JP3848697B2 - Ultraviolet shielding composite fine particles, production method thereof and cosmetics - Google Patents

Description

【００９０】
（式中、Ｒ¹ 及びＲ² はそれぞれ炭素数１〜４のアルキル基を示し、Ｒ³ は炭素数１〜40の直鎖、分岐鎖又は環状のアルキル基、アルケニル基又はフルオロアルキル基を示し、Ｒ⁴ は炭素数７〜40の直鎖、分岐鎖又は環状のアルキル基、アルケニル基又はフルオロアルキル基を示し、ｅは２以上の数で、ｆは３以上の数で、ｅ＋ｆ＝５〜6000となる数を示す。）で表される単位を有するオルガノポリシロキサン等を挙げることができる。
これらのシリコーン油の配合量は、化粧料中において２〜80重量％が配合でき、好ましくは５〜50重量％、さらに好ましくは８〜４０重量％である。
【００９１】
エーテル変性シリコーンとしてはシロキサンの少なくとも一部にエーテル結合を有する基が置換した化合物であれば特に制限されるものではなく、例えば下記のものを挙げることができ、それらは単独又は２種以上を組み合わせて用いることができる。
かかるエーテル変性シリコーンの具体例としては、例えば下記▲１▼〜▲４▼の化合物が挙げられる。
▲１▼一般式（３）
【００９２】
【化２】

【００９３】
（式中、Ｒ¹¹、Ｒ¹²及びＲ¹³のうち少なくとも一つは、次式；R¹⁴(OC₃H₆)b(OC₂H₄)aO(CH₂)p−（Ｒ¹⁴は水素原子または炭素数1 〜12のアルキル基を示し、ａ及びｂは平均値で、それぞれ０〜35の数を示し、ｐは１〜５の数を示す。）で表される基を示し、残余はメチル基を示し、ｍ及びｎは平均値であり、ｍは１〜200 の数を示し、ｎは0 〜50の数を示す。）で表されるエーテル変性シリコーン。
これらのうち分子量が2000〜50000 であり、Ｒ¹¹〜Ｒ¹³の占める割合が分子量の5 〜40％であるのもが好ましい。更に、一般式（３）中、ｍが5 〜80、ｎが0 〜2 、ａが9 〜10、ｂが0 、ｐが3 、Ｒ¹⁴が水素原子であるもの又はｍが90〜110 、ｎが0 、ａが11〜13、ｂが0 、ｐが3 、Ｒ¹⁴が水素原子であるものが好ましい。
このような（３）で表されるエーテル変性シリコーンとしては、東レ・ダウコーニング社製のＳＨ-3775 シリーズの市販品を用いることもできる。
▲２▼一般式（４）
【００９４】
【化３】

【００９５】
（式中、Ｒ²¹は炭素数1 〜5 の炭化水素基を示し、Ｒ²²は炭素数6 〜16の炭化水素基を示し、Ｑはアルキレン基を示し、Ｒ²³は次式；−(OC₂H₄)q−(OC₃H₆)r−OR²⁴（Ｒ²⁴は水素原子又は低級アルキル基を示し、ｑ及びｒはｑ≦ｒで、かつ−(OC₂H₄)q−(OC₃H₆)rの分子量が600 〜3500となる数を示す。）で表される基を示し、ｚは1 〜3 の数を示し、ｘ及びｙは、ｘ＜3 ｙで、かつｘ＋ｙ＋ｚ＝30〜400 となる数を示す。ただし、−(OC₂H₄)q−(OC₃H₆)rの総重量は式（４）で表されるポリエーテル・アルキル変性シリコーンの全重量の1/3 を超えない。）で表されるポリエーテル・アルキル変性シリコーン。
【００９６】
一般式（４）中のＲ²¹で示される炭素数1 〜5 の炭化水素基としては、炭素数1 〜5 のアルキル基またはアルケニル基、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基又はビニル基等を挙げることができ、これらのなかでもメチル基が好ましい。また、Ｒ²²で示される炭素数6 〜16の炭化水素基としては、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラドデシル基、ヘキサデシル基等の直鎖アルキル基、イソオクチル基、ｓ- オクチル基、2-エチルヘキシル基等の分岐鎖アルキル基を挙げることができ、これらの中でもドデシル基が好ましい。なお、ｙ＞1 の場合には、Ｒ²²は繰り返し単位ごとに同一であっても任意に異なる物であってもよい。
【００９７】
式（４）中のＱで示されるアルキレン基としては、メチレン基、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基を挙げることができ、これらの中でもプロピレン基、トリメチレン基が好ましい。
式（４）中、Ｒ²³を示す基中のＲ²⁴は水素原子又は低級アルキル基（例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基）を示すが、これらの中でも水素原子が好ましい。また、ｑ及びｒとしては、ｑ＝15でｒ＝0 、ｑ＝ｒ＝25、又はｑ＝29でｒ＝7 が好ましい。
このような式（４）で表されるポリエーテル・アルキル変性シリコーンとしては、東レ・ダウコーニング社製の「ＤＣ Ｑ2-2500」（ラウリルメチコンコポリオール；式（４）においてＲ²¹がメチル基、Ｒ²²がドデシル基、ｘ＝0 ）等も用いることもできる。
▲３▼一般式（５）
【００９８】
【化４】

【００９９】
（式中、Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴のうち少なくとも1 個が次の式（６）；−Ａ−OCH₂CH(OR⁴¹)CH₂OR⁴² （ここで、Ａは炭素数3 〜20の2 価の炭化水素基を示し、Ｒ⁴¹およびＲ⁴²はそれぞれ水素原子又は炭素数1 〜5 の炭化水素基を示す。ただし、Ｒ⁴¹及びＲ⁴²のいずれか一方は水素原子を示す。）で表される基を示し、残余が炭素数1 〜30の直鎖、分岐鎖もしくは環状の炭化水素基又は次の式；−BR⁴³（ここで、Ｂはエーテル結合及び／又はエステル結合を含む2 価の炭化水素基を示し、Ｒ⁴³は炭素数1 〜30の直鎖、分岐鎖もしくは環状の炭化水素基を示す。）で表される基を示し、ｓ、ｔ及びｕはそれぞれ0 〜200 の数を示し、ｓ＋ｔ＋ｕ＝0 のときＲ³¹のうち１以上は前記式（６）で表される基を示す（ただし、Ｒ³¹のうち一つが一般式（６）中のＡがトリメチレン基で、Ｒ⁴¹及びＲ⁴²が水素原子のものであり、残余のＲ³¹ Ｒ³²、Ｒ³³及びＲ³⁴がすべてメチル基である場合を除く。）。）で表されるアルキルグリセリルエーテル変性シリコーン。
【０１００】
上記一般式（５）中のＡで示される炭素数3 〜20の2 価の炭化水素基としては、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、ウンデカメチレン基、ドデカメチレン基、テトラデカメチレン基、ヘキサデカメチレン基、オクタデカメチレン基等の直鎖アルキレン基、プロピレン基、2-メチルトリメチレン基、2-メチルテトラメチレン基、2-メチルペンタメチレン基、3-ペンタメチレン基等の分岐鎖アルキレン基を挙げることができる。Ｒ⁴¹及びＲ⁴²で表される炭素数1 〜5 の炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、ｓ- ブチル基、ｔ- ブチル基、ネオペンチル基、シクロペンチル基等の直鎖、分岐鎖もしくは環状のアルキル基を挙げることができる。更に、Ｂで示されるエーテル結合及び／又はエステル結合を含む2 価の炭化水素基としては、次式；−(CH₂)h−(OC₂H₄)i−(OC₃H₆)j−O −、−(CH₂)h−O −CO−、−(CH₂)h−COO −（これらのなかで、ｈは3 〜20の整数を示し、ｉ及びｊは0 〜50の数を示す。）で表される基等を挙げることができる。
【０１０１】
また、Ｒ⁴³で示される炭素数1 〜30の直鎖、分岐鎖もしくは環状の炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、ドエイコシル基、テトラエイコシル基、ヘキサエイコシル基、オクタエイコシル基、トリアコンチル基等の直鎖アルキル基、イソプロピル基、ｓ- ブチル基、ｔ- ブチル基、ネオペンチル基、1-エチルプロピル基、1-ヘプチルデシル基等の分岐鎖アルキル基、シクロペンチル基、シクロヘキシル基、アビエチル基、コレステリル基等の環状アルキル基を挙げることができる。
このような式（５）で表されるアルキルグリセリルエーテル変性シリコーンは、特開平４−１０８７９５号公報記載の方法により製造することができる。
これらのエーテル変性シリコーンの配合量は、化粧料中において0.05〜20重量％が好ましく、特に１〜10重量％が更に好ましい。
【０１０２】
本発明の紫外線遮蔽性複合微粒子の化粧料における配合量は、化粧料の種類により異なるが、０．０１〜５０重量％が好ましく、０．０５〜４０重量％がさらに好ましく、０．１〜３０重量％が特に好ましい。この範囲未満では紫外線遮蔽効果が充分発揮できず、この範囲を超えると化粧料としての感触が損なわれる。また、本発明の紫外線遮蔽性複合微粒子の分散油剤を化粧料に用いる場合の配合量は、上記分散油剤中に含有される上述の紫外線遮蔽性複合微粒子の化粧料における配合量を満たすように決定される。
本発明の化粧料は、常法により種々の形態で使用され、その形態は特に制限されないが、化粧水、乳液、クリーム、軟膏、エアゾール化粧料、パウダーファンデーション、パウダーアイシャドー、乳化型ファンデーション、口紅等のメーキャップ化粧料、毛髪化粧料、皮膚洗浄剤等として使用される。
【０１０３】
また、本発明の化粧料は、ジ オプトメトリクス グループ（The Optometrics Group ）社製のＳＰＦ−２９０アナライザーを用いてＳＰＦを測定した場合、その値が８以上であり、皮膚塗布前後の、ＪＩＳ Ｚ８７２９−１９８０において定義されるΔＥ^* abが３以下であるものが好適である。紫外線防御効果を充分に発揮させる観点から、ＳＰＦは８以上が好ましく、さらに好ましくは１０以上であり、特に好ましくは１３以上である。また、ΔＥ^* abは、皮膚塗布時の外観を損なわせない観点から３以上が好ましく、より好ましくは２以下、特に好ましくは１以下である。
【０１０４】
【実施例】
以下に本発明の実施例及び比較例を示し、本発明をさらに詳細に説明するが、本発明はこれらの実施例等によって限定されるものではない。
実施例１
シリカゾル（日産化学工業（株）製ＳＴ−Ｃ、ＳｉＯ₂ 濃度２０．５重量％）３６６．５ｇ、酸化チタン超微粒子（石原産業（株）製ＴＴＯ−５１（Ａ）、ルチル型）２０．０ｇ及び水を混合して１Ｌとし、原料液とした（即ち、当該原料液のＳｉＯ₂ 及びＴｉＯ₂ の濃度はそれぞれ１．２５ｍｏｌ／Ｌ及び０．２５ｍｏｌ／Ｌであり、当該原料液は粒子混合物を約１０重量％含有するものである。）。
【０１０５】
調製した原料液とガラスビーズ（平均粒子径０．１ｍｍ）を重量比で１７５：３２５になるように混合した混合物を、ビーズミル（ＩＧＡＲＡＳＨＩＫＩＫＡＩ製ＴＳＧ−６Ｈ）を用いて、翼回転数２０００ｒ．ｐ．ｍ．、６時間の分散処理を行った。分散処理の終了後、ガラスビーズを分離し、ＴｉＯ₂ ／ＳｉＯ₂ （子粒子／母粒子、以下も同様に表示する）複合微粒子の分散液を得た。
【０１０６】
上記分散液８４．６ｇ、エタノール１５００ｇ、テトラエトキシシラン１６．２６ｇを混合し、ウォーターバス中にて５０℃に昇温した。この分散液の温度が５０℃に到達した後、１Ｎ塩酸３．９ｍＬとエタノール３００ｇの混合溶液を滴下した。滴下後５０℃で２時間３０分反応を行い、複合微粒子をＳｉＯ₂ で表面被覆した。被覆終了後、４Ｎ水酸化ナトリウム水溶液０．９８ｍＬとエタノール５０ｇの混合溶液を加えて塩酸を中和した。以上の工程は全て撹拌下で行った。
【０１０７】
被覆処理後の分散液を遠心分離器にかけて固液分離を行い、含エタノールケーキを得た。このケーキにエタノールを加え、ケーキをエタノール中に分散させ、再び遠心分離器にかけて固液分離を行うといった工程を５回行い、固形分濃度約４０重量％の複合微粒子含エタノールケーキを得た。
このケーキ１２．５ｇをアセトン５００ｇと混合し、超音波分散を行った。ケーキがアセトン中に完全に分散した後、メチルハイドロジェンポリシロキサン（信越シリコーン（株）製、ＫＦ９９Ｐ）２．０ｇを加え混合して撥水処理を行った。その後、該分散液を８０℃で乾燥させ、１３０℃で２時間焼き付けし、複合微粒子の乾燥処理を行った。生成した粉体をミル（ＩＫＡ社製Ａ１０）で１０回繰り返し粉砕し、複合微粒子を得た。
【０１０８】
複合微粒子含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（大塚電子（株）製ＤＬＳ−７００）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０８μｍであった。
【０１０９】
撥水処理後の複合微粒子は白色で、走査型電子顕微鏡（日本電子（株）製ＪＳＭ−Ｔ１００）により観察した結果、平均粒子径は約１μｍであった。また、透過型電子顕微鏡（日本電子（株）製ＪＥＭ−２０００ＦＸ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１（ルチル型））が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子であった。
【０１１０】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 及びＴｉＯ₂ の粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約８．５体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．５７であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約１３．６体積％であった。
【０１１１】
撥水処理前および撥水処理後の複合微粒子を、白色ワセリンと複合微粒子の混合物中で子粒子がその１重量％となる量、白色ワセリン（和光純薬工業（株）製）中に分散させた。これを紫外線光源（SPECTRONICS 社製ＥＮＢ−２６０Ｃ／Ｊ）を用いて中心波長３１２ｎｍの光を６０分照射したところ、いずれについても白色ワセリンの変色は見られなかった。このことより、得られた複合微粒子は触媒活性が抑制されていることが分かった。
【０１１２】
撥水処理後の複合微粒子を水と混合したところ強い撥水性を示し、シリコーンオイル（信越シリコーン（株）製ＫＦ９６Ａ：屈折率＝１．４０）と混合したところ速やかに分散した。この複合微粒子８．４ｍｇをシリコーンオイル２ｇ中に分散させ、この分散液の光透過率を、紫外／可視分光光度計（島津製作所（株）製ＵＶ−１６０Ａ）を用いて光路長１ｍｍの石英セルを用いて波長域２００〜８００ｎｍでの透過率を測定した。結果を図１に示す。
【０１１３】
この図では、波長３００ｎｍ以下の紫外線Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで５２％、８００ｎｍで８１％と波長４００〜８００ｎｍの可視光全域において光透過率が高い値になっており、生成複合微粒子は可視光線域における高透明性及び、紫外線域における高遮蔽性を有していることがわかった。
【０１１４】
実施例２
シリカゾル（実施例１に同じ）３６６．５ｇ、酸化亜鉛超微粒子（堺化学工業（株）製ＦＩＮＥＸ７５）２０．３ｇ及び水を混合して１Ｌとし、原料液とした（即ち、当該原料液のＳｉＯ₂ 及びＺｎＯの濃度はそれぞれ１．２５ｍｏｌ／Ｌ及び０．２５ｍｏｌ／Ｌであり、当該原料液は粒子混合物を約１０重量％含有するものである。）。
調製した原料液を高圧分散器（ナノマイザー社製ＬＡ−３１）を用いて、解砕圧力１０００ｋｇ／ｃｍ² で分散させる工程を１０回繰り返した。以上の処理によってＺｎＯ／ＳｉＯ₂ 複合微粒子の分散液を得た。
【０１１５】
エタノール１５００ｇ、テトラエトキシシラン１６．２６ｇ、１Ｎ塩酸３．９ｍＬを混合し、ウォーターバス中にて５０℃に昇温した。この溶液温度が５０℃に到達した後、２時間３０分熟成を行った。熟成終了後、４Ｎ水酸化ナトリウム水溶液０．９８ｍＬとエタノール５０ｇの混合溶液を加えて塩酸を中和したのち、上記の複合微粒子の分散液８４．６ｇとエタノール３００ｇの混合溶液を滴下した。滴下後、５０℃で２時間３０分反応を行い、複合微粒子をＳｉＯ₂ で表面被覆した。以上の工程は全て撹拌下で行った。
【０１１６】
得られた被覆処理後の分散液を実施例１に倣って固液分離を行い、複合微粒子含エタノールケーキ（固形分濃度約４０重量％）を得た後、このケーキ１２．５ｇをアセトン５００ｇと混合し、超音波分散を行った。ケーキがアセトン中に完全に分散した後、メチルハイドロジェンポリシロキサン（実施例１に同じ）０．５ｇを加え混合して撥水処理を行った。その後、該分散液を８０℃で乾燥させ、１３０℃で２時間焼き付けし、複合微粒子の乾燥処理を行った。生成した粉体をミル（実施例１に同じ）で１０回繰り返し粉砕し、複合微粒子を得た。
【０１１７】
複合微粒子含エタノールケーキを水に分散させ、実施例１と同様にして撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０７μｍであった。
撥水処理後の複合微粒子は白色で、走査型電子顕微鏡（実施例１に同じ）により観察した結果、平均粒子径は約１μｍであった。また、透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＺｎＯ超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＺｎＯ（バンドギャップエネルギーが約３．２ｅＶ、屈折率が約１．９９）が子粒子であるＺｎＯ／ＳｉＯ₂ 複合微粒子であった。
【０１１８】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 及びＺｎＯの粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、５．７８ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約５．９体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．４９であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約９．６体積％であった。
撥水処理前および撥水処理後の複合微粒子を、白色ワセリンと複合微粒子の混合物中でＺｎＯがその１重量％となる量、白色ワセリン中に分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
【０１１９】
撥水処理後の複合微粒子を水と混合したところ強い撥水性を示し、シリコーンオイル（実施例１に同じ）と混合したところ速やかに分散した。この複合微粒子２８ｍｇをシリコーンオイル２ｇ中に分散させ、実施例１と同様の方法により光透過率を測定した。結果を図２に示す。
この図では、波長３５０ｎｍ以下の紫外線Ａ、Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで３０％、８００ｎｍで８４％と波長４００〜８００ｎｍの可視光全域において光透過率が高い値になっており、生成複合微粒子は可視光線域における高透明性及び、紫外線域における高遮蔽性を有していることがわかった。
【０１２０】
実施例３
実施例１と同様にＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の生成、ＳｉＯ₂ による表面被覆、固液分離を行って該複合微粒子含エタノールケーキ（固形分濃度約４０重量％）を得た。
このケーキ１２．５ｇを酢酸エチル５００ｇと混合し、超音波分散を行った。ケーキが酢酸エチル中に完全に分散した後、アミノ変性シリコーン（信越シリコーン（株）製、Ｘ−２２−９２６１、分子量３００００、アミノ当量４９８０）２．５ｇを加え、５０℃で３時間超音波処理を行い、この複合微粒子の撥水処理を行った。
【０１２１】
この分散液にシリコーンオイル（実施例１に同じ）４２．５ｇを加え、撹拌、混合した後、ロータリーエバポレーターを用いて、酢酸エチルを８０℃でトッピングして複合微粒子をシリコーンオイル中に転相・分散し、複合微粒子分散シリコーンオイル（複合微粒子１０重量％）を得た。
複合微粒子含エタノールケーキを水に分散させ、実施例１と同様にして撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０８μｍであった。
【０１２２】
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子であった。
上記複合微粒子中での子粒子の割合は、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約８．５体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．５７であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約１３．６体積％であった。
【０１２３】
得られた複合微粒子分散シリコーンオイルを、白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリン中で希釈し、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
得られた複合微粒子分散シリコーンオイル０．１ｇにシリコーンオイル４．９ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図３に示す。
【０１２４】
この図では、波長３００ｎｍ以下の紫外線Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで８０％、８００ｎｍで９７％と波長４００〜８００ｎｍの可視光全域において光透過率が極めて高い値になっており、生成複合微粒子は可視光線域における高透明性及び、紫外線域における高遮蔽性を有していることがわかった。
【０１２５】
実施例４
シリカゾル（実施例１に同じ）３６６．５ｇ、酸化チタン超微粒子（実施例１に同じ）１０．０ｇ、酸化亜鉛超微粒子（実施例２に同じ）４０．７ｇ及び水を混合して１Ｌとし、原料液とした（即ち、当該原料液のＳｉＯ₂ 、ＴｉＯ₂ 、ＺｎＯの濃度はそれぞれ１．２５ｍｏｌ／Ｌ、０．１２５ｍｏｌ／Ｌ及び、０．５ｍｏｌ／Ｌであり、当該原料液は粒子混合物を約１２重量％含有するものである。）。
【０１２６】
この原料液を実施例１に倣って分散処理し、ＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子の分散液を得た後、実施例２に倣って、ＳｉＯ₂ による表面被覆を行った。被覆処理後の分散液を７０℃に昇温した後、アミノ変性シリコーン（東芝シリコーン（株）製、ＸＦ４２−Ｂ０８１９、分子量１００００、アミノ当量１６００）０．７４ｇを加えて攪拌した後、７０℃で２時間超音波処理を行い、ＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
【０１２７】
この分散液をロータリーエバポレーターを用いて、エタノール、及び水を７５℃でトッピングして約３倍に濃縮した後、ｎ−ヘキサン９００ｇを加えて、７０℃で還流脱水を行った。
この分散液にシリコーンオイル（実施例１に同じ）１３２．８ｇを加え、撹拌、混合した後、ロータリーエバポレーターを用いて、エタノール、及び水を８０℃でトッピングして複合微粒子をシリコーンオイル中に転相・分散し、複合微粒子分散シリコーンオイル（複合微粒子１０重量％）を得た。
【０１２８】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０９μｍであった。
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）及びＺｎＯ超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）及びＺｎＯ（バンドギャップエネルギーが約３．２ｅＶ、屈折率が約１．９９）が子粒子であるＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子であった。
【０１２９】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 、ＴｉＯ₂ 及びＺｎＯの粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ 、５．７８ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約１４．１体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．５６であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約２２．６体積％であった。
【０１３０】
撥水処理前の複合微粒子を、白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリン中に分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
得られた複合微粒子分散シリコーンオイル０．１ｇにシリコーンオイル４．９ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図４に示す。
【０１３１】
この図では、波長３５０ｎｍ以下の紫外線Ａ、Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで４０％、８００ｎｍで９４％と波長４００〜８００ｎｍの可視光全域において光透過率が極めて高い値になっており、生成複合微粒子は可視光線域における高透明性及び紫外線域における高遮蔽性を有していることがわかった。
【０１３２】
実施例５
実施例１と同様に原料液調製及び分散処理を行いＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子分散液を得た。
上記の分散液８４．６ｇ、エタノール１５００ｇ、テトラエトキシシラン１６．２６ｇを混合し、ウォーターバス中にて５０℃に昇温した。分散液温度が５０℃に到達した後、１Ｎ塩酸３．９ｍＬとエタノール３００ｇの混合溶液を滴下した。滴下後、５０℃で２時間３０分反応を行い、分散液中の複合微粒子をＳｉＯ₂ で表面被覆した。被覆後、０．０４重量％アルミニウムイソプロポキシド／イソプロピルアルコール溶液１９９．１ｇを滴下し、７５℃で５時間反応を行い、さらにＡｌ₂ Ｏ₃ で表面被覆した。被覆終了後、４Ｎ水酸化ナトリウム水溶液０．９８ｍＬとエタノール５０ｇの混合溶液を加えて塩酸を中和した。以上の工程は全て撹拌下で行った。
【０１３３】
被覆処理後の分散液にオレイン酸６．６ｇを加えて撹拌した後、５０℃で３時間超音波処理を行い、ＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
この分散液をロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、及び水を７５℃でトッピングして約３倍に濃縮した後、ｎ−ヘキサン９００ｇを加えて、７０℃で還流脱水を行った。
この分散液にシリコーンオイル（実施例１に同じ）１１１．７ｇを加え、撹拌、混合した後、ロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、及び水を８０℃でトッピングして複合微粒子をシリコーンオイル中に転相・分散し、複合微粒子分散シリコーンオイル（複合微粒子１０重量％）を得た。
【０１３４】
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１（ルチル型））が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子であった。
【０１３５】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 及びＴｉＯ₂ の粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約８．５体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．５７であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約１３．６体積％であった。
撥水処理前および撥水処理後の複合微粒子を、白色ワセリンと複合微粒子の混合物中で子粒子がその１重量％となる量、白色ワセリン中に分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
【０１３６】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子の含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０９μｍであった。
【０１３７】
得られた複合微粒子分散シリコーンオイル０．１５ｇにシリコーンオイル４．８５ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図５に示す。
この図では、波長３００ｎｍ以下の紫外線Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで５９％、８００ｎｍで８７％と波長４００〜８００ｎｍの可視光全域において光透過率が非常に高い値になっており、生成複合微粒子は可視光線域における高透明性及び、紫外線域における高遮蔽性を有していることがわかった。
【０１３８】
実施例６
実施例４と同様に原料液調製及び分散処理を行いＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子分散液を生成させた。
エタノール１５００ｇ、テトラエトキシシラン１６．２６ｇ、１Ｎ塩酸３．９ｍＬを混合し、ウォーターバス中にて５０℃に昇温した。溶液温度が５０℃に到達した後、２時間３０分熟成を行った。熟成終了後、４Ｎ水酸化ナトリウム水溶液０．９８ｍＬとエタノール５０ｇの混合溶液を加えて塩酸を中和したのち、生成したＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子の分散液８４．６ｇとエタノール３００ｇの混合溶液を滴下した。滴下後、５０℃で２時間３０分反応を行い、分散液中のＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子をＳｉＯ₂ で表面被覆した。被覆後、０．０４重量％アルミニウムイソプロポキシド／イソプロピルアルコール分散液１９９．１ｇを滴下し、７５℃で５時間反応を行い、さらにＡｌ₂ Ｏ₃ で表面被覆した。以上の工程は全て撹拌下で行った。
【０１３９】
被覆処理後の分散液にステアリン酸１．５ｇを加えて撹拌した後、７０℃で２時間超音波処理を行い、ＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
この分散液を実施例５に倣って還流脱水した後、シリコーンオイル（実施例１に同じ）１３２．０ｇを加え、撹拌、混合した後、ロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、及び水を８０℃でトッピングして複合微粒子をシリコーンオイル中に転相・分散し、複合微粒子分散シリコーンオイル（複合微粒子１０重量％）を得た。
【０１４０】
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＺｎＯ超微粒子（平均粒子径約０．０１μｍ）及びＴｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＺｎＯ（バンドギャップエネルギーが約３．２ｅＶ、屈折率が約１．９９）及びＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）が子粒子であるＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子であった。
【０１４１】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 、ＴｉＯ₂ 及びＺｎＯの粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ 、５．７８ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約１４．１体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．５６であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約２２．６体積％であった。
【０１４２】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子の含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．１０μｍであった。
【０１４３】
上記複合微粒子の含エタノールケーキより得られる撥水処理前の複合微粒子を、白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリン中に分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
【０１４４】
得られた複合微粒子分散シリコーンオイル０．１ｇにシリコーンオイル４．９ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図６に示す。
【０１４５】
この図では、波長３５０ｎｍ以下の紫外線Ａ、Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで３３％、８００ｎｍで９３％と波長４００〜８００ｎｍの可視光全域において光透過率が高い値になっており、生成複合微粒子は可視光線域における高透明性及び、紫外線域における高遮蔽性を有していることがわかった。
【０１４６】
実施例７
実施例１と同様にＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の生成を行い、実施例５に倣ってＳｉＯ₂ 、Ａｌ₂ Ｏ₃ による表面被覆を行った。
被覆処理後の分散液にジアルキルフォスフェイト（花王（株）製ＤＡＰ６０Ｈ）０．６６ｇを加えて撹拌した後、７５℃で１時間超音波処理を行い、ＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
この分散液をロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、及び水を７５℃でトッピングして約３倍に濃縮した後、シクロヘキサン９００ｇを加えて、７０℃で還流脱水を行った。
【０１４７】
この分散液にシリコーンオイル（実施例１に同じ）１１７．７ｇを加え、撹拌、混合した後、ロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、及び水を８０℃でトッピングして複合微粒子をシリコーンオイル中に転相・分散し、複合微粒子分散シリコーンオイル（複合微粒子１０重量％）を得た。
【０１４８】
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子であった。
【０１４９】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 及びＴｉＯ₂ の粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約８．５体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．５７であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約１３．６体積％であった。
【０１５０】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子の含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０９μｍであった。
【０１５１】
上記複合微粒子の含エタノールケーキより得られる撥水処理前の複合微粒子を、白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリン中に分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
【０１５２】
得られた複合微粒子分散シリコーンオイル０．１ｇにシリコーンオイル４．９ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図７に示す。
【０１５３】
この図では、波長３００ｎｍ以下の紫外線Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで７４％、８００ｎｍで９６％と波長４００〜８００ｎｍの可視光全域において光透過率が極めて高い値になっており、生成複合微粒子は可視光線域における高透明性及び、紫外線域における高遮蔽性を有していることがわかった。
【０１５４】
実施例８
実施例６と同様にＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子の生成、ＳｉＯ₂ 、Ａｌ₂ Ｏ₃ による表面被覆を行った。
被覆処理後の分散液にジアルキルフォスフェイト（実施例７に同じ）０．７１ｇを加えて撹拌した後、７５℃で１時間超音波処理を行い、ＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
【０１５５】
この分散液を実施例５に倣って還流脱水した後、シリコーンオイル（実施例１に同じ）１３２．８ｇを加え、撹拌、混合した後、ロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、及び水を８０℃でトッピングして複合微粒子をシリコーンオイル中に転相・分散し、複合微粒子分散シリコーンオイル（複合微粒子１０重量％）を得た。
【０１５６】
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＺｎＯ超微粒子（平均粒子径約０．０１μｍ）及びＴｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＺｎＯ（バンドギャップエネルギーが約３．２ｅＶ、屈折率が約１．９９）及びＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）が子粒子であるＴｉＯ₂ ・ＺｎＯ／ＳｉＯ₂ 複合微粒子であった。
【０１５７】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 、ＴｉＯ₂ 及びＺｎＯの粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ 、５．７８ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約１４．１体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．５６であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約２２．６体積％であった。
【０１５８】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子の含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．１０μｍであった。
【０１５９】
上記複合微粒子の含エタノールケーキより得られる撥水処理前の複合微粒子を、白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリン中に分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
【０１６０】
得られた複合微粒子分散シリコーンオイル０．１ｇにシリコーンオイル４．９ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図８に示す。
【０１６１】
この図では、波長３５０ｎｍ以下の紫外線Ａ、Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで３６％、８００ｎｍで９３％と波長４００〜８００ｎｍの可視光全域において光透過率が非常に高い値になっており、生成複合微粒子は可視光線域における高透明性及び、紫外線域における高遮蔽性を有していることがわかった。
【０１６２】
実施例９
実施例２と同様に原料液調製及び分散処理を行いＺｎＯ／ＳｉＯ₂ 複合微粒子分散液を得た。
【０１６３】
エタノール１５００ｇ、テトラエトキシシラン１６．２６ｇ、１Ｎ塩酸３．９ｍｌを混合し、ウォーターバス中にて５０℃に昇温した。溶液温度が５０℃に到達した後、２時間３０分熟成を行った。熟成終了後、４Ｎ水酸化ナトリウム水溶液０．９８ｍｌとエタノール５０ｇの混合溶液を加えて塩酸を中和したのち、生成したＺｎＯ／ＳｉＯ₂ 複合微粒子の分散液８４．６ｇとエタノール３００ｇの混合溶液を滴下した。滴下後、５０℃で２時間３０分反応を行い、溶液中のＺｎＯ／ＳｉＯ₂ 複合微粒子をＳｉＯ₂ で表面被覆した。被覆後、アルミニウムトリ−ｓｅｃ−ブトキシド／イソプロピルアルコール／エタノール溶液（重量％１：９：９０）９．６ｇを滴下し、７５℃で５時間反応を行い、Ａｌ₂ Ｏ₃ で表面被覆した。以上の工程は全て溶液を攪拌しつつ行った。
【０１６４】
被覆処理後の分散液にジアルキルフォスフェイト（実施例７に同じ）０．６６ｇを加えて撹拌した後、７５℃で１時間超音波処理を行い、ＺｎＯ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
この分散液を実施例５に倣って還流脱水した後、シリコーンオイル（実施例１に同じ）１１７．７ｇを加え、撹拌、混合した後、ロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、及び水を８０℃でトッピングして複合微粒子をシリコーンオイル中に転相・分散し、複合微粒子分散シリコーンオイル（複合微粒子１０重量％）を得た。
【０１６５】
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＺｎＯ超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＺｎＯ（バンドギャップエネルギーが約３．２ｅＶ、屈折率が約１．９９）が子粒子であるＺｎＯ／ＳｉＯ₂ 複合微粒子であった。
【０１６６】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 及びＺｎＯの粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、５．７８ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約５．９体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．４９であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約９．６体積％であった。
【０１６７】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子の含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０８μｍであった。
【０１６８】
上記複合微粒子の含エタノールケーキより得られる撥水処理前の複合微粒子を、白色ワセリンと複合微粒子の混合物中でＺｎＯがその１重量％となる量、白色ワセリン中に分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
【０１６９】
得られた複合微粒子分散シリコーンオイル０．４ｇにシリコーンオイル４．６ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図９に示す。
【０１７０】
この図では、波長３５０ｎｍ以下の紫外線Ａ、Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで３０％、８００ｎｍで９３％と波長４００〜８００ｎｍの可視光全域において光透過率が高い値になっており、生成複合微粒子は可視光線域における高透明性及び、紫外線域における高遮蔽性を有していることがわかった。
【０１７１】
実施例１０
シリカゾル（実施例１に同じ）３６６．５ｇ、酸化チタン超微粒子（出光興産（株）製ＩＴ−Ｓ、アモルファス型）３９．９ｇ及び水を混合して１Ｌとし、原料液とした（即ち、当該原料液のＳｉＯ₂ 及びＴｉＯ₂ の濃度はそれぞれ１．２５ｍｏｌ／Ｌ及び０．５ｍｏｌ／Ｌであり、当該原料液は粒子混合物を約１１重量％含有するものである。）。
【０１７２】
調製した原料液を分散機（（株）日本精機製バイオミキサー）を用いて、翼回転数１５０００ｒ．ｐ．ｍ．で３０分間分散させ、ＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の分散液を得た。この分散液を実施例５に倣ってＳｉＯ₂ 、Ａｌ₂ Ｏ₃ による表面被覆を行った。
【０１７３】
被覆処理後の分散液にジアルキルフォスフェイト（実施例７に同じ）０．７０ｇを加えて撹拌した後、７５℃で１時間超音波処理を行い、ＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
【０１７４】
この分散液を実施例５に倣って還流脱水した後、シリコーンオイル（実施例１に同じ）１２５．６ｇを加え、撹拌、混合した後、ロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、及び水を８０℃でトッピングして複合微粒子をシリコーンオイル中に転相・分散し、複合微粒子分散シリコーンオイル（複合微粒子１０重量％）を得た。
【０１７５】
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径約０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．４ｅＶ、屈折率が約２．５２）が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子であった。
【０１７６】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 及びＴｉＯ₂ の粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約１５．１体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．６２であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約２３．９体積％であった。
【０１７７】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子の含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．１０μｍであった。
【０１７８】
上記複合微粒子の含エタノールケーキより得られる撥水処理前の複合微粒子を、白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリン中に分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
【０１７９】
得られた複合微粒子分散シリコーンオイル０．１ｇにシリコーンオイル４．９ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図１０に示す。
【０１８０】
この図では、波長３００ｎｍ以下の紫外線Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで４３％、８００ｎｍで８３％と波長４００〜８００ｎｍの可視光全域において光透過率が高い値になっており、生成複合微粒子は可視光線域における高透明性及び、紫外線域における高遮蔽性を有していることがわかった。
【０１８１】
実施例１１
シリカゲル（日産化学工業（株）製、ＳＴ−Ｃ、ＳｉＯ₂ 濃度２０．５重量％）２６８．３ｇ、酸化チタン超微粒子（石原産業（株）製、ＴＴＯ−５１（Ａ）、ルチル型）５０．０ｇ及び水を混合して１リットルとし、原料液とした（即ち、当該原料液のＳｉＯ₂ 及びＴｉＯ₂ の濃度はそれぞれ０．９２ｍｏｌ／Ｌ及び０．６３ｍｏｌ／Ｌであり、当該原料液は粒子混合物を約１１重量％含有するものである。）。
調製した原料液を、ダイノーミル（Ｗｉｌｌｙ Ａ Ｂａｃｈｏｆｅｎ ＡＧ製、ＫＤＬ−ＰＩＬＯＴ）を用いて、翼回転数３６００ｒ．ｐ．ｍ．、溶液：メディア比６００ｃｃ：１２００ｃｃ、８分間×３回の分散処理を行い、ＳｉＯ₂ が母粒子であり、ＴｉＯ₂ が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 超微粒子凝集体の分散液を生成させた。
【０１８２】
上記分散液１８８ｇ、エタノール１４００ｇ、テトラエトキシシラン３２．６ｇを混合し、ウォーターバス中にて５０℃に昇温した。この分散液の温度が５０℃に到達した後、１Ｎ塩酸１．５６ｍｌとエタノール６００ｇの混合溶液を滴下した。滴下後、５０℃で２時間３０分反応を行い、複合微粒子をＳｉＯ₂ で表面被覆した。以上の工程は全て溶液を攪拌しつつ行った。
この分散液をロータリーエバポレーターを用いて、エタノール、及び水を７５℃でトッピングして約１０倍に濃縮した後、攪拌しつつイソプロピルアルコール２７８２ｇを滴下して加えた。
この分散液をロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール及び水を７５℃でトッピングして約５倍に濃縮した。
濃縮終了後、４Ｎ水酸化ナトリウム水溶液０．３９ｍｌとイソプロピルアルコール２０ｇの混合溶液を加えて塩酸を中和した。この工程は溶液を攪拌しつつ行った。
【０１８３】
この分散液を攪拌しつつ、シリコーンオイル（東レ・ダウコーニング（株）製、ＳＨ２４４：屈折率１．３９）６００ｇを滴下、混合した。その後、アミノ変性シリコーン（東芝シリコーン（株）製、ＸＦ４２−Ｂ０８１９、分子量１００００、アミノ当量１６００）０．６ｇとシリコーンオイル２４０ｇの混合溶液を、滴下、混合し、ロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、及び水を８０℃でトッピングした後、更にアミノ変性シリコーン２．４ｇとシリコーンオイル３６０ｇの混合溶液を滴下、混合し、ＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
この分散液を超音波分散器を用いて、１時間分散を行い、再びロータリーエバポレーターを用いて、エタノール、イソプロピルアルコール、水、及びシリコーンオイルを８０℃でトッピングして複合微粒子をシリコーンオイル中に転相、分散し、複合微粒子分散シリコーンオイル（複合微粒子３５重量％）を得た。
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０８μｍであった。
【０１８４】
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）が子粒子であるＴｉＯ₂ ・ＳｉＯ₂ 複合微粒子であった。
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 、およびＴｉＯ₂ の粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約２２．３体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．７４であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約３５．０体積％であった。
【０１８５】
撥水処理前の複合微粒子を白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリンに分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
得られた複合微粒子分散シリコーンオイル０．０５７ｇにシリコーンオイル９．９４３ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図１１に示す。
この図では、波長３００ｎｍ以下の紫外線Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで５７％、８００ｎｍで９５％と波長４００〜８００ｎｍの可視光全域において光透過率が極めて高い値となっており、生成複合微粒子は可視光線域における高透明性及び紫外線域における高遮蔽性を有していることがわかった。
【０１８６】
実施例１２
実施例１１と同様にＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の生成、ＳｉＯ₂ による表面被覆を行った。
被覆後、４Ｎ水酸化ナトリウム水溶液０．３９ｍｌとエタノール２０ｇの混合溶液を加えて塩酸を中和した。この工程は溶液を攪拌しつつ行った。
この分散液を攪拌しつつ、オキサゾリン変性シリコーン（花王（株）製、ＯＳ９６−２０）３．０ｇをエタノール８６０ｇに溶解させた溶液を滴下、混合し、ＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
この分散液をロータリーエバポレーターを用いて、エタノール、及び水を７５℃でトッピングして約５倍に濃縮した。
この分散液を攪拌しつつ、シリコーンオイル（東レ・ダウコーニング（株）製、ＳＨ２４４：屈折率１．３９）５７５ｇを滴下、混合した後、ロータリーエバポレーターを用いて、エタノール、及び水を８０℃でトッピングした。
この分散液をホモジナイザーを用いて、１時間分散を行った後、再びロータリーエバポレーターを用いて、エタノール、水、及びシリコーンオイルを８０℃でトッピングして複合微粒子をシリコーンオイル中に転相、分散し、複合微粒子分散シリコーンオイル（複合微粒子１５重量％）を得た。
【０１８７】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０８μｍであった。
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子であった。
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 、およびＴｉＯ₂ の粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約２２．３体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．７４であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約３５．０体積％であった。
【０１８８】
撥水処理前の複合微粒子を白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリンに分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
得られた複合微粒子分散シリコーンオイル０．１３ｇにシリコーンオイル９．８７ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図１２に示す。
この図では、波長３００ｎｍ以下の紫外線Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで６５％、８００ｎｍで９５％と波長４００〜８００ｎｍの可視光全域において光透過率が極めて高い値となっており、生成複合微粒子は可視光線域における高透明性及び紫外線域における高遮蔽性を有していることがわかった。
【０１８９】
実施例１３
実施例１１と同様にＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の生成、ＳｉＯ₂ による表面被覆を行った。
被覆後、４Ｎ水酸化ナトリウム水溶液０．３９ｍｌとエタノール２０ｇの混合溶液を加えて塩酸を中和した。この工程は溶液を攪拌しつつ行った。
この分散液を攪拌しつつ、ポリビニルピロリドン（和光純薬（株）製、化粧品用Ｋ−３０）０．６ｇをエタノール３０ｇに溶解させた溶液を滴下、混合した。滴下後、オキサゾリン変性シリコーン（実施例１２に同じ）３．０ｇをエタノール８６０ｇに溶解させた溶液を滴下、混合し、ＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
この分散液をロータリーエバポレーターを用いて、エタノール、及び水を７５℃でトッピングして約５倍に濃縮した。
この分散液を攪拌しつつ、シリコーンオイル（東レ・ダウコーニング（株）製、ＳＨ２４４：屈折率１．３９）５７５ｇを滴下、混合した後、ロータリーエバポレーターを用いて、エタノール、及び水を８０℃でトッピングした。
この分散液をホモジナイザーを用いて、１時間分散を行った後、再びロータリーエバポレーターを用いて、エタノール、水、及びシリコーンオイルを８０℃でトッピングして複合微粒子をシリコーンオイル中に転相、分散し、複合微粒子分散シリコーンオイル（複合微粒子２５重量％）を得た。
【０１９０】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０８μｍであった。
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子であった。
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 、およびＴｉＯ₂ の粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約２２．３体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．７４であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約３５．０体積％であった。
【０１９１】
撥水処理前の複合微粒子を白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリンに分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
得られた複合微粒子分散シリコーンオイル０．０８ｇにシリコーンオイル９．９２ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図１３に示す。
この図では、波長３００ｎｍ以下の紫外線Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで３９％、８００ｎｍで８７％と波長４００〜８００ｎｍの可視光全域において光透過率が極めて高い値となっており、生成複合微粒子は可視光線域における高透明性及び紫外線域における高遮蔽性を有していることがわかった。
【０１９２】
実施例１４
実施例１１と同様にＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の生成、ＳｉＯ₂ による表面被覆を行った。
被覆後、４Ｎ水酸化ナトリウム水溶液０．３９ｍｌとエタノール２０ｇの混合溶液を加えて塩酸を中和した。この工程は溶液を攪拌しつつ行った。
この分散液を攪拌しつつ、ポリビニルピロリドン０．６ｇをエタノール３０ｇに溶解させた溶液を滴下、混合した。滴下後、オキサゾリン変性シリコーン（実施例１２に同じ）３．０ｇをエタノール８６０ｇに溶解させた溶液を滴下、混合し、ＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
この分散液を８０℃で乾燥させ、複合微粒子の乾燥処理を行った。生成した粉体をミル（実施例１に同じ）で２回粉砕し、複合微粒子を得た。
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．０８μｍであった。
【０１９３】
撥水処理後の複合微粒子は白色で走査型電子顕微鏡（実施例１に同じ）により観察した結果、平均粒子径は約１μｍであった。また、透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 超微粒子（平均粒子径０．０１μｍ）の凝集体の中に、ＴｉＯ₂ 超微粒子（平均粒子径０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子であった。
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 、およびＴｉＯ₂ の粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約２２．３体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約１．７４であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約３５．０体積％であった。
撥水処理前および撥水処理後の複合微粒子を白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリンに分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
【０１９４】
撥水処理後の複合微粒子を水と混合したところ強い撥水性を示し、シリコーンオイル（東レ・ダウコーニング（株）製、ＳＨ２４４：屈折率１．３９）と混合したところ速やかに分散した。
この複合微粒子１０ｍｇをシリコーンオイル１０ｇ中に分散させ、この分散液を実施例１と同様の方法により光透過率を測定した。結果を図１４に示す。
この図では、波長３００ｎｍ以下の紫外線Ｂ領域において光透過率が３％以下、波長２６０ｎｍ以下の紫外線Ｃ領域においては光透過率がほぼ０％になっていると同時に、４００ｎｍで４８％、８００ｎｍで８２％と波長４００〜８００ｎｍの可視光全域において光透過率が極めて高い値となっており、生成複合微粒子は可視光線域における高透明性及び紫外線域における高遮蔽性を有していることがわかった。
【０１９５】
実施例１５
シリカゾル（日産化学工業（株）製ＳＴ−Ｃ、ＳｉＯ₂ 濃度２０．５重量％）６１．０ｇ、酸化チタン超微粒子（（株）テイカ製ＭＴ−６００Ｂ、ルチル型）８７．５ｇ及び水を混合して１Ｌとし、原料液とした。（即ち、当該原料液のＳｉＯ₂ 及びＴｉＯ₂ の濃度はそれぞれ０．２１ｍｏｌ／Ｌ及び１．１０ｍｏｌ／Ｌであり、当該原料液は粒子混合物を約１０重量％含有するものである。）
【０１９６】
調製した原料液を、ホモジナイザー（特殊機化（株）製Ｔ．Ｋ．−ＲＯＢＯＭＩＣＳ）１２０００ｒ．ｐ．ｍ．で９０分間前処理を行った後、７０００ｒ．ｐ．ｍ．で攪拌しつつ、ダイノーミル（Ｗｉｌｌｙ Ａ Ｂａｃｈｏｆｅｎ ＡＧ製ＫＤＬ−ＰＩＬＯＴ）を用いて、翼回転数３６００ｒ．ｐ．ｍ．、溶液：メディア比６００ｃｃ：１２００ｃｃ、８分間×３回の分散処理を行い、ＳｉＯ₂ が母粒子であり、ＴｉＯ₂ が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の分散液を生成させた。
【０１９７】
上記分散液１８８ｇをロータリーエバポレーターを用いて水をトッピングして約３倍に濃縮した後、ホモジナイザー（上記と同じ）で攪拌しつつ、エタノール１３００ｇに滴下・分散させ、更に超音波分散器を用いて３０分間分散させた。その後、エタノール１００ｇに溶解したテトラエトキシシラン３２．６ｇを混合し、ウォーターバス中にて５０℃に昇温した。この分散液の温度が５０℃に到達した後、１Ｎ塩酸１．５６ｍｌとエタノール６００ｇの混合溶液を滴下した。滴下後、５０℃で２時間３０分反応を行い、複合微粒子をＳｉＯ₂ で表面被覆した。以上の工程は全て溶液を攪拌しつつ行った。
被覆後、４Ｎ水酸化ナトリウム水溶液０．３９ｍｌとエタノール２０ｇの混合溶液を加えて塩酸を中和した。この工程は溶液を攪拌しつつ行った。
この分散液を攪拌しつつ、オキサゾリン変性シリコーン（花王（株）製ＯＳ９６−２０）２．９ｇをエタノール８４２ｇに溶解させた溶液を滴下、混合し、ＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子の撥水処理を行った。
この分散液をロータリーエバポレーターを用いて、エタノール、及び水を７５℃でトッピングして約５倍に濃縮した。
【０１９８】
この分散液を攪拌しつつ、シリコーンオイル（東レ・ダウコーニング（株）製ＳＨ２４４：屈折率１．３９）５８２．８ｇを滴下、混合した後、ロータリーエバポレーターを用いて、エタノール、及び水を８０℃でトッピングした。
この分散液をホモジナイザーを用いて、１時間分散を行った後、再びロータリーエバポレーターを用いて、エタノール、水、及びシリコーンオイルを８０℃でトッピングして複合微粒子をシリコーンオイル中に転相、分散し、複合微粒子分散シリコーンオイル（複合微粒子２５重量％）を得た。
【０１９９】
被覆処理後の分散液を実施例１に倣って固液分離して生成した複合微粒子含エタノールケーキを水に分散させ、レーザードップラー型粒子径測定器（実施例１に同じ）を用いて、撥水処理前の複合微粒子の粒子径測定を行ったところ、平均粒子径（体積基準）は約０．１０μｍであった。
【０２００】
撥水処理後の複合微粒子は透過型電子顕微鏡（実施例１に同じ）を用いた超薄切片法によりその断面を観察した結果、ＳｉＯ₂ 相の中に、ＴｉＯ₂ 超微粒子（平均粒子径０．０１μｍ）が分散・固定化されて存在していることがわかった。即ち、この粒子はＳｉＯ₂ （バンドギャップエネルギーが約６．２ｅＶ、屈折率が約１．４６）の凝集体が母粒子であり、ＴｉＯ₂ （バンドギャップエネルギーが約３．３ｅＶ、屈折率が約２．７１）が子粒子であるＴｉＯ₂ ／ＳｉＯ₂ 複合微粒子であった。
【０２０１】
上記複合微粒子中での子粒子の割合は、ＳｉＯ₂ 、およびＴｉＯ₂ の粒子密度をそれぞれ２．２７ｇ／ｃｍ³ 、３．８４ｇ／ｃｍ³ とし、原料液の組成比及びＳｉＯ₂ 被覆量から計算して約４５．３体積％であった。複合微粒子中の子粒子の割合より、上記複合微粒子の屈折率は約２．０３であった。なお、母粒子内に分散・固定化されている子粒子の割合（ＳｉＯ₂ 被覆部含まず）は約８０．５体積％であった。
【０２０２】
撥水処理前の複合微粒子を白色ワセリンと複合微粒子の混合物中でＴｉＯ₂ がその１重量％となる量、白色ワセリンに分散させ、実施例１と同様の試験を行った。その結果、白色ワセリンの変色は見られず、得られた複合微粒子は触媒活性が抑制されていることが分かった。
得られた複合微粒子分散シリコーンオイル０．０４６ｇにシリコーンオイル９．９５４ｇを加えて希釈した後、実施例１と同様の方法により光透過率を測定した。結果を図１５に示す。
【０２０３】
この図では、波長３００ｎｍ以下の紫外線Ｂ及びＣ領域において光透過率がほぼ０％になっていると同時に、４００ｎｍで３０％、８００ｎｍで８１％と波長４００〜８００ｎｍの可視光全域において光透過率が高い値になっており、生成複合微粒子は可視光線域における高透明性及び紫外線域における高遮蔽性を有していることがわかった。
【０２０４】
実施例１６（化粧水）
エタノール ３０．０（重量％）
グリセリン ５．０
ポリエチレングリコール１５００ ４．０
ポリオキシエチレン（２０）オレイルエーテル １．０
ポリオキシエチレン（３０）硬化ヒマシ油 ０．５
複合微粒子（実施例２） １０．０
ウロカニン酸 ２．０
香料 ０．２
精製水 バランス
上記処方によって調製された化粧水をＳＰＦアナライザーで測定した結果、ＳＰＦ＝３．０、ＰＦＡ＝１．５であった。また、塗布後、不自然な白浮きがなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２０５】
実施例１７（乳液）
セタノール １．０（重量％）
スクワラン ２．０
オリーブ油 ５．０
メトキシ桂皮酸オクチル ４．０
ポリオキシエチレン（１０）硬化ヒマシ油 １．０
モノステアリン酸ソルビタン １．０
複合微粒子の分散油剤（実施例３） ２５．０
ブチルパラベン ０．１
メチルパラベン ０．１
エタノール ３．０
グリセリン ２．０
１，３−ブチレングリコール ２．０
香料 ０．１
精製水 バランス
上記処方によって調製された乳液をＳＰＦアナライザーで測定した結果、ＳＰＦ＝１５．９、ＰＦＡ＝５．０であった。また、塗布後、不自然な白浮きがなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２０６】
実施例１８（乳液）
複合微粒子の分散油剤（実施例３） ３０．０（重量％）
ジメチルシロキサン・メチル（ポリオキシエチレン）
シロキサン共重合体 ３．５
オクタメチルテトラシクロシロキサン ２０．０
オルガノポリシロキサンＢ １．０
スクワラン ２．０
ミリスチル酸オクチルドデシル １．０
ブチルパラベン ０．１
メチルパラベン ０．１
グリセリン ５．０
香料 ０．１
精製水 バランス
上記処方によって調製された乳液をＳＰＦアナライザーで測定した結果、ＳＰＦ＝２．５、ＰＦＡ＝１．２であった。また、塗布後、不自然な白浮きがなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２０７】
実施例１９（クリーム）
ステアリン酸 ２．０（重量％）
セタノール １．０
コレステロール １．０
スクワラン ５．０
オリーブ油 ５．０
メトキシ桂皮酸オクチル ４．０
セチルリン酸 ０．５
モノステアリン酸ソルビタン ２．０
ポリオキシエチレン（４０）硬化ヒマシ油 ０．５
複合微粒子の分散油剤（実施例４） １５．０
微粒子酸化チタン ２．０
ブチルパラベン ０．１
メチルパラベン ０．１
グリセリン １０．０
Ｌ−アルギニン ０．３
香料 ０．１
精製水 バランス
上記処方によって調製されたクリームをＳＰＦアナライザーで測定した結果、ＳＰＦ＝１８．５、ＰＦＡ＝７．２であった。また、塗布後、不自然な白浮きがなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２０８】
実施例２０（クリーム）
複合微粒子の分散油剤（実施例４） ２０．０（重量％）
ジメチルシロキサン・メチル（ポリオキシエチレン）
シロキサン共重合体 ４．０
メチルポリシロキサン（６ｃＳｔ） ５．０
２−エチルヘキシル ｐ−メトキシシンナメート ３．０
４−メトキシ−４’−ｔ−ブチルベンゾイルメタン ２．０
オクタメチルテトラシクロシロキサン １０．０
スクワラン ２．０
ミリスチル酸オクチルドデシル １．０
硫酸マグネシウム ０．５
ブチルパラベン ０．１
メチルパラベン ０．１
グリセリン ６．０
ジグリセリン ２．０
ポリメチルシルセスキオキサン粉末 ４．０
香料 ０．１
精製水 バランス
上記処方によって調製されたクリームをＳＰＦアナライザーで測定した結果、ＳＰＦ＝２３．０、ＰＦＡ＝１２．２であった。また、塗布後、不自然な白浮きがなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２０９】
実施例２１（エアゾール化粧料）
トリクロサン ０．０１（重量％）
アルミニウムヒドロキシクロライド １．５
タルク １．０
複合微粒子（実施例２） ５．０
ミリスチン酸イソプロピル ２．０
香料 ０．２
噴射剤 バランス
上記処方によって調製されたエアゾール化粧料をＳＰＦアナライザーで測定した結果、ＳＰＦ＝１．４、ＰＦＡ＝１．２であった。また、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２１０】
実施例２２（パウダーファンデーション） （重量％）
（１）複合微粒子（実施例１） １０
（２）フッ素化合物処理（＊１）マイカ 残量
（３）フッ素化合物処理（＊１）タルク ２０
（４）フッ素化合物処理（＊１）酸化チタン ８
（５）フッ素化合物処理（＊１）酸化鉄（赤、黄、黒） ３
（６）フッ素化合物処理（＊１）微粒子酸化亜鉛 ２
（７）フッ素化合物処理（＊１）微粒子酸化チタン（平均粒子径35nm) １
（８）フッ素化合物処理（＊１）ナイロンパウダー １０
（９）ジメチルポリシロキサン（１０ｃＳｔ） ４
（10）パーフルオロポリエーテル（FOMBLIN HC-04 アウシモント社) ８
（11）硬化油（シンクロワックス） １
（12）メトキシ桂皮酸オクチル １
（13）防腐剤、香料 １
（＊１):パーフルオロアルキルエチルリン酸エステルにて５％被覆したもの
【０２１１】
成分（１）〜（８）をヘンシェルミキサーで混合し、この混合物に対し成分（９）〜（13）を８０℃にて加熱混合したものを添加して混合した。このものをパルベライザーで粉砕し、これを金属製の皿に一定量とり、プレス機で加圧成型してパウダーファンデーションを調製した。
得られたパウダーファンデーションは、高い紫外線遮蔽効果があり、伸展性が良く、自然な仕上がりのあるものであった。
【０２１２】

【０２１３】
成分（１）〜（６）をヘンシェルミキサーで混合し、この混合物に対し成分（７）〜（11）を８０℃にて加熱混合したものを添加して混合する。このものをパルベライザーで粉砕し、これを金属製の皿に一定量とり、プレス機で加圧成型して両用ファンデーションを調製した。
得られた両用ファンデーションは、高い紫外線遮蔽効果があり、伸展性が良く、自然な仕上がりのあるものであった。
【０２１４】

【０２１５】
成分（１）〜（７）をヘンシェルミキサーで混合し、この混合物に対し成分（８）〜（11）を８０℃にて加熱混合したものを添加して混合する。このものをパルベライザーで粉砕し、これを金属製の皿に一定量とり、プレス機で加圧成型してパウダーアイシャドーを調製した。
得られたパウダーアイシャドーは、高い紫外線遮蔽効果があり、伸展性が良く、優れた発色性のあるものであった。
【０２１６】

【０２１７】
成分（１）〜（４）をヘンシェルミキサーで混合する。別に成分（５）〜（７）を混合し、これに予め混合しておいた（１）〜（４）を加え攪拌機で分散混合する。このものに（８）〜（10）の混合物を３０分かけてゆっくりと攪拌しながら添加し、さらに１０分間ホモミキサーで攪拌して乳化した。乳化物を脱泡してボトルに充填し、乳化型ファンデーションを調製した。
得られた乳化型ファンデーションは、高い紫外線遮蔽効果があり、伸展性が良く、自然な仕上がりがあるものであった。
【０２１８】
実施例２６（スティック状口紅） （重量％）
（１）複合微粒子の分散油剤（実施例８） １１
（２）シリコーン処理（＊６）赤色２０１号 １
（３）シリコーン処理（＊６）赤色２０２号 ２
（４）シリコーン処理（＊６）黄色４号アルミニウムレーキ １
（５）シリコーン処理（＊６）酸化チタン １
（６）パラフィンワックス ５
（７）キャンデリラワックス １０
（８）カルナバワックス ９
（９）イソパルミチン酸イソプロピル ２０
（10）イソノナン酸イソノニル １５
（11）リンゴ酸ジイソステアリル ２０
（12）ジメチルポリシロキサン（１０００ｃＳｔ） ５
（＊６):メチルハイドロジェンポリシロキサンにて２％被覆したもの
【０２１９】
成分（１）〜（12）を８０℃にて加熱して均一に混合した。混合物を３０℃まで冷却し、三本ローラーで十分に混練し、再び８０℃に加熱し、成形用型に流し込み、冷却固化させ、スティック状口紅を調製した。
得られたスティック状口紅は、高い紫外線遮蔽効果があり、伸展性が良く、鮮やかな発色を有するものであった。尚、実施例８で得た複合微粒子の分散油剤の油剤をシリコーンオイルからエステル油（リンゴ酸ジイソステアリル：コスモール２２２（日清製油（株）製）に替えたものを用いた場合においても、上記と同等の性能が確認された。
【０２２０】
また、以下の実施例、比較例において、エーテル変性シリコーンとして下記の5 種のものを用いたが、本発明は下記に限定されるものではない。
（イ）エーテル変性シリコーンＡ：
式（３）で表されるジメチルシロキサン・メチル（ポリオキシエチレン）シロキサン共重合体。ただし、Ｒ¹¹＝Ｒ¹²＝メチル基、Ｒ¹³＝H(OC₃H₆)b(OC₂H₄)aO(CH₂)p−（ａ＝7 〜15、ｂ＝0 、ｐ＝3 ）、ｍ＝50〜100 、ｎ＝1 〜5 。
（ロ）エーテル変性シリコーンＢ：
式（３）で表されるジメチルシロキサン・メチル（ポリオキシエチレン）シロキサン共重合体。ただし、Ｒ¹¹＝Ｒ¹²＝メチル基、Ｒ¹³＝H(OC₃H₆)b(OC₂H₄)aO(CH₂)p−（ａ＝2 〜5 、ｂ＝0 、ｐ＝3 ）、ｍ＝20〜30、ｎ＝2 〜5 。
（ハ）エーテル変性シリコーンＣ：
式（３）で表されるジメチルシロキサン・メチル（ポリオキシエチレン）シロキサン共重合体。ただし、Ｒ¹¹＝Ｒ¹²＝メチル基、Ｒ¹³＝H(OC₃H₆)b(OC₂H₄)aO(CH₂)p−（ａ＝0 、ｂ＝7 〜13、ｐ＝3 ）、ｍ＝4 〜10、ｎ＝1 〜6 。
（ニ）エーテル変性シリコーンＤ：
式（４）で表されるラウリルメチコンコポリオール。ただし、Ｒ²¹＝メチル基、Ｒ²²＝ドデシル基、Ｒ²³＝−(OC₂H₄)q−(OC₃H₆)r−OH（ｑ＝10〜30、ｒ＝10〜30）、Ｑ＝トリメチレン基、ｘ＝0 、ｙ＝30〜70、ｚ＝1 〜6 。
（ホ）エーテル変性シリコーンＥ：
式（５）で表されるアルキルグリセリルエーテル変性シリコーン。ただし、Ｒ³⁴の一方が、−Ａ−OCH₂CH(OR⁴¹)CH₂OR⁴² （Ａ＝C₁₁H₂₃、Ｒ⁴¹＝Ｒ⁴²＝Ｈ）、ｓ＋ｔ＝60、ｕ＝40。
【０２２１】
実施例２７ （乳液）
１）セタノール 1.0 （重量％）
２）スクワラン 2.0
３）ホホバ油 4.0
４）メトキシ桂皮酸オクチル 4.0
５）ポリオキシエチレン（10）硬化ヒマシ油 1.0
６）モノステアリン酸ソルビタン 1.0
７）複合微粒子の分散油剤（実施例12） 25.0
８）ブチルパラベン 0.1
９）メチルパラベン 0.1
10）エタノール 3.0
11）グリセリン 4.0
12）香料 0.05
13）精製水 バランス
上記乳液をＳＰＦアナライザーで測定した結果、ＳＰＦ＝１５．９、ＰＦＡ＝６．２であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２２２】
実施例２８（クリーム）
１）セタノール 1.0 （重量％）
２）ステアリン酸 2.0
３）コレステロール 1.0
４）スクワラン 5.0
５）ホホバ油 4.0
６）メトキシ桂皮酸オクチル 4.0
７）ポリオキシエチレン（40）硬化ヒマシ油 1.0
８）モノステアリン酸ソルビタン 2.0
９）複合微粒子の分散油剤（実施例13） 15.0
10）ブチルパラベン 0.1
11）メチルパラベン 0.1
12）エタノール 3.0
13）グリセリン 10.0
14）香料 0.05
15）精製水 バランス
上記クリームをＳＰＦアナライザーで測定した結果、ＳＰＦ＝１５．７、ＰＦＡ＝６．３であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２２３】

上記乳化型ファンデーションをＳＰＦ及びＰＦＡについて実施例１と同様に評価した。その結果、実施例１と比較して同等以上の紫外線遮蔽効果が得られた。
【０２２４】
実施例３０（スティック状口紅）
１）複合微粒子の分散油剤（実施例13） 11.0 （重量％）
２）シリコーン処理（*8）赤色201 号 1.0
３）シリコーン処理（*8）赤色202 号 2.0
４）シリコーン処理（*8）黄色4 号アルミニウムレーキ 1.0
５）シリコーン処理（*8）酸化チタン 1.0
６）パラフィンワックス 5.0
７）キャンデリラワックス 10.0
８）カルバナワックス 9.0
９）イソパルミチン酸イソプロピル 20.0
10）イソノナン酸イソノニル 15.0
11）リンゴ酸ジイソステアリル 20.0
12）ジメチルポリシロキサン（1000cSt ） 5.0
（*8）：メチルハイドロジェンポリシロキサンにて２％被覆したもの。
上記スティック状口紅をＳＰＦ及びＰＦＡについて実施例１と同様に評価した。その結果、実施例１と比較して同等以上の紫外線遮蔽効果が得られた。
【０２２５】

上記クリームをＳＰＦアナライザーで測定した結果、ＳＰＦ＝１９．６、ＰＦＡ＝９．２であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２２６】
実施例３２ Ｗ／Ｏ型乳液
１）複合微粒子分散油剤（実施例１３） ２５. ０重量％
２）エーテル変性シリコーンＣ １. ５
（日本ユニカ社製 ＦＺ−２１１０Ｃ）
３）エーテル変性シリコーンＢ １. ５
（信越シリコーン社製 ＫＦ−６０１５）
４）エーテル変性シリコーンＤ １. ０
（東レ・ダウコーニング社製 ＤＣ Ｑ２−２５００）
５）メチルポリシロキサン（６ｃＳｔ） ５. ０
６）デカメチルシクロペンタシロキサン ５. ０
７）２−エチルヘキシル ｐ−メトキシシンナメート ３. ０
８）スクワラン ２. ０
９）グリセリン ３. ０
１０）ブチルパラベン ０. １
１１）メチルパラベン ０. １
１２）香料 ０. ０５
１３）精製水 バランス
上記乳液をＳＰＦアナライザーで測定した結果、ＳＰＦ＝１９．２、ＰＦＡ＝８．７であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２２７】
実施例３３ Ｗ／Ｏ型クリーム
１）複合微粒子分散油剤（実施例１２） ２０. ０重量％
２）エーテル変性シリコーンＥ １. ５
３）エーテル変性シリコーンＢ ０. ５
（信越シリコーン社製 ＫＦ−６０１５）
４）メチルポリシロキサン（６ｃＳｔ） ５. ０
５）デカメチルシクロペンタシロキサン ５. ０
６）２−エチルヘキシル ｐ−メトキシシンナメート ３. ０
７）４−メトキシ−４’−ｔ−ブチルベンゾイルメタン ２. ０
８）スクワラン ２. ０
９）硫酸マグネシウム ０. ５
１０）グリセリン ５. ０
１１）ブチルパラベン ０. １
１２）メチルパラベン ０. １
１３）香料 ０. ０５
１４）精製水 バランス
上記クリームをＳＰＦアナライザーで測定した結果、ＳＰＦ＝１５．８、ＰＦＡ＝１０．２であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２２８】
実施例３４ Ｗ／Ｏ型乳液
１）複合微粒子分散油剤（実施例１２） ５. ０重量％
２）エーテル変性シリコーンＢ ０. ５
（信越シリコーン社製 ＫＦ−６０１５）
３）エーテル変性シリコーンＡ １. ０
（東レ・ダウコーニング社製 ＳＨ−３７７５Ｃ）
４）メチルポリシロキサン（６ｃＳｔ） ５. ０
５）デカメチルシクロペンタシロキサン ５. ０
６）４−メトキシ−４’−ｔ−ブチルベンゾイルメタン ２. ０
７）２−エチルヘキシル ｐ−メトキシシンナメート ３. ０
８）スクワラン ２. ０
９）グリセリン ３. ０
１０）ブチルパラベン ０. １
１１）メチルパラベン ０. １
１２）香料 ０. ０５
１３）精製水 バランス
上記乳液をＳＰＦアナライザーで測定した結果、ＳＰＦ＝１４．９、ＰＦＡ＝１０．８であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２２９】

上記クリームをＳＰＦアナライザーで測定した結果、ＳＰＦ＝１７．５、ＰＦＡ＝６．９であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２３０】
実施例３６ Ｗ／Ｏ型乳液
１）複合微粒子（実施例２） ５. ０重量％
２）エーテル変性シリコーンＣ １. ５
（日本ユニカ社製 ＦＺ−２１１０Ｃ）
３）エーテル変性シリコーンＢ １. ５
（信越シリコーン社製 ＫＦ−６０１５）
４）エーテル変性シリコーンＤ １. ０
（東レ・ダウコーニング社製 ＤＣ Ｑ２−２５００）
５）メチルポリシロキサン（６ｃＳｔ） ５. ０
６）デカメチルシクロペンタシロキサン ５. ０
７）２−エチルヘキシル ｐ−メトキシシンナメート ３. ０
８）スクワラン ２. ０
９）グリセリン ３. ０
１０）ブチルパラベン ０. １
１１）メチルパラベン ０. １
１２）香料 ０. ０５
１３）精製水 バランス
上記乳液をＳＰＦアナライザーで測定した結果、ＳＰＦ＝１６．８、ＰＦＡ＝６．８であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２３１】
実施例３７ Ｗ／Ｏ型クリーム
１）複合微粒子分散油剤（実施例３） ５. ０重量％
２）エーテル変性シリコーンＥ １. ５
３）エーテル変性シリコーンＢ ０. ５
（信越シリコーン社製 ＫＦ−６０１５）
４）メチルポリシロキサン（６ｃＳｔ） ５. ０
５）デカメチルシクロペンタシロキサン ５. ０
６）２−エチルヘキシル ｐ−メトキシシンナメート ３. ０
７）４−メトキシ−４’−ｔ−ブチルベンゾイルメタン ２. ０
８）スクワラン ２. ０
９）硫酸マグネシウム ０. ５
１０）グリセリン ５. ０
１１）ブチルパラベン ０. １
１２）メチルパラベン ０. １
１３）香料 ０. ０５
１４）精製水 バランス
上記クリームをＳＰＦアナライザーで測定した結果、ＳＰＦ＝１８．５、ＰＦＡ＝９．６であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２３２】
実施例３８ Ｗ／Ｏ型乳液
１）複合微粒子分散油剤（実施例４） ５. ０重量％
２）エーテル変性シリコーンＢ ０. ５
（信越シリコーン社製 ＫＦ−６０１５）
３）エーテル変性シリコーンＡ １. ０
（東レ・ダウコーニング社製 ＳＨ−３７７５Ｃ）
４）メチルポリシロキサン（６ｃＳｔ） ５. ０
５）デカメチルシクロペンタシロキサン ５. ０
６）４−メトキシ−４’−ｔ−ブチルベンゾイルメタン ２. ０
７）２−エチルヘキシル ｐ−メトキシシンナメート ３. ０
８）スクワラン ２. ０
９）グリセリン ３. ０
１０）ブチルパラベン ０. １
１１）メチルパラベン ０. １
１２）香料 ０. ０５
１３）精製水 バランス
上記乳液をＳＰＦアナライザーで測定した結果、ＳＰＦ＝１８．７、ＰＦＡ＝９．７であった。また、塗布後に不自然な白浮きもなく、紫外線遮蔽効果にすぐれた化粧料であることが分かった。
【０２３３】

【０２３４】

【０２３５】
比較例３ Ｗ／Ｏ型乳液
１）ＴＴＯ−５５（Ｃ） ５. ０重量％
（石原産業（株）製 微粒子酸化チタン 平均粒径30〜50μｍ）
２）エーテル変性シリコーンＢ ０. ５
（信越シリコーン社製 ＫＦ−６０１５）
３）エーテル変性シリコーンＡ １. ０
（東レ・ダウコーニング社製 ＳＨ−３７７５Ｃ）
４）メチルポリシロキサン（６ｃＳｔ） ５. ０
５）デカメチルシクロペンタシロキサン ５. ０
６）４−メトキシ−４’−ｔ−ブチルベンゾイルメタン ２. ０
７）２−エチルヘキシル ｐ−メトキシシンナメート ３. ０
８）スクワラン ２. ０
９）グリセリン ３. ０
１０）ブチルパラベン ０. １
１１）メチルパラベン ０. １
１２）香料 ０. ０５
１３）精製水 バランス
【０２３６】
比較例４ Ｗ／Ｏ型乳液
１）ＴＴＯ−５１（Ｃ） ５. ０重量％
（石原産業（株）製 微粒子酸化チタン 平均粒径10〜30μｍ）
２）エーテル変性シリコーンＢ ０. ５
（信越シリコーン社製 ＫＦ−６０１５）
３）エーテル変性シリコーンＡ １. ０
（東レ・ダウコーニング社製 ＳＨ−３７７５Ｃ）
４）メチルポリシロキサン（６ｃＳｔ） ５. ０
５）デカメチルシクロペンタシロキサン ５. ０
６）４−メトキシ−４’−ｔ−ブチルベンゾイルメタン ２. ０
７）２−エチルヘキシル ｐ−メトキシシンナメート ３. ０
８）スクワラン ２. ０
９）グリセリン ３. ０
１０）ブチルパラベン ０. １
１１）メチルパラベン ０. １
１２）香料 ０. ０５
１３）精製水 バランス
【０２３７】
実施例３１、比較例１及び比較例２の紫外線防御効果と塗布前後の外観の変化を調べた。結果を表１に示す。また、実施例３４、比較例３及び４の紫外線防御効果と塗布前後の外観の変化（透明性）の結果は表２に示す。
紫外線防御効果は、紫外線防御指数としてＰＦＢ値により評価した。紫外線防御指数は、ハートレー白色モルモットを用いて、下式で求められる値である。また、ＰＦＢ値は、J.Soc.Cosmet.Chem.Jpn.28(3),254-261,(1994)に記載のＵＶＢ法におけるＰＦＢ値である。
【０２３８】
【数１】

【０２３９】
また塗布前後の外観の変化は、色差計（ミノルタカメラ（株）製色彩色差計ＣＲ−３１０）で白色校正を行った後、皮膚塗布前の色差（Ｌ^*0、ａ^*0、ｂ^*0）と皮膚塗布後の色差（Ｌ^*1、ａ^*1、ｂ^*1）の変化（ΔＥ^* ab）で評価した。ΔＥ^* abはＪＩＳ Ｚ８７２９−１９８０において定義される値であり、下式により求めた。なお、式中のＬ^*0、ａ^*0、ｂ^*0、Ｌ^*1、ａ^*1、ｂ^*1はそれぞれ、Ｌ^*0：皮膚塗布前のＬ^* 値（明度指数）、ａ^*0：皮膚塗布前のａ^* 値（クロマティクネス指数）、ｂ^*0：皮膚塗布前のｂ^* 値（クロマティクネス指数）、Ｌ^*1：皮膚塗布後のＬ^* 値、ａ^*1：皮膚塗布後のａ^* 値、ｂ^*1：皮膚塗布後のｂ^* 値を示す。
【０２４０】
【数２】

【０２４１】
また、ＳＰＦ、ＰＦＡはジ オプトメトリクス グループ（The Optometrics Group ）社製のＳＰＦ−２９０アナライザーを用い、添付マニュアルに記載の基本測定方法により測定して求めた。なお、ＰＦＡは当該マニュアル中ではAverage UVA Protection Factor として表示されている。
【０２４２】
【表１】

【０２４３】
【表２】

【０２４４】
上記の結果から、本発明品は高い紫外線防御効果と透明性を有するものであることが分かった。
【０２４５】
【発明の効果】
本発明の複合微粒子は、液体または固体の媒質中に分散すれば、可視光線域においては高い光透過率を示し、紫外線域においては子粒子による散乱及び吸収能が現れて高い遮蔽性を発現する。また触媒活性能の高い子粒子が母粒子内部及び表面に存在するが、子粒子及び母粒子からなる複合微粒子表面を触媒活性の実質的に無い無機物質で被覆することにより、子粒子の有する触媒活性が周りの分散剤、媒質等を実質的に劣化させない。すなわち、本発明の複合微粒子は、紫外線遮蔽能を有する超微粒子を複合微粒子化し、触媒活性が実質的に無い無機物質で複合微粒子表面が被覆されることにより、触媒活性が実質的に無く、可視光線域においては高透明性で、かつ紫外線域においては高遮蔽性である超微粒子の光学的性質を、ハンドリングの容易な微粒子サイズにて安定して発現するという特徴を有するものである。また、本発明の複合微粒子は、撥水処理を施すことができるので、その場合Ｗ／Ｏ型又はＯ／Ｗ型の化粧料に配合しても均一にかつ安定に分散でき、化粧料基剤の劣化が生じさせなくすることができる。本発明の複合微粒子を化粧料に配合した場合、すべりが良く、肌上での伸展性に優れ、むらづきしないとともに、透明性に優れ、不自然な白浮きがなく、高い紫外線遮蔽効果を有し、かつ安全性、安定性の高い化粧料である。さらに、本発明の複合微粒子は、透明性に優れているので、化粧料の色彩を損なうことなく、しかも化粧料への配合量の自由度が高い。
【図面の簡単な説明】
【図１】図１は、実施例１で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図２】図２は、実施例２で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図３】図３は、実施例３で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図４】図４は、実施例４で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図５】図５は、実施例５で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図６】図６は、実施例６で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図７】図７は、実施例７で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図８】図８は、実施例８で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図９】図９は、実施例９で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図１０】図１０は、実施例１０で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図１１】図１１は、実施例１１で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図１２】図１２は、実施例１２で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図１３】図１３は、実施例１３で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図１４】図１４は、実施例１４で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。
【図１５】図１５は、実施例１５で得られた紫外線遮蔽性複合微粒子の紫外可視分光光度計による光透過率の測定結果を示すチャート図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to ultraviolet shielding composite fine particles having substantially no catalytic activity, high transparency in the visible light region, and high shielding properties in the ultraviolet region, a method for producing the same, and a cosmetic.
[0002]
[Prior art]
Of the sunlight (infrared rays, visible rays, and ultraviolet rays) reaching the earth, 5 to 6% is ultraviolet rays. Ultraviolet rays are electromagnetic waves with a short wavelength and therefore high energy, and are known to be degradable to many substances and to cause damage to living bodies.
Therefore, UV screening agents are used, for example, in cosmetics to protect the skin from inflammation and skin cancer caused by UV rays, and to prevent pigments from being decomposed by UV rays and fading when mixed with paint. Yes. At this time, by increasing the transparency in the visible light region, it is possible to prevent whitening in the case of cosmetics, and in the case of paints, it is possible to prevent impairing the color caused by the pigment. It is desirable to protect against ultraviolet rays while maintaining the properties.
[0003]
An ultraviolet shielding agent using an organic compound as an active ingredient is one that prevents its transmission due to absorption of characteristics of the composition against ultraviolet rays. For example, an ultraviolet absorbing composition comprising substituted N, N′-bis-aromatic formamidines. (Japanese Examined Patent Publication No. 61-09993) and the like. However, the organic ultraviolet shielding agent has a drawback in that it absorbs ultraviolet light and at the same time undergoes its action and decomposes, and thus has a drawback that the shielding ability attenuates with time. Moreover, in the application to cosmetics, there are restrictions on the types and amounts that can be blended from the point of influence on the human body, and it is difficult to express high functions within the regulations.
[0004]
On the other hand, an ultraviolet shielding agent using an inorganic compound is one in which inorganic fine particles are blended as a composition, and its transmission is prevented by the ability of the composition to absorb and scatter ultraviolet rays. Such an inorganic ultraviolet shielding agent is superior to an organic shielding agent in that the composition does not deteriorate over time and has little influence on the human body.
However, since the inorganic system is in the form of particles compared to the organic UV screening agent, it has been difficult for the inorganic system to prevent UV protection while maintaining high transparency in the visible light region. .
[0005]
In order to effectively exhibit the shielding ability in the ultraviolet region while maintaining high transparency in the visible light region (light wavelength 400 to 800 nm), the composition is made into ultrafine particles and highly dispersed, and the ultraviolet scattering ability is increased. Need to increase. However, when ultrafine particles are used, the dispersion stability of the ultrafine particles and the catalytic activity of the ultrafine particles due to the cohesiveness are problematic.
[0006]
In order to enhance the dispersibility, there is a method in which the surface of the ultrafine particles is coated and modified with another substance. For example, a skin cosmetic (Japanese Examined Patent Publication No. 59-1585) in which a hydrophobic titanium oxide powder is blended with an oily cosmetic base. However, it is necessary to select a solvent to be dispersed according to the properties of the surface coating layer, and even if surface modification is performed, the form of ultrafine particles does not change, so the cohesive force is also limited. There is. Other than the above publication, for example, titanium oxide having an average particle size of 30 to 70 nm and a substantially spherical or amorphous shape is coated with a mixed hydrate composed of a specific amount of silicic acid hydrate and alumina hydrate, and further with silicon oil. There is a cosmetic (JP-A-2-247109) characterized in that it contains a powder obtained by coating the surface, but is coated with a mixed hydrate consisting of silicic acid hydrate and alumina hydrate. After the treatment or after coating the surface with silicon oil, the above powder is obtained through drying and pulverization processes, so it is extremely difficult to pulverize the titanium oxide ultrafine particles into primary particles, that is, the titanium oxide ultrafine particles agglomerate. Accordingly, the particle size is large, and the transparency and ultraviolet shielding ability of the powder are lowered. In addition, since a new surface that is not covered by the pulverization process appears, the water repellency or oil repellency decreases on the surface. There are technical problems as described above in maintaining the dispersibility of ultrafine particles stably, and how to maintain the dispersibility of ultrafine particles high and stable is an important issue. Means were sought.
[0007]
Next, for the purpose of providing a cosmetic capable of easily dispersing ultrafine particles uniformly and eliminating the difficulty of handling ultrafine powder, ultrafine metal oxide with a particle size of 0.1 μm or less is provided. There is a cosmetic raw material (Japanese Patent Laid-Open No. 6-239728) containing a product, a dispersion medium and a dispersant, and the content of the ultrafine particles is 10% by weight or more. The deterioration of the dispersant, the dispersion medium, the cosmetic base, and the aggregation of the ultrafine particles due to the deterioration of the dispersant are not considered at all even though they are problems to be solved. In consideration of blending into cosmetics, the content of ultrafine metal oxide in the cosmetic raw material is 10% by weight or more, but the ultrafine metal oxide is uniformly and stably dispersed. Thus, it is considered that the function of the ultrafine metal oxide is high, and it is not necessary to limit the content of the ultrafine metal oxide to 10% by weight or more in the cosmetic raw material for all cosmetics.
[0008]
Therefore, there is an example in which inorganic ultrafine particles are aggregated with other relatively large particles as a carrier so that the ultraviolet light scattering ability is not lost. For example, a flaky substance containing dispersed fine metal compounds (special No. 63-126818), however, there is no disclosure of a specific configuration of the fine particles for improving the performance of both the ultraviolet shielding ability and the transparency in visible light.
[0009]
On the other hand, composite fine particles in which ultra fine particles are dispersed and fixed in a solid substance have been devised. As conventional ultraviolet shielding composite fine particles, for example, SiO₂TiO in the metal oxide plate-like particles₂A powder of zirconium oxide or aluminum oxide is supported on the surface of a composite powder (Japanese Patent Laid-Open No. 1-143821) in which fine particles such as uniform particles are uniformly dispersed, or base material particles made of nylon resin, silicone resin, silicon oxide, etc. And composite particles (Japanese Patent Laid-Open No. 2-49717) in which titanium oxide or zinc oxide powder is dispersed inside the base material particles.
[0010]
However, in order to use these composite particles as an ultraviolet shielding agent, it is usually necessary to disperse the composite particles in a certain medium in an actual use environment. At this time, since metal oxides such as titanium oxide contained in the composite particles have catalytic activity, the deterioration of the medium occurs, and the refractive index of the composite particles and the refractive index of the medium If the difference is large, light scattering occurs at the interface between the composite particle and the medium, and the transparency in the visible light region and the shielding property in the ultraviolet region are deteriorated. This publication does not consider the situation at all.
[0011]
Therefore, in order to suppress the catalytic activity of the ultrafine particles, there is a method of coating the surface of the ultrafine particles with various substances. For example, when titanium hydroxide is produced by hydrolysis of titanium alkoxide, the basic compound and the boiling point are 100 to 100. There is a cosmetic (Japanese Patent Laid-Open No. 5-70331) containing a fine particle powder obtained by adding a hydrocarbon at 200 ° C. and / or a silicone having a specific molecular structure. In order to obtain it, it has undergone a drying and pulverization process, the particle size of titanium hydroxide fine particles is large, and the scattering effect of ultraviolet B (light wavelength 280 to 320 nm) is highly expressed while maintaining high transparency in the visible light region. It is difficult.
[0012]
In addition, in the above-mentioned publication, in order to achieve both high transparency in the visible light region and high shielding property for ultraviolet rays, a method of making titanium hydroxide fine particles ultrafine particles or titanium hydroxide fine particles in an ultrafine particle state in cosmetics. No consideration is given to the method of dispersion and no disclosure is made. Moreover, in the ultraviolet shielding material described in this publication, the ultraviolet ray B (light wavelength 280 to 320 nm) that transmits only to a relatively shallow portion of the epidermis and upper dermis and causes sunburn and skin cancer is as follows. It is considered that there is an absorption effect by titanium hydroxide or titanium oxide, but it is particularly visible among ultraviolet rays A (light wavelength: 320 to 400 nm) that reach the deep skin of the dermis layer and cause suntan and intradermal fiber degeneration. There is no absorption effect at a light wavelength of 350 to 400 nm close to light. That is, the ultraviolet absorber described in this publication exhibits an absorption effect of mainly ultraviolet B by titanium hydroxide or titanium oxide, and an ultraviolet ray having an optical wavelength of about 300 nm for the anatase type and an optical wavelength of about 320 nm for the rutile type. It is limited to exhibiting an absorption effect.
[0013]
Among the ultraviolet rays that reach the earth's surface, the ultraviolet ray A has an energy ratio of about 15 times that of the ultraviolet ray B. Therefore, when the ultraviolet ray energy ratio is considered, not only the ultraviolet ray B but also the ultraviolet ray B is shielded. It is important to. Moreover, it is a big problem to shield the ultraviolet rays B and A while maintaining high transparency in the visible light region. In particular, when the ultraviolet ray A is shielded, it is important to shield the ultraviolet ray having a light wavelength of 350 to 400 nm close to visible light.
[0014]
As described above, in order to effectively express the shielding ability in the ultraviolet region while maintaining high transparency in the visible light region, the ultraviolet shielding material may be made into ultrafine particles to be in a highly dispersed state. Further, in order to improve the transparency in the visible light region, it is important to reduce the difference in refractive index between the ultraviolet absorber and the surrounding dispersion medium. However, Japanese Patent Laid-Open Nos. 1-143821 and 6 In the composite powder containing titania described in JP-A-116119, the refractive index of the composite powder is roughly determined by the composition ratio of the constituents thereof. Therefore, the refractive index of the composite powder is adjusted to a dispersion medium having a certain refractive index value. However, a limit naturally arises, and it has been a big problem to control the refractive index of the composite powder so as to match the refractive index of the dispersion medium. An effective means for solving the problems to be solved has been demanded.
[0015]
Further, in metal compound-containing solid porous silica beads, a method for producing the same, and a powder deodorant (JP-A-4-65312), metal compound fine particles 0.1 to 30 having a primary particle diameter of 0.001 to 0.3 μm are used. Porous silica beads containing a weight percent in the particles and substantially free of pores of 0.3 μm or more in the particles, and containing the metal compound fine particles close to the refractive index of silica (refractive index If 1.4 to 2.0) is selected, silica particles with further improved transparency can be obtained. However, this also only defines the refractive index range of the metal compound fine particles inside the composite particles, not the refractive index of the entire composite particles.
[0016]
As described above, attempts have been made mainly to use composites of metal oxides in order to solve the problems of ultrafine particle ultraviolet screening agents. However, TiO₂Many compounds having a UV-absorbing ability such as ZnO and ZnO have a relatively high refractive index. Actually, the refractive index of composite fine particles composed of these ultrafine particles is higher than that of aqueous solutions, general organic solvents, and polymers. It is quite high. When such composite fine particles are dispersed in a medium, even though visible light scattering occurs at the interface between the composite fine particles and the medium and the transparency is greatly impaired, the refraction of the composite fine particle type UV shielding particles is refracted. There has never been a concept of controlling the rate.
[0017]
On the other hand, in the field of resin fillers, MgF is known as a highly transparent low refractive index substance.₂And CaF₂A technique for reducing the refractive index of a powder or the like by blending, as a raw material, a fluorine-based inorganic compound such as polytetrafluoroethylene or a fluorine-based organic polymer compound such as polytetrafluoroethylene is known.
[0018]
For example, as a transparent inorganic powder for resin filling, JP-A-4-85346 discloses SiO 2₂, Al₂O_Three, B₂O_Three, BaO, SrO, ZnO, MgO and other metal oxides and metal fluorides, and the refractive index (Nd) is adjusted to the range of 1.44 to 1.70. Since these have high light transmittance and do not show strong alkalinity, it is described that the instability of resin alteration and curing can be extremely reduced. However, this publication only describes that a highly transparent inorganic powder for resin filling can be obtained by changing the composition ratio of the substances. Things do not exist in the form of particles, and the UV shielding function is not mentioned. Furthermore, there is no description about the composite fine particles which are aggregates of two or more kinds of fine particles according to the present invention and the composition dependency of the average refractive index, and there is no concept thereof.
[0019]
[Problems to be solved by the invention]
The present invention solves various problems in the above-described ultraviolet shielding agent, that is, it has substantially no catalytic activity, is uniformly and stably dispersed in a medium (for example, cosmetics or paints), and is visible light. It is an object of the present invention to provide UV-shielding composite fine particles having high transparency and high UV-shielding properties and good handling properties, a production method thereof, and a cosmetic using the same.
[0020]
[Means for Solving the Problems]
In order to achieve high performance of the inorganic ultraviolet shielding agent, the present inventors have combined a fine particle (child particle) having an ultraviolet shielding ability and a fine particle aggregate (mother particle) as a base material in which the child particle is dispersed and contained. By devising composite fine particles that combine the ultraviolet scattering and absorption ability of the former and the high dispersibility of the child particles of the latter, focusing on both band gap energies and determining the combination based on their magnitude relationship And found that the effect of ultrafine particles can be maximized.
[0021]
In addition, in controlling the refractive index of the composite fine particles, the present inventors use a metal oxide or a fluorine compound having a low refractive index as particles constituting the mother particles, and control the composition of the child particles and the mother particles, thereby controlling the composite fine particles. Was controlled to be equal to the refractive index of the medium. As a result, the scattering of light at the interface between the composite fine particles and the medium is suppressed, so that the inside of the composite fine particles regardless of the shape of the composite fine particles, that is, spherical, plate-like, needle-like, or the surface roughness of these composite fine particles. It has been found that the light penetrates well and the transparency in the visible light region is dramatically improved, and at the same time, the function of the ultrafine particles dispersed inside is effectively expressed and the high UV shielding property can be exhibited. It was. In addition, when a low refractive index substance is used in the form of fine particles of 0.3 μm or less, even if a fine particle unit domain is formed in the composite fine particles, visible light is not scattered, and the refractive index of the whole particles is lowered. I found that it was possible.
[0022]
Further, the present inventors can substantially suppress the catalytic activity of the composite fine particles by covering the surface of the composite fine particles with an inorganic substance having substantially no catalytic activity in suppressing the catalytic activity of the composite fine particles. I found out.
[0023]
Furthermore, the present inventors have performed a water-repellent treatment on the surface of the composite fine particles coated with an inorganic substance having substantially no catalytic activity and pulverized to obtain a composite fine particle powder, or the surface of the composite fine particles has been subjected to a water-repellent treatment. It has been found that ultraviolet-shielding composite fine particles having good handling properties can be obtained by dispersing in a post-oil agent.
[0024]
  That is, the gist of the present invention is as follows.
(1) A base particle in which particles having an average primary particle diameter of 0.001 to 0.3 μm are aggregated while maintaining the shape thereof, and an average particle diameter dispersed and fixed in the base particle A composite fine particle comprising 0.001 to 0.1 μm child particles, the child particles having a smaller band gap energy than the particles constituting the mother particles and an ultraviolet absorbing ability;And the child particles are dispersed and fixed in the mother particles at a ratio of 0.1 to 30% by volume,UV-shielding composite fine particles having transparency in the visible light region, characterized by having substantially no catalytic activity as composite fine particles,
(2) A mother particle in which particles having an average primary particle diameter of 0.001 to 0.3 μm are aggregated while maintaining the shape thereof, and an average particle diameter dispersed and fixed in the mother particle is Composite fine particles comprising 0.001-0.1 μm child particles, the composite fine particle surface having a structure coated with an inorganic substance having substantially no catalytic activity, and the child particles constitute the mother particles Has a smaller band gap energy than the particles to beThe child particles are dispersed and fixed in the mother particles at a ratio of 0.1 to 30% by volume,Ultraviolet shielding composite fine particles having transparency in the visible light region, characterized by having ultraviolet absorbing ability,
[0025]
(3) The ultraviolet shielding composite fine particles according to (1) or (2), wherein the band gap energy of the particles constituting the mother particles is 3 to 9 eV,
(4) The ultraviolet shielding composite fine particles according to any one of (1) to (3), wherein the band gap energy of the child particles is 0.2 eV or more smaller than that of the particles constituting the mother particles,
(5) Child particles0.5-20UV-shielding composite fine particles according to any one of (1) to (4), wherein the ultraviolet-shielding composite fine particles are dispersed and fixed in the mother particles at a volume percentage
(6) The ultraviolet shielding composite fine particles according to any one of (1) to (5), wherein the composite fine particles have an average particle size of 0.5 μm or less,
(7) The ultraviolet shielding composite fine particles according to any one of (1) to (6), wherein the composite fine particles have an average refractive index of 1.3 to 2.5,
(8) The ultraviolet shielding composite fine particles according to any one of (1) to (7), wherein the particles constituting the mother particles are selected from metal oxides and / or fluorine compounds,
(9) The metal oxide is SiO₂ And / or Al₂O_Three The ultraviolet shielding composite fine particles according to (8), selected from:
(10) The child particles are TiO₂ , ZnO, CeO₂, SiC, SnO₂ , WO_Three , BaTiO_Three , CaTiO_Three And SrTiO_ThreeThe ultraviolet shielding composite fine particles according to any one of (1) to (9), which are one or more selected from the group consisting of:
[0026]
(11) The ultraviolet shielding composite fine particles according to any one of (2) to (10), wherein the inorganic substance is a metal oxide,
(12) The metal oxide which is the inorganic substance is SiO₂And / or Al₂O_ThreeThe ultraviolet shielding composite fine particles according to (11), selected from
(13) The ultraviolet shielding composite fine particles according to any one of (1) to (12), wherein the surface of the composite fine particles is further treated with a water repellent.
(14) When suspended in a medium having a refractive index substantially the same as the refractive index of the composite fine particles and measured for light transmittance with an ultraviolet-visible spectrophotometer using an optical cell having an optical path length of 1 mm, the wavelength is 800 nm. The ultraviolet ray according to any one of (1) to (13), wherein the transmittance is 80% or more, the transmittance is 20% or more at a wavelength of 400 nm, and the transmittance is 5% or less at a light wavelength of 380 to 300 nm. Shielding composite fine particles,
[0027]
(15) Obtained from the following steps, the above (2) To (14) the ultraviolet shielding composite fine particles according to any one of
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or two or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated,
(B) a step of coating the composite fine particles obtained in step (a) with an inorganic substance;
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in step (b), and
(D) drying and / or pulverizing the water-repellent-treated composite fine particles obtained in the step (c);
(16) Obtained from the following steps, the above (2) To (14) UV-shielding composite fine particle dispersion oil agent,
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or two or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated,
(B) a step of coating the composite fine particles obtained in step (a) with an inorganic substance;
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in step (b), and
(D ') a step of dispersing the water-repellent-treated composite fine particles obtained in step (c) in an oil agent;
[0028]
(17) Ultraviolet shielding composite fine particles comprising the mother particles and the child particles dispersed and fixed in the mother particles, having substantially no catalytic activity and having transparency in the visible light region, comprising the following steps: Manufacturing method,
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or two or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated, and
(B) a step of coating the composite fine particles obtained in step (a) with an inorganic substance;
(18) Next to step (b),
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in step (b),
The production method according to (17), further comprising:
(19) After step (c),
(D) drying and / or pulverizing the water-repellent-treated composite fine particles obtained in the step (c);
The production method according to (18), further comprising:
[0029]
(20) Ultraviolet-shielding composite fine particles comprising the mother particles and the child particles dispersed and fixed in the mother particles, having substantially no catalytic activity and having transparency in the visible light region, comprising the following steps: Manufacturing method of dispersed oil agent,
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or two or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated,
(B) a step of coating the composite fine particles obtained in step (a) with an inorganic substance;
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in step (b), and
(D ') a step of dispersing the water-repellent-treated composite fine particles obtained in step (c) in an oil agent;
[0030]
(21) A cosmetic comprising the ultraviolet shielding composite fine particles according to any one of (1) to (15),
(22) A cosmetic comprising the ultraviolet shielding composite fine particle dispersion oil according to (16),
(23) The cosmetic according to (21), comprising 0.01 to 50% by weight of ultraviolet shielding composite fine particles,
(24) The cosmetic according to any one of (21) to (23), further comprising an ultraviolet protective agent, and
(25) When SPF is measured using an SPF-290 analyzer manufactured by The Optometrics Group, the value is 8 or more, and ΔE defined in JIS Z8729-1980 before and after skin application.^*The cosmetics according to any one of (21) to (24), wherein ab is 3 or less.
[0031]
DETAILED DESCRIPTION OF THE INVENTION
Fine particles having a relatively small particle diameter and having a high shielding ability against ultraviolet rays tend to agglomerate, so it is difficult to disperse them in a medium and to exhibit their functions well. Therefore, by dispersing such fine particles with relatively large particles, that is, by immobilizing them as child particles in a mother particle as a carrier, the dispersed state can be maintained and the ultraviolet shielding ability can be maintained. Furthermore, by covering the surface of the composite fine particles with an inorganic substance having substantially no catalytic activity, the catalytic activity of the composite fine particles can be substantially suppressed. Therefore, even if the surface of the composite fine particle is modified by covering the surface of the composite fine particle with an inorganic substance having substantially no catalytic activity, the modifier does not deteriorate due to the catalytic activity or the photocatalytic activity.
[0032]
Further, as described above, the surface of the composite fine particles coated with the inorganic substance is subjected to water repellent treatment and pulverized to obtain a composite fine particle powder, or the surface of the composite fine particles is dispersed in an oil agent after the water repellent treatment. Good ultraviolet shielding composite fine particles can be obtained. In the present specification, the mother particle of composite fine particles refers to a mother body in which child particles are dispersed and contained, and the mother particle is formed as an aggregate in which the particles constituting the mother particle are aggregated while maintaining their shape. Child particles are particles having an ultraviolet shielding ability other than mother particles.
[0033]
1. A preferred embodiment of the composite fine particle of the present invention will be described in detail in terms of the band gap energy of the particle, the refractive index of the composite fine particle, the grain boundary of the particle, and the coating of the surface of the composite fine particle with an inorganic substance.
[0034]
(1) Particle band gap energy
In the composite fine particles of the present invention, the fine particles used as the child particles are required to have a shielding property in the ultraviolet region, which is classified into ultraviolet absorbing property and ultraviolet scattering property. Ultraviolet absorptivity is mainly due to exciton absorption of semiconductor compounds for inorganic compounds, and compounds having a band gap energy of 3.0 to 4.0 eV effectively exhibit their properties. Ultraviolet scattering is strongly manifested by Mie scattering, which is TiO₂In the case of such a high refractive index material, the particle diameter becomes remarkable when the particle diameter is about 1/2 of the wavelength of ultraviolet rays, that is, 0.2 μm or less.
That is, it is known that ceramics absorb light having a wavelength corresponding to energy equal to or higher than the band gap energy, which is the energy difference between the two levels, because the valence band and the conduction band are not continuous. For example, ZnO has a band gap energy of 3.2 eV and absorbs light having a wavelength of 390 nm or less. The property that the inorganic ultraviolet shielding agent absorbs ultraviolet rays is because its band gap energy is in the wavelength region of ultraviolet rays.
[0035]
Therefore, in the composite fine particles of the present invention, in order to effectively express the scattering and absorption ability of ultraviolet rays by the child particles, it is necessary that the band gap energy of the particles constituting the mother particles is larger than that of the child particles. For example, TiO as the mother particle₂When using an aggregate of (rutile) particles, TiO₂If ZnO fine particles having a smaller band gap energy are contained as child particles, ultraviolet rays having a wavelength of 320 nm or less constitute particles (TiO 2).₂) By the exciton absorption based on the band gap energy of the child particles while being absorbed by the exciton absorption corresponding to the band gap energy of Absorbed. The composite fine particles can block ultraviolet rays in a wavelength region of 350 nm or less.
[0036]
On the other hand, TiO as a particle constituting the mother particle₂SnO having a larger band gap energy than this₂If the fine particles are child particles, ultraviolet rays with a wavelength of 320 nm or less are TiO.₂UV light having a wavelength of around 350 nm that is absorbed by the mother particles by the exciton absorption corresponding to the band gap energy of₂It is not absorbed by exciton absorption based on the band gap energy. Therefore, this composite fine particle cannot obtain a shielding effect against ultraviolet rays in the wavelength region near 350 nm.
[0037]
From these points, in the composite fine particles of the present invention, the band gap energy of the particles constituting the mother particles is preferably 3 to 9 eV, more preferably 5 to 9 eV. In addition, in order to make ultraviolet rays in a wavelength region expected to be absorbed and scattered by the child particles reach the child particles more reliably, the band gap energy of the child particles having the minimum band gap energy constitutes the mother particle. It is preferably 0.2 eV or more smaller than the band gap energy of the particles.
[0038]
(2) Refractive index of composite fine particles
When the ultraviolet shielding fine particles are actually used, it is necessary to exhibit high transparency in the visible light region while maintaining high shielding properties in the ultraviolet region. Here, (i) in order to maintain a high shielding property, if the difference in refractive index between the mother particle and the child particle increases, the ultraviolet shielding ability of the child particle is improved, so that the difference in refractive index between the two is large. In the present invention, it is preferably 0.1 or more. Therefore, in the present invention, a metal oxide or fluorine compound having a relatively low refractive index is used as a constituent material of the mother particle for the child particles having a relatively high refractive index. In addition, (ii) in order to express high transparency, it is necessary to reduce the difference in refractive index between the composite fine particles and the medium as much as possible in consideration of the difference in refractive index with the material (medium) around the composite fine particles. Therefore, the refractive index of the composite fine particles must be controlled. The present invention has the features of the present invention in that the refractive index is controlled by controlling the volume ratio of the mother particles and the child particles, and further by making the refractive index control easier by using a fluorine compound.
[0039]
That is, in a suspension system of composite fine particles (for example, when used in cosmetics), if the refractive index is different between the composite fine particles and the medium, visible light is refracted and reflected at the interface between the two, and transparency is impaired. It is. Here, the refractive index is generally measured by a liquid immersion method (for example, Toshiharu Tadashi et al., “Optical Measurement Handbook” P.475, published by Asakura Shoten in 1981), and has the highest transmittance for light having a wavelength of 589.3 nm. Is the refractive index of the sample. However, since the liquid immersion method is complicated to operate and requires time, it can be simply calculated from the refractive index and volume ratio of the primary particles of the child particles and the mother particles. Since the calculated refractive index may be very close to the data obtained by the immersion method, in such a case, the refractive index of the composite fine particles in the present invention uses such a simple method. This is also the value obtained.
[0040]
Refractive index n of commonly used media_D ²⁰Is 1.3 to 1.8, whereas TiO has high ultraviolet shielding properties.₂Most of metal oxides such as ZnO have a refractive index n_D ²⁰Therefore, when these are used as the child particles, it is necessary to make the refractive index of the composite fine particles close to the value of the medium by using a low refractive index substance for the mother particles. That is, the average refractive index of the composite fine particles is 1.3 to 2.5, preferably 1.3 to 2.0, more preferably 1.3 to 1.8, particularly preferably 1.3 to 1.7, and most preferably. Is 1.4 to 1.5. Further, the difference in refractive index between the mother particle and the child particle in the composite fine particle of the present invention is preferably 0.1 or more. This is because the ultraviolet scattering ability by the child particles is improved.
[0041]
(3) Grain boundary of particles
Regarding the primary particles of the mother particles, from the viewpoint of grain boundaries, the smaller the particle size, that is, the smaller the grain boundaries inside the mother particles, the more visible light cannot recognize the fine grain boundaries, and the crystals of the primary particles of the mother particles Regardless of the nature, the mother particles have transparency, and the child particles that are ultrafine particles also have transparency, so that it can be explained that the composite fine particles also have transparency as a result.
[0042]
(4) Covering the surface of the composite fine particles with an inorganic substance
In order to suppress the catalytic activity of the ultrafine particles, when the composite fine particle surface is coated with an inorganic substance having substantially no catalytic activity, the coating layer may be either a film or a fine particle film. It is sufficient that the active point on the surface of the composite fine particle is substantially covered and the surface activity does not reach the medium around the composite fine particle. That is, by substantially suppressing the surface activity of the composite fine particles, it is possible to prevent deterioration of the dispersant on the surface of the composite fine particles and the medium (for example, a cosmetic base, paint, etc.) in contact with the surface, Since there is no deterioration of the dispersant, the dispersibility of the composite fine particles can be stably maintained over a long period of time. These are generally problems that are difficult to avoid when using inorganic UV screening agents dispersed in various media, but the present invention provides means for solving the problems. .
[0043]
2. Next, the method for producing the ultraviolet shielding composite fine particles of the present invention will be described for each step.
In the process, the water repellent treatment of the composite fine particles is optionally performed as desired. However, when the obtained composite fine particles are blended in a cosmetic or the like, it is preferable to perform the water repellent treatment. The manufacturing process including water repellent treatment will be exemplified below. In this case, the production process of the present invention has two aspects, (1) an aspect in which the composite fine particles are pulverized by drying and pulverization, and (2) an aspect in which the composite fine particles are dispersed in the oil agent. There are the following processes.
[0044]
(1) A mode in which composite fine particles are pulverized by drying and pulverization
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or two or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated, and
(B) A step of coating the composite fine particles obtained in the step (a) with an inorganic substance.
In this aspect,
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in step (b), and
(D) A step of drying and / or crushing the water-repellent-treated composite fine particles obtained in step (c) may be provided.
[0045]
(2) A mode in which composite fine particles are dispersed in an oil agent
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or two or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated,
(B) a step of coating the composite fine particles obtained in step (a) with an inorganic substance;
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in step (b), and
(D ′) A step of dispersing the water-repellent treated composite fine particles obtained in the step (c) in an oil agent.
[0046]
Here, in the preparation step of the mixed liquid, which is the step (a), in the case where an ultrafine particle powder having an average particle diameter of 0.001 to 0.1 μm is used as the child particle, the child particle powder is milled, high pressure It is desirable to keep the dispersed state of the child particles in the mixed solution by crushing and / or pulverizing by a treatment such as dispersion. Examples of the mill include a bead mill, a sand mill, and a ball mill, and examples of the high-pressure dispersion apparatus include a microfluidizer and a nanomizer.
Here, when the above-mentioned ultrafine particle powder is used for the child particles, and the mixed solution having a high proportion and concentration of the child particles is subjected to mill treatment and / or high-pressure dispersion treatment, before such treatment, a super mixer such as a homomixer or a homogenizer is used. It is preferable to perform the primary treatment with a disperser or the like having the ability to pulverize the fine particle powder. The reason is that, in the primary treatment, the high-concentration ultrafine powder in an agglomerated state is crushed so that it can be crushed and / or pulverized in subsequent milling and / or high-pressure dispersion treatment. This is because the required load can be reduced, and dispersion can be performed by efficiently crushing and / or crushing.
[0047]
In the coating step with the inorganic substance in the step (b), the coating method is not particularly limited, but for example, a coating method using a sol-gel reaction method, a precipitation reaction method or the like is used. The inorganic material to be coated is not particularly limited as long as it is an inorganic material having no catalytic activity, but among these, a metal oxide is preferable, and particularly SiO.₂And / or Al₂O_ThreeIs preferred. The inorganic material raw material used in the coating step is not particularly limited, and metal salts such as metal alkoxide, metal nitrate, and metal sulfate can be used. Examples thereof include tetraethoxysilane, aluminum isopropoxide, aluminum tri-sec-butoxide, sodium silicate, aluminum sulfate and the like. Depending on the properties of these inorganic material raw materials, the surface of the composite fine particles can be coated with an inorganic material by utilizing a precipitation reaction, a sol-gel reaction, or the like. In addition, after the coating step, a neutralization reaction step may be performed as necessary before or after the water repellent treatment step.
[0048]
Here, the sol-gel reaction method refers to a method in which colloidal particles grow from condensation or aggregation from a sol (colloid solution) to be gelled. When this method is used for coating the particle surface, it is possible to perform the above-mentioned gelation on the particle surface. The precipitation reaction method is a method in which a precipitation agent is obtained by adding a precipitation agent to a solution containing a metal salt, and it is possible to attach precipitation particles to the particle surface by controlling the concentration, pH, temperature and the like. Examples of the precipitation reaction method include a coprecipitation method, a uniform precipitation method, and a compound precipitation method.
In addition, the coating amount of the inorganic substance is not particularly limited, but if the coating amount is too large, the composite fine particle diameter becomes large and the optical properties of the composite fine particles are remarkably impaired, and if the coating amount is too small, the catalytic activity is expressed. In order to prevent this from happening, the coating amount of the inorganic substance must be adjusted appropriately.
[0049]
In the step of performing the water repellent treatment in the step (c), the water repellent and the water repellent treatment method are not particularly limited. For example, methyl hydrogen polysiloxane, high viscosity silicone oil, oxazoline-modified silicone, amino-modified silicone, silicone resin Treatment with silicone compounds such as stearic acid, oleic acid and other anionic and cationic surfactants, surfactants such as nylon, polymethyl methacrylate, polyethylene, Teflon, polyamino acid, Examples of the method include treatment with a fluoro group-containing compound, lecithin, collagen, metal soap, lipophilic wax, polyhydric alcohol partial ester or complete ester, treatment with a phosphoric acid compound such as monoalkyl phosphate, dialkyl phosphate, etc. . The water repellent treatment method is not limited to these methods. In principle, the electrostatic force between the surface of the composite fine particle and the water repellent or the nucleated condensation of the water repellent with the composite fine particle as the core is used. Can do. In addition, before or after the water repellent process, a neutralization reaction process may be included as necessary.
Although this step is an optional step in the aspect of (1), it is more preferable to provide this step because of suppression of surface activity and dispersibility of the composite fine particles.
[0050]
Next, in the step of drying and pulverizing the composite fine particles subjected to the water-repellent treatment in step (d), the drying method and the pulverization method are not particularly limited. For example, the drying method includes hot air drying, topping, etc. A sand mill, a blade mill or the like is used. The composite fine particles obtained after pulverization may be classified and used with the same particle diameter. An electron microscope can be used to grasp the particle diameter and shape of the generated composite fine particles and the particle diameters of the child particles and the mother particles.
[0051]
In the step of dispersing the composite fine particles in the step (d ′) in the oil agent, the dispersion method in the oil agent is not particularly limited. For example, after mixing the dispersion containing the water-repellent treated composite fine particles and the oil agent When the solvent of the dispersion is volatile such as ethanol, topping or the like can be used, and when the solvent is not volatile, a usual solvent replacement method or the like can be used. Oils include squalane, paraffin wax, liquid paraffin, petrolatum, microcrystalline wax, ozokerite, ceresin, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, cetyl alcohol, hexadecyl alcohol, oleyl alcohol, 2 Cetyl ethylhexanoate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, neopentyl glycol di-2-ethylhexanoate, glycerol tri-2-ethylhexanoate, 2-octyldodecyl oleate, isopropyl myristate, Glycerol triisostearate, triglyceride fatty acid glycerol, olive oil, avocado oil, coconut oil, jojoba oil, beeswax, whale wax, carnauba wax, myristyl myristate, Ink oils, various hydrocarbons and lanolin, higher fatty acids, fats and oils, esters, higher alcohols, waxes, silicone oils such as volatile silicone oils and non-volatile silicone oils can be used. In addition, when dispersing fine particles surface-treated with a volatile agent into an oil agent, it is necessary to remove the fine particles and the water in the dispersion before the dispersion step, so that water and the oil agent are emulsified. Is preferable in that it can be suppressed. As the dehydration method, for example, reflux topping using hexane, cyclohexane or the like can be used.
The concentration of the composite fine particles in the oil is not particularly limited, but the composite fine particle concentration dispersible in the oil is related to the size of the composite fine particles, the type of the water repellent and the oil, and the composite fine particle concentration is too large. As the composite fine particles aggregate in the oil agent, the dispersibility and optical properties of the composite fine particles are remarkably impaired, and the properties of the oil agent are often deteriorated. The composite fine particle concentration must be adjusted.
[0052]
3. Next, each raw material used for the manufacturing method of this invention is demonstrated.
(1) Child particles
The child particles constituting the composite fine particles have transparency in the visible light region and shielding properties in the ultraviolet region. That is, the child particles must be particles having a size that does not absorb in the visible light region and does not scatter visible light.
[0053]
As a substance constituting the child particles, a substance in which an exciton absorption edge based on the band gap energy exists in the wavelength region of ultraviolet rays because of the requirement that it has no absorption in the visible light region and has an ultraviolet absorption property, that is, A semiconductor compound having a band gap energy of 3.0 to 4.0 eV is preferable.₂, ZnO, CeO₂, SiC, SnO₂, WO_Three, SrTiO_Three, BaTiO_Three, CaTiO_ThreeEtc. strongly show its properties, among them TiO₂ZnO and CeO₂Are commonly used as ultraviolet screening agents, and one or more selected from the group consisting of these are particularly preferred. In particular, in order to shield the ultraviolet A region (320 to 400 nm), ZnO, CeO₂Etc. are effective, and TiO is used for shielding the ultraviolet B region (280 to 320 nm).₂Is effective. In order to shield the ultraviolet B and A regions, the child particles are made of TiO.₂And (ZnO, CeO₂, BaTiO_Three, CaTiO_Three, SrTiO_Three, SiC) and preferably used in combination with one or more selected from the group consisting of SiC).
Alternatively, TiO₂In the case of using the element, a shielding region is obtained by containing a pentavalent or higher element such as W, P, Ta, Nb, Sb, Mo, or a trivalent or lower element such as Zn, Al, Mg, or Ca as impurity doping. Can be extended to the A region of the UV.
[0054]
The shape of the child particles is not particularly limited, such as a spherical shape, a plate shape, or a needle shape. The particle diameter of the child particles is preferably about the same as that of the primary particles of the mother particles in order to improve the dispersion state of the child particles. On the other hand, the ultraviolet scattering property appears strongly by Mie scattering, and this becomes remarkable when the particle diameter is about 1/2 of the wavelength of ultraviolet light, that is, 0.2 μm or less, and the average particle diameter is specifically in the visible light region. In order to satisfy transparency and shielding properties in the ultraviolet region, 0.2 μm or less is preferable, 0.1 μm or less, more preferably 0.001 to 0.1 μm, and particularly preferably 0.05 μm or less. In addition, the child particle in this invention means the aggregate which the primary particle disperse | distributes and fix | immobilizes independently and / or the primary particle aggregates. Therefore, the average particle diameter of the child particles also means the particle diameter of the aggregate.
[0055]
In the present invention, in production, a sol containing child particles and child particle powder are used as the child particle raw materials. Since it is preferable that the child particles exist in a dispersed state inside the composite fine particles, it is preferable to improve the dispersibility and stability of the child particles in the sol. For this purpose, the surface of the child particles is covered with another substance. It may be coated or mixed with a sol stabilizer. For example TiO₂When ultrafine particles are used as the child particles, the surface of the ultrafine particles is made of SiO.₂And Al₂O_ThreeEtc. to improve dispersibility, basic stabilizers (for example, NH_ThreeEtc.) and mixed with TiO₂It is also possible to stabilize the sol state. In addition, when the ultrafine particle powder is surface-modified and can be dispersed well, it can be used as a raw material for child particles. In general, the sol used in the present invention is not recognized by an ordinary microscope, but is a substance in which a substance is dispersed in a liquid as particles larger than atoms or small molecules (Rikagaku Dictionary 3rd edition; Iwanami Shoten) To tell. For example, silica hydrosol, TiO₂Examples include ultrafine particle suspensions.
[0056]
(2) Mother particles
The mother particles constituting the composite fine particles need to satisfy the transparency in the visible light region in the same manner as the child particles in order to express the transparency of the composite fine particle suspension system. That is, it is desirable that the material is composed of a substance that does not absorb visible light and does not have primary particles exceeding 0.3 μm. For example, an aggregate of ultrafine particles having an average particle diameter of 0.01 μm is preferable.
[0057]
The substance constituting the mother particles is a substance made of a highly transparent metal oxide and / or fluorine compound, such as a metal oxide, a mixture of a metal oxide and a fluorine compound, or a substance consisting only of a fluorine compound. Used. As described above, the aggregate of fine particles normally constitutes the mother particle, so that the average particle diameter of the fine particles (that is, primary particles) constituting the aggregate is 0.3 μm in order to satisfy the requirements of the mother particle. In other words, it is 0.001 to 0.3 μm, preferably 0.15 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. In the production, a sol containing particles constituting the mother particles and mother particle powder are used as the mother particle raw material. Further, for the same reason as in the case of the child particles, the surface of the fine particles constituting the mother particles may be coated with another substance, or a sol stabilizer may be mixed. Examples of the coating material and stabilizer used here are the same as in the case of the child particles.
[0058]
Many metal oxides are chemically stable solids and are suitable as substances constituting the mother particles. As a metal oxide contained in the mother particle, for example, TiO₂, CuO, ZnO, MgO, CeO₂, SnO₂, SiO₂, Fe₂O_Three, Al₂O_ThreeNiO₂, MnO₂Etc., and SiO₂And Al₂O_ThreeIs particularly preferable from the viewpoint of the above-described refractive index and transparency. From the viewpoint of ceramic fine particles having a large band gap energy, for example, SnO₂, In₂O_Three, SiO₂, ZnO, Al₂O_ThreeEtc. are preferred.
[0059]
Many fluorine compounds contained in the mother particles are chemically stable and have a low refractive index, and are useful for controlling the refractive index of the resulting composite fine particles. Fluorine compounds include those that are solid or liquid at room temperature. Examples of inorganic fluorine compounds that are solid at room temperature include MgF₂, CaF₂, AlF_Three, LiF, NiF₂, BaF₂Examples of organic fluorine compounds include polytetrafluoroethylene (hereinafter abbreviated as PTFE), tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, and polyvinyl fluoride. Fluorine resin etc. are mentioned. Among them, fluorine compounds are MgF₂In the case of polytetrafluoroethylene, it is preferable from the viewpoint of refractive index and transparency.
[0060]
The average particle size of such a fluorine compound that is solid at room temperature is preferably 0.3 μm or less, and more preferably 0.2 μm or less. This is because, when the average particle diameter exceeds 0.3 μm, the cohesive force between the particles becomes weak and the strength of the composite fine particles decreases.
Examples of the fluorine compound that is liquid at room temperature include perfluoropolyether (hereinafter abbreviated as PFPE). Examples of PFPE include perfluoropolymethyl isopropyl ether (FOMBLIN HC manufactured by Nikko Chemicals Co., Ltd.). Such PFPE not only lowers the refractive index of the composite fine particles but also has an effect of imparting a wet feel, and can be suitably used for fine particles for cosmetics and the like. When such a liquid fluorine compound is used, a solvent must be selected so that the child particle raw material and the mother particle raw material do not phase-separate in the solvent, but when the solvent is water, various surfactants are used. It is preferable to use a liquid fluorine compound emulsified at room temperature. For example, perfluoropolyether emulsion (O / W type) can be mentioned. The emulsion diameter is preferably not more than 0.1 times the size of the droplet. When the emulsion diameter exceeds 0.1 times the size of the droplet, the emulsion becomes larger than the generated particles, and particle generation becomes difficult.
[0061]
As described above, in the present invention, a fluorine compound that is liquid at room temperature can be used as a substance having a low refractive index to be contained in the mother particles. In this case, in order to increase the degree of freedom in controlling the refractive index, It is used in combination with a metal oxide and / or a fluorine compound that is solid at room temperature.
[0062]
As an example of the combination of the child particle and the mother particle in the present invention as described above, the child particle is TiO 2.₂And / or ZnO, and the mother particle is SiO.₂And / or Al₂O_ThreeOr SiO₂And perfluoropolyether, and the coating inorganic material is SiO₂And / or Al₂O_ThreeIn the case where the water repellent is one or more water repellents selected from methyl hydrogen polysiloxane, oxazoline-modified silicone, amino-modified silicone, stearic acid, monoalkyl phosphate and dialkyl phosphate, an ultraviolet shielding agent It is preferable from the viewpoint of safety and stability.
In the present invention, the child particles and the mother particles may contain a substance that does not correspond to the metal oxide and fluorine compound as described above. For example, there is a raw material sol stabilizer or a sol particle coating agent, which may be mixed as long as it does not hinder the expression of optical characteristics of the composite fine particles.
[0063]
4). Next, the preparation of the raw material liquid using the raw materials as described above and the method for producing composite fine particles will be specifically described.
When preparing the raw material liquid, the mixed liquid containing the above-mentioned child particle raw material and the mother particle raw material can be present in a state where the child particles are dispersed on the surface of the mother particle and / or inside. It is important to mix well and uniformly disperse and mix the mixed solution so that the child particles are easily dispersed in the mother particles. At this time, aggregated fine particles are generated by the electrostatic force or the like between the child particles and the fine particles that are the raw material of the mother particles.
[0064]
For example, TiO₂Ultra fine particle powder, SiO₂When sol (water-based, ST-C, manufactured by Nissan Chemical Industries, pH 8.5-9.0) is selected, when the pH of the mixed solution is 7 and milling or high-pressure dispersion treatment is performed under appropriate conditions, from the isoelectric point TiO₂(Isoelectric point is about pH 5-7) is negatively charged, SiO₂Is positively charged (the surface of the electric double layer), so TiO is a child particle.₂And SiO, the mother particle₂As a result, composite particles in which the child particles and the mother particles are aggregated by electrostatic force are generated. Also, for example, ZnO ultrafine powder as a child particle material, and SiO as a mother particle material₂When sol (water-based, ST-C, manufactured by Nissan Chemical Industries, pH 8.5-9.0) is selected, when the pH of the mixed solution is 7 and milling or high-pressure dispersion treatment is performed under appropriate conditions, from the isoelectric point ZnO (isoelectric point is about pH 9.3) is positively charged, SiO₂Is positively charged (the surface of the electric double layer), but as a result of observation with a transmission electron microscope, ZnO as a child particle and SiO as a mother particle are SiO.₂It was found that composite microparticles in which flocculates were produced. At this time, SiO₂It is considered that the sliding surface in the electric double layer is broken and the negatively charged surface is in contact with ZnO.
Here, as in the example above, SiO₂The sol is (1) a role as a medium that efficiently pulverizes child particles that are normally in an agglomerated state to the extent of the primary particle size and / or pulverization to a particle size equal to or less than the primary particle size, and (2) pulverization. And / or the role of adhering to the child particles at the same time as the pulverization to form the skeleton of the mother particles, and (3) after the formation of the composite particles in which the child particles / the mother particles are aggregated, the aggregation of the composite particles on the particle surface Some SiO₂It plays a role like a dispersant to prevent by electrostatic repulsion. Where SiO₂What is necessary is just to select suitably as a particle diameter of sol according to the role of said (1)-(3). For example, when the role of (3) is particularly emphasized, SiO₂The particle size of the sol is preferably a particle size that is about the same as or smaller than the child particle size. That is, in this case, SiO₂The particle size of the sol is suitably 0.1 μm or less, preferably 0.05 μm or less, more preferably 0.02 μm or less. In addition, SiO₂Sol solvents include hydrosol (water) and organosol, but may be appropriately selected and used in consideration of the type of child particles, dispersion stability, and the like.
[0065]
By the above method, composite fine particles in which the child particles / mother particles are aggregated are produced. In order to maintain the state firmly and to substantially eliminate the catalytic activity by the child particles, the surface of the composite fine particles is catalytically active. Is coated with an inorganic substance substantially free of As described above, the coating layer may be either a film or a fine particle film, and the coating layer thickness substantially covers the active points on the surface of the composite fine particles, and the surface activity extends to the medium around the composite fine particles. As long as there is no such thing.
[0066]
Water or an organic solvent is used as the solvent for the child particle raw material and the mother particle raw material described above, but a solvent that does not hinder the generation of composite fine particles composed of child particles / mother particles in the raw material liquid is preferable. Examples of organic solvents include alcohols such as methanol and ethanol, and polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, and ethyl acetate, which adversely affect the production of UV-shielding composite fine particles. May be the same as or different from the solvent of the metal oxide sol described above.
[0067]
The concentration of the mother particle raw material in the mixed liquid containing the child particle raw material and the mother particle raw material as the raw material liquid is 10^-FiveThe range of -10 mol / L is preferable.^-FourA range of ˜1 mol / L is more preferable. That is, from the viewpoint of maintaining good dispersibility of the child particles, 10^-FiveMol / L or more is preferable, and 10 mol / L or less is preferable from the viewpoint of maintaining good raw material dispersibility of the mother particles and the child particles in the liquid.
[0068]
When a fluorine compound is used as the mother particle raw material, the concentration of the fluorine compound in the mixed liquid containing the child particle raw material and the mother particle raw material as the raw material liquid is 10^-FiveThe range of 10 mol / L is preferred, desirably 10^-FourA range of ˜1 mol / L is good. That is, from the viewpoint of generating an effective amount of fluorine compound fine particles, 10^-FiveMol / L or more is preferable, and 10 mol / L or less is preferable from the viewpoint of the solubility of the fluorine compound.
[0069]
The density | concentration of the child particle raw material in the liquid mixture containing the child particle raw material and mother particle raw material which are raw material liquids is 10^-FiveThe range of 10 mol / L is preferred, desirably 10^-FourA range of ˜1 mol / L is good. That is, from the viewpoint of the amount necessary for expressing the optical properties of the child particles in the composite fine particles, 10^-FiveIt is preferably at least 10 mol / L from the viewpoint of sufficiently dispersing the raw material of the child particles in the liquid to produce composite fine particles having a uniform composition.
[0070]
  The proportion of the child particles dispersed and immobilized in the mother particles may be such that the child particles are dispersed without causing significant aggregation in the mother particles., 0. 1-30% by volumeGoodPreferably, it is 0.5 to 20% by volume (however, when the composite fine particles of the present invention are coated with an inorganic substance, this is a value calculated by excluding the inorganic substance). When the mother particles contain a metal oxide and a fluorine compound, the ratio of the fluorine compound is at least 1% by weight with respect to the composite fine particles. The ratio of the child particles can be calculated from the density of the substances constituting the composite fine particles (particle density in the case of particles) and the composition ratio of the raw material liquid.
[0071]
The amount of the inorganic material raw material in the mixed liquid containing the composite fine particles composed of the child particles / the mother particles is 10%.^-Five10 to 10 mol / L as an inorganic substance^-FiveThe range of -10 mol / L is preferable.^-FourA range of ˜1 mol / L is more preferable. That is, from the viewpoint of coating the surface of the composite fine particles to such an extent that the coating effect is exhibited.^-FiveMol / L or more is preferable, and 10 mol / L or less is preferable from the viewpoint of the solubility of the inorganic material raw material.
[0072]
The average particle diameter in the dispersion of the composite fine particles of the present invention consisting of the child particles / mother particles dispersed in the mixed liquid is preferably 0.002 to 0.5 μm, more preferably. Is 0.4 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.2 μm or less. The particle size distribution is preferably as narrow as possible. This is because, when the average particle size is larger than 0.5 μm, a decrease in transparency and a decrease in ultraviolet shielding ability due to the scattering of visible light due to the particle size effect begin to occur. On the other hand, when the thickness is 0.5 μm or less, even if the refractive index difference between the composite fine particles and the dispersion medium is large, the transparency can be increased without scattering visible light. The average particle size here is measured by dispersing a cake of composite fine particles after coating treatment in water and using a particle measuring device (for example, laser Doppler type particle measuring device, DLS-700 manufactured by Otsuka Electronics Co., Ltd.) or the like.
[0073]
The ultraviolet shielding composite fine particles of the present invention are obtained by the production method as described above. The structure is an aggregate formed by closely aggregating the primary particles while maintaining the shape of the mother particles, and the child particles are present dispersed on the mother particle surface and inside the mother particles, The composite fine particles composed of the child particles and the mother particles may be coated with an inorganic substance having substantially no catalytic activity. If the dispersibility of the child particles is poor, the optical properties of the child particles will not be expressed. The ultraviolet rays hitting the child particles existing on the surface of the mother particles are partly absorbed and the rest are scattered outside the composite particles, but the ultraviolet rays that have entered the mother particles without hitting the child particles are Ultraviolet rays are absorbed and scattered by the child particles existing inside, and the ultraviolet rays are effectively shielded. Further, by having the inorganic material coating layer, the catalytic activity of the child particles and the mother particles is substantially suppressed, and the composite fine particles can exist stably in any medium without causing deterioration of the medium.
[0074]
The shape and size of the composite fine particle powder of the present invention finally obtained by drying and pulverizing in the step (d) are not particularly limited. Various shapes and sizes are used according to the usage scene. For example, as a powder for cosmetics, a spherical particle powder of sub-μm to several μm is preferable in terms of good touch and handling, and a plate-like particle powder of the same size is attached to the skin. It is preferable in terms of good elongation on the skin and handling.
[0075]
5). Optical properties of composite particles
  The optical properties of the ultraviolet shielding composite fine particles of the present invention can be quantified, for example, by measuring light transmittance by ultraviolet / visible light spectroscopic analysis.
  Here, the composite fine particles were dispersed in a medium having a refractive index similar to the refractive index of the ultraviolet shielding composite fine particles, and the light transmittance was measured with an ultraviolet-visible spectrophotometer using an optical cell having an optical path length of 1 mm. In the case where the transmittance is 80% or more at a wavelength of 800 nm, the transmittance is 20% or more at a wavelength of 400 nm, and the transmittance is 5% or less at a light wavelength having a wavelength range of 380 to 300 nm, the ultraviolet shielding ability of the composite fine particle is It can be said that it is preferable. That is, it is not always necessary that the transmittance is 5% or less in the range of 380 to 300 nm. With this performance, it is possible to satisfy high transparency particularly in the visible light region and high shielding property in the ultraviolet region. Note that the same refractive index as that of the composite fine particles means that the difference in refractive index between the composite fine particles and the medium is ± 0.1 or less.To be withinmeans. In this case, the concentration of the composite fine particles dispersed in the medium is, for example, 0.1% by weight or more.
[0076]
Specifically, the evaluation by the ultraviolet / visible light spectroscopic analysis is performed as follows.
Composite fine particles are added and dispersed in a medium having a refractive index comparable to that of the composite fine particles of the present invention to prepare a composite fine particle dispersion having an arbitrary concentration. The composite particles are well dispersed using an ultrasonic disperser or the like while stirring so that the dispersion becomes uniform. An optical cell having an optical path length of 1 mm is prepared and filled with the dispersion. The optical cell has no absorption or scattering in the ultraviolet and visible light regions, and for example, a quartz cell is used. The transmittance of light transmitted through this optical cell is measured using an ultraviolet-visible spectrophotometer. At this time, the same optical cell filled with only the medium before the suspension of the composite fine particles is used as a control, and the background is removed.
[0077]
  Further, the composite fine particles of the present invention substantially have catalytic activity ability.HoldingIt ’s not good, but this, DoubleThe composite fine particles are dispersed in white petrolatum so that the concentration of the child particles is 1% by weight, and this is used for 60 minutes with ultraviolet light having a central wavelength of 312 nm using an ultraviolet light source (SPECTRONICS, ENB-260C / J).whileIrradiation and presence of white petrolatum discolorationByConfirmationIsThe When white petrolatum deteriorates due to catalytic activity, white petrolatum turns brownYouThe
  Therefore, in the present specification, the term “composite fine particles having substantially no catalytic activity ability” means composite fine particles whose catalytic activity is suppressed so that the catalytic activity is not problematic in practical use.SaidIt means that no discoloration of petrolatum is confirmed by the method.
[0078]
6). Cosmetics
In the cosmetic of the present invention, in addition to the ultraviolet shielding composite fine particles and the dispersion oil of the ultraviolet shielding composite fine particles, other components usually used in cosmetics can be appropriately blended as necessary. Listed below.
(1) Talc, kaolin, sericite, muscovite, phlogopite, saucite, biotite, synthetic fluorine phlogopite, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate , Inorganic powders such as barium silicate, barium sulfate, strontium silicate, metal tungstate, silica, hydroxyapatite, zeolite, boron nitride and ceramic powder.
(2) Organic powders such as nylon powder, polyethylene powder, polystyrene powder, benzoguanamine resin powder, polytetrafluoroethylene powder, distyrenebenzene polymer powder, epoxy resin powder, acrylic resin powder, and microcrystalline cellulose.
[0079]
(3) Inorganic white pigments such as titanium oxide and zinc oxide; Inorganic red pigments such as iron oxide (Bengara) and iron titanate; Inorganic brown pigments such as γ iron oxide; Inorganic yellow pigments such as yellow iron oxide and loess Pigments; inorganic black pigments such as black iron oxide and carbon black; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate; inorganics such as ultramarine and bitumen Blue pigments: pearl pigments such as titanium oxide-coated mica, titanium oxide-coated bismuth oxychloride, bismuth oxychloride, titanium oxide-coated talc, fish scale foil, colored titanium oxide-coated mica; metal powder pigments such as aluminum powder and copper powder.
(4) Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401 And organic pigments such as Blue No. 404; Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230 (1), Red No. 230 (2), Red No. 401, Red No. 505, Orange Organic pigments such as 205, yellow 4, yellow 5, yellow 202 (1), yellow 202 (2), yellow 203, green 3 and blue 1 zirconium, barium or aluminum lake.
(5) Natural pigments such as chlorophyll and β-carotene.
[0080]
(6) Squalane, paraffin wax, liquid paraffin, petrolatum, microcrystalline wax, ozokerite, ceresin, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, cetyl alcohol, hexadecyl alcohol, oleyl alcohol, 2-ethylhexane Cetyl acid, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, neopentyl glycol di-2-ethylhexanoate, glycerol tri-2-ethylhexanoate, 2-octyldodecyl oleate, isopropyl myristate, triisostearic acid Glycerol, tricoconut oil fatty acid glycerol, olive oil, avocado oil, camellia oil, jojoba oil, beeswax, whale wax, carnauba wax, myristyl myristate, mink oil, la Various hydrocarbons, higher fatty acids such as phosphorus, fats and oils, esters, higher alcohols, waxes, silicone oils such as volatile silicone and a nonvolatile silicone oil.
[0081]
(7) Ultraviolet protective agents such as the following ultraviolet absorbers can be appropriately blended as necessary.
1) Benzoic acid derivative system
Paraaminobenzoic acid (PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA amyl ester, N, N-dimethyl PABA octyl ester, etc.
2) Anthranilic acid derivative system
Homomentil N-acetyl anthranilate, etc.
[0082]
3) Salicylic acid derivative system
Amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.
4) Cinnamic acid derivative system
Octylcinnamate, ethyl 4-isopropylcinnamate, methyl 2,5-diisopropylcinnamate, ethyl 2,4-diisopropylcinnamate, methyl 2,4-diisopropylcinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinna Mate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate (2-ethylhexyl p-methoxycinnamate), 2-ethoxyethyl p-methoxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α-cyano-β- Phenylcinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate, glyceryl mono 2-ethylhexanoyl-diparamethoxycinnamate, etc.
[0083]
5) Benzophenone derivative system
2,4-dihydroxybenzophenone, 2,2′-dihydroxy 4-methoxybenzophenone, 2,2′-dihydroxy 4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone, 2-hydroxy 4-methoxy-4'-methylbenzophenone, 2-hydroxy 4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl 4'-phenylbenzophenone-2-carboxylate, 2-hydroxy 4-n-octoxybenzophenone, 4-hydroxy 3-carboxybenzophenone, etc.
[0084]
6) Other UV absorbers
3- (4′-methylbenzylidene) d, l-camphor, 3-benzylidene d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl 5-methylbenzoxazole, 2,2′-hydroxy 5- Methylphenylbenzotriazole, 2- (2′-hydroxy-5 ′ t-octylphenyl) benzotriazole, dibenzaracin, dianisoylmethane, 4-methoxy4′-t-butyldibenzoylmethane, 5- (3,3′- Dimethyl-2-norbornylidene) -3-pentan-2-one, 1- (3,4-dimethoxyphenyl) -4,4′-dimethyl-1,3-pentadione, etc.
[0085]
(8) Moreover, surfactant can also be mix | blended suitably as needed.
Examples of such surfactants include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene hydrogenated castor oil alkyl sulfate ester, polyoxyethylene alkyl sulfate ester Examples thereof include silicone-based activators such as esters, alkyl phosphate esters, polyoxyethylene alkyl phosphate esters, fatty acid alkali metal salts, sorbitan fatty acid esters, glycerin fatty acid esters, and polyether-modified silicones.
[0086]
(9) Moreover, water-soluble polyhydric alcohol can also be mix | blended suitably as needed. Such a water-soluble polyhydric alcohol is a water-soluble polyhydric alcohol having two or more hydroxyl groups in the molecule, such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, di-ethylene. Polyglycerin such as propylene glycol, glycerin, diglycerin, triglycerin, tetraglycerin, glucose, maltose, maltitol, sucrose, fructose, xylitol, sorbitol, maltotriose, threitol, erythritol, amylolytic sugar reducing alcohol, etc. Can be mentioned.
[0087]
(10) In addition, amino acids such as lysine and arginine; organic acids such as lactic acid, citric acid, succinic acid, and glycolic acid, and organic acid salts thereof; resins such as alkyd resin and urea resin; camphor, tributyl citrate, and the like Plasticizers; antioxidants such as α-tocopherol; preservatives such as butylparaben and methylparaben; plant extracts such as cornflower, altea and hypericum; medicinal agents such as retinol and allantoin; thickeners such as xanthan gum and carrageenan Other fragrances and the like can be appropriately blended.
[0088]
In the cosmetic of the present invention, silicone oil or ether-modified silicone can be blended in order to enhance the durability such as feeling of use and UV protection effect.
The silicone oil is not particularly limited as long as it can be blended with ordinary cosmetics. For example, octamethylpolysiloxane, tetradecamethylpolysiloxane, methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane. In addition to siloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc., trimethylsiloxysilicic acid, the following general formula (1) or general formula (2)
[0089]
[Chemical 1]

[0090]
(Wherein R¹And R²Each represents an alkyl group having 1 to 4 carbon atoms, and R^ThreeRepresents a linear, branched or cyclic alkyl group, alkenyl group or fluoroalkyl group having 1 to 40 carbon atoms, R^FourRepresents a linear, branched or cyclic alkyl group, alkenyl group or fluoroalkyl group having 7 to 40 carbon atoms, e is a number of 2 or more, f is a number of 3 or more, and e + f = 5 to 6000. Indicates a number. An organopolysiloxane having a unit represented by
The blending amount of these silicone oils can be 2 to 80% by weight in the cosmetic, preferably 5 to 50% by weight, and more preferably 8 to 40% by weight.
[0091]
The ether-modified silicone is not particularly limited as long as it is a compound in which at least a part of the siloxane is substituted with a group having an ether bond, and examples thereof include the following, and these may be used alone or in combination of two or more. Can be used.
Specific examples of such ether-modified silicone include the following compounds (1) to (4).
(1) General formula (3)
[0092]
[Chemical 2]

[0093]
(Wherein R¹¹, R¹²And R¹³At least one of the following formula: R¹⁴(OC_ThreeH₆) b (OC₂H_Four) aO (CH₂) p- (R¹⁴Represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a and b are average values, each representing a number of 0 to 35, and p represents a number of 1 to 5. ), The remainder represents a methyl group, m and n are average values, m represents a number from 1 to 200, and n represents a number from 0 to 50. Ether-modified silicone represented by
Of these, the molecular weight is 2000-50000 and R¹¹~ R¹³It is also preferred that the proportion occupied by 5 to 40% of the molecular weight. Further, in the general formula (3), m is 5 to 80, n is 0 to 2, a is 9 to 10, b is 0, p is 3, R¹⁴Is a hydrogen atom or m is 90 to 110, n is 0, a is 11 to 13, b is 0, p is 3, R¹⁴Is preferably a hydrogen atom.
As the ether-modified silicone represented by (3), a commercial product of SH-3775 series manufactured by Toray Dow Corning Co. can be used.
(2) General formula (4)
[0094]
[Chemical Formula 3]

[0095]
(Wherein R^{twenty one}Represents a hydrocarbon group having 1 to 5 carbon atoms, R^{twenty two}Represents a hydrocarbon group having 6 to 16 carbon atoms, Q represents an alkylene group, R^{twenty three}Is the following formula:-(OC₂H_Four) q− (OC_ThreeH₆r−OR^{twenty four}(R^{twenty four}Represents a hydrogen atom or a lower alkyl group, q and r are q ≦ r, and — (OC₂H_Four) q− (OC_ThreeH₆) The number of molecular weight of r is 600-3500. ), Z represents a number of 1 to 3, and x and y represent a number satisfying x <3 y and x + y + z = 30 to 400. However, − (OC₂H_Four) q− (OC_ThreeH₆) The total weight of r does not exceed 1/3 of the total weight of the polyether-alkyl-modified silicone represented by formula (4). A polyether alkyl-modified silicone represented by:
[0096]
R in the general formula (4)^{twenty one}Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by the above include an alkyl group or alkenyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, or a vinyl group. Among these, a methyl group is preferable. R^{twenty two}As the hydrocarbon group having 6 to 16 carbon atoms represented by hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, linear alkyl group such as dodecyl group, tetradodecyl group, hexadecyl group, isooctyl group, etc. A branched alkyl group such as a group, s-octyl group, 2-ethylhexyl group, etc., among which a dodecyl group is preferred. If y> 1, then R^{twenty two}May be the same for each repeating unit or may be arbitrarily different.
[0097]
Examples of the alkylene group represented by Q in the formula (4) include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group. Among these, a propylene group and a trimethylene group are preferable.
In formula (4), R^{twenty three}R in the group showing^{twenty four}Represents a hydrogen atom or a lower alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group), and among these, a hydrogen atom is preferable. Further, q and r are preferably q = 15 and r = 0, q = r = 25, or q = 29 and r = 7.
Examples of the polyether-alkyl-modified silicone represented by the formula (4) include “DC Q2-2500” (laurylmethicone copolyol; manufactured by Toray Dow Corning; R in the formula (4)^{twenty one}Is a methyl group, R^{twenty two}May also be a dodecyl group, x = 0) or the like.
(3) General formula (5)
[0098]
[Formula 4]

[0099]
(Wherein R³¹, R³², R³³And R³⁴At least one of the following formula (6): -A-OCH₂CH (OR⁴¹) CH₂OR⁴²(Here, A represents a divalent hydrocarbon group having 3 to 20 carbon atoms, R⁴¹And R⁴²Each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. However, R⁴¹And R⁴²Any one of represents a hydrogen atom. ), The remainder being a straight, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms or the following formula: -BR⁴³(Here, B represents a divalent hydrocarbon group containing an ether bond and / or an ester bond, and R⁴³Represents a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms. ), S, t and u each represent a number from 0 to 200, and when s + t + u = 0, R³¹One or more of them represent a group represented by the formula (6) (provided that R³¹One of them is A in the general formula (6) is a trimethylene group, R⁴¹And R⁴²Is a hydrogen atom and the remaining R³¹  R³², R³³And R³⁴Except when all are methyl groups. ). ) Alkyl glyceryl ether-modified silicone represented by
[0100]
Examples of the divalent hydrocarbon group having 3 to 20 carbon atoms represented by A in the general formula (5) include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, Nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tetradecamethylene group, hexadecamethylene group, octadecamethylene group and other linear alkylene groups, propylene group, 2-methyltrimethylene group, 2-methyltetramethyl group Examples include branched chain alkylene groups such as a methylene group, 2-methylpentamethylene group, and 3-pentamethylene group. R⁴¹And R⁴²Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by: methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, s-butyl group, t-butyl group, neopentyl group, cyclopentyl group, etc. And a straight chain, branched chain or cyclic alkyl group. Further, the divalent hydrocarbon group containing an ether bond and / or an ester bond represented by B includes the following formula: — (CH₂) h− (OC₂H_Four) i− (OC_ThreeH₆) j−O − 、 − (CH₂) h-O -CO-,-(CH₂) h—COO— (in which h represents an integer of 3 to 20, i and j represent a number of 0 to 50), and the like.
[0101]
R⁴³Examples of the straight chain, branched chain or cyclic hydrocarbon group having 1 to 30 carbon atoms represented by: methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Linear alkyl group such as decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, doeicosyl group, tetraeicosyl group, hexaeicosyl group, octaeicosyl group, triacontyl group, isopropyl group A branched alkyl group such as s-butyl group, t-butyl group, neopentyl group, 1-ethylpropyl group, 1-heptyldecyl group, and cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, abiethyl group, cholesteryl group, etc. Can do.
Such an alkyl glyceryl ether-modified silicone represented by the formula (5) can be produced by a method described in JP-A-4-108795.
The compounding amount of these ether-modified silicones is preferably 0.05 to 20% by weight, more preferably 1 to 10% by weight in the cosmetic.
[0102]
The blending amount of the ultraviolet shielding composite fine particles of the present invention in the cosmetic varies depending on the type of the cosmetic, but is preferably 0.01 to 50% by weight, more preferably 0.05 to 40% by weight, and more preferably 0.1 to 30%. Weight percent is particularly preferred. If it is less than this range, the ultraviolet ray shielding effect cannot be exhibited sufficiently, and if it exceeds this range, the feel as a cosmetic is impaired. Further, the blending amount of the ultraviolet shielding composite fine particle dispersion oil of the present invention used in cosmetics is determined so as to satisfy the blending amount of the above-described ultraviolet shielding composite fine particles contained in the dispersion oil in the cosmetic. Is done.
The cosmetics of the present invention are used in various forms according to conventional methods, and the form is not particularly limited, but lotion, emulsion, cream, ointment, aerosol cosmetics, powder foundation, powder eye shadow, emulsified foundation, lipstick Used as makeup cosmetics, hair cosmetics, skin cleansing agents and the like.
[0103]
Further, the cosmetic of the present invention has an SPF value of 8 or more when measured using an SPF-290 analyzer manufactured by The Optometrics Group, and JIS Z8729- before and after application to the skin. ΔE as defined in 1980^*What ab is 3 or less is suitable. From the viewpoint of sufficiently exhibiting the UV protection effect, the SPF is preferably 8 or more, more preferably 10 or more, and particularly preferably 13 or more. ΔE^*ab is preferably 3 or more, more preferably 2 or less, and particularly preferably 1 or less from the viewpoint of not impairing the appearance when applied to the skin.
[0104]
【Example】
EXAMPLES Examples and comparative examples of the present invention will be shown below, and the present invention will be described in more detail. However, the present invention is not limited to these examples and the like.
Example 1
Silica sol (ST-C, SiO, manufactured by Nissan Chemical Industries, Ltd.)₂Concentration 20.5% by weight) 366.5 g, titanium oxide ultrafine particles (TTO-51 (A) manufactured by Ishihara Sangyo Co., Ltd., rutile type) 20.0 g and water were mixed to make 1 L to obtain a raw material liquid (ie , SiO of the raw material liquid₂And TiO₂Are respectively 1.25 mol / L and 0.25 mol / L, and the raw material liquid contains about 10% by weight of the particle mixture. ).
[0105]
Using a bead mill (TSG-6H manufactured by IGARASHIKIKAI), a mixture in which the prepared raw material liquid and glass beads (average particle diameter 0.1 mm) were mixed so as to have a weight ratio of 175: 325 was used. p. m. , 6 hours of dispersion treatment was performed. After the dispersion treatment is finished, the glass beads are separated and TiO₂/ SiO₂A dispersion of composite fine particles (child particles / mother particles, the same shall be indicated in the same manner) was obtained.
[0106]
84.6 g of the above dispersion, 1500 g of ethanol, and 16.26 g of tetraethoxysilane were mixed and heated to 50 ° C. in a water bath. After the temperature of this dispersion reached 50 ° C., a mixed solution of 3.9 mL of 1N hydrochloric acid and 300 g of ethanol was added dropwise. After dropping, the reaction is performed at 50 ° C. for 2 hours and 30 minutes, and the composite fine particles are converted into SiO 2.₂The surface was coated with. After the coating was completed, a mixed solution of 0.98 mL of 4N sodium hydroxide aqueous solution and 50 g of ethanol was added to neutralize hydrochloric acid. All the above steps were performed under stirring.
[0107]
The dispersion after the coating treatment was subjected to solid-liquid separation using a centrifugal separator to obtain an ethanol-containing cake. Ethanol was added to the cake, the cake was dispersed in ethanol, and the solid-liquid separation was performed again by centrifuging, and the process was repeated five times to obtain a composite fine particle-containing ethanol cake having a solid concentration of about 40% by weight.
12.5 g of this cake was mixed with 500 g of acetone and subjected to ultrasonic dispersion. After the cake was completely dispersed in acetone, 2.0 g of methyl hydrogen polysiloxane (manufactured by Shin-Etsu Silicone Co., Ltd., KF99P) was added and mixed to perform water repellent treatment. Thereafter, the dispersion was dried at 80 ° C. and baked at 130 ° C. for 2 hours to dry the composite fine particles. The produced powder was repeatedly pulverized 10 times with a mill (IKA A10) to obtain composite fine particles.
[0108]
The composite fine particle ethanol cake was dispersed in water, and the particle size of the composite fine particles before water repellent treatment was measured using a laser Doppler type particle size measuring device (DLS-700 manufactured by Otsuka Electronics Co., Ltd.). The particle diameter (volume basis) was about 0.08 μm.
[0109]
The composite fine particles after the water repellent treatment were white and were observed with a scanning electron microscope (JSM-T100 manufactured by JEOL Ltd.). As a result, the average particle diameter was about 1 μm. Moreover, as a result of observing the cross section by an ultrathin section method using a transmission electron microscope (JEM-2000FX manufactured by JEOL Ltd.), SiO₂In the aggregate of ultrafine particles (average particle diameter of about 0.01 μm), TiO₂It was found that ultrafine particles (average particle diameter of about 0.01 μm) were dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 (rutile type) is a child particle₂/ SiO₂It was a composite fine particle.
[0110]
The ratio of the child particles in the composite fine particles is SiO.₂And TiO₂Particle density of 2.27 g / cm respectively^Three3.84 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 8.5% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.57. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 13.6% by volume.
[0111]
The composite fine particles before and after the water repellent treatment are dispersed in white petrolatum (Wako Pure Chemical Industries, Ltd.) in an amount such that the child particles are 1% by weight in the mixture of white petrolatum and composite fine particles. It was. When this was irradiated with light having a center wavelength of 312 nm for 60 minutes using an ultraviolet light source (ENB-260C / J, manufactured by SPECTRONICS), no discoloration of white petrolatum was observed. From this, it was found that the obtained composite fine particles have suppressed catalytic activity.
[0112]
When the composite fine particles after the water repellent treatment were mixed with water, they showed strong water repellency. When mixed with silicone oil (KF96A manufactured by Shin-Etsu Silicone Co., Ltd .: refractive index = 1.40), it was quickly dispersed. 8.4 mg of the composite fine particles are dispersed in 2 g of silicone oil, and the light transmittance of this dispersion is measured using a UV / visible spectrophotometer (UV-160A manufactured by Shimadzu Corporation) and a quartz cell having an optical path length of 1 mm. Was used to measure the transmittance in the wavelength range of 200 to 800 nm. The results are shown in FIG.
[0113]
In this figure, the light transmittance is almost 0% in the ultraviolet B and C regions having a wavelength of 300 nm or less, and at the same time, the light transmittance is 52% at 400 nm, 81% at 800 nm, and the entire visible light with a wavelength of 400 to 800 nm. It was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0114]
Example 2
366.5 g of silica sol (same as Example 1), 20.3 g of zinc oxide ultrafine particles (FINEX75 manufactured by Sakai Chemical Industry Co., Ltd.) and water were mixed to make 1 L to obtain a raw material liquid (that is, SiO of the raw material liquid)₂The ZnO concentrations are 1.25 mol / L and 0.25 mol / L, respectively, and the raw material liquid contains about 10% by weight of the particle mixture. ).
The prepared raw material liquid was crushed pressure 1000 kg / cm using a high pressure disperser (LA-31 manufactured by Nanomizer).²The process of dispersing in was repeated 10 times. By the above treatment, ZnO / SiO₂A dispersion of composite fine particles was obtained.
[0115]
Ethanol 1500g, tetraethoxysilane 16.26g, and 1N hydrochloric acid 3.9mL were mixed, and it heated up at 50 degreeC in the water bath. After the solution temperature reached 50 ° C., aging was performed for 2 hours and 30 minutes. After completion of aging, a mixed solution of 0.98 mL of 4N aqueous sodium hydroxide and 50 g of ethanol was added to neutralize hydrochloric acid, and then a mixed solution of 84.6 g of the composite fine particle dispersion and 300 g of ethanol was added dropwise. After dropping, the reaction is performed at 50 ° C. for 2 hours and 30 minutes, and the composite fine particles are converted into SiO 2.₂The surface was coated with. All the above steps were performed under stirring.
[0116]
The obtained dispersion after the coating treatment was subjected to solid-liquid separation according to Example 1 to obtain a composite fine particle-containing ethanol cake (solid content concentration of about 40% by weight), and then 12.5 g of this cake was added to 500 g of acetone. Mixing and ultrasonic dispersion were performed. After the cake was completely dispersed in acetone, 0.5 g of methyl hydrogen polysiloxane (same as in Example 1) was added and mixed to perform a water repellent treatment. Thereafter, the dispersion was dried at 80 ° C. and baked at 130 ° C. for 2 hours to dry the composite fine particles. The produced powder was repeatedly pulverized 10 times with a mill (same as in Example 1) to obtain composite fine particles.
[0117]
When the composite fine particle-containing ethanol cake was dispersed in water and the particle size of the composite fine particles before water-repellent treatment was measured in the same manner as in Example 1, the average particle size (volume basis) was about 0.07 μm.
The composite fine particles after the water repellent treatment were white, and as a result of observation with a scanning electron microscope (same as in Example 1), the average particle diameter was about 1 μm. Further, as a result of observing the cross section by an ultrathin section method using a transmission electron microscope (same as Example 1), SiO 2₂It was found that ZnO ultrafine particles (average particle diameter of about 0.01 μm) were dispersed and fixed in the aggregate of ultrafine particles (average particle diameter of about 0.01 μm). That is, the particles are SiO₂Aggregates (with a band gap energy of about 6.2 eV and a refractive index of about 1.46) are mother particles, and ZnO (with a band gap energy of about 3.2 eV and a refractive index of about 1.99) is a child particle. Some ZnO / SiO₂It was a composite fine particle.
[0118]
The ratio of the child particles in the composite fine particles is SiO.₂And ZnO have a particle density of 2.27 g / cm, respectively.^Three5.78 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 5.9% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.49. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 9.6% by volume).
The composite fine particles before and after the water-repellent treatment were dispersed in white petrolatum in an amount of 1% by weight of ZnO in a mixture of white petrolatum and composite fine particles, and the same test as in Example 1 was performed. . As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
[0119]
When the composite fine particles after water repellent treatment were mixed with water, strong water repellency was exhibited, and when mixed with silicone oil (same as in Example 1), it was quickly dispersed. 28 mg of the composite fine particles were dispersed in 2 g of silicone oil, and the light transmittance was measured by the same method as in Example 1. The results are shown in FIG.
In this figure, the light transmittance is almost 0% in the ultraviolet A, B, and C regions having a wavelength of 350 nm or less, and at the same time, 30% at 400 nm, 84% at 800 nm, and light in the entire visible light range from 400 to 800 nm. The transmittance was a high value, and it was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0120]
Example 3
TiO as in Example 1₂/ SiO₂Formation of composite fine particles, SiO₂The composite fine particle-containing ethanol cake (solid content concentration of about 40% by weight) was obtained by performing surface coating and solid-liquid separation by the above method.
12.5 g of this cake was mixed with 500 g of ethyl acetate and subjected to ultrasonic dispersion. After the cake is completely dispersed in ethyl acetate, 2.5 g of amino-modified silicone (manufactured by Shin-Etsu Silicone Co., Ltd., X-22-9261, molecular weight 30000, amino equivalent 4980) is added and sonicated at 50 ° C. for 3 hours. The composite fine particles were subjected to a water repellent treatment.
[0121]
42.5 g of silicone oil (same as in Example 1) was added to this dispersion, stirred and mixed, and then topped with ethyl acetate at 80 ° C. using a rotary evaporator to invert the composite fine particles into the silicone oil. Dispersion was performed to obtain composite fine particle-dispersed silicone oil (composite fine particle 10% by weight).
When the composite fine particle-containing ethanol cake was dispersed in water and the particle size of the composite fine particles before water-repellent treatment was measured in the same manner as in Example 1, the average particle size (volume basis) was about 0.08 μm.
[0122]
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂In the aggregate of ultrafine particles (average particle diameter of about 0.01 μm), TiO₂It was found that ultrafine particles (average particle diameter of about 0.01 μm) were dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 is a child particle₂/ SiO₂It was a composite fine particle.
The ratio of the child particles in the composite fine particles depends on the composition ratio of the raw material liquid and SiO₂It was about 8.5% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.57. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 13.6% by volume.
[0123]
The obtained composite fine particle-dispersed silicone oil was mixed with TiO 2 in a mixture of white petrolatum and composite fine particles.₂Was diluted in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
After 4.9 g of silicone oil was added to 0.1 g of the obtained composite fine particle-dispersed silicone oil for dilution, the light transmittance was measured in the same manner as in Example 1. The results are shown in FIG.
[0124]
In this figure, the light transmittance is almost 0% in the ultraviolet B and C regions having a wavelength of 300 nm or less, and at the same time, the light transmittance is 80% at 400 nm, 97% at 800 nm, and the entire visible light having a wavelength of 400 to 800 nm. It was found that the composite fine particles had high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0125]
Example 4
366.5 g of silica sol (same as in Example 1), 10.0 g of titanium oxide ultrafine particles (same as in Example 1), 40.7 g of zinc oxide ultrafine particles (same as in Example 2) and water are mixed to make 1 L. A raw material liquid (that is, SiO of the raw material liquid)₂TiO₂The concentrations of ZnO are 1.25 mol / L, 0.125 mol / L and 0.5 mol / L, respectively, and the raw material liquid contains about 12% by weight of the particle mixture. ).
[0126]
This raw material liquid was dispersed according to Example 1, and TiO₂・ ZnO / SiO₂After obtaining a dispersion of composite fine particles, following Example 2, SiO 2₂Surface coating with was performed. After heating the dispersion after the coating treatment to 70 ° C., 0.74 g of amino-modified silicone (manufactured by Toshiba Silicone Co., Ltd., XF42-B0819, molecular weight 10000, amino equivalent 1600) was added and stirred, then at 70 ° C. Ultrasonic treatment for 2 hours, TiO₂・ ZnO / SiO₂The composite fine particles were subjected to water repellent treatment.
[0127]
Using a rotary evaporator, this dispersion was topped with ethanol and water at 75 ° C. and concentrated about 3 times, and 900 g of n-hexane was added thereto, followed by reflux dehydration at 70 ° C.
To this dispersion, 132.8 g of silicone oil (same as in Example 1) was added, stirred and mixed, and then topped with ethanol and water at 80 ° C. using a rotary evaporator to convert the composite fine particles into silicone oil. Phase-dispersed to obtain composite fine particle-dispersed silicone oil (10% by weight of composite fine particles).
[0128]
The composite fine particle ethanol-containing cake produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 is dispersed in water and repellent using a laser Doppler type particle size measuring instrument (same as Example 1). When the particle size of the composite fine particles before water treatment was measured, the average particle size (volume basis) was about 0.09 μm.
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂In the aggregate of ultrafine particles (average particle diameter of about 0.01 μm), TiO₂It was found that ultrafine particles (average particle size of about 0.01 μm) and ZnO ultrafine particles (average particle size of about 0.01 μm) were dispersed and immobilized. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO having a child particle of (a band gap energy of about 3.3 eV and a refractive index of about 2.71) and ZnO (a band gap energy of about 3.2 eV and a refractive index of about 1.99)₂・ ZnO / SiO₂It was a composite fine particle.
[0129]
The ratio of the child particles in the composite fine particles is SiO.₂TiO₂And ZnO have a particle density of 2.27 g / cm, respectively.^Three3.84 g / cm^Three5.78 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 14.1% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.56. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 22.6% by volume.
[0130]
Composite fine particles before water-repellent treatment are mixed with TiO in a mixture of white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
After 4.9 g of silicone oil was added to 0.1 g of the obtained composite fine particle-dispersed silicone oil for dilution, the light transmittance was measured in the same manner as in Example 1. The results are shown in FIG.
[0131]
In this figure, the light transmittance is almost 0% in the ultraviolet A, B, and C regions having a wavelength of 350 nm or less, and at the same time, 40% at 400 nm, 94% at 800 nm, and light in the entire visible light range from 400 to 800 nm The transmittance was an extremely high value, and it was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0132]
Example 5
TiO 2 was prepared and dispersed in the same manner as in Example 1.₂/ SiO₂A composite fine particle dispersion was obtained.
84.6 g of the above dispersion, 1500 g of ethanol, and 16.26 g of tetraethoxysilane were mixed and heated to 50 ° C. in a water bath. After the dispersion temperature reached 50 ° C., a mixed solution of 3.9 mL of 1N hydrochloric acid and 300 g of ethanol was added dropwise. After dropping, the reaction is performed at 50 ° C. for 2 hours and 30 minutes, and the composite fine particles in the dispersion are converted into SiO₂The surface was coated with. After coating, 199.1 g of 0.04% by weight aluminum isopropoxide / isopropyl alcohol solution was added dropwise and reacted at 75 ° C. for 5 hours.₂O_ThreeThe surface was coated with. After the coating was completed, a mixed solution of 0.98 mL of 4N sodium hydroxide aqueous solution and 50 g of ethanol was added to neutralize hydrochloric acid. All the above steps were performed under stirring.
[0133]
After adding 6.6 g of oleic acid to the dispersion after the coating treatment and stirring, ultrasonic treatment was performed at 50 ° C. for 3 hours, and TiO 2 was added.₂/ SiO₂The composite fine particles were subjected to water repellent treatment.
Using a rotary evaporator, this dispersion was topped with ethanol, isopropyl alcohol, and water at 75 ° C. and concentrated about 3 times, and then 900 g of n-hexane was added, followed by reflux dehydration at 70 ° C.
To this dispersion, 111.7 g of silicone oil (same as Example 1) was added, stirred and mixed, and then, using a rotary evaporator, ethanol, isopropyl alcohol and water were topped at 80 ° C. to form composite fine particles into silicone oil. Phase inversion and dispersion were carried out to obtain composite fine particle-dispersed silicone oil (10% by weight of composite fine particles).
[0134]
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂In the aggregate of ultrafine particles (average particle diameter of about 0.01 μm), TiO₂It was found that ultrafine particles (average particle diameter of about 0.01 μm) were dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 (rutile type) is a child particle₂/ SiO₂It was a composite fine particle.
[0135]
The ratio of the child particles in the composite fine particles is SiO.₂And TiO₂Particle density of 2.27 g / cm respectively^Three3.84 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 8.5% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.57. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 13.6% by volume.
The composite fine particles before and after the water-repellent treatment were dispersed in white petrolatum in an amount of 1% by weight of the child particles in a mixture of white petrolatum and composite fine particles, and the same test as in Example 1 was performed. It was. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
[0136]
The ethanol-containing cake of composite fine particles produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 was dispersed in water, and a laser Doppler type particle size measuring device (same as Example 1) was used. When the particle diameter of the composite fine particles before water repellent treatment was measured, the average particle diameter (volume basis) was about 0.09 μm.
[0137]
After adding and diluting 4.85 g of silicone oil to 0.15 g of the obtained composite fine particle-dispersed silicone oil, light transmittance was measured by the same method as in Example 1. The results are shown in FIG.
In this figure, the light transmittance is almost 0% in the ultraviolet B and C regions having a wavelength of 300 nm or less, and at the same time, the light transmittance is 59% at 400 nm, 87% at 800 nm, and the entire visible light wavelength of 400 to 800 nm. It was found that the composite fine particles had high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0138]
Example 6
TiO 2 was prepared and dispersed in the same manner as in Example 4.₂・ ZnO / SiO₂A composite fine particle dispersion was produced.
Ethanol 1500g, tetraethoxysilane 16.26g, and 1N hydrochloric acid 3.9mL were mixed, and it heated up at 50 degreeC in the water bath. After the solution temperature reached 50 ° C., aging was performed for 2 hours and 30 minutes. After completion of the aging, a mixed solution of 0.98 mL of 4N sodium hydroxide aqueous solution and 50 g of ethanol was added to neutralize hydrochloric acid, and then TiO formed₂・ ZnO / SiO₂A mixed solution of 84.6 g of the composite fine particle dispersion and 300 g of ethanol was added dropwise. After the dropwise addition, the reaction is performed at 50 ° C. for 2 hours and 30 minutes, and TiO in the dispersion is performed.₂・ ZnO / SiO₂Composite fine particles are made of SiO₂The surface was coated with. After coating, 199.1 g of 0.04 wt% aluminum isopropoxide / isopropyl alcohol dispersion was added dropwise, reacted at 75 ° C. for 5 hours, and further Al₂O_ThreeThe surface was coated with. All the above steps were performed under stirring.
[0139]
After 1.5 g of stearic acid is added to the dispersion after the coating treatment and stirred, ultrasonic treatment is performed at 70 ° C. for 2 hours, and TiO 2 is added.₂・ ZnO / SiO₂The composite fine particles were subjected to water repellent treatment.
This dispersion was refluxed and dehydrated according to Example 5, 132.0 g of silicone oil (same as Example 1) was added, stirred and mixed, and then ethanol, isopropyl alcohol and water were added using a rotary evaporator. The composite fine particles were phase-inverted and dispersed in silicone oil by topping at 80 ° C. to obtain composite fine particle-dispersed silicone oil (composite fine particles 10 wt%).
[0140]
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂Among the aggregates of ultrafine particles (average particle size of about 0.01 μm), ZnO ultrafine particles (average particle size of about 0.01 μm) and TiO₂It was found that ultrafine particles (average particle diameter of about 0.01 μm) were dispersed and fixed. That is, the particles are SiO₂Aggregates (with a band gap energy of about 6.2 eV and a refractive index of about 1.46) are mother particles, ZnO (band gap energy of about 3.2 eV, refractive index of about 1.99) and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 is a child particle₂・ ZnO / SiO₂It was a composite fine particle.
[0141]
The ratio of the child particles in the composite fine particles is SiO.₂TiO₂And ZnO have a particle density of 2.27 g / cm, respectively.^Three3.84 g / cm^Three5.78 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 14.1% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.56. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 22.6% by volume.
[0142]
The ethanol-containing cake of composite fine particles produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 was dispersed in water, and a laser Doppler type particle size measuring device (same as Example 1) was used. When the particle size of the composite fine particles before water repellent treatment was measured, the average particle size (volume basis) was about 0.10 μm.
[0143]
The composite fine particles before water repellent treatment obtained from the above-mentioned composite fine particle-containing ethanol cake are mixed with TiO 2 in a mixture of white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
[0144]
After 4.9 g of silicone oil was added to 0.1 g of the obtained composite fine particle-dispersed silicone oil for dilution, the light transmittance was measured in the same manner as in Example 1. The results are shown in FIG.
[0145]
In this figure, the light transmittance is almost 0% in the ultraviolet A, B, and C regions having a wavelength of 350 nm or less, and at the same time, 33% at 400 nm, 93% at 800 nm, and light in the entire visible light range from 400 to 800 nm The transmittance was a high value, and it was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0146]
Example 7
TiO as in Example 1₂/ SiO₂Composite fine particles were produced, and in accordance with Example 5, SiO₂, Al₂O_ThreeSurface coating with was performed.
After adding 0.66 g of dialkyl phosphate (DAP60H manufactured by Kao Corporation) to the dispersion after the coating treatment and stirring, sonication is performed at 75 ° C. for 1 hour, and TiO 2 is added.₂/ SiO₂The composite fine particles were subjected to water repellent treatment.
Using a rotary evaporator, this dispersion was topped with ethanol, isopropyl alcohol, and water at 75 ° C. and concentrated about 3 times, and then 900 g of cyclohexane was added, followed by reflux dehydration at 70 ° C.
[0147]
Add 117.7 g of silicone oil (same as in Example 1) to this dispersion, and stir and mix. Then, using a rotary evaporator, topping ethanol, isopropyl alcohol, and water at 80 ° C. Phase inversion and dispersion were carried out to obtain composite fine particle-dispersed silicone oil (10% by weight of composite fine particles).
[0148]
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂In the aggregate of ultrafine particles (average particle diameter of about 0.01 μm), TiO₂It was found that ultrafine particles (average particle diameter of about 0.01 μm) were dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 is a child particle₂/ SiO₂It was a composite fine particle.
[0149]
The ratio of the child particles in the composite fine particles is SiO.₂And TiO₂Particle density of 2.27 g / cm respectively^Three3.84 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 8.5% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.57. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 13.6% by volume.
[0150]
The ethanol-containing cake of composite fine particles produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 was dispersed in water, and a laser Doppler type particle size measuring device (same as Example 1) was used. When the particle diameter of the composite fine particles before water repellent treatment was measured, the average particle diameter (volume basis) was about 0.09 μm.
[0151]
The composite fine particles before water repellent treatment obtained from the above-mentioned composite fine particle-containing ethanol cake are mixed with TiO 2 in a mixture of white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
[0152]
After 4.9 g of silicone oil was added to 0.1 g of the obtained composite fine particle-dispersed silicone oil for dilution, the light transmittance was measured in the same manner as in Example 1. The results are shown in FIG.
[0153]
In this figure, the light transmittance is almost 0% in the ultraviolet B and C regions having a wavelength of 300 nm or less, and at the same time, the light transmittance is 74% at 400 nm, 96% at 800 nm, and the entire visible light having a wavelength of 400 to 800 nm. It was found that the composite fine particles had high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0154]
Example 8
TiO as in Example 6₂・ ZnO / SiO₂Formation of composite fine particles, SiO₂, Al₂O_ThreeSurface coating with was performed.
After adding 0.71 g of dialkyl phosphate (same as in Example 7) to the dispersion after coating treatment and stirring, sonication was performed at 75 ° C. for 1 hour, and TiO 2 was added.₂・ ZnO / SiO₂The composite fine particles were subjected to water repellent treatment.
[0155]
This dispersion was reflux-dehydrated according to Example 5, 132.8 g of silicone oil (same as Example 1) was added, stirred and mixed, and then ethanol, isopropyl alcohol, and water were added using a rotary evaporator. The composite fine particles were phase-inverted and dispersed in silicone oil by topping at 80 ° C. to obtain composite fine particle-dispersed silicone oil (composite fine particles 10 wt%).
[0156]
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂Among the aggregates of ultrafine particles (average particle size of about 0.01 μm), ZnO ultrafine particles (average particle size of about 0.01 μm) and TiO₂It was found that ultrafine particles (average particle diameter of about 0.01 μm) were dispersed and fixed. That is, the particles are SiO₂Aggregates (with a band gap energy of about 6.2 eV and a refractive index of about 1.46) are mother particles, ZnO (band gap energy of about 3.2 eV, refractive index of about 1.99) and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 is a child particle₂・ ZnO / SiO₂It was a composite fine particle.
[0157]
The ratio of the child particles in the composite fine particles is SiO.₂TiO₂And ZnO have a particle density of 2.27 g / cm, respectively.^Three3.84 g / cm^Three5.78 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 14.1% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.56. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 22.6% by volume.
[0158]
The ethanol-containing cake of composite fine particles produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 was dispersed in water, and a laser Doppler type particle size measuring device (same as Example 1) was used. When the particle size of the composite fine particles before water repellent treatment was measured, the average particle size (volume basis) was about 0.10 μm.
[0159]
The composite fine particles before water repellent treatment obtained from the above-mentioned composite fine particle-containing ethanol cake are mixed with TiO 2 in a mixture of white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
[0160]
After 4.9 g of silicone oil was added to 0.1 g of the obtained composite fine particle-dispersed silicone oil for dilution, the light transmittance was measured in the same manner as in Example 1. The results are shown in FIG.
[0161]
In this figure, the light transmittance is almost 0% in the ultraviolet A, B, and C regions having a wavelength of 350 nm or less, and at the same time, light is emitted in the entire visible light range of 36% at 400 nm and 93% at 800 nm. The transmittance was a very high value, and it was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0162]
Example 9
The raw material solution was prepared and dispersed in the same manner as in Example 2 to obtain ZnO / SiO₂A composite fine particle dispersion was obtained.
[0163]
Ethanol 1500g, tetraethoxysilane 16.26g, and 1N hydrochloric acid 3.9ml were mixed, and it heated up at 50 degreeC in the water bath. After the solution temperature reached 50 ° C., aging was performed for 2 hours and 30 minutes. After completion of the aging, a mixed solution of 0.98 ml of 4N sodium hydroxide solution and 50 g of ethanol was added to neutralize hydrochloric acid, and then the formed ZnO / SiO₂A mixed solution of 84.6 g of the composite fine particle dispersion and 300 g of ethanol was added dropwise. After the dropwise addition, the reaction is carried out at 50 ° C. for 2 hours 30 minutes, and ZnO / SiO in the solution₂Composite fine particles are made of SiO₂The surface was coated with. After coating, 9.6 g of aluminum tri-sec-butoxide / isopropyl alcohol / ethanol solution (wt% 1: 9: 90) was added dropwise and reacted at 75 ° C. for 5 hours.₂O_ThreeThe surface was coated with. All the above steps were performed while stirring the solution.
[0164]
After adding 0.66 g of dialkyl phosphate (same as in Example 7) to the dispersion after the coating treatment and stirring, ultrasonic treatment was performed at 75 ° C. for 1 hour, and ZnO / SiO₂The composite fine particles were subjected to water repellent treatment.
This dispersion was refluxed and dehydrated according to Example 5, then 117.7 g of silicone oil (same as Example 1) was added, stirred and mixed, and then ethanol, isopropyl alcohol and water were added using a rotary evaporator. The composite fine particles were phase-inverted and dispersed in silicone oil by topping at 80 ° C. to obtain composite fine particle-dispersed silicone oil (composite fine particles 10 wt%).
[0165]
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂It was found that ZnO ultrafine particles (average particle diameter of about 0.01 μm) were dispersed and fixed in the aggregate of ultrafine particles (average particle diameter of about 0.01 μm). That is, the particles are SiO₂Aggregates (with a band gap energy of about 6.2 eV and a refractive index of about 1.46) are mother particles, and ZnO (with a band gap energy of about 3.2 eV and a refractive index of about 1.99) is a child particle. Some ZnO / SiO₂It was a composite fine particle.
[0166]
The ratio of the child particles in the composite fine particles is SiO.₂And ZnO have a particle density of 2.27 g / cm, respectively.^Three5.78 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 5.9% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.49. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 9.6% by volume).
[0167]
The ethanol-containing cake of composite fine particles produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 was dispersed in water, and a laser Doppler type particle size measuring device (same as Example 1) was used. When the particle size of the composite fine particles before water repellent treatment was measured, the average particle size (volume basis) was about 0.08 μm.
[0168]
The composite fine particles before water-repellent treatment obtained from the ethanol-containing cake of the composite fine particles are dispersed in white petrolatum in an amount of 1% by weight of ZnO in a mixture of white petrolatum and composite fine particles. The test was conducted. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
[0169]
After diluting by adding 4.6 g of silicone oil to 0.4 g of the obtained composite fine particle-dispersed silicone oil, light transmittance was measured in the same manner as in Example 1. The results are shown in FIG.
[0170]
In this figure, the light transmittance is almost 0% in the ultraviolet A, B, and C regions having a wavelength of 350 nm or less, and at the same time, 30% at 400 nm, 93% at 800 nm, and light in the entire visible light range from 400 to 800 nm. The transmittance was a high value, and it was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0171]
Example 10
366.5 g of silica sol (same as Example 1), 39.9 g of titanium oxide ultrafine particles (IT-S, amorphous type manufactured by Idemitsu Kosan Co., Ltd.) and water were mixed to make 1 L to obtain a raw material liquid (that is, Raw material SiO₂And TiO₂Are 1.25 mol / L and 0.5 mol / L, respectively, and the raw material liquid contains about 11% by weight of the particle mixture. ).
[0172]
Using the disperser (Nippon Seiki Biomixer Co., Ltd.) p. m. Disperse for 30 minutes with TiO₂/ SiO₂A dispersion of composite fine particles was obtained. This dispersion was made into SiO 2 according to Example 5.₂, Al₂O_ThreeSurface coating with was performed.
[0173]
After 0.70 g of dialkyl phosphate (same as in Example 7) was added to the dispersion after the coating treatment and stirred, sonication was performed at 75 ° C. for 1 hour, and TiO 2 was added.₂/ SiO₂The composite fine particles were subjected to water repellent treatment.
[0174]
This dispersion was reflux-dehydrated according to Example 5, then 125.6 g of silicone oil (same as Example 1) was added, stirred and mixed, and then ethanol, isopropyl alcohol, and water were added using a rotary evaporator. The composite fine particles were phase-inverted and dispersed in silicone oil by topping at 80 ° C. to obtain composite fine particle-dispersed silicone oil (composite fine particles 10 wt%).
[0175]
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂In the aggregate of ultrafine particles (average particle diameter of about 0.01 μm), TiO₂It was found that ultrafine particles (average particle diameter of about 0.01 μm) were dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.4 eV and refractive index is about 2.52 is a child particle.₂/ SiO₂It was a composite fine particle.
[0176]
The ratio of the child particles in the composite fine particles is SiO.₂And TiO₂Particle density of 2.27 g / cm respectively^Three3.84 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 15.1% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.62. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 23.9% by volume).
[0177]
The ethanol-containing cake of composite fine particles produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 was dispersed in water, and a laser Doppler type particle size measuring device (same as Example 1) was used. When the particle size of the composite fine particles before water repellent treatment was measured, the average particle size (volume basis) was about 0.10 μm.
[0178]
The composite fine particles before water repellent treatment obtained from the above-mentioned composite fine particle-containing ethanol cake are mixed with TiO 2 in a mixture of white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
[0179]
After 4.9 g of silicone oil was added to 0.1 g of the obtained composite fine particle-dispersed silicone oil for dilution, the light transmittance was measured in the same manner as in Example 1. The results are shown in FIG.
[0180]
In this figure, the light transmittance is almost 0% in the ultraviolet B and C regions having a wavelength of 300 nm or less, and at the same time, the light transmittance is 43% at 400 nm, 83% at 800 nm, and the entire visible light range from 400 to 800 nm. It was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0181]
Example 11
Silica gel (Nissan Chemical Industries, ST-C, SiO₂Concentration 20.5 wt%) 268.3 g, titanium oxide ultrafine particles (Ishihara Sangyo Co., Ltd., TTO-51 (A), rutile type) 50.0 g and water were mixed to make 1 liter, and a raw material solution was obtained. (That is, SiO of the raw material liquid₂And TiO₂Are respectively 0.92 mol / L and 0.63 mol / L, and the raw material liquid contains about 11% by weight of the particle mixture. ).
Using the dyno mill (manufactured by Willy A Bachofen AG, KDL-PILOT), the prepared raw material liquid was subjected to blade rotation speed 3600 r. p. m. , Solution: media ratio 600 cc: 1200 cc, 8 minutes x 3 times dispersion treatment, SiO 2₂Is the mother particle and TiO₂Is a child particle TiO₂/ SiO₂A dispersion of ultrafine particle aggregates was produced.
[0182]
188 g of the above dispersion, 1400 g of ethanol, and 32.6 g of tetraethoxysilane were mixed and heated to 50 ° C. in a water bath. After the temperature of the dispersion reached 50 ° C., a mixed solution of 1.56 ml of 1N hydrochloric acid and 600 g of ethanol was added dropwise. After dropping, the reaction is performed at 50 ° C. for 2 hours and 30 minutes, and the composite fine particles are converted into SiO 2.₂The surface was coated with. All the above steps were performed while stirring the solution.
Using a rotary evaporator, this dispersion was topped with ethanol and water at 75 ° C. and concentrated about 10 times, and then 2882 g of isopropyl alcohol was added dropwise with stirring.
Using a rotary evaporator, this dispersion was concentrated about 5 times by topping ethanol, isopropyl alcohol and water at 75 ° C.
After the completion of concentration, a mixed solution of 0.39 ml of 4N aqueous sodium hydroxide and 20 g of isopropyl alcohol was added to neutralize hydrochloric acid. This step was performed while stirring the solution.
[0183]
While stirring this dispersion, 600 g of silicone oil (manufactured by Toray Dow Corning Co., Ltd., SH244: refractive index 1.39) was added dropwise and mixed. Thereafter, a mixed solution of 0.6 g of amino-modified silicone (manufactured by Toshiba Silicone Co., Ltd., XF42-B0819, molecular weight 10000, amino equivalent 1600) and 240 g of silicone oil was dropped and mixed, and ethanol, isopropyl were used using a rotary evaporator. After topping with alcohol and water at 80 ° C., a mixed solution of 2.4 g of amino-modified silicone and 360 g of silicone oil was added dropwise and mixed, and TiO 2 was mixed.₂/ SiO₂The composite fine particles were subjected to water repellent treatment.
This dispersion was dispersed for 1 hour using an ultrasonic disperser, and again using a rotary evaporator, ethanol, isopropyl alcohol, water, and silicone oil were topped at 80 ° C. to convert the composite fine particles into silicone oil. Phase and dispersion were obtained to obtain composite fine particle-dispersed silicone oil (35% by weight of composite fine particles).
The composite fine particle ethanol-containing cake produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 is dispersed in water and repellent using a laser Doppler type particle size measuring instrument (same as Example 1). When the particle size of the composite fine particles before water treatment was measured, the average particle size (volume basis) was about 0.08 μm.
[0184]
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂In the aggregate of ultrafine particles (average particle diameter 0.01 μm), TiO₂It was found that ultrafine particles (average particle size 0.01 μm) were present dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 is a child particle₂・ SiO₂It was a composite fine particle.
The ratio of the child particles in the composite fine particles is SiO.₂And TiO₂Particle density of 2.27 g / cm respectively^Three3.84 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 22.3% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.74. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 35.0% by volume).
[0185]
Composite fine particles before water repellent treatment are mixed with TiO in white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
After diluting by adding 9.943 g of silicone oil to 0.057 g of the obtained composite fine particle dispersed silicone oil, light transmittance was measured by the same method as in Example 1. The results are shown in FIG.
In this figure, the light transmittance is almost 0% in the ultraviolet B and C regions having a wavelength of 300 nm or less, and at the same time, the light transmittance is 57% at 400 nm, 95% at 800 nm, and the entire visible light range from 400 to 800 nm. It was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0186]
Example 12
TiO as in Example 11₂/ SiO₂Formation of composite fine particles, SiO₂Surface coating with was performed.
After coating, a mixed solution of 0.39 ml of 4N aqueous sodium hydroxide and 20 g of ethanol was added to neutralize hydrochloric acid. This step was performed while stirring the solution.
While stirring this dispersion, a solution prepared by dissolving 3.0 g of oxazoline-modified silicone (manufactured by Kao Corporation, OS96-20) in 860 g of ethanol was dropped and mixed, and TiO 2 was mixed.₂/ SiO₂The composite fine particles were subjected to water repellent treatment.
This dispersion was concentrated about 5 times by topping ethanol and water at 75 ° C. using a rotary evaporator.
While stirring this dispersion, 575 g of silicone oil (manufactured by Dow Corning Toray Co., Ltd., SH244: refractive index 1.39) was added dropwise and mixed, and then ethanol and water were added at 80 ° C. using a rotary evaporator. Topped.
This dispersion was dispersed for 1 hour using a homogenizer, and then again using a rotary evaporator, ethanol, water, and silicone oil were topped at 80 ° C. to phase invert and disperse the composite fine particles in the silicone oil. A composite fine particle-dispersed silicone oil (15% by weight of composite fine particles) was obtained.
[0187]
The composite fine particle ethanol-containing cake produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 is dispersed in water and repellent using a laser Doppler type particle size measuring instrument (same as Example 1). When the particle size of the composite fine particles before water treatment was measured, the average particle size (volume basis) was about 0.08 μm.
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂In the aggregate of ultrafine particles (average particle diameter 0.01 μm), TiO₂It was found that ultrafine particles (average particle size 0.01 μm) were present dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 is a child particle₂/ SiO₂It was a composite fine particle.
The ratio of the child particles in the composite fine particles is SiO.₂And TiO₂Particle density of 2.27 g / cm respectively^Three3.84 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 22.3% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.74. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 35.0% by volume).
[0188]
Composite fine particles before water repellent treatment are mixed with TiO in white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
After adding and diluting 9.87 g of silicone oil to 0.13 g of the obtained composite fine particle-dispersed silicone oil, light transmittance was measured by the same method as in Example 1. The results are shown in FIG.
In this figure, the light transmittance is almost 0% in the ultraviolet B and C regions having a wavelength of 300 nm or less, and at the same time, the light transmittance is 65% at 400 nm, 95% at 800 nm, and the entire visible light range from 400 to 800 nm. It was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0189]
Example 13
TiO as in Example 11₂/ SiO₂Formation of composite fine particles, SiO₂Surface coating with was performed.
After coating, a mixed solution of 0.39 ml of 4N aqueous sodium hydroxide and 20 g of ethanol was added to neutralize hydrochloric acid. This step was performed while stirring the solution.
While stirring this dispersion, a solution prepared by dissolving 0.6 g of polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., K-30 for cosmetics) in 30 g of ethanol was dropped and mixed. After dropping, a solution of 3.0 g of oxazoline-modified silicone (same as Example 12) dissolved in 860 g of ethanol was dropped and mixed, and TiO 2 was mixed.₂/ SiO₂The composite fine particles were subjected to water repellent treatment.
This dispersion was concentrated about 5 times by topping ethanol and water at 75 ° C. using a rotary evaporator.
While stirring this dispersion, 575 g of silicone oil (manufactured by Dow Corning Toray Co., Ltd., SH244: refractive index 1.39) was added dropwise and mixed, and then ethanol and water were added at 80 ° C. using a rotary evaporator. Topped.
This dispersion was dispersed for 1 hour using a homogenizer, and then again using a rotary evaporator, ethanol, water, and silicone oil were topped at 80 ° C. to phase invert and disperse the composite fine particles in the silicone oil. A composite fine particle-dispersed silicone oil (25% by weight of composite fine particles) was obtained.
[0190]
The composite fine particle ethanol-containing cake produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 is dispersed in water and repellent using a laser Doppler type particle size measuring instrument (same as Example 1). When the particle size of the composite fine particles before water treatment was measured, the average particle size (volume basis) was about 0.08 μm.
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂In the aggregate of ultrafine particles (average particle diameter 0.01 μm), TiO₂It was found that ultrafine particles (average particle size 0.01 μm) were present dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 is a child particle₂/ SiO₂It was a composite fine particle.
The ratio of the child particles in the composite fine particles is SiO.₂And TiO₂Particle density of 2.27 g / cm respectively^Three3.84 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 22.3% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.74. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 35.0% by volume).
[0191]
Composite fine particles before water repellent treatment are mixed with TiO in white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
After adding and diluting 9.92 g of silicone oil to 0.08 g of the obtained composite fine particle-dispersed silicone oil, light transmittance was measured by the same method as in Example 1. The results are shown in FIG.
In this figure, the light transmittance is almost 0% in the ultraviolet B and C regions having a wavelength of 300 nm or less, and at the same time, the light transmittance is 39% at 400 nm, 87% at 800 nm, and the entire visible light wavelength of 400 to 800 nm. It was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0192]
Example 14
TiO as in Example 11₂/ SiO₂Formation of composite fine particles, SiO₂Surface coating with was performed.
After coating, a mixed solution of 0.39 ml of 4N aqueous sodium hydroxide and 20 g of ethanol was added to neutralize hydrochloric acid. This step was performed while stirring the solution.
While stirring this dispersion, a solution prepared by dissolving 0.6 g of polyvinylpyrrolidone in 30 g of ethanol was added dropwise and mixed. After dropping, a solution of 3.0 g of oxazoline-modified silicone (same as Example 12) dissolved in 860 g of ethanol was dropped and mixed, and TiO 2 was mixed.₂/ SiO₂The composite fine particles were subjected to water repellent treatment.
This dispersion was dried at 80 ° C. to dry the composite fine particles. The produced powder was pulverized twice with a mill (same as in Example 1) to obtain composite fine particles.
The composite fine particle ethanol-containing cake produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 is dispersed in water and repellent using a laser Doppler type particle size measuring instrument (same as Example 1). When the particle size of the composite fine particles before water treatment was measured, the average particle size (volume basis) was about 0.08 μm.
[0193]
The composite fine particles after the water repellent treatment were white and observed with a scanning electron microscope (same as in Example 1). As a result, the average particle size was about 1 μm. Further, as a result of observing the cross section by an ultrathin section method using a transmission electron microscope (same as Example 1), SiO 2₂In the aggregate of ultrafine particles (average particle diameter 0.01 μm), TiO₂It was found that ultrafine particles (average particle size 0.01 μm) were present dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 is a child particle₂/ SiO₂It was a composite fine particle.
The ratio of the child particles in the composite fine particles is SiO.₂And TiO₂Particle density of 2.27 g / cm respectively^Three3.84 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 22.3% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 1.74. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 35.0% by volume).
The composite fine particles before and after the water repellent treatment are mixed with TiO in a mixture of white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
[0194]
When mixed with water, the composite fine particles after water repellent treatment showed strong water repellency. When mixed with silicone oil (manufactured by Dow Corning Toray Co., Ltd., SH244: refractive index 1.39), it rapidly dispersed.
10 mg of the composite fine particles were dispersed in 10 g of silicone oil, and the light transmittance of this dispersion was measured in the same manner as in Example 1. The results are shown in FIG.
In this figure, the light transmittance is 3% or less in the ultraviolet B region having a wavelength of 300 nm or less, and the light transmittance is almost 0% in the ultraviolet C region having a wavelength of 260 nm or less, and at the same time, 48% at 400 nm and 800 nm. The light transmittance is 82% and the light transmittance is extremely high in the entire visible light with a wavelength of 400 to 800 nm, and it can be seen that the generated composite fine particles have high transparency in the visible light region and high shielding property in the ultraviolet region. It was.
[0195]
Example 15
Silica sol (ST-C, SiO, manufactured by Nissan Chemical Industries, Ltd.)₂A concentration of 20.5 wt%) 61.0 g, titanium oxide ultrafine particles (MT-600B manufactured by Teika Co., Ltd., 87.5 g) and water were mixed to make 1 L, and a raw material solution was obtained. (I.e.₂And TiO₂The concentration of each is 0.21 mol / L and 1.10 mol / L, and the raw material liquid contains about 10% by weight of the particle mixture. )
[0196]
The prepared raw material liquid was mixed with a homogenizer (TK-ROBOMICS manufactured by Tokushu Kaika Co., Ltd.) 12000r. p. m. For 90 minutes and then 7000 r. p. m. While stirring at a blade speed of 3600 rpm, a dyno mill (KDL-PILOT manufactured by Willy A Bachofen AG) was used. p. m. , Solution: media ratio 600 cc: 1200 cc, 8 minutes x 3 times dispersion treatment, SiO 2₂Is the mother particle and TiO₂Is a child particle TiO₂/ SiO₂A dispersion of composite fine particles was produced.
[0197]
After 188 g of the above dispersion was topped with water using a rotary evaporator and concentrated about 3 times, it was dropped and dispersed in 1300 g of ethanol while stirring with a homogenizer (same as above), and further using an ultrasonic disperser. Dispersed for 30 minutes. Thereafter, 32.6 g of tetraethoxysilane dissolved in 100 g of ethanol was mixed and heated to 50 ° C. in a water bath. After the temperature of the dispersion reached 50 ° C., a mixed solution of 1.56 ml of 1N hydrochloric acid and 600 g of ethanol was added dropwise. After dropping, the reaction is performed at 50 ° C. for 2 hours and 30 minutes, and the composite fine particles are converted into SiO 2.₂The surface was coated with. All the above steps were performed while stirring the solution.
After coating, a mixed solution of 0.39 ml of 4N aqueous sodium hydroxide and 20 g of ethanol was added to neutralize hydrochloric acid. This step was performed while stirring the solution.
While stirring this dispersion, a solution prepared by dissolving 2.9 g of oxazoline-modified silicone (OS96-20 manufactured by Kao Corporation) in 842 g of ethanol was dropped and mixed, and TiO 2 was mixed.₂/ SiO₂The composite fine particles were subjected to water repellent treatment.
This dispersion was concentrated about 5 times by topping ethanol and water at 75 ° C. using a rotary evaporator.
[0198]
While stirring the dispersion, 582.8 g of silicone oil (SH244: refractive index 1.39 manufactured by Toray Dow Corning Co., Ltd.) was dropped and mixed, and then ethanol and water were added at 80 ° C. using a rotary evaporator. Topped with.
This dispersion was dispersed for 1 hour using a homogenizer, and then again using a rotary evaporator, ethanol, water, and silicone oil were topped at 80 ° C. to phase invert and disperse the composite fine particles in the silicone oil. A composite fine particle-dispersed silicone oil (25% by weight of composite fine particles) was obtained.
[0199]
The composite fine particle ethanol-containing cake produced by solid-liquid separation of the dispersion after the coating treatment according to Example 1 is dispersed in water and repellent using a laser Doppler type particle size measuring instrument (same as Example 1). When the particle size of the composite fine particles before water treatment was measured, the average particle size (volume basis) was about 0.10 μm.
[0200]
As a result of observing the cross section of the composite fine particles after the water repellent treatment by an ultrathin section method using a transmission electron microscope (same as in Example 1), SiO 2₂TiO in the phase₂It was found that ultrafine particles (average particle size 0.01 μm) were present dispersed and fixed. That is, the particles are SiO₂Aggregates having a band gap energy of about 6.2 eV and a refractive index of about 1.46 are mother particles, and TiO₂TiO whose band gap energy is about 3.3 eV and refractive index is about 2.71 is a child particle₂/ SiO₂It was a composite fine particle.
[0201]
The ratio of the child particles in the composite fine particles is SiO.₂And TiO₂Particle density of 2.27 g / cm respectively^Three3.84 g / cm^ThreeAnd composition ratio of raw material liquid and SiO₂It was about 45.3% by volume calculated from the coating amount. From the ratio of the child particles in the composite fine particles, the refractive index of the composite fine particles was about 2.03. The proportion of child particles dispersed and immobilized in the mother particles (SiO₂About 80.5% by volume).
[0202]
Composite fine particles before water repellent treatment are mixed with TiO in white petrolatum and composite fine particles.₂Was dispersed in white petrolatum in an amount of 1% by weight, and the same test as in Example 1 was performed. As a result, discoloration of white petrolatum was not observed, and it was found that the obtained composite fine particles had suppressed catalytic activity.
After adding and diluting 9.954 g of silicone oil to 0.046 g of the obtained composite fine particle dispersed silicone oil, light transmittance was measured by the same method as in Example 1. The results are shown in FIG.
[0203]
In this figure, the light transmittance is almost 0% in the ultraviolet B and C regions having a wavelength of 300 nm or less, and at the same time, the light transmittance is 30% at 400 nm, 81% at 800 nm, and the entire visible light with a wavelength of 400 to 800 nm. It was found that the generated composite fine particles have high transparency in the visible light region and high shielding properties in the ultraviolet region.
[0204]
Example 16 (skin lotion)
Ethanol 30.0 (wt%)
Glycerin 5.0
Polyethylene glycol 1500 4.0
Polyoxyethylene (20) oleyl ether 1.0
Polyoxyethylene (30) hydrogenated castor oil 0.5
Composite fine particles (Example 2) 10.0
Urocanic acid 2.0
Fragrance 0.2
Purified water balance
As a result of measuring the lotion prepared by the above formulation with an SPF analyzer, SPF = 3.0 and PFA = 1.5. Moreover, it turned out that it is the cosmetics which did not have an unnatural white floating after application | coating and was excellent in the ultraviolet-ray shielding effect.
[0205]
Example 17 (milky lotion)
Cetanol 1.0 (wt%)
Squalane 2.0
Olive oil 5.0
Octyl methoxycinnamate 4.0
Polyoxyethylene (10) hydrogenated castor oil 1.0
Sorbitan monostearate 1.0
Dispersing oil of composite fine particles (Example 3) 25.0
Butylparaben 0.1
Methylparaben 0.1
Ethanol 3.0
Glycerin 2.0
1,3-butylene glycol 2.0
Fragrance 0.1
Purified water balance
As a result of measuring the emulsion prepared by the above formulation with an SPF analyzer, SPF = 15.9 and PFA = 5.0. Moreover, it turned out that it is the cosmetics which did not have an unnatural white floating after application | coating and was excellent in the ultraviolet-ray shielding effect.
[0206]
Example 18 (Emulsion)
Dispersed oil of composite fine particles (Example 3) 30.0 (% by weight)
Dimethylsiloxane methyl (polyoxyethylene)
Siloxane copolymer 3.5
Octamethyltetracyclosiloxane 20.0
Organopolysiloxane B 1.0
Squalane 2.0
Octyldodecyl myristate 1.0
Butylparaben 0.1
Methylparaben 0.1
Glycerin 5.0
Fragrance 0.1
Purified water balance
As a result of measuring the emulsion prepared by the above formulation with an SPF analyzer, SPF = 2.5 and PFA = 1.2. Moreover, it turned out that it is the cosmetics which did not have an unnatural white floating after application | coating and was excellent in the ultraviolet-ray shielding effect.
[0207]
Example 19 (cream)
Stearic acid 2.0 (wt%)
Cetanol 1.0
Cholesterol 1.0
Squalane 5.0
Olive oil 5.0
Octyl methoxycinnamate 4.0
Cetyl phosphate 0.5
Sorbitan monostearate 2.0
Polyoxyethylene (40) hydrogenated castor oil 0.5
Oil dispersion of composite fine particles (Example 4) 15.0
Fine particle titanium oxide 2.0
Butylparaben 0.1
Methylparaben 0.1
Glycerin 10.0
L-Arginine 0.3
Fragrance 0.1
Purified water balance
As a result of measuring the cream prepared by the above formulation with an SPF analyzer, SPF = 18.5 and PFA = 7.2. Moreover, it turned out that it is the cosmetics which did not have an unnatural white floating after application | coating and was excellent in the ultraviolet-ray shielding effect.
[0208]
Example 20 (cream)
Dispersing oil of composite fine particles (Example 4) 20.0 (wt%)
Dimethylsiloxane methyl (polyoxyethylene)
Siloxane copolymer 4.0
Methyl polysiloxane (6cSt) 5.0
2-Ethylhexyl p-methoxycinnamate 3.0
4-Methoxy-4'-t-butylbenzoylmethane 2.0
Octamethyltetracyclosiloxane 10.0
Squalane 2.0
Octyldodecyl myristate 1.0
Magnesium sulfate 0.5
Butylparaben 0.1
Methylparaben 0.1
Glycerin 6.0
Diglycerin 2.0
Polymethylsilsesquioxane powder 4.0
Fragrance 0.1
Purified water balance
As a result of measuring the cream prepared by the above formulation with an SPF analyzer, SPF = 23.0 and PFA = 12.2. Moreover, it turned out that it is the cosmetics which did not have an unnatural white floating after application | coating and was excellent in the ultraviolet-ray shielding effect.
[0209]
Example 21 (aerosol cosmetics)
Triclosan 0.01 (wt%)
Aluminum hydroxychloride 1.5
Talc 1.0
Composite fine particles (Example 2) 5.0
Isopropyl myristate 2.0
Fragrance 0.2
Propellant balance
As a result of measuring the aerosol cosmetics prepared by the above formulation with an SPF analyzer, SPF = 1.4 and PFA = 1.2. Moreover, it turned out that it is the cosmetics excellent in the ultraviolet-ray shielding effect.
[0210]
Example 22 (powder foundation) (wt%)
(1) Composite fine particles (Example 1) 10
(2) Fluorine compound treatment (* 1) Mica remaining amount
(3) Fluorine compound treatment (* 1) Talc 20
(4) Fluorine compound treatment (* 1) Titanium oxide 8
(5) Fluorine compound treatment (* 1) Iron oxide (red, yellow, black) 3
(6) Fluorine compound treatment (* 1) Fine zinc oxide 2
(7) Fluorine compound treatment (* 1) Fine particle titanium oxide (average particle size 35 nm) 1
(8) Fluorine compound treatment (* 1) Nylon powder 10
(9) Dimethylpolysiloxane (10 cSt) 4
(10) Perfluoropolyether (FOMBLIN HC-04 AUSHIMONT) 8
(11) Hardened oil (synchro wax) 1
(12) Octyl methoxycinnamate 1
(13) Preservatives, perfumes 1
(* 1): 5% coated with perfluoroalkylethyl phosphate
[0211]
Components (1) to (8) were mixed with a Henschel mixer, and components obtained by mixing components (9) to (13) with heating at 80 ° C. were added to the mixture and mixed. This was pulverized with a pulverizer, and a certain amount of this was placed in a metal dish and pressure-molded with a press to prepare a powder foundation.
The obtained powder foundation had a high UV shielding effect, good extensibility, and a natural finish.
[0212]

[0213]
Components (1) to (6) are mixed with a Henschel mixer, and components (7) to (11) heated and mixed at 80 ° C. are added to the mixture and mixed. This was pulverized with a pulverizer, and a certain amount of this was placed in a metal dish and pressure-molded with a press machine to prepare a dual-use foundation.
The resulting amphibious foundation had a high UV shielding effect, good extensibility, and a natural finish.
[0214]

[0215]
Components (1) to (7) are mixed with a Henschel mixer, and components (8) to (11) heated and mixed at 80 ° C. are added to the mixture and mixed. This product was pulverized with a pulverizer, and a certain amount of this was taken into a metal dish and pressure-molded with a press to prepare a powder eye shadow.
The obtained powder eye shadow had a high ultraviolet shielding effect, good extensibility, and excellent color development.
[0216]

[0217]
Components (1) to (4) are mixed with a Henschel mixer. Separately, components (5) to (7) are mixed, and (1) to (4) previously mixed are added thereto and dispersed and mixed with a stirrer. To this, the mixture of (8) to (10) was added over 30 minutes with slow stirring, and the mixture was further stirred for 10 minutes with a homomixer to emulsify. The emulsion was defoamed and filled into a bottle to prepare an emulsified foundation.
The resulting emulsified foundation had a high ultraviolet shielding effect, good extensibility, and a natural finish.
[0218]
Example 26 (stick-like lipstick) (% by weight)
(1) Oil dispersion of composite fine particles (Example 8) 11
(2) Silicone treatment (* 6) Red 201 No. 1
(3) Silicone treatment (* 6) Red No. 202 2
(4) Silicone treatment (* 6) Yellow No. 4 aluminum lake 1
(5) Silicone treatment (* 6) Titanium oxide 1
(6) Paraffin wax 5
(7) Candelilla wax 10
(8) Carnauba wax 9
(9) Isopropyl isopalmitate 20
(10) Isononyl isononanoate 15
(11) Diisostearyl malate 20
(12) Dimethylpolysiloxane (1000 cSt) 5
(* 6): 2% coated with methyl hydrogen polysiloxane
[0219]
Components (1) to (12) were heated at 80 ° C. and uniformly mixed. The mixture was cooled to 30 ° C., sufficiently kneaded with three rollers, heated again to 80 ° C., poured into a mold, cooled and solidified, and a stick-shaped lipstick was prepared.
The obtained stick-shaped lipstick had a high ultraviolet shielding effect, good extensibility, and a vivid color. In addition, even when the oil agent of the dispersion oil agent of the composite fine particles obtained in Example 8 was changed from silicone oil to ester oil (diisostearyl malate: Cosmol 222 (Nisshin Oil Co., Ltd.)), The same performance as above was confirmed.
[0220]
In the following Examples and Comparative Examples, the following five types of ether-modified silicones were used, but the present invention is not limited to the following.
(A) Ether-modified silicone A:
A dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer represented by the formula (3): However, R¹¹= R¹²= Methyl group, R¹³= H (OC_ThreeH₆) b (OC₂H_Four) aO (CH₂p- (a = 7-15, b = 0, p = 3), m = 50-100, n = 1-5.
(B) Ether-modified silicone B:
A dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer represented by the formula (3): However, R¹¹= R¹²= Methyl group, R¹³= H (OC_ThreeH₆) b (OC₂H_Four) aO (CH₂) p- (a = 2-5, b = 0, p = 3), m = 20-30, n = 2-5.
(C) Ether-modified silicone C:
A dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer represented by the formula (3): However, R¹¹= R¹²= Methyl group, R¹³= H (OC_ThreeH₆) b (OC₂H_Four) aO (CH₂) p- (a = 0, b = 7-13, p = 3), m = 4-10, n = 1-6.
(D) Ether-modified silicone D:
Lauryl methicone copolyol represented by formula (4). However, R^{twenty one}= Methyl group, R^{twenty two}= Dodecyl group, R^{twenty three}=-(OC₂H_Four) q− (OC_ThreeH₆) r-OH (q = 10-30, r = 10-30), Q = trimethylene group, x = 0, y = 30-70, z = 1-6.
(E) Ether-modified silicone E:
An alkyl glyceryl ether-modified silicone represented by the formula (5). However, R³⁴Is one of -A-OCH₂CH (OR⁴¹) CH₂OR⁴²(A = C₁₁H_{twenty three}, R⁴¹= R⁴²= H), s + t = 60, u = 40.
[0221]
Example 27 (Emulsion)
1) Cetanol 1.0 (wt%)
2) Squalane 2.0
3) Jojoba oil 4.0
4) Octyl methoxycinnamate 4.0
5) Polyoxyethylene (10) hydrogenated castor oil 1.0
6) Sorbitan monostearate 1.0
7) Oil dispersion of fine composite particles (Example 12) 25.0
8) Butylparaben 0.1
9) Methylparaben 0.1
10) Ethanol 3.0
11) Glycerin 4.0
12) Fragrance 0.05
13) Purified water balance
As a result of measuring the said emulsion with a SPF analyzer, it was SPF = 15.9 and PFA = 6.2. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect, without the unnatural whitening after application | coating.
[0222]
Example 28 (cream)
1) Cetanol 1.0 (wt%)
2) Stearic acid 2.0
3) Cholesterol 1.0
4) Squalane 5.0
5) Jojoba oil 4.0
6) Octyl methoxycinnamate 4.0
7) Polyoxyethylene (40) hydrogenated castor oil 1.0
8) Sorbitan monostearate 2.0
9) Oil dispersion of fine composite particles (Example 13) 15.0
10) Butylparaben 0.1
11) Methylparaben 0.1
12) Ethanol 3.0
13) Glycerin 10.0
14) Fragrance 0.05
15) Purified water balance
As a result of measuring the said cream with a SPF analyzer, they were SPF = 15.7 and PFA = 6.3. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect, without the unnatural whitening after application | coating.
[0223]

The emulsified foundation was evaluated in the same manner as in Example 1 for SPF and PFA. As a result, an ultraviolet shielding effect equivalent to or higher than that of Example 1 was obtained.
[0224]
Example 30 (stick lipstick)
1) Dispersing oil of composite fine particles (Example 13) 11.0 (% by weight)
2) Silicone treatment (* 8) Red 201 No. 1.0
3) Silicone treatment (* 8) Red 202 No. 2.0
4) Silicone treatment (* 8) Yellow No. 4 aluminum lake 1.0
5) Silicone treatment (* 8) Titanium oxide 1.0
6) Paraffin wax 5.0
7) Candelilla wax 10.0
8) Carbana wax 9.0
9) Isopropyl isopalmitate 20.0
10) Isononyl isononanoate 15.0
11) Diisostearyl malate 20.0
12) Dimethylpolysiloxane (1000cSt) 5.0
(* 8): 2% coated with methyl hydrogen polysiloxane.
The stick-like lipstick was evaluated in the same manner as in Example 1 for SPF and PFA. As a result, an ultraviolet shielding effect equivalent to or higher than that of Example 1 was obtained.
[0225]

As a result of measuring the said cream with an SPF analyzer, they were SPF = 19.6 and PFA = 9.2. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect, without the unnatural whitening after application | coating.
[0226]
Example 32 W / O type emulsion
1) Composite fine particle dispersed oil (Example 13) 25.0 wt%
2) Ether-modified silicone C 1.5
(Nippon Unica FZ-2110C)
3) Ether-modified silicone B 1.5
(Shin-Etsu Silicone KF-6015)
4) Ether-modified silicone D 1.0
(Toray Dow Corning DC Q2-2500)
5) Methylpolysiloxane (6cSt) 5.0
6) Decamethylcyclopentasiloxane 5.0
7) 2-Ethylhexyl p-methoxycinnamate 3.0
8) Squalane 2.0
9) Glycerin 3.0
10) Butylparaben 0.1
11) Methylparaben 0.1
12) Fragrance 0.05
13) Balance of purified water
As a result of measuring the said emulsion with a SPF analyzer, it was SPF = 19.2 and PFA = 8.7. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect, without the unnatural whitening after application | coating.
[0227]
Example 33 W / O type cream
1) Composite fine particle dispersed oil agent (Example 12) 20.0% by weight
2) Ether-modified silicone E 1.5
3) Ether-modified silicone B 0.5
(Shin-Etsu Silicone KF-6015)
4) Methylpolysiloxane (6cSt) 5.0
5) Decamethylcyclopentasiloxane 5.0
6) 2-Ethylhexyl p-methoxycinnamate 3.0
7) 4-Methoxy-4'-t-butylbenzoylmethane 2.0
8) Squalane 2.0
9) Magnesium sulfate 0.5
10) Glycerin 5.0
11) Butylparaben 0.1
12) Methylparaben 0.1
13) Fragrance 0.05
14) Balance of purified water
As a result of measuring the said cream with an SPF analyzer, they were SPF = 15.8 and PFA = 10.2. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect without the unnatural whitening after application | coating.
[0228]
Example 34 W / O type emulsion
1) Composite fine particle dispersed oil agent (Example 12) 5.0% by weight
2) Ether-modified silicone B 0.5
(Shin-Etsu Silicone KF-6015)
3) Ether-modified silicone A 1.0
(SH-3775C manufactured by Toray Dow Corning)
4) Methylpolysiloxane (6cSt) 5.0
5) Decamethylcyclopentasiloxane 5.0
6) 4-Methoxy-4'-t-butylbenzoylmethane 2.0
7) 2-Ethylhexyl p-methoxycinnamate 3.0
8) Squalane 2.0
9) Glycerin 3.0
10) Butylparaben 0.1
11) Methylparaben 0.1
12) Fragrance 0.05
13) Balance of purified water
As a result of measuring the said emulsion with a SPF analyzer, it was SPF = 14.9 and PFA = 10.8. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect without the unnatural whitening after application | coating.
[0229]

As a result of measuring the said cream with a SPF analyzer, they were SPF = 17.5 and PFA = 6.9. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect without the unnatural whitening after application | coating.
[0230]
Example 36 W / O type emulsion
1) Composite fine particles (Example 2) 5.0% by weight
2) Ether-modified silicone C 1.5
(Nippon Unica FZ-2110C)
3) Ether-modified silicone B 1.5
(Shin-Etsu Silicone KF-6015)
4) Ether-modified silicone D 1.0
(Toray Dow Corning DC Q2-2500)
5) Methylpolysiloxane (6cSt) 5.0
6) Decamethylcyclopentasiloxane 5.0
7) 2-Ethylhexyl p-methoxycinnamate 3.0
8) Squalane 2.0
9) Glycerin 3.0
10) Butylparaben 0.1
11) Methylparaben 0.1
12) Fragrance 0.05
13) Balance of purified water
As a result of measuring the said emulsion with a SPF analyzer, it was SPF = 16.8 and PFA = 6.8. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect without the unnatural whitening after application | coating.
[0231]
Example 37 W / O type cream
1) Complex fine particle dispersed oil agent (Example 3) 5.0% by weight
2) Ether-modified silicone E 1.5
3) Ether-modified silicone B 0.5
(Shin-Etsu Silicone KF-6015)
4) Methylpolysiloxane (6cSt) 5.0
5) Decamethylcyclopentasiloxane 5.0
6) 2-Ethylhexyl p-methoxycinnamate 3.0
7) 4-Methoxy-4'-t-butylbenzoylmethane 2.0
8) Squalane 2.0
9) Magnesium sulfate 0.5
10) Glycerin 5.0
11) Butylparaben 0.1
12) Methylparaben 0.1
13) Fragrance 0.05
14) Balance of purified water
As a result of measuring the said cream with a SPF analyzer, they were SPF = 18.5 and PFA = 9.6. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect without the unnatural whitening after application | coating.
[0232]
Example 38 W / O type emulsion
1) Composite fine particle dispersed oil agent (Example 4) 5.0% by weight
2) Ether-modified silicone B 0.5
(Shin-Etsu Silicone KF-6015)
3) Ether-modified silicone A 1.0
(SH-3775C manufactured by Toray Dow Corning)
4) Methylpolysiloxane (6cSt) 5.0
5) Decamethylcyclopentasiloxane 5.0
6) 4-Methoxy-4'-t-butylbenzoylmethane 2.0
7) 2-Ethylhexyl p-methoxycinnamate 3.0
8) Squalane 2.0
9) Glycerin 3.0
10) Butylparaben 0.1
11) Methylparaben 0.1
12) Fragrance 0.05
13) Balance of purified water
As a result of measuring the said emulsion with a SPF analyzer, they were SPF = 18.7 and PFA = 9.7. Moreover, it turned out that it is the cosmetics which were excellent in the ultraviolet-ray shielding effect without the unnatural whitening after application | coating.
[0233]

[0234]

[0235]
Comparative Example 3 W / O type emulsion
1) TTO-55 (C) 5.0% by weight
(Ishihara Sangyo Co., Ltd. fine particle titanium oxide average particle size 30-50μm)
2) Ether-modified silicone B 0.5
(Shin-Etsu Silicone KF-6015)
3) Ether-modified silicone A 1.0
(SH-3775C manufactured by Toray Dow Corning)
4) Methylpolysiloxane (6cSt) 5.0
5) Decamethylcyclopentasiloxane 5.0
6) 4-Methoxy-4'-t-butylbenzoylmethane 2.0
7) 2-Ethylhexyl p-methoxycinnamate 3.0
8) Squalane 2.0
9) Glycerin 3.0
10) Butylparaben 0.1
11) Methylparaben 0.1
12) Fragrance 0.05
13) Balance of purified water
[0236]
Comparative Example 4 W / O type emulsion
1) TTO-51 (C) 5.0% by weight
(Ishihara Sangyo Co., Ltd. fine particle titanium oxide average particle size 10-30μm)
2) Ether-modified silicone B 0.5
(Shin-Etsu Silicone KF-6015)
3) Ether-modified silicone A 1.0
(SH-3775C manufactured by Toray Dow Corning)
4) Methylpolysiloxane (6cSt) 5.0
5) Decamethylcyclopentasiloxane 5.0
6) 4-Methoxy-4'-t-butylbenzoylmethane 2.0
7) 2-Ethylhexyl p-methoxycinnamate 3.0
8) Squalane 2.0
9) Glycerin 3.0
10) Butylparaben 0.1
11) Methylparaben 0.1
12) Fragrance 0.05
13) Balance of purified water
[0237]
The ultraviolet protection effect of Example 31, Comparative Example 1 and Comparative Example 2 and the change in appearance before and after application were examined. The results are shown in Table 1. Table 2 shows the results of the UV protection effect of Example 34 and Comparative Examples 3 and 4 and the change in appearance (transparency) before and after application.
The ultraviolet protective effect was evaluated by the PFB value as an ultraviolet protective index. The UV protection index is a value obtained from the following formula using Hartley white guinea pigs. The PFB value is the PFB value in the UVB method described in J. Soc. Cosmet. Chem. Jpn. 28 (3), 254-261, (1994).
[0238]
[Expression 1]

[0239]
The change in the appearance before and after application is the difference between the color difference (L after applying white calibration with a color difference meter (CR-310, color difference meter manufactured by Minolta Camera Co., Ltd.))^{* 0}, A^{* 0}, B^{* 0}) And color difference after skin application (L^{* 1}, A^{* 1}, B^{* 1}) Change (ΔE^*It was evaluated in ab). ΔE^*ab is a value defined in JIS Z8729-1980, and was obtained by the following equation. In the formula, L^{* 0}, A^{* 0}, B^{* 0}, L^{* 1}, A^{* 1}, B^{* 1}Are respectively L^{* 0}: L before skin application^*Value (brightness index), a^{* 0}: A before skin application^*Value (Chromaticness index), b^{* 0}: B before skin application^*Value (Chromaticness index), L^{* 1}: L after skin application^*Value, a^{* 1}: A after skin application^*Value, b^{* 1}: B after skin application^*Indicates the value.
[0240]
[Expression 2]

[0241]
In addition, SPF and PFA were obtained by measuring with the basic measurement method described in the attached manual using an SPF-290 analyzer manufactured by The Optometrics Group. PFA is displayed as Average UVA Protection Factor in the manual.
[0242]
[Table 1]

[0243]
[Table 2]

[0244]
From the above results, it was found that the product of the present invention has a high ultraviolet protection effect and transparency.
[0245]
【The invention's effect】
When dispersed in a liquid or solid medium, the composite fine particles of the present invention exhibit a high light transmittance in the visible light region, and exhibit a high shielding property due to the scattering and absorption ability of the child particles in the ultraviolet region. . In addition, child particles having high catalytic activity are present inside and on the surface of the mother particles, and the surface of the composite fine particles comprising the child particles and the mother particles is coated with an inorganic substance having substantially no catalytic activity, whereby the catalyst possessed by the child particles The activity does not substantially degrade surrounding dispersants, media, etc. In other words, the composite fine particles of the present invention are obtained by forming ultrafine particles having ultraviolet shielding ability into composite fine particles and coating the surface of the composite fine particles with an inorganic substance having substantially no catalytic activity. The optical properties of ultrafine particles having high transparency in the light range and high shielding properties in the ultraviolet range are characterized by stable expression at a fine particle size that is easy to handle. In addition, since the composite fine particles of the present invention can be subjected to a water repellent treatment, in that case, even if they are blended in a W / O type or O / W type cosmetic, they can be dispersed uniformly and stably. It is possible to prevent the deterioration of. When the composite fine particles of the present invention are blended in cosmetics, it has good slip, excellent extensibility on the skin, non-uniformity, excellent transparency, no unnatural whitening, and high UV shielding effect. However, it is a highly safe and stable cosmetic. Furthermore, since the composite fine particles of the present invention are excellent in transparency, they do not impair the color of the cosmetic and have a high degree of freedom in the amount of the cosmetic.
[Brief description of the drawings]
FIG. 1 is a chart showing the measurement results of light transmittance of ultraviolet shielding composite fine particles obtained in Example 1 using an ultraviolet-visible spectrophotometer.
FIG. 2 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 2 using an ultraviolet-visible spectrophotometer.
FIG. 3 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 3 using an ultraviolet-visible spectrophotometer.
4 is a chart showing the results of measuring the light transmittance of the ultraviolet shielding composite fine particles obtained in Example 4 using an ultraviolet-visible spectrophotometer. FIG.
FIG. 5 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 5 using an ultraviolet-visible spectrophotometer.
6 is a chart showing measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 6 with an ultraviolet-visible spectrophotometer. FIG.
7 is a chart showing measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 7 using an ultraviolet-visible spectrophotometer. FIG.
FIG. 8 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 8 using an ultraviolet-visible spectrophotometer.
FIG. 9 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 9 using an ultraviolet-visible spectrophotometer.
FIG. 10 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 10 using an ultraviolet-visible spectrophotometer.
11 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 11 using an ultraviolet-visible spectrophotometer. FIG.
FIG. 12 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 12 using an ultraviolet-visible spectrophotometer.
13 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 13 using an ultraviolet-visible spectrophotometer. FIG.
14 is a chart showing measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 14 using an ultraviolet-visible spectrophotometer. FIG.
15 is a chart showing the measurement results of light transmittance of the ultraviolet shielding composite fine particles obtained in Example 15 using an ultraviolet-visible spectrophotometer. FIG.

Claims (25)

A primary particle having an average primary particle size of 0.001 to 0.3 μm aggregated while maintaining its shape, and an average particle size dispersed and fixed in the primary particle is 0.001. a composite fine particles composed of the daughter particles ～0.1Myuemu, having ultraviolet absorbing ability and having a smaller band gap energy than the particles that the child particle constitutes a mother particle, and the child particles 0.1 Ultraviolet-shielding composite fine particles having transparency in the visible light region, characterized by being dispersed and fixed in the mother particles at a ratio of ˜30% by volume and having substantially no catalytic activity as composite fine particles. A primary particle having an average primary particle size of 0.001 to 0.3 μm aggregated while maintaining its shape, and an average particle size dispersed and fixed in the primary particle is 0.001. A composite fine particle comprising ~ 0.1 μm child particles having a structure in which the surface of the composite fine particle is coated with an inorganic substance having substantially no catalytic activity, and the child particles are composed of particles constituting the mother particle And a small band gap energy, and the child particles are dispersed and fixed in the mother particles at a ratio of 0.1 to 30% by volume , and have an ultraviolet absorbing ability. Ultraviolet shielding composite fine particles having transparency in the light range. The ultraviolet shielding composite fine particles according to claim 1 or 2, wherein the band gap energy of the particles constituting the mother particles is 3 to 9 eV. The ultraviolet shielding composite fine particles according to any one of claims 1 to 3, wherein the band gap energy of the child particles is 0.2 eV or more smaller than that of the particles constituting the mother particles. The ultraviolet shielding composite fine particles according to any one of claims 1 to 4, wherein the child particles are dispersed and fixed in the mother particles at a ratio of 0.5 to 20 % by volume. The ultraviolet shielding composite fine particles according to claim 1, wherein the composite fine particles have an average particle size of 0.5 μm or less. The ultraviolet shielding composite fine particles according to any one of claims 1 to 6, wherein the composite fine particles have an average refractive index of 1.3 to 2.5. The ultraviolet shielding composite fine particles according to any one of claims 1 to 7, wherein the particles constituting the mother particles are selected from metal oxides and / or fluorine compounds. The ultraviolet shielding composite fine particles according to claim 8, wherein the metal oxide is selected from SiO ₂ and / or Al ₂ O ₃ . Daughter particles are _{TiO 2, ZnO, CeO 2,} SiC, SnO 2, WO 3, BaTiO 3, CaTiO 3, and at least one selected from the group consisting of SrTiO _3, according to any one of claims 1 to 9 Ultraviolet shielding composite fine particles. The ultraviolet shielding composite fine particles according to any one of claims 2 to 10, wherein the inorganic substance is a metal oxide. The ultraviolet shielding composite fine particles according to claim 11, wherein the metal oxide which is an inorganic substance is selected from SiO ₂ and / or Al ₂ O ₃ . The ultraviolet shielding composite fine particles according to claim 1, wherein the surface of the composite fine particles is further treated with a water repellent. When suspended in a medium having a refractive index substantially the same as the refractive index of the composite fine particles and measured for light transmittance with an ultraviolet-visible spectrophotometer using an optical cell having an optical path length of 1 mm, the transmittance at a wavelength of 800 nm The ultraviolet shielding composite fine particle according to any one of claims 1 to 13, which has a transmittance of 20% or more at a wavelength of 400 nm and 80% or more and a transmittance of 5% or less at a light wavelength having a wavelength range of 380 to 300 nm. The ultraviolet shielding composite fine particles according to any one of claims 2 to 14, which are obtained from the following steps.
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more kinds selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated,
(B) a step of coating the composite fine particles obtained in step (a) with an inorganic substance;
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in the step (b), and (d) drying and / or pulverizing the water repellent treated fine particles obtained in the step (c). Process, The dispersion oil agent for ultraviolet shielding composite fine particles according to any one of claims 2 to 14, which is obtained from the following steps.
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more kinds selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated,
(B) a step of coating the composite fine particles obtained in step (a) with an inorganic substance;
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in step (b), and (d ′) the water repellent composite fine particles obtained in step (c) are dispersed in the oil. Process, A process for producing UV-shielding composite fine particles comprising the mother particles and the child particles dispersed and fixed in the mother particles, having substantially no catalytic activity and having transparency in the visible light region, comprising the following steps: .
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or two or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated; and (b) a step of coating the composite fine particles obtained in step (a) with an inorganic substance. , After step (b)
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in step (b),
The manufacturing method of Claim 17 further provided. After step (c)
(D) drying and / or pulverizing the water-repellent-treated composite fine particles obtained in the step (c);
The manufacturing method of Claim 18 further provided. An ultraviolet shielding composite fine particle-dispersed oil agent comprising a mother particle and child particles dispersed and immobilized in the mother particle, having substantially no catalytic activity and having transparency in the visible light region, comprising the following steps: Production method.
(A) a sol containing particles constituting a mother particle having an average particle diameter of 0.001 to 0.3 μm of primary particles, a mother particle raw material composed of one or more kinds selected from the group consisting of a mother particle powder; After preparing a liquid mixture containing a sol containing child particles having an average particle size of 0.001 to 0.1 μm, a mixture with one or more child particle raw materials selected from the group consisting of child particle powders A step of milling and / or high-pressure dispersion treatment of the mixed solution to produce composite fine particles in which child particles / mother particles are aggregated,
(B) a step of coating the composite fine particles obtained in step (a) with an inorganic substance;
(C) water repellent treatment of the composite fine particles coated with the inorganic substance obtained in step (b), and (d ′) water repellent composite fine particles obtained in step (c) are dispersed in the oil. Process, Cosmetics containing the ultraviolet shielding composite fine particles according to any one of claims 1 to 15. A cosmetic comprising the ultraviolet shielding composite fine particle dispersed oil agent according to claim 16. The cosmetic according to claim 21, comprising 0.01 to 50% by weight of ultraviolet shielding composite fine particles. The cosmetic according to any one of claims 21 to 23, further comprising an ultraviolet protective agent. When SPF was measured using an SPF-290 analyzer manufactured by The Optometrics Group, the value was 8 or more, and ΔE ^* ab defined in JIS Z8729-1980 before and after skin application was The cosmetic according to any one of claims 21 to 24, which is 3 or less.

Images