles were wetted by the mixed liquid No. 70 (surface tension 70 mN/m) described below, the wetting tension of the particle surface was 70 mN/m or more, and it was determined that the particles were hydrophilic.
The particle surface being wetted by the mixed liquid means that the mixed liquid penetrates the particles, whereas the particle not being wetted by the mixed liquid means that the particle is separated from (or repelled by) the mixed liquid even when the particle and the mixed liquid are mixed.
The wetting tension of each particle surface was measured by carrying out the above-mentioned test using the following mixture for wetting tension test. For example, a surface tension of 23 mN/m of a particle surface means that in the above-mentioned test, when No. 25.4 (surface tension 25.4 mN/m) was used as the mixture for wetting tension test, the particle surface was not wetted by the mixture, and when No. 22.6 (surface tension 22.6 mN/m) was used as the mixture for wetting tension test, the particle surface was wetted by the mixture.
<Fujifilm Wako Pure Chemical Co., Ltd. Wetting tension test mixture>
No. 73 (surface tension 73 mN/m), No. 70 (surface tension 70 mN/m), No. 67 (surface tension 67 mN/m), No. 64 (surface tension 64 mN/m), No. 62 (surface tension 62 mN/m), No. 60 (surface tension 60 mN/m), No. 58 (surface tension 58 mN/m), No. 56 (surface tension 56 mN/m), No. 54 (surface tension 54 mN/m), No. 52 (surface tension 52 mN/m), No. 32 (surface tension 32 mN/m), No. 30 (surface tension 30 mN/m), No. 27.3 (surface tension 27.3 mN/m), No. 25.4 (surface tension 25.4 mN/m), No. 22.6 (Surface tension 22.6 mN/m)

(Volume Median Particle Size (D50) of Hydrophilic Inorganic Particles)
Using a laser diffraction/scattering particle size distribution analyzer LA-960 manufactured by HORIBA, Ltd., distilled water was added to a measurement cell, and the particle size distribution of each of the hydrophilic inorganic particles was measured at a concentration at which the absorbance was in an appropriate range. From the particle size distribution thus obtained, the volume median particle size (D50) of the hydrophilic inorganic particles was calculated.

(Evaluation of sustained repellent effect against pests)
(I) Preparation of Aedes albopictus The Aedes albopictus mosquitoes used were prepared by rearing Aedes albopictus eggs purchased from Sumitomo Technoservice Co., Ltd. in a cage under conditions of 27° C. and a relative humidity (RH) of 60% and allowing them to grow into adults.
A transparent plastic pan was filled with water to a depth of about 1 cm, and the filter paper on which the purchased eggs were laid was placed in the pan, and the pupae were allowed to hatch. The hatched pupae were then fed tropical fish food (Tetramine) daily as larval food. After one week, the pupae were collected with a dropper, transferred to a 20 mL plastic cup, and transferred to a cage covered with a net. The pupae were fed 10% by mass sucrose in a 25 mL plastic tube as adult food. After emergence, males and females were reared in the same cage for 5 days to allow mating. After 5 days of rearing, the adults were collected using an aspirator, anesthetized on ice for 5 minutes, and then separated into males and females under visual observation. Only the females were collected and used for evaluation.

(II) Measurement of repellent effect duration 100 mated female mosquitoes (Aedes albopictus) were placed in a plastic cage (30 x 30 x 30 cm: BugDorm-1 cage) surrounded by mesh. An arm was inserted into a 10 cm x 3 cm rectangular cut in a Qualatech super long glove (50 cm) (AS ONE Corporation, Catalog number: 3-6432-02). To activate the mosquitoes, the arm was blown into the cage for 5 seconds. In a state where nothing was applied to the exposed part from the cut, the arm was inserted into the cage under conditions of 27°C and relative humidity (RH) 60%, and it was confirmed that the mosquito landed on two exposed parts of the skin within 2 minutes and then stayed there for 1 second or more. If the mosquito did not stay there for 1 second or more, a new mosquito was prepared. Hereinafter, a stay of 1 second or more is simply referred to as a stay. The evaluation sample, which was a solution of the pest repellent, was tested by applying the evaluation sample evenly to exposed skin (10 cm x 3 cm) to a concentration of 3.3 mg/ ^cm2 .
The test was performed by inserting the arm onto which the evaluation sample had been applied into a cage for 2 minutes and counting the number of times the arm stayed in place.
The test was terminated when the subject had stayed in the arm twice in total, and the subject was asked to insert the arm for 2 minutes every 30 minutes until the end of the test. If the subject stayed in the arm for the second time at 30 minutes, the duration of the repellent effect was determined to be 0 minutes, and if the subject stayed in the arm for the second time at 60 minutes, the duration of the repellent effect was determined to be 30 minutes. The test was conducted on three subjects, and the average duration of the repellent effect was calculated.

(Evaluation of texture (smooth feeling when applied to skin))
Three expert panelists applied 0.02 mL of each composition to a 3 cm diameter circle on the inside of the forearm, and spread it evenly over one minute at 25°C and 57% relative humidity (RH). Sensory evaluation was performed on a 5-point scale based on the following criteria for the smooth feeling from the time of drying to after drying, and the average scores of the three panelists are shown in the table. The evaluation result of No. (4) was rated as "1".
5: No sticky feeling at all, and a good, smooth feel.
4: Feels slightly sticky, but has a smooth feel.
3: Some stickiness is felt, but the feeling is more of a dry texture.
2: Feels sticky and lacks a smooth feel.
1: Feels sticky and not smooth to the touch.

(Long-term storage stability evaluation)
80 mL of each composition was placed in a 100 mL glass bottle, sealed, and stored at 50° C. for one month. The presence or absence of separation of the oil phase in the composition was then visually confirmed and ranked according to the following criteria.
A: No change.
B: No composition remains on the surface of the glass bottle that comes into contact with the oil.
C: The oil phase is united, and some seepage from the emulsion to the surface is observed.
D: Separation of the oil phase is observed.

(Preparation and Evaluation of Compositions)
No. 1
Component (B1) and component (E) were placed in a glass beaker, and while stirring with a stirrer, component (C1) dissolved in a mixed solvent of water and ethanol (ethanol concentration: 95 V/V%) was added, and stirred for 1 hour to prepare an aqueous phase. Component (A1), component (D1) and component (D2) were added to another glass beaker, and the stirring part of T. K. Robomix (Tokushu Kika Kogyo Co., Ltd.) was replaced with T. K. Homo Disper 2.5 type to prepare an oil phase by stirring for 10 minutes. The oil phase was gradually added to the aqueous phase and pre-emulsified by propeller stirring, and then the stirring part of T. K. Robomix (Tokushu Kika Kogyo Co., Ltd.) was replaced with T. K. Homo Mixer MARKII 2.5 type to obtain an oil-in-water composition by stirring at 8,000 rpm for 3 minutes. Using the obtained composition, various evaluations were performed by the above-mentioned method. The results are shown in the table. The production and evaluation of the compositions were carried out at room temperature (25 to 28° C.).

No. 2-55, No. (1) to (14)
Nos. 2 to 55 and (1) to (14) were prepared in the same manner as in the preparation of composition No. 1, except that the composition was changed as shown in the table. The compositions thus obtained were used to carry out various evaluations according to the above-mentioned methods. The results are shown in the table. The preparation and evaluation of the compositions were carried out at room temperature (25 to 28°C). .

As shown in the table, in compositions No. 1 to 55, the amount of component (C) adsorbed to component (B) was 2 to 12 mass%.

No. (15)
Ethanol (95 V/V%) was added to the glass beaker containing component (E) while stirring with a stirrer to prepare an aqueous phase. Component (A1), component (b1), component (D1) and component (D2) were added to the glass beaker, and mixed using a T. K. Robomix (Tokushu Kika Kogyo Co., Ltd.) with the stirring part replaced with a T. K. Homo Disper 2.5 type to prepare an oil phase.
The oil phase was gradually added to the aqueous phase while pre-emulsifying with a propeller, and then the mixture was stirred for 3 minutes at 8,000 rpm using a T.K. Robomix (Tokushu Kika Kogyo Co., Ltd.) with the stirring section replaced by a T.K. Homomixer MARKII 2.5 type, to obtain an oil-in-water composition. The obtained composition was used to carry out various evaluations according to the above-mentioned methods. The results are shown in the table. The production and evaluation of the composition were carried out at room temperature (25 to 28°C).

Compositions No. 1 to 55 shown in the table are compositions of the present invention, and compositions No. (1) to (15) are compositions outside the scope of the present invention.
The designations (A) to (E) in the table correspond to components (A) to (E) in this specification, respectively, and the designations (a), (b), and (c) correspond to liquid oily components outside the scope of component (A), particles outside the scope of component (B), and modified silicones outside the scope of component (C) in this specification, respectively. For the sake of convenience, the physical properties and contents in the composition of components (a) to (c) are listed in the table in correspondence with components (A) to (C).
The ingredients used in Tables 2 to 8 are shown in Table 1. The blending amount shown in each table is the amount of active ingredient (mass %) of each ingredient.
For the content listed in the row of component (C3) for composition No. 27, the content of PEG/PPG-19/19 dimethicone in the composition (content of component (C)) is shown in parentheses. Similarly, for Nos. 37, 38, 42, 44, (7) to (9), the content of (component (C) or components outside the range of component (C)) in the composition is shown in parentheses.
"O/W" means an oil-in-water composition and "W/O" means a water-in-oil composition.

From Tables 2 to 8, it can be seen that the compositions of the present invention, each containing a specified amount of components (A) to (E), have a smooth and pleasant feel when applied to the skin, have excellent long-term storage stability, and can maintain a repellent effect for a long period of time of more than 2 hours. In addition, for example, when compositions No. 1 to 14 and 21 to 44 are compared with composition No. (15), it can be seen that the repellent effect can be maintained for a longer period of time by using a combination of component (B) and component (C) as specified in the present invention instead of the hydrophobic organic particles (polymethyl methacrylate) used in composition No. (15).

The present invention provides an oil-in-water pest repellent composition that has a good feel when applied to the skin and excellent long-term storage stability, and a method for repelling pests.

Claims (8)

An oil-in-water type pest repellent composition comprising the following components (A) to (E):
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C). The oil-in-water pest repellent composition according to claim 1, wherein component (A) is one or more selected from silicone oils, ester oils, and hydrocarbon oils. The oil-in-water pest repellent composition according to claim 1 or 2, wherein the mass ratio of component (B) to component (A) [(B)/(A)] is 0.02 or more and 0.7 or less. The oil-in-water pest repellent composition according to claim 1 or 2, wherein the mass ratio of component (C) to component (A) [(C)/(A)] is 0.005 or more and 0.1 or less. The oil-in-water pest repellent composition according to claim 1 or 2, wherein the mass ratio of component (C) to component (B) [(C)/(B)] is 0.01 or more and 0.3 or less. A method for producing an oil-in-water type pest repellent composition, comprising the step of mixing a mixture containing the following components (B), (C), and (E) with a mixture containing the following components (A) and (D):
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less; (C) one or more substances selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.; (D) a thickener; and (E) water, provided that the viscosity of component (A) at 23° C. as measured with a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C). In addition, in the oil-in-water type pest repellent composition, the content of component (A) is 13 mass% or more and 50 mass% or less, the content of component (B) is 0.5 mass% or more and 35 mass% or less, the content of component (C) is 0.1 mass% or more and 3 mass% or less, the content of component (D) is 0.05 mass% or more and 3 mass% or less, and the content of component (E) is 30 mass% or more and 86.35 mass% or less. A method for repelling pests, comprising applying an oil-in-water type pest repellent composition containing the following components (A) to (E) to the surface of human skin:
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C). A method for repelling pests, which prevents pests from remaining on human skin by attaching an oil-in-water pest repellent composition containing the following components (A) to (E) to the legs of the pests:
(A) one or more non-volatile liquid oily components selected from silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol: 13% by mass or more and 50% by mass or less; (B) hydrophilic inorganic particles containing silica particles and/or silicate mineral particles and having a volume median particle size of 1 μm or more and 40 μm or less: 0.5% by mass or more and 35% by mass or less; (C) one or more selected from polyether-modified silicone, polyglycerin-modified silicone, branched polyglycerol-modified silicone, alkyl glyceryl ether-modified silicone, and carboxy-modified silicone, which are liquid at 25° C.: 0.1% by mass or more and 3% by mass or less; (D) thickener: 0.05% by mass or more and 3% by mass or less; (E) water: 30% by mass or more and 86.35% by mass or less, provided that the viscosity of component (A) at 23° C. as measured by a B-type rotational viscometer is 1 mPa·s or more and 400 mPa·s or less, and the silicone oil of component (A) does not contain component (C).