JP2020200317A - Method for suppressing attachment of air pollutants - Google Patents

Abstract

To provide a method for suppressing the attachment of air pollutants, having a good feeling of use when applying an external preparation to skin, and capable of effectively suppressing the attachment of air pollutants to skin.SOLUTION: The present invention provides a method for suppressing the attachment of air pollutants, by applying an external preparation to skin to suppress the attachment of air pollutants to the skin. The external preparation contains the following component (A) and component (B), and in the external preparation, a mass ratio between the component (B) content to the component (A) content [(B)/(A)] is 3.5 or less. The component (A): a hydrophobic metal oxide having an average primary particle diameter dA of 800 nm or less. The component (B): nonvolatile hydrocarbon oil.SELECTED DRAWING: None

Description

The present invention relates to a method for suppressing adhesion of atmospheric harmful substances.

In recent years, pollen such as sugi and hinoki, air pollutants such as soot and dust, and harmful substances floating in the air such as yellow sand (hereinafter, also referred to as "air harmful substances") cause various health hazards to the human body. It is a problem. Among atmospheric harmful substances, PM2.5, which is a particulate matter with a diameter of 2.5 μm or less, is composed of carbon components, sulfates, nitrates, ammonium salts, etc., and PM2.5 and yellow sand are inhaled. It is known to cause diseases of the circulatory system and respiratory system. Further, it has been pointed out that PM2.5, yellow sand, and pollen cause skin troubles by adhering to or penetrating into the skin. For example, Non-Patent Document 1 has an academic report on PM2.5 damaging the skin. Therefore, there is a growing demand for cosmetics that protect the skin from harmful air substances.
For example, Patent Document 1 describes skin care cosmetics containing a specific amount of magnesium aluminometasilicate and a specific amount of an ultraviolet protective agent as skin care cosmetics that protect the skin from external stimuli such as air pollutants. Have been described.

International Publication 2014/136993

Shiraiwa et al., Nature Chemistry 3,291-295 (2011)

In the technique of Patent Document 1, magnesium aluminometasilicate adsorbs air pollutants by its adsorptive ability and does not reach the skin, and even if an acidic substance adheres, it can be neutralized by the pH buffering ability. It is described to reduce skin damage caused by external stimuli. It is also described that UV protection agents effectively protect the skin from UV rays. Although such techniques can reduce the effects of air pollutants on the skin, they do not prevent air pollutants from adhering to the skin and there is room for improvement. In addition, when the inorganic powder is blended with the external preparation, the feeling of squeaking or the like may be deteriorated when the external preparation is applied to the skin. Therefore, a good usability at the time of application is also required.
The present invention provides a method for suppressing the adhesion of an air toxic substance, which has a good feeling of use when the external preparation is applied to the skin and can effectively suppress the adhesion of the air toxic substance to the skin. That is the issue.

The present inventors do not adsorb air pollutants as shown in Patent Document 1, but hydrophobicized metal oxides having an average primary particle size in a specific range and non-volatile hydrocarbon oils. By applying an external preparation containing a specific mass ratio to the skin, nano-sized irregularities can be formed on the skin surface without deteriorating the feel at the time of application, and the adhesion of air harmful substances to the skin can be suppressed. We found that the above problems could be solved.
That is, the present invention is a method for suppressing the adhesion of an air toxic substance by applying an external preparation to the skin to suppress the adhesion of the air toxic substance to the skin.
The external preparation contains the following component (A) and component (B), and the mass ratio of the content of the component (B) to the content of the component (A) in the external preparation [(B) / (A) ] Is 3.5 or less, to provide a method for suppressing adhesion of air harmful substances.
Component (A): Hydrophobicized metal oxide having an average primary particle diameter d _A of 800 nm or less Component (B): Non-volatile hydrocarbon oil

According to the method of the present invention, when an external preparation is applied to the skin, it has a good feeling of use and can effectively suppress the adhesion of air harmful substances to the skin.

It is the schematic which shows the evaluation method of the adhesion suppression effect of an air toxic substance.

[Method of suppressing adhesion of atmospheric harmful substances]
The method for suppressing the adhesion of air harmful substances of the present invention is a method for suppressing the adhesion of air harmful substances to the skin by applying an external agent to the skin, and the external agent is as follows. The mass ratio [(B) / (A)] of the content of the component (B) to the content of the component (A) in the external preparation containing the component (A) and the component (B) is 3.5 or less. Is.
Component (A): Hydrophobized metal oxide having an average primary particle diameter d _A of 800 nm or less Component (B): Non-volatile hydrocarbon oil In the present invention, "air toxic substances" are cedar, hinoki, etc. Pollen; soot and dust such as sulfur oxides, soot and nitrogen oxides, automobile emissions, harmful air pollutants such as benzene, trichloroethylene and tetrachloroethylene, and air pollutants such as particles containing volatile organic compounds (VOC) ; Means harmful substances (including PM2.5) floating in the atmosphere such as yellow sand.
Further, in the present invention, the "hydrophobicized metal oxide" refers to a metal oxide whose surface is hydrophobized.
In the following description, the adhesion suppressing effect on atmospheric harmful substances in the present invention is simply referred to as "adhesion suppressing effect".

The adhesion suppressing method of the present invention has a good feeling of use when the external preparation is applied to the skin, and has a high effect of suppressing adhesion to air harmful substances, particularly fine particle air harmful substances. The reason is not clear, but it can be considered as follows.
In the present invention, nano-sized irregularities are formed on the skin surface by applying a metal oxide having an average primary particle size in a specific range and the surface thereof being hydrophobized. It is considered that the contact area when the air harmful substance comes into contact with the metal oxide can be reduced, and the adhesion of the air harmful substance can be effectively suppressed.
Further, since the external preparation used in the present invention contains a hydrophobized metal oxide and a non-volatile hydrocarbon oil as an oil agent in a specific mass ratio, it inhibits the above-mentioned effect of suppressing adhesion of atmospheric harmful substances. It is considered that a good usability is exhibited due to the lubricating effect of the hydrocarbon oil. Further, the hydrophobized metal oxide spreads smoothly on the skin surface together with the hydrocarbon oil, and is considered to contribute to a good usability.

<External agent>
The external preparation used in the present invention contains the above-mentioned components (A) and (B) from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin.

[Component (A): Hydrophobized metal oxide]
The component (A) is a hydrophobized metal oxide having an average primary particle diameter d _A of 800 nm or less (hereinafter, also referred to as “hydrophobicized metal oxide”).
The average primary particle diameter d _A of the component (A) is 800 nm or less, preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, still more preferably 80 nm or less, from the viewpoint of improving the adhesion suppressing effect. , More preferably 50 nm or less, and from the viewpoint of versatility, preferably 5 nm or more, more preferably 10 nm or more. More specifically, the average primary particle diameter d _A is preferably 5 to 800 nm, more preferably 5 to 500 nm, still more preferably 5 to 300 nm, from the viewpoint of improving the adhesion suppressing effect and versatility. It is even more preferably 5 to 200 nm, even more preferably 5 to 80 nm, even more preferably 5 to 50 nm, and even more preferably 10 to 50 nm.
The average primary particle diameter d _A in the present invention can be obtained from an observation image by a transmission electron microscope (TEM). Specifically, it is obtained by observing with a TEM under the condition of an observation magnification of 50,000 times, measuring the maximum minor axis of 300 primary particles in the observed image, and calculating the number average value thereof. Here, the maximum minor diameter means the minor diameter having the maximum length among the minor diameters orthogonal to the major diameter when the component (A) has a shape other than the plate shape. When the component (A) is plate-shaped, it is obtained by measuring the thickness of 300 primary particles in the observation image observed under the same conditions as above and calculating the average value thereof. Be done. Specifically, it is measured by the method described in Examples.

The metal oxide of the component (A) is not particularly limited as long as it is usually used for external preparations such as cosmetics. Specific examples thereof include titanium oxide, zinc oxide, cerium oxide, aluminum oxide (alumina), magnesium oxide, calcium oxide, zirconium oxide, iron oxide and chromium oxide. Among these, from the viewpoint of imparting ultraviolet protection ability, it is preferably one or more selected from titanium oxide, zinc oxide and cerium oxide, and more preferably one or more selected from titanium oxide and zinc oxide.
When the metal oxide of the component (A) is titanium oxide, the crystal structure of titanium oxide may be any of anatase type, rutile type and brookite type, but from the viewpoint of versatility, it is preferably rutile type or anatase type. is there.

Examples of the shape of the component (A) include a spherical shape, a spindle shape, a plate shape, and a needle shape. Among these, spherical, spindle-shaped, and plate-shaped are preferable from the viewpoint of improving the adhesion suppressing effect.
When the metal oxide of the component (A) is titanium oxide, it is preferably spindle-shaped from the viewpoint of improving the adhesion suppressing effect.
When the metal oxide of the component (A) is zinc oxide, it is preferably spherical or plate-shaped from the viewpoint of improving the adhesion suppressing effect.
The existing form of the component (A) may be a form of primary particles as long as the average primary particle diameter d _A satisfies the above range, and a form including aggregates (secondary particles) in which primary particles are aggregated. It may be.

By containing the hydrophobized component (A), the external preparation used in the present invention improves the dispersibility of the component (A) in the external preparation containing the component (B) and improves the adhesion suppressing effect. be able to.
The hydrophobization treatment includes fatty acid treatment; alkylalkoxysilane treatment; silicone treatment; fluorine-containing compound treatment such as perfluoroalkyl phosphate, perfluoroalcohol, and perfluoroalkylalkoxysilane; amino acid treatment such as N-acylglutamic acid; alkyl. Examples thereof include phosphoric acid ester treatment.
Among these, fatty acid treatment, alkylalkoxysilane treatment, and silicone treatment are preferable from the viewpoint of enhancing the dispersibility of the component (A) in the external preparation containing the component (B) and improving the adhesion suppressing effect.
That is, the component (A) is preferably the following component (A1) and component (A2) from the viewpoint of enhancing the dispersibility of the component (A) in the external preparation containing the component (B) and improving the adhesion suppressing effect. And one or more selected from the component (A3).
Component (A1): an average primary particle diameter d _A is 800nm or less fatty acid treated metal oxide component (A2): an alkyl alkoxy silane treated metal oxide component having an average primary particle diameter d _A is 800nm or less ( A3): Silicone-treated metal oxide having an average primary particle diameter d _A of 800 nm or less

Examples of the surface treatment agent used for the fatty acid treatment of the component (A1) include straight-chain or branched-chain fatty acids having 12 to 22 carbon atoms. Among them, straight-chain or branched-chain higher fatty acids having 14 to 22 carbon atoms are preferable, from the viewpoint of enhancing the dispersibility of the component (A) in the external preparation containing the component (B) and improving the adhesion suppressing effect. A linear or branched higher fatty acid having a number of 16 or more and 20 or less is more preferable, and stearic acid and isostearic acid are further preferable.
The surface treatment agent used for the alkylalkoxysilane treatment of the component (A2) has 6 carbon atoms from the viewpoint of enhancing the dispersibility of the component (A) in the external preparation containing the component (B) and improving the adhesion suppressing effect. Those having a linear or branched alkyl group of 20 or more are preferable, and octyltriethoxysilane and octyltrimethoxysilane are more preferable.

Examples of the surface treatment agent used for the silicone treatment of the component (A3) include methylpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, dodecamethylcyclohexanesiloxane, and tetradecamethylhexane. Siloxane, dimethylsiloxane / methyl (polyoxyethylene) siloxane / methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxypropylene) siloxane copolymer Examples thereof include various silicone oils such as coalescing, dimethylsiloxane / methylcetyloxysiloxane copolymer, dimethylsiloxane / methylstealoxysiloxane copolymer, and alkylacrylate / dimethicone copolymer. Among these, methylhydrogenpolysiloxane and dimethylpolysiloxane are preferable from the viewpoint of enhancing the dispersibility of the component (A) in the external preparation containing the component (B) and improving the adhesion suppressing effect.

The above-mentioned surface treatment agents may be used alone or in combination of two or more.
The treatment amount of the hydrophobizing treatment is preferably 0.1 with respect to the component (A) from the viewpoint of increasing the dispersibility of the component (A) in the external preparation containing the component (B) and improving the adhesion suppressing effect. It is 5% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less.
In the present invention, the mass, coating amount, and average primary particle diameter d _A of the component (A) mean the mass including the surface treatment agent, coating amount, and average primary particle diameter d _A.

When the component (A) is hydrophobized titanium oxide, the content of TiO _{2 in} the hydrophobized titanium oxide is preferably 60% by mass or more, more preferably from the viewpoint of improving the adhesion suppressing effect. Is 70% by mass or more, and preferably less than 100% by mass.
When the component (A) is the hydrophobized zinc oxide, the content of ZnO in the hydrophobized zinc oxide is preferably 60% by mass or more, more preferably 60% by mass or more from the viewpoint of improving the adhesion suppressing effect. It is 70% by mass or more, and preferably less than 100% by mass.

From the viewpoint of enhancing the dispersibility of the component (A) in the external preparation containing the component (B) and improving the adhesion suppressing effect, the component (A) is preferably treated as the component (A1) with titanium oxide and fatty acid treatment. Zinc oxide, one or more selected from alkylalkoxysilane-treated titanium oxide and alkylalkoxysilane-treated zinc oxide as the component (A2), and silicone-treated titanium oxide and silicone-treated zinc oxide as the component (A3), more preferably. The component (A1) is one or more selected from fatty acid-treated titanium oxide and fatty acid-treated zinc oxide, and the component (A2) is selected from alkylalkoxysilane-treated titanium oxide and alkylalkoxysilane-treated zinc oxide, and more preferably the component (A2). ) Is one or more selected from alkyl alkoxysilane treated titanium oxide and alkyl alkoxysilane treated zinc oxide.

As a commercial product of the component (A1), "STR-100C-LF" (stearic acid-treated titanium oxide) manufactured by Sakai Chemical Industry Co., Ltd .; "MPT-171" (stearic acid-treated titanium oxide) manufactured by Ishihara Sangyo Co., Ltd. Titanium); Examples thereof include "MT-100TV" (stearic acid-treated titanium oxide) and "MT-100Z" (stearic acid-treated titanium oxide) manufactured by TAYCA CORPORATION.
Commercially available products of component (A2) include "STR-100C-OTS" (octyltriethoxysilane treated titanium oxide) and "STR-100W-OTS" (octyltriethoxysilane treated titanium oxide) manufactured by Sakai Chemical Industry Co., Ltd. ), "FINEX-50-OTS" (octyltriethoxysilane treated zinc oxide), "FINEX-30-OTS" (octyltriethoxysilane treated zinc oxide) and the like.
Commercially available products of the component (A3) include "STR-100A-LP" (silicone-treated titanium oxide) and "FINEX-50-LPTM" (silicone-treated zinc oxide) manufactured by Sakai Chemical Industry Co., Ltd .; Teika Co., Ltd. "JR-800S" (silicone treated titanium oxide), "MPY-70M" (silicone treated titanium oxide), "MICRO ZINC OXIDE MZ-504R3M" (silicone treated zinc oxide), "MT-600KS" (silicone treated zinc oxide) Zinc); Examples thereof include "D-FZN" (silicone-treated zinc oxide) manufactured by Daito Kasei Kogyo Co., Ltd.

[Component (B): Non-volatile hydrocarbon oil]
The component (B) is an oil agent and is a non-volatile hydrocarbon oil.
"Non-volatile" in the present invention means that the amount of evaporation at 25 ° C. for 6 hours, as measured by the following method, is less than 20%.
Measuring method: A filter paper having a diameter of 90 mm is placed in a glass petri dish having a diameter of 120 mm, 1 g of a sample is placed on the filter paper, and the sample is stored in a room (25 ° C.) at 65% RH for 6 hours. The mass of the sample before and after storage is measured, and the amount of evaporation is calculated by the following formula.
Evaporation amount (%) = (sample mass before storage-sample mass after storage) / sample mass before storage x 100

The component (B) is preferably a saturated or unsaturated hydrocarbon having 18 or more carbon atoms from the viewpoint of improving the usability when applied to the skin.
Specific examples of the component (B) include squalane, squalane, liquid paraffin, hydrocarbon polyisobutene (liquid isoparaffin, heavy liquid isoparaffin), liquid zokerite, α-olefin oligomer, cycloparaffin, polybutene, and pristane, which are liquid at 25 ° C. Hydrocarbon oils in the form; examples thereof include hydrocarbon oils in the form of petrolatum, ceresin, ozokerite, paraffin wax, microcrystalline wax, polyethylene wax and the like, which are solid at 25 ° C. As the component (B), one type can be used alone or two or more types can be used in combination.
Among these, from the viewpoint of improving the usability when applied to the skin, a hydrocarbon oil having no melting point and liquid at 25 ° C. is preferable, and the kinematic viscosity at 25 ° C. is 5 mm ² / s or more and 100,000. Hydrocarbon oils of mm ² / s or less are more preferred, hydrogenated polyisobutene is even more preferred, and liquid isoparaffin is even more preferred.
The kinematic viscosity of the component (B) at 25 ° C. is more preferably 6 mm ² / s or more from the viewpoint of improving the usability when applied to the skin, and further preferably from the same viewpoint as described above. 10,000 mm ² / s or less, even more preferably 5,000 mm ² / s or less, even more preferably 1,000mm ² / s or less, even more preferably 500 mm ² / s or less, even more preferably 300 mm ² / It is s or less, more preferably 100 mm ² / s or less, still more preferably 50 mm ² / s or less, and even more preferably 30 mm ² / s or less.
The kinematic viscosity of component (B) at 25 ° C. can be measured with an Ubbelohde viscometer according to ASTM D 445-46T or JIS Z 8803.
Examples of commercially available products of the component (B) include "Pearl Ream EX" (liquid isoparaffin) manufactured by NOF CORPORATION.

In addition to the components (A) and (B), the external preparation includes beauty ingredients and medicinal ingredients used depending on the use of the external preparation, or ingredients usually used for external preparations such as skin cosmetics. It may be appropriately contained as long as the object of the invention is not impaired. Examples of the component include oils, antioxidants, ultraviolet absorbers, surfactants, thickeners, pH adjusters, bactericides, anti-inflammatory agents, preservatives, and coloring agents other than the components (A) and (B). Examples thereof include agents, chelating agents, moisturizers, pearl agents, ceramides, anti-inflammatory agents, and fragrances.

[Component (C): Non-volatile oil other than component (B)]
The external preparation may further contain a non-volatile oil agent other than the component (B) as the component (C). Examples of the component (C) include one or more selected from ester oils, silicone oils, higher fatty acids, and higher alcohols. Among them, one or more selected from ester oil (C1) (hereinafter, also referred to as “component (C1)”) and non-volatile silicone oil (C2) (hereinafter, also referred to as “component (C2)”) are preferable.

Examples of the component (C1) include synthetic ester oils and natural fats and oils. Specifically, esters of monovalent carboxylic acid and monohydric alcohol, esters of monovalent carboxylic acid and polyhydric alcohol, and polyhydric carboxylic acid Examples thereof include an ester of an acid and a monohydric alcohol.
Examples of the ester of the monovalent carboxylic acid and the monohydric alcohol include an ester represented by the following general formula (1).
R ^1- COO-R ² (1)
In the general formula (1), R ¹ may be substituted with a hydroxyl group, and is a straight-chain or branched alkyl group or alkenyl group having 1 to 25 carbon atoms, or an aromatic group having 6 to 24 carbon atoms. It indicates a hydrocarbon group contained, and R ² indicates a linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms.

When R ¹ is an alkyl group or an alkenyl group, the number of carbon atoms is preferably 7 or more, more preferably 9 or more, still more preferably 11 or more, from the viewpoint of improving the usability when applied to the skin. Then, from the same viewpoint as described above, it is preferably 23 or less, more preferably 21 or less, and further preferably 19 or less.
When R ¹ is an aromatic-containing hydrocarbon group, the number of carbon atoms is preferably 8 or more, more preferably 10 or more, and the same as described above, from the viewpoint of improving the usability when applied to the skin. From the viewpoint of, it is preferably 22 or less, more preferably 20 or less.
The carbon number of R ² is preferably 2 or more from the viewpoint of improving the usability when applied to the skin, and preferably 28 or less, more preferably 20 or less, from the same viewpoint as described above. More preferably, it is 18 or less.
Further, from the viewpoint of improving the usability when applied to the skin, it is preferable that at least one of R ¹ and R ² is a branched alkyl group.

Specific examples of the ester represented by the general formula (1) include myristyl 2-ethylhexanoate, cetyl 2-ethylhexanoate, steearl 2-ethylhexanoate, isodecyl octanate, cetyl octanate, isocetyl octanoate, and the like. Isononyl isononanoate, isotridecyl isononanoate, hexyldecyl dimethyloctanoate, hexyl laurate, isopropyl myristate, isotridecyl myristate, 2-hexyldecyl myristate, myristyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-palmitate Ethylhexyl, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, butyl stearate, 2-ethylhexyl stearate, stearyl stearate, isocetyl stearate, cetyl stearate, isosetyl isostearate, cholesteryl isostearate, decyl oleate , Oleyl oleate, octyldodecyl oleate, lanolin acetate, cholesteryl hydroxystearate, isopropyl lanolin fatty acid, cholesteryl lanolin fatty acid, methyl castor oil fatty acid (methyl ricinoleate), cetyl lactate, myristyl lactate, and alkyl benzoate (carbon of alkyl). One or more selected from the numbers 12 to 15) can be mentioned.

Examples of the ester of the monovalent carboxylic acid and the monohydric alcohol include an ester represented by the following general formula (2).
R ^3- COO- (AO) _n- R ⁴ (2)
In the general formula (2), R ³ may be substituted with a hydroxyl group and represents a linear or branched alkyl group or alkenyl group having 1 to 25 carbon atoms, and R ⁴ has 6 to 24 carbon atoms. The following aromatic-containing hydrocarbon groups are shown. AO represents an alkyleneoxy group having 2 or more and 4 or less carbon atoms, and n represents an average number of moles added of 1 or more and 50 or less.
R ³ preferably has 7 or more carbon atoms from the viewpoint of improving the usability when applied to the skin, and preferably 23 or less, more preferably 21 or less, from the same viewpoint as described above. More preferably, it is an alkyl group of 19 or less.
R ⁴ preferably has 6 or more carbon atoms from the viewpoint of improving the usability when applied to the skin, and preferably 22 or less, more preferably 20 or less, from the same viewpoint as described above. It is more preferably 18 or less aromatic-containing hydrocarbon groups, and even more preferably benzyl groups.
The AO group is preferably a propyleneoxy group from the viewpoint of improving the usability when applied to the skin, and from the same viewpoint as described above, n is preferably 1 or more and 10 or less, more preferably 1 or more. It is 5 or less.
Specific examples of the ester represented by the general formula (2) include an ester of myristic acid and a 3 mol adduct of propylene oxide of benzyl alcohol (“Clodamol STS” manufactured by Claude), 2-ethylcaproic acid and benzyl. Examples thereof include an ester of alcohol with a 3-molar adduct of propylene oxide (“Kurodamol SFX” manufactured by Claude).

Examples of the ester of the monovalent carboxylic acid and the polyhydric alcohol include the ester represented by the following general formula (3).
R ^5- (OCOR ⁶ ) _p (3)
In the general formula (3), R ⁵ represents a polyhydric alcohol residue, preferably a linear or branched hydrocarbon group having 2 or more and 10 or less carbon atoms, and R ⁶ has 1 or more and 25 or less carbon atoms. It indicates a monovalent carboxylic acid residue, and p indicates an integer of 2 or more and 10 or less.
In addition, R ⁵ may have an ether bond. Further, p is preferably the same number as the hydroxy group of the polyhydric alcohol.
R ⁶ preferably has 7 or more carbon atoms, more preferably 9 or more, still more preferably 11 or more, from the viewpoint of improving the usability when applied to the skin, and from the same viewpoint as described above. The alkyl group is preferably 23 or less, more preferably 21 or less, and even more preferably 19 or less.

Examples of the ester represented by the general formula (3) include neopentyl glycol dicaprate, neopentyl glycol di2-ethylhexanoate, di (caprylic acid / capric acid) provandiol, propanediol diisostearate, and di2-ethylhexane. Ethylene glycol acid acid, tri (caprylic acid / capric acid) glyceryl, tri2-ethylhexylate glyceryl, tri2-heptylundecanoate glyceryl, trimyristate glyceryl, tri2-ethylhexylate trimethylolpropane, triisostearate trimethylolpropane, Examples thereof include pentaerythritol tetra2-ethylhexanoate, dipentaerythritol fatty acid, and natural fats and oils.
Natural fats and oils include sunflower oil, cacao oil, mink oil, avocado oil, olive oil, sunflower oil, camellia oil, kyonin oil, almond oil, wheat germ oil, theobroma grungeflorum seed oil, grape seed oil, babas oil, jojoba oil. , Macademia nut oil, yucha oil, shea butter oil, tsubaki seed oil, meadowfoam oil.

Examples of the ester of the polyvalent carboxylic acid and the monohydric alcohol include an ester represented by the following general formula (4).
R ⁷ − (COOR ⁸ ) _q (4)
In the general formula (4), R ⁷ is a polyvalent carboxylic acid residue having 2 or more and 10 or less carbon atoms, R ⁸ is a monohydric alcohol residue having 1 or more and 25 or less carbon atoms, and q is 2 or more and 10 or more. It is the following integer. Further, q is preferably the same number as the carboxy group of the polyvalent carboxylic acid.
R ⁸ is preferably 3 or more, more preferably 7 or more from the viewpoint of improving the usability when applied to the skin, and preferably 23 or less, more preferably from the same viewpoint as described above. It is 21 or less, more preferably 19 or less.
Specifically, diisostearyl malate, di2-ethylhexyl succinate, diisobutyl adipate, di2-heptylundesyl adipate, di2-hexyldecyl adipate, di2-ethylhexyl sebacate, diisopropyl sebacate, etc. Can be mentioned.

From the viewpoint of protecting the skin from damage caused by ultraviolet rays, the component (C1) may be an ester-based ultraviolet absorber having an ultraviolet absorbing ability due to its structure.
Ester-based UV absorbers include salicylic acid-based UV absorbers such as homomentyl salicylate, octyl salicylate, and triethanolamine salicylate; paraaminobenzoic acid, ethyldihydroxypropyl paraaminobenzoic acid, glyceryl paraaminobenzoate, octyl dimethylparaaminobenzoate, and dimethylparaamino. Paraaminobenzoic acid-based ultraviolet absorbers such as amyl benzoate and 2-ethylhexyl dimethylparaaminobenzoate; 2-ethylhexyl paramethoxycinnamic acid (for example, "Ubinal MC80" manufactured by BASF Japan Co., Ltd.), diparamethoxy Mono-2-ethyl silicate glyceryl silicate, methyl 2,5-diisopropyl cinnamic acid, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5- Triazine (ethylhexyltriazone) (for example, "Ubinal T150" manufactured by BASF Japan Co., Ltd.), methylbis (trimethylsiloxy) trimethoxycinnamic acid, silylisopentyl, isopropyl paramethoxycinnamic acid / diisopropylcinnamic acid ester mixture, Cinnamic acid-based ultraviolet absorbers such as p-methoxyhydrocinnamic acid diethanolamine salt; octocrylen (for example, "Parasol 340" manufactured by DSM Nutrition Japan Co., Ltd.); , "Soft Shade DH" manufactured by Ajinomoto Co., Ltd .; Synoxate; Methyl-O-aminobenzoate; Hexil diethylaminohydroxybenzoyl benzoate (for example, "Ubinal Aplus" and "Ubinal Aplus GRANULAR" manufactured by BASF Japan Co., Ltd.) And so on.

The component (C1) is preferably an ester oil in a liquid state at 25 ° C. from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin. The ester oil liquid at 25 ° C. is an ester oil having a melting point of 25 ° C. or lower. That is, the component (C1) is preferably an ester oil having fluidity at 25 ° C. under 1 atm. Specifically, it is preferably an ester represented by the general formula (1) or the general formula (3), and more preferably isopropyl palmitate, isononyl isononanoate, neopentyl glycol dicaprate, di2-ethylhexane. One or more selected from neopentyl glycol acid acid and glyceryl tri2-ethylhexylate.
When an ester-based ultraviolet absorber is used as the component (C1), the component (C1) is preferably paramethoxycin from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin. One or more selected from 2-ethylhexyl dermal acid, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, and hexyl diethylaminohydroxybenzoylbenzoate. is there.

The component (C2) is a non-volatile silicone oil, specifically, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, dimethiconol (dimethylpolysiloxane sealed with hydroxy groups at both ends) and the like. Linear organopolysiloxane; modified silicone such as amino-modified silicone (dimethylpolysiloxane having an amino group in the molecule), polyglycerin-modified silicone having branched polyglycerol chains at both ends; amino derivative silicone; silicone wax, etc. Examples thereof include liquid, semi-solid, and solid silicone oils. As the component (C2), one type can be used alone or two or more types can be used in combination.
Among these, linear organopolysiloxane is preferable, and dimethylpolysiloxane is more preferable, from the viewpoint of improving the usability when applied to the skin.

As the component (C2), the kinematic viscosity at 25 ° C. is 5 mm ² / s or more and 100,000 mm ² / s or less from the viewpoint of improving the usability when applied to the skin and improving the adhesion suppressing effect. Silicone oil is preferable.
The kinematic viscosity of the component (C2) at 25 ° C. is more preferably 6 mm ² / s or more from the viewpoint of improving the usability when applied to the skin, and from the viewpoint of improving the adhesion suppressing effect, and From the viewpoint of improving the usability when applied to the skin, it is more preferably 10,000 mm ² / s or less, further preferably 5,000 mm ² / s or less, and even more preferably 1,000 mm ² / s or less. Even more preferably 500 mm ² / s or less, even more preferably 300 mm ² / s or less, even more preferably 100 mm ² / s or less, even more preferably 50 mm ² / s or less, still more preferably 30 mm ² / s or less. is there.
The kinematic viscosity of the component (C2) at 25 ° C. can be measured in the same manner as described above.
Examples of commercially available products of the component (C2) include "KF-96A-6cs" (dimethylpolysiloxane) and "KF-96A-10cs" (dimethylpolysiloxane) manufactured by Shin-Etsu Chemical Co., Ltd.

[Component (D): Volatile oil]
The external preparation may further contain a volatile oil as the component (D).
"Volatility" in the present invention means that the amount of evaporation at 25 ° C. for 6 hours, as measured by the method described above, is more than 20%.

Examples of the component (D) include volatile silicone oil and volatile hydrocarbon oil.
As the volatile silicone oil in the present invention, a silicone oil having a kinematic viscosity at 25 ° C. of less than 5 mm ² / s is preferable. The kinematic viscosity of the component (D) at 25 ° C. can be measured in the same manner as described above.
Examples of the volatile silicone oil include linear organopolysiloxane and cyclic organopolysiloxane.
Specific examples of the linear organopolysiloxane include octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, 1,1,1,3,5,5,5-heptamethyl-3-[(trimethylsilyl) oxy. ] -Trisiloxane can be mentioned.
Examples of the cyclic organopolysiloxane include 4- to 6-membered cyclic siloxanes having an alkyl group having 1 or more and 5 or less carbon atoms as a substituent, and specific examples thereof include octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. Can be mentioned.
Commercially available volatile silicone oils include "KF-96A-1cs" (octamethyltrisiloxane), "KF-96L-1.5cs" (decamethyltetrasiloxane), and "Decamethyltetrasiloxane" manufactured by Shinetsu Chemical Industry Co., Ltd. KF-96L-2cs "(dodecamethylpentasiloxane)," KF-995 "(decamethylcyclopentasiloxane)," TMF-1.5 "(1,1,1,3,5,5,5-heptamethyl-" 3-[(trimethylsilyl) oxy] -trisiloxane); "SH200C Fluid 1cs" (octamethyltrisiloxane), "SH200C Fluid 1.5cs" (decamethyltetrasiloxane), "SH200C" manufactured by Toray Dow Corning Co., Ltd. Examples thereof include "Fluid 2cs" (dodecamethylpentasiloxane), "SH245 Fluid"(decamethylcyclopentasiloxane);"TSF405A" (decamethylcyclopentasiloxane) manufactured by Momentive Performance Materials.

As the volatile hydrocarbon oil, a saturated or unsaturated hydrocarbon oil having 8 to 16 carbon atoms is preferable, and for example, paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; isodecane, Isoparaffin-based hydrocarbon oils such as isododecane and hydrogenated polyisobutene (light liquid isoparaffin); cyclic paraffin hydrocarbon oils such as cyclodecan and cyclododecane can be mentioned.

[Manufacturing of external preparation]
The external preparation used in the present invention can be produced by appropriately using a known method according to the dosage form of the external preparation. For example, a method of blending the component (A), the component (B), and other components described above as necessary, and stirring and mixing with a disper or the like can be mentioned.
When the external preparation is a water-in-oil (W / O) type or an oil-in-water (O / W) type, which will be described later, a method of preparing an aqueous phase and an oil phase, respectively, and then mixing the two. Can also be used.

(Content of component (A) in external preparation)
The content of the component (A) in the external preparation is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and from the viewpoint of improving the adhesion suppressing effect. From the viewpoint of improving the usability when applied to the skin and from the viewpoint of economic efficiency, it is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less. More specifically, the content of the component (A) is preferably 1 to 40% by mass, from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin. It is preferably 2 to 35% by mass, more preferably 3 to 30% by mass.

(Total content of component (A1), component (A2) and component (A3) in the external preparation)
The total content of the component (A1), the component (A2) and the component (A3) in the external preparation is preferably 1% by mass or more, more preferably 2% by mass or more, and further, from the viewpoint of improving the adhesion suppressing effect. It is preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably, from the viewpoint of improving the usability when applied to the skin and from the viewpoint of economic efficiency. Is 30% by mass or less. More specifically, the total content of the component (A1), the component (A2), and the component (A3) has a viewpoint of improving the adhesion suppressing effect and a viewpoint of improving the usability when applied to the skin. Therefore, it is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and further preferably 3 to 30% by mass.

(Content of component (B) in external preparation)
The content of the component (B) in the external preparation is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further, from the viewpoint of improving the usability when applied to the skin. It is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably 10% by mass or more, and the same as described above. From the viewpoint of improving the adhesion suppressing effect, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 25. It is 0% by mass or less, more preferably 20% by mass or less, still more preferably 18% by mass or less, still more preferably 16% by mass or less.

(Mass ratio [(B) / (A)])
The mass ratio of the content of the component (B) to the content of the component (A) in the external preparation [(B) / (A)] (hereinafter referred to as “x1”) is from the viewpoint of improving the adhesion suppressing effect. , 3.5 or less, preferably 3 or less, more preferably 2.5 or less, still more preferably 2 or less, and preferably 0 from the viewpoint of improving the usability when applied to the skin. It is 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, still more preferably 0.1 or more. More specifically, x1 is preferably 3.5 or less and 0.01 or more, more preferably 3 or less and 0, from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin. It is 0.03 or more, more preferably 2.5 or less and 0.05 or more, and even more preferably 2 or less and 0.1 or more.

(Mass ratio [(B) / [(A1) + (A2) + (A3)]])
When the component (A) is one or more selected from the component (A1), the component (A2) and the component (A3), the component (A1), the component (A2) and the component (A3) in the external preparation are used. The mass ratio of the content of the component (B) to the total content [(B) / [(A1) + (A2) + (A3)]] (hereinafter referred to as “xI”) is a viewpoint for improving the adhesion suppressing effect. Therefore, it is 3.5 or less, preferably 3 or less, more preferably 2.5 or less, still more preferably 2 or less, and preferably from the viewpoint of improving the usability when applied to the skin. It is 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, still more preferably 0.1 or more. More specifically, xI is preferably 3.5 or less and 0.01 or more, more preferably 3 or less, from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin. It is 0.03 or more, more preferably 2.5 or less and 0.05 or more, and even more preferably 2 or less and 0.1 or more.

When the external preparation further contains the component (C1) (ester oil), the mass ratio β1 (=) of the total content of the component (B) and the component (C1) to the content of the component (A) in the external preparation. [[(B) + (C1)] / (A)]) is preferably 9 or less, more preferably 8 or less, still more preferably 6 or less, still more preferably 4 or less, from the viewpoint of improving the adhesion suppressing effect. , More preferably 3 or less, and from the viewpoint of improving the usability when applied to the skin, preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more. Is.
Then, from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin, the mass ratio x1 is preferably 3.5 or less and 0.01 or more, and the mass ratio β1 is 9 or less and 0. 0.01 or more, more preferably mass ratio x1 is 3 or less and 0.03 or more, and mass ratio β1 is 8 or less and 0.01 or more, more preferably mass ratio x1 is 2.5 or less and 0.05 or more, and mass ratio β1 Is 6 or less and 0.05 or more, more preferably the mass ratio x1 is 2 or less and 0.1 or more, and the mass ratio β1 is 4 or less and 0.1 or more, and even more preferably the mass ratio x1 is 2 or less and 0.1 or more. And the mass ratio β1 is 3 or less and 0.1 or more.

When the external preparation further contains the component (C1), the total content of the component (B) and the component (C1) with respect to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation. The preferable numerical range of the mass ratio βI of the amount (= [[(B) + (C1)] / [(A1) + (A2) + (A3)]]) is the same as the preferable numerical range of the mass ratio β1. ..
Then, from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin, the mass ratio xI is preferably 3.5 or less and 0.01 or more, and the mass ratio βI is 9 or less and 0. 0.01 or more, more preferably mass ratio xI of 3 or less and 0.03 or more, mass ratio βI of 8 or less and 0.01 or more, still more preferably mass ratio xI of 2.5 or less and 0.05 or more, and mass ratio βI Is 6 or less and 0.05 or more, more preferably the mass ratio xI is 2 or less and 0.1 or more, and the mass ratio βI is 4 or less and 0.1 or more, and even more preferably the mass ratio xI is 2 or less and 0.1 or more. And the mass ratio βI is 3 or less and 0.1 or more.

When the external preparation further contains the component (C2) (nonvolatile silicone oil), the content of the component (C2) relative to the content of the component (A) in the external preparation from the viewpoint of improving the adhesion suppressing effect. The mass ratio α2 (= [(C2) / (A)]) of is preferably 0.85 or less, more preferably 0.80 or less, still more preferably 0.75 or less, from the viewpoint of improving the adhesion suppressing effect. It is even more preferably 0.70 or less, and from the viewpoint of improving the usability when applied to the skin, it is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03. That is all.
In addition, the mass ratio of the total content of the component (B) and the component (C2) to the content of the component (A) in the external preparation β2 (= [[(B) + (C2)] / (A)]) Is preferably 3.5 or less, more preferably 3 or less, still more preferably 2.5 or less, still more preferably 2 or less, and used when applied to the skin, from the viewpoint of improving the adhesion suppressing effect. From the viewpoint of improving the feeling, it is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, still more preferably 0.1 or more.
Then, from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin, the mass ratio α2 is preferably 0.85 or less and 0.01 or more, and the mass ratio β2 is 3.5. Less than 0.01, more preferably mass ratio α2 is 0.80 or less and 0.01 or more, and mass ratio β2 is 3 or less and 0.03 or more, and more preferably mass ratio α2 is 0.75 or less and 0.02 or more. And the mass ratio β2 is 2.5 or less and 0.05 or more, more preferably the mass ratio α2 is 0.70 or less and 0.03 or more, and the mass ratio β2 is 2 or less and 0.1 or more.

When the external preparation further contains the component (C2), the mass ratio of the content of the component (C2) to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation αII ( The preferable numerical range of = [(C2) / [(A1) + (A2) + (A3)]]) is the same as the preferable numerical range of the mass ratio α2.
Further, the mass ratio of the total content of the component (B) and the silicone oil (C2) to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation βII (= [[(B) ) + (C2)] / [(A1) + (A2) + (A3)]]) is the same as the preferred numerical range of the mass ratio β2.
Then, from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin, the mass ratio αII is preferably 0.85 or less and 0.01 or more, and the mass ratio βII is 3.5. Less than 0.01, more preferably mass ratio αII is 0.80 or less and 0.01 or more, and mass ratio βII is 3 or less and 0.03 or more, and more preferably mass ratio αII is 0.75 or less and 0.02 or more. And the mass ratio βII is 2.5 or less and 0.05 or more, more preferably the mass ratio αII is 0.70 or less and 0.03 or more, and the mass ratio βII is 2 or less and 0.1 or more.

When the external preparation further contains the component (C1) and the component (C2), the total content of the component (B), the component (C1) and the component (C2) with respect to the content of the component (A) in the external preparation. The mass ratio β (1-2) (= [[(B) + (C1) + (C2)] / (A)]) of is preferably 9 or less, more preferably 9 or less from the viewpoint of improving the adhesion suppressing effect. It is 8 or less, more preferably 6 or less, even more preferably 4 or less, even more preferably 3 or less, and preferably 0.01 or more from the viewpoint of improving the usability when applied to the skin. It is more preferably 0.05 or more, still more preferably 0.1 or more.
Then, from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin, the mass ratio α2 is preferably 0.85 or less and 0.01 or more, and the mass ratio β2 is 3. 5 or less 0.01 or more and mass ratio β (1-2) 9 or less 0.01 or more, more preferably mass ratio α2 0.80 or less 0.01 or more and mass ratio β2 3 or less 0.03 The mass ratio β (1-2) is 8 or less and 0.01 or more, more preferably the mass ratio α2 is 0.75 or less and 0.02 or more, and the mass ratio β2 is 2.5 or less and 0.05 or more. The mass ratio β (1-2) is 6 or less and 0.05 or more, more preferably the mass ratio α2 is 0.70 or less and 0.03 or more, the mass ratio β2 is 2 or less and 0.1 or more, and the mass ratio β ( 1-2) is 4 or less and 0.1 or more, more preferably the mass ratio α2 is 0.70 or less and 0.03 or more, and the mass ratio β2 is 2 or less and 0.1 or more, and the mass ratio β (1-2). Is 3 or less and 0.1 or more.

When the external preparation further contains the component (C1) and the component (C2), the component (B) and the component (B) with respect to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation. Mass ratio of total content of C1) and component (C2) β (I-II) (= [[(B) + (C1) + (C2)] / [(A1) + (A2) + (A3)] ]) The preferred numerical range is the same as the preferable numerical range of the mass ratio β (1-2).
Then, from the viewpoint of improving the adhesion suppressing effect and improving the usability when applied to the skin, the mass ratio αII is preferably 0.85 or less and 0.01 or more, and the mass ratio βII is 3.5. The mass ratio β (I-II) is 9 or less and 0.01 or more, more preferably the mass ratio αII is 0.80 or less and 0.01 or more, and the mass ratio βII is 3 or less and 0.03 or more. And the mass ratio β (I-II) is 8 or less and 0.01 or more, more preferably the mass ratio αII is 0.75 or less and 0.02 or more, and the mass ratio βII is 2.5 or less and 0.05 or more and the mass. The ratio β (I-II) is 6 or less and 0.05 or more, more preferably the mass ratio αII is 0.70 or less and 0.03 or more, the mass ratio βII is 2 or less and 0.1 or more, and the mass ratio β (I). -II) is 4 or less and 0.1 or more, more preferably the mass ratio αII is 0.70 or less and 0.03 or more, the mass ratio βII is 2 or less and 0.1 or more, and the mass ratio β (I-II) is 3 or less and 0.1 or more.

(Content of component (C1))
When the external preparation contains the component (C1), the content of the component (C1) in the external preparation is preferably 0.1% by mass from the viewpoint of improving the usability when applied to the skin. The above is more preferably 1% by mass or more, further preferably 3% by mass or more, and from the same viewpoint as described above and from the viewpoint of improving the adhesion suppressing effect, preferably 25% by mass or less, more preferably 20% by mass. % Or less, more preferably 18% by mass or less, still more preferably 16% by mass or less.

(Content of component (C2))
When the external preparation contains the component (C2), the content of the component (C2) in the external preparation is preferably 0.1% by mass from the viewpoint of improving the usability when applied to the skin. The above is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and from the same viewpoint as described above and from the viewpoint of improving the adhesion suppressing effect, preferably 15% by mass or less, more preferably. It is 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less.

(Content of component (D))
When the external preparation contains the component (D), the content of the component (D) in the external preparation is preferably 20% by mass or more, more preferably 25% by mass or more from the viewpoint of improving the adhesion suppressing effect. It is more preferably 30% by mass or more, and preferably 97% by mass or less, more preferably 95% by mass or less, still more preferably 93% by mass or less.

The form of the external preparation used in the present invention includes an oil-based type using one oil phase as a dispersion medium, a water droplet type in oil (hereinafter, also referred to as “W / O type”), and an oil droplet type in water (hereinafter, “O /”). (Also referred to as "W type") and the like can be appropriately selected.
In the present invention, the external preparation can be applied, for example, as an external preparation to be applied to skin and hair. From the viewpoint of the adhesion suppressing effect, the external preparation is preferably a cosmetic, and more preferably a skin cosmetic.
The dosage form of the external preparation is not particularly limited, and any dosage form such as liquid, foam, paste, cream, and solid can be used.
When the form of the external preparation is an oil-based type, the content of each component and each mass ratio are as described above. When the external preparation is W / O type or O / W type, the content and mass ratio of each component are as follows.

(Content and mass ratio of each component in the case of water droplet (W / O) type in oil)
When the external preparation is a W / O type, the content of the component (A) in the external preparation is preferably 1% by mass or more, more preferably 2% by mass or more, and further, from the viewpoint of improving the adhesion suppressing effect. It is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, still more preferably 10% by mass or more, and to have a good usability when applied to the skin. From the viewpoint of the above, and from the viewpoint of economic efficiency, it is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.

When the external preparation is a W / O type, the total content of the component (A1), the component (A2) and the component (A3) in the external preparation is preferably 1% by mass from the viewpoint of improving the adhesion suppressing effect. The above is more preferably 2% by mass or more, further preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably 10% by mass or more, and the skin. It is preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, from the viewpoint of improving the usability when applied to the above and from the viewpoint of economic efficiency.

When the external preparation is a W / O type, the content of the component (B) in the external preparation is preferably 0.05% by mass or more from the viewpoint of improving the usability when applied to the skin. It is more preferably 0.1% by mass or more, still more preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 8% by mass or more, and adhere. From the viewpoint of improving the suppressing effect and improving the usability when applied to the skin, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably. Is 16% by mass or less, more preferably 12% by mass or less.

When the external preparation is a W / O type, the mass ratio of the content of the component (B) to the content of the component (A) in the external preparation [(B) / (A)] improves the adhesion suppressing effect. From the viewpoint of making it 3.5 or less, preferably 3 or less, more preferably 2.5 or less, still more preferably 2 or less, and from the viewpoint of improving the usability when applied to the skin. It is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, and even more preferably 0.1 or more.

When the external preparation is a W / O type and the component (A) is one or more selected from the component (A1), the component (A2) and the component (A3), the component (A1) in the external preparation ), The mass ratio of the content of the component (B) to the total content of the component (A2) and the component (A3) [(B) / [(A1) + (A2) + (A3)]] has an adhesion suppressing effect. From the viewpoint of improving the above, it is 3.5 or less, preferably 3 or less, more preferably 2.5 or less, still more preferably 2 or less, and the viewpoint of improving the usability when applied to the skin. Therefore, it is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, still more preferably 0.1 or more.

When the external preparation is a W / O type and the external preparation contains a component (C1), the content of the component (C1) in the external preparation is such that the feeling of use when applied to the skin is good. From the viewpoint of, preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and from the same viewpoint as described above and from the viewpoint of improving the adhesion suppressing effect. It is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 18% by mass or less, still more preferably 16% by mass or less.

When the external preparation is a W / O type and the external preparation contains a component (C2), the content of the component (C2) in the external preparation is such that the feeling of use when applied to the skin is good. From the viewpoint of, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and the same viewpoint as described above and the viewpoint of improving the adhesion suppressing effect. Therefore, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 6% by mass or less.

When the external preparation is a W / O type and the external preparation contains a component (D), the content of the component (D) in the external preparation is preferably from the viewpoint of improving the adhesion suppressing effect. It is 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less.

(Content and mass ratio of each component in the case of oil droplet (O / W) type in water)
When the external preparation is an O / W type, the content of the component (A) in the external preparation is preferably 1% by mass or more, more preferably 2% by mass or more, and further, from the viewpoint of improving the adhesion suppressing effect. It is preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably, from the viewpoint of improving the usability when applied to the skin and from the viewpoint of economic efficiency. Is 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

When the external preparation is an O / W type, the total content of the component (A1), the component (A2) and the component (A3) in the external preparation is preferably 1% by mass from the viewpoint of improving the adhesion suppressing effect. The above is more preferably 2% by mass or more, further preferably 3% by mass or more, and preferably 40% by mass or less from the viewpoint of improving the usability when applied to the skin and from the viewpoint of economic efficiency. , More preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less.

When the external preparation is an O / W type, the content of the component (B) in the external preparation is preferably 0.05% by mass or more from the viewpoint of improving the usability when applied to the skin. More preferably 0.1% by mass or more, still more preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably 10 It is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, from the viewpoint of improving the adhesion suppressing effect and the usability such as stickiness. More preferably, it is 16% by mass or less.

When the external preparation is an O / W type, the mass ratio of the content of the component (B) to the content of the component (A) in the external preparation [(B) / (A)] improves the adhesion suppressing effect. From the viewpoint of making it 3.5 or less, preferably 3 or less, more preferably 2.5 or less, still more preferably 2 or less, and from the viewpoint of improving the usability when applied to the skin. It is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, and even more preferably 0.1 or more.

When the external preparation is an O / W type and the component (A) is one or more selected from the component (A1), the component (A2) and the component (A3), the component (A1) in the external preparation ), The mass ratio of the content of the component (B) to the total content of the component (A2) and the component (A3) [(B) / [(A1) + (A2) + (A3)]] has an adhesion suppressing effect. From the viewpoint of improving the above, it is preferably 3.5 or less, more preferably 3 or less, further preferably 2.5 or less, still more preferably 2 or less, and to have a good usability when applied to the skin. From this point of view, it is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, still more preferably 0.1 or more.

When the external preparation is an O / W type and the external preparation contains a component (C1), the content of the component (C1) in the external preparation makes the feeling of use when applied to the skin good. From the viewpoint, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably. It is 10% by mass or more, and from the same viewpoint as described above and from the viewpoint of improving the adhesion suppressing effect, it is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 18% by mass or less, still more. It is preferably 16% by mass or less.

When the external preparation is an O / W type and the external preparation contains a component (C2), the content of the component (C2) in the external preparation makes the feeling of use when applied to the skin good. From the viewpoint, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and from the same viewpoint as described above and from the viewpoint of improving the adhesion suppressing effect. It is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 6% by mass or less.

When the external preparation is an O / W type and the external preparation contains a component (D), the content of the component (D) in the external preparation is preferably from the viewpoint of improving the adhesion suppressing effect. 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, and preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 3 It is mass% or less.

[Applying method]
In the present invention, as a method of applying the external preparation to the skin, it can be applied by a known method depending on the usage pattern or purpose of the external preparation. Here, "applying to the skin" includes not only directly applying the external preparation to the skin surface by hand or the like, but also adhering the external preparation to the skin surface by spraying or the like. When the external preparation is in the form of liquid, foam, paste, cream or solid, it can be usually applied as it is by application, spraying or the like.

(Applying amount of component (A))
The coating amount to the skin surface of the component (A), from the viewpoint of improving the adhesion inhibiting effect, preferably 0.03 mg / cm ² or more, more preferably 0.04 mg / cm ² or more, more preferably 0.05 mg / It is cm ² or more, more preferably 0.07 mg / cm ² or more, and is preferably 0.8 mg / cm ² from the viewpoint of improving the usability when applied to the skin and from the viewpoint of economic efficiency. Below, it is more preferably 0.7 mg / cm ² or less, still more preferably 0.6 mg / cm ² or less. More specifically, the amount of the component (A) applied to the skin surface is determined from the viewpoint of improving the adhesion suppressing effect, from the viewpoint of improving the usability when applied to the skin, and from the viewpoint of economic efficiency. , Preferably 0.03 to 0.8 mg / cm ² , more preferably 0.04 to 0.8 mg / cm ² , still more preferably 0.05 to 0.8 mg / cm ² , and even more preferably 0.07 to 0.07 to. 0.8 mg / cm ^2, even more preferably 0.07~0.7mg / cm ^2, even more preferably 0.07~0.6mg / cm ^2.

When the component (A) is one or more selected from the component (A1), the component (A2) and the component (A3), the total of the component (A1), the component (A2) and the component (A3) on the skin surface. the coating amount, in terms of improving the adhesion inhibiting effect, preferably 0.03 mg / cm ² or more, more preferably 0.04 mg / cm ² or more, more preferably 0.05 mg / cm ² or more, even more preferably 0 It is .07 mg / cm ² or more, and is preferably 0.8 mg / cm ² or less, more preferably 0.7 mg / cm, from the viewpoint of improving the usability when applied to the skin and from the viewpoint of economic efficiency. It is cm ² or less, more preferably 0.6 mg / cm ² or less. More specifically, the total amount of the component (A1), the component (A2) and the component (A3) applied to the skin surface is good from the viewpoint of improving the adhesion suppressing effect and the feeling of use when applied to the skin. From the viewpoint of the above, and from the viewpoint of economic efficiency, it is preferably 0.03 to 0.8 mg / cm ² , more preferably 0.04 to 0.8 mg / cm ² , and further preferably 0.05 to 0.8 mg / cm ² . It is cm ² , more preferably 0.07 to 0.8 mg / cm ² , even more preferably 0.07 to 0.7 mg / cm ² , and even more preferably 0.07 to 0.6 mg / cm ² .

When the external preparation is a W / O type, the amount of the component (A) applied to the skin surface is preferably 0.03 mg / cm ² or more, more preferably 0.04 mg / from the viewpoint of improving the adhesion suppressing effect. cm ² or more, more preferably 0.05 mg / cm ² or more, even more preferably 0.07 mg / cm ² or more, even more preferably 0.10 mg / cm ² or more, even more preferably 0.20 mg / cm ² or more From the viewpoint of improving the usability when applied to the skin and from the viewpoint of economic efficiency, it is preferably 0.8 mg / cm ² or less, more preferably 0.7 mg / cm ² or less, still more preferable. Is 0.6 mg / cm ² or less. More specifically, the amount of the component (A) applied to the skin surface is determined from the viewpoint of improving the adhesion suppressing effect, from the viewpoint of improving the usability when applied to the skin, and from the viewpoint of economic efficiency. preferably 0.03~0.8mg / cm ^2, more preferably 0.04~0.8mg / cm ^2, more preferably 0.05~0.8mg / cm ^2, even more preferably 0.07 to 0.8 mg / cm ^2, even more preferably 0.10~0.8mg / cm ^2, even more preferably 0.20~0.7mg / cm ^2, even more preferably 0.20~0.6mg / cm It is ² .

When the external preparation is a W / O type and the component (A) is one or more selected from the component (A1), the component (A2) and the component (A3), the component (A1) and the component (A2) and the total coating amount to the skin surface of the component (A3), from the viewpoint of improving the adhesion inhibiting effect, preferably 0.03 mg / cm ² or more, more preferably 0.04 mg / cm ² or more, more preferably is 0.05 mg / cm ² or more, even more preferably 0.07 mg / cm ² or more, even more preferably 0.10 mg / cm ² or more, even more preferably at 0.20 mg / cm ² or more, and the skin From the viewpoint of improving the usability when applied to, and from the viewpoint of economic efficiency, it is preferably 0.8 mg / cm ² or less, more preferably 0.7 mg / cm ² or less, and further preferably 0.6 mg / cm. ² or less. More specifically, the total amount of the component (A1), the component (A2) and the component (A3) applied to the skin surface is good from the viewpoint of improving the adhesion suppressing effect and the feeling of use when applied to the skin. From the viewpoint of the above, and from the viewpoint of economic efficiency, it is preferably 0.03 to 0.8 mg / cm ² , more preferably 0.04 to 0.8 mg / cm ² , and further preferably 0.05 to 0.8 mg / cm ² . cm ² , even more preferably 0.07 to 0.8 mg / cm ² , even more preferably 0.10 to 0.8 mg / cm ² , even more preferably 0.25 to 0.7 mg / cm ² , even more. It is preferably 0.25 to 0.6 mg / cm ² .

When the external preparation is an O / W type, the amount of the component (A) applied to the skin surface is preferably 0.03 mg / cm ² or more, more preferably 0.04 mg / from the viewpoint of improving the adhesion suppressing effect. It is cm ² or more, more preferably 0.05 mg / cm ² or more, even more preferably 0.07 mg / cm ² or more, and from the viewpoint of improving the usability when applied to the skin, and economically. From the viewpoint, it is preferably 0.8 mg / cm ² or less, more preferably 0.7 mg / cm ² or less, still more preferably 0.6 mg / cm ² or less, still more preferably 0.3 mg / cm ² or less. More specifically, the amount of the component (A) applied to the skin surface is determined from the viewpoint of improving the adhesion suppressing effect, from the viewpoint of improving the usability when applied to the skin, and from the viewpoint of economic efficiency. preferably 0.03~0.8mg / cm ^2, more preferably 0.04~0.8mg / cm ^2, more preferably 0.05~0.8mg / cm ^2, even more preferably 0.07 to 0.8 mg / cm ^2, even more preferably 0.07~0.7mg / cm ^2, even more preferably 0.07~0.6mg / cm ^2, even more preferably 0.07~0.3mg / cm It is ² .

When the external preparation is an O / W type and the component (A) is one or more selected from the component (A1), the component (A2) and the component (A3), the component (A1) and the component (A2) and the total coating amount to the skin surface of the component (A3), from the viewpoint of improving the adhesion inhibiting effect, preferably 0.03 mg / cm ² or more, more preferably 0.04 mg / cm ² or more, more preferably Is 0.05 mg / cm ² or more, more preferably 0.07 mg / cm ² or more, and is preferably 0 from the viewpoint of improving the usability when applied to the skin and from the viewpoint of economic efficiency. .8mg / cm ² or less, more preferably 0.7 mg / cm ² or less, more preferably 0.6 mg / cm ² or less, even more preferably 0.3 mg / cm ² or less. More specifically, the total amount of the component (A1), the component (A2) and the component (A3) applied to the skin surface is good from the viewpoint of improving the adhesion suppressing effect and the feeling of use when applied to the skin. From the viewpoint of the above, and from the viewpoint of economic efficiency, it is preferably 0.03 to 0.8 mg / cm ² , more preferably 0.04 to 0.8 mg / cm ² , and further preferably 0.05 to 0.8 mg / cm ² . cm ² , even more preferably 0.07 to 0.8 mg / cm ² , even more preferably 0.07 to 0.7 mg / cm ² , even more preferably 0.07 to 0.6 mg / cm ² , even more. It is preferably 0.07 to 0.3 mg / cm ² .

With respect to the embodiments described above, the present invention further discloses the following embodiments.
<1> A method for suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin.
The external preparation contains one or more selected from the following components (A1), component (A2) and component (A3), and component (B), and the component (A1) and component (A2) in the external preparation. And the mass ratio of the content of the component (B) to the total content of the component (A3) [(B) / [(A1) + (A2) + (A3)]] is 3.5 or less and 0.01 or more. , How to control the adhesion of air harmful substances.
Component (A1): an average primary particle diameter d _A is one or more components selected from titanium oxide and zinc oxide which has been treated with fatty acid is 5nm or more 80nm or less (A2): the average primary particle diameter d _A is at 5nm or 80nm or less there alkylalkoxysilane-treated titanium oxide and one or more components selected from zinc oxide (A3): mean one of primary particle diameter d _A is selected from titanium oxide and zinc oxide treated with silicone is 5nm or more 80nm or less Component (B): Non-volatile hydrocarbon oil

<2> A method of suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin.
The external preparation contains one or more selected from the following components (A1), component (A2) and component (A3), and component (B), and the component (A1) and component (A2) in the external preparation. And the mass ratio of the content of the component (B) to the total content of the component (A3) [(B) / [(A1) + (A2) + (A3)]] is 3.5 or less and 0.01 or more. , How to control the adhesion of air harmful substances.
Component (A1): an average primary particle diameter d _A is one or more components selected from titanium oxide and zinc oxide which has been treated with fatty acid is 5nm or more 50nm or less (A2): the average primary particle diameter d _A is at 5nm or 50nm or less there alkylalkoxysilane-treated titanium oxide and one or more components selected from zinc oxide (A3): mean one of primary particle diameter d _A is selected from titanium oxide and zinc oxide treated with silicone is 5nm or more 50nm or less Component (B): Non-volatile hydrocarbon oil

<3> The air toxic substance according to <1> or <2> above, wherein the mass ratio [(B) / [(A1) + (A2) + (A3)]] is 2.5 or less and 0.05 or more. Adhesion suppression method.
<4> Adhesion of air harmful substances according to <1> or <2> above, wherein the mass ratio [(B) / [(A1) + (A2) + (A3)]] is 2 or less and 0.1 or more. Suppression method.

<5> The total amount of the component (A1), the component (A2) and the component (A3) applied to the skin is 0.03 mg / cm ² or more and 0.8 mg / cm ² or less, the above <1> to <4>. The method for suppressing adhesion of air harmful substances according to any one of.
<6> The total amount of the component (A1), the component (A2) and the component (A3) applied to the skin is 0.05 mg / cm ² or more and 0.8 mg / cm ² or less, the above <1> to <4>. The method for suppressing adhesion of air harmful substances according to any one of.
<7> The total amount of the component (A1), the component (A2) and the component (A3) applied to the skin is 0.07 mg / cm ² or more and 0.7 mg / cm ² or less, the above <1> to <4>. The method for suppressing adhesion of air harmful substances according to any one of.

<8> The above-mentioned <1> to <7>, wherein the total content of the component (A1), the component (A2) and the component (A3) in the external preparation is 1% by mass or more and 40% by mass or less. How to control the adhesion of atmospheric harmful substances.
<9> The above-mentioned <1> to <7>, wherein the total content of the component (A1), the component (A2) and the component (A3) in the external preparation is 2% by mass or more and 35% by mass or less. How to control the adhesion of atmospheric harmful substances.
<10> The above-mentioned <1> to <7>, wherein the total content of the component (A1), the component (A2) and the component (A3) in the external preparation is 3% by mass or more and 30% by mass or less. How to control the adhesion of atmospheric harmful substances.

<11> A method for suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin.
The external preparation contains one or more selected from the following components (A1), component (A2) and component (A3), and component (B), and the component (A1) and component (A2) in the external preparation. And the mass ratio of the content of the component (B) to the total content of the component (A3) [(B) / [(A1) + (A2) + (A3)]] is 2.5 or less and 0.05 or more. , A method for suppressing adhesion of air harmful substances, wherein the total amount of the component (A1), the component (A2) and the component (A3) applied to the skin is 0.03 mg / cm ² or more and 0.8 mg / cm ² or less.
Component (A1): an average primary particle diameter d _A is one or more components selected from titanium oxide and zinc oxide which has been treated with fatty acid is 5nm or more 80nm or less (A2): the average primary particle diameter d _A is at 5nm or 80nm or less there alkylalkoxysilane-treated titanium oxide and one or more components selected from zinc oxide (A3): mean one of primary particle diameter d _A is selected from titanium oxide and zinc oxide treated with silicone is 5nm or more 80nm or less Component (B): Non-volatile hydrocarbon oil

<12> A method for suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin.
The external preparation contains one or more selected from the following components (A1), component (A2) and component (A3), and component (B), and the component (A1) and component (A2) in the external preparation. And the mass ratio of the content of the component (B) to the total content of the component (A3) [(B) / [(A1) + (A2) + (A3)]] is 2 or less and 0.1 or more, and the component A method for suppressing adhesion of air harmful substances, wherein the total amount of (A1), component (A2) and component (A3) applied to the skin is 0.03 mg / cm ² or more and 0.8 mg / cm ² or less.
Component (A1): an average primary particle diameter d _A is one or more components selected from titanium oxide and zinc oxide which has been treated with fatty acid is 5nm or more 50nm or less (A2): the average primary particle diameter d _A is at 5nm or 50nm or less there alkylalkoxysilane-treated titanium oxide and one or more components selected from zinc oxide (A3): mean one of primary particle diameter d _A is selected from titanium oxide and zinc oxide treated with silicone is 5nm or more 50nm or less Component (B): Non-volatile hydrocarbon oil

<13> A method for suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin.
The external preparation contains one or more selected from the following components (A1), component (A2) and component (A3), and component (B), and the component (A1) and component (A2) in the external preparation. And the mass ratio of the content of the component (B) to the total content of the component (A3) [(B) / [(A1) + (A2) + (A3)]] is 2.5 or less and 0.05 or more. A method for suppressing adhesion of air harmful substances, wherein the total content of the component (A1), the component (A2) and the component (A3) in the external preparation is 1% by mass or more and 40% by mass or less.
Component (A1): an average primary particle diameter d _A is one or more components selected from titanium oxide and zinc oxide which has been treated with fatty acid is 5nm or more 80nm or less (A2): the average primary particle diameter d _A is at 5nm or 80nm or less there alkylalkoxysilane-treated titanium oxide and one or more components selected from zinc oxide (A3): mean one of primary particle diameter d _A is selected from titanium oxide and zinc oxide treated with silicone is 5nm or more 80nm or less Component (B): Non-volatile hydrocarbon oil

<14> A method for suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin.
The external preparation contains one or more selected from the following components (A1), component (A2) and component (A3), and component (B), and the component (A1) and component (A2) in the external preparation. And the mass ratio of the content of the component (B) to the total content of the component (A3) [(B) / [(A1) + (A2) + (A3)]] is 2 or less and 0.1 or more, and is used externally. A method for suppressing adhesion of air harmful substances, wherein the total content of the component (A1), the component (A2) and the component (A3) in the agent is 1% by mass or more and 40% by mass or less.
Component (A1): an average primary particle diameter d _A is one or more components selected from titanium oxide and zinc oxide which has been treated with fatty acid is 5nm or more 50nm or less (A2): the average primary particle diameter d _A is at 5nm or 50nm or less there alkylalkoxysilane-treated titanium oxide and one or more components selected from zinc oxide (A3): mean one of primary particle diameter d _A is selected from titanium oxide and zinc oxide treated with silicone is 5nm or more 50nm or less Component (B): Non-volatile hydrocarbon oil

<15> A method for suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin.
The external preparation contains at least one selected from the following component (A1), component (A2) and component (A3), component (B) and component (C1), and the component (A1) in the external preparation. , The mass ratio of the content of the component (B) to the total content of the component (A2) and the component (A3) [(B) / [(A1) + (A2) + (A3)]] is 2 or less 0.1 As described above, the mass ratio of the total content of the component (B) and the component (C1) to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation [[(B) + (C1)] / [(A1) + (A2) + (A3)]] is 4 or less and 0.1 or more, and the total content of the component (A1), the component (A2), and the component (A3) in the external preparation. A method for suppressing adhesion of atmospheric harmful substances, wherein the amount is 1% by mass or more and 40% by mass or less.
Component (A1): an average primary particle diameter d _A is one or more components selected from titanium oxide and zinc oxide which has been treated with fatty acid is 5nm or more 50nm or less (A2): the average primary particle diameter d _A is at 5nm or 50nm or less One or more selected from certain alkylalkoxysilane-treated titanium oxide and zinc oxide Component (A3): One selected from silicone-treated titanium oxide and zinc oxide having an average primary particle diameter d _A of 5 nm or more and 50 nm or less. Component (B): Non-volatile hydrocarbon oil Component (C1): Ester oil

<16> A method for suppressing the adhesion of air harmful substances to the skin by applying an external preparation to the skin.
The external preparation contains at least one selected from the following component (A1), component (A2) and component (A3), component (B) and component (C2), and the component (A1) in the external preparation. , The mass ratio of the content of the component (B) to the total content of the component (A2) and the component (A3) [(B) / [(A1) + (A2) + (A3)]] is 2 or less 0.1 As described above, the mass ratio of the content of the component (C2) to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation [(C2) / [(A1) + (A2) ) + (A3)]] is 0.70 or less and 0.03 or more, and the component (B) and the component (A3) with respect to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation. The mass ratio of the total content of C2) [[(B) + (C2)] / [(A1) + (A2) + (A3)]] is 2 or less and 0.1 or more, and the components in the external preparation ( A method for suppressing adhesion of air harmful substances, wherein the total content of A1), the component (A2) and the component (A3) is 1% by mass or more and 40% by mass or less.
Component (A1): an average primary particle diameter d _A is one or more components selected from titanium oxide and zinc oxide which has been treated with fatty acid is 5nm or more 50nm or less (A2): the average primary particle diameter d _A is at 5nm or 50nm or less there alkylalkoxysilane-treated titanium oxide and one or more components selected from zinc oxide (A3): mean one of primary particle diameter d _A is selected from titanium oxide and zinc oxide treated with silicone is 5nm or more 50nm or less Component (B): Non-volatile hydrocarbon oil,
Ingredient (C2): Non-volatile silicone oil

<17> A method for suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin.
The external preparation contains at least one selected from the following components (A1), component (A2) and component (A3), component (B), component (C1) and component (C2), and is contained in the external preparation. The mass ratio of the content of the component (B) to the total content of the component (A1), the component (A2) and the component (A3) [(B) / [(A1) + (A2) + (A3)]] is 2. Below, it is 0.1 or more, and the mass ratio of the content of the component (C2) to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation [(C2) / [(A1) ) + (A2) + (A3)]] is 0.70 or less and 0.03 or more, and the component (B) with respect to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation. ) And the mass ratio of the total content of the component (C2) [[(B) + (C2)] / [(A1) + (A2) + (A3)]] is 2 or less and 0.1 or more. Mass ratio of the total content of the component (B), the component (C1) and the component (C2) to the total content of the component (A1), the component (A2) and the component (A3) in the agent [[(B) + ( C1) + (C2)] / [(A1) + (A2) + (A3)]] is 4 or less and 0.1 or more, and the component (A1), component (A2) and component (A3) in the external preparation A method for suppressing adhesion of air harmful substances, wherein the total content of the above is 1% by mass or more and 40% by mass or less.
Component (A1): an average primary particle diameter d _A is one or more components selected from titanium oxide and zinc oxide which has been treated with fatty acid is 5nm or more 50nm or less (A2): the average primary particle diameter d _A is at 5nm or 50nm or less One or more selected from certain alkylalkoxysilane-treated titanium oxide and zinc oxide Component (A3): One selected from silicone-treated titanium oxide and zinc oxide having an average primary particle size d _A of 5 nm or more and 50 nm or less. Component (B): Non-volatile hydrocarbon oil Component (C1): Ester oil Component (C2): Non-volatile silicone oil

<18> The external preparation is a water droplet type in oil, and the total content of the component (A1), the component (A2) and the component (A3) in the external preparation is 10% by mass or more and 40% by mass or less, <11. > ~ <17> Method for suppressing adhesion of air harmful substances.
<19> The external preparation is an oil droplet type in water, and the total content of the component (A1), the component (A2) and the component (A3) in the external preparation is 1% by mass or more and 15% by mass or less, <11. > ~ <17> Method for suppressing adhesion of air harmful substances.
<20> The method for suppressing adhesion of air harmful substances according to <11> to <19>, wherein the content of the component (B) in the external preparation is 1% by mass or more and 18% by mass or less.
<21> The total amount of the component (A1), the component (A2) and the component (A3) applied to the skin is 0.05 mg / cm ² or more and 0.8 mg / cm ² or less, the above <11> to <20>. The method for suppressing adhesion of air harmful substances according to any one of.
<22> The total amount of the component (A1), the component (A2) and the component (A3) applied to the skin is 0.07 mg / cm ² or more and 0.7 mg / cm ² or less, the above <11> to <20>. The method for suppressing adhesion of air harmful substances according to any one of.

In the following examples and comparative examples, "parts" and "%" are "parts by mass" and "% by mass" unless otherwise specified.

(Average primary particle diameter d _{A of} component (A))
When the component (A) has a shape other than the plate shape, the dispersion liquid of the component (A) prepared in advance is used as a sample of a transmission electron microscope (TEM) (manufactured by JEOL Ltd., trade name "JEM1400Plus"). After placing it on a table and air-drying it, the maximum minor axis of 300 primary particles in the image observed under the condition of an observation magnification of 50,000 times was measured by TEM, and the number average value was measured as the average primary particle diameter d _A. And said. Here, the maximum minor axis means the minor axis having the maximum length among the minor diameters orthogonal to the major axis.
When the component (A) is plate-shaped, the thickness of 300 primary particles in the image observed under the same observation magnification conditions as above is measured, and the average value thereof is the average primary particle diameter d _A. And said.
The dispersion of component (A) was prepared by adding 95 g of ethanol as a solvent to 5 g of component (A) and ultrasonically dispersing it.

(Kinematic viscosity at 25 ° C)
The kinematic viscosity at 25 ° C. was measured using an Ubbelohde viscometer according to ASTM D 445-46T or JIS Z 8803.

In the examples and comparative examples, commercially available products of the component (A) shown in Table 1 below were used.

Examples 1 to 22, Comparative Examples 1 to 10, Reference Examples 1 to 4
In the composition shown in Tables 2 to 6, the component (A) or the component (A'), the component (B) and the component (D) are stirred and mixed at room temperature, and the components of Examples 1 to 22 and Comparative Examples 1 to 10 are mixed. Obtained an external preparation.
Liquid isoparaffin (manufactured by NOF Corporation, trade name "Pearl Ream EX", hydrogenated polyisobutene) as component (B), dodecamethylpentasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KF") as component (D) -96L-2cs ", kinematic viscosity at 25 ° C.: 2 mm ² / s) was used.
In addition, as a component (A'), a methylsiloxane reticulated polymer (“Tospearl 145A” manufactured by Momentive Performance Materials Japan LLC (spherical silicone fine particles, average particle size: 4.5 μm (catalog value))) and Silica particles (AGC SITEC Co., Ltd. "Sunsphere NP-30" (average particle size: 4 μm (catalog value))) were used.
In Reference Examples 1 to 4, the component (A) and the component (D) were stirred and mixed with the compositions shown in Tables 2 to 5 without using the component (B), and used as an external preparation.
Using the obtained external preparation, the effect of suppressing the adhesion of atmospheric harmful substances was evaluated by the method shown below. The results are shown in Tables 2-6.

<Evaluation method of adhesion suppression effect of atmospheric harmful substances>
White artificial leather (trade name "Laforet S2923", (trade name "Laforet S2923")) is used as a substitute for the skin so that the amount of the component (A) or the component (A') applied to the external preparation obtained above is 0.12 mg / cm ^2. It was applied to Okamoto Shinwa Co., Ltd.) and left overnight at room temperature to dry.
The surface of the artificial leather coated with the external preparation is exposed in the blowing environment of the air toxic substance for evaluation, the L ^* a ^* b ^* value is measured using a colorimeter, and the color difference ΔE before and after the exposure is measured by the following method. It was measured.
[Measurement of color difference ΔE]
Using a colorimeter (trade name "CM-2002", manufactured by Konica Minolta Co., Ltd.), L ₁ ^* , a ₁ ^* , on the surface of artificial leather coated with an external preparation before exposure to atmospheric harmful substances for evaluation. The b ₁ ^* value was measured.
Separately, in a glove bag (product number "3-118-01", manufactured by AS ONE Corporation), a blower (trade name "Silky Wind 9ZF002RH02", size: 129 x 106 x 83 mm, manufactured by Rhythm Watch Industry Co., Ltd.), A net sieve (Test sieves test sieve JIS Z 8801, frame size: φ100 × 45H, opening: 106 μm, manufactured by Tokyo Screen Co., Ltd.) was fixed. The installation height of the net sieve was set to 17 cm.
The artificial leather (5 cm × 4 cm) coated with the external preparation of the test sample was attached to the support so that the height of the lower end of the artificial leather was 11 cm. The distance between the artificial leather coated surface of the support and the blower is set to 15 cm, and as shown in FIG. 1, the artificial leather coated surface is perpendicular to the blowing direction of the blower, the center height of the blower blades and the artificial leather. It was installed so that the center height of the leather was the same.
For evaluation, set the temperature inside the glove bag to 25 ° C, relative humidity to 57% RH, and use a clogging removal brush (trade name "JNB-5", brush diameter 53 μm, manufactured by Tokyo Screen Co., Ltd.) from the net sieve. In front of the blower outlet with the blower scale set to 1 while classifying 50 mg of graphite powder (trade name "J-CPB", average particle size: 5.5 μm, manufactured by Nippon Graphite Industry Co., Ltd.) as an air toxic substance. The surface of the artificial leather coated with the external preparation was exposed to the air environment of the air toxic substance for evaluation.
Next, the L ₂ ^* , a ₂ ^* , and b ₂ ^* values of the exposed artificial leather surface were measured using the above colorimeter, and the color difference ΔE value was obtained from the following formula (I).
ΔE = [(L ₁ ^* −L ₂ ^* ) ² + (a ₁ ^* −a ₂ ^* ) ² + (b ₁ ^* −b ₂ ^* ) ² ] ^0.5 (I)
The above operation was performed three times for each test sample, and the average value of the color difference ΔE of the artificial leather coated with the external preparation of the test sample was defined as ΔEt. Further, for the artificial leather to which the external preparation was not applied as a standard sample, the same operation as above was performed three times, the average value of the color difference ΔE was set to ΔEs, and the adhesion suppression rate was calculated from the following formula (II). The higher the adhesion suppression rate, the better the adhesion suppression effect of air harmful substances.
Adhesion suppression rate of atmospheric harmful substances (%) = 100 × (ΔEs-ΔEt) / ΔEs (II)

From Tables 2 to 6, Examples 1 to 22 contain the component (A) and the component (B), and the mass ratio of the component (B) to the component (A) [(B) / (A)] is 3. It can be seen that by applying an external preparation of 5 or less, the effect of suppressing adhesion is higher than that of Comparative Examples 1 to 10.
Further, as compared with Reference Examples 1 to 4, the external preparations of Examples 1 to 22 contain the component (B), and therefore have a better usability (feel).

Examples 23-26
Except for the preparation of the external preparations shown in Formulation Examples 1 to 4 below and the application of 2 mg / cm ² of each external preparation to the white artificial leather, the evaluation was carried out in the same manner as the above-mentioned evaluation method for the effect of suppressing the adhesion of atmospheric harmful substances. went. The results are shown in Table 7.
In addition, each notation in the prescription example is as follows.
* 1: "STR-100C-LF" manufactured by Sakai Chemical Industry Co., Ltd.
* 2: "MICRO ZINC OXIDE MZ-504R3M" manufactured by TAYCA CORPORATION
* 3: "Esthetic Mall N-01" manufactured by Nisshin Oillio Group Co., Ltd.
* 4: "Pearl Dream EX" manufactured by NOF CORPORATION
* 5: "Nikkor Squalene" manufactured by Nippon Surfant Industry Co., Ltd.
* 6: "KF-96A-10CS" manufactured by Shin-Etsu Chemical Co., Ltd.
* 7: "Sphingolipid E" manufactured by Kao Corporation
* 8: "KF-6015" manufactured by Shin-Etsu Chemical Co., Ltd.
* 9: "KF-96L-2CS" manufactured by Shin-Etsu Chemical Co., Ltd.
* 10: "Tospearl 145A" manufactured by Momentive Performance Materials Japan LLC
* 11: "SI-Talc JA-46R" manufactured by Miyoshi Kasei Co., Ltd.
* 12: "Exepearl TGO" manufactured by Kao Corporation
* 13: "KF-96A-6CS" manufactured by Shin-Etsu Chemical Co., Ltd.

Formulation Example 1 (W / O type external preparation, mass ratio [(C1) / (A)] = 0.12, mass ratio [(B) / (A)] = 0.35)
(Ingredients (amount))
Stearic acid-treated titanium oxide (component (A1)) * 1 7 parts Silicone-treated zinc oxide (component (A3)) * 2 19 parts Neopentyl glycol dicaprate (component (C1)) * 3 3 parts Liquid isoparaffin (component (B)) )) * 4 6 parts Squalane (component (B)) * 5 3 parts N- (hexadecyloxyhydroxypropyl) -N-hydroxyethylhexadecanamid * 7 1.5 parts Polyoxyethylene / methylpolysiloxane co-weight Combined (HLB: 4.5) * 8 1.4 parts Dodecamethylpentasiloxane (25 ° C kinematic viscosity: 2 mm ² / s) (Component (D)) * 9 40.1 parts Methylsiloxane reticulated polymer * 10 1 part Silicone coated talc * 11 1.9 parts Glycerin (86%) 1 part
Purified water balance
100 copies in total

Formulation Example 2 (W / O type external preparation, mass ratio [(C1) / (A)] = 0.31, mass ratio [(B) / (A)] = 0.35, mass ratio [(C2) / (A)] = 0.04)
(Ingredients (amount))
Stearic acid-treated titanium oxide (component (A1)) * 1 7 parts Silicone-treated zinc oxide (component (A3)) * 2 19 parts Neopentyl glycol dicaprate (component (C1)) * 3 3 parts Tri2-ethylhexanoic acid Glyceryl (component (C1)) * 12 5 parts Liquid isoparaffin (component (B)) * 4 5 parts Squalane (component (B)) * 5 4 parts Dimethylpolysiloxane (25 ° C kinematic viscosity: 10 mm ² / s) (component (C2)) * 6 1 part N- (hexadecyloxyhydroxypropyl) -N-hydroxyethylhexadecanamid * 7 1.5 parts polyoxyethylene / methylpolysiloxane copolymer (HLB: 4.5) * 8 1.4 parts Dodecamethylpentasiloxane (25 ° C kinematic viscosity: 2 mm ² / s) (Component (D)) * 9 35.1 parts Methylsiloxane reticulated polymer * 10 3 parts Silicone-coated talc * 11 1.9 parts Glycerin (86%) 1 copy
Purified water balance
100 copies in total

Formulation Example 3 (W / O type external preparation) (mass ratio [(C1) / (A)] = 0.12, mass ratio [(B) / (A)] = 0.35, mass ratio [(C2)) / (A)] = 0.23)
(Ingredients (amount))
Stearic acid-treated titanium oxide (component (A1)) * 1 7 parts Silicone-treated zinc oxide (component (A3)) * 2 19 parts Neopentyl glycol dicaprate (component (C1)) * 3 3 parts Liquid isoparaffin (component (B)) )) * 4 7 parts squalane (component (B)) * 5 2 parts dimethylpolysiloxane (25 ° C kinematic viscosity: 10 mm ² / s) (component (C2)) * 6 1 part dimethylpolysiloxane (25 ° C kinematic viscosity: 6 mm ² / s) (Component (C2)) * 13 5 parts N- (hexadecyloxyhydroxypropyl) -N-hydroxyethylhexadecanamid * 7 1.5 parts Polyoxyethylene / methylpolysiloxane copolymer ( HLB: 4.5) * 8 1.4 parts Dodecamethylpentasiloxane (25 ° C kinematic viscosity: 2 mm ² / s) (Component (D)) * 9 35.1 parts Glycerin (86%) 1 part
Purified water balance
100 copies in total

Formulation Example 4 (W / O type external preparation, mass ratio [(B) / (A)] = 0.41, mass ratio [(C2) / (A)] = 0.14)
(Ingredients (amount))
Stearic acid-treated titanium oxide (component (A1)) * 1 10 parts Silicone-treated zinc oxide (component (A3)) * 2 19 parts Liquid isoparaffin (component (B)) * 4 10 parts Squalane (component (B)) * 5 2 parts dimethylpolysiloxane (25 ° C kinematic viscosity: 10 mm ² / s) (component (C2)) * 6 1 part dimethylpolysiloxane (25 ° C kinematic viscosity: 6 mm ² / s) (component (C2)) * 13 3 parts N- (hexadecyloxyhydroxypropyl) -N-hydroxyethylhexadecanamid * 7 1.5 parts Polyoxyethylene / methylpolysiloxane copolymer (HLB: 4.5) * 8 1.4 parts Dodecamethylpenta Siloxane (25 ° C. kinematic viscosity: 2 mm ² / s) (Component (D)) * 9 35.1 parts Glycerin (86%) 1 part
Purified water balance
100 copies in total

From Table 7, it can be seen that Examples 23 to 26 have an adhesion suppressing effect by applying the external preparations shown in Formulation Examples 1 to 4.
Further, as compared with Reference Examples 1 to 4, the external preparations used in Examples 23 to 26 contain the component (B), and therefore have a good usability (feel).

Since the adhesion suppressing method of the present invention has a high effect of suppressing the adhesion of air harmful substances, it is particularly useful as a method of suppressing the adhesion of air harmful substances to the skin.

1: Sample to be evaluated 2: Support 3: Net sieve 4: Air toxic substances for evaluation 5: Blower

Claims (13)

It is a method of suppressing the adhesion of atmospheric harmful substances by applying an external preparation to the skin to suppress the adhesion of atmospheric harmful substances to the skin.
The external preparation contains the following component (A) and component (B), and the mass ratio of the content of the component (B) to the content of the component (A) in the external preparation [(B) / (A) ] Is 3.5 or less, a method for suppressing adhesion of air harmful substances.
Component (A): Hydrophobicized metal oxide having an average primary particle diameter d _A of 800 nm or less Component (B): Non-volatile hydrocarbon oil The method for suppressing adhesion of atmospheric harmful substances according to claim 1, wherein the metal oxide of the component (A) is at least one selected from titanium oxide and zinc oxide. The method for suppressing adhesion of air harmful substances according to claim 1 or 2, wherein the amount of the component (A) applied to the skin is 0.03 mg / cm ² or more. The method for suppressing adhesion of air harmful substances according to any one of claims 1 to 3, wherein the content of the component (A) in the external preparation is 1% by mass or more and 40% by mass or less. The method for suppressing adhesion of air harmful substances according to any one of claims 1 to 4, wherein the average primary particle diameter d _{A of the} component (A) is 5 nm or more. The method for suppressing adhesion of air harmful substances according to any one of claims 3 to 5, wherein the amount of the component (A) applied to the skin is 0.8 mg / cm ² or less. The method for suppressing adhesion of air harmful substances according to any one of claims 1 to 6, wherein the component (A) is one or more selected from the following component (A1), component (A2) and component (A3).
Component (A1): an average primary particle diameter d _A is 800nm or less fatty acid treated metal oxide component (A2): an alkyl alkoxy silane treated metal oxide component having an average primary particle diameter d _A is 800nm or less ( A3): Silicone-treated metal oxide having an average primary particle diameter d _A of 800 nm or less Mass ratio of the content of the component (B) to the total content of the component (A1), the component (A2) and the component (A3) in the external preparation [(B) / [(A1) + (A2) + (A3)) ]] Is 3.5 or less, the method for suppressing adhesion of air harmful substances according to claim 7. The method for suppressing adhesion of air harmful substances according to claim 7 or 8, wherein the total amount of the component (A1), the component (A2) and the component (A3) applied to the skin is 0.03 mg / cm ² or more. Adhesion of an air harmful substance according to any one of claims 7 to 9, wherein the total content of the component (A1), the component (A2) and the component (A3) in the external preparation is 1% by mass or more and 40% by mass or less. Suppression method. The adhesion of an air harmful substance according to any one of claims 7 to 10, wherein the metal oxide of the component (A1), the component (A2) and the component (A3) is at least one selected from titanium oxide and zinc oxide. Suppression method. The method for suppressing adhesion of air harmful substances according to any one of claims 7 to 11, wherein the average primary particle diameter d _{A of the} component (A1), the component (A2) and the component (A3) is 5 nm or more. The method for suppressing adhesion of air harmful substances according to any one of claims 9 to 12, wherein the total amount of the component (A1), the component (A2) and the component (A3) applied to the skin is 0.8 mg / cm ² or less. ..