JP3558409B2 - Silicone-containing cosmetics - Google Patents

Description

【００１５】
Ｑ^３（３価の有機基）：
【００１６】
【化３】

【００１７】
Ｑ^４（４価の有機基）：
【００１８】
【化４】

【００１９】
次に一般式（ＩＩ）の（Ｒ^１）_３ＳｉＯ_１／２ユニットであるが、このユニットのＲ^１は、互いに同一であっても異なっていてもよく、炭化水素基、又は水素原子の少なくとも一部がフッ素原子で置換された炭化水素基を表し、且つ三つのＲ^１の内、少なくとも一つは前記フッ素置換炭化水素基でなければならないが、好ましくは、アルキル基、フェニル基、アリール基及びこれらの基の水素原子の少なくとも一部がフッ素原子で置換された基より選ばれる基であり、具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等のアルキル基；フェニル基；アリール基；又は、これらの基の水素原子の少なくとも一部がフッ素原子で置換された基等が挙げられる。
【００２０】
以上のようなユニットで構成される本発明に用いるシリコーンのネットワーク構造例を、Ｑ^ｎのｎが２、すなわち２価の有機基の場合を例にして、下記に示す。
【００２１】
【化５】

【００２２】
（但し、化５中Ｑ^２は２価の有機基を表す。また、Ｒ^１は互いに同一であっても異なっていてもよく、炭化水素基、又は水素原子の少なくとも一部がフッ素原子で置換された炭化水素基を表し、且つ三つのＲ^１の内、少なくとも一つは前記フッ素置換炭化水素基でなければならない。）
【００２３】
また、本発明に用いるシリコーンの具体例は次の通りである。
イ）［｛ＣＦ_３（ＣＦ_２）_２｝_３ＳｉＯ_１／２］のユニット及び［Ｏ_３／２ＳｉＱ^２ＳｉＯ_{３ ／２}］（但し、Ｑ^２は−（ＣＨ_２）_３−で示される２価の有機基を表す。）のユニットからなるシリコーン。
【００２４】
ロ）［（ＣＦ_３ＣＨ_２）_３ＳｉＯ_１／２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は下記式（１ａ）で示される２価の有機基を表す。）のユニット及び［Ｏ_３／２ＳｉＱ’^２ＳｉＯ_３／２］（但し、Ｑ’^２は−（ＣＨ_２）_２Ｓ（ＣＨ_２）_３−で示される２価の有機基を表す。）のユニットからなるシリコーン。
【００２５】
【化６】

【００２６】
ハ）［｛ＣＦ_３（ＣＦ_２）_５｝（ＣＨ_３）_２ＳｉＯ_１／２］のユニット、［ＳｉＯ_２］のユニット及び［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は下記式（２ａ）で示される２価の有機基を表す。）のユニットからなるシリコーン。
【００２７】
【化７】

【００２８】
ニ）［｛ＣＦ_３（ＣＦ_２）_３｝_２（Ｃ_２Ｈ_５）ＳｉＯ_１／２］のユニット及び［（Ｏ_３／２Ｓｉ）_３Ｑ^３］（但し、Ｑ^３は式（３ａ）で示される３価の有機基を表す。）のユニットからなるシリコーン。
【００２９】
【化８】

【００３０】
ホ）［｛ＣＦ_３（ＣＦ_２）_５｝（ＣＨ_３）_２ＳｉＯ_１／２］のユニット、［ＳｉＯ_２］のユニット及び［（Ｏ_３／２Ｓｉ）_３Ｑ^３］（但し、Ｑ^３は式（４ａ）で示される３価の有機基を表す。）のユニットからなるシリコーン。
【００３１】
【化９】

【００３２】
ヘ）［｛ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２｝_２（Ｃ_２Ｈ_５）ＳｉＯ_１／２］のユニット及び［（Ｏ_３／_２Ｓｉ）_３Ｑ^３］（但し、Ｑ^３は式（５ａ）で示される３価の有機基を表す。）のユニットからなるシリコーン。
【００３３】
【化１０】

【００３４】
ト）［（ＣＦ_３ＣＨ_２）_３ＳｉＯ_１／２］のユニット、［ＳｉＯ_２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は−（ＣＨ_２）_２Ｓ（ＣＨ_２）_３−で示される２価の有機基を表す。）のユニット及び［（Ｏ_３／２Ｓｉ）_４Ｑ^４］（但し、Ｑ^４は式（６ａ）で示される４価の有機基を表す。）のユニットからなるシリコーン。
【００３５】
【化１１】

【００３６】
チ）［｛ＣＦ_３（ＣＦ_２）_２｝_３ＳｉＯ_１／２］のユニット、［（Ｏ_３／２Ｓｉ）_４Ｑ^４］（但し、Ｑ^４は式（７ａ）で示される４価の有機基を表す。）のユニット及び［ＳｉＯ_２］のユニットからなるシリコーン。
【００３７】
【化１２】

【００３８】
リ）［｛ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２｝_２（Ｃ_２Ｈ_５）ＳｉＯ_１／２］のユニット及び［（Ｏ_３／２Ｓｉ）_４Ｑ^４］（但し、Ｑ^４は式（８ａ）で示される４価の有機基を表す。）のユニットからなるシリコーン。
【００３９】
【化１３】

【００４０】
ヌ）［｛ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２｝_２｛Ｃ_２Ｈ_５｝ＳｉＯ_１／２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は−（ＣＨ_２）_３−を表す。）のユニット及び［Ｏ_３／２ＳｉＱ^２’ＳｉＯ_３／２］（但し、Ｑ^２’は式（９ａ）で示される２価の有機基を表す。）のユニットからなるシリコーン。
【００４１】
【化１４】

【００４２】
ル）［｛ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２｝｛Ｃ_２Ｈ_５｝_２ＳｉＯ_１／２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は−（ＣＨ_２）_２Ｓ（ＣＨ_２）_３−を表す。）のユニット及び［Ｏ_３／２ＳｉＱ^２’ＳｉＯ_３／２］（但しＱ^２’は、前記式（９ａ）で示される２価の有機基を表す。）のユニットからなるシリコーン。
【００４３】
ヲ）［｛ＣＦ_３（ＣＦ_２）_５｝｛ＣＨ_３｝_２ＳｉＯ_１／２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但しＱ^２は、前記式（１ａ）で示される２価の有機基を表す。）のユニット、［Ｏ_３／２ＳｉＱ^２’ＳｉＯ_３／２］（但しＱ^２’は、前記式（９ａ）で示される２価の有機基を表す。）のユニット及び［ＳｉＯ_２］のユニットからなるシリコーン。
【００４４】
次に、本発明に用いるシリコーンの製造方法について説明する。
（２）シリコーンの製造方法
本発明に用いる上記シリコーンを製造するには、基本的には、一般式（ＩＩＩ）：
Ｑ^ｎ［Ｓｉ（Ｘ）_３］_ｎ
（但し、Ｑ^ｎはｎ価の有機基を表し、またｎは２〜６の整数のいずれか１つを表す。Ｘは互いに同一でも異なっていてもよく、加水分解性の基を表す。）
で示される加水分解性珪素化合物を加水分解重縮合させた後、これに一般式（ＩＶ）：
（Ｒ^１）_３ＳｉＸ
（但し、Ｒ^１は互いに同一であっても異なっていてもよく、炭化水素基、又は水素原子の少なくとも一部がフッ素原子で置換された炭化水素基を表し、且つ三つのＲ^１の内、少なくとも一つは前記フッ素置換炭化水素基でなければならない。またＸは加水分解性の基を表す。）
で示される珪素化合物を末端封鎖剤として反応させて前記重縮合物の末端を封鎖するという製造方法を取ればよい。
【００４５】
この様な方法で、本発明に用いる上記シリコーンを製造するためには、まず一般式（ＩＩＩ）の加水分解性珪素化合物Ｑ^ｎ［Ｓｉ（Ｘ）_３］_ｎに水を添加し、加水分解重縮合を行う。この場合、必要に応じて珪素化合物Ｓｉ（Ｘ）_４（但し、Ｘは互いに同一でも異なっていてもよく、加水分解性の基を表す。）を混合し、前記珪素化合物（ＩＩＩ）との共加水分解重縮合を行ってもよい。水の添加量は、反応の進行を制御するため、用いた珪素化合物の加水分解性の基Ｘを加水分解させるのに必要な理論量以下の量が好ましい。
【００４６】
この時、反応を均一に進行させるため有機溶媒を用いることが好ましい。有機溶媒は反応に用いる珪素化合物を溶解できるものであればよく、特に限定されない。反応温度は０〜８０℃が好ましい。低すぎると溶媒の凝固が起こったり、高すぎると溶媒の極端な蒸発が起こったりして反応の進行が不均一になる。
【００４７】
また、反応の進行を促進するため、塩基及び／又は酸を触媒として用いることが好ましい。塩基及び／又は酸触媒の添加量は反応に用いる珪素化合物の５モル％以下が好ましい。
【００４８】
この加水分解重縮合の反応式の一例を化１５に、また得られる重縮合体のネットワーク構造の一例を化１６に示す。
【００４９】
【化１５】

【００５０】
（但し、化１５中Ｑ^２は２価の有機基を表す。）
【００５１】
【化１６】

【００５２】
（但し、化１６中Ｑ^２は２価の有機基を表す。）
以上の加水分解重縮合工程で使用される材料の詳細は次の通りである。
【００５３】
一般式（ＩＩＩ）の加水分解性珪素化合物Ｑ^ｎ［Ｓｉ（Ｘ）_３］_ｎ：
公知の珪素化合物の公知の有機反応によって合成される。例えばアミノ基を有するアルコキシシラン、クロロシラン［ＮＨ_２Ｃ_３Ｈ_６Ｓｉ（ＯＲ）_３、ＮＨ_２Ｃ_３Ｈ_６Ｃｌ_３］等と酸クロライド、無水酸等の酸誘導体との反応；不飽和結合を有する化合物へのハイドロジェンシラン又はメルカプトシランの付加反応；アルコキシシラン化合物又はクロロシラン化合物とグリニャール試薬又は有機リチウム化合物との反応などにより合成される。この一般式（ＩＩＩ）の加水分解性珪素化合物Ｑ^ｎ［Ｓｉ（Ｘ）_３］_ｎ中におけるＱ^ｎについては、前述の一般式（Ｉ）でのＱ^ｎと同様である。また、一般式（ＩＩＩ）中においてＸは、加水分解性の基であれば特に制限されず、互いに同一であっても異なっていてもよい。
【００５４】
本発明に用いるシリコーンの製造に際しては、この加水分解性珪素化合物の少なくとも１種を原料として用いるが、好ましくは、加水分解性珪素化合物として、一般式（ＩＩＩ）にＱ^ｎとしてジカルボン酸のジアミドを含む２価の有機基を導入した加水分解性珪素化合物及び一般式（ＩＩＩ）にＱ^ｎとしてジカルボン酸のジアミドを含む２価の有機基以外の２価の有機基を導入した加水分解性珪素化合物を組み合わせて用いる。
【００５５】
珪素化合物Ｓｉ（Ｘ）_４：
シリコーンの固さを調節するために添加する。添加量が多ければシリコーンは固くなり、少なければ柔らかくなる。上記一般式中のＸは、加水分解性の基であれば特に制限されず、互いに同一であっても異なっていてもよい。この様な珪素化合物の具体例としては四塩化珪素、テトラメトキシシラン、テトラエトキシシラン、テトラｎ−プロポキシシラン、テトライソプロポキシシラン等、好ましくは四塩化珪素、テトラメトキシシラン、テトラエトキシシランが挙げられる。
【００５６】
有機溶媒：
上記二種の珪素化合物、水、触媒などを溶解するものであれば特に限定されず、メチルアルコール、エチルアルコール、イソプロピルアルコール等のアルコール類；アセトン、メチルエチルケトン等のケトン類；メチルセロソルブ、エチルセロソルブ等のセロソルブ類；テトラヒドロキシフラン；ジメチルスルフォキシド等が挙げられる。
【００５７】
塩基及び／又は酸触媒：
塩酸、硝酸等の無機酸；酢酸、クエン酸等の有機酸；水酸化ナトリウム、アンモニア水等の無機塩基；アミン、モルフォリン等の有機塩基；３−アミノアルコキシシランのような塩基性基含有シラン等、好ましくはアミノ置換基、４，５−ジヒドロイミダゾール置換基等の塩基性基含有シラン、例えば３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−（４，５−ジヒドロイミダゾール）プロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン等が挙げられる。
【００５８】
次に、一定時間重縮合反応を行った後、得られた重縮合体の反応末端を封鎖して重縮合体を安定に取り出すため、末端封鎖剤として一般式（ＩＶ）の珪素化合物（Ｒ^１）_３ＳｉＸを添加し反応させる。この時、末端封鎖剤の加水分解を促進して末端封鎖反応を進行しやすくするため、水及び酸触媒も合わせて添加する。水の添加量は特に限定されないが、添加した末端封鎖剤を加水分解するのに必要な理論量以上の量を添加することが望ましい。また酸触媒の添加量は一般式（ＩＶ）の末端封鎖剤の２モル％以上が好ましい。
【００５９】
またこの末端封鎖工程は、反応を均一に進行させるため攪拌条件下で行う。反応時間は４〜２０時間が好ましい。反応終了後は重縮合体が相分離する場合はデカンテーションで、また相分離しない場合は溶媒留去、凍結乾燥などの方法によって目的物を取り出す。
【００６０】
上記重縮合体と末端封鎖剤との反応で得られるシリコーンのネットワーク構造における末端封鎖状況の一例を下記に示す。
【００６１】
【化１７】

【００６２】
（但し、化１７中Ｑ^２は２価の有機基を表す。また、Ｒ^１は互いに同一であっても異なっていてもよく、炭化水素基、又は水素原子の少なくとも一部がフッ素原子で置換された炭化水素基を表し、且つ三つのＲ^１の内、少なくとも一つは前記フッ素置換炭化水素基でなければならない。）
以上の末端封鎖工程で使用される材料の詳細は次の通りである。
【００６３】
一般式（ＩＶ）の（Ｒ^１）_３ＳｉＸ ：
上記一般式（ＩＶ）中、Ｒ^１は互いに同一であっても異なっていてもよく、炭化水素基、又は水素原子の少なくとも一部がフッ素原子で置換された炭化水素基を表し、且つ三つのＲ^１の内、少なくとも一つは前記フッ素置換炭化水素基でなければならないが、好ましくは、アルキル基、フェニル基、アリール基及びこれらの基の水素原子の少なくとも一部がフッ素原子で置換された基より選ばれる基であり、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等のアルキル基；フェニル基；アリール基；又は、これらの基の水素原子の少なくとも一部がフッ素原子で置換された基等が挙げられる。また、上記一般式（ＩＶ）中、Ｘは加水分解性の基であれば特に制限されないが、アルコキシ基、ハロゲン原子又はアルコキシアルコキシ基等を好ましく挙げることができる。
【００６４】
この様な化合物として具体的には、（ＣＦ_３ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）、［ＣＦ_３（ＣＦ_２）_２］_２（ＣＨ_３）ＳｉＣｌ、［ＣＦ_３（ＣＦ_２）_５］（ＣＨ_３）_２Ｓｉ（ＯＣ_２Ｈ_５）、［ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２］_２（Ｃ_２Ｈ_５）ＳｉＣｌ等が挙げられ、該当するフルオロアルキル基を有するグリニャール試薬又はリチウム塩と公知の珪素化合物との反応によって容易に合成できる。すなわち
【００６５】
【化１８】

【００６６】
（但し、化１８中、Ｒ_ｆはフルオロアルキル基、Ｒは炭化水素基、ＺはＢｒ又はＩ、ｎは０〜２のいずれか、ｍは１〜３のいずれかを表す。）
【００６７】
酸触媒：
具体的には塩酸、硝酸等の無機酸；酢酸、クエン酸等の有機酸；好ましくは塩酸、硝酸、酢酸等の揮発性の酸が挙げられる。
【００６８】
（３）本発明の化粧料
本発明の化粧料は上記シリコーンの１種又は２種以上を含有する。本発明の化粧料には上記シリコーンを配合することにより優れた撥水性と共に撥油性が付与される。これは、本発明の化粧料に配合する上記シリコーンが撥水性に優れ、更に末端ユニットにフッ素原子を有することから撥油性に優れることによるが、上記シリコーンは、また化粧料に一般的に配合される多くの原料成分との相溶性にも優れることから、化粧料の多くの剤形に適用可能であるという特徴を有する。更に、本発明で用いるシリコーンは肌や頭髪上に被膜を形成する際、その被膜は柔軟性を有することから、これを化粧料に配合することにより肌や頭髪に滑らかさやしっとり感を与え、肌や頭髪へのなじみのよい化粧料が得られることになる。この様なシリコーン被膜の優れた撥水性、撥油性、柔軟性等が総合的に作用して、本発明の化粧料に化粧持ちのよさを付与している。
【００６９】
本発明の化粧料における上記シリコーンの好適な含有量は、剤形の種類や使用目的により異なるが、大凡０．１〜８０重量％であり、具体的に剤形毎に見るならば、クリームや乳液などの基礎化粧料においては０．５〜４０重量％が更に好ましく、ファンデーション、リップカラー、アンダーメークアップ等のメークアップ化粧料としては０．５〜６０重量％、スカルプローションやコーティングエッセンス等の頭髪用の化粧料としては０．５〜２０重量％が更に好ましい。
【００７０】
本発明の化粧料の剤形は、特に限定されるものではなく、例えば、ローション、乳液、クリーム、水性ゲル、オイルゲル、軟膏、アンダーメークアップ、ファンデーション、パウダー、リップカラー、アイライナー、スカルプローション、コーティングエッセンス、ヘアトニック、シャンプー、リンス、ポマード、ヘアトリートメント、ヘアパック、ヘアリキッド、ヘアローション、スタイリングフォーム、ヘアブロースプレー等の通常、皮膚用や頭髪用の化粧料として用いられているものが挙げられる。これらの化粧料は、上記シリコーンを、好ましくは上記配合量の範囲で、配合する以外は、通常の化粧料と同様の方法で製造することができる。
【００７１】
また、本発明の化粧料には、上記シリコーン以外に、通常、化粧料に適用される、流動パラフィン、ワセリン、スクワラン等の炭化水素類、ミリスチン酸イソプロピル（ＩＰＭ）や合成ゲイロウ、ホホバ油、カルナウバワックス等のエステル類、オリーブ油、牛脂等の動植物油脂、セタノール、ステアリルアルコール等の高級アルコール類、ステアリン酸、オレイン酸等の高級脂肪酸類、ラウリル硫酸ナトリウム、アルキルスルホコハク酸エステル等のアニオン界面活性剤、４級アルキルアミン塩等のカチオン界面活性剤、脂肪酸モノグリセライド、ポオキシエチレン硬化ヒマシ油等のノニオン界面活性剤、アルキルベタイン等の両性界面活性剤等の界面活性剤類、グリセリンやプロピレングリコール等の多価アルコール類、エタノール、プロパノール等の低級アルコール類、パラベン類やグルコン酸クロルヘキシジン等の防腐剤類、パラアミノ安息香酸誘導体、ベンゾフェノン誘導体等の紫外線吸収剤類、ビタミンＥやブチルヒドロキシトルエン等の酸化防止剤、アラビアゴム、カルボキシビニルポリマー等の増粘剤、ポリエチレングリコール等の保湿剤、クエン酸塩、酢酸塩等のｐＨ調整剤、酸化チタン、シリカゲル、タルク等の粉体類、香料、色素等、ヒアルロン酸、胎盤抽出物、朝鮮人参エキス、ステロール配糖体等の各種目的に応じた薬効成分などが適宜選択されて配合される。また、上記シリコーン以外に従来から化粧料に撥水性向上等のために配合されている三次元シリコーン等のシリコーン類やパーフルオロポリエーテル等のフッ素系油剤を配合することもできる。
【００７２】
【実施例】
以下に本発明の実施例を説明する。まず本発明に用いるシリコーンの製造例について、上記一般式（ＩＩＩ）の珪素化合物Ｑ^ｎ［Ｓｉ（Ｘ）_３］_ｎ及び一般式（ＩＶ）のフッ素置換型末端封鎖珪素化合物（Ｒ^１）_３ＳｉＸの製造例と共に説明する。
＜Ｑ^ｎ［Ｓｉ（Ｘ）_３］_ｎの製造例＞
【００７３】
【製造例１】
耐圧ビン型の反応容器にアリルトリクロロシラン７０．２ｇ、モノハイドロジェントリクロロシラン５４．２ｇを採り混合した。次に塩化白金酸Ｈ_２ＰｔＣｌ_６・６Ｈ_２Ｏをテトラヒドロフラン中で加熱し、白金０．２ミリモルに相当するこの溶液を前述の混合溶液に添加した後、反応容器を８０℃で４時間加熱した。ろ過、分留を行ってテトラヒドロフラン、塩化白金酸を除去して透明液体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この液体が式（１ｂ）で表される化合物であることが確認された。
【００７４】
【化１９】
Ｃｌ_３Ｓｉ（ＣＨ_２ ）_３ＳｉＣｌ_３ ・・・（１ｂ）
【００７５】
【製造例２】
還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコにテレフタル酸ジアリル４９．３ｇ、３−メルカプトトリメトキシシラン７８．６ｇ、ベンゼン４５０ｍｌを採り、攪拌混合した。さらに、この溶液に、アゾビスイソブチロニトリル０．５ｇをベンゼン５０ｍｌに溶解した溶液を添加し、攪拌混合した。攪拌を続けながら、室温で乾燥窒素ガスによるバブリングを１時間行った後、加熱してベンゼンの沸点で２４時間還流を行って反応を完結させた。ロータリーエバポレーターでベンゼンを除去して粘性液体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この液体が式（２ｂ）で表される化合物であることが確認された。
【００７６】
【化２０】

【００７７】
【製造例３】
還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコにビニルトリメトキシシラン４４．５ｇ、３−メルカプトトリメトキシシラン５８．９ｇ、ベンゼン４００ｍｌを採り攪拌混合した。さらにこの溶液に、アゾビスイソブチロニトリル０．５ｇをベンゼン５０ｍｌに溶解した溶液を添加し、攪拌混合した。攪拌を続けながら、室温で乾燥窒素ガスによるバブリングを１時間行った後、加熱してベンゼンの沸点で２４時間還流を行って反応を完結させた。ロータリーエバポレーターでベンゼンを除去して粘性液体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この液体が式（３ｂ）で表される化合物であることが確認された。
【００７８】
【化２１】
（ＣＨ_３Ｏ）_３Ｓｉ（ＣＨ_２）_２Ｓ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３ ・・・（３ｂ）
【００７９】
【製造例４】
還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコに３−アミノプロピルトリエトキシシラン１１０．７ｇ、ジエチルエーテル４００ｍｌ、トリエチルアミン１００ｍｌを採り氷冷しつつ攪拌混合した。さらに、氷冷攪拌を続けながらこの溶液に、３−ブテノイルクロライド４５．３ｇをジエチルエーテル１００ｍｌに溶解した溶液を滴下した。滴下後さらに１時間攪拌を続けた。生成した白色沈殿をろ別した後、ロータリーエバポレーターでジエチルエーテル、トリエチルアミンを除去して粘性液体を得た。
【００８０】
耐圧ビン型の反応容器に上記の液体８２．７ｇ、モノハイドロジェントリエトキシシラン４９．３ｇを採り混合した。次に塩化白金酸Ｈ_２ＰｔＣｌ_６・６Ｈ_２Ｏをテトラヒドロフラン中で加熱し、白金０．２ミリモルに相当するこの溶液を前述の混合溶液に添加した後、反応容器を８０℃で４時間加熱した。ろ過、分留を行ってテトラヒドロフラン、塩化白金酸を除去して透明液体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この液体が式（４ｂ）で表される化合物であることが確認された。
【００８１】
【化２２】

【００８２】
【製造例５】
耐圧ビン型の反応容器にグリセリントリ１０−ウンデセノエート１７７．３ｇ、モノハイドロジェントリメトキシシラン１１０．０ｇを採り混合した。次に塩化白金酸Ｈ_２ＰｔＣｌ_６・６Ｈ_２Ｏをテトラヒドロフラン中で加熱し、白金０．２ミリモルに相当するこの溶液を前述の混合溶液に添加した後、反応容器を８０℃で４時間加熱した。ろ過、分留を行ってテトラヒドロフラン、塩化白金酸を除去して透明液体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この液体が式（５ｂ）で表される化合物であることが確認された。
【００８３】
【化２３】

【００８４】
【製造例６】
還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコに１，２，４−トリビニルシクロヘキサン４８．７ｇ、３−メルカプトトリス（β−メトキシメトキシ）シラン２５７．８ｇ、ベンゼン８００ｍｌを採り攪拌混合した。さらにこの溶液に、アゾビスイソブチロニトリル０．８ｇをベンゼン１００ｍｌに溶解した溶液を添加し、攪拌混合した。攪拌を続けながら、室温で乾燥窒素ガスによるバブリングを１時間行った後、加熱してベンゼンの沸点で２４時間還流を行って反応を完結させた。ロータリーエバポレーターでベンゼンを除去して粘性液体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この液体が式（６ｂ）で表される化合物であることが確認された。
【００８５】
【化２４】

【００８６】
【製造例７】
還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコに３−アミノプロピルトリクロロシラン５７．９ｇ、ジエチルエーテル３２０ｍｌ、トリエチルアミン８０ｍｌを採り氷冷しつつ攪拌混合した。さらに、氷冷攪拌を続けながらこの溶液にトリメゾイルクロライド２６．８ｇをジエチルエーテル１００ｍｌに溶解した溶液を滴下した。滴下後さらに１時間を攪拌を続けた。生成した白色沈殿をろ別した後、ロータリーエバポレーターでジエチルエーテル、トリエチルアミンを除去して白色固体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この固体が式（７ｂ）で表される化合物であることが確認された。
【００８７】
【化２５】

【００８８】
【製造例８】
還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコに３，３’−ジアミノベンジジン６４．３ｇ、テトラヒドロフラン９００ｍｌ、トリエチルアミン２００ｍｌを採り、氷冷しつつ攪拌混合した。さらに、氷冷攪拌を続けながらこの溶液に、アクリロイルクロライド１０８．６ｇをテトラヒドロフラン３００ｍｌに溶解した溶液を滴下した。滴下後さらに１時間攪拌を続けた。生成した白色沈殿をろ別した後、ロータリーエバポレーターで、テトラヒドロフラントリエチルアミンを除去して白色固体を得た。
【００８９】
耐圧ビン型の反応容器に上記の固体８６．１ｇ、モノハイドロジェントリメトキシシラン９７．８ｇを採り混合した。次に塩化白金酸Ｈ_２ＰｔＣｌ_６・６Ｈ_２Ｏをテトラヒドロフラン中で加熱し、白金０．２ミリモルに相当するこの溶液を前述の混合溶液に添加した後、反応容器を８０℃で４時間加熱した。ろ過、分留を行ってテトラヒドロフラン、塩化白金酸を除去して白色固体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この固体が式（８ｂ）で表される化合物であることが確認された。
【００９０】
【化２６】

【００９１】
【製造例９】
還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコにペンタエリトリトールテトラメタクリレート８１．７ｇ、３−メルカプトトリエトキシシラン１９０．７ｇ、ベンゼン８００ｍｌを採り、攪拌混合した。さらにこの溶液に、アゾビスイソブチロニトリル０．５ｇをベンゼン１００ｍｌに溶解した溶液を添加し、攪拌混合した。攪拌を続けながら、室温で乾燥窒素ガスによるバブリングを１時間行った後、加熱してベンゼンの沸点で２４時間還流を行って反応を完結させた。ロータリーエバポレーターでベンゼンを除去して粘性液体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この液体が式（９ｂ）で表される化合物であることが確認された。
【００９２】
【化２７】

【００９３】
【製造例１０】
還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコにグリセロール−１，３−ジアリルエーテル２７．６ｇ、テトラヒドロフラン２００ｍｌ、トリエチルアミン５０ｍｌを採り、氷冷しつつ攪拌混合した。さらに、氷冷攪拌を続けながらこの溶液に、アジポイルクロライド１４．６ｇをテトラヒドロフラン１００ｍｌに溶解した溶液を滴下した。滴下後さらに１時間攪拌を続けた。生成した白色沈殿をろ別した後、ロータリーエバポレーターでジエチルエーテル、トリエチルアミンを除去して粘性液体を得た。
【００９４】
耐圧ビン型の反応容器に上記の液体２８．２ｇ、モノハイドロジェントリクロロシシラン５４．２ｇを採り混合した。次に、塩化白金酸Ｈ_２ＰｔＣｌ_６・６Ｈ_２ Ｏをテトラヒドロフラン中で加熱し、白金０．２ミリモルに相当するこの溶液を前述の混合溶液に添加した後、反応容器を８０℃で４時間加熱した。分留を行ってテトラヒドロフラン、塩化白金酸を除去して透明液体を得た。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この液体が式（１０ｂ）で表される化合物であることが確認された。
【００９５】
【化２８】

【００９６】
【製造例１１】
還流冷却器、攪拌装置およびガス導入管付き三つ口フラスコに３−アミノプロピルトリメトキシシラン１０７．６ｇ、テトラヒドロフラン６００ｍｌ、トリエチルアミン２００ｍｌを採り氷冷しつつ攪拌混合した。さらに、氷冷攪拌を続けながらこの溶液に、テレフタル酸クロリド６０．９ｇをテトラヒドロフラン２００ｍｌに溶解した溶液を滴下した。滴下後さらに１時間攪拌を続けた。生成した白色沈殿をろ別した後、ロータリーエバポレーターでテトラヒドロフラン、トリエチルアミンを除去して白色固体を得た。ＩＲ、^１ Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この固体が式（１１ｂ）で表される化合物であることが確認された。
【００９７】
【化２９】

【００９８】
【製造例１２】
還流冷却器、攪拌装置およびガス導入管付き三つ口フラスコに３−アミノプロピルトリクロロシシラン９６．５ｇ、ジエチルエーテル５００ｍｌ、トリエチルアミン１５０ｍｌを採り氷冷しつつ攪拌混合した。さらに、氷冷攪拌を続けながらこの溶液に、イソフタル酸クロリド５０．８ｇをジエチルエーテル１５０ｍｌに溶解した溶液を滴下した。滴下後さらに１時間攪拌を続けた。生成した白色沈殿をろ別した後、ロータリーエバポレーターでジエチルエーテル、トリエチルアミンを除去して白色固体を得た。ＩＲ、^１ Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この固体が（１２ｂ）で表される化合物であることが確認された。
【００９９】
【化３０】

【０１００】
＜（Ｒ^１）_３ＳｉＸの製造例＞
【０１０１】
【製造例１３】
十分に乾燥を行った還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコに金属マグシウム８．７ｇを採り、乾燥窒素ガスで十分置換を行う。さらに、この反応容器に金属ナトリウムによる還流と蒸留とによって脱水精製したテトラヒドロフラン１５０ｍｌを採り、攪拌混合した。攪拌を続けながら、この溶液に、前述のテトラヒドロフラン２００ｍｌに２、２、２−トリフルオロエチルヨーダイド６３．０ｇを溶解した溶液を滴下した。さらに攪拌を続けながら、氷冷下で、前述のテトラヒドロフラン１５０ｍｌにテトラメトキシシラン１５．２ｇを溶解した溶液を滴下した。滴下終了後、テトラヒドロフランの沸点で還流を２４時間行って反応を完結させた。生成した沈殿をろ別後、分留を行って目的化合物を単離した。なお、全ての操作は乾燥窒素ガス気流下で行った。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、式（１３ｂ）で表される目的化合物が単離されていることを確認した。
【０１０２】
【化３１】
（ＣＦ_３ＣＨ_２）_３Ｓｉ（ＯＣＨ_３） ・・・（１３ｂ）
【０１０３】
【製造例１４】
十分に乾燥を行った還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコに金属マグシウム３．０ｇを採り、乾燥窒素ガスで十分置換を行う。さらに、この反応容器に金属ナトリウムによる還流と蒸留とによって脱水精製したテトラヒドロフラン１００ｍｌを採り、攪拌混合した。攪拌を続けながら、この溶液に、前述のテトラヒドロフラン３００ｍｌにパーフルオロヘキシルヨーダイド４４．６ｇを溶解した溶液を滴下した。さらに攪拌を続けながら、氷冷下で、前述のテトラヒドロフラン２００ｍｌにジメチルジエトキシシラン１４．８ｇを溶解した溶液を滴下した。滴下終了後、テトラヒドロフランの沸点で還流を２４時間行って反応を完結させた。生成した沈殿をろ別後、分留を行って目的化合物を単離した。なお、全ての操作は乾燥窒素ガス気流下で行った。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行って式（１４ｂ）で表される目的化合物が単離されていることを確認した。
【０１０４】
【化３２】
［ＣＦ_３（ＣＦ_２）_５］（ＣＨ_３）_２Ｓｉ（ＯＣ_２Ｈ_５） ・・・（１４ｂ）
【０１０５】
【製造例１５】
十分に乾燥を行った還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコに金属マグシウム５．３ｇ及びよう素０．０５ｇを採り、乾燥窒素ガスで十分置換を行う。さらに、この反応容器に金属ナトリウムによる還流と蒸留とによって脱水精製したジエチルエーテル５００ｍｌにパーフルオロブチルヨーダイド６９．２ｇ及びエチルトリメトキシラン１５．０ｇを溶解した溶液を滴下した。滴下終了後、攪拌を続けながら室温で２時間放置し反応を完結させた。生成した沈殿をろ別後、分留を行って目的化合物を単離した。尚、全ての操作は乾燥窒素ガス気流下で行った。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、式（１５ｂ）で表される目的化合物が単離されていることを確認した。
【０１０６】
【化３３】
［ＣＦ_３（ＣＦ_２）_３ ］_２（Ｃ_２Ｈ_５）Ｓｉ（ＯＣＨ_３） ・・・（１５ｂ）
【０１０７】
【製造例１６】
十分に乾燥を行った還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコに金属マグシウム５．６ｇを採り、乾燥窒素ガスで十分置換を行う。さらに、この反応容器に金属ナトリウムによる還流と蒸留とによって脱水精製したテトラヒドロフラン１００ｍｌを採り、攪拌混合した。攪拌を続けながら、この溶液に、前述のテトラヒドロフラン３００ｍｌにパーフルオロプロピルブロミド５２．３ｇを溶解した溶液を滴下した。さらに攪拌を続けながら、氷冷下で、前述のテトラヒドロフラン１００ｍｌにテトラクロロシラン１１．９ｇを溶解した溶液を滴下した。滴下終了後、テトラヒドロフランの沸点で還流を２４時間行って反応を完結させた。生成した沈殿をろ別後、分留を行って目的化合物を単離した。なお、全ての操作は乾燥窒素ガス気流下で行った。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、式（１６ｂ）で表される目的化合物が単離されていることを確認した。
【０１０８】
【化３４】
［ＣＦ_３（ＣＦ_２）_２］_３ＳｉＣｌ ・・・（１６ｂ）
【０１０９】
【製造例１７】
乾燥窒素ガスで十分置換を行った還流冷却器、攪拌装置及びガス導入管付き三つ口フラスコに１Ｈ，１Ｈ，２Ｈ，２Ｈ−ノナフルオロヘキシルリチウム５０．８ｇを及び金属ナトリウムによる還流と蒸留とによって脱水精製したジエチルエーテル４００ｍｌ採り攪拌混合した。攪拌を続けながら、この溶液に、前述のジエチルエーテル１００ｍｌにエチルトリクロロシラン１６．４ｇを溶解した溶液を滴下した。滴下終了後、さらに２時間攪拌を続けた後、還流を８時間行って反応を完結させた。生成した沈殿をろ別後、分留を行って目的化合物を単離した。なお、全ての操作は乾燥窒素ガス気流下で行った。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、式（１７ｂ）で表される目的化合物が単離されていることを確認した。
【０１１０】
【化３５】
［ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２］_２（Ｃ_２Ｈ_５）ＳｉＣｌ ・・・（１７ｂ）
【０１１１】
【製造例１８】
充分に乾燥を行った還流冷却器、攪拌装置およびガス導入管付き三つ口フラスコに金属マグネシウム５．８ｇを採り、乾燥窒素ガスで充分置換を行った。さらに、この反応容器に金属ナトリウムによる還流と蒸留とによって脱水生成したジエチルエーテル２００ｍｌを採り攪拌混合した。攪拌を続けながら、この溶液に前述のジエチルエーテル３００ｍｌに１Ｈ，１Ｈ，２Ｈ，２Ｈヘプタデカフルオロデキシルヨーダイド１１４．８ｇを溶解した溶液を滴下した。さらに、攪拌を続けながら、氷零下で、前述のジエチルエーテル２００ｍｌにジエチルジメトキシシラン２９．７ｇを溶解した溶液を滴下した。滴下終了後ジエチルエーテルの沸点で還流を２４時間行って反応を完結させた。生成した沈殿をろ別後、分留を行って、目的の化合物を単離した。なお全ての操作は乾燥窒素ガス気流下で行った。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、式（１８ｂ）で表される目的化合物が単離されていることを確認した。
【０１１２】
【化３６】
［ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２］［Ｃ_２Ｈ_５］_２Ｓｉ（ＯＣＨ_３） ・・・（１８ｂ）
＜シリコーンの製造例＞
【０１１３】
【製造例１９】
冷却器、攪拌装置付き三つ口フラスコに製造例１の珪素化合物６４．０ｇ、メチルエチルケトン１５０ｍｌを採り、混合溶解した。攪拌を続けながらこの溶液に、水９．０ｇをメチルエチルケトン５０ｍｌに溶解した溶液を添加した。添加終了後、攪拌を続けながら４０℃で３０分間放置した。この混合溶液に、製造例１６の珪素化合物２８５．２ｇ、水４０．５ｇ、メチルエチルケトン１００ｍｌ、濃塩酸１．３ｍｌからなる溶液を添加し、攪拌をさらに続けながら４０℃で４時間放置した。反応終了後、系は二相に分離したので、デカンテーションにより溶媒相を除去し、さらに５％炭酸水素ナトリウム溶液及び水で洗浄後、再びデカンテーションにより水を除去し、８０℃で一昼夜乾燥して重縮合物を単離した。ＩＲ、^１３Ｃ−ＮＭＲ、^１Ｈ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体は［｛ＣＦ_３（ＣＦ_２）_２｝_３ＳｉＯ_１／２］のユニット及び［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は−（ＣＨ_２）_３−で示される２価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン１として後述の化粧料の実施例に用いた。
【０１１４】
【製造例２０】
冷却器、攪拌装置付き三つ口フラスコに製造例２の珪素化合物８９．６ｇ、製造例３の珪素化合物４８．２ｇ、３−アミノプロピルトリメトキシシラン０．８ｇおよびエチルアルコール／テトラヒドロフラン混合溶媒（重量比で７／３）３００ｍｌを採り、混合溶解した。攪拌を続けながらこの溶液に、水９．１ｇを前述の混合溶媒１００ｍｌに溶解した溶液を添加した。添加終了後、攪拌を続けながら２５℃で４時間放置した。この混合溶液に製造例１３の珪素化合物１５９．３ｇ、水１００．８ｇ、前述の混合溶媒２００ｍｌ、濃塩酸２．８ｍｌからなる溶液を添加し、攪拌をさらに続けながら２５℃で１０時間放置した。反応終了後、系は二相に分離したので、デカンテーションにより溶媒相を除去し、さらに５％炭酸水素ナトリウム溶液及び水で洗浄後、再びデカンテーションにより水を除去し、８０℃で一昼夜乾燥して重縮合物を単離した。ＩＲ、^１３Ｃ−ＮＭＲ、^１Ｈ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［（ＣＦ_３ＣＨ_２）_３ＳｉＯ_１／２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は前記式（１ａ）で示される２価の有機基を表す。）のユニット及び［Ｏ_３／２ＳｉＱ’^２ＳｉＯ_３／２］（但し、Ｑ’^２は−（ＣＨ_２）_２Ｓ（ＣＨ_２）_３−で示される２価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン２として後述の化粧料の実施例に用いた。
【０１１５】
【製造例２１】
冷却器、攪拌装置付き三つ口フラスコに製造例４の珪素化合物４４．０ｇ、テトラメトキシシラン２２．８ｇ、３−（４，５−ジヒドロイミダゾール）プロピルトリエトキシシラン２．１ｇおよびイソプロピルアルコール４００ｍｌを採り、混合溶解した。攪拌を続けながらこの溶液に、水１０．１ｇをイソプロピルアルコール１００ｍｌに溶解した溶液を添加した。添加終了後、攪拌を続けながら６０℃で２時間放置した。この混合溶液に製造例１４の珪素化合物５０６．８ｇ、水５４．０ｇ、イソプロピルアルコール２００ｍｌ、濃硝酸３．０ｍｌからなる溶液を添加し、攪拌をさらに続けながら６０℃で１６時間放置した。反応終了後、系は二相に分離したので、デカンテーションにより溶媒相を除去し、さらに５％炭酸水素ナトリウム溶液及び水で洗浄後、凍結乾燥により水を除去して重縮合物を単離した。ＩＲ、^１３Ｃ−ＮＭＲ、^１Ｈ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［｛ＣＦ_３（ＣＦ_２）_５｝（ＣＨ_３）_２ＳｉＯ_１／２］のユニット、［ＳｉＯ_２］のユニット、及び［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は前記式（２ａ）で示される２価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン３として後述の化粧料の実施例に用いた。
【０１１６】
【製造例２２】
冷却器、攪拌装置付き三つ口フラスコに製造例５の珪素化合物７６．６ｇ、トリエチルアミン０．４５ｇおよびエチルセロソルブ３００ｍｌを採り、混合溶解した。攪拌を続けながらこの溶液に、水３．９ｇをエチルセロソルブ１００ｍｌに溶解した溶液を添加した。添加終了後、攪拌を続けながら５℃で２時間放置した。この混合溶液に、製造例１５の珪素化合物２５２．６ｇ、水４３．２ｇ、エチルセロソルブ１５０ｍｌ、濃硝酸３．０ｍｌからなる溶液を添加し、攪拌をさらに続けながら２０℃で８時間放置した。反応終了後、系は二相に分離したので、デカンテーションにより溶媒相を除去し、さらに５％炭酸水素ナトリウム溶液、水で洗浄後再びデカンテーションにより水を除去し、８０℃で一昼夜乾燥して重縮合物を単離した。ＩＲ、^１３Ｃ−ＮＭＲ、^１Ｈ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［｛ＣＦ_３（ＣＦ_２）_３｝_２（Ｃ_２Ｈ_５）ＳｉＯ_１／２］のユニット及び［（Ｏ_３／２Ｓｉ）_３Ｑ^３］（但し、Ｑ^３は前記式（３ａ）で示される３価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン４として後述の化粧料の実施例に用いた。
【０１１７】
【製造例２３】
冷却器、攪拌装置付き三つ口フラスコに製造例６の珪素化合物３２．２ｇ、テトラエトキシシラン２．８ｇ、酢酸０．１８ｇおよびジメチルスルフォキシド２５０ｍｌを採り、混合溶解した。攪拌を続けながらこの溶液に、水５．５ｇをジメチルスルフォキシド５０ｍｌに溶解した溶液を添加した。添加終了後、攪拌を続けながら６０℃で６時間放置した。この混合溶液に、製造例１４の珪素化合物１１４．０ｇ、水１３．４ｇ、ジメチルスルフォキシド１５０ｍｌ、クエン酸４．０ｇからなる溶液を添加し、攪拌をさらに続けながら６０℃で１８時間放置した。反応終了後、系は二相に分離したので、デカンテーションにより溶媒相を除去し、さらに５％炭酸水素ナトリウム溶液及び水で洗浄後、凍結乾燥により水を除去して重縮合物を単離した。ＩＲ、^１３Ｃ−ＮＭＲ、^１Ｈ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［｛ＣＦ_３（ＣＦ_２）_５｝（ＣＨ_３）_２ＳｉＯ_１／２］のユニット、［ＳｉＯ_２］のユニット及び［（Ｏ_３／２Ｓｉ）_３Ｑ^３］（但し、Ｑ^３は前記式（４ａ）で示される３価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン５として後述の化粧料の実施例に用いた。
【０１１８】
【製造例２４】
冷却器、攪拌装置付き三つ口フラスコに製造例７の珪素化合物８８．５ｇ、テトラヒドロフラン５００ｍｌを採り混合溶解した。攪拌を続けながらこの溶液に、水１５．６ｇ及び濃アンモニア水１．５ｍｌをテトラヒドロフラン１００ｍｌに溶解した溶液を添加した。添加終了後、攪拌を続けながら１０℃で１時間放置した。この混合溶液に製造例１７の珪素化合物３６６．１ｇ、水４５．Ｏｇ、テトラヒドロフラン３００ｍｌ、酢酸５．０ｇからなる溶液を添加し、攪拌をさらに続けながら１０℃で４時間放置した。反応終了後、系は二相に分離したので、デカンテーションにより溶媒相を除去し、さらに５％炭酸水素ナトリウム溶液及び水で洗浄後、再びデカンテーションにより水を除去し、８０℃で一昼夜乾燥して重縮合物を単離した。ＩＲ、^１３Ｃ−ＮＭＲ、^１Ｈ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［｛ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２｝_２（Ｃ_２Ｈ_５）ＳｉＯ_１／２］のユニット及び［（Ｏ_３／_２Ｓｉ）_３Ｑ^３］（但し、Ｑ^３は前記式（５ａ）で示される３価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン６として後述の化粧料の実施例に用いた。
【０１１９】
【製造例２５】
冷却器、攪拌装置付き三つ口フラスコに製造例８の珪素化合物１８．１ｇ、製造例３の珪素化合物４．１ｇ、テトラメトキシシラン０．９ｇ、テトラヒドロフラン３００ｍｌ及び３−アミノプロピルメトキシシラン０．６ｇを採り、混合溶解した。攪拌を続けながらこの溶液に、水６．０ｇをテトラヒドロフラン１００ｍｌに溶解した溶液を添加した。添加終了後、攪拌を続けながら２０℃で３時間放置した。この混合溶液に製造例１３の珪素化合物８５．３ｇ、水５９．４ｇ、テトラヒドロフラン２５０ｍｌ、濃塩酸３．０ｍｌからなる溶液を添加し、攪拌をさらに続けながら２０℃で１２時間放置した。反応終了後、系は二相に分離したので、デカンテーションにより溶媒相を除去し、さらに５％炭酸水素ナトリウム溶液及び水で洗浄後、再びデカンテーションにより水を除去し、８０℃で一昼夜乾燥して重縮合物を単離した。ＩＲ、^１３Ｃ−ＮＭＲ、^１Ｈ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［（ＣＦ_３ＣＨ_２）_３ＳｉＯ_１／２］のユニット、［ＳｉＯ_２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は−（ＣＨ_２）_２Ｓ（ＣＨ_２）_３−で示される２価の有機基を表す。）のユニット及び［（Ｏ_３／２Ｓｉ）_４Ｑ^４］（但し、Ｑ^４は前記式（６ａ）で示される４価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン７として後述の化粧料の実施例に用いた。
【０１２０】
【製造例２６】
冷却器、攪拌装置付き三つ口フラスコに製造例９の珪素化合物９８．１ｇ、テトラエトキシシラン１．７ｇ、イソプロピルアルコール／テトラヒドロフラン混合溶媒（重量比７／３）７００ｍｌ及びモルフォリン２．１ｇを採り、混合溶解した。攪拌を続けながらこの溶液に、水３．１ｇを前述の混合溶媒１００ｍｌに溶解した溶液を添加した。添加終了後、攪拌を続けながら２０℃で４時間放置した。この混合溶液に製造例１６の珪素化合物４５６．４ｇ、水６４．８ｇ、前述の混合溶媒４００ｍｌ、濃塩酸７．５ｍｌからなる溶液を添加し、攪拌をさらに続けながら２０℃で１２時間放置した。反応終了後、系は二相に分離したので、デカンテーションにより溶媒相を除去し、さらに５％炭酸水素ナトリウム溶液及び水で洗浄後、再びデカンテーションにより水を除去し、８０℃で一昼夜乾燥して重縮合物を単離した。ＩＲ、^１３Ｃ−ＮＭＲ、^１Ｈ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［｛ＣＦ_３（ＣＦ_２）_２｝_３ＳｉＯ_１／２］のユニット、［（Ｏ_３／２Ｓｉ）_４Ｑ^４］（但し、Ｑ^４は前記式（７ａ）で示される４価の有機基を表す。）のユニット及び［ＳｉＯ_２］のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン８として後述の化粧料の実施例に用いた。
【０１２１】
【製造例２７】
冷却器、攪拌装置付き三つ口フラスコに製造例１０の珪素化合物８２．４ｇ、アセトン４００ｍｌを採り、混合溶解した。攪拌を続けながらこの溶液に、水２１．６ｇをアセトン１００ｍｌに溶解した溶液を添加した。添加終了後、攪拌を続けながら２０℃で１時間放置した。この混合溶液に、製造例１７の珪素化合物２３４．７ｇ、水３６．０ｇ、アセトン２００ｍｌ、濃塩酸７．０ｍｌからなる溶液を添加し、攪拌をさらに続けながら２０℃で４時間放置した。反応終了後、系は二相に分離したので、デカンテーションにより溶媒相を除去し、さらに５％炭酸水素ナトリウム溶液及び水で洗浄後、再びデカンテーションにより水を除去し、８０℃で一昼夜乾燥して重縮合物を単離した。ＩＲ、^１３Ｃ−ＮＭＲ、^１Ｈ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［｛ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２｝_２（Ｃ_２Ｈ_５）ＳｉＯ_１／２］のユニット及び［（Ｏ_３／２Ｓｉ）_４Ｑ^４］（但し、Ｑ^４は式（８ａ）で示される４価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン９として後述の化粧料の実施例に用いた。
【０１２２】
【製造例２８】
冷却器、攪拌装置付き三つ口フラスコに製造例１の化合物２４．９ｇ、製造例１２の化合物６１．９ｇ、テトラヒドロフラン２５０ｍｌを採り混合溶解した。攪拌を続けながらこの溶液に水１６．２ｇをテトラヒドロフラン７０ｍｌに溶解した溶液を添加した。添加終了後攪拌を続けながら２０℃で１時間放置した。この混合溶液に製造例１７の珪素化合物４６９．３ｇ、水２４．３ｇ、テトラヒドロフラン１５０ｍｌ、濃塩酸３ｍｌからなる溶液を添加し、攪拌をさらに続けながら２０℃で８時間放置した。反応後水を少量加えると系は二相に分離したので、デカンテーションにより溶媒相を除去し、ロータリーエバポレーターで残存する揮発成分を除去して重縮合物を単離した。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［｛ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２｝_２｛Ｃ_２Ｈ_５｝ＳｉＯ_１／２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は−（ＣＨ_２）_３−を表す。）のユニット及び［Ｏ_３／２ＳｉＱ^２’ＳｉＯ_３／２］（但しＱ^２’は、前記式（９ａ）で示される２価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン１０として後述の化粧料の実施例に用いた。
【０１２３】
【製造例２９】
冷却器、攪拌装置付き三つ口フラスコに製造例３の化合物３８．８ｇ、製造例１１の化合物１８．３ｇ、３−アミノプロピルトリメトキシシラン１．１ｇ、エチルアルコール１００ｍｌを採り混合溶解した。攪拌を続けながらこの溶液に水８．２ｇをエチルアルコール４０ｍｌに溶解した溶液を添加した。添加終了後攪拌を続けながら２０℃で２時間放置した。この混合溶液に製造例１８の珪素化合物１６９．２ｇ、水１２．２ｇ、エチルアルコール６０ｍｌ、濃塩酸１．５ｍｌからなる溶液を添加し、攪拌をさらに続けながら２０℃で１６時間放置した。反応後系は二相に分離したので、デカンテーションにより溶媒相を除去し、５％炭酸水素ナトリウム溶液および水で洗浄後ロータリーエバポレーターで残存する揮発成分を除去して重縮合物を単離した。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［｛ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２｝｛Ｃ_２Ｈ_５｝_２ＳｉＯ_１／２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但し、Ｑ^２は−（ＣＨ_２）_２Ｓ（ＣＨ_２）_３−を表す。）のユニット及び［Ｏ_３／２ＳｉＱ^２’ＳｉＯ_３／２］（但しＱ^２’は、前記式（９ａ）で示される２価の有機基を表す。）のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン１１として後述の化粧料の実施例に用いた。
【０１２４】
【製造例３０】
冷却器、攪拌装置付き三つ口フラスコに製造例２の化合物５７．５ｇ、製造例１１の化合物１４．７ｇ、テトラメトキシシラン４．６ｇ、３−アミノプロピルトリメトキシシラン０．３ｇ、エチルアルコール／テトラヒドロフラン混合溶媒（重量比で７／３）２００ｍｌを採り混合溶解した。攪拌を続けながらこの溶液に水１５．０ｇを前記の混合溶媒５０ｍｌに溶解した溶液を添加した。添加終了後攪拌を続けながら２０℃で２時間放置した。この混合溶液に製造例１４の珪素化合物２５３．４ｇ、水２０．０ｇ、２０℃の混合溶媒１００ｍｌ、濃硝酸２．５ｍｌからなる溶液を添加し、攪拌をさらに続けながら室温で１２時間放置した。反応後少量の水の添加により系は二相に分離したので、デカンテーションにより溶媒相を除去し、５％炭酸水素ナトリウム溶液および水で洗浄後ロータリーエバポレーターで残存する揮発成分を除去して重縮合物を単離した。ＩＲ、^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ、^２９Ｓｉ−ＮＭＲ測定を行ったところ、この重縮合体が［｛ＣＦ_３（ＣＦ_２）_５｝｛ＣＨ_３｝_２ＳｉＯ_１／２］のユニット、［Ｏ_３／２ＳｉＱ^２ＳｉＯ_３／２］（但しＱ^２は、前記式（１ａ）で示される２価の有機基を表す。）のユニット、［Ｏ_３／２ＳｉＱ^２’ＳｉＯ_３／２］（但しＱ^２’は、前記式（９ａ）で示される２価の有機基を表す。）のユニット及び［ＳｉＯ_２］のユニットからなるシリコーンであることが確認された。得られたシリコーンをシリコーン１２として後述の化粧料の実施例に用いた。
【０１２５】
次に、上記各製造例で得られたシリコーン１〜１２を含有する本発明の化粧料の実施例について説明する。尚、以下に示す配合量は全て重量部である。
【０１２６】
【実施例１〜４】クリーム
表１に示すＡ成分、Ｂ成分をそれぞれ８０℃に加熱溶解した後、Ａ成分にＢ成分を徐々に加え乳化し撹拌冷却してクリームを得た。このＡ成分にＢ成分を加える時の速度は、上記製造例で得られたシリコーンを含むＡ成分と水性成分（Ｂ成分）とが互いに乳化されにくいため、徐々に行うことに特に注意して製造された。また表１に組成を示す、実施例１のクリームにおける製造例のシリコーンの代わりにポリジメチルシロキサンを用いた比較例１のクリームを、上記実施例と同様に製造した。更に、実施例１のクリームにおけるシリコーン１の代わりにパーフルオロポリエーテルとしてフォンブリンＨＣ−４（モンテフルオス社製）を同量用いた以外は、実施例１と同様にして別の比較例のクリームを製造しようとしたところ、各成分は乳化できずに二層に分離してしまいクリームは得られなかった。
【０１２７】
【表１】

【０１２８】
【実施例５〜８】ファンデーション
表２に示す各成分をニーダーに秤込み、８０℃に加熱しながら混練りし、金皿に詰めて加圧成型してファンデーションを得た。また表２に組成を示す、実施例８のファンデーションにおける製造例のシリコーンの代わりにポリジメチルシロキサンを用いた比較例２のファンデーションを、上記実施例と同様に製造した。
【０１２９】
【表２】

【０１３０】
【実施例９〜１２】リップカラー
表３に示す各成分を８０℃で加熱溶解分散し、６０℃の加温ロールをかけ、再度９０℃に加熱し、金型に流し込み冷却して取り出してリップカラーを得た。また表３に組成を示す、実施例１２のリップカラーにおける製造例のシリコーンの代わりに三次元構造のシリコーンであるシリコーンワニス（シリコーンＫＦ７３１２Ｆ：信越化学製）を用いた比較例３のリップカラーを、上記実施例と同様に製造した。
【０１３１】
【表３】

【０１３２】
【実施例１３〜１６】ヘアブロースプレー
表４に示す各成分を加熱溶解冷却し、スプレーノズル付き耐圧容器に充填し、天然ガスを注入し密閉してヘアブロースプレーを得た。また表４に組成を示す、実施例１４のヘアブロースプレーにおける製造例のシリコーンの代わりにポリジメチルシロキサン（１００ｃ．ｓ．）を用いた比較例４のヘアブロースプレーを、上記実施例と同様に製造した。
【０１３３】
【表４】

【０１３４】
上記各実施例で得られた本発明の４種類の剤形の化粧料について、上記製造例のシリコーンの代わりに従来のシリコーンを含有する比較例の化粧料との比較において、撥水性、なじみのよさ、滑らかさやしっとり感、化粧持ちのよさ等の官能評価を行った。
【０１３５】
（１）クリームの評価
実施例１〜４及び比較例１で得られたクリームの官能評価を専門パネラー５名により行った。評価項目は、しっとり感、水滴を落としたときの撥水性、肌なじみのよさ、メークアップ料を上に乗せたときのメークアップ料の崩れにくさ、総合評価で、良いを評点５、やや良いを評点４、普通を評点３、やや悪いを評点２、悪いを評点１とした五段階評価で行った。結果は、全ての実施例のクリームにおいて比較例１のクリームに比べ、全ての評価項目で評点が高かった。その代表的な結果（実施例１及び比較例１）を表５に示す。
【０１３６】
【表５】

【０１３７】
この結果より、本発明に用いるシリコーンの代わりに従来のシリコーンを含する比較例のクリームに比べ、実施例のクリームが撥水性をはじめとする上記全ての評価項目において優れた官能を有することがわかる。また、実施例のクリームで肌を整えた後、メークアップすると化粧の持ちがよいことが確認され、このクリームは基礎化粧料であると同時にアンダーメークアップの機能も有することがわかった。
【０１３８】
（２）ファンデーションの評価
実施例５〜８及び比較例２で得られたファンデーションの官能評価を専門パネラー５名により行った。評価項目はしっとり感、水滴を落としたときの撥水性、肌なじみのよさ、化粧崩れのしにくさ、総合評価で、良いを評点５、やや良いを評点４、普通を評点３、やや悪いを評点２、悪いを評点１とした五段階評価で行った。結果は、全ての実施例のファンデーションにおいて比較例２のファンデーションに比べ、全ての評価項目で評点が高かった。その代表的な結果（実施例８及び比較例２）を表６に示す。
【０１３９】
【表６】

【０１４０】
この結果より、本発明に用いるシリコーンの代わりに従来のシリコーンを含する比較例のファンデーションに比べ、実施例のファンデーションが撥水性をはじめとする上記全ての評価項目において優れた官能を有することがわかる。また、実施例５〜８及び比較例２で得られたファンデーションを上腕部に塗布し、流水下指で擦する試験を行ったところ、比較例２で得られたファンデーションが流水下の擦りに対して抵抗性が少なかったのに比べ、実施例のファンデーションについては何れもファンデーションの落ちは認められず化粧持ちがよいことが確認された。
【０１４１】
（３）リップカラーの評価
実施例９〜１２及び比較例３で得られたリップカラーの官能評価を専門パネラー５名により行った。評価項目は色移りのしにくさ、水滴を落としたときの撥水性、唇へのなじみのよさ、化粧崩れのしにくさ、総合評価で、良いを評点５、やや良いを評点４、普通を評点３、やや悪いを評点２、悪いを評点１とした五段階評価で行った。結果は、全ての実施例のリップカラーにおいて比較例３のリップカラーに比べ、全ての評価項目で評点が高かった。その代表的な結果（実施例１２及び比較例３）を表７に示す。
【０１４２】
【表７】

【０１４３】
この結果より、本発明に用いるシリコーンの代わりに従来のシリコーンを含する比較例のリップカラーに比べ、実施例のリップカラーが撥水性をはじめとする上記全ての評価項目において優れた官能を有することがわかる。更に、比較例３のリップカラーを塗布しその上に市販の口紅オーバーコートを塗布した場合と実施例９〜１２のリップカラーのみを塗布した場合とを対比したところ、色移りのしにくさは比較例と従来品の組み合わせよりも実施例のリップカラーの方が優っており、本発明のリップカラーは一品にして、従来のリップカラー及び口紅オーバーコートの二品の組み合わせ以上の機能を有することがわかった。
【０１４４】
（４）ヘアブロースプレーの評価
実施例１３〜１６及び比較例４で得られたヘアブロースプレーの官能評価を専門パネラー５名により行った。評価項目は艶の持続性、水滴を落としたときの撥水性、櫛通りのよさ、セットの崩れにくさ、総合評価で、良いを評点５、やや良いを評点４、普通を評点３、やや悪いを評点２、悪いを評点１とした五段階評価で行った。結果は、全ての実施例のヘアブロースプレーにおいて比較例４のヘアブロースプレーに比べ、全ての評価項目で評点が高かった。その代表的な結果（実施例１４及び比較例４）を表８に示す。
【０１４５】
【表８】

【０１４６】
この結果より、本発明に用いるシリコーンの代わりに従来のシリコーンを含する比較例のヘアブロースプレーに比べ、実施例のヘアブロースプレーが撥水性をはじめとする上記全ての評価項目において優れた官能を有することがわかる。また、実施例１３〜１６と比較例４で得られたヘアブロースプレーの櫛通りのよさの持続性について評価したところ、実施例のヘアブロースプレーを使用したときの櫛通りのよさは、比較例のヘアブロースプレーを使用したときに比べ、長く持続した。
【０１４７】
これらの結果を総合的に評価すると、本発明の化粧料は、従来のシリコーンを含有する化粧料に比べ、撥水性、化粧持ちに優れると共に、肌や頭髪によくなじんで滑らかさやしっとり感を与える効果に優れることがわかる。
【０１４８】
【発明の効果】
本発明の化粧料は、通常化粧料に配合される多くの成分との相溶性に優れると共に、優れた撥水性、柔軟性の被膜形成能を有するシリコーンを含有するので、多様な剤形を取ることが可能であり、撥水性に優れ化粧持ちがよく、更に、肌や頭髪によくなじんで滑らかさやしっとり感を与える効果に優れる。[0001]
[Industrial applications]
The present invention relates to cosmetics, and in particular, contains silicone having a unit in which a silicon atom is bonded by an organic chain as a main constituent unit and contains a silicone having a fluorine atom-containing terminal blocking unit, and has water repellency, smoothness, and moist feeling. Related to cosmetics that are excellent.
[0002]
[Prior art]
In cosmetics, imparting water repellency to skin and hair via cosmetics is very useful in consideration of protection of skin and hair and improvement in durability of cosmetics. From this point of view, various compounds for improving the water repellency of cosmetics, for example, fluorine-based oils such as silicone and perfluoropolyether having a three-dimensional structure have been developed and incorporated into cosmetics. Was. As described above, the above compounds were incorporated into cosmetics in order to improve water repellency. Adding these compounds to cosmetics, in addition to improving water repellency, also provides smooth and moisturizing skin and hair. It also greatly contributed to enhancing the effect of giving a feeling.
[0003]
Such cosmetics containing the above-mentioned compound have no particular problem in terms of safety, and in terms of water repellency, they are superior technology compared to the previous technology, but have a three-dimensional structure. Some cosmetics containing silicone have an insufficient water-repellent level, and there is room for improvement in compatibility with other components in cosmetics containing a fluorinated oil such as perfluoropolyether. . That is, since a fluorine-based oil such as perfluoropolyether is hardly compatible with other components of cosmetics, the dosage form in which it can be blended is often limited to a special one such as a lipstick overcoat.
[0004]
Therefore, as a component for improving the water repellency of the cosmetic, while being excellent in compatibility with many components usually blended in cosmetics, a sufficient water repellent effect is obtained when blended in cosmetics. Research and development of compounds that have the effect of imparting smoothness and moist feeling to the skin and hair like conventional compound compounds, and water repellency that can correspond to various dosage forms containing compounds having such characteristics There has been a demand for the development of cosmetics having excellent smoothness and moist feeling.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above, and has excellent compatibility with many components usually blended in cosmetics, and has sufficient water repellency, smoothness, and moist feeling when blended in cosmetics. It is an object of the present invention to provide a cosmetic that can be used in various dosage forms containing such a compound and is excellent in water repellency, smoothness, and moist feeling.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in search of a novel compound having both hydrophobicity and solvent affinity in order to solve the above problems, and found that a unit in which a silicon atom-silicon atom is bonded by an organic chain. Silicone having a fluorine atom-containing terminal blocking unit as a main constituent unit has been found to have a film forming ability having excellent solvent repellency and excellent water repellency and flexibility. The present inventors have found that a cosmetic that can be applied to a dosage form and has excellent water repellency, smoothness, and moist feeling can be obtained, and the present invention has been completed.
[0007]
That is, the present invention provides a compound represented by the general formula (I):
Qⁿ(SiO_3/2)_n
(However, QⁿRepresents an n-valent organic group, and n represents any one of integers of 2 to 6. )
And at least one of the units represented by the formula (II) is a main constituent unit,
(R¹)₃SiO_1/2
(However, R¹May be the same as or different from each other, and represent a hydrocarbon group or a hydrocarbon group in which at least a part of a hydrogen atom is substituted with a fluorine atom, and three R¹At least one of them must be the above-mentioned fluorine-substituted hydrocarbon group. )
Is a cosmetic containing silicone blocked by a unit represented by
[0008]
Hereinafter, the present invention will be described in detail.
(1) Silicone used in the present invention
The silicone used in the cosmetic of the present invention is basically a silicone represented by the general formula (I)ⁿ(SiO_3/2)_nAt least one of the units is a main constituent unit, and the terminal is represented by the general formula (II).¹)₃SiO_1/2Blocked by unit. Further, in the present invention, the main constituent unit of the silicone is further SiO 2₂Units can be included, but in this case SiO 2₂Unit content is SiO₂/ Qⁿ(SiO_3/2)_nThe molar ratio is preferably (3/2) or less, particularly preferably (1/2) or less. (R¹)₃SiO_1/2Unit Qⁿ(SiO_3/2)_nUnit and SiO₂The molar ratio to the unit is not particularly limited.
[0009]
In the silicone used in the present invention, the above general formula (I): Qⁿ(SiO_3/2)_nQ in unitⁿExamples of 1) are: 1) an alkylene group; 2) a polymethylene group; 3) a phenylene group; 4) an arylene group; 5) a hydrogen atom of the above groups 1) to 4) further comprising an alkyl group, a phenyl group, an aryl group, A group substituted with at least one member of the group consisting of an alkylene group, a polymethylene group, a phenylene group and an arylene group; 6) an ether, thioether, ester, ketone, amide, imide, A group containing at least one functional group selected from the group consisting of amines and imines; and 7) at least one group such as a group in which a hydrogen atom of the above groups 1) to 6) is substituted with a chlorine atom or a bromine atom. can do.
[0010]
Further, in the silicone used in the present invention, as described above, Q in formula (I)ⁿN represents any of integers of 2 to 6. Q illustrated aboveⁿAbout QⁿExamples of the divalent organic group in which n is 2 include 1) an alkylene group, 2) a polymethylene group, 3) a phenylene group, 4) an arylene group, and 5) a hydrogen atom of the above groups 1) to 4) is further alkyl. 6) at least one functional group of the group consisting of ethers, thioethers, esters, ketones, amides, imides, amines, and imines in the structure of the above groups 1) to 4) And 7) a group in which the hydrogen atom of the above groups 1) to 6) is substituted with a chlorine atom or a bromine atom. Examples of the trivalent organic group in which n is 3 include a hydrogen atom, a chlorine atom, or a bromine atom of the divalent organic group (groups 1 to 7) above, an alkylene group, an arylene group, or a polymethylene group. And a group in which a hydrogen atom of these groups is substituted with a chlorine atom or a bromine atom.
[0011]
Similarly, when the number of hydrogen atoms, chlorine atoms or bromine atoms substituted with a divalent group such as an alkylene group, an arylene group, a polymethylene group, or a phenylene group in the divalent organic group is increased to 2, 3, or 4, n Are 4, a pentavalent organic group, 5, a pentavalent organic group, and 6, a hexavalent organic group. Thus, Q in the above general formula (I)ⁿCan be obtained, wherein n is 2 to 6. In the silicone used in the present invention, QⁿN is preferably 2, 3, or 4, and more preferably 2. This is QⁿQ to express the properties ofⁿMust be located inside the molecule (between silicon atoms), and for that purpose, it is necessary to be divalent or more, but the cost increases as the valence increases. Further, more preferable QⁿExamples include a divalent organic group containing a diamide of a dicarboxylic acid. Considering such preferable conditions, the silicone preferably used according to the present invention has a main constituent unit represented by Q in the general formula (I).ⁿAnd a unit in which a divalent organic group containing a diamide of a dicarboxylic acid is introduced andⁿIs a silicone composed of a unit into which a divalent organic group other than a divalent organic group containing a diamide of a dicarboxylic acid is introduced.
[0012]
The main constituent unit of the silicone used in the present invention is such a QⁿIs a constituent of at least one unit represented by the above general formula (I),ⁿThe following is a more specific example. In the following formula, a, b, c, d, e, and f each represent an integer of 1 or more.
Q²(Divalent organic group):
[0013]
Embedded image
− (CH₂)_a-... (1), -CH (CH₃)-(CH₂)_a-… (2),
− (CH₂)_a−C (C₂H₅) (CH₃)-... (3), -C₆H₄-… (4),
− (CH₂)_a-C₆H₄− (CH₂Cl)-... (5),
-CH (CH₃) -C₆H₄− (CH₂)_a-… (6),
− (CH₂)_a-S- (CH₂)_b-... (7),-(CH₂)_a-SC₆H₄-… (8),
-CH (CH₃) -S- (CH₂)_a-… (9)
[0014]
Embedded image

[0015]
Q³(Trivalent organic group):
[0016]
Embedded image

[0017]
Q⁴(Tetravalent organic group):
[0018]
Embedded image

[0019]
Next, (R) of the general formula (II)¹)₃SiO_1/2Unit, but the R¹May be the same or different from each other, and represent a hydrocarbon group or a hydrocarbon group in which at least a part of a hydrogen atom is substituted with a fluorine atom, and three R¹At least one of which must be the above-mentioned fluorine-substituted hydrocarbon group, preferably an alkyl group, a phenyl group, an aryl group or a group in which at least a part of the hydrogen atoms of these groups is substituted with a fluorine atom. A selected group, and specific examples include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group; a phenyl group; an aryl group; Alternatively, groups in which at least a part of hydrogen atoms of these groups are substituted with fluorine atoms, and the like can be given.
[0020]
An example of the silicone network structure used in the present invention composed of the units described above is QⁿIs shown below, taking as an example the case where n is 2, that is, a divalent organic group.
[0021]
Embedded image

[0022]
(However, Q in Chemical Formula 5²Represents a divalent organic group. Also, R¹May be the same as or different from each other, and represent a hydrocarbon group or a hydrocarbon group in which at least a part of a hydrogen atom is substituted with a fluorine atom, and three R¹At least one of them must be the above-mentioned fluorine-substituted hydrocarbon group. )
[0023]
Specific examples of the silicone used in the present invention are as follows.
B) [｛CF₃(CF₂)₂｝₃SiO_1/2] Unit and [O_3/2SiQ²SiO_{3 / 2}] (However, Q²Is-(CH₂)₃Represents a divalent organic group represented by-. A) silicone consisting of units.
[0024]
B) [(CF₃CH₂)₃SiO_1/2] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Represents a divalent organic group represented by the following formula (1a). ) Unit and [O_3/2SiQ '²SiO_3/2] (However, Q '²Is-(CH₂)₂S (CH₂)₃Represents a divalent organic group represented by-. A) silicone consisting of units.
[0025]
Embedded image

[0026]
C) [｛CF₃(CF₂)₅｝ (CH₃)₂SiO_1/2] Unit, [SiO₂] Unit and [O_3/2SiQ²SiO_3/2] (However, Q²Represents a divalent organic group represented by the following formula (2a). A) silicone consisting of units.
[0027]
Embedded image

[0028]
D) [｛CF₃(CF₂)₃｝₂(C₂H₅) SiO_1/2] Unit and [(O_3/2Si)₃Q³] (However, Q³Represents a trivalent organic group represented by the formula (3a). A) a silicone unit.
[0029]
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[0030]
E) [｛CF₃(CF₂)₅｝ (CH₃)₂SiO_1/2] Unit, [SiO₂] Unit and [(O_3/2Si)₃Q³] (However, Q³Represents a trivalent organic group represented by the formula (4a). A) silicone consisting of units.
[0031]
Embedded image

[0032]
F) [｛CF₃(CF₂)₃(CH₂)₂｝₂(C₂H₅) SiO_1/2] Unit and [(O₃/₂Si)₃Q³] (However, Q³Represents a trivalent organic group represented by the formula (5a). A) silicone consisting of units.
[0033]
Embedded image

[0034]
G) [(CF₃CH₂)₃SiO_1/2] Unit, [SiO₂] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Is-(CH₂)₂S (CH₂)₃Represents a divalent organic group represented by-. ) Unit and [(O_3/2Si)₄Q⁴] (However, Q⁴Represents a tetravalent organic group represented by the formula (6a). A) a silicone unit.
[0035]
Embedded image

[0036]
H) [｛CF₃(CF₂)₂｝₃SiO_1/2] Unit, [(O_3/2Si)₄Q⁴] (However, Q⁴Represents a tetravalent organic group represented by the formula (7a). ) Unit and [SiO₂] The silicone which consists of a unit of.
[0037]
Embedded image

[0038]
R) [｛CF₃(CF₂)₃(CH₂)₂｝₂(C₂H₅) SiO_1/2] Unit and [(O_3/2Si)₄Q⁴] (However, Q⁴Represents a tetravalent organic group represented by the formula (8a). A) a silicone unit.
[0039]
Embedded image

[0040]
Nu) [｛CF₃(CF₂)₃(CH₂)₂｝₂｛C₂H₅｝ SiO_1/2] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Is-(CH₂)₃Represents-. ) Unit and [O_3/2SiQ²'SiO_3/2] (However, Q²'Represents a divalent organic group represented by the formula (9a). A) a silicone unit.
[0041]
Embedded image

[0042]
Le) [｛CF₃(CF₂)₇(CH₂)₂｝ ｛C₂H₅｝₂SiO_1/2] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Is-(CH₂)₂S (CH₂)₃Represents-. ) Unit and [O_3/2SiQ²'SiO_3/2] (However, Q²'Represents a divalent organic group represented by the formula (9a). A) a silicone unit.
[0043]
ヲ) [｛CF₃(CF₂)₅｝ ｛CH₃｝₂SiO_1/2] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Represents a divalent organic group represented by the formula (1a). ) Unit, [O_3/2SiQ²'SiO_3/2] (However, Q²'Represents a divalent organic group represented by the formula (9a). ) Unit and [SiO₂] The silicone which consists of a unit of.
[0044]
Next, a method for producing the silicone used in the present invention will be described.
(2) Method for producing silicone
In order to produce the above silicone used in the present invention, basically, the general formula (III):
Qⁿ[Si (X)₃]_n
(However, QⁿRepresents an n-valent organic group, and n represents any one of integers of 2 to 6. Xs may be the same or different and represent a hydrolyzable group. )
After hydrolytic polycondensation of a hydrolyzable silicon compound represented by the formula (IV):
(R¹)₃Six
(However, R¹May be the same as or different from each other, and represent a hydrocarbon group or a hydrocarbon group in which at least a part of a hydrogen atom is substituted with a fluorine atom, and three R¹At least one of them must be the above-mentioned fluorine-substituted hydrocarbon group. X represents a hydrolyzable group. )
May be reacted as a terminal blocking agent to block the terminal of the polycondensate.
[0045]
In order to produce the silicone used in the present invention by such a method, first, the hydrolyzable silicon compound Q of the general formula (III)ⁿ[Si (X)₃]_n, And water is subjected to hydrolysis polycondensation. In this case, if necessary, the silicon compound Si (X)₄(However, Xs may be the same or different and represent a hydrolyzable group.), And co-hydrolysis polycondensation with the silicon compound (III) may be performed. In order to control the progress of the reaction, the amount of water to be added is preferably not more than the theoretical amount required to hydrolyze the hydrolyzable group X of the silicon compound used.
[0046]
At this time, it is preferable to use an organic solvent in order to allow the reaction to proceed uniformly. The organic solvent is not particularly limited as long as it can dissolve the silicon compound used in the reaction. The reaction temperature is preferably from 0 to 80C. If the temperature is too low, solidification of the solvent occurs. If the temperature is too high, the solvent evaporates extremely, and the progress of the reaction becomes uneven.
[0047]
In order to promote the progress of the reaction, it is preferable to use a base and / or an acid as a catalyst. The addition amount of the base and / or acid catalyst is preferably 5 mol% or less of the silicon compound used in the reaction.
[0048]
An example of a reaction formula of this hydrolysis polycondensation is shown in Chemical formula 15, and an example of a network structure of the obtained polycondensate is shown in Chemical formula 16.
[0049]
Embedded image

[0050]
(However, Q in Chemical 15²Represents a divalent organic group. )
[0051]
Embedded image

[0052]
(However, Q²Represents a divalent organic group. )
The details of the materials used in the above hydrolysis polycondensation step are as follows.
[0053]
Hydrolyzable silicon compound Q of general formula (III)ⁿ[Si (X)₃]_n:
It is synthesized by a known organic reaction of a known silicon compound. For example, alkoxysilane having an amino group, chlorosilane [NH₂C₃H₆Si (OR)₃, NH₂C₃H₆Cl₃Reaction with an acid derivative such as acid chloride or anhydride; addition reaction of hydrogen silane or mercapto silane to a compound having an unsaturated bond; reaction of an alkoxysilane compound or a chlorosilane compound with a Grignard reagent or an organic lithium compound It is synthesized by such as. The hydrolyzable silicon compound Q of the general formula (III)ⁿ[Si (X)₃]_nQ inⁿAbout Q in the aforementioned general formula (I)ⁿIs the same as In the general formula (III), X is not particularly limited as long as it is a hydrolyzable group, and may be the same or different.
[0054]
In the production of the silicone used in the present invention, at least one kind of the hydrolyzable silicon compound is used as a raw material.ⁿAnd a hydrolyzable silicon compound having a divalent organic group containing a diamide of a dicarboxylic acid introduced therein, and Q in the general formula (III)ⁿAnd a hydrolyzable silicon compound into which a divalent organic group other than a divalent organic group containing a diamide of dicarboxylic acid is introduced.
[0055]
Silicon compound Si (X)₄:
It is added to adjust the hardness of silicone. The larger the amount added, the harder the silicone, and the lower the amount, the softer the silicone. X in the above general formula is not particularly limited as long as it is a hydrolyzable group, and may be the same or different from each other. Specific examples of such a silicon compound include silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane and the like, preferably silicon tetrachloride, tetramethoxysilane, tetraethoxysilane. .
[0056]
Organic solvent:
There is no particular limitation as long as it dissolves the above two silicon compounds, water, catalyst and the like, and alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; methyl cellosolve, ethyl cellosolve and the like Cellosolves; tetrahydroxyfuran; dimethyl sulfoxide and the like.
[0057]
Base and / or acid catalyst:
Inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid and citric acid; inorganic bases such as sodium hydroxide and aqueous ammonia; organic bases such as amine and morpholine; silanes containing basic groups such as 3-aminoalkoxysilane And the like, preferably a silane containing a basic group such as an amino substituent or a 4,5-dihydroimidazole substituent, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (4,5-dihydroimidazole) ) Propyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and the like.
[0058]
Next, after performing a polycondensation reaction for a certain period of time, in order to block the reaction end of the obtained polycondensate and stably take out the polycondensate, a silicon compound of the general formula (IV) (R) is used as a terminal blocking agent.¹)₃Add SiX and react. At this time, water and an acid catalyst are also added in order to promote the hydrolysis of the terminal blocking agent and facilitate the terminal blocking reaction. The amount of water to be added is not particularly limited, but it is desirable to add water in an amount equal to or more than the theoretical amount necessary for hydrolyzing the added terminal blocking agent. The addition amount of the acid catalyst is preferably at least 2 mol% of the terminal blocking agent of the general formula (IV).
[0059]
This terminal blocking step is carried out under stirring conditions in order to allow the reaction to proceed uniformly. The reaction time is preferably 4 to 20 hours. After completion of the reaction, the target product is taken out by decantation when the polycondensate undergoes phase separation, or by solvent distillation or freeze-drying when no phase separation occurs.
[0060]
An example of the terminal blocking situation in the network structure of the silicone obtained by the reaction between the polycondensate and the terminal blocking agent is shown below.
[0061]
Embedded image

[0062]
(However, Q in Chemical 17²Represents a divalent organic group. Also, R¹May be the same as or different from each other, and represent a hydrocarbon group or a hydrocarbon group in which at least a part of a hydrogen atom is substituted with a fluorine atom, and three R¹At least one of them must be the above-mentioned fluorine-substituted hydrocarbon group. )
The details of the materials used in the above terminal blocking step are as follows.
[0063]
(R) of the general formula (IV)¹)₃Six:
In the above general formula (IV), R¹May be the same as or different from each other, and represent a hydrocarbon group or a hydrocarbon group in which at least a part of a hydrogen atom is substituted with a fluorine atom, and three R¹At least one of which must be the above-mentioned fluorine-substituted hydrocarbon group, preferably, an alkyl group, a phenyl group, an aryl group, and a group in which at least a part of the hydrogen atoms of these groups is substituted with a fluorine atom. A group selected, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group; a phenyl group; an aryl group; And a group in which at least a part of the hydrogen atoms of the group (a) is substituted with a fluorine atom. In the general formula (IV), X is not particularly limited as long as it is a hydrolyzable group, but preferably includes an alkoxy group, a halogen atom or an alkoxyalkoxy group.
[0064]
As such a compound, specifically, (CF₃CH₂)₃Si (OCH₃), [CF₃(CF₂)₂]₂(CH₃) SiCl, [CF₃(CF₂)₅] (CH₃)₂Si (OC₂H₅), [CF₃(CF₂)₃(CH₂)₂]₂(C₂H₅) SiCl and the like, and can be easily synthesized by reacting a Grignard reagent or lithium salt having a corresponding fluoroalkyl group with a known silicon compound. Ie
[0065]
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[0066]
(However, in Chemical Formula 18, R_fRepresents a fluoroalkyl group, R represents a hydrocarbon group, Z represents Br or I, n represents any of 0 to 2, and m represents any of 1 to 3. )
[0067]
Acid catalyst:
Specific examples include inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid and citric acid; and volatile acids such as hydrochloric acid, nitric acid and acetic acid.
[0068]
(3) The cosmetic of the present invention
The cosmetic of the present invention contains one or more of the above silicones. The cosmetic of the present invention is imparted with excellent water repellency and oil repellency by blending the above silicone. This is because the silicone compounded in the cosmetic of the present invention is excellent in water repellency and further excellent in oil repellency because it has a fluorine atom in a terminal unit, but the silicone is also generally compounded in cosmetics. Because of its excellent compatibility with many raw materials, it is applicable to many dosage forms of cosmetics. Further, when the silicone used in the present invention forms a film on the skin or the hair, the film has flexibility, so that when it is added to a cosmetic, it gives the skin or the hair a smooth and moist feeling, And a cosmetic that is familiar to hair and hair. Such excellent water repellency, oil repellency, flexibility and the like of the silicone film act comprehensively to give the cosmetic of the present invention a long lasting cosmetic.
[0069]
The preferred content of the silicone in the cosmetic of the present invention varies depending on the type of the dosage form and the purpose of use, but is generally about 0.1 to 80% by weight. 0.5 to 40% by weight is more preferable in a basic cosmetic such as an emulsion, and 0.5 to 60% by weight as a make-up cosmetic such as a foundation, a lip color and an under-make-up. As a cosmetic for hair, 0.5 to 20% by weight is more preferable.
[0070]
The dosage form of the cosmetic of the present invention is not particularly limited, and examples thereof include lotions, emulsions, creams, aqueous gels, oil gels, ointments, under makeup, foundations, powders, lip colors, eye liners, sculptures, Coating essences, hair tonics, shampoos, rinses, pomades, hair treatments, hair packs, hair liquids, hair lotions, styling foams, hair blow sprays, etc., which are usually used as cosmetics for the skin and hair Can be These cosmetics can be produced by the same method as that for ordinary cosmetics, except that the above-mentioned silicone is preferably added in the above-mentioned amount.
[0071]
In addition to the above silicones, the cosmetics of the present invention generally include hydrocarbons such as liquid paraffin, vaseline, squalane, isopropyl myristate (IPM), synthetic gay wax, jojoba oil and carna, which are usually applied to cosmetics. Esters such as Uba wax, animal and vegetable oils such as olive oil and tallow, higher alcohols such as cetanol and stearyl alcohol, higher fatty acids such as stearic acid and oleic acid, and anionic surfactants such as sodium lauryl sulfate and alkyl sulfosuccinate. Cationic surfactants such as quaternary alkylamine salts, nonionic surfactants such as fatty acid monoglyceride and pooxyethylene hydrogenated castor oil, surfactants such as amphoteric surfactants such as alkyl betaine, and glycerin and propylene glycol. Polyhydric alcohols, ethanol, Lower alcohols such as panol, preservatives such as parabens and chlorhexidine gluconate, ultraviolet absorbers such as paraaminobenzoic acid derivatives and benzophenone derivatives, antioxidants such as vitamin E and butylhydroxytoluene, gum arabic, carboxyvinyl Thickeners such as polymers, humectants such as polyethylene glycol, pH adjusters such as citrate and acetate, powders such as titanium oxide, silica gel and talc, flavors and pigments, hyaluronic acid, placenta extract, Pharmaceutical ingredients according to various purposes, such as ginseng extract and sterol glycoside, are appropriately selected and blended. In addition to the above silicones, silicones such as three-dimensional silicones and fluorine-based oils such as perfluoropolyether which have been conventionally added to cosmetics for improving water repellency can also be added.
[0072]
【Example】
Hereinafter, examples of the present invention will be described. First, regarding the production example of the silicone used in the present invention, the silicon compound Q of the above general formula (III)ⁿ[Si (X)₃]_nAnd a fluorine-substituted end-blocking silicon compound of the general formula (IV) (R¹)₃A description will be given together with a manufacturing example of SiX.
<Qⁿ[Si (X)₃]_nManufacturing Example>
[0073]
[Production Example 1]
70.2 g of allyltrichlorosilane and 54.2 g of monohydrogentrichlorosilane were taken and mixed in a pressure-resistant bottle-type reaction vessel. Next, chloroplatinic acid H₂PtCl₆・ 6H₂O was heated in tetrahydrofuran, and after adding this solution corresponding to 0.2 mmol of platinum to the above-mentioned mixed solution, the reaction vessel was heated at 80 ° C. for 4 hours. After filtration and fractionation, tetrahydrofuran and chloroplatinic acid were removed to obtain a transparent liquid. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that this liquid was a compound represented by the formula (1b).
[0074]
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Cl₃Si (CH₂  )₃SiCl₃  ... (1b)
[0075]
[Production Example 2]
49.3 g of diallyl terephthalate, 78.6 g of 3-mercaptotrimethoxysilane and 450 ml of benzene were placed in a three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube, and stirred and mixed. Further, a solution in which 0.5 g of azobisisobutyronitrile was dissolved in 50 ml of benzene was added to the solution, and the mixture was stirred and mixed. While continuing stirring, bubbling with dry nitrogen gas was performed at room temperature for 1 hour, followed by heating and refluxing at the boiling point of benzene for 24 hours to complete the reaction. The benzene was removed with a rotary evaporator to obtain a viscous liquid. IR,¹H-NMR,^ThirteenC-NMR,²⁹When a Si-NMR measurement was performed, it was confirmed that this liquid was a compound represented by the formula (2b).
[0076]
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[0077]
[Production Example 3]
In a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, 44.5 g of vinyltrimethoxysilane, 58.9 g of 3-mercaptotrimethoxysilane and 400 ml of benzene were stirred and mixed. Further, a solution in which 0.5 g of azobisisobutyronitrile was dissolved in 50 ml of benzene was added to this solution, followed by stirring and mixing. While continuing stirring, bubbling with dry nitrogen gas was performed at room temperature for 1 hour, followed by heating and refluxing at the boiling point of benzene for 24 hours to complete the reaction. The benzene was removed with a rotary evaporator to obtain a viscous liquid. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that this liquid was a compound represented by the formula (3b).
[0078]
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(CH₃O)₃Si (CH₂)₂S (CH₂)₃Si (OCH₃)₃    ... (3b)
[0079]
[Production Example 4]
In a three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube, 110.7 g of 3-aminopropyltriethoxysilane, 400 ml of diethyl ether, and 100 ml of triethylamine were taken and mixed while cooling with ice. Further, a solution prepared by dissolving 45.3 g of 3-butenoyl chloride in 100 ml of diethyl ether was added dropwise to this solution while stirring with ice cooling. After the addition, stirring was continued for another hour. After the formed white precipitate was filtered off, diethyl ether and triethylamine were removed with a rotary evaporator to obtain a viscous liquid.
[0080]
82.7 g of the above liquid and 49.3 g of monohydrogentriethoxysilane were taken and mixed in a pressure-resistant bottle-type reaction vessel. Next, chloroplatinic acid H₂PtCl₆・ 6H₂O was heated in tetrahydrofuran, and after adding this solution corresponding to 0.2 mmol of platinum to the above-mentioned mixed solution, the reaction vessel was heated at 80 ° C. for 4 hours. After filtration and fractionation, tetrahydrofuran and chloroplatinic acid were removed to obtain a transparent liquid. IR,¹H-NMR,^ThirteenC-NMR,²⁹When a Si-NMR measurement was performed, it was confirmed that this liquid was a compound represented by the formula (4b).
[0081]
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[0082]
[Production Example 5]
177.3 g of glycerin tri-10-undecenoate and 110.0 g of monohydrogentrimethoxysilane were taken and mixed in a pressure-resistant bottle-type reaction vessel. Next, chloroplatinic acid H₂PtCl₆・ 6H₂O was heated in tetrahydrofuran, and after adding this solution corresponding to 0.2 mmol of platinum to the above-mentioned mixed solution, the reaction vessel was heated at 80 ° C. for 4 hours. After filtration and fractionation, tetrahydrofuran and chloroplatinic acid were removed to obtain a transparent liquid. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that this liquid was a compound represented by the formula (5b).
[0083]
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[0084]
[Production Example 6]
48.7 g of 1,2,4-trivinylcyclohexane, 257.8 g of 3-mercaptotris (β-methoxymethoxy) silane and 800 ml of benzene were placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, and stirred and mixed. did. Further, a solution in which 0.8 g of azobisisobutyronitrile was dissolved in 100 ml of benzene was added to this solution, and the mixture was stirred and mixed. While continuing stirring, bubbling with dry nitrogen gas was performed at room temperature for 1 hour, followed by heating and refluxing at the boiling point of benzene for 24 hours to complete the reaction. The benzene was removed with a rotary evaporator to obtain a viscous liquid. IR,¹H-NMR,^ThirteenC-NMR,²⁹When a Si-NMR measurement was performed, it was confirmed that this liquid was a compound represented by the formula (6b).
[0085]
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[0086]
[Production Example 7]
In a three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube, 57.9 g of 3-aminopropyltrichlorosilane, 320 ml of diethyl ether, and 80 ml of triethylamine were taken and mixed while cooling with ice. Further, a solution prepared by dissolving 26.8 g of trimesoyl chloride in 100 ml of diethyl ether was added dropwise to this solution while continuing to stir with ice cooling. After the addition, stirring was continued for another hour. After the generated white precipitate was filtered off, diethyl ether and triethylamine were removed with a rotary evaporator to obtain a white solid. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that this solid was a compound represented by the formula (7b).
[0087]
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[0088]
[Production Example 8]
In a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, 64.3 g of 3,3'-diaminobenzidine, 900 ml of tetrahydrofuran and 200 ml of triethylamine were taken and mixed while cooling with ice. Further, a solution prepared by dissolving 108.6 g of acryloyl chloride in 300 ml of tetrahydrofuran was added dropwise to this solution while stirring with ice cooling. After dropping, stirring was continued for another hour. After the formed white precipitate was filtered off, tetrahydrofurantriethylamine was removed with a rotary evaporator to obtain a white solid.
[0089]
86.1 g of the above solid and 97.8 g of monohydrogentrimethoxysilane were taken and mixed in a pressure-resistant bottle-type reaction vessel. Next, chloroplatinic acid H₂PtCl₆・ 6H₂O was heated in tetrahydrofuran, and after adding this solution corresponding to 0.2 mmol of platinum to the above-mentioned mixed solution, the reaction vessel was heated at 80 ° C. for 4 hours. Filtration and fractionation were performed to remove tetrahydrofuran and chloroplatinic acid to obtain a white solid. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that this solid was a compound represented by the formula (8b).
[0090]
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[0091]
[Production Example 9]
81.7 g of pentaerythritol tetramethacrylate, 190.7 g of 3-mercaptotriethoxysilane and 800 ml of benzene were placed in a three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube, and stirred and mixed. Further, to this solution, a solution in which 0.5 g of azobisisobutyronitrile was dissolved in 100 ml of benzene was added, followed by stirring and mixing. While continuing stirring, bubbling with dry nitrogen gas was performed at room temperature for 1 hour, followed by heating and refluxing at the boiling point of benzene for 24 hours to complete the reaction. The benzene was removed with a rotary evaporator to obtain a viscous liquid. IR,¹H-NMR,^ThirteenC-NMR,²⁹Si-NMR measurement confirmed that the liquid was a compound represented by the formula (9b).
[0092]
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[0093]
[Production Example 10]
Glycerol-1,3-diallyl ether (27.6 g), tetrahydrofuran (200 ml) and triethylamine (50 ml) were placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, and stirred and mixed while cooling with ice. Furthermore, a solution in which 14.6 g of adipoyl chloride was dissolved in 100 ml of tetrahydrofuran was added dropwise to this solution while stirring with ice cooling. After the addition, stirring was continued for another hour. After the formed white precipitate was filtered off, diethyl ether and triethylamine were removed with a rotary evaporator to obtain a viscous liquid.
[0094]
28.2 g of the above liquid and 54.2 g of monohydrogentrichlorosilane were taken and mixed in a pressure-resistant bottle-type reaction vessel. Next, chloroplatinic acid H₂PtCl₆・ 6H₂  O was heated in tetrahydrofuran, and after adding this solution corresponding to 0.2 mmol of platinum to the above-mentioned mixed solution, the reaction vessel was heated at 80 ° C. for 4 hours. By performing fractional distillation, tetrahydrofuran and chloroplatinic acid were removed to obtain a transparent liquid. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that this liquid was a compound represented by the formula (10b).
[0095]
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[0096]
[Production Example 11]
In a three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube, 107.6 g of 3-aminopropyltrimethoxysilane, 600 ml of tetrahydrofuran, and 200 ml of triethylamine were taken and mixed with ice cooling. Further, a solution obtained by dissolving 60.9 g of terephthalic acid chloride in 200 ml of tetrahydrofuran was added dropwise to this solution while stirring with ice cooling. After the addition, stirring was continued for another hour. After the generated white precipitate was filtered off, tetrahydrofuran and triethylamine were removed with a rotary evaporator to obtain a white solid. IR,¹  H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that the solid was a compound represented by the formula (11b).
[0097]
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[0098]
[Production Example 12]
In a three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube, 96.5 g of 3-aminopropyltrichlorosilane, 500 ml of diethyl ether, and 150 ml of triethylamine were taken and mixed while cooling with ice. Further, a solution obtained by dissolving 50.8 g of isophthalic acid chloride in 150 ml of diethyl ether was added dropwise to this solution while stirring with ice cooling. After the addition, stirring was continued for another hour. After the generated white precipitate was filtered off, diethyl ether and triethylamine were removed with a rotary evaporator to obtain a white solid. IR,¹  H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that this solid was a compound represented by (12b).
[0099]
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[0100]
<(R¹)₃Manufacturing Example of SiX>
[0101]
[Production Example 13]
8.7 g of metallic magnesium is placed in a sufficiently dried three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube, and sufficiently replaced with dry nitrogen gas. Further, 150 ml of tetrahydrofuran dehydrated and purified by refluxing with sodium metal and distillation was taken into the reaction vessel, and mixed by stirring. While stirring was continued, a solution in which 63.0 g of 2,2,2-trifluoroethyl iodide was dissolved in 200 ml of the above-mentioned tetrahydrofuran was dropped into this solution. A solution of 15.2 g of tetramethoxysilane dissolved in 150 ml of the above-mentioned tetrahydrofuran was added dropwise while cooling with ice while continuing to stir. After completion of the dropwise addition, reflux was carried out at the boiling point of tetrahydrofuran for 24 hours to complete the reaction. After the formed precipitate was separated by filtration, the target compound was isolated by fractional distillation. All operations were performed under a dry nitrogen gas stream. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that the target compound represented by the formula (13b) was isolated.
[0102]
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(CF₃CH₂)₃Si (OCH₃) (13b)
[0103]
[Production Example 14]
In a three-necked flask equipped with a sufficiently cooled reflux condenser, stirrer, and gas inlet tube, 3.0 g of metal magnesium is taken, and sufficiently replaced with dry nitrogen gas. Further, 100 ml of tetrahydrofuran, which was dehydrated and purified by refluxing with sodium metal and distillation, was taken in the reaction vessel, and mixed by stirring. While the stirring was continued, a solution in which 44.6 g of perfluorohexyl iodide was dissolved in 300 ml of the above-mentioned tetrahydrofuran was dropped into this solution. A solution of 14.8 g of dimethyldiethoxysilane dissolved in 200 ml of the above-mentioned tetrahydrofuran was added dropwise while cooling with ice while continuing to stir. After completion of the dropwise addition, reflux was carried out at the boiling point of tetrahydrofuran for 24 hours to complete the reaction. After the formed precipitate was separated by filtration, the target compound was isolated by fractional distillation. All operations were performed under a dry nitrogen gas stream. IR,¹H-NMR,^ThirteenC-NMR,²⁹Si-NMR measurement was performed to confirm that the target compound represented by the formula (14b) was isolated.
[0104]
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[CF₃(CF₂)₅] (CH₃)₂Si (OC₂H₅) (14b)
[0105]
[Production Example 15]
5.3 g of metallic magnesium and 0.05 g of iodine are placed in a three-necked flask equipped with a sufficiently cooled reflux condenser, stirrer and gas inlet tube, and sufficiently substituted with dry nitrogen gas. Further, a solution prepared by dissolving 69.2 g of perfluorobutyl iodide and 15.0 g of ethyltrimethoxylane in 500 ml of diethyl ether dehydrated and purified by refluxing and distillation with sodium metal was dropped into the reaction vessel. After completion of the dropwise addition, the mixture was left at room temperature for 2 hours while stirring to complete the reaction. After the formed precipitate was separated by filtration, the target compound was isolated by fractional distillation. All operations were performed under a dry nitrogen gas stream. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that the target compound represented by the formula (15b) was isolated.
[0106]
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[CF₃(CF₂)₃  ]₂(C₂H₅) Si (OCH₃) (15b)
[0107]
[Production Example 16]
5.6 g of metallic magnesium is placed in a three-necked flask equipped with a sufficiently cooled reflux condenser, stirrer, and gas inlet tube, and sufficiently replaced with dry nitrogen gas. Further, 100 ml of tetrahydrofuran, which was dehydrated and purified by refluxing with sodium metal and distillation, was taken in the reaction vessel, and mixed by stirring. While the stirring was continued, a solution prepared by dissolving 52.3 g of perfluoropropyl bromide in 300 ml of the above-mentioned tetrahydrofuran was dropped into this solution. Further, a solution of 11.9 g of tetrachlorosilane dissolved in 100 ml of the above-mentioned tetrahydrofuran was added dropwise while cooling with ice while continuing to stir. After completion of the dropwise addition, reflux was carried out at the boiling point of tetrahydrofuran for 24 hours to complete the reaction. After the formed precipitate was separated by filtration, the target compound was isolated by fractional distillation. All operations were performed under a dry nitrogen gas stream. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that the target compound represented by the formula (16b) was isolated.
[0108]
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[CF₃(CF₂)₂]₃SiCl (16b)
[0109]
[Production Example 17]
50.8 g of 1H, 1H, 2H, 2H-nonafluorohexyllithium was placed in a three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube sufficiently purged with dry nitrogen gas, and refluxed and distilled with sodium metal. 400 ml of dehydrated and purified diethyl ether was taken and mixed with stirring. While stirring was continued, a solution in which 16.4 g of ethyltrichlorosilane was dissolved in 100 ml of the above-mentioned diethyl ether was dropped into this solution. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then refluxed for 8 hours to complete the reaction. After the formed precipitate was separated by filtration, the target compound was isolated by fractional distillation. All operations were performed under a dry nitrogen gas stream. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that the target compound represented by the formula (17b) was isolated.
[0110]
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[CF₃(CF₂)₃(CH₂)₂]₂(C₂H₅) SiCl (17b)
[0111]
[Production Example 18]
5.8 g of metallic magnesium was placed in a sufficiently dried three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube, and sufficiently replaced with dry nitrogen gas. Further, 200 ml of diethyl ether dehydrated and generated by refluxing with sodium metal and distillation was taken into the reaction vessel and mixed with stirring. While stirring was continued, a solution prepared by dissolving 114.8 g of 1H, 1H, 2H, 2H heptadecafluorodexyl iodide in 300 ml of the above-mentioned diethyl ether was added dropwise to this solution. Further, a solution obtained by dissolving 29.7 g of diethyldimethoxysilane in 200 ml of the above-mentioned diethyl ether was added dropwise under ice-cooling while stirring. After the completion of the dropwise addition, reflux was carried out at the boiling point of diethyl ether for 24 hours to complete the reaction. After the generated precipitate was separated by filtration, fractional distillation was performed to isolate the target compound. All operations were performed under a stream of dry nitrogen gas. IR,¹H-NMR,^ThirteenC-NMR,²⁹When the Si-NMR measurement was performed, it was confirmed that the target compound represented by the formula (18b) was isolated.
[0112]
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[CF₃(CF₂)₇(CH₂)₂] [C₂H₅]₂Si (OCH₃) (18b)
<Production example of silicone>
[0113]
[Production Example 19]
In a three-necked flask equipped with a condenser and a stirrer, 64.0 g of the silicon compound of Production Example 1 and 150 ml of methyl ethyl ketone were mixed and dissolved. A solution of 9.0 g of water in 50 ml of methyl ethyl ketone was added to this solution while stirring was continued. After the addition was completed, the mixture was left at 40 ° C. for 30 minutes while stirring was continued. To this mixed solution, a solution consisting of 285.2 g of the silicon compound of Production Example 16, 40.5 g of water, 100 ml of methyl ethyl ketone, and 1.3 ml of concentrated hydrochloric acid was added, and the mixture was allowed to stand at 40 ° C. for 4 hours while further stirring. After completion of the reaction, the system was separated into two phases. The solvent phase was removed by decantation, and after washing with 5% sodium hydrogen carbonate solution and water, water was removed again by decantation and dried at 80 ° C. overnight. To isolate the polycondensate. IR,^ThirteenC-NMR,¹H-NMR,²⁹When the Si-NMR measurement was performed, this polycondensate was [｛CF₃(CF₂)₂｝₃SiO_1/2] Unit and [O_3/2SiQ²SiO_3/2] (However, Q²Is-(CH₂)₃Represents a divalent organic group represented by-. ) Was confirmed to be silicone. The obtained silicone was used as silicone 1 in Examples of cosmetics described below.
[0114]
[Production Example 20]
In a three-necked flask equipped with a condenser and a stirrer, 89.6 g of the silicon compound of Production Example 2, 48.2 g of the silicon compound of Production Example 3, 0.8 g of 3-aminopropyltrimethoxysilane, and a mixed solvent of ethyl alcohol / tetrahydrofuran (weight) 300 ml was taken at a ratio of 7/3) and mixed and dissolved. While stirring, a solution of 9.1 g of water dissolved in 100 ml of the above-mentioned mixed solvent was added to this solution. After completion of the addition, the mixture was left at 25 ° C. for 4 hours while stirring. A solution composed of 159.3 g of the silicon compound of Production Example 13, 100.8 g of water, 200 ml of the above-mentioned mixed solvent and 2.8 ml of concentrated hydrochloric acid was added to this mixed solution, and the mixture was left at 25 ° C. for 10 hours while further stirring. After completion of the reaction, the system was separated into two phases. The solvent phase was removed by decantation, and after washing with 5% sodium hydrogen carbonate solution and water, water was removed again by decantation and dried at 80 ° C. overnight. To isolate the polycondensate. IR,^ThirteenC-NMR,¹H-NMR,²⁹When the Si-NMR measurement was performed, this polycondensate was identified as [(CF₃CH₂)₃SiO_1/2] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Represents a divalent organic group represented by the formula (1a). ) Unit and [O_3/2SiQ '²SiO_3/2] (However, Q '²Is-(CH₂)₂S (CH₂)₃Represents a divalent organic group represented by-. ) Was confirmed to be silicone. The obtained silicone was used as Silicone 2 in Examples of cosmetics described below.
[0115]
[Production Example 21]
In a three-necked flask equipped with a condenser and a stirrer, 44.0 g of the silicon compound of Production Example 4, 22.8 g of tetramethoxysilane, 2.1 g of 3- (4,5-dihydroimidazole) propyltriethoxysilane and 400 ml of isopropyl alcohol were placed. Samples were mixed and dissolved. A solution of 10.1 g of water in 100 ml of isopropyl alcohol was added to this solution while stirring was continued. After completion of the addition, the mixture was left at 60 ° C. for 2 hours while stirring was continued. A solution composed of 506.8 g of the silicon compound of Production Example 14, 54.0 g of water, 200 ml of isopropyl alcohol, and 3.0 ml of concentrated nitric acid was added to this mixed solution, and the mixture was left at 60 ° C. for 16 hours while further stirring. After the completion of the reaction, the system was separated into two phases. The solvent phase was removed by decantation, and after washing with a 5% sodium hydrogen carbonate solution and water, water was removed by lyophilization to isolate a polycondensate. . IR,^ThirteenC-NMR,¹H-NMR,²⁹When a Si-NMR measurement was carried out, this polycondensate was [｛CF₃(CF₂)₅｝ (CH₃)₂SiO_1/2] Unit, [SiO₂] Unit, and [O]_3/2SiQ²SiO_3/2] (However, Q²Represents a divalent organic group represented by the formula (2a). ) Was confirmed to be silicone. The obtained silicone was used as silicone 3 in Examples of cosmetics described below.
[0116]
[Production Example 22]
In a three-necked flask equipped with a condenser and a stirrer, 76.6 g of the silicon compound of Production Example 5, 0.45 g of triethylamine, and 300 ml of ethyl cellosolve were mixed and dissolved. A solution of 3.9 g of water in 100 ml of ethyl cellosolve was added to this solution while stirring was continued. After completion of the addition, the mixture was left at 5 ° C. for 2 hours while stirring. To this mixed solution, a solution composed of 252.6 g of the silicon compound of Production Example 15, 43.2 g of water, 150 ml of ethyl cellosolve, and 3.0 ml of concentrated nitric acid was added, and the mixture was allowed to stand at 20 ° C. for 8 hours while further stirring. After completion of the reaction, the system was separated into two phases, so the solvent phase was removed by decantation, and further washed with a 5% sodium hydrogen carbonate solution and water, and then water was removed again by decantation, followed by drying at 80 ° C. all day and night. The polycondensate was isolated. IR,^ThirteenC-NMR,¹H-NMR,²⁹When a Si-NMR measurement was carried out, this polycondensate was [｛CF₃(CF₂)₃｝₂(C₂H₅) SiO_1/2] Unit and [(O_3/2Si)₃Q³] (However, Q³Represents a trivalent organic group represented by the formula (3a). ) Was confirmed to be silicone. The obtained silicone was used as a silicone 4 in the cosmetic examples described below.
[0117]
[Production Example 23]
32.2 g of the silicon compound of Production Example 6, 2.8 g of tetraethoxysilane, 0.18 g of acetic acid, and 250 ml of dimethyl sulfoxide were placed in a three-necked flask equipped with a condenser and a stirrer, and mixed and dissolved. A solution of 5.5 g of water in 50 ml of dimethyl sulfoxide was added to this solution while stirring was continued. After completion of the addition, the mixture was left at 60 ° C. for 6 hours while continuing to stir. To this mixed solution, a solution composed of 114.0 g of the silicon compound of Production Example 14, 13.4 g of water, 150 ml of dimethyl sulfoxide, and 4.0 g of citric acid was added, and the mixture was left at 60 ° C. for 18 hours while further stirring. . After completion of the reaction, the system was separated into two phases, so the solvent phase was removed by decantation, washed with a 5% sodium hydrogen carbonate solution and water, and then lyophilized to remove water to isolate a polycondensate. . IR,^ThirteenC-NMR,¹H-NMR,²⁹When a Si-NMR measurement was carried out, this polycondensate was [｛CF₃(CF₂)₅｝ (CH₃)₂SiO_1/2] Unit, [SiO₂] Unit and [(O_3/2Si)₃Q³] (However, Q³Represents a trivalent organic group represented by the formula (4a). ) Was confirmed to be silicone. The obtained silicone was used as a silicone 5 in the cosmetic examples described below.
[0118]
[Production Example 24]
In a three-necked flask equipped with a condenser and a stirrer, 88.5 g of the silicon compound of Production Example 7 and 500 ml of tetrahydrofuran were mixed and dissolved. A solution of 15.6 g of water and 1.5 ml of concentrated aqueous ammonia in 100 ml of tetrahydrofuran was added to this solution while stirring was continued. After completion of the addition, the mixture was left at 10 ° C. for 1 hour while stirring was continued. 366.1 g of the silicon compound of Production Example 17 and 45. A solution consisting of Og, 300 ml of tetrahydrofuran and 5.0 g of acetic acid was added, and the mixture was allowed to stand at 10 ° C. for 4 hours while further stirring. After completion of the reaction, the system was separated into two phases. The solvent phase was removed by decantation, and further washed with 5% sodium hydrogen carbonate solution and water. Then, water was removed again by decantation and dried at 80 ° C. overnight. To isolate the polycondensate. IR,^ThirteenC-NMR,¹H-NMR,²⁹When a Si-NMR measurement was carried out, this polycondensate was [｛CF₃(CF₂)₃(CH₂)₂｝₂(C₂H₅) SiO_1/2] Unit and [(O₃/₂Si)₃Q³] (However, Q³Represents a trivalent organic group represented by the formula (5a). ) Was confirmed to be silicone. The obtained silicone was used as silicone 6 in Examples of cosmetics described below.
[0119]
[Production Example 25]
18.1 g of the silicon compound of Preparation Example 8, 4.1 g of the silicon compound of Preparation Example 3, 0.9 g of tetramethoxysilane, 300 ml of tetrahydrofuran and 0.6 g of 3-aminopropylmethoxysilane in a three-necked flask equipped with a condenser and a stirrer. And mixed and dissolved. A solution of 6.0 g of water in 100 ml of tetrahydrofuran was added to this solution while stirring was continued. After the completion of the addition, the mixture was left at 20 ° C. for 3 hours while stirring was continued. A solution consisting of 85.3 g of the silicon compound of Preparation Example 13, 59.4 g of water, 250 ml of tetrahydrofuran and 3.0 ml of concentrated hydrochloric acid was added to this mixed solution, and the mixture was left at 20 ° C. for 12 hours while further stirring. After completion of the reaction, the system was separated into two phases. The solvent phase was removed by decantation, and further washed with 5% sodium hydrogen carbonate solution and water. Then, water was removed again by decantation and dried at 80 ° C. overnight. To isolate the polycondensate. IR,^ThirteenC-NMR,¹H-NMR,²⁹When the Si-NMR measurement was performed, this polycondensate was identified as [(CF₃CH₂)₃SiO_1/2] Unit, [SiO₂] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Is-(CH₂)₂S (CH₂)₃Represents a divalent organic group represented by-. ) Unit and [(O_3/2Si)₄Q⁴] (However, Q⁴Represents a tetravalent organic group represented by the formula (6a). ) Was confirmed to be silicone. The obtained silicone was used as silicone 7 in the cosmetic examples described below.
[0120]
[Production Example 26]
In a three-necked flask equipped with a condenser and a stirrer, 98.1 g of the silicon compound of Production Example 9, 1.7 g of tetraethoxysilane, 700 ml of a mixed solvent of isopropyl alcohol / tetrahydrofuran (7/3 by weight), and 2.1 g of morpholine were placed. , Mixed and dissolved. A solution of 3.1 g of water in 100 ml of the above-mentioned mixed solvent was added to this solution while stirring was continued. After completion of the addition, the mixture was left at 20 ° C. for 4 hours while stirring. To this mixed solution, a solution composed of 456.4 g of the silicon compound of Production Example 16, 64.8 g of water, 400 ml of the above-mentioned mixed solvent, and 7.5 ml of concentrated hydrochloric acid was added, and the mixture was left at 20 ° C. for 12 hours while further stirring. After completion of the reaction, the system was separated into two phases. The solvent phase was removed by decantation, and after washing with 5% sodium hydrogen carbonate solution and water, water was removed again by decantation and dried at 80 ° C. overnight. To isolate the polycondensate. IR,^ThirteenC-NMR,¹H-NMR,²⁹When a Si-NMR measurement was carried out, this polycondensate was [｛CF₃(CF₂)₂｝₃SiO_1/2] Unit, [(O_3/2Si)₄Q⁴] (However, Q⁴Represents a tetravalent organic group represented by the formula (7a). ) Unit and [SiO₂] Was confirmed. The obtained silicone was used as silicone 8 in Examples of cosmetics described below.
[0121]
[Production Example 27]
In a three-necked flask equipped with a condenser and a stirrer, 82.4 g of the silicon compound of Production Example 10 and 400 ml of acetone were mixed and dissolved. A solution of 21.6 g of water in 100 ml of acetone was added to this solution while stirring was continued. After the completion of the addition, the mixture was left at 20 ° C. for 1 hour while stirring was continued. To this mixed solution, a solution composed of 234.7 g of the silicon compound of Production Example 17, 36.0 g of water, 200 ml of acetone, and 7.0 ml of concentrated hydrochloric acid was added, and the mixture was allowed to stand at 20 ° C. for 4 hours while further stirring. After completion of the reaction, the system was separated into two phases. The solvent phase was removed by decantation, and after washing with 5% sodium hydrogen carbonate solution and water, water was removed again by decantation and dried at 80 ° C. overnight. To isolate the polycondensate. IR,^ThirteenC-NMR,¹H-NMR,²⁹When a Si-NMR measurement was carried out, this polycondensate was [｛CF₃(CF₂)₃(CH₂)₂｝₂(C₂H₅) SiO_1/2] Unit and [(O_3/2Si)₄Q⁴] (However, Q⁴Represents a tetravalent organic group represented by the formula (8a). ) Was confirmed to be silicone. The obtained silicone was used as silicone 9 in Examples of cosmetics described below.
[0122]
[Production Example 28]
In a three-necked flask equipped with a condenser and a stirrer, 24.9 g of the compound of Production Example 1, 61.9 g of the compound of Production Example 12, and 250 ml of tetrahydrofuran were mixed and dissolved. A solution of 16.2 g of water in 70 ml of tetrahydrofuran was added to this solution while stirring was continued. After the addition was completed, the mixture was left at 20 ° C. for 1 hour while continuing to stir. To this mixed solution, a solution composed of 469.3 g of the silicon compound of Production Example 17, 24.3 g of water, 150 ml of tetrahydrofuran, and 3 ml of concentrated hydrochloric acid was added, and the mixture was left at 20 ° C. for 8 hours while further stirring. When a small amount of water was added after the reaction, the system separated into two phases. The solvent phase was removed by decantation, and the remaining volatile components were removed by a rotary evaporator to isolate a polycondensate. IR,¹H-NMR,^ThirteenC-NMR,²⁹When a Si-NMR measurement was carried out, this polycondensate was [｛CF₃(CF₂)₃(CH₂)₂｝₂｛C₂H₅｝ SiO_1/2] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Is-(CH₂)₃Represents-. ) Unit and [O_3/2SiQ²'SiO_3/2] (However, Q²'Represents a divalent organic group represented by the formula (9a). ) Was confirmed to be silicone. The obtained silicone was used as silicone 10 in the cosmetic examples described below.
[0123]
[Production Example 29]
In a three-necked flask equipped with a condenser and a stirrer, 38.8 g of the compound of Production Example 3, 18.3 g of the compound of Production Example 11, 1.1 g of 3-aminopropyltrimethoxysilane, and 100 ml of ethyl alcohol were mixed and dissolved. A solution of 8.2 g of water in 40 ml of ethyl alcohol was added to this solution while stirring was continued. After completion of the addition, the mixture was left at 20 ° C. for 2 hours while continuing to stir. A solution consisting of 169.2 g of the silicon compound of Production Example 18, 12.2 g of water, 60 ml of ethyl alcohol, and 1.5 ml of concentrated hydrochloric acid was added to this mixed solution, and the mixture was left at 20 ° C. for 16 hours while further stirring. After the reaction, the system was separated into two phases. Therefore, the solvent phase was removed by decantation, and after washing with 5% sodium hydrogen carbonate solution and water, the remaining volatile components were removed by a rotary evaporator to isolate a polycondensate. IR,¹H-NMR,^ThirteenC-NMR,²⁹When a Si-NMR measurement was carried out, this polycondensate was [｛CF₃(CF₂)₇(CH₂)₂｝ ｛C₂H₅｝₂SiO_1/2] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Is-(CH₂)₂S (CH₂)₃Represents-. ) Unit and [O_3/2SiQ²'SiO_3/2] (However, Q²'Represents a divalent organic group represented by the formula (9a). ) Was confirmed to be silicone. The obtained silicone was used as silicone 11 in Examples of cosmetics described below.
[0124]
[Production Example 30]
In a three-necked flask equipped with a condenser and a stirrer, 57.5 g of the compound of Production Example 2, 14.7 g of the compound of Production Example 11, 4.6 g of tetramethoxysilane, 0.3 g of 3-aminopropyltrimethoxysilane, and ethyl alcohol / 200 ml of a tetrahydrofuran mixed solvent (7/3 by weight ratio) was taken and mixed and dissolved. A solution of 15.0 g of water dissolved in 50 ml of the above mixed solvent was added to this solution while stirring was continued. After completion of the addition, the mixture was left at 20 ° C. for 2 hours while continuing to stir. A solution composed of 253.4 g of the silicon compound of Production Example 14, 20.0 g of water, 100 ml of a mixed solvent at 20 ° C., and 2.5 ml of concentrated nitric acid was added to this mixed solution, and the mixture was left at room temperature for 12 hours while further stirring. After the reaction, the system was separated into two phases by adding a small amount of water. The solvent phase was removed by decantation, washed with 5% sodium bicarbonate solution and water, and the remaining volatile components were removed with a rotary evaporator to perform polycondensation. Was isolated. IR,¹H-NMR,^ThirteenC-NMR,²⁹When a Si-NMR measurement was carried out, this polycondensate was [｛CF₃(CF₂)₅｝ ｛CH₃｝₂SiO_1/2] Unit, [O_3/2SiQ²SiO_3/2] (However, Q²Represents a divalent organic group represented by the formula (1a). ) Unit, [O_3/2SiQ²'SiO_3/2] (However, Q²'Represents a divalent organic group represented by the formula (9a). ) Unit and [SiO₂] Was confirmed. The obtained silicone was used as silicone 12 in Examples of cosmetics described below.
[0125]
Next, examples of the cosmetic of the present invention containing the silicones 1 to 12 obtained in the above-mentioned respective production examples will be described. The amounts shown below are all parts by weight.
[0126]
[Examples 1 to 4] Cream
The components A and B shown in Table 1 were each heated and dissolved at 80 ° C., and then the component B was gradually added to the component A, emulsified, stirred and cooled to obtain a cream. The rate at which the component B is added to the component A is particularly important because the component A and the aqueous component (component B) containing silicone obtained in the above Production Example are hardly emulsified with each other. Was done. Further, the cream of Comparative Example 1 using the polydimethylsiloxane instead of the silicone of the production example of the cream of Example 1 whose composition is shown in Table 1 was produced in the same manner as in the above example. Further, a cream of another comparative example was prepared in the same manner as in Example 1 except that the same amount of Fomblin HC-4 (manufactured by Montefluos) was used as perfluoropolyether instead of silicone 1 in the cream of Example 1. When trying to produce, each component could not be emulsified and separated into two layers, and no cream was obtained.
[0127]
[Table 1]

[0128]
Examples 5 to 8 Foundation
Each component shown in Table 2 was weighed in a kneader, kneaded while heating to 80 ° C., packed in a gold plate, and pressure molded to obtain a foundation. In addition, the foundation of Comparative Example 2, in which polydimethylsiloxane was used in place of the silicone of Production Example in the foundation of Example 8 and whose composition is shown in Table 2, was produced in the same manner as in the above Example.
[0129]
[Table 2]

[0130]
Embodiments 9 to 12 Lip Color
The components shown in Table 3 were dissolved and dispersed by heating at 80 ° C., applied to a heating roll at 60 ° C., heated again to 90 ° C., poured into a mold, cooled and taken out to obtain a lip color. The lip color of Comparative Example 3 using a silicone varnish (Silicone KF7312F, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone having a three-dimensional structure, in place of the silicone of the lip color of Example 12 whose composition is shown in Table 3, It was manufactured in the same manner as in the above example.
[0131]
[Table 3]

[0132]
Examples 13 to 16 Hair blow spray
Each component shown in Table 4 was heated, melted and cooled, filled in a pressure-resistant container equipped with a spray nozzle, injected with natural gas and sealed to obtain a hair blow spray. The hair blow spray of Comparative Example 4 using polydimethylsiloxane (100 cs) instead of the silicone of the production example of the hair blow spray of Example 14 whose composition is shown in Table 4 was used in the same manner as in the above example. Manufactured.
[0133]
[Table 4]

[0134]
The cosmetics of the four dosage forms of the present invention obtained in each of the above Examples were compared with the cosmetics of Comparative Examples containing conventional silicones in place of the silicones of the above Production Examples. Sensory evaluations such as goodness, smoothness, moist feeling, and good makeup durability were performed.
[0135]
(1) Evaluation of cream
The sensory evaluation of the creams obtained in Examples 1 to 4 and Comparative Example 1 was performed by five specialized panelists. Evaluation items were moist feeling, water repellency when dropping water drops, good familiarity with the skin, difficulty in breaking down the makeup when the makeup was placed on top, and a good score of 5, good in the overall evaluation. Was evaluated on a five-point scale, with a score of 4, a normal score of 3, a slightly poor score of 2, and a bad score of 1. As a result, the scores of all the evaluation items were higher in the creams of all the examples than in the cream of Comparative Example 1. Table 5 shows the typical results (Example 1 and Comparative Example 1).
[0136]
[Table 5]

[0137]
From these results, it can be seen that the creams of the examples have excellent functionality in all the above-mentioned evaluation items including the water repellency as compared with the creams of the comparative examples containing the conventional silicones instead of the silicones used in the present invention. . In addition, it was confirmed that makeup was good when makeup was applied after the skin was adjusted with the cream of the example, and it was found that this cream was a basic cosmetic and also had an under makeup function.
[0138]
(2) Foundation evaluation
Sensory evaluation of the foundations obtained in Examples 5 to 8 and Comparative Example 2 was performed by five specialized panelists. The evaluation items were moist feeling, water repellency when dropping water drops, good skin familiarity, difficulty in makeup collapse, and comprehensive evaluation. Good evaluation was 5, good evaluation was 4, good evaluation was 4, and normal evaluation was 3, poor. The evaluation was performed on a five-point scale with a score of 2 and a rating of 1 for bad. As a result, the scores of all the evaluation items were higher in the foundations of all Examples than in the foundation of Comparative Example 2. Table 6 shows representative results (Example 8 and Comparative Example 2).
[0139]
[Table 6]

[0140]
From these results, it can be seen that, compared to the foundation of the comparative example containing the conventional silicone in place of the silicone used in the present invention, the foundations of the examples have excellent functionality in all the above-mentioned evaluation items including the water repellency. . In addition, the foundations obtained in Examples 5 to 8 and Comparative Example 2 were applied to the upper arm, and a test of rubbing with a finger under running water was performed. As a result, the foundation obtained in Comparative Example 2 was resistant to rubbing under running water. In comparison with the fact that the resistance was low, no drop in the foundation was observed in any of the foundations of the examples, and it was confirmed that the makeup lasted well.
[0141]
(3) Evaluation of lip color
The sensory evaluation of the lip colors obtained in Examples 9 to 12 and Comparative Example 3 was performed by five specialized panelists. The evaluation items were: difficulty in color transfer, water repellency when dropping water drops, familiarity with lips, difficulty in makeup collapse, comprehensive evaluation, good score 5, good score 4, good The evaluation was performed on a five-point scale, with a score of 3, a slightly poor score of 2, and a bad score of 1. The results were higher in all evaluation items in the lip colors of all examples than in the lip color of Comparative Example 3. Table 7 shows representative results (Example 12 and Comparative Example 3).
[0142]
[Table 7]

[0143]
From these results, it can be seen that the lip color of the example has excellent functionality in all of the above-mentioned evaluation items including water repellency as compared with the lip color of the comparative example containing the conventional silicone instead of the silicone used in the present invention. I understand. Furthermore, when the case where the lip color of Comparative Example 3 was applied and a commercially available lipstick overcoat was applied thereon and the case where only the lip color of Examples 9 to 12 were applied were compared, the difficulty of color transfer was found. The lip color of the example is superior to the combination of the comparative example and the conventional product, and the lip color of the present invention is a single product and has a function more than the combination of the conventional lip color and the lipstick overcoat. I understood.
[0144]
(4) Evaluation of hair blow spray
The sensory evaluation of the hair blow sprays obtained in Examples 13 to 16 and Comparative Example 4 was performed by five specialized panelists. The evaluation items were persistence of gloss, water repellency when water drops were dropped, good combability, difficulty of set collapse, and comprehensive evaluation. Good evaluation was 5, good evaluation was 4, good evaluation was 4, and normal evaluation was 3, slightly poor. Was given on a five-point scale with a score of 2 and a bad score of 1. The results were higher in all the evaluation items in the hair blow sprays of Comparative Example 4 in the hair blow sprays of all Examples. Table 8 shows the representative results (Example 14 and Comparative Example 4).
[0145]
[Table 8]

[0146]
From these results, the hair blow sprays of the examples have excellent sensuality in all the above-mentioned evaluation items including water repellency as compared with the hair blow sprays of the comparative examples including the conventional silicone instead of the silicone used in the present invention. It turns out that it has. In addition, when the durability of the combability of the hair blow sprays obtained in Examples 13 to 16 and Comparative Example 4 was evaluated, the combability when the hair blow spray of the example was used was compared with the comparative example. It lasted longer than when using a hair blow spray.
[0147]
Comprehensively evaluating these results, the cosmetic of the present invention is superior to conventional silicone-containing cosmetics in terms of water repellency and long-lasting makeup, and blends well with skin and hair to give a smooth and moist feeling. It can be seen that the effect is excellent.
[0148]
【The invention's effect】
The cosmetic of the present invention has excellent compatibility with many components usually blended in cosmetics, and also contains a silicone having excellent water repellency and flexible film forming ability, so that it takes various dosage forms. It has excellent water repellency and good makeup lasting, and is excellent in the effect of blending well with skin and hair to give smoothness and moist feeling.

Claims (6)

General formula (I):
Q ⁿ (SiO _3/2 ) _n
(However, ^{Q n} is 1) an alkylene group; 2) a polymethylene group; 3) a phenylene group; 4) an arylene group; 5) the 1) to 4) hydrogen atoms by alkyl groups, a phenyl group, an aryl group , An alkylene group, a polymethylene group, a phenylene group, and an arylene group; a group substituted with at least one of the above groups; 6) ethers, thioethers, esters, ketones, amides, imides in the structure of the above groups 1) to 5) A group comprising at least one functional group selected from the group consisting of: an amine and an imine; and 7) a group wherein the hydrogen atom of the groups 1) to 6) is replaced by a chlorine atom or a bromine atom. It represents an n-valent organic group which is a seed, and n represents any one of integers of 2 to 4. At least one of the units represented by the formula (II) is a main constituent unit, and the terminal is represented by the formula (II):
(R ¹ ) ₃ SiO _1/2
(However, R ¹ may be the same or different from each other, and represents a hydrocarbon group or a hydrocarbon group in which at least a part of a hydrogen atom is substituted with a fluorine atom, and among three R ¹ s, At least one must be the above-mentioned fluorine-substituted hydrocarbon group.) A cosmetic containing silicone blocked with a unit represented by the formula: Main constituent units, cosmetic of claim 1, wherein the general formula (I) containing units introduced a divalent organic group consisting of diamide dicarboxylic acid as Q ⁿ in the silicone. The main constituent units in the silicone, divalent consisting diamide dicarboxylic acid in formula (I) units were introduced a divalent organic group consisting of diamide dicarboxylic acid as Q ⁿ in the general formula (I) as Q ⁿ The cosmetic according to claim 1, comprising a unit into which a divalent organic group other than the organic group is introduced. R ¹ of the general formula (II) in the silicone is ^one of a group consisting of an alkyl group, a phenyl group, an aryl group, and a group in which at least a part of hydrogen atoms of these groups is substituted with a fluorine atom. The cosmetic according to any one of claims 1 to 3. The silicone, further SiO ₂ ^units, any one of claims 1 to 4, a silicone containing a molar ratio 3/2 or less with respect to the unit represented by Q _{n (SiO 3/2) n} as the main constituting unit 2. The cosmetic according to item 1. The cosmetic according to any one of claims 1 to 5, wherein the content of the silicone is 0.1 to 80% by weight based on the total amount of the cosmetic.