JP4046394B2 - Cosmetics and makeup method - Google Patents
Cosmetics and makeup method Download PDFInfo
- Publication number
- JP4046394B2 JP4046394B2 JP34710597A JP34710597A JP4046394B2 JP 4046394 B2 JP4046394 B2 JP 4046394B2 JP 34710597 A JP34710597 A JP 34710597A JP 34710597 A JP34710597 A JP 34710597A JP 4046394 B2 JP4046394 B2 JP 4046394B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- cosmetic
- particle diameter
- silicone elastomer
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002537 cosmetic Substances 0.000 title claims description 65
- 238000000034 method Methods 0.000 title claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 102
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 93
- 239000000843 powder Substances 0.000 claims description 57
- 229920002379 silicone rubber Polymers 0.000 claims description 31
- 239000011164 primary particle Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000011163 secondary particle Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 239000013081 microcrystal Substances 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 description 29
- 238000011282 treatment Methods 0.000 description 22
- 239000000049 pigment Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 15
- 230000037303 wrinkles Effects 0.000 description 15
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- -1 perfluoroalkyl phosphoric acid Fluorine compounds Chemical class 0.000 description 9
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- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 210000002374 sebum Anatomy 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
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- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 3
- 239000000346 nonvolatile oil Substances 0.000 description 3
- 239000010702 perfluoropolyether Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000195940 Bryophyta Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 240000002871 Tectona grandis Species 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
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- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
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- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
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Landscapes
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Description
【０００１】
【発明の属する技術分野】
本発明は、透明感のある白色を有する酸化チタンと、シリコーンエラストマー球状粉体を配合することで、肌のキメやシワを隠し、美しい外観を与える化粧料、および美しい外観を与える化粧方法に関する。
【０００２】
【従来の技術】
従来、化粧料に用いられる酸化チタンは、白色顔料として隠蔽を目的とする顔料級酸化チタン（一次粒子径０．１５〜０．３μｍ）と、紫外線防御を目的とする超微粒子酸化チタン（一次粒子径０．０１〜０．０５μｍ）の２つの流れで開発が行われてきた。こうした中で特開平９−２２１４１１号公報によれば、顔料級酸化チタンと超微粒子酸化チタンの中間の領域にある一次粒子径が０．１０μｍを超えて０．１４μｍ以下の範囲にある酸化チタン（以後、中間粒径酸化チタンと言う）が適度な仕上がりと自然な隠蔽力を持つことが開示されている。同公報に記載された方法にて再現実験を行うと、酸化チタンの持つ白色の美しさと言う点では、従来の顔料級酸化チタンと比較して優れているが、超微粒子酸化チタン程ではないものの青白さが発生し、隠蔽素材として多用するには限度がある。そのため、中間粒径酸化チタンを黄色に着色処理することによって、酸化チタンは青みが消えて自然な肌色を形成することができる。
【０００３】
一方、特開平９−７１５０９号公報に提案されているように、シリコーンエラストマー球状粉体を配合した化粧料にはつや消し効果やシワを隠す効果があることが知られている。これは光学的に肌の微細な凹凸をぼかして見せる効果であるが、シリコーンエラストマー球状粉体だけではシミなど肌のトラブルを隠すまでの効果は無いため、一般的にはシリコーンエラストマー球状粉体と、隠蔽力のある顔料とを併用して用いている。
【０００４】
【発明が解決しようとする課題】
隠蔽用顔料の光学特性が、シリコーンエラストマー球状粉体の効果を上回った時には、キメやシワが目立ってしまう問題があり、シリコーンエラストマー球状粉体の効果を引き出すためには、それに適した隠蔽用顔料の開発が必要であった。これに対して、隠蔽用顔料として従来の酸化チタンを用いた場合では、キメやシワが目立ったり、青白さが発生するなど何らかの問題があり、光学特性が適しているとは言えなかった。
【０００５】
【課題を解決するための手段】
本発明者らは、これらの問題点を解決すべく鋭意検討した結果、（１）四塩化チタンを苛性ソーダで中和することによって得られる酸化チタン微結晶核の存在下、硫酸チタニル水溶液を加熱加水分解する工程と、（２）加水分解生成物を６００〜９００℃の温度で焼成する工程によって得られる、一次粒子径を０．０１〜０．１μｍ、かつ二次粒子径を０．６〜２．０μｍとしたアナタース型酸化チタンが、特に着色を行わなくても自然で適度な白色を与えかつ紫外線防御能を有することを見出した。そして、この酸化チタンとシリコーンエラストマー球状粉体とを共に配合した化粧料がキメやシワを目立たせず、美しい塗布色を示すことを見出し、本発明を完成した。さらに、白色以外の着色剤を加えずに白色の化粧料を作製したところ、特に化粧下地料または補正料としてより美しい仕上がりを得られることを見出した。
即ち、本発明は、（１）四塩化チタンを苛性ソーダで中和することによって得られる酸化チタン微結晶核の存在下、硫酸チタニル水溶液を加熱加水分解する工程と、（２）加水分解生成物を６００〜９００℃の温度で焼成する工程によって得られる、一次粒子径が０．０１〜０．１μｍ、かつ二次粒子径が０．６〜２．０μｍであり、結晶形がアナタースである強凝集性酸化チタンと、シリコーンエラストマー球状粉体を配合した化粧料にある。
【０００６】
【発明の実施の形態】
本発明で用いる強凝集性酸化チタンは、一次粒子径が０．０１〜０．１μｍ、かつ二次粒子径が０．６〜２．０μｍであり、結晶形がアナタースである強凝集性酸化チタンである。この強凝集性酸化チタンとは、通常工業的に用いる条件、即ち粉体０．５ｇを石川式攪拌らい潰機（株式会社石川工場製）にて１０分間粉砕して機械的分散を行っても容易に一次粒子まで解砕されず、ほとんどが二次粒子として残るものを言う。光の散乱能は媒体に分散された状態、即ち二次粒子径によって決まるため、二次粒子径が上記範囲であると、可視光に対して透明感が生じ、かつ超微粒子酸化チタンのように青色光を優先的に散乱することがないため、青味感のない自然な色調を与える。さらに、強凝集性と雖も比表面積は一次粒子径に応じて大きいため、二次粒子径が同程度で、かつ一次粒子径が大きい場合と比べ、紫外線の吸収能はかなり高くなる。
【０００７】
本発明において一次粒子径は、以下の方法で求めたものとする。まず、粉体０．５ｇを石川式攪拌らい潰機（株式会社石川工場製）にて１０分間粉砕した後、透過型電子顕微鏡写真を撮影する。その写真から、一次粒子径をParticle Analyzer(カールツアイス株式会社製) にて測定し、算出された重量平均径をもって一次粒子径とする。次に、二次粒子径についてであるが、これは粉体を水中に分散させ、堀場製作所製レーザ回折／散乱式粒度分布装置ＬＡ−９１０にて計測した場合のメジアン径で表すものとする。ここで粉体を水中に分散させるには、イオン交換水にヘキサメタリン酸ナトリウムを溶解して１．０％の水溶液とし、この水溶液１７．０ｇと粉体１７．０ｇを０．５ｍｍジルコンビーズ４０ｇとともに容量１４０ｃｃのガラス製マヨネーズ瓶に加え、ペイントシェーカー分散を５分間行った後に計測することとする。尚、顔料酸化チタンや超微粒子酸化チタンの二次粒子径をこの方法で求めた場合においても一次粒子径と同じ値となるとは限らず、凝集粒子の値が得られる場合もあるが、せいぜい一次粒子径が２〜３個凝集しているのみであり、０．５μｍ以下となる。
【０００８】
以上の方法で粒子径が規定されるが、本発明で用いる強凝集性酸化チタンは、一次粒子径が、０．０１〜０．１μｍ、かつ二次粒子径が０．６〜２．０μｍであることを特徴とする。一次粒子径が前記範囲を超えると、強凝集性酸化チタンが得られ難く、また紫外線吸収能が低下する。また、二次粒子径が０．６μｍ未満では、顔料酸化チタンと同等の隠蔽性を有するようになり、強凝集性酸化チタンの有する適度な透明性と自然な風合いが得られない。さらに、二次粒子径が２．０μｍを超えるものは実質的に得られ難く、また壊れやすくなり強凝集性とはなり難い。
【０００９】
以上は、本発明で用いられる強凝集性酸化チタンの特徴を一般的に説明したものだが、この特徴をより具体的に、かつ簡便に表す指標を述べる。
即ち、本発明で用いられる強凝集性酸化チタンは、以下の方法で酸化チタン含有塗膜を作製し、色差計で測定したとき、Ｌ値が３５〜５０、ｂ値が−１０〜０であることを特徴とする。
【００１０】
２．塗膜作成および塗色測定方法
モレストチャート紙にアプリケーターにて塗布（乾燥後膜厚８μｍ）した後、自然乾燥して得られた塗膜について、黒地上のカラーを色差計（スガ試験機製ＳＭカラーコンピューターＳＭ−５型）にて測色する。
【００１２】
この方法で他の材料と比較すると、一般的に、顔料酸化チタンの場合は隠蔽力が大きく高い白色度を有するためＬ値が５０を超え、超微粒子酸化チタンの場合は青色光の散乱によりｂ値が−１０未満となる。
【００１３】
本発明で用いる強凝集性酸化チタンは、固体触媒活性や光触媒活性を抑制する目的で、粒子表面に、Ａｌ、Ｓｉ、Ｚｒ、Ｔｉ、Ｚｎから成る群より選ばれた少なくとも１種の含水酸化物および／または酸化物が被覆されていても良く、さらにこれらの処理と同時、または単独でシリコーン化合物、シラン、金属石鹸、フッ素化合物、水溶性高分子化合物、Ｎ−アシル化リジン、ポリオール、アクリル樹脂、メタクリル樹脂、スチレン樹脂、ウレタン樹脂などから成る群より選ばれた少なくとも１種の有機物が被覆されていても良い。これらの表面処理により、濡れ性の改善、耐皮脂性付与、分散性の改良を適宜行うことができる。この内、メチルハイドロジェンポリシロキサン、トリメチルシロキシケイ酸、フルオロアルキル・ポリオキシアルキレン共変性シリコーンなどのシリコーン化合物、オクチルトリエトキシシランなどのシラン類、ステアリン酸亜鉛などの金属石鹸、パーフルオロアルキルリン酸ジエタノールアミン塩、テフロン、パーフルオロアルキルシランなどのフッ素化合物、デオキシリボ核酸、ヒアルロン酸などの水溶性高分子化合物、Ｎ−ラウロイルリジンなどのＮ−アシル化リジンで処理されたものは化粧料に配合時の上記特性に特徴がでるため特に好ましい。
【００１４】
本発明で用いる強凝集性酸化チタンの製造方法としては、例えば、以下の２段階の方法を用いることが出来る。
▲１▼硫酸チタニル水溶液を、核の存在下、加熱加水分解する工程
▲２▼加水分解生成物を６００〜９００℃の温度で焼成する工程
出発原料となる硫酸チタニルは、通常、イルメナイト鉱石を硫酸と反応させて製造することができる。これは酸化チタン工業において蒸解と呼ばれるが、イルメナイト鉱石に限らず、例えば、含水酸化チタンを蒸解しても良い。この生成物を水で希釈し、必要に応じて不純物を除去した後、加熱により加水分解を行う。この際、加水分解反応を促進させ、かつ粒度や結晶性を調整する目的で、酸化チタンの微結晶である核を添加する。こうして得た加水分解生成物を濾過し、必要に応じて洗浄した後、６００〜９００℃で焼成を行う。焼成温度がこの範囲よりも低いと一次粒子径は小さくなるが強凝集とはならず、逆に高いと一次粒子径が大きくなり過ぎ、本発明の酸化チタンが得られない。この後、必要に応じ粉砕、整粒を行った後、常法によりＡｌ、Ｓｉ、Ｚｒ、Ｔｉ、Ｚｎなどの含水酸化物および／または酸化物を被覆しても良い。
【００１５】
本発明で用いる酸化チタンが強凝集性であることは、主として上述の製造方法に由来すると考えられる。強凝集性となるメカニズムの詳細は必ずしも明らかではないが、加水分解あるいは焼成工程における結晶成長の段階で表面エネルギーが非常に大きくなる状態があり、その際に粒子同士が強く凝集するものと考えられる。
【００１６】
本発明で用いるシリコーンエラストマー球状粉体とは、３次元架橋型シリコーン末のことであり、その一次粒子形状が球状である粉体の集合体を指す。具体的には、東レ・ヴウコーニング・シリコーン社製のトレフィルＥ−５０５Ｃ、トレフィルＥ−５０６、トレフィルＥ−５０７などが該当するが、臭いなどの対策が採られているトレフィルＥ−５０７が最も好ましい。尚、これらの粉末の一次粒子はほとんどが、一次粒子径として０．１〜２０μｍの範囲に該当する。
【００１７】
本発明で用いるシリコーンエラストマー球状粉体は、従来公知の表面処理、例えば、シリコーン処理、シリコーンレジン処理、シラン処理、無機酸化物処理、樹脂処理、粘剤処理、フッ素化合物処理、メカノケミカル処理などの表面処理が行ってあってもなくても構わない。
【００１８】
本発明で用いるシリコーンエラストマー球状粉体は、事前に混練り処理、または湿式粉砕処理が行われたシリコーンエラストマー球状粉体混練ペーストとして使用することが、化粧料の感触を向上させ、より均一な塗膜を形成でき、キメやシワをより隠蔽できる効果があるため好ましい。例えば、シリコーンエラストマー球状粉体を揮発性油剤および／または不揮発性油剤と事前に混練装置や湿式粉砕装置を用いてペースト状に変化させることが挙げられる。揮発性油剤の例としては、環状シリコーン、低分子直鎖状シリコーン、軽質流動イソパラフィン、次世代フロン、パーフルオロポリエーテル、アルコール類、石油エーテル、テルペン類などが挙げられる。また、不揮発性油剤の例としては、常温で液状、固形状、ペースト状であって従来公知の原料であれば問題ないが、例えば、シリコーン油、エステル油、極性油、油脂、フッ素系油などが挙げられる。また、トリメチルシロキシケイ酸の様に他の油剤に溶解して用いるものも使用可能である。これらの内、特に環状シリコーン、ジメチルポリシロキサン、ポリエーテル変性シリコーン、パーフルオロアルキル・ポリオキシアルキレン共変性シリコーン、シリコーン樹脂などのシリコーン油やエステル油がシリコーンエラストマー球状粉体との相性に優れるため好ましい。また、シリコーン油と組み合わせた場合には、より透明性の高いペーストが得られる。
【００１９】
混練装置や湿式粉砕装置を用いてシリコーンエラストマー球状粉体をペースト状に変化させる場合には、ロールミル、エクストルーダー（連続式押し出し混練装置）、ビーズミル、サンドミル、マイクロス（奈良機械製作所製）などの湿式媒体粉砕装置を用いることが好ましいが、揮発性溶媒や非液状油を用いる場合には多軸式のエクストルーダーが最も好ましく、非揮発性油を用いる場合では、粉砕力の強さからロールミルが好ましい。
【００２０】
本発明で用いるシリコーンエラストマー球状粉体と、上記油剤の混合比率（重量比）としては、３：９７〜８０：２０の範囲であることが好ましく、特に好ましくは２５：７５〜６０：４０である。シリコーンエラストマー球状粉体の混合比率が３重量％未満ではエラストマーの効果が得られ難く、また８０重量％を超えると混練の効果が得られにくい問題がある。
【００２１】
本発明の化粧料に、強凝集性酸化チタンと、シリコーンエラストマー球状粉体を配合する割合としては、化粧料総量に対して、強凝集性酸化チタンが０．５〜５０重量％、シリコーンエラストマー球状粉体が０．３〜７０重量％の範囲にあることが好ましく、さらに好ましくは 強凝集性酸化チタンが１〜３０重量％、シリコーンエラストマー球状粉体が１〜３０重量％の範囲である。
【００２２】
本発明の化粧料では、上記の強凝集性酸化チタン以外に、通常化粧料に用いられる粉体（顔料、色素、樹脂）、油剤、フッ素化合物、樹脂、界面活性剤、紫外線防御剤、抗酸化剤、粘剤、防腐剤、香料、保湿剤、生理活性成分、塩類、溶媒、キレート剤、中和剤、ｐＨ調整剤などの成分を同時に配合することができる。
【００２３】
粉体としては、例えば、赤色１０４号、赤色２０１号、黄色４号、青色１号、黒色４０１号などの色素、黄色４号Ａｌレーキ、黄色２０３号Ｂａレーキなどのレーキ色素、ナイロンパウダー、シルクパウダー、ウレタンパウダー、テフロンパウダー、シリコーンパウダー、セルロースパウダー、キチン、キトサン、アルギン酸カルシウムなどの高分子、黄酸化鉄、赤色酸化鉄、黒酸化鉄、酸化クロム、カーボンブラック、群青、紺青などの有色顔料、酸化チタン、酸化セリウムなどの白色顔料、タルク、マイカ、セリサイト、カオリンなどの体質顔料、雲母チタンなどのパール顔料、硫酸バリウム、炭酸カルシウム、炭酸マグネシウム、珪酸アルミニウム、珪酸マグネシウムなどの金属塩、シリカ、アルミナなどの無機粉体、微粒子酸化チタン、微粒子酸化亜鉛、粒子酸化鉄、アルミナ処理微粒子酸化チタン、シリカ処理微粒子酸化チタン、ベントナイト、スメクタイトなどが挙げられる。これらの粉体の形状、大きさに特に制限はない。この内、強凝集性酸化チタンと、微粒子酸化チタン、微粒子酸化亜鉛などの無機系紫外線防御成分とを組み合わせて使用することは、紫外線防御効果を向上させる上で好ましい。
【００２４】
また、上記の粉体は、従来公知の各種表面処理、例えば、シリコーン処理、シラン処理、フッ素化合物処理、油剤処理、金属石鹸処理、ワックス処理、Ｎ−アシル化リジン処理、水溶性高分子化合物処理、樹脂処理、金属酸化物処理、プラズマ処理、メカノケミカル処理、粘剤処理などが行われていてもいなくても構わない。
【００２５】
油剤の例としては、セチルアルコール、イソステアリルアルコール、ラウリルアルコール、ヘキサデシルアルコール、オクチルドデカノールなどの高級アルコール、イソステアリン酸、ウンデシレン酸、オレイン酸などの脂肪酸、グリセリン、ソルビトール、エチレングリコール、プロピレングリコール、ポリエチレングリコールなどの多価アルコール、ミリスチン酸ミリスチル、ラウリン酸ヘキシル、オレイン酸デシル、ミリスチン酸イソプロピル、ジメチルオクタン酸ヘキシルデシル、モノステアリン酸グリセリン、フタル酸ジエチル、モノステアリン酸エチレングリコール、オキシステアリン酸オクチルなどのエステル類、流動パラフィン、ワセリン、スクワランなどの炭化水素、ラノリン、還元ラノリン、カルナバロウなどのロウ、ミンク油、カカオ脂、ヤシ油、パーム核油、ツバキ油、ゴマ油、ヒマシ油、オリーブ油などの油脂、エチレン・α−オレフィン・コオリゴマーなどが挙げられる。
【００２６】
また、別の形態の油剤の例としては、例えば、ジメチルポリシロキサン、メチルハイドロジェンポリシロキサン、メチルフェニルポリシロキサン、ポリエーテル変性オルガノポリシロキサン、フルオロアルキル・ポリオキシアルキレン共変性オルガノポリシロキサン、アルキル変性オルガノポリシロキサン、末端変性オルガノポリシロキサン、フッ素変性オルガノポリシロキサン、アモジメチコーン、アミノ変性オルガノポリシロキサン、シリコーンゲル、アクリルシリコーン、トリメチルシロキシケイ酸、シリコーンＲＴＶゴムなどのシリコーン化合物、パーフルオロポリエーテル、フッ化ピッチ、フルオロカーボン、フルオロアルコール、フッ素化シリコーンレジンなどのフッ素化合物が挙げられる。
【００２７】
界面活性剤としては、例えば、アニオン型界面活性剤、カチオン型界面活性剤、ノニオン型界面活性剤、ベタイン型界面活性剤を用いることができる。
【００２８】
溶媒としては、精製水、エタノール、軽質流動イソパラフィン、低級アルコール、エーテル類、ＬＰＧ、フルオロカーボン、Ｎ−メチルピロリドン、フルオロアルコール、パーフルオロポリエーテル、代替フロン、揮発性シリコーンなどが挙げられる。
【００２９】
また、有機系の紫外線防御剤である紫外線吸収剤の例としては、例えば、パラメトキシケイ皮酸２−エチルヘキシル、パラジメチルアミノ安息香酸２−エチルヘキシル、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−５−硫酸、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、ｐ−メトキシハイドロケイ皮酸ジエタノールアミン塩、パラアミノ安息香酸（以後、ＰＡＢＡと略す）、サリチル酸ホモメンチル、メチル−Ｏ−アミノベンゾエート、２−エチルヘキシル−２−シアノ−３，３−ジフェニルアクリレート、オクチルジメチルＰＡＢＡ、メトキシケイ皮酸オクチル、サリチル酸オクチル、２−フェニル−ベンズイミダゾール−５−硫酸、サリチル酸トリエタノールアミン、３−（４−メチルベンジリデン）カンフル、２，４−ジヒドロキシベンゾフェニン、２，２’，４，４’−テトラヒドロキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン、２−ヒドロキシ−４−Ｎ−オクトキシベンゾフェノン、４−イソプロピルジベンゾイルメタン、ブチルメトキシジベンゾイルメタン、４−（３，４−ジメトキシフェニルメチレン）−２，５−ジオキソ−１−イミダゾリジンプロピオン酸２−エチルヘキシル、これらの高分子誘導体などが挙げられる。これらの紫外線吸収剤も強凝集性酸化チタンや無機系紫外線防御成分と併用して用いると製品の紫外線防御能を向上させるのに効果的である。
【００３０】
また、本発明の化粧料では抗酸化剤を併用することが、酸化亜鉛粉末等の光触媒活性による他の配合成分の変質を防止するためにも好ましく、抗酸化剤の例としては、例えば、トコフェロール類、ＳＯＤ、フェノール類、テルペン類、ブチルヒドロキシトルエン、ビタミンＣ、ビタミンＥ、カテキン類、グルコース、ヒアルロン酸、β−カロチン、テトラヒドロクルクミン、茶抽出物、ゴマ抽出物、アントシアニン、配糖体などの植物系等の抗酸化剤など従来公知の物質を用いることができる。
【００３１】
本発明の化粧料としては、ファンデーション、白粉、アイシャドウ、アイライナー、チーク、口紅、ネイルカラーなどのメイクアップ化粧料、乳液、クリーム、ローション、カラミンローション、サンスクリーン剤、化粧下地料、補正料、サンタン剤、アフターシェーブローション、プレシェーブローション、パック料、クレンジング料、洗顔料、アクネ対策化粧料などの基礎化粧料、ヘアカラー、ボディパウダー、デオドラント、石鹸、ボディシャンプー、入浴剤、香水などが挙げられる。
【００３２】
本発明の化粧料の剤型としては、二層状、油中水型エマルション、水中油型エマルション、ジェル状、スプレー、ムース状、油性、固型状など従来公知の剤型を使用することができる。特に、ファンデーション用途としては、固型状、固型エマルション状、ジェル状、油中水型エマルション、水中油型エマルション、油性、ムースなどが好ましい。
【００３３】
本発明の化粧料としては、白色以外の着色料を用いずに、外観が白色である化粧料、特にファンデーションなどのメイクアップ化粧料、化粧下地料、補正料がその効果を発揮する場合に好適である。白色の化粧料等は一般的に、化粧下地料として用いた場合には肌色を補正し、ファンデーションを明るく見せる効果があるが、本発明で用いた強凝集性酸化チタンとシリコーンエラストマー球状粉体の組み合わせによる白色化粧料は、化粧下地料として用いた場合に、その効果をより強くすることが可能である。また、本発明の組み合わせによる白色化粧料を他のファンデーションと混ぜ合わせて使用した場合には、使用者の肌色にファンデーションの色を合わせることが可能である以外に、ファンデーション自体のつきを良くし、化粧持続性を向上させる効果を付与することができる。
【００３４】
すなわち、本発明の好適な化粧方法としては、本発明の白色化粧料を化粧下地料として用いた後、ファンデーション、アイシャドウ、チーク、フィルターカラー、頬紅、白粉などのメイク行為を行う方法、および本発明の白色化粧料とファンデーションを使用時に混合して、自分の肌の色に合わせて用いる方法が挙げられる。
【００３５】
【実施例】
以下、製造例および実施例にて本発明を具体的に説明する。
尚、製造例の評価方法は前記の方法を用いた。
また、化粧料の評価は、以下の方法と基準に従って実施した。
【００３６】
〔官能特性評価〕
専門パネラー２０名を用いて、試作品（化粧料）の官能特性を評価した。評価項目としては、「キメ、シワが目立たないか」、「外観が自然で美しいと感じるか」、「感触に優れるか」の３項目で行った。「キメ、シワが目立たない」、「外観が自然で美しいと感じる」、「感触に優れる」を＋５点、「キメ、シワが目立つ」、「きたなくつく」、「感触が悪い」を０点とし、その間を計４段階で評価し、全員の点数の合計を以て評価結果とした。従って、点数が高いほど、評価が高いことを示す。
【００３７】
製造例１（強凝集性酸化チタン）
イルメナイト鉱石の蒸解によって得られた硫酸チタニル水溶液（ＴｉＯ2 として２００ｇ／ｌ）に、四塩化チタンを苛性ソーダで中和することによって得られる核を添加した後、１１０℃で３時間加熱加水分解し、含水酸化チタンを含む水性懸濁液を得た。この水性懸濁液を濾過し、十分に洗浄を行った。得られた洗浄ケーキを７００℃で３時間焼成する事により、酸化チタンを得た。
（表面処理）
上記の酸化チタンを２００ｇ／ｌの水性スラリーとし、硫酸アルミニウムと水酸化ナトリウムを添加することにより、酸化チタン表面に含水酸化アルミニウムを被覆した。尚、表面処理量は、Ａｌ2 Ｏ3 換算でＴｉＯ2 に対し５．０重量％とした。この後スラリーを濾過、洗浄して、得られた洗浄ケーキを１２０℃で一昼夜乾燥し、粉砕して本発明のアナタース形の強凝集性酸化チタンを得た。
【００３８】
製造例１の強凝集性酸化チタン、市販の超微粒子酸化チタン（ルチル型）（サンプルＡ）、顔料級酸化チタン（アナタース型）（サンプルＢ）、顔料級酸化チタン（ルチル型）（サンプルＣ）、および中間粒径酸化チタン（ルチル型）（サンプルＤ）について評価した結果を表１に示す。尚、各試料の結晶型は粉末Ｘ線回折法を用いて測定し、透過率としては、各試料を前述の方法で塗料化した後、三酢酸セルロースフィルムに塗布し、分光光度計（島津製作所製ＵＶ−２２００Ａ型、積分球付き）にて３００ｎｍの透過率を測定した。また、サンプルＤは、比表面積が１２．７ｍ2 ／ｇのものを合成して使用した。
【００３９】
【表１】
表１より、本発明で用いられる強凝集性酸化チタンは既存の顔料級酸化チタン（サンプルＢ、サンプルＣ）と比較して塗膜のＬ値が低い、即ち隠蔽力が低く、紫外線遮蔽能が高いことが判る。また、超微粒子酸化チタン（サンプルＡ）と比較して塗膜のｂ値が高い、即ち青味が少ない事が判る。さらに、中間粒径酸化チタン（サンプルＤ）と比較しても、隠蔽力が低く、青みが少ないことが判る。
【００４１】
実施例１（白色油性化粧料）
製造例１の強凝集性酸化チタンおよびシリコーンエラストマー球状粉体（東レ・ダウコーニング・シリコーン社製トレフィルＥ−５０７）を用いて表２の処方に従って白色油性化粧料を作製した。
【００４２】
【表２】
表２の各成分を粗混合した後、マイクロス（奈良機械製作所製）を用いて１３００ｒｐｍで１０分間混練り粉砕を行った。さらに、かきとりと粗混合を行い、この操作を合計３回繰り返して得られた溶液を容器に充填して製品とした。
【００４４】
比較例１（白色油性化粧料）
実施例１の強凝集性酸化チタンの代わりに前記超微粒子酸化チタン（サンプルＡ）を配合した他は全て実施例１と同様にして製品を得た。
【００４５】
比較例２（白色油性化粧料）
実施例１の強凝集性酸化チタンの代わりに前記顔料級酸化チタン（サンプルＣ）を配合した他は全て実施例１と同様にして製品を得た。
【００４６】
比較例３（白色油性化粧料）
実施例１の強凝集性酸化チタンの代わりに前記中間粒径酸化チタン（サンプルＤ）を配合した他は全て実施例１と同様にして製品を得た。
【００４７】
比較例４（白色油性化粧料）
実施例１のシリコーンエラストマー球状粉体の代わりにシリコーン処理セリサイトを配合した他は全て実施例１と同様にして製品を得た。
【００４８】
実施例２（ファンデーション）
製造例１の強凝集性酸化チタンおよびシリコーンエラストマー球状粉体（東レ・ダウコーニング・シリコーン社製トレフィルＥ−５０７）を用いて表３の処方に従ってファンデーションを作製した。但し、シリコーンエラストマー球状粉体は事前にロールミルを用いて、シリコーンエラストマー球状粉体とトリ（カプリル・カプリン酸）グリセリンで混合比率（重量比）が５０：５０のペーストを作製し、ペースト状シリコーンエラストマーとして配合した。また、強凝集性酸化チタンのシリコーン処理としては、メチルハイドロジェンポリシロキサン３重量％加熱処理を行った。
【００４９】
【表３】
表３の各成分を粗混合した後、ロールミルを用いて混合を行い、容器に充填して製品を得た。
【００５１】
実施例３（化粧方法）
ローションで肌を整えた後、実施例１の白色油性化粧料を化粧下地として使用し、次いで市販の２ウェイ型耐皮脂性パウダーファンデーションを使用した。
【００５２】
実施例４（化粧方法）
ローションで肌を整えた後、実施例１の白色油性化粧料と市販のリクイドファンデーション（Ｗ／Ｏ型）を手の甲で自分の肌の色に合うように混ぜ合わせたものを使用した。
【００５３】
比較例５（化粧方法）
ローションで肌を整えた後、比較例１の白色油性化粧料を化粧下地として使用し、次いで市販の２ウェイ型耐皮脂性パウダーファンデーションを使用した。
【００５４】
比較例６（化粧方法）
ローションで肌を整えた後、比較例２の白色油性化粧料を化粧下地として使用し、次いで市販の２ウェイ型耐皮脂性パウダーファンデーションを使用した。
【００５５】
比較例７（化粧方法）
ローションで肌を整えた後、比較例３の白色油性化粧料を化粧下地として使用し、次いで市販の２ウェイ型耐皮脂性パウダーファンデーションを使用した。
【００５６】
比較例８（化粧方法）
ローションで肌を整えた後、比較例４の白色油性化粧料を化粧下地として使用し、次いで市販の２ウェイ型耐皮脂性パウダーファンデーションを使用した。
【００５７】
表４に、化粧料の実施例１〜２および比較例１〜４の評価結果を示す。また、表５に各化粧方法についての評価結果を示す。
【００５８】
【表４】
【表５】
表４より、本発明の実施例１〜２は、キメ、シワが目立たずに、外観が美しく、感触にも優れていることが判った。これに対して、シリコーンエラストマー球状粉体と従来の超微粒子酸化チタンを配合した比較例１の化粧料は青白さが出て血色が悪く見え、顔料級酸化チタンを配合した比較例２の化粧料はキメやシワが目立ち、中間粒子径酸化チタンを配合した比較例３の化粧料では全体的な評価は高いものの青白さに由来する原因のために評価がやや悪い結果になった。さらに、シリコーンエラストマー球状粉体を配合せずに強凝集性酸化チタンのみを配合した比較例４の場合では、強い油性感が発生し、全ての項目で評価が悪くなった。
【００６１】
表５より、本発明の実施例３〜４の化粧方法は、キメ、シワが目立たずに、外観が美しく、感触にも優れていることが判った。特に、化粧下地料として本発明の白色化粧料を用いることで、外観が自然で美しい化粧仕上がりが得られること、また、本発明の白色化粧料をファンデーションと混合することで、自分の肌色にあった違和感のない化粧仕上がりが得られ、化粧効果の持続性に優れることが確認された。これに対して、従来の超微粒子酸化チタンや顔料級酸化チタンを配合した化粧料を使用した場合では評価が悪くなっていることが判る。さらに、中間粒径酸化チタンを用いた化粧料を使用した場合では、前記同様に全体の評価は高いものの、外観に多少違和感が出てしまった。また、シリコーンエラストマー球状粉体を配合せずに強凝集性酸化チタンのみを配合した場合では、油性感が強すぎ評価が悪くなった。
【００６２】
【発明の効果】
以上述べたように、強凝集性酸化チタンとシリコーンエラストマー球状粉体を配合した本発明の化粧料は、肌のキメ、シワが目立たずに、外観が美しく、感触にも優れている。さらに、本発明の化粧料を用いた化粧方法により、外観が自然で美しい化粧仕上がりが簡単に得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cosmetic that provides a beautiful appearance by hiding skin texture and wrinkles by blending a transparent white titanium oxide and a silicone elastomer spherical powder, and a cosmetic method that provides a beautiful appearance.
[0002]
[Prior art]
Conventionally, titanium oxides used in cosmetics are pigment grade titanium oxide (primary particle size 0.15 to 0.3 μm) for the purpose of hiding as a white pigment and ultrafine titanium oxide (primary particles for the purpose of UV protection). Development has been carried out with two flows having a diameter of 0.01 to 0.05 μm. In these circumstances, according to Japanese Patent Laid-Open No. 9-221411, a titanium oxide having a primary particle diameter in the intermediate region between pigment grade titanium oxide and ultrafine titanium oxide in the range of more than 0.10 μm and 0.14 μm or less ( Hereinafter, it is disclosed that the intermediate particle size titanium oxide) has an appropriate finish and a natural hiding power. When a reproduction experiment is performed by the method described in the publication, it is superior to conventional pigment-grade titanium oxide in terms of the white beauty of titanium oxide, but not as good as ultrafine titanium oxide. There is a limit to how many things can be used as a concealment material. Therefore, by tinting the intermediate particle size titanium oxide yellow, the bluishness of the titanium oxide disappears and a natural skin color can be formed.
[0003]
On the other hand, as proposed in Japanese Patent Application Laid-Open No. 9-71509, it is known that a cosmetic containing a silicone elastomer spherical powder has a matting effect and an effect of hiding wrinkles. This is an effect that optically blurs the fine unevenness of the skin, but the silicone elastomer spherical powder alone does not have the effect of concealing skin troubles such as stains. In combination with a pigment having a hiding power.
[0004]
[Problems to be solved by the invention]
When the optical properties of the concealing pigment exceed the effect of the silicone elastomer spherical powder, there is a problem that texture and wrinkles become conspicuous. Development was necessary. On the other hand, when conventional titanium oxide is used as a concealing pigment, there are some problems such as noticeable texture and wrinkles and bluish white, and it cannot be said that the optical characteristics are suitable.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve these problems, the present inventors have (1) a step of hydrolyzing a titanyl sulfate aqueous solution in the presence of titanium oxide microcrystal nuclei obtained by neutralizing titanium tetrachloride with caustic soda; and (2) a temperature of 600 to 900 ° C. of the hydrolysis product. The primary particle diameter obtained by the step of firing at 0.01 to 0.1 It has been found that anatase-type titanium oxide having a μm and a secondary particle diameter of 0.6 to 2.0 μm gives a natural and appropriate white color and has an ultraviolet protection ability even without coloring. And the cosmetics which mix | blended both this titanium oxide and the silicone elastomer spherical powder discovered that a texture and a wrinkle were not conspicuous and showed a beautiful coating color, and completed this invention. Furthermore, when a white cosmetic was prepared without adding a colorant other than white, it was found that a more beautiful finish can be obtained particularly as a makeup base or correction material.
That is, the present invention (1) a step of hydrolyzing a titanyl sulfate aqueous solution in the presence of titanium oxide microcrystal nuclei obtained by neutralizing titanium tetrachloride with caustic soda; and (2) a temperature of 600 to 900 ° C. of the hydrolysis product. The primary particle size obtained by the step of firing at 0.01 to 0.1 It is in cosmetics blended with highly agglomerated titanium oxide having a μm, secondary particle size of 0.6 to 2.0 μm and anatase crystal form, and a silicone elastomer spherical powder.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Strongly cohesive titanium oxide used in the present invention has a primary particle size of 0.01-0.1 It is a highly cohesive titanium oxide having a μm, a secondary particle diameter of 0.6 to 2.0 μm, and a crystal form of anatase. This highly cohesive titanium oxide is a condition that is usually used industrially. That is, 0.5 g of the powder was pulverized for 10 minutes with an Ishikawa-type stirring crusher (made by Ishikawa Factory) Even when mechanical dispersion is performed, the primary particles are not easily crushed and most of them remain as secondary particles. Since the light scattering ability is determined by the state of being dispersed in the medium, that is, the secondary particle diameter, when the secondary particle diameter is in the above range, a transparent feeling is generated with respect to visible light, and as in the case of ultrafine titanium oxide. Since blue light is not preferentially scattered, it gives a natural color tone with no blueness. Furthermore, since the specific surface area of both strong agglomeration and soot is large according to the primary particle size, the ability to absorb ultraviolet rays is considerably higher than when the secondary particle size is the same and the primary particle size is large.
[0007]
In the present invention, the primary particle size is determined by the following method. First, 0.5 g of the powder is pulverized for 10 minutes with an Ishikawa-type stirring crusher (manufactured by Ishikawa Factory Co., Ltd.), and then a transmission electron micrograph is taken. From the photograph, the primary particle diameter is measured with Particle Analyzer (manufactured by Carl Zeiss Co., Ltd.), and the calculated weight average diameter is defined as the primary particle diameter. Next, regarding the secondary particle diameter, this is expressed as the median diameter when the powder is dispersed in water and measured with a laser diffraction / scattering particle size distribution apparatus LA-910 manufactured by Horiba. Here, in order to disperse the powder in water, sodium hexametaphosphate is dissolved in ion-exchanged water to make a 1.0% aqueous solution, and 17.0 g of this aqueous solution and 17.0 g of the powder are mixed with 40 g of 0.5 mm zircon beads. In addition to the glass mayonnaise bottle having a capacity of 140 cc, the paint shaker dispersion is performed for 5 minutes before measurement. Even when the secondary particle diameter of pigment titanium oxide or ultrafine titanium oxide is obtained by this method, it is not always the same value as the primary particle diameter, and the value of aggregated particles may be obtained. Only 2 to 3 particles are aggregated, and the particle size is 0.5 μm or less.
[0008]
Although the particle size is defined by the above method, the primary particle size of the strongly cohesive titanium oxide used in the present invention is 0.01-0.1 It is characterized by having a secondary particle diameter of 0.6 to 2.0 μm. When the primary particle size exceeds the above range, it is difficult to obtain strongly cohesive titanium oxide, and the ultraviolet absorbing ability is lowered. Ma On the other hand, when the secondary particle diameter is less than 0.6 μm, it has a concealing property equivalent to that of pigment titanium oxide, and the appropriate transparency and natural texture of strong cohesive titanium oxide cannot be obtained. Further, those having a secondary particle diameter exceeding 2.0 μm are hardly obtained, are easily broken, and are not easily agglomerated.
[0009]
The above is a general explanation of the characteristics of the highly cohesive titanium oxide used in the present invention, but an index that expresses this characteristic more specifically and simply will be described.
That is, the strongly cohesive titanium oxide used in the present invention has a titanium oxide-containing coating film prepared by the following method and has a L value of 35 to 50 and a b value of -10 to 0 when measured with a color difference meter. It is characterized by that.
[0010]
2. Coating film creation and coating color measurement method
Apply the color of the black ground to the color difference meter (SM color computer SM-5 model made by Suga Test Instruments) for the coating film obtained by applying it to the Morest chart paper with an applicator (film thickness after drying 8 μm) and then drying it naturally. To measure the color.
[0012]
Compared with other materials by this method, in general, pigment titanium oxide has a high hiding power and high whiteness, so the L value exceeds 50, and in the case of ultrafine titanium oxide, b is scattered by blue light. The value is less than −10.
[0013]
The strongly cohesive titanium oxide used in the present invention has at least one hydrous oxide selected from the group consisting of Al, Si, Zr, Ti, and Zn on the particle surface for the purpose of suppressing solid catalytic activity and photocatalytic activity. And / or an oxide may be coated, and at the same time or alone with these treatments, a silicone compound, silane, metal soap, fluorine compound, water-soluble polymer compound, N-acylated lysine, polyol, acrylic resin In addition, at least one organic substance selected from the group consisting of methacrylic resin, styrene resin, urethane resin and the like may be coated. By these surface treatments, wettability, sebum resistance, and dispersibility can be appropriately improved. Of these, silicone compounds such as methylhydrogenpolysiloxane, trimethylsiloxysilicic acid, fluoroalkyl / polyoxyalkylene co-modified silicone, silanes such as octyltriethoxysilane, metal soaps such as zinc stearate, perfluoroalkyl phosphoric acid Fluorine compounds such as diethanolamine salt, Teflon and perfluoroalkylsilane, water-soluble polymer compounds such as deoxyribonucleic acid and hyaluronic acid, and those treated with N-acylated lysine such as N-lauroyl lysine This is particularly preferable because the above characteristics are characteristic.
[0014]
As a method for producing strongly cohesive titanium oxide used in the present invention, for example, the following two-stage method can be used.
(1) A step of hydrolyzing an aqueous titanyl sulfate solution in the presence of a nucleus
(2) A step of baking the hydrolysis product at a temperature of 600 to 900 ° C
The starting material titanyl sulfate can be usually produced by reacting ilmenite ore with sulfuric acid. This is called cooking in the titanium oxide industry, but is not limited to ilmenite ore, and for example, hydrous titanium oxide may be cooked. The product is diluted with water and impurities are removed as necessary, followed by hydrolysis by heating. At this time, nuclei which are microcrystals of titanium oxide are added for the purpose of promoting the hydrolysis reaction and adjusting the particle size and crystallinity. The hydrolyzed product thus obtained is filtered, washed as necessary, and then calcined at 600 to 900 ° C. If the calcination temperature is lower than this range, the primary particle size is reduced but does not cause strong agglomeration. Conversely, if it is higher, the primary particle size becomes too large and the titanium oxide of the present invention cannot be obtained. Thereafter, pulverization and sizing may be performed as necessary, and then a hydrous oxide such as Al, Si, Zr, Ti, Zn and / or an oxide may be coated by a conventional method.
[0015]
It is considered that the titanium oxide used in the present invention is strongly cohesive mainly derived from the above-described production method. The details of the mechanism of strong agglomeration are not always clear, but there is a state in which the surface energy becomes very large at the stage of crystal growth in the hydrolysis or baking process, and it is considered that the particles strongly aggregate at that time. .
[0016]
The silicone elastomer spherical powder used in the present invention is a three-dimensional cross-linked silicone powder and refers to an aggregate of powders whose primary particle shape is spherical. Specifically, Trefill E-505C, Trefill E-506, Trefill E-507, etc. manufactured by Toray Vu Corning Silicone Co., Ltd. are applicable, and Trefill E-507, which is countermeasures against odors, is most preferable. In addition, most primary particles of these powder correspond to the range of 0.1-20 micrometers as a primary particle diameter.
[0017]
The silicone elastomer spherical powder used in the present invention is a conventionally known surface treatment such as silicone treatment, silicone resin treatment, silane treatment, inorganic oxide treatment, resin treatment, adhesive treatment, fluorine compound treatment, mechanochemical treatment, etc. The surface treatment may or may not be performed.
[0018]
The silicone elastomer spherical powder used in the present invention can be used as a silicone elastomer spherical powder kneaded paste that has been previously kneaded or wet pulverized to improve the feel of the cosmetic and provide a more uniform coating. It is preferable because a film can be formed and the texture and wrinkles can be more concealed. For example, the silicone elastomer spherical powder may be changed into a paste form with a volatile oil and / or a non-volatile oil in advance using a kneading device or a wet grinding device. Examples of volatile oils include cyclic silicones, low molecular weight linear silicones, light liquid isoparaffins, next-generation fluorocarbons, perfluoropolyethers, alcohols, petroleum ethers, terpenes and the like. Examples of non-volatile oils are liquid, solid, and paste at room temperature, and any known material may be used. For example, silicone oil, ester oil, polar oil, oil and fat, fluorine oil, etc. Is mentioned. Moreover, what is melt | dissolved and used for another oil agent like trimethylsiloxy silicic acid can also be used. Of these, silicone oils and ester oils such as cyclic silicone, dimethylpolysiloxane, polyether-modified silicone, perfluoroalkyl / polyoxyalkylene co-modified silicone, and silicone resin are particularly preferable because of their excellent compatibility with silicone elastomer spherical powder. . Moreover, when combined with silicone oil, a more transparent paste is obtained.
[0019]
When the silicone elastomer spherical powder is changed into a paste using a kneader or wet pulverizer, roll mill, extruder (continuous extrusion kneader), bead mill, sand mill, Micros (manufactured by Nara Machinery Co., Ltd.), etc. It is preferable to use a wet medium pulverizer, but when a volatile solvent or non-liquid oil is used, a multiaxial extruder is most preferable, and when a non-volatile oil is used, a roll mill is used because of the strength of pulverization. preferable.
[0020]
The mixing ratio (weight ratio) of the silicone elastomer spherical powder used in the present invention and the above oil agent is preferably in the range of 3:97 to 80:20, particularly preferably 25:75 to 60:40. . When the mixing ratio of the silicone elastomer spherical powder is less than 3% by weight, it is difficult to obtain the effect of the elastomer, and when it exceeds 80% by weight, it is difficult to obtain the kneading effect.
[0021]
The proportion of the highly cohesive titanium oxide and the silicone elastomer spherical powder blended into the cosmetic of the present invention is 0.5 to 50% by weight of the strong cohesive titanium oxide and the silicone elastomer spherical to the total amount of the cosmetic. The powder is preferably in the range of 0.3 to 70% by weight, more preferably in the range of 1 to 30% by weight of the highly cohesive titanium oxide and 1 to 30% by weight of the silicone elastomer spherical powder.
[0022]
In the cosmetic of the present invention, in addition to the above-mentioned highly cohesive titanium oxide, powders (pigments, pigments, resins), oils, fluorine compounds, resins, surfactants, UV protection agents, antioxidants that are usually used in cosmetics Components such as an agent, a sticking agent, a preservative, a fragrance, a humectant, a physiologically active ingredient, a salt, a solvent, a chelating agent, a neutralizing agent, and a pH adjuster can be blended at the same time.
[0023]
Examples of the powder include pigments such as Red No. 104, Red No. 201, Yellow No. 4, Blue No. 1, Black No. 401, Lake No. 4 such as Yellow No. 4 Al lake, Yellow No. 203 Ba lake, nylon powder, silk Colored pigments such as powder, urethane powder, Teflon powder, silicone powder, cellulose powder, chitin, chitosan, calcium alginate and other polymers, yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black, ultramarine blue, and bitumen , White pigments such as titanium oxide, cerium oxide, extender pigments such as talc, mica, sericite, kaolin, pearl pigments such as mica titanium, metal salts such as barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate, Inorganic powders such as silica and alumina, fine particle oxide oxide , Zinc oxide particles, particles of iron oxide, alumina-treated fine titanium oxide particles, silica treated ultrafine titanium dioxide, bentonite, smectite and the like. There are no particular restrictions on the shape and size of these powders. Among these, it is preferable to use a strong cohesive titanium oxide in combination with inorganic ultraviolet protection components such as fine particle titanium oxide and fine particle zinc oxide in order to improve the ultraviolet ray protection effect.
[0024]
In addition, the above powder is subjected to various conventionally known surface treatments such as silicone treatment, silane treatment, fluorine compound treatment, oil agent treatment, metal soap treatment, wax treatment, N-acylated lysine treatment, and water-soluble polymer compound treatment. The resin treatment, the metal oxide treatment, the plasma treatment, the mechanochemical treatment, the adhesive treatment or the like may or may not be performed.
[0025]
Examples of oils include higher alcohols such as cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyldodecanol, fatty acids such as isostearic acid, undecylenic acid, oleic acid, glycerin, sorbitol, ethylene glycol, propylene glycol, Polyhydric alcohols such as polyethylene glycol, myristyl myristate, hexyl laurate, decyl oleate, isopropyl myristate, hexyl decyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, octyl oxystearate, etc. Esters, liquid paraffin, petrolatum, hydrocarbons such as squalane, lanolin, reduced lanolin, wax such as carnauba wax, Ink oil, cacao butter, coconut oil, palm kernel oil, camellia oil, sesame oil, castor oil, oils such as olive oil, and ethylene-alpha-olefin co-oligomer and the like.
[0026]
Examples of other forms of oil include, for example, dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, polyether-modified organopolysiloxane, fluoroalkyl / polyoxyalkylene co-modified organopolysiloxane, alkyl-modified Organopolysiloxane, terminal-modified organopolysiloxane, fluorine-modified organopolysiloxane, amodimethicone, amino-modified organopolysiloxane, silicone gel, acrylic silicone, trimethylsiloxysilicate, silicone compounds such as silicone RTV rubber, perfluoropolyether, fluoride Fluorine compounds such as pitch, fluorocarbon, fluoroalcohol, and fluorinated silicone resin can be mentioned.
[0027]
As the surfactant, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, or a betaine surfactant can be used.
[0028]
Examples of the solvent include purified water, ethanol, light liquid isoparaffin, lower alcohol, ethers, LPG, fluorocarbon, N-methylpyrrolidone, fluoroalcohol, perfluoropolyether, alternative chlorofluorocarbon, and volatile silicone.
[0029]
Examples of UV absorbers that are organic UV protective agents include, for example, 2-methoxyhexyl paramethoxycinnamate, 2-ethylhexyl paradimethylaminobenzoate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy -4-methoxybenzophenone-5-sulfuric acid, 2,2'-dihydroxy-4-methoxybenzophenone, p-methoxyhydrocinnamic acid diethanolamine salt, paraaminobenzoic acid (hereinafter abbreviated as PABA), homomenthyl salicylate, methyl-O- Aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, octyldimethyl PABA, octyl methoxycinnamate, octyl salicylate, 2-phenyl-benzimidazole-5-sulfate, triethanolamine salicylate, 3- (4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenine, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy- 4-N-octoxybenzophenone, 4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, 4- (3,4-dimethoxyphenylmethylene) -2,5-dioxo-1-imidazolidine-2-ethylhexyl propionate, these And the like. When these ultraviolet absorbers are also used in combination with strong cohesive titanium oxide and inorganic ultraviolet protective components, they are effective in improving the ultraviolet protective ability of the product.
[0030]
Further, in the cosmetic of the present invention, it is preferable to use an antioxidant together in order to prevent alteration of other compounding components due to photocatalytic activity such as zinc oxide powder. As an example of the antioxidant, for example, tocopherol , SOD, phenols, terpenes, butylhydroxytoluene, vitamin C, vitamin E, catechins, glucose, hyaluronic acid, β-carotene, tetrahydrocurcumin, tea extract, sesame extract, anthocyanin, glycoside, etc. Conventionally known substances such as plant-based antioxidants can be used.
[0031]
As cosmetics of the present invention, makeup cosmetics such as foundation, white powder, eye shadow, eyeliner, teak, lipstick, nail color, emulsion, cream, lotion, calamine lotion, sunscreen agent, cosmetic base material, correction material , Suntan, after-shave lotion, pre-shave lotion, pack, cleansing, facial cleanser, anti-acne cosmetics, basic cosmetics, hair color, body powder, deodorant, soap, body shampoo, bath preparation, perfume, etc. .
[0032]
As the dosage form of the cosmetic of the present invention, conventionally known dosage forms such as a bilayer, a water-in-oil emulsion, an oil-in-water emulsion, a gel, a spray, a mousse, an oil, and a solid can be used. . In particular, as a foundation application, a solid form, a solid emulsion form, a gel form, a water-in-oil emulsion, an oil-in-water emulsion, oiliness, mousse and the like are preferable.
[0033]
As the cosmetics of the present invention, it is suitable when cosmetics having a white appearance, especially makeup cosmetics such as foundations, makeup bases, and corrections exhibit their effects without using colorants other than white. It is. White cosmetics and the like generally have an effect of correcting the skin color and making the foundation appear bright when used as a makeup base material, but the strong cohesive titanium oxide and silicone elastomer spherical powder used in the present invention are effective. When the white cosmetics by combination are used as a makeup base material, the effect can be made stronger. In addition, when the white cosmetics according to the combination of the present invention are used in combination with other foundations, in addition to being able to match the foundation color to the user's skin color, the foundation itself is improved, The effect of improving makeup persistence can be imparted.
[0034]
That is, as a suitable cosmetic method of the present invention, after using the white cosmetic composition of the present invention as a makeup base material, a makeup act such as foundation, eye shadow, teak, filter color, blusher, white powder, etc. The method of mixing the white cosmetics and foundations of the invention at the time of use and using them according to the color of their own skin can be mentioned.
[0035]
【Example】
The present invention will be specifically described below with reference to production examples and examples.
In addition, the said method was used for the evaluation method of a manufacture example.
The cosmetics were evaluated according to the following methods and standards.
[0036]
[Evaluation of sensory characteristics]
Twenty professional panelists were used to evaluate the sensory characteristics of the prototype (cosmetics). The evaluation items were three items: “Is texture or wrinkle inconspicuous”, “Is the appearance look natural and beautiful”, or “Is it excellent in touch”? +5 points for "feeling that wrinkles and wrinkles are inconspicuous", "feeling natural and beautiful", "excellent in touch", 0 points for "feeling wrinkles and wrinkles stand out", "getting messed up", and "feeling bad" The evaluation was made in four stages, and the total score of all members was used as the evaluation result. Therefore, it shows that evaluation is so high that a score is high.
[0037]
Production Example 1 (Strongly Cohesive Titanium Oxide)
Titanyl sulfate aqueous solution (TiO2) obtained by cooking of ilmenite ore 2 To 200 g / l), a nucleus obtained by neutralizing titanium tetrachloride with caustic soda was added, followed by hydrolysis with heating at 110 ° C. for 3 hours to obtain an aqueous suspension containing hydrous titanium oxide. This aqueous suspension was filtered and washed thoroughly. The obtained washed cake was baked at 700 ° C. for 3 hours to obtain titanium oxide.
(surface treatment)
The titanium oxide was made into an aqueous slurry of 200 g / l, and aluminum sulfate and sodium hydroxide were added to coat the surface of the titanium oxide with the hydrous aluminum oxide. The surface treatment amount is Al. 2 O Three TiO in conversion 2 The content was 5.0% by weight. Thereafter, the slurry was filtered and washed, and the resulting washed cake was dried at 120 ° C. for a whole day and night and pulverized to obtain anatase-type strongly cohesive titanium oxide of the present invention.
[0038]
Strongly cohesive titanium oxide of Production Example 1, commercially available ultrafine titanium oxide (rutile type) (sample A), pigment grade titanium oxide (anatase type) (sample B), pigment grade titanium oxide (rutile type) (sample C) Table 1 shows the results of the evaluation of titanium oxide having an intermediate particle size (rutile type) (sample D). The crystal form of each sample was measured using a powder X-ray diffraction method, and the transmittance was applied to a cellulose triacetate film after coating each sample by the above-described method, and a spectrophotometer (Shimadzu Corporation). The transmittance at 300 nm was measured with a UV-2200A model (with an integrating sphere). Sample D has a specific surface area of 12.7 m. 2 / G was synthesized and used.
[0039]
[Table 1]
From Table 1, the strongly cohesive titanium oxide used in the present invention has a lower L value of the coating film than the existing pigment grade titanium oxide (sample B, sample C), that is, the hiding power is low, and the ultraviolet shielding ability is low. It turns out to be expensive. Moreover, it turns out that b value of a coating film is high compared with an ultrafine particle titanium oxide (sample A), ie, there is little blueness. Furthermore, it can be seen that the hiding power is low and the bluish color is small even when compared with the intermediate particle size titanium oxide (sample D).
[0041]
Example 1 (white oily cosmetic)
A white oily cosmetic was prepared according to the formulation of Table 2 using the strongly cohesive titanium oxide of Production Example 1 and a silicone elastomer spherical powder (Torefil E-507 manufactured by Toray Dow Corning Silicone).
[0042]
[Table 2]
After roughly mixing the components shown in Table 2, the mixture was kneaded and ground at 1300 rpm for 10 minutes using Micros (manufactured by Nara Machinery Co., Ltd.). Further, scraping and rough mixing were performed, and a solution obtained by repeating this operation three times in total was filled in a container to obtain a product.
[0044]
Comparative Example 1 (white oily cosmetic)
A product was obtained in the same manner as in Example 1 except that the ultrafine titanium oxide (Sample A) was blended in place of the highly cohesive titanium oxide of Example 1.
[0045]
Comparative Example 2 (white oily cosmetic)
A product was obtained in the same manner as in Example 1 except that the pigment-grade titanium oxide (Sample C) was blended in place of the highly cohesive titanium oxide of Example 1.
[0046]
Comparative Example 3 (white oily cosmetic)
A product was obtained in the same manner as in Example 1 except that the intermediate particle size titanium oxide (Sample D) was blended in place of the highly cohesive titanium oxide of Example 1.
[0047]
Comparative Example 4 (white oily cosmetic)
A product was obtained in the same manner as in Example 1 except that silicone-treated sericite was blended in place of the silicone elastomer spherical powder of Example 1.
[0048]
Example 2 (Foundation)
A foundation was prepared according to the formulation in Table 3 using the strongly cohesive titanium oxide of Production Example 1 and a silicone elastomer spherical powder (Trefil E-507 manufactured by Toray Dow Corning Silicone). However, the silicone elastomer spherical powder is prepared in advance by using a roll mill to prepare a paste having a mixing ratio (weight ratio) of 50:50 with the silicone elastomer spherical powder and tri (capryl / capric acid) glycerin. Was formulated as In addition, as the silicone treatment of the highly cohesive titanium oxide, 3% by weight of methyl hydrogen polysiloxane was heat-treated.
[0049]
[Table 3]
After roughly mixing the components in Table 3, mixing was performed using a roll mill, and the product was obtained by filling into a container.
[0051]
Example 3 (makeup method)
After conditioning the skin with lotion, the white oily cosmetic of Example 1 was used as a makeup base, and then a commercially available 2-way type sebum resistant powder foundation was used.
[0052]
Example 4 (makeup method)
After preparing the skin with a lotion, the white oily cosmetic of Example 1 and a commercially available liquid foundation (W / O type) were mixed with the back of the hand to match the color of their skin.
[0053]
Comparative Example 5 (makeup method)
After preparing the skin with lotion, the white oily cosmetic of Comparative Example 1 was used as a makeup base, and then a commercially available 2-way type sebum resistant powder foundation was used.
[0054]
Comparative Example 6 (makeup method)
After preparing the skin with lotion, the white oily cosmetic of Comparative Example 2 was used as a makeup base, and then a commercially available 2-way type sebum resistant powder foundation was used.
[0055]
Comparative Example 7 (makeup method)
After preparing the skin with lotion, the white oily cosmetic of Comparative Example 3 was used as a makeup base, and then a commercially available 2-way type sebum resistant powder foundation was used.
[0056]
Comparative Example 8 (makeup method)
After preparing the skin with lotion, the white oily cosmetic of Comparative Example 4 was used as a makeup base, and then a commercially available 2-way sebum-resistant powder foundation was used.
[0057]
In Table 4, the evaluation result of Examples 1-2 of cosmetics and Comparative Examples 1-4 is shown. Table 5 shows the evaluation results for each makeup method.
[0058]
[Table 4]
[Table 5]
From Table 4, it was found that Examples 1 and 2 of the present invention were not noticeable for texture and wrinkles, had a beautiful appearance, and were excellent in touch. On the other hand, the cosmetic of Comparative Example 1 in which the silicone elastomer spherical powder and the conventional ultrafine titanium oxide were blended appeared bluish white and poor in color, and the cosmetic of Comparative Example 2 in which pigment grade titanium oxide was blended. Although the texture and wrinkles were conspicuous and the overall evaluation of the cosmetic of Comparative Example 3 blended with titanium oxide having an intermediate particle size was high, the evaluation was somewhat poor due to the cause derived from bluish white. Furthermore, in the case of the comparative example 4 which mix | blended only the strong cohesive titanium oxide, without mix | blending a silicone elastomer spherical powder, the strong oily feeling generate | occur | produced and evaluation deteriorated in all the items.
[0061]
From Table 5, it was found that the cosmetic methods of Examples 3 to 4 of the present invention were not noticeable for texture and wrinkles, had a beautiful appearance, and were excellent in touch. In particular, by using the white cosmetic composition of the present invention as a makeup base material, a natural and beautiful cosmetic finish can be obtained, and by blending the white cosmetic composition of the present invention with a foundation, It was confirmed that the cosmetic finish without any sense of incongruity was obtained and the makeup effect was excellent in sustainability. On the other hand, it turns out that evaluation is getting worse when the cosmetics which mix | blended the conventional ultrafine particle titanium oxide and pigment grade titanium oxide are used. Furthermore, when a cosmetic using intermediate particle size titanium oxide was used, although the overall evaluation was high as described above, the appearance was somewhat uncomfortable. In addition, when only the highly cohesive titanium oxide was blended without blending the silicone elastomer spherical powder, the oily feeling was too strong and the evaluation was poor.
[0062]
【The invention's effect】
As described above, the cosmetic of the present invention containing the highly cohesive titanium oxide and the silicone elastomer spherical powder has a beautiful appearance and excellent touch without noticeable skin texture and wrinkles. Furthermore, a cosmetic finish using the cosmetic composition of the present invention can easily provide a cosmetic finish with a natural appearance.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34710597A JP4046394B2 (en) | 1997-12-01 | 1997-12-01 | Cosmetics and makeup method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34710597A JP4046394B2 (en) | 1997-12-01 | 1997-12-01 | Cosmetics and makeup method |
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| Publication Number | Publication Date |
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| JPH11158036A JPH11158036A (en) | 1999-06-15 |
| JP4046394B2 true JP4046394B2 (en) | 2008-02-13 |
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| JP34710597A Expired - Lifetime JP4046394B2 (en) | 1997-12-01 | 1997-12-01 | Cosmetics and makeup method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10096926B2 (en) | 2009-07-01 | 2018-10-09 | Koninklijke Philips N.V. | Low cost-low profile lead set connector |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1136064A3 (en) * | 2000-03-21 | 2001-10-17 | Avon Products, Inc. | Method for improving the apperance of skin and topical compositions for practicing the same |
| WO2002003934A2 (en) | 2000-07-10 | 2002-01-17 | The Procter & Gamble Company | Transfer-resistant makeup removing compositions |
| DE60239874D1 (en) * | 2001-08-10 | 2011-06-09 | Kao Corp | COSMETICS AND MAKEUP METHOD |
| GB0125778D0 (en) | 2001-10-26 | 2001-12-19 | Procter & Gamble | Silicone elastomer emulsion cosmetic composition comprising colorant inclusive internal phase |
| WO2006118940A1 (en) * | 2005-05-03 | 2006-11-09 | The Procter & Gamble Company | Compositions comprising discrete particle aggregates and/or agglomerate for application to keratin fibers |
| JP2007084478A (en) * | 2005-09-21 | 2007-04-05 | Tayca Corp | Cosmetics |
| JP5422973B2 (en) * | 2008-11-18 | 2014-02-19 | 株式会社豊田中央研究所 | Spherical oxide semiconductor particles, and integrated body and photoelectrode using the same |
| FR2967349B1 (en) * | 2010-11-15 | 2013-06-14 | Oreal | COSMETIC COSMETIC SOLID COMPOSITION FOR MAKE-UP AND / OR CARE |
| KR101269405B1 (en) * | 2011-03-11 | 2013-05-30 | 코스맥스 주식회사 | Make-up cosmetic composition containing silicone elastomer |
| JP5594782B2 (en) * | 2011-04-29 | 2014-09-24 | 独立行政法人産業技術総合研究所 | Method for producing aggregate |
| JP6513686B2 (en) | 2014-01-14 | 2019-05-15 | ザ プロクター アンド ギャンブル カンパニー | Multi-step product for improving the appearance and feel of human skin |
| US10512595B2 (en) | 2014-01-14 | 2019-12-24 | The Procter & Gamble Company | Multi-step product for improving the appearance and feel of human skin |
| US20150196464A1 (en) * | 2014-01-14 | 2015-07-16 | The Procter & Gamble Company | Cosmetic Composition |
| JP5913411B2 (en) * | 2014-03-26 | 2016-04-27 | 株式会社 資生堂 | Oil-in-water emulsified cosmetic |
| US10206859B2 (en) | 2014-07-29 | 2019-02-19 | The Procter & Gamble Company | Cosmetic composition |
| KR102012169B1 (en) * | 2017-08-21 | 2019-08-20 | 코스맥스 주식회사 | Make-up cosmetic composition comprising synthetic mica and coated inorganic sunscreen |
| JP2019151564A (en) * | 2018-02-28 | 2019-09-12 | 黒田総合技研株式会社 | Silicone elastomer composition and skin cosmetics |
-
1997
- 1997-12-01 JP JP34710597A patent/JP4046394B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10096926B2 (en) | 2009-07-01 | 2018-10-09 | Koninklijke Philips N.V. | Low cost-low profile lead set connector |
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|---|---|
| JPH11158036A (en) | 1999-06-15 |
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