Oil-in-water type pest insect repellent composition

Abstract

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 type of non-volatile liquid oily component selected from among 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 among 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).

Description

Oil-in-water pest repellent composition

[0001] The present invention relates to an oil-in-water pest repellent composition.

[0002] Pests, such as flying insects such as mosquitoes and flies, transmit pathogens to humans and other animals, causing infectious diseases and dermatitis. In particular, some mosquitoes are extremely harmful insects from a hygienic standpoint 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 (JP 2020-109075 A) describes an oil-in-water pest repellent composition and an oil-in-water pest retention suppression composition, which have an excellent long-lasting repellent effect against pests, particularly flying pests, are safe, have a pleasant feel when applied to the skin, and have excellent long-term storage stability. The oil-in-water pest repellent composition and the oil-in-water pest retention suppression composition contain: (A) 13% by mass to 50% by mass of one or more non-volatile liquid oily components selected from the group consisting of silicone oil, ester oil, ether oil, hydrocarbon oil, aliphatic alcohol, and polyhydric alcohol, 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 to 35% by mass of hydrophobic particles having a volume median particle size of 0.1 μm to 40 μm; and (C) 30% by mass to 86.5% by mass of water.

[0003] The present invention provides the following items [1] to [4]: ​​[1] An oil-in-water pest repellent 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 to 40 μm: 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 with a Brookfield 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, the method comprising the step of mixing a mixture containing the following component (B), the following component (C), and the following component (E) with a mixture containing the following component (A) and the following component (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 materials 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 pest repellent composition, the content of component (A) is 13% by mass or more and 50% by mass or less, the content of component (B) is 0.5% by mass or more and 35% by mass or less, the content of component (C) is 0.1% by mass or more and 3% by mass or less, the content of component (D) is 0.05% by mass or more and 3% by mass or less, and the content of component (E) is 30% by mass or more and 86.35% by mass or less. [3] A method for repelling pests, which comprises applying to the surface of human skin an oil-in-water pest repellent 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 to 40 μm: 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 with a Brookfield 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, which prevents pests from lodging 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 to 40 μm: 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 with a Brookfield 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). Detailed Description of the Invention

[0004] The oil-in-water pest repellent composition described in Patent Document 1 has a pleasant feel when applied to the skin and good long-term storage stability. However, the inventors have found that there is room for further improvement in the repellent duration. The present invention relates to an oil-in-water pest repellent composition that has a pleasant feel when applied to the skin, excellent long-term storage stability, and excellent long-term 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.

[0005] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by an oil-in-water 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.

[0006] According to the present invention, it is possible to provide an oil-in-water pest repellent composition that has a pleasant feel when applied to the skin, has excellent long-term storage stability, and 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.

[0007] Preferred embodiments of the present invention will be described below. In this specification, the range "X to Y" means "X or more and Y or less." In addition, in this specification, the upper and lower limits of a numerical range can be combined in any combination.

[0008] [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 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 to 40 μm: 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 with a Brookfield 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).

[0009] The composition of the present invention is an oil-in-water composition that contains specific amounts of components (A) to (E), has a pleasant feel when applied to the skin, has excellent long-term storage stability, and has an excellent, sustained repellent effect against pests, particularly flying pests.

[0010] In the present invention, the "repellent effect against pests" includes the effect of pests immediately leaving an object without remaining on it even when they come into contact with the object (retention-inhibiting effect), and may further include one or more of keeping pests away from the object and exterminating them. The composition of the present invention at least exhibits a pest-repelling effect by preventing pests such as mosquitoes from remaining on the object and immediately leaving it, even when the composition is applied or attached to the object. Specifically, the composition exhibits a retention-inhibiting effect of preventing pests such as mosquitoes from remaining on a predetermined area of ​​the skin surface for a time sufficient for their stingers to penetrate the skin of an animal such as a human, specifically for one second or more. This effect is safe and does not cause side effects such as rough skin. In the present invention, the "prolonged repellent effect against pests" means that the repellent effect persists even after the application of the composition of the present invention to an object. In the following description, the prolonged repellent effect, particularly against flying pests, in the present invention will be simply referred to as the "prolonged repellent effect."

[0011] The composition of the present invention contains specific amounts of 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 to 40 μm; component (C) one or more liquid silicones selected from polyether-modified silicones, polyglycerin-modified silicones, branched polyglycerol-modified silicones, alkyl glyceryl ether-modified silicones, and carboxy-modified silicones at 25° C.; component (D) a thickener; and component (E) water. The composition of the present invention has a pleasant feel when applied to the skin, excellent long-term storage stability, and excellent long-lasting repellent effect against pests, particularly flying pests. The reasons for this are unclear, but are thought to be as follows: Flying pests such as mosquitoes have a tendency to avoid landing on surfaces where their legs become wet in order to avoid the attractive force generated from the landing surface when their legs become wet. When flying pests land on a skin surface coated or adhered with component (A), their legs become wet, and they fly away without remaining at the landing point, avoiding the gravitational force generated by the landing surface. Furthermore, in the composition, a portion of component (C) is adsorbed to component (B), improving the pleasant feel of component (B) on the skin. Furthermore, a portion of component (C) is mixed with component (A), imparting thixotropy to component (A), preventing component (A) from dripping due to gravity and allowing it to wet and spread across the legs when subjected to external force due to landing of flying pests. As a result, when the composition is applied to the skin surface, the composition remains evenly applied to the skin surface for a long time, providing a pleasant feel and improving the sustained repellent effect. Furthermore, the inclusion of a specific amount of component (D) contributes to the long-term storage stability of the composition of the present invention. In this specification, "landing" refers to a flying pest, such as a mosquito, coming into contact with the target object for less than one second. In addition, the term "stationary" in the present invention refers to a state in which a flying pest such as a mosquito continues to contact an object for one second or more.

[0012] <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, with the proviso that the silicone oil of component (A) does not include component (C).

[0013] From the viewpoints of facilitating application to the skin and improving the duration of the 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. Note that the term "liquid" for a liquid oily component means that the viscosity at 23°C measured with a B-type rotational viscometer is 120,000 mPa s or less. From the viewpoint of improving the duration of the repellent effect, component (A) is preferably a water-insoluble or slightly water-soluble component, and specifically, the solubility 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 substantially 0 g.

[0014] 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 duration of repellency. Here, the non-volatile liquid oily component in the present invention refers to a component whose volatility after drying at 25°C for 60 minutes under 1 atmosphere is 50% or less, and preferably refers to a component whose volatility after drying at 25°C for 120 minutes under 1 atmosphere is 50% or less. The volatility is evaluated in accordance with German test standard DIN 53249, and specifically, is carried out in the following steps 1 to 4. 1. The weight (P(g)) of a round filter paper with a diameter of 150 mm is measured. 2. A 0.3 g sample of component (A) is dropped onto the round filter paper using a pipette, and immediately afterwards the weight (W ０ 3. Measure the weight of the filter paper at 25°C in a ventilated environment at 5-minute intervals using a gravimetric measurement with an accuracy of approximately 0.001 g. The weight of the filter paper measured 60 minutes after measuring 2 is W ６０ (g). 4. Calculation formula {((W ０ -P)-(W ６０ -P)) / (W ０The value obtained by the formula {( ...

[0015] The surface tension of component (A) at 25°C is preferably 15 mN / m or more, more preferably 17 mN / m or more, from the viewpoint of availability, and 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, from the viewpoint of improving the repellent durability. When two or more liquid oily components with different surface tensions are used, the surface tension refers to the surface tension of the mixture of these liquid oily components. The viscosity of component (A) at 23°C as measured with a Brookfield 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, even more preferably 100 mPa·s or less, even more preferably 60 mPa·s or less, even more preferably 40 mPa·s or less, and even more preferably 30 mPa·s or less. When two or more liquid oily components with different viscosities are used, the viscosity refers to the viscosity of a mixture of these liquid oily components. The viscosity of component (A) at 23°C as measured with a Brookfield rotational viscometer is preferably at least the lower limit mentioned above in order to suppress volatility and improve the sustained repellent effect, and is preferably at most the upper limit mentioned above in order to ensure long-term storage stability. The surface tension and viscosity of component (A) at 23°C as measured with a Brookfield rotational viscometer are measured by the methods described in the Examples.

[0016] (a) Silicone Oil From the viewpoint of improving the repellent durability, the silicone oil is preferably one or more selected from dimethylpolysiloxane (dimethicone), dimethiconol (dimethylpolysiloxane having a hydroxyl group at the terminal), methylphenylpolysiloxane, and modified silicone. Examples of modified silicone include amino-modified silicone (dimethylpolysiloxane having an amino group), amino derivative silicone, fatty acid-modified silicone, alcohol-modified silicone, aliphatic alcohol-modified silicone, epoxy-modified silicone, fluorine-modified silicone, and alkyl-modified silicone.

[0017] Among the silicone oils, from the viewpoint of improving the 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.

[0018] Examples of dimethylpolysiloxanes include one or more selected from linear dimethylpolysiloxanes and cyclic dimethylpolysiloxanes. Among these, linear dimethylpolysiloxanes are more preferred from the viewpoint of improving the durability of the 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 Momentive Performance Materials' "Silsoft DML," "Element14 PDMS 5-JC," "Element14 PDMS 10-JC," and "Element14 PDMS 20-JC."

[0019] (b) Ester Oil As the ester oil, from the viewpoint of improving the repellent duration 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.

[0020] R 1 -COO-R 2(1) In general formula (1), R 1 represents a linear or branched alkyl group having 7 to 23 carbon atoms, or an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may be substituted with a hydroxyl group; R 2 represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms. 1 When R is an alkyl group, the number of carbon atoms is preferably 7 or more, more preferably 9 or more, from the viewpoint of improving the repellent effect and, from the viewpoint of providing a good feel when applied to the skin, it is preferably 21 or less, more preferably 17 or less. 1 When R 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, and is preferably 22 or less, more preferably 20 or less, from the viewpoint of providing a good feel when applied to the skin. 2 From the viewpoint of providing a good feel when applied to the skin, R is preferably a linear or branched alkyl or alkenyl group having 20 or less carbon atoms, more preferably 18 or less carbon atoms. 1 or R 2 At least one of them is preferably a branched alkyl group.

[0021] Examples of the ester oil represented by 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 2-ethylhexanoate, isodecyl octanoate, methyl laurate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, isocetyl palmitate, stearyl 2-ethylhexanoate, methyl laurate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, isocetyl palmitate, methyl laurate, isopropyl myristate, methyl laurate, isopropyl myristate, 2-ethylhexyl palmitate ...methyl laurate, isopropyl myristate, 2-ethylhexyl palmitate, methyl laurate, isopropyl myristate and at least one selected from the group consisting of 2-ethylhexyl stearate, 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 having 12 to 15 carbon atoms), and diethylhexyl naphthalenedicarboxylate.

[0022] (R 3 O)-CH2CH(OR 4 )-CH2(OR 5 ) (2) In the general formula (2), R 3 , R 4 and R 5 are each independently a hydrogen atom or a group represented by the following general formula (2-1), provided that they are not all hydrogen atoms. 6 (2-1) (wherein, R 6 represents an alkyl or alkenyl group having 7 to 23 carbon atoms, preferably 17 or less, which may be substituted with a hydroxyl group.) Examples of the ester oil represented by general formula (2) include one or more selected from glyceryl tri-2-ethylhexanoate and glyceryl tricaprylate. These may also be plant-derived ester oils such as jojoba oil, olive oil, sunflower oil, soybean oil, 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.

[0023] R 7O-(AO)m-COR 8 (3) In the general formula (3), R 7 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 8 represents an alkyl group or alkenyl group having 1 to 23 carbon atoms; AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and m represents the average number of moles added of 1 to 50. 7 R preferably has 6 or more carbon atoms from the viewpoint of improving the repellent effect, and is preferably an aromatic hydrocarbon group having 12 or less carbon atoms, more preferably 10 or less carbon atoms, and even more preferably a benzyl group from the viewpoint of providing a pleasant feel when applied to the skin. 8 is an alkyl group having preferably 7 or more carbon atoms, more preferably 11 or more, from the viewpoint of improving the duration of repellency, and preferably 21 or less, more preferably 15 or less, from the viewpoint of providing a good feel when applied to the skin. The AO group is preferably a propyleneoxy group from the viewpoint of improving the duration of repellency, and m is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, from the viewpoint of improving the duration of repellency and providing a good feel when applied to the skin. Examples of the ester oil represented by general formula (3) include one or more selected from an ester of a propylene oxide 3-mol adduct of benzyl alcohol and myristic acid ("Crodamol STS" available from Croda) and an ester of a propylene oxide 3-mol adduct of benzyl alcohol and 2-ethylhexanoic acid ("Crodamol SFX" available from Croda).

[0024] R 9 -O-(CH2CH2O)v-CO-(OCH2CH2)w-OR 10 (4) In the general formula (4), R 9 and R 10 each independently represents an alkyl group or an alkenyl group having 6 to 22 carbon atoms, and v and w each independently represent 0 or the average number of moles added of 1 to 50. 9 and R 10is preferably an alkyl group having 8 or more carbon atoms from the viewpoint of improving the sustained repellent effect, and is preferably an alkyl group having 18 or less, more preferably 12 or less, from the viewpoint of improving the feel when applied to the skin. v and w are preferably 0 or a number of 1 or more and 5 or less, more preferably 0, from the viewpoint of improving the feel when applied to the skin. Examples of dialkyl carbonate compounds represented by general formula (4) include dioctyl carbonate ("Cetiol CC" by Cognis).

[0025] Other ester oils include esters of polycarboxylic acids and alcohols, and esters of polyhydric alcohols (excluding glycerin) and fatty acids. Specific examples include one or more selected from diisopropyl dimerate, diisopropyl adipate, diethoxyethyl succinate, 2-ethylhexyl succinate, propanediol dicaprate, neopentyl glycol dicaprate, and neopentyl glycol di-2-ethylhexanoate. Among these, from the viewpoint of improving the durability of the 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. Among the above (b) ester oils, one or more selected from ester oils represented by general formula (1) and esters of neopentyl glycol and fatty acids are preferred.

[0026] (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 preferred.

[0027] R 11 -O-R 12 (5) In the general formula (5), R 11 and R 12 R each independently represents a linear or branched alkyl or alkenyl group having from 6 to 22 carbon atoms, or an aromatic hydrocarbon group having from 6 to 24 carbon atoms. 11 and R 12is preferably an alkyl group from the viewpoint of improving the duration of repellency, and the number of carbon atoms therein is preferably 8 or more from the viewpoint of improving the duration of repellency, and is preferably 18 or less, more preferably 16 or less, and even more preferably 12 or less from the viewpoint of providing a good feel when applied to the skin. Examples of dialkyl ether compounds represented by general formula (5) include dihexyl ether, dioctyl ether ("Cetiol OE" manufactured by Cognis), dicaprylyl ether, cetyl-1,3-dimethylbutyl ether ("ASE-166K" manufactured by Kao Corporation), and the like.

[0028] R 13 -O-(PO)r(EO)s-H (6) In the general formula (6), R 13 represents an alkyl or alkenyl group having 6 to 22 carbon atoms, PO represents a propyleneoxy group, and EO represents an ethyleneoxy group. r represents the average number of moles added of 0.1 to 15, and s represents the average number of moles added of 0 to 10. When s is not 0, the addition of PO and EO may be random or block. R 13The number of carbon atoms in the alkyl ether compound (c) is preferably 8 or more from the viewpoint of improving the repellent duration, and is preferably 20 or less, more preferably 18 or less, and even more preferably 12 or less from the viewpoint of improving the feel upon application to the skin. The average number of added moles 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 duration, and is preferably 13 or less, more preferably 10 or less from the viewpoint of improving the feel upon application to the skin. The average number of added moles s is preferably 5 or less, more preferably 1 or less, and even more preferably 0 from the viewpoint of improving the feel upon application to the skin. The polyoxyalkylene alkyl ether compound represented by general formula (6) is preferably one or more selected from polypropylene glycol, polyoxypropylene octyl ether, polyoxypropylene decyl ether, and polyoxypropylene lauryl ether, each of which has an average number of added moles r of propyleneoxy groups of 3 or more and 10 or less. Among the above-mentioned (c) ether oils, the ether oil represented by general formula (5) is preferred from the viewpoint of improving the repellent duration.

[0029] (d) Hydrocarbon Oil Examples of the hydrocarbon oil include liquid paraffin, liquid isoparaffin, squalane, isohexadecane, isoeicosane, hydrogenated polyisobutene, light liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, cycloparaffin, etc. Among these, from the viewpoint of improving the sustained repellent effect and improving the feel when applied to the skin, one or more selected from liquid paraffin, liquid isoparaffin, and squalane are preferred.

[0030] (e) Aliphatic Alcohols Examples of aliphatic alcohols include monohydric chain or cyclic aliphatic alcohols, with monohydric chain aliphatic alcohols being preferred from the viewpoint of improving the duration of repellency. 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 duration of repellency, 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 upon application to the skin. The aliphatic alcohol may be either linear or branched, and may be either saturated or unsaturated. However, from the viewpoint of improving the duration of repellency and improving the feel upon application to the skin, branched saturated aliphatic alcohols are preferred. Examples of linear saturated aliphatic alcohols include oleyl alcohol, and examples of branched saturated aliphatic alcohols include butyloctanol, butyldecanol, hexyldecanol, and octyldodecanol. Among these, from the viewpoint of improving the repellent effect and improving the feel when applied to the skin, branched-chain aliphatic saturated alcohols are preferred, and one or more selected from hexyldecanol and octyldodecanol are preferred.

[0031] (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 they may be either saturated or unsaturated. From the viewpoint of providing a good feel when applied to the skin, however, one or more selected from aliphatic alcohols having 2 to 10 carbon atoms, aromatic alcohols, and sugar alcohols having 4 to 10 carbon atoms are preferred. Among 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 alcohols include sorbitol, erythritol, pentaerythritol, xylitol, and mannitol.

[0032] Among the liquid oily components, from the viewpoint of improving the duration of repellency, preferably one or more selected from (a) silicone oil, (b) ester oil, (c) ether oil, and (d) hydrocarbon oil, more preferably one or more selected from (a) silicone oil, (b) ester oil, and (d) hydrocarbon oil, even more preferably one or more selected from (a) silicone oil and (b) ester oil, and even more preferably (a) silicone oil.Of the (a) silicone oil, from the viewpoint of improving the duration of repellency, preferably one or more selected from dimethylpolysiloxane, dimethiconol, methylphenylpolysiloxane, and modified silicone, more preferably one or more selected from dimethylpolysiloxane and dimethiconol, even more preferably dimethylpolysiloxane, and even more preferably linear dimethylpolysiloxane.

[0033] (Content of Component (A)) From the viewpoint of improving the sustained repellent effect, the content of component (A) in the composition of the present invention is 13% by mass or more, preferably 18% by mass or more, and more preferably 25% by mass or more. Furthermore, from the viewpoint of improving the feel when applied to the skin and ensuring the long-term storage stability of the composition, the content is 50% by mass or less, preferably 40% by mass or less, and 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, and more preferably 25 to 35% by mass.

[0034] <Component (B): Hydrophilic Inorganic Particles> The composition of the present invention contains, as component (B), silica particles and / or silicate mineral particles, hydrophilic inorganic particles having a volume median particle size of 1 μm or more and 40 μm or less. By including component (B), the composition of the present invention improves the sustained repellent effect of component (A) and provides a pleasant feel when applied to the skin.

[0035] As used herein, "hydrophilic inorganic particles" refers to inorganic particles having a particle surface wetting tension of 70 mN / m or more at 23°C. When the particles of component (B) are hydrophilic inorganic particles having a specific particle size, the repellent duration effect is improved and a composition with a good feel when applied to the skin is obtained. From the viewpoint of improving the repellent duration effect and achieving a good 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.

[0036] Component (B) contains silica particles and / or silicate mineral particles. From the viewpoint of providing a pleasant feel when applied to the skin, the silicate mineral particles preferably contain at least one selected from talc particles, mica particles, sericite particles, smectite particles, montmorillonite particles, bentonite particles, and kaolin particles, and more preferably contain at least one selected from talc particles and mica particles. From the viewpoint of providing a pleasant feel when applied to the skin, component (B) preferably contains at least one particle selected from silica particles, talc particles, and mica particles, more preferably contains silica particles, and even more preferably contains porous silica particles.

[0037] The shape of component (B) may be, for example, 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 is more preferred. More specifically, when component (B) is silica particles, spherical is more preferred, and when component (B) is silicate mineral particles, flat is more preferred.

[0038] 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 is 40 μm or less, preferably 30 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, and still more preferably 12 μm or less.

[0039] (Content of Component (B)) From the viewpoint of providing a pleasant feel when applied to the skin and ensuring long-term storage stability, 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 sustained repellent effect, the content 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. From the viewpoint of providing a pleasant feel when applied to the skin and improving the sustained repellent effect, 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 100% by mass or less, preferably 100% by mass.

[0040] <Component (C): Modified Silicone> The composition of the present invention contains, as component (C), one or more modified 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. "Liquid at 25°C" refers to a state in which the silicone has fluidity in a bulk state under 1 atmosphere at 25°C. Specifically, "liquid at 25°C" refers to a viscosity of 120,000 mPa·s or less as measured at 25°C using a Brookfield viscometer in accordance with JIS Z8803:v2011 "Method for measuring viscosity of liquids." In the composition of the present invention, a portion of component (C) adsorbs to component (B) via hydrogen bonding or the like, thereby coating part or all of component (B), thereby improving the sustained repellent effect of component (A) and providing a pleasant feel when the composition is applied to the skin. From the viewpoint of improving the duration of the repellent effect and improving the feel when applied to the skin, the amount of component (C) contained in the composition of the present invention that adsorbs to component (B) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 4% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 6% by mass or less.

[0041] Polyether-modified silicones have a structure in which the hydrocarbon groups on the side chains and / or ends of silicone oil are substituted with polyether groups. The polyether groups in polyether-modified silicones are preferably polyethyleneoxy groups, polypropyleneoxy groups, or polyalkyleneoxy groups in which ethyleneoxy groups (EO) and propyleneoxy groups (trimethyleneoxy groups or propane-1,2-diyloxy groups; PO) are added in a block or random manner, with polyethyleneoxy groups being more preferred. Examples of polyether-modified silicones that can be used include compounds in which polyether groups are grafted onto a silicone main chain, and compounds in which silicone and polyether groups are bonded in a block manner.

[0042] 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 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, and even more preferably 15.0 or less. Here, the HLB value is a value that indicates the affinity of the polyether-modified silicone for water and oil, and can be calculated using the Griffin method using the following formula: HLB = 20 × [(sum of molecular weights of hydrophilic groups contained in the polyether-modified silicone) / (molecular weight of the polyether-modified silicone)] Examples of the hydrophilic group include a hydroxy group and an ethyleneoxy group.

[0043] 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 viscosity can be measured at 25°C using a Brookfield viscometer in accordance with JIS Z8803:2011 "Method for measuring viscosity of liquids."

[0044] 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, and KF-6048) manufactured by Shin-Etsu Chemical Co., Ltd., and the DOWSIL series (BY25-337, BY25-339, SH3775M, FZ-2203, and ES-5300 Formulation Aid) manufactured by Dow Chemical Japan Ltd.

[0045] Polyglycerin-modified silicone refers to silicone having a monovalent polyglyceryl group in its structure, and examples thereof include polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone. In this specification, branched polyglycerol-modified silicones are excluded from polyglycerin-modified silicones. Commercially available polyglycerin-modified silicones include the KF series (e.g., KF-6100, KF-6104, KF-6106, and KF-6105) manufactured by Shin-Etsu Chemical Co., Ltd.

[0046] From the viewpoint of ensuring 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 viscosity can be measured at 25°C using a Brookfield viscometer in accordance with JIS Z8803:2011 "Method for measuring viscosity of liquids."

[0047] Examples of branched polyglycerol-modified silicones include compounds represented by the following formula (1), which have a structure in which branched polyglycerol chains are bonded to both ends of dimethylpolysiloxane via linking groups containing oxyphenylene groups:

[0048] (In formula (1), R １２ each independently represents a branched polyglycerol chain, and m represents an integer of 0 or more and 10,000 or less.

[0049] In formula (1), the oxygen atom in the phenylene group portion and the trimethylene group (-C ３ H ６ The bonding mode of R is not particularly limited, and may be at the ortho, meta, or para position. m represents an integer of 0 to 10,000, preferably 1 to 300. 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 terminates with a glycerol unit represented by structural formula (5). The average total number of bonds of glycerol units in the branched polyglycerol chain is 3 to 200, preferably 3 to 30.

[0050]

[0051] From the viewpoint of ensuring 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 viscosity can be measured at 25°C using a Brookfield viscometer in accordance with JIS Z8803:2011 "Method for measuring viscosity of liquids."

[0052] The branched polyglycerol-modified silicone represented by formula (1) can be produced by, for example, 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 the resulting mixture is subjected to graft polymerization, or by other commonly known methods. Commercially available branched polyglycerol-modified silicones include, for example, SOFCARE GS-G (manufactured by Kao Corporation).

[0053] Examples of alkyl glyceryl ether-modified silicones include those represented by the following formula (6).

[0054] [In formula (6), Q represents a divalent hydrocarbon group having 3 to 20 carbon atoms, and R １ ~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; １０ and R １１ may be different from each other. p represents a number of 1 or more and 500 or less, and q represents a number of 1 or more and 50 or less. Note that p and q represent the alkyl glyceryl ether group [-Q-OCH ２ -CH(OR １０ )-CH ２ (OR １１) is preferably a number such that the content of is 1% by mass or more and 50% by mass or less.

[0055] In formula (6), the divalent hydrocarbon group having 3 to 20 carbon atoms represented by Q is preferably a linear or branched alkylene group having 3 to 20 carbon atoms. More specific examples include linear alkylene groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, and octadecamethylene; and branched alkylene groups such as propylene, 2-methyltrimethylene, 2-methyltetramethylene, 2-methylpentamethylene, and 3-methylpentamethylene.

[0056] Also, R １ ~R １１ In the definition of R, examples of the linear or branched hydrocarbon group having from 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. １ ~R ９ is preferably a linear or branched alkyl group having 1 to 25 carbon atoms (which may contain a hydrogen atom in part), and more preferably a linear or branched alkyl group having 1 to 22 carbon atoms (which may contain a hydrogen atom in part). １０ , R １１ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom.

[0057] Furthermore, p and q are each an alkyl glyceryl ether group [-Q-OCH ２ -CH(OR １０ )-CH ２ (OR １１) is preferably a number such that the content of 1% by mass or more and 50% by mass or less, more preferably a number such that the content of 5% by mass or more and 40% by mass or less, and even more preferably a number such that the content of 10% by mass or more and 30% by 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.

[0058] From the viewpoint of ensuring 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 viscosity can be measured at 25°C using a Brookfield viscometer in accordance with JIS Z8803:2011 "Method for measuring viscosity of liquids."

[0059] 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. Commercially available alkyl glyceryl ether-modified silicones include SI-UGE and SOFCARE RS-U (both manufactured by Kao Corporation).

[0060] Examples of carboxy-modified silicones include compounds having a structure in which a carboxy group is bonded to the side chain and / or terminal 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 carboxy-modified silicones include carboxydecyl dimethicone, carboxydecyl trisiloxane, and biscarboxydecyl dimethicone. From the viewpoint of ensuring 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, and even more preferably 1,500 mPa·s or more, and preferably 3,500 mPa·s or less, more preferably 3,000 mPa·s or less, and even more preferably 2,500 mPa·s or less. The viscosity can be measured at 25°C using a Brookfield viscometer in accordance with JIS Z8803:2011 "Method for measuring viscosity of liquids." Both synthetic and commercially available carboxy-modified silicones can be used. Commercially available carboxy-modified silicones include, for example, 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.

[0061] These modified silicones may be used alone or in combination of two or more, and it is preferred to use two of them in combination.

[0062] (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 sustained repellent effect and ensuring a good 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.

[0063] 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 pleasant 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.

[0064] 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.

[0065] In addition, 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 still 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 still more preferably 0.3 or less, from the viewpoint of improving the feel when applied to the skin and ensuring long-term storage stability.

[0066] <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, of ensuring excellent application properties to the skin by well dispersing or dissolving each component, and of ensuring long-term storage stability of the composition, it is preferable that the thickener has a moderate emulsifying ability (i.e., surfactant ability). In the present invention, an agent having emulsifying ability and a thickening effect is referred to as a thickener. Specifically, component (D) may be a water-soluble cationic polymer, an anionic polymer, a nonionic polymer, or an amphoteric or dipolar polymer.

[0067] Specific examples of the cationic polymer 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.

[0068] Specific examples of anionic polymers include carboxyvinyl polymer, carboxymethylcellulose, carrageenan, xanthan gum, polystyrene sulfonate, agar, ghatti gum, karaya gum, pectin, alginate salts, 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 an alkali metal salt thereof.

[0069] Specific examples of nonionic polymers include cellulose ethers (hydroxybutyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose stearoxy ether, etc.), propylene glycol alginate, poly(ethylene oxide), polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl guar gum, locust bean gum, amylose, hydroxyethyl amylose, starch, starch derivatives, and mixtures thereof.

[0070] Specific examples of amphoteric or dipolar polymers include octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer, polyquaternium-47, polyquaternium-43, and the like.

[0071] 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, of ensuring excellent application properties to the skin by well dispersing or dissolving each component, and of ensuring long-term storage stability of the composition, component (D) is preferably one or more selected from anionic polymers and nonionic polymers, and is 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, and more preferably one or more selected from (ammonium acryloyldimethyltaurate / beheneth-25 methacrylate) crosspolymers, hydroxypropyl methylcellulose stearoxy ether, and (acrylates / alkyl acrylate (C10-C30)) crosspolymers. Commercially available products of component (D) include, for example, "CARBOPOL 980," "CARBOPOL 981," "CARBOPOL 1342," "CARBOPOL ETD2020," "PEMULEN TR-1," and "PEMULEN TR-2" from Lubrizol Advanced Materials, "Aculyn 22" from The Dow Chemical Company, "Aristoflex AVC," "Aristoflex HMB," and "Aristoflex Velvet" from Clariant Iberica Production S.A., and "Sangelose 60L" from Daido Chemical Industry Co., Ltd. The thickener can also be blended as a dispersion in which it is dispersed in a dispersion medium.

[0072] From the viewpoint of obtaining the above-mentioned effects, the content of component (D) in the composition of the present invention is 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and from the same viewpoint, preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1.5% by mass or less. The content of component (D) in the composition of the present invention is 0.05 to 3% by mass, preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass. When the composition of the present invention contains a thickener having surfactant properties, the content of other surfactants is preferably 1.5% by mass or less, more preferably 1% by mass or less.

[0073] <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 forming 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 providing a pleasant feel when applied to the skin. Furthermore, from the viewpoint of improving the sustained repellent effect and providing a pleasant feel when applied to the skin, the content 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.

[0074] (Surfactant) The composition of the present invention may further contain a surfactant from the viewpoint of forming an oil-in-water composition. Known surfactants can be used as the surfactant, and any of anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. can be used. These surfactants may be used alone or in combination of two or more. When the composition of the present invention contains a surfactant, the content of the surfactant in the composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of forming an oil-in-water composition; and from the same viewpoint, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0075] <Other Components> The composition of the present invention may also contain other components besides those described 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, whitening agents, disinfectants, etc., to the extent that the effects of the invention are not impaired. Each of these components can also be used for other purposes, and for example, a fragrance can be used as a disinfectant.

[0076] 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.

[0077] The composition of the present invention preferably contains component (A) as a pest repellent active ingredient and does not contain any other pest repellents in effective amounts, from the viewpoint of preventing allergies and rough skin in users. The composition of the present invention has a sustained repellent effect even without containing an effective amount of an existing pest repellent, which will be 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, the retention-inhibiting effect of the present invention is exhibited as long as the retention-inhibiting effect of preventing pests from remaining in place even after landing is exhibited. In other words, the composition of the present invention does not need to substantially contain any pest repellents other than component (A).

[0078] 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, even more preferably 4% by mass or less, even 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, for example, by referring to the minimum effective amount published by the manufacturer of each repellent product. More specifically, the effective amount of DEET: N,N-diethyltoluamide, an existing pest repellent described below, 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.

[0079] 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) were placed in a mesh-enclosed plastic cage (30 x 30 x 30 cm: BugDorm-1 cage). A rectangular slit measuring 10 cm long and 3 cm wide was made in a pair of Qualatech Super Long Gloves (50 cm) (AS ONE Corporation, Catalog Number: 3-6432-02), and the arm was inserted into the glove. To activate the mosquitoes, the cage was ventilated for 5 seconds. With nothing applied to the exposed area through the slit, the arm was inserted into the cage under conditions of 27°C and 60% relative humidity (RH). After the mosquitoes landed on two exposed areas of the skin within 2 minutes, it was confirmed that they remained there for at least 1 second. If the mosquitoes did not remain there for at least 1 second, a new mosquito was prepared. Hereinafter, a stay of at least 1 second will be referred to simply as "stay." The test of the evaluation sample, which is a solution of the pest repellent, was carried out by applying the evaluation sample to the exposed skin (10 cm x 3 cm) at a concentration of 3.3 mg / cm ２The concentration is adjusted with ethanol so that it can be applied easily. Using a pipette, the adjusted concentration solution is applied to the exposed area and spread over the entire exposed skin. The test is then allowed to stand for 3 minutes before the test begins. The test is conducted by inserting the arm to which the evaluation sample has been applied into the cage for 2 minutes and counting the number of stops. The test is terminated when a total of two stops have been made, and the arm is inserted for 2 minutes every 30 minutes until the end of the test. If a second stop occurs at 30 minutes, the duration of the repellent effect is determined to be 0 minutes, and if a second stop occurs at 60 minutes, the duration of the repellent effect is determined to be 30 minutes. The test is conducted on three subjects, and the average duration of the repellent effect is calculated. In this test, the concentration of the pest repellent that shows an average duration of repellent effect of 2 hours or more can be considered the effective concentration (effective amount) of the pest repellent. Furthermore, from the viewpoint of safety and the fact that the composition of the present invention has a sustained repellent effect even without containing an effective amount of an existing pest repellent, it is preferable that it contains substantially no 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.

[0080] 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 that have a pest repellent effect and are obtained by extracting, distilling, or compressing components contained in plants.

[0081] From the viewpoint of environmental compatibility, it is preferable that the composition of the present invention substantially does not 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 such organic particles in the composition of the present invention is less than 1.0% by mass, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0% by mass.

[0082] Although there is no particular limitation on the pests that the composition of the present invention repels, it is more effective against flying pests. "Flying pests" refers to pests that fly towards animals such as humans and suck blood from their skin, pests that fly without sucking blood but transmit pathogenic bacteria, and pests that cause discomfort to humans by flying. Specific examples of flying pests include mosquitoes such as Culex pipiens pallens, Culex tritaeniorhynchus, Culex molestus, and Culex quinquefasciatus, mosquitoes such as Aedes aegypti, Aedes albopictus, Anopheles sinensis, Aedes togoi, Anopheles gambiae, and Anopheles stephensis; chironomids such as Chironomid midges and Chironomid midges; black flies such as Simulium nigricans, Simulium japonica, Simulium japonica, and Simulium japonica; house flies, houseflies, and houseflies. Examples of repellent flies include flies such as house flies, little house flies, blow flies, flesh flies, seed flies, onion flies, fruit flies, Drosophila melanogaster, moth flies, chechi flies, and stable flies; horse flies such as black flies, horse flies, deer flies, and spotted flies; midges such as Culicoides tokunaga, Culicoides oshimaensis, and chicken midges; and wasps such as yellow hornets, Polistes chinensis, and honeybees.The composition of the present invention is particularly effective in long-lasting repellent effects against mosquitoes.Among the mosquitoes mentioned above, the composition is excellent in long-lasting repellent effects against Culex pipiens pallens, Culex tritaeniorhynchus, Culex molestus, Culex quinquefasciatus, Aedes aegypti, and Aedes albopictus.

[0083] [Method for producing pest repellent composition] The composition of the present invention can be obtained by mixing components (A) to (E). The order of mixing components (A) to (E) is not particularly limited as long as an oil-in-water mixture is obtained. However, for example, from the viewpoint of adsorbing at least a portion of component (C) to the surface of component (B), it is preferable to have a step of mixing a mixture containing components (B), (C), and (E) (hereinafter referred to as "mixture (1)") with a mixture containing components (A) and (D) (hereinafter referred to as "mixture (2)"). Mixture (1) can be obtained by mixing components (B), (C), and (E). The order of mixing components (B), (C), and (E) is not particularly limited. However, it is preferable to mix components (B) and (E) first, and then mix components (B) and (E) with component (C). From the viewpoint of uniformly adsorbing component (C) on the surface of component (B), it is more preferable to mix components (B) and (E) and then mix them with component (C) dissolved in a solvent. A mixed solvent of water and an organic solvent can be used as the solvent. The organic solvent is not particularly limited, but examples include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol. Among these alcohols, at least one selected from ethanol and 2-propanol is more preferred, with ethanol being even more preferred. From the viewpoint of uniformly mixing 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 preferably 99% V / V or less, more preferably 98% V / V or less.

[0084] 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 for components (B), (C), and (E) is preferably 20 minutes or longer, more preferably 30 minutes or longer, from the viewpoint of sufficiently adsorbing component (C) into component (B), and is preferably 3 hours or shorter, more preferably 2 hours or shorter, from the viewpoint of production efficiency.

[0085] Mixture (2) can be obtained by mixing component (A) and component (D). From the viewpoint of uniformly mixing components (A) and (D), the temperature when mixing components (A) and (D) is preferably 5° C. or higher, more preferably 10° C. or higher, and preferably 70° C. or lower, more preferably 50° C. or lower. From the viewpoint of uniformly mixing components (A) and (D), the mixing time of components (A) and (D) is preferably 20 minutes or longer, more preferably 30 minutes or longer, and preferably 3 hours or shorter, more preferably 2 hours or shorter.

[0086] 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. The mixing time for mixing mixture (1) and mixture (2) is preferably 1 minute or higher, more preferably 2 minutes or higher, from the viewpoint of uniformly dispersing the oil phase in the aqueous phase, and is preferably 15 minutes or lower, more preferably 10 minutes or lower.

[0087] 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, from the viewpoint of uniformly dispersing the oil phase in the aqueous phase, and is preferably 20,000 rpm or less, more preferably 15,000 rpm or less.

[0088] A known stirring device can be used in the step of mixing component (B), component (C), and component (E), the step of mixing component (A) and component (D), and the step of mixing mixture (1) and mixture (2).

[0089] [Method for 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 of the present invention is to attach the pest repellent composition of the present invention to the legs of pests, particularly flying pests, thereby preventing the pests from remaining on human skin. Hereinafter, these methods are collectively referred to as the "method of the present invention."

[0090] Here, "applying to the skin surface" includes not only applying the composition directly to the skin surface with the hands, etc., but also attaching the composition to the skin surface by spraying, etc. The amount of the composition to be applied to the skin surface is set to 1 cm from the viewpoint of improving the sustained repellent effect. ２ The upper limit of the amount of application 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 cm from the viewpoints of suppressing stickiness and economic efficiency. ２ It is preferably 10 mg or less, more preferably 8 mg or less, and even more preferably 5 mg or less per unit area.

[0091] In addition to the above-described embodiments, the present invention further discloses the following embodiments: <1> An oil-in-water pest repellent 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 to 40 μm: 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 with a Brookfield 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 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> The oil-in-water pest repellent composition according to any one of <1> to <3>, wherein the mass ratio of component (C) to 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 component (B) has a volume median particle size of 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% by mass or more, preferably 2% by mass or more, more preferably 4% by mass or more, and is 27% by mass or less, preferably 16% by mass or less, more preferably 8% by 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% by mass or more, preferably 0.3% by mass or more, more preferably 0.4% by mass or more, and 2.3% by mass or less, preferably 1.6% by mass or less, and more preferably 1.0% by mass or less. <8> The oil-in-water pest repellent composition according to any one of <1> to <7>, wherein the mass ratio of component (C) to 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 preferably 0.7 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.

[0092] <9> A method for producing an oil-in-water pest repellent composition, the method comprising the step of mixing a mixture containing the following component (B), the following component (C), and the following component (E) with a mixture containing the following component (A) and the following component (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 materials 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 pest repellent composition, the content of component (A) is 13% by mass or more and 50% by mass or less, the content of component (B) is 0.5% by mass or more and 35% by mass or less, the content of component (C) is 0.1% by mass or more and 3% by mass or less, the content of component (D) is 0.05% by mass or more and 3% by mass or less, and the content of component (E) is 30% by mass or more and 86.35% by mass or less. <10> A method for producing an oil-in-water pest repellent composition according to <9>, wherein component (A) is one or more oils selected from silicone oils, ester oils, and hydrocarbon oils. <11> A 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> A method for producing an oil-in-water pest repellent composition according to any one of <9> to <11>, wherein the mass ratio of component (C) to component (A) [(C) / (A)] is 0.005 or more and 0.1 or less. <13> A method for producing an oil-in-water pest repellent composition according to any one of <9> to <12>, wherein component (B) has a volume median particle size of 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> A 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% by mass or more, preferably 2% by mass or more, more preferably 4% by mass or more, and 27% by mass or less, preferably 16% by mass or less, more preferably 8% by mass or less. <15> A method for producing an oil-in-water pest repellent composition according to any one of <9> to <14>, 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 2.3% by mass or less, preferably 1.6% by mass or less, more preferably 1.0% by 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 component (C) to 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.

[0093] <17> A method for repelling pests, comprising applying to the surface of human skin an oil-in-water pest repellent 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 to 40 μm: 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 with a Brookfield 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 pest repellent method according to <17>, wherein component (A) is one or more selected from silicone oil, ester oil, and hydrocarbon oil. <19> The pest repellent method according to <17> or <18>, wherein the mass ratio of component (B) to component (A) [(B) / (A)] is 0.02 or more and 0.7 or less. <20> The pest repellent method according to any of <17> to <19>, wherein the mass ratio of component (C) to component (A) [(C) / (A)] is 0.005 or more and 0.1 or less. <21> The pest repellent method according to any of <17> to <20>, wherein component (B) has a volume median particle size of 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 pest repellent method according to any one of <17> to <21>, wherein the content of component (B) is 1% by mass or more, preferably 2% by mass or more, more preferably 4% by mass or more, and is 27% by mass or less, preferably 16% by mass or less, more preferably 8% by mass or less.<23> The pest repellent method 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 2.3% by mass or less, preferably 1.6% by mass or less, and more preferably 1.0% by mass or less. <24> The pest repellent method according to any one of <17> to <23>, wherein the mass ratio of component (C) to 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 preferably 0.7 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.

[0094] <25> A method for repelling pests, which comprises applying an oil-in-water pest repellent composition containing the following components (A) to (E) to the legs of pests, thereby preventing the pests from lodging 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 to 40 μm: 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 with a Brookfield 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 pest repellent method according to <25>, wherein component (A) is one or more selected from silicone oil, ester oil, and hydrocarbon oil. <27> The pest repellent method according to <25> or <26>, wherein the mass ratio of component (B) to component (A) [(B) / (A)] is 0.02 or more and 0.7 or less. <28> The pest repellent method according to any of <25> to <27>, wherein the mass ratio of component (C) to component (A) [(C) / (A)] is 0.005 or more and 0.1 or less. <29> The pest repellent method according to any of <25> to <28>, wherein component (B) has a volume median particle size of 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 pest repellent method according to any one of <25> to <29>, wherein the content of component (B) is 1% by mass or more, preferably 2% by mass or more, more preferably 4% by mass or more, and is 27% by mass or less, preferably 16% by mass or less, more preferably 8% by mass or less.<31> The pest repellent method 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 2.3% by mass or less, preferably 1.6% by mass or less, and more preferably 1.0% by mass or less. <32> The pest repellent method according to any one of <25> to <31>, wherein the mass ratio of component (C) to 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 preferably 0.7 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.

[0095] 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 carried out by the following methods.

[0096] (Surface tension of liquid oily component) The surface tension of the liquid oily component is measured in an environment of 25°C using an automatic surface tensiometer "Tensiometer K100" (KRUSS) by the Wilhelmy method using a platinum plate.

[0097] (Viscosity of Liquid Oily Components) A Toki Sangyo Co., Ltd. "Viscometer TVB-10" was used as a B-type rotational viscometer in accordance with JIS K7117-1:1999. Because the viscosity values ​​of the components to be measured vary greatly for each sample, it is difficult to accurately measure all of them under a single 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 viscosity values. On the other hand, components with a viscosity of 20 mPa·s or less were measured again using an L adapter, a low-viscosity rotor, at a rotation speed of 30 rpm in a 23°C environment to obtain viscosity values.

[0098] (Wet Tension of Particle Surface) Measurement was performed as follows using a mixture for wetting tension testing manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 0.2 mL of mixture for wetting tension testing No. 70 (surface tension 70 mN / m) was weighed into a container in a 23°C environment. Then, 0.01 g of particles to be measured was gently added to the mixture. 30 seconds after the particles were added, it was visually confirmed whether the particles were wetted by the mixture. If the particles were wetted by the mixture No. 70 (surface tension 70 mN / m), the wetting tension of the particle surface was determined to be 70 mN / m or more. If the particles were wetted by the mixture No. 70 (surface tension 70 mN / m) described below, the wetting tension of the particle surface was determined to be 70 mN / m or more, and the particles were determined to be hydrophilic. "Wetting the particle surface with the mixture" means that the mixture penetrates into the particles. The state in which particles are not wetted by the mixed liquid means that even when the particles and the mixed liquid are mixed, the particles separate from (or are repelled by) the mixed liquid. The wetting tension of each particle surface was measured by conducting the above-mentioned test using the mixed liquid for wetting tension test described below. For example, a surface tension of 23 mN / m on the particle surface means that in the above-mentioned test, when No. 25.4 (surface tension 25.4 mN / m) was used as the mixed liquid for wetting tension test, the particle surface did not wet with the mixed liquid, and when No. 22.6 (surface tension 22.6 mN / m) was used as the mixed liquid for wetting tension test, the particle surface wet with the mixed liquid. <Wetting tension test mixed liquids from Fujifilm Wako Pure Chemical Corporation> No. 73 (surface tension 73 mN / m), No. 70 (surface tension 70 mN / m), No. 67 (surface tension 67 mN / m), No. 74 (surface tension 74 mN / m), No. 76 (surface tension 76 mN / m), No. 78 (surface tension 78 mN / m), No. 79 (surface tension 79 mN / m), No. 80 (surface tension 80 mN / m), No. 81 (surface tension 81 mN / m), No. 82 (surface tension 82 mN / m), No. 83 (surface tension 83 mN / m), No. 84 (surface tension 84 mN / m), No. 85 (surface tension 85 mN / m), No. 86 (surface tension 86 mN / m), No. 87 (surface tension 87 mN / m), No. 88 (surface tension 88 mN / m), No. 89 (surface tension 89 mN / m), No. 90 (surface tension 90 mN / m), 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)

[0099] (Volume Median Particle Diameter (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 diameter distribution of each hydrophilic inorganic particle was measured at a concentration that brought the absorbance into an appropriate range. The volume median particle diameter (D50) of the hydrophilic inorganic particles was calculated from the particle diameter distribution obtained.

[0100] (Evaluation of sustained repellent effect against pests) (I) Preparation of Aedes albopictus Aedes albopictus eggs purchased from Sumitomo Technoservice Co., Ltd. were reared in a cage under conditions of 27 ° C. and 60% relative humidity (RH) and grown to adulthood. Approximately 1 cm of water was poured into a transparent plastic pan, and the filter paper on which the purchased eggs had been laid was placed inside, allowing the eggs to hatch into pupae. 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 then transferred to a cage 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, adult flies were collected using an insect aspirator, anesthetized on ice for 5 minutes, and then visually separated into males and females. Only the females were collected and used for evaluation.

[0101] (II) Measurement of Repellent Effect Duration One hundred mated female mosquitoes (Aedes albopictus) were placed in a mesh-enclosed plastic cage (30 x 30 x 30 cm: BugDorm-1 cage). A rectangular slit measuring 10 cm long x 3 cm wide was made in a Qualatech Super Long Glove (50 cm) (AS ONE Corporation, Catalog number: 3-6432-02), and the arm was inserted into the glove. To activate the mosquitoes, the breath was blown into the cage for 5 seconds. The arm was inserted into the cage under conditions of 27°C and 60% relative humidity (RH) without any coating on the exposed area through the slit. Within 2 minutes, the mosquitoes landed on two exposed areas of the skin, and it was confirmed that they remained there for at least 1 second. If the mosquito did not remain there for at least 1 second, a new mosquito was prepared. Hereinafter, a stay of at least 1 second will be simply referred to as a stay. The test of the evaluation sample, which is a solution of the pest repellent, was carried out by applying the evaluation sample to the exposed skin (10 cm x 3 cm) at a concentration of 3.3 mg / cm ２ The test was conducted by inserting the arm coated with the evaluation sample into a cage for 2 minutes and counting the number of times the subject stayed in the cage. The test was terminated when the subject stayed in the cage a total of two times, and the subject continued to insert the arm for 2 minutes every 30 minutes until the end of the test. If the subject stayed in the cage 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 cage 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.

[0102] (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 a relative humidity (RH) of 57%. A sensory evaluation was conducted on a 5-point scale based on the following criteria for the smooth feeling from when the composition was dried 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, good smooth feeling. 4: Slight stickiness, but smooth feeling. 3: Some stickiness, but the smooth feeling is stronger. 2: Stickiness, but the smooth feeling is weak. 1: Stickiness, no smooth feeling.

[0103] (Evaluation of long-term storage stability) 80 mL of the composition of each example 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 rated according to the following criteria: A: No change. B: No composition remains on the surface of the glass bottle that came into contact with the oil. C: The oil phases coalesced, and some oozing of the emulsion onto the surface was observed. D: Separation of the oil phase was observed.

[0104] (Preparation and Evaluation of Composition) No. 1: Components (B1) and (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, followed by stirring for 1 hour to prepare an aqueous phase. Components (A1), (D1), and (D2) were added to another glass beaker, and the stirring unit of a T.K. Robomix (Tokushu Kika Kogyo Co., Ltd.) was replaced with a 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 while pre-emulsifying with a propeller, and then the stirring unit of a T.K. Robomix (Tokushu Kika Kogyo Co., Ltd.) was replaced with a T.K. Homo Mixer MARKII 2.5 type to obtain an oil-in-water composition. The resulting composition was subjected to various evaluations using the methods described above. The results are shown in the table. The production and evaluation of the compositions were carried out at room temperature (25 to 28°C).

[0105] Compositions No. 2 to 55, No. (1) to (14) Compositions No. 2 to 55 and No. (1) to (14) were produced in the same manner as composition No. 1, except that the formulation was changed as shown in the table. Using the obtained compositions, various evaluations were carried out using the methods described above. The results are shown in the table. The production and evaluation of the compositions were carried out at room temperature (25 to 28°C).

[0106] 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%.

[0107] No. (15) Ethanol (95% v / v) was added to a glass beaker containing component (E) while stirring with a stirrer to prepare an aqueous phase. Components (A1), (b1), (D1), and (D2) were added to the glass beaker and mixed using a T.K. Robomix (Tokushu Kika Kogyo Co., Ltd.) with the stirring unit replaced with a T.K. Homo Disper 2.5 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 at 8,000 rpm for 3 minutes using a T.K. Robomix (Tokushu Kika Kogyo Co., Ltd.) with the stirring unit replaced with a T.K. Homo Mixer MARK II 2.5 to obtain an oil-in-water composition. The resulting composition was subjected to various evaluations using the methods described above. The results are shown in the table. The production and evaluation of the composition were carried out at room temperature (25-28°C).

[0108] Compositions No. 1 to 55 in the table are compositions of the present invention, while 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 a liquid oily component outside the scope of component (A), particles outside the scope of component (B), and modified silicone outside the scope of component (C), respectively. For convenience, the physical properties and content in the composition of components (a) to (c) are listed in the table in correspondence with components (A) to (C). The components used in Tables 2 to 8 are listed in Table 1. The blending amounts listed in each table are the amount of active ingredient (mass %) of each component. Regarding the content listed in the row for component (C3) of composition No. 27, the content of PEG / PPG-19 / 19 dimethicone in the composition (the content of component (C)) is indicated in parentheses. Similarly, for Nos. 37, 38, 42, 44, and (7) to (9), the content of component (C) or a component outside the scope of component (C) in the composition is indicated in parentheses. "O / W" means an oil-in-water composition, and "W / O" means a water-in-oil composition.

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] Tables 2 to 8 show that the compositions of the present invention, each containing a predetermined amount of components (A) to (E), have a smooth, 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, such as 2 hours or more. Furthermore, when comparing compositions Nos. 1 to 14 and 21 to 44 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) specified in the present invention instead of the hydrophobic organic particles (polymethyl methacrylate) used in composition No. (15).

[0118] According to the present invention, it is possible to provide an oil-in-water pest repellent composition that feels good when applied to the skin and has excellent long-term storage stability, and a method for repelling pests.

Claims

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 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).

2. The oil-in-water pest repellent composition according to claim 1, wherein component (A) is one or more oils selected from the group consisting of silicone oils, ester oils, and hydrocarbon oils.

3. An 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.

4. An oil-in-water pest repellent composition according to any one of claims 1 to 3, wherein the mass ratio of component (C) to component (A) [(C) / (A)] is 0.005 or more and 0.1 or less.

5. An oil-in-water pest repellent composition according to any one of claims 1 to 4, wherein the mass ratio of component (C) to component (B) [(C) / (B)] is 0.01 or more and 0.3 or less.

6. 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 materials 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.

7. A method for repelling pests, which comprises 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 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).

8. 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 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).

Images