JP3677610B2 - Iron oxide-containing titanium dioxide and composition containing the same - Google Patents
Iron oxide-containing titanium dioxide and composition containing the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、特定の平均粒子径及び比表面積をもつ酸化鉄含有二酸化チタン及びこれを含有する組成物に関し、更に詳しくは、適度な隠蔽力、紫外線遮断能及び分散性に優れ、組成物に配合した時にも、自然な仕上がり、つまり青白さがなく、適度な隠蔽力が得られる酸化鉄含有二酸化チタン及びこれを含有する組成物に関する。
【０００２】
【従来の技術】
従来、化学的に安定で、安全性の高い二酸化チタンは、白色顔料として各種業界で多く用いられてきている。たとえば、平均粒子径が０．２〜０．２５μｍの顔料級二酸化チタンはその高い隠蔽力や着色力が利用されており、また平均粒子径が０．０３〜０．０５μｍ程度の微粒子二酸化チタンは高い紫外線遮断能を持つことから、紫外線遮断剤として配合されている。しかしながら、顔料級二酸化チタンはその紫外線遮断効果を向上させるために、多量に配合すると、隠蔽力や着色力が高くなり、白くなりすぎ、その塗膜もいわゆる白塗り、白浮きなどが生じ不自然であった。また、微粒子二酸化チタンは高い紫外線遮断能を有するが、最近の紫外線防止に対する意識の高揚により、紫外線遮断効果を高めるため多量に配合すると、微粒子二酸化チタン特有の青白さが出て組成物及び塗膜等も青白く不自然な仕上がりになっていた。
これらの欠点を解消するために、ベンガラなどの無機顔料やタール色素等で着色された組成物も用いられてきたが、二酸化チタンと着色に用いたベンガラ等の着色顔料や色素との色別れを生じることがあった。また、顔料級二酸化チタン及び微粒子二酸化チタンは、分散性が良くないため、組成物に配合すると凝集し、特に化粧料などに於いては仕上がりが悪くなるという欠点も有していた。使用感に於いては、顔料級二酸化チタンを多量に配合すると、とまりがきつくなり、微粒子二酸化チタンを配合するとなめらかさがなくなるなどの欠点もあった。また更に、微粒子二酸化チタンは、ＵＶ−Ｂ領域（２９０〜３２０ｎｍ）に於ける遮断能は高いが、ＵＶ−Ａ領域（３２０〜４００ｎｍ）における遮断能はあまり高くないという特性がある。
これらの欠点を解消するために、従来、顔料級二酸化チタン及び微粒子二酸化チタンと酸化鉄との複合化（二酸化チタン表面への被覆や二酸化チタン結晶内部への複合）が試みられてきた。
【０００３】
【発明が解決しようとする課題】
しかしながら、顔料級二酸化チタン又は微粒子二酸化チタンと酸化鉄との複合化物においては色別れの問題は解消されたにもかかわらず、顔料級二酸化チタンが本来持つ塗膜の白塗り、白浮き、特には組成物に配合したときの凝集、止まりのきつさなどの欠点、又は微粒子二酸化チタンが本来持つ多量配合時の塗膜の青白さ、特には組成物中でのなめらかさの欠如、ＵＶ−Ａ領域（３２０〜４００ｎｍ）における遮断能不足等の欠点を解消するには十分ではなかった。特に、酸化鉄を二酸化チタン結晶内部に複合化した微粒子二酸化チタンでは、その表面活性がより高くなり、油剤の酸化などを招いていた。
これらの欠点を解消するために、顔料級二酸化チタンと微粒子二酸化チタンの粒子径の異なる二酸化チタン、及びこれらの二酸化チタンと酸化鉄との複合化物を組み合わせて紫外線遮断能を上げたり、更には形状の異なる二酸化チタンを組み合わせて官能面を向上させたりしているが、よりよい効果を得るためには、配合比や配合量を限定する必要があり、また、分散性を向上させるために予め油分散物や水分散物に調製して配合するなど煩雑な前処理を行うことから、満足できるものは得られていなかった。
そこで適度な隠蔽力、紫外線遮断能（ＵＶ−Ａ及びＵＶ−Ｂ遮断能）及び分散性に優れ、組成物に配合した時、青白さがなく適度に隠蔽されている状態である自然な仕上がりが得られる酸化鉄含有二酸化チタンが望まれていた。
【０００４】
【課題を解決するための手段】
かかる事情に鑑み、本発明者らは、鋭意研究を行った結果、特定の粒子径、比表面積及び特定の粒度分布、更には、特定の組成比をもつ酸化鉄含有二酸化チタンが適度な隠蔽力、紫外線遮断能（ＵＶ−Ａ及びＵＶ−Ｂ遮断能）及び分散性に優れ、これを含有する組成物自体及びその塗膜は、仕上がりが自然で、紫外線遮断能にも優れていることを見出し、本発明を完成するに至った。すなわち本発明は、平均粒子径が０．１０μｍを超えて０．１４μｍ以下で、比表面積が１０ｍ2／ｇ〜３０ｍ2／ｇの範囲に調製された酸化鉄含有二酸化チタンであり、且つ全粒子中７０重量％以上が平均粒子径の±０．０３μｍである酸化鉄含有二酸化チタンを含有することを特徴とする化粧料である。更には、上記の酸化鉄含有二酸化チタンが、二酸化チタン含量が９７．０〜９９．５重量％および酸化鉄含量が０．５〜３．０重量％の酸化鉄含有二酸化チタンである化粧料である。
【０００５】
以下、本発明を詳細に説明する。
本発明の平均粒子径が０．１０μｍを超えて０．１４μｍ以下で、且つ二酸化チタン含量が９７．０〜９９．５重量％で酸化鉄含量が０．５〜３．０重量％である酸化鉄含有二酸化チタン（以下「本発明の鉄含有二酸化チタン」と記述する）は、平均粒子径が０．１０μｍを超えて０．１４μｍ以下で、比表面積が１０ｍ2／ｇ〜３０ｍ2／ｇであり、且つ全粒子中の７０重量％以上が平均粒子径の±０．０３μｍであればその形状は球状、板状、扁平状、針状、紡錘状、不定形等いずれのものであっても構わない。
【０００６】
本発明の鉄含有二酸化チタンを調製する方法は、平均粒子径が０．１０μｍを超えて０．１４μｍ以下で、比表面積が１０ｍ2／ｇ〜３０ｍ2／ｇであり、且つ全粒子中の７０重量％以上が平均粒子径の±０．０３μｍである鉄含有二酸化チタンが得られれば、いずれの方法でも調製ができる。具体的には、まず硫酸チタニルあるいは四塩化チタンの加水分解、四塩化チタンの直接酸化ないしチタンアルコキシドの加水分解等の従来公知の方法によって、少なくとも０．１０μｍよりも小さい平均粒子径に調製された二酸化チタン得る。これをを焼成し、粒子を成長させることによって、その一次粒子の平均粒子径がおおよそ０．１０μｍ〜０．１４μｍの範囲内にあり、任意の平均粒子径を持つ二酸化チタンを得る。
次いで、この二酸化チタンに酸化鉄を含有する方法は、従来公知の方法を用いることができ特に限定するものではないが、前記所望の平均粒子径に調製された二酸化チタンの表面に硫酸鉄あるいは塩化鉄等の加水分解によって水酸化鉄を析出後、焼成する方法等を挙げることができる。または、前記方法によって、少なくとも０．１０μｍよりも小さい平均粒子径に調製された二酸化チタンの表面に硫酸鉄あるいは塩化鉄等の加水分解によって水酸化鉄を析出後、８３０℃〜８８０℃の範囲に於いて焼成する方法等を挙げることもできる。かかる方法によって得られた焼成物は、エネルギー流体ミル等の粉砕機による粉砕、水簸等による分級、または用途に応じて水洗あるいは表面処理を施すことができる。
【０００７】
本発明の鉄含有二酸化チタンの平均粒子径が０．１０μｍ以下の場合には、微粒子酸化チタンに特徴的な、青白く不自然な仕上がりの組成物となる傾向が顕著に現れ、０．１４μｍを超えると顔料級酸化チタンに特徴的な白塗りや白浮きが生じて厚ぼったく不自然な仕上がりの組成物となる傾向が顕著に現れる。
また、本発明の鉄含有二酸化チタンは、全粒子中の７０重量％（以下、単に「％」で示す）以上が平均粒子径の±０．０３μｍの範囲に含まれる。この範囲の鉄含有二酸化チタンは組成物に配合したとき、更に良好な分散状態が得られ、これを配合した組成物、特に化粧料は更に使用感及び紫外線遮断などの光学的特性が向上する。また、この粒度分布であれば、仕上がりがきれいな組成物とすることが可能である。
【０００８】
本発明の鉄含有二酸化チタンに含有される酸化鉄量は、０．５〜３．０重量％の範囲であれば組成物自体及びその塗膜の仕上がりが自然であり、紫外線遮断効果も優れるという点で特に好ましい。
【０００９】
本発明の鉄含有二酸化チタンは、更に目的に応じて、例えば金属酸化物、金属水酸化物、フッ素化合物、シリコーン系化合物、金属石鹸、ロウ、油脂、炭化水素等で表面処理して用いることが可能である。また、本発明の鉄含有二酸化チタンは、粒子径、比表面積又は形状の異なる２種以上を組み合わせて用いることができる。
【００１０】
【発明の実施の形態】
本発明の鉄含有二酸化チタンは、化粧料、塗料、インキ、プラスチック、繊維、ゴム等の各種組成物に配合することができる。
本発明の鉄含有二酸化チタンを含有する化粧料の剤型は、粉末状、粉末固型状、クリーム状、乳液状、ローション状、油性固型状、油性液状、ペースト状等のいずれであってもよく、特にメークアップ化粧料、スキンケア化粧料、ヘアケア化粧料等とすることが好ましい。効果がより発現する点ではメークアップ化粧料が最も好ましい。本発明のメークアップ化粧料としては、ファンデーション、白粉、ほほ紅、口紅、美爪料、アイ製品、日焼け止め化粧料、コンシーラー等が挙げられる。化粧料中の本発明の鉄含有二酸化チタンの配合量は、その化粧料の特質に応じて任意に選択されるが、官能上の特性及び効果の発現において、０．１〜５０％が好ましい。
【００１１】
本発明の化粧料には通常化粧料に用いられる成分を必要に応じて適宜配合することが出来る。粉体としては、例えば、タルク、カオリン、セリサイト、マイカ、炭酸マグネシウム、炭酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム、ケイ酸アルミニウムマグネシウム、ケイ酸カルシウム、無水ケイ酸等の無機体質顔料、酸化亜鉛等の無機白色顔料、ベンガラ、黄酸化鉄、黒酸化鉄、グンジョウ、コンジョウ、カーボンブラック等の無機着色顔料、雲母チタン、酸化鉄雲母チタン、オキシ塩化ビスマス等のパール剤、タール系色素、天然色素等の有機着色顔料、ナイロンパウダー、シルクパウダー、ポリスチレン、ポリエチレンパウダー、結晶セルロース、Ｎ−アシルリジン等の有機粉体が挙げられる。なお、これら粉体は、フッ素化合物、シリコーン系化合物、金属石鹸、ロウ、油脂、炭化水素等を用いて表面処理を施したものであってもよい。また、特に本発明の鉄含有二酸化チタンの利点を損なわない範囲において、様々な平均粒子径及び粒度分布や形状を有する顔料級二酸化チタン又は微粒子二酸化チタン及びこれらの酸化鉄等との複合化物を併用することも可能である。
油分としては、例えば、オリーブ油、ひまし油、ホホバ油、ミンク油等の油脂類、ミツロウ、ラノリン、キャンデリラロウ等のロウ類、流動パラフィン、スクワラン、ワセリン、パラフィンワックス、マイクロクリスタリンワックス等の炭化水素、ステアリン酸、オレイン酸等の脂肪酸、セタノール、ステアリルアルコール、ベヘニルアルコール等の高級アルコール、ミリスチン酸イソプロピル、トリオクタン酸グリセリル、トリイソステアリン酸ジグリセリル等のエステル類、ラノリン脂肪酸イソプロピル、ラノリンアルコール等のラノリン誘導体、ジメチルポリシロキサン、メチルフェニルポリシロキサン等のシリコーン油、ポリオキシアルキレン変性やアルキル変性したシリコーン油、パーフルオロデカン、パーフルオロオクタン等のフッ素系油類等を挙げることができる。
その他、有機溶剤、樹脂、可塑剤、紫外線吸収剤、酸化防止剤、防腐剤、界面活性剤、保湿剤、香料、水、アルコール、増粘剤等が挙げられる。
【００１２】
【実施例】
次に実施例を挙げて本発明を更に説明するが、本発明はこれによって何ら限定されるものではない。
【００１３】
製造実施例１：本発明の鉄含有二酸化チタン（０．１２μｍ鉄含有二酸化チタン）
常法により硫酸チタニル溶液を加熱分解し、ろ過、洗浄した含水酸化チタンスラリーに苛性ソーダ溶液を攪拌しながら投入し、９５℃で２時間加熱した。次いでこの処理物を十分洗浄して得られたスラリーに塩酸を攪拌しながら投入し、９５℃で２時間加熱しチタニアゾルを作成した。この様にして得られたチタニアゾルに更に塩化第一鉄水溶液を添加しｐＨ７．０に調整した。熟成後、ろ過及び洗浄をおこない、次いで１０５℃で乾燥した。これを電気炉にて８５０℃で２時間焼成した後、エアージェットミルにて粉砕することで平均粒子径０．１２μｍの鉄含有二酸化チタンを得た。次いで水簸による分級をおこない全粒子中の７０％以上が平均粒子径の±０．０３μｍの範囲にはいるように調整し、再び乾燥し、粉砕をおこなった。
上記の方法で調製された鉄含有二酸化チタンを透過型電子顕微鏡を用いて粒子径及びその分布を測定したところ、平均粒子径は０．１２μｍで、全粒子中７０％以上が平均粒子径の±０．０３μｍの範囲にはいることが確認された。
また、ＢＥＴ法により比表面積を測定したところ、比表面積は１０ｍ2／ｇ〜３０ｍ2／ｇの範囲にはいることが確認された。
【００１４】
製造比較例１：０．１２μｍ酸化鉄・二酸化チタン混合物
顔料級二酸化チタン｛酸化チタンＪＲ−７０１：テイカ社製（平均粒子径０．２５μｍ）｝３１．４重量部と微粒子二酸化チタン｛微粒子酸化チタンＰ−２５：デグッサ社製（平均粒子径０．０３μｍ）｝６７．１重量部を混合攪拌し、平均粒子径を０．１２μｍとした二酸化チタン混合物を得た。これに、更にベンガラ１．５重量部を混合攪拌し、平均粒子径が約０．１２μｍの酸化鉄及び二酸化チタン混合物を得た。
ＢＥＴ法により比表面積を測定したところ、比表面積は３０ｍ2／ｇを超えるものであった。
【００１５】
製造比較例２：鉄含有顔料級二酸化チタン
顔料級二酸化チタン｛酸化チタンＪＲ−７０１：テイカ社製（平均粒子径０．２５μｍ）｝を用い、特公平４−５００１号公報の実施例１に記載されている方法に準じて、二酸化チタンと酸化鉄の比が９８：２の鉄含有顔料級二酸化チタンを得た。
【００１６】
製造比較例３：鉄含有微粒子二酸化チタン
特開平５−３３０８２５号公報の実施例に準じて、平均粒子径０．０３μｍ，酸化鉄含量３％の鉄含有微粒子二酸化チタンを得た。
【００１７】
（試験方法）
製造実施例１の０．１2μｍ鉄含有二酸化チタンと製造比較例１〜３記載の各鉄含有（及び混合）二酸化チタンについて特定波長域における遮断率及び分散性を測定した。
【００１８】
（１）遮断率
石英板上にポリビニルピロリドンのアルコール溶液を２５μｍのドクターブレードを用いて塗布した。アルコール蒸発後、粘着面に柔らかいブラシにて各鉄含有二酸化チタン（及び混合物）を均一に塗布し、測定用検体とした。
上記検体について島津自記分光光度計ＵＶ−２６５ＦＷ及び同ユニット積分計ＩＳＲ−２６０にて透過率を測定した。測定波長は可視光領域（４００〜８００ｎｍ）、ＵＶ−Ａ領域（３２０ｎｍ〜４００ｎｍ）、ＵＶ−Ｂ領域（２９０ｎｍ〜３２０ｎｍ）とし、分光曲線を測定し、各領域の透過面積をチャートより求めた。遮断率は、下記式（１）により算出し、その結果を表１に示した。
【００１９】
【数１】
（２）分散性
各鉄含有二酸化チタンを１０％濃度で１，３−ブチレングリコール中に混合し、ロールミルを用いて１回分散させたものを測定用検体とし、下記判定基準に従って、目視にて分散性を判定した。その結果も併せて表１に示した。
（判定基準）
○：分散性が良好で、凝集が観察されない。
△：分散性は良好であるが、少し凝集が観察される。
×：分散性が悪く、かなり凝集が観察される。
【００２１】
【表１】
表１から明かなように、製造実施例１の０．１２μｍ鉄含有二酸化チタンは可視光においては、製造比較例１の酸化鉄・二酸化チタン混合物や製造比較例２の鉄含有顔料級二酸化チタンよりも遮断率が低く、透明性が高いことが示され、また紫外線領域においては、製造比較例１の酸化鉄・二酸化チタン混合物や製造比較例２の鉄含有顔料級二酸化チタンよりも遮断率が高いことが示された。製造比較例３の鉄含有微粒子二酸化チタンは可視光領域では遮断率が低く透明性は高いが、透明性が高すぎて隠蔽力は不足している。又、紫外線領域ではＵＶ−Ｂ領域では本発明の鉄含有二酸化チタンよりも遮断率が高いが、ＵＶ−Ａ領域では本発明の鉄含有二酸化チタンの方が遮断率が高いことが示された。
これらの鉄含有（混合）二酸化チタンを肌上に塗布したとき、その塗布膜の外観は、製造比較例３の鉄含有微粒子二酸化チタンでは隠蔽力が不足し、製造比較例１の酸化鉄・二酸化チタン混合物や製造比較例２の鉄含有顔料級二酸化チタンは白く浮いてしまい不自然な仕上がりであったのに対し、製造実施例１の鉄含有二酸化チタンでは青白さのない適度な白さの自然な外観が得られた。
本発明の鉄含有二酸化チタンは、可視光線の中〜長波長の光散乱が短波長光散乱に比べて低いことから、肌色を構成する主たる波長域（黄色〜赤色）の光は化粧膜を透過しやすく、且つ、くすんだ肌、色素沈着した肌等が有する青色系の短波長の光を化粧塗膜中で散乱するため、自然で健康的な肌色を演出する効果に優れている。
【００２３】
また、分散性については、製造比較例１〜３の酸化鉄・二酸化チタン混合物，鉄含有顔料級二酸化チタン、及び鉄含有微粒子二酸化チタンは、凝集が観察されたのに対し、製造実施例１の鉄含有二酸化チタンは、分散性も良好で、凝集が観察されなかった。
【００２４】
更に、塗布時の感触は、製造比較例１の酸化鉄・二酸化チタン混合物はのびが悪く、きしみ感があり、製造比較例２の鉄含有顔料級二酸化チタンはのびが悪く止まりがきつく、また製造比較例３の鉄含有微粒子二酸化チタンではきしみ感があるのに対し、製造実施例１の本発明の鉄含有二酸化チタンではのびが良くソフトな感触であった。
【００２５】
製造実施例２：本発明の鉄含有二酸化チタン（０．１４μｍ鉄含有二酸化チタン）
製造実施例１の焼成温度を８８０℃に変更することで平均粒子径０．１４μｍの鉄含有二酸化チタンを得た。
上記方法により得られた鉄含有二酸化チタンをＢＥＴ法により比表面積を測定したところ、比表面積は１０ｍ2／ｇ〜３０ｍ2／ｇの範囲にはいることが確認された。
【００２６】
実施例１〜４及び比較例１〜３ パウダーファンデーション
表２に示す組成のパウダーファンデーションを調製し、使用性（のび・ひろがり）、隠蔽力（カバー力）、自然な仕上がり（白く厚ぼったさのなさ）、くすみのなさ（青白さのなさ）について官能評価を行い、紫外線遮断効果については透過率を測定し判定した。その結果も併せて表２に示す。
【００２７】
【表２】
（製法）
Ａ：成分（１）〜（８）を混合する。
Ｂ：成分（９）〜（１２）を加熱溶解し混合する。
Ｃ：ＡとＢを混合分散し、金皿に充填する。
【００２９】
（評価方法）
（評価項目）
１．のび・ひろがり
２．カバー力
３．白く厚ぼったさのなさ
４．青白さのなさ
５．紫外線遮断効果
【００３０】
（評価及び評価基準）
評価項目１〜４は、専門パネル１６人による使用テストを行ない、５段階評価の平均点に基づいて下記基準で判定した。
評価基準
５点：非常に良好
４点：良好
３点：普通
２点：やや不良
１点：不良
判定基準
◎：４．０〜５．０点
○：３．０〜４．０点未満
△：２．０〜３．０点未満
×：１．０〜２．０点未満
【００３１】
評価項目５は各試料について製造実施例１及び製造比較例１〜３における試験方法を用い、以下のように紫外線遮断効果を判定した。
◎：紫外部の透過率が非常に低く、遮断効果が高い。
○：紫外部の透過率が低く、遮断効果がやや高い。
△：紫外部の透過率がやや高く、遮断効果がやや低い
×：紫外部の透過率が高く、遮断効果が劣っている。
【００３２】
本発明の０．１２μｍ鉄含有二酸化チタンを配合した実施例１〜３及び０．１４μｍの鉄含有二酸化チタンを配合した実施例４のパウダーファンデーションは比較例１〜３に比べ、使用性、隠蔽力、自然な仕上がり、くすみのなさ、紫外線遮断効果の点で優れたものであった。
【００３３】
実施例５及び比較例４〜５：Ｏ／Ｗ型日焼け止め化粧料
表３に示す組成のＯ／Ｗ型日焼け止め化粧料を調製し、使用性（のび・ひろがり）、隠蔽力（カバー力）、自然な仕上がり（白く厚ぼったさのなさ）、くすみのなさ（青白さのなさ）、紫外線遮断効果について実施例１〜４及び比較例１〜３の評価方法と同様の評価を行なった。但し、紫外線遮断効果に用いた試料は石英板に直接ドクターブレードを使用して塗布した。その結果も併せて表３に示す。
【００３４】
【表３】
（製法）
Ａ：成分（１）〜（９）を加熱し混合分散する。
Ｂ：成分（１０）〜（１３）を混合分散する。
Ｃ：ＡとＢを混合し乳化する。
Ｄ：Ｃに（１４）〜（１７）を加えて混合する。
本発明の０．１２μｍ鉄含有二酸化チタンを配合した実施例５のＯ／Ｗ型日焼け止め乳液は比較例４〜５に比べ使用性、隠蔽力、自然な仕上がり、くすみのなさ、紫外線遮断効果の優れたものであった。
【００３６】
実施例６及び比較例６〜７：Ｗ／Ｏ型クリーム
表４に示す組成のＷ／Ｏ型クリームを調製し、使用性（のび・ひろがり）、隠蔽力（カバー力）、自然な仕上がり（白く厚ぼったさのなさ）、くすみのなさ（青白さのなさ）、紫外線遮断効果について実施例１〜４及び比較例１〜３の評価方法と同様の評価を行なった。但し、紫外線遮断効果に用いた試料は、石英板に直接ドクターブレードを使用して塗布した。
【００３７】
【表４】
（製法）
Ａ：（１）〜（９）を加えて混合分散する。
Ｂ：Ａに（１２）〜（１３）を加えて乳化する。
Ｃ：Ｂに（１０）〜（１１）を加えて混合する。
本発明の０．１２μｍ鉄含有二酸化チタンを配合した実施例６のＷ／Ｏ型クリームは比較例６〜７に比べて、使用性、隠蔽力、自然な仕上がり、くすみのなさ、紫外線遮断効果の優れたものであった。
【００３９】
実施例７：コンシーラー
（成分） （％）
１．キャンデリラワックス ４．０
２．パラフィンワックス ６．０
３．ワセリン ５．０
４．メチルポリシロキサン １０．０
５．スクワラン １０．０
６．トリイソステアリン酸ジグリセリル 残量
７．製造実施例１の鉄含有二酸化チタン ４５．０
８．ナイロンパウダー ５．０
９．着色顔料 適量
１０．抗酸化剤 適量
１１．香料 適量
【００４０】
（製法）
成分（１）〜（６）を加熱溶解した後、（７）〜（１１）を加え均一に混合し、冷却固化してコンシーラーを得た。
本発明のコンシーラーは、使用性、隠蔽力、自然な仕上がり、くすみのなさ、紫外線遮断効果共に優れたものであった。
【００４１】
実施例８：口紅
（成分） （％）
１．マイクロクリスタリンワックス ９．０
２．キャンデリラワックス ６．０
３．パラフィンワックス ５．０
４．トリイソステアリン酸ジグリセリル 残量
５．トリオクタン酸グリセリル ２０．０
６．スクワラン ３．０
７．赤色２０２号 ３．０
８．黄色４号 １．０
９．製造実施例１の鉄含有二酸化チタン ０．５
１０．美容成分 適量
１１．香料 適量
【００４２】
（製法）
成分（１）〜（６）を１１０℃〜１２０℃に加熱溶解した後、（７）〜（１１）を加え均一に混合し、成型用の型に流し込み、冷却固化して口紅を製造した。
本発明の口紅は、使用性、隠蔽力、自然な仕上がり、くすみのなさ、紫外線遮断効果共に優れたものであった。
【００４３】
実施例９：日焼け止め用パウダーファンデーション
（成分） （％）
１．製造実施例１の鉄含有二酸化チタン ２０．０
２．微粒子酸化チタン ５．０
３．タルク ２０．０
４．マイカ 残量
５．着色顔料 適量
６．ワセリン １．０
７．流動パラフィン １．０
８．パラメトキシケイ皮酸−２エチルヘキシル ２．０
９．ジメチルポリシロキサン １．０
１０．美容成分 適量
１１．香料 適量
【００４４】
（製法）
Ａ：成分（１）〜（５）を混合する。
Ｂ：成分（６）〜（１１）を加熱溶解する。
Ｃ：ＡとＢを混合分散し、金皿に充填して日焼け止め用パウダーファンデーションを製造した。
本発明の日焼け止め用パウダーファンデーションは、適度な隠蔽力、自然な仕上がり、くすみのなさ、紫外線遮断効果、使用性に優れたものであった。
【００４５】
【発明の効果】
本発明の鉄含有二酸化チタンを配合した化粧料は、適度な隠蔽力を有すると共に紫外線遮断能（ＵＶ−Ａ及びＵＶ−Ｂ遮断能）及び分散性に優れ、自然な仕上がりが得られるものであった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an iron oxide-containing titanium dioxide having a specific average particle size and specific surface area and a composition containing the same, and more specifically, it has excellent moderate hiding power, ultraviolet blocking ability and dispersibility, and is incorporated into the composition. The present invention also relates to iron oxide-containing titanium dioxide and a composition containing the same, which have a natural finish, that is, no bluish white and can provide an appropriate hiding power.
[0002]
[Prior art]
Conventionally, titanium dioxide that is chemically stable and highly safe has been widely used in various industries as a white pigment. For example, pigment-grade titanium dioxide having an average particle size of 0.2 to 0.25 μm uses its high hiding power and coloring power, and fine particle titanium dioxide having an average particle size of about 0.03 to 0.05 μm is used. Because of its high UV blocking ability, it is formulated as a UV blocking agent. However, pigment-grade titanium dioxide improves its UV blocking effect, so if it is added in a large amount, the hiding power and coloring power become high and it becomes too white, and the coating film also becomes so-called white coating, white floating, etc. Met. Fine titanium dioxide has a high UV blocking ability, but due to the recent increase in awareness of UV protection, when added in a large amount to increase the UV blocking effect, the composition and coating film exhibit a bluish white characteristic of fine titanium dioxide. Etc. were also pale and unnatural.
In order to eliminate these drawbacks, compositions colored with inorganic pigments such as Bengala and tar dyes have also been used, but the color separation between titanium dioxide and colored pigments and dyes such as Bengala used for coloring has been avoided. It sometimes occurred. In addition, pigment grade titanium dioxide and fine particle titanium dioxide have poor dispersibility, so that they aggregate when blended into a composition, and have the disadvantage that the finish is particularly poor in cosmetics. In terms of the feeling in use, when pigment-grade titanium dioxide is blended in a large amount, the anchoring becomes tight, and when fine-particle titanium dioxide is blended, there is a drawback that smoothness is lost. Furthermore, fine particle titanium dioxide has a high blocking ability in the UV-B region (290 to 320 nm), but has a characteristic that the blocking ability in the UV-A region (320 to 400 nm) is not so high.
In order to eliminate these disadvantages, attempts have been made in the past to combine pigment grade titanium dioxide and fine particle titanium dioxide with iron oxide (coating on the surface of titanium dioxide or compounding inside titanium dioxide crystals).
[0003]
[Problems to be solved by the invention]
However, in the composite of pigment grade titanium dioxide or fine particle titanium dioxide and iron oxide, the problem of color separation has been solved, but the white coating of the coating film inherent to pigment grade titanium dioxide, white floating, especially Defects such as agglomeration and tightness when blended into the composition, or the paleness of the coating film when fine titanium dioxide is inherently blended in a large amount, particularly lack of smoothness in the composition, UV-A region (320 to 400 nm) was not sufficient to eliminate defects such as insufficient blocking ability. In particular, fine particle titanium dioxide in which iron oxide is compounded inside a titanium dioxide crystal has a higher surface activity, leading to oxidation of the oil.
In order to eliminate these disadvantages, the combination of titanium dioxide with different particle diameters of pigment grade titanium dioxide and fine particle titanium dioxide, and a composite of these titanium dioxide and iron oxide increases the UV blocking ability, and further improves the shape. In order to obtain a better effect, it is necessary to limit the blending ratio and blending amount, and in order to improve dispersibility, it is necessary to improve the sensory surface by combining different titanium dioxides. Since a complicated pretreatment such as preparation and blending into a dispersion or an aqueous dispersion is performed, satisfactory products have not been obtained.
Therefore, it has an excellent hiding power, ultraviolet blocking ability (UV-A and UV-B blocking ability) and dispersibility, and when blended into the composition, it has a natural finish that is not covered with blue and white and is appropriately hidden. The resulting iron oxide-containing titanium dioxide has been desired.
[0004]
[Means for Solving the Problems]
In view of such circumstances, the present inventors have conducted intensive research. As a result, the iron oxide-containing titanium dioxide having a specific particle size, specific surface area and specific particle size distribution, and a specific composition ratio has an appropriate hiding power. It has been found that it has excellent ultraviolet blocking ability (UV-A and UV-B blocking ability) and dispersibility, and the composition itself and the coating film containing it have a natural finish and excellent ultraviolet blocking ability. The present invention has been completed. That is, the present invention provides the following 0.14μm average particle diameter exceeds the 0.10 .mu.m, a iron oxide-containing titanium dioxide prepared in a range specific surface area of 10m 2 / g~30m 2 / g, and the total particles It is a cosmetic characterized by containing iron oxide-containing titanium dioxide having an average particle size of ± 0.03 μm in an amount of 70% by weight or more. Further, in the cosmetic , wherein the iron oxide-containing titanium dioxide is an iron oxide-containing titanium dioxide having a titanium dioxide content of 97.0 to 99.5% by weight and an iron oxide content of 0.5 to 3.0% by weight. There is .
[0005]
Hereinafter, the present invention will be described in detail.
Oxidation having an average particle diameter of more than 0.10 μm and not more than 0.14 μm, titanium dioxide content of 97.0 to 99.5% by weight and iron oxide content of 0.5 to 3.0% by weight of the present invention iron-containing titanium dioxide (hereinafter referred to as "iron-containing titanium dioxide of the present invention") is, 0.14 .mu.m or less average particle diameter exceeds the 0.10 .mu.m, specific surface area of at 10m 2 / g~30m 2 / g And 70% by weight or more of all particles have an average particle diameter of ± 0.03 μm, the shape may be any of spherical, plate-like, flat, needle-like, spindle-like, irregular shape, etc. I do not care.
[0006]
Methods of preparing iron-containing titanium dioxide of the present invention has an average particle diameter exceeds the 0.10μm at 0.14μm or less and a specific surface area of 10m 2 / g~30m 2 / g, and 70 in the total grain If iron-containing titanium dioxide having an average particle size of ± 0.03 μm in weight percent or more is obtained, it can be prepared by any method. Specifically, it was first prepared to have an average particle size of at least smaller than 0.10 μm by a conventionally known method such as hydrolysis of titanyl sulfate or titanium tetrachloride, direct oxidation of titanium tetrachloride or hydrolysis of titanium alkoxide. Get titanium dioxide. By baking this and growing the particles, the average particle diameter of the primary particles is approximately in the range of 0.10 μm to 0.14 μm, and titanium dioxide having an arbitrary average particle diameter is obtained.
Next, the method of containing iron oxide in titanium dioxide can be a conventionally known method, and is not particularly limited. However, the surface of titanium dioxide prepared to have the desired average particle size is coated with iron sulfate or chloride. An example is a method in which iron hydroxide is precipitated by hydrolysis of iron or the like and then fired. Alternatively, iron hydroxide is precipitated by hydrolysis of iron sulfate or iron chloride on the surface of titanium dioxide prepared to have an average particle size of at least smaller than 0.10 μm by the above method, and then in the range of 830 ° C. to 880 ° C. In this case, a firing method can also be mentioned. The fired product obtained by such a method can be pulverized by a pulverizer such as an energetic fluid mill, classified by a water tank or the like, or washed with water or surface-treated depending on the application.
[0007]
When the average particle size of the iron-containing titanium dioxide of the present invention is 0.10 μm or less, a tendency to become a pale and unnatural finish composition characteristic of fine particle titanium oxide appears remarkably, exceeding 0.14 μm. As a result, the white coating and white floating characteristic of pigment grade titanium oxide are generated, and the tendency to become a thick and unnaturally finished composition is prominent.
Further, in the iron-containing titanium dioxide of the present invention, 70% by weight (hereinafter simply indicated by “%”) or more in all particles is included in the range of ± 0.03 μm of the average particle diameter. When iron-containing titanium dioxide in this range is blended into the composition, a better dispersion state can be obtained, and the composition blended with this, particularly cosmetics, further improves optical properties such as feeling of use and ultraviolet blocking. Further, with this particle size distribution, it is possible to obtain a composition with a fine finish.
[0008]
If the amount of iron oxide contained in the iron-containing titanium dioxide of the present invention is in the range of 0.5 to 3.0% by weight, the composition itself and the finish of the coating film are natural, and the ultraviolet blocking effect is also excellent. Particularly preferred in terms.
[0009]
The iron-containing titanium dioxide of the present invention may be used after being surface-treated with, for example, a metal oxide, a metal hydroxide, a fluorine compound, a silicone compound, a metal soap, wax, fats and oils, or the like, depending on the purpose. Is possible. Moreover, the iron-containing titanium dioxide of this invention can be used in combination of 2 or more types from which a particle diameter, a specific surface area, or a shape differs.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The iron-containing titanium dioxide of the present invention can be blended in various compositions such as cosmetics, paints, inks, plastics, fibers and rubbers.
The cosmetic dosage form containing the iron-containing titanium dioxide of the present invention is any of powder, powder solid, cream, emulsion, lotion, oily solid, oily liquid, paste, etc. In particular, makeup cosmetics, skin care cosmetics, hair care cosmetics and the like are preferable. Makeup cosmetics are most preferred in terms of more effective effects. Examples of the makeup cosmetics of the present invention include foundations, white powder, cheeks, lipsticks, beauty nails, eye products, sunscreen cosmetics, concealers and the like. Although the compounding quantity of the iron-containing titanium dioxide of this invention in cosmetics is arbitrarily selected according to the characteristic of the cosmetics, 0.1-50% is preferable in the expression of a sensory characteristic and an effect.
[0011]
In the cosmetic of the present invention, components usually used in cosmetics can be appropriately blended as necessary. Examples of powders include inorganic extender pigments such as talc, kaolin, sericite, mica, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, magnesium magnesium silicate, calcium silicate, and anhydrous silicic acid, zinc oxide Inorganic white pigments such as Bengala, yellow iron oxide, black iron oxide, Gunjo, conger, carbon black, etc., pearlescent agents such as mica titanium, iron oxide mica titanium, bismuth oxychloride, tar dyes, natural dyes Organic pigments such as nylon powder, silk powder, polystyrene, polyethylene powder, crystalline cellulose, N-acyl lysine and the like. These powders may be subjected to surface treatment using a fluorine compound, a silicone compound, metal soap, wax, fats and oils, hydrocarbons, or the like. In addition, in the range that does not impair the advantages of the iron-containing titanium dioxide of the present invention, pigment grade titanium dioxide or fine particle titanium dioxide having various average particle diameters and particle size distributions and shapes, and composites thereof with these iron oxides are used in combination. It is also possible to do.
Examples of oils include oils and fats such as olive oil, castor oil, jojoba oil and mink oil, waxes such as beeswax, lanolin and candelilla wax, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax and microcrystalline wax, Fatty acids such as stearic acid and oleic acid, higher alcohols such as cetanol, stearyl alcohol and behenyl alcohol, esters such as isopropyl myristate, glyceryl trioctanoate and diglyceryl triisostearate, lanolin derivatives such as lanolin fatty acid isopropyl and lanolin alcohol, dimethyl Silicone oil such as polysiloxane and methylphenylpolysiloxane, silicone oil modified with polyoxyalkylene or alkyl, perfluorodecane, perfluorooctane, etc. Tsu Motokei oil, and the like can be mentioned.
Other examples include organic solvents, resins, plasticizers, ultraviolet absorbers, antioxidants, preservatives, surfactants, moisturizers, fragrances, water, alcohols, thickeners, and the like.
[0012]
【Example】
EXAMPLES Next, although an Example is given and this invention is further demonstrated, this invention is not limited at all by this.
[0013]
Production Example 1: Iron-containing titanium dioxide of the present invention (0.12 μm iron-containing titanium dioxide)
The titanyl sulfate solution was thermally decomposed by a conventional method, and the caustic soda solution was added to the hydrous titanium oxide slurry filtered and washed with stirring, and heated at 95 ° C. for 2 hours. Next, hydrochloric acid was added to the slurry obtained by thoroughly washing this treated product with stirring, and heated at 95 ° C. for 2 hours to prepare a titania sol. To the titania sol thus obtained, an aqueous ferrous chloride solution was further added to adjust the pH to 7.0. After aging, filtration and washing were performed, followed by drying at 105 ° C. This was fired at 850 ° C. for 2 hours in an electric furnace, and then pulverized with an air jet mill to obtain iron-containing titanium dioxide having an average particle size of 0.12 μm. Subsequently, classification was carried out with starch syrup, and 70% or more of all particles were adjusted so as to be in the range of ± 0.03 μm of the average particle diameter, dried again, and pulverized.
When the particle size and distribution of the iron-containing titanium dioxide prepared by the above method were measured using a transmission electron microscope, the average particle size was 0.12 μm, and 70% or more of all particles had an average particle size of ± It was confirmed that it was in the range of 0.03 μm.
The measured specific surface area by the BET method, the specific surface area to fall within the scope of 10m 2 / g~30m 2 / g was confirmed.
[0014]
Production Comparative Example 1: 0.12 μm Iron Oxide / Titanium Dioxide Mixture Pigment Grade Titanium Dioxide {Titanium Oxide JR-701: Made by Teika (Average Particle Diameter 0.25 μm)} 31.4 parts by Weight and Fine Titanium Dioxide {Fine Particle Titanium Oxide P-25: Degussa (average particle size 0.03 μm)} 67.1 parts by weight were mixed and stirred to obtain a titanium dioxide mixture having an average particle size of 0.12 μm. Further, 1.5 parts by weight of Bengala was further mixed and stirred to obtain a mixture of iron oxide and titanium dioxide having an average particle size of about 0.12 μm.
When the specific surface area was measured by the BET method, the specific surface area exceeded 30 m 2 / g.
[0015]
Production Comparative Example 2: Iron-containing pigment-grade titanium dioxide Pigment-grade titanium dioxide {titanium oxide JR-701: manufactured by Teika Co., Ltd. (average particle size: 0.25 µm)}, described in Example 1 of JP-B-4-5001 According to a known method, iron-containing pigment grade titanium dioxide having a ratio of titanium dioxide to iron oxide of 98: 2 was obtained.
[0016]
Production Comparative Example 3: Iron-containing fine particle titanium dioxide According to the example of JP-A-5-330825, iron-containing fine particle titanium dioxide having an average particle size of 0.03 μm and an iron oxide content of 3% was obtained.
[0017]
(Test method)
With respect to 0.12 μm iron-containing titanium dioxide of Production Example 1 and each iron-containing (and mixed) titanium dioxide described in Production Comparative Examples 1 to 3, the blocking rate and dispersibility in a specific wavelength range were measured.
[0018]
(1) Blocking rate An alcohol solution of polyvinylpyrrolidone was applied onto a quartz plate using a doctor blade of 25 μm. After evaporation of the alcohol, each iron-containing titanium dioxide (and mixture) was evenly applied to the adhesive surface with a soft brush to obtain a measurement sample.
The transmittance of the specimen was measured with Shimadzu spectrophotometer UV-265FW and unit integrator ISR-260. The measurement wavelength was a visible light region (400 to 800 nm), a UV-A region (320 nm to 400 nm), and a UV-B region (290 nm to 320 nm), a spectral curve was measured, and the transmission area of each region was obtained from the chart. The blocking rate was calculated by the following formula (1), and the result is shown in Table 1.
[0019]
[Expression 1]
(2) Dispersibility Each iron-containing titanium dioxide mixed in 1,3-butylene glycol at a concentration of 10% and dispersed once using a roll mill is used as a measurement sample, and visually in accordance with the following criteria. Dispersibility was determined. The results are also shown in Table 1.
(Criteria)
○: Dispersibility is good and aggregation is not observed.
Δ: Dispersibility is good, but a little aggregation is observed.
X: Dispersibility is poor and considerable aggregation is observed.
[0021]
[Table 1]
As is apparent from Table 1, the 0.12 μm iron-containing titanium dioxide of Production Example 1 is more visible than the iron oxide / titanium dioxide mixture of Production Comparative Example 1 and the iron-containing pigment-grade titanium dioxide of Production Comparative Example 2 in visible light. In the ultraviolet region, the blocking rate is higher than that of the iron oxide / titanium dioxide mixture of Production Comparative Example 1 and the iron-containing pigment grade titanium dioxide of Production Comparative Example 2. It was shown that. The iron-containing fine particle titanium dioxide of Production Comparative Example 3 has a low blocking rate and high transparency in the visible light region, but is too high in transparency and has insufficient hiding power. Further, in the UV region, the blocking rate was higher in the UV-B region than in the iron-containing titanium dioxide of the present invention, but in the UV-A region, the blocking rate was higher in the iron-containing titanium dioxide of the present invention.
When these iron-containing (mixed) titanium dioxides were applied to the skin, the appearance of the coating film was insufficient in the hiding power of the iron-containing fine particle titanium dioxide of Production Comparative Example 3, and the iron oxide / dioxide of Production Comparative Example 1 was insufficient. While the titanium mixture and the iron-containing pigment-grade titanium dioxide of Production Comparative Example 2 floated white and had an unnatural finish, the iron-containing titanium dioxide of Production Example 1 had a natural whiteness with no whiteness. Appearance was obtained.
Since the iron-containing titanium dioxide of the present invention has low light scattering in the medium to long wavelength of visible light compared to short wavelength light scattering, light in the main wavelength region (yellow to red) constituting the skin color is transmitted through the cosmetic film. It is easy to do and scatters blue short-wavelength light in dull skin, pigmented skin, etc. in the cosmetic coating film, so it is excellent in the effect of producing a natural and healthy skin color.
[0023]
Regarding dispersibility, the iron oxide-titanium dioxide mixture, iron-containing pigment-grade titanium dioxide, and iron-containing fine particle titanium dioxide of Production Comparative Examples 1 to 3 were observed to be agglomerated, whereas Production Example 1 The iron-containing titanium dioxide had good dispersibility and no aggregation was observed.
[0024]
Furthermore, the feel at the time of application is that the iron oxide / titanium dioxide mixture of Production Comparative Example 1 has a poor spread and a squeaky feeling, and the iron-containing pigment grade titanium dioxide of Production Comparative Example 2 has a poor spread and is hard to stop. The iron-containing fine particle titanium dioxide of Comparative Example 3 has a squeaky feeling, whereas the iron-containing titanium dioxide of Production Example 1 of the present invention has a good spread and a soft feel.
[0025]
Production Example 2: Iron-containing titanium dioxide of the present invention (0.14 μm iron-containing titanium dioxide)
By changing the firing temperature of Production Example 1 to 880 ° C., iron-containing titanium dioxide having an average particle size of 0.14 μm was obtained.
Was the iron-containing titanium dioxide obtained by the above method to measure the specific surface area by the BET method, the specific surface area to fall within the scope of 10m 2 / g~30m 2 / g was confirmed.
[0026]
Examples 1 to 4 and Comparative Examples 1 to 3 Powder Foundation A powder foundation having the composition shown in Table 2 was prepared. Usability (spreading / spreading), hiding power (covering power), natural finish (white and thick) Sensory evaluation was performed for the absence of dullness (the absence of bluish white), and the transmittance was measured for the UV blocking effect. The results are also shown in Table 2.
[0027]
[Table 2]
(Manufacturing method)
A: Components (1) to (8) are mixed.
B: Components (9) to (12) are dissolved by heating and mixed.
C: A and B are mixed and dispersed and filled into a metal pan.
[0029]
(Evaluation methods)
(Evaluation item)
1. Nobi and Hirogari2. 2. Cover force 3. White and thick. 4. No paleness UV blocking effect 【0030】
(Evaluation and evaluation criteria)
Evaluation items 1 to 4 were used according to the following criteria based on the average score of the five-step evaluation.
Evaluation criteria 5 points: Very good 4 points: Good 3 points: Normal 2 points: Slightly defective 1 point: Defect criteria ◎: 4.0 to 5.0 points ○: 3.0 to less than 4.0 points Δ: 2.0 to less than 3.0 points x: 1.0 to less than 2.0 points
Evaluation item 5 used the test methods in Production Example 1 and Production Comparative Examples 1 to 3 for each sample to determine the ultraviolet blocking effect as follows.
(Double-circle): The transmittance | permeability of an ultraviolet part is very low, and the interruption | blocking effect is high.
○: The transmittance in the ultraviolet region is low and the blocking effect is slightly high.
Δ: Slightly high transmittance in the ultraviolet region and slightly low blocking effect ×: High transmittance in the ultraviolet region and poor blocking effect.
[0032]
The powder foundations of Examples 1 to 3 blended with 0.12 μm iron-containing titanium dioxide of the present invention and Example 4 blended with 0.14 μm iron-containing titanium dioxide compared to Comparative Examples 1 to 3, usability and hiding power It was excellent in terms of natural finish, lack of dullness and UV blocking effect.
[0033]
Example 5 and Comparative Examples 4 to 5: O / W-type sunscreen cosmetics O / W-type sunscreen cosmetics having the compositions shown in Table 3 were prepared, usability (spreading / spreading), and hiding power (covering power). Evaluations similar to the evaluation methods of Examples 1 to 4 and Comparative Examples 1 to 3 were performed with respect to the natural finish (no white thickness), no dullness (no blueness), and an ultraviolet blocking effect. However, the sample used for the UV blocking effect was applied directly to a quartz plate using a doctor blade. The results are also shown in Table 3.
[0034]
[Table 3]
(Manufacturing method)
A: Components (1) to (9) are heated and mixed and dispersed.
B: Components (10) to (13) are mixed and dispersed.
C: A and B are mixed and emulsified.
D: (14) to (17) are added to C and mixed.
The O / W type sunscreen emulsion of Example 5 formulated with 0.12 μm iron-containing titanium dioxide of the present invention has usability, hiding power, natural finish, dullness, and UV blocking effect as compared with Comparative Examples 4 to 5. It was excellent.
[0036]
Example 6 and Comparative Examples 6 to 7: W / O type cream W / O type creams having the composition shown in Table 4 were prepared, usability (expansion / spreading), hiding power (covering power), and natural finish (white) Evaluations similar to the evaluation methods of Examples 1 to 4 and Comparative Examples 1 to 3 were performed for the absence of thickness), dullness (no bluishness), and ultraviolet blocking effect. However, the sample used for the ultraviolet blocking effect was applied directly to a quartz plate using a doctor blade.
[0037]
[Table 4]
(Manufacturing method)
A: (1) to (9) are added and mixed and dispersed.
B: (12) to (13) are added to A and emulsified.
C: (10) to (11) are added to B and mixed.
The W / O type cream of Example 6 formulated with 0.12 μm iron-containing titanium dioxide of the present invention has usability, hiding power, natural finish, dullness, and UV blocking effect as compared with Comparative Examples 6-7. It was excellent.
[0039]
Example 7: Concealer (ingredient) (%)
1. Candelilla wax 4.0
2. Paraffin wax 6.0
3. Vaseline 5.0
4). Methyl polysiloxane 10.0
5. Squalane 10.0
6). 6. Diglyceryl triisostearate remaining amount Iron-containing titanium dioxide of Production Example 1 45.0
8). Nylon powder 5.0
9. Coloring pigment appropriate amount10. Antioxidant appropriate amount11. Perfume appropriate amount [0040]
(Manufacturing method)
After components (1) to (6) were dissolved by heating, (7) to (11) were added, mixed uniformly, cooled and solidified to obtain a concealer.
The concealer of the present invention was excellent in terms of usability, hiding power, natural finish, dullness, and UV blocking effect.
[0041]
Example 8: Lipstick (ingredient) (%)
1. Microcrystalline wax 9.0
2. Candelilla wax 6.0
3. Paraffin wax 5.0
4). 4. Diglyceryl triisostearate remaining amount Glyceryl trioctanoate 20.0
6). Squalane 3.0
7. Red No. 202 3.0
8). Yellow No. 1.0
9. Iron-containing titanium dioxide of Production Example 1 0.5
10. Cosmetic ingredients appropriate amount11. Perfume appropriate amount [0042]
(Manufacturing method)
After components (1) to (6) were heated and dissolved at 110 ° C. to 120 ° C., (7) to (11) were added and mixed uniformly, poured into a mold for molding, and cooled and solidified to produce a lipstick.
The lipstick of the present invention was excellent in terms of usability, hiding power, natural finish, dullness, and UV blocking effect.
[0043]
Example 9: Powder foundation for sunscreen (component) (%)
1. Iron-containing titanium dioxide of Production Example 1 20.0
2. Fine particle titanium oxide 5.0
3. Talc 20.0
4). 4. Mica remaining amount Coloring pigment appropriate amount 6. Vaseline 1.0
7. Liquid paraffin 1.0
8). Paramethoxycinnamic acid-2-ethylhexyl 2.0
9. Dimethylpolysiloxane 1.0
10. Cosmetic ingredients appropriate amount11. Perfume appropriate amount [0044]
(Manufacturing method)
A: Components (1) to (5) are mixed.
B: Components (6) to (11) are dissolved by heating.
C: A and B were mixed and dispersed and filled in a metal pan to produce a sunscreen powder foundation.
The sunscreen powder foundation of the present invention was excellent in moderate hiding power, natural finish, no dullness, UV blocking effect and usability.
[0045]
【The invention's effect】
Cosmetics containing iron-containing titanium dioxide of the present invention, ultraviolet shielding performance while having a moderate hiding power (UV-A and UV-B blocking ability) and superior in dispersibility, those natural finish is obtained Met.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15615796A JP3677610B2 (en) | 1996-05-28 | 1996-05-28 | Iron oxide-containing titanium dioxide and composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15615796A JP3677610B2 (en) | 1996-05-28 | 1996-05-28 | Iron oxide-containing titanium dioxide and composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09315818A JPH09315818A (en) | 1997-12-09 |
| JP3677610B2 true JP3677610B2 (en) | 2005-08-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15615796A Expired - Fee Related JP3677610B2 (en) | 1996-05-28 | 1996-05-28 | Iron oxide-containing titanium dioxide and composition containing the same |
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| JP (1) | JP3677610B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60137759D1 (en) * | 2000-04-25 | 2009-04-09 | Showa Denko Kk | METHOD FOR PRODUCING FINE, TITANIUM OXIDE-CONTAINING OXIDE COMPOSITE PARTICLES |
| US6548169B2 (en) | 2000-04-25 | 2003-04-15 | Showa Denko Kabushiki Kaisha | Production process for ultrafine particulate complex oxide containing titanium oxide |
| JP2015110529A (en) * | 2013-12-06 | 2015-06-18 | ロレアル | Powdery cosmetic composition |
| JP7017326B2 (en) * | 2017-06-26 | 2022-02-08 | 株式会社 資生堂 | Cosmetics containing titanium dioxide powder |
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1996
- 1996-05-28 JP JP15615796A patent/JP3677610B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH09315818A (en) | 1997-12-09 |
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