JP7325346B2 - Cosmetic composition using rutile-type titanium oxide hollow particles - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cosmetic composition using rutile-type titanium oxide hollow particles. More specifically, the present invention relates to a cosmetic composition having excellent UV shielding ability and excellent transparency.

BACKGROUND ART Conventionally, cosmetic compositions are required to have a transparency and a color adjustment function as aesthetic roles. At the same time, feel during use and UV shielding properties are also required properties. The feel is, for example, the absence of a foreign object feeling, slipperiness, smoothness, elongation at the time of application, etc. Makeup cosmetics such as foundation, white powder, blush, eye shadow, eyebrow, body powder such as body powder, baby powder, etc. It can be said that it is an essential characteristic in cosmetics, compositions for skin cosmetics such as lotions and milky lotions, and various improvements have been studied (Patent Documents 1 to 3, etc.). In addition, UV shielding is important as a function of suppressing damage to the skin, but it is considered difficult to achieve both the above-mentioned transparency.

For example, in Patent Document 3, titanium dioxide having specific parameters such as an average crystallite size measured by an X-ray diffraction method is used to realize a powder cosmetic having excellent hiding power and red light selective transmission function. there is However, as described above, further improvement is desired from the viewpoint of achieving both the properties of transparency and UV shielding, which are difficult to achieve at the same time, and also the feel.

In addition, the storage stability due to sedimentation of ingredients is also a problem for liquid cosmetics. This is an important characteristic especially in cosmetics in which particles such as pigments are dispersed. For example, Patent Document 4 uses polyorganosiloxane to improve storage stability. However, it cannot be said that the use of a conversion agent specialized for storage stability is the best from the viewpoint of influence on other properties.

WO2017/195642 WO2019/98134 Japanese Patent Application Laid-Open No. 2019-6640 JP 2005-171145 A

As described above, the problem to be solved by the present invention is to propose a cosmetic composition that achieves both opacity and UV shielding properties, has excellent texture during use, and has excellent storage stability.

As a result of intensive studies, the inventors of the present invention have found that cosmetic compositions using metal oxide hollow particles have excellent storage stability and are smooth to the touch, giving an excellent feel during use. In addition, the inventors have found the property of having very excellent wavelength selectivity, and achieved both opacity and UV shielding properties.
That is, the present invention relates to the following 1) to 8).
1)
(A) A cosmetic composition containing rutile-type titanium oxide hollow particles.
2)
The cosmetic composition according to 1) above, wherein the component (A) is rutile-type titanium oxide hollow particles containing silica.
3)
The component (A) is rutile-type titanium oxide hollow particles containing single crystal titanium oxide and silica, wherein the content of titanium oxide is 86.0 mol% or more and 99.5 mol% or less, and silica is contained. 2) above, wherein the ratio is 0.5 mol % or more and 14.0 mol % or less.
4)
The cosmetic according to any one of the above 1) to 3), wherein the value of A/B is 0.3 or more and 0.95 or less, where A is the hollow diameter of the component (A) and B is the particle diameter. composition.
5)
The cosmetic composition according to any one of 1) to 4) above, wherein the component (A) has a primary particle size of 10 nm or more and 1000 nm or less.
6)
The cosmetic composition according to any one of 1) to 5) above, wherein the coefficient of variation of the primary particle size of the component (A) is 10% or less.
7)
The cosmetic composition according to any one of 1) to 6) above, wherein the component (A) has a sphericity of 0.5 or more and 1.0 or less.
8)
The cosmetic composition according to any one of 1) to 7) above, further comprising (B) an oily component.

ADVANTAGE OF THE INVENTION According to this invention, the cosmetic composition which is excellent in the touch at the time of use, and is excellent in storage stability can be implement|achieved, while having both transparency and UV shielding property. As a result, the user can obtain a suitable feeling of use, excellent transparency, and suppression of damage to the skin, and the manufacturer can produce cosmetics with stable quality.

[(A) Rutile-type titanium oxide hollow particles]
The cosmetic composition of the present invention contains rutile-type titanium oxide hollow particles as component (A).
Rutile-type titanium oxide has a low photocatalytic function and a high refractive index, so it is excellent in controlling the reflectance with respect to wavelength. The proportion of rutile-type titanium oxide in titanium oxide is generally 80% to 100%, preferably 85% to 100%, more preferably 90% to 100%. In this specification, "-" includes the numerical values before and after. Moreover, the said ratio is a value calculated from an X-ray-diffraction peak.
Further, the hollow particles are spherical, approximately spherical, uneven, or irregularly shaped particles having holes formed therein and having shells made of the above rutile-type titanium oxide, and may be spherical or approximately spherical. Preferably, it is more preferably spherical. Moreover, it is preferable that the holes inside the hollow particles have a high degree of circularity when the holes are regarded as spheres.
In this specification, rutile-type titanium oxide hollow particles may be simply referred to as hollow particles, and rutile-type titanium oxide may be simply referred to as titanium oxide.

[silica]
The rutile-type titanium oxide hollow particles used in the cosmetic composition of the present invention preferably contain silica in the titanium oxide portion. The silica may be crystalline or amorphous, preferably amorphous. It can be confirmed by a known method that silica is amorphous. Known methods include, for example, a method of measuring diffraction peaks derived from silica crystals (eg, α-SiO ₂ ) using an X-ray diffractometer or the like. As used herein, the term "amorphous" means that no distinct diffraction peaks derived from crystals appear.
When silica is contained, the content of titanium oxide is preferably 86.0 mol % or more and 99.5 mol % or less, more preferably 90.0 mol % or more and 97.5 mol % or less. In addition, the hollow particles according to the present embodiment preferably have a silica content of 0.5 mol% or more and 14.0 mol% or less, more preferably 2.5 mol% or more and 10 mol% or less. .

[Hollow diameter and particle diameter parameters A/B]
Rutile-type titanium oxide hollow particles used in the cosmetic composition of the present invention have a value of A/B of 0.3 to 0.95, where A is the hollow particle diameter and B is the particle diameter of the hollow particles. is preferred. That is, more than 5% and less than 70% of the particle diameter is rutile-type titanium oxide shell, and the structure is hollow inside.
It should be noted that the hollow particles according to this embodiment preferably do not have pores leading from the surface of the particles to the internal pores. Whether or not it has such pores can be determined, for example, by using a pore distribution measuring device (eg, BELSORP-mini II manufactured by Microtrack Bell Co., Ltd.) to measure the amount of adsorption and desorption with respect to relative pressure. can be confirmed by As used herein, "having no pores leading to internal pores" means that the adsorption-desorption isotherm created from the adsorption and desorption amounts is not type IV or type V in the IUPAC classification. . Within the IUPAC classification, Types II and III are preferred, with Type II being more preferred.
A preferable upper limit of the value of A/B is 0.9, more preferably 0.85, and particularly preferably 0.8. A preferred lower limit is 0.4, more preferably 0.5, and particularly preferably 0.6. Therefore, the most preferable range is 0.6 or more and 0.8 or less.
The hollow diameter A of the hollow particles and the primary particle diameter B of the hollow particles are the hollow diameter A of the hollow structure of 10 hollow structure particles randomly photographed with a transmission electron microscope (TEM), and the primary particles of the hollow particles. It is the arithmetic mean value of the diameter B. When the effective figure of the ratio A/B is one decimal place, it is calculated by rounding off the second decimal place. When the effective digits of the ratio A/B are two digits after the decimal point, the third digit after the decimal point is rounded off.
In this specification, the hollow diameter of the hollow particles may be expressed as the inner diameter.

[Primary particle diameter of hollow particles]
The primary particle size of the rutile-type titanium oxide hollow particles used in the cosmetic composition of the present invention is preferably 10 nm or more and 1000 nm or less. Such a range tends to facilitate formation of a hollow structure. The term "primary particles" is synonymous with the primary particle diameter B of the hollow particles, including the measurement method.
The upper limit of the primary particles of the hollow particles is more preferably 750 nm, still more preferably 700 nm, and particularly preferably 500 nm. Moreover, as a lower limit, 50 nm is more preferable, 100 nm is still more preferable, and 180 nm is especially preferable. Therefore, 180 nm or more and 500 nm is a particularly preferable range.

[Coefficient of variation of primary particles]
The rutile-type titanium oxide hollow particles used in the cosmetic composition of the present invention preferably have a variation coefficient of primary particles of 10% or less.
The variation coefficient of the primary particle diameter of the hollow particles can be calculated from the following formula.
Variation coefficient (%) = standard deviation of primary particle size (nm) / arithmetic mean particle size (nm)
A smaller coefficient of variation is preferable because it indicates that particles of uniform size are obtained. The coefficient of variation is usually 10% or less, preferably 8% or less, more preferably 7% or less, still more preferably 5% or less. The lower limit is preferably as small as possible, ideally 0%.

[Sphericality]
The rutile-type titanium oxide hollow particles used in the cosmetic composition of the present invention preferably have a sphericity of 0.5 or more and 1.0 or less.
Sphericity can be measured by a transmission electron microscope (TEM).
That is, it is an arithmetic mean value calculated using the following formula from the long axes and areas of ten hollow particles photographed at random. When the sphericity has only one significant figure after the decimal point, the second decimal place is rounded off for calculation. Also, when the sphericity has two significant digits below the decimal point, it is calculated by rounding off to the third decimal place.
Sphericality = (4 x particle area (nm ² )) / (π x (major axis (nm)) ² )
Also, the sphericity may be calculated using image analysis software Image J.
When the sphericity is within the above range, the dispersibility is improved, and when used as a powder cosmetic, the slipperiness on the skin is excellent.

<Other Configurations of Hollow Particles>
The rutile-type titanium oxide hollow particles used in the cosmetic composition of the present invention include, in addition to the rutile-type titanium oxide, the silica described above, and further, for example, Sn, Cd, Fe, Ni, Zn, Mn, Co, Cr, An element selected from Cu, K, Na, Li, P, S and the like may be contained. These elements may be of one type or two or more types.

When the rutile-type titanium oxide hollow particles used in the cosmetic composition of the present invention further contain elements other than titanium oxide and silica, the total content of these elements is is usually 0.1 mol % to 15 mol %, preferably 0.1 mol % to 10 mol %, more preferably 0.1 mol % to 5 mol %. By setting it to such a range, there is a tendency to easily obtain hollow particles with little coloring (that is, high whiteness).

The rutile-type titanium oxide hollow particles used in the cosmetic composition of the present invention may further have a layer of other substance on the surface, if necessary. Other substances include, for example, alumina, aluminum hydroxide, zinc oxide, zinc hydroxide, zirconia, organic substances, and the like.

<Method for producing hollow particles>
The rutile-type titanium oxide hollow particles used in the cosmetic composition of the present invention are described, for example, in Xiong Wen (David) Lou, Lynden A.; Archer and Zichao Yang, Adv. Mater. , 2008, 20, 3987-4019 and the like. However, it is not limited to this manufacturing method.

In particular, a step of forming a shell containing a titanium oxide precursor and a silica precursor on the surface of a template particle serving as a core to obtain a core/shell particle (hereinafter also referred to as “first step”); A step of removing the template particles from the particles to obtain shell particles (hereinafter also referred to as a “second step”) and a step of firing the shell particles in an air atmosphere to obtain hollow particles (hereinafter referred to as a “third step”). Also referred to as.) and a manufacturing method including.

Unless otherwise specified, each step described below is preferably carried out under stirring.

[First step]
The first step includes a step of reacting template particles with a titanium oxide precursor and a silica precursor in an organic solvent in the presence of a base. The silica precursor may be added after adding the titanium oxide precursor, or may be added simultaneously with the titanium oxide precursor. Through the first step, it is possible to obtain core/shell particles in which a shell containing a titanium oxide precursor and a silica precursor is formed on the surface of a template particle serving as a core.

Template particles include particles selected from polymeric particles and inorganic particles. Specific examples include polymer particles obtained by polymerizing at least one type of monomer selected from (meth)acrylate, vinyl, styrene, and urethane; calcium carbonate, iron oxide, cobalt oxide, inorganic particles such as manganese oxide, chromium oxide, and nickel oxide; Among these, polymer particles are preferred, polymer particles containing styrene as a constituent monomer are more preferred, styrene-(meth)acrylic acid polymer particles are still more preferred, and styrene-methacrylic acid polymer particles are particularly preferred.
In this specification, "(meth)acrylate" means both acrylate and methacrylate, and "(meth)acrylic acid" means both acrylic acid and methacrylic acid.

The titanium oxide precursor is not particularly limited as long as it can be converted into titanium oxide by a chemical or physical method. Among the titanium oxide precursors, titanium alkoxides are preferred. Titanium alkoxide is preferably titanium tetraalkoxide, more preferably titanium tetra-C1-C6 alkoxide, and still more preferably titanium tetrabutoxide.

By controlling the amount of titanium oxide precursor added, the thickness of the shell can be controlled. The titanium oxide precursor may be added at once or in several batches in an amount necessary for the shell to have a specific thickness. By adding the titanium oxide precursor in several batches, the thickness of the shell tends to be more uniform.

The silica precursor is not particularly limited as long as it can be converted into silica by a chemical or physical method. Among silica precursors, silane alkoxides are preferred. The silane alkoxide is preferably silane tetraalkoxide, more preferably silane tetra C1-C4 alkoxide, and still more preferably silane tetraethoxide.

Examples of organic solvents include hydrocarbon solvents (toluene, xylene, hexane, cyclohexane, n-heptane, etc.), alcohol solvents (methanol, ethanol, isopropyl alcohol, butanol, t-butanol, benzyl alcohol, etc.), ketone solvents, Solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, acetylacetone, etc.), ester solvents (ethyl acetate, methyl acetate, butyl acetate, cellosolve acetate, amyl acetate, etc.), ether solvents (isopropyl ether, methyl cellosolve, butyl cellosolve, tetrahydrofuran, 1,4-dioxane, etc.), glycol solvents (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, octylene glycol, etc.), glycol ether solvents (diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), Glycol ester solvents (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.), glyme solvents (monoglyme, diglyme, etc.), halogen solvents (dichloromethane, chloroform, etc.), amide solvents (N , N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone), pyridine, sulfolane, acetonitrile, dimethylsulfoxide and the like.

An organic solvent may be used individually by 1 type, and may use 2 or more types together. By using two or more kinds of organic solvents in combination and controlling the ratio thereof, the concentration of the template particles, the method of adding the base, etc., the first step can be performed while maintaining a good dispersion state of the reaction solution.

Bases include inorganic bases and organic bases. Examples of inorganic bases include hydroxides of Group 1 or Group 2 elements of the periodic table, preferably hydroxides of Na, K, Ca, Mg, Al, Fe and the like; ammonia; and the like. Examples of organic bases include heteroaromatic ring compounds such as pyridine; alkylamines such as triethylamine (preferably trialkylamines, more preferably triC1-C4 alkylamines); hydroxyalkylamines such as triethanolamine (preferably trialkylamines). (hydroxyalkyl)amine, more preferably tri(hydroxy C1-C4 alkylamine)); and the like.

The first step is preferably performed under an inert gas atmosphere such as nitrogen or argon.
The reaction temperature in the first step is usually -30°C to 80°C, preferably 0°C to 50°C.
Since the reaction time of the first step varies depending on the reaction temperature, shell thickness, etc., it is difficult to determine it unconditionally. As a standard, it is usually 0.1 hour to 10 hours, preferably about 0.5 hour to 7 hours.

When the template particles are polymer particles and the surface potential thereof has the same sign as that of titanium oxide, core/shell particles can also be formed by the following method.
That is, an organic polymer (for example, polyethylenimine, etc.) having a sign opposite to the above surface potential is adsorbed onto the surface of the template particles. The core/shell particles can then be formed by depositing or adsorbing fine particles of titanium oxide onto the surface of the organic polymer and optionally adding a titanium oxide precursor. By using, for example, rutile-type titanium oxide as the fine particles of titanium oxide, the crystal type of titanium oxide produced from the titanium oxide precursor can be rutile-type.

In the first step, the reaction is carried out in the state of dispersion. Therefore, in order to improve the dispersion stability of the dispersion, the first step is preferably carried out in the presence of a dispersant. The type of dispersant is not particularly limited as long as it does not interfere with shell formation. Examples of such dispersants include polyalkylene glycols such as polyethylene glycol and polypropylene glycol; polyvinylpyrrolidone; Floren series manufactured by Kyoeisha Chemical Co., Ltd.; DISPERBYK series manufactured by BYK-Chemie Japan; Solspers series; Ajinomoto Fine-Techno Co., Inc. Ajisper series; Kusumoto Kasei Co., Ltd. Disparlon series;

[Second step]
The second step includes a step of dissolving and removing the template particles with a solvent. As such a solvent, a solvent that does not dissolve or destroy the shell particles is preferred. When the template particles are polymer particles, the solvent used in the second step includes organic solvents such as methyl ethyl ketone, toluene, tetrahydrofuran and chloroform. When the template particles are inorganic particles, examples of the solvent used in the second step include aqueous solutions of acids such as dilute hydrochloric acid, dilute nitric acid and dilute sulfuric acid.

[Third step]
The third step includes a step of obtaining hollow particles by firing the shell particles obtained in the second step. Generally, the firing can be performed in an atmosphere of a gas selected from one or more of air, nitrogen, argon, hydrogen, ammonia, etc. However, in order to obtain single-crystal titanium oxide, the firing must be performed in an air atmosphere. preferably. As used herein, the term "air" refers to the gas that constitutes the lowest layer of the earth's atmosphere and is obtained in the normal environment in which humans live.

The sintering temperature in the third step varies depending on the material of the hollow particles and the like, so it is difficult to determine indiscriminately. As a guideline, it is usually 600°C to 1500°C or less, preferably 650°C to 1400°C, more preferably 700°C to 1300°C, and still more preferably about 750°C to 1200°C.
Since the firing time in the third step varies depending on the firing temperature and the like, it is difficult to generally determine the firing time. As a guideline, it is usually 0.5 hours to several tens of hours, preferably about 1 hour to 10 hours.

In addition, when the template particles are polymer particles, the second step is not necessary. That is, by the third step of firing the core/shell particles obtained in the first step, removal of the template particles and firing of the shell particles can be performed at the same time. Therefore, the hollow particles can be produced by only two steps, ie, the first step and the third step.

The hollow particles obtained in the third step may contain by-product particles having non-uniform shapes. The proportion of by-product particles is usually 10% or less, preferably 5% or less. Generation of by-product particles can be suppressed by, for example, precisely controlling the synthesis conditions. The content of by-products can be calculated from the number of non-uniformly shaped particles among 100 hollow particles randomly photographed with a transmission electron microscope (TEM) or scanning electron microscope (SEM). can.

The cosmetic composition of the present invention preferably contains (A) the rutile-type titanium oxide hollow particles and (B) an oily component. Components other than (A) and (B) are aqueous media such as water and alcohol.
The content of (A) rutile-type titanium oxide hollow particles is preferably 1 to 100% by mass with respect to the total mass of the cosmetic composition of the present invention. The content varies depending on whether the target cosmetic is a powder cosmetic or a liquid cosmetic.
For example, when powder cosmetics are used, the upper limit of the content is more preferably 30% by mass, still more preferably 20% by mass, and particularly preferably 15% by mass. Moreover, as a lower limit, 1 mass % is more preferable, 3 mass % is still more preferable, and 5 mass % is especially preferable. Therefore, the most preferable content of (A rutile-type titanium oxide hollow particles is 5% by mass or more and 15% by mass or less.
For example, in the case of a liquid cosmetic, the upper limit of the content is more preferably 20% by mass, still more preferably 15% by mass, and particularly preferably 10% by mass. Moreover, as a lower limit, 1 mass % is more preferable, 3 mass % is still more preferable, and 4 mass % is especially preferable. Therefore, the most preferable content of (A) metal oxide hollow particles is 4% by mass or more and 10% by mass or less.

[(B) Oily component]
As the component (B) oily component, one or more of oily components such as higher alcohols, hydrocarbon oils, ester oils, oils and silicones can be used. Higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, Cholesterol, phytosterol, sitosterol, lanosterol, monostearyl glycerin ether (batyl alcohol), etc.; hydrocarbon oils such as ozokerite, squalane, squalene, ceresin, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, vaseline Ester oils such as diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, di-2 Ethylene glycol-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, oleic acid Octyldodecyl, Decyl Oleate, Neopentyl Glycol Dicaprate, Triethyl Citrate, 2-Ethylhexyl Succinate, Isocetyl Stearate, Butyl Stearate, Diisopropyl Sebacate, Di-2-Ethylhexyl Sebacate, Cetyl Lactate, Myristyl Lactate, Palmitin isopropyl acid, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, diisostearyl malate, etc.; silicones such as low polymerization degree dimethylpolysiloxane, high polymerization degree dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, Polyoxyalkylene/alkylmethylpolysiloxane/methylpolysiloxane copolymer, alkoxy-modified polysiloxane, alkyl-modified polysiloxane, crosslinked organopolysiloxane, fluorine-modified polysiloxane, amino-modified polysiloxane, glycerin-modified polysiloxane, higher alkoxy-modified Examples include silicone, higher fatty acid-modified silicone, silicone resin, silicone rubber, and silicone resin.
When the cosmetic composition of the present invention is used for lipstick, it preferably contains a hydrocarbon wax. (manufactured by Paramelt), Hi-Mic-1045, 1070, 2045 (manufactured by Nippon Seiro Co., Ltd.), refined microcrystalline wax (manufactured by Nikko Rica), 155° micro wax (manufactured by Nippon Oil Co., Ltd.), etc. Examples of ceresin include ceresin #810 (manufactured by Nikko Rica) and ceresin wax SP-1020P (manufactured by STRAHL &PITSCH); paraffins include paraffin wax 145, 155 and HNP-9 (manufactured by Nippon Seiro Co., Ltd.). Examples of polyethylene waxes include PERFORMALENE 400, 500, 655, 700EP, PL (manufactured by NEWPHASETECHNOLOGIES), LASHWAXP (deodorized product) (manufactured by Japan Natural Products Co., Ltd.), polyethylene wax PW-655N (manufactured by Toshiki Pigment Co., Ltd.), etc. Examples of synthetic hydrocarbon waxes include Lip Wax A-4 (manufactured by Japan Natural Products Co., Ltd.).

When the (B) oily component is used in the cosmetic composition of the present invention, the content of (B) the oily component is preferably 1 to 99% by mass relative to the total mass of the cosmetic composition. The content varies depending on whether the target cosmetic is a powder cosmetic or a liquid cosmetic.
For example, when powder cosmetics are used, the upper limit of the content is more preferably 30% by mass, still more preferably 20% by mass, and particularly preferably 15% by mass. Moreover, as a lower limit, 1 mass % is more preferable, 3 mass % is still more preferable, and 5 mass % is especially preferable. Therefore, the content of (B) the oily component is most preferably 5% by mass or more and 15% by mass or less.
For example, in the case of liquid cosmetics, the upper limit of the content is more preferably 99% by mass, still more preferably 95% by mass, particularly preferably 80% by mass, and even more preferably 70% by mass. Moreover, as a lower limit, 15 mass % is more preferable, 20 mass % is still more preferable, and 40 mass % is especially preferable. Therefore, the content of (B) the oily component is most preferably 40% by mass or more and 70% by mass or less.

[Other ingredients]
The cosmetic composition of the present invention contains, in addition to the components (A) and (B), an aqueous medium, a surfactant, powders other than the component (A), a water-soluble polymer, a moisturizer, a film-forming agent, and an ultraviolet absorber. agents, sequestering agents, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, etc., may be contained as necessary.

<Aqueous medium>
As the water, water used in cosmetics, quasi-drugs, etc. can be used, and for example, purified water, ion-exchanged water, tap water, etc. can be used. The aqueous phase can further contain a water-soluble alcohol depending on the purpose.
Examples of water-soluble alcohols include lower alcohols, polyhydric alcohols, polyhydric alcohol polymers, dihydric alcohol alkyl ethers, dihydric alcohol alkyl ethers, dihydric alcohol ether esters, glycerin monoalkyl ethers, sugar alcohols, At least one selected from monosaccharides, oligosaccharides, polysaccharides, derivatives thereof, and the like can be mentioned.
Examples of lower alcohols include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.
Polyhydric alcohols include, for example, dihydric alcohols (e.g., ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trihydric alcohols (e.g., glycerin, trimethylolpropane, etc.); tetrahydric alcohols (e.g., 1,2,6 -pentaerythritol such as hexanetriol); pentahydric alcohols (e.g., xylitol, etc.); hexahydric alcohols (e.g., sorbitol, mannitol, etc.); polyhydric alcohol polymers (e.g., diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); dihydric alcohol alkyl ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc. ); dihydric alcohol alkyl ethers (e.g., diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.); dihydric alcohol ether ester (e.g., Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazibate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerin monoalkyl ether (e.g., xyl alcohol, selachyl alcohol, batyl alcohol, etc.); sugar alcohol ( For example, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitose, amylolytic sugar reducing alcohol, etc.); Glysolid; Tetrahydrofurfuryl alcohol; POE-tetra POP-butyl ether; POP.POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphoric acid;
Monosaccharides include, for example, three-carbon sugar (eg, D-glycerylaldehyde, dihydroxyacetone, etc.), four-carbon sugar (eg, D-erythrose, D-erythrulose, D-threose, erythritol, etc.), pentose (eg, , L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.), hexoses (e.g., D-glucose, D -Talose, D-busicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.), heptose (e.g., aldoheptose, heprose, etc.), heptose (e.g., octulose, etc.) , deoxy sugars (e.g., 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.), amino sugars (e.g., D-glucosamine, D-galactosamine, sialic acid, aminouronic acid , muramic acid, etc.), uronic acid (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.) and the like.
Examples of oligosaccharides include at least one selected from sucrose, guntianose, umbelliferose, lactose, planteose, isoliquinoses, α,α-trehalose, raffinose, lignoses, umbilicin, stachyose, verbascoses, and the like. can be mentioned.
Examples of polysaccharides include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, and keratosulfate. , locust bean gum, succinoglucan, caroninic acid and the like.
Other polyols include, for example, at least one selected from polyoxyethylene methyl glucoside (glucum E-10), polyoxypropylene methyl glucoside (glucum P-10), and the like.

<Surfactant>
Examples of surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, lipophilic nonionic surfactants, and hydrophilic nonionic surfactants. The content of the surfactant is 0 to 20% by mass, preferably 5 to 15% by mass, based on the total mass of the cosmetic composition of the present invention.

(Anionic surfactant)
Examples of anionic surfactants include fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate salts (e.g., , POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.); N-acylsarcosic acid (e.g., sodium lauroyl sarcosinate, etc.); -myristoyl-N-methyltaurate sodium, coconut oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc.); phosphate ester salts (POE-oleyl ether phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinates (For example, sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); sulfonic acid triethanolamine, linadodecylbenzene sulfonic acid, etc.); higher fatty acid ester sulfate salts (eg, hydrogenated coconut oil fatty acid sodium glycerol sulfate, etc.); disodium stearoyl glutamate, monosodium N-myristoyl-L-glutamate, etc.); sulfated oil (e.g. funnel oil, etc.); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate higher fatty acid ester sulfonate; secondary alcohol sulfate; higher fatty acid alkylolamide sulfate; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartic acid ditriethanolamine; .

(Cationic surfactant)
Cationic surfactants include, for example, alkyltrimethylammonium salts (e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (e.g., cetylpyridinium chloride, etc.); distearyldimethylammonium chloride dialkyldimethylammonium salts; Poly(N,N'-dimethyl-3,5-methylenepiperidinium) chloride; alkyl quaternary ammonium salts; alkyldimethylbenzylammonium salts; alkylisoquinolinium salts; dialkylmorphonium salts; POE-alkylamines; alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

(Amphoteric surfactant)
sil-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.); betaine-based surfactants (e.g. , 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amidobetaine, sulfobetaine, etc.).

(Lipophilic nonionic surfactant)
Lipophilic nonionic surfactants include, for example, sorbitan fatty acid esters (e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, etc.); , α,α'-pyroglutamic acid glyceryl monostearate, glycerol monostearate, malic acid, etc.); propylene glycol fatty acid esters (eg, propylene glycol monostearate, etc.); hydrogenated castor oil derivatives;

(Hydrophilic nonionic surfactant)
Hydrophilic nonionic surfactants include, for example, POE-sorbitan fatty acid esters (eg, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.); POE-sorbitol fatty acid esters (eg, POE-sorbitol monolaurate, POE-sorbitol monooleate, POE-sorbitol pentaoleate, POE-sorbitol monostearate, etc.); POE-glycerin fatty acid esters (eg, POE-glycerol mono stearate, POE-monooleate such as POE-glycerin monoisostearate, POE-glycerin triisostearate, etc.); POE-fatty acid esters (e.g., POE-distearate, POE-monodioleate, ethylene glycol distearate, etc.); Alkyl ethers (eg, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic types (eg, Pluronic, etc.); POE/POP-alkyl ether (e.g., POE/POP-cetyl ether, POE/POP-2-decyltetradecyl ether, POE/POP-monobutyl ether, POE/POP-hydrogenated lanolin, POE/POP-glycerin ether, etc.) tetra-POE/tetra-POP-ethylenediamine condensates (e.g., Tetronic, etc.); POE-castor oil hydrogenated castor oil derivatives (e.g., POE-castor oil, POE-hydrogenated castor oil, POE-hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE-hydrogenated castor oil maleic acid, etc.); amides (eg, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid esters; POE-alkylamines; POE-fatty acid amides; sucrose fatty acid esters; trioleyl phosphate and the like.
The surfactant content is 0 to 20% by weight, preferably 5 to 15% by weight, relative to the total weight of the dispersion of the invention.

<Powder>
As the powder, apart from the rutile-type titanium oxide hollow particles that are the component (A), if it is used in ordinary cosmetics, its shape (spherical, needle-like, plate-like, etc.) and particle size (fumes) can be used. , fine particles, pigment grade, etc.) and particle structure (porous, non-porous, etc.). Inorganic powders such as magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, synthetic mica, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, red mica, biotite , lethia mica, silicic acid, silicic anhydride, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hygilite, montmorillonite , zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, etc.; organic powders such as polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, Polymethylbenzoguanamine powder, Tetrafluoroethylene powder, Polymethyl methacrylate powder, Cellulose powder, Silk powder, Nylon powder, Nylon 12 powder, Nylon 6 powder, Styrene-acrylic acid copolymer powder, Divinylbenzene-styrene copolymer powder, Vinyl resin powder, urea resin powder, phenol resin powder, fluorine resin powder, silicon resin powder, acrylic resin powder, melamine resin powder, epoxy resin powder, polycarbonate resin powder, microcrystalline fiber powder, lauroyl lysine, etc.; Inorganic red pigments such as iron oxide, iron hydroxide and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron oxide and ocher; inorganic black pigments such as black iron oxide and carbon black; Inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate; inorganic blue pigments such as navy blue and ultramarine blue; Lakes of pigments, composite powders obtained by combining these powders, etc.; pearl pigments such as titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, and titanium oxide-coated Talc, fish scale foil, titanium oxide-coated colored mica, etc.; Metal powder pigments such as aluminum powder, copper powder, stainless steel powder, etc.; Tar pigments such as Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 227, Red 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202 , Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, etc.; Examples of natural pigments include carminic acid, laccaic acid, calsamine, brazilin, crocin and the like. It should be noted that these powders may be combined, or powders surface-treated with an oil agent, silicone, fluorine compound, or the like may be used.

<Water-soluble polymer>
Both natural and synthetic water-soluble polymers can be used, and they can be used in combination.
Examples of natural water-soluble polymers include plant-based polymers (e.g., gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), algecolloid (cassou extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial macromolecules (e.g., xanthan gum, dextran, succinoglucan, bullulan, etc.); animal macromolecules (e.g., collagen, casein, albumin, gelatin, etc.), etc. is mentioned.
Examples of synthetic water-soluble polymers include starch-based polymers (e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); polyvinyl pyrrolidone, carboxyvinyl polymer, etc.); , sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymer;

<Moisturizer>
Examples of moisturizing agents include proteins, mucopolysaccharides, collagen, elastin, and keratin. Examples of antioxidants include α-tocopherol and ascorbic acid. Examples of beauty ingredients include vitamins, antiphlogistic agents, crude drugs, and the like. , preservatives such as paraoxybenzoate, phenoxyethanol, 1,2-pentanediol, polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, Mucoitin sulfate, caroninic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carboxylate, alkylene oxide derivatives, short-chain soluble collagen, diglycerin (EO) PO adduct, Rosa rosea extract yarrow extract, melilot extract and the like.

<Film forming agent>
Film-forming agents include, for example, anionic film-forming agents (e.g., (meth)acrylic acid/(meth)acrylic acid ester copolymer, methyl vinyl ether/maleic anhydride high polymer, etc.), cationic film-forming agents (e.g., cationized cellulose, dimethyldiallylammonium chloride polymer, dimethyldiallylammonium chloride/acrylamide copolymer, etc.), nonionic film agents (e.g., polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyacrylate copolymer, (meth ) acrylamide, polymer silicone, silicone resin, trimethylsiloxysilicate, etc.).

<Ultraviolet absorber>
Examples of ultraviolet absorbers include benzoic acid-based ultraviolet absorbers (e.g., para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester. , N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA ethyl ester, etc.); Salicylic acid-based UV absorbers (e.g., amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.); cinnamic acid-based UV absorbers (e.g., octyl methoxycinnamate, ethyl -4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxy Cinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl -α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, etc.); benzophenone-based ultraviolet absorbers (e.g., 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl- benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3-(4′-methylbenzylidene)-d,l-camphor, 3-benzylidene- d,l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole;2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole;2-(2′-hydroxy-5-methylphenylbenzotriazole;dibenzalazine;dianisoylmethane;4-methoxy-4′-t-butyldibenzoylmethane; 5-(3,3-dimethyl-2-norbornylidene)-3 -pentan-2-one, dimorpholinopyridazino; 2-ethylhexyl-2-cyano-3,3-diphenylacrylate; 2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]- phenyl}-6-(4-methoxyphenyl)-(1,3,5)-triazine and the like.

<Sequestering agent>
Examples of sequestering agents include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. , sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate, and the like.

<Amino acid>
Amino acids include, for example, neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of amino acid derivatives include sodium acyl sarcosinate (sodium lauroyl sarcosinate), acyl glutamate, sodium acyl β-alanine, glutathione, pyrrolidone carboxylic acid and the like.

<Organic amine>
Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and the like. is mentioned.

<Polymer emulsion>
Examples of polymer emulsions include acrylic resin emulsions, polyethyl acrylate emulsions, acrylic resin liquids, polyacryl alkyl ester emulsions, polyvinyl acetate resin emulsions, and natural rubber latex.

<pH adjuster>
Examples of pH adjusters include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

<Vitamins>
Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

<Antioxidant>
Examples of antioxidants include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, and gallic acid esters.

<Antioxidant aid>
Examples of antioxidant aids include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

<Perfume>
Perfumes are not particularly limited as long as they are commonly used as cosmetics. carvone, methyl salicylate, estragole, citronellal, hydroxycitronellal, citronellol, geraniol, nerol, linalool, linalyl acetate, terpineol, terpinyl acetate, terpinen-4-ol, dimetol, borneol, thymol, p-cymene, p - methylacetophenone, eugenol, ethyl acetate, allyl amyl glycolate, allyl heptanoate, allyl caproate, amyl acetate, iso-amyl acetate, iso-amyl butyrate, amyl propionate, anisaldehyde, anethole, benzaldehyde, pt-butyl cyclohexyl acetate, ot-butyl cyclohexyl acetate, dimethylbenzylcarbyl acetate, cis-3-hexenyl acetate, limonene, cis-jasmone, methyl amyl ketone, ethyl amyl ketone, fenchyl alcohol, hydrotropic alcohol , methyl anthranilate, phenoxyethanol, phenylacetaldehyde, phenylethyl alcohol, rose oxide, iso-amyl salicylate, acetylcedrene, amyl cinnamic aldehyde, styraryl acetate, cedryl acetate, vanillin, heliotropin, methyl ionone, lyrial, γ - One or more of undecalactone and the like can be used.
Also, natural essential oils containing these fragrant ingredients as main ingredients may be used, such as sage oil, basil oil, peppermint oil, spearmint oil, rosemary oil, eucalyptus oil, thyme oil, anise oil, bay oil, clove oil, coriander oil. , laurel leaf oil, lavandin oil, lavender oil, marjoram oil, orange oil, lemon oil, grapefruit oil, lime oil, bergamot oil, cedarwood oil, patchouli oil, geranium oil, etc. be able to.

Other ingredients that can be blended include, for example, preservatives (ethylparaben, butylparaben, chlorphenesin, phenoxyethanol, etc.); ); whitening agent (e.g., placenta extract, saxifrage extract, arbutin, etc.); , coix seed, loofah, lily, saffron, cnidium, ginger, hypericum, ononis, garlic, red pepper, chimp, angelica, seaweed, etc.), activator (e.g., royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (e.g., , Nonylic Acid Valenylamide, Nicotinic Acid Benzyl Ester, Nicotinic Acid β-Butoxyethyl Ester, Capsaicin, Zingerone, Cantharis Tincture, Ictamol, Tannic Acid, α-Borneol, Tocopherol Nicotinate, Inositol Hexanicotinate, Cyclanderate, Cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthine, γ-oryzanol, etc.); antiseborrheic agents (eg, sulfur, thianthol, etc.); anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.), and the like.

[Usage]
The cosmetic composition of the present invention can be used in various applications for the purpose of controlling and/or coloring the color of skin and lips, and/or shielding against ultraviolet rays. The cosmetic composition of the present invention can be suitably used for solid cosmetics, liquid cosmetics, and powder cosmetics.
Examples of liquid cosmetics include lotions, milky lotions, gels, creams, beauty essences, sunscreen cosmetics, packs, masks, hand creams, body lotions, and basic cosmetics such as body creams; Cleansing (makeup remover), body shampoo, shampoo, rinse, and cleansing cosmetics such as treatments. Further, for example, a cosmetic composition that functions as both a basic cosmetic and a cleansing cosmetic, such as a so-called cleansing lotion that functions as both a lotion and cleansing agent, a cleansing milk, and a cleansing cream, may be used. Furthermore, the cosmetic composition of the present invention may be a rinse-off (rinse off) type or a leave-on (without rinsing off) type.
Examples of solid cosmetics include loose powder-type cosmetics; solid powder cosmetics formed by compressing or removing a solvent after being filled in a container; pouring a paste into a container. paste-like cosmetics formed by; stick-type cosmetics; and the like. Specific examples include foundation, stick foundation, face powder, lipstick, blusher, eye color, eyebrow, makeup base, daytime serum, sunscreen, concealer, bronzer, lip color, BB cream, and the like.
As the product form of powder cosmetics, it is possible to take any product form within the category of powder cosmetics. Specifically, it can take product forms such as foundation, eye shadow, cheek color, body powder, perfume powder, baby powder, pressed powder, deodorant powder, face powder, and the like.

[container]
The cosmetic composition of the present invention can be used by being housed in a container having a shape and material appropriately selected according to the purpose and application. Examples of container shapes include bottle type, tube type, jar type, dropper type, dispenser type, stick type, pouch bag, and chia pack. Examples of materials include polyethylene terephthalate, polypropylene, polyethylene (HDPE, LDPE, LLDPE, etc.), ABS resin, ethylene vinyl alcohol resin, polystyrene, glass, and metals (aluminum, etc.). In addition, considering the strength, flexibility, weather resistance, and stability of the components, these materials are subjected to various coating treatments, or are combined by, for example, mixing, or laminated. , can be used as a container material. In addition, those skilled in the art can select the diameter and material of the nozzle of the container and the elution portion of the formulation in order to limit the discharge amount from the container and reduce the adhesion to the container.

[Production method]
Examples of the cosmetic composition of the present invention and the method for producing cosmetics using the same are as follows.
<Liquid cosmetics>
The cosmetic composition of the present invention can be prepared by heating each component to 20 to 80° C. or at room temperature and dissolving them with stirring. A known method can be used as the stirring method, and for example, devices such as a blade type stirrer, a disper, and a homomixer can be used. The cosmetic composition of the present invention can be obtained by cooling the dissolved and homogenous mixture to room temperature. Depending on the formulation of the cosmetic composition, a liquid, paste or solid liquid cosmetic can be obtained upon cooling.
<Powder cosmetics>
Rutile-type titanium oxide hollow particles, an oily component and other components are mixed in advance with a Henschel mixer, and then pulverized twice with a pulperizer. Then, the obtained mixture is filled in a resin-made medium dish container, and dry press molding is performed by a known method to obtain a solid powder cosmetic in which the titanium oxide of the present invention is blended with the cosmetic.

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. It should be noted that the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In the following text and Tables 2 to 5, Examples 3, 5, 6, 9, 11, 12, 15, 17, 18, 21, 23, and 24 shall be read as Reference Examples 1 to 12, respectively. .

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited only to the examples.
In the Hollow Structure Particle Synthesis Example, when the desired amount of the substance could not be obtained by one synthesis operation, the synthesis operation was repeated until the desired amount of the substance was obtained.
When it was necessary to measure the primary particle diameter of the hollow structure particles and the inner diameter of the hollow structure, they were measured using a transmission electron microscope (JEM-2800 manufactured by JEOL Ltd.).
Moreover, the quantitative ratio of the anatase type and the rutile type was calculated by the following formula (1) using a powder X-ray diffractometer (manufactured by PANalytical, X'Pert PRO).

Abbreviations and the like in the following formula (1) have the following meanings.
F _R : Mass content of rutile-type titanium oxide.
I _A (101): The intensity of the anatase crystal (101) face measured with a powder X-ray diffractometer.
I _R (110): The intensity of the rutile crystal (110) face measured with a powder X-ray diffractometer.

[Formula 1]

[Preparation of Ethanol Dispersion of Template Particles (Dispersion 1)]
27 g of styrene, 2 g of methacrylic acid and 0.1 g of potassium persulfate were added to 900 g of distilled water, and emulsion polymerization was carried out at 75° C. to obtain an aqueous dispersion containing styrene-methacrylic acid polymer particles. The primary particle diameter of the obtained template particles was 260 nm.
Dispersion 1 was prepared by adding ethanol while concentrating the aqueous dispersion obtained as described above with an evaporator to replace water with ethanol. The content of template particles in Dispersion 1 was 9%.
[Preparation of Ethanol Dispersion of Template Particles (Dispersion 2)]
Dispersion 2 was prepared in the same manner as in Synthesis Example 1, except that 27 g of styrene used in Synthesis Example 1 was changed to 10 g. The primary particle size of the obtained template particles was 170 nm. The content of template particles in Dispersion 2 was 6%.

[Synthesis Example 1]
[Step 1]: Step of obtaining the first core/shell particles.
8 g of acetonitrile, 0.1 g of polyvinylpyrrolidone, and Dispersion 1 (17 g) were cooled to 10° C. to obtain a liquid. To this liquid, 18 g of titanium tetrabutoxide and 6 g of 2% aqueous ammonia were added in 6 portions at intervals of 0.5 hours, and reacted at 10°C for 4 hours to form the first core/shell particles. I got the liquid. The obtained liquid was used for the following "Step 2" without isolation/purification.

[Step 2]: Step of obtaining the second core/shell particles.
To the liquid obtained in step 1 of Example 1, 0.35 g of tetraethyl orthosilicate and 7 g of distilled water were added at 25°C and reacted at 25°C for 10 hours to obtain a liquid.
The resulting liquid was centrifuged at 15,000 rpm for 25 minutes to remove the supernatant, and the residue was dried in a vacuum dryer heated to 60°C to obtain 7.5 g of the desired second core/shell particles. Obtained.

[Step 3]: Step of firing the second core/shell particles to remove the template particles and produce hollow-structured particles.
2.0 g of the second core/shell particles obtained in step 2 of Example 1 were placed on a ceramic board, set in a firing furnace, and fired at 1000° C. for 1 hour in an air atmosphere to produce titanium oxide and silica. 0.9 g of hollow structure particles containing

[Synthesis Example 2]
[Step 1]: Step of obtaining the first core/shell particles.
12 g of ethanol, 8 g of acetonitrile, 0.1 g of polyvinylpyrrolidone, and Dispersion 2 (12 g) were cooled to 10° C. to obtain a liquid. To this solution, 9 g of titanium tetrabutoxide and 3 g of 2% aqueous ammonia are added in three portions at intervals of 0.5 hours, and reacted at 10° C. for 4 hours to form the first core/shell particles. I got the liquid. The obtained liquid was used for the following "Step 2" without isolation/purification.

[Step 2]: Step of obtaining the second core/shell particles.
To the liquid obtained in step 1 of Example 1, 0.17 g of tetraethyl orthosilicate and 7 g of distilled water were added at 25°C and reacted at 25°C for 10 hours to obtain a liquid.
The resulting liquid was centrifuged at 15,000 rpm for 25 minutes to remove the supernatant, and the residue was dried in a vacuum dryer heated to 60°C to obtain 4 g of the desired second core/shell particles. .

[Step 3]: Step of firing the second core/shell particles to remove the template particles and produce hollow-structured particles.
2.0 g of the second core/shell particles obtained in step 2 of Example 1 were placed on a ceramic board, set in a firing furnace, and fired at 1000° C. for 1 hour in an air atmosphere to produce titanium oxide and silica. 0.9 g of hollow structure particles containing

[Synthesis Example 3]
Titanium oxide and silica were prepared in the same manner as in Example 1 except that 9 g of titanium tetrabutoxide used in Example 2 was changed to 150 g, 33 g of 2% aqueous ammonia, and 0.17 g of tetraethyl orthosilicate used in Example 2 were changed to 2.8 g. 3.2 g of hollow-structured particles were obtained.

[Synthesis Example 4]
In the same manner as in Example 1, except that 18 g of titanium tetrabutoxide used in Example 1 was changed to 15 g, and 0.35 g of tetraethyl orthosilicate was changed to 1.5 g, hollow structure particles containing titanium oxide and silica were obtained. 5 g was obtained.

[Synthesis Example 5]
The dispersion liquid 1 used in Example 4 was used as the dispersion liquid 2, and 1.5 g of tetraethyl orthosilicate was added to 9 g. 0.6 g of hollow structure particles containing titanium oxide and silica were obtained in the same manner as in Example 4, except that the time was changed to 1 hour at ℃.

[Synthesis Example 6]
In the same manner as in Example 1, except that 15 g of titanium tetrabutoxide used in Example 5 was changed to 3 g, and 9 g of tetraethyl orthosilicate was changed to 1 g, respectively, 0.6 g of hollow structure particles containing titanium oxide and silica were added. Obtained.

[Surface treatment of hollow structure particles]
After dispersing the synthesized hollow structure particles in ion-exchanged water and heating, 3% by mass of stearic acid was adsorbed on the hollow structure particles, followed by washing and drying to obtain surface-treated hollow structure particles.

[Comparative particles]
Titanium oxide particles (CR-50-2, manufactured by Ishihara Sangyo Co., Ltd.) were used as comparative particles for the cosmetic composition.

[Powdery foundation]
A powdery foundation containing the obtained surface-treated hollow structure particles was prepared at the compounding ratio shown in Table 2, and the evaluation when applied to the skin was evaluated by the following method.

[Method for producing powdery foundation]
Mix talc and color pigment in a blender. The rest of the powder is added to this and mixed well, then a binder and a preservative are added, and after toning, perfume is sprayed and mixed uniformly. After pulverizing this with a pulverizer, it is passed through a sieve and compression-molded into a medium plate.

[Evaluation method]
Concerning the concealability and spreadability, each cosmetic was used by panelists (10 persons), and sensory evaluation (score) was performed on a scale of 5. Based on the score average value, evaluation was made according to the following evaluation criteria.
(Score)
5: Very good 4: Excellent 3: Normal 2: Poor 1: Very poor (evaluation criteria)
⊚: Average evaluation value of 4.0 or more and 5.0 or less ◯: Evaluation average value of 3.0 or more and less than 4.0 △: Evaluation average value of 2.0 or more and less than 3.0 ×: Evaluation average value of 1.0 or more and 2.0 less than 0

[O/W emulsified foundation]
An O/W emulsified foundation containing the obtained surface-treated hollow structure particles was prepared at the compounding ratio shown in Table 3.

[Method for producing O/W emulsified foundation]
Propylene glycol in which bentonite was dispersed was added to purified water and homomixed at 70° C. After that, the remaining aqueous phase components were added and thoroughly stirred. The sufficiently mixed and pulverized powder portion was added to this while stirring, and treated with a homomixer at 70°C. Then, the oil phase dissolved by heating at 70 to 80°C was gradually added and treated with a homomixer at 70°C. This was cooled with stirring, added perfume at 45°C and cooled to room temperature. Finally, it was degassed and filled into containers.

[lipstick]
Lipsticks containing the obtained surface-treated hollow-structured particles were prepared at the compounding ratios shown in Table 4, and evaluations when applied to the skin were evaluated by the following methods.

[Method for producing lipstick]
Surface-treated hollow-structured particles, or titanium oxide of Comparative Examples and Red No. 201 and Red No. 202 were added to a portion of castor oil and treated with a roller (pigment portion). Red No. 223 is dissolved in a portion of castor oil (dye portion). After the other components were mixed and melted by heating, the pigment part and the dye part were added and treated with a homomixer. After treatment, it was poured into a mold and quenched to form a stick.

[Evaluation method]
Each cosmetic was used by panelists (10 persons), and sensory evaluation (score) was carried out on a scale of 5 for color development and roughness. The average score and evaluation criteria were the same as those for the powdery foundation.

[sunscreen cosmetics]
A sunscreen cosmetic containing the obtained surface-treated hollow structure particles was prepared at the compounding ratio shown in Table 5.

[Method for producing sunscreen cosmetics]
The powder, the oily component and the aqueous medium are heated to 70° C. and dissolved. The powder and the oily component are obtained by sufficiently dispersing the surface-treated hollow structure particles or the titanium oxide of the comparative example, and adding an aqueous medium while performing a homogenizer treatment. The emulsion is cooled using a heat exchanger.

ADVANTAGE OF THE INVENTION According to this invention, the cosmetic composition which is excellent in the touch at the time of use, and is excellent in storage stability can be implement|achieved, while having both transparency and UV shielding property. As a result, the user can obtain a suitable feeling of use, excellent transparency, and suppression of damage to the skin, and the manufacturer can produce cosmetics with stable quality.

Claims (5)

(A) Rutile-type titanium oxide hollow particles containing single-crystal titanium oxide and silica, wherein the titanium oxide content is 86.0 mol% or more and 99.5 mol% or less, and the silica content is 0 A cosmetic composition containing rutile-type titanium oxide hollow particles having a sphericity of 0.5 to 1.0 in a range of 5 mol % to 14.0 mol % . 2. The cosmetic composition according to claim 1 , wherein the value of A/B is 0.3 or more and 0.95 or less, where A is the hollow diameter of the component (A) and B is the particle diameter. 3. The cosmetic composition according to claim 1, wherein the component (A) has a primary particle size of 10 nm or more and 1000 nm or less . 4. The cosmetic composition according to any one of claims 1 to 3, wherein the coefficient of variation of the primary particle size of the component (A) is 10% or less. 5. The cosmetic composition according to any one of claims 1 to 4 , further comprising (B) an oily component.