Air hazardous substance adhesion inhibiting method

Abstract

To provide an air hazardous substance adhesion inhibiting method that enables a high adhesion inhibiting effect on air hazardous substances and achieves excellence in the feel after its application to the skin, particularly in the feeling of dryness and smoothness.SOLUTION: Provided is a an air hazardous substance adhesion inhibiting method which applies an external preparation to the skin to thereby inhibit air hazardous substances from adhering to the skin, the external preparation containing the following component (A) and component (B), and the mass ratio between the content of the component (A) and the content of the component (B) being 0.30 or more and 5.0 or less. Component (A): a metal oxide having an average primary particle diameter dA of 800 nm or less. Component (B): non-disintegratable particles having an average primary particle diameter DB of 1 μm or more and 10 μm or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for suppressing the adhesion of harmful substances in the atmosphere.

Background Art

[0002] In recent years, harmful substances floating in the atmosphere such as pollen of Cryptomeria japonica, Chamaecyparis obtusa, etc., air pollutants such as dust and powder, and yellow sand (hereinafter also referred to as "atmospheric harmful substances") have become a problem because they cause various health damages to the human body. Among the atmospheric harmful substances, particulate matter with a diameter of 2.5 μm or less called PM2.5 has components composed of carbon components, sulfates, nitrates, ammonium salts, etc., and it is known that PM2.5 and yellow sand cause diseases of the circulatory system and respiratory system by inhalation. In addition, it has been pointed out that PM2.5, pollen, and yellow sand cause skin problems by adhering to or penetrating the skin. For example, Non-Patent Document 1 has an academic report on the damage of PM2.5 to the skin. Therefore, there is a strong demand for cosmetics that protect the skin from atmospheric harmful substances. For example, Patent Document 1 describes a skin care cosmetic containing a specific amount of magnesium aluminometasilicate and a specific amount of an ultraviolet ray protecting agent as a skin care cosmetic that protects the skin from external stimuli such as air pollutants.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Non-Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the technology of Patent Document 1, magnesium aluminum metasilicate adsorbs air pollutants by its adsorption ability so that they do not reach the skin, and even if acidic substances adhere, they can be neutralized by the pH buffering ability, and it is described that skin damage caused by these external stimuli can be reduced. Also, it is described that the ultraviolet ray protectant can effectively protect the skin from ultraviolet rays. Such technology can reduce the influence of air pollutants on the skin, but it does not prevent the adhesion of air pollutants to the skin and there is room for improvement. Further, when inorganic powders such as titanium oxide and zinc oxide are blended into an external preparation as an ultraviolet ray protectant, the feel after applying the external preparation to the skin, particularly the smoothness, may be inferior. Therefore, a good feel after application is also required. An object of the present invention is to provide a method for suppressing the adhesion of harmful substances in the air, which has a high adhesion suppressing effect on harmful substances in the air and is excellent in the feel after application to the skin, particularly the smoothness.

Means for Solving the Problems

[0006] The present inventors have noted that, rather than adsorbing air pollutants as shown in Patent Document 1, by applying an external preparation containing a metal oxide having an average primary particle diameter in a predetermined range and non-collapsible particles having an average particle diameter in a predetermined range at a predetermined mass ratio to the skin to form nano-sized irregularities on the skin surface, it is possible to suppress the adhesion of harmful substances in the air to the skin without deteriorating the feel after application to the skin, and have found that the above problems can be solved. That is, the present invention provides the following [1] and [2]. [1] A method for suppressing the adhesion of harmful substances in the air to the skin by applying an external preparation to the skin, wherein the external preparation contains the following component (A) and component (B), and the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.30 or more and 5.0 or less. A method for suppressing the adhesion of air pollutants. Component (A): The average primary particle diameter d A is a metal oxide of 800 nm or less Component (B): Average particle diameter D B Non-disintegrating particles with an average particle diameter D of 1 μm or more and 10 μm or less [2] The following components (A) and (B): Component (A): Average primary particle diameter d A Metal oxide with an average primary particle diameter d of 800 nm or less Component (B): Average particle diameter D B Non-disintegrating particles with an average particle diameter D of 1 μm or more and 10 μm or less containing Component (B) is a composite particle (B1) formed by coating at least a part of the surface of core particles (b1-1) with inorganic fine particles (b1-2), The core particles (b1-1) are one or more selected from poly(meth)acrylate particles and silica particles, The surface of the core particles (b1-1) is coated with one or more binders (c) selected from homopolymers or copolymers of poly(N-vinylpyrrolidone), poly(meth)acrylamide, and oxazolines, The inorganic fine particles (b1-2) are one or more selected from titanium oxide and zinc oxide surface-treated with one or more selected from silica, hydrous silica, and aluminum hydroxide, An external preparation in which the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) is 0.30 or more and 5.0 or less.

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a method for suppressing the adhesion of harmful substances in the atmosphere, which has a high adhesion suppression effect on harmful substances in the atmosphere and is excellent in the feeling after application to the skin, particularly in the smooth feeling.

Brief Description of the Drawings

[0008]

Figure 1

Modes for Carrying Out the Invention

[0009] [Method for Suppressing Adhesion of Harmful Substances in the Atmosphere] The method for suppressing the adhesion of atmospheric harmful substances of the present invention is a method for suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin, wherein the external preparation contains the following component (A) and component (B), and the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.30 or more and 5.0 or less. Component (A): Metal oxide having an average primary particle diameter d A of 800 nm or less Component (B): Non-collapsible particles having an average particle diameter D B of 1 μm or more and 10 μm or less In the present invention, the "atmospheric harmful substances" include pollen such as cedar and cypress; soot, dust, automobile exhaust gas, harmful air pollutants such as sulfur oxides, dust, nitrogen oxides, benzene, trichloroethylene, tetrachloroethylene, etc., and volatile organic compounds (VOCs), etc. Particles; harmful substances floating in the atmosphere such as yellow sand (including PM2.5).

[0010] The adhesion suppression method of the present invention has a high adhesion suppression effect on atmospheric harmful substances, especially particulate atmospheric harmful substances, and is excellent in the feel (smooth feeling) after application to the skin. The reason is not clear, but it is considered as follows. In the present invention, by applying a metal oxide having an average primary particle diameter within a predetermined range to the skin, nano-sized irregularities are formed on the skin surface, so that the contact area when the atmospheric harmful substances come into contact with the metal oxide can be reduced, and it is considered that the adhesion of the atmospheric harmful substances can be effectively suppressed. In addition, the external preparation used in the present invention contains the metal oxide and non-collapsible particles having an average particle diameter within a predetermined range at a specific mass ratio. Since the non-collapsible particles applied on the skin surface are difficult to collapse even when rubbed and can maintain a particle diameter of a predetermined size, it is considered that a good feel (smooth feeling) is exhibited. In the following description, the adhesion suppression effect on the atmospheric harmful substances in the present invention is simply referred to as the "adhesion suppression effect", and the feel (smooth feeling) in the present invention is simply referred to as the "feel".

[0011] <External preparation> 〔Component (A)〕 Component (A) is a metal oxide having an average primary particle diameter d A of 800 nm or less. The average primary particle diameter d of Component (A) A is 800 nm or less, preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, even more preferably 80 nm or less, and even more preferably 50 nm or less, from the viewpoint of improving the adhesion suppression effect. From the viewpoint of versatility, it is preferably 1 nm or more, more preferably 5 nm or more, and still more preferably 10 nm or more. More specifically, the average primary particle diameter d A is preferably 1 to 800 nm, more preferably 1 to 500 nm, still more preferably 1 to 300 nm, even more preferably 1 to 200 nm, even more preferably 1 to 80 nm, even more preferably 5 to 80 nm, even more preferably 5 to 50 nm, and even more preferably 10 to 50 nm, from the viewpoints of improving the adhesion suppression effect and versatility. The average primary particle diameter d in the present invention A can be determined from an observation image by a transmission electron microscope (TEM). Specifically, it is determined by observing at an observation magnification of 50,000 times by TEM, measuring the maximum minor axis of 300 primary particles in the observation image, and calculating the number average value thereof. Here, the maximum minor axis means the minor axis having the maximum length among the minor axes orthogonal to the major axis when Component (A) has a shape other than a plate shape. When Component (A) has a plate shape, it is determined by measuring the thickness of 300 primary particles in the observation image observed under the same conditions as above and calculating the number average value thereof. Specifically, it is measured by the method described in the examples.

[0012] Component (A) is not particularly limited as long as it is commonly used in external preparations such as cosmetics. Specifically, examples include titanium oxide, zinc oxide, cerium oxide, aluminum oxide (alumina), magnesium oxide, calcium oxide, zirconium oxide, iron oxide, chromium oxide, etc. Among these, from the viewpoint of imparting ultraviolet ray protection ability, it is preferably at least one selected from titanium oxide, zinc oxide, and cerium oxide, more preferably at least one selected from titanium oxide and zinc oxide, and even more preferably titanium oxide from the viewpoint of further improving the adhesion suppression effect. When 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.

[0013] Examples of the shape of component (A) include spherical, spindle-shaped, plate-shaped, needle-shaped, etc. Among these, from the viewpoint of improving the adhesion suppression effect, spherical, spindle-shaped, and plate-shaped are preferred. When component (A) is titanium oxide, from the viewpoint of improving the adhesion suppression effect, it is preferably spindle-shaped. When component (A) is zinc oxide, from the viewpoint of improving the adhesion suppression effect, it is preferably spherical or plate-shaped. The form of existence of component (A) is such that the average primary particle diameter d A If it satisfies the above-mentioned range, it may be in the form of primary particles, or may be in a form containing aggregates (secondary particles) in which primary particles are aggregated.

[0014] Component (A) may be untreated on its surface or may be treated on its surface. However, from the viewpoint of enhancing the dispersibility of component (A) in the external preparation and improving the adhesion suppression effect, those treated to modify their surfaces are preferred. Examples of the surface treatment include hydrophobic treatment and hydrophilic treatment, but from the same viewpoint as above, hydrophobic treatment is preferred.

[0015] Examples of the hydrophobization treatment include silicone treatment; alkylalkoxysilane treatment; fatty acid treatment; treatment with a fluorine-containing compound such as perfluoroalkyl phosphate ester, perfluoroalcohol, or perfluoroalkylalkoxysilane; amino acid treatment such as N-acylglutamic acid; and alkyl phosphate ester treatment. These surface treatments may be used alone or in combination of two or more. Among these, from the viewpoint of enhancing the dispersibility of component (A) in the external preparation and improving the adhesion inhibitory effect, one or more selected from silicone treatment, alkylalkoxysilane treatment, and fatty acid treatment are preferable.

[0016] Examples of the surface treatment agent used for the silicone treatment include various silicone oils such as methylpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, dodecamethylcyclohexasiloxane, tetradecamethylhexasiloxane, dimethylsiloxane / methyl(polyoxyethylene)siloxane / methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane / methyl(polyoxyethylene)siloxane copolymer, dimethylsiloxane / methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane / methylcetoxysiloxane copolymer, dimethylsiloxane / methylstearoxysiloxane copolymer, and (alkyl acrylate / dimethicone) copolymer. Among these, from the viewpoint of enhancing the dispersibility of component (A) in the external preparation and improving the adhesion inhibitory effect, methylhydrogenpolysiloxane and dimethylpolysiloxane are preferable.

[0017] As the surface treatment agent used for the alkylalkoxysilane treatment, from the viewpoint of enhancing the dispersibility of component (A) in the external preparation and improving the adhesion inhibitory effect, those having a linear or branched alkyl group with 6 to 20 carbon atoms are preferable, and octyltriethoxysilane and octyltrimethoxysilane are more preferable. Examples of the surface treatment agent used for the fatty acid treatment include linear or branched fatty acids having 12 to 22 carbon atoms. Among them, from the viewpoint of enhancing the dispersibility of component (A) in the external preparation and improving the adhesion inhibition effect, linear or branched higher fatty acids having 14 to 22 carbon atoms are preferable, linear or branched higher fatty acids having 16 to 20 carbon atoms are more preferable, and stearic acid and isostearic acid are even more preferable.

[0018] The above-mentioned surface treatment agent can be used alone or in combination of two or more. From the viewpoint of enhancing the dispersibility of component (A) in the external preparation and improving the adhesion inhibition effect, the treatment amount of the hydrophobization treatment in component (A) is preferably 0.1% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, based on component (A). In the case where component (A) has its surface hydrophobized, the mass, coating amount, and average primary particle diameter d of component (A) A mean the mass, coating amount, and average primary particle diameter d including the surface treatment agent. A

[0019] In the case where component (A) is titanium oxide, the content of TiO2 in the titanium oxide is preferably 60% by mass or more, more preferably 70% by mass or more, and preferably 100% by mass or less, from the viewpoint of improving the adhesion inhibition effect. In the case where component (A) is zinc oxide, the content of ZnO in the zinc oxide is preferably 60% by mass or more, more preferably 70% by mass or more, and preferably 100% by mass or less, from the viewpoint of improving the adhesion inhibition effect.

[0020] ​Component (A) is preferably at least one selected from hydrophobized titanium oxide and hydrophobized zinc oxide from the viewpoint of enhancing the dispersibility of component (A) in the external preparation and improving the adhesion suppression effect. More preferably, it is at least one selected from silicone-treated titanium oxide, silicone-treated zinc oxide, alkylalkoxysilane-treated titanium oxide, alkylalkoxysilane-treated zinc oxide, fatty acid-treated titanium oxide, and fatty acid-treated zinc oxide. Even more preferably, it is at least one selected from fatty acid-treated titanium oxide and alkylalkoxysilane-treated zinc oxide.

[0021] Commercially available products of component (A) include "JR-800S" (silicone-treated titanium oxide), "MPY-70M" (silicone-treated titanium oxide), "MZ-504R3M" (silicone-treated zinc oxide), "MT-600KS" (silicone-treated zinc oxide), "MT-100TV" (stearic acid-treated titanium oxide), "MT-100Z" (stearic acid-treated titanium oxide) manufactured by Teika Co., Ltd.; "MPT-171" (stearic acid-treated titanium oxide) manufactured by Ishihara Sangyo Co., Ltd.; "D-FZN" (silicone-treated zinc oxide) of Daito Kasei Kogyo Co., Ltd.; "STR-100A-LP" (silicone-treated titanium oxide), "FINEX-50-LPTM" (silicone-treated zinc oxide), "FINEX-30-OTS" (octyltriethoxysilane-treated zinc oxide), "STR-100C-LF" (stearic acid-treated titanium oxide), "STR-100W-OTS" (octyltriethoxysilane-treated titanium oxide), "FINEX-50-OTS" (octyltriethoxysilane-treated zinc oxide), etc. manufactured by Sakai Chemical Industry Co., Ltd.

[0022] [Component (B)] Component (B) is a non-disintegrating particle having an average particle diameter D B of 1 μm or more and 10 μm or less. In the present invention, the "non-disintegrating particles" are particles that are difficult to disintegrate when loaded and rubbed with a predetermined load. Specifically, in the test method for confirming the disintegrating property described in the examples, when reciprocally rubbed 10 times using a surface property measuring machine, Tribogear TYPE:14 (manufactured by Shin-Toyo Kagaku Co., Ltd.), the particle size ratio before and after rubbing represented by the following formula (I) is 50% or more. Particle size ratio before and after rubbing (%) = (average particle size D B ’ after rubbing / average particle size D B ) × 100 (I) The average particle size D B is 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, from the viewpoint of making the feel good after application to the skin, and is 10 μm or less, preferably 9 μm or less, more preferably 8 μm or less, from the viewpoint of improving the adhesion suppression effect. The specific range of the average particle size D B is preferably 1 to 9 μm, more preferably 2 to 9 μm, still more preferably 3 to 9 μm, and even more preferably 3 to 8 μm, from the viewpoint of improving the adhesion suppression effect and the viewpoint of making the feel good after application to the skin. The average particle size D B is measured by the method described in the examples.

[0023] Component (B) is preferably at least one selected from inorganic particles and organic particles. Examples of the inorganic particles include particles containing one or more inorganic substances selected from silicon-containing compounds such as silicon dioxide (silica), silicon nitride, silicon carbide, aluminum silicate, magnesium silicate, and calcium silicate; metal oxides such as titanium oxide, zinc oxide, aluminum oxide (alumina), magnesium oxide, calcium oxide, zirconium oxide, iron oxide, cerium oxide, and chromium oxide; metal salts such as magnesium carbonate, calcium carbonate, barium sulfate, barium carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate, lithium carbonate, calcium phosphate, titanium phosphate, silver chloride, and silver bromide; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; metals such as titanium, iron, chromium, nickel, gold, silver, platinum, copper, lead, and zinc, and alloys of these metals; diamond; boron-containing compounds such as boron nitride and boron carbide; metal carbides such as titanium carbide, tantalum carbide, and zirconium carbide; metal nitrides such as aluminum nitride and titanium nitride; and mixtures such as magnesium aluminometasilicate (magnesium aluminum silicate). These inorganic particles can be used alone or in combination of two or more kinds. The inorganic particles may or may not be surface-treated. The content of the inorganic substance in the inorganic particles is preferably 60% by mass or more, more preferably 70% by mass or more, and preferably 100% by mass or less. When the inorganic particles are surface-treated on their surfaces, the mass and average particle diameter D B of the inorganic particles mean the mass and average particle diameter D B including the surface treatment agent.

[0024] When component (B) is inorganic particles, from the viewpoint of improving the feel after application to the skin, component (B) is preferably particles containing at least one selected from silicon-containing compounds, metal oxides, metal salts, metal nitrides, and metal carbides, more preferably particles containing at least one selected from silicon-containing compounds and metal oxides, still more preferably particles containing at least one selected from silica, calcium silicate, titanium oxide, zinc oxide, and magnesium aluminometasilicate, even more preferably particles containing at least one selected from silica and calcium silicate, and even more preferably silica particles containing silica.

[0025] As the organic particles, from the viewpoint of improving the feel after application to the skin, those preferably containing at least one selected from natural polymers, semi-synthetic polymers, and synthetic polymers are mentioned. Specifically, polysaccharides such as cellulose, starch, chitosan and their derivatives; addition polymerization type polymers such as polyolefins such as polystyrene, poly(meth)acrylate, polyvinyl acetate, polyethylene, polypropylene; condensation type polymers such as polyesters such as polyamide, polylactic acid, polyurethane; polymer particles such as silicone powder. The polymer particles may be polymer particles having a crosslinked structure or polymer particles not having a crosslinked structure. Among these, from the same viewpoint as above, preferably particles containing at least one selected from polystyrene, poly(meth)acrylate, polyamide, polylactic acid, silicone powder, cellulose, cellulose derivatives, starch, and starch derivatives, more preferably particles containing at least one selected from polystyrene, poly(meth)acrylate, cellulose, and cellulose derivatives, and from the viewpoint of versatility, still more preferably poly(meth)acrylate particles containing poly(meth)acrylate. In this specification, “(meth)acrylate” means at least one selected from acrylate and methacrylate.

[0026] Examples of the poly(meth)acrylate include homopolymers or copolymers of (meth)acrylic monomers. Examples of the (meth)acrylic monomers include (meth)acrylic acid; (meth)acrylates such as (meth)acrylates having a hydrocarbon group derived from an aliphatic alcohol having 1 to 18 carbon atoms. One kind of (meth)acrylic monomer can be used alone or two or more kinds can be used. In this specification, "(meth)acrylic acid" means one or more selected from acrylic acid and methacrylic acid. In addition to (meth)acrylic acid and (meth)acrylate, the poly(meth)acrylate may be a poly(meth)acrylate having a crosslinked structure obtained by further copolymerizing a polyfunctional (meth)acrylate such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, or hexanediol di(meth)acrylate.

[0027] Specific examples of the poly(meth)acrylate include polymethyl methacrylate and acrylic acid / methyl acrylate copolymer. Examples of the (poly)acrylate having a crosslinked structure include butyl acrylate / ethylene glycol dimethacrylate / sodium methacrylate copolymer and lauryl methacrylate / ethylene glycol dimethacrylate / sodium methacrylate copolymer. Examples of the poly(meth)acrylate particles include particles described as "crosslinked (meth)acrylate resin particles" in JP-A-2006-8980 and the Gantperl series of Aica Kogyo Co., Ltd.

[0028] The form of component (B) may be in the form of primary particles or in a form containing aggregates (secondary particles) in which the primary particles are aggregated. The form may also include aggregates (secondary particles) in which the primary particles are aggregated. Examples of the particle structure of component (B) include non-porous particles, porous particles, and composite particles composed of core particles and fine particles covering the surface of the core particles. In the present invention, "non-porous particles" means particles having a specific surface area of 50 m 2 / g or less, and "porous particles" means particles having a specific surface area of 50 m2 It means particles that are / g super. The specific surface area can be measured in accordance with JIS Z 8830:2013. From the viewpoint of improving the adhesion suppression effect and the viewpoint of making the feel good after application to the skin, component (B) is preferably at least one selected from composite particles (B1) obtained by coating at least a part of the surface of core particles (b1-1) with inorganic fine particles (b1-2), and porous particles (B2).

[0029] (Composite particles (B1)) Composite particles (B1) are particles obtained by coating at least a part of the surface of core particles (b1-1) with inorganic fine particles (b1-2). The core particles (b1-1) may be either non-porous particles or porous particles. The average particle diameter of the core particles (b1-1) is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, and preferably 10 μm or less, more preferably 9 μm or less, still more preferably 8 μm or less. The average particle diameter of the core particles (b1-1) can be measured by the method described in the examples. Any of the aforementioned organic particles and inorganic particles can be used as the core particles (b1-1). Among them, from the viewpoint of improving the adhesion suppression effect and making the feel good after application to the skin, at least one selected from poly(meth)acrylate particles and silica particles is preferable. Commercially available products of the core particles (b1-1) include particles described as "crosslinked (meth)acrylate resin particles" in JP-A-2006-8980, poly(meth)acrylate particles such as the Ganz Pearl series of Aika Kogyo Co., Ltd.; silica particles such as "NP-100" of AGC Si-Tech Co., Ltd., and the like.

[0030] From the perspective of the productivity of the composite particles, the core particle (b1-1) preferably has its surface coated with a binder (c). As a result, the composite particle (B1) can have a structure in which the inorganic fine particle (b1-2) is adsorbed to the core particle (b1-1) via the binder (c). The binder (c) preferably has a functional group capable of interacting with the surface hydroxyl group of the inorganic fine particle (b1-2), and more preferably a polymer having an amide bond or an amide group in the side chain. By using a polymer having an amide bond or an amide group in the side chain as the binder (c), a structure in which the inorganic fine particle (b1-2) is adsorbed to the surface of the core particle (b1-1) via a hydrogen bond can be formed. From the same perspective as described above, the binder (c) is preferably at least one selected from vinyl polymers obtained by addition polymerization of vinyl monomers having an amide bond or an amide group, and homopolymers or copolymers of oxazolines, more preferably at least one selected from poly(N-vinylpyrrolidone), poly(meth)acrylamide, and homopolymers or copolymers of oxazolines, and still more preferably at least one selected from poly(N-vinylpyrrolidone) and homopolymers or copolymers of oxazolines. As used herein, “(meth)acrylamide” means at least one selected from acrylamide and methacrylamide.

[0031] Examples of the vinyl monomer constituting the vinyl polymer include N-vinyl compounds such as N-vinylpyrrolidone, N-vinylacetamide, N-vinylformamide, and N-vinylcaprolactam; (meth)acrylamide-based monomers such as (meth)methacrylamide and N-alkyl(meth)acrylamide. Among these, at least one selected from poly(N-vinylpyrrolidone) and poly(meth)acrylamide is preferred, and poly(N-vinylpyrrolidone) is more preferred. Examples of the poly(N-vinylpyrrolidone) include N-vinylpyrrolidone homopolymer; copolymers of N-vinylpyrrolidone and other monomers such as N-vinylpyrrolidone / vinyl acetate copolymer and N-vinylpyrrolidone / vinyl acetate / vinyl propionate copolymer. Examples of commercially available poly(N-vinylpyrrolidone) include PVP K-90 (manufactured by Ashland Specialty Ingredients), PVP K-25, K-30, K-90 (above, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., trade name); PVA-6450, Acorn M (above, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name); Kolidon VA64 (trade name, vinylpyrrolidone / vinyl acetate copolymer, manufactured by BASF Japan Ltd.), and the like. Examples of the poly(meth)acrylamide include homopolymers of (meth)acrylic monomers; copolymers of (meth)acrylic monomers and other monomers such as (meth)acrylate and (meth)acrylic acid, and salts thereof. Examples of the poly(meth)acrylamide include, for example, the N-tert-butylacrylamide / N,N-dimethylacrylamide / N-[3-(dimethylamino)propyl]acrylamide / methoxypolyethylene glycol methacrylate copolymer described in JP-A-2005-162700.

[0032] As the homopolymer or copolymer of oxazolines, from the viewpoint of providing a good feel after application to the skin, a copolymer of oxazolines is preferred, and an oxazoline-modified silicone having a poly(N-acylalkyleneimine) chain formed by ring-opening polymerization of a cyclic imino ether in the side chain is more preferred. Examples of the oxazoline-modified silicone include poly(N-acylalkyleneimine) / organopolysiloxane copolymers such as poly(N-formylethyleneimine) organopolysiloxane copolymer, poly(N-acetylethyleneimine) organopolysiloxane copolymer, and poly(N-propionylethyleneimine) / organopolysiloxane copolymer. Among them, poly(N-propionylethyleneimine) / methylpolysiloxane copolymer (POLYSILICONE-9) is preferred. The poly(N-acylalkyleneimine) / organopolysiloxane copolymer can be obtained, for example, by reacting a poly(N-acylalkyleneimine) which is a ring-opening polymer of a cyclic imino ether with an organopolysiloxane forming a main chain segment. As POLYSILICONE-9, for example, those described in JP-A-2016-6029 can be used.

[0033] The average primary particle diameter of the inorganic fine particles (b1-2) is preferably 1 nm or more, more preferably 2 nm or more, still more preferably 3 nm or more, and is preferably 30 nm or less, more preferably 25 nm or less, still more preferably 20 nm or less. The average primary particle diameter of the inorganic fine particles (b1-2) can be measured by the method described in the examples. Examples of the inorganic fine particles (b1-2) include the aforementioned inorganic particles. When a metal oxide is used as the inorganic fine particles (b1-2), the metal oxide preferably has a surface hydrophilized. Examples of the hydrophilization treatment include treatment with silica, hydrous silica; hydrous oxides, oxides or hydroxides of metals such as aluminum and zirconia; water-soluble polymers such as polyacrylic acid, alginic acid or salts thereof. Among these, one or more selected from silica treatment, hydrous silica treatment and aluminum hydroxide treatment are preferable. The treatment amount of the hydrophilization treatment in the inorganic fine particles (b1-2) is preferably 0.1% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, based on the inorganic fine particles (b1-2).

[0034] The inorganic fine particles (b1-2) are preferably at least one selected from silicon-containing compounds and metal oxides from the viewpoint of improving the adhesion suppression effect and making the feel good after application to the skin. More preferably, they are at least one selected from hydrophilic silica and hydrophilized metal oxides. Even more preferably, they are hydrophilic silica, and at least one selected from titanium oxide and zinc oxide surface-treated with at least one selected from silica, hydrous silica, and aluminum hydroxide. Even more preferably, they are at least one selected from titanium oxide and zinc oxide surface-treated with at least one selected from silica, hydrous silica, and aluminum hydroxide. Examples of commercially available products of the inorganic fine particles (b1-2) include "MT-100WP" (hydrous silica-treated fine particle titanium oxide) manufactured by Teika Co., Ltd., "STR-100W" (hydrous silica-treated fine particle titanium oxide), "STR-100C" (aluminum hydroxide-treated fine particle titanium oxide), "FINEX-33W" (hydrous silica-treated fine particle zinc oxide), and "AEROSIL200" (hydrophilic fine particle silica) manufactured by Evonik Corporation.

[0035] The composite particles (B1) are preferably produced by mixing the core particles (b1-1) and the inorganic fine particles (b1-2). Thereby, a structure in which at least a part of the surface of the core particles (b1-1) is coated with the inorganic fine particles (b1-2) can be formed by heteroaggregation of the core particles (b1-1) having a large average particle diameter and the inorganic fine particles (b1-2) having a small average primary particle diameter. There is no particular limitation on the mixing method, but examples include a method of adding the inorganic fine particles (b1-2) to a dispersion of the core particles (b1-1). The dispersion medium of the core particles (b1-1) is not particularly limited, and examples include lower alcohols such as ethanol; water and the like. When using particles whose surface is coated with the binder (c) as the core particles (b1-1), it is preferable to use particles obtained by previously mixing the particles constituting the core particles (b1-1) and the binder (c).

[0036] The blending amount of the binder (c) with respect to the core particles (b1-1) is preferably 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 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, from the viewpoint of the productivity of the composite particles. The blending amount of the inorganic fine particles (b1-2) with respect to the core particles (b1-1) is preferably 0.05% by mass or more, more preferably 0.15% by mass or more, still more preferably 0.25% by mass or more, and preferably 10% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, from the viewpoint of the productivity of the composite particles.

[0037] (porous particles (B2)) The porous particles (B2) are preferably those obtained by aggregating inorganic fine particles (b2) having an average primary particle diameter of 1 nm or more and 30 nm or less. Examples of the inorganic fine particles (b2) are the same as those of the aforementioned inorganic particles. Among them, from the viewpoint of improving the feel after application and the usability of the external preparation, particles containing at least one selected from silicon-containing compounds and metal oxides are preferable, and particles containing at least one selected from silica and titanium oxide are more preferable. The average primary particle diameter of the porous particles (B2) can be measured by the method described in the examples. Examples of commercially available products of the porous particles (B2) include "Sunsphere H-51" (porous silica particles) manufactured by AGC Si-Tech Co., Ltd.; "HCS Refle 50" (aggregate of silica and titanium oxide) manufactured by JGC Catalysts and Chemicals Ltd., etc.

[0038] In addition to the components (A) and (B), the external preparation may appropriately contain, within a range not impairing the object of the present invention, beauty components or medicinal components used according to the use of the external preparation, or components usually used in external preparations such as skin cosmetics. Examples of such components include, other than the components (A) and (B), oil agents, solvents, antioxidants, ultraviolet absorbers, surfactants, thickeners, emulsifiers, neutralizing agents, pH adjusters, bactericides, anti-inflammatory agents, preservatives, coloring agents, chelating agents, moisturizing agents, pearl agents, ceramides, antiperspirants, fragrances, etc.

[0039] [Manufacture of External Preparation] The external preparation used in the present invention can be manufactured by appropriately using known methods according to the dosage form of the external preparation. For example, a method of blending component (A), component (B), and, if necessary, the other components described above, and stirring and mixing them with a disper or the like can be mentioned. When the external preparation is a water-in-oil (W / O) type or oil-in-water (O / W) type described later, a method of preparing the aqueous phase and the oil phase respectively and then mixing the two can also be used. The content of each component and each mass ratio are as follows.

[0040] (Content of Component (A) in the External Preparation) The content of component (A) in the external preparation is preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more from the viewpoint of improving the adhesion inhibitory effect, and preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less from the viewpoints of making the feel good after application to the skin and economy. More specifically, the content of the component (A) is preferably 1 to 40% by mass, more preferably 1.5 to 20% by mass, still more preferably 1.5 to 10% by mass, and even more preferably 2 to 10% by mass from the viewpoints of improving the adhesion inhibitory effect, making the feel good after application to the skin, and making the usability good when using the external preparation.

[0041] (Content of Component (B) in the External Preparation) The content of component (B) in the external preparation is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more from the viewpoint of making the feel good after application to the skin, and preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less from the viewpoint of improving the adhesion inhibitory effect.

[0042] (Mass Ratio [(A) / (B)]) The mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.30 or more, preferably 0.32 or more, more preferably 0.35 or more, still more preferably 0.40 or more, even more preferably 0.60 or more, and even more preferably 0.80 or more from the viewpoint of improving the adhesion inhibitory effect, and is 5.0 or less, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.5 or less, even more preferably 3.0 or less, and even more preferably 2.5 or less from the viewpoint of making the feel after application to the skin good. More specifically, the mass ratio [(A) / (B)] is preferably 0.32 to 4.5, more preferably 0.35 to 4.0, still more preferably 0.40 to 3.5, even more preferably 0.60 to 3.0, and even more preferably 0.80 to 2.5 from the viewpoints of improving the adhesion inhibitory effect and making the feel after application to the skin good.

[0043] When the external preparation further contains an oil agent, the content of the oil agent in the external preparation is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 7% by mass or more from the viewpoints of improving the adhesion inhibitory effect and making the feel after application to the skin good, and is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.

[0044] Examples of the form of the external preparation used in the present invention include an aqueous type having an aqueous single phase as a dispersion medium, an oily type having an oily single phase as a dispersion medium, an oil-in-water type (hereinafter also referred to as "O / W type"), a water-in-oil type (hereinafter also referred to as "W / O type"), etc., and can be appropriately selected. In the present invention, the external preparation can be applied, for example, as an external preparation for application to the skin and hair. The external preparation is preferably a cosmetic, more preferably a skin cosmetic, from the viewpoint of the adhesion inhibitory effect. There is no particular limitation on the dosage form of the external preparation, and it can be any dosage form such as liquid, foamy, paste, cream, solid, etc.

[0045] 〔Coating method〕 In the present invention, as a method of applying the external preparation to the skin, it can be applied by a known method according to the usage form 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 attaching the external preparation to the skin surface by spraying or the like. When the external preparation is in a liquid, foam, paste, cream, or solid form, it can usually be applied as it is or applied by spraying or the like.

[0046] (Application amount of component (A)) The application amount of component (A) to the skin surface is preferably 0.01 mg / cm from the viewpoint of improving the adhesion inhibitory effect. 2 or more, more preferably 0.02 mg / cm 2 or more, still more preferably 0.03 mg / cm 2 or more, even more preferably 0.04 mg / cm 2 or more, and from the viewpoints of making the feeling after application to the skin good and economy, it is preferably 0.8 mg / cm 2 or less, more preferably 0.7 mg / cm 2 or less. More specifically, the application amount of component (A) to the skin surface is preferably 0.01 to 0.8 mg / cm from the viewpoint of improving the adhesion inhibitory effect, and from the viewpoints of making the feeling after application to the skin good and economy. 2 , more preferably 0.02 to 0.8 mg / cm 2 , still more preferably 0.03 to 0.8 mg / cm 2 , even more preferably 0.04 to 0.8 mg / cm 2 , even more preferably 0.04 to 0.7 mg / cm 2 is.

[0047] When the external preparation is of the W / O type, the application amount of component (A) to the skin surface is preferably 0.01 mg / cm from the viewpoint of improving the adhesion inhibitory effect. 2 or more, more preferably 0.02 mg / cm 2 or more, still more preferably 0.03 mg / cm 2 or more, even more preferably 0.04 mg / cm 2The above, and from the viewpoints of improving the usability and economy when applying to the skin, it is preferably 0.8 mg / cm 2 or less, more preferably 0.7 mg / cm 2 or less. More specifically, the application amount of component (A) to the skin surface is preferably 0.01 to 0.8 mg / cm from the viewpoint of improving the adhesion suppression effect, and from the viewpoints of improving the feel after application to the skin and economy. 2 More preferably 0.02 to 0.8 mg / cm 2 Even more preferably 0.03 to 0.8 mg / cm 2 Even more preferably 0.04 to 0.8 mg / cm 2 Even more preferably 0.04 to 0.7 mg / cm 2 That is.

[0048] When the external preparation is of the O / W type, the application amount of component (A) to the skin surface is preferably 0.01 mg / cm or more from the viewpoint of improving the adhesion suppression effect. 2 More preferably 0.02 mg / cm or more 2 Even more preferably 0.03 mg / cm or more 2 Even more preferably 0.04 mg / cm or more 2 And from the viewpoints of improving the feel after application to the skin and economy, it is preferably 0.8 mg / cm or less. 2 More preferably 0.7 mg / cm or less 2 Even more preferably 0.5 mg / cm or less 2 Even more preferably 0.3 mg / cm or less 2 That is. More specifically, the application amount of component (A) to the skin surface is preferably 0.01 to 0.8 mg / cm from the viewpoint of improving the adhesion suppression effect, and from the viewpoints of improving the feel after application to the skin and economy. 2 More preferably 0.02 to 0.8 mg / cm 2 Even more preferably 0.03 to 0.8 mg / cm 2 Even more preferably 0.04 to 0.7 mg / cm 2 Even more preferably 0.04 to 0.5 mg / cm 2, more preferably 0.04 to 0.3 mg / cm 2 is.

[0049] Regarding the above-described embodiments, 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, comprising: The external preparation contains the following component (A) and component (B), and the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.32 or more and 4.5 or less. A method for suppressing the adhesion of atmospheric harmful substances. Component (A): The average primary particle diameter d A is one or more selected from titanium oxide and zinc oxide having a diameter of 1 nm or more and 80 nm or less Component (B): The average particle diameter D B is a non-collapsible particle having a diameter of 1 μm or more and 10 μm or less <2> A method for suppressing the adhesion of atmospheric harmful substances to the skin by applying an external preparation to the skin, comprising: The external preparation contains the following component (A) and component (B), and the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.32 or more and 4.5 or less. A method for suppressing the adhesion of atmospheric harmful substances. Component (A): The average primary particle diameter d A is one or more selected from titanium oxide and zinc oxide having a diameter of 5 nm or more and 50 nm or less Component (B): The average particle diameter D B is a non-collapsible particle having a diameter of 3 μm or more and 8 μm or less <3> The method for suppressing the adhesion of atmospheric harmful substances according to <1> or <2>, wherein the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.40 or more and 3.5 or less. <4> The method for suppressing the adhesion of atmospheric harmful substances according to <1> or <2>, wherein the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.80 or more and 2.5 or less.

[0050] <5> The application amount of component (A) to the skin is 0.03 mg / cm 20.8 mg / cm or more above 2 The method for suppressing adhesion of harmful substances in the atmosphere according to any one of <1> to <4>, which is as follows. <6> The external preparation is an oil-in-water (O / W) type, and the amount of component (A) applied to the skin is 0.04 mg / cm 2 0.3 mg / cm or more above 2 The method for suppressing adhesion of harmful substances in the atmosphere according to any one of <1> to <4>, which is as follows. <7> The method for suppressing adhesion of harmful substances in the atmosphere according to any one of <1> to <6>, wherein the content of component (A) in the external preparation is 1% by mass or more and 40% by mass or less. <8> The method for suppressing adhesion of harmful substances in the atmosphere according to any one of <1> to <6>, wherein the content of component (A) in the external preparation is 1.5% by mass or more and 20% by mass or less. <9> The method for suppressing adhesion of harmful substances in the atmosphere according to any one of <1> to <6>, wherein the content of component (A) in the external preparation is 2% by mass or more and 10% by mass or less.

[0051] <10> A method for suppressing adhesion of harmful substances in the atmosphere, which comprises applying an external preparation to the skin to suppress the adhesion of harmful substances in the atmosphere to the skin. The external preparation contains the following component (A) and component (B), the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.40 or more and 3.5 or less, and the amount of component (A) applied to the skin is 0.03 mg / cm 2 0.8 mg / cm or more above 2 The method for suppressing adhesion of harmful substances in the atmosphere, which is as follows. Component (A): Titanium oxide and zinc oxide having an average primary particle diameter d A which is 1 nm or more and 80 nm or less, and one or more selected therefrom Component (B): Average particle diameter D B which is 1 μm or more and 10 μm or less, and non-collapsible particles <11> A method for suppressing adhesion of harmful substances in the atmosphere, which comprises applying an oil-in-water (O / W) type external preparation to the skin to suppress the adhesion of harmful substances in the atmosphere to the skin. The external preparation contains the following component (A) and component (B), the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.80 or more and 2.5 or less, and the application amount of component (A) to the skin is 0.04 mg / cm 2 or more and 0.3 mg / cm 2 or less, a method for suppressing the adhesion of atmospheric harmful substances. Component (A): The average primary particle diameter d A is 5 nm or more and 50 nm or less, and one or more selected from titanium oxide and zinc oxide Component (B): The average particle diameter D B is 3 μm or more and 8 μm or less, non-collapsible particles

[0052] <12> A method for suppressing the adhesion of atmospheric harmful substances, which comprises 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), the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.40 or more and 3.5 or less, and the content of component (A) in the external preparation is 1% by mass or more and 40% by mass or less, a method for suppressing the adhesion of atmospheric harmful substances. Component (A): The average primary particle diameter d A is 1 nm or more and 80 nm or less, and one or more selected from titanium oxide and zinc oxide Component (B): The average particle diameter D B is 1 μm or more and 10 μm or less, non-collapsible particles <13> A method for suppressing the adhesion of atmospheric harmful substances, which comprises 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), the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.80 or more and 2.5 or less, and the content of component (A) in the external preparation is 2% by mass or more and 10% by mass or less, a method for suppressing the adhesion of atmospheric harmful substances. Component (A): The average primary particle diameter d A is 5 nm or more and 50 nm or less, and one or more selected from titanium oxide and zinc oxide Component (B): The average particle diameter D B is 3 μm or more and 8 μm or less, non-collapsible particles

[0053] <14> The method for suppressing adhesion of atmospheric harmful substances according to any one of <1> to <13>, wherein component (B) is at least one selected from composite particles (B1) formed by coating at least a part of the surface of core particles (b1-1) with inorganic fine particles (b1-2) and porous particles (B2). <15> The method for suppressing adhesion of atmospheric harmful substances according to <14>, wherein the core particles (b1-1) constituting the composite particles (B1) are at least one selected from poly(meth)acrylate particles and silica particles. <16> The method for suppressing adhesion of atmospheric harmful substances according to <14> or <15>, wherein the surface of the core particles (b1-1) constituting the composite particles (B1) is coated with at least one binder (c) selected from poly(N-vinylpyrrolidone), poly(meth)acrylamide, and homopolymers or copolymers of oxazolines. <17> The method for suppressing adhesion of atmospheric harmful substances according to any one of <14> to <16>, wherein the inorganic fine particles (b1-2) constituting the composite particles (B1) are at least one selected from titanium oxide and zinc oxide surface-treated with at least one selected from silica, hydrous silica, and aluminum hydroxide.

[0054] <18> The following component (A) and component (B): Component (A): Titanium oxide and zinc oxide having an average primary particle diameter d A of 1 nm or more and 80 nm or less, and at least one selected therefrom Component (B): Non-collapsible particles having an average particle diameter D B of 1 μm or more and 10 μm or less containing Component (B) is composite particles (B1) formed by coating at least a part of the surface of core particles (b1-1) with inorganic fine particles (b1-2), the core particles (b1-1) are at least one selected from poly(meth)acrylate particles and silica particles, The surface of the core particle (b1-1) is coated with one or more binders (c) selected from homopolymers or copolymers of poly(N-vinylpyrrolidone), poly(meth)acrylamide, and oxazolines. The inorganic fine particles (b1-2) are one or more selected from titanium oxide and zinc oxide, which are surface-treated with one or more selected from silica, hydrous silica, and aluminum hydroxide. An external preparation wherein the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) is 0.32 or more and 4.5 or less.

[0055] <19> The following component (A) and component (B): Component (A): Titanium oxide and zinc oxide having an average primary particle diameter d A of 5 nm or more and 50 nm or less, and one or more selected therefrom Component (B): Non-disintegrable particles having an average particle diameter D B of 3 μm or more and 8 μm or less containing Component (B) is a composite particle (B1) formed by coating at least a part of the surface of the core particle (b1-1) with inorganic fine particles (b1-2). The core particle (b1-1) is one or more selected from poly(meth)acrylate particles and silica particles. The surface of the core particle (b1-1) is coated with one or more binders (c) selected from homopolymers or copolymers of poly(N-vinylpyrrolidone), poly(meth)acrylamide, and oxazolines. The inorganic fine particles (b1-2) are one or more selected from titanium oxide and zinc oxide, which are surface-treated with one or more selected from silica, hydrous silica, and aluminum hydroxide. An external preparation wherein the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) is 0.32 or more and 4.5 or less.

[0056] <20> The external preparation according to <18> or <19>, wherein the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.40 or more and 3.5 or less. <21> The external preparation according to <18> or <19>, wherein the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.80 or more and 2.5 or less. <22> The external preparation according to any one of <18> to <21>, wherein the content of component (A) in the external preparation is 1% by mass or more and 40% by mass or less. <23> The external preparation according to any one of <18> to <21>, wherein the content of component (A) in the external preparation is 1.5% by mass or more and 20% by mass or less. <24> The external preparation according to any one of <18> to <21>, wherein the content of component (A) in the external preparation is 2% by mass or more and 10% by mass or less.

[0057] <25> The following component (A) and component (B): Component (A): Titanium oxide and zinc oxide having an average primary particle diameter d A which is 1 nm or more and 80 nm or less, and at least one selected therefrom Component (B): Non-collapsible particles having an average particle diameter D B which is 1 μm or more and 10 μm or less The external preparation contains Component (B) is a composite particle (B1) formed by coating at least a part of the surface of the core particle (b1-1) with inorganic fine particles (b1-2), The core particle (b1-1) is at least one selected from poly(meth)acrylate particles and silica particles, The surface of the core particle (b1-1) is coated with at least one binder (c) selected from homopolymers or copolymers of poly(N-vinylpyrrolidone), poly(meth)acrylamide, and oxazolines, The inorganic fine particles (b1-2) are at least one selected from silica, hydrous silica, and aluminum hydroxide, and are surface-treated with at least one selected from titanium oxide and zinc oxide, The external preparation, wherein the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.40 or more and 3.5 or less, and the content of component (A) in the external preparation is 1% by mass or more and 40% by mass or less.

[0058] <26> The following component (A) and component (B): Component (A): The average primary particle diameter d A is 5 nm or more and 50 nm or less, and is one or more selected from titanium oxide and zinc oxide Component (B): The average particle diameter D B is 3 μm or more and 8 μm or less, and is a non-collapsible particle The external preparation contains Component (B) is a composite particle (B1) formed by coating at least a part of the surface of the core particle (b1-1) with inorganic fine particles (b1-2). The core particle (b1-1) is one or more selected from poly(meth)acrylate particles and silica particles The surface of the core particle (b1-1) is coated with one or more binders (c) selected from homopolymers or copolymers of poly(N-vinylpyrrolidone), poly(meth)acrylamide, and oxazolines The inorganic fine particles (b1-2) are one or more selected from silica, hydrous silica, and aluminum hydroxide, and are surface-treated with one or more selected from titanium oxide and zinc oxide The mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) in the external preparation is 0.80 or more and 2.5 or less, and the content of component (A) in the external preparation is 2% by mass or more and 10% by mass or less. An external preparation

Examples

[0059] In the following Examples and Comparative Examples, "parts" and "%" are "parts by mass" and "mass%" unless otherwise specified

[0060] (1) The average primary particle diameter d of component (A) A , the average primary particle diameter of the inorganic fine particles (b1-2) and the porous particles (B2) When the measurement sample has a shape other than plate-like, a dispersion of the measurement sample prepared in advance is placed on the sample stage of a transmission electron microscope (TEM) (trade name "JEM1400Plus", manufactured by JEOL Ltd.), air-dried, and then the maximum minor axis of 300 primary particles in the image observed at a magnification of 50,000 times by TEM is measured, and the number average value thereof is taken as the average primary particle diameter of each. Here, the maximum minor axis means the minor axis orthogonal to the major axis and having the maximum length. When the measurement sample has a plate-like shape, the thickness of 300 primary particles in the image observed under the same method and observation magnification conditions as above is measured, and the number average value thereof is taken as the average primary particle diameter of each. The dispersion of the measurement sample was prepared by adding 95 g of ethanol as a solvent to 5 g of the measurement sample and subjecting it to ultrasonic dispersion.

[0061] (2) Average particle diameter D of component (B) B and the average particle diameter of the core particles (b1-1) Using a laser diffraction / scattering particle size distribution analyzer (trade name "LA-920", manufactured by Horiba, Ltd.), measurement was performed using ion-exchanged water as a dispersion medium. In the measurement of organic particles, the relative refractive index was set to 1.10, and in the measurement of inorganic particles, the relative refractive index was set to 1.09. The measurement was carried out under the measurement conditions of using a flow cell, circulation rate: 15, ultrasonic irradiation: none, distribution form: standard, and particle size standard: volume.

[0062] (3) Confirmation of disintegrability 0.04 g of the dispersion of each particle (dispersion medium: ethanol, solid content concentration: 5%) was uniformly spread on artificial leather (trade name "Rafoore S2923", manufactured by Okamoto Showa Co., Ltd.) (5 cm × 4 cm) in 20 seconds (amount of particle adhesion: 0.1 mg / cm 2) Samples for each measurement were obtained by drying at room temperature for 24 hours. Using a surface property measuring machine (trade name "Tribogear TYPE:14", manufactured by Shin-Tech Co., Ltd.) (vertical load: 360 g, moving distance: 50 mm, moving speed: 600 mm / min), a jig (3 cm × 3 cm) with an artificial leather (Rafure S2923) (3 cm × 10 cm) with nothing applied was attached, and the surface coated with the particles of the measurement sample was reciprocally rubbed 10 times. Subsequently, using a field emission scanning electron microscope (FE-SEM-4800 (5.0 kV)) (manufactured by Hitachi High-Tech Corporation), the rubbed surface of the measurement sample was observed under the condition of an observation magnification of 15,000 times. For 30 particles in the observation image, the major axis and minor axis were measured respectively, and the average value of the major axis and minor axis was taken as the particle diameter of each particle. The volume-based particle diameter was calculated from the particle diameters of 30 particles, and the average particle diameter D B ' after rubbing was obtained. The average particle diameter D B ' after rubbing and the average particle diameter D B before rubbing measured in (2) above were used. Particles with a particle diameter ratio represented by the following formula (I) of less than 50% were defined as "easily collapsible particles", and particles with a particle diameter ratio represented by the following formula (I) of 50% or more were defined as "non-collapsible particles". Particle diameter ratio before and after rubbing (%) = (average particle diameter D B ' after rubbing / average particle diameter D B before rubbing) × 100 (I)

[0063] (Production of polymethacrylate particles P1) Production Example 1 According to Example 1 of JP-A-2006-8980, polymethacrylate particles P1 (particles of a copolymer of lauryl methacrylate / ethylene glycol dimethacrylate / sodium methacrylate) were synthesized. The average particle diameter of the polymethacrylate particles P1 was 3 μm.

[0064] (Preparation of composite particles (B1)) Preparation Example 1 As the core particles (b1-1), 100 g of the polymethacrylate particles P1 obtained in Production Example 1 were dispersed in 150 g of purified water, 0.1 g of oxazoline-modified silicone (trade name “OS-50TE-E”, manufactured by Kao Corporation) was added, and then the mixture was stirred for 1 hour to obtain coated polymethacrylate particles P1-1 coated with oxazoline-modified silicone (hereinafter also referred to as “coated polymethacrylate particles P1-1”). Next, 0.5 g of the water-containing silica-treated fine titanium oxide shown in Table 1 was added as the inorganic fine particles (b1-2), and then the mixture was stirred for 30 minutes to obtain composite particles B1-1. The composite particles B1-1 were used in the external preparation described below without purification.

[0065] Preparation Example 2 As the core particles (b1-1), after obtaining coated polymethacrylate particles P1-1 coated with oxazoline-modified silicone in the same manner as in Preparation Example 1, 0.5 g of the aluminum hydroxide-treated fine titanium oxide shown in Table 1 was added as the inorganic fine particles (b1-2), and then the mixture was stirred for 30 minutes to obtain composite particles B1-2. The composite particles B1-2 were used in the external preparation described below without purification.

[0066] Preparation Example 3 As the core particles (b1-1), 100 g of the polymethacrylate particles P1 obtained in Production Example 1 were dispersed in 150 g of purified water, 0.1 g of polyvinylpyrrolidone (trade name “PVP K-90”, manufactured by Ashland Specialty Ingredients) was added, and then the mixture was stirred for 1 hour to obtain coated polymethacrylate particles P1-2 coated with polyvinylpyrrolidone (hereinafter also referred to as “coated polymethacrylate particles P1-2”). Next, 0.5 g of the hydrophilic fine silica shown in Table 1 was added as the inorganic fine particles (b1-2), and then the mixture was stirred for 30 minutes to obtain composite particles B1-3. The composite particles B1-3 were used in the external preparation described below without purification.

[0067] Preparation Example 4 As the core particles (b1-1), 100 g of silica particles P2 (trade name "Sunsphere NP-100", manufactured by AGC SI TECH Co., Ltd., average particle diameter 10 μm) were dispersed in 150 g of purified water, and 0.1 g of polyvinylpyrrolidone (PVP K-90) was added. After stirring for 1 hour, coated silica particles P2-1 coated with polyvinylpyrrolidone (hereinafter also referred to as "coated silica particles P2-1") were obtained. Next, 0.5 g of the hydrophilic fine particle silica shown in Table 1 was added as the inorganic fine particles (b1-2), and the mixture was stirred for 30 minutes to obtain composite particles B1-4. The composite particles B1-4 were used in the external preparation described below without purification.

[0068] Preparation Example 5 As the core particles (b1-1), after obtaining coated polymethacrylate particles P1-1 coated with oxazoline-modified silicone in the same manner as in Preparation Example 1, 0.5 g of the hydrous silica-treated fine particle zinc oxide shown in Table 1 was added as the inorganic fine particles (b1-2), and the mixture was stirred for 30 minutes to obtain composite particles B1-5. The composite particles B1-5 were used in the external preparation described below without purification.

[0069] Preparation Example 6 As the core particles (b1-1), 100 g of silica particles P3 (trade name "Sciqas", manufactured by Sakai Chemical Industry Co., Ltd., surface untreated product, average particle diameter 0.4 μm) were dispersed in 150 g of purified water, and 0.1 g of polyvinylpyrrolidone (PVP K-90) was added. After stirring for 1 hour, coated silica particles P3-1 coated with polyvinylpyrrolidone (hereinafter also referred to as "coated silica particles P3-1") were obtained. Next, 0.5 g of the hydrophilic fine particle silica shown in Table 1 was added as the inorganic fine particles (b1-2), and the mixture was stirred for 30 minutes to obtain composite particles B1'-6. The composite particles B1'-6 were used in the external preparation described below without purification.

[0070] Preparation Example 7 As the core particles (b1-1), after obtaining coated polymethacrylate particles P1-2 coated with polyvinylpyrrolidone in the same manner as in Preparation Example 3, 0.5 g of hydrous silica-treated fine particle titanium oxide was added as the inorganic fine particles (b1-2), and the mixture was stirred for 30 minutes to obtain composite particles B1-7. The composite particles B1-7 were used in the external preparation described below without purification.

[0071]

Table 1

[0072] Examples 1 to 12, Comparative Examples 1 to 7 At a temperature of 25°C, with the compositions shown in Tables 2 to 4, component (B) or component (B'), a thickener, an emulsifier, and a solvent were added to a mixing tank containing water while stirring to prepare an aqueous phase. Separately, at a temperature of 80°C, component (A) and an oil agent were mixed to prepare an oil phase. Then, the oil phase and a neutralizing agent were added to the aqueous phase and stirred to obtain an external preparation having the compositions described in Tables 2 to 4. Using the obtained external preparation, the adhesion inhibitory effect and feel of atmospheric harmful substances were evaluated by the methods shown below. The results are shown in Tables 2 to 4.

[0073] In addition, each notation in Tables 2 to 4 is as follows. Average primary particle diameter d of component (A) A , and average particle diameter D of component (B) or component (B') B And the disintegration property of the particles is shown in Tables 2 to 4. Stearic acid-treated fine particle titanium oxide A1: Trade name "MT-100TV", manufactured by Teika Co., Ltd., spindle-shaped fine particle titanium oxide treated with stearic acid Octyltriethoxysilane-treated fine particle zinc oxide A2: "FINEX-30-OTS", manufactured by Sakai Chemical Industry Co., Ltd., spherical fine particle zinc oxide treated with octyltriethoxysilane Porous particle B2-1: Trade name "HCS Refle 50", manufactured by JGC Catalysts and Chemicals Ltd., aggregate of 160 nm silica and 250 nm titanium oxide (silica:titanium oxide = 50:50), oil absorption amount 50 mL / 100 g Porous particle B2-2: Trade name "Sunsphere H-51", manufactured by AGC SI-Tech Co., Ltd., specific surface area 800 m 2 / g Silica particle P'4: Trade name "Sunsphere H-121", manufactured by AGC SI-Tech Co., Ltd. Silica particles P’5: Trade name "Sunfair H-52", manufactured by AGC SI TECH Co., Ltd. Isopropyl palmitate: Trade name "Exceparl IPP", manufactured by Kao Corporation Acrylic acid / methacrylic acid alkyl copolymer 1: Trade name "PEMULEN TR-1", manufactured by Lubrizol Advanced Materials Acrylic acid / methacrylic acid alkyl copolymer 2: Trade name "PEMULEN TR-2", manufactured by Lubrizol Advanced Materials

[0074] <Evaluation of the effect of suppressing the adhesion of atmospheric harmful substances> The external preparation obtained above was applied to white artificial leather (trade name "Rafoore S2923", manufactured by Okamoto Shinwa Co., Ltd.) as a substitute for skin so as to achieve the application amounts of component (A) shown in Tables 2 to 4, and left at room temperature overnight to dry. The surface of the artificial leather coated with the external preparation was exposed to the blowing environment of the atmospheric harmful substances for evaluation, and the L * a * b * values were measured, and the color difference ΔE before and after exposure was measured by the following method. 〔Measurement of color difference ΔE〕 Using a colorimeter (trade name "CM-2002", manufactured by Konica Minolta, Inc.), the L1 of the surface of the artificial leather coated with the external preparation before exposure to the atmospheric harmful substances for evaluation * , a1 * , b1 * values were measured. Separately, in a glove bag (product number "3-118-01", manufactured by AS ONE Corporation), a blower (trade name "Silky Wind 9ZF002RH02", size: 129×106×83 mm, manufactured by Rhythm Watch Industry Co., Ltd.) and a wire mesh sieve (Test sieves test sieve JIS Z 8801, frame size: φ100×45H, mesh opening: 106 μm, manufactured by Tokyo Screen Co., Ltd.) were fixed. The installation height of the wire mesh sieve was set to 17 cm. An artificial leather (5 cm × 4 cm) coated with an external preparation of the test sample was attached to a support so that the height of the lower end of the artificial leather was at a position of 11 cm. The distance between the coated surface of the artificial leather on the support and the blower was set to 15 cm, and as shown in Fig. 1, the coated surface of the artificial leather was perpendicular to the blowing direction of the blower, and the center height of the blower blades and the center height of the artificial leather were set to be the same. The temperature inside the glove bag was set to 25°C and the relative humidity was set to 57%RH. Using a mesh sieve and a clogging removal brush (product name: "JNB-5", brush diameter 53 μm, manufactured by Tokyo Screen Co., Ltd.), 50 mg of graphite powder (product name: "J-CPB", average particle size 5.5 μm, manufactured by Nippon Graphite Industry Co., Ltd.) as an evaluation atmospheric harmful substance was classified and dropped in front of the outlet of a blower with an air volume scale set to 1 for 1 minute, and the surface of the artificial leather coated with the external preparation was exposed to the blowing environment of the evaluation atmospheric harmful substance. Next, using the above colorimeter, the L2 * , a2 * , b2 * values of the exposed artificial leather surface were measured, and the color difference ΔE value was obtained from the following formula (II-1). ΔE = [(L1 * - L2 * ) 2 + (a1 * - a2 * ) 2 + (b1 * - b2 * ) 2 0.5 (II-1) The above operations were performed 3 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 designated as ΔEt. Furthermore, for an artificial leather not coated with the external preparation as a standard sample, the same operations as above were performed 3 times, and the average value of the color difference ΔE was designated as ΔEs, and the adhesion inhibition rate was calculated from the following formula (II-2). The higher the adhesion inhibition rate, the better the adhesion inhibition effect of the atmospheric harmful substance. Adhesion inhibition rate of atmospheric harmful substance (%) = 100 × (ΔEs - ΔEt) / ΔEs (II-2)

[0075] <Evaluation of feeling (crispy feeling)> Three expert panelists applied 0.02 mL of each external preparation in a circular shape with a diameter of 3 cm to the inner part of the forearm, and spread it evenly over 20 seconds under the conditions of 25°C and 57% RH. The feeling (smooth feeling) 15 minutes after the application of the external preparation was evaluated by sensory evaluation on a five-point scale according to the following criteria, and the average score of the three panelists was obtained. The results are shown in Tables 2 to 4. 5: Feel a very smooth feeling. 4: Feel a smooth feeling. 3: Do not feel a smooth feeling. 2: Feel a sticky feeling or a squeaky feeling. 1: Feel a very sticky feeling or a squeaky feeling.

[0076]

Table 2

[0077]

Table 3

[0078]

Table 4

[0079] From Tables 2 to 4, it can be seen that Examples 1 to 12 are external preparations containing a metal oxide with an average primary particle diameter d A within a predetermined range as component (A) and non-collapsible particles with an average particle diameter D B within a predetermined range as component (B) in a predetermined mass ratio. By applying these external preparations, it has a higher adhesion suppression effect compared to Comparative Examples 1 to 7, and the feeling (smooth feeling) after application to the skin is good.

[0080] Examples 13, 14 At a temperature of 25°C, with the compositions shown in Formulation Examples 1 and 2 of Table 5, component (B), a thickener, an emulsifier, and a solvent were added to a mixing tank filled with water while stirring to prepare an aqueous phase. Separately, at a temperature of 80°C, component (A) and an oil agent were mixed to prepare an oil phase. Then, the oil phase, a neutralizing agent, and other components were added to the aqueous phase and stirred to obtain an external preparation having the composition described in Table 5. Using the obtained external preparation, the adhesion inhibitory effect of atmospheric harmful substances and the feel were evaluated by the method shown above. The results are shown in Table 5. In Table 5, each notation other than the components shown in Tables 2 to 4 is as follows. Also, the average primary particle diameter d of component (A) A , and the average particle diameter D of component (B) B and the particle disintegration property are shown in Table 5. Octyltriethoxysilane-treated fine particle titanium oxide A3: Trade name "STR-100W-OTS", manufactured by Sakai Chemical Industry Co., Ltd., spindle-shaped fine particle titanium oxide treated with octyltriethoxysilane *1: Trade name "Ubinar MC80", manufactured by BASF Japan Ltd. *2: Trade name "Ubinar T-150", manufactured by BASF Japan Ltd. *3: Trade name "Tinosorb S", manufactured by BASF Japan Ltd. *4: Trade name "Pearl Reem EX", manufactured by NOF Corporation *5: Trade name "KF-96A-10CS", manufactured by Shin-Etsu Chemical Co., Ltd. *6: Trade name "Cetyl Alcohol NX", manufactured by Kao Alcohol Industry Co., Ltd.

[0081]

Table 5

[0082] From Table 5, in Examples 13 and 14, the metal oxide having an average primary particle diameter d as component (A) A is within a predetermined range, and the average particle diameter D as component (B) BTo apply an external preparation containing non-disintegrating particles within a predetermined range at a predetermined mass ratio, it can be seen that it has a high adhesion inhibitory effect and has a good feel (smooth feeling) after being applied to the skin.

Industrial Applicability

[0083] The adhesion inhibitory method of the present invention is particularly useful as a method for inhibiting the adhesion of atmospheric harmful substances to the skin because it has a high adhesion inhibitory effect on atmospheric harmful substances.

Explanation of Signs

[0084] 1: Sample to be evaluated 2: Support 3: Sieve 4: Atmospheric harmful substances for evaluation 5: Blower

Claims

1. The following components (A) and component (B): Component (A): Metal oxide with an average primary particle diameter d A of 5 nm or more and 50 nm or less Component (B): Non-collapsible particles with an average particle diameter D B of 1 µm or more and 10 µm or less Containing: Component (A) is one or more selected from titanium oxide and zinc oxide and has a hydrophobic surface treatment; Component (B) is one or more selected from composite particles (B1) formed by coating at least a part of the surface of core particles (b1-1) with inorganic fine particles (b1-2) and porous particles (B2); An external preparation for suppressing the adhesion of atmospheric harmful substances to the skin, wherein the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) is 0.30 or more and 5.0 or less.

2. The external preparation according to claim 1, wherein the content of component (A) in the external preparation is 1% by mass or more and 40% by mass or less.

3. The external preparation according to claim 1 or 2, wherein the core particles (b1-1) constituting the composite particles (B1) are one or more selected from poly(meth)acrylate particles and silica particles.

4. The external preparation according to claim 1 or 2, wherein the surface of the core particles (b1-1) constituting the composite particles (B1) is coated with one or more binders (c) selected from poly(N-vinylpyrrolidone), poly(meth)acrylamide, and homopolymers or copolymers of oxazolines.

5. The external preparation according to claim 1 or 2, wherein the inorganic fine particles (b1-2) constituting the composite particles (B1) are one or more selected from titanium oxide and zinc oxide, which are surface-treated with one or more selected from silica, hydrous silica, and aluminum hydroxide.

6. The following components (A) and component (B): Component (A): A metal oxide having an average primary particle diameter d A of 5 nm or more and 50 nm or less Component (B): Non-collapsible particles with an average particle diameter D B of 1 μm or more and 10 μm or less Containing: Component (A) is one or more selected from titanium oxide and zinc oxide and has a hydrophobic surface treatment; Component (B) is one or more selected from composite particles (B1) formed by coating at least a part of the surface of core particles (b1-1) with inorganic fine particles (b1-2) and porous particles (B2); An atmospheric harmful substance adhesion inhibitor, wherein the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) is 0.30 or more and 5.0 or less.

Images