JP3799171B2 - Dissimilar metal-containing organic silicone resin and cosmetics - Google Patents

Description

【００５８】
Ｉ・・・不溶 Ｓ・・・可溶
＜２．７ 屈折率＞
ＴＭＳＴ及びＴＭＳにつき、精密アッペ屈折率計３Ｔ（（株）アタゴ製）を用いて２０℃で測定した。
＜２．８ 透明性試験＞
ＴＭＳＴ及びＴＭＴにつき、以下の方法に従って透明性を評価した。
【００５９】
先ず、ＴＭＳＴの５０重量％オクタメチルシクロテトラシロキサン溶液及びＴＭＴの５０重量％オクタメチルシクロテトラシロキサン溶液を、それぞれ厚さ３mmの石英ガラス板上に塗布量が１．５mg／cm²になるように塗布し、室温（２３℃）で２４時間自然乾燥させて、前記石英ガラス板上にＴＭＳＴ及びＴＭＴのフィルムを形成した。
【００６０】
次いで、印刷された文字の上に前記石英ガラス板を置き、ＴＭＳＴフィルムを通したときの文字の見え方とＴＭＴフィルムを通したときの文字の見え方とを比較して透明性を評価した。ＴＭＳＴフィルムを通して見た文字と、ＴＭＴフィルムを通して見た文字とを図６に示す。尚、図６におけるＡはＴＭＳＴフィルムを通して見た文字を示し、Ｂは、ＴＭＴを通して見たた文字を示す。
＜２．９ 撥水性試験＞
ＴＭＳＴにつき、以下のようにして撥水性を評価した。前記石英ガラス板上に形成されたＴＭＳＴフィルム、及び表面が清浄な石英ガラス板の両方に、室温（２３℃）下において１０mlのビュレットを用いて３cmの高さから水滴を１滴落とし、その水滴の状態を目視で観察した。このときの水滴の状態を図７に示す。図７において、Ａは、ＴＭＳＴフィルム上の水滴の様子を示し、Ｂは石英ガラス面上の水滴の様子を示す。
＜２．１０ 紫外線吸光特性試験＞
ＴＭＳＴ、ＴＭＳ、及びシア脂のそれぞれにつき、紫外分光光度計ＵＶ−２２００（（株）島津製作所製）を用い、濃度０．４ｇ／Lのイソプロパノール溶液の紫外線領域（２９０〜４００ｎｍ）でのＵＶスペクトルを、厚さ１０mmのセルを用いて２０℃で測定した。測定されたＵＶスペクトルを図８に示す。図８において、ＡはＴＭＳＴのＵＶスペクトルを示し、Ｂはシア脂のＵＶスペクトルを示し、ＣはＴＭＳのＵＶスペクトルを示す。
＜２．１１ 塑性と付着性試験＞
ＴＭＳＴ及びＴＭＳにつき、レオメータ ＲＴ−２００２Ｄ・Ｄ（不動工業（株）製）を用い、先端にステンレス球が形成されたアダプタによって歪みを加えていき、アダプタに設定荷重が加わるまでの時間を測定して塑性を評価した。そして、設定荷重が加えられた前記アダプタをＴＭＳＴ又はＴＭＳから引き剥がすのに必要な力と時間とを測定して付着性を評価した。
【００６１】
測定方法： ＴＭＳＴ及びＴＭＳをそれぞれ内径３１，０mmの円筒状のガラスセル内に１０mmの高さ迄流し込み、セルを密閉して水平な場所で２４時間静置した。前記レオメータの試料台に先のガラスセルを固定し、試料台を一定速度で上昇させ、前記アダプタに設定荷重が加わったら直ちに試料台を一定速度で下降させて、これらの一連の操作においてアダプタに加えられる荷重の推移を連続的に記録した。結果を図９に示す。図９においてＡは、ＴＭＳＴにおける荷重の推移を示し、ＢはＴＭＳにおける荷重の推移を示す。
【００６２】
測定条件：テーブル速度…２cm／分（上昇時、下降時とも）、荷重…４．９×１０^-2Ｎ、荷重付加保持時間…０．０秒、測定温度…２３℃、アダプタ…ステンレス製剛体球（直径６mm）付ステンレス製シリンダロッド（直径２mm、長さ６３mm）。
＜２．１２ 転写防止試験＞
ＴＭＳＴ及び他の成分を、表２に示される配合組成に従って配合し、口紅Ａを調製した。一方、ＴＭＳＴを配合しない以外は前記口紅と同一の配合組成を有する口紅Ｂを調製した。前記口紅Ａ及び口紅Ｂの何れかを唇に塗布した後、室温で５分間自然乾燥させ、紅茶茶碗への口紅の二次転写を目視によって観察した。尚、前記転写防止試験は、専門パネラーによるブラインド試験として実施した。
【００６３】
【表２】

＜３．結果＞
＜３．１ 表面観察＞
図１に示された電子顕微鏡写真から明らかなように、ＴＭＳＴの表面は平滑であり、何らの粒子も凹凸も確認されなかった。このことから、前記ＴＭＳＴには形態的な成分偏析はなく、ＴＭＳＴは良好な連続性を有するフィルムに形成することができることが判る。
＜３．２ 定性分析＞
図２に示されたＴＭＳＴの定性分析チャートは、ＴＭＳＴからＳｉ及びＴｉの両方が検出されたことを示している。又、図３に示されたマッピング画像から、Ｓｉ及びＴｉの何れもイメージ像のばらつきが均一であることが判った。これらの結果から、ＴＭＳＴ中においては、Ｓｉ及びＴｉの何れも、顕著な偏析を示すことなく均一に分散されていることが判る。
＜３．３ 定量分析＞
誘導結合高周波プラズマ発光分析装置によるＴＭＳＴの定量分析の結果から、ＴＭＳＴ中には、Ｔｉ原子が５．４重量％（ＴｉＯ₂換算で９．０重量％、即ち２４．５０×０．０９＝２．２４ｇ）含まれていることが判った。実施例１におけるＴＭＳＴの調製においては、チタニウムイソプロポキシドの仕込量（４．５ｇ）から算出されるＴＭＳＴ中のＴｉ量の理論値は、ＴｉＯ₂に換算して２．１ｇである。よって、前記定量分析の結果から求められたＴＭＳＴ中のＴｉ量は、理論値の１０６％になるから、ＴｉＯ₂構造はほぼ定量的にＴＭＳＴに取り込まれていると考えられる。又、ＴＭＳＴを構成する金属元素のモル比は、Ｔｉ／Ｓｉ＝０．１４であることが判った。
＜３．４ 構造解析＞
(a)ＩＲスペクトル
図４に示されたＴＭＳＴ及びＴＭＳの何れのＩＲスペクトルにおいても、波数１０８０cm^-1にＳｉ−Ｏ−Ｓｉに帰属されるピークが認められ、波数８４０cm^-1にトリメチルシリル基に帰属される吸収が認められた。この結果から、ＴＭＳＴもＴＭＳと同様、分子中に構成単位［（ＣＨ₃）₃ＳｉＯ_1/2］及び［ＳｉＯ₂］を有することが判る。更に、ＴＭＳＴにおいては、波数９６０cm^-1付近に、ＴＭＳにおいては見られなかったＴｉ−Ｏ−Ｓｉに帰属されるピークが観測された。この結果から、ＴＭＳＴ中のＴｉ原子がＯ原子を介してＳｉ原子と化学的に結合していることは明らかであると考えられる。
【００６４】
(b) ＮＭＲスペクトル
図５から明らかなように、ＴＭＳＴ及びＴＭＳの何れにおいても、＋１１ｐｐｍ付近及び−１１０ｐｐｍ付近に幅広いピークが認められた。ここで、²⁹Ｓｉ−ＮＭＲにおいては、＋１１ｐｐｍ付近のピークは［（ＣＨ₃）₃ＳｉＯ_1/2］単位に対応するピークであり、−１１０ｐｐｍ付近のピークは三次元架橋フレームワーク（［ＳｉＯ₂］単位）に対応するピークであることが知られている。よって、図５のＮＭＲスペクトルから、前記ＴＭＳＴは、ＴＭＳと同様に［（ＣＨ₃）₃ＳｉＯ_1/2］単位と［ＳｉＯ₂］単位とを備えていることが明らかである。そして、ＴＭＳＴがＴｉ−Ｏ−Ｓｉ結合を有することは、前記ＩＲスペクトルに示されている。前記ＩＲスペクトルとＮＭＲスペクトルとの結果から、ＴＭＳＴは、主に［（ＣＨ₃）₃ＳｉＯ_1/2］単位と［ＳｉＯ₂］単位と［ＴｉＯ₂］単位とから構成されていると考えることができる。
【００６５】
尚、前記図５のＮＭＲスペクトルから、＋１１ｐｐｍ付近のピークと−１１０ｐｐｍ付近のピークとの面積比を計算し、その面積比から［（ＣＨ₃）₃ＳｉＯ_1/2］単位に対応するＳｉ原子と、［ＳｉＯ₂］単位に対応するＳｉ原子との割合を計算したところ、ＴＭＳでは０．９：１．１であったのに対し、ＴＭＳＴにおいては、１．１：０．９であった。この結果と、前記誘導結合高周波プラズマ発光分析によって求められたＴＭＳＴ中のＳｉに対するＴｉのモル比０．１４を合わせ、ＴＭＳＴにおける各構成単位の比率を算出したところ、
［（ＣＨ₃）₃ＳｉＯ_1/2］：［ＳｉＯ₂］：［ＴｉＯ₂］
＝１．４：１．２：０．４
と算定された。尚、前記式において、［（ＣＨ₃）₃ＳｉＯ_1/2］は［（ＣＨ₃）₃ＳｉＯ_1/2］構造のモル比を、［ＳｉＯ₂］は［ＳｉＯ₂］構造のモル比を、［ＴｉＯ₂］は［ＴｉＯ₂］構造のモル比を示す。
＜３．５ 分子量測定＞
高速液体クロマトグラフを用いて分子量を測定した結果、ＴＭＳＴの重量平均分子量は２，１００であり、重量平均分子量／数平均分子量で示される多分散度は１．５であった。これに対して、ＴＭＳの重量平均分子量は２，５００であり、重量平均分子量／数平均分子量で示される多分散度は１．３であった。
＜３．６ 溶解性試験＞
前記表１から明らかなように、ＴＭＳＴは、ＴＭＳと同様に、水及びメタノールには溶解しなかったものの、エタノール、イソプロパノール、トルエン、ベンゼン、ヘキサン、軽質イソパラフィン、各種エステル、及びオクタメチルシクロテトラシロキサン等各種溶媒に溶解することが判った。これは、ＴＭＳＴの基本的骨格がＴＭＳの基本骨格に類似し、ＴＭＳＴにおける［ＴｉＯ₂］はＴＭＳＴの溶解性に対して顕著な影響を及ぼしていない故であると考えられる。
＜３．７ 屈折率測定＞
屈折率測定の結果、ＴＭＳＴは、屈折率（２０℃）が１．４３２であり、ＴＭＳは、屈折率（２０℃）が１．４０９であることが判った。ＴＭＳＴがＴＭＳと比較して大きな屈折率を示した理由としては、ＴＭＳＴがその構造中にＴｉＯ₂構造を有していることが考えられる。これは、ルチル型ＴｉＯ₂において２．７６、アナターゼ型ＴｉＯ₂において２．５２と、ＴｉＯ₂は、ＳｉＯ₂の屈折率１．５５よりも高い屈折率を有していることからも支持される。
＜３．８ 透明性試験＞
図６から明らかなように、ＴＭＳＴは、ＴｉＯ₂を９．０重量％も含有しているにもかかわらず、ＴＭＳＴのフィルムを通して見た文字は、フィルムを形成しなかった石英ガラス板を通して見た文字と同様に明瞭であった。これに対して、ＴＭＴのフィルムは白色不透明であり、前記ＴＭＴのフィルムを通して見た文字はぼやけていた。これは、ＴＭＳＴにおいては、ＴｉＯ₂がＴｉ−Ｏ−Ｓｉ結合を介してトリメチルシロキシケイ酸骨格に結合し、ポリマー構造の一部を形成していることによるものと考えられる。
＜３．９ 撥水性試験＞
図７に示されるように、ＴＭＳＴフィルム上における水滴の接触角は９０°以上あった。これに対して、表面が清浄な石英ガラス板における水滴の接触角は約３０°程度に過ぎなかった。このことから、ＴＭＳＴフィルムは撥水性に優れていることが明らかである。これは、ＴＭＳＴのポリマー構造中に包含されるトリメチルシリル基がフィルム表面に配列することによると考えられる。
＜３．１０ 紫外線吸光特性試験＞
図８に示されるように、紫外線領域（２９０〜４００nm）においてＴＭＳには殆ど吸収が見られなかったのに対し、ＴＭＳＴにおいては、３４０nm以下の波長領域において著しい吸収を示した。前記波長領域におけるＴＭＳＴの吸収は、紫外線吸収能を有することで知られる天然植物性油脂であるシア脂と比較しても高かった。このことから、ＴＭＳＴが著しい紫外線遮蔽能を有することは明らかである。尚、ＴＭＳＴの吸収端は約３７０nmであり、これはルチル型ＴｉＯ₂の４１０nm及びアナターゼ型ＴｉＯ₂の３９０nmと比較して短波長側であった。
＜３．１１ 塑性と付着性試験＞
(a)塑性試験
図９に示された塑性と付着性試験の結果から明らかなように、ＴＭＳＴでは、アダプタが試料に接触した後、直ちに設定荷重が加わった。これに対してＴＭＳでは、アダプタが試料に接触した後設定荷重が加わる迄８秒を要し、試料中にアダプタがより深く貫入した。
(b)付着性試験
前記図９に示されるように、ＴＭＳＴにおいては、付着力は８．６×１０^-2Ｎと高かったものの、引き剥がしには７秒間しか要しなかった。これに対して、ＴＭＳにおいては、付着力は３．３×１０^-2Ｎと低かったものの、引き剥がしには８０秒間と長時間を要した。更に、ＴＭＳにおいては、引き剥がし後、アダプタに大量に試料が付着していた。
(c)考察
前記塑性試験の結果から、ＴＭＳＴは、ＴＭＳに類似するポリマー骨格を有し、ＴＭＳと比較して分子量が若干小さいにもかかわらず、塑性変形が起こりにくく硬度の高い膜を形成し得ることが判った。又、前記付着性試験においては、ＴＭＳＴは、ＴＭＳと比較して、アダプタから引き離す瞬間には大きな力が必要なものの、引き剥がし時間が短く、アダプタへの付着が少ないという結果を示した。この結果から、ＴＭＳＴはＴＭＳと比較してべたつき感を呈し難いポリマーであることが判った。これは、ＴＭＳＴのフィルムとＴＭＳのフィルムとについて触感を比較したところ、ＴＭＳＴのフィルムの方がべたつきが弱かったことと一致すると考えられる。これは、Ｔｉ−Ｏ結合はＳｉ−Ｏ結合と比較してイオン結合性が強い故に、Ｔｉ−Ｏ結合を有するＴＭＳＴでは、Ｔｉ−Ｏ結合を有しないＴＭＳと比較してポリマーが緻密化されたことによると考えられる。
＜３．１２ 転写防止試験＞
ＴＭＳＴを７．５重量％配合した口紅においては、唇から紅茶茶碗への口紅の転写は殆ど見られなかった。これに対し、ＴＭＳＴを配合しなかった口紅においては、紅茶茶碗に唇の跡がはっきり残った。これは、ＴＭＳＴを配合した口紅においては、唇の表面にべたつきの極めて少ない保護被膜が形成されたことによると考えられる。この結果から、口紅にＴＭＳＴを配合することにより、転写防止効果に優れた口紅が得られることが判る。
＜４．総括＞
実施例１において調製されたＴＭＳＴは、透明性に優れ、汎用の化粧品基剤に対する溶解性が良好であり、更に、従来化粧料に広く用いられてきた比較例１のＴＭＳには見られない高い屈折率及び高い紫外線遮蔽能を有するという特長を有する。又、ＴＭＳＴにいは、べたつきの少ない皮膜が得られるという特長、及び前記特長に関連して、口紅等の化粧料に配合することによって転写防止効果に優れた化粧料が得られるという特長を有する。
【００７３】
【発明の効果】
本発明によれば、使用感が良好で、自然な仕上がり感を有し、皮脂や汗、あるいは他の化粧料の油分などによって生じる化粧くずれを効果的に防止することができ、優れた化粧効果持続性を有し、衣服などへの転写防止効果に優れた化粧料を提供することができる。
【００７４】
本発明の化粧料においては、異種金属含有有機シリコーン樹脂を、例えば、Ｍ単位とＱ単位とを有する非置換型有機シリコーン樹脂中のケイ素元素をケイ素以外の金属元素で置換することにより得ることができ、この異種金属含有有機シリコーン樹脂を被膜形成剤として採用することにより、被膜を緻密化することができるので、従来の非置換型有機シリコーン樹脂特有のべたつき感を抑制することができ、かつ化粧料塗布膜の被膜強度を増大させることができる。また、本発明においては、前記異種金属含有有機シリコーン樹脂の屈折率を増加させることができ、化粧料に配合される他の原料、特に、屈折率の高い粉体成分との屈折率差を減少させることができるので、化粧料塗布膜の仕上がり感を向上させることができる。
【００７５】
さらに本発明の化粧料においては、前記異種金属含有有機シリコーン樹脂における金属−酸素結合のイオン結合性を増大させることにより、化粧料塗布膜を緻密化することが可能となる。また、その結果として、非置換型有機シリコーン樹脂特有のべたつき感を抑制することができ、且つ、化粧料塗布膜の被膜強度を増大させることができる。
【図面の簡単な説明】
【図１】図１は、走査型電子顕微鏡ＪＳＭ−Ｔ２２０（日本電子（株）製）を用いて撮影したＴＭＳＴフィルムの表面の電子顕微鏡写真である。
【図２】図２は、ＴＭＳＴにつきエネルギー分散型Ｘ線分光器を用いて測定したエネルギー分散型Ｘ線分光スペクトルである。
【図３】図３は、ＴＭＳＴについて前記エネルギー分散型Ｘ線分光分析の結果から作成され、Ｓｉ及びＴｉの存在確率の大小を表すマッピング画像である。
【図４】図４は、ＴＭＳＴ及びＴＭＳのＩＲスペクトルである。
【図５】図５は、ＴＭＳＴ及びＴＭＳの²⁹ＳｉＮＭＲスペクトルである。
【図６】図６は、ＴＭＳＴフィルムを通して見た文字、及びＴＭＴフィルムを通して見た文字の写真である。
【図７】図７は、石英ガラス板上に形成されたＴＭＳＴフィルム、及び表面が清浄な石英ガラス板の両方における水滴の状態を示す写真である。
【図８】図８は、ＴＭＳＴ、シア脂、及びＴＭＳのＵＶスペクトルである。
【図９】図９は、ＴＭＳＴ及びＴＭＳについての塑性・付着性試験における荷重の推移を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dissimilar metal-containing organosilicone resin and a cosmetic, and more particularly to a novel dissimilar metal-containing organosilicone resin and a cosmetic containing the dissimilar metal-containing organosilicone resin. In particular, the present inventionWater resistance, sweat resistance, oil resistance, good feeling when applying cosmetics, and good finish, natural finish after applying cosmetics, good skin feel, good adhesion to skin, lasting cosmetic effect The present invention relates to makeup cosmetics and skin cosmetics and other cosmetics that are excellent in properties and transfer prevention effects.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, cosmetics include makeup cosmetics and skin cosmetics, for example. Examples of the makeup cosmetics include solid foundations, solid eye shadows, oily foundations, lipsticks, and emulsified foundations. In these makeup cosmetics, various powder components, oily components, aqueous components, etc., regardless of the form, for the purpose of satisfying the user's preference such as color tone, feeling of use, finish Are combined in an appropriate combination. However, in these makeup cosmetics, common problems of users include, for example, problems caused by sebum and sweat, or oily components of other cosmetics, for example, problems of mottled cosmetics, In addition, there is a problem of makeup loss that causes makeup to break down due to warp or flow. In particular, there is an opportunity for the cosmetic coating film formed by applying cosmetics to be exposed to sweat and water, such as during rain, snow, hot and humid in the summer, and vacations at the pool and the beach. In many cases, this problem becomes more serious. Also, in skin cosmetics, the fact that cosmetics run off due to sweating, water work, etc. is also a serious problem, and there is an urgent need for imparting high durability to a cosmetic coating film by a film forming agent. Yes.
[0003]
For the purpose of improving the durability of the cosmetic coating film, it has been proposed to use a cellulose derivative as a film forming agent (Japanese Patent Laid-Open No. 8-175929). A sufficiently satisfactory film could not be formed.
[0004]
Further, it has been proposed to use an organic silicone resin as a film forming agent using ester oil or volatile silicone oil in make-up cosmetics (Japanese Patent Publication No. 6-72085, Japanese Patent Laid-Open No. 8-143426). Publication). Furthermore, with regard to skin cosmetics, it has been proposed to form a protective film against the skin by using an organosilicone resin as a film forming agent to effectively protect the skin from water work (Japanese Patent Publication No. 6-15448). Issue gazette). There are also proposals for imparting more oil repellency by modifying an organic silicone resin or the like used as a film-forming agent with a fluorine substituent (Japanese Patent Laid-Open Nos. 1-83086 and 5-78491). Publication, JP-A-6-135818, JP-A-7-233027).
[0005]
In these proposals, for example, (R)_ThreeSiO_1/2Unit represented by (R)₂Unit represented by SiO, RSiO_3/2Units represented by₂An organosilicone resin composed of units appropriately selected from the group consisting of units represented by: and a side chain or terminal of the organosilicone resin, or (R)_ThreeSiO_1/2And the unit represented by (R)₂Examples of the film forming agent include fluorine-substituted silicones in which a fluorine substituent is introduced into the side chain or terminal of a polymer silicone having a unit represented by SiO (wherein R represents an organic group).
[0006]
However, most of these organic silicone resins and fluorine group-substituted silicones are two-dimensional silicones having a two-dimensional (linear) molecular structure, and three-dimensional silicones having a three-dimensional molecular structure. However, since the network structure is cleaved by the organic group and the continuity of the molecule is lowered, the resulting water-repellent (or oil-repellent) coating is flexible but has insufficient coating strength, and there is a problem with the durability of the coating There is. That is, when blending the film-forming agent in cosmetics, increasing the blending amount of the film-forming agent to supplement the durability and sustain the cosmetic effect, the cosmetic coating film is unique to silicone oil. It exhibits glare and the sense of unity between the skin and the cosmetic coating film is lost, making it difficult to obtain a natural finish. In addition, the coating film of the organic silicone resin-blended cosmetic compounded with the organic silicone resin as a film forming agent has a strong stickiness, and when clothing or the like comes into contact with the coated film, the secondary adhesion of the cosmetic material to the contact portion Happens. In addition, SiO in the organic silicone resin₂By increasing the unit ratio, a certain degree of coating strength can be obtained, but sufficient coating strength cannot be obtained.
[0007]
Based on such circumstances, the present inventor provides a cosmetic material that has a good feeling of use and a finished feeling, is excellent in water repellency and oil repellency, and has a long-lasting makeup effect (makeup breakage prevention effect) and transfer prevention effect. As a result of earnest research for the purpose of obtaining, for example, a specific amount of a dissimilar metal-containing organosilicone resin in which the silicon atom of the organosilicone resin is partially substituted with a metal atom other than silicon By doing so, it has a good spread, a refreshing feeling of use, a good feeling of finish, excellent water repellency and oil repellency, and further, makeup loss caused by sebum, sweat and other cosmetic oils, etc. It has been found that a cosmetic material excellent in the effect of preventing and the effect of preventing secondary adhesion to clothing and cups can be obtained, and the present invention has been completed based on this finding.
[0008]
An object of this invention is to solve the conventional problems in cosmetics.
[0009]
The object of the present invention is to have good water resistance, sweat resistance, oil resistance, a feeling of use at the time of applying cosmetics, and a feeling of finishing, and the finish after applying the cosmetics is natural and has a feeling of bare skin. Another object of the present invention is to provide cosmetics such as make-up cosmetics and skin cosmetics which have good properties and are excellent in cosmetic effect persistence and transfer prevention effect.
[0010]
[Means for Solving the Problems]
  Means for solving the above problems is R.¹ _ThreeSiO_1/2(However, R¹Represents a hydrocarbon group having 1 to 6 carbon atoms. M unit represented by₂And the ratio of the number of moles to the number of moles of the Q unit is 0.001 to 0.5.TiO ₂ unitAnd containing 0.5 to 80% by weight of a dissimilar metal-containing organosilicone resin having a weight average molecular weight of 1,000 to 100,000.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, the configuration of the present invention will be described in detail.
  The cosmetic of the present invention comprises an M unit, a Q unit,TiO ₂ unitAnd 0.5 to 80% by weight of a dissimilar metal-containing organosilicone resin.
[0012]
Examples of the M unit include a general formula a; R^a _ThreeSiO_1/2(However, R^aRepresents an organic group. And a unit represented by general formula 1; R¹ _ThreeSiO_1/2(However, R¹Represents at least one selected from the group consisting of a hydrocarbon group having 1 to 6 carbon atoms, a phenyl group, and a fluoroalkyl group. ). R in the M unit represented by the general formula 1¹Examples of the hydrocarbon group when is a hydrocarbon group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group.
[0013]
The Q unit is SiO.₂Unit. Furthermore, the Q unit is a unit having a structure in which one oxygen atom is bonded to each of four bonds of Si atoms, and each oxygen atom has one other bond. .
[0014]
MeO_{A / 2}Examples of Me in the unit (where Me represents a metal element other than silicon and A represents the oxidation number of the metal element) include metal elements such as IIb group elements, IIIb group elements, and IVa group elements. be able to. As preferable Me, for example, an element capable of forming a metal oxide widely used in cosmetics from the viewpoint of safety and capable of obtaining a relatively strong covalent bond with an oxygen atom is used. Examples thereof include at least one metal element selected from the group consisting of Ti, Zn, Zr, and Al. MeO_{A / 2}Specifically, for example, TiO₂, ZnO, ZrO₂, Al₂O_ThreeEtc.
[0015]
The different metal-containing organosilicone resin preferably further has at least one unit structure selected from the group consisting of D units and T units.
[0016]
Examples of the D unit include a general formula b; R^b ₂SiO (however, R^bRepresents an organic group. And a unit represented by general formula 2; R² ₂SiO (however, R²Represents at least one selected from the group consisting of a hydrocarbon group having 1 to 6 carbon atoms, a phenyl group, and a fluoroalkyl group. ). R in the D unit represented by the general formula 2²Examples of the hydrocarbon group when is a hydrocarbon group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group.
[0017]
Examples of the T unit include a general formula c; R^cSiO_3/2(However, R^cRepresents an organic group. And a unit represented by general formula 3; R^ThreeSiO_3/2(However, R^ThreeRepresents at least one selected from the group consisting of a hydrocarbon group having 1 to 6 carbon atoms, a phenyl group, and a fluoroalkyl group. ). R in T unit represented by general formula 3^ThreeExamples of the hydrocarbon group when is a hydrocarbon group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group.
[0018]
The different metal-containing organosilicone resin includes, for example, a silicon compound that can form the M unit, a silicon compound that can form the Q unit, and the MeO._{A / 2}It can be easily obtained by reacting a metal compound other than a silicon compound capable of forming a unit. The dissimilar metal-containing organosilicone resin further includes a silicon compound that can form the M unit, a silicon compound that can form the Q unit, and a silicon compound that can form the D unit. A silicon compound capable of forming the T unit, and the MeO._{A / 2}It can also be easily obtained by using a metal compound other than a silicon compound capable of forming a unit.
[0019]
Examples of the silicon compound include a hydrolyzable silicon compound having a hydrolyzable group, and examples of the metal compound other than the silicon compound include a hydrolyzable heterogeneous metal compound having a hydrolyzable group. Etc.
[0020]
Examples of the silicon compound that can form the M unit include a general formula aX; R^a _ThreeSiX (however, R^aRepresents an organic group, and X represents a hydrolyzable group. And a hydrolyzable silicon compound represented by the general formula 1X; R¹ _ThreeSiX¹(However, R¹Is R in the general formula 1¹Represents the same group as X¹Represents at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group. ) Can be mentioned. Specific examples of the silicon compound capable of forming the M unit include (CH_Three)_ThreeSiCl, (CH_Three)_ThreeSiOCH_Three, (CH_Three)_ThreeSiOC₂H_Five, (CH_Three)_ThreeSiOC_ThreeH₇, And (CH_Three)_ThreeSiOSi (CH_Three)_ThreeEtc.
[0021]
Examples of the silicon compound that can form the D unit include a general formula bX; R^b ₂SiX₂(However, R^bRepresents an organic group, and X represents a hydrolyzable group. And a hydrolyzable silicon compound represented by the general formula 2X;² ₂SiX² ₂(However, R²R in the general formula 2²Represents the same group as X²Represents at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group. And hydrolyzable silicon compounds represented by Specific examples of the silicon compound that can form the D unit include (CH_Three)₂SiCl₂, (CH_Three)₂Si (OCH_Three)₂, (CH_Three)₂Si (OC₂H_Five)₂, And (CH_Three)₂Si (OC_ThreeH₇)₂Etc.
[0022]
Examples of the silicon compound that can form the T unit include a general formula cX; R^cSiX_Three(However, R^cRepresents an organic group, and X represents a hydrolyzable group. And a hydrolyzable silicon compound represented by the general formula 3X; R^ThreeSiX^Three _Three(However, R^ThreeR in the general formula 3^ThreeRepresents the same group as X^ThreeRepresents at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group. And hydrolyzable silicon compounds represented by Specific examples of the silicon compound that can form the T unit include CH._ThreeSiCl_Three, CH_ThreeSi (OCH_Three)_Three, CH_ThreeSi (OC₂H_Five)_ThreeAnd CH_ThreeSi (OC _Three H ₇ )_ThreeEtc.
[0023]
Examples of the silicon compound that can form the Q unit include a general formula sX; SiX_Four(Wherein X represents a hydrolyzable group), and a hydrolyzable silicon compound represented by formula 4X; SiX is preferred.^Four _Four(However, X^FourRepresents at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group. And hydrolyzable silicon compounds represented by Specific examples of the silicon compound capable of forming the Q unit include, for example, SiCl._Four, Si (OCH_Three)_Four, Si (OC₂H_Five)_Four, Si (OC_ThreeH₇)_FourAnd water glass.
[0024]
MeO_{A / 2}Examples of metal compounds other than silicon that can form units include, for example, the general formula mX; MeX_A(Wherein Me represents a metal element other than silicon, A represents the oxidation number of the metal element, and X represents a hydrolyzable group). Is the general formula 5X; TiX^Five _FourA hydrolyzable titanium compound represented by the general formula 6X; ZnX⁶ ₂A hydrolyzable zinc compound represented by the general formula 7X; ZrX⁷ _FourA hydrolyzable zirconium compound represented by the general formula 8X; AlX⁸ _ThreeA hydrolyzable aluminum compound represented by the formula (X^Five, X⁶, X⁷And X⁸Represents at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group. And the like. MeO_{A / 2}Specific examples of the metal compound that can form a unit include, for example, TiCl._Four, Ti (OCH_Three)_Four, Ti (OC₂H_Five)_Four, Ti (OC_ThreeH₇)_Four, Ti (OC_FourH₉)_FourZn (OC₂H_Five)₂, Zr (OCH_Three)_Four, Zr (OC₂H_Five)_Four, Zr (OC_ThreeH₇)_Four, Zr (OC_FourH₉)_Four, Al (OCH_Three)_Three, Al (OC₂H_Five)_Three, Al {OCH (CH_Three)₂}_Three, Al (OC_FourH₉)_ThreeEtc.
[0025]
The dissimilar metal-containing organosilicone resin of the present invention is, for example, a hydrolyzable silicon compound represented by the general formula aX and a silicon compound that forms the M unit, and a general formula sX that forms the Q unit. Obtained by combining these hydrolyzable silicon compounds and the hydrolyzable heterogeneous metal compound by at least one of hydrolysis reaction, dealcoholization reaction, dehydration condensation reaction and the like. Can do.
[0026]
In addition to the silicon compound forming the M unit and the silicon compound forming the Q unit, the heterogeneous metal-containing organosilicone resin of the present invention is represented by the general formula bX as a hydrolyzable silicon compound, Using at least one of the silicon compound forming the D unit and the silicon compound represented by the general formula cX and forming the T unit, the hydrolyzable silicon compound and the hydrolyzable foreign metal compound are hydrolyzed. It can also be obtained by combining a decomposition reaction with at least one of a dealcoholization reaction and a dehydration condensation reaction.
[0027]
The reaction between the hydrolyzable silicon compound and the hydrolyzable foreign metal compound may be performed, for example, by reacting the hydrolyzable silicon compound and the hydrolysable foreign metal compound with a target different metal-containing organosilicone resin composition. The monomer solution is dissolved in a predetermined amount in one or more organic solvents selected from lower alcohols such as methanol, ethanol, isopropanol, and propanol, and aromatic solvents such as benzene, toluene, and xylene, etc. It can be prepared and allowed to proceed by adding a sufficient amount of water to the monomer solution to effect the desired hydrolysis and condensation at a given temperature.
The reaction can be performed, for example, at a temperature in the range of room temperature or higher and lower than the boiling point of water, specifically, for example, in the range of 40 to 100 ° C.
Examples of the method of adding water include a method of preparing a water-containing organic solvent by adding a predetermined amount of water to the organic solvent and adding the water-containing organic solvent to the monomer solution.
The reaction between the hydrolyzable silicon compound and the hydrolyzable foreign metal compound may proceed in the presence of an acid catalyst or in the absence of an acid catalyst, as necessary. After the reaction between the hydrolyzable silicon compound and the hydrolyzable foreign metal compound is completed, the aqueous phase is removed from the obtained two-phase system, and the solvent is distilled off to obtain the target foreign metal-containing organosilicone. A resin can be obtained.
[0028]
In the case where the hydrolyzable group in the hydrolyzable silicon compound and the hydrolyzable foreign metal compound is an alkoxy group, the reaction rate is easy to control and the handling is simple. In the production of the organic silicone resin, it is preferable to use a silicon alkoxide compound and a metal alkoxide compound having 1 to 4 alkoxy groups as the hydrolyzable silicon compound and the hydrolyzable foreign metal compound.
[0029]
When the hydrolyzable silicon compound and the hydrolyzable foreign metal compound are reacted in the presence of an acid catalyst, after completion of the reaction, the aqueous phase is removed from the resulting two-phase system, and the organic phase is converted to sodium carbonate. After neutralizing with an aqueous solution and the like, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, and then distilling off the solvent, the desired different metal-containing organosilicone resin can be obtained.
[0030]
Examples of the acid catalyst 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 are preferable.
[0031]
According to the above method, the hydrolyzed foreign metal compound coexisting in the reaction system and the hydrolyzed silicon compound co-condensate, so that different metal atoms other than silicon are present at the atomic level in the organosilicon resin containing the different metal. It is taken in without difficulty. In this case, in fact, a hydrolyzable group that has not been hydrolyzed may also participate in the cocondensation. Metal atoms other than silicon incorporated in the organosilicon resin containing different metals are MeO depending on the oxidation number of the metal atoms._{A / 2}The unit can be present in the organosilicone resin as a unit, and in effect, the silicon atom in the ordinary organosilicone resin is partially substituted with a different metal atom. In this case, when the dissimilar metal present in the organosilicone resin is, for example, Ti, TiO₂Is taken in as ZnO when the dissimilar metal is Zn, and Al when the dissimilar metal is Al.₂O_ThreeWhen the dissimilar metal is Zr, ZrO₂Is taken in as. The different metal atom replacing the silicon atom in the organic silicone resin may be one kind or plural kinds.
[0032]
In the present invention, for example, in the organosilicon resin containing a different metal, R in the M unit¹, R in D units², And R in T units^ThreeIf any of these is at least one group selected from the group consisting of a hydrocarbon group having 1 to 6 carbon atoms and a phenyl group, the compatibility of the dissimilar metal-containing organosilicone resin with a cosmetic base is further improved. It is possible to improve the usability when applying cosmetics. Further, in the dissimilar metal-containing organosilicone resin, R in M units¹, R in D units², And R in T units^ThreeIf any of the above is a fluoroalkyl group, the water repellency of the different metal-containing organosilicone resin can be improved, and oil repellency can be effectively imparted to the different metal-containing organic silicone resin. Excellent water repellency and oil repellency can be imparted to the coating film.
[0033]
Examples of the fluoroalkyl group include a general formula 4; — (CH₂)_mC_nF_{2n + 1}(Wherein m represents an integer of 2 to 4 and n represents an integer of 1 to 12). R¹, R²And R^ThreeExamples of the hydrolyzable silicon compound represented by the general formula 1X, the general formula 2X, and the general formula 3X in the case where the Rf group is employed for Rf_ThreeSiX¹, Rf₂Si (R¹) X¹, RfSi (R¹)₂X¹, RfSi (R²) X² ₂, Rf₂SiX² ₂, RfSiX^Three _ThreeThese can be used as starting materials depending on the desired resin composition. Specifically, for example, CF_ThreeCH₂CH₂Si (CH_Three) Cl₂, CF_ThreeCH₂CH₂Si (CH_Three) (OCH_Three)₂, (CF_ThreeCH₂CH₂)₂Si (OCH_Three)₂, CF_ThreeCH₂CH₂SiCl_Three, CF_ThreeCH₂CH₂Si (OCH_Three)_ThreeEtc.
[0034]
In the present invention, for the purpose of enhancing effects such as water repellency in a cosmetic coating film, functional groups remaining in the different metal-containing organosilicone resin, such as hydroxyl groups directly bonded to metal atoms by hydrolysis reaction, etc. By reacting the residual hydrophilic group remaining slightly or an unreacted active residue directly bonded to a metal atom with a silicon compound capable of forming the M unit as a terminal blocking agent, The unreacted active residue can be blocked.
[0035]
Conventionally, the end-capping reaction of an active unreacted group in a hydrolyzing siloxane polymer is known as a trimethylsilylation reaction [Kanichi Kanichi, Yokoo Toshinobu, Sakuhana Saio, Journal of Ceramic Industry Association, 92, 242-247 (1984)]. In the present invention, for example, the method of Sakuhana et al. Can be adopted. That is, after completion of the hydrolysis reaction in the present invention, in the obtained reaction mixture, for example, the R^a _ThreeHydrolyzable silicon compound represented by SiX, or R^a _ThreeSiOSiR^a _ThreeR prepared separately by hydrolysis of^a _ThreeSiOH or the like can be added as an end-capping agent to end-cleave the remaining hydrophilic groups or hydrolyzable active unreacted groups that remain slightly in the different metal-containing organosilicone resin.
[0036]
The R^aWhen a hydrolyzable silicon compound employing a fluoroalkyl group is used as the end-capping agent, it is possible to effectively impart excellent water repellency and oil repellency to the resulting different metal-containing organosilicone resin.
[0037]
The constitutional unit composition (unit molar ratio) of the dissimilar metal-containing organosilicone resin in the present invention is such that the dissimilar metal-containing organosilicone resin is the M unit, the Q unit, and the MeO._{A / 2}As long as it has units, there is no particular limitation.
[0038]
The dissimilar metal-containing organosilicone resin is composed of the M unit, Q unit and MeO._{A / 2}In the case of having the D unit and the T unit in addition to the unit, the number of moles of the T unit (hereinafter sometimes referred to as “(T)”) and the number of moles of the Q unit (hereinafter referred to as “(Q)”). M number of moles of M units (hereinafter sometimes referred to as “(M)”) and the number of moles of D units (hereinafter referred to as “(D)”). Is within a range of 0.7 to 3.5 (0.7 ≦ [(M) + (D)] / [(T) + (Q)] ≦ 3.5). Preferably there is. When the ratio of the sum of (M) and (D) to the sum of (T) and (Q) becomes larger, the two-dimensionality (linearity) in this resin increases, and the oily group in the cosmetic is increased. Although there is a tendency to improve the compatibility with the material and the flexibility of the resulting coating, for example, when the ratio is greater than 3.5, the coating strength may be insufficient in this resin, and the resulting coating Durability may be reduced. When the ratio of the sum of (M) and (D) to the sum of (T) and (Q) is smaller, the coating strength of this resin tends to be improved. Accordingly, for example, when the ratio is smaller than 0.7, the molecule becomes bulky, and hence the plasticity is lowered, and further, the rubbery or glass flakes exhibiting brittleness become worse. In addition, particles may be formed in the course of the reaction, and a suitable film forming agent may not be obtained.
[0039]
In the present invention, the MeO in the dissimilar metal-containing organosilicone resin._{A / 2}The ratio of the units can be controlled, for example, by changing the composition ratio between the silicon compound as a starting material and a metal compound other than silicon. The composition ratio between the metal element other than silicon and the silicon element in the organosilicon resin containing different metals can be referred to as the degree of substitution when a part of the silicon atoms in the organosilicone resin is substituted with different metal atoms other than silicon. The degree of substitution is such that the resin-blended cosmetic obtained by blending this resin can be given a good feeling of use, a natural finish, an excellent makeup effect sustainability, an excellent anti-transfer effect, etc. Can be determined as appropriate.
[0040]
In the different metal-containing organosilicone resin, MeO with respect to the number of moles of Q units._{A / 2}The ratio of the number of moles of units is in the range of 0.001 to 0.5 (0.001 ≦ [MeO_{A / 2}] / (Q) ≦ 0.5). In the dissimilar metal-containing organosilicone resin, characteristics required for this resin, for example, excellent usability in a resin-containing cosmetic obtained by blending this resin into cosmetics, a feeling of finish, and a cosmetic effect sustainability, The degree of substitution between the silicon atom and the dissimilar metal atom can be appropriately determined and adjusted according to the characteristics such as the transfer prevention effect. However, MeO for (Q)_{A / 2}When the ratio of the number of moles of the unit is less than 0.001, the remarkable effect according to the present invention may not be obtained. On the other hand, MeO for (Q)_{A / 2}When the ratio of moles of units exceeds 0.5, MeO_{A / 2}Substitution at the atomic level of the unit may be difficult, or by promoting the curing of the foreign metal-containing silicone resin, the resin may become too hard, and the foreign metal-containing organosilicone resin becomes too dense and plastic. May deteriorate and the feeling of use may deteriorate.
[0041]
When the dissimilar metal-containing organosilicone resin further has T units, MeO with respect to the sum of the number of moles of T units and the number of moles of Q units._{A / 2}The ratio of the number of moles of units is in the range of 0.001 to 0.5 (0.001 ≦ [MeO_{A / 2}] / [(T) + (Q)] ≦ 0.5). MeO with respect to the sum of (T) and (Q)_{A / 2}When the ratio of the number of moles of the unit is less than 0.001, the remarkable effect according to the present invention may not be obtained, and MeO with respect to the sum of (T) and (Q)._{A / 2}When the ratio of the number of moles of units is more than 0.5, the same problem as described in the case of the different metal-containing organosilicone resin may occur.
[0042]
Regarding the degree of polymerization of the different metal-containing organosilicone resin, the weight average molecular weight is preferably in the range of 1,000 to 100,000. When the weight average molecular weight is, for example, less than 1,000, the sticky feeling in the cosmetic coating film may become worse, and a sufficient film strength may not be obtained. The weight average molecular weight is, for example, If it exceeds 100,000, a uniform coating film may not be obtained in the cosmetic coating film.
[0043]
The structural unit composition and the degree of polymerization are preferably selected appropriately according to the intended use, taking into consideration the water repellency, film-forming ability, and feeling of use required for cosmetic coating films.
[0044]
In the present invention, by including different metal atoms in the organosilicone resin, for example, some silicon in the non-substituted organosilicone resin in which silicon in the organosilicone resin is not substituted with different metal atoms other than silicon. Realizes the same state as when atoms are substituted with different metal atoms other than silicon, thereby increasing the ionicity of the metal-oxygen bond in the molecule and densifying the film formed by the organosilicone resin containing the different metal It becomes possible to do. Moreover, as a result, the peculiar stickiness which the non-substituted organic silicone resin which does not contain a different metal atom has can be suppressed, and film strength can be increased. Furthermore, by allowing the structural unit of a metal oxide having a high refractive index to be present in the organosilicon resin containing a different metal, the refractive index can be increased compared to an unsubstituted organosilicone resin. The feeling of finish of the cosmetic coating film can be improved by reducing the difference in refractive index with other raw material components to be blended, particularly with the powder component having a high refractive index. Examples of the metal oxide having a high refractive index include a metal oxide having at least one selected from the group consisting of Ti, Zn, Zr, and Al as the metal element.
[0045]
The cosmetic of the present invention contains 0.5 to 80% by weight of the different metal-containing organosilicone resin. That is,The compounding quantity of the said different metal containing organosilicone resin in the cosmetics of this invention is 0.5 to 80 weight% in the cosmetics whole quantity, Preferably it is 5 to 30 weight%. When the blending amount of the dissimilar metal-containing organosilicone resin is less than 0.5% by weight, the effect of this resin may not be exhibited. When the blending amount of the dissimilar metal-containing organosilicone resin exceeds 80% by weight, When a cosmetic coating film is formed, a feeling of pressure may be generated even if there is no stickiness, and in some cases, a feeling of pressure may be generated together with the feeling of stickiness, which may reduce usability.
[0046]
The dissimilar metal-containing organosilicone resin can be dissolved in, for example, a low-polarity solvent such as benzene, toluene, xylene, hexane, and the like. The resin can be diluted to a desired concentration using volatile silicone oil as a solvent. Examples of the volatile silicone oil include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tetradecamethylcycloheptasiloxane. Can be mentioned.
[0047]
In addition to the different metal-containing organosilicone resin, for example, water and a surfactant can be blended with the cosmetic of the present invention. In this case, the cosmetic is prepared using conventional emulsification techniques. Can be prepared. Examples of the cosmetic include emulsified cosmetics, water-in-oil cosmetics, and oil-in-water cosmetics.
[0048]
The cosmetic composition of the present invention has a qualitative and quantitative range that does not impair the effects of the present invention depending on the purpose. Ingredients, drugs, fragrances and the like can be blended.
[0049]
Next, an embodiment of the present invention will be described in detail. Note that the present invention is not limited to this. All compounding amounts are in weight percent. The cosmetic of the present invention may be, for example, a solid foundation, a solid eye shadow, an oily foundation, a lipstick, an emulsified foundation, a milky lotion, a cream, or the like, and is not particularly limited.
Example
(Example 1)
<Production of dissimilar metal-containing organosilicone resin (A)>
In a sealed glove box, put a 500 ml insulator flask containing a stir bar, tetramethoxysilane, titanium isopropoxide, methoxytrimethylsilane, thermometer, and silica gel, and thoroughly dry the inside of the glove box over 12 hours. The humidity was 25%.
[0050]
Tetramethoxysilane 25.00 g (0.164 mol), methoxytrimethylsilane 42.78 g (0.410 mol), and titanium isopropoxide 7.50 g (0.026 mol) were sequentially charged into a well-dried insulator flask. A silica gel tube and a reflux condenser with a dropping funnel were immediately attached, and stirring was started using a stirrer. Subsequently, the reaction solution was gradually heated, heated and stirred at 60 ° C. for 45 minutes, and then added to the reaction solution prepared separately.₂128.25 g of 4% by weight isopropanol solution of O (ion exchange water) was added dropwise over 7 hours. After completion of dropping, the reaction solution is heated at 60 ° C. for 15 hours.refluxWent. Thereafter, 109.33 g (1.048 mol) of methoxytrimethylsilane was dropped into the reaction solution over 15 minutes, and the temperature of the reaction solution was adjusted to 70 ° C. Next, separately prepared H₂122.20 g of a 20% by weight O (ion-exchanged water) isopropanol solution was divided into three equal portions, and each 1/3 amount was carried out over 7 hours. Each time 1/3 of the isopropanol solution was dropped, the reaction solution was heated to reflux at 70 ° C. for 16 hours. After completion of the dropwise addition of the isopropanol solution, the temperature of the reaction solution was set to 80 ° C., and the reaction was completed by heating and refluxing for 90 hours.
[0051]
After completion of the reaction, vacuum distillation was performed at 80 ° C. using a rotary evaporator, the solvent and unreacted substances were distilled off from the reaction mixture under reduced pressure, and the remaining water was removed by azeotropy with 250 ml of cyclohexane. The reaction mixture was further dried under reduced pressure at 75 ° C. in a desiccator containing phosphorus pentoxide to obtain a target dissimilar metal-containing organosilicone resin (A) (hereinafter abbreviated as “TMST”). The obtained TMST was a transparent waterglass-like high-viscosity product, and the yield was 24.90 g.
(Comparative Example 1)
Octamethylcyclotetrasiloxane was removed by distillation under reduced pressure from a commercially available octamethylcyclotetrasiloxane solution of trimethylsiloxysilicic acid (KF-9002 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.), and the pressure was reduced by a desiccator containing phosphorus pentoxide. Drying gave trimethylsiloxysilicic acid (hereinafter abbreviated as “TMS”). Here, octamethylcyclotetrasiloxane is a kind of silicone solvent.
(Comparative Example 2)
In the octamethylcyclotetrasiloxane solution of trimethylsiloxysilicic acid, TiO₂Fine particle titanium oxide (SI-UFTR-) surface-treated with methylhydrogenpolysiloxane so that the content of the same is the same (9.0% by weight) as the different metal-containing organosilicone resin (A) in Example 1 above. Z (manufactured by Miyoshi Kasei Co., Ltd.) is ultrasonically dispersed, octamethylcyclotetrasiloxane is distilled off, dried under reduced pressure, and fine particle TiO₂Was prepared by simply mixing TMS (hereinafter abbreviated as “TMT”).
(Comparative Example 3)
In Comparative Example 3, a commercially available shea fat (Cropure Liquid Vegelan, manufactured by Croda Japan) was used as it was.
<2. Measurement>
<2.1 Surface observation>
Using a scanning electron microscope JSM-T220 (manufactured by JEOL Ltd.), an electron micrograph of the surface of the TMST film was taken and the state of the surface was observed. One of the electron micrographs is shown in FIG.
<2.2 Qualitative analysis>
TMST was subjected to qualitative analysis of metal elements using a scanning electron microscope JSM-5800LV and an energy dispersive X-ray spectrometer JED-2140 (both manufactured by JEOL Ltd.). The qualitative analysis was performed on a sample coated on a carbon sample stage under the conditions of an effective time of 200.00 seconds, an acceleration voltage of 15 kV, a take-off angle of 35 °, and a working distance of 10 mm. FIG. 2 shows an energy dispersive X-ray spectroscopic spectrum measured using the energy dispersive X-ray spectrometer, and FIG. And the mapping image showing the magnitude of the existence probability of Ti and Ti is shown. In FIG. 3, (A) is an image showing the magnitude of the existence probability of Si, and (B) is an image showing the magnitude of the existence probability of Ti. On the right side of each of the images (A) and (B), a scale representing the magnitude of the existence probability is shown.
<2.3 Quantitative analysis>
TMST was quantitatively analyzed for metal elements under the following conditions using an inductively coupled high-frequency plasma emission analyzer ICPS-1000III (manufactured by Shimadzu Corporation).
[0052]
(a) Preparation of sample solution: About 0.1 g of TMST was accurately weighed in a platinum crucible, 2 ml of nitric acid was added thereto, and the mixture was gently heated and evaporated to dryness. To this, 1.5 g of an alkali mixture (sodium carbonate: lithium tetraborate = 3: 1) was added and dissolved by heating (900 ° C., 1 hour). After cooling, 6 ml of sulfuric acid (1 + 1) was added and dissolved by heating, and the volume was adjusted to 50 ml. This solution was diluted 20 times to obtain a sample solution for inductively coupled radio frequency plasma emission analysis.
[0053]
(b) Measurement conditions: The measurement wavelength was 251.61 nm for Si and 336.12 nm for Ti.
<2.4 Structural analysis>
(a) IR spectrum: For TMST and TMS, an infrared spectrophotometer 270-30 type (manufactured by Hitachi, Ltd.) was used, and a sample was applied as a thin film on a KBr cell, and an IR spectrum was measured. The obtained IR spectrum is shown in FIG. In FIG. 4, A shows the IR spectrum of TMST, and B shows the IR spectrum of TMS.
[0054]
(b) Nuclear magnetic resonance spectrum: For TMST and TMS, a nuclear magnetic resonance apparatus EX-400WB (manufactured by JEOL Ltd.) was used according to the following measurement conditions.²⁹Si NMR spectrum was measured. The obtained NMR spectrum is shown in FIG. In FIG. 5, A shows the NMR spectrum of TMST, and B shows the spectrum of TMS.
[0055]
Measurement condition;
External reference material: Tetramethylsilane (0.00ppm)
: Deuterated chloroform
: 78.5 MHz (²⁹Si)
: 45 ° pulse
: Decoupling with gate
: 11.088 seconds
(Data acquisition time 1.088 seconds + waiting time 10.000 seconds)
: Chromium acetylacetonate
: Room temperature (24.5 ° C)
<2.5 Molecular weight measurement>
About TMST and TMS, molecular weight was measured using the high performance liquid chromatograph LC-6A and C-R4A (made by Shimadzu Corporation). The molecular weight was determined by measuring the GPC chromatogram using a GPC column in the high performance liquid chromatograph and converting the obtained GPC chromatogram to the molecular weight of polystyrene having a known molecular weight. The measurement conditions are as follows.
[0056]
: Shim-pak GPC-801, 802, 803,
804 and 806,
: Type ... tetrahydrofuran, flow rate ... 1.0ml / min,
: Suggested refractometer RID-6A
Column temperature: 40 ° C
<2.6 Solubility test>
TMST and TMS were evaluated for solubility in various organic solvents and cosmetic liquid bases. To evaluate the solubility, TMST or TMS is mixed with an organic solvent and a cosmetic liquid base so that the concentration becomes 2.5% by weight, and the dissolution state at room temperature (23 ° C.) is visually observed. evaluated. The results are shown in Table 1.
[0057]
[Table 1]

[0058]
I ... Insoluble S ... Soluble
<2.7 Refractive index>
TMST and TMS were measured at 20 ° C. using a precision Appe refractometer 3T (manufactured by Atago Co., Ltd.).
<2.8 Transparency test>
For TMST and TMT, transparency was evaluated according to the following method.
[0059]
First, a 50 wt% octamethylcyclotetrasiloxane solution of TMST and a 50 wt% octamethylcyclotetrasiloxane solution of TMT were each applied on a quartz glass plate having a thickness of 3 mm to a dose of 1.5 mg / cm 3.²Then, it was naturally dried at room temperature (23 ° C.) for 24 hours to form TMST and TMT films on the quartz glass plate.
[0060]
Next, the quartz glass plate was placed on the printed characters, and the transparency was evaluated by comparing the appearance of the characters when passing through the TMST film and the appearance of the characters when passing through the TMT film. The characters viewed through the TMST film and the characters viewed through the TMT film are shown in FIG. In addition, A in FIG. 6 shows the character seen through the TMST film, and B shows the character seen through TMT.
<2.9 Water Repellency Test>
TMST was evaluated for water repellency as follows. A drop of water was dropped from a height of 3 cm onto a TMST film formed on the quartz glass plate and a quartz glass plate having a clean surface using a 10 ml burette at room temperature (23 ° C.). The state of was observed visually. The state of the water droplet at this time is shown in FIG. In FIG. 7, A shows the state of water droplets on the TMST film, and B shows the state of water droplets on the quartz glass surface.
<2.10 Ultraviolet absorption characteristics test>
UV spectrum in the ultraviolet region (290 to 400 nm) of an isopropanol solution having a concentration of 0.4 g / L using an ultraviolet spectrophotometer UV-2200 (manufactured by Shimadzu Corporation) for each of TMST, TMS, and shea fat. Was measured at 20 ° C. using a 10 mm thick cell. The measured UV spectrum is shown in FIG. In FIG. 8, A shows the UV spectrum of TMST, B shows the UV spectrum of shea fat, and C shows the UV spectrum of TMS.
<2.11 Plasticity and adhesion test>
For TMST and TMS, use a rheometer RT-2002D / D (manufactured by Fudo Kogyo Co., Ltd.) and apply distortion with an adapter with a stainless steel ball formed at the tip. The plasticity was evaluated. Then, the adhesiveness was evaluated by measuring the force and time required to peel the adapter to which the set load was applied from TMST or TMS.
[0061]
Measurement method: TMST and TMS were each poured into a cylindrical glass cell having an inner diameter of 31.0 mm to a height of 10 mm, and the cell was sealed and allowed to stand in a horizontal place for 24 hours. The previous glass cell is fixed to the sample table of the rheometer, the sample table is raised at a constant speed, and immediately after the set load is applied to the adapter, the sample table is lowered at a constant speed. The applied load was continuously recorded. The results are shown in FIG. In FIG. 9, A shows the transition of load in TMST, and B shows the transition of load in TMS.
[0062]
Measurement conditions: Table speed: 2 cm / min (both when rising and falling), load: 4.9 × 10^-2N, load addition holding time: 0.0 seconds, measurement temperature: 23 ° C., adapter: stainless steel cylinder rod (diameter: 2 mm, length: 63 mm) with stainless steel hard sphere (diameter: 6 mm).
<2.12 Transfer prevention test>
TMST and other ingredients were blended according to the blending composition shown in Table 2 to prepare lipstick A. On the other hand, lipstick B having the same composition as the lipstick was prepared except that TMST was not blended. After either lipstick A or lipstick B was applied to the lips, the lipstick was naturally dried at room temperature for 5 minutes, and the secondary transfer of the lipstick to the tea bowl was visually observed. The transfer prevention test was conducted as a blind test by a specialized panelist.
[0063]
[Table 2]

<3. Result>
<3.1 Surface observation>
As is clear from the electron micrograph shown in FIG. 1, the surface of TMST was smooth, and no particles or irregularities were observed. This shows that TMST has no morphological component segregation, and TMST can be formed into a film having good continuity.
<3.2 Qualitative analysis>
The qualitative analysis chart of TMST shown in FIG. 2 shows that both Si and Ti were detected from TMST. Further, from the mapping image shown in FIG. 3, it was found that the variation of the image image was uniform for both Si and Ti. From these results, it can be seen that in TMST, both Si and Ti are uniformly dispersed without showing significant segregation.
<3.3 Quantitative analysis>
From the results of quantitative analysis of TMST using an inductively coupled high-frequency plasma emission spectrometer, Ti atoms contained 5.4 wt% (TiO 2 in TMST).₂9.0% by weight, that is, 24.50 × 0.09 = 2.24 g). In the preparation of TMST in Example 1, the theoretical value of Ti amount in TMST calculated from the charged amount of titanium isopropoxide (4.5 g) is TiO 2.₂Converted to 2.1g. Therefore, the amount of Ti in TMST obtained from the result of the quantitative analysis becomes 106% of the theoretical value.₂The structure is considered to be incorporated into TMST almost quantitatively. It was also found that the molar ratio of metal elements constituting TMST was Ti / Si = 0.14.
<3.4 Structural analysis>
(a) IR spectrum
In both the IR spectra of TMST and TMS shown in FIG.^-1The peak attributed to Si-O-Si is observed, and the wave number is 840 cm.^-1The absorption attributed to the trimethylsilyl group was observed. From this result, TMST also has a structural unit [(CH_Three)_ThreeSiO_1/2] And [SiO₂]. Furthermore, in TMST, wave number 960cm^-1In the vicinity, a peak attributed to Ti—O—Si that was not observed in TMS was observed. From this result, it is considered that Ti atoms in TMST are chemically bonded to Si atoms via O atoms.
[0064]
(b) NMR spectrum
As is clear from FIG. 5, broad peaks were recognized around +11 ppm and around −110 ppm in both TMST and TMS. here,²⁹In Si-NMR, the peak near +11 ppm is [(CH_Three)_ThreeSiO_1/2] Corresponding to the unit, and the peak near -110 ppm is a three-dimensional crosslinking framework ([SiO₂It is known that the peak corresponds to the unit). Therefore, from the NMR spectrum of FIG. 5, the TMST is similar to [(CH_Three)_ThreeSiO_1/2] Units and [SiO₂It is clear that a unit is provided. It is shown in the IR spectrum that TMST has a Ti—O—Si bond. From the results of the IR spectrum and the NMR spectrum, TMST is mainly represented by [(CH_Three)_ThreeSiO_1/2] Units and [SiO₂] Units and [TiO₂It can be considered that it is composed of units.
[0065]
  From the NMR spectrum of FIG. 5, the area ratio between the peak near +11 ppm and the peak near −110 ppm is calculated, and the [(CH_Three)_ThreeSiO_1/2] Si atom corresponding to the unit, and [SiO₂The ratio of Si atoms corresponding to the unit was calculated to be 0.9: 1.1 in TMS, but 1.1: 0.9 in TMST. When this result was combined with a molar ratio of Ti to Si in TMST of 0.14 determined by inductively coupled high-frequency plasma emission analysis, the ratio of each structural unit in TMST was calculated.
[(CH_Three)_ThreeSiO_1/2]: [SiO₂]: [TiO₂]
            = 1.4: 1.2: 0.4
It was calculated. In the above formula, [(CH_Three)_ThreeSiO_1/2] Is [(CH_Three)_ThreeSiO_1/2] The molar ratio of the structure to [SiO₂] Is [SiO₂] The molar ratio of the structure is [TiO₂] Is [TiO₂] Shows the molar ratio of the structure.
<3.5 Molecular weight measurement>
  As a result of measuring the molecular weight using a high performance liquid chromatograph, the weight average molecular weight of TMST was 2,100, and the polydispersity indicated by the weight average molecular weight / number average molecular weight was 1.5. On the other hand, the weight average molecular weight of TMS was 2,500, and the polydispersity represented by the weight average molecular weight / number average molecular weight was 1.3.
<3.6 Solubility test>
  As apparent from Table 1, TMST did not dissolve in water and methanol, as in TMS, but ethanol, isopropanol, toluene, benzene, hexane, light isoparaffin, various esters, and octamethylcyclotetrasiloxane. It was found to be soluble in various solvents. This is because the basic skeleton of TMST is similar to the basic skeleton of TMS.₂] Is thought to be because it has no significant effect on the solubility of TMST.
<3.7 Refractive index measurement>
  As a result of refractive index measurement, it was found that TMST had a refractive index (20 ° C.) of 1.432, and TMS had a refractive index (20 ° C.) of 1.409. The reason why TMST showed a large refractive index compared to TMS is that TMST has TiO in its structure.₂It is conceivable to have a structure. This is rutile TiO₂2.76, anatase TiO₂2.52 and TiO₂Is SiO₂This is also supported by having a refractive index higher than 1.55.
<3.8 Transparency test>
  As is apparent from FIG. 6, TMST is a TiO₂Even though it contained 9.0% by weight, the characters seen through the TMST film were as clear as those seen through the quartz glass plate that did not form the film. In contrast, the TMT film was white and opaque, and the characters viewed through the TMT film were blurred. This is because, in TMST, TiO₂Is considered to be bonded to the trimethylsiloxysilicate skeleton through a Ti—O—Si bond to form a part of the polymer structure.
<3.9 Water Repellency Test>
  As shown in FIG. 7, the contact angle of water droplets on the TMST film was 90 ° or more. In contrast, the contact angle of water droplets on a quartz glass plate with a clean surface was only about 30 °. From this, it is clear that the TMST film is excellent in water repellency. This is considered to be due to the arrangement of trimethylsilyl groups included in the polymer structure of TMST on the film surface.
<3.10 UV absorption characteristic test>
  As shown in FIG. 8, TMS showed almost no absorption in the ultraviolet region (290 to 400 nm), whereas TMST showed significant absorption in the wavelength region of 340 nm or less. The absorption of TMST in the wavelength region was higher than that of shea fat, which is a natural vegetable oil known to have ultraviolet absorbing ability. From this, it is clear that TMST has a remarkable ultraviolet shielding ability. The absorption edge of TMST is about 370 nm, which is rutile TiO.₂410nm and anatase TiO₂Compared to 390 nm, the short wavelength side.
<3.11 Plasticity and adhesion test>
(a) Plasticity test
  As is apparent from the results of the plasticity and adhesion tests shown in FIG. 9, in TMST, a set load was applied immediately after the adapter contacted the sample. On the other hand, in TMS, it took 8 seconds until the set load was applied after the adapter contacted the sample, and the adapter penetrated deeper into the sample.
(b) Adhesion test
  As shown in FIG. 9, in TMST, the adhesive force is 8.6 × 10.^-2Although it was as high as N, it took only 7 seconds to peel off. On the other hand, in TMS, the adhesive force is 3.3 × 10.^-2Although it was as low as N, it took 80 seconds to peel off. Further, in TMS, a large amount of sample adhered to the adapter after peeling.
(c) Consideration
  From the results of the plasticity test, it was found that TMST has a polymer skeleton similar to TMS and can form a film with high hardness that hardly undergoes plastic deformation even though its molecular weight is slightly smaller than TMS. It was. Further, in the adhesion test, TMST showed that, compared with TMS, a large force was required at the moment of separation from the adapter, but the peeling time was short and the adhesion to the adapter was small. From this result, it was found that TMST is a polymer that hardly exhibits stickiness as compared with TMS. This is considered to be consistent with the fact that when the tactile sensation was compared between the TMST film and the TMS film, the stickiness of the TMST film was weaker. This is because the Ti-O bond is stronger in ionic bond than the Si-O bond, and therefore the polymer is densified in TMST having a Ti-O bond compared to TMS not having a Ti-O bond. It is thought that.
<3.12 Transfer Prevention Test>
  In the lipstick containing 7.5% by weight of TMST, almost no transfer of lipstick from the lips to the black tea bowl was observed. On the other hand, in the lipstick that did not contain TMST, the mark of the lips remained clearly in the tea bowl. This is considered to be due to the fact that a protective coating with very little stickiness was formed on the lip surface in the lipstick containing TMST. From this result, it can be seen that a lipstick having an excellent anti-transfer effect can be obtained by adding TMST to the lipstick.
<4. Summary>
  TMST prepared in Example 1 is excellent in transparency, has good solubility in general-purpose cosmetic bases, and is not found in TMS of Comparative Example 1 that has been widely used in conventional cosmetics. It has the feature of having a refractive index and high ultraviolet shielding ability. In addition, TMST has a feature that a film with less stickiness can be obtained, and in relation to the above feature, it has a feature that a cosmetic having an excellent anti-transfer effect can be obtained by blending with a cosmetic such as lipstick. .
[0073]
【The invention's effect】
According to the present invention, it has a good feeling of use, has a natural finish, can effectively prevent makeup slippage caused by sebum, sweat, or other cosmetic oils, and has an excellent cosmetic effect. It is possible to provide a cosmetic material that is durable and has an excellent effect of preventing transfer to clothes and the like.
[0074]
In the cosmetic of the present invention, the different-metal-containing organosilicone resin can be obtained, for example, by replacing the silicon element in the unsubstituted organosilicone resin having M units and Q units with a metal element other than silicon. By adopting this heterogeneous metal-containing organosilicone resin as a film-forming agent, the film can be densified, so that the sticky feeling peculiar to conventional non-substituted organosilicone resins can be suppressed, and makeup The coating strength of the coating material can be increased. Further, in the present invention, the refractive index of the organosilicon resin containing different metals can be increased, and the difference in refractive index from other raw materials blended in cosmetics, in particular, a powder component having a high refractive index is reduced. Therefore, the finished feeling of the cosmetic coating film can be improved.
[0075]
Furthermore, in the cosmetic of the present invention, it is possible to densify the cosmetic coating film by increasing the ionic bondability of the metal-oxygen bond in the different metal-containing organosilicone resin. Moreover, as a result, the stickiness peculiar to an unsubstituted organic silicone resin can be suppressed, and the coating strength of a cosmetic coating film can be increased.
[Brief description of the drawings]
FIG. 1 is an electron micrograph of the surface of a TMST film taken using a scanning electron microscope JSM-T220 (manufactured by JEOL Ltd.).
FIG. 2 is an energy dispersive X-ray spectroscopic spectrum measured with an energy dispersive X-ray spectrometer for TMST.
FIG. 3 is a mapping image created from the results of the energy dispersive X-ray spectroscopic analysis for TMST and showing the magnitude of the existence probability of Si and Ti.
FIG. 4 is an IR spectrum of TMST and TMS.
FIG. 5 shows TMST and TMS.²⁹It is a SiNMR spectrum.
FIG. 6 is a photograph of characters viewed through a TMST film and characters viewed through a TMT film.
FIG. 7 is a photograph showing the state of water droplets on both a TMST film formed on a quartz glass plate and a quartz glass plate having a clean surface.
FIG. 8 is a UV spectrum of TMST, shea fat, and TMS.
FIG. 9 is a graph showing transition of load in a plasticity / adhesion test for TMST and TMS.

Claims (1)

R ¹ ₃ SiO _1/2 (wherein R ¹ represents any hydrocarbon group having 1 to 6 carbon atoms), Q unit represented by SiO ₂ , The dissimilar metal-containing organosilicone resin having a TiO ₂ unit having a mole ratio to a mole number of 0.001 to 0.5 and a weight average molecular weight of 1,000 to 100,000 is 0.5 to 80. Cosmetics characterized by containing weight%.

Images