WO2022172799A1 - Oil-in-water emulsion cosmetic - Google Patents

Abstract

Provided is a cosmetic which has an excellent protective effect against infrared light and gives a unique fresh sense when applied.　The cosmetic is an oil-in-water emulsion cosmetic which comprises the following components (a) to (d): (a) metal oxide particles having an average particle diameter of 500-1500 nm and having undergone a surface-hydrophobizing treatment, (b) a hydrophobized alkyl cellulose, (c) an aqueous-phase thickener, and (d) an oil. In the cosmetic, the metal oxide particles are dispersed in the oil and the content of a nonionic surfactant having an HLB value of 10 or greater is less than 1.0 mass%.

Description

Oil-in-water emulsified cosmetic

The present invention relates to an oil-in-water emulsified cosmetic, particularly an infrared protective oil-in-water emulsified cosmetic.

Conventionally, UV protection cosmetics are known from the viewpoint of skin protection against sunlight.

For example, in Patent Document 1, as an oil-in-water emulsified cosmetic containing an ultraviolet absorber and an ultraviolet scattering agent and having a high ultraviolet protection function (SPF) and a unique fresh feeling in use, (A) 0.05 to (B) 5 to 40% by weight of oil; (C) 2.5 to 30% by weight of an ultraviolet scattering agent having a hydrophobic surface; and (D) an aqueous phase with low salt resistance. There is disclosed an oil-in-water emulsified cosmetic comprising a thickener and (C) an ultraviolet scattering agent dispersed in an oil phase.

On the other hand, in recent years, health awareness has increased, and not only ultraviolet rays (wavelength: about 290 to about 400 nm), but also infrared rays (wavelength: about 750 nm to about 1 mm) are cut to reduce the heat of the sun and improve the skin. There is a demand for cosmetics that can prevent photoaging.

For example, in Patent Document 2, titanium oxide (A) with an average particle size of 5 to 100 nm and titanium oxide with an average particle size of 300 to 3000 nm are disclosed as heat-shielding cosmetics that improve the heat-shielding effect of infrared rays while having an ultraviolet-shielding effect. (B) is blended in a ratio of (A):(B)=1:9 to 9:1 (weight ratio), a heat-shielding cosmetic is disclosed.

JP 2015-120682 A JP 2013-194041 A

However, the heat-shielding cosmetic disclosed in Patent Document 2, for example, has a problem that it is difficult to obtain a fresh feeling in use because the nonionic surfactant is contained in a large amount.

The present invention is intended to improve the above circumstances, and the purpose thereof is to provide a cosmetic that has an excellent infrared shielding effect and a unique fresh feeling when used.

The present invention that achieves the above objects is as follows.

<Aspect 1>
Contains ingredients (a)-(d):
(a) metal oxide particles having an average particle size of 500 to 1500 nm and having a surface hydrophobically treated;
(b) a hydrophobically modified alkyl cellulose,
(c) an aqueous phase thickener, and (d) an oil,
The metal oxide particles are dispersed in the oil, and the content of the nonionic surfactant having an HLB value of 10 or more is less than 1.0% by mass.
Oil-in-water emulsified cosmetic.
<Aspect 2>
(e) The cosmetic according to aspect 1, further comprising polyhydroxystearic acid.
<Aspect 3>
The content of the metal oxide particles is 1.0% by mass or more and 30.0% by mass or less,
The content of the hydrophobically-modified alkyl cellulose is 0.05% by mass or more and 1.0% by mass or less,
The content of the aqueous phase thickener is 0.05 mass% or more and 3.0 mass% or less, and the oil content is 5.0 mass% or more and 40.0 mass% or less.
Cosmetics according to aspect 1 or 2.
<Aspect 4>
The cosmetic according to any one of aspects 1 to 3, wherein the metal oxide particles are titanium oxide.
<Aspect 5>
The cosmetic material according to any one of aspects 1 to 4, wherein the hydrophobically modified alkylcellulose is hydrophobically modified hydroxypropylmethylcellulose.
<Aspect 6>
The cosmetic according to any one of aspects 1 to 5, wherein the aqueous phase thickener comprises a vinyl polymer or an acrylic polymer.
<Aspect 7>
7. The cosmetic according to any one of aspects 1 to 6, wherein 55% by mass or more of the oil content is polar oil.
<Aspect 8>
(f) The cosmetic according to any one of aspects 1 to 7, further comprising an ionic surfactant.
<Aspect 9>
(g) The cosmetic according to any one of aspects 1 to 8, further comprising a water-soluble polyether-modified silicone wax.
<Aspect 10>
The cosmetic according to any one of aspects 1 to 9, which is an infrared protective cosmetic.

According to the present invention, it is possible to provide a cosmetic that has an excellent infrared shielding effect and a unique fresh feeling in use.

In the present invention, the “unique fresh feeling in use” means that when the cosmetic is applied to the skin with a finger or the like, the viscosity of the cosmetic suddenly drops and the skin collapses. It means to give a fresh feel to the skin.

The embodiment of the present invention will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the gist of the invention.

《Oil-in-water emulsified cosmetic》
The oil-in-water emulsified cosmetic of the present invention (hereinafter also simply referred to as "the cosmetic of the present invention") is
Contains ingredients (a)-(d):
(a) metal oxide particles having an average particle size of 500 to 1500 nm and having a surface hydrophobically treated;
(b) a hydrophobically modified alkyl cellulose,
(c) an aqueous phase thickener, and (d) an oil,
The metal oxide particles are dispersed in the oil, and the content of the nonionic surfactant having an HLB value of 10 or more is less than 1.0% by mass.

The cosmetic of the present invention exhibits the effect of the present invention by containing a specific component and by suppressing the content of a nonionic surfactant having an HLB value of 10 or more to less than 1.0% by mass. That is, it can have excellent infrared protection effect and a unique fresh feeling in use.

The cosmetic material of Patent Document 1 mentioned above is mainly intended to block ultraviolet rays, and uses an ultraviolet scattering agent with a relatively small average particle size. Therefore, in Patent Document 1, instead of using a nonionic surfactant with a strong emulsifying action, a hydrophobically modified alkylcellulose with a relatively weak emulsifying action is used, and an ultraviolet scattering agent with a relatively small average particle size is contained. It is disclosed that an oil-in-water emulsified cosmetic in which a hydrophobic powder is dispersed in the inner oil phase is obtained by emulsifying the oil contained in the oil.

On the other hand, it is difficult to emulsify an oil containing metal oxide particles with a relatively large average particle size, and in general, it is difficult to add a large amount of a surfactant with a relatively strong emulsifying effect. Are known. For example, Patent Document 2 discloses that a large amount of nonionic surfactant having a content of 1% by mass or more is used as an emulsifier to obtain an oil-in-water emulsified cosmetic in which a hydrophobic powder is dispersed in an internal oil phase. ing.

On the other hand, without being bound by the conventional stereotypes described above, the present inventors have conducted intensive research and found that "oil containing metal oxide particles with a relatively large average particle size", which was considered difficult to emulsify. Using a hydrophobically modified alkyl cellulose having an appropriate emulsifying power, we succeeded in obtaining an oil-in-water emulsified cosmetic in which a hydrophobic powder is dispersed in the internal oil phase, even for systems such as the above, leading to the present invention. rice field.

Although not limited to theory, this is because a stable interfacial film can be formed when a surfactant with a strong emulsifying action (that is, a nonionic surfactant with an HLB value of 10 or more) is used. , the size of the emulsion particles is relatively small. Therefore, metal oxide particles having a relatively large average particle size are relatively close in size to the emulsified particles, and are likely to be easily detached from the emulsified particles (oil droplets). In contrast, in the present invention, emulsified particles become relatively large by using a surfactant with relatively weak emulsifying action such as hydrophobically modified alkyl cellulose. Therefore, in this case, it is considered that the metal oxide particles having a relatively large average particle size are difficult to detach from the emulsified particles.

Thus, in the present invention, by suppressing the content of nonionic surfactants with an HLB value of 10 or more to less than 1.0% by mass, the emulsified particle size is not made smaller than desired, and a stable internal surfactant is obtained. It is possible to not only obtain an oil-in-water emulsified cosmetic in which hydrophobic powder is dispersed in an oil phase, but also to suppress the sticky feeling in use caused by a large amount of nonionic surfactant, thereby obtaining a unique fresh feeling in use. I was able to

In the cosmetic of the present invention, the content of the nonionic surfactant having an HLB value of 10 or more is 0.9% by mass or less, 0.8% by mass or less, 0.7% by mass or less, and 0.6% by mass. 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, 0.2% by mass or less, 0.1% by mass or less, or 0% by mass or less.

<(a) Metal oxide particles>
The metal oxide particles contained in the cosmetic of the present invention (hereinafter also simply referred to as "the metal oxide particles of the present invention") have an average particle size of 500 to 1500 nm and are surface-hydrophobicized metal oxide particles. is.

Because the metal oxide particles of the present invention have an average particle size of 500 to 1500 nm, they have the function of protecting against infrared rays, especially near infrared rays.

In the present invention, "average particle size" refers to the average particle size of primary particles.

In addition, in the present invention, the average particle diameter can be calculated as the projected area circle equivalent diameter of the primary particles observed by SEM or TEM.

The metal oxide particles of the present invention are surface-hydrophobicized. Here, the hydrophobization treatment may be performed using a known surface treatment agent that is hydrophobized. Examples include fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, and titanium coupling. agent treatment, oil treatment, N-acylated lysine treatment, polyacrylic acid treatment, isostearic acid treatment, metallic soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, silane compound treatment, silazane compound treatment, etc. be done. Among these treatments, treatment with silicone or silicone resin, treatment with a silane compound or silazane compound, and isostearic acid treatment are preferred from the viewpoint of dispersion stability and the like.

The metal oxide particles of the present invention may be surface-hydrophobicized titanium oxide, surface-hydrophobicized zinc oxide, surface-hydrophobicized cerium oxide, or mixtures thereof, etc., but have a shielding effect in the infrared region. From the viewpoint of improving the surface resistance, it is preferable to use titanium oxide that has been surface-hydrophobicized.

The shape of the metal oxide particles of the present invention is not particularly limited, and examples thereof include spherical, plate-like, rod-like, spindle-like, needle-like, and irregular shapes.

As the metal oxide particles of the present invention, commercially available ones may be used.

In addition, as the metal oxide particles of the present invention, commercially available products in which metal oxide particles are dispersed with a dispersant such as polyhydroxystearic acid may be used.

In the cosmetic of the present invention, the content of the metal oxide particles is not particularly limited. 3.0% by mass or more, 3.5% by mass or more, 4.0% by mass or more, 4.5% by mass or more, 5.0% by mass or more, 5.5% by mass or more, 6.0% by mass or more, 6 .5% by mass or more, 7.0% by mass or more, 7.5% by mass or more, 8.0% by mass or more, 8.5% by mass or more, 9.0% by mass or more, 9.5% by mass or more, or 10 0% by mass or more, or 30.0% by mass or less, 20.0% by mass or less, or 10.0% by mass or less. When the metal oxide particles are dispersed in a dispersant such as polyhydroxystearic acid, the content of the metal oxide particles referred to here is the content of the solid content in the cosmetic of the present invention. point to

<(b) Hydrophobic modified alkyl cellulose>
The hydrophobically modified alkyl cellulose contained in the cosmetic of the present invention does not belong to "nonionic surfactants having an HLB value of 10 or more", and is usually classified as "polymeric surfactants".

In the present invention, hydrophobically modified alkyl cellulose refers to alkyl cellulose that has been hydrophobically modified with an alkyl group having 14 to 22 carbon atoms. This hydrophobically modified alkylcellulose is a compound obtained by introducing a long-chain alkyl group, which is a hydrophobic group, into a water-soluble cellulose ether derivative, and is represented by the following general formula (I).

［式中、Ｒは、同一でも異なってもよく、水素原子、炭素原子数が１～４のアルキル基、基－［ＣＨ_２ＣＨ（ＣＨ_３）Ｏ］_ｍ－Ｈ（式中、ｍは、１～５、好適には１～３の整数である）、基－ＣＨ_２ＣＨ_２ＯＨ、及び、基－ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２ＯＲ’（式中、Ｒ’は、炭素原子数が１４～２２のアルキル基である）から選ばれる１種以上の基であるが、基－ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２ＯＲ’を必ず含むものとする。また、Ａは、基－（ＣＨ_２）_ｑ－（ｑは、１～３の整数であり、好適には１である）であり、ｎは、１００～１００００、好適には５００～５０００の整数である。］

[In the formula, R may be the same or different, and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group -[CH ₂ CH(CH ₃ )O] _m -H (wherein m is an integer of 1 to 5, preferably 1 to 3), the group —CH ₂ CH ₂ OH, and the group —CH ₂ CH(OH)CH ₂ OR′, where R′ is an integer having the number of carbon atoms 14 to 22 alkyl groups), but necessarily including the group —CH ₂ CH(OH)CH ₂ OR′. A is a group —(CH ₂ ) _q — (q is an integer of 1 to 3, preferably 1); n is an integer of 100 to 10,000, preferably 500 to 5,000; is. ]

The method for producing the hydrophobically modified alkyl cellulose of the formula (I) is generally based on a water-soluble cellulose ether derivative, specifically methyl cellulose (where R is a hydrogen atom or a methyl group), ethyl cellulose (where R is a hydrogen atom or ethyl group), propyl cellulose (R is a hydrogen atom or a propyl group), butyl cellulose (R is a hydrogen atom or a butyl group), hydroxypropyl cellulose [R is a hydrogen atom or a hydroxypropyl group (the group -[CH ₂ CH (CH ₃ ) O] _m —H (wherein m is an integer of 1 to 5, preferably 1 to 3))], hydroxypropylmethylcellulose (R is a hydrogen atom, a methyl group, or a hydroxypropyl group (same as above)) etc., can be obtained by contacting a compound for introducing a long-chain alkyl group having 14 to 22 carbon atoms, specifically, a long-chain alkyl glycidyl ether of the following formula (II) in the presence of an alkali catalyst. .

［式中、Ｒ’は、炭素原子数が１４～２２のアルキル基である。］

[In the formula, R′ is an alkyl group having 14 to 22 carbon atoms. ]

The content of the group —CH ₂ CH(OH)CH ₂ OR′ introduced into the hydrophobically-modified alkylcellulose of the present invention is preferably about 0.1 to 5.0% by mass relative to the entire hydrophobically-modified alkylcellulose. . In order to achieve such a content, the molar ratio, reaction time, type of alkali catalyst, etc. during the reaction between the water-soluble cellulose ester derivative and the long-chain alkyl glycidyl ether may be appropriately selected for production. After the above reaction, purification steps such as neutralization, filtration, washing, drying, and sieving of the reaction product may be performed.

Among the above water-soluble cellulose ether derivatives, it is particularly preferable to select hydroxypropylmethylcellulose (wherein R in formula (I) is a hydrogen atom, a methyl group, or a group -[CH ₂ CH ( CH ₃ )O] _m H and the group —CH ₂ CH(OH)CH ₂ OR′, q of the group A becomes 1, and the A becomes a methylene group).

Furthermore, R' in the long-chain alkyl glycidyl ether of formula (II) is an alkyl group having 14 to 22 carbon atoms, preferably an alkyl group having 14 to 20 carbon atoms, more preferably a stearyl group having 18 carbon atoms (-C _{18 H37} ). If the number of carbon atoms in the alkyl group R' is less than 14 or 23 or more, the emulsion stability of the obtained hydrophobically modified alkyl cellulose is not sufficient.

The weight average molecular weight of the hydrophobically modified alkyl cellulose is preferably 100,000 to 1000,000, more preferably 300,000 to 800,000, still more preferably 550,000 to 750,000.

In the present invention, as the hydrophobically modified alkylcellulose, it is preferable to use hydrophobically modified hydroxypropylmethylcellulose (hydrophobicized hydroxypropylmethylcellulose), more specifically, stearoxyhydroxypropylcellulose. Commercially available products can also be used as the hydrophobically modified alkyl cellulose, such as Sangelose 90L (display name: hydrophobized hydroxypropyl methylcellulose; manufactured by Daido Kasei Co., Ltd.), Natrosol Plus 330cs (manufactured by Ashland), Examples include Polysurf 67cs (manufactured by Ashland), but are not limited to these.

In the cosmetic of the present invention, the content of the hydrophobically-modified alkyl cellulose is not particularly limited, and is 0.25% by mass or more, 0.30% by mass or more, 0.35% by mass or more, 0.40% by mass or more, 0.45% by mass or more, or 0.50% by mass or more, and 1 0% by mass or less, 0.80% by mass or less, 0.50% by mass or less, or 0.30% by mass or less.

<(c) Aqueous phase thickener>
The water-phase thickener contained in the cosmetic of the present invention is a thickener having a function of thickening the water phase. may be generated. Further, in the present invention, such an aqueous phase thickener that causes a decrease in viscosity due to an increase in electrolyte concentration is also referred to as an "aqueous phase thickener with low salt resistance". Such a thickener with low salt tolerance is selected from water-soluble thickeners conventionally blended in cosmetics and the like for the purpose of adjusting the viscosity of the aqueous phase.

Specific examples include polyvinyl alcohol, polyvinyl acetate, polyvinyl methyl ether, polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, vinyl polymers such as carboxyvinyl polymer; sodium polyacrylate, polyethyl acrylate, and polyalkanol acrylate. Amine, copolymer of alkyl methacrylate and dimethylaminoethyl methacrylate, poly 2-acrylamido-2-methylpropanesulfonic acid, polymethacryloyloxytrimethylammonium, (acryloyldimethyltaurate ammonium/VP) copolymer, dimethylacrylamide/acryloyldimethyltaurate Na) cross Examples include, but are not limited to, acrylic macromolecules such as polymers.

However, among thickeners with low salt tolerance, compared to thickeners that thicken by entanglement of polymer chains, they form water-swellable microgels in the aqueous phase, and the swollen microgel particles It is preferable to use a type of thickening agent that thickens due to friction because it can further suppress sliminess when the cosmetic is applied to the skin. This is because the hydrophobically modified alkyl cellulose blended as an emulsifier also has a thickening effect due to the entanglement of polymer chains, so if a thickener that thickens by the same mechanism is further blended, the thickening effect is promoted. This is because it can cause sliminess.

In the cosmetic of the present invention, the content of the aqueous phase thickener is not particularly limited, and is, for example, 0.05% by mass or more, 0.07% by mass or more, 0.10% by mass or more, 0.15% by mass or more. , 0.17% by mass or more, 0.20% by mass or more, 0.25% by mass or more, 0.27% by mass or more, 0.275% by mass or more, 0.30% by mass or more, 0.35% by mass or more, 0.37% by mass or more, 0.40% by mass or more, 0.45% by mass or more, 0.47% by mass or more, or 0.50% by mass or more, and 3.0% by mass or less, 2 0% by mass or less, or 1.0% by mass or less.

<(d) oil content>
The oil contained in the cosmetic of the present invention can be one or more selected from oily components commonly used in cosmetics and the like.

The content of oil in the cosmetic of the present invention is not particularly limited, and is % by mass or more, 10.0% by mass or more, 11.0% by mass or more, 12.0% by mass or more, 13.0% by mass or more, 14.0% by mass or more, 15.0% by mass or more, or 16.0% by mass It may be 40.0% by mass or less, 30.0% by mass or less, or 20.0% by mass or less.

In the present invention, it is particularly preferred that the oil contains polar oil. For example, in the cosmetic composition of the present invention, when polar oil accounts for 55% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, the emulsion stability is improved. can be further improved. Moreover, the upper limit of the ratio of the polar oil to the oil content is not particularly limited.

In the present invention, the "polar oil" is not particularly limited as long as it has a high polarity among oils generally used in cosmetics. For example, the dielectric constant is about 5 or more, preferably about 10 or more is preferably used.

Representative examples of polar oils include ester oils and UV absorbers. In addition, since it contains a larger amount of polar oil than conventional cosmetics, it is possible to stably incorporate, for example, a highly polar perfume.

(ester oil)
Specific examples of ester oils that can be used as polar oils in the present invention include tripropylene glycol dineopentanoate, isononyl isononanoate, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, and laurin. Hexyl acid, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, cetyl ethylhexanoate, di-2- Ethylene glycol ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylol tri-2-ethylhexanoate Propane, trimethylolpropane triisostearate, pentaerythrityl tetra-2-ethylhexanoate, triethylhexanoin (glyceryl tri-2-ethylhexanoate), glyceryl trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate , cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, palmitic acid 2 -hexyldecyl, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate and the like.

(Ultraviolet absorber)
Specific examples of UV absorbers that can be used as polar oils in the present invention include benzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, dibenzoylmethane derivatives, β,β-diphenylacrylate derivatives, benzophenone derivatives, and benzylidene camphor. derivatives, phenylbenzimidazole derivatives, triazine derivatives, phenylbenzotriazole derivatives, anthranyl derivatives, imidazoline derivatives, benzalmalonate derivatives, 4,4-diarylbutadiene derivatives and the like, but are not limited thereto. In addition, some specific examples and trade names of these will be exemplified below.

Examples of benzoic acid derivatives include ethyl para-aminobenzoate (PABA), ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA (eg "Escarol 507"; manufactured by ISP), glyceryl PABA, PEG-25-PABA (eg "Uvinal P25"; manufactured by BASF), and hexyl diethylaminohydroxybenzoylbenzoate (eg, "Uvinal A Plus"), etc., but not limited thereto.

Examples of salicylic acid derivatives include homosalate (“Eusolex HMS”; manufactured by Rona/EM Industries), ethylhexyl salicylate (for example, “NeoHeliopan OS”; manufactured by Harman & Reimer), Examples include, but are not limited to, propylene glycol salicylate (e.g., "Dipsal"; manufactured by Skell) and TEA salicylate (e.g., "Neo Heliopan TS"; manufactured by Harman & Reimer).

Examples of cinnamic acid derivatives include ethylhexyl methoxycinnamate (e.g., "Parsol MCX"; manufactured by Hoffmann-La Roche), isopropyl methoxycinnamate, and isoamyl methoxycinnamate (e.g., "Neo Heliopan E1000"; Harman &・Laymer), cinnoxate, DEA methoxycinnamate, diisopropyl methylcinnamate, glyceryl-ethylhexanoate-dimethoxycinnamate, and di-(2-ethylhexyl)-4'-methoxybenzalmalonate. but not limited to these.

Dibenzoylmethane derivatives include, but are not limited to, 4-tert-butyl-4'-methoxydibenzoylmethane (eg, "Parsol 1789").

Examples of the β,β-diphenyl acrylate derivative include, but are not limited to, octocrylene (eg, "Ubinal N539"; manufactured by BASF).

Benzophenone derivatives include benzophenone-1 (eg "Uvinal 400"; manufactured by BASF), benzophenone-2 (eg "Ubinal D50"; manufactured by BASF), benzophenone-3 or oxybenzone (eg "Ubinal M40"; manufactured by BASF). ), benzophenone-4 (eg “Ubinal MS40”; manufactured by BASF), benzophenone-5, benzophenone-6 (eg “Helisorb 11”; Norquai), benzophenone-8 (eg “Spectra-sorb (Spectra- Sorb) UV-24"; manufactured by American Cyanamid), benzophenone-9 (eg, "Ubinal DS-49"; manufactured by BASF), and benzophenone-12, etc., but are not limited thereto.

Examples of benzylidene camphor derivatives include 3-benzylidene camphor (eg, "Mexoryl SD"; manufactured by Simex), 4-methylbenzylidene camphor, benzylidene camphor sulfonic acid (eg, "Megizolyl SL"; manufactured by Simex), methosulfate camphor. benzalkonium (e.g., "Megizolyl SO"; manufactured by Simex), terephthalylidene dicamphor sulfonic acid (eg, "Megizolyl SX"; manufactured by Simex), and polyacrylamidemethylbenzylidene camphor (eg, "Megizolyl SW"; manufactured by Simex) ) and the like, but are not limited to these.

Phenylbenzimidazole derivatives include phenylbenzimidazole sulfonic acid (e.g. "Usolex 232"; manufactured by Merck) and disodium phenyldibenzimidazole tetrasulfonate (e.g. "Neo Heliopan AP"; manufactured by Harman & Reimer). ) and the like, but are not limited to these.

Examples of triazine derivatives include anisotriazine (e.g., "Tinosorb S"; manufactured by Ciba Specialty Chemicals), ethylhexyl triazone (e.g., "Ubinal T150"; manufactured by BASF), and diethihexylbutamide triazone ( Examples thereof include, but are not limited to, "Uvasorb HEB" (manufactured by Sigma 3V) and 2,4,6-tris(diisobutyl-4'-aminobenzalmalonate)-s-triazine.

Phenylbenzotriazole derivatives include drometrizole trisiloxane (e.g. "Silatrizole"; manufactured by Rhodia Shimmy) and methylenebis(benzotriazolyltetramethylbutylphenol) (e.g. "Tinosorb M" (Ciba Specialties). (Tea Chemicals Co., Ltd.)), etc., but are not limited to these.

Examples of anthranil derivatives include, but are not limited to, menthyl anthranilate (eg, "Neo Heliopan MA"; manufactured by Harman & Reimer).

Examples of imidazoline derivatives include, but are not limited to, ethylhexyldimethoxybenzylidene dioxoimidazoline propionate.

Examples of benzalmalonate derivatives include, but are not limited to, polyorganosiloxanes having benzalmalonate functional groups (for example, polysilicone-15; "Parsol SLX"; manufactured by DSM Nutrition Japan).

4,4-diarylbutadiene derivatives include, but are not limited to, 1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene and the like.

<Other ingredients>
In addition to the essential components (a) to (d) described above, the cosmetic of the present invention may further contain other components within a range that does not impair the effects of the present invention. Other components are exemplified below.

((e) polyhydroxy stearic acid)
The cosmetic of the present invention may further contain polyhydroxystearic acid. Polyhydroxystearic acid is preferable from the viewpoint of having the effect of uniformly dispersing the metal oxide particles of the present invention in oil.

Polyhydroxystearic acid is an oligomerized compound obtained by forming an ester bond with hydroxystearic acid. (manufactured by Sei Oillio Co., Ltd.), etc., and these can be used. The degree of polymerization of polyhydroxystearic acid is not particularly limited, and may be, for example, 4-8.

In the cosmetic composition of the present invention, when polyhydroxystearic acid is contained, the content of polyhydroxystearic acid is, for example, 0.01 to 3.0% by mass, 0.05 to 2.0% by mass, or 0.10 to 3.0% by mass. It may be 1.0% by mass.

((f) ionic surfactant)
The cosmetic of the present invention may further contain an ionic surfactant. Ionic surfactants are preferable from the viewpoint of electrostatic repulsion and prevention of coalescence of emulsified particles.

Ionic surfactants are surfactants that dissociate into ions when dissolved in water, and are specifically classified into anionic surfactants, cationic surfactants, and amphoteric surfactants.

Examples of ionic surfactants include N-stearoyl-N-methyltaurine, sodium N-stearoyl-N-methyltaurate, disodium N-stearoyl-L-glutamate, sodium N-stearoyl-L-glutamate, and polyoxyethylene lauryl ether. Anionic surfactants such as sodium acetate, polyoxyethylene lauryl ether triethanolamine acetate, sodium taurate laurate, sodium lauroylmethyltaurate, and triethanolamine laurate; cationic surfactants such as stearyldimethylamine oxide and stearyltrimethylammonium chloride and amphoteric surfactants such as lauryldimethylbetaine and betaine lauryldimethylaminoacetate, but are not limited thereto.

In the cosmetic composition of the present invention, when the ionic surfactant is contained, the content of the ionic surfactant is, for example, 0.01 to 2.0% by mass, 0.05 to 1.0% by mass, or 0.10 to 0.10% by mass. It may be 0.50% by mass.

(Other surfactants)
Regarding the nonionic surfactant (“nonionic surfactant”), the cosmetic of the present invention has a nonionic surfactant with an HLB value of 10 or more, if it satisfies the condition that the content of the nonionic surfactant is less than 1.0% by mass. , a nonionic surfactant having an HLB value of less than 10.

Nonionic surfactants with an HLB value of less than 10 include, for example, bisbutyl dimethicone polyglyceryl-3 (HLB value: 0.5), PEG-10 dimethicone (HLB value: 2.0), or PEG-9 polydimethylsiloxy Examples include, but are not limited to, ethyl dimethicone (HLB value: 4.0).

When the cosmetic of the present invention further contains a nonionic surfactant having an HLB value of less than 10, the content thereof is, for example, 0.01 to 2.0% by mass, or 0.05 to 1.0% by mass. you can

In addition to the surfactants described above, for example, polymeric surfactants or natural surfactants may also be added to the cosmetics of the present invention as long as they do not impair the effects of the present invention.

((g) water-soluble polyether-modified silicone wax)
The cosmetic of the present invention may further contain a water-soluble polyether-modified silicone wax. A water-soluble polyether-modified silicone wax is preferable from the viewpoint of the effect of making the cosmetic of the present invention non-sticky, further improving the emulsion stability, and providing a refreshing emulsion.

Examples of water-soluble polyether-modified silicone waxes include, but are not limited to, bis-PEG-18 methyl ether dimethylsilane, bis-PEG-15 methyl ether dimethicone, PEG-32 methyl ether dimethicone, and PEG-17 dimethicone. .

Further, water-soluble polyether-modified silicone waxes can be obtained from commercial products, for example, CosmeticWax2501 (manufactured by Dow Corning Toray Co., bisPEG-18 methyl ether dimethylsilane, melting point 36-42°C), DMC 6038 (Wacker company, bis PEG-15 methyl ether dimethicone, melting point about 30 ° C.), KF-6004 (manufactured by Shin-Etsu Chemical Co., Ltd., PEG-32 methyl ether dimethicone, melting point 45 ° C.), and Silsoft (registered trademark) 895 (MOMENTIVE Co., Ltd.) PEG-17 Dimethicone) and the like, but are not limited to these.

When the cosmetic of the present invention contains a water-soluble polyether-modified silicone wax, the content of the water-soluble polyether-modified silicone wax is, for example, 0.1 to 20.0% by mass, 0.5 to 15.0% by mass. , or 1.0 to 10.0% by mass.

((h) cooling agent)
The cosmetic of the present invention may further contain a cooling agent. A cooling agent is preferable from the viewpoint of enhancing the refreshing feeling.

Cooling agents include menthol, peppermint oil, l-menthyl glyceryl ether, menthyl lactate, camphor, isopulegol, borneolol, cineol menthone, spearmint, peppermint, menthyl malonate, glycosyl-mono-menthyl-O-acetate, 3- One or more selected from the group consisting of L-menthoxypropane-1,2-diol and 1-menthyl-3-hydroxybutyrate may be used.

In the cosmetic of the present invention, the content of the water refreshing agent when containing the refreshing agent is, for example, 0.1 to 10.0% by mass, 0.5 to 10.0% by mass, or 1.0 to 5% by mass. 0 mass %.

In addition to the above-mentioned "other ingredients", the cosmetic of the present invention contains, for example, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and the like. Glycols; Glycerols such as glycerin, diglycerin and polyglycerin; Sugar alcohols such as sorbitol, mannitol, maltitol, xylitol and erythritol; Sugars such as fructose, glucose, galactose, maltose, lactose and trehalose; Natural pigments such as carotene; plant-based polymers such as gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, gellan gum, and carrageenan; microbial-based polymers such as xanthan gum, dextran, succinoglucan, and pullulan; collagen, casein, albumin , animal polymers such as gelatin; starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch; methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose, crystalline cellulose Cellulose-based polymers such as sodium alginate, alginic acid-based polymers such as propylene glycol alginate; Other thickeners; Vitamins such as magnesium ascorbyl phosphate, ascorbyl glucoside, vitamin B6 hydrochloride, and pantothenyl ethyl ether Bactericides, antiphlogistic agents, antiseptics, plant extracts, amino acids and other drugs; Lower alcohols such as ethanol and isopropyl alcohol; Aromatic alcohols such as phenoxyethanol and benzyl alcohol; Various ingredients may also be included.

The cosmetic of the present invention can be prepared according to a method commonly used for oil-in-water emulsified cosmetics. That is, it can be prepared by separately mixing the water phase component and the oil phase component, adding the oil phase component while stirring the water phase component, and emulsifying the water phase component.

Although the cosmetic of the present invention is not particularly limited, it may have an emulsion particle size of 7.5 μm on average and about 20 μm at maximum. The emulsified particle size can be obtained by, for example, using a microscope to comprehensively determine the size of the emulsified particles (measured with a micrometer) and the distribution of the particles (uniformity of the particles in the microscopic field of view) with the naked eye. can ask.

The cosmetic of the present invention can exhibit the effects of the present invention described above, so it may be an infrared protective cosmetic.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, the contents are shown in % by mass.

Cosmetics of Examples and Comparative Examples were prepared according to the formulations shown in Table 1 below, and the stability, infrared cut rate, feel during use, and emulsion particle size of each of the obtained cosmetics were evaluated according to the following criteria. Table 2 shows those results.

<Stability>
Two screw tubes (50 ml) were filled with each of the cosmetics obtained in Examples and Comparative Examples and allowed to stand in a constant temperature bath at 0° C. or 50° C. for 2 weeks. Before and after standing, the viscosity change was measured using a rotational viscometer (Vismetron rotational viscometer), and the emulsified particles and appearance were observed:
"Evaluation criteria"
"A": No decrease in viscosity was observed at both temperature levels of 0°C and 50°C, and there was no problem with emulsified particles and appearance.
"B": At any temperature level, a slight decrease in viscosity, an increase in emulsified particles, or a change in appearance was observed.
"C": Popping out of metal oxide particles was observed at any temperature level.

<Infrared cut rate>
Each cosmetic obtained in Examples and Comparative Examples was applied to a PMMA (polymethyl methacrylate resin) substrate (HD6 manufactured by HelioScreen), dried for 15 minutes, and used as a sample for measurement. A PMMA substrate with no coating was used as a control sample. The transmittance at 1500 nm was measured with a spectrophotometer (UV-3600 manufactured by Shimadzu Corporation, integrating sphere mode) for each of the measurement sample and the control sample. During the measurement, the coated surface of the PMMA substrate was brought into close contact with the outer edge of the opening of the integrating sphere using double-sided tape. The transmittance was obtained by dividing the transmittance of the measurement sample by the transmittance of the control sample, and (100%-transmittance) was defined as the infrared cut rate (%).

<Feel of use>
Each of the cosmetics obtained in Examples and Comparative Examples was comprehensively evaluated by a panel of three experts with respect to feel in use, based on the following criteria:
"A": Very good freshness.
"B": Excellent freshness.
"C": Poor freshness.

<Emulsion particle size>
Using a microscope, the size of emulsified particles (measured by a micrometer) and their distribution (uniformity of particles in the speculum field) were comprehensively judged with the naked eye, and the results obtained in Examples and Comparative Examples The emulsified particle size of each cosmetic was determined. In Table 2, the expression "1 to 10 (20)" means that the diameter of most of the emulsified particles was in the range of about 1 to 10 µm, and there were also a few emulsified particles up to about 20 µm. ing. The same applies to other expressions.

As is clear from Tables 1 and 2, the cosmetics of Examples 1 to 9 were found to have an excellent infrared protection effect and to have a unique fresh feeling in use.

In addition, it is considered that the cosmetics of Examples 1 to 6 are superior in stability to the cosmetics of Examples 7 to 9 because they further contain polyhydroxystearic acid. The cosmetics of Examples 7 to 9 further contained surfactants such as sorbitan sesquiisostearate, isostearic acid, and bisbutyl dimethicone polyglyceryl-3 instead of polyhydroxystearic acid. Although these surfactants have a function as a powder dispersant, it has been analyzed that their dispersibility, especially for large-sized metal oxide particles, is slightly inferior to that of polyhydroxystearic acid. be.

Claims (10)

Contains ingredients (a)-(d):
(a) metal oxide particles having an average particle size of 500 to 1500 nm and having a surface hydrophobically treated;
(b) a hydrophobically modified alkyl cellulose,
(c) an aqueous phase thickener, and (d) an oil,
The metal oxide particles are dispersed in the oil, and the content of the nonionic surfactant having an HLB value of 10 or more is less than 1.0% by mass.
Oil-in-water emulsified cosmetic. The cosmetic according to claim 1, further comprising (e) polyhydroxystearic acid. The content of the metal oxide particles is 1.0% by mass or more and 30.0% by mass or less,
The content of the hydrophobically-modified alkyl cellulose is 0.05% by mass or more and 1.0% by mass or less,
The content of the aqueous phase thickener is 0.05 mass% or more and 3.0 mass% or less, and the oil content is 5.0 mass% or more and 40.0 mass% or less.
Cosmetics according to claim 1 or 2. The cosmetic material according to any one of claims 1 to 3, wherein the metal oxide particles are titanium oxide. The cosmetic material according to any one of claims 1 to 4, wherein the hydrophobically modified alkylcellulose is hydrophobically modified hydroxypropylmethylcellulose. The cosmetic according to any one of claims 1 to 5, wherein the aqueous phase thickener contains a vinyl polymer or an acrylic polymer. The cosmetic composition according to any one of claims 1 to 6, wherein 55% by mass or more of the oil content is polar oil. (f) The cosmetic according to any one of claims 1 to 7, further comprising an ionic surfactant. The cosmetic according to any one of claims 1 to 8, further comprising (g) a water-soluble polyether-modified silicone wax. The cosmetic according to any one of claims 1 to 9, which is an infrared protective cosmetic.