JP4683536B2 - Sunscreen emulsified cosmetics - Google Patents

Description

  The present invention relates to a sunscreen emulsified cosmetic containing a hydrophobized zinc oxide powder. More specifically, the present invention relates to an emulsified sunscreen emulsified cosmetic with improved detergency.

  Among the ultraviolet rays of sunlight, the wavelength of 280 to 320 nm in the middle wavelength ultraviolet region causes erythema called sunburn on the skin, and in severe cases, causes water bubbles similar to burns. Further, it is known that the wavelength of 320 to 400 nm in the long-wavelength ultraviolet part causes skin darkening, and when any wavelength repeatedly acts for a long time, it promotes skin aging.

  In order to prevent the harmful effects of ultraviolet rays on the skin, sunscreen cosmetics containing ultraviolet absorbers and ultraviolet protective powders are used.

  Among these, fine zinc oxide powder is used as a material that effectively protects the long wavelength ultraviolet region and has high transparency in the visible region. In addition, it is known that the W / O type emulsion composition is good in terms of sweat resistance.

  When blending fine particle zinc oxide with the W / O emulsion composition, surface treatment is necessary from the viewpoint of the stability of the preparation. However, if the surface treatment is not uniform, zinc ions may elute and harm the stability of the system, and the finely divided zinc oxide is extremely difficult to be stably incorporated into the surface treatment method and W / O type emulsion composition. It was a powder.

On the other hand, sunscreen cosmetics such as sunscreens are used in swimming pools and sea bathing, so they are required to have water and oil repellency and do not need to be repainted many times (water and oil repellency). An excellent one is required. For this reason, water-in-oil emulsified cosmetics containing hydrophobic powder are used as sunscreen cosmetics. For example, Patent Documents 5 to 8 describe water-in-oil emulsified cosmetics containing a hydrophobic powder. As a technique for improving the longevity of cosmetics, it has been used as a conventional means to blend oils and resin components that have a refreshing usability compared to ordinary oils and a high water-repellent effect.
However, there is a problem that these components remain after use and are difficult to wash with a shower or the like.

  Patent Document 9 also discloses sunscreen cosmetics containing silicon-treated zinc oxide powder. This sunscreen cosmetic contains an isononanoic acid ester and a silicone-based surfactant and has a good spread and excellent touch feeling. However, as with the above-described emulsified cosmetics of Patent Documents 5 to 8, the sunscreen cosmetics are used. However, it was not preferable and there was a problem that it was difficult to drop.

Japanese Patent No. 2724257 Japanese Patent No. 2672913 Japanese Patent Publication No. 5-86984 JP-A-3-246210 Japanese Patent No. 2691654 JP-A-11-246330 JP-A-9-202714 JP-A-6-321735 JP 2000-169353 A

  In view of the above-mentioned viewpoints, the inventors of the sunscreen cosmetic blended with fine zinc oxide powder useful as a highly transparent ultraviolet light scattering agent have a specific oil content, not a silicone surfactant, a specific nonionic property. When emulsified with a surfactant, it has been found that a sunscreen emulsified cosmetic with good makeup and easy to wash off after use can be obtained, and the present invention has been completed.

  An object of the present invention is to provide a sunscreen emulsified cosmetic that is extremely excellent in cleanability after use.

That is, the present invention
(A) 1 to 40% by mass of hydrophobized zinc oxide powder produced by surface-treating fine particle zinc oxide powder having a primary particle diameter of 1 μm or less, and (b) 10 to 40% by mass of volatile silicone. (C) 3 to 10% by mass of isononyl isononanoate and (d) 1 to 4% by mass of a nonionic surfactant which is a lipophilic surfactant having an HLB of 7 or less other than the silicone surfactant. And (e) water, and (d) a nonionic surfactant is polyglyceryl diisostearate or PEG-20 glyceryl triisostearate, and provides a water-in-sun emulsion oil-based cosmetic. To do.
Furthermore, the present invention provides
(A) 1 to 40% by mass of hydrophobized zinc oxide powder produced by surface-treating fine particle zinc oxide powder having a primary particle diameter of 1 μm or less, and (b) 10 to 40% by mass of volatile silicone. (C) 1 to 10% by mass of liquid paraffin and isonononyl isononanoate, and (d) 1 to 4 nonionic surfactants which are lipophilic surfactants having an HLB of 7 or less other than silicone surfactants. A sunscreen oil-in-water emulsified cosmetic, comprising: (e) water, and (d) the nonionic surfactant is polyglyceryl diisostearate or PEG-20 glyceryl triisostearate A fee is provided.

The present invention also provides the water-in-oil-in-sun emulsified cosmetic described above, characterized by substantially not using a silicone-based surfactant .

  The sunscreen emulsified cosmetic of the present invention exhibits a remarkable effect that it can be easily washed off after use, while having excellent makeup (water and oil repellency). In other words, it is not necessary to use a cleansing cleansing agent dedicated to sunscreen cosmetics or makeup cosmetics, and can be easily washed off with soap and body soap, which is extremely convenient. Moreover, it is easy to apply and excellent in the feeling of use during application.

  Hereinafter, the present invention will be described in detail.

（式中、Rfは炭素数３〜21のパーフルオロアルキル基または、パーフルオロオキシアルキル基を示し、直鎖状あるいは分岐状であって、単一鎖長のものであっても複合鎖長のものであってもよい。ｎは１〜12の整数を示し、yは1〜3の数を示す。）

(A) Hydrophobized zinc oxide powder The usable hydrophobized zinc oxide powder includes metal soap-treated zinc oxide treated with aluminum stearate and the like, and fatty acid-dextrin-treated powder treated with cyclodextrin-fatty acid ester ( WSX-Transparon ^™, etc.), amino acid-treated powder treated with N-lauroyl-L-lysine, etc. (LL5-ST (HS) ^™, etc.), methylhydrogenpolysiloxane, methylhydrogenpolysiloxane, dimethylpolysiloxane Copolymers, silicone-treated powders treated with dimethylpolysiloxane, silica + dimethylpolysiloxane, etc. (SS-Activox80 ^™, etc.), fluorine-treated powders treated with perfluoroalkylphosphoric acid, etc. (PF ^™, etc.) Silane coupling treated with octyltriethoxysilane, etc. Grayed agent treated powder (OTS ^TM, etc.). Among these, a particularly preferable treated powder includes a silane coupling agent-treated powder treated with octyltriethoxysilane or the like.
The hydrophobized zinc oxide powder used in the present invention is not particularly limited.
However, the zinc oxide powder is dispersed in a solvent, the phosphoric acid ester having perfluoroalkyl represented by the general formula (1), and the molecular weight represented by the general formula (2) is 30,000 to 300,000. Hydrophobized by surface treatment with 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate copolymer and ester of methylpolysiloxane partially substituted with hydroxypropyl group In the method for producing a treated zinc oxide powder, by using a fine particle zinc oxide powder having a primary particle diameter of 1 μm or less and using a solvent in an amount in the range of 50 to 90 mass% with respect to the zinc oxide powder. It is preferable to use the hydrophobized zinc oxide powder produced. Because it is easy to obtain a low-viscosity formulation even when blended into a continuous phase of a general W / O type formulation, and since the specific surface area is maintained, the share when applied to the skin is loosened. This is because it is possible to effectively protect the long-wavelength ultraviolet part without causing white floating.

(In the formula, Rf represents a perfluoroalkyl group having 3 to 21 carbon atoms or a perfluorooxyalkyl group, which is linear or branched and has a single chain length or a complex chain length. (N represents an integer of 1 to 12, and y represents a number of 1 to 3).

  This hydrophobized zinc oxide powder is obtained by surface-treating fine zinc oxide powder having a primary particle diameter of 1 μm or less in place of the cosmetic pigment to be surface-treated in the method described in JP-A-2001-302455. Manufactured by. Preferably, a fine particle zinc oxide powder of 0.1 μm or less is used. The primary particle size is the average particle size of primary particles.

  Examples of the fine particle zinc oxide having a primary particle diameter of 1 μm or less include FINEX-50 manufactured by Sakai Chemical Co., Ltd., ZnO-350 manufactured by Sumitomo Osaka Cement Co., Ltd., and zinc oxide FZO-50 manufactured by Ishihara Sangyo Co., Ltd. Alternatively, fine zinc oxide MZ-500 manufactured by Teika Co., Ltd. can be used. In addition, fine zinc oxide powder (having a carnation petal-like appearance) described in WO99 / 25654 (Japanese Patent Application No. 11-525984) can be used.

  As the phosphoric acid ester having a perfluoroalkyl group represented by the general formula (1), for example, perfluoroalkyl phosphoric acid which is a solid content of an aqueous dispersion emulsion commercially available under the name AG-530 from Asahi Glass Co., Ltd. Ester diethanolamine salt or perfluoroalkyl phosphate sodium salt, perfluoroalkyl phosphate potassium salt, perfluoroalkyl phosphate ammonium salt, etc. having the same molecular structure but different salt form using amine What removed salt, ammonium salt, and alkali metal salt can be used.

  Examples of the ester represented by the general formula (2) (hereinafter sometimes referred to as “acrylic silicone copolymer”) include the names KP-541, KP-543 and KP-545 from Shin-Etsu Chemical Co., Ltd. Examples include commercially available isopropyl alcohol, butyl acetate, a copolymer dissolved in volatile silicone, or an acrylic silicone copolymer called KP-544 dissolved in another organic solvent.

The total coating amount of the perfluoroalkyl phosphate ester and acrylic silicone copolymer represented by the general formulas (1) and (2) is X / 5 to 5 when the specific surface area of the fine zinc oxide powder is Xm ² / g. By adjusting to X / 10% by weight, sufficient water repellency and oil repellency can be obtained. If the coating amount is outside this range, the phosphoric acid ester of the general formula (1) is deposited in a powder form other than the powder surface and coexists in the powder, and excessive aggregation of the powder can be ignored. There is a possibility that the defensive ability of the long-wavelength ultraviolet part may be reduced and the water repellency and oil repellency may be insufficient.
Therefore, when the specific surface area of the finely divided zinc oxide powder to be surface-treated is X (m ² / g), the sum of the amounts used of the phosphate ester of the general formula (1) and the ester of the general formula (2) is It is preferable to carry out in the range of X / 10 to X / 5% by mass with respect to the zinc oxide powder.

  Moreover, the mass ratio of the usage-amount of the phosphate ester of General formula (1) and the ester of the said General formula (2) is the ester of General formula (1) / ester of General formula (2) = 1-5. It is preferable to carry out with 2-4. If the content is outside this range, the resulting powder may have poor affinity with commonly used cosmetic oils, or water resistance (oil repellency) may be insufficient when applied to the skin as a formulation. There is.

  This production method is characterized in that the amount of the solvent is in the range of 50 to 90% by mass with respect to the zinc oxide powder. Surprisingly, when the surface treatment is carried out according to a conventional method using the phosphoric acid ester of the general formula (1) and the ester of the general formula (2), the low oil absorption and the apparent specific volume are low. Hydrophobized finely divided zinc oxide powder with excellent water and oil repellency is produced. The amount of the solvent is the amount of all the solvents present in the system in which the powder is dispersed, and is all the solutions excluding the compounds of the general formulas (1) and (2). The powder need not be dispersed in a solvent in advance and added to the processing container. A method is preferred in which the powder is first added to the processing container, then the processing agent solutions (solutions) of the general formulas (1) and (2) are added, and finally the solvent is added and stirred.

  The solvent is a lower alcohol such as methyl alcohol, ethyl alcohol or isopropyl alcohol, an ester solvent such as ethyl acetate or butyl acetate, or an organic solvent such as volatile silicone or acetone. Isopropyl alcohol (hereinafter referred to as IPA) is preferably used. In addition, in this invention, the solvent used 50 to 90 mass% with respect to zinc oxide powder is the total amount of solvent containing the solvent used when dissolving a surface treating agent previously.

A flow sheet of the above manufacturing method is shown in FIG.
(1) First, a fine particle zinc oxide powder having a primary particle diameter of 1 μm or less, a phosphate ester of the general formula (1), an ester of the general formula (2), and a solvent are added to the processing container. The order of addition is not particularly limited, but it is preferable to add in the order of powder, treating agent (solution), and solvent.
The surface treatment agent may be added as it is, or may be added in a state dissolved in a solvent in advance, but it is preferably added in a state dissolved in a solvent in advance for production efficiency.
The solvent that dissolves the surface treatment agent is not limited. Usually, it is easy to handle by adding it in a state of about 30 to 70% dissolved in a solvent such as isopropyl alcohol.
Further, as the amount of the solvent to be added, the total amount with the solvent for dissolving the treating agent in advance is preferably 50 to 90% by mass, more preferably 60 to 80% by mass with respect to the amount of powder to be treated. If it is less than 50% by mass, the ratio of the powder that cannot be sufficiently dispersed in the solvent and is agglomerated and coated (incomplete surface treatment) becomes high. On the other hand, if the amount exceeds 90% by mass, the powder is sufficiently dispersed, but the apparent specific volume is unlikely to decrease, and the coating itself is performed at the timing when the solvent is almost removed. The time will be longer. That is, it is not preferable because the solvent is excessive and inefficient.
The method of mixing (dispersing) the powder is not particularly limited, but usually a suitable mixing (dispersing) machine, such as a rotating ball mill, vibratory ball mill, planetary ball mill, sand mill, attritor, bag mill, poni mixer, planetary mixer, lei It is carried out using a paddle machine, a Henschel mixer, a super mixer, a kneader, a medium stirring mill (bead mill) or the like.
The mixing time is not limited, but is usually 0.1 to 2 hours.
(2) Next, the solvent is removed. Solvent removal is carried out with stirring and optionally heating the dispersion. More efficiently, it can be carried out by maintaining a reduced pressure state with a vacuum pump provided with a trap.
(3) Next, pulverization is performed. The grinding method is not particularly limited, but a high-speed rotary grinding machine (hammer mill, cage mill, pin mill, disintegrator, screen mill, turbo mill, centrifugal classification mill, etc.), ball mill (rolling mill, vibrating ball mill, planetary mill), stirring Milling (tower mill, stirring tank mill, flow pipe mill, annular mill), lab mill, jet mill, shear mill, compression-type mill, colloid mill, etc.
(4) Finally, dry.
Drying is performed using an electric heating type heat dryer or a dryer which is supplied with heated gas.
Although drying time is not specifically limited, It is desirable to perform in 1-250h and drying temperature in the range of 50-150 degreeC. Otherwise, sufficient drying may not be performed or the processing agent may be deteriorated.

The finely divided zinc oxide powder obtained as described above has a remarkable effect of low oil absorption and low apparent specific volume.
The preferred oil absorption of the fine zinc oxide powder is 15 to 40 mL / 100 g.
This oil absorption is a numerical value measured using a method according to JISK5101 21. or using a commercially available oil absorption measuring instrument.
The preferred specific volume of the fine zinc oxide powder used in the present invention is 0.5 to 0.9 mL / g.
This apparent specific volume is a numerical value (mL / g) representing a volume (mL) per gram measured according to the tap method described in JISK5101 20.2.

  The (a) hydrophobized zinc oxide powder preferably used in the present invention is as described above. This fine zinc oxide powder has the excellent effects of low oil absorption and low apparent specific volume, and at the same time, it is excellent in water and oil repellency, and can be stably blended into the preparation, and also has an ultraviolet scattering effect. Are better.

<Description of blending amount>
In the sunscreen makeup of the present invention, the hydrophobized zinc oxide powder (a) is preferably blended in an amount of 0.1 to 60% by mass, more preferably about 1 to 40% by mass. If the amount is less than 0.1% by mass, a sufficient ultraviolet protective effect cannot be obtained. Conversely, if the amount exceeds 60% by mass, the coated part may whiten. Moreover, it may become powdery usability.
In the case of a water-in-oil emulsified cosmetic, 1 to 40% by mass is preferably blended.

(B) Volatile silicone The volatile silicone of component (b) used in the present invention is decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, methyltrimethicone, decamethyltetrasiloxane, A single compound or a combination of two or more compounds is blended depending on the purpose.

<Description of blending amount>
Although a compounding quantity is determined suitably, it is preferable to mix | blend 10-40 mass%. When the amount is less than 10% by mass, in order to obtain a stable water-in-oil emulsion composition, the blending amount of other oils inevitably increases, so that it is difficult to obtain the merit of volatile silicone blending such as a refreshing feel. If it exceeds 40% by mass, the familiarity during application becomes slow and the feeling of use becomes oily, which is not preferable.

(C) Liquid paraffin and / or isononyl isononanoate (1) Usability point of view (free, familiar, non-sticky), (2) Other silicone oils and silicone activators (basically poor cleanability) From the viewpoints of high compatibility, (3) improvement in stability due to high compatibility, and (4) high solubility of the ultraviolet absorber, isononyl isononanoate is preferred. However, when liquid paraffin is blended in place of the conventional non-volatile silicone oil, detergency is greatly improved.
It is also preferable to use liquid paraffin and isononyl isononanoate in combination.
A commercially available product of isononyl isononanoate is Cetiol ININ (Henkel).

<Description of blending amount of liquid paraffin>
The blending amount is preferably 1 to 10% by mass relative to the total amount of the sunscreen emulsified cosmetic. When the amount is less than 1.0% by mass, it is difficult to obtain the effect of improving the cleaning property. If it exceeds 10% by mass, stickiness is felt and the spread becomes heavy.

<Description of blending amount of isononyl isononanoate>
The blending amount is preferably 1 to 10% by mass relative to the total amount of the sunscreen emulsified cosmetic. When the amount is less than 1.0% by mass, it is difficult to obtain the effect of improving the cleaning property. If it exceeds 10% by mass, stickiness is felt and the spread becomes heavy.

The sunscreen emulsified cosmetic of the present invention has excellent detergency by blending (d) a nonionic surfactant into a water-in-oil emulsified sunscreen cosmetic. In addition, it has good elongation and can exhibit a refreshing usability.
In the present invention, a silicone-based surfactant {for example, silicone KF-6017 and silicone KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.), which are polyoxyalkylene-modified organopolysiloxanes well-known as lipophilic surfactants) is substantially used. do not do. When a silicone-based surfactant is blended, the washability after use is lowered.
Preferred nonionic surfactants are lipophilic surfactants having an HLB of 7 or less other than silicone surfactants, and examples thereof include polyglyceryl diisostearate and PEG-20 glyceryl triisostearate . Examples of commercially available products include WOGEL18DV (manufactured by Matsumoto Pharmaceutical Co., Ltd.), Emarex GWIS320 (manufactured by Nippon Emulsion Co., Ltd.), and Este Mall 182V (manufactured by Nisshin Oil Co., Ltd.).

<Description of blending amount>
The blending amount is preferably 1 to 4% by mass with respect to the total amount of the sunscreen emulsified cosmetic. If it is 1% by mass or less, the emulsion stability may be deteriorated when a water-in-oil emulsion cosmetic is used. Further, even when blended in an amount of 4% by mass or more, further improvement in emulsification stability cannot be obtained, which may cause skin irritation and stickiness.

(E) Water When the sunscreen cosmetic of the present invention is used as a water-in-oil emulsified sunscreen cosmetic, water is appropriately blended in the range of 1 to 60% by mass.

（但し、Ｘ＝Ａｌ，Ｆｅ（III），Ｍｎ（III），Ｃｒ（III）、Ｙ＝Ｍｇ，Ｆｅ（II），Ｎｉ，Ｚｎ，Ｌｉ、Ｚ＝Ｋ，Ｎａ，Ｃａ）
具体的にはモンモリロナイト、サポナイト、ヘクトライト等の天然または合成（この場合、式中の（ＯＨ）基がフッ素で置換されたもの）のモンモリロナイト群（市販品ではビーガム、クニピア、ラポナイト等がある。）およびナトリウムシリシックマイカやナトリウムまたはリチウムテニオライトの名で知られる合成雲母（市販品ではダイモナイト：トピー工業（株）等がある。）等の粘土鉱物を第四級アンモニウム塩型カチオン界面活性剤で処理して得られる。
ここで用いられる第四級アンモニウム塩型カチオン界面活性剤は、下記一般式（４）で表されるものである。

（式中、Ｒ¹は炭素数１０〜２２のアルキル基またはベンジル基、Ｒ²はメチル基または炭素数１０〜２２のアルキル基、Ｒ³およびＲ⁴は炭素数１〜３のアルキル基またはヒドロキシアルキル基、Ｘはハロゲン原子またはメチルサルフェート残基を表す。）
かかる第四級アンモニウム塩型カチオン界面活性剤としては、例えばドデシルトリメチルアンモニウムクロリド、ミリスチルトリメチルアンモニウムクロリド、セチルトリメチルアンモニウムクロリド、ステアリルトリメチルアンモニウムクロリド、アラキルトリメチルアンモニウムクロリド、ベヘニルトリメチルアンモニウムクロリド、ミリスチルジメチルエチルアンモニウムクロリド、セチルジメチルエチルアンモニウムクロリド、ステアリルジメチルエチルアンモニウムクロリド、アラキルジメチルエチルアンモニウムクロリド、ベヘニルジメチルエチルアンモニウムクロリド、ミリスチルジエチルメチルアンモニウムクロリド、セチルジエチルメチルアンモニウムクロリド、ステアリルジエチルメチルアンモニウムクロリド、アラキルジエチルメチルアンモニウムクロリド、ベヘニルジエチルメチルアンモニウムクロリド、ベンジルジメチルミリスチルアンモニウムクロリド、ベンジルジメチルセチルアンモニウムクロリド、ベンジルジメチルステアリルアンモニウムクロリド、ベンジルジメチルベヘニルアンモニウムクロリド、ベンジルメチルエチルセチルアンモニウムクロリド、ベンジルメチルエチルステアリルアンモニウムクロリド、ジベヘニルジヒドロキシエチルアンモニウムクロリド、および相当するブロミド等、更にはジパルミチルプロピルエチルアンモニウムメチルサルフェート等が挙げられる。本発明の実施にあたっては、これらのうち一種または二種以上が任意に選択される。
有機変性粘土鉱物の代表的なものとしては、ジメチルアルキルアンモニウムヘクトライト、ベンジルジメチルステアリルアンモニウムヘクトライト、塩化ジステアリルジメチルアンモニウム処理ケイ酸アルミニウムマグネシウム等が挙げられる。市販品としては、ベントン２７（ベンジルジメチルステアリルアンモニウムクロライド処理ヘクトライト：ナショナルレッド社製）およびベントン３８（ジステアリルジメチルアンモニウムクロライド処理ヘクトライト：ナショナルレッド社製）が好ましい。 The water-in-oil emulsified sunscreen cosmetic of the present invention can further improve stability by adding (f) an organically modified clay mineral, has good elongation at the time of application, and can give a fresh feeling of use. it can.
The (f) organically modified clay mineral blended in the present invention is used as an emulsification aid. This organically modified clay mineral is a kind of colloidal hydrous aluminum silicate having a three-layer structure, and is generally a clay mineral represented by the following general formula (3) modified with a quaternary ammonium salt type cationic surfactant. It is.

(However, X = Al, Fe (III), Mn (III), Cr (III), Y = Mg, Fe (II), Ni, Zn, Li, Z = K, Na, Ca)
Specifically, there are montmorillonite groups of natural or synthetic (in this case, the (OH) group in the formula is substituted with fluorine) such as montmorillonite, saponite, hectorite (commercially available products include bee gum, kunipia, laponite). ) And synthetic mineral mica known as sodium silicic mica and sodium or lithium teniolite (commercially available products include Dimonite: Topy Industries, Ltd.). Quaternary ammonium salt type cationic surfactants Is obtained by processing.
The quaternary ammonium salt type cationic surfactant used here is represented by the following general formula (4).

Wherein R ¹ is an alkyl group having 10 to 22 carbon atoms or a benzyl group, R ² is a methyl group or an alkyl group having 10 to 22 carbon atoms, R ³ and R ⁴ are alkyl groups having 1 to 3 carbon atoms or hydroxy An alkyl group, X represents a halogen atom or a methyl sulfate residue.)
Examples of the quaternary ammonium salt type cationic surfactant include dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium. Chloride, cetyldimethylethylammonium chloride, stearyldimethylethylammonium chloride, aralkyldimethylethylammonium chloride, behenyldimethylethylammonium chloride, myristyldiethylmethylammonium chloride, cetyldiethylmethylammonium chloride, stearyldiethylmethylammonium chloride, arachi Diethylmethylammonium chloride, behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, di Examples include behenyl dihydroxyethylammonium chloride and the corresponding bromide, and further dipalmitylpropylethylammonium methyl sulfate. In carrying out the present invention, one or more of these are arbitrarily selected.
Representative examples of the organically modified clay mineral include dimethylalkylammonium hectorite, benzyldimethylstearylammonium hectorite, distearyldimethylammonium chloride-treated aluminum magnesium silicate, and the like. Benton 27 (benzyldimethylstearyl ammonium chloride-treated hectorite: National Red) and Benton 38 (distearyldimethylammonium chloride-treated hectorite: National Red) are preferable as commercial products.

In the sunscreen emulsified cosmetic of the present invention, an ultraviolet absorber such as octyl methoxycinnamate is preferably dissolved in the oil. Although the compounding quantity of a ultraviolet absorber is suitably determined according to the compounding quantity of an oil component, Preferably it is 1-10 mass% with respect to the total amount of sunscreen emulsified cosmetics.
The sunscreen emulsified cosmetic of the present invention is produced by a conventional method according to the form of the product by appropriately blending the components usually blended into the cosmetic within a range not impairing the effects of the present invention.

  The present invention will be specifically described with reference to examples. The technical scope of the present invention is not limited by these examples. In addition, unless otherwise indicated about a compounding quantity, it shows with the mass%.

(A) Hydrophobized zinc oxide powder “Production Example 1”
300 g of perfluoroalkyl phosphate ester of general formula (1) having 12 carbon atoms (Rf: carbon number 10, n = 2, 1 ≦ y ≦ 2) and ester of general formula (2) (acryl silicone copolymer) : Shin-Etsu Chemical Co., Ltd. KP-544: a copolymer of 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate having a molecular weight of 30,000 to 300,000 represented by the general formula (2) 100 g of an ester obtained by substituting a part of methyl groups of methylpolysiloxane with a hydroxypropyl group) and 3.5 kg of IPA (solvent) were prepared. Using these, a 50 mass% solution of the phosphoric acid ester of the general formula (1) and a 60 mass% solution of the ester of the general formula (2) were prepared.
Fine particle zinc oxide powder described in WO 99/25654 (Japanese Patent Application No. 11-525984) (with carnation petal-like appearance, specific surface area (X) = 60 m ² / g) in a 20 L high-speed stirring mixer 5 kg was added, and a solution of the phosphoric acid ester of the general formula (1) and a solution of the ester of the general formula (2) were added. Further, the remaining IPA was added, and the total amount of IPA as the total amount of solvent was 3.5 kg. Then, after stirring at 60 ° C. for 1 hour, the mixture was heated to 120 ° C. and the inside of the high-speed stirring mixer was reduced in pressure and maintained for about 2 hours to completely remove IPA as a solvent.

  Next, after discharging from the inside of the mixer, the mixture was pulverized with a hammer mill equipped with a 2 mm screen and heated at 45130 ° C. for 24 hours to obtain 6% perfluoroalkyl phosphate ester having 12 carbon atoms and an acrylic silicone copolymer. Particulate zinc oxide surface-coated with 2% was obtained.

The amount of oil absorption of the powder was 30.8 mL / 100 g as a result of measurement using silicone oil as the oil content according to the method of JISK5101. The apparent specific volume of the powder was 0.71 mL / g as a result of measurement according to the tap method described in JISK5101 20.2. The contact angle of the powder was 52 ° as a result of measuring the contact angle formed by preparing pellets of the powder using a tablet molding machine or the like and dropping liquid paraffin thereon.
The amount of the solvent used in the production method of Production Example 1 is 70% by mass with respect to the zinc oxide powder.
Moreover, the sum of the usage-amount of the phosphate ester of General formula (1) and the ester of General formula (2) is 8%, and the ester of General formula (1) / ester of General formula (2) = 3.

"Production Examples 2 to 10, Comparative Production Examples 1 to 3"
Manufactured in the same manner as in Production Example 1. That is, in accordance with “Table 1” of the production recipe described later, fine zinc oxide powder, perfluoroalkyl phosphate ester of general formula (1) having 12 carbon atoms (Rf: carbon number 10, n = 2, 1 ≦ y ≦ 2 ), And ester of general formula (2) (acrylic silicone copolymer: KP-544 manufactured by Shin-Etsu Chemical Co., Ltd .: 2-ethylhexyl acrylate having a molecular weight of 30,000 to 300,000 represented by general formula (2) , An ester of a copolymer of methacrylic acid, methyl methacrylate, butyl methacrylate and a methylpolysiloxane in which some of the methyl groups are substituted with hydroxypropyl groups), and IPA (solvent).
Into a 20 L high-speed stirring mixer, 5 kg of fine zinc oxide powder was added, and then a 50 mass% solution of the phosphoric acid ester of the above general formula (1) and 60 of the ester of the above general formula (2) dissolved in IPA in advance. A mass% solution was added. Furthermore, IPA was added in order to adjust the total amount of IPA to be the total amount of solvent. Then, after stirring at 60 ° C. for 1 hour, the mixture was heated to 120 ° C. and the inside of the high-speed stirring mixer was reduced in pressure and maintained for about 2 hours to completely remove IPA as a solvent to obtain surface-coated fine particle zinc oxide.
In the same manner as in Production Example 1, the oil absorption, apparent specific volume, and contact angle with liquid paraffin of the obtained powder were measured.

＊１）ＷＯ９９／２５６５４号公報（特願平１１−５２５９８４号）記載の微粒子酸化亜鉛粉末（カーネーションの花びら状の外観を有するもの，比表面積（Ｘ）＝６０m²/g）
＊２）微粒子酸化亜鉛ＦＩＮＥＸ−５０（堺化学社製、比表面積（Ｘ）＝５０m²/g）

Production examples and comparative production examples are summarized in “Table 1” and “Table 2” as follows.

* 1) Fine zinc oxide powder described in WO99 / 25654 (Japanese Patent Application No. 11-525984) (having a carnation petal-like appearance, specific surface area (X) = 60 m ² / g)
* 2) Fine zinc oxide FINEX-50 (manufactured by Sakai Chemical Co., Ltd., specific surface area (X) = 50 m ² / g)

  Further, the above surface treatment conditions are graphs of the amount of oil absorption and the apparent specific volume with respect to the parameter of the amount of solvent used relative to the amount of powder and the ratio of phosphate ester of general formula (1) / ester of general formula (2). As shown in FIG. 2, “FIG. 2”, “FIG. 3” and “FIG. 4” are obtained.

  From these figures, by controlling the amount of solvent with respect to the amount of powder and appropriately controlling the apparent specific volume and oil absorption, it is extremely blended (dispersed) in cosmetics, especially in cosmetics characterized by being dispersed in oil. Can be made easier. In addition, the ratio and amount of the treatment agent not only affects the specific volume and the oil absorption amount, but also has a relation with the oil repellency that contributes to the improvement of makeup durability (water repellency / oil repellency). This makes it possible to satisfy both the prescription width at the time of cosmetic preparation (particularly, the improvement in the affinity between the powder coated with the fluorine compound and the existing raw material) and the function as a cosmetic. Therefore, it can be seen that the (a) hydrophobized zinc oxide powder used in the present invention is a hydrophobized powder that is extremely useful for sunscreen cosmetics.

Next, examples of the sunscreen cosmetics of the present invention will be described. Water-in-oil emulsified cosmetics having the formulations shown in Tables 3 and 4 were produced by a conventional method, and the effects were evaluated as follows.
<Evaluation of easy cleaning>
Ten professional panels actually used it, and the ease of cleaning (easy to drop) was determined according to the following criteria.
A: 8 to 10 people answered that it was easy to clean.
○ : 5 to 7 people answered that it was easy to clean.
Δ: 2 to 4 people answered that it was easy to wash.
X: 0 to 1 person answered that it was easy to wash.

“(A) Hydrophobized zinc oxide powder in Table 3 and Table 4”
(A) Hydrophobized zinc oxide powder * 1: perfluoroalkyl phosphate-treated zinc oxide powder (trade name FSA-ZnO (SF), Daito Kasei Kogyo Co., Ltd.)
(A) Hydrophobized zinc oxide powder * 2: Silane coupling agent-cationic surfactant-treated zinc oxide powder (a) Hydrophobized zinc oxide powder * 3: Fatty acid-dextrin treated zinc oxide powder (trade name WSX-MZ -700, Teika Corporation)
(A) Hydrophobized zinc oxide powder * 4: Metal soap-treated zinc oxide powder (trade name MT-Finex25, Miyoshi Kasei Co., Ltd.)
(A) Hydrophobized zinc oxide powder * 5: Silicone-treated zinc oxide powder (trade name SS-ActivoxC80, Showa Denko KK)

A sunscreen emulsified cosmetic containing (a) a hydrophobized zinc oxide powder and (b) a volatile silicone combined with (c) liquid paraffin or isononanoyl isononanoate and (d) a nonionic surfactant. When blended, the ease of cleaning increases. In particular, when isononyl isononanoate is blended, the removability is remarkably high.
When only one of (c) liquid paraffin, (c) isononyl isononanoate, or (d) a nonionic surfactant is blended, the effect of the present invention is halved. However, the contribution of the component (c) and the component (d) to the ease of cleaning is greater in the component (c).

  Other examples of the present invention are listed below. Both of these are sunscreen cosmetics that have a long-lasting makeup (water and oil repellency) and are easy to clean. In addition, in the following Example, it is possible to mix | blend the arbitrary hydrophobized zinc oxide powder of manufacture examples 1-10.

Example 11: W / O type emulsion sunscreen cream dimethylpolysiloxane 0.5
Decamethylcyclopentasiloxane 28
Lauryl Methicone 6
Trimethylsiloxysilicate 0.5
Polyether modified silicone 1
(Shin-Etsu Chemical KF-6017)
Dipropylene glycol 5
PEG-20 glyceryl triisostearate 2
Zinc oxide obtained in Production Example 2 18
Isononyl isononanoate (or liquid paraffin) 5
Paraben Appropriate amount Phenoxyethanol Appropriate amount Trisodium edetate Appropriate amount 2-methoxyhexyl paramethoxycinnamate 7.5
Dimethyl distearyl ammonium hectorite 1
Spherical PMMA powder 4
Purified water Residual fragrance

Example 12: W / O type emulsifying sunscreen cream hexylyl methicone 5
Decamethylcyclopentasiloxane 25
Methyl trimethicone 5
1,3-butylene glycol 5
Fine particle titanium oxide (MT-100TV manufactured by Teika) 5
Sorbitan sesquiisostearate 2
Zinc oxide obtained in Production Example 3 18
Isononyl isononanoate (or liquid paraffin) 5
Paraben Appropriate amount Phenoxyethanol Appropriate amount Trisodium edetate Appropriate amount Dimethyl distearyl ammonium hectorite 1
Spherical polymethylsilsesquioxane powder 5
Purified water Residual fragrance

Example 13: Two-layer W / O daytime emulsion caprylyl methicone 7
Decamethylcyclopentasiloxane 15
Decamethyltetrasiloxane 13
Branched polyether-modified silicone 1.5
(Shin-Etsu Chemical KF-6028)
1,3-butylene glycol 5
Squalane 0.5
Talc 1
Dipotassium glycyrrhizinate 0.1
Tocopherol acetate 0.1
Edetate trisodium 0.05
2-methoxyhexyl paramethoxycinnamate 5
Polyglyceryl diisostearate 2
Zinc oxide obtained in Production Example 3 18
Isononyl isononanoate (or liquid paraffin) 5
Dimethyl distearyl ammonium hectorite 0.5
Spherical polyethylene powder 3
Phenoxyethanol Appropriate amount of ethanol 5
Purified water Residual fragrance

  According to the present invention, it is possible to provide a sunscreen emulsified cosmetic that has a long lasting makeup (water and oil repellency) and is easy to clean.

It is process drawing of the manufacturing method of the hydrophobic treatment zinc oxide powder preferable for this invention. It is a graph of the value of the oil absorption amount with respect to the solvent usage-amount with respect to the powder amount, and the apparent specific volume. It is a graph of the amount of solvent use with respect to the amount of powder and the value of the oil absorption amount and the apparent specific volume with respect to the parameter of the ratio of phosphate ester of the general formula (1) / ester of the general formula (2). It is a graph of the contact angle (vs. liquid paraffin) with respect to the parameter of the ratio of the ester of the general formula (1) / the ester of the general formula (2).

Claims (3)

(A) 1 to 40% by mass of hydrophobized zinc oxide powder produced by surface-treating fine particle zinc oxide powder having a primary particle diameter of 1 μm or less, and (b) 10 to 40% by mass of volatile silicone. (C) 3 to 10% by mass of isononyl isononanoate and (d) 1 to 4% by mass of a nonionic surfactant which is a lipophilic surfactant having an HLB of 7 or less other than the silicone surfactant. (E) A water -in- sun emulsified cosmetic with sunscreen oil, wherein the nonionic surfactant (d) is polyglyceryl diisostearate or PEG-20 glyceryl triisostearate . (A) 1 to 40% by mass of hydrophobized zinc oxide powder produced by surface-treating fine particle zinc oxide powder having a primary particle diameter of 1 μm or less, and (b) 10 to 40% by mass of volatile silicone. (C) 1 to 10% by mass of liquid paraffin and isonononyl isononanoate, and (d) 1 to 4 nonionic surfactants which are lipophilic surfactants having an HLB of 7 or less other than silicone surfactants. A sunscreen oil-in-water emulsified cosmetic, comprising: (e) water, and (d) the nonionic surfactant is polyglyceryl diisostearate or PEG-20 glyceryl triisostearate Fee.   3. A sunscreen water-in-water emulsified cosmetic according to claim 1 or 2, wherein substantially no silicone surfactant is used.

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