JP3878352B2 - Processed powder and composition containing the same - Google Patents

Description

（但し、式中Ｒは炭素数１〜４のアルキル基を表す。）
【０００８】
【発明の実施の形態】
（１）本発明の処理粉体
本発明の処理粉体は、シリカ、架橋ジメチルポリシロキサン及びメチルシロキサン網状重合体を除く、粉体を一般式（Ｉ）に表される部分構造、即ちメルカプト基を有するアルキルオキシシラン誘導体やハロゲン化シラン誘導体で処理し、メルカプト基を導入した粉体であり、これらはアミノ酸、ペプチド、タンパク等の吸着能に優れる。尚、シリカ、架橋ジメチルポリシロキサン及びメチルシロキサン網状重合体にメルカプト基を導入した粉体もこの様な作用を有しており、この様な粉体については、本発明者らによって、別途特許出願が為されている。
【０００９】
本発明の処理粉体は、一般式（ＩＩ）に表されるアルキルオキシシラン誘導体やハロゲン化シラン誘導体で、粉体表面に存在する水酸基をシリル化することにより得られる。かかる一般式（ＩＩ）に表されるシラン誘導体の内では一般式（ＩＶ）に表されるシラン誘導体を用いるのが特に好ましい。尚、この様な処理に際しては、一般式（ＩＩＩ）に表されるようなメルカプト基を有しないシラン誘導体を供に加えて処理し、粉体全体をメルカプト基を有する珪素化合物でコーティングする。ここで、処理に使用する一般式（ＩＩ）に表される化合物の量は、処理される粉体に対して１〜１００重量％が好ましく、１０〜５０重量％が更に好ましい。これは、処理量が少なすぎると、吸着作用を発現しない場合があり、多すぎると、粉体そのものの特性を損なう場合があるからである。又、一般式（ＩＩＩ）に表される化合物を加えて処理する場合には、処理剤を全量で２〜２００重量％、好ましくは２０〜６０重量％とするのが好ましく、この時の一般式（ＩＩ）の化合物と一般式（ＩＩＩ）の化合物の割合は、３０：７０〜７０：３０が好ましい。この量比は、メルカプト基の存在密度が希釈されるためと、これらの化合物を強固に粉体上に固定するために好ましい範囲であるからである。処理は、例えば、これらの化合物で表面をコーティングした後、１００〜２００℃で焼成する方法、アルカリ触媒或いは酸触媒の存在下溶媒などともに縮合させる方法などが例示できる。又、処理される粉体としては、化粧料で使用されるものでシリカ、架橋ジメチルポリシロキサン及びメチルシロキサン網状重合体以外のものであれば、特段の限定はなく使用でき、例えば、二酸化チタン、酸化鉄、酸化ジルコニウム、酸化亜鉛、マイカ、セリサイト、タルク、炭酸カルシウム、珪酸カルシウム、炭酸マグネシウム、珪酸マグネシウム、チタン酸リチウムコバルト、グンジョウ、紺青、チタンマイカ、チタンセリサイト及びこれらから選ばれる２種以上の焼成物等が好ましく例示できる。これら、本発明の処理粉体は、アミノ酸、ペプチド及びタンパクを吸着する作用を有するばかりでなく、化粧料などに含有させた場合、優れた延展性、疎水性、皮膚密着性などの化粧料用粉体として好ましい性質も副次的効果により有する。
【００１０】
【化６】

（但し、式中、Ｒ１’、Ｒ２’、Ｒ３’及びＲ４’はそれぞれ独立にハロゲン原子、ＯＲ５’、Ｒ５’を表し、Ｒ５’はそれぞれ独立に水素原子又はメルカプト基を有していても良い炭素数１〜４のアルキル基を表し、且つ、Ｒ１’、Ｒ２’、Ｒ３’又はＲ４’の少なくとも１個はメルカプト基を有する炭素数１〜４のアルキル基であり、且つ、少なくとも１個は炭素数１〜４のアルキルオキシ基又はハロゲン原子又は水酸基であるものとする。）
【００１１】
【化７】

（但し、式中Ｒ６、Ｒ７、Ｒ８及びＲ９はそれぞれ独立に、ハロゲン原子、ＯＨ、Ｏ−Ｒ１０又はＲ１０を表し、Ｒ１０は炭素数１〜４のアルキル基を表し、Ｒ６、Ｒ７、Ｒ８及びＲ９の内、少なくとも２個はハロゲン原子、水酸基又はアルキルオキシ基であるものとする。）
【００１２】
【化８】

（但し、式中、Ｒ１’はメルカプト基を有する炭素数１〜４のアルキル基を表し、、Ｒ２’、Ｒ３’及びＲ４はそれぞれ独立にハロゲン原子又は炭素数１〜４のアルキルオキシ基を表す。）
【００１３】
（２）本発明の化粧料
本発明の化粧料は、上記本発明の処理粉体又は前記一般式（ＩＩ）に表される化合物で粉体を処理して得られた処理粉体（但し、粉体として、シリカ、架橋ジメチルポリシロキサン及びメチルシロキサン網状重合体を除く。）と一般式（ＩＩ）の化合物と一般式（ＩＩＩ）の化合物を重合させて得られる珪素化合物とを含有することを特徴とする。また、本発明の処理粉体と同様にシリカ、架橋型ジメチルポリシロキサン、メチルシロキサン網状重合体などの珪素化合物を処理して得られた処理粉体などのメルカプト基を導入された粉体を含有することも可能である。この様な粉体を含有することにより、本発明の化粧料は、例えば、ダニアレルゲン、杉花粉等のアレルゲンとなるようなペプチドやタンパクが生体内に侵入することを防ぐ作用を有する。この様なアレルゲンは、花粉症に代表される、呼吸器系の炎症や眼粘膜等の炎症の原因となっているほか、例えばアトピー性皮膚炎などの皮膚疾患にも関与していると言われている。又、敏感肌の人に於いては、環境由来のペプチドやタンパクへの被曝により、皮膚状態を悪化させることも示唆されている。本発明の化粧料は、この様な好ましくない生体への働きかけをするアミノ酸、ペプチド、タンパクを吸着し、これによる好ましくない反応発現を抑制する作用を有する。本発明の化粧料としては、通常使用されているものであれば特段の限定なく使用することが出来、例えば、乳液、クリーム、化粧水、パックなどの基礎化粧料、アンダーメークアップ、ファンデーション、プレストパウダー、ルースパウダー、リップカラー、アイカラー、マスカラ等のメークアップ化粧料、シャンプー、リンス、石鹸などの洗浄化粧料、ヘアクリーム、ヘアリキッド、ヘアトニック等の毛髪化粧料等が好ましく例示できる。本発明の化粧料に於ける、上記処理粉体の好ましい含有量は、０．１〜６０重量％であり、更に好ましくは１〜５０重量％である。以下に、本発明に係る珪素化合物粉体の製造例を示す。
【００１４】
＜製造例１＞
次に示す方法に従って、珪素化合物粉体を得た。即ち、テトラメトキシシラン３４．２ｇ（０．２５モル）とγ−メルカプトプロピルトリメトキシシラン４４．２（０．２５モル）とメタノール３６．５ｇとを冷却器をとりつけた反応容器に秤込み良く混合撹拌した。濃塩酸０．９ｍｌを水に溶解して１６２ｇに調整した液を４０．５ｇ加え、５０℃で二時間撹拌を続け、トリエタノールアミン３．６ｇをメタノール３６．５ｇに溶解した溶液を添加し撹拌を続け、系をゲル化させた。このゲルを濾過、洗浄、乾燥させ珪素化合物粉体１を得た。このものは珪素原子１に対し硫黄原子を０．４５含有していることが多核核磁気共鳴よりわかった。
【００１５】
製造例１のγ−メルカプトプロピルトリメトキシシランをγ−メルカプトプロピルトリエトキシシランに変え、珪素化合物粉体２を得た。
【００１６】
＜製造例３＞
製造例１のγ−メルカプトプロピルトリメトキシシランをジメチルメチル−γ−メルカプトプロピルシランに変え、珪素化合物粉体３を得た。
【００１７】
＜製造例４＞
製造例１のγ−メルカプトプロピルトリメトキシシランをエチルジメチル−γ−メルカプトプロピルシランに変え、珪素化合物粉体４を得た。
【００２１】
【実施例】
以下に、実施例を挙げて本発明について更に詳細に説明を加えるが、本発明がこれら実施例にのみ限定されないことは言うまでもない。
【００２２】
＜実施例１＞
二酸化チタン２０ｇにジメトキシ−γ−メルカプトプロピルシランクロリド５ｇをコーティングし、窒素気流下１３０℃で４８時間加熱し、本発明に係る処理粉体１を得た。
【００２３】
＜実施例２＞
次に示す方法に従って、本発明の処理粉体を得た。即ち、テトラメトキシシラン３４．２ｇ（０．２５モル）とγ−メルカプトプロピルトリメトキシシラン４４．２（０．２５モル）をメタノール３６．５ｇとを冷却器をとりつけた反応容器に秤込み良く混合撹拌した。濃塩酸０．９ｍｌを水に溶解して１６２ｇに調整した液を４０．５ｇ加え、５０℃で二時間撹拌を続けコーティング処理液とした。また、別に、二酸化チタン７０ｇとトリエタノールアミン３．６ｇとメタノール３６．５ｇとを冷却器をとりつけた反応容器に秤込み良く混合撹拌した。この分散液に、撹拌しながら、上記のコーティング液を二時間かけて滴下し、得られた粉体を濾過、洗浄、乾燥させ本発明の処理粉体２を得た。
【００２４】
＜実施例３＞
上記実施例１と同様に鉄ドープ二酸化チタン（タイペークＴＴ０−Ｆ−６；石原産業株式会社製）２０ｇを処理し、本発明に係る処理粉体３を得た。
【００２５】
＜実施例４＞
上記実施例１と同様にベンガラ２０ｇを処理し、本発明に係る処理粉体４を得た。
【００２６】
＜実施例５＞
上記実施例１と同様に黄色酸化鉄２０ｇを処理し、本発明に係る処理粉体５を得た。
【００２７】
＜実施例６＞
上記実施例１と同様にマイカ２０ｇを処理し、本発明に係る処理粉体６を得た。
【００２８】
＜実施例７＞
上記実施例１と同様にセリサイト２０ｇを処理し、本発明に係る処理粉体７を得た。
【００２９】
＜実施例８＞
上記実施例１と同様にチタンセリサイト２０ｇを処理し、本発明に係る処理粉体８を得た。
【００３０】
＜実施例９＞
上記実施例１と同様にチタンマイカ２０ｇを処理し、本発明に係る処理粉体９を得た。
【００３１】
＜実施例１０＞
上記実施例１と同様にタルク２０ｇを処理し、本発明に係る処理粉体１０を得た。
【００３２】
＜実施例１１＞
上記実施例１〜１０の本発明の処理粉体２並びに本発明に係る処理粉体１及び３〜１０と珪素化合物粉体１〜４について、アルブミンを指標として、タンパクの吸着力を確かめた。方法は、５０ｐｐｍのアルブミン水溶液２５ｍｌを１Ｎの硝酸でｐＨ４に調整し、これに粉体１ｇを加え、２４時間２０℃で振とうし、濾過し、アルブミン検知試薬（テストワコー）を加え発色させ、これを無処理の粉体と比較し、その薄くなり具合からタンパクの吸着性を○：優れた吸着（如実に発色が少ない）、△：やや吸着（明らかに発色は薄くなっているもののそれほどの差違はない。）、×：吸着無し（無処理粉体と同程度の発色）で判定した。珪素化合物粉体１〜４の比較の粉体としてはシリカゲルを用いた。結果を表１に示す。これより、これら珪素化合物粉体並びに本発明の処理粉体及び本発明に係る処理粉体は、タンパクの吸着能に優れることがわかる。
【００３３】
【表１】

【００３４】
＜実施例１２＞
下記に示す処方に従って、本発明の化粧料であるファンデーションを製造した。即ち、処方成分イをヘンシェルミキサーで混合した後、０．９ｍｍ丸穴スクリーンを装着したパルベライザーで粉砕し、これをヘンシェルミキサーで混合しながら処方成分ロを徐々に加えコーティングし、１ｍｍヘリングボーンスクリーンを装着したパルベライザーで粉砕し、金皿に充填し加圧成形してファンデーション１を得た。このファンデーションは延展性に優れ、優れた使用感を有していた。
イ
処理粉体１ ５ 重量部
処理粉体２ ５ 重量部
処理粉体３ １０ 重量部
処理粉体４ ０．１重量部
処理粉体５ ２．９重量部
処理粉体６ １５ 重量部
処理粉体７ １２ 重量部
処理粉体８ １ 重量部
処理粉体９ １ 重量部
処理粉体１０ ３ 重量部
珪素化合物粉体１ ５ 重量部
シリコーン処理セリサイト ２０ 重量部
メチルシロキサン網状重合体 １０ 重量部
ロ
オレイン酸オクチルドデシル ５ 重量部
ジメチコン ５ 重量部
【００３５】
＜実施例１３＞
ハートレー系白色種モルモット（雄性、５００ｇ）１群２０匹を用いて、本発明の化粧料のアレルゲン侵入抑制作用を調べた。即ち、７０匹のモルモットにウサギ血清をフロインドの完全アジュバントとともに０．１ｍｌづつ４回（１回／３日）皮内注射し、インダクションし、２週間の休止期間の後、上部背部を剃毛し、ウサギ血清を２４時間クローズドパッチし、パッチ除去後１時間で陽性であった動物より、皮膚反応の強かったものから２０匹選び出し、実験動物とした。これらの動物の背部の残りの部分を剃毛し、右面には実施例１２のファンデーションを塗布し、左面には実施例１２のファンデーションの処理粉体及び珪素化合物粉体を無処理のものに置換した、メルカプト基を有する粉体を含まないファンデーション（比較例１）を塗布し、この上にウサギ血清を２４時間クローズドパッチし、パッチ除去後皮膚反応を判定した。結果を表２に示す。これより、本発明の化粧料はアレルゲンによる炎症の惹起を抑制していることがわかる。これより、本発明の化粧料がアミノ酸、ペプチド、タンパクの皮膚への侵入を抑制し、皮膚を保護していることがわかる。尚、皮膚反応の判定基準としてはドレーズの基準を用いた。即ち、＋＋：浮腫を伴う反応、＋：明らかな紅斑を伴う反応、±：微弱な紅斑を伴う反応、−：無反応の基準である。
【００３６】
【表２】

【００３９】
【発明の効果】
本発明によれば、生体親和性の高いアレルゲンの生体への侵入を防ぐ手段を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a treated powder suitable for a cosmetic raw material and the like and a cosmetic containing the treated powder.
[0002]
[Prior art]
The powder has various functions and properties, and such functions and properties may be preferable or not preferable depending on circumstances. From such a point of view, so-called surface treatment is actively performed in which the surface of the powder is treated to develop only desirable characteristics. Examples of such surface treatment include coating treatment with a phosphate to improve dispersibility in an aqueous carrier, silica coating treatment for suppressing radical generation during light absorption, and silicone that imparts hydrophobicity to the powder surface. A baking process, a silane coupling process, etc. are mentioned. In the field of analytical chemistry, amination treatment, octadecylation treatment, phenylation treatment, cyanation treatment, etc., which increase the selective adsorption property so as to be suitable for a column carrier, can be mentioned. However, treatments involving interactions with proteins and the like are only known to adsorb specific ligands with weak binding as a means of increasing affinity. That is, the actual condition is that a surface treatment having a strong affinity for amino acids, peptides or proteins is not yet known. The powder that has been treated in this way has awaited its appearance because it can embody the action of blocking undesired proteins such as allergens.
[0003]
On the other hand, many cosmetics contain powders or treated powders, such as makeup cosmetics. However, allergens enter the body by, for example, allergen adsorption. Nothing has yet been known to have a preventive action. Also, the existence of cosmetics that prevent allergens is not known.
[0004]
From a different point of view, peptide-related substances such as amino acids, peptides, and proteins are substances that are familiar to living organisms, but they vary depending on the sequence and configuration of their constituent amino acids and are specific to the species. Therefore, many foreign substances are recognized as foreign substances and become allergens. However, because of their biocompatibility, it is difficult to prevent such substances from entering the body, and many people develop allergic symptoms. I can't deny that. That is, development of such allergen intrusion prevention means has been desired.
[0005]
[Problems to be solved by the invention]
The present invention has been made under such circumstances, and an object of the present invention is to provide a means for preventing an allergen having high biocompatibility from entering the living body.
[0006]
[Means for solving problems]
In view of such a situation, the present inventors have intensively studied for a means for preventing the entry of a highly biocompatible allergen into a living body, and as a result, the partial structure represented by the general formula (I) That is, the present inventors have found an adsorption action of peptide-related substances such as amino acids, peptides, and proteins excellent in treated powders described later, such as treated powders, having a mercapto group. As a result of further studies, it has been found that the inclusion of this in cosmetics and application on the skin can prevent the entry of such allergenic substances into the living body, leading to the completion of the invention. It was. Hereinafter, the present invention will be described in detail focusing on the implementation of the invention.
[0007]
[Chemical formula 5]

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)
[0008]
DETAILED DESCRIPTION OF THE INVENTION
(1) Treated powder of the present invention The treated powder of the present invention is a powder having a partial structure represented by the general formula (I) excluding silica, crosslinked dimethylpolysiloxane and methylsiloxane network polymer , ie, a mercapto group. It is a powder in which a mercapto group is introduced by treatment with an alkyloxysilane derivative or a halogenated silane derivative having an amino acid. Incidentally, a powder obtained by introducing a mercapto group into silica, a crosslinked dimethylpolysiloxane, and a methylsiloxane network polymer also has such a function. Such a powder is separately filed by the present inventors with a patent application. Has been made.
[0009]
The treated powder of the present invention is obtained by silylating a hydroxyl group present on the powder surface with an alkyloxysilane derivative or a halogenated silane derivative represented by the general formula (II). Of the silane derivatives represented by the general formula (II), it is particularly preferable to use the silane derivative represented by the general formula (IV). In such a treatment, a silane derivative having no mercapto group represented by the general formula (III) is added and treated, and the whole powder is coated with a silicon compound having a mercapto group . In here, the amount of the compound represented by formula in (II) to be used for treatment is preferably 1 to 100% by weight with respect to the powder to be treated, more preferably 10 to 50 wt%. This is because if the treatment amount is too small, the adsorption action may not be exhibited, and if it is too large, the characteristics of the powder itself may be impaired. In addition, when the compound represented by the general formula (III) is added for treatment, the total amount of the treatment agent is preferably 2 to 200% by weight, preferably 20 to 60% by weight. The ratio of the compound of (II) and the compound of general formula (III) is preferably 30:70 to 70:30. This is because this amount ratio is a preferable range for diluting the density of the mercapto group and firmly fixing these compounds on the powder. Examples of the treatment include a method of coating the surface with these compounds and then baking at 100 to 200 ° C., a method of condensing together with a solvent in the presence of an alkali catalyst or an acid catalyst, and the like. Further, the powder to be treated can be used without particular limitation as long as it is used in cosmetics and is other than silica, crosslinked dimethylpolysiloxane and methylsiloxane network polymer, such as titanium dioxide, Iron oxide, zirconium oxide, zinc oxide, mica, sericite, talc, calcium carbonate, calcium silicate, magnesium carbonate, magnesium silicate, lithium cobalt titanate, gunjo, bitumen, titanium mica, titanium sericite and two kinds selected from these The above baked product etc. can be illustrated preferably. These treated powders of the present invention not only have an action of adsorbing amino acids, peptides and proteins, but also have excellent spreadability, hydrophobicity, skin adhesion and the like when incorporated in cosmetics. Properties desirable as a powder also have secondary effects.
[0010]
[Chemical 6]

(In the formula, R1 ′, R2 ′, R3 ′ and R4 ′ each independently represent a halogen atom, OR5 ′, R5 ′, and R5 ′ may each independently have a hydrogen atom or a mercapto group. Represents an alkyl group having 1 to 4 carbon atoms, and at least one of R1 ′, R2 ′, R3 ′ or R4 ′ is a C1 to C4 alkyl group having a mercapto group, and at least one of them is (It shall be a C1-C4 alkyloxy group, a halogen atom, or a hydroxyl group.)
[0011]
[Chemical 7]

(In the formula, R6, R7, R8 and R9 each independently represents a halogen atom, OH, O—R10 or R10, R10 represents an alkyl group having 1 to 4 carbon atoms, and R6, R7, R8 and R9) Of which at least two are halogen atoms, hydroxyl groups or alkyloxy groups.)
[0012]
[Chemical 8]

(However, in the formula, R1 ′ represents a C1-C4 alkyl group having a mercapto group, and R2 ′, R3 ′ and R4 each independently represent a halogen atom or a C1-C4 alkyloxy group. .)
[0013]
(2) Cosmetic of the present invention The cosmetic of the present invention is a treated powder obtained by treating a powder with the treated powder of the present invention or the compound represented by the general formula (II) (however, as a powder, silica, by containing a crosslinked dimethylpolysiloxane and excluding methylsiloxane reticular polymer.) and the general formula compound with the general formula compound is polymerized obtained silicon compound (III) in (II) Features. In addition to the treated powder of the present invention, it contains a powder introduced with a mercapto group such as a treated powder obtained by treating a silicon compound such as silica, cross-linked dimethylpolysiloxane, or methylsiloxane network polymer. Ru also possible der be. By containing such a powder, the cosmetic of the present invention has an action of preventing invasion of peptides and proteins that become allergens such as mite allergen and cedar pollen. Such allergens are said to be involved in respiratory diseases such as hay fever and inflammation of the ocular mucosa, as well as skin diseases such as atopic dermatitis. ing. It has also been suggested that in people with sensitive skin, exposure to environmentally derived peptides and proteins exacerbates the skin condition. The cosmetic of the present invention has an action of adsorbing amino acids, peptides, and proteins that act on such an unfavorable living body and suppressing undesired reaction expression. The cosmetics of the present invention can be used without particular limitation as long as they are usually used. For example, basic cosmetics such as emulsions, creams, skin lotions, packs, under makeup, foundations, presto Preferred examples include makeup cosmetics such as powder, loose powder, lip color, eye color and mascara, cleaning cosmetics such as shampoo, rinse and soap, and hair cosmetics such as hair cream, hair liquid and hair tonic. The preferable content of the treated powder in the cosmetic of the present invention is 0.1 to 60% by weight, more preferably 1 to 50% by weight. Below, the manufacture example of the silicon compound powder which concerns on this invention is shown.
[0014]
<Production Example 1>
A silicon compound powder was obtained according to the following method. That is, 34.2 g (0.25 mol) of tetramethoxysilane, 44.2 (0.25 mol) of γ-mercaptopropyltrimethoxysilane, and 36.5 g of methanol were weighed in a reaction vessel equipped with a condenser and mixed well. Stir. 40.5 g of a solution prepared by dissolving 0.9 ml of concentrated hydrochloric acid in water to 162 g was added, and stirring was continued for 2 hours at 50 ° C., and a solution obtained by dissolving 3.6 g of triethanolamine in 36.5 g of methanol was added and stirred. The system was gelled. This gel was filtered, washed and dried to obtain silicon compound powder 1. It was found from multinuclear nuclear magnetic resonance that this material contains 0.45 sulfur atom per silicon atom.
[0015]
Silicon compound powder 2 was obtained by replacing γ-mercaptopropyltrimethoxysilane of Production Example 1 with γ-mercaptopropyltriethoxysilane.
[0016]
<Production Example 3>
Silicon compound powder 3 was obtained by changing γ-mercaptopropyltrimethoxysilane of Production Example 1 to dimethylmethyl-γ-mercaptopropylsilane.
[0017]
<Production Example 4>
Silicon compound powder 4 was obtained by replacing γ-mercaptopropyltrimethoxysilane of Production Example 1 with ethyldimethyl-γ-mercaptopropylsilane.
[0021]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited only to these examples.
[0022]
<Example 1>
20 g of titanium dioxide was coated with 5 g of dimethoxy-γ-mercaptopropylsilane chloride and heated at 130 ° C. for 48 hours under a nitrogen stream to obtain treated powder 1 according to the present invention.
[0023]
<Example 2>
The treated powder of the present invention was obtained according to the following method. That is, 34.2 g (0.25 mol) of tetramethoxysilane and 44.2 (0.25 mol) of γ-mercaptopropyltrimethoxysilane and 36.5 g of methanol were weighed in a reaction vessel equipped with a condenser and mixed well. Stir. 40.5 g of a solution prepared by dissolving 0.9 ml of concentrated hydrochloric acid in water to 162 g was added, and stirring was continued for 2 hours at 50 ° C. to obtain a coating treatment solution. Separately, 70 g of titanium dioxide, 3.6 g of triethanolamine, and 36.5 g of methanol were weighed into a reaction vessel equipped with a condenser and mixed and stirred well. The above-mentioned coating solution was dropped into this dispersion over 2 hours while stirring, and the obtained powder was filtered, washed and dried to obtain the treated powder 2 of the present invention.
[0024]
<Example 3>
In the same manner as in Example 1 , 20 g of iron-doped titanium dioxide (Typaque TT0-F-6; manufactured by Ishihara Sangyo Co., Ltd.) was treated to obtain treated powder 3 according to the present invention.
[0025]
<Example 4>
Like Example 1 was treated red iron oxide 20g, to obtain a treated powder 4 according to the present invention.
[0026]
<Example 5>
20 g of yellow iron oxide was treated in the same manner as in Example 1 to obtain treated powder 5 according to the present invention.
[0027]
<Example 6>
20 g of mica was treated in the same manner as in Example 1 to obtain treated powder 6 according to the present invention.
[0028]
<Example 7>
It was treated similarly sericite 20g as in Example 1 to obtain a treated powder 7 of the present invention.
[0029]
<Example 8>
Like Example 1 was treated titanium sericite 20g, to obtain a treated powder 8 according to the present invention.
[0030]
<Example 9>
20 g of titanium mica was treated in the same manner as in Example 1 to obtain treated powder 9 according to the present invention.
[0031]
<Example 10>
Like Example 1 was treated talc 20g, to obtain a treated powder 10 according to the present invention.
[0032]
<Example 11>
About the processed powder 2 of the said Example 1-10 of this invention, the processed powder 1 and 3-10 which concern on this invention, and silicon compound powder 1-4 , albumin was used as the parameter | index, and the protein adsorptive power was confirmed. In the method, 25 ml of 50 ppm albumin aqueous solution was adjusted to pH 4 with 1N nitric acid, 1 g of powder was added thereto, shaken at 20 ° C. for 24 hours, filtered, and albumin detection reagent (Test Wako) was added to develop color. Compared to the untreated powder, the thinness of the protein adsorbs ○: excellent adsorption (definitely less color development), △: slightly adsorbed (although the color development is obviously thin, but much There was no difference.), X: No adsorption (development similar to that of untreated powder). Silica gel was used as a comparative powder of silicon compound powders 1-4 . The results are shown in Table 1. This shows that these silicon compound powders , the treated powder of the present invention, and the treated powder according to the present invention are excellent in protein adsorption ability.
[0033]
[Table 1]

[0034]
<Example 12>
According to the prescription shown below, the foundation which is the cosmetics of this invention was manufactured. That is, after mixing the prescription component A with a Henschel mixer, it is pulverized with a pulverizer equipped with a 0.9 mm round hole screen. The foundation 1 was obtained by pulverizing with an attached pulverizer, filling in a metal pan, and press molding. This foundation was excellent in spreadability and had an excellent feeling of use.
A treated powder 1 5 parts by weight treated powder 2 5 parts by weight treated powder 3 10 parts by weight treated powder 4 0.1 parts by weight treated powder 5 2.9 parts by weight treated powder 6 15 parts by weight treated powder 7 12 parts by weight treated powder 8 1 part by weight treated powder 9 1 part by weight treated powder 10 3 parts by weight
Silicon compound powder 1 5 parts by weight Silicone-treated sericite 20 parts by weight Methylsiloxane network polymer 10 parts by weight Octyldodecyl looleate 5 parts by weight Dimethicone 5 parts by weight
<Example 13>
Using the Hartley white guinea pig (male, 500 g), 20 per group, the allergen invasion inhibitory action of the cosmetic of the present invention was examined. That is, 70 guinea pigs were injected intradermally with 0.1 ml of rabbit serum together with Freund's complete adjuvant (1/3 days), induction, and after a 2-week rest period, the upper back was shaved. The rabbit serum was patched for 24 hours, and 20 animals with strong skin reaction were selected from animals that were positive 1 hour after the removal of the patch, and were used as experimental animals. The remaining part of the back of these animals is shaved, the foundation of Example 12 is applied to the right side, and the treated powder and silicon compound powder of Example 12 are replaced on the left side with untreated ones. The foundation containing no mercapto group-containing powder (Comparative Example 1) was applied, and the rabbit serum was closed patch for 24 hours, and the skin reaction was determined after removing the patch. The results are shown in Table 2. From this, it can be seen that the cosmetic of the present invention suppresses inflammation caused by allergen. From this, it can be seen that the cosmetic of the present invention suppresses the entry of amino acids, peptides and proteins into the skin and protects the skin. In addition, the criteria of Draise was used as a criterion for skin reaction. That is, ++: reaction with edema, +: reaction with obvious erythema, ±: reaction with weak erythema,-: no response.
[0036]
[Table 2]

[0039]
【The invention's effect】
According to the present invention, it is possible to provide a means for preventing an allergen having high biocompatibility from entering the living body.

Claims (6)

A treated powder (however, as a powder , characterized by being obtained by treating a powder with a compound represented by the general formula (II) and a compound represented by the general formula (III)) Excluding silica, crosslinked dimethylpolysiloxane and methylsiloxane network polymer) .

Formula (II)
(In the formula, R1 ′, R2 ′, R3 ′ and R4 ′ each independently represent a halogen atom, OR5 ′, R5 ′, and R5 ′ may each independently have a hydrogen atom or a mercapto group. Represents an alkyl group having 1 to 4 carbon atoms, and at least one of R1 ′, R2 ′, R3 ′ or R4 ′ is a C1 to C4 alkyl group having a mercapto group, and at least one of them is (It shall be a C1-C4 alkyloxy group, a halogen atom, or a hydroxyl group.)

Formula (III)
(In the formula, R6, R7, R8 and R9 each independently represents a halogen atom, OH, O—R10 or R10, R10 represents an alkyl group having 1 to 4 carbon atoms, and R6, R7, R8 and R9) Of which at least two are halogen atoms, hydroxyl groups or alkyloxy groups.) The treated powder according to claim 1 , wherein the ratio of the compound represented by the general formula (II) and the compound represented by the general formula (III) is 30:70 to 70:30. The body . The treated powder according to claim 1 or 2 , wherein the compound represented by the general formula (II) is a compound represented by the general formula (IV) .

Formula (IV)
(However, in formula, R1 'represents a C1-C4 alkyl group which has a mercapto group , and R2', R3 ', and R4 represent a halogen atom or a C1-C4 alkyloxy group each independently. ) A treated powder obtained by treating a powder with the treated powder according to any one of claims 1 to 3 or the compound represented by the general formula (II) (provided that silica, Selected from silicon compound powders obtained by polymerizing a compound represented by general formula (II) and a compound represented by general formula (III), excluding crosslinked dimethylpolysiloxane and methylsiloxane network polymer. Cosmetics containing 1 type or 2 types or more. Cosmetics according to claim 4 , characterized in that they are for protection against amino acids, peptides or proteins. The cosmetic according to claim 4 or 5 , wherein the cosmetic is used for protection from allergens.