JP4047140B2 - Cosmetic composition - Google Patents

Description

【００３５】
〔式中、Ｒ¹は水素原子又は炭素数１〜６の炭化水素基を示し、複数個のＲ¹は同一でも異なっていてもよい。Ｒ²はＲ¹又はＸのいずれかを示し、Ｘは−Ｒ³−Ｚ（Ｒ³は直接結合又は炭素数１〜２０の二価炭化水素基、Ｚは１〜３級アミノ基含有基又は四級アンモニウム基含有基を示す）で表される反応性官能基を示す。ａは２以上の数、ｂは１以上の数を示す。〕
一般式（Ｉ）中、Ｒ¹は、互いに独立して、水素原子又は炭素数１〜６の炭化水素基、例えばアルキル基もしくはフェニル基を示し、好ましくはメチル基、エチル基、更に好ましくはメチル基である。Ｒ³は、好ましくは炭素数１〜６の直鎖又は分岐鎖状のアルキレン基であり、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基等が挙げられ、より好ましくはトリメチレン基又はプロピレン基である。ａ及びｂは、それぞれ重合単位の繰り返し数を示し、ａは２〜１０００の数が好ましく、ｂは１〜５０の数が好ましい。また、Ｚは、下記の一般式(II)又は一般式(III)で表わされるアミノ基又はアンモニウム基含有基が好ましい。
【００３６】
【化２】

【００３７】
また、一般式(III)において、複数個のＲ⁵は同一でも異なっていてもよい。またＴ^-の具体例としては、塩素、ヨウ素、臭素等のハロゲンイオン、メトサルフェート、エトサルフェート、メトフォスフェート、エトフォスフェート等の有機アニオンが挙げられる。
【００３８】
一般式（Ｉ）中、好ましいＸ基は、−(ＣＨ₂)₃−ＮＨ₂、−(ＣＨ₂)₃−Ｎ(ＣＨ₃)₂、−(ＣＨ₂)₃−ＮＨ−(ＣＨ₂)₂−ＮＨ₂、−(ＣＨ₂)₃−ＮＨ−(ＣＨ₂)₂−Ｎ(ＣＨ₃)₂、−(ＣＨ₂)₃−Ｎ⁺(ＣＨ₃)₃・Ｃｌ^-であり、更に好ましくは、−(ＣＨ₂)₃−ＮＨ−(ＣＨ₂)₂−ＮＨ₂である。
【００３９】
アミノ変性シリコーンの重量平均分子量は、好ましくは３０００〜２０万であり、アミン当量は、吸水性ポリマーのアニオン性官能基と反応し易く、またシリコーン化合物が疎水性であるためには、好ましくは２５０〜１００００ｇ／mol、更に好ましくは１０００〜５０００ｇ／molである。即ち、アミノ基又はアンモニウム基のポリマー中の存在量は、好ましくは０．１〜４mmol／ｇ、更に好ましくは０．２〜１mmol／ｇである。アミン当量はエタノール等の溶媒中、濃度既知の塩酸で滴定することができる。
【００４０】
（１−２）カルボキシ基を有するシリコーン化合物（以下、カルボキシ変性シリコーンという）
カルボキシ変性シリコーンは、ケイ素原子とカルボキシ基とが飽和炭化水素で結合している化合物、並びに特開２００２−１１４８４９号公報に記載されているカルボキシ基及び／又はその塩が、一般式(IV)及び（Ｖ）の少なくともいずれか一方で表わされる構造で、ケイ素原子に結合しているオルガノポリシロキサン化合物が好ましい。
【００４１】
【化３】

【００４２】
〔式中、Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰は、同一又は異なって、ヘテロ原子を含む置換基を有していてもよい、炭素数２〜２２の直鎖もしくは分岐鎖状のアルキレン基もしくはアルケニレン基、又はアリーレン基を示す。Ｙは−Ｏ−又は−ＮＨ−基を示す。Ｍは水素原子、金属、アンモニウム、総炭素数１〜２２のアルキルもしくはアルケニルアンモニウム、炭素数１〜２２のアルキルもしくはアルケニル置換ピリジニウム、総炭素数１〜２２のアルカノールアンモニウム、又は塩基性アミノ酸を示す。〕
また、特開平６−１７１１号公報に記載されているカルボキシ基及びアンモニウム基の両官能基を有する両性イオノマーシロキサンも、好ましく用いることができる。
【００４３】
カルボキシ変性シリコーンの重量平均分子量は、好ましくは、３０００〜２０万である。カルボキシ当量は、吸水性ポリマーのカチオン性官能基と反応しやすく、シリコーン化合物が疎水性であるためには、好ましくは２５０〜１００００ｇ／ｍｏｌ、更に好ましくは１０００〜５０００ｇ／ｍｏｌである。即ち、カルボキシ基のポリマー中の存在量は、好ましくは０．１〜４mmol／ｇ、更に好ましくは０．２〜１mmol／ｇである。カルボキシ当量は、エタノール等の溶媒中、濃度既知のＮａＯＨで滴定することにより求めることができる。
【００４４】
（１−３）ヒドロキシ基を有するシリコーン化合物（以下、ヒドロキシ変性シリコーンという）
ヒドロキシ変性シリコーンとして、下記一般式(VI)で表される分岐型シリコーン、下記一般式(VII)で表される両末端型シリコーン、下記一般式(VIII)で表される片末端型シリコーン、特開平５−１１２４２４号公報に記載のアルキルグリセリルエーテル変性シリコーン等を挙げることができる。
【００４５】
【化４】

【００４６】
〔式中、Ｒ¹¹は同一又は異なって炭素数１〜３のアルキル基を示し、メチル基が好ましい。Ｒ¹²は同一又は異なって、炭素数１〜８のアルキレン基を示し、トリメチレン基が好ましい。ＡＯは同一又は異なって、オキシエチレン基又はオキシプロピレン基を示し、ｆ及びｇは、それぞれ１以上の整数を示し、ｈは０又は１以上の整数を示す。〕
（１−４）エポキシ基を有するシリコーン化合物（以下、エポキシ変性シリコーンという）
エポキシ変性シリコーンとして、一般式(IX)で表される、片末端及び／又は両末端エポキシ基含有シリコーン化合物が好ましく挙げられる。
【００４７】
【化５】

【００４８】
〔式中、Ｒ¹³はそれぞれ同一又は異なって１価の炭化水素基、Ｒ¹⁴はエポキシ含有基又は１価の炭化水素基、Ａはエポキシ含有基、ｎは１〜１００００の数を示す。〕
Ｒ¹³で表される１価の炭化水素としては、メチル基、エチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基、トリフルオロプロピル基等のフッ素原子置換アルキル基等が挙げられる。Ｒ¹³は全てが同一であっても異なってもよいが、すべてのＲ¹³がメチル基であることが望ましい。
【００４９】
一般式(IX)中、Ａで表されるエポキシ含有基としては特に制限はないが、具体的には下記一般式(Ｘ)〜(XII)で表される基が挙げられる。
【００５０】
【化６】

【００５１】
一般式(IX)において、Ｒ¹⁴が、Ｒ¹³と同じものである場合は、片末端エポキシ基含有シリコーンとなり、Ａと同じものである場合は、両末端エポキシ基含有シリコーンとなる。
【００５２】
エポキシ変性シリコーンとしては、Ｒ¹⁴が、Ｒ¹³と同じである片末端エポキシ基含有シリコーンが好ましく、炭化水素基としては、メチル基、エチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基、トリフルオロプロピル基等のフッ素原子置換アルキル基等が挙げられ、メチル基であることが好ましい。
【００５３】
一般式(IX)中、ｎは、１〜５００が好ましく、５〜１００が更に好ましく、１０〜５０が特に好ましい。
【００５４】
（１−５）ラジカル重合性の不飽和基を有するシリコーン化合物
ラジカル重合性の不飽和基を有するシリコーン化合物として、特開平１１−１８１００３号公報に記載の片末端にラジカル重合性基を有するポリシロキサン化合物が好ましく挙げられる。
【００５５】
（２）吸水性ポリマー粒子の表面が、疎水性ビニルモノマーの重合体により被覆された、表面疎水化吸水性ポリマー粒子
この表面疎水化吸水性ポリマー粒子は、吸水性ポリマー粒子の表面が１種類以上の疎水性ビニルモノマーの重合体により被覆されてなる吸水性ポリマー粒子である。
【００５６】
吸水膨潤粒子の表面のべとつきを抑えられる程度に少なくとも吸水性ポリマー粒子の粒子表面の一部を被覆していることが好ましい。
【００５７】
疎水性ビニルモノマーの重合体の、表面疎水化吸水性ポリマー粒子中の存在量は、吸水性ポリマー粒子１００質量部に対し、下限は、好ましくは１質量部以上、更に好ましくは５質量部以上、特に好ましくは１０質量部以上である。上限は、好ましくは１０００質量部以下、更に好ましくは４００質量部以下、特に好ましくは２００質量部以下である。この範囲であれば、吸水後のべとつき感がなく、また吸水速度もとくに阻害されることがなく好ましい。
【００５８】
本発明に用いられる疎水性ビニルモノマーは、重合により疎水性重合体が得られる重合性モノマーであり、一般的なラジカル重合開始剤や紫外線照射等の重合法により重合することができる。
【００５９】
疎水性ビニルモノマーは、前記で定義した疎水性を有するモノマーであり、通常のラジカル重合性の疎水性ビニルモノマーが好適に用いられる。かかるモノマーの具体例として、例えば、スチレン、酢酸ビニル、ジビニルベンゼン、アクリル酸ブチル、アクリル酸２−エチルヘキシル、アクリル酸シクロヘキシル、アクリル酸デシル、アクリル酸ラウリル、アクリル酸ドデセニル、アクリル酸ミリスチル、アクリル酸パルミチル、アクリル酸ヘキサデセニル、アクリル酸ステアリル、アクリル酸オクタデセニル、アクリル酸ベヘニル等のアクリル酸エステル類、メタクリル酸ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸シクロヘキシル、メタクリル酸デシル、メタクリル酸ラウリル、メタクリル酸ドデセニル、メタクリル酸ミリスチル、メタクリル酸パルミチル、メタクリル酸ヘキサデセニル、メタクリル酸ステアリル、メタクリル酸オクタデセニル、メタクリル酸ベヘニル等のメタクリル酸エステル類、トリフルオロエチルメタクリレート等のフッ素系単量体、シリコーンマクロモノマー等が挙げられる。これらの疎水性モノマーは１種以上を使用することが出来る。これらの中で、スチレン、アルキル基の炭素数１〜22のアルキル（メタ）アクリレートが、疎水性が高く、モノマーが入手し易く、好ましい。
【００６０】
本発明に用いられる疎水性重合体の重量平均分子量は、好ましくは１０００〜５０万、更に好ましくは３０００〜２０万、特に好ましくは１万〜２０万である。この重量平均分子量の測定方法は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー、ポリスチレン換算）による。カラムは、昭和電工製、Ｓｈｏｄｅｘ ＫＦ−８０６。
【００６１】
また、得られる重合体の疎水性を極度に阻害しない程度に、生成する重合体の吸水性ポリマーへの接着性を向上させる目的で、前述の親水性ビニルモノマーを共重合させてもよい。
【００６２】
そのような親水性ビニルモノマーは、（メタ）アクリル酸、マレイン酸、イタコン酸等のα，β−不飽和カルボン酸、無水マレイン酸、クロロメチルスチレン、グリシジル（メタ）アクリレート、（メタ）アクリロイルオキシエチルイソシアネート、３−（トリメトキシシリル）プロピル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ビニルピリジン、（メタ）アクリルアミド等を挙げることができる。これらの親水性ビニルモノマーは１種以上を使用することができる。親水性ビニルモノマーの使用量は、疎水性ビニルモノマーの重合体を構成する全モノマーに対して、好ましくは０〜５０質量％、更に好ましくは０〜２０質量％である。
【００６３】
（３）吸水性ポリマー粒子の表面が、フッ素系界面活性剤で処理された、表面疎水化吸水性ポリマー粒子
フッ素系界面活性剤の親水部は、アニオン、ノニオン、カチオン又は両性の４種類何れを用いてもよく、疎水部は、フルオロカーボン鎖又はパーフルオロカーボン鎖を用いることができる。吸水性ポリマー粒子表面と反応することが出来る官能基を持つことが好ましく、親水部はアニオン、カチオン又は両性であることが好ましく、カチオン又は両性のものが更に好ましい。また、疎水部である炭素鎖は、直鎖であっても分枝鎖状であってもよい。例えば、次のようなフッ素系界面活性剤が挙げられる。
【００６４】
フルオロアルキル（Ｃ₂〜Ｃ₁₀）カルボン酸、Ｎ−パーフルオロオクタンスルホニルグルタミン酸ジナトリウム、３−［フルオロアルキル（Ｃ₆〜Ｃ₁₁）オキシ］−１−アルキル（Ｃ₃〜Ｃ₄）スルホン酸ナトリウム、３−［ω−フルオロアルカノイル（Ｃ₆〜Ｃ₈）−Ｎ−エチルアミノ］−１−プロパンスルホン酸ナトリウム、Ｎ−［３−（パーフルオロオクタンスルホンアミド）プロピル］−Ｎ，Ｎ−ジメチル−Ｎ−カルボキシメチレンアンモニウムベタイン、フルオロアルキル（Ｃ₁₁〜Ｃ₂₀）カルボン酸、パーフルオロアルキルカルボン酸（Ｃ₇〜Ｃ₁₃）、パーフルオロオクタンスルホン酸ジエタノールアミド、パーフルオロアルキル（Ｃ₄〜Ｃ₁₂）スルホン酸塩（Ｌｉ、Ｋ、Ｎａ）、Ｎ−プロピル−Ｎ−（２−ヒドロキシエチル）パーフルオロオクタンスルホンアミド、パーフルオロアルキル（Ｃ₆〜Ｃ₁₀）スルホンアミドプロピルトリメチルアンモニウム塩、パーフルオロアルキル（Ｃ₆〜Ｃ₁₀）−Ｎ−エチルスルホニルグリシン塩（Ｋ）、リン酸ビス（Ｎ−パーフルオロオクチルスルホニル−Ｎ−エチルアミノエチル）、モノパーフルオロアルキル（Ｃ₆〜Ｃ₁₆）エチルリン酸エステル、パーフルオロアルキル第四級アンモニウムヨウ化物（商品名 フロラードＦＣ−１３５、住友スリーエム株式会社製カチオン性フッ素系界面活性剤）、パーフルオロアルキルアルコキシレート（商品名 フロラードＦＣ−１７１、住友スリーエム株式会社製ノニオン性界面活性剤）、パーフルオロアルキルスルホン酸カリウム塩（商品名 フロラードＦＣ−９５およびＦＣ−９８、住友スリーエム株式会社製アニオン性界面活性剤）。
【００６５】
（４）吸水性ポリマー粒子の表面が、シランカップリング剤で処理された、表面疎水化吸水性ポリマー粒子
シランカップリング剤として、特開昭６１−２１１３０５号公報記載のシランカップリング剤を用いることができる。
【００６６】
好ましい具体例として、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルメチルジエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−クロロプロピルメチルジメトキシシラン等が挙げられる。
【００６７】
［吸水性ポリマー粒子の製造法］
（１）親水性ビニルモノマーを重合して吸水性ポリマー粒子を製造する方法
吸水性ポリマーに、親水性ビニルモノマーの重合体を用いる場合は、親水性ビニルモノマー及び架橋剤の重合方法としては、如何なる方法を採用してもよいが、親水性ビニルモノマーの水溶液（好ましくは濃度１〜７０質量％）を重合させる方法が好ましく、例えば、水溶液重合法、逆相懸濁重合法、パール重合法等の各種の方法を採用することができる。中でも、重合時の作業性や、得られる吸水性ポリマーの吸水性能の点から、水溶液重合法又は逆相懸濁重合法が好ましく、吸水性ポリマーの吸水性能が高い点から、逆相懸濁重合法が特に好ましい。親水性ビニルモノマーの重合温度は２０〜１２０℃であることが好ましく、重合時間は２０〜１８０分であることが好ましい。
【００６８】
重合開始剤は、水溶性ラジカル重合開始剤、例えば過酸化物、ハイドロパーオキシド、あるいはアゾ化合物等が既知の量で用いられる。これらの重合開始剤は、２種以上を混合して使用することも可能であり、更には、クロムイオン、亜硫酸塩、ヒドロキシルアミン、ヒドラジン等を加えてレドックス系重合開始剤として使用することも可能である。必要に応じて、油溶性ラジカル重合開始剤、例えば、ベンゾイルパーオキシド、ラウロイルパーオキシド、ターシャリーブチルパーオキシピバレート、ジイソプロピルパーオキシジカーボネート等のパーオキシド系開始剤、アゾビス（イソブチロニトリル）、アゾビス（２，４−ジメチルバレロニトリル）、アゾビス（ジメチルイソブチレート）、アゾビス（シクロヘキサンカルボニトリル）等のアゾ系開始剤も用いることができる。
【００６９】
水溶性重合開始剤の使用量は、親水性ビニルモノマーに対して０．０３〜５質量％が好ましく、０．１〜２質量％が更に好ましい。
【００７０】
親水性ビニルモノマーを、油相（溶剤）中に分散安定化させるために分散剤を使用する。分散剤としては、一般のアニオン性、カチオン性、ノニオン性及び両性の界面活性剤、天然、半合成及び合成ポリマー等が挙げられる。例えば、ポリオキシエチレンドデシルエーテル硫酸エステルナトリウム、ドデシルエーテル硫酸エステルナトリウム等のアニオン性界面活性剤；トリメチルステアリルアンモニウムクロリド及びカルボキシメチルジメチルセチルアンモニウム等のカチオン性及び両性の界面活性剤；ショ糖モノステアレート、ショ糖ジラウレート等のショ糖脂肪酸エステル、ソルビタンモノステアレート等のソルビタンエステル、ポリオキシエチレンソルビタンモノステアレート等のソルビタンエステルのポリオキシアルキレン付加物等のノニオン性界面活性剤；デンプン及びその誘導体、エチルセルロース等のセルロースエーテル、セルロースアセテート等のセルロースエステル等のセルロース誘導体等の天然及び半合成ポリマー； ポリビニルアルコール及びその誘導体、マレイン化ポリブタジエン、スチレン−ジメチルアミノエチルメタクリレート４級塩等の合成ポリマーが挙げられる。
【００７１】
表面疎水化吸水性ポリマー粒子を製造するためには、前述の１種以上の官能基を有するシリコーン化合物あるいは前述のフッ素系界面活性剤を分散剤として用いることが好ましい。前述の他の分散剤と併用してもよい。シリコーン化合物中、分散剤として好ましいものは、アミノ基、アンモニウム基、ヒドロキシ基、及びカルボキシ基からなる群から選ばれる１種以上の官能基を有するシリコーン化合物である。
【００７２】
分散剤は、吸水性ポリマー粒子を構成する全ビニルモノマー１００質量部に対して、０．５〜３０質量部が好ましく、１〜１０質量部が更に好ましく、１〜７質量部存在させることが特に好ましい。
【００７３】
逆相懸濁重合法に用いる溶剤は、好ましくは、炭化水素系溶剤もしくはシリコーン系溶剤又はそれらの混合物である。炭化水素系溶剤として、ヘキサン、ヘプタン、ドデカン、シクロヘキサン、メチルシクロヘキサン、イソオクタン、水添トリイソブチレン等の脂肪族炭化水素、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素等が例示され、シリコーン系溶剤として、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ヘキサメチルジシロキサン、オクタメチルトリシロキサン等が例示される。これらの中でヘキサン、シクロヘキサンが特に好ましい。
【００７４】
重合後、反応系中の水もしくは溶剤を留去する前に、架橋剤を後から添加して、好ましくは４０〜１５０℃に加熱し、表面架橋させても良い。
【００７５】
（２）吸水性ポリマー粒子から表面疎水化吸水性ポリマー粒子を製造する方法表面疎水化吸水性ポリマー粒子は、重合後の吸水性ポリマー粒子、又は天然ポリマー等の予め得られた吸水性ポリマー粒子から製造することができる。
【００７６】
吸水性ポリマー粒子と、１種以上の官能基を有するシリコーン化合物、フッ素系界面活性剤又はシランカップリング剤存在下、更に必要に応じ、架橋剤及び／又はラジカル重合開始剤を加え、水存在下、好ましくは溶剤中、加熱する製造法が好ましい。水が存在することで、吸水性ポリマー粒子の官能基が解離し、１種以上の官能基を有するシリコーン化合物、フッ素系界面活性剤又はシランカップリング剤の官能基と反応し易くなる。１種以上の官能基を有するシリコーン化合物、フッ素系界面活性剤又はシランカップリング剤の存在量は、吸水性ポリマー（粒子）１００質量部に対して、好ましくは０．００１質量部以上、更に好ましくは０．０１質量部以上、特に好ましくは０．１質量部以上であり、上限は、好ましくは２０質量部以下、更に好ましくは１０質量部以下、特に好ましくは５質量部以下である。
【００７７】
溶剤としては、前述の炭化水素系溶剤もしくはシリコーン系溶剤又はそれらの混合物が好ましく用いられる。水の反応系中の存在量は、吸水性ポリマー（粒子）１００質量部に対して、好ましくは１〜２００質量部、更に好ましくは１０〜１００質量部である。水は反応後、留去等により脱水される。架橋剤は、使用する場合、吸水性ポリマー（粒子）１００質量部に対して、好ましくは０．０１〜１０質量部、更に好ましくは０．０１〜５質量部、特に好ましくは０．０１〜３質量部存在させる。
【００７８】
ラジカル重合性の不飽和基を有するシリコーン化合物を用いる場合、前述の油溶性ラジカル重合開始剤を共に存在させることが好ましい。１種以上の官能基を有するシリコーン化合物又はフッ素系界面活性剤は、直接、又は有機溶媒、界面活性剤もしくは分散剤で、可溶化もしくは乳化分散した溶液にし、場合によっては噴霧状で添加することができる。表面処理を円滑に行うための加熱は、４０〜１５０℃の範囲が好ましい。
【００７９】
１種以上の官能基を有するシリコーン化合物、フッ素系界面活性剤又はシランカップリング剤の混合時期は、吸水性ポリマーの重合体の粉砕前又は粉砕後いずれでもよいが、より好ましくは、吸水性ポリマーを粉砕後、吸水性ポリマー粒子とし、必要に応じ乾燥などにより含水量を適当な範囲に調整し、例えばニーダー中で混合させる。
【００８０】
疎水性ビニルモノマーの重合体により被覆された吸水性ポリマー粒子は、吸水性ポリマー粒子の重合中又は重合後の逆相懸濁重合溶液、すなわち溶剤中に吸水性ポリマー粒子が懸濁したスラリーに、疎水性ビニルモノマー及び前述の油溶性重合開始剤を添加し、重合させることにより得られるものが好ましい。溶剤としては、前述の炭化水素系溶剤もしくはシリコーン系溶剤又はそれらの混合物が好ましく挙げられる。
【００８１】
油溶性重合開始剤の使用量は、疎水性ビニルモノマーに対して０．０３〜５質量％が好ましく、０．１〜２質量％が更に好ましい。重合開始剤はあらかじめ他の成分と混合溶解して使用されるが、残存モノマーを低減する目的から重合途中で溶剤等に希釈して、一括あるいは連続的に添加することが可能である。重合温度は２０〜１２０℃であることが好ましく、重合時間は２０〜１８０分であることが好ましい。
【００８２】
本発明に用いられる表面疎水化吸水性ポリマー粒子としては、親水性ビニルモノマー及び架橋剤を、１種以上の官能基を有するシリコーン化合物又はフッ素系界面活性剤の存在下、逆相懸濁重合法で、重合して得られるもの、吸水性ポリマー粒子と、１種以上の官能基を有するシリコーン化合物、フッ素系界面活性剤又はシランカップリング剤を、水存在下、加熱して得られるもの、又は親水性ビニルモノマー及び架橋剤を、水溶性重合開始剤及び分散剤の存在下、逆相懸濁重合させ、重合中又は重合後に、疎水性ビニルモノマー及び油溶性重合開始剤を添加し、重合して得られるものが好ましく挙げられる。
【００８３】
［抗菌剤］
本発明の化粧料組成物には、抗菌や殺菌により皮膚常在菌を抑制及び／又は殺菌するために、抗菌剤を用いることが好ましい。抗菌剤の種類は、本発明の目的を損なわない限り何れでもよい。
【００８４】
抗菌剤としては、例えば、ベンザルコニウム塩、ベンゼトニウム塩、アルキル４級アンモニウム塩、クロルヘキシジン塩、ピリジニウム塩等のカチオン系化合物；イソプロピルメチルフェノール等のフェノール化合物；トリクロロカルバン等のカルバニリド化合物；トリクロサン等のジフェニルエーテル化合物；ヘキサクロロフェン；銀担持シリカ、銀担持ゼオライト、８−オキシキノリン銅等の抗菌性の金属又は有機金属が好ましく挙げられる。
【００８５】
カチオン系化合物としては、次の一般式(XIII)で表わされる第４級アンモニウム塩、一般式(XIV)で表わされるベンザルコニウム塩、ベンゼトニウム塩、一般式(XV)で表わされるクロルヘキシジン塩、一般式(XVI)で表わされるピリジニウム塩等が好ましく挙げられる。
【００８６】
【化７】

【００８７】
（式中、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸の内、少なくとも１つは、炭素数１６〜２６のアルキル基、アルケニル基又はヒドロキシアルキル基を示し、それらは互いに同一であっても異なっていてもよい。残りは、炭素数１〜３のアルキル基、ヒドロキシアルキル基又はエチレンオキサイド平均付加モル数１０以下のポリオキシエチレン基を示し、互いに同一であっても異なっていてもよい。Ｚ^1-はハロゲンイオン又は有機アニオンを示す。）
【００８８】
【化８】

【００８９】
（式中、Ｒ¹⁹は炭素数８〜２０の直鎖もしくは分岐鎖のアルキル基又はアルケニル基あるいは式
【００９０】
【化９】

【００９１】
で表わされる基を示し、Ｚ^1-は前記と同じ意味を示す。）
【００９２】
【化１０】

【００９３】
（式中、Ｚ²はグルコン酸、酢酸又は塩酸を示す。）
【００９４】
【化１１】

【００９５】
（式中、Ｒ²⁰は炭素数６〜２０の直鎖もしくは分岐鎖のアルキル基又はアルケニル基を示し、Ｚ^1-は前記と同じ意味を示す。）
上記一般式(XIII)、(XIV)及び(XVI)中のＺ^1-としては、塩素、ヨウ素、臭素等のハロゲンイオンが好ましく、塩素イオンが更に好ましい。
【００９６】
カチオン系化合物の好適なものの具体例としては、塩化ベンザルコニウム、塩化ベンゼトニウム、塩酸クロルヘキシジン、グルコン酸クロルヘキシジンが挙げられる。
【００９７】
抗菌剤は、１種単独又は２種類以上を混合して用いることができる。抗菌剤中、殺菌効果のあるカチオン系化合物が更に好ましく、塩化ベンザルコニウムが特に好ましい。
【００９８】
［消臭剤］
本発明の化粧料組成物は、汗の成分が菌により分解され、発生した臭いを消臭するために、消臭剤を含有することが好ましい。消臭剤は本発明の目的を損なわない限り、従来の化粧料に慣用的に用いられているものであれば何でもよい。消臭方法は臭気物質の物理的吸着、化学的中和などの物理的消臭剤、中和消臭剤が挙げられる。好ましいものは、酸化カルシウム、酸化マグネシウム、酸化亜鉛、及び酸化バリウムからなる群から選ばれる１種以上の金属酸化物である。 金属酸化物は１種類又は２種類以上を混合して用いることができる。これらの中でも、酸化亜鉛が特に好ましい。化粧料中の分散性を向上させるため、また汗で流されないために、金属酸化物の表面が疎水化処理されたもの、特にシリコーン及び／又はフッ素化合物で被覆したものが好ましい。被覆するためには、表面処理を行うことが好ましい。処理剤としては、メチルハイドロジェンポリシロキサン、ジメチルポリシロキサン、特開平５−３３９５１８号公報や特開平７−１９６９４６号公報に記載されているように、ヒドロキシ基、ハロゲン原子、アミノ基又はアルコキシ基等を有する反応性アルキルポリシロキサン（これらの官能基は、片末端、両末端、側鎖中にあってもよく、ケイ素原子に直接、又は置換基を有していてもよい２価の炭化水素基を介して結合している）、特開平６−２３２６２号公報に記載されているフッ素基含有ハイドロジェンポリシロキサン等が挙げられる。これらは、必要なら加熱等を行い金属酸化物と反応させることができる。シリコーン及び／又はフッ素化合物の被覆量は、金属酸化物１００質量部に対して、０．１〜２０質量部が好ましく、１〜１０質量部が更に好ましい。
【００９９】
本発明に用いられる消臭剤としては、例えば、「微細亜鉛華」、「ＦＩＮＥＸ−２５」、「ＦＩＮＥＸ−２５ＬＰ」、「ＦＩＮＥＸ−５０」「ＦＩＮＥＸ−５０ＬＰ」、「ＦＩＮＥＸ−７５」（以上、堺化学工業（株）製）、「ＺｎＯ−３０５」、「ＺｎＯ−３１０」「ＺｎＯ−３５０」（以上、住友大阪セメント（株）製）、「ＭＺ−５００」（テイカ社製）等が挙げられる。より好ましくは、表面が疎水化処理された金属酸化物が微分散したものであり、例えば、「コスメサーブ ＷＰＡ−６５ＭＰ」、「コスメサーブ ＷＰＡ−ＳＴＤ」（以上、大日本化成（株）製）、「ダイトパーションＺｎ５０」（大東化成工業（株）製）等が挙げられる。
【０１００】
金属酸化物の平均粒径は特に限定されないが、０．００１〜５μｍが好ましく、０．０１〜１μｍが更に好ましく、０．１〜１μｍが特に好ましい。
【０１０１】
［化粧料組成物］
本発明の化粧料組成物は、乳化化粧料、油性化粧料、スプレー化粧料、スティック状化粧料、パウダー状化粧料、ロールオン型化粧料のいずれでもよいが、制汗剤用であることが好ましい。
【０１０２】
本発明の化粧料組成物中、吸水性ポリマー粒子の含有量（水膨潤していない状態の含有量）は、０．１〜５０質量％が好ましく、１〜３０質量％が更に好ましく、１〜２０質量％が特に好ましい。この範囲内では、吸汗後のべとつきを抑えることができるため好ましい。更に、表面疎水化吸水性ポリマー粒子を用いることにより、吸汗後も粒子のサラサラ感を維持するため、皮膚上の感触がよく好ましい。
【０１０３】
本発明の化粧料組成物中、抗菌剤の含有量は、０．００１〜５質量％が好ましく、０．０１〜３質量％が更に好ましく、０．０１〜１質量％が特に好ましい。この範囲内では、殺菌効果が高く、配合安定性がよく好ましい。
【０１０４】
本発明の化粧料組成物中、消臭剤の含有量は、０．０１〜３０質量％が好ましく、０．０５〜２０質量％が更に好ましく、０．１〜１０質量％が特に好ましい。この範囲内では、好ましい消臭効果が得られ、塗布後の白さが目だたず好ましい。
【０１０５】
吸水性ポリマー粒子と消臭剤の割合は、消臭剤／吸水性ポリマー粒子（質量比）＝１／３０〜１／１が好ましく、１／２０〜１／２が更に好ましい。この範囲内では、消臭剤により、吸水性ポリマー粒子の吸水効果に影響を与えないために好ましい。
【０１０６】
また、本発明の化粧料組成物は、更にシリコーン油を含有することにより、よりべとつき感を低減し、さっぱりした使用感を与える化粧料が得られる。かかるシリコーン油としては、特に限定されないが、具体例としては、ジメチルポリシロキサン、メチルフェニルポリシロキサン等の鎖状シリコーン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン等の環状シリコーン等が挙げられ、必要に応じて、これらの１種又は２種以上を適宜選択して用いることができる。本発明の化粧料組成物が、スティック状である場合、シリコーン油は、組成物中に、好ましくは５〜９０質量％、更に好ましくは３０〜８０質量％含有される。
【０１０７】
本発明の化粧料組成物には、更に化粧料成分として一般に使用されているその他の成分を、本発明の効果を損なわない範囲で、上記化粧料の形態、種類等に応じて適宜配合することができる。
【０１０８】
かかる化粧料成分としては、例えばマイカ、タルク、セリサイト、カオリン、ポリメチルシルセスキオキサン、硫酸バリウム等の体質顔料；酸化チタン、亜鉛華、酸化鉄等の無機顔料；ナイロンパウダー等の有機粉体；これら粉体をシリコーン処理、金属石けん処理、Ｎ−アシルグルタミン酸処理等の表面疎水化処理した粉体；固体状又は液状のパラフィン、固形パラフィン、マイクロクリスタリンワックス、ワセリン、セレシン、オゾケライト、モンタンろう等の炭化水素類；オリーブ、地ろう、カルナウバろう、ラノリン、鯨ろう等の植物性油脂、動物性油脂又はロウ；ステアリン酸、パルミチン酸、オレイン酸、グリセリンモノステアリン酸エステル、グリセリンジステアリン酸エステル、グリセリンモノオレイン酸エステル、イソプロピルミリスチン酸エステル、イソプロピルステアリン酸エステル、ブチルステアリン酸エステル等の脂肪酸又はそのエステル類；セチルアルコール、ステアリルアルコール、パルミチルアルコール、ヘキシルドデシルアルコール等の高級アルコール類；カチオン化セルロース、カルボキシベタイン型ポリマー、カチオン化シリコーン等の吸着又は増粘剤；グリコール、ソルビトール等の保湿作用を有する多価アルコール類；美白剤、鎮痛消炎剤、鎮痒剤、収斂剤、皮膚軟化剤、ホルモン剤等の薬効成分；水；界面活性剤；Ｗ／Ｏ又はＯ／Ｗ型乳化剤；ポリエーテル変性シリコーン、ポリエーテル・アルキル変性シリコーン、グリセリルエーテル変性シリコーン等のシリコーン油用の乳化剤；メチルセルロース、エチルセルロース、カルボキシメチルセルロース、ポリアクリル酸、トラガント、寒天、ゼラチン等の増粘剤；エタノール、グリセリン、１，３−ブチレングリコール、プロピレングリコール等の低級アルコール；その他、乳化安定剤、キレート剤、紫外線防御剤、ｐＨ調整剤、防腐剤、色素類、香料等が挙げられる。
【０１０９】
本発明の化粧料は、それぞれ常法に従って製造される。
【０１１０】
【実施例】
以下の例における「％」は、特に断らない限り、「質量％」を示す。
【０１１１】
合成例１
メタクリル酸（三菱レイヨン(株)製）５００ｇとイオン交換水２１０ｇを２Ｌのビーカーに取り、冷却しつつ攪拌下、３０％の苛性ソーダ水溶液５８１ｇを滴下して７５％の中和を行った後、過硫酸カリウム２．０ｇ（０．４％対メタクリル酸）を４０．０ｇのイオン交換水に溶解した溶液と、架橋剤であるエチレングリコールジグリシジルエーテル（商品名、デナコールＥＸ８１０、長瀬化成(株)製）１０ｇ（２．０％対メタクリル酸）を加え、均一に溶解した。得られた溶液を２Ｌのビーカー中、シクロヘキサン１１３０ｍｌにアミノ変性シリコーン（ジーイー東芝シリコーン（株）製ＴＳＦ４７０３、粘度（２５℃）：１０００ｍｍ²／ｓ、アミン当量：１６００ｇ／ｍｏｌ）１５ｇを溶解して得られた溶液に添加し、ホモミキサーを用い、回転数１００００ｒ／minで５分間強攪拌を行い微細な油中水型分散滴を作った。次に還流冷却器を付した５Ｌのステンレス製反応釜に、シクロヘキサン１１８０ｍｌにアミノ変性シリコーン（ジーイー東芝シリコーン（株）製ＴＳＦ４７０３、粘度（２５℃）：１０００ｍｍ²／ｓ、アミン当量：１６００ｇ／ｍｏｌ）１０ｇを入れ３５０ｒ／minで攪拌し、予め系内を７５℃に加熱し、窒素置換した溶液の中に、上記のメタクリル酸部分中和油中水型分散滴を滴下し、同時に重合を開始させた。全量を２．０時間で滴下した後、還流温度で更に４時間熟成を行った。その後脱水管を取り付け、昇温し６００ｍｌの脱水を行い、更に２３１０ｍｌのシクロヘキサンを蒸発留去後、放冷し合成を完結した。減圧下で蒸発乾固を行うことによって６３０ｇの微粉末状の白色乾燥ポリマーを得た。得られた吸水性ポリマー粒子の平均粒径は３．０μｍであった。吸水量は２２ｇ／ｇであった。
【０１１２】
合成例２
架橋剤であるエチレングリコールジグリシジルエーテルの量を２５ｇにした以外は合成例１と同様の操作を行い、吸水性ポリマー粒子を得た。得られた吸水性ポリマー粒子の平均粒径は２．８μｍであった。吸水量は１５ｇ／ｇであった。
【０１１３】
合成例３
メタクリル酸（三菱レイヨン(株)製）５００ｇとイオン交換水２１０ｇを２Ｌのビーカーに取り、冷却しつつ攪拌下、３０％の苛性ソーダ水溶液５８１ｇを滴下して７５％の中和を行った後、過硫酸カリウム２．０ｇ（０．４％対メタクリル酸）を４０．０ｇのイオン交換水に溶解した溶液と、架橋剤であるエチレングリコールジグリシジルエーテル（商品名、デナコールＥＸ８１０、長瀬化成(株)製）２５ｇ（５．０％対メタクリル酸）を加え、均一に溶解した。得られた溶液を２Ｌのビーカー中、シクロヘキサン１１３０ｍｌにアミノ変性シリコーン（信越化学工業（株）製 ＫＦ−８６１、粘度（２５℃）：３５００ｍｍ²／ｓ、アミン当量：２０００ｇ／ｍｏｌ）１５ｇを溶解して得られた溶液に添加し、ホモミキサーを用い、回転数５０００ｒ／minで５分間強攪拌を行い微細な油中水型分散滴を作った。次に還流冷却器を付した５Ｌのステンレス製反応釜に、シクロヘキサン１１８０ｍｌにアミノ変性シリコーン（信越化学工業（株）製 ＫＦ−８６１、粘度（２５℃）：３５００ｍｍ²／ｓ、アミン当量：２０００ｇ／ｍｏｌ）１０ｇを入れ３５０ｒ／minで攪拌し、予め系内を７５℃に加熱し、窒素置換した溶液の中に、上記のメタクリル酸部分中和油中水型分散滴を滴下し、同時に重合を開始させた。全量を２．０時間で滴下した後、還流温度で更に４時間熟成を行った。その後脱水管を取り付け、昇温し６００ｍｌの脱水を行い、デカメチルシクロペンタシロキサン（ＳＨ２４５、東レダウコーニングシリコーン社製）３５０ｇを加えて、更に２３１０ｍｌのシクロヘキサンのみを蒸発留去後、放冷し合成を完結した。９５０ｇの白色スラリー状のポリマーを得た。得られた吸水性ポリマー粒子の平均粒径は６．３μｍであった。吸水量は２５ｇ／ｇであった。
【０１１４】
合成例４
架橋剤であるエチレングリコールジグリシジルエーテルの量を５ｇ、ホモミキサーの回転数を３０００ｒ／minにした以外は合成例３と同様の操作を行い、吸水性ポリマー粒子を得た。得られた吸水性ポリマー粒子の平均粒径は１２．１μｍであった。吸水量は３８ｇ／ｇであった。
【０１１５】
実施例１〜５及び比較例１〜２
２００ｍｌのビーカーに、下記に示す、オイル類、制汗成分、吸水性ポリマー粒子、粉体類、抗菌剤、消臭剤を入れ、室温で２０分間混合した。８０℃まで昇温後、高級アルコールを混ぜて更に２０分間攪拌した。６５℃まで冷却させて取り出すことで、スティック状制汗剤を製造した。得られた制汗剤について、下記方法で制汗試験及び防臭試験を行った。結果を表１に示す。
【０１１６】
＜配合成分＞
オイル類
ａ−１：デカメチルシクロペンタシロキサン、ＳＨ２４５、東レダウコーニングシリコーン社製
ａ−２：ジメチルポリシロキサン、ＫＦ９６Ａ−１０ｃｓ、信越化学工業（株）製
粉体類
ｂ−１：シリコンレジン、ＫＭＰ５９９、信越化学工業（株）製
高級アルコール
ｃ−１：ステアリルアルコール
吸水性ポリマー粒子
ｄ−１：合成例１で得られたもの
ｄ−２：合成例２で得られたもの
ｄ−３：合成例３で得られたもの
ｄ−４：合成例４で得られたもの
制汗成分
ｅ−１：アルミニウムハイドロキシクロライド
ｅ−２：パラフェノールスルホン酸亜鉛
抗菌剤
ｆ−１：塩化ベンザルコニウム
ｆ−２：イソプロピルメチルフェノール
ｆ−３：トリクロサン
消臭剤
ｇ−１：酸化亜鉛、ＦＩＮＥＸ−５０ＬＰ、堺化学工業（株）製
ｇ−２：酸化亜鉛、ダイトパーションＺｎ５０、大東化成工業（株）製
ｇ−３：酸化亜鉛、コスメサーブ ＷＰＡ−６５ＭＰ、大日本化成（株）製
＜制汗試験＞
健康な男性パネラー５名に制汗剤を塗布後、温室(４０℃／８０％ＲＨ)に５分間入室した時の腋の濡れ具合を、下記項目の４段階で評価し、その平均値で判定した。未塗布では３．７であった。
【０１１７】
１：乾いている
２：やや湿っている
３：明らかに湿っている
４：濡れている
＜防臭試験＞
腋臭を有する健康な男性パネラー５名に、制汗剤を朝、腋に塗布して８時間後に腋の臭気強度を、３名の官能評価者によって下記項目の６段階で評価し、その平均値で判定した。未塗布では３．５であった。
【０１１８】
０：無臭
１：微臭
２：やや臭う
３：やや強く臭う
４：強く臭う
５：非常に強く臭う
【０１１９】
【表１】

【０１２０】
注）
*1：吸水性ポリマー粒子の配合量はポリマー量である
*2：酸化亜鉛としての配合量である
比較例１及び２の制汗剤は、塗布後、腋にきしみ感が生じた。
【０１２１】
以下に処方例を示す。
【０１２２】
処方例１：ボディーローション
＜組成＞
吸水性ポリマー粒子（合成例１） ３．０％
酸化亜鉛（ダイトパーションＺｎ５０） １．０
塩化ベンザルコニウム ０．１
グリセリン ８０．０
ステアリルアルコール ５．０
ジメチルポリシロキサン^* ２．０
シリコーン処理タルク ３．０
水 残量
＊：ＫＦ９６Ａ−１０ｃｓ、信越化学工業（株）製。
【０１２３】
処方例２：パウダースプレー型制汗剤
＜組成＞
吸水性ポリマー粒子（合成例２） ２．０％
酸化亜鉛（ＦＩＮＥＸ−５０ＬＰ） ０．２
塩化ベンザルコニウム ０．０２
シリコーンパウダー^* １．０
タルク １２．０
パルミチン酸イソプロピル ２．０
香料 ０．２
液化石油ガス 残 量
＊：ＫＭＰ５９９、信越化学工業（株）製。
【０１２４】
処方例３：ロールオン型制汗剤
＜組成＞
ジメチルポリシロキサン^* ５．０％
エタノール ２０．０
グリセリン ４．０
吸水性ポリマー粒子（合成例３） ５．０
酸化亜鉛（コスメサーブ ＷＰＡ−６５ＭＰ） １．０
塩化ベンザルコニウム ０．１
オクタメチルシクロテトラシロキサン 残量
＊：ＫＦ９６Ａ−１０ｃｓ、信越化学工業（株）製
【０１２５】
【発明の効果】
本発明の化粧料組成物は、汗によるべたつきを防ぎ、消臭効果が高く、好ましい使用感を有するものである。また、表面疎水化吸水性ポリマー粒子を用いることで、更に吸汗後もサラサラ感が高く、感触的に好ましいものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cosmetic composition useful as an external preparation for skin, and particularly to a cosmetic composition for antiperspirant.
[0002]
[Prior art]
Conventionally, cosmetics having an antiperspirant effect have been used because the sweaty part, especially wrinkles, makes the skin feel bad and unpleasant odors are generated. In particular, an aluminum compound is used as a main component exhibiting an antiperspirant effect (see Patent Document 1). However, the feeling such as stickiness due to sweat remained, and the deodorizing effect and the sustainability of the effect were insufficient.
[0003]
Thus, Patent Document 2 discloses a cosmetic containing a hydrophobized powder and a water-absorbing polymer in order to reduce the stickiness of sweat. The odor effect was not yet sufficient. Furthermore, Patent Document 3 discloses a cosmetic containing an antiperspirant component and / or a bactericidal component and a superabsorbent polymer compound. However, since an aluminum compound is used as an antiperspirant component, a squeaky sensation is generated, which is not preferable in touch. In addition, since the aluminum compound is a strong acid, when a water-absorbing polymer composed of an α, β-unsaturated carboxylic acid monomer is used together, it affects sweat absorption depending on the blending ratio.
[0004]
[Patent Document 1]
JP 52-99236 A
[Patent Document 2]
JP-A-4-356415
[Patent Document 3]
JP-A-3-284617
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a cosmetic composition that can suppress stickiness after sweating, maintain a smooth feeling of use, and has an excellent deodorizing effect, particularly a cosmetic composition for an antiperspirant.
[0006]
[Means for Solving the Problems]
The present invention The surface of the water-absorbing polymer particles is coated with a silicone compound having at least one functional group selected from the group consisting of an amino group, an ammonium group, a carboxy group, a hydroxy group, an epoxy group, and a radically polymerizable unsaturated group. The average particle size is 0.1-50 μm Provided is a cosmetic composition, particularly a cosmetic composition for an antiperspirant, comprising surface-hydrophobized water-absorbing polymer particles and at least one selected from the group consisting of an antibacterial agent and a deodorant.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
[Water-absorbing polymer particles]
The shape of the water-absorbing polymer particles of the present invention is not particularly limited, and examples thereof include a true spherical shape, an egg shape, and a lump shape. Any of irregular shapes can be used. Preferred are a spherical shape, an egg shape, and a lump shape from the viewpoint of availability, and a spherical shape is preferable because it is preferable in touch. These may be porous.
[0008]
When the water-absorbing polymer particles used in the present invention are spherical, egg-shaped, or massive, as a cosmetic, it does not stand out visually as a white powder, does not cause discomfort after water absorption, has a smooth texture, In order not to easily fall off from the skin, the average particle diameter is preferably 0.1 μm or more, more preferably 0.5 μm or more, and the upper limit is preferably 50 μm or less, more preferably 20 μm or less, particularly preferably 10 μm. Hereinafter, it is most preferably 5 μm or less. The average particle size is a particle size that is not water-swelled and is obtained by measuring with a light scattering type particle size measuring device (for example, LS-230 type manufactured by Coulter, Inc. in cyclohexane).
[0009]
The water absorption amount of the water-absorbing polymer particles used in the present invention is preferably 5 g / g or more, more preferably 10 g / g or more in order to obtain a sufficient antiperspirant ability, and the upper limit is the water absorption that has absorbed sweat on the skin. In order to prevent a slimy feeling from being imparted by the functional polymer and make it difficult to fall off from the skin, it is preferably 100 g / g or less, more preferably 50 g / g or less, and particularly preferably 30 g / g or less. The amount of water absorption was determined by adding 1000 ml of water to 5 g of each sample, suspending and stirring for 30 minutes (100 r / min, 25 ° C.), centrifuging at 2,000 G for 30 minutes, and gently discarding the supernatant. Can be obtained from the difference from the initial sample weight.
[0010]
As the polymer used in the water-absorbing polymer particles of the present invention, any of natural polymers, semi-synthetic polymers, and synthetic polymers can be used as long as they have a function of absorbing moisture. In order to have water content, a polymer having a cross-linked structure is preferable. As such a polymer, a cross-linked product of a (co) polymer by a cross-linking method described later, or cross-linking via a hydrogen bond or a hydrophobic bond, partial It is a (co) polymer having a crosslink derived from a crystal structure, a crosslink derived from a helix structure or the like (however, the (co) polymer means a polymer or a copolymer).
[0011]
For example, natural polymers, semi-synthetic polymers such as starch, carrageenan, gelatin, agar, draggant gum, viscose, cellulose (eg, crystalline cellulose), methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc., or cross-linked products thereof, such as Starch- (meth) acrylate graft copolymer (or cross-linked product) (however, (meth) acrylic acid means acrylic acid, methacrylic acid or a mixture thereof) and the like.
[0012]
Synthetic polymers include hydrophilic vinyl monomers such as anionic monomers or salts thereof, nonionic hydrophilic group-containing monomers, amino group-containing unsaturated monomers or neutralized products thereof, or quaternized (co) polymer crosslinked products. Can be mentioned. The hydrophilicity of the hydrophilic vinyl monomer means that the solubility in 100 g of water (20 ° C.) is preferably 6% by mass or more, more preferably more than 20% by mass. Examples of monomers used in the production of synthetic polymers include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2- (meth) acryloylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid, Anionic monomers such as 2- (meth) acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid or salts thereof; (meth) acrylamide, N-substituted (meth) acrylamide, 2-hydroxyethyl (meth) Nonionic hydrophilic group-containing monomers such as acrylate, 2-hydroxypropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, N-vinylpyrrolidone, N-vinylacetamide; N, N-dimethyl Amino group-containing unsaturated monomers such as aminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, or acid neutralized products or quaternized products thereof Can be specifically mentioned. Preferred acids for obtaining an acid neutralized product include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, maleic acid, fumaric acid, citric acid, tartaric acid, adipic acid, lactic acid and the like. Common alkylating agents such as alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide, dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate can be mentioned. Examples of the counter ion include a halogen ion such as chlorine and an organic anion such as methosulfate. Further, hydrophobic vinyl monomers such as acrylates and styrene are preferably added in an amount of 0 to 50% by mass, more preferably 0 to 20% by mass, so that the hydrophilicity of the resulting polymer is not significantly inhibited. % Can be used together for copolymerization.
[0013]
The hydrophobic vinyl monomer is hydrophobic so that its solubility in 100 g of water (20 ° C.) is preferably less than 6% by mass. Although there is no particular lower limit, it may be 0.01% by mass or more.
[0014]
As the monomer component, one or more of these can be selected and used. (Meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, which are α, β-unsaturated carboxylic acid monomers, A cross-linked product of a (co) polymer of itaconic acid or a salt thereof is preferable because it has a high water absorption capacity and is easily available. In addition to the α, β-unsaturated carboxylic acid monomer, other monomers can also be copolymerized.
[0015]
In order to increase the water absorption capacity, the blending amount of the hydrophilic vinyl monomer is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, based on all monomers constituting the water-absorbing polymer particles. It is.
[0016]
The water-absorbing polymer particles are preferably a crosslinked polymer or copolymer of a hydrophilic vinyl monomer and / or a salt thereof, more preferably an α, β-unsaturated carboxylic acid monomer and / or a salt thereof. It is a crosslinked product of a polymer or a copolymer, and particularly preferably a crosslinked poly (meth) acrylate. The water-absorbing polymers may be used alone or in combination of two or more.
[0017]
Examples of the “salt” include alkali metal salts (sodium salt, potassium salt, lithium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, barium salt, etc.), ammonium salts (quaternary ammonium salt, etc.). And quaternary alkyl ammonium salts). Of these, sodium salts are the cheapest and preferred. Here, the degree of neutralization of the water-absorbing polymer particles is preferably 0.01 to 100%, more preferably 1 to 99%, particularly preferably 40, based on the number of moles of acid groups in the water-absorbing polymer. ~ 95%. In the present invention, the “neutralization degree” means the ratio (molar basis) of the acid groups in the water-absorbing polymer that constitute the salt, that is, (the acid groups constituting the salt). Number of moles) / (total number of moles of free acid groups that can form a salt and acid groups that form a salt) × 100 (%).
[0018]
As a method of forming a crosslinked product of the (co) polymer, a covalent bond crosslinked by a method such as (a) self-crosslinking during polymerization, (b) copolymerization with a polyfunctional monomer, (c) irradiation with radiation, etc. And (d) ion-bonding crosslinking via polyvalent metal ions. Among these, (b) is preferable from the viewpoint of stability of the crosslinked structure and ease of production, and a crosslinkable vinyl monomer having at least two reactive unsaturated groups in the molecule as a polyfunctional monomer, and intramolecular And a compound having a functional group other than at least two unsaturated groups (hereinafter, both are collectively referred to as a crosslinking agent).
[0019]
Crosslinkable vinyl monomers having at least two reactive unsaturated groups in the molecule include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, pentaerythritol triallyl ether, pentaerythritol tetraallyl. More preferred are ether and methylenebisacrylamide.
[0020]
As the compound having a functional group other than at least two unsaturated groups in the molecule, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether are more preferable.
[0021]
The amount of the crosslinking agent used varies depending on the type of the crosslinking agent and the crosslinking method, but is preferably 0.001 part by mass or more, more preferably 0.001 part by mass with respect to 100 parts by mass of the total monomer constituting the water-absorbing polymer particles. The upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less. If the amount is 0.001 part by mass or more, the ratio of the water-soluble component of the resulting water-absorbing polymer is small, so that the amount of water absorption can be maintained. The water absorption of the functional polymer is also sufficient.
[0022]
The water-absorbing polymer particles used in the present invention are preferably water-absorbing polymer particles (hereinafter referred to as surface-hydrophobized water-absorbing polymer particles) in which at least a part of the surface of the water-absorbing polymer particles is subjected to a hydrophobic treatment.
[0023]
Examples of such surface-hydrophobized water-absorbing polymer particles include: (1) surface-hydrophobized water-absorbing polymer particles in which the surface of the water-absorbing polymer particles is coated with a silicone compound having one or more functional groups; ) Surface hydrophobized water-absorbing polymer particles whose surface of water-absorbing polymer particles is coated with a polymer of hydrophobic vinyl monomer, (3) The surface of water-absorbing polymer particles is treated with a fluorosurfactant, Surface hydrophobized water-absorbing polymer particles, (4) Surface hydrophobized water-absorbing polymer particles, etc., wherein the surface of water-absorbing polymer particles is treated with a silane coupling agent. Among these, surface-hydrophobized water-absorbing polymer particles in which the surface of the water-absorbing polymer particles is coated with a silicone compound having one or more functional groups are preferable. Hereinafter, each surface-hydrophobized water-absorbing polymer particle will be described in detail.
[0024]
(1) Surface-hydrophobized water-absorbing polymer particles in which the surface of water-absorbing polymer particles is coated with a silicone compound having one or more kinds of functional groups
The silicone compound having one or more functional groups preferably has at least two or more silicon atoms having at least one functional group capable of chemical bonding, more preferably covalent bonding and / or ionic bonding, on the surface of the water-absorbing polymer particles. It is a silicone compound containing.
[0025]
In the surface-hydrophobized water-absorbing polymer particles, the surface of the water-absorbing polymer particles is preferably coated with a silicone compound having one or more functional groups by chemical bonding. Thereby, even if it mix | blends in cosmetics, a silicone compound can exist stably on the surface of a water absorbing polymer particle. The chemical bonding means that the silicone-modified polymer particles (10% by mass of chloroform) in chloroform are stirred for 2 hours (30 r / min, 50 ° C.) and centrifuged three times. This can be confirmed by the presence of the silicone compound in the water-absorbing polymer particles.
[0026]
It is preferable that the coating amount of the silicone compound covers at least the surface of the water-absorbing polymer particles so that the stickiness of the surface of the water-absorbing swollen particles can be suppressed.
[0027]
The amount of the silicone compound having one or more kinds of functional groups in the water-absorbing polymer particles is 100 parts by mass of the total polymer particles (including the silicone compound), and the lower limit is preferably 0.1 parts by mass or more. More preferably, it is 0.5 parts by mass or more, and particularly preferably 1 part by mass or more. The upper limit is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.
[0028]
The silicone compound having one or more kinds of functional groups is preferably hydrophobic in order to suppress gel blocking between polymer particles and stickiness during use. In particular, when the silicone compound has a plurality of types of functional groups and has a functional group that does not contribute to the reaction, it is preferably hydrophobic.
[0029]
Here, the term “hydrophobic” means that the solubility of a silicone compound having one or more functional groups at 25 ° C. in 100 g of water is 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less. Particularly preferred is 0.1% by mass or less. Although there is no particular lower limit, it may be 0.01% by mass or more.
[0030]
The weight average molecular weight of the silicone compound having one or more functional groups is preferably 1000 to 500,000, more preferably 3000 to 200,000, and particularly preferably 10,000 to 200,000. The weight average molecular weight is measured by GPC (gel permeation chromatography, chloroform eluent, polystyrene conversion).
[0031]
The functional group is preferably at least one functional group selected from the group consisting of an amino group, an ammonium group, a carboxy group, a hydroxy group, an epoxy group, or a radical polymerizable unsaturated group, and may be an amino group and / or an ammonium group. More preferably it is. These functional groups may be located at any of the side chain, one end and / or both ends of the siloxane, or a mixture thereof.
[0032]
Typical examples of silicone compounds having one or more functional groups used in the present invention are shown below.
[0033]
(1-1) Silicone compound having an amino group and / or an ammonium group (hereinafter referred to as amino-modified silicone)
The amino-modified silicone preferably has a polymer unit represented by the following general formula (I).
[0034]
[Chemical 1]

[0035]
[In the formula, R ¹ Represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ May be the same or different. R ² Is R ¹ Or X, where X is -R ^Three -Z (R ^Three Represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a reactive functional group represented by a primary to tertiary amino group-containing group or a quaternary ammonium group-containing group. a represents a number of 2 or more, and b represents a number of 1 or more. ]
In general formula (I), R ¹ Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, such as an alkyl group or a phenyl group, preferably a methyl group, an ethyl group, and more preferably a methyl group. R ^Three Is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, such as methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, more preferably trimethylene group or propylene group. It is. a and b each represent the number of repeating polymer units, a is preferably a number of 2 to 1000, and b is preferably a number of 1 to 50. Z is preferably an amino group or an ammonium group-containing group represented by the following general formula (II) or general formula (III).
[0036]
[Chemical 2]

[0037]
In the general formula (III), a plurality of R ^Five May be the same or different. T ^- Specific examples thereof include halogen ions such as chlorine, iodine and bromine, and organic anions such as methosulfate, ethosulfate, methophosphate and ethophosphate.
[0038]
In general formula (I), a preferred X group is — (CH ₂ ) _Three -NH ₂ ,-(CH ₂ ) _Three -N (CH _Three ) ₂ ,-(CH ₂ ) _Three -NH- (CH ₂ ) ₂ -NH ₂ ,-(CH ₂ ) _Three -NH- (CH ₂ ) ₂ -N (CH _Three ) ₂ ,-(CH ₂ ) _Three -N ⁺ (CH _Three ) _Three ・ Cl ^- And more preferably — (CH ₂ ) _Three -NH- (CH ₂ ) ₂ -NH ₂ It is.
[0039]
The weight average molecular weight of the amino-modified silicone is preferably 3000 to 200,000, and the amine equivalent is preferably 250 in order for the amine compound to easily react with the anionic functional group of the water-absorbing polymer and for the silicone compound to be hydrophobic. It is -10000 g / mol, More preferably, it is 1000-5000 g / mol. That is, the abundance of amino groups or ammonium groups in the polymer is preferably 0.1 to 4 mmol / g, more preferably 0.2 to 1 mmol / g. The amine equivalent can be titrated with hydrochloric acid of known concentration in a solvent such as ethanol.
[0040]
(1-2) Silicone compound having a carboxy group (hereinafter referred to as carboxy-modified silicone)
The carboxy-modified silicone includes a compound in which a silicon atom and a carboxy group are bonded with a saturated hydrocarbon, and a carboxy group and / or a salt thereof described in JP-A No. 2002-14849 are represented by the general formula (IV) and An organopolysiloxane compound having a structure represented by at least one of (V) and bonded to a silicon atom is preferred.
[0041]
[Chemical 3]

[0042]
[In the formula, R ⁷ , R ⁸ , R ⁹ And R ^Ten Are the same or different and each represents a C 2-22 linear or branched alkylene group, alkenylene group, or arylene group which may have a substituent containing a hetero atom. Y represents an —O— or —NH— group. M represents a hydrogen atom, a metal, ammonium, an alkyl or alkenyl ammonium having 1 to 22 carbon atoms, an alkyl or alkenyl-substituted pyridinium having 1 to 22 carbon atoms, an alkanol ammonium having 1 to 22 carbon atoms, or a basic amino acid. ]
Also, amphoteric ionomer siloxanes having both carboxy and ammonium functional groups described in JP-A-6-1711 can be preferably used.
[0043]
The weight average molecular weight of the carboxy-modified silicone is preferably 3000 to 200,000. The carboxy equivalent is preferably 250 to 10000 g / mol, more preferably 1000 to 5000 g / mol, because it easily reacts with the cationic functional group of the water-absorbing polymer and the silicone compound is hydrophobic. That is, the abundance of the carboxy group in the polymer is preferably 0.1 to 4 mmol / g, more preferably 0.2 to 1 mmol / g. The carboxy equivalent can be determined by titrating with a known concentration of NaOH in a solvent such as ethanol.
[0044]
(1-3) Silicone compound having a hydroxy group (hereinafter referred to as hydroxy-modified silicone)
Examples of hydroxy-modified silicones include branched silicones represented by the following general formula (VI), double-ended silicones represented by the following general formula (VII), single-ended silicones represented by the following general formula (VIII), Examples thereof include alkyl glyceryl ether-modified silicones described in Kaihei 5-111424.
[0045]
[Formula 4]

[0046]
[In the formula, R ¹¹ Are the same or different and each represents an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. R ¹² Are the same or different and each represents an alkylene group having 1 to 8 carbon atoms, preferably a trimethylene group. AO is the same or different and represents an oxyethylene group or an oxypropylene group, f and g each represent an integer of 1 or more, and h represents 0 or an integer of 1 or more. ]
(1-4) Silicone compound having an epoxy group (hereinafter referred to as epoxy-modified silicone)
Preferred examples of the epoxy-modified silicone include a single-end and / or both-end epoxy group-containing silicone compound represented by the general formula (IX).
[0047]
[Chemical formula 5]

[0048]
[In the formula, R ¹³ Are the same or different and are monovalent hydrocarbon groups, R ¹⁴ Represents an epoxy-containing group or a monovalent hydrocarbon group, A represents an epoxy-containing group, and n represents a number of 1 to 10,000. ]
R ¹³ As the monovalent hydrocarbon represented by the formula, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, a fluorine atom-substituted alkyl group such as a trifluoropropyl group, or the like. Can be mentioned. R ¹³ May be all the same or different, but all R ¹³ Is preferably a methyl group.
[0049]
In the general formula (IX), the epoxy-containing group represented by A is not particularly limited, but specific examples include groups represented by the following general formulas (X) to (XII).
[0050]
[Chemical 6]

[0051]
In the general formula (IX), R ¹⁴ But R ¹³ When it is the same, it becomes a one-end epoxy group-containing silicone, and when it is the same as A, it becomes a both-end epoxy group-containing silicone.
[0052]
As epoxy-modified silicone, R ¹⁴ But R ¹³ The one-end epoxy group-containing silicone that is the same as is preferable, and the hydrocarbon group includes an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and a trifluoropropyl group. Examples thereof include a fluorine atom-substituted alkyl group, and a methyl group is preferable.
[0053]
In general formula (IX), n is preferably 1 to 500, more preferably 5 to 100, and particularly preferably 10 to 50.
[0054]
(1-5) Silicone compound having a radical polymerizable unsaturated group
Preferred examples of the silicone compound having a radically polymerizable unsaturated group include polysiloxane compounds having a radically polymerizable group at one end as described in JP-A No. 11-181003.
[0055]
(2) Surface-hydrophobized water-absorbing polymer particles whose surfaces are coated with a polymer of hydrophobic vinyl monomer
The surface-hydrophobized water-absorbing polymer particles are water-absorbing polymer particles obtained by coating the surface of the water-absorbing polymer particles with a polymer of one or more kinds of hydrophobic vinyl monomers.
[0056]
It is preferable that at least a part of the surface of the water-absorbing polymer particles is coated to such an extent that stickiness of the surface of the water-absorbing swollen particles can be suppressed.
[0057]
The amount of the hydrophobic vinyl monomer in the surface-hydrophobized water-absorbing polymer particles is preferably 1 part by mass or more, more preferably 5 parts by mass or more, with respect to 100 parts by mass of the water-absorbing polymer particles. Particularly preferably, it is 10 parts by mass or more. The upper limit is preferably 1000 parts by mass or less, more preferably 400 parts by mass or less, and particularly preferably 200 parts by mass or less. Within this range, there is no feeling of stickiness after water absorption, and the water absorption speed is not particularly hindered.
[0058]
The hydrophobic vinyl monomer used in the present invention is a polymerizable monomer from which a hydrophobic polymer is obtained by polymerization, and can be polymerized by a general radical polymerization initiator or a polymerization method such as ultraviolet irradiation.
[0059]
The hydrophobic vinyl monomer is a monomer having hydrophobicity as defined above, and a normal radical polymerizable hydrophobic vinyl monomer is preferably used. Specific examples of such monomers include, for example, styrene, vinyl acetate, divinylbenzene, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, decyl acrylate, lauryl acrylate, dodecenyl acrylate, myristyl acrylate, palmityl acrylate. Acrylates such as hexadecenyl acrylate, stearyl acrylate, octadecenyl acrylate, behenyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, decyl methacrylate, lauryl methacrylate, dodecenyl methacrylate, methacrylic acid Myristyl acid, palmityl methacrylate, hexadecenyl methacrylate, stearyl methacrylate, octadecenyl methacrylate, behenic methacrylate Methacrylic acid esters and the like, fluorine-based monomers such as trifluoroethyl methacrylate, and silicone macromonomers. One or more of these hydrophobic monomers can be used. Among these, styrene and alkyl (meth) acrylates having 1 to 22 carbon atoms in the alkyl group are preferable because they are highly hydrophobic and easily available.
[0060]
The weight average molecular weight of the hydrophobic polymer used in the present invention is preferably 1000 to 500,000, more preferably 3000 to 200,000, and particularly preferably 10,000 to 200,000. The weight average molecular weight is measured by GPC (gel permeation chromatography, converted to polystyrene). The column is Showex Denko, Shodex KF-806.
[0061]
In addition, the above-mentioned hydrophilic vinyl monomer may be copolymerized for the purpose of improving the adhesion of the resulting polymer to the water-absorbing polymer to the extent that the hydrophobicity of the resulting polymer is not significantly inhibited.
[0062]
Such hydrophilic vinyl monomers include α, β-unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, itaconic acid, maleic anhydride, chloromethylstyrene, glycidyl (meth) acrylate, (meth) acryloyloxy Examples include ethyl isocyanate, 3- (trimethoxysilyl) propyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, vinyl pyridine, (meth) acrylamide and the like. One or more of these hydrophilic vinyl monomers can be used. The amount of the hydrophilic vinyl monomer used is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, based on all monomers constituting the polymer of the hydrophobic vinyl monomer.
[0063]
(3) Surface-hydrophobized water-absorbing polymer particles whose surface is treated with a fluorosurfactant
The hydrophilic part of the fluorosurfactant may be any of anion, nonion, cation or amphoteric, and the hydrophobic part may be a fluorocarbon chain or a perfluorocarbon chain. It is preferable to have a functional group capable of reacting with the surface of the water-absorbent polymer particles, and the hydrophilic portion is preferably an anion, cation or amphoteric, and more preferably a cation or amphoteric. Further, the carbon chain which is a hydrophobic part may be linear or branched. For example, the following fluorosurfactant is mentioned.
[0064]
Fluoroalkyl (C ₂ ~ C _Ten ) Carboxylic acid, N-perfluorooctanesulfonyl glutamate disodium, 3- [fluoroalkyl (C ₆ ~ C ₁₁ ) Oxy] -1-alkyl (C _Three ~ C _Four ) Sodium sulfonate, 3- [ω-fluoroalkanoyl (C ₆ ~ C ₈ ) -N-ethylamino] -1-propanesulfonic acid sodium, N- [3- (perfluorooctanesulfonamido) propyl] -N, N-dimethyl-N-carboxymethyleneammonium betaine, fluoroalkyl (C ₁₁ ~ C ₂₀ ) Carboxylic acid, perfluoroalkylcarboxylic acid (C ₇ ~ C ₁₃ ), Perfluorooctanesulfonic acid diethanolamide, perfluoroalkyl (C _Four ~ C ₁₂ ) Sulfonate (Li, K, Na), N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (C ₆ ~ C _Ten ) Sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C ₆ ~ C _Ten ) -N-ethylsulfonylglycine salt (K), bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkyl (C ₆ ~ C ₁₆ ) Ethyl phosphate ester, perfluoroalkyl quaternary ammonium iodide (trade name Fluorard FC-135, a cationic fluorosurfactant manufactured by Sumitomo 3M Limited), perfluoroalkyl alkoxylate (trade name Fluorard FC-171, Sumitomo) 3M nonionic surfactant), perfluoroalkyl sulfonic acid potassium salt (trade names Fluorard FC-95 and FC-98, anionic surfactant manufactured by Sumitomo 3M Limited).
[0065]
(4) Surface hydrophobized water-absorbing polymer particles whose surface is treated with a silane coupling agent
As the silane coupling agent, a silane coupling agent described in JP-A-61-211305 can be used.
[0066]
Preferred examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyl. Examples include methyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-chloropropylmethyldimethoxysilane.
[0067]
[Production method of water-absorbing polymer particles]
(1) Method for producing water-absorbing polymer particles by polymerizing a hydrophilic vinyl monomer
When a polymer of hydrophilic vinyl monomer is used as the water-absorbing polymer, any method may be adopted as a polymerization method of the hydrophilic vinyl monomer and the crosslinking agent, but an aqueous solution (preferably a concentration of the hydrophilic vinyl monomer). 1 to 70% by mass) is preferable, and various methods such as an aqueous solution polymerization method, a reverse phase suspension polymerization method, and a pearl polymerization method can be employed. Among them, the aqueous solution polymerization method or the reverse phase suspension polymerization method is preferable from the viewpoint of workability at the time of polymerization and the water absorption performance of the obtained water absorbent polymer, and the reverse phase suspension weight is preferable from the point of high water absorption performance of the water absorbent polymer. Legal is particularly preferred. The polymerization temperature of the hydrophilic vinyl monomer is preferably 20 to 120 ° C., and the polymerization time is preferably 20 to 180 minutes.
[0068]
As the polymerization initiator, a water-soluble radical polymerization initiator such as a peroxide, hydroperoxide, or azo compound is used in a known amount. These polymerization initiators can be used in a mixture of two or more, and can also be used as a redox polymerization initiator by adding chromium ions, sulfites, hydroxylamine, hydrazine, etc. It is. If necessary, oil-soluble radical polymerization initiators, for example, peroxide-based initiators such as benzoyl peroxide, lauroyl peroxide, tertiary butyl peroxypivalate, diisopropyl peroxydicarbonate, azobis (isobutyronitrile), Azo initiators such as azobis (2,4-dimethylvaleronitrile), azobis (dimethylisobutyrate), azobis (cyclohexanecarbonitrile) can also be used.
[0069]
The amount of the water-soluble polymerization initiator used is preferably 0.03 to 5% by mass and more preferably 0.1 to 2% by mass with respect to the hydrophilic vinyl monomer.
[0070]
A dispersant is used to disperse and stabilize the hydrophilic vinyl monomer in the oil phase (solvent). Examples of the dispersant include general anionic, cationic, nonionic and amphoteric surfactants, natural, semi-synthetic and synthetic polymers. For example, anionic surfactants such as sodium polyoxyethylene dodecyl ether sulfate and sodium dodecyl ether sulfate; cationic and amphoteric surfactants such as trimethylstearylammonium chloride and carboxymethyldimethylcetylammonium; sucrose monostearate Nonionic surfactants such as sucrose fatty acid esters such as sucrose dilaurate, sorbitan esters such as sorbitan monostearate, polyoxyalkylene adducts of sorbitan esters such as polyoxyethylene sorbitan monostearate; starch and its derivatives; Natural and semi-synthetic polymers such as cellulose ethers such as ethyl cellulose, cellulose derivatives such as cellulose acetate, etc .; polyvinyl alcohol and And synthetic polymers such as derivatives thereof, maleated polybutadiene, and styrene-dimethylaminoethyl methacrylate quaternary salts.
[0071]
In order to produce the surface-hydrophobized water-absorbing polymer particles, it is preferable to use the above-mentioned silicone compound having one or more kinds of functional groups or the above-mentioned fluorosurfactant as a dispersant. You may use together with the other dispersing agent mentioned above. Among the silicone compounds, preferred as a dispersant is a silicone compound having one or more functional groups selected from the group consisting of an amino group, an ammonium group, a hydroxy group, and a carboxy group.
[0072]
The dispersant is preferably from 0.5 to 30 parts by weight, more preferably from 1 to 10 parts by weight, particularly preferably from 1 to 7 parts by weight, based on 100 parts by weight of the total vinyl monomers constituting the water-absorbing polymer particles. preferable.
[0073]
The solvent used in the reverse phase suspension polymerization method is preferably a hydrocarbon solvent, a silicone solvent, or a mixture thereof. Examples of hydrocarbon solvents include hexane, heptane, dodecane, cyclohexane, methylcyclohexane, isooctane, hydrogenated triisobutylene, and other aliphatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, and other aromatic hydrocarbons. Examples of the solvent include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane and the like. Of these, hexane and cyclohexane are particularly preferred.
[0074]
After the polymerization, before distilling off the water or solvent in the reaction system, a crosslinking agent may be added later and preferably heated to 40 to 150 ° C. for surface crosslinking.
[0075]
(2) Method for producing surface-hydrophobized water-absorbing polymer particles from water-absorbing polymer particles Surface-hydrophobized water-absorbing polymer particles are obtained from polymerized water-absorbing polymer particles or previously obtained water-absorbing polymer particles such as natural polymers. Can be manufactured.
[0076]
In the presence of water-absorbing polymer particles and a silicone compound having one or more kinds of functional groups, a fluorosurfactant or a silane coupling agent, and if necessary, a crosslinking agent and / or a radical polymerization initiator are added, and in the presence of water. A production method in which heating is preferably performed in a solvent is preferable. By the presence of water, the functional group of the water-absorbing polymer particles is dissociated and easily reacts with the functional group of a silicone compound, a fluorosurfactant or a silane coupling agent having one or more functional groups. The amount of the silicone compound having one or more functional groups, the fluorosurfactant or the silane coupling agent is preferably 0.001 part by mass or more, more preferably 100 parts by mass with respect to 100 parts by mass of the water-absorbing polymer (particle). Is 0.01 parts by mass or more, particularly preferably 0.1 parts by mass or more, and the upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.
[0077]
As the solvent, the above-mentioned hydrocarbon solvents, silicone solvents or mixtures thereof are preferably used. The amount of water present in the reaction system is preferably 1 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the water-absorbing polymer (particles). After the reaction, water is dehydrated by distillation or the like. When used, the crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the water-absorbing polymer (particles). Mass part is present.
[0078]
When using the silicone compound which has a radically polymerizable unsaturated group, it is preferable to make the above-mentioned oil-soluble radical polymerization initiator exist together. The silicone compound or fluorosurfactant having one or more kinds of functional groups should be added directly or in the form of a solubilized or emulsified dispersion with an organic solvent, surfactant or dispersant, and in some cases added as a spray. Can do. Heating for smooth surface treatment is preferably in the range of 40 to 150 ° C.
[0079]
The mixing timing of the silicone compound having one or more functional groups, the fluorosurfactant or the silane coupling agent may be any before or after pulverization of the polymer of the water-absorbing polymer, more preferably the water-absorbing polymer. After being pulverized, water-absorbing polymer particles are obtained, and if necessary, the water content is adjusted to an appropriate range by drying or the like, and mixed in, for example, a kneader.
[0080]
The water-absorbing polymer particles coated with the polymer of the hydrophobic vinyl monomer are mixed into a reversed phase suspension polymerization solution during or after the polymerization of the water-absorbing polymer particles, that is, a slurry in which the water-absorbing polymer particles are suspended in a solvent. What is obtained by adding a hydrophobic vinyl monomer and the above-mentioned oil-soluble polymerization initiator and polymerizing them is preferable. Preferred examples of the solvent include the above-mentioned hydrocarbon solvents, silicone solvents, and mixtures thereof.
[0081]
The amount of the oil-soluble polymerization initiator used is preferably 0.03 to 5% by mass and more preferably 0.1 to 2% by mass with respect to the hydrophobic vinyl monomer. The polymerization initiator is used by mixing and dissolving with other components in advance, but for the purpose of reducing the residual monomer, it can be diluted in a solvent or the like during the polymerization and added all at once or continuously. The polymerization temperature is preferably 20 to 120 ° C., and the polymerization time is preferably 20 to 180 minutes.
[0082]
As the surface-hydrophobized water-absorbing polymer particles used in the present invention, a hydrophilic vinyl monomer and a crosslinking agent are used in the presence of a silicone compound having one or more functional groups or a fluorosurfactant in a reverse phase suspension polymerization method. Or obtained by heating water-absorbing polymer particles and a silicone compound having one or more functional groups, a fluorosurfactant or a silane coupling agent in the presence of water, or A hydrophilic vinyl monomer and a crosslinking agent are subjected to reverse phase suspension polymerization in the presence of a water-soluble polymerization initiator and a dispersing agent, and a hydrophobic vinyl monomer and an oil-soluble polymerization initiator are added during or after the polymerization to polymerize. Those obtained are preferably mentioned.
[0083]
[Antimicrobial agent]
In the cosmetic composition of the present invention, it is preferable to use an antibacterial agent in order to suppress and / or sterilize skin resident bacteria by antibacterial or sterilization. Any antibacterial agent may be used as long as the object of the present invention is not impaired.
[0084]
Antibacterial agents include, for example, cationic compounds such as benzalkonium salts, benzethonium salts, alkyl quaternary ammonium salts, chlorhexidine salts, pyridinium salts; phenol compounds such as isopropylmethylphenol; carbanilide compounds such as trichlorocarban; Preferred examples include diphenyl ether compounds; hexachlorophenes; antibacterial metals or organic metals such as silver-supported silica, silver-supported zeolite, and 8-oxyquinoline copper.
[0085]
Examples of cationic compounds include quaternary ammonium salts represented by the following general formula (XIII), benzalkonium salts represented by the general formula (XIV), benzethonium salts, chlorhexidine salts represented by the general formula (XV), Pyridinium salts represented by the formula (XVI) are preferred.
[0086]
[Chemical 7]

[0087]
(Wherein R ¹⁵ , R ¹⁶ , R ¹⁷ And R ¹⁸ At least one of them represents an alkyl group, alkenyl group or hydroxyalkyl group having 16 to 26 carbon atoms, which may be the same or different from each other. The remainder represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having an ethylene oxide average addition mole number of 10 or less, which may be the same or different. Z ^1- Represents a halogen ion or an organic anion. )
[0088]
[Chemical 8]

[0089]
(Wherein R ¹⁹ Is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, or a formula
[0090]
[Chemical 9]

[0091]
Z represents a group represented by ^1- Indicates the same meaning as described above. )
[0092]
Embedded image

[0093]
(Where Z ² Represents gluconic acid, acetic acid or hydrochloric acid. )
[0094]
Embedded image

[0095]
(Wherein R ²⁰ Represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms; ^1- Indicates the same meaning as described above. )
Z in the above general formulas (XIII), (XIV) and (XVI) ^1- Is preferably a halogen ion such as chlorine, iodine or bromine, more preferably a chlorine ion.
[0096]
Specific examples of suitable cationic compounds include benzalkonium chloride, benzethonium chloride, chlorhexidine hydrochloride, and chlorhexidine gluconate.
[0097]
An antimicrobial agent can be used individually by 1 type or in mixture of 2 or more types. Among the antibacterial agents, cationic compounds having a bactericidal effect are more preferable, and benzalkonium chloride is particularly preferable.
[0098]
[Deodorants]
The cosmetic composition of the present invention preferably contains a deodorant so that the sweat component is decomposed by bacteria and the generated odor is deodorized. Any deodorant may be used as long as it is conventionally used in conventional cosmetics as long as the object of the present invention is not impaired. Deodorizing methods include physical deodorants such as physical adsorption of odorous substances, chemical neutralization, and neutralized deodorants. Preferable is one or more metal oxides selected from the group consisting of calcium oxide, magnesium oxide, zinc oxide, and barium oxide. A metal oxide can be used 1 type or in mixture of 2 or more types. Among these, zinc oxide is particularly preferable. In order to improve the dispersibility in cosmetics and not to be washed away by perspiration, a metal oxide surface that has been subjected to a hydrophobic treatment, particularly a silicone and / or fluorine compound-coated surface is preferred. In order to coat, it is preferable to perform a surface treatment. Examples of the treating agent include methyl hydrogen polysiloxane, dimethyl polysiloxane, hydroxy group, halogen atom, amino group, alkoxy group and the like as described in JP-A-5-339518 and JP-A-7-196946. (These functional groups may be present at one end, both ends, or in the side chain, and may be a divalent hydrocarbon group which may have a substituent directly on the silicon atom, or And fluorine group-containing hydrogen polysiloxane described in JP-A-6-23262. These can be reacted with the metal oxide by heating or the like if necessary. 0.1-20 mass parts is preferable with respect to 100 mass parts of metal oxides, and, as for the coating amount of a silicone and / or a fluorine compound, 1-10 mass parts is still more preferable.
[0099]
Examples of the deodorant used in the present invention include “fine zinc white”, “FINEX-25”, “FINEX-25LP”, “FINEX-50”, “FINEX-50LP”, “FINEX-75” (and above, Sakai Chemical Industry Co., Ltd.), "ZnO-305", "ZnO-310", "ZnO-350" (above, manufactured by Sumitomo Osaka Cement Co., Ltd.), "MZ-500" (manufactured by Teika), etc. It is done. More preferably, the metal oxide whose surface has been hydrophobized is finely dispersed. For example, “Cosmeserve WPA-65MP”, “Cosmeserve WPA-STD” (above, manufactured by Dainippon Kasei Co., Ltd.) , “Daitopartition Zn50” (manufactured by Daito Kasei Kogyo Co., Ltd.) and the like.
[0100]
Although the average particle diameter of a metal oxide is not specifically limited, 0.001-5 micrometers is preferable, 0.01-1 micrometer is more preferable, 0.1-1 micrometer is especially preferable.
[0101]
[Cosmetic composition]
The cosmetic composition of the present invention may be any of emulsified cosmetics, oily cosmetics, spray cosmetics, stick cosmetics, powder cosmetics, and roll-on cosmetics, but is preferably used for antiperspirants. .
[0102]
In the cosmetic composition of the present invention, the content of the water-absorbing polymer particles (the content in a state in which the water-swelling is not performed) is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, 20% by mass is particularly preferred. Within this range, the stickiness after sweat absorption can be suppressed, which is preferable. Furthermore, since the surface-hydrophobic water-absorbing polymer particles are used to maintain the smoothness of the particles even after sweating, the feel on the skin is good and preferable.
[0103]
In the cosmetic composition of the present invention, the content of the antibacterial agent is preferably 0.001 to 5% by mass, more preferably 0.01 to 3% by mass, and particularly preferably 0.01 to 1% by mass. Within this range, the bactericidal effect is high and the blending stability is good and preferable.
[0104]
In the cosmetic composition of the present invention, the content of the deodorant is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, and particularly preferably 0.1 to 10% by mass. Within this range, a preferable deodorizing effect can be obtained, and the whiteness after application is not noticeable.
[0105]
The ratio between the water-absorbing polymer particles and the deodorant is preferably deodorant / water-absorbing polymer particles (mass ratio) = 1/30 to 1/1, and more preferably 1/20 to 1/2. Within this range, it is preferable because the deodorizer does not affect the water absorption effect of the water-absorbing polymer particles.
[0106]
In addition, the cosmetic composition of the present invention further contains a silicone oil, whereby a cosmetic that further reduces the sticky feeling and gives a refreshing feeling of use can be obtained. Such silicone oil is not particularly limited, and specific examples include chain silicones such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic silicones such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, and the like. If necessary, one or more of these can be appropriately selected and used. When the cosmetic composition of the present invention is in a stick form, the silicone oil is preferably contained in the composition in an amount of 5 to 90% by mass, more preferably 30 to 80% by mass.
[0107]
In the cosmetic composition of the present invention, other ingredients generally used as cosmetic ingredients are appropriately blended according to the form, type, etc. of the cosmetics as long as the effects of the present invention are not impaired. Can do.
[0108]
Examples of such cosmetic ingredients include extender pigments such as mica, talc, sericite, kaolin, polymethylsilsesquioxane, and barium sulfate; inorganic pigments such as titanium oxide, zinc white, and iron oxide; organic powders such as nylon powder Body; powder obtained by hydrophobizing surface such as silicone treatment, metal soap treatment, N-acyl glutamic acid treatment; solid or liquid paraffin, solid paraffin, microcrystalline wax, petrolatum, ceresin, ozokerite, montan wax Hydrocarbons such as olive oil, earth wax, carnauba wax, lanolin, whale wax, etc., vegetable oils, animal oils or waxes; stearic acid, palmitic acid, oleic acid, glycerol monostearate, glycerol distearate, Glycerol monooleate, isop Fatty acids such as pyrmyristic acid ester, isopropyl stearic acid ester, butyl stearic acid ester or the like; higher alcohols such as cetyl alcohol, stearyl alcohol, palmityl alcohol, hexyl decyl alcohol; cationized cellulose, carboxybetaine type polymer, Adsorption or thickeners such as cationized silicones; polyhydric alcohols having a moisturizing action such as glycol and sorbitol; medicinal components such as whitening agents, analgesics, antiphlogistics, astringents, emollients, hormones, etc .; water Surfactants; W / O or O / W type emulsifiers; emulsifiers for silicone oils such as polyether-modified silicone, polyether-alkyl-modified silicone, glyceryl ether-modified silicone; methylcellulose, ethylcellulose, carboxy Thickeners such as methylcellulose, polyacrylic acid, tragacanth, agar, and gelatin; lower alcohols such as ethanol, glycerin, 1,3-butylene glycol, and propylene glycol; other emulsion stabilizers, chelating agents, UV protection agents, pH adjustment Agents, preservatives, pigments, fragrances and the like.
[0109]
The cosmetics of the present invention are produced according to conventional methods.
[0110]
【Example】
“%” In the following examples represents “% by mass” unless otherwise specified.
[0111]
Synthesis example 1
After taking 500 g of methacrylic acid (Mitsubishi Rayon Co., Ltd.) and 210 g of ion-exchanged water into a 2 L beaker and stirring with cooling, 581 g of 30% aqueous sodium hydroxide solution was added dropwise to neutralize 75%. A solution obtained by dissolving 2.0 g of potassium sulfate (0.4% with respect to methacrylic acid) in 40.0 g of ion-exchanged water and ethylene glycol diglycidyl ether (trade name, Denacol EX810, manufactured by Nagase Kasei Co., Ltd.) as a crosslinking agent ) 10 g (2.0% vs. methacrylic acid) was added and dissolved uniformly. The obtained solution was added to 1130 ml of cyclohexane in a 2 L beaker with amino-modified silicone (TSF4703 manufactured by GE Toshiba Silicone Co., Ltd., viscosity (25 ° C.): 1000 mm. ² / S, amine equivalent: 1600 g / mol) is added to a solution obtained by dissolving 15 g, and using a homomixer, vigorously stirred for 5 minutes at a rotational speed of 10,000 r / min to form fine water-in-oil dispersion droplets. It was. Next, in a 5 L stainless steel reaction kettle equipped with a reflux condenser, 1180 ml of cyclohexane and amino-modified silicone (TSF4703 manufactured by GE Toshiba Silicone Co., Ltd., viscosity (25 ° C.): 1000 mm ² / S, amine equivalent: 1600 g / mol) 10 g was added, stirred at 350 r / min, the system was heated to 75 ° C. in advance, and nitrogen-substituted solution was mixed with the above methacrylic acid partially neutralized oil-in-water dispersion. Drops were dropped and polymerization was started simultaneously. The whole amount was dropped in 2.0 hours, and then aging was further performed for 4 hours at the reflux temperature. Thereafter, a dehydrating tube was attached, the temperature was raised, 600 ml of dehydration was performed, and 2310 ml of cyclohexane was evaporated and evaporated, and then allowed to cool to complete the synthesis. By evaporating to dryness under reduced pressure, 630 g of a fine powdery white dry polymer was obtained. The average particle diameter of the obtained water-absorbing polymer particles was 3.0 μm. The water absorption was 22 g / g.
[0112]
Synthesis example 2
Except that the amount of ethylene glycol diglycidyl ether as a crosslinking agent was 25 g, the same operation as in Synthesis Example 1 was performed to obtain water-absorbing polymer particles. The average particle diameter of the obtained water-absorbing polymer particles was 2.8 μm. The water absorption was 15 g / g.
[0113]
Synthesis example 3
After taking 500 g of methacrylic acid (Mitsubishi Rayon Co., Ltd.) and 210 g of ion-exchanged water into a 2 L beaker and stirring with cooling, 581 g of 30% aqueous sodium hydroxide solution was added dropwise to neutralize 75%. A solution obtained by dissolving 2.0 g of potassium sulfate (0.4% with respect to methacrylic acid) in 40.0 g of ion-exchanged water and ethylene glycol diglycidyl ether (trade name, Denacol EX810, manufactured by Nagase Kasei Co., Ltd.) as a crosslinking agent ) 25 g (5.0% vs. methacrylic acid) was added and dissolved uniformly. The resulting solution was added to 1130 ml of cyclohexane in a 2 L beaker with amino-modified silicone (KF-861 manufactured by Shin-Etsu Chemical Co., Ltd., viscosity (25 ° C.): 3500 mm. ² / S, amine equivalent: 2000 g / mol) is added to a solution obtained by dissolving 15 g, and using a homomixer, vigorously stirred for 5 minutes at a rotational speed of 5000 r / min to form fine water-in-oil dispersion droplets. It was. Next, in a 5 L stainless steel reaction kettle equipped with a reflux condenser, 1180 ml of cyclohexane and amino-modified silicone (KF-861 manufactured by Shin-Etsu Chemical Co., Ltd., viscosity (25 ° C.): 3500 mm ² / S, amine equivalent: 2000 g / mol) 10 g was added and stirred at 350 r / min, and the system was heated to 75 ° C. in advance, and the above-described water-dispersed methacrylic acid partially neutralized oil was added to the nitrogen-substituted solution. Drops were dropped and polymerization was started simultaneously. The whole amount was dropped in 2.0 hours, and then aging was further performed for 4 hours at the reflux temperature. A dehydration tube was attached, the temperature was raised, 600 ml was dehydrated, 350 g of decamethylcyclopentasiloxane (SH245, manufactured by Toray Dow Corning Silicone) was added, and only 2310 ml of cyclohexane was evaporated and allowed to cool and then synthesized. Was completed. 950 g of a white slurry polymer was obtained. The average particle diameter of the obtained water-absorbing polymer particles was 6.3 μm. The water absorption was 25 g / g.
[0114]
Synthesis example 4
A water-absorbing polymer particle was obtained in the same manner as in Synthesis Example 3 except that the amount of ethylene glycol diglycidyl ether as a cross-linking agent was 5 g and the rotation speed of the homomixer was 3000 r / min. The average particle diameter of the water-absorbing polymer particles obtained was 12.1 μm. The water absorption was 38 g / g.
[0115]
Examples 1-5 and Comparative Examples 1-2
In a 200 ml beaker, oils, antiperspirant components, water-absorbing polymer particles, powders, antibacterial agents and deodorizers shown below were added and mixed at room temperature for 20 minutes. After raising the temperature to 80 ° C., higher alcohol was mixed and further stirred for 20 minutes. A stick-like antiperspirant was produced by cooling to 65 ° C. and taking out. About the obtained antiperspirant, the antiperspirant test and the deodorization test were done by the following method. The results are shown in Table 1.
[0116]
<Composition ingredients>
Oils
a-1: Decamethylcyclopentasiloxane, SH245, manufactured by Toray Dow Corning Silicone
a-2: Dimethylpolysiloxane, KF96A-10cs, manufactured by Shin-Etsu Chemical Co., Ltd.
Powders
b-1: Silicone resin, KMP599, manufactured by Shin-Etsu Chemical Co., Ltd.
Higher alcohol
c-1: Stearyl alcohol
Water-absorbing polymer particles
d-1: obtained in Synthesis Example 1
d-2: obtained in Synthesis Example 2
d-3: obtained in Synthesis Example 3
d-4: obtained in Synthesis Example 4
Antiperspirant ingredient
e-1: Aluminum hydroxide
e-2: Zinc paraphenol sulfonate
Antibacterial agent
f-1: Benzalkonium chloride
f-2: Isopropylmethylphenol
f-3: Triclosan
Deodorants
g-1: Zinc oxide, FINEX-50LP, manufactured by Sakai Chemical Industry Co., Ltd.
g-2: Zinc oxide, dietopartition Zn50, manufactured by Daito Kasei Kogyo Co., Ltd.
g-3: Zinc oxide, Cosmeserve WPA-65MP, manufactured by Dainippon Kasei Co., Ltd.
<Antiperspirant test>
After applying antiperspirant to 5 healthy male panelists, we evaluated the wetness of cocoon when entering the greenhouse (40 ° C / 80% RH) for 5 minutes according to the following four items, and determined the average value. did. The uncoated value was 3.7.
[0117]
1: Dry
2: A little wet
3: Clearly wet
4: Wet
<Odor control test>
Five healthy male panelists who have a habit odor, applied antiperspirant to the wrinkle in the morning, and after 8 hours, the odor intensity of the wrinkle was evaluated by three sensory evaluators in the following 6 levels, and the average value Judged by. The uncoated value was 3.5.
[0118]
0: Odorless
1: Smell
2: It smells a little
3: Slightly strong smell
4: Strong smell
5: It smells very strongly
[0119]
[Table 1]

[0120]
note)
* 1: The amount of water-absorbing polymer particles is the amount of polymer.
* 2: The amount of zinc oxide
The antiperspirant of Comparative Examples 1 and 2 produced a squeaky sensation after application.
[0121]
A prescription example is shown below.
[0122]
Formulation Example 1: Body lotion
<Composition>
Water-absorbing polymer particles (Synthesis example 1) 3.0%
Zinc oxide (dietopartition Zn50) 1.0
Benzalkonium chloride 0.1
Glycerin 80.0
Stearyl alcohol 5.0
Dimethylpolysiloxane ^* 2.0
Silicone-treated talc 3.0
Water remaining
*: KF96A-10cs, manufactured by Shin-Etsu Chemical Co., Ltd.
[0123]
Formulation Example 2: Powder spray antiperspirant
<Composition>
Water-absorbing polymer particles (Synthesis example 2) 2.0%
Zinc oxide (FINEX-50LP) 0.2
Benzalkonium chloride 0.02
Silicone powder ^* 1.0
Talc 12.0
Isopropyl palmitate 2.0
Fragrance 0.2
Liquefied petroleum gas residue
*: KMP599, manufactured by Shin-Etsu Chemical Co., Ltd.
[0124]
Formulation example 3: Roll-on antiperspirant
<Composition>
Dimethylpolysiloxane ^* 5.0%
Ethanol 20.0
Glycerin 4.0
Water-absorbing polymer particles (Synthesis Example 3) 5.0
Zinc oxide (Cosmeserve WPA-65MP) 1.0
Benzalkonium chloride 0.1
Octamethylcyclotetrasiloxane
*: KF96A-10cs, manufactured by Shin-Etsu Chemical Co., Ltd.
[0125]
【The invention's effect】
The cosmetic composition of the present invention prevents stickiness due to sweat, has a high deodorizing effect, and has a preferable feeling of use. In addition, the use of surface-hydrophobized water-absorbing polymer particles provides a smooth feeling even after sweat absorption, which is preferable to the touch.

Claims (9)

The surface of the water-absorbing polymer particles is coated with a silicone compound having at least one functional group selected from the group consisting of an amino group and an ammonium group , the average particle diameter is 0.1 to 50 μm , and the water absorption is 5 to 5 A cosmetic composition comprising 100 g / g of a surface-hydrophobized water-absorbing polymer particle and at least one selected from the group consisting of an antibacterial agent and a deodorant. The surface of the water-absorbing polymer particles is coated with a silicone compound having at least one functional group selected from the group consisting of an amino group and an ammonium group , the average particle diameter is 0.1 to 50 μm , and the water absorption is 5 to 5 The cosmetic composition according to claim 1, comprising 100 g / g of surface-hydrophobized water-absorbing polymer particles, an antibacterial agent, and a deodorant. The cosmetic composition according to claim 1 or 2, wherein the water-absorbing polymer particles are a crosslinked product of a polymer or a copolymer of an α, β-unsaturated carboxylic acid monomer and / or a salt thereof. The cosmetic composition according to claim 3, wherein the amount of the crosslinking agent used is 0.001 to 20 parts by mass with respect to 100 parts by mass of the total amount of monomers constituting the water-absorbing polymer particles. The makeup according to any one of claims 1 to 4, wherein the silicone compound having at least one functional group selected from the group consisting of an amino group and an ammonium group has a polymer unit represented by the general formula (I). Composition.

[In the formula, R ¹ Represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ May be the same or different. R ² Is R ¹ Or X, where X is -R ^Three -Z (R ^Three Represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a reactive functional group represented by a primary to tertiary amino group-containing group or a quaternary ammonium group-containing group. a represents a number of 2 or more, and b represents a number of 1 or more. ] The amine equivalent of the silicone compound having at least one functional group selected from the group consisting of an amino group and an ammonium group is 250 to 10,000 g / mol The cosmetic composition according to any one of claims 1 to 5. The cosmetic composition according to any one of claims 1 to 6 , wherein the antibacterial agent is a cationic compound. The cosmetic composition according to any one of claims 1 to 7 , wherein the deodorant is one or more metal oxides selected from the group consisting of calcium oxide, magnesium oxide, zinc oxide and barium oxide. The cosmetic composition according to any one of claims 1 to 8, which is used for an antiperspirant.