JP3851365B2 - Cosmetics containing colored metal oxide gel - Google Patents
Cosmetics containing colored metal oxide gel Download PDFInfo
- Publication number
- JP3851365B2 JP3851365B2 JP23898395A JP23898395A JP3851365B2 JP 3851365 B2 JP3851365 B2 JP 3851365B2 JP 23898395 A JP23898395 A JP 23898395A JP 23898395 A JP23898395 A JP 23898395A JP 3851365 B2 JP3851365 B2 JP 3851365B2
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- colored
- pigment
- dispersed phase
- cosmetic according
- 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
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 41
- 150000004706 metal oxides Chemical class 0.000 title claims description 41
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- 229910052751 metal Inorganic materials 0.000 claims description 24
- 150000004703 alkoxides Chemical class 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000000049 pigment Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 235000012730 carminic acid Nutrition 0.000 claims description 13
- 239000004106 carminic acid Substances 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
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- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
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- 239000004147 Sorbitan trioleate Substances 0.000 claims description 5
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- 229940114118 carminic acid Drugs 0.000 description 9
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- 239000011780 sodium chloride Substances 0.000 description 4
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- 239000004094 surface-active agent Substances 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 2
- RHAXKFFKGZJUOE-UHFFFAOYSA-N 7-acetyl-6-ethyl-3,5,8-trihydroxy-9,10-dioxoanthracene-1,2-dicarboxylic acid Chemical compound O=C1C2=CC(O)=C(C(O)=O)C(C(O)=O)=C2C(=O)C2=C1C(O)=C(CC)C(C(C)=O)=C2O RHAXKFFKGZJUOE-UHFFFAOYSA-N 0.000 description 1
- NEZONWMXZKDMKF-JTQLQIEISA-N Alkannin Chemical compound C1=CC(O)=C2C(=O)C([C@@H](O)CC=C(C)C)=CC(=O)C2=C1O NEZONWMXZKDMKF-JTQLQIEISA-N 0.000 description 1
- 241001237961 Amanita rubescens Species 0.000 description 1
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- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- SEBIKDIMAPSUBY-JAUCNNNOSA-N Crocin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C(=O)OC1OC(COC2OC(CO)C(O)C(O)C2O)C(O)C(O)C1O)C=CC=C(/C)C(=O)OC3OC(COC4OC(CO)C(O)C(O)C4O)C(O)C(O)C3O SEBIKDIMAPSUBY-JAUCNNNOSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、着色金属酸化物ゲルを配合した化粧料に関する。
【０００２】
【従来の技術】
従来から、化粧料の着色剤として、無機顔料や有機顔料を含む有機系色素が使用されているが、これら着色剤は、化粧料へ配合される際、基材や調色助剤との間の親和性、表面活性、比重、結晶形、粒度などの相違により、製造、輸送、保管あるいは使用時に着色剤と基材とが互いに分離して、色分かれ、偏析、色差等が生じるという問題がある。そこで、近年では、この問題を解決するため、着色金属酸化物ゲル、例えば着色シリカゲルが配合された化粧料が提案されている。
【０００３】
この着色シリカゲルは、シリカゲルを各種の色素により着色を施したものであるが、その製造方法としては、例えば特開昭５５−３２７７５号に記載されているものがある。この方法は、以下の通りである。すなわち、先ず、原料の珪酸ソーダに着色剤を予め分散させ、それに酸（希硫酸）を加えて分散液とする。次に、この溶液を乳化剤が存在する分散媒中に撹拌注加し、昇温ゲル化して、シリカゲルを生成する。そして、この生成されたシリカゲルを洗浄して、副生混入しているソーダ塩（酸が希硫酸の場合芒硝）を除去した後、乾燥するものである。
【０００４】
【発明が解決しようとする課題】
しかしながら、従来からあるこの種の着色シリカゲルの製造方法は、アルカリ金属の珪酸塩を原料としているため、それに配合させる着色剤は、水不溶性の顔料か、またはアルカリ性水溶液に可溶でかつ中性若しくは酸性水溶液に不溶の色素に限定され、必ずしも適切な着色剤を選択することができないという問題点がある。
【０００５】
また、従来からある着色シリカゲルは、その骨格形成のため昇温や水熱処理等の熱的な処理、あるいは、熟成といった工程、および、その形状を球状とするための特別な工程を必要とするという問題点がある。
【０００６】
そこで、本発明は、従来に比べて複雑な製造工程や手間を必要としない着色シリカゲルが配合された化粧料を提供することを目的とする。
【０００７】
【課題を解決するための手段】
以上の目的を達成するために、本発明は、油剤からなる連続相と、水に対する溶解度が５％以下の有機溶媒に不溶、且つ、酸性若しくは中性水溶液に可溶である水溶性の有機系色素を含有する水溶液からなる分散相とから構成されるＷ／Ｏ型乳濁液に、金属アルコキシドを添加して生成される着色金属酸化物ゲルを配合している化粧料であって、前記水溶性の有機系色素が、クチナシ黄、クチナシ青、シソニン、グレープスキンエキストラクト、カカオ色素、ベニバナ黄、ハイビスカス色素、ラック色素、コチニール、シコン、ビートレッド、紅麹色素及びブラジリンからなる群より選択された天然色素、または、赤色２号、１０２号、１０６号、２２７号、５０２号、５０３号、５０４号、５０６号、黄色４号、５号、２０３号、４０２号、４０３号の（１）、４０７号、青色１号、２号、２０５号、緑色３号、４０１号、４０２号、褐色２０１号、紫色４０１号及び黒色４０１号からなる群より選択されたタール系色素であり、前記分散相には、酸触媒が含有されており、前記連続相には、ソルビタントリオレエートまたはソルビタンセスキオレエートからなる乳化剤が含有されている化粧料である。
【０００８】
前記有機系色素は、水に対する溶解度が５％以下の有機溶媒に不溶であること、酸性若しくは中性水溶液に可溶であることが好ましい。また、前記着色金属酸化物ゲルには、金属元素が、Ｓｉ、Ｔｉ、Ｚｒ、Ｎｉ、Ａｌ、Ｚｎのいずれかである金属アルコキシドを一種あるいは二種以上含んでいることが好ましい。
【０００９】
前記分散相には、酸触媒、有機高分子化合物、酸化防止剤、または、紫外線吸収剤等が含有されていることが好ましく、前記連続相には、乳化剤が含有されていることが好ましい。
【００１０】
以上のように本発明によれば、油剤および乳化剤を備える連続相と、水溶性の有機系色素を含有する水溶液とからなるＷ／Ｏ型乳濁液に、金属アルコキシドを添加すると、油剤に溶解した金属アルコキシドを含む連続相と、有機系色素を含む水溶液からなる分散相との界面で、金属アルコキシドが加水分解されて水親和性化合物が生成され、この水親和性化合物が分散相中で重縮合されることによって、着色金属酸化物ヒドロゲルが得られるのである。
【００１１】
この着色金属酸化物ヒドロゲルは、球状の分散相中で重縮合されることによって生成されるので、その着色金属酸化物ヒドロゲルが乾燥して得られる着色金属酸化物ゲルの形状が球状となる。また、界面活性剤や機械的な撹拌強度等によりその分散相の大きさを調整することによって、着色金属酸化物ゲルの粒子径を調整することができる。したがって、従来のように着色金属酸化物ゲルの粒子径を調整するための特別な成型工程を必要としない。この着色金属酸化物ゲルの粒子径は、０．１〜５００μｍの広範囲で調整することができる。さらに、この着色金属酸化物ゲルは、球状に形成されるため、球状粉体特有のローリング効果によって、化粧料使用時に良好な感触を得ることができる。
【００１２】
また、本発明によれば、分散相となる水相に溶解し、かつ、水相の均質性を保つことができる範囲内で、色素を金属酸化物ゲルに含有させることができるので、使用可能な色素の種類を大幅に増加することができる。
【００１３】
さらに、本発明では、出発原料に金属アルコキシドを使用するため、その製造工程において、アルコールと水のみが副生するだけである。これら副生物は、着色金属酸化物ヒドロゲルを濾過によって油剤と分離し、ｎ−ヘキサン等の水に対する溶解度の低い揮発性の有機溶剤によって洗浄した後、乾燥させるだけで除去することができる。
また、本発明の着色金属酸化物ヒドロゲルは、着色剤が含有された分散相中で重縮合されることによって生成されるので、保持されきれない着色剤の回収・再利用等の処理、または、水和金属酸化物による被覆などの色素の前処理を必要としない。
【００１４】
【発明の実施の形態】
本発明に係る金属アルコキシドは、シリコンアルコキシドまたはチタンアルコキシド等が好ましく、例えばＳｉ（ＯＲ）4、Ｔｉ（ＯＲ）4等が挙げられる。この他に、本発明に使用される金属アルコキシドとしては、Ｚｎ、Ａｌ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｒ等のアルコキシドがあり、それぞれの目的によってこれらは単独または混合して用いることができる。例えば、透明感を付与させたい場合にはＳｉを、反射率を高くしたい場合にはＴｉやＺｎを、強度、耐アルカリ性の向上が必要な場合にはＺｒを、耐候性をより向上させたい場合にはＮｉ等を混合することが有効である。金属アルコキシドのアルキル基（Ｒ）として、例えばメチル基、エチル基、プロピル基等がある。
【００１５】
酸触媒は、金属アルコキシドの加水分解反応の触媒となり、酢酸、塩酸、硫酸、硝酸等が好ましいが、反応性に高い金属アルコキシドを使用する場合は、触媒を用いなくても良い。
【００１６】
油剤としては、水に対する溶解度が５％以下の有機溶媒、例えばｎ−ヘキサン、シクロヘキサン、ベンゼン、トルエン、流動パラフィン等を用いることができるが、金属アルコキシド自体を用いることも可能である。
【００１７】
乳化剤は、上述のように調製される球状粒子の粒子径の大きさに影響を及ぼすものであるが、例えばソルビタントリオレエート、ソルビタンセスキオレエート等のＨＬＢが比較的低い非イオン性界面活性剤を用いると良い。また、所望する粒子径によっては、界面活性剤を使用しなくても良い。
【００１８】
本反応においては、着色金属酸化物ヒドロゲルの調製完了に至るまで室温で反応を進行させることが可能である。また、８０℃程度の高温域で反応速度を増大させることができるが、その温度については使用する着色剤の耐熱性を考慮する必要がある。また、着色金属酸化物ヒドロゲルの乾燥温度は、室温〜１２０℃程が好ましい。
【００１９】
本発明に使用される有機高分子化合物は、アミド基あるいはウレタン基を有するものが好ましく、例えばポリビニルピロリドン、ナイロン、ポリウレタン等がある。これらアミノ基あるいはウレタン基は、金属酸化物の表面水酸基と強い水素結合を形成するので、これらを使用することによって、機械的強度およびガスバリヤ性に優れている着色金属酸化物ゲルを調製することができる。
【００２０】
本発明に使用される着色剤としては、Ｗ／Ｏ型乳濁液中で金属アルコキシドの加水分解を酸性触媒の存在下に行わせるという点から、酸性若しくは中性水溶液に可溶で水に対する溶解度が５％以下の有機溶媒に不溶である天然色素及びタール系色素を示す。これには、例えば、天然色素として、クチナシ黄（主成分：クロシン）、クチナシ青、シソニン、グレープスキンエキストラクト、カカオ色素、ベニバナ黄、ハイビスカス色素、ラック色素（主成分：ラッカイン酸）、コチニール（主成分：カルミン酸）、シコン（主成分：シコニン）、ビートレッド、紅麹色素、ブラジリン等があり、タール系色素としては、赤色２号、１０２号、１０６号、２２７号、５０２号、５０３号、５０４号、５０６号、黄色４号、５号、２０３号、４０２号、４０３号の（１）、４０７号、青色１号、２号、２０５号、緑色３号、４０１号、４０２号、褐色２０１号、紫色４０１号、黒色４０１号等がある。
【００２１】
また、本発明に係る着色金属酸化物ゲルには、上記色素以外の他の成分を含有させても良い。その他の成分としては、例えば、酸化防止剤や紫外線吸収剤がある。酸化防止剤は、着色金属酸化物ヒドロゲルが分散相（水相）において形成されるため、Ｌ−アスコルビン酸等水溶性のものを使用するのが好ましい。また、紫外線吸収剤は、同様に、ベンゾフェノン−４等の水溶性のものを使用するのが好ましいが、水に不溶性のものであっても、アルコールに溶解するものであれば、上記分散相となる水溶液に若干のアルコールを添加し、紫外線吸収剤を溶解させＷ／Ｏ型乳濁液を調製することによって、着色金属酸化物ヒドロゲル内に保持させることができる。これら酸化防止剤や紫外線吸収剤を使用することにより、耐熱性、耐光性等の色調安定性をさらに向上させることができる。
【００２２】
本発明に係る着色金属酸化物ゲルの調製法は、金属アルコキシドの加水分解反応とそれに続く重縮合反応が連続的に起こることを利用したものである。
【００２３】
すなわち、反応の第１段階として、金属アルコキシドの加水分解反応がＷ／Ｏ型乳濁液の分散相と連続相との界面で起こり、水酸基を有する金属アルコキシドの加水分解物が生成される。この金属アルコキシドの加水分解物は、水に対する親和性を有するため、分散相に取り込まれ、その分散相中、若しくは、その付近で反応の第２段階である重縮合反応が起こる。
【００２４】
【実施例】
次に、本発明の実施例について説明する。
【００２５】
先ず、本発明の実施例に配合される着色金属酸化物ゲルの第１の例について説明する。この第１の着色金属酸化物ゲルは、以下のように生成される。すなわち、先ず、油剤である流動パラフィン２４０ｇに乳化剤（界面活性剤）であるソルビタントリオレエート（ＨＬＢ１．７）１．４４ｇを溶解させ、油剤からなる連続相を調製した。次に、これを高速回転万能撹拌機（特殊機化工業製：ＴＫオートホモミクサー）を用いて３０００ｒｐｍで撹拌させ、その中に別途調製された有機系色素である０．１Ｍのカルミン酸（コチニールの主成分）水溶液１．７５ｍｌと２Ｎの塩酸３．００ｍｌの混合溶液をゆっくりと滴下し、分散相にカルミン酸が溶解するＷ／Ｏ型乳濁液を調製した。次いで、この乳濁液をマグネティックスター（池田理化製：強磁力スターラー）により１０００ｒｐｍで撹拌を加えながら、その中に金属アルコキシドであるテトラエトキシシラン［Ｓｉ（ＯＣ2Ｈ5）4］３６．４７ｇを入れて、さらに２時間撹拌を続けて、着色シリカヒドロゲルを得た。次に、この着色シリカヒドロゲルを濾過し、ｎ−ヘキサンにより洗浄した。さらに、これを８０℃の空気中で２４時間、および、続いて五酸化二リンを用いて減圧下で２４時間乾燥し、赤色の着色シリカゲル１２．９ｇを得た。この着色シリカゲルの走査型電子顕微鏡写真を図１に示す。この第１の着色金属酸化物ゲル５．０ｇを２００ｍｌの塩化ナトリウム飽和水溶液に分散し２４時間撹拌したが、分散液への着色は殆ど見られなかった。また、この着色シリカゲルの洗浄・乾燥後の着色濃度が、洗浄・乾燥前の着色濃度に劣るということはなかった。さらに、この着色シリカゲルを１２０℃の空気中で６時間加熱し、加熱前のものと比較したが、変色や退色は見られなかった。またさらに、この着色シリカヒドロゲルを皮膚に塗布した場合、さらさらとした滑らかさを持つ良好な感触の粉体であった。
【００２６】
次に本発明の実施例に配合される着色金属酸化物ゲルの第２の例について説明する。この第２の着色金属酸化物ゲルは、以下のように製造される。先ず、油剤である流動パラフィン２００ｇに乳化剤（界面活性剤）であるソルビタントリオレエート（ＨＬＢ１．７）０．７２ｇを溶解させ、これをマグネティックスターにより１２００ｒｐｍで撹拌させることによって、油剤からなる連続相を生成した。次いで、この油剤の中に別途調製された有機系色素である０．１５Ｍの青色２号の水溶液２．２７ｍｌと２．５Ｎの塩酸２．５０ｍｌの混合液をゆっくりと滴下し、分散相に青色２号が溶解するＷ／Ｏ型乳濁液を調製した。続いて、この乳濁液を撹拌させながら、その中に金属アルコキシドであるテトラエトキシシラン［Ｓｉ（ＯＣ2Ｈ5）4］を入れて、さらに２．０時間撹拌を続けて着色シリカヒドロゲルを得た。次に、この着色シリカヒドロゲルを濾過し、ｎ−ヘキサンにより洗浄した。さらに、これを８０℃の空気中で２４時間、および、続いて五塩化二リンを用いて減圧下で２４時間乾燥し、着色シリカゲル１３．２ｇを得た。この着色シリカゲルの走査型電子顕微鏡写真を図２に示す。この第２の着色金属酸化物ゲル５．０ｇを２００ｍｌの塩化ナトリウム飽和水溶液に分散し２４時間撹拌したが、分散液への着色は殆ど見られなかった。また、この着色シリカゲルの洗浄・乾燥後の着色濃度が洗浄・乾燥前のそれに劣るということはなかった。さらに、この着色シリカゲルを１２０℃の空気中で６時間加熱し、加熱前のものと比較したが、変色や退色は見られなかった。またさらに、この着色シリカゲルを皮膚に塗布した場合、さらさらとした滑らかさを持つ良好な感触の粉体であった。
【００２７】
次に、これら第１および第２の着色金属酸化物ゲルを配合した本発明の実施例に係るアイシャドウについて説明する。このアイシャドウの成分は表１のとおりである。
【００２８】
【表１】
【００２９】
次に、上記第１および第２の着色金属酸化物ゲルとの比較例について説明する。先ず、以下のように第１比較例を製造し、これと上記第１の着色金属酸化物ゲルとの比較を行った。すなわち、第１の着色金属酸化物ゲルと同様の方法により、着色剤を配合しないシリカゲルを製造し、このシリカゲルと着色剤の重量比が第１の着色金属酸化物ゲルと同じになるように、カルミン酸のエタノール含有水溶液中にシリカゲルを分散させ、８０℃以下で分散媒を除去し、乾燥させカルミン酸／シリカゲル混合物を得た。
【００３０】
この例で得られたカルミン酸／シリカゲル混合物５．０ｇを２００ｍｌの塩化ナトリウム飽和水溶液に分散させたところ、カルミン酸／シリカゲル混合物の添加と同時に、分散液は着色された。また、この２４時間後、これを濾過・洗浄したところ、シリカゲルは殆ど着色されていなかった。さらに、カルミン酸／シリカゲル混合物を１２０℃の空気中で６時間加熱し、加熱前のものと比較したところ、著しい退色が見られた。
【００３１】
次に、以下のように第２比較例を製造し、これと上記第２の着色金属酸化物ゲルとの比較を行った。先ず、第２の着色金属酸化物ゲルと同様な方法により、着色剤を配合しないシリカヒドロゲルを製造し、これから得られるシリカゲルと着色剤の重量比が上記実施例２と同じになるように、このシリカヒドロゲルを青色２号のエタノール含有水溶液中に分散させ、８０℃以下で分散媒を除去し、乾燥させて青色２号／シリカゲル混合物を得た。
【００３２】
この例で得られた青色２号／シリカゲル混合物５．０ｇを２００ｍｌ塩化ナトリウム飽和水溶液に分散したところ、青色２号／シリカゲル混合物の添加と同時に、分散液は着色された。さらに、この２４時間後、これを濾過・洗浄したところ、シリカゲルに若干の着色が見られたが、分散液は著しく着色していた。
【００３３】
次に、本発明の実施例に係るアイシャドウの比較を行うため、上記第１および第２比較例を配合したアイシャドウを製造し、その比較を行った。この比較例のアイシャドウを湿度９０％ＲＨ／２５℃のチャンバー内に一週間放置し吸湿させた後、室温で乾燥させたところ、化粧料表面に色にじみが見られた。また、この化粧料を１２０℃の空気中で１２時間加熱し、加熱前のものと比較したところ、著しい退色が見られた。
【００３４】
以上のように、本実施例は、アイシャドウであるが、これに限定する必要はなく、例えばボディパウダー、粉白粉、固形白粉、頬紅、打粉、口紅、ローション、クリーム、パック等の化粧料でも良い。化粧料への各成分の配合率は、処方の相違や、所望する着色力に応じて適宜変更されるものである。また、本実施例においては、金属アルコキシドとして、テトラエトキシシランを使用したが、これに限定する必要はなく、例えばテトラメトキシシランやチタンエトキシド等を用いても良い。さらに、本実施例においては、着色剤としてカルミン酸または青色２号を使用したが、これに限定する必要はなく、有機系色素であれば、例えばシコンや黄色４号等を使用しても良い。
【図面の簡単な説明】
【図１】第１の着色金属酸化物ゲルの走査型電子顕微鏡写真（×２，０００）である。
【図２】第２の着色金属酸化物ゲルの走査型電子顕微鏡写真（×１，５００）である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cosmetic containing a colored metal oxide gel.
[0002]
[Prior art]
Conventionally, organic colorants including inorganic pigments and organic pigments have been used as colorants for cosmetics. These colorants, when incorporated into cosmetics, are used between base materials and toning aids. Due to differences in affinity, surface activity, specific gravity, crystal form, particle size, etc., the colorant and the substrate are separated from each other during production, transportation, storage or use, resulting in color separation, segregation, color difference, etc. is there. Therefore, in recent years, in order to solve this problem, cosmetics containing a colored metal oxide gel such as colored silica gel have been proposed.
[0003]
This colored silica gel is obtained by coloring silica gel with various pigments, and a method for producing the same is described in, for example, JP-A-55-32775. This method is as follows. That is, first, a colorant is dispersed in advance in a raw material sodium silicate, and an acid (dilute sulfuric acid) is added thereto to obtain a dispersion. Next, this solution is stirred and poured into a dispersion medium in which an emulsifier is present, and is heated to gel, thereby producing silica gel. Then, the produced silica gel is washed to remove the soda salt mixed as a by-product (sodium salt when the acid is dilute sulfuric acid) and then dried.
[0004]
[Problems to be solved by the invention]
However, since this type of conventional method for producing colored silica gel uses an alkali metal silicate as a raw material, the colorant to be blended therein is a water-insoluble pigment or soluble in an alkaline aqueous solution and neutral or There is a problem that it is limited to a dye insoluble in an acidic aqueous solution, and an appropriate colorant cannot always be selected.
[0005]
In addition, the conventional colored silica gel requires a process such as a thermal treatment such as a temperature rise or a hydrothermal treatment or an aging process for forming a skeleton, and a special process for making the shape spherical. There is a problem.
[0006]
The present invention has an object to provide a cosmetic coloring gel is formulated that does not require a complicated manufacturing process and labor as compared to traditional.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a continuous phase composed of an oil agent, a water-soluble organic system that is insoluble in an organic solvent having a water solubility of 5% or less, and is soluble in an acidic or neutral aqueous solution. A cosmetic comprising a W / O emulsion composed of an aqueous solution containing a dye and a colored metal oxide gel produced by adding a metal alkoxide, the water-soluble emulsion Organic organic pigments are selected from the group consisting of gardenia yellow, gardenia blue, shisonin, grape skin extract, cacao pigment, safflower yellow, hibiscus pigment, lac pigment, cochineal, sicon, beet red, red maple pigment and bradylin Natural pigments, or red 2, 102, 106, 227, 502, 503, 504, 506, yellow 4, 5, 203, 402 Tar system selected from the group consisting of No. 403 (1), No. 407, Blue No. 1, No. 2, 205, Green No. 3, No. 401, No. 402, Brown No. 201, Purple No. 401 and Black No. 401 The cosmetic is a pigment, wherein the dispersed phase contains an acid catalyst, and the continuous phase contains an emulsifier made of sorbitan trioleate or sorbitan sesquioleate .
[0008]
The organic dye is preferably insoluble in an organic solvent having a solubility in water of 5% or less, or soluble in an acidic or neutral aqueous solution. The colored metal oxide gel preferably contains one or more metal alkoxides whose metal elements are any one of Si, Ti, Zr, Ni, Al, and Zn.
[0009]
The dispersed phase preferably contains an acid catalyst, an organic polymer compound, an antioxidant, an ultraviolet absorber, or the like, and the continuous phase preferably contains an emulsifier.
[0010]
As described above, according to the present invention, when a metal alkoxide is added to a W / O emulsion composed of a continuous phase comprising an oil agent and an emulsifier and an aqueous solution containing a water-soluble organic pigment, it dissolves in the oil agent. The metal alkoxide is hydrolyzed to produce a water-affinity compound at the interface between the continuous phase containing the metal alkoxide and the dispersed phase composed of an aqueous solution containing an organic dye. By condensation, a colored metal oxide hydrogel is obtained.
[0011]
Since this colored metal oxide hydrogel is produced by polycondensation in a spherical dispersed phase, the shape of the colored metal oxide gel obtained by drying the colored metal oxide hydrogel becomes spherical. Moreover, the particle diameter of the colored metal oxide gel can be adjusted by adjusting the size of the dispersed phase by using a surfactant, mechanical stirring strength, or the like. Therefore, there is no need for a special molding step for adjusting the particle diameter of the colored metal oxide gel as in the prior art. The particle diameter of the colored metal oxide gel can be adjusted over a wide range of 0.1 to 500 μm. Furthermore, since this colored metal oxide gel is formed in a spherical shape, a good feel can be obtained when using cosmetics due to the rolling effect unique to the spherical powder.
[0012]
In addition, according to the present invention, the pigment can be contained in the metal oxide gel within the range in which it can be dissolved in the aqueous phase serving as the dispersed phase and the homogeneity of the aqueous phase can be maintained. The number of types of pigments can be greatly increased.
[0013]
Furthermore, in the present invention, since a metal alkoxide is used as a starting material, only alcohol and water are by-produced in the production process. These by-products can be removed by separating the colored metal oxide hydrogel from the oil agent by filtration, washing with a volatile organic solvent having low solubility in water such as n-hexane, and then drying.
Moreover, since the colored metal oxide hydrogel of the present invention is produced by polycondensation in a dispersed phase containing a colorant, the process such as recovery / reuse of a colorant that cannot be retained, or No pretreatment of the dye such as coating with a hydrated metal oxide is required.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The metal alkoxide according to the present invention is preferably silicon alkoxide or titanium alkoxide, and examples thereof include Si (OR) 4 and Ti (OR) 4 . In addition, examples of the metal alkoxide used in the present invention include alkoxides such as Zn, Al, Fe, Co, Ni, and Zr, and these can be used alone or in combination depending on the purpose. For example, if you want to give a sense of transparency, Si, if you want to increase the reflectivity Ti or Zn, if you need to improve strength and alkali resistance, Zr, if you want to further improve the weather resistance It is effective to mix Ni or the like. Examples of the alkyl group (R) of the metal alkoxide include a methyl group, an ethyl group, and a propyl group.
[0015]
The acid catalyst serves as a catalyst for the hydrolysis reaction of the metal alkoxide, and acetic acid, hydrochloric acid, sulfuric acid, nitric acid and the like are preferable. However, when a metal alkoxide having high reactivity is used, the catalyst may not be used.
[0016]
As the oil agent, an organic solvent having a solubility in water of 5% or less, such as n-hexane, cyclohexane, benzene, toluene, liquid paraffin, etc. can be used, but metal alkoxide itself can also be used.
[0017]
The emulsifier affects the size of the spherical particles prepared as described above. For example, a nonionic surfactant having a relatively low HLB such as sorbitan trioleate and sorbitan sesquioleate is used. It is good to use. Further, depending on the desired particle size, a surfactant may not be used.
[0018]
In this reaction, the reaction can be allowed to proceed at room temperature until the preparation of the colored metal oxide hydrogel is completed. Moreover, although the reaction rate can be increased in a high temperature range of about 80 ° C., it is necessary to consider the heat resistance of the colorant used for the temperature. The drying temperature of the colored metal oxide hydrogel is preferably about room temperature to 120 ° C.
[0019]
The organic polymer compound used in the present invention preferably has an amide group or a urethane group, and examples thereof include polyvinyl pyrrolidone, nylon and polyurethane. Since these amino groups or urethane groups form strong hydrogen bonds with the surface hydroxyl groups of the metal oxide, it is possible to prepare a colored metal oxide gel having excellent mechanical strength and gas barrier properties by using these amino groups or urethane groups. it can.
[0020]
The coloring agent used in the present invention, the hydrolysis of the metal alkoxide in W / O type emulsion in terms causing the presence of an acidic catalyst, solubility in water soluble in acidic or neutral aqueous solution Represents natural pigments and tar pigments that are insoluble in 5% or less of organic solvents. This includes, for example, gardenia yellow (main component: crocin), gardenia blue, shisonin, grape skin extract, cacao pigment, safflower yellow, hibiscus pigment, lac pigment (main component: laccaic acid), cochineal ( Active ingredient: carminic acid), lithospermum (main component: shikonin), beet red, Monascus pigment, there is brazilin, and examples of the tar pigments include red No. 2, No. 102, No. 106, 2 27 No. 502 No., 503, 504, 506, yellow 4, 5, 203, 402, 403 (1), 407, blue 1, 2, 205, green 3, 401, 402 No., brown 201, purple 401, black 401 and the like.
[0021]
Moreover, you may make the colored metal oxide gel which concerns on this invention contain other components other than the said pigment | dye. Examples of other components include an antioxidant and an ultraviolet absorber. As the antioxidant, since a colored metal oxide hydrogel is formed in a dispersed phase (aqueous phase), it is preferable to use a water-soluble one such as L-ascorbic acid. Similarly, it is preferable to use a water-soluble UV absorber such as benzophenone-4, but even if it is insoluble in water, it can be dissolved in alcohol as long as it is dissolved in the above-mentioned dispersed phase. A slight amount of alcohol is added to the resulting aqueous solution to dissolve the ultraviolet absorber to prepare a W / O type emulsion, which can be retained in the colored metal oxide hydrogel. By using these antioxidants and ultraviolet absorbers, color tone stability such as heat resistance and light resistance can be further improved.
[0022]
The method for preparing a colored metal oxide gel according to the present invention utilizes the fact that a hydrolysis reaction of a metal alkoxide and a subsequent polycondensation reaction occur continuously.
[0023]
That is, as a first stage of the reaction, a hydrolysis reaction of the metal alkoxide occurs at the interface between the dispersed phase and the continuous phase of the W / O emulsion, and a hydrolyzate of the metal alkoxide having a hydroxyl group is generated. Since the hydrolyzate of this metal alkoxide has an affinity for water, it is taken into the dispersed phase, and a polycondensation reaction, which is the second stage of the reaction, occurs in or near the dispersed phase.
[0024]
【Example】
Next, examples of the present invention will be described.
[0025]
First, the 1st example of the colored metal oxide gel mix | blended with the Example of this invention is demonstrated. This first colored metal oxide gel is produced as follows. That is, first, 1.44 g of sorbitan trioleate (HLB1.7) as an emulsifier (surfactant) was dissolved in 240 g of liquid paraffin as an oil agent to prepare a continuous phase composed of the oil agent. Next, this was stirred at 3000 rpm using a high-speed rotating universal stirrer (manufactured by Tokushu Kika Kogyo Co., Ltd .: TK auto homomixer), and 0.1 M carminic acid (cochineal) which is an organic dye separately prepared therein. A mixed solution of 1.75 ml of aqueous solution and 3.00 ml of 2N hydrochloric acid was slowly added dropwise to prepare a W / O type emulsion in which carminic acid was dissolved in the dispersed phase. Next, while stirring this emulsion at 1000 rpm with a magnetic star (manufactured by Ikeda Rika: strong magnetic stirrer), 36.47 g of tetraethoxysilane [Si (OC 2 H 5 ) 4 ], which is a metal alkoxide, was added therein. The mixture was further stirred for 2 hours to obtain a colored silica hydrogel. Next, this colored silica hydrogel was filtered and washed with n-hexane. Furthermore, this was dried in air at 80 ° C. for 24 hours and subsequently under reduced pressure using diphosphorus pentoxide for 24 hours to obtain 12.9 g of red colored silica gel. A scanning electron micrograph of the colored silica gel is shown in FIG. Although 5.0 g of this first colored metal oxide gel was dispersed in 200 ml of a saturated aqueous sodium chloride solution and stirred for 24 hours, the dispersion was hardly colored. Further, the coloring concentration after washing and drying of the colored silica gel was not inferior to the coloring concentration before washing and drying. Further, this colored silica gel was heated in air at 120 ° C. for 6 hours and compared with that before heating, but no discoloration or fading was observed. Furthermore, when this colored silica hydrogel was applied to the skin, it was a finely touched powder with a smooth smoothness.
[0026]
Next, the 2nd example of the colored metal oxide gel mix | blended with the Example of this invention is demonstrated. This second colored metal oxide gel is produced as follows. First, 0.72 g of sorbitan trioleate (HLB1.7) which is an emulsifier (surfactant) is dissolved in 200 g of liquid paraffin which is an oil agent, and this is stirred at 1200 rpm by a magnetic star. Generated. Next, a mixed solution of 2.27 ml of 0.15M blue No. 2 aqueous solution, which is a separately prepared organic dye, and 2.50 ml of 2.5N hydrochloric acid is slowly dropped into this oil agent, and blue is added to the dispersed phase. A W / O type emulsion in which No. 2 was dissolved was prepared. Subsequently, while stirring the emulsion, tetraethoxysilane [Si (OC 2 H 5 ) 4 ], which is a metal alkoxide, is put therein, and stirring is further continued for 2.0 hours to obtain a colored silica hydrogel. It was. Next, this colored silica hydrogel was filtered and washed with n-hexane. Further, this was dried in air at 80 ° C. for 24 hours and subsequently under reduced pressure using diphosphorus pentachloride for 24 hours to obtain 13.2 g of colored silica gel. A scanning electron micrograph of the colored silica gel is shown in FIG. This second colored metal oxide gel (5.0 g) was dispersed in 200 ml of a saturated aqueous sodium chloride solution and stirred for 24 hours, but almost no color was observed in the dispersion. Further, the coloring concentration of this colored silica gel after washing and drying was not inferior to that before washing and drying. Further, this colored silica gel was heated in air at 120 ° C. for 6 hours and compared with that before heating, but no discoloration or fading was observed. Furthermore, when this colored silica gel was applied to the skin, it was a fine-feeling powder with a smooth smoothness.
[0027]
Next, an eye shadow according to an example of the present invention in which these first and second colored metal oxide gels are blended will be described. Table 1 shows the components of this eye shadow.
[0028]
[Table 1]
[0029]
Next, a comparative example with the first and second colored metal oxide gels will be described. First, a first comparative example was manufactured as follows, and this was compared with the first colored metal oxide gel. That is, by a method similar to that for the first colored metal oxide gel, silica gel containing no colorant is produced, and the weight ratio of the silica gel to the colorant is the same as that of the first colored metal oxide gel. Silica gel was dispersed in an ethanol-containing aqueous solution of carminic acid, the dispersion medium was removed at 80 ° C. or lower, and dried to obtain a carminic acid / silica gel mixture.
[0030]
When 5.0 g of the carminic acid / silica gel mixture obtained in this example was dispersed in 200 ml of a saturated aqueous sodium chloride solution, the dispersion was colored simultaneously with the addition of the carminic acid / silica gel mixture. Further, after 24 hours, when this was filtered and washed, the silica gel was hardly colored. Furthermore, when the carminic acid / silica gel mixture was heated in air at 120 ° C. for 6 hours and compared with that before heating, significant fading was observed.
[0031]
Next, the second comparative example was manufactured as follows, and this was compared with the second colored metal oxide gel. First, a silica hydrogel containing no colorant is produced by the same method as the second colored metal oxide gel, and the weight ratio of silica gel and colorant obtained therefrom is the same as in Example 2 above. Silica hydrogel was dispersed in a blue No. 2 ethanol-containing aqueous solution, the dispersion medium was removed at 80 ° C. or lower, and dried to obtain a blue No. 2 / silica gel mixture.
[0032]
When 5.0 g of the blue No. 2 / silica gel mixture obtained in this example was dispersed in 200 ml of a saturated aqueous solution of sodium chloride, the dispersion was colored simultaneously with the addition of the blue No. 2 / silica gel mixture. Further, after 24 hours, when this was filtered and washed, the silica gel was slightly colored, but the dispersion was markedly colored.
[0033]
Next, in order to compare the eye shadows according to the examples of the present invention, eye shadows blended with the first and second comparative examples were manufactured and compared. When the eye shadow of this comparative example was left in a chamber with a humidity of 90% RH / 25 ° C. for one week to absorb moisture and then dried at room temperature, color blur was observed on the cosmetic surface. Moreover, when this cosmetic was heated in air at 120 ° C. for 12 hours and compared with that before heating, significant fading was observed.
[0034]
As described above, the present embodiment is an eye shadow, but it is not necessary to be limited thereto. For example, body powder, powdered white powder, solid white powder, blusher, powdered powder, lipstick, lotion, cream, pack, and other cosmetics good. The compounding ratio of each component in the cosmetic is appropriately changed according to the difference in prescription and the desired coloring power. In this embodiment, tetraethoxysilane is used as the metal alkoxide. However, the present invention is not limited to this. For example, tetramethoxysilane or titanium ethoxide may be used. Further, in this example, carminic acid or blue No. 2 was used as a colorant, but it is not necessary to limit to this, and for example, silicon or yellow No. 4 may be used as long as it is an organic dye. .
[Brief description of the drawings]
FIG. 1 is a scanning electron micrograph (× 2,000) of a first colored metal oxide gel.
FIG. 2 is a scanning electron micrograph (× 1,500) of a second colored metal oxide gel.
Claims (6)
前記水溶性の有機系色素が、クチナシ黄、クチナシ青、シソニン、グレープスキンエキストラクト、カカオ色素、ベニバナ黄、ハイビスカス色素、ラック色素、コチニール、シコン、ビートレッド、紅麹色素及びブラジリンからなる群より選択された天然色素、または、赤色２号、１０２号、１０６号、２２７号、５０２号、５０３号、５０４号、５０６号、黄色４号、５号、２０３号、４０２号、４０３号の（１）、４０７号、青色１号、２号、２０５号、緑色３号、４０１号、４０２号、褐色２０１号、紫色４０１号及び黒色４０１号からなる群より選択されたタール系色素であり、
前記分散相には、酸触媒が含有されており、
前記連続相には、ソルビタントリオレエートまたはソルビタンセスキオレエートからなる乳化剤が含有されている化粧料。It consists of a continuous phase composed of an oil agent and a dispersed phase composed of an aqueous solution containing a water-soluble organic dye that is insoluble in an organic solvent having a water solubility of 5% or less and is soluble in an acidic or neutral aqueous solution. A cosmetic comprising a colored metal oxide gel produced by adding a metal alkoxide to a W / O type emulsion,
The water-soluble organic pigment is selected from the group consisting of gardenia yellow, gardenia blue, shisonin, grape skin extract, cacao pigment, safflower yellow, hibiscus pigment, lac pigment, cochineal, sicon, beet red, red maple pigment and bradylin Selected natural pigments, or red 2, 102, 106, 227, 502, 503, 504, 506, yellow 4, 5, 203, 402, 403 ( 1), 407, blue 1, 2, 205, green 3, 401, 402, brown 201, purple 401 and black 401,
The dispersed phase contains an acid catalyst,
Cosmetics containing the emulsifier which consists of sorbitan trioleate or sorbitan sesquioleate in the said continuous phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23898395A JP3851365B2 (en) | 1995-08-25 | 1995-08-25 | Cosmetics containing colored metal oxide gel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23898395A JP3851365B2 (en) | 1995-08-25 | 1995-08-25 | Cosmetics containing colored metal oxide gel |
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| Publication Number | Publication Date |
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| JPH0959121A JPH0959121A (en) | 1997-03-04 |
| JP3851365B2 true JP3851365B2 (en) | 2006-11-29 |
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| JP23898395A Expired - Lifetime JP3851365B2 (en) | 1995-08-25 | 1995-08-25 | Cosmetics containing colored metal oxide gel |
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