JP6869149B2 - Water-in-oil cosmetics - Google Patents

Description

The present disclosure relates to water-in-oil cosmetics.

Water-in-oil cosmetics having an oily component as a continuous phase are widely known, and various water-in-oil cosmetics have been proposed that claim UV protection, skin appearance correction effect, usability, and the like.
For example, Patent Document 1 contains (a) a phenyl group-containing partially crosslinked organopolysiloxane polymer, (b) a film-forming silicone resin, and (c) a powder having a refractive index of 1.4 to 1.8. The unevenness-correcting cosmetics characterized by this are disclosed. The unevenness-correcting cosmetics described in Patent Document 1 are said to be excellent in the unevenness-correcting effect and its durability, the cosmetics fit well on the skin, and the cosmetic film is soft.

Further, the water-absorbent polymer is used in various applications such as sanitary products, gardening products, and industrial products. In cosmetic applications, the water-absorbent polymer is used not only as a gelling agent but also as a fixing agent for preparations.
For example, Patent Document 2 discloses a cosmetic product having a cosmetic formulation mixed with a super absorbent polymer such as sodium polyacrylate as a cosmetic product contained in a container having a predetermined configuration. The container disclosed in Patent Document 2 is provided with a campus area in a storage tank constituting a contact portion with the cosmetics to be housed, and when the container is used, only the fluid part of the cosmetics passes through the campus area. , The super-absorbent polymer is retained in the storage tank. That is, the super-absorbent polymer disclosed in Patent Document 2 is used as a fixing agent for holding cosmetics in a storage tank provided in a container.

Japanese Unexamined Patent Publication No. 2013-1038885 Japanese Unexamined Patent Publication No. 2017-60738

By the way, in the conventional water-in-oil cosmetics, as one measure for improving the spreadability when applied to the skin, the amount of the oil agent is increased to reduce the viscosity of the oil phase. However, increasing the amount of the oil agent in the water-in-oil type cosmetics reduces the usability of the cosmetics. Specifically, both the oiliness when the fingers touch the skin to which the cosmetic is applied and the shine of the skin to which the cosmetic is applied become apparent.
Further, the water-in-oil cosmetics are preferably applied to cosmetics containing an ultraviolet inhibitor, but the conventional water-in-oil cosmetics obtain the desired ultraviolet protection ability without deteriorating the usability. It was difficult. That is, when an ultraviolet absorber is applied as an ultraviolet inhibitor, most of the ultraviolet absorbers are lipophilic compounds and are used by being dissolved in an oil agent. Therefore, ultraviolet rays are used so as to improve the ultraviolet protection ability to a desired level. The use of absorbents and oils may increase the oiliness. In addition, when an ultraviolet scattering agent is applied as an ultraviolet blocking agent, the ultraviolet scattering agent is a powder. Therefore, if the ultraviolet scattering agent is used to a level at which the ultraviolet blocking ability is desired, the cosmetic is applied to the skin. In addition, the elongation may be reduced, and the feeling of use may be impaired due to the rubbing of the inorganic powders against each other when spreading.

Therefore, the problem to be solved by one embodiment of the present invention is that it has an ultraviolet ray blocking ability, is excellent in elongation when applied to the skin, and is applied with both the oiliness felt by the fingers and the shine of the skin. It is to provide a water-in-oil cosmetic that is suppressed at the site.

Specific means for solving the above problems include the following embodiments.
<1> At least one UV inhibitor selected from the group consisting of oils containing silicone oil, modified silicone surfactants having a hydrophilic-lipophilic balance value of less than 6, UV absorbers and UV scatterers, water in oil. A water-in-oil type cosmetic containing 0% by mass or more and 5% by mass or less of a water-absorbent polymer and water with respect to the total amount of the type cosmetic.
<2> The water-in-oil cosmetic according to claim 1, further containing at least one inorganic pigment selected from the group consisting of color pigments, white pigments, pearl pigments and extender pigments.
<3> The water-in-oil cosmetic according to <1> or <2>, wherein the content of the ultraviolet inhibitor is 3% by mass or more with respect to the total amount of the water-in-oil cosmetic.
<4> The method according to any one of <1> to <3>, wherein the water-absorbent polymer is at least one polymer selected from crosslinked sodium polyacrylate and partially crosslinked carbomer or a salt thereof. Water-in-oil cosmetics.
<5> The water-in-oil cosmetic according to any one of <1> to <4>, wherein the ultraviolet inhibitor is a composite powder of titanium oxide and an ultraviolet absorber.
<6> The water-in-oil cosmetic according to any one of <1> to <5>, wherein the oil containing silicone oil contains 60% by mass or more of silicone oil with respect to the total amount of the oil.

According to one embodiment of the present invention, an oil having an ultraviolet ray blocking ability, excellent elongation when applied to the skin, and suppressing both the oiliness felt by the fingers and the shine of the skin at the application site. Medium water type cosmetics can be provided.

Hereinafter, an embodiment of the water-in-oil cosmetics of the present disclosure will be described. However, the water-in-oil cosmetics of the present disclosure are not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present disclosure.

The numerical range indicated by using "~" in the present disclosure means a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
In the present disclosure, the amount of each component in the water-in-oil cosmetic is the amount of each component in the water-in-oil cosmetic, unless otherwise specified, when a plurality of substances corresponding to each component are present in the water-in-oil cosmetic. It means the total amount of multiple substances present in the charge.
In the present disclosure, the combination of preferred embodiments is a more preferred embodiment.
In the present disclosure, the "oil phase" means a continuous phase of a water-based cosmetic in oil, and includes a liquid medium of the continuous phase and a component dispersed or dissolved in the liquid medium.
In the present disclosure, the "aqueous phase" means a dispersed phase of a water-based cosmetic in oil, and includes a liquid medium of the dispersed phase and a component dispersed or dissolved in the liquid medium.

In the present disclosure, the particle size of the inorganic particles can be determined by analyzing an image of an electron microscope such as a transmission electron microscope. Specifically, it can be obtained as the arithmetic mean of the major axis and the minor axis of the particles from the transmission electron micrograph.
When a commercially available product is used as the inorganic particles, the values described in the catalog or the like can be applied as they are. Here, the inorganic particles include both the inorganic particles as the ultraviolet scattering agent and the inorganic pigment.
The form of the inorganic particles present in the water-in-oil cosmetic is not particularly limited, and may be in the state of primary particles, or the primary particles aggregate to form a quadratic aggregate. You may be. When the inorganic particles form a secondary aggregate, the primary particle size may be confirmed by measuring the specific surface area such as a gas adsorption method, a transmission electron microscope, or the like.
Further, the shape of the inorganic particles is not particularly limited. Examples of the shape of the inorganic particles include a spherical shape, an elliptical shape, a plate shape, a crushed shape, and the like, but other shapes may be used.

<Water-in-oil cosmetics>
The water-in-oil cosmetic of the present disclosure is at least one selected from the group consisting of an oil containing silicone oil, a modified silicone surfactant having a hydrophilic-lipophilic balance value of less than 6, an ultraviolet absorber and an ultraviolet scattering agent. Contains a water-absorbing polymer of more than 0% by mass and 5% by mass or less based on the total amount of the UV inhibitor, water-based cosmetics in oil, and water.

In the present disclosure, at least one type of UV protection selected from the group consisting of the above-mentioned oil containing silicone oil, a modified silicone surfactant having a hydrophilic-lipophilic balance value of less than 6, an ultraviolet absorber and an ultraviolet scattering agent. The agent and the water-absorbent polymer may be appropriately referred to as "oil agent A", "modified silicone surfactant B", "ultraviolet inhibitor C" and "water-absorbent polymer D", respectively.
Further, the hydrophilic-lipophilic balance value of the modified silicone surfactant B may be abbreviated as an HLB (Hydrophile-Lipophile Balance) value.

In the present disclosure, "oil possa" means an undesired oily feeling felt by a finger touching an application site of a water-in-oil cosmetic.
In the present disclosure, "shiny" means an undesired oily luster that is confirmed at the application site of water-in-oil cosmetics.
The shine can be analyzed not only by visual evaluation but also by using an optical system measuring device. The shine can be analyzed by changing the angle between the incident light and the reflected light and measuring the reflected light applied to the sample, for example, like a goniometer. Specific examples of the measuring device include a goniometer automatic measuring device (Nikka Densoku Co., Ltd.).

By adopting the above-mentioned structure, the water-in-oil cosmetics of the present disclosure have excellent elongation when applied to the skin, and both the oiliness felt by the fingers and the shine of the skin are suppressed at the application site. To.
As described above, the reason why the water-in-oil cosmetics of the present disclosure are excellent in elongation when applied to the skin, and the reason why both the oiliness felt by the fingers and the shine of the skin are suppressed at the application site. Is presumed as follows, but is not limited to this.

The water-in-oil cosmetics of the present disclosure contain an oil agent A, a modified silicone surfactant B, an ultraviolet inhibitor C, a water-absorbent polymer D, and water.

The water-absorbent polymer D usually has a granular form, swells when it comes into contact with water, and has a function of retaining water, while it has a function of releasing water by an external force or a drying process, and absorbs water. A polymer that changes to its previous state.
The water-in-oil cosmetics of the present disclosure are applied to the skin by containing the water-absorbent polymer D in a content of more than 0% by mass and 5% by mass or less with respect to the total amount of the water-in-oil cosmetics. Excellent growth. It is considered that this is because the water-absorbent polymer D acts as a tactile improving agent. On the other hand, in the water-in-oil type cosmetic containing more than 5% by mass of the water-absorbent polymer D, a residue-like substance is generated when the cosmetic is applied (that is, when it is spread), and the usability or palatability Does not meet.
Then, on the skin after applying the water-in-oil cosmetics of the present disclosure (that is, after spreading), both the oiliness felt by the fingers and the shine of the skin are suppressed at the application site. This is because water is released from the water-absorbent polymer D by the coating operation and further evaporates with time, and the water-absorbent polymer D existing on the skin surface becomes a granular form, so that the oily feeling felt by the fingers touching the skin is reduced. However, it is considered that the light scattering effect is obtained by the water-absorbent polymer D in the granular form.

The user of the water-in-oil cosmetics of the present disclosure can realize that the oiliness and shine are suppressed, and that the skin feels plump and soft.

On the other hand, the above-mentioned Patent Document 1 (Japanese Unexamined Patent Publication No. 2017-60738) does not pay attention to the water-absorbent polymer.
Further, in Patent Document 2 (Japanese Unexamined Patent Publication No. 2017-60738), a super absorbent polymer such as sodium polyacrylate (corresponding to the superabsorbent polymer D in the present disclosure) as a cosmetic contained in a container having a predetermined configuration. A cosmetic formulation mixed with) is disclosed. However, the super-absorbent polymer disclosed in Patent Document 2 is used as a fixing agent for holding cosmetics in a storage tank provided in a container, and this super-absorbent polymer is intended to improve usability. It is not an ingredient to be used.

Hereinafter, the components that can be contained in the water-in-oil cosmetics of the present disclosure will be described in detail.

[Oil containing silicone oil]
The water-in-oil cosmetic contains an oil agent [oil agent A] containing silicone oil.
The oil agent A is a component that serves as a solvent or a dispersion medium in the composition that forms the oil phase of the water-in-oil cosmetic. Here, the oil agent is intended to be an oil agent that exhibits a liquid state at room temperature (25 ° C.).

The oil agent A contains a silicone oil from the viewpoint of emulsification stability of water-in-oil cosmetics and dispersibility of powders (for example, inorganic pigments, ultraviolet scattering agents, etc.) contained in the cosmetics. In the oil agent A, the silicone oil may be contained alone or in combination of two or more.
The oil agent A may contain only silicone oil, or may contain silicone oil and other oil agents.

The oil agent A preferably contains 60% by mass or more of silicone oil with respect to the total amount of the oil agent A, preferably 65% by mass or more, from the viewpoints of emulsion stability, powder dispersibility, sebum absorption of the oil-absorbing powder, and the like. Is more preferable, 75% by mass or more is more preferable, 80% by mass or more is more preferable, and 90% by mass or more is further preferable. Of course, all of the oil agent A may be silicone oil (that is, the content of the silicone oil in the oil agent A is 100% by mass).

Examples of the silicone oil include linear or branched polysiloxanes such as trisiloxane, methyltrimethicone, dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, methylhydrogenpolysiloxane, and diphenylsiloxyphenyltrimethicone, and octamethylcyclotetra. Examples thereof include cyclic polysiloxanes such as siloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, and caprylyl methicone. Among these, as the silicone oil, dimethylpolysiloxane (dimethicone) or decamethylcyclopentasiloxane is preferable.

Commercially available silicone oil products include KF-96L-0.65cs, KF-96L-1cs, KF-96L-1.5cs, KF-96L-2cs, KF-96L-5cs, KF-96A-6cs, KF- 96-10cs, KF-96-20cs, KF-995, KF-56A (Shin-Etsu Chemical Co., Ltd.), SH200 C Fluid 1CS, SH200 Fluid 1.5CS, SH200 C 2CS, SH200 C Fluid 5CS, SH200 C Fluid 6CS, SH200 C Fluid 10CS, SH200 C Fluid 20CS, 2-1184 Fluid, SH245 Fluid, DC246 Fluid, DC345 Fluid, SS-3408 (above, Toray Dow Corning Co., Ltd.), TSF404, TSF405, TSF45 Momentive Performance Materials Co., Ltd.).

Examples of the other oil agent contained in the oil agent A together with the silicone oil include ester oil and hydrocarbon oil.
The oil agent other than the silicone oil in the oil agent A may be contained alone or in combination of two or more.
When the ultraviolet inhibitor C described later contains an ultraviolet absorber, it preferably contains an ester oil from the viewpoint of solubility of the ultraviolet absorber.

Ester oils include pentaerythrityl tetraethylcaproate, cetyl ethylcaproate, jojoba oil, di (phytosteryl / octyldodecyl) lauroyl glutamate, triisostea, glyceryl diisostearate, triethylhexanoin, dimer dilinoleic acid (phytosteryl / behenyl). , Dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), isopropyl palmitate, macadamia nut fatty acid phytosteryl, tetra (bechenic acid / benzoic acid / ethylcaproic acid) pentaerythrityl, ethylhexyl palmitate, myristyl myristate, Examples thereof include tripropylene glycol dipivalate and isotridecyl isononanoate.

The hydrocarbon oil may be either linear or branched. Examples of the hydrocarbon oil include isoalkane (isoparaffin) having 8 to 16 carbon atoms such as isodecan, isododecane, and isohexadecane, mineral oil, and squalane.

The viscosity of the oil agent A at room temperature (25 ° C.) is preferably 1 mPa · s to 300 mPa · s, and from the viewpoint of elongation when the water-in-oil cosmetic is applied to the skin, stickiness at the time of application, and the like. 1 mPa · s to 50 mPa · s is more preferable, and 1 mPa · s to 30 mPa · s is even more preferable.

In the present disclosure, the viscosity of the oil agent A at room temperature (25 ° C.) can be measured by a known measuring method. Specifically, as the viscosity of the oil agent A, a value measured by the same measurement principle as the viscosity of the water-in-oil cosmetics described later at 25 ° C. can be used. The rotor, rotation speed, rotation time, etc. used for the measurement can be appropriately and appropriately changed according to the viscosity.

The content of the oil agent A in the water-in-oil cosmetics can be, for example, 1% by mass to 60% by mass, and 5% by mass to 50% by mass, based on the total amount of the water-in-oil cosmetics. It is preferably 10% by mass to 40% by mass, more preferably 12% by mass to 30% by mass.
The content of the oil agent A is such that the water-in-oil cosmetic contains the silicone oil contained together with the silicone gel when the water-in-oil cosmetic further contains the silicone gel containing the silicone oil among the silicone gels described later. The rate.

[Modified silicone surfactant with HLB value less than 6]
The water-in-oil cosmetic contains a modified silicone surfactant [modified silicone surfactant B] having an HLB value of less than 6.
The modified silicone surfactant refers to a silicone surfactant in which the silicone chains forming the main chain skeleton are not crosslinked and are modified with a hydrophilic organic group.
Depending on the structure of the organic group used for modification, there are various types such as polyether-modified silicone surfactant, polyglycerin-modified silicone surfactant, polyether-alkyl co-modified silicone surfactant, and polyglycerin-alkyl co-modified silicone surfactant. is there. The modified silicone surfactant B does not include a crosslinked organopolysiloxane polymer.
Further, as the modified silicone surfactant B, there are those in which the silicone chain forming the main chain skeleton is linear and those in which the silicone chain is branched.
As the modified silicone surfactant B, any of them can be used without limitation as long as the HLB value is less than 6.

Among the modified silicone surfactants B, a polyether-modified silicone surfactant and a polyether-alkyl co-modified silicone surfactant are preferable from the viewpoint of emulsifying property.
Further, among the modified silicone surfactant B, from the viewpoint of emulsion stability, it is preferable that the silicone chain forming the main chain skeleton is branched, that is, the branched silicone chain is preferably included in the structure, and the branched silicone chain is used. Polyether-modified silicones in the structure are particularly preferred.

The HLB value of the modified silicone surfactant B is preferably 1 or more and less than 6, more preferably 2 or more and less than 6, and 2 or more and 5 or less, from the viewpoint of emulsification stability of water-in-oil cosmetics. Is more preferable.
In the present disclosure, the HLB value of the modified silicone surfactant B is a value obtained from the molecular weight and the number of hydrophilic organic groups such as ethylene oxide groups. When a commercially available product is used, the HLB value described in a catalog or the like can be applied as it is.

Specific examples of the modified silicone surfactant B include PEG-3 dimethicone, PEG-9 methylether dimethicone, PEG-10 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and cetyl. Examples thereof include PEG / PPG-10 / 1 dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone.

Commercially available products of the modified silicone surfactant B include, for example, KF-6015, KF-6016, KF-6017, KF-6017P, KF-6028, KF-6028P, KF-6038, KF-6048 (above, Shin-Etsu Chemical). Industry Co., Ltd., etc.

Among the modified silicone surfactant B, at least one selected from PEG-9 polydimethylsiloxyethyl dimethicone and lauryl PEG-9 polydimethylsiloxyethyl dimethicone is preferable from the viewpoint of emulsifying property and emulsifying stability.

The content of the modified silicone surfactant B is preferably 0.03% by mass or more and less than 10% by mass, based on the total amount of the water-in-oil cosmetics, from the viewpoint of emulsifying property and emulsifying stability. It is preferably 0.05% by mass or more and 6% by mass or less, and most preferably 0.1% by mass or more and 5% by mass or less.
The modified silicone surfactant B may be contained alone or in combination of two or more in the water-in-oil type cosmetics.

[At least one UV protection agent selected from the group consisting of UV absorbers and UV scatterers]
The water-in-oil cosmetic contains at least one UV protection agent [UV protection agent C] selected from the group consisting of UV absorbers and UV scatterers.
The UV protection agent C may be contained alone or in combination of two or more in the water-in-oil cosmetics.

(UV absorber)
When the ultraviolet absorber C contains an ultraviolet absorber, the ultraviolet absorber may be contained alone or in combination of two or more in the water-in-oil cosmetics.

The ultraviolet absorber which is one aspect of the ultraviolet inhibitor C is not particularly limited as long as it is an ultraviolet absorber usually used for water-in-oil cosmetics.
In the water-in-oil cosmetics of the present disclosure, the ultraviolet absorber C may be dissolved and contained in the oil phase, or may be contained as a composite powder of the ultraviolet absorber and the inorganic powder as a base material. It may have been done.

Specific examples of the ultraviolet absorber include methoxycinnamic acid derivative, paraaminobenzoic acid (PABA) derivative, benzotriazine derivative, benzophenone derivative, benzalmalonate derivative, imidazoline derivative, phenylbenzimidazole derivative, salicylic acid derivative and the like. Ethylhexyl methoxycinnamate, hexyl diethylaminohydroxybenzoyl benzoate, octylriazone, bisethylhexyloxyphenol methoxyphenyltriazine, methylenebisbenzotriazolyltetramethylbutylphenol, octocrylene, polysilicone-15, t-butylmethoxydibenzoyl. Examples thereof include organic ultraviolet absorbers such as methane, ethylhexyl dimethoxybenzidioxyimidazolidine propionate, phenylbenzimidazole sulfonic acid, octyl salicylate, homosalate, and oxybenzone.
As the ultraviolet absorber, a commercially available product may be used.

As the ultraviolet absorber, at least one selected from ethylhexyl methoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate, t-butylmethoxydibenzoylmethane, octocrylene, octylriazone, and polysilicone-15) is suitable.

The UV inhibitor C may be titanium oxide or a composite powder of zinc oxide and a UV absorber (hereinafter, also referred to as a specific composite powder), and from the viewpoint of versatility, titanium dioxide and a UV absorber. The composite powder with and is more preferable. The specific composite powder may have an ultraviolet scattering ability.
The form of the composite powder is preferably a surface-treated powder containing titanium dioxide or zinc oxide as a base material and having an ultraviolet absorber on the surface. Examples of the composite powder that can be applied as the UV protection agent C include titanium dioxide as a base material and are also referred to as t-butylmethoxydibenzoylmethane (4-tert-butyl-4'-methoxydibenzoylmethane). A surface-treated powder having (.) On its surface is preferable (hereinafter, also referred to as UV absorber-coated titanium dioxide).
Examples of the composite powder applicable as the ultraviolet inhibitor C include the surface-treated powders described in paragraphs 0012 to 0017 of International Publication No. 2014-185316.
Examples of commercially available products of the above-mentioned composite powder include HXMT-100ZA (Tayca Corporation) and the like. Here, HXMT-100ZA is a composite powder in which surface-treated titanium dioxide is further surface-treated with t-butylmethoxydibenzoylmethane.

When the ultraviolet absorber is contained, the content of the ultraviolet absorber is preferably 3% by mass or more, more preferably 4% by mass or more, based on the total amount of the water-in-oil cosmetics. The content of the ultraviolet absorber is preferably 15% by mass or less, more preferably 10% by mass or less. The specific range of the content of the ultraviolet absorber is preferably 3% by mass to 15% by mass, more preferably 4% by mass to 10% by mass, based on the total amount of the water-in-oil cosmetics. ..
When the specific composite powder is contained as the UV absorber, the content of the UV absorber contained in the water-in-oil cosmetics, which is carried by the specific composite powder, is within the above range. Is preferable.
When the content of the ultraviolet absorber is within the above range, the ultraviolet protection effect is further improved.

(Ultraviolet scattering agent)
The ultraviolet scattering agent which is one aspect of the ultraviolet blocking agent C is not limited as long as it is an ultraviolet scattering agent usually used in cosmetics, and examples thereof include inorganic powders such as titanium dioxide and zinc oxide. The ultraviolet scattering agent referred to here does not include the above-mentioned specific composite powder.

<Zinc oxide>
The zinc oxide applied as an ultraviolet scattering agent is not particularly limited, and examples thereof include zinc oxide usually used as an ultraviolet scattering agent in cosmetics.

The zinc oxide applied as an ultraviolet scattering agent preferably has an average primary particle size of 40 nm or less, and more preferably zinc oxide having an average primary particle size of 30 nm or less. The content of zinc oxide having an average primary particle size of much larger than 40 nm tends to cause whitening or white residue. The lower limit of the average primary particle size of zinc oxide is not particularly limited, but the smaller the particle size, the more expensive it is. Therefore, considering economic efficiency, it may be 5 nm or more, preferably 10 nm or more. Zinc oxide.

The zinc oxide is preferably more dispersible, and for example, zinc oxide surface-treated by a known method can be used, if necessary.

As a method of surface treatment of zinc oxide, silicone treatment of methylhydrogenpolysiloxane, methylpolysiloxane, etc.; fluorine treatment with perfluoroalkyl phosphate, perfluoroalcohol, etc.; amino acid treatment with N-acylglutamic acid, etc.; Examples thereof include lecithin treatment; metal soap treatment; fatty acid treatment; alkyl phosphate treatment. Of these, zinc oxide with a silicone surface treatment is preferable.

The silicone used for the surface treatment of zinc oxide is not particularly limited, and is, for example, methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodeca. Methylcyclohexasiloxane, octamethyltrisiloxane, tetradecamethylhexasiloxane, dimethylsiloxane / methyl (polyoxyethylene) siloxane / methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxyethylene) siloxane co-weight Various silicone oils such as coalescing, dimethylsiloxane / methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane / methylcetyloxysiloxane copolymer, and dimethylsiloxane / methylstealoxysiloxane copolymer can be mentioned. The silicone used for the surface treatment of zinc oxide is preferably methylhydrogenpolysiloxane.
Silicone-treated zinc oxide is rich in water repellency, UV shielding property, transparency, adhesion, and dispersibility, and is useful when applying the water-in-oil cosmetics of the present disclosure to, for example, sunscreen cosmetics.

The amount of silicone used for the surface treatment of zinc oxide is usually in the range of 1% by mass to 20% by mass, preferably 2 to 14% by mass, and more preferably 2 to 10% by mass, based on 100% by mass of the silicone-treated zinc oxide. It is by mass, particularly preferably 2 to 5% by mass.
The method for treating zinc oxide with silicone is not particularly limited, and a conventionally known method can be appropriately selected and carried out.

Examples of commercially available zinc oxide products applied as ultraviolet scattering agents include MZ-300 (without surface treatment agent, particle size 30 to 40 nm, Teika Co., Ltd.), MZ-303S (methicone treatment, particle size 30 to 40 nm). , Teika Co., Ltd., MZ-303M (dimethicone treatment, particle size 30-40 nm, Teika Co., Ltd.), MZ-500 (no surface treatment agent, particle size 20-30 nm, Teika Co., Ltd.), MZ-505S (Meticcon treatment, particle size 20 to 30 nm, manufactured by Teika Co., Ltd.), MZ-505M (Dimethicon treatment, particle size 20 to 30 nm, Teika Co., Ltd.), MZ-700 (no surface treatment agent, particle size 10 to 20 nm) , Teika Co., Ltd., MZ-707S (Meticcon treatment, particle size 10 to 20 nm, Teika Co., Ltd.), FINEX-25 (no surface treatment agent, particle size 60 nm, manufactured by Sakai Chemical Co., Ltd.), FINEX-25LP (Dimethicone treatment, particle size 60 nm, Sakai Chemical Co., Ltd.), FINEX-50 (no surface treatment agent, particle size 20 nm, Sakai Chemical Co., Ltd.), FINEX-50LP (Dimethicone treatment, particle size 20 nm, Sakai Chemical Co., Ltd.) )), FINEX-75 (without surface treatment agent, particle size 10 nm, manufactured by Sakai Chemical Co., Ltd.) and the like.

A more preferred embodiment of the silicone-treated zinc oxide is dimethylhydrogenpolysiloxane-treated zinc oxide (surface treatment of 1% by mass to 5% by mass) having an average primary particle size of 5 nm to 40 nm.

<Titanium dioxide>
The titanium dioxide applied as an ultraviolet scattering agent is not particularly limited, and examples thereof include titanium dioxide usually used as an ultraviolet scattering agent in cosmetics.

The titanium dioxide applied as an ultraviolet scattering agent has an average primary particle size of several nm or more and 100 nm or less, and preferably has an average primary particle size of 30 nm or less, more preferably 20 nm or less. ..
When the average primary particle size is 30 nm or less, whitening or white residue tends to be less likely to occur. The lower limit of the average primary particle size is not particularly limited, but the smaller the particle size, the more expensive it becomes. Therefore, considering economic efficiency, it may be 5 nm or more, preferably 10 nm or more.

As the titanium dioxide applied as an ultraviolet scattering agent, one that has been surface-treated in order to enhance the ultraviolet scattering effect is preferable. As a surface treatment method for titanium dioxide, any treatment usually used in cosmetics can be used without any particular limitation. Examples of the surface treatment method include a method of adsorbing fats and oils on the surface of titanium dioxide; a fatty acid treatment method of treating titanium dioxide that has been esterified or etherified using a functional group such as a hydroxyl group with a fatty acid; in a fatty acid treatment method. , Metal soap treatment method using aluminum salt or zinc salt of fatty acid such as aluminum stearate or zinc stearate instead of fatty acid; silicone using methyl polysiloxane or methyl hydrogen polysiloxane instead of fatty acid in fatty acid treatment method. Treatment method: In the fatty acid treatment method, a method of further treating with a fluorine compound having a perfluoroalkyl group instead of the fatty acid and the like can be mentioned.

The titanium dioxide applied as an ultraviolet scattering agent is preferably aluminum stearate-treated titanium dioxide treated with aluminum stearate. The content of aluminum stearate contained in the aluminum stearate-treated titanium dioxide is not particularly limited, and may be 1% by mass to 20% by mass. The content of titanium dioxide contained in the aluminum stearate-treated titanium dioxide is preferably 80% by mass to 99% by mass.

Specific examples of titanium dioxide applied as an ultraviolet scattering agent include Typake CR-50 (aluminum oxide treatment, particle size 25 nm, manufactured by Ishihara Sangyo Co., Ltd.), Bayer Titanium R-KB-1 (zinc oxide treatment, aluminum oxide treatment). , Silicon dioxide treatment, particle size 30nm-40nm, manufactured by Bayer), Typake TTO-M-1 (zirconium oxide, aluminum oxide treatment, particle size 10nm-25nm, manufactured by Ishihara Sangyo Co., Ltd.), Typake TTO-D-1 (Zirconium oxide treatment, aluminum oxide treatment, particle size 20 nm to 30 nm, manufactured by Ishihara Sangyo Co., Ltd.), Sorabert CT-100, Soraber CT-200, Soraber CT-300, Soraber CT-434 manufactured by Crowder Japan Co., Ltd.) , STR-100 series, STR-40 (manufactured by Sakai Chemical Co., Ltd.). However, the present invention is not limited to these examples.

When the ultraviolet scattering agent C contains an ultraviolet scattering agent, the content of the ultraviolet scattering agent is preferably 0.5% by mass or more with respect to the total amount of the water-in-oil cosmetics from the viewpoint of the ultraviolet blocking effect. , More preferably 1% by mass or more, still more preferably 3% by mass or more. The content of the ultraviolet scattering agent is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of the effect corresponding to the increase in the blending amount and the formulation.
The specific range of the content of the ultraviolet scattering agent is preferably 5% by mass to 40% by mass, preferably 5% by mass to 40% by mass, if zinc oxide is contained in the total amount of the water-in-oil cosmetics. In the case of containing, the range of 0.5% by mass to 15% by mass is preferable.

The total content of the UV protection agent C is preferably 20% by mass or less, preferably 15% by mass or less, based on the total amount of the water-in-oil cosmetics, from the viewpoint of suppressing stickiness, creaking, and whitening after application. Is more preferable. Further, from the viewpoint of UV protection ability, 3% by mass or more is preferable, and 4% by mass or more is more preferable.

[Water-absorbent polymer]
The water-in-oil cosmetic contains a water-absorbent polymer [water-absorbent polymer D] of more than 0% by mass and 5% by mass or less based on the total amount of the water-in-oil cosmetics.
In water-in-oil cosmetics, the water-absorbent polymer D is preferably contained in the aqueous phase composition constituting the aqueous phase.

The water-absorbent polymer D in the present disclosure has a water absorption capacity of 10 to 2000 times, preferably 15 to 1500 times, more preferably 20 to 1000 times its own weight. That is, the water-absorbent polymer D is a polymer that absorbs 10 g to 2000 g of water per gram of the polymer.

The water absorption characteristics of the water-absorbent polymer D are defined under the conditions of normal temperature (25 ° C.) and normal pressure (760 mmHg, that is, 100,000 Pa) in distilled water.

The water-absorbent polymer D is contained in the water-in-oil cosmetic in the form of particles.
The form of the particles may be the form of primary particles such as spherical or substantially spherical, or the form of secondary particles (that is, agglomerate particles) in which primary particles are aggregated.

The average medium particle size of the water-absorbent polymer D is preferably 1 μm to 500 μm, more preferably 10 to 400 μm, and further preferably 15 to 300 μm from the viewpoint of usability after coating or water absorption.

The average medium particle size of the water-absorbent polymer D is measured by the following method.
The particle size of the water-absorbent polymer D is defined as the medium particle size, and is measured as follows.
0.25 g of amorphous silica (Degussa Japan Co., Ltd., Sipernat 200) is mixed with 50 g of the water-absorbent polymer D as a lubricant.
The water-absorbent polymer D is passed through a JIS standard sieve having a mesh size of 250 μm, and when the passing amount is 50% by mass or more, the combination of the sieves of (A) is passed, and the passing amount is less than 50% by mass. In the case of, the medium particle size is measured using the combination of sieves (B).
(A) From the top, a JIS standard sieve with a mesh size of 425 μm, a mesh size of 250 μm, a mesh size of 180 μm, a mesh size of 150 μm, a mesh size of 106 μm, a mesh size of 75 μm, and a mesh size of 45 μm. Combine the sieve and saucer in that order.
(B) From the top of the JIS standard sieve, a sieve with an opening of 850 μm, a sieve with an opening of 600 μm, a sieve with an opening of 500 μm, a sieve with an opening of 425 μm, a sieve with an opening of 300 μm, a sieve with an opening of 250 μm, and a sieve with an opening of 150 μm. Combine the sieve and saucer in that order.
The water-absorbent polymer D is placed in the best combined sieve and shaken for 20 minutes using a low-tap shaker to classify.
After classification, the mass of the water-absorbent resin remaining on each sieve is calculated as a mass percentage with respect to the total amount, and by integrating in order from the one having the largest particle size, the mesh of the sieve and the water-absorbent polymer D remaining on the sieve are calculated. The relationship with the integrated value of the mass percentage is plotted on a logarithmic probability paper. By connecting the plots on the probability paper with a straight line, the particle size corresponding to the cumulative mass percentage of 50% by mass is set as the medium particle size.

An example of the water-absorbent polymer D is sodium polyacrylate. Sodium polyacrylate is produced by polymerizing acrylic acid mixed with sodium hydroxide in the presence of an initiator to obtain polyacrylic acid, and further forming a sodium salt of polyacrylic acid. As described later, a suitable water-absorbent polymer D in the present disclosure is a polymer having a crosslinked structure (hereinafter, also referred to as a crosslinked polymer) or a salt thereof, and the sodium polyacrylate mentioned in this example is also a crosslinked polyacrylic acid polymer. Or it is preferably one aspect of the salt thereof.
Other examples of the water-absorbent polymer D include polyacrylamide copolymers, ethylene anhydride maleic acid copolymers, crosslinked carboxymethyl celluloses, polyvinyl alcohol copolymers, crosslinked polyethylene oxides, starch polyacrylonitrile graft copolymers and the like. ..
Other examples of water-absorbent polymer D include starch grafted with an acrylic polymer (homopolymer or copolymer) (eg, starch grafted with sodium polyacrylate), water grafted with an acrylic polymer (homopolymer or copolymer). Degraded starch, acryloacrylamide / sodium acrylate copolymer, starch-based polymer, hydrolyzed starch grafted with rubber and cellulose derivatives and the like can also be mentioned.

The water-absorbent polymer D is preferably selected from a crosslinked polymer or a salt thereof.
The water-absorbent polymer used in the present invention is preferably a crosslinked polyacrylic acid polymer or a salt thereof. The crosslinked polyacrylic acid polymer may be a homopolymer or a copolymer. The salt is preferably a sodium salt. The crosslinked polyacrylic acid polymer is preferably neutralized and in the form of agglomerates or particles.

The water-absorbent polymer D is preferably a crosslinked polyacrylic acid homopolymer or a salt thereof, and is at least one polymer selected from crosslinked sodium polyacrylate and a partially crosslinked carbomer or a salt thereof. More preferred.
These crosslinked polyacrylic acid homopolymers or salts thereof contain components labeled by cosmetic labeling names such as Acrylate Crosspolymer-2-Na and Carbomer Na. Examples of these commercially available products include AQUA KEEP 10SH-NFC and Akpek MG. "AQUA KEEP" and "Akpek" are registered trademarks of Sumitomo Seika Chemical Co., Ltd.

Specific examples of commercially available products of the water-absorbent polymer D include the following products, but these are not particularly limited.

Examples of the crosslinked polyacrylic acid polymer and its salt include AQUA KEEP SA60S, AQUA KEEP SA60NSX II, AQUA KEEP SA60N TYPE II, AQUA KEEP SA60N TYPE II, AQUA KEEP CA300N, AQUA KEEP 10SH, AQUA KEEP SA60S, AQUA KEEP SA60NSX II, AQUA KEEP SA60N TYPE II, AQUA KEEP SA60N CA180N, AQUA KEEP 10SH-NF, AQUA KEEP 10SH-NFC, Akpek MG, San-Dia Polymers Sanwet770H, Dow Chemical's DOWN S100R, Evonik's CREALBLOC Innospec Performance Chemicals, Inc. of Activsoft MS100, the Dow Chemical Company, Inc. of ACUSOL 445, ACUSOL 445N, ACUSOL 445ND, BASF Personal Care and Nutrition Inc. of Cosmedia SP, Sensient Cosmetic Technologies, Inc. of Covacryl Ac, Covacryl J22, Covacryl MV60, Covacryl RH, Examples include Ashland's RapiTix A-100, Toa Synthetic's Rheogic250H, Rheogic270, Rheogic260H, and Rheolabs' Rheosol AP.
In addition to the above, starch grafted with an acrylic polymer such as Makimousse SV12, Makimousse SV25 manufactured by Daito Kasei Kogyo Co., Ltd., Lysorb 220 manufactured by Lysac, etc., or hydrolyzed starch can also be mentioned.

The content of the water-absorbent polymer D is more than 0% by mass and 5.0% by mass or less, preferably 0.01% by mass or more and 5% by mass or less, more preferably, based on the total amount of the water-in-oil cosmetics. Is in the range of 0.1% by mass or more and 5% by mass or less, more preferably 0.2% by mass or more and 2% by mass or less.

It is preferable that the water-absorbent polymer D is hydrated with water (that is, the water-absorbent polymer in a dry state absorbs water) before being contained in the water-in-oil cosmetic. The water-absorbent polymer may be absorbed to a saturated state, or may be in a state of partially absorbing water.
The water-absorbent polymer D may be mixed with the aqueous phase composition in the production of the water-in-oil cosmetic, or may be mixed with the aqueous phase composition and the emulsion prepared in advance by the oil phase composition.

The water-in-oil cosmetics of the present disclosure contain the water-absorbent polymer D, so that they have excellent elongation when applied to the skin, and both the oiliness felt by the fingers and the shine of the skin are present at the application site. It is suppressed. Further, a soft focus effect can be expected due to the fact that the water-absorbent polymer D is in the form of particles.

The soft focus effect is an effect of increasing diffused light, reducing shadows, and blurring when light is applied to an object. To confirm the soft focus effect, specifically, a permeable membrane coated with the water-in-oil cosmetics of the present disclosure as a soft focus base is installed between the object and the observation point, and the applied object and the object are confirmed. It can be judged by the clarity of.
As the object, characters, lines and the like may be printed, and a resolution test chart, a linear test chart and the like are also preferably used.

〔water〕
Water-in-oil cosmetics contain water.
Water is a component that serves as a solvent or a dispersion medium in the composition that forms the aqueous phase of water-in-oil cosmetics.
The water is not particularly limited as long as it can be applied to cosmetics.
The water content is not particularly limited as long as the amount of the cosmetic can be emulsified in a water-in-oil type. The water content can be, for example, 80% by mass or less, preferably 20% by mass to 75% by mass, and more preferably 30% by mass to 70% by mass, based on the total amount of the water-based cosmetics in oil.

[At least one inorganic pigment selected from the group consisting of color pigments, white pigments, pearl pigments and extender pigments]
The water-in-oil cosmetics of the present disclosure contain at least one inorganic pigment (hereinafter, also referred to as "inorganic pigment E") selected from the group consisting of coloring pigments, white pigments, pearl pigments and extender pigments. Is preferable.

In the present disclosure, the "colored pigment" means a colored pigment whose hue can be adjusted, and a pigment other than a white pigment and a pearl pigment.
In the present disclosure, the "white pigment" means a pigment exhibiting a white hue.
In the present disclosure, the "constituent pigment" means a pigment that does not substantially contribute to the adjustment of hue.
In the present invention, the "pearl pigment" is a pigment that can contribute to the adjustment of hue or glossiness, and means a pigment having brightness or pearly luster.

The inorganic particles E may be appropriately selected depending on the use of the water-in-oil cosmetic, compatibility with the oil agent A, and the like.
Further, the inorganic particles E may be contained alone or in combination of two or more in the water-in-oil cosmetic.
Further, the surface of the inorganic particles E may be hydrophobized.

Specific examples of the coloring pigment include iron oxide, chromium oxide and the like.
Specific examples of the white pigment include titanium dioxide, zinc oxide, cerium oxide and the like.
Specific examples of the pearl pigment include mica titanium, fish phosphorus foil, bismuth oxychloride and the like.
Specific examples of extender pigments include talc, mica, sericite, kaolin, alumina, silica, silicic anhydride, barium sulfate, boron silicate, synthetic phlogopite and the like.

The inorganic pigment E has a larger particle size than the above-mentioned ultraviolet scattering agent, and is clearly distinguished from the ultraviolet scattering agent. Specifically, the inorganic pigment E has a particle size of 0.15 μm or more. For example, in the case of titanium dioxide, which is one aspect of a white pigment, the average primary particle size is several hundred nm or more. On the other hand, the average primary particle size of titanium dioxide applied as an ultraviolet scattering agent is several nm or more and 100 nm or less as described above.

As the inorganic particles E, a commercially available product can also be used. Examples of commercially available products are given below, but the present invention is not limited thereto.
Examples of commercially available color pigments include OTS-2 RED R-516L (red iron oxide), OTS-2 BLACK BL-100 (black iron oxide), and OTS-2 YELLOW LLXLO (yellow iron oxide) (above, Daito). Kasei Kogyo Co., Ltd., etc. can be mentioned.
Examples of the white pigment include OTS-2 TIM ₂ CR-50, SI06 TiO ₂ TTO-55, SI06 TiO ₂ CR-50 (all, Daito Kasei Kogyo Co., Ltd.) and the like.
Examples of commercially available pearl pigments include Ronaflare Balance Gold and Ronaflare Balance Red (Merck).
Examples of commercially available extender pigments include mica such as SERICITE FSE (Sanshin Mining Ind. Co., Ltd.) and synthetic phlogopite PDM series (Topy Industries, Ltd.).

The water-in-oil cosmetics preferably contain the inorganic pigment E in the oil phase.
Here, the fact that the inorganic particles E are contained in the oil phase means that the inorganic particles E are present in the oil phase which is a continuous phase. The inorganic particles E are preferably dispersed in the oil phase in order to facilitate the function of the inorganic particles E themselves.
In order to include the inorganic pigment E in the oil phase, the inorganic particles E may be mixed with other components constituting the oil phase composition in the production of the water-in-oil cosmetic.

The method for confirming the presence of the inorganic particles E in the oil phase in the present disclosure is as follows.
That is, the measurement sample (water-in-oil cosmetic) is subjected to centrifugation, the layer obtained by separating or extracting by centrifugation is subjected to elemental analysis, and based on the result, the components used in the formulation of the measurement sample. The presence of the inorganic particles E in the oil phase can be confirmed by the analysis in comparison with (the ingredient display of cosmetics may be used). At the time of this measurement, the measurement sample may be diluted with an organic solvent or water, or means necessary for analysis and analysis may be appropriately used, such as a step or treatment for removing substances other than the inorganic particles E.

The content of the inorganic pigment E is preferably 0.5% by mass or more and 30% by mass or less with respect to the total amount of the water-in-oil cosmetics. The content of the inorganic pigment E is preferably 30% by mass or less from the viewpoint of emulsion stability. Further, from the viewpoint of the expression of the function expected of the inorganic pigment E (for example, concealment of stains and the like), it is more preferably 3% by mass or more. A more preferable range of the content of the inorganic pigment E is 5% by mass or more and 25% by mass or less.

[Silicone gel]
The water-in-oil cosmetics of the present disclosure may contain a silicone gel from the viewpoint of emulsion stability and the like.
In the present disclosure, the silicone gel refers to a crosslinked product in which the silicone chains forming the main chain skeleton are crosslinked with a polyether chain, a polyglycerin chain, a silicone chain, or the like.
Depending on the structure of the chain used for cross-linking, there are types such as polyether-modified silicone gel, polyglycerin-modified silicone gel, polyether-alkyl co-modified silicone gel, and polyglycerin-alkyl co-modified silicone gel. The water-in-oil cosmetics of the present disclosure can be used without limitation.

Specific examples of the silicone gel include (dimethicone / (PEG-10 / 15) crosspolymer, (PEG-15 / lauryldimethicone) crosspolymer, (PEG-10 / lauryldimethicone) crosspolymer, (PEG-15 / lauryl). Polydimethylsiloxyethyl dimethicone) crosspolymer, (dimethicone / polyglycerin-3) crosspolymer, (lauryldimethicone / polyglycerin-3) crosspolymer, (polyglyceryl-3 / laurylpolydimethylsiloxyethyl dimethicone) crosspolymer, (dimethicone / Examples include (vinyl dimethicone) crosspolymer, (dimethicone / phenylvinyldimethicone) crosspolymer, (vinyldimethicone / lauryldimethicone) crosspolymer, (laurylpolydimethylsiloxyethyldimethicone / bisvinyldimethicone) crosspolymer, etc.

Commercially available silicone gel products include KSG-210, KSG-240, KSG-310, KSG-320, KSG-330, KSG-340, KSG-320Z, KSG-350Z, KSG-360Z, KSG-380Z, KSG- 710, KSG-810, KSG-820, KSG-830, KSG-840, KSG-820Z, KSG-850Z, KSG-15, KSG-1510, KSG-16, KSG-1610, KSG-18A, KSG-19, Examples thereof include KSG-016F, KSG-41A, KSG-42A, KSG-43A, KSG-44A, KSG-042Z, KSG-045Z, KSG-048Z (above, Shin-Etsu Chemical Co., Ltd.).

Among silicone gels, (dimethicone / (PEG-10 / 15) crosspolymer and (dimethicone / vinyldimethicone) crosspolymer are available from the viewpoint of availability, swellability to oil agent A such as silicone oil, and emulsion stability. At least one selected from the group consisting of (dimethicone / (PEG-10 / 15) crosspolymer is preferable, and (dimethicone / vinyldimethicone) crosspolymer is more preferable in combination.

The content of the silicone gel in the water-in-oil cosmetics is preferably, for example, 0.1% by mass to 8% by mass, and 0.25% by mass to the total amount of the water-in-oil cosmetics. It is more preferably 4.5% by mass, and even more preferably 0.5% by mass to 3% by mass.
The silicone gel in the water-in-oil cosmetic of the present embodiment may be contained alone or in combination of two or more.

[Other ingredients]
The water-in-oil cosmetic may contain other components other than the above-mentioned components as long as the effects are not impaired.
Other ingredients may be ingredients that can be blended in cosmetics, such as moisturizers, tactile improvers, surfactants other than modified silicone surfactant B, water-soluble organic solvents, preservatives (phenoxyethanol, methylparaben, etc.), Examples include pH adjusters, antioxidants, whitening agents, and fragrances.

Examples of the moisturizing agent and the feel improving agent include glycerin, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and the like. Polyols such as trimethylolpropane, pentaerythritol, hexylene glycol, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymers and their polymers; diethylene glycol monoethyl ether Glycoalkyl ethers such as (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether; (eicosandioic acid / tetradecanedioic acid) polyglyceryl-10 esters and the like can be mentioned.

[Viscosity of water-based cosmetics in oil]
In the water-in-oil cosmetics of the present disclosure, the viscosity corresponding to the filling container may be appropriately determined. When the water-in-oil cosmetic is stored in a tubular container, the viscosity at 25 ° C. is preferably 3000 mPa · s or more, more preferably 4000 mPa · s or more, and from the viewpoint of viscosity stability, due to concerns about dripping. Therefore, 15,000 mPa · s or more is more preferable, and 20,000 mPa · s or more is particularly preferable. When the water-in-oil cosmetic is stored in a pump container, it is preferable that the viscosity at 25 ° C. is 4000 mPa · s or less from the viewpoint of suppressing the residue on the container wall. When the water-in-oil cosmetic is stored in the airless pump, the viscosity is not particularly limited as long as it can be discharged. Further, the viscosity of the water-in-oil cosmetics of the present disclosure at 25 ° C. is preferably 60,000 mPa · s or less from the viewpoint of good elongation.
In the present disclosure, the viscosity of water-in-oil cosmetics at 25 ° C. is not limited as long as it is a known method for measuring viscosity. For example, for the measurement of viscosity, a value measured by stirring for 60 seconds at a rotor rotation speed of 6 rotations / minute can be used using a BL type viscometer (M4 rotor). As the BL type viscometer, for example, VISCOMETER TVB-10 manufactured by Toki Sangyo Co., Ltd. can be preferably used. However, the BL type viscometer is not limited to this.

[Aqueous phase ratio of water-based cosmetics in oil]
In the water-in-oil cosmetics, the aqueous phase ratio, which is the dispersed phase, is preferably 20% by mass or more, more preferably 25% by mass or more, and more preferably 30% by mass from the viewpoints of emulsion stability, inhibition of precipitation of aqueous components, and the like. % Or more is more preferable.
The upper limit of the aqueous phase ratio is preferably 85% by mass, more preferably 80% by mass, from the viewpoint of emulsifying property and emulsifying stability.
The aqueous phase ratio referred to here represents the ratio of the total amount of the components constituting the aqueous phase (that is, the content of the aqueous phase composition) to the total amount of all the components (the total amount of water-based cosmetics in oil). It is a thing.

<Use of water-based cosmetics in oil>
Examples of the use of water-in-oil cosmetics include makeup cosmetics, and in particular, makeup bases, base makeup cosmetics such as BB (Blemish Balm) cream, sunscreen cosmetics, and the like. There are no restrictions.

<Manufacturing method of water-based cosmetics in oil>
The method for producing the water-in-oil cosmetics of the present disclosure is not particularly limited, and can be produced according to a known method for producing water-in-oil cosmetics.
For example, an oil phase composition containing an oil agent A, a modified silicone surfactant B, and an ultraviolet inhibitor C is prepared, and the obtained oil phase composition contains a water-absorbent polymer D and water. By mixing and emulsifying the aqueous phase composition to be used, a water-in-oil cosmetic can be produced.
An oil phase composition containing an oil agent A, a modified silicone surfactant B, an ultraviolet inhibitor C, an inorganic pigment E, and a silicone gel, an aqueous phase composition containing a water-absorbent polymer D, and water. It is more preferable to prepare the product and each of them, mix the aqueous phase composition with the obtained oil phase composition, and emulsify the product to produce a water-in-oil cosmetic.

The emulsification method when the oil phase composition and the aqueous phase composition are mixed to obtain a water-in-oil emulsion as a water-in-oil emulsion is not particularly limited and can be carried out according to a conventional method. ..
The conditions for emulsification may be determined by adjusting the shear rate, treatment time, etc. according to the viscosity required for the water-in-oil cosmetic, the size of the emulsified particles (aqueous phase), and the like.

Hereinafter, the water-in-oil cosmetics of the present disclosure will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.

[Examples 1 to 4, Comparative Examples 1 to 4]
An oil phase composition was obtained using each component shown in Table 1.
Specifically, a slurry was prepared with an ultraviolet absorber-coated titanium dioxide, sorbitan sesquioleate, a part of dimethicone, and a part of PEG-9 polydimethylsiloxydiethyldimethicone, and the remaining silicon-based polymer was added to the obtained slurry. , Silicone surfactant, silicone oil, and polysilicone 15 were mixed and treated with a disper to obtain an oil phase composition.

An aqueous phase composition was obtained using each component shown in Table 1.
Specifically, a part of purified water and a water-absorbing polymer were allowed to absorb water, and then the remaining aqueous components were mixed and dissolved to obtain an aqueous phase composition.
Next, the aqueous composition is added to the oily composition and emulsified by anchor stirring so as not to separate, and after mixing the aqueous composition, a water-absorbing polymer soaked with water is added to form a water-in-oil type. An emulsion was obtained. If necessary, the water-absorbent polymer may be added to the oily composition before emulsification, or the anchor stirring may be changed to the homomixer treatment.

Each component used in Examples 1 to 4 and Comparative Examples 1 to 4 and the content (% by mass) thereof are shown in the column of composition in Table 1. In addition, "-" in the column of composition indicates that the component is not contained.
The "content rate of silicone oil in the oil agent" in Table 1 indicates the content rate (mass%) of the silicone oil in the oil agent included in the oil agent A.
Details of each component used in Examples and Comparative Examples in the present disclosure are as follows.

-Dimethicone: KF-96A-5cs (Shin-Etsu Chemical Co., Ltd.)
-Cyclopentasiloxane: KF-995 (Shin-Etsu Chemical Co., Ltd.)
・ Tri (caprylic acid / capric acid) glyceryl: Coconade (Kao Corporation)
-Cetyl 2-ethylhexanoate: NIKKOL (registered trademark) CIO (Nikko Chemicals Co., Ltd.)

(Dimethicone / (PEG-10 / 15)) Crosspolymer: KSG-210 (swelling due to dimethicone, containing 30% by mass of crosspolymer, Shin-Etsu Chemical Co., Ltd.)
-(Dimethicone / Vinyl dimethicone) Crosspolymer: KSG-15 (swelling of cyclopentasiloxane, containing 5% by mass of crosspolymer, Shin-Etsu Chemical Co., Ltd.)
・ Diphenylsiloxyphenyltrimethicone: KF-56A, Shin-Etsu Chemical Co., Ltd.

-PEG-9 polydimethylsiloxyethyl dimethicone: KF-6028 (HLB value 4.5, Shin-Etsu Chemical Co., Ltd.)
・ Sorbitan sesquioleate: Leodor AO-15V, Kao Corporation

UV absorber-coated titanium dioxide: HXMT-100ZA (titanium oxide surface-treated with aluminum hydroxide and stearic acid, further surface-treated with 4-tert-butyl-4'-methoxydibenzoylmethane, TAYCA ( stock))
-Polysilicone-15: Pulsol SLX (DSM Nutrition)

・ Acrylate Cross Polymer-2-Na: Aqua Keep 10SH-NFC (crosslinked sodium polyacrylate, Sumitomo Seika Chemical Co., Ltd.)
・ Carbomer Na: Akpek MG NR40 (partially cross-linked carbomer: Sumitomo Seika Chemical Co., Ltd.)
-Carbo-mer: Carbo-mer 980 (non-crosslinked carbomer, Lubrizol)
-Polymethylsilcesioxane: KMP-591 (feel improver, Shin-Etsu Chemical Co., Ltd.)

-Mixture of inorganic pigment: Mixture of the following iron oxide ... Red Iron oxide Red (OTS-2 RED R-516L, Daito Kasei Kogyo Co., Ltd.)
・ ・ Black Iron Oxide Black (OTS-2 BLACK BL-100, Daito Kasei Kogyo Co., Ltd.)
・ ・ Yellow Iron Oxide Yellow (OTS-2 YELLOW LLXLO, Daito Kasei Kogyo Co., Ltd.)

・ BG: 1,3-butylene glycol

[Evaluation]
The emulsions of Examples 1 to 4 and the water-in-oil emulsions obtained in Comparative Examples 1 to 3 (that is, water-in-oil cosmetics) were evaluated as follows. The evaluation of "covering power" was performed only on Example 4 containing a mixture of inorganic pigments (included in inorganic pigment E).
When the emulsion of Comparative Example 4 was applied and spread, it could not be applied uniformly because it gathered in the form of residue on the skin. Therefore, in Comparative Example 4, the following evaluations were not performed, and the evaluation result column was described as "cannot be evaluated". Therefore, it is determined that the emulsion of Comparative Example 4 is an emulsion in a state where it cannot be applied as a cosmetic.

(Good growth)
We asked four specialized panelists to spread 100 μL of water-in-oil cosmetics in the examples and comparative examples on the inside of the forearm with their fingers, and at that time, did the emulsion follow the movement of the fingers and spread easily? Was evaluated. The evaluation criteria are as follows.
Evaluation levels 3, 4 and 5 are practically acceptable levels. It is judged that the larger the evaluation level value is, the more preferable it is. The results are shown in Table 1.
-Evaluation criteria-
5: Very good growth.
4: Good growth.
3: It grows moderately to the extent that it is acceptable as a cosmetic.
2: It does not spread well and feels heavy when spread.
1: Very poor spread and difficult to spread.

(Oilness)
We asked four specialized panelists to apply 100 μL of water-in-oil cosmetics of Examples and Comparative Examples to the inside of the forearm with their fingers, and when they touched the skin after application, they felt it on their fingers. The oily feeling was evaluated as oily. Evaluation levels 3, 4 and 5 are practically acceptable levels. It is judged that the larger the evaluation level value is, the more preferable it is. The results are shown in Table 1.
The evaluation criteria are as follows.
-Evaluation criteria-
5: Smooth and does not feel oily at all.
4: It is not petty and feels almost no oiliness.
3: It's petty and oily, but it doesn't bother me.
2: It's petty and oily.

(Shikari)
Four specialized panelists were asked to apply 100 μL of water-in-oil cosmetics of Examples and Comparative Examples to the inside of the forearm, and the arm after application was held over the light, and the light was reflected on the applied part. Was visually evaluated and evaluated as shiny. The evaluation criteria are as follows. Evaluation levels 3, 4 and 5 are practically acceptable levels. It is judged that the larger the evaluation level value is, the more preferable it is. The results are shown in Table 1.
-Evaluation criteria-
5: There is no shine and it feels matte.
4: I don't feel shiny.
3: There is shine, but I don't care.
2: I'm worried about the shine.

(Cover power)
The water-in-oil cosmetic of Example 4 was applied to a bioskin sheet (Bulux Co., Ltd.) having a dyeing part simulating a stain ^{so as to be 0.6 mg / cm 2,} and after leaving it to stand, the color was changed. The dyed and unstained areas were measured with a color difference meter CR-700d (Konica Minolta Co., Ltd.) to obtain brightness L *, a *, b *, and saturation C * at the respective C light sources. .. The results are shown in Table 1.
The color difference ΔE between the value obtained in the dyed part and the value obtained in the undyed part was calculated by the following formula.
Color difference (ΔE) = {(ΔL *) ² + (Δa *) ² + (Δb *) ² } ^1/2
The evaluation criteria are as follows.
-Evaluation criteria-
3: The color difference (ΔE) was 2 or less.
2: The color difference (ΔE) was more than 2 and 4 or less.
1: The color difference (ΔE) is larger than 4.

(UV protection)
When the SPF value of each of the water-in-oil cosmetics of Examples and Comparative Examples was measured by the following measuring methods, it was confirmed that all of them had an SPF of 20 or more and had a practically acceptable level of UV protection. It was.
Each of the water-in-oil makeup of Examples and Comparative Examples was weighed and applied to a PMMA plate at 32 mg / sheet to prepare a sample. The sample is dried and the SPF value is calculated using an SPF analyzer.

As shown in Table 1, the water-in-oil cosmetics of each example have excellent UV protection ability, excellent spreadability when applied to the skin, and both oiliness and shine. It can be seen that it is suppressed. Further, it can be seen that the water-in-oil type cosmetic of Example 4 is further excellent in covering power.

On the other hand, in Comparative Example 1, since the water-absorbent polymer D was not contained, the elongation when the cosmetic was applied was inferior in comparison with each example, and the oiliness and shine were practically unacceptable levels. ..
Comparative Example 2 does not contain the water-absorbent polymer D and contains a non-crosslinked carbomer, and although elongation when applying the cosmetic is obtained, oiliness and shine are unacceptable levels for the cosmetic. Met.
Comparative Example 3 does not contain the water-absorbent polymer D and contains polymethylsilcesioxane (feel improver), and although oiliness and shine are suppressed, when applying cosmetics to the skin. The growth was at a practically unacceptable level.
Comparative Example 4 was an emulsion in a state where it could not be applied as a cosmetic, as described above.

[Example 5: Liquid foundation]
A liquid foundation (W / O emulsion) having the following composition was prepared by a conventional method (total amount 100% by mass).
[Composition] [Content (% by mass)]
・ Acrylate Cross Polymer-2-Na 0.5
・ Dipotassium glycyrrhizinate 0.2
・ Composite powder pigment ^{* 1} 0.5
・ Constituent pigment ^{* 2} 7.0
・ Color material pigment ^{* 3} 12.0
・ Pearl pigment ^{* 4} 1.0
・ Cyclopentasiloxane 20.0
・ Dimethicone 10.0
Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 3.0
PEG-9 polydimethylsiloxyethyl dimethicone 1.2
・ Squalene 0.1
・ Sorbitan sesquiisostearate 1.0
・ Disteardimonium hectorite 0.8
-Ethylhexyl methoxycinnamate 2.5
・ Hematococcus bulbiaris oil 0.1
・ Tocopherol 0.1
・ Damask rose flower oil trace amount ・ Fragrance appropriate amount ・ Phenoxyethanol 0.3
・ Glycerin 10.0
・ Dipropylene glycol 4.0
・ 1,3-butylene glycol 3.0
・ Water-soluble collagen 0.1
・ Royal jelly extract 0.1
-Polyoxyethylene hydrogenated castor oil (60EO) 0.2
・ Ca chloride 1.0
・ Citric acid 1.0
・ Sodium citrate Appropriate amount ・ Remaining amount of purified water

In the above composition, the following pigments were used as the pigments shown by * 1 to * 4. (The same applies to the subsequent examples.)
* 1: HNB RED7 (manufactured by Daito Kasei Co., Ltd.)
* 2: OTS-2 SERICITE PSE and OTS-2 TALK JA-46R (both manufactured by Daito Kasei Co., Ltd.) mixed at a ratio of 7: 3 * 3 OTS-2 TIO2 CR-50 and OTS-2 YELLOW LLXLO, OTS-2 RED R-516L and OTS-2 BLACK BL-100 (all manufactured by Daito Kasei Co., Ltd.) mixed at a ratio of 78: 19: 1: 2 * 4 Ronaflare Balance Gold and Ronaflare Balance red (both manufactured by MERCK) mixed at a ratio of 1: 1

[Example 6: Sunscreen agent]
A sunscreen agent having the following composition was prepared by a conventional method (total amount 100% by mass).
[Composition] [Content (% by mass)]
・ Acrylate Cross Polymer-2-Na 0.75
・ Cyclopentasiloxane 20.0
・ Dimethicone 10.0
Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 2.0
PEG-9 polydimethylsiloxyethyl dimethicone 1.0
-KSG-15 ((dimethicone / vinyl dimethicone) crosspolymer cyclopentasiloxane swelling, containing 5% by mass of crosspolymer, Shin-Etsu Chemical Co., Ltd.) 2.0
・ HXMT-100ZA (TAYCA, average primary particle size 15 nm) 12.0
・ Sorbitan sesquioleate 1.0
・ Dipotassium glycyrrhizinate 0.5
-Phosphate-L-ascorbyl magnesium 0.1
・ Krill extract 0.5
・ Water-soluble collagen 1.0
・ Citric acid 0.7
・ Suitable amount of sodium citrate ・ Tocopherol 0.5
・ Color material pigment * 3 5.0
-Polyoxyethylene hydrogenated castor oil (60EO) 0.2
・ Fragrance ・ Methyl paraoxybenzoate 0.15
・ Remaining amount of purified water

[Example 7: Makeup base]
A makeup base having the following composition was prepared by a conventional method (total amount 100% by mass).
[Composition] [Content (% by mass)]
・ Acrylate Cross Polymer-2-Na 0.75
・ Dimethicone 4.0
・ Cyclopentasiloxane 8.0
-KSG-210 (dimethicone / (PEG-10 / 15)) crosspolymer dimethicone swelling, containing 30% by mass of crosspolymer, Shin-Etsu Chemical Co., Ltd. 2.0
-KSG-15 ((dimethicone / vinyl dimethicone) crosspolymer cyclopentasiloxane swelling, containing 5% by mass of crosspolymer, Shin-Etsu Chemical Co., Ltd.) 2.0
-PEG-9 polydimethylsiloxyethyl dimethicone 0.3
Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 0.5
Hydrophobicized surface treatment Titanium oxide (HXMT-100ZA, TAYCA CORPORATION) 4.5
・ Composite powder pigment * 1 0.01
・ Constituent pigment * 2 2.0
・ Color material pigment * 3 5.0
・ Sodium chloride 1.0
・ Ethanol 1.0
・ Glycerin 3.0
・ Phenoxyethanol 0.5
PEG-6 1.0
PEG-32 1.0
・ Snow fungus polysaccharide 0.02
-Particulate titanium oxide dispersion (GT-10W2, containing 50% by mass of fine particle titanium oxide, Sakai Chemical Industry Co., Ltd.) 0.5
-Astaxanthin-containing emulsified composition 0.1
-Ceramide dispersion composition 0.1
・ Water residue

Details of the astaxanthin emulsified composition and the ceramide dispersion composition used in Example 7 are described below.

<Preparation of astaxanthin-containing emulsified composition>
The following components were dissolved for 1 hour while heating at 70 ° C. to obtain an aqueous phase composition A.
-Sucrose stearic acid ester (Mitsubishi Chemical Foods, Ryoto Sugar Ester S-1670): 3.3 g
-Decaglyceryl monooleate (Nikko Chemicals, NIKKOL (registered trademark) Decaglin1-OV): 6.7 g
・ Glycerin (alcohol): 45.0 g
・ Pure water: 30.0 g

The following components were dissolved for 1 hour while heating at 70 ° C. to obtain an oil phase composition A.
Haematococcus algae extract (Fujifilm, ASTOTS-S, astaxanthin content: 20% by mass): 3.76 g
・ Mixed tocopherol (RIKEN Vitamin, RIKEN E Oil 800): 0.96g
・ Coconut oil (Kao, Coconard MT): 5.69g
・ Lecithin (RIKEN Vitamin, Resion P): 1.0g
-Retinol palmitate-containing oil (RIKEN Vitamin, RIKEN A Palmitate 1000 (E), retinol palmitate content: 55%): 3.6 g

The aqueous phase composition A obtained above is kept at 70 ° C. and stirred with a homogenizer (model name: HP93, SMT Co., Ltd.) (10000 rpm), and the oil phase composition A is added to the aqueous phase composition A. To obtain a preliminary emulsion.
Subsequently, the obtained preliminary emulsion was cooled to about 40 ° C., and high-pressure emulsification was performed at a pressure of 245 MPa using Starburst Mini HJP-25001 (Sugino Machine Limited). After high-pressure emulsification, an astaxanthin-containing emulsified composition was prepared by filtering through a microfilter having an average pore size of 1 μm.

The obtained astaxanthin-containing emulsified composition was diluted to 1% by mass with Milli-Q water, and the particle size of the dispersed particles was measured using a particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.). It was 9 nm.
The Milli-Q water is ultrapure water obtained by the Milli-Q water production device, which is an ultrapure water production device of Merck Group.

<Preparation of ceramide dispersion composition>
The following components were stirred at room temperature for 1 hour to prepare an oil phase composition B. Ceramide 3 [ceramide compound]: 0.1 g
-Ceramide 6 [Ceramide compound]: 0.1 g
・ Phytosphingosine: 0.07 g
-Ethanol [water-soluble organic solvent]: 150 g
・ 1 mol / L hydrochloric acid (adjusted so that the pH immediately after dispersion is 7 or less)

The obtained oil phase composition B and water were micromixed at a ratio of 1: 7 (mass ratio) using a collision type KM type micromixer 100/100 to obtain a ceramide dispersion composition. ..
The conditions for using the micromixer are as follows.
-Micro channel-
Oil phase side micro channel Cross-sectional shape / width / depth / length = rectangle / 70 μm / 100 μm / 10 mm
Aquatic side microchannel Cross-sectional shape / width / depth / length = rectangle / 490 μm / 100 μm / 10 mm-flow rate-water in the outer ring 21.0 ml / min. The oil phase composition B was added to the inner ring at a flow rate of 3.0 ml / min. The mixture was introduced at the same flow rate as above and micromixed to obtain a pre-emulsion.
The obtained pre-emulsion was desolvated using Okawara Seisakusho Evapol (CEP-lab) until the ethanol concentration was 0.1% or less, and concentrated so that the emulsion concentration was 2.0%. The mixture was prepared to obtain a ceramide dispersion composition. The emulsion concentration referred to here is a concentration based on the total amount of solids added to the oil phase.

Claims (5)

At least one UV inhibitor selected from the group consisting of oils containing silicone oils, modified silicone surfactants with a hydrophilic-lipophilic balance value of less than 6, UV absorbers and UV scatterers, water-in-oil cosmetics. A water-in-oil cosmetic containing 0% by mass and 5% by mass or less of a water-absorbent polymer and water with respect to the total amount of the oil .
Water-in-oil cosmetics in which the UV protection agent is a composite powder of titanium oxide and a UV absorber . The water-in-oil cosmetic according to claim 1, further comprising at least one inorganic pigment selected from the group consisting of color pigments, white pigments, pearl pigments and extender pigments. The water-in-oil cosmetic according to claim 1 or 2, wherein the content of the ultraviolet inhibitor is 3% by mass or more with respect to the total amount of the water-in-oil cosmetic. The water in oil according to any one of claims 1 to 3, wherein the water-absorbing polymer is at least one polymer selected from crosslinked sodium polyacrylate and partially crosslinked carbomer or a salt thereof. Mold cosmetics. The water-in-oil cosmetic according to any one of claims 1 to 4 , wherein the oil containing silicone oil contains 60% by mass or more of silicone oil with respect to the total amount of the oil.