JP3702742B2 - Pearlescent pigment, method for producing the same, and cosmetics containing pearlescent pigment - Google Patents

Description

【００１５】
また、超音波の照射時間が増加するにしたがって、シリカガラスのフレークの平均粒径は小さくなることが確認される。具体的には、超音波洗浄装置（ヴェルヴォクーリア商会社製 ＶＳ−７０Ｒ）を６０Ｗで出力させ、シリカガラスのフレークに超音波を照射すると、その平均粒径は経時的に下記「表２」のように変化する。
【００１６】
【表２】

【００１７】
「表１」および「表２」より、シリカガラスのフレークは、粒径が大きいほど超音波による破砕が起こり易いことが判る。また、経時的には、超音波照射の初期に破砕が起こり易いことが判る。このようにシリカガラスのフレークは、超音波の衝撃によっても破砕されてしまうが、フレーク状ガラスではこのような現象は確認されない。これは、フレーク状ガラスがシリカガラスのフレークほど硬度が高くなく若干の柔軟性を有するためであると考えられる。したがって、フレーク状ガラスを母材とする真珠光沢顔料は、化粧料の材料として他の材料と配合され練り込まれた場合に、シリカガラスのフレークよりも当初の粒径を維持でき、その結果化粧料中でより効果的に光輝感を発現できる。なお、フレーク状ガラスのシリカの含有率は、母材に必要な強度と適度な柔軟性とを兼ね備えるために、５０〜７０質量％、さらには５５〜６５質量％であることが好ましい。
【００１８】
この真珠光沢顔料は、その名の如く外観上真珠に似た光沢を示すものであり、これはフレーク状ガラスにチタニア(TiO₂)、ジルコニアまたは酸化鉄などの金属酸化物からなる被膜を設けることにより得られる。この被膜の成形方法は、公知の技術を利用すればよく、たとえば特公昭４３−２５６４４号公報、特開昭４７−３４５２９号公報に記載されている。具体的には、硫酸チタニル溶液または四塩化チタン溶液にフレーク状ガラスを懸濁させ、かかる溶液を昇温することによりチタニアを析出させ、フレーク状ガラス上に被膜を設ける方法である。ただし、この方法に限定するものではなく、フレーク状ガラス上に薄く被膜を設けることができる方法であれば、どのような方法でもよい。
【００１９】
フレーク状ガラス上の被膜の厚さを制御することにより、干渉による任意の色調を発現させることができる。この被膜の厚さは、２０〜２５０nmが好ましく、２０nm未満では光輝感が発現し難く、一方２５０nmより厚ければ原料が多く必要となるためコスト的に好ましくない。
【００２０】
この被膜にチタニアを用いる場合は、被膜成形後にフレーク状ガラスを８００〜１，２００℃で加熱処理することが多い。これは、チタニアにはアナタース型、ブルーカイト型およびルチル型の３つの結晶系があり、アナタース型をルチル型に転移させるために行われるものである。上述のように溶液からの析出によりチタニア被膜を設ける場合は、まずアナタース型が析出する。アナタース型はルチル型に比べ化学的に不安定型であるため、フレーク状ガラスに耐久性および耐候性が要求される場合は、アナタース型よりルチル型が指向される。さらに、ルチル型のチタニア被膜は、アナタース型よりも緻密な膜を形成することから、より高い光輝感すなわち鮮やかな色感を発現する。よって、フレーク状ガラスの被膜としては、ルチル型のチタニアからなるものが好ましく、また指向されている。
【００２１】
上記結晶系転移のための加熱処理温度が８００℃以下の場合は、チタニアの結晶系はアナタース型のままであるが、一方８００℃より高くするとルチル型に転移することが知られている。しかし、８００℃以上に加熱した場合、フレーク状ガラスは変形することがある。この変形を防止するため、本発明者は、８００℃以下の加熱処理でもルチル型に転移する方法を、鋭意研究の末見出した。それは、上記の溶液からチタニアを析出させる際に、フレーク状ガラスに貴金属を微量触媒として付着させておく方法である。ここで貴金属とは、金、銀および白金族(Ru,Rh,Pd,Os,Ir,Pt)を指す。貴金属をフレーク状ガラスに付着させる方法は、とくに限定されるものではなく、たとえば塩化白金酸の溶液中にフレーク状ガラスを投入してしばらく放置する方法が挙げられる。この方法において、６００℃以下の加熱処理でルチル型への結晶系転移が起こることを確認した。
【００２２】
フレーク状ガラス上の被膜の屈折率によって、ある色調を発現させる被膜の厚さは若干異なるが、一般的には被膜の厚さと発色（反射光）の関係は以下の「表３」のとおりである。
【００２３】
【表３】
−−−−−−−−−−−−−−−−−−−−−−
発色 被膜厚さ（nm）
−−−−−−−−−−−−−−−−−−−−
シルバー 40〜60
黄 60〜80
赤 80〜100
青 100〜140
緑 120〜160
−−−−−−−−−−−−−−−−−−−−−−
【００２４】
上記金属酸化物の被膜を備えた特定の形状のフレーク状ガラスすなわち真珠光沢顔料を配合することにより、くすみがなく澄んだ発色を示し、肌上でざらつき感がなく、さらに肌上でののびおよびフィット感に優れる化粧料が得られる。
【００２５】
この化粧料における真珠光沢顔料の配合率は、１〜１００質量％が好ましい。配合率が１質量％未満の場合は、真珠光沢顔料の光輝感が十分に発揮されない。一方、１００質量％であっても、肌上では人脂などが存在するため、これらと結合し化粧料として機能しうる。
【００２６】
この化粧料には、フェーシャル化粧料、メーキャップ化粧料、ヘア化粧料など幅広い範囲の化粧料が含まれる。これらの中でも、とくにファンデーション、粉白粉、アイシャドー、ブラッシャー、化粧下地、ネイルエナメル、アイライナー、マスカラ、口紅、ファンシーパウダーなどのメーキャップ化粧料において、この真珠光沢顔料は好適に使用される。
【００２７】
この真珠光沢顔料は、化粧料の目的に応じて、適宜疎水化処理が施されてもよい。疎水化処理の方法としては、第一にメチルハイドロジェンポリシロキサン、高粘度シリコーンオイルおよびシリコーン樹脂などのシリコーン化合物による処理方法、第二にアニオン活性剤、カチオン活性剤などの界面活性剤による処理方法、第三にナイロン、ポリメチルメタクリレート、ポリエチレン、テフロン、ポリアミノ酸などの高分子化合物による処理方法、第四にパーフルオロ基含有化合物、レシチン、コラーゲン、金属石鹸、親油性ワックス、多価アルコール部分エステルまたは完全エステルなどによる処理方法、第五にこれらを複合した処理方法が挙げられる。ただし、一般に粉末の疎水化処理に適用できる方法であれば、上記の方法に限定されるのではない。
【００２８】
この化粧料には、通常化粧料に用いられる他の材料を必要に応じて適宜配合することができる。たとえば、タルク、カオリン、セリサイト、白雲母、金雲母、紅雲母、黒雲母、リチア雲母、バーミキュライト、炭酸マグネシウム、炭酸カルシウム、珪ソウ土、ケイ酸マグネシウム、ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸バリウム、硫酸バリウム、ケイ酸ストロンチウム、タングステン酸金属塩、シリカ、ヒドロキシアパタイト、ゼオライト、窒化ホウ素、セラミックスパウダーなどの無機粉末、ナイロンパウダー、ポリエチレンパウダー、ポリスチレンパウダー、ベンゾグアナミンパウダー、ポリ四弗化エチレンパウダー、ジスチレンベンゼンポリマーパウダー、エポキシパウダー、アクリルパウダー、微結晶性セルロースなどの有機粉末、酸化チタン、酸化亜鉛などの無機白色顔料、酸化鉄（ベンガラ）、チタン酸鉄などの無機赤色系顔料、γ酸化鉄などの無機褐色系顔料、黄酸化鉄、黄土などの無機黄色系顔料、黒酸化鉄、カーボンブラックなどの無機黒色系顔料、マンゴバイオレット、コバルトバイオレットなどの無機紫色系顔料、酸化クロム、水酸化クロム、チタン酸コバルトなどの無機緑色系顔料、群青、紺青などの無機青色系顔料、酸化チタン被膜雲母、酸化チタン被膜オキシ塩化ビスマス、オキシ塩化ビスマス、酸化チタン被膜タルク、魚鱗箔、着色酸化チタン被膜雲母などのパール顔料、アルミニウムパウダー、カッパーパウダーなどの金属粉末顔料、赤色２０１号、赤色２０２号、赤色２０４号、赤色２０５号、赤色２２０号、赤色２２６号、赤色２２８号、赤色４０５号、橙色２０３号、橙色２０４号、黄色２０５号、黄色４０１号および青色４０４号などの有機顔料、赤色３号、赤色１０４号、赤色１０６号、赤色２２７号、赤色２３０号、赤色４０１号、赤色５０５号、橙色２０５号、黄色４号、黄色５号、黄色２０２号、黄色２０３号、緑色３号および青色１号のジルコニウム、バリウムまたはアルミニウムレーキなどの有機顔料、クロロフィル、β-カロチンなどの天然色素、スクワラン、流動パラフィン、ワセリン、マイクロクリスタリンワックス、オケゾライト、セレシン、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、イソステアリン酸、セチルアルコール、ヘキサデシルアルコール、オレイルアルコール、２−エチルヘキサン酸セチル、パルミチン酸２−エチルヘキシル、ミリスチン酸２−オクチルドデシル、ジ−２−エチルヘキサン酸ネオペンチルグリコール、トリ−２−エチルヘキサン酸グリセロール、オレイン酸−２−オクチルドデシル、ミリスチン酸イソプロピル、トリイソステアリン酸グリセロール、トリヤシ油脂肪酸グリセロール、オリーブ油、アボガド油、ミツロウ、ミリスチン酸ミリスチル、ミンク油、ラノリンなどの各種炭化水素、シリコーン油、高級脂肪酸、油脂類のエステル類、高級アルコール、ロウなどの油性成分、アセトン、トルエン、酢酸ブチル、酢酸エステルなどの有機溶剤、アルキド樹脂、尿素樹脂などの樹脂、カンファ、クエン酸アセチルトリブチルなどの可塑剤、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、増粘剤などが挙げられる。
【００２９】
この化粧料の形態は、とくに限定されるものではなく、粉末状、ケーキ状、ペンシル状、スティック状、軟膏状、液状、乳液状、クリーム状などである。
【００３０】
なお、この発明は次のような実施形態として具現化することも可能である。
・フレーク状ガラスに白金などの貴金属を付着させ、そこにアナタース型のチタニアを付着させ、６００℃以下に加熱することにより、ルチル型チタニアからなる被膜を備えたフレーク状ガラスを製造する方法。
【００３１】
【実施例】
以下に実施例および比較例を挙げてこの発明をより詳細に説明するが、この発明の要旨を越えない限り、以下の実施例に限定されるものではない。
まず、フレーク状ガラスに金属酸化物を被膜した真珠光沢顔料について説明する。
【００３２】
（参考例１）〜（参考例４）
Ｃガラス（SiO₂：６５質量％、Al₂O₃：４質量％、CaO：１４質量％、MgO：３質量％、B₂O₃：５質量％、Na₂O：８質量％、K₂O：１質量％）を１，２００℃で熔融し、円筒形にブローし延伸薄膜化して冷却固化することにより所定の厚さにし、それを粉砕分級して、所定の厚さ、粒度およびアスペクト比を有するフレーク状ガラスを製造した。このフレーク状ガラスを硫酸チタニル溶液中に懸濁させ、この懸濁液を加熱し１時間沸騰させることにより、フレーク状ガラス表面に種々の厚さのチタニアを被膜させ、濾過水洗後乾燥させ、その後６００℃で３０分間熱処理して、チタニア被膜を備えたフレーク状ガラスを得た。チタニア被膜の結晶系をＸ線回折で調べたところ、いずれもアナタース型であった。
【００３３】
ここで、チタニア被膜の厚さによりフレーク状ガラスの発色が異なり、またフレーク状ガラスの厚さおよび粒度により比表面積が異なるため、各実施例で目的とするチタニア被膜を得るための条件は一義的には決定できない。そのため、チタニア被膜の形成段階でフレーク状ガラスを懸濁液中から適宜サンプリングし、その色目を確認しながら硫酸チタニルの添加量を加減して、任意の色調のフレーク状ガラスを製造した。
【００３４】
これら種々の厚さ、粒度およびアスペクト比を有するフレーク状ガラスを、直径６０mm×高さ１０mmのシリカのセル中に詰め、それを色彩色差計（ミノルタ社製 ＣＲ３００）で明度（Ｌ値）を測定した。また、光沢計（日本電色工業株式会社製 ＶＧＳ−１００１ＤＰ）で、４５°／０°の拡散反射率を測定し、輝度を評価した。これらフレーク状ガラスの特性および輝度評価の結果を、下記「表４」に示す。
【００３５】
（参考比較例１）〜（参考比較例３）
市販のアナタース型のチタニア被膜を備えたマイカと、フレーク状ガラス（ＲＣＦ−１４０ 日本板硝子社製）に上記実施例の方法でアナタース型のチタニア被膜を成形したものとについて、上記と同様の方法で、明度（Ｌ値）および４５°／０°の拡散反射率を測定し、その輝度を評価した。その結果を、下記「表４」に併せて示す。なお、参考比較例３のフレーク状ガラスには、貴金属は付着していない。
【００３６】
参考例１〜４のフレーク状ガラスは、いずれも輝度（Ｌ値および拡散反射率）が参考比較例１および２のマイカに比べ高く、非常に澄んだ明るく高い光輝感を示すことが判る。
【００３７】
【表４】
アナタース型のチタニア被膜を備えたフレーク状ガラスおよびマイカの輝度と光沢性
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
参考例 参考比較例
１ ２ ３ ４ １ ２ ３
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
母材 ガラス ガラス ガラス ガラス マイカ マイカ ガラス
平均厚さ(μm) 2.3 2.3 2.3 1.3 0.4 0.6 5.0
平均粒径(μm) 450 80 40 25 40 80 140
アスペクト比 196 35 17 19 100 113 28
反射色 シルバー シルバー シルバー 赤 シルバー シルバー シルバー
明度(L値) 93 92 91 91 88 89 90
拡散反射率 66 62 61 63 52 54 60
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００３８】
（実施例１）〜（実施例４）
上記参考例１〜４と同様にして、所定の形状のフレーク状ガラスを製造した。このフレーク状ガラスを塩化白金酸を添加した四塩化チタン溶液中に懸濁させ、この懸濁液を加熱し１時間沸騰して、フレーク状ガラス表面に種々の厚さのチタニア被膜を設けた。このフレーク状ガラスを濾過水洗後乾燥させ、その後６００℃で３０分間熱処理した。チタニア被膜の結晶系をＸ線回折で調べたところ、いずれもルチル型であった。これは、フレーク状ガラスに付着した白金が、ルチル型への転移を促進する触媒として作用したためと考えられる。これら種々の厚さ、粒度およびアスペクト比を有するフレーク状ガラスについて、上記参考例１〜４と同様にして輝度を評価した。その結果を下記「表５」に示す。
【００３９】
（比較例１）〜（比較例４）
市販のルチル型のチタニア被膜を備えるマイカについて、上記同様にして輝度を評価した。その結果を下記「表６」に示す。
【００４０】
【表５】
ルチル型のチタニア被膜を備えたフレーク状ガラスの輝度と光沢性
−−−−−−−−−−−−−−−−−−−−−−−−−−−
実施例 １ ２ ３ ４
−−−−−−−−−−−−−−−−−−−−−−−−−
母材 ガラス ガラス ガラス ガラス
平均厚さ(μm) 2.3 1.3 1.3 0.7
平均粒径(μm) 300 80 80 25
アスペクト比 130 62 62 36
反射色 シルバー ゴールド 赤 青
明度(Ｌ値) 95 94 93 92
拡散反射率 70 62 74 74
−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００４１】
【表６】
ルチル型のチタニア被膜を備えたマイカの輝度と光沢性
−−−−−−−−−−−−−−−−−−−−−−−−−−−
比較例 １ ２ ３ ４
−−−−−−−−−−−−−−−−−−−−−−−−−
母材 マイカ マイカ マイカ マイカ
平均厚さ(μm) 0.4 0.4 0.4 0.6
平均粒径(μm) 40 40 40 80
アスペクト比 100 100 100 133
反射色 シルバー ゴールド 赤 青
明度(Ｌ値) 91 90 90 89
拡散反射率 50 60 65 63
−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００４２】
「表５」および「表６」より、実施例１〜４のフレーク状ガラスは、いずれも輝度（Ｌ値および拡散反射率）が比較例１〜４のマイカに比べ高く、非常に澄んだ明るく高い光輝感を示すことが判る。
【００４３】
つぎに、上記チタニア被膜を備えたフレーク状ガラスすなわち真珠光沢顔料を配合した化粧料について説明する。化粧料の評価は、下記「表７」に基づきパネラー１０人による５段階の官能評価により行った。
【００４４】
【表７】
化粧料に関する官能評価
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
評価＼項目 のび 密着感 滑らかさ 光輝感 色のきれいさ
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
１ 悪い ない ない ない 汚い
２ やや悪い ややない ややない あまりない ややくすむ
３ 普通 普通 普通 ややある 普通
４ ややよい ややある ややある ある きれい
５ よい 非常にある 非常にある 非常に高い 非常にきれい
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００４５】
官能評価の結果は、パネラー１０名の５段階評価の平均値であり、その評価を分かり易くするために下記の記号で表す。
◎・・・４．５以上５．０まで
○・・・３．５以上４．５未満
●・・・２．５以上３．５未満
△・・・１．５以上２．５未満
×・・・１．０以上１．５未満
【００４６】
（参考例５）：パウダーファンデーション
下記「表８」に示す材料からなるパウダーファンデーションを製造した。
【００４７】
【表８】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
（１）酸化チタン ７
（２）タルク ２０
（３）白雲母 ３
（４）参考例２のフレーク状ガラス ５５
（５）ナイロンパウダー ２
（６）赤色酸化鉄 ０．５
（７）黄色酸化鉄 １
（８）黒色酸化鉄 ０．１
（９）シリコーンオイル １
（１０）バルミチン酸２−エチルヘキシル ９
（１１）セスキオレイン酸ソルビタン １
（１２）防腐剤 ０．３
（１３）香料 ０．１ （質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００４８】
上記材料（１）〜（８）をヘンシェルミキサーで混合し、この混合物に上記材料（９）〜（１３）を加熱溶解させ混合したものを添加混合し、これをパルベライザーで粉砕した。さらに、これを直径５．３mmの中皿に吐出し、１６０kg/cm²の圧力で押圧成形し、パウダーファンデーションを製造した。この化粧料の官能評価の結果を、下記「表９」に示す。
【００４９】
（参考比較例４）：パウダーファンデーション
上記材料（４）フレーク状ガラスを参考比較例１のマイカに置換し、それ以外を参考例５と同様にしてパウダーファンデーションを製造した。この化粧料の官能評価の結果を、下記「表９」に示す。
【００５０】
（参考比較例５）：パウダーファンデーション
上記材料（４）フレーク状ガラスを参考比較例３のフレーク状ガラスに置換し、それ以外を参考例５と同様にしてパウダーファンデーションを製造した。この化粧料の官能評価の結果を、下記「表９」に併せて示す。
【００５１】
【表９】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
項目 のび 密着感 滑らかさ 光輝感 色のきれいさ
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
参考例５ ○ ○ ○ ◎ ◎
参考比較例４ ○ ○ ○ ○ ○
参考比較例５ ● ● △ ○ ◎
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００５２】
「表９」より、参考例５の化粧料は、参考比較例４と比べ光輝感および色のきれいさで、参考比較例５と比べのび、密着感および滑らかさで優れていることが判る。
【００５３】
（参考例６）：ブラッシャー
下記「表１０」に示す材料からなるブラッシャーを製造した。
【００５４】
【表１０】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
（１）タルク １２．６
（２）絹雲母 ８．１
（３）マイカ ２５．４
（４）参考例３のフレーク状ガラス ４５．０
（５）赤色２２６号 ０．４
（６）スクワラン ３．０
（７）パルミチン酸２−エチルヘキシル ５．０
（８）防腐剤 ０．３
（９）香料 ０．２ （質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００５５】
上記材料（１）〜（５）をヘンシェルミキサーで混合し、この混合物に上記材料（６）〜（９）を加熱溶解させ混合したものを吹き付け混合した後、パルベライザーを用いてこれを粉砕した。さらに、これを４×６cmの中皿に吐出し、１２０kg/cm²で押圧成形して、ブラッシャーを製造した。この化粧料の官能評価の結果を、下記「表１１」に示す。
【００５６】
（参考比較例６）：ブラッシャー
参考例６の材料（４）フレーク状ガラスを参考比較例２のマイカに置換し、それ以外を参考例６と同様にしてブラッシャーを製造した。この化粧料の官能評価の結果を、下記「表１１」に示す。
【００５７】
（参考比較例７）：ブラッシャー
参考例６の材料（４）フレーク状ガラスを参考比較例３のフレーク状ガラスに置換し、それ以外を参考例６と同様にしてブラッシャーを製造した。この化粧料の官能評価の結果を、下記「表１１」に併せて示す。
【００５８】
【表１１】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
項目 のび 密着感 滑らかさ 光輝感 色のきれいさ
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
参考例６ ○ ○ ○ ◎ ◎
参考比較例６ ○ ○ ○ ○ ○
参考比較例７ ● ● △ ○ ◎
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００５９】
「表１１」より、参考例６の化粧料は、参考比較例６と比べ光輝感および色のきれいさで、参考比較例７と比べのび、密着感、滑らかさおよび光輝感で優れていることが判る。
【００６０】
（実施例５）：ネイルエナメル
下記「表１２」に示す材料からなるネイルエナメルを製造した。
【００６１】
【表１２】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
（１）ニトロセルロース １２
（２）変成アルキド樹脂 １２
（３）クエン酸アセチルトリブチル ５
（４）酢酸ｎ−ブチル ３６．４
（５）酢酸エチル ６
（６）ｎ−ブチルアルコール ２
（７）トルエン ２１
（８）酸化鉄顔料 ０．５
（９）二酸化チタン ０．１
（１０）実施例３のフレーク状ガラス ３
（１１）マイカ １
（１２）有機変成モンモリロナイト １ （質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００６２】
上記材料（１）〜（７）（ただし材料（４）は一部分）を溶解し、この溶液に材料（１２）と材料（４）の残部とを混合してゲル状にしたものを添加混合し、さらに材料（８）〜（１１）を添加混合した。この混合物を所定の容器に充填し、ネイルエナメルを製造した。この化粧料の官能評価の結果を、下記「表１３」に示す。
【００６３】
（比較例５）：ネイルエナメル
実施例５の材料（１０）フレーク状ガラスを比較例３のマイカに置換し、それ以外は実施例５と同様にしてネイルエナメルを製造した。この化粧料の官能評価の結果を、下記「表１３」に示す。
【００６４】
（参考比較例８）：ネイルエナメル
実施例５の材料（１０）フレーク状ガラスを参考比較例３のフレーク状ガラスに置換し、それ以外は実施例５と同様にしてネイルエナメルを製造した。この化粧料の官能評価の結果を、下記「表１３」に示す。
【００６５】
【表１３】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
項目 のび 密着感 滑らかさ 光輝感 色のきれいさ
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
実施例５ ○ ○ ◎ ◎ ◎
比較例５ ○ ○ ○ ○ ○
参考比較例８ ● ● △ ○ ◎
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００６６】
「表１３」より、実施例５の化粧料は、比較例５と比べ滑らかさ、光輝感および色のきれいさで、参考比較例８と比べのび、密着感、滑らかさおよび光輝感で優れていることが判る。
【００６７】
（実施例６）：乳化ファンデーション
下記「表１４」に示す材料からなる乳化ファンデーションを製造した。
【００６８】
【表１４】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
（１）ステアリン酸 ０．４
（２）イソステアリン酸 ０．３
（３）２−エチルヘキサン酸セチル ４
（４）流動パラフィン １１
（５）ポリオキシエチレン（１０）ステアリルエーテル ２
（６）タルク ８
（７）顔料 ４
（８）セチルアルコール ０．３
（９）防腐剤 ０．０７
（１０）実施例２のフレーク状ガラス １０
（１１）トリエタノールアミン ０．４２
（１２）プロピレングリコール ５
（１３）防腐剤 ０．０２
（１４）イオン交換水 ５４．１９
（１５）香料 ０．３ （質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００６９】
上記材料（１）〜（９）を８５℃で溶解させ混合し、これに上記材料（１０）を添加し均一に分散させた。また、これに上記材料（１１）〜（１４）を８５℃で溶解させ混合した混合物を徐々に添加し乳化させた。乳化時の温度を１０分間保持して攪拌した後、攪拌しながら４５℃まで冷却した。これに材料（１５）を加え３５℃まで攪拌冷却を続け、その後これを容器に充填して乳化ファンデーションを得た。この化粧料の官能評価の結果を、下記「表１５」に示す。
【００７０】
（比較例６）：乳化ファンデーション
実施例６の材料（１０）フレーク状ガラスを比較例２のマイカに置換し、それ以外を実施例６と同様にして乳化ファンデーションを製造した。この化粧料の官能評価の結果を、下記「表１５」に示す。
【００７１】
（参考比較例９）：乳化ファンデーション
実施例６の材料（１０）フレーク状ガラスを参考比較例３のフレーク状ガラスに置換し、それ以外を実施例６と同様にして乳化ファンデーションを製造した。この化粧料の官能評価の結果を、下記「表１５」に併せて示す。
【００７２】
【表１５】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
項目 のび 密着感 滑らかさ 光輝感 色のきれいさ
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
実施例６ ○ ○ ◎ ◎ ◎
比較例６ ○ ○ ○ ○ △
参考比較例９ ● ● △ ○ ◎
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００７３】
「表１５」より、実施例６の化粧料は、比較例６と比べ滑らかさ、光輝感および色のきれいさで、参考比較例９と比べのび、密着感、滑らかさおよび光輝感で優れていることが判る。
【００７４】
（実施例７）：口紅
下記「表１６」に示す材料からなる口紅を製造した。
【００７５】
【表１６】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
（１）炭化水素ワックス ２０
（２）キャンデリラワックス ３
（３）グリセリルイソステアレート ４０
（４）流動パラフィン ２６．８
（５）二酸化チタン ４
（６）実施例３のフレーク状ガラス ４
（７）有機顔料 ２
（８）香料 ０．２ （質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００７６】
上記材料（１）〜（４）を８５℃で加熱溶解させ、これに（５）〜（７）を加え攪拌混合した後、さらに（８）を混合攪拌し、その後所定の容器に充填して口紅を得た。この化粧料の官能評価の結果を、下記「表１７」に示す。
【００７７】
（比較例７）：口紅
実施例７の材料（６）フレーク状ガラスを比較例３のマイカに置換し、それ以外を実施例７と同様にして口紅を製造した。この化粧料の官能評価の結果を、下記「表１７」に示す。
【００７８】
（参考比較例１０）：口紅
実施例７の材料（６）フレーク状ガラスを参考比較例３のフレーク状ガラスに置換し、それ以外を実施例７と同様にして口紅を製造した。この化粧料の官能評価の結果を、下記「表１７」に併せて示す。
【００７９】
【表１７】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
項目 のび 密着感 滑らかさ 光輝感 色のきれいさ
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
実施例７ ○ ○ ◎ ◎ ◎
比較例７ ○ ○ ○ ○ ○
参考比較例１０ ● ● △ ○ ◎
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００８０】
「表１７」より、実施例７の化粧料は、比較例７と比べ滑らかさ、光輝感および色のきれいさ、参考比較例１０と比べのび、密着感、滑らかさおよび光輝感で優れていることが判る。
【００８１】
（実施例８）：アイシャドー
下記「表１８」に示す材料からなるアイシャドーを製造した。
【００８２】
【表１８】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
（１）タルク ２１
（２）白雲母 ２０
（３）実施例４のフレーク状ガラス ４０
（４）顔料 １２
（５）スクワラン ４
（６）セチル２−エチルヘキサノエート １．９
（７）ソルビタンセスキオレート ０．８
（８）防腐剤 ０．１
（９）香料 ０．２ （質量％）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００８３】
上記材料（１）〜（４）をヘンシェルミキサーで混合し、これに（５）〜（９）を加熱混合したものを吹き付け混合した後粉砕した。これを所定の中皿に吐出して、アイシャドーを得た。この化粧料の官能評価の結果を、下記「表１９」に示す。
【００８４】
（比較例８）：アイシャドー
実施例８の材料（３）フレーク状ガラスを比較例４のマイカに置換し、それ以外を実施例８と同様にしてアイシャドーを製造した。この化粧料の官能評価の結果を、下記「表１９」に示す。
【００８５】
（参考比較例１１）：アイシャドー
実施例８の材料（３）フレーク状ガラスを参考比較例３のフレーク状ガラスに置換し、それ以外を実施例８と同様にしてアイシャドーを製造した。この化粧料の官能評価の結果を、下記「表１９」に示す。
【００８６】
【表１９】
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
項目 のび 密着感 滑らかさ 光輝感 色のきれいさ
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
実施例８ ◎ ◎ ◎ ◎ ◎
比較例８ ○ ○ ○ ○ △
参考比較例１１ ● ● △ ○ ◎
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
【００８７】
「表１９」より、実施例８の化粧料は、比較例８と比べのび、密着感、滑らかさ、光輝感および色のきれいさで、参考比較例１１と比べのび、密着感、滑らかさおよび光輝感で優れていることが判る。
【００８８】
【発明の効果】
この発明は、以上のように構成されているため、次のような効果を奏する。
この発明の真珠光沢顔料によれば、平均厚さ０．１〜２．５μm、平均粒径１〜３００μmおよびアスペクト比１０〜５００であり、母材がシリカを４５〜７５質量％含有する表面が平滑なフレーク状ガラスであって、さらに母材表面に貴金属およびチタニアが付着した真珠光沢顔料であるので、化粧料材料としてくすみがなく、非常に良好な光輝感を発現し、肌上でのざらつき感がなく、のび、フィット感に優れる安価な真珠光沢顔料を提供することができる。この効果に加えて、母材の表面に貴金属およびチタニアが付着するので、６００℃以下の加熱で緻密で安定型のルチル型チタニアの膜が形成された真珠光沢顔料を提供することができる。
【００８９】
この発明の化粧料によれば、この真珠光沢顔料を化粧料材料として用いるので、肌上でののびがよくかつフィット感に優れ、ざらつき感を生じさせることのない、光輝感に優れる発色のきれいな化粧料を提供することができる。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a pigment having a pearly luster in which the composition, thickness, particle size and aspect ratio of a base material are within a certain range, and a cosmetic containing the pigment. Further, the pearlescent pigment has a metal oxide coating.Flaky glassAbout what is.
[0002]
[Prior art]
  As a brilliant flaky powder exhibiting pearly luster, so-called pearl mica is known which has natural or synthetic mica (mica) as a base material and is coated with titanium oxide or iron oxide on the surface thereof. However, since mica has a cleaving property, a step is easily formed on its surface, and surface smoothness is often insufficient. Therefore, it is difficult to say that a pearlescent pigment based on mica exhibits a good glitter. In addition, since natural mica contains a large amount of impurities, pearlescent pigments using this as a base material cause dullness when blended in cosmetics.
[0003]
  As a pearlescent pigment, JP-A-9-176515 discloses metal oxide-coated flaky powder having an average shape ratio (average thickness / average particle size) of 1 / 9-1 and a particle size of 25-500 μm. . When this flake powder is used as a cosmetic material, the thickness of the flake is calculated to be 2.78 μm or more. Therefore, the flake powder gives a rough feeling on the skin and has a large average shape ratio and a shape close to a cube. Therefore, the spread or fit on the skin is poor, andmassSince the number of sheets is smaller than that of thin flakes, there are problems such as less glitter due to reflection.
[0004]
  Japanese Patent Application Laid-Open No. 6-116507 describes a pearlescent pigment having a flaky silica glass produced from a metal alkoxide as a base material and coated with titania or zirconia. This flaky silica glass has a problem in cost because the metal alkoxide is very expensive. In addition, silica glass has higher silica content and higher hardness than ordinary glass, so when used in cosmetic materials, it is crushed when kneaded in the material blending process, and its particle size may not be maintained. Is expensive. There is an advantage that the smaller the particle size is, the easier it is to be uniformly dispersed in the cosmetic, but there is a problem that it is difficult to express the glitter feeling as a pearlescent pigment.
[0005]
  Furthermore, Japanese Patent Application Laid-Open No. 62-187770 discloses:Flaky glassDescribes an ultraviolet shielding pigment obtained by coating finely divided titanium oxide. However, this ultraviolet shielding pigment coats titanium oxide in such an amount that a pearly luster is practically not exhibited.
[0006]
[Problems to be solved by the invention]
  As mentioned above, pearlescent pigments have been widely used in cosmetics.TheHowever, pearlescent pigments based on natural or synthetic mica are difficult to say because of their insufficient surface smoothness. Further, when natural mica is used as a base material, impurities are included, and therefore, when blended in cosmetics, it causes dullness. Furthermore, when flaky silica glass is used as a base material, there is a problem that cost and particle size cannot be maintained.
[0007]
  The present invention has been made paying attention to such problems existing in the prior art. The purpose of this product is to provide an inexpensive pearlescent pigment that has no dullness, expresses very good luster, does not feel rough on the skin, and has excellent stretch and fit when blended in cosmetics. It is to provide. Another object of the present invention is to provide a cosmetic material that has a good feeling of spreading, excellent fit, and does not produce a rough feeling.
[0008]
[Means for Solving the Problems]
  In order to achieve the above object, the pearlescent pigment of the invention according to claim 1 is composed of silica (SiO 2) as a base material.₂) 45-75massThe average thickness is 0.1 to 2.5 μm, the average particle size is 1 to 300 μm, and the aspect ratio is 10 to 500.The gist of the pearlescent pigment is that noble metal and titania adhere to the surface of the base material.. The aspect ratio refers to a value obtained by dividing the average particle diameter by the average thickness (average particle diameter / average thickness).
[0009]
  The pearl luster pigment of the invention described in claim 2 is summarized in that, in the pearl luster pigment according to claim 1, the titania is anatase titania or rutile titania. The pearlescent pigment of the invention described in claim 3 is the pearlescent pigment according to claim 1 or 2, wherein the noble metal is at least one of gold, silver, Ru, Rh, Pd, Os, Ir, and Pt. The gist is to be one. The pearl luster pigment of the invention described in claim 4 is the pearl luster pigment according to any one of claims 1 to 3, wherein the base material is flaky glass produced by a melting method. And The gist of the cosmetic of the invention described in claim 5 is a cosmetic containing the pearl luster pigment according to any one of claims 1 to 4.
[0010]
  In the method for producing a pearlescent pigment according to the invention of claim 6, a noble metal is attached to flake-like glass, anatase titania is attached thereto, and heated to 600 ° C. or less to form a coating made of rutile titania. The gist is to form the flaky glass provided. The gist of the cosmetic of the invention described in claim 7 is a cosmetic containing the pearlescent pigment produced by the method for producing a pearlescent pigment according to claim 6.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, embodiments of the present invention will be described in detail.
  The pearlescent pigment of the present invention has a base material of silica (SiO₂) 45-75mass% Content. This base material is manufactured by the melting methodFlaky glassIs mentioned.Frey GlassCan be produced by a known technique, for example, a method described in Japanese Patent Publication No. 41-17148 and Japanese Patent Publication No. 45-3541. That is, it is manufactured by a method of extruding molten glass from a circular slit, injecting air or the like into the glass, and expanding it into a hollow cylinder to form a thin and uniform glass film, which is then pulverized. thisFlaky glassIs manufactured by melting an inexpensive raw material, so that the cost can be kept low. Moreover, since the molten glass having a free surface is cooled and solidified, the surface is very smooth. Furthermore, since it is amorphous and does not have cleavage properties, no step is generated on its surface. Silica is 80massSince it has a slight flexibility as compared with silica glass containing at least%, it is difficult to be crushed even when blended in cosmetics, and the particle size during blending can be maintained. The glass may have any composition as long as it can be melt-molded, and examples include commonly used soda lime glass, C glass, and E glass. These glasses contain silica in the above range.
[0012]
  Moreover, by pulverizing and classifying a glass film having an average thickness of 0.1 to 2.5 μm, an average particle size of 1 to 300 μm and an aspect ratio of 10 to 500 are obtained.Flaky glassIs manufactured.Flaky glassHowever, if the thickness is less than 0.1 μm due to the production technology, while it is thicker than 2.5 μm, it causes a feeling of roughness in the cosmetics in which it is blended and lowers the glitter. When the aspect ratio is less than 10, the spread and fit of the blended cosmetics are worsened, while when the aspect ratio is greater than 500, the paste of the cosmetics on the skin is worsened and the glare is enhanced. Pass. When the average particle size is less than 1 μm, sufficient brightness cannot be imparted to the blended cosmetic, while when it is greater than 300 μm, the particles are too conspicuous in the blended cosmetic, resulting in a finished feeling. It will be unnatural.
[0013]
  When the shape of the base material is in the above range, depending on the silica content of the base material,Flaky glassThe nature of is different. Silica content is 75massIf it is higher than%, production by the melting method becomes difficult, and production by the sol-gel method becomes the main. A glass having a high silica content and manufactured by the sol-gel method is hereinafter referred to as “silica glass”, but the silica glass flakes having a shape within the above range have a high hardness and are brittle as described above, so that the external force exceeds a certain level. Is easily crushed when added. For example, when the silica glass flakes are irradiated with ultrasonic waves, it is confirmed that the average particle size becomes small. Specifically, when the laser diffraction particle size distribution measuring apparatus with an ultrasonic irradiation device (Pro7000S manufactured by Seishin Enterprise Co., Ltd.) is output at 65 W for 1 minute, and the silica glass lake is irradiated with ultrasonic waves, the average particle size is as follows. 1 ".
[0014]
[Table 1]

[0015]
  Moreover, it is confirmed that the average particle diameter of the silica glass flakes becomes smaller as the irradiation time of ultrasonic waves increases. Specifically, when an ultrasonic cleaning device (VS-70R manufactured by Vervo Coolia Trading Company) is output at 60 W and the silica glass flakes are irradiated with ultrasonic waves, the average particle diameter is shown in the following “Table 2” over time. It changes as follows.
[0016]
[Table 2]

[0017]
  From "Table 1" and "Table 2", it can be seen that silica glass flakes are more likely to be crushed by ultrasonic waves as the particle size increases. It can also be seen that over time, crushing is likely to occur at the initial stage of ultrasonic irradiation. Thus, the silica glass flakes are crushed by the impact of ultrasonic waves,Flaky glassThen, such a phenomenon is not confirmed. this is,Flaky glassHowever, it is considered that the silica glass flakes are not so hard and have some flexibility. Therefore,Flaky glassWhen used as a cosmetic material and blended with other materials, pearlescent pigments can maintain their original particle size compared to silica glass flakes, resulting in greater effectiveness in cosmetics. Can express a sense of brightness. In addition,Flaky glassThe silica content is 50 to 70 in order to combine the strength necessary for the base material and appropriate flexibility.mass%, Or even 55-65mass% Is preferred.
[0018]
  As the name suggests, this pearl luster pigment has a luster that resembles pearl in appearance.Flaky glassTitania (TiO₂), A coating made of a metal oxide such as zirconia or iron oxide. A known technique may be used for forming the coating film, which is described in, for example, Japanese Patent Publication No. 43-25644 and Japanese Patent Publication No. 47-34529. Specifically, in titanyl sulfate solution or titanium tetrachloride solutionFlaky glassAnd titania is precipitated by raising the temperature of the solution,Flaky glassIt is a method of providing a film on top. However, it is not limited to this method,Flaky glassAny method may be used as long as a thin film can be provided thereon.
[0019]
  Flaky glassBy controlling the thickness of the upper coating, an arbitrary color tone due to interference can be developed. The thickness of this coating is preferably 20 to 250 nm, and if it is less than 20 nm, it is difficult to develop a glittering feeling.
[0020]
  If titania is used for this coating,Flaky glassIs often heat-treated at 800 to 1,200 ° C. Titania has three crystal systems of anatase type, brookite type and rutile type, and this is performed to transfer the anatase type to the rutile type. As described above, when a titania film is provided by precipitation from a solution, an anatase type is first deposited. Since the anatase type is chemically unstable compared to the rutile type,Flaky glassWhen durability and weather resistance are required, the rutile type is directed to the anatase type. Further, the rutile-type titania film forms a denser film than the anatase-type film, and thus expresses a higher brightness, that is, vivid color. Therefore,Flaky glassAs the coating, a film made of rutile type titania is preferable and oriented.
[0021]
  It is known that when the heat treatment temperature for the crystal system transition is 800 ° C. or lower, the titania crystal system remains anatase type, but when it is higher than 800 ° C., it transitions to the rutile type. However, when heated above 800 ° C,Flaky glassMay be deformed. In order to prevent this deformation, the present inventor has found out a method of transitioning to the rutile type even by heat treatment at 800 ° C. or less after extensive research. When depositing titania from the above solution,Flaky glassIn this method, a precious metal is attached as a trace catalyst. Here, the noble metal refers to gold, silver, and platinum group (Ru, Rh, Pd, Os, Ir, Pt). Precious metalFlaky glassThere is no particular limitation on the method of adhering to the substrate. For example, in a solution of chloroplatinic acidFlaky glassCan be left for a while. In this method, it was confirmed that the crystal system transition to the rutile type occurred by heat treatment at 600 ° C. or lower.
[0022]
  Flaky glassDepending on the refractive index of the upper coating, the thickness of the coating that develops a certain color tone is slightly different, but generally the relationship between the thickness of the coating and the color development (reflected light) is as shown in Table 3 below.
[0023]
[Table 3]
----------------------
      Color development Film thickness (nm)
  --------------------
      Silver 40-60
      Yellow 60-80
      Red 80-100
      Blue 100-140
      Green 120 ~ 160
----------------------
[0024]
  Specific shape with the above metal oxide coatingFlaky glassThat is, by blending the pearl luster pigment, it is possible to obtain a cosmetic that shows clear coloration without dullness, does not feel rough on the skin, and has excellent spread and fit on the skin.
[0025]
  The blending ratio of the pearl luster pigment in this cosmetic is 1-100.mass% Is preferred. Mixing rate is 1massIf it is less than%, the glittering feeling of the pearl luster pigment is not sufficiently exhibited. On the other hand, 100massEven if it is%, since human fat etc. exist on skin, it couple | bonds with these and can function as cosmetics.
[0026]
  This cosmetic includes a wide range of cosmetics such as facial cosmetics, makeup cosmetics, and hair cosmetics. Among these, the pearl luster pigment is preferably used in makeup cosmetics such as foundations, powdered white powder, eye shadow, blusher, makeup base, nail enamel, eyeliner, mascara, lipstick, and fancy powder.
[0027]
  This pearlescent pigment may be appropriately hydrophobized depending on the purpose of the cosmetic. As the hydrophobizing treatment method, first, treatment with a silicone compound such as methyl hydrogen polysiloxane, high-viscosity silicone oil and silicone resin, and second, treatment with a surfactant such as an anionic surfactant or cationic surfactant. , Third, treatment method with high molecular compounds such as nylon, polymethyl methacrylate, polyethylene, Teflon, polyamino acid, Fourth, perfluoro group-containing compound, lecithin, collagen, metal soap, lipophilic wax, polyhydric alcohol partial ester Or the processing method by perfect ester etc., and the processing method which combined these 5th are mentioned. However, the method is not limited to the above method as long as it is generally applicable to powder hydrophobization treatment.
[0028]
  In this cosmetic, other materials usually used in cosmetics can be appropriately blended as necessary. For example, talc, kaolin, sericite, muscovite, phlogopite, sauroite, biotite, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate, silicic acid Barium, barium sulfate, strontium silicate, metal tungstate, silica, hydroxyapatite, zeolite, boron nitride, ceramic powder and other inorganic powders, nylon powder, polyethylene powder, polystyrene powder, benzoguanamine powder, polytetrafluoroethylene powder, Organic powders such as distyrenebenzene polymer powder, epoxy powder, acrylic powder, microcrystalline cellulose, inorganic white pigments such as titanium oxide and zinc oxide, iron oxide (Bengara), iron titanate, etc. Machine red pigments, inorganic brown pigments such as γ iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher, inorganic black pigments such as black iron oxide and carbon black, inorganic purple pigments such as mango violet and cobalt violet Pigments, inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine and bitumen, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, bismuth oxychloride, titanium oxide coated talc, Pearl pigments such as fish scale foil, colored titanium oxide-coated mica, metal powder pigments such as aluminum powder and copper powder, red 201, red 202, red 204, red 205, red 220, red 226, red 228 No., Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 4 Organic pigments such as No. 04, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202 , Yellow 203, green 3 and blue 1 organic pigments such as zirconium, barium or aluminum lakes, natural pigments such as chlorophyll, β-carotene, squalane, liquid paraffin, petrolatum, microcrystalline wax, okezolite, ceresin, myristin Acid, palmitic acid, stearic acid, oleic acid, isostearic acid, cetyl alcohol, hexadecyl alcohol, oleyl alcohol, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, di-2-ethylhexane Neopentyl glyco acid Glycerol, tri-2-ethylhexanoic acid glycerol, oleic acid-2-octyldodecyl, isopropyl myristate, glycerol triisostearate, triglyceride fatty acid glycerol, olive oil, avocado oil, beeswax, myristyl myristate, mink oil, lanolin, etc. Various hydrocarbons, silicone oils, higher fatty acids, oils and fats, oily components such as higher alcohols and waxes, organic solvents such as acetone, toluene, butyl acetate, and acetates, resins such as alkyd resins and urea resins, camphor, Examples include plasticizers such as acetyltributyl citrate, ultraviolet absorbers, antioxidants, preservatives, surfactants, moisturizers, fragrances, water, alcohols, thickeners, and the like.
[0029]
  The form of the cosmetic is not particularly limited, and may be powder, cake, pencil, stick, ointment, liquid, emulsion, cream or the like.
[0030]
  The present invention can also be embodied as the following embodiment..
  ・Flaky glassA noble metal such as platinum was attached to the surface, and anatase-type titania was attached thereto, and heated to 600 ° C. or less to provide a coating made of rutile-type titania.Flaky glassHow to manufacture.
[0031]
【Example】
  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
  First,Flaky glassA pearlescent pigment coated with a metal oxide is described below.
[0032]
(Reference example 1) ~ (Reference example 4)
  C glass (SiO₂: 65mass%, Al₂O_Three: 4mass%, CaO: 14mass%, MgO: 3mass%, B₂O_Three: 5mass%, Na₂O: 8mass%, K₂O: 1mass%) Is melted at 1,200 ° C., blown into a cylindrical shape, drawn into a thin film, cooled and solidified to a predetermined thickness, and pulverized and classified to have a predetermined thickness, particle size and aspect ratio.Flaky glassManufactured. thisFlaky glassIs suspended in the titanyl sulfate solution and the suspension is heated to boiling for 1 hour,Flaky glassThe surface was coated with titania of various thicknesses, washed with filtered water, dried, and then heat treated at 600 ° C. for 30 minutes to provide a titania coating.Flaky glassGot. When the crystal system of the titania coating was examined by X-ray diffraction, all were of anatase type.
[0033]
  Here, depending on the thickness of the titania coatingFlaky glassThe color of theFlaky glassSince the specific surface area varies depending on the thickness and particle size, the conditions for obtaining the intended titania coating in each example cannot be uniquely determined. Therefore, in the titania coating formation stageFlaky glassThe sample is appropriately sampled from the suspension, and the amount of titanyl sulfate added is adjusted while confirming the color of the suspension.Flaky glassManufactured.
[0034]
  With these various thicknesses, grain sizes and aspect ratiosFlaky glassWas packed in a silica cell having a diameter of 60 mm and a height of 10 mm, and the lightness (L value) was measured with a color difference meter (CR300 manufactured by Minolta). Moreover, the diffuse reflectance of 45 ° / 0 ° was measured with a gloss meter (Nippon Denshoku Industries Co., Ltd. VGS-1001DP), and the luminance was evaluated. theseFlaky glassThe characteristics and luminance evaluation results are shown in Table 4 below.
[0035]
(Reference Comparative Example 1) ~ (Reference Comparative Example 3)
  Mica with a commercially available anatase-type titania coating,Flaky glassWith respect to the one in which an anatase-type titania film was molded by the method of the above example (RCF-140 manufactured by Nippon Sheet Glass Co., Ltd.), the lightness (L value) and the diffuse reflectance of 45 ° / 0 ° were the same as described above. Was measured and its luminance was evaluated. The results are also shown in the following “Table 4”. In addition,Reference Comparative Example 3ofFlaky glassThere is no precious metal attached.
[0036]
  Reference example 1~4ofFlaky glassBoth have luminance (L value and diffuse reflectance)Reference Comparative Example 1and2It is higher than that of Mica, and it is clear that it is very clear and bright.
[0037]
[Table 4]
  With anatase-type titania coatingFlaky glassAnd mica brightness and gloss
-----------------------------------
              Reference example                          Reference comparison example
               1      2       3      4      1      2      3
----------------------------------
Base material Glass Glass Glass Glass Mica Mica Glass
Average thickness (μm) 2.3 2.3 2.3 1.3 0.4 0.6 5.0
Average particle size (μm) 450 80 40 25 40 80 140
Aspect ratio 196 35 17 19 100 113 28
Reflective color Silver Silver Silver Red Silver Silver Silver
Lightness (L value) 93 92 91 91 88 89 90
Diffuse reflectance 66 62 61 63 52 54 60
-----------------------------------
[0038]
(Example1)~(Example4)
  the aboveReference example 1~4In the same way asFlaky glassManufactured. thisFlaky glassIs suspended in a titanium tetrachloride solution to which chloroplatinic acid is added, and the suspension is heated and boiled for 1 hour.Flaky glassThe surface was provided with titania coatings of various thicknesses. thisFlaky glassThe filtrate was washed with water and dried, and then heat-treated at 600 ° C. for 30 minutes. When the crystal system of the titania coating was examined by X-ray diffraction, all were rutile types. this is,Flaky glassThis is thought to be because platinum attached to the metal acted as a catalyst for promoting the transition to the rutile type. With these various thicknesses, grain sizes and aspect ratiosFlaky glassAbout aboveReference example 1~4The luminance was evaluated in the same manner as described above. The results are shown in “Table 5” below.
[0039]
(Comparative example1) ~ (Comparative example4)
  For mica provided with a commercially available rutile-type titania film, the luminance was evaluated in the same manner as described above. The results are shown in “Table 6” below.
[0040]
[Table 5]
  With rutile-type titania coatingFlaky glassBrightness and gloss
--------------------------
    Example 1        2        3        4
  ------------------------
  Base material Glass Glass Glass Glass
  Average thickness (μm) 2.3 1.3 1.3 0.7
  Average particle size (μm) 300 80 80 25
  Aspect ratio 130 62 62 36
  Reflection color Silver Gold Red Blue
  Lightness (L value) 95 94 93 92
  Diffuse reflectance 70 62 74 74
--------------------------
[0041]
[Table 6]
  Brightness and gloss of mica with rutile-type titania coating
--------------------------
    Comparative example1        2        3        4
  ------------------------
  Base material Mica Mica Mica Mica
  Average thickness (μm) 0.4 0.4 0.4 0.6
  Average particle size (μm) 40 40 40 80
  Aspect ratio 100 100 100 133
  Reflection color Silver Gold Red Blue
  Lightness (L value) 91 90 90 89
  Diffuse reflectance 50 60 65 63
--------------------------
[0042]
  From "Table 5" and "Table 6", Examples1~4ofFlaky glassAre comparative examples of brightness (L value and diffuse reflectance).1~4It is higher than that of Mica, and it is clear that it is very clear and bright.
[0043]
  Next, the titania coating was provided.Flaky glassThat is, a cosmetic containing a pearlescent pigment will be described. The cosmetics were evaluated by a five-step sensory evaluation by 10 panelists based on the following “Table 7”.
[0044]
[Table 7]
  Sensory evaluation of cosmetics
-----------------------------------
  Evaluation \ Item Nodularity Adhesion Smoothness Brightness Color cleanliness
  ----------------------------------
      1 bad no no no dirty
      2 Somewhat bad Somewhat not Somewhat not much Not much
      3 Normal Normal Normal Somewhat normal
      4 Somewhat good Somewhat some Some pretty
      5 good very very very high very clean
-----------------------------------
[0045]
  The result of sensory evaluation is an average value of five-level evaluation of 10 panelists, and is expressed by the following symbols for easy understanding of the evaluation.
  ◎ ... 4.5 to 5.0
  ○ ... 3.5 or more and less than 4.5
  ● ・ ・ ・ 2.5 to 3.5
  Δ: 1.5 or more and less than 2.5
  × ... 1.0 or more and less than 1.5
[0046]
(Reference Example 5): Powder foundation
  The powder foundation which consists of a material shown to the following "Table 8" was manufactured.
[0047]
[Table 8]
----------------------------------
  (1) Titanium oxide 7
  (2) Talc 20
  (3) muscovite 3
  (4)Reference example 2ofFlaky glass            55
  (5) Nylon powder 2
  (6) Red iron oxide 0.5
  (7) Yellow iron oxide 1
  (8) Black iron oxide 0.1
  (9) Silicone oil 1
  (10) 2-ethylhexyl valmitate 9
  (11) Sorbitan sesquioleate 1
  (12) Preservative 0.3
  (13) Fragrance 0.1 (mass%)
----------------------------------
[0048]
  The materials (1) to (8) were mixed with a Henschel mixer, the materials (9) to (13) were heated and dissolved in the mixture, mixed and added, and pulverized with a pulverizer. Furthermore, this is discharged into a dish with a diameter of 5.3 mm, and 160 kg / cm²The powder foundation was manufactured by press molding at a pressure of 5 m. The results of sensory evaluation of this cosmetic are shown in “Table 9” below.
[0049]
(Reference Comparative Example 4): Powder foundation
  The above material (4)Flaky glassTheReference Comparative Example 1Replace with other micaReference Example 5A powder foundation was produced in the same manner as described above. The results of sensory evaluation of this cosmetic are shown in “Table 9” below.
[0050]
(Reference Comparative Example 5): Powder foundation
  The above material (4)Flaky glassTheReference Comparative Example 3ofFlaky glassReplace withReference Example 5A powder foundation was produced in the same manner as described above. The results of sensory evaluation of this cosmetic are also shown in the following “Table 9”.
[0051]
[Table 9]
----------------------------------
    Item No. Feeling of adhesion Smoothness Brightness Color cleanliness
  -------------------------------
  Reference Example 5        ○ ○ ○ ◎ ◎
  Reference Comparative Example 4    ○ ○ ○ ○ ○
  Reference Comparative Example 5    ● ● △ ○ ◎
----------------------------------
[0052]
  From "Table 9"Reference Example 5CosmeticsReference Comparative Example 4Compared with shine and color,Reference Comparative Example 5It can be seen that it is excellent in adhesion, smoothness and smoothness.
[0053]
(Reference Example 6): Brusher
  A blusher made of the material shown in Table 10 below was manufactured.
[0054]
[Table 10]
-------------------------------
  (1) Talc 12.6
  (2) Mica 8.1
  (3) Mica 25.4
  (4)Reference example 3ofFlaky glass          45.0
  (5) Red No. 226 0.4
  (6) Squalane 3.0
  (7) 2-ethylhexyl palmitate 5.0
  (8) Preservative 0.3
  (9) Fragrance 0.2 (mass%)
---------------------------------
[0055]
  The materials (1) to (5) were mixed with a Henschel mixer, the materials (6) to (9) were heated and dissolved in the mixture, and the mixture was sprayed and mixed, and then pulverized using a pulverizer. Furthermore, this is discharged into a 4 x 6 cm pan, 120 kg / cm²A blusher was manufactured by press molding. The results of sensory evaluation of this cosmetic are shown in “Table 11” below.
[0056]
(Reference Comparative Example 6): Brusher
  Reference Example 6Material (4)Flaky glassTheReference Comparative Example 2Replace with other micaReference Example 6A blusher was produced in the same manner. The results of sensory evaluation of this cosmetic are shown in “Table 11” below.
[0057]
(Reference Comparative Example 7): Brusher
  Reference Example 6Material (4)Flaky glassTheReference Comparative Example 3ofFlaky glassReplace withReference Example 6A blusher was produced in the same manner. The results of sensory evaluation of this cosmetic are also shown in the following “Table 11”.
[0058]
[Table 11]
-----------------------------------
    Item No. Feeling of adhesion Smoothness Brightness Color cleanliness
  ---------------------------------
  Reference Example 6        ○ ○ ○ ◎ ◎
  Reference Comparative Example 6    ○ ○ ○ ○ ○
  Reference Comparative Example 7    ● ● △ ○ ◎
-----------------------------------
[0059]
  From "Table 11"Reference Example 6CosmeticsReference Comparative Example 6Compared with shine and color,Reference Comparative Example 7It can be seen that it is superior in terms of adhesion, smoothness and radiance.
[0060]
(Example5): Nail enamel
  Nail enamels made of the materials shown in Table 12 below were produced.
[0061]
[Table 12]
--------------------------------
  (1) Nitrocellulose 12
  (2) Modified alkyd resin 12
  (3) Acetyltributyl citrate 5
  (4) n-butyl acetate 36.4
  (5) Ethyl acetate 6
  (6) n-Butyl alcohol 2
  (7) Toluene 21
  (8) Iron oxide pigment 0.5
  (9) Titanium dioxide 0.1
  (10) Examples3ofFlaky glass            3
  (11) Mica 1
  (12) Organic metamorphic montmorillonite 1 (mass%)
--------------------------------
[0062]
  Dissolve the above materials (1) to (7) (however, material (4) is a part), and mix and mix the material (12) and the rest of material (4) into a gel. Further, the materials (8) to (11) were added and mixed. This mixture was filled in a predetermined container to produce a nail enamel. The results of sensory evaluation of this cosmetic are shown in “Table 13” below.
[0063]
(Comparative example5): Nail enamel
  Example5Material of (10)Flaky glassThe comparative example3Example of replacing with other mica5Nail enamel was produced in the same manner as described above. The results of sensory evaluation of this cosmetic are shown in “Table 13” below.
[0064]
(Reference Comparative Example 8): Nail enamel
  Example5Material of (10)Flaky glassTheReference Comparative Example 3ofFlaky glassTo the other examples5Nail enamel was produced in the same manner as described above. The results of sensory evaluation of this cosmetic are shown in “Table 13” below.
[0065]
[Table 13]
-----------------------------------
    Item No. Feeling of adhesion Smoothness Brightness Color cleanliness
  ---------------------------------
  Example5        ○ ○ ◎ ◎ ◎
  Comparative example5        ○ ○ ○ ○ ○
  Reference Comparative Example 8    ● ● △ ○ ◎
-----------------------------------
[0066]
  From “Table 13”, Examples5Cosmetics are comparative examples5Compared with smoothness, radiance and clean color,Reference Comparative Example 8It can be seen that it is superior in terms of adhesion, smoothness and radiance.
[0067]
(Example6): Emulsion foundation
  An emulsified foundation made of the materials shown in Table 14 below was produced.
[0068]
[Table 14]
----------------------------------
  (1) Stearic acid 0.4
  (2) Isostearic acid 0.3
  (3) Cetyl 2-ethylhexanoate 4
  (4) Liquid paraffin 11
  (5) Polyoxyethylene (10) stearyl ether 2
  (6) Talc 8
  (7) Pigment 4
  (8) Cetyl alcohol 0.3
  (9) Preservative 0.07
  (10) Examples2ofFlaky glass                10
  (11) Triethanolamine 0.42
  (12) Propylene glycol 5
  (13) Preservative 0.02
  (14) Ion exchange water 54.19
  (15) Fragrance 0.3 (mass%)
-----------------------------------
[0069]
  The materials (1) to (9) were dissolved and mixed at 85 ° C., and the material (10) was added thereto and dispersed uniformly. Moreover, the said material (11)-(14) was melt | dissolved in this at 85 degreeC, and the mixture which mixed was gradually added and emulsified. After stirring for 10 minutes at the temperature during emulsification, the mixture was cooled to 45 ° C. while stirring. The material (15) was added thereto, and stirring and cooling were continued to 35 ° C., after which this was filled in a container to obtain an emulsified foundation. The results of sensory evaluation of this cosmetic are shown in “Table 15” below.
[0070]
(Comparative example6): Emulsion foundation
  Example6Material of (10)Flaky glassThe comparative example2Example of replacing mica6An emulsified foundation was produced in the same manner as described above. The results of sensory evaluation of this cosmetic are shown in “Table 15” below.
[0071]
(Reference Comparative Example 9): Emulsion foundation
  Example6Material of (10)Flaky glassTheReference Comparative Example 3ofFlaky glassTo the other examples6An emulsified foundation was produced in the same manner as described above. The results of sensory evaluation of this cosmetic are also shown in the following “Table 15”.
[0072]
[Table 15]
----------------------------------
    Item No. Feeling of adhesion Smoothness Brightness Color cleanliness
  --------------------------------
  Example6        ○ ○ ◎ ◎ ◎
  Comparative example6        ○ ○ ○ ○ △
  Reference Comparative Example 9    ● ● △ ○ ◎
----------------------------------
[0073]
  From “Table 15”, Examples6Cosmetics are comparative examples6Compared with smoothness, radiance and clean color,Reference Comparative Example 9It can be seen that it is superior in terms of adhesion, smoothness and radiance.
[0074]
(Example7):lipstick
  Lipsticks made of the materials shown in Table 16 below were produced.
[0075]
[Table 16]
-----------------------------------
  (1) Hydrocarbon wax 20
  (2) Candelilla wax 3
  (3) Glyceryl isostearate 40
  (4) Liquid paraffin 26.8
  (5) Titanium dioxide 4
  (6) Examples3ofFlaky glass                    4
  (7) Organic pigment 2
  (8) Fragrance 0.2 (mass%)
-----------------------------------
[0076]
  The above materials (1) to (4) are heated and dissolved at 85 ° C., (5) to (7) are added and stirred and mixed, and then (8) is further mixed and stirred, and then filled into a predetermined container. I got lipstick. The results of sensory evaluation of this cosmetic are shown in “Table 17” below.
[0077]
(Comparative example7):lipstick
  Example7Material (6)Flaky glassThe comparative example3Example of replacing mica7Lipsticks were produced in the same manner as described above. The results of sensory evaluation of this cosmetic are shown in “Table 17” below.
[0078]
(Reference Comparative Example 10):lipstick
  Example7Material (6)Flaky glassTheReference Comparative Example 3ofFlaky glassTo the other examples7Lipsticks were produced in the same manner as described above. The results of sensory evaluation of this cosmetic are also shown in the following “Table 17”.
[0079]
[Table 17]
----------------------------------
    Item No. Feeling of adhesion Smoothness Brightness Color cleanliness
  -------------------------------
  Example7          ○ ○ ◎ ◎ ◎
  Comparative example7          ○ ○ ○ ○ ○
  Reference Comparative Example 10    ● ● △ ○ ◎
----------------------------------
[0080]
  From “Table 17”, Examples7Cosmetics are comparative examples7Compared with smoothness, glitter and color cleanliness,Reference Comparative Example 10It can be seen that it is superior in terms of adhesion, smoothness and radiance.
[0081]
(Example8): Eye shadow
  Eye shadows made of the materials shown in Table 18 below were produced.
[0082]
[Table 18]
---------------------------------
  (1) Talc 21
  (2) muscovite 20
  (3) Examples4ofFlaky glass              40
  (4) Pigment 12
  (5) Squalane 4
  (6) Cetyl 2-ethylhexanoate 1.9
  (7) Sorbitan sesquioleate 0.8
  (8) Preservative 0.1
  (9) Fragrance 0.2 (mass%)
---------------------------------
[0083]
  The materials (1) to (4) were mixed with a Henschel mixer, and the mixture obtained by heating and mixing (5) to (9) was sprayed and mixed, followed by pulverization. This was discharged into a predetermined middle dish to obtain an eye shadow. The results of sensory evaluation of this cosmetic are shown in “Table 19” below.
[0084]
(Comparative example8): Eye shadow
  Example8Material (3)Flaky glassThe comparative example4Example of replacing mica8An eye shadow was produced in the same manner. The results of sensory evaluation of this cosmetic are shown in “Table 19” below.
[0085]
(Reference Comparative Example 11): Eye shadow
  Example8Material (3)Flaky glassTheReference Comparative Example 3ofFlaky glassTo the other examples8An eye shadow was produced in the same manner. The results of sensory evaluation of this cosmetic are shown in “Table 19” below.
[0086]
[Table 19]
----------------------------------
    Item No. Feeling of adhesion Smoothness Brightness Color cleanliness
  -------------------------------
  Example8          ◎ ◎ ◎ ◎ ◎
  Comparative example8          ○ ○ ○ ○ △
  Reference Comparative Example 11    ● ● △ ○ ◎
----------------------------------
[0087]
  From Table 19, Examples8Cosmetics are comparative examples8Compared with, with a feeling of adhesion, smoothness, radiance and color,Reference Comparative Example 11It can be seen that it is superior in terms of adhesion, smoothness and radiance.
[0088]
【The invention's effect】
  Since this invention is comprised as mentioned above, there exist the following effects.
  ThisAccording to the pearl luster pigment of the invention, the average thickness is 0.1 to 2.5 μm, the average particle size is 1 to 300 μm, the aspect ratio is 10 to 500, and the base material is 45 to 75 silica.mass% Containing surface is smoothFlaky glassAnd on the surface of the base materialPrecious metal and titania adheredBecause it is a pearlescent pigment, it is possible to provide an inexpensive pearlescent pigment that has no dullness as a cosmetic material, expresses a very good radiance, does not feel rough on the skin, and has an excellent stretch and fit. it can.ThisIn addition to the above effects, noble metal and titania adhere to the surface of the base material, so that a dense and stable rutile titania film is formed by heating at 600 ° C. or lower.Can provide pearlescent pigments.
[0089]
  ThisAccording to the cosmetic of the present invention, since this pearl luster pigment is used as a cosmetic material, it has good color development with excellent radiance without causing a feeling of roughness, with good stretch on the skin and excellent fit. Cosmetics can be provided.

Claims (7)

In the pearlescent pigment in which the base material contains 45 to 75% by mass of silica (SiO ₂ ), the average thickness is 0.1 to 2.5 μm, the average particle diameter is 1 to 300 μm, and the aspect ratio is 10 to 500 ,
A pearlescent pigment characterized in that noble metal and titania adhere to the surface of the base material . The pearlescent pigment according to claim 1, wherein the titania is anatase titania or rutile titania. The pearlescent pigment according to claim 1 or 2, wherein the noble metal is at least one of gold, silver, Ru, Rh, Pd, Os, Ir, and Pt. The pearlescent pigment according to any one of claims 1 to 3, wherein the base material is flaky glass produced by a melting method. Cosmetics which mix | blended the pearl luster pigment as described in any one of Claims 1-4. A pearlescent pigment characterized by forming a flake-like glass having a coating made of rutile-type titania by attaching a noble metal to the flake-like glass, attaching anatase-type titania thereto, and heating to 600 ° C. or less. Manufacturing method. Cosmetics which mix | blended the pearl luster pigment manufactured with the manufacturing method of the pearl luster pigment of Claim 6.