JP4205206B2 - Coated powder and cosmetic comprising the same - Google Patents

Description

【００３７】
【表２】

【００３８】
【表３】

【００３９】
【表４】

【００４０】
この結果から明らかなように、本発明の被覆粉体は、被覆しないで各成分を配合した比較例や、鉄をドープした二酸化チタンだけを被覆した場合に比べ、ＳＰＦ値が格段に向上することが証明された。
【００４１】
次に、上記製造例で得られた粉末を配合したメークアップ化粧料について説明する。
【００４２】
［参考例５］
パウダーファンデーション
重量部
黄酸化鉄 ４．０
弁柄 １．０
二酸化チタン １５．０
タルク ２５．０
ナイロンパウダー １５．０
製造例１の被覆粉体 ３０．０
ジメチルシリコーン ５．０
トリ−２−エチルヘキサン酸グリセリル ５．０
上記成分を混合撹拌し、均一化してパウダーファンデーションとした。
【００４３】
また、被覆粉体をセリサイトと鉄ドープ二酸化チタンに置き換えた比較例９のパウダーファンデーションを同様の方法で製造した。
【００４４】
［比較例９］
重量部
黄酸化鉄 ４．０
弁柄 １．０
二酸化チタン １５．０
タルク ２５．０
ナイロンパウダー １５．０
セリサイト ２４．０
鉄ドープ二酸化チタン ６．０
ジメチルシリコーン ５．０
トリ−２−エチルヘキサン酸グリセリル ５．０
【００４５】
＜本発明の化粧料の評価＞
上記参考例５及び比較例９で得られたパウダーファンデーションについてＳＰＦ値をＳＰＦアナライザーで評価した。ＰＦＡ値については下記の方法により実施した。ＰＦＡ値は主としてＵＶ−Ａに対する防御力を反映するものである。結果を表５に示す。
【００４６】
＜ＰＦＡ値測定法＞日本化粧品工業連合会ＵＶＡ防止効果測定法基準に準拠して測定した。即ち公比１．２５倍となるよう、それぞれ２Ｊ／ｍｉｎ．、１．６０Ｊ／ｍｉｎ．、１．２８Ｊ／ｍｉｎ．、１．０２Ｊ／ｍｉｎ．、０．８２Ｊ／ｍｉｎ．、０．６６Ｊ／ｍｉｎ．にエネルギー量を調整したハロゲンランプ光をパネラーの試料無塗布の背部部位に約６分照射し、照射部位の全体にわずかな黒化が認められるエネルギー量を最小持続型黒化量（ＭＰＰＤ：Minimal Persistent Pigment darkening Dose）として求めた。次に試料を５０ｃｍ ² の面積に２ｍｇ／ｃｍ ² となるように塗布し、ＳＰＦアナライザーの測定値から推測されるＰＦＡ値に応じたエネルギー量を照射して、２時間後、及び３時間後に観察を行い、照射部位の全体にわずかな黒化が認められるエネルギー量を決定し、このエネルギー量を先に求めたＭＰＰＤで除してＰＦＡ値を算出した。
【００４７】
【表５】

【００４８】
これらの結果から明らかなように、上記参考例５のメークアップ化粧料は、比較例のメークアップ化粧料に比べ、ＳＰＦ値、ＰＦＡ値とも大きく向上することが実証された。
【００４９】
【発明の効果】
本発明の被覆粉体は、被覆しないものに比べて、ＳＰＦ値、ＰＦＡ値ともに高いものである。また、この被覆粉体を配合した本発明のメークアップ化粧料も同様にＳＰＦ値、ＰＦＡ値の高いものであり、パネラーによる使用感の官能評価も優れていた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coating powder excellent in UV protection and a cosmetic containing the same.
[0002]
[Prior art]
In recent years, the destruction of the ozone layer in the atmosphere has progressed, and the amount of ultraviolet rays falling on the ground has increased, so the effects of ultraviolet rays on the skin have been studied in detail as a cause of skin cancer. It has been known that ultraviolet rays in the UV-A region, which have high penetrability into the skin, cause damage to the dermis layer, which later causes severe sagging and large wrinkles in the skin. For this reason, the functions of cosmetics are attracting attention as daily UV protection measures, and cosmetics having excellent UV protection power, especially UV-A protection power are demanded.
[0003]
Technologies to improve UV protection include technologies that combine inorganic powders that have UV scattering and shielding effects such as titanium dioxide, fine zinc oxide, and metal aluminum pieces, and UV absorption such as cinnamic acid esters and aminobenzoic acid esters. Techniques for blending agents and techniques for using these in combination are known.
[0004]
[Problems to be solved by the invention]
However, although inorganic powders such as titanium dioxide and zinc oxide have high ultraviolet scattering and shielding power, they also have strong hiding power, and therefore tend to become unnatural white when blended in large quantities. In addition, when a large amount of metal aluminum piece is blended, the metallic luster appears and the film becomes dull blackish, so the blending amount is naturally limited.
[0005]
Ultraviolet absorbers such as cinnamic acid esters and aminobenzoic acid esters can be added up to the theoretically acceptable amount, but in practice it is difficult to add a large amount due to safety issues with living bodies. .
[0006]
In addition, these substances do not have sufficient UV protection in the UV-A region.
[0007]
As a method for improving the unnatural whiteness of the titanium dioxide, it is also possible to combine or sinter with iron to obtain a skin-colored coloring pigment, and as a result, the absorption characteristics in the UV-A region are slightly improved. However, there is almost no change in the strength of UV protection itself.
[0008]
This invention is made | formed from the said viewpoint, and makes it a subject to provide the powder for cosmetics with high ultraviolet-ray shielding power and high defense power also with respect to the ultraviolet-ray of a UV-A area | region.
[0009]
[Means for Solving the Problems]
As a result of diligent research on powder coating treatment in order to solve the above-mentioned problems, the present inventors coat the surface of sericite, talc, mica, etc. with iron-doped titanium dioxide and zinc carboxylate. And a skin-colored pigment that does not cause unnatural whiteness is obtained, and when ultraviolet radiation shielding power is simply compounded with titanium dioxide doped with iron, or with titanium dioxide doped with iron or zinc carboxylate independently. I found it to be much better than the case.
[0010]
That is, the present invention is a coated powder in which the surface of a flaky powder is coated with titanium dioxide doped with iron and zinc carboxylate . Furthermore, the present invention also provides a cosmetic containing the coating powder.
[0011]
Such a coated powder of the present invention is, for example, a method in which titanium dioxide doped with iron and zinc carboxylate are simultaneously dry-mixed or wet-milled on the surface of a flaky powder such as mica, or doped with iron. The method of mixing and grinding titanium dioxide and zinc carboxylate separately in two stages, dry or wet, after the iron compound and the titanium compound are chemically deposited on the substrate surface, dried and fired at a sufficient temperature , A method of mixing and grinding this and zinc carboxylate in a dry or wet manner, chemically depositing an iron compound and a titanium compound on the surface of the substrate, drying and firing at a sufficient temperature, It can be obtained by a method of coating the substrate surface while chemically reacting with the zinc compound.
[0012]
In addition, when the present inventors dope iron into titanium dioxide, which is one of the components coated on the surface of the flaky substrate used in the present invention, from the group of aluminum, silicon, titanium, zirconium, tin and antimony. The present invention was completed by finding that when at least one selected element was doped or coated, an improvement in UV protection was observed as compared with the case of using iron doped titanium dioxide.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
[0014]
<1> Coated powder of the present invention The flaky substrate used in the coated powder of the present invention is an opaque or transparent flaky substrate, and clay minerals such as talc, sericite, mica, kaolin, and their synthesis. Products, bismuth oxychloride, flaky silica, glass flakes, flaky crystallized glass, flaky ceramics, etc., talc, sericite, mica and kaolin are preferred, and sericite is particularly preferred.
[0015]
The flaky substrate preferably has a thickness of about 0.05 to 2 μm. The size of the major axis and the minor axis is 0.5 to 100 μm, preferably about 1 to 50 μm.
[0016]
The amount of iron-doped titanium dioxide to be coated is preferably such that the final weight ratio of iron-doped titanium dioxide: flaky substrate = 8: 2 to 1:99 with respect to the flaky substrate. . If the ratio is less than 1% by weight, the necessary ultraviolet shielding ability cannot be obtained, and coloring is weak. On the other hand, if it exceeds 80% by weight, the ultraviolet ray shielding power and coloring are excellent, but it becomes difficult to obtain a smooth elongation when blended in cosmetics. The iron doping amount is suitably 1 to 30% by weight in terms of Fe with respect to titanium dioxide. If it is less than this amount, no flesh-colored tint is produced, and even if it is doped beyond this amount, no change in tint is observed, and it is difficult to dope completely.
[0017]
In the present invention, in addition to iron doped in titanium dioxide, examples of elements that can be doped or coated to improve UV protection include aluminum, silicon, titanium, zirconium, tin, and antimony. These elements can be doped simultaneously with iron or separately by a method such as firing, or the surface of titanium dioxide particles doped with iron may be coated in the form of hydroxide or oxide.
[0018]
Further, for the purpose of enhancing the dispersibility, the coated powder may be further subjected to surface treatment such as silicone treatment or fluorine treatment to modify the surface.
[0019]
The zinc carboxylate preferably has 8 to 22 carbon atoms in the carboxylic acid residue, and specific examples include zinc laurate, zinc palmitate, zinc stearate, and zinc behenate. The coating amount is preferably in the range of flaky substrate: zinc carboxylate = 1: 1 to 99.5: 0.5 and iron-doped titanium dioxide : zinc carboxylate = 99: 1 to 5: 1 by weight ratio. . The iron-doped titanium dioxide referred to here includes titanium dioxide doped or coated with at least one element selected from the group of aluminum, silicon, titanium, zirconium, tin and antimony in addition to iron. If it is less than this range, the improvement of the UV protection power is not sufficient, and even if it exceeds this range, the UV protection power is not improved.
[0020]
Further, for the purpose of enhancing the dispersibility, the surface of the coated powder may be further modified by performing a surface treatment such as silicone treatment, fluorine treatment, plasma treatment or the like.
[0021]
<2> Cosmetics of the Present Invention The cosmetics of the present invention contain one or more powders obtained by coating the flaky powder with titanium dioxide doped with iron and zinc carboxylate. This iron-doped titanium dioxide may be further doped or coated with one or more elements selected from aluminum, silicon, titanium, zirconium, tin and antimony.
[0022]
The amount of the coating powder of the present invention to the cosmetic depends on the form of the cosmetic, so it cannot be generally stated, but is usually 0.1 to 80% by weight, preferably about 1 to 50% by weight. . When the blending amount is less than 0.1% by weight, the ultraviolet shielding power is poor. On the other hand, if it exceeds 80% by weight, the usability as a cosmetic is deteriorated.
[0023]
Cosmetic forms include, for example, makeup foundations such as liquid foundation, powder foundation, pressed powder, cake foundation, stick foundation, face powder, lip color, eyeliner, cheek color, eye shadow, body powder, and control. Examples include sweating agents, sunscreen cosmetics, lotions, milky lotions, and creams. Moreover, these cosmetics can be manufactured by the same method as a normal cosmetic except that the coated powder of the present invention is blended.
[0024]
In the cosmetic of the present invention, in addition to the above-mentioned coated powder, oils, surfactants, alcohols, polymer compounds, water, and other components that are usually blended in cosmetics are used depending on the application, dosage form, purpose, etc. Can be appropriately blended.
The above oils include liquid oils such as liquid paraffin, squalane, cetyl 2-ethylhexanoate, isopropyl myristate, olive oil and castor oil; half oil such as petrolatum, solid para, beef tallow, lanolin, beeswax, whale wax, cholesterol, etc. Solid to solid fats; higher alcohols such as cetanol and behenyl alcohol; higher fatty acids such as palmitic acid and stearic acid; fluorine oils such as perfluoropolyether; silicone oils; silicone derivatives and the like.
[0025]
Examples of the surfactant include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene (hereinafter abbreviated as “POE”) sorbitan fatty acid ester, POE glycerin fatty acid ester, POE alkyl ether, POE polyoxypropylene alkyl ether, and POE polyoxypropylene. Nonionic surfactants such as copolymers, POE alkyl phenyl ethers, POE hydrogenated castor oil, polyethylene glycol fatty acid esters, decaglycerin fatty acid esters, alkyl diethanolamides; alkyl sulfates, POE alkyl ether sulfates, POE alkyl ether acetates, Alkyl phosphates, POE alkyl ether phosphates, higher fatty acid salts, higher fatty acid hydrolyzed collagen salts, amino acid anionic surfactants; Anionic surfactants such as acid surfactants and olefin sulfonates; amphoteric surfactants such as lecithin, betaine acetate, and imidazolinium betaine; alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylchloride Examples include cationic surfactants such as benzylammonium.
[0026]
Examples of alcohols include monovalent alcohols such as ethanol, propanol, and benzyl alcohol; and polyhydric alcohols such as 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin, polyethylene glycol, and sorbitol.
[0027]
Examples of the polymer compound include polyvinyl pyrrolidone, vinyl pyrrolidone-vinyl acetate copolymer, acrylic resin alkanolamine, vinyl acetate-crotonic acid copolymer, methyl vinyl ether-maleic acid monoalkyl ester copolymer, N-methacryloylethyl N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer, diethylpyrrole vinylpyrrolidone-N, N′-dimethylaminoethylmethacrylic acid copolymer, hydroxyethylcellulose dimethyldiallylammonium chloride, hydroxyethylcellulose hydroxy Propyltrimethylammonium chloride ether, carboxyvinyl polymer, carboxymethylcellulose salt, xanthan gum, hydroxyethylcellulose, etc. It is.
[0028]
In addition, the other components include humectants such as amino acids, hyaluronic acid and sulfated trehalose; ultraviolet absorbers such as oxybenzone and paraaminobenzoate; antioxidants such as tocopherol and dibutylhydroxytoluene; parabens and phenoxyethanol. Preservatives; bactericides such as isopropylmethylphenol and trichlorocarban, hydrolysates of proteins such as collagen, keratin and silk (for example, hydrolyzed collagen manufactured by Seiwa Kasei Co., Ltd .: Promois W42R); Anti-inflammatory agents such as dipotassium glycyrrhizinate; chelating agents, pigments, fragrances and the like.
[0029]
【Example】
Examples of the present invention will be described below. First, a production example of the powder of the present invention in which a flaky substrate is coated with iron-doped titanium dioxide and zinc carboxylate will be described.
[0030]
[Production Example 1]
1 kg of sericite having an average particle size of 50 μm was put into 5 L of water, and suspended by stirring. This was heated to 70 ° C. and adjusted to pH 3 using 1N HCl aqueous solution. Next, a mixed acidic aqueous solution by adding a ferrous chloride tetrahydrate aqueous solution containing 7.0 wt% iron as Fe to TiO ₂ to a titanium tetrachloride aqueous solution having a concentration of 200 g / L as TiO _2. Was prepared. 2 L of the mixed acidic aqueous solution is added to 5 L of the previously prepared sericite suspension while adjusting the pH to 9 with a 1N NaOH aqueous solution over 1 hour to hydrolyze titanium tetrachloride and ferrous chloride to sericite. A precipitate formed on the surface. The sericite where the precipitate was formed was then aged for 60 minutes, filtered and washed. The obtained washed cake was baked at 800 ° C. for 6 hours, pulverized, and sericite coated with iron-doped titanium dioxide was obtained. 60 kg of zinc stearate was added to 1 kg of the obtained coated sericite, and the mixture was sufficiently mixed and coated with a Henschel mixer to obtain sericite coated with iron-doped titanium dioxide and zinc stearate.
[0031]
[Production Example 2]
300 kg of commercial iron-doped titanium dioxide TTO-F6 (Ishihara Sangyo) and 30 g of zinc stearate are mixed with 1 kg of sericite, and mixed and coated with sufficient stirring with a Henschel mixer, and iron-doped titanium dioxide and zinc stearate. A sericite coated with was obtained.
[0032]
[Production Example 3]
1 kg of sericite having an average particle size of 50 μm was put into 5 L of water, and suspended by stirring. This was heated to 70 ° C. and adjusted to pH 3 using 1N HCl aqueous solution. Next, a mixed acidic aqueous solution by adding a ferrous chloride tetrahydrate aqueous solution containing 7.0 wt% iron as Fe to TiO ₂ to a titanium tetrachloride aqueous solution having a concentration of 200 g / L as TiO _2. Was prepared. 2 L of the mixed acidic aqueous solution is added to 5 L of the previously prepared sericite suspension while adjusting the pH to 9 with a 1N NaOH aqueous solution over 1 hour to hydrolyze titanium tetrachloride and ferrous chloride to sericite. A precipitate formed on the surface. The sericite where the precipitate was formed was then aged for 60 minutes, filtered and washed, and then 5 L of water was added again to form a slurry. This slurry was heated to 70 ° C., and then 2.0 wt% aqueous aluminum sulfate solution as Al ₂ O _{3 with} respect to TiO ₂ was added over 30 minutes with stirring, followed by addition of sodium hydroxide solution, pH Was adjusted to 7.0, and hydrous alumina was precipitated and coated on the sericite surface. The obtained washed cake was baked at 800 ° C. for 6 hours, pulverized, and sericite coated with titanium dioxide doped with iron and aluminum was obtained. 60 kg of zinc stearate was added to 1 kg of the coated sericite, and the mixture was sufficiently mixed and coated with a Henschel mixer to obtain sericite coated with titanium dioxide doped with iron and aluminum and zinc stearate.
[0033]
[Production Example 4]
After sufficiently stirring and mixing 100 parts of talc having an average particle size of 30 μm with 800 parts of an aqueous solution containing 20 parts of ferric chloride, 5 parts of zirconium oxychloride, and 160 parts of titanyl sulfate, a uniform dispersion state was obtained. 1N NaOH aqueous solution was gradually added to adjust to pH 8, and the mixture was heated and stirred at 90 ° C. for 4 hours as it was. After allowing to cool, the slurry was filtered, washed, dried, and fired at 500 ° C. to obtain a skin-colored iron-zirconium-doped titanium dioxide-coated talc. 60 g of zinc stearate was added to 1 Kg of the obtained coated talc, and the mixture was sufficiently mixed and coated with a Henschel mixer to obtain talc coated with titanium dioxide doped with iron and zirconium and zinc stearate.
[0034]
Samples having the compositions shown in Tables 1 to 4 were prepared using the coated powders of Production Examples 1 to 4, and SPF values were measured. The SPF value mainly reflects the defense power against UV-B. As the iron-doped titanium dioxide- coated sericite of the comparative example sample, the powder before coating with zinc stearate in Production Example 1 was used, and as the iron-doped titanium dioxide , commercially available iron-doped titanium dioxide TTO-F6 (manufactured by Ishihara Sangyo Co., Ltd.). ) Was used. The obtained result is described in Tables 1-4.
[0035]
<SPF value measuring method> The SPF value was measured using an SPF analyzer (manufactured by Opto-Meplix). That is, the SPF value was obtained from the average defense spectrum obtained by applying the sample of Table 1 to a tape at a size of 6.4 cm × 6.4 cm so as to be ² mg / cm ² and measuring 6 times.
[0036]
[Table 1]

[0037]
[Table 2]

[0038]
[Table 3]

[0039]
[Table 4]

[0040]
As is clear from this result, the coated powder of the present invention has a markedly improved SPF value compared to the comparative example in which each component is blended without coating and the case where only iron-doped titanium dioxide is coated. Proved.
[0041]
Next, a makeup cosmetic containing the powder obtained in the above production example will be described.
[0042]
[ Reference Example 5]
Powder foundation
Parts by weight yellow iron oxide 4.0
Petal 1.0
Titanium dioxide 15.0
Talc 25.0
Nylon powder 15.0
Coated powder of Production Example 1 30.0
Dimethyl silicone 5.0
Glyceryl tri-2-ethylhexanoate 5.0
The above components were mixed and stirred and homogenized to obtain a powder foundation.
[0043]
Moreover, the powder foundation of Comparative Example 9 in which the coating powder was replaced with sericite and iron-doped titanium dioxide was produced by the same method.
[0044]
[Comparative Example 9]
Parts by weight yellow iron oxide 4.0
Petal 1.0
Titanium dioxide 15.0
Talc 25.0
Nylon powder 15.0
Sericite 24.0
Iron-doped titanium dioxide 6.0
Dimethyl silicone 5.0
Glyceryl tri-2-ethylhexanoate 5.0
[0045]
<Evaluation of Cosmetics of the Present Invention>
The SPF values of the powder foundations obtained in Reference Example 5 and Comparative Example 9 were evaluated using an SPF analyzer. About the PFA value, it implemented by the following method. The PFA value mainly reflects the defense against UV-A. The results are shown in Table 5.
[0046]
<PFA value measurement method> Measurement was performed according to the Japan Cosmetic Industry Association UVA prevention effect measurement method standard. In other words, 2 J / min. 1.60 J / min. 1.28 J / min. 1.02 J / min. 0.82 J / min. 0.66 J / min. Irradiate the back part of the panel with no sample applied to the back of the panel for about 6 minutes, and the amount of energy at which slight blackening is observed throughout the irradiated part is reduced to the minimum sustained blackening amount (MPPD: Minimal) Persistent Pigment darkening dose). Then coated to a 2 mg / cm ² of sample area of 50 cm ^2, and irradiation energy amount corresponding to the PFA value deduced from the measured value of SPF analyzer, after 2 hours, and after 3 hours observation Then, the amount of energy at which slight blackening was observed in the entire irradiated region was determined, and this amount of energy was divided by the previously determined MPPD to calculate the PFA value.
[0047]
[Table 5]

[0048]
As is clear from these results, it was demonstrated that the makeup cosmetic of Reference Example 5 was greatly improved in both SPF value and PFA value as compared with the makeup cosmetic of the comparative example.
[0049]
【The invention's effect】
The coated powder of the present invention has a higher SPF value and PFA value than those not coated. Further, the makeup cosmetic of the present invention blended with this coating powder also has a high SPF value and PFA value, and the sensory evaluation of the feeling of use by the panel was also excellent.

Claims (7)

To the flaky substrate, 1) titanium dioxide further doped with at least one element selected from the group of aluminum, silicon, titanium, zirconium, tin and antimony in addition to iron doping, and 2) of carboxylic acid residues A powder obtained by coating zinc carboxylate having 8 to 22 carbon atoms. The zinc carboxylate having 8 to 22 carbon atoms of the carboxylic acid residue is one or more zinc carboxylates selected from zinc laurate, zinc palmitate, zinc stearate, and zinc behenate. The powder according to claim 1. In addition to iron doping, the weight ratio of titanium dioxide and flaky substrate further doped with at least one element selected from the group of aluminum, silicon, titanium, zirconium, tin and antimony is from 8: 2 to 1:99. The powder according to claim 1 or 2, wherein: The powder according to any one of claims 1 to 3, wherein a weight ratio between the flaky substrate and the zinc carboxylate is 1: 1 to 99.5: 0.5. In addition to iron doping, the ratio of titanium dioxide further doped with at least one element selected from the group of aluminum, silicon, titanium, zirconium, tin and antimony and the zinc carboxylate is 99: 1 to 5: The powder according to claim 1, wherein the powder is 1. The powder according to any one of claims 1 to 5, wherein the flaky substrate is selected from sericite, talc, mica and kaolin. A cosmetic comprising the powder according to any one of claims 1 to 6.