JP6445251B2 - Emulsified cosmetics - Google Patents

Description

  In the present invention, while blending a poorly soluble ultraviolet absorber or ultraviolet scattering agent, by selecting a specific powder surface treatment agent or a specific oil agent, there is no stickiness or creaking, and the cosmetic film is uniform and durable. The present invention relates to an emulsified cosmetic having a high UV protection effect.

  Conventionally, for the purpose of blocking ultraviolet rays in sunlight and protecting the skin from the adverse effects of ultraviolet rays, studies have been made to provide ultraviolet protection effects to makeup cosmetics, and metal oxides such as zinc oxide and titanium dioxide. Cosmetics having a high UV protection effect have been developed by adding organic UV absorbers. In particular, in recent years, attention has been paid to the UV protection effect in the UVA region. However, since UV absorbers that can absorb UVA in the long wavelength have a higher molecular weight than UVB absorbers, they are hardly soluble (non-polar in water). Many of them are difficult to dissolve in oil), causing various problems when blended into emulsified cosmetics.

  For example, the technique of blending an organic ultraviolet absorber in a finely divided form (for example, Patent Document 1) is sticky due to the blending of a dispersant and a thickener, and the cosmetic film tends to be non-uniform so that the ultraviolet protection is avoided. The effect may be reduced. Further, when an ultraviolet absorbent is dissolved in a polar oil or the like, stickiness or weight may be generated during use, and stability such as crystal precipitation or drainage over time may be deteriorated. Furthermore, usually when emulsifying cosmetics contain a large amount of metal oxide, there are problems such as a powdery squeaky sensation, and the cosmetic film does not become a beautiful and uniform film, resulting in poor durability of the cosmetic film. Consideration has been made. (For example, see Patent Documents 2 and 3)

JP 2001-199857 A JP 2012-046447 A JP 2010-229067 A

  An object of the present invention is to provide an emulsified cosmetic having excellent usability and uniformity and durability of a cosmetic film, and having a high UV protection effect, while containing a large amount of a poorly soluble UV absorber and UV scattering agent. It is.

  In view of this situation, the present inventors have intensively studied, and as a result, in emulsified cosmetics, a specific surface treatment-treated metal oxide, a specific polar oil, and a specific organic ultraviolet absorber are blended. As a result, it was found that the film has a good feeling of use without stickiness and squeak, and is very excellent in the uniformity and durability of the cosmetic film, and also in the UV protection effect, thereby completing the present invention.

That is, the present invention
[1] The following components (a) to (d);
(A) Fine-grained zinc oxide whose surface has been hydrophobized (b) Titanium dioxide surface-treated with a compound containing nitrogen (c) Liquid oil having an IOB value of 0.1 to 0.4 (d) Bisethylhexyl One or two ultraviolet absorbers selected from oxyphenol methoxyphenyl triazine and diethylaminohydroxybenzoyl hexyl benzoate are blended ,
The amount of the component (a) is 5 to 25% by mass, and
The amount of the component (b) is 3 to 20% by mass,
Emulsified cosmetics,
[2] The emulsified cosmetic according to the above [1], further comprising component (e) methylene bis-benzotriazolyl tetramethylbutylphenol,
[3] The emulsified cosmetic according to the above [1] or [2], wherein the hydrophobizing treatment of (a) is a treatment selected from silicone treatment, fluorine treatment, and organic titanate treatment,
[4] The emulsified cosmetic according to any one of [1] to [3] , wherein the nitrogen-containing compound (b) is lecithin,
[5] The emulsified makeup according to any one of [1] to [4] , wherein (c) is one or more selected from esters of fatty acids having 8 to 10 carbon atoms and polyhydric alcohols. It is a fee.
[6] The emulsified cosmetic according to any one of [1] to [5], wherein an average particle size of the fine particle zinc oxide whose surface is hydrophobized is 100 nm or less.
[7] The emulsified cosmetic according to any one of [1] to [6], wherein the titanium dioxide surface-treated with the nitrogen-containing compound has an average particle size of 0.1 to 0.3 μm. .

  The emulsified cosmetic of the present invention is highly UV-protective because it contains a lot of UV scattering agents and poorly soluble UV absorbers, has excellent crispness and stickiness, and is excellent in use film uniformity and durability. Has an effect.

Hereinafter, the configuration of the present invention will be described in detail.
The component (a) used in the present invention is finely divided zinc oxide surface-treated with a hydrophobizing agent. The shape of the finely divided zinc oxide to be treated is not particularly limited, but the average particle diameter is ultraviolet rays. The protective effect is 100 nm or less. It is preferable that it is 10-100 nm in the point of handling. These particle sizes can be measured by a measuring instrument using a dynamic light scattering method. Examples of commercially available fine particle zinc oxide include FINEX-50 (manufactured by Sakai Chemical Industry Co., Ltd.), ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.), zinc oxide FZO-50 (manufactured by Ishihara Sangyo Co., Ltd.), and fine particle zinc oxide MZ-500. (Manufactured by Teika).

  The hydrophobizing agent of component (a) is not particularly limited as long as it is a hydrophobizing agent usually used in cosmetics. For example, silicone treating agent, fluorine treating agent, organic titanate treating agent, metal soap treating agent, Examples include lecithin treating agents. In particular, silicone treatment agents, fluorine treatment agents, and organic titanate treatment agents are preferred from the viewpoint of dispersibility and uniformity of the decorative film.

Specifically, silicone treatment agents include low-polymerization dimethylpolysiloxane, high-polymerization dimethylpolysiloxane, chain silicones such as methylphenylpolysiloxane, amino-modified silicones, alkyl-modified silicones, alkoxy-modified silicones, etc. Silicones, silicone resins such as trimethylsiloxysilicic acid and acrylic-silicone graft copolymers, silicone rubbers, partially or fully crosslinked organopolysiloxanes, silylating agents, silane coupling agents, etc. 1 type (s) or 2 or more types can be used.
Of the silane coupling agents, trialkoxyalkylsilane is preferred. A trialkoxyalkylsilane is a compound in which three alkoxy groups and one alkyl group are bonded to a silicon atom, and the surface of the powder is chemically modified by the reaction of the alkoxy group with a hydroxyl group or the like on the surface of the powder. A compound. In the trialkoxyalkylsilane, the alkoxy group is preferably methoxy, ethoxy, propoxy or the like, which is an alkoxy group having 1 to 3 carbon atoms. In the trialkoxyalkylsilane, the alkyl group is preferably a hexyl group, octyl group, decyl group, octadecyl group or the like, which is an alkyl group having 6 to 18 carbon atoms. Such trialkoxyalkylsilanes include, for example, trimethoxyhexylsilane, trimethoxyoctylsilane, trimethoxydecylsilane, trimethoxyoctadecylsilane, triethoxyhexylsilane, triethoxyoctylsilane, triethoxydecylsilane, triethoxyoctadecylsilane Etc. Among these trialkoxyalkyl silanes, trimethoxy octyl silane and triethoxy octyl silane are particularly preferable because affinity with skin is improved.

  Examples of the fluorine treatment agent include fluorine compounds such as fluorine-modified silicone, perfluoroalkyl phosphoric acid and its salt, perfluoropolyether, fluoroalkoxysilane, perfluoropolyetheralkyl phosphoric acid and its salt, and perfluoroalkylsilane. These 1 type (s) or 2 or more types can be used.

  Examples of the organic titanate treatment agent include long-chain carboxylic acid type, pyrophosphoric acid type, phosphorous acid type, amino acid type alkyl titanate and the like, and alkyl titanate having an alkyl group having 8 to 24 carbon atoms is preferable. Specifically, the alkyl titanate is, as a long chain carboxylic acid type alkyl titanate, isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, diisostearoyl ethylene. Titanates and the like, and as pyrophosphate type alkyl titanates, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis ( Ditridecyl phosphite) titanate and the like, and phosphite-type alkyl titanates include isopropyl tri (dioctyl pyrophosphate) titanate. , Bis (dioctyl pyrophosphate) oxy acetate titanate, bis (dioctyl pyrophosphate) ethylene titanate and the like, as an amino acid alkyl titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate. In the present invention, among these alkyl titanates, it is preferable to select a long-chain carboxylic acid type alkyl titanate, and it is particularly preferable to select isopropyl triisostearoyl titanate because the affinity with the skin is improved.

  The method of surface treatment in component (a) and component (b) described later is not particularly limited, and can be usually produced by a known method. For example, a hydrophobic treatment agent and powder particles to be treated are added to a solvent, stirred with a ball mill or the like, then dried as necessary, washed with water and filtered repeatedly to remove impurities, and then dried. The desired hydrophobized powder can be obtained by pulverization. Further, several types of compounds that are surface treatment agents can be simultaneously surface treated, and after surface treatment with any one compound in advance, other compounds can be surface treated. The amount of treatment varies depending on the type of surface treatment agent, the combination thereof, and the type of powder to be treated, and is not particularly limited, but is 0.1 to 10% by mass (hereinafter simply referred to as “surface treatment powder”). Abbreviated “%”). When the treatment amount is within this range, a surface-treated powder having particularly excellent water resistance and adhesion to the skin can be obtained.

  Although the compounding quantity of the component (a) in the cosmetics of this invention is not restrict | limited in particular, 5 to 25% is preferable. If it is this range, the emulsified cosmetics which are excellent in the uniformity of a cosmetic film and have a high ultraviolet-ray protective effect can be obtained.

  The component (b) used in the present invention is titanium dioxide surface-treated with a nitrogen-containing compound, and the titanium dioxide to be treated is not particularly limited in average particle diameter or shape, but makeup ( The average particle size is preferably 0.1 to 0.3 μm from the viewpoint of the cover) effect, and these particle sizes can be measured by a measuring instrument using a dynamic light scattering method. As a commercial item, TIPAQUE CR-50 (made by Ishihara Sangyo Co., Ltd.) etc. are mentioned, for example.

  The surface treatment agent of component (b) is a compound containing nitrogen, such as lecithin and derivatives thereof, amino acids and salts thereof, acylated amino acids and salts thereof, peptides, ceramides, among these, Lecithin, acylated amino acids, and ceramides are preferable from the viewpoint of affinity for the skin, and lecithin is particularly preferable from the viewpoint of uniformity of the cosmetic film.

  Lecithin is a lipid having a phosphate group regardless of animality, vegetableity, hydrogenation, non-hydrogenation, PC (phosphatidylcholine) purity or the like. Specifically, commercial products such as Ajinomoto Lecithin (manufactured by Ajinomoto Co., Inc.), which is a soybean phospholipid, and Resinol S-10 and S-10E (hydrogenated soy lecithin, both manufactured by Nikko Chemicals Co., Ltd.) can be used as they are. . Examples of the phospholipid (lecithin) derivative include a copolymer of phospholipid and an acrylic polymer.

  The acylated amino acid is an amino acid in which a hydrogen atom of an amino group is substituted with an acyl group, and the acyl group is a saturated or unsaturated linear or cyclic group having 1 to 20 carbon atoms. Examples thereof include N-acetylglutamic acid, N-lauroylglutamic acid, N-myristylalanine, NN-oleylthreonine, N-cinnamoylglycine, N-nicotinoylglutamic acid and the like. Examples of the salt include sodium salt, potassium salt, and triethanolamine salt.

  Ceramides include ceramides and derivatives thereof, and may be natural extracts or synthetic products. Usually, it is not limited as long as it can be used in cosmetics. For example, one or more long-chain linear and / or branched alkyl or alkenyl groups in the molecule, and at least two or more hydroxyl groups, one or more It is expressed as a nonionic amphiphile having an amide group (and / or amino group), or a derivative in which a phosphatidylcholine residue or a sugar residue is bonded to the hydroxyl group of the nonionic amphiphile. It is a series of ceramides. Specifically, natural ceramides such as sphingosine, phytosphingosine and their long chain fatty acid amides such as ceramide 1, ceramide 2, ceramide 3, ceramide 3B, ceramide 4, ceramide 5, ceramide 6, ceramide 6I, ceramide 6II; Examples include sphingosine, sphingomyelin, which is a phospholipid derivative of phytosphingosine, and sphingophospholipids such as phytosphingomyelin; glycosphingolipids such as cerebroside and ganglioside, phytosphingoglycolipids, and the like.

  Although the compounding quantity of the component (b) in the cosmetics of this invention is not restrict | limited in particular, 5 to 20% is preferable. If it is this range, the emulsified cosmetics which are excellent in the cover effect and the uniformity and sustainability of a cosmetic film, and have a high ultraviolet-ray protective effect can be obtained.

  The component (c) used in the present invention is a liquid oil having an IOB value of 0.1 to 0.4. If the IOB value is within this range, the dispersibility of the blended powder and the skin The balance of the affinity becomes appropriate, the cosmetic film is excellent in uniformity and persistence, and further, the squeaky feeling and stickiness of the UV absorber and the scattering agent are reduced, and a cosmetic having an excellent usability can be obtained. The IOB value refers to the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, that is, “inorganic value (IV) / organic value (OV)”.

  Liquid oils having an IOB value of 0.1 to 0.4 include cetyl 2-ethylhexanoate (IOB = 0.13), isotridecyl isononanoate (IOB = 0.15), neopentyl glycol dicaprate (IOB = 0.25), propylene glycol dicaprate (IOB = 0.26), diisostearyl malate (IOB = 0.28), trimethylolpropane triisostearate (IOB = 0.16), tri-2-ethylhexane Glyceryl acid (IOB = 0.35), isopropyl myristate (IOB = 0.18), isodecyl isononanoate (IOB = 0.19), octyldodecyl neopentanoate (IOB = 0.13), isostearyl neopentanoate (IOB) = 0.14), isopropyl palmitate (IOB = 0.16), laurin Hexyl (IOB = 0.17), hexyldecyl ethylhexanoate (IOB = 0.13), isopropyl isostearate (IOB = 0.15), neopentyl glycol diethylhexanoate (IOB = 0.32), triethylhexanoic acid Trimethylolpropane (IOB = 0.33), pentaerythrityl tetraethylhexanoate (IOB = 0.35), isodecylbenzoate (IOB = 0.23), propylene glycol dicaprylate (IOB = 0.32), isononanoic acid Isononyl (IOB = 0.2), ethylhexyl isononanoate (IOB = 0.2), isodecyl neopentanoate (IOB = 0.22), ethylhexyl ethylhexanoate (IOB = 0.2), glyceryl triethylhexanoate (IOB = 0.36), di-succinate Hexyl (IOB = 0.32), 2-ethylhexyl p-methoxycinnamate (IOB value = 0.28), and the like.

  Among them, an ester of a fatty acid having 8 to 10 carbon atoms and a polyhydric alcohol is preferable, and in particular, one or more ester oils selected from neopentyl glycol dicaprate and propylene glycol dicaprate are more preferable. preferable.

  Although the compounding quantity of the component (c) in the cosmetics of this invention is not restrict | limited in particular, 1 to 20% is preferable. If it is this range, the emulsified cosmetics which were excellent in the uniformity and sustainability of the cosmetic film, and were excellent also in the usability | use_condition can be obtained.

  Component (d) used in the present invention is a solid hardly soluble ultraviolet absorber at 25 ° C., but is soluble in component (c), and is composed of bisethylhexyloxyphenol methoxyphenyltriazine, diethylaminohydroxybenzoyl hexyl benzoate. One or two selected. Examples of commercially available products include TINOSORB S (bisethylhexyloxyphenol methoxyphenyl triazine, manufactured by BASF), UVINUL A PLUS (hexyl diethylaminohydroxybenzoyl benzoate, manufactured by BASF), and the like.

  The content of component (d) in the present invention is not particularly limited, but is preferably 3 to 15%. If it is this range, it is excellent in a usability | use_condition and the emulsified cosmetics which have a high ultraviolet-ray protective effect can be obtained.

  Furthermore, in the emulsified cosmetic of the present invention, it is preferable to add methylene bis-benzotriazolyl tetramethylbutylphenol as the component (e) because the ultraviolet protection effect is improved. Methylene bis-benzotriazolyl tetramethylbutylphenol has low solubility in cosmetic oils and is insoluble in water, so it is preferably blended in a form dispersed in an aqueous phase. At that time, for example, commercially available TINOSORB M (aqueous dispersion of methylenebis-benzotriazolyl tetramethylbutylphenol, manufactured by BASF) can be used as it is. Although the compounding quantity of the component (e) in the cosmetics of this invention is not restrict | limited in particular, 1 to 5% is preferable.

  In the emulsified cosmetic of the present invention, an oily component other than the component (c), a surfactant, and an aqueous solution are added as necessary to the ordinary cosmetic as long as the effects of the present invention are not impaired. Components, UV absorbers other than components (d) and (e), powders other than components (a) and (b), water-soluble polymers, moisturizers, antioxidants, anti-fading agents, preservatives, medicinal ingredients, stability Agents, pigments, fragrances and the like can be appropriately blended for imparting various effects.

  The oil component is not particularly limited as long as it is usually used in cosmetics in addition to the component (c), and it is a solid oil, semi-solid oil, liquid oil, volatile oil of origin such as animal oil, vegetable oil or synthetic oil. Regardless of the nature, hydrocarbons, oils and fats, waxes, hardened oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorinated oils, lanolin derivatives, oily gelling agents, oils Soluble resin etc. are mentioned.

  Specifically, liquid paraffin, squalane, petrolatum, paraffin wax, ceresin wax, microcrystalline wax, ethylene propylene copolymer, montan wax, fisher trops wax, light liquid isoparaffin, hydrocarbons such as isododecane, molasses, olive oil, castor Oils, oils such as mink oil, macadamian nut oil, beeswax, carnauba wax, candelilla wax, wax such as gay wax, jojoba oil, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate , Glyceryl trioctanoate, diglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, diisostearyl malate, neodioctanoate Nylglycol, tridecyl isononanoate, alkyl benzoate, diisopropyl sebacate, diethylhexyl sebacate, cholesterol fatty acid ester, N-lauroyl-L-glutamate di (cholesteryl / behenyl / octyldodecyl), stearyl alcohol, cetyl Alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, higher alcohols such as behenyl alcohol, silicone oils such as cyclomethicone, methylpolysiloxane, methyltrimethicone, phenyltrimethicone, methylphenylpolysiloxane, perfluorodecane, perfluoro Fluorine oils such as octane and perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin alcohol Lanolin derivatives such as octanoic acid dextrin, lauric acid dextrin, palmitic acid dextrin, myristic acid dextrin, stearic acid dextrin, behenic acid dextrin, palm oil fatty acid dextrin, (palmitic acid / octanoic acid) dextrin, sucrose fatty acid ester, starch fatty acid Examples thereof include oil-based gelling agents such as esters, 12-hydroxystearic acid and calcium stearate, oil-soluble resins such as hydrogenated rosin acid pentaerythrityl and specific alkyl methyl polysiloxane acrylates. These oily components can be used singly or in combination of two or more as required, and alkyl benzoate, diisopropyl sebacate, and diethylhexyl sebacate are particularly preferable from the viewpoint of stability.

  As the surfactant, any surfactant that is generally used in cosmetics can be used. Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Is mentioned. Specifically, glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, sucrose fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene Examples thereof include alkyl co-modified organopolysiloxane and polyether-modified organopolysiloxane. These surfactants can be used alone or in combination of two or more as required. In the emulsified cosmetic of the present invention, it is preferable to use a water-in-oil emulsion in order to obtain the durability of the cosmetic film and a higher UV protection effect. However, in order to obtain a water-in-oil emulsion, HLB7 or less. It is essential to add a nonionic surfactant. Among them, from the viewpoint of stability, a nonionic surfactant comprising an ester bond of polyhydroxystearic acid such as PEG-30 dihydroxystearic acid or a lipophilic silicone surfactant such as PEG-9 polydimethyl Siloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone and the like are preferable.

  Examples of the aqueous component include so-called water such as deionized water, distilled water, purified water, hot spring water, plant-derived steam distilled water such as rose water, lavender water, and the like, which are soluble in water and can be used as a solvent. For example, alcohols such as ethyl alcohol and isopropyl alcohol, glycols such as propylene glycol, 1,2-pentylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol, glycerin, diglycerin, polyglycerin, and the like Glycerols.

  Examples of the ultraviolet absorber include those other than components (d) and (e), such as benzophenone, PABA, cinnamic acid, salicylic acid, and silicon. Specifically, oxybenzone, 4-tert-4′-methoxydibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, 2-ethylhexyl salicylate, ethyl paradihydroxypropylbenzoate, dimethoxybenzylidenedioxoimidazolidinepropionic acid 2 -Ethylhexyl, dimethicodiethylbenzalmalonate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, octocrylene and the like.

  Any powder can be used as long as it is a powder commonly used in cosmetics other than components (a) and (b). For the purpose of adjusting the feel, for example, silicone powder, talc, sericite, etc. Powders such as silica, mica, kaolin, calcium carbonate, aluminum oxide, polyethylene powder, polymethyl methacrylate, and nylon powder can be used. These powders are prepared by known surface treatment methods such as silica treatment, alumina treatment, aluminum hydroxide treatment, fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, organic titanate treatment, oil agent. Surface treatment may be performed by a method such as treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, acrylic resin treatment, or metal oxide treatment.

  The emulsified cosmetic of the present invention is an oil-in-water type, a water-in-oil type, or a multiphase emulsion type cosmetic that is a composite thereof, but is preferably a water-in-oil type in terms of makeup sustainability. The production method is not particularly limited and is prepared by a conventional method. The emulsified cosmetic of the present invention is not particularly limited, but it can easily be used in makeup cosmetics such as foundations and base cosmetics, sunscreen cosmetics, and the like, and can be suitably used.

  Hereinafter, the present invention will be described in more detail with reference to examples. Note that these do not limit the present invention.

Examples 1-4 and Comparative Examples 1-4: Foundation (water-in-oil type)
A foundation was prepared by the composition shown in Table 1 and the following production method. The obtained cosmetic was evaluated by the following method, and the results are shown in Table 1.

(Production method)
A: Components (1) to (16) are mixed.
B: Components (17) to (20) are heated and mixed.
C: A and components (21) to (25) are added to B and mixed uniformly.
D: The component (31) is dispersed in advance in the components (32) to (34).
E: D is added to components (26) to (30) and mixed with heating.
F: E is added to C and emulsified.
G: F was defoamed to obtain a foundation.

(Evaluation Method 1: Appearance)
After the foundations of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared, the emulsifiability was visually confirmed from the presence or absence of color unevenness in appearance.
[Criteria]
(Judgment): (Evaluation)
◎: No color unevenness and good emulsification ○: Some color unevenness is observed △: Color unevenness is observed and emulsification is unstable ×: Drainage is observed and emulsification is poor

(Evaluation method 2: Sensory evaluation)
20 professional cosmetics evaluation panels used the foundations of Examples 1 to 5 and Comparative Examples 1 to 3, and “no stickiness”, “no powder squeak”, “evenness of makeup film”, Each evaluation item of “Durability of cosmetic film” was evaluated on a five-point scale using the following absolute evaluation criteria. Thereafter, the average value of the scores of each sample was calculated and judged using a four-step criterion.
[Absolute evaluation criteria]
(Score): (Result)
5 points: Very good 4 points: Good 3 points: Normal 2 points: Slightly bad 1 point: Bad [4 step criteria]
(Judgment): (Average score)
◎: 4.5 to 5.0 points ○: 3.5 to less than 4.5 points Δ: 2.0 to less than 3.5 points ×: Less than 1.0 to 2.0 points

(Evaluation method 3: UV protection effect)
20 mg each of the foundations of Examples 1 to 6 and Comparative Examples 1 to 4 were uniformly coated on a 5 cm × 5 cm square polymethyl methacrylate plate (manufactured by Sanyo Trading Co., Ltd.), and SPF Analyzer System UV-1000S (manufactured by Labsphere) ), The transmittance of 290 nm to 400 nm that is the UVA and UVB regions was calculated from the average value of 15 measurements per sample (N = 3), and the determination was made using the following criteria.
[Criteria]
(Judgment): (Evaluation)
◎: Ultra low UV protection effect with a transmittance of less than 10% ○: Excellent UV protection effect with a transmittance of 10% to less than 30% △: Ultraviolet protection effect with a transmittance of 30% to less than 40% Slightly inferior ×: The transmittance is 40% or more and the UV protection effect is inferior

As is clear from the results in Table 1, the foundations of Examples 1 to 4 were used without any stickiness or squeaky sensation during use, while containing a large amount of metal oxide and a hardly soluble ultraviolet absorber. Since it was excellent in feeling and also in the uniformity and sustainability of the decorative film, the UV protection effect was also very excellent.
On the other hand, Comparative Example 1 in which untreated fine zinc oxide was blended instead of component (a) was poor in dispersibility of fine zinc oxide and inferior in UV protection effect, and the squeaky feeling and uniformity of the cosmetic film It was also inferior in sustainability. Comparative Example 2 in which untreated titanium dioxide was blended instead of component (b) felt a squeaky feeling because it was an untreated powder, and was very inferior in terms of uniformity and durability of the cosmetic film. In addition, Comparative Example 3 in which silicone-treated titanium dioxide containing no nitrogen was used in place of component (b), but the squeaky feeling of the powder was alleviated, but the cosmetic film was very uniform and durable. The result was inferior. Furthermore, the comparative example 4 which does not contain a component (c) was very inferior to the uniformity and sustainability of a decorative film, and was also inferior also about the ultraviolet-ray protective effect by it. From the above results, it was shown that an emulsified cosmetic with improved UV protection effect can be obtained by combining each component of the present invention with excellent uniformity and durability of the cosmetic film.

Examples 5 and 6: Foundation (shaking oil-in-water type, double layer)
A foundation was prepared by the composition shown in Table 2 and the following production method. The obtained cosmetic was evaluated by the above method, and the results are shown in Table 2.

(Production method)
A: Components (1) to (6) are mixed.
B: Components (7) to (17) are heated and mixed.
C: A is added to B and mixed uniformly.
D: Components (18) to (23) are mixed.
E: D is added to C and emulsified.
F: E was defoamed to obtain a foundation.

  As is clear from the results in Table 2, the foundations of Examples 5 and 6 are excellent in the uniformity of the cosmetic film and its sustainability while blending both the metal oxide and the poorly soluble ultraviolet absorber. The UV protection effect was high, and the feeling of use was also excellent.

Example 7: Base (water-in-oil type)
(Ingredient) (%)
1. Silicone-treated fine particle zinc oxide * 1 8
2. N-lauroylglutamic acid (3%) treated titanium dioxide 6
3. Silicone-treated Bengala Cloisonne * 4 0.1
4). Silicone-treated yellow iron oxide * 4 0.2
5). Spherical silica 0.3
6). Neopentyl glycol dicaprate 3
7). Cyclopentasiloxane 12
8). Methyl trimethicone 2
9. Methyl polysiloxane 3
10. Ethyl hexyl methoxycinnamate 2
11. Diethylaminohydroxybenzoyl hexyl benzoate 5
12 Bisethylhexyloxyphenol methoxyphenyl triazine 1
13. 2-ethylhexyl palmitate 4
14 PEG-9 polydimethylsiloxyethyl dimethicone 2
15. Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone 1
16. Dimethylstearylammonium hectorite 0.3
17. Benzyldimethylstearylammonium hectorite 0.3
18. Methyl paraoxybenzoate 0.1
19. Ethanol 5
20.1,3-butylene glycol 1
21. Purified water remaining amount 23. L-ascorbyl magnesium phosphate 2
24. Sodium chloride 0.3
25. Methylenebis-benzotriazolyl tetramethylbutylphenol dispersion * 7 2

(Production method)
A: Components (1) to (9) are mixed.
B: Components (10) to (13) are heated and mixed.
C: A and components (14) to (17) are added to B and mixed uniformly.
D: Components (18) to (25) are mixed.
E: D is added to C and emulsified.
F: E was defoamed to obtain a base.
(result)
The base of Example 7 was a base with high emulsifiability and usability, and also a high UV protection effect due to excellent uniformity and durability of the decorative film.

Example 8: Sunscreen (oil-in-water type)
(Ingredient) (%)
1. Polyoxyethylene hydrogenated castor oil (100EO) 2
2. Glycerin 5
3. 1,3-butylene glycol 5
4). 4. Purified water remaining amount Acrylic acid / Acroyldimethyltaurine sodium copolymer * 9 2
6). Cetostearyl alcohol 1
7). Glyceryl stearate 1
8). Behenyl alcohol 1
9. Ethyl hexyl methoxycinnamate 3
10. Glyceryl triethylhexanoate 20
11. Polysilicone-15 1
12 Diethylaminohydroxybenzoyl hexyl benzoate 2
13. Bisethylhexyloxyphenol methoxyphenyl triazine 1
14 t-Butylmethoxydibenzoylmethane 1
15. Octyl rearzone 1
16. Octyl salicylate 3
17. Triethoxyoctylsilane (5%) treated fine particle zinc oxide 12
18. Lecithin-treated titanium dioxide * 3 3
19. Polyhydroxystearic acid 0.5
20. Glyceryl triethylhexanoate 10
* 9 SIMULGEL-EG (SEPPIC: solid content 37.5%)

(Production method)
A: Components (17) to (20) are uniformly mixed and dispersed.
B: Components (6) to (16) are uniformly mixed and dissolved at 70 ° C.
C: Components (1) to (5) are mixed and dissolved at 70 ° C.
D: B is uniformly mixed with A and the oil system is adjusted at 70 ° C.
E: D is uniformly mixed and dispersed in C and emulsified at 70 ° C.
F: E was cooled to obtain a sunscreen.
(result)
The sunscreen of Example 8 had no stickiness, was excellent in the uniformity of the cosmetic film and its durability, and was therefore excellent in the UV protection effect.

Example 9: Sunscreen (water-in-oil type)
(Ingredient) (%)
1. Silicone-treated fine particle zinc oxide * 1 10
2. Lauroyllysine (3%) treated titanium dioxide 3
3. Silica 0.5
4). Polymethylsilsesquioxane powder 2
5). Di (caprylic / capric) propylene glycol 3
6). Cyclopentasiloxane 13
7). Dimethylpolysiloxane (6cs) 3
8). Neopentyl glycol dicaprate 3
9. Ethyl hexyl methoxycinnamate 7
10. Diethylaminohydroxybenzoyl hexyl benzoate 2
11. Bisethylhexyloxyphenol methoxyphenyl triazine 3
12 Diethylhexyl sebacate 4
13. PEG-9 polydimethylsiloxyethyl dimethicone 2
14 Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 1
15. Phenoxyethanol 0.1
16. Ethanol 5
17.1,3-Butylene glycol 1
18. Purified water remaining amount 19. Methylenebis-benzotriazolyltetramethylbutylphenol 2
20.1,3-butylene glycol 0.5
21. Polyglyceryl laurate-10 0.5
22. Purified water 3

(Production method)
A: Components (1) to (8) are mixed.
B: Components (9) to (12) are heated and mixed.
C: A and components (13) to (15) are added to B and mixed uniformly.
D: Component (19) is dispersed in advance in components (20) to (22).
E: D is added to components (16) to (18) and mixed with heating.
F: E is added to C and emulsified.
G: F was defoamed to obtain a sunscreen.
(result)
The sunscreen of Example 9 had no stickiness, was excellent in the uniformity of the cosmetic film and its durability, and was also excellent in the UV protection effect.

Claims (7)

The following components (a) to (d);
(A) Fine-grained zinc oxide whose surface has been hydrophobized (b) Titanium dioxide surface-treated with a compound containing nitrogen (c) Liquid oil having an IOB value of 0.1 to 0.4 (d) Bisethylhexyl One or two ultraviolet absorbers selected from oxyphenol methoxyphenyl triazine and diethylaminohydroxybenzoyl hexyl benzoate are blended ,
The amount of the component (a) is 5 to 25% by mass, and
The amount of the component (b) is 3 to 20% by mass,
Emulsified cosmetic.   The emulsified cosmetic according to claim 1, further comprising component (e) methylenebis-benzotriazolyltetramethylbutylphenol.   The emulsified cosmetic according to claim 1 or 2, wherein the hydrophobizing treatment of component (a) is a treatment selected from silicone treatment, fluorine treatment, and organic titanate treatment. The emulsified cosmetic according to any one of claims 1 to 3 , wherein the nitrogen-containing compound of component (b) is lecithin and derivatives thereof, amino acids and salts thereof, acylated amino acids and salts thereof, and ceramides. The emulsified cosmetic according to any one of claims 1 to 4 , wherein the component (c) is one or more selected from esters of fatty acids having 8 to 10 carbon atoms and polyhydric alcohols. The emulsified cosmetic according to any one of claims 1 to 5, wherein an average particle diameter of the fine particle zinc oxide whose surface is hydrophobized is 100 nm or less. The emulsified cosmetic according to any one of claims 1 to 6, wherein the titanium dioxide surface-treated with a nitrogen-containing compound has an average particle size of 0.1 to 0.3 µm.