JP4025950B2 - Bactericidal compound-containing composition - Google Patents

Description

【００２９】
（但し、上記式中、Ｒ²は、１〜１７個の炭素原子を有するアルキル基、２〜１７個の炭素原子を有するアルケニル基、５〜８個の炭素原子を有するシクロアルキル基、７〜９個の炭素原子を有するビシクロアルキル基、シクロアルキル基が５〜８個の炭素原子を有し、且つアルキル基が１〜４個の炭素原子を有するシクロアルキル−アルキル基（但し、シクロアルキル基は、その水素原子の一部が炭素数１〜４のアルキル基によって置換されていてもよい）、６〜１４個の炭素原子を有するアリール基、アリール基が６〜１４個の炭素原子を有し、且つアルキル基が１〜４個の炭素原子を有するアラルキル基、アリール基が６〜１４個の炭素原子を有し、且つアルケニル基が２〜４個の炭素原子を有するアリールアルケニル基、アリール基が６〜１４個の炭素原子を有し、且つアルキル基がそれぞれ１〜４個の炭素原子を有するアリールオキシアルキル基もしくはアリールメルカプトアルキル基、ベンズヒドリル基、アルキル基が１〜４個の炭素原子を有するフェニルスルホニルアルキル基、フリル基又はアルケニル基が２〜４個の炭素原子を有するフリルアルケニル基を表す。但し、上述のアリール基は、その水素原子の一部が１〜４個の炭素原子を有するアルキル基、１〜４個の炭素原子を有するアルコキシ基、ニトロ基、シアノ基又はハロゲン原子によって置換されていてもよい。Ｒ³は、水素原子、１〜４個の炭素原子を有するアルキル基、２〜４個の炭素原子を有するアルケニル基、２〜４個の炭素原子を有するアルキニル基、ハロゲン原子、フェニル基又はベンジル基を表す。Ｘは、有機塩基、アルカリ金属イオン、アンモニウムイオン又は２〜４価の陽イオンを表す。）
【００３０】
上記一般式（２）で表される化合物の具体例としては、例えば下記化合物及びその塩などを挙げることができる。
【００３１】
１−ヒドロキシ−２−ピリドン、１−ヒドロキシ−４−メチル−２−ピリドン、１−ヒドロキシ−６−メチル−２−ピリドン、１−ヒドロキシ−４，６−ジメチル−２−ピリドン、１−ヒドロキシ−４−メチル−６−ヘプチル−２−ピリドン、１−ヒドロキシ−４−メチル−６−（１−エチルペンチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（２，４，４−トリメチルペンチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−ウンデシル−２−ピリドン、１−ヒドロキシ−４−メチル−６−プロペニル−２−ピリドン、１−ヒドロキシ−４−メチル−６−オクテニル−２−ピリドン、１−ヒドロキシ−４−メチル−６−（２，２−ジブチル−ビニル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（シクロヘキセニリデン−メチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−シクロヘキシル−２−ピリドン、１−ヒドロキシ−４−メチル−６−（メチル−シクロヘキシル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（２−ビシクロ〔２，２，１〕ヘプチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−〔２−（ジメチルシクロヘキシル）−プロピル〕−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−メチル−フェニル）−２−ピリドン、１−ヒドロキシ−４―メチル−６−（３−メチル−フェニル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−第３ブチル−フェニル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（３−メチル−４−クロル−フェニル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（３，５−ジクロル−フェニル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（３−ブロム−４−クロル−フェニル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−メトキシスチリル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−〔１−（４−ニトロフェノキシ）−ブチル〕−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−シアノフェノキシメチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（フェニルスルホニルメチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−〔１−（４−クロルフェニルスルホニル）−ブチル〕−２−ピリドン、１−ヒドロキシ−４−メチル−６−ベンジル−２−ピリドン、１−ヒドロキシ−４−メチル−６−（２，４−ジメチルベンジル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（第３ブチル−ベンジル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（２−クロル−ベンジル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−クロルベンジル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（２，５−ジクロル−ベンジル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−ブロム−ベンジル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（フェノキシメチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（３−メチルフェノキシ−メチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−第２ブチルフェノキシ−メチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（２，４，５−トリクロルフェノキシ−メチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−ブロムフェノキシ−メチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−クロルフェニルメルカプト−メチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（４−メチルフェニルメルカプト−メチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−（２−ナフチル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−ベンズヒドリル−２−ピリドン、１−ヒドロキシ−４−メチル−６−フリル−２−ピリドン、１−ヒドロキシ−４−メチル−６−（フリルビニル）−２−ピリドン、１−ヒドロキシ−４−メチル−６−スチリル−２−ピリドン、１−ヒドロキシ−４−メチル−６−（フェニルブタジエニル）−２−ピリドン、１−ヒドロキシ−４−フェニル−６−メチル−２−ピリドン、１−ヒドロキシ−４，６−ジフェニル−２−ピリドン等を挙げることができる。
【００３２】
上記化合物は、塩として用いられ、例えば有機アミンとの塩として好適に使用することができる。具体的には、例えばエタノールアミン、ジエタノールアミン、Ｎ−エチルエタノールアミン、Ｎ−メチル−ジエタノールアミン、トリエタノールアミン、ジエチルアミノ−エタノール、２−アミノ−２−メチル−ｎ−プロパノール、ジメチルアミノプロパノール、２−アミノ−２−メチル−プロパンジオール、トリ−イソプロパノールアミン、エチレンジアミン、ヘキサメチレンジアミン、モルホリン、ピペリジン、シクロヘキシルアミン、トリブチルアミン、ドデシルアミン、Ｎ，Ｎ−ジメチル−ドデシルアミン、ステアリルアミン、オレイルアミン、ベンジルアミン、ジベンジルアミン、Ｎ−エチルベンジルアミン、ジメチルステアリルアミン、Ｎ−メチル−モルホリン、Ｎ−メチルピペラジン、４−メチルシクロヘキシルアミン、Ｎ−ヒドロキシエチル−モルホリン等が挙げられる。
【００３３】
また、本発明に用いられる１−ヒドロキシ−２−ピリドン系化合物は、無機イオンとの塩であってもよく、例えばナトリウム塩、カリウム塩等のアルカリ金属塩、アンモニウム塩及びマグネシウム塩、カルシウム塩等のアルカリ土類金属塩などを用いることができる。更に、亜鉛塩、アルミニウム塩、ジルコニウム塩等の２〜４価の陽イオンとの塩も用いることができる。
【００３４】
本発明の組成物における上記ｂ）成分の配合量は、特に制限されるものではないが、これら化合物の１種を単独で又は２種以上を適宜組み合わせて使用する場合、通常組成物全体の０．０１〜３％、特に０．０５〜２％とすることが好ましい。殺菌性化合物の配合量が少なすぎると充分な殺菌効果が得られない場合があり、一方、多すぎると例えば殺菌性化合物の溶解が不充分で、低温での保存において析出するなど、保存安定性がよくなかったり、また、保存の過程で容器への吸着などにより、配合量が有効に生かされなかったりする場合がある。
【００３５】
更に、本発明の組成物は、２５℃で１０ｍＰａ・ｓ以上の粘度を有することが必要であり、好ましくは１０〜１００００ｍＰａ・ｓ、より好ましくは１５〜８０００ｍＰａ・ｓである。粘度が低すぎると、使用時に手にとった場合、こぼれ落ちる、あるいは例えばシャンプーとして使用した場合、頭皮を流れ落ちて目に入るなどの不具合が生じ、使い勝手が良好でなかったり、安全上好ましくなかったりすることがある。
【００３６】
本発明の組成物の粘度を上記範囲とするためには、上記ａ）アルキルエトキシサルフェートを配合することによって、組成物の粘性が得られるが、更に、目的とする粘性を得るために、必要に応じて公知の増粘剤を併用することもでき、このような増粘剤としては、その種類が特に制限されるものではなく、例えば脂肪酸アルカノールアミド、アルキルエーテル、エステルなどのノニオン類、糖系の活性剤や高分子化合物、ベタイン類等を好適に使用することができる。
【００３７】
また、本発明の組成物を例えば毛髪用洗浄剤等の毛髪用組成物又は皮膚用洗浄剤等の皮膚外用組成物として使用する場合、通常これらの洗浄剤に含有されるアニオン界面活性剤、両性界面活性剤及び半極性界面活性剤の中から選ばれる１種又は２種以上の界面活性剤を本発明の効果を妨げない範囲で含有することができ、これによって、いっそう泡立ちや泡感触、洗浄力、すすぎや仕上がりの感触などに優れ、マイルドで保存安定性が良好な組成物を得ることができる。
【００３８】
具体的には、例えばアニオン界面活性剤としては、従来のエチレンオキシド付加モル数分布の広いポリオキシエチレンアルキルエーテル硫酸塩やアルキル硫酸塩も使用することができるが、先に述べたように、本発明の組成物の特徴であるエチレンオキシド付加モル数の分布の狭い上記ａ）成分の特徴を消去しない程度の併用量とする必要があり、他の成分とのバランスを勘案して決定する必要がある。この他にも、α−オレフィンスルホン酸塩、アシルメチルタウリン塩、アミドエーテル硫酸塩、エーテルカルボン酸塩、アルカンスルホン酸塩、アミノ酸系アニオン活性剤等を挙げることができ、これらは１種単独で又は２種以上を適宜組み合わせて使用することができるが、特にこれらに限定されるものではない。なお、これらのアニオン界面活性剤を併用する場合、これらの合計配合量は、組成物全体に対して０〜４０％程度とすることが好ましい。
【００３９】
また、両性界面活性剤としては、その種類が特に限定されるものではないが、例えばベタイン型やイミダゾリン型、アミノカルボン酸型などの両性界面活性剤を１種又は２種以上用いることができる。具体的には、アルキルベタイン、アルキルアミドプロピルベタイン、スルホベタイン、イミダゾリニウムベタイン、アミノカルボン酸、アミノプロピオン酸やこれらの塩などを挙げることができる。両性界面活性剤の配含量は、通常、組成物全体の０〜１５％、特に好適には０〜６％とすることが好ましい。
【００４０】
更に、半極性界面活性剤としては、その種類が特に限定されるものではないが、例えばアミンオキシド型ノニオン性界面活性剤が代表的なものとして挙げることができる。具体的には、ラウリルジメチルアミンオキシドやポリオキシエチレンラウリルジメチルアミンオキシド等を挙げることができ、これらのアミンオキシドは１種単独で又は２種以上を適宜組み合わせて組成物に配合することができる。配合量は、組成物全体の０〜１５％、好ましくは０〜６％とすると好適である。
【００４１】
本発明の組成物を毛髪用組成物又は皮膚外用組成物として使用する場合、特に殺菌性化合物の毛髪や皮膚への滞留性を高める目的で、膜形成性の高分子化合物を併用することができる。このような高分子化合物としては、例えばカチオン化セルロース，カチオン化グアーガムなどのカチオン性高分子化合物、ベタイン化ジアルキルアミノアルキル（メタ）アクリレート又はジアルキルアミノアルキル（メタ）アクリルアミドなどの両性重合体やポリベタイン系などの両性高分子化合物、アクリル系のアニオン系高分子化合物、ヒドロキシエチルセルロースなどの非イオン性高分子化合物等を挙げることができ、これらは１種単独で又は２種以上を適宜組み合わせて使用することができる。
【００４２】
本発明の組成物は、本発明の効果を妨げない限り、その種類や使用態様などに応じて、必要により任意成分として、上記成分に加えて、例えば毛髪用組成物又は皮膚外用組成物の常用成分であるカチオン性界面活性剤や、疎水性ノニオン界面活性剤などを配合することもでき、また、固体または液体油分、高級アルコール類、エステル油、多価アルコール、防腐剤、ハイドロトロープ類、無機塩、増粘剤、香料、動植物の抽出物、フケ防止剤、薬効剤、乳濁剤、パール化剤、紫外線吸収剤、紫外線散乱剤、トニック剤、ｐＨ調整剤、色素、酸化防止剤、低級アルコール、ビタミン類、揮発性油分、疎水性溶媒、希釈性溶媒などを含有することができるが、これらについては特に限定されず、目的に応じた配合がなされてよい。
【００４３】
【発明の効果】
本発明の殺菌性化合物含有組成物は、殺菌性化合物の毛髪や皮膚等への滞留性に優れるのみならず、使用性に優れ、且つマイルドで保存安定性が良好なものであるので、毛髪用、皮膚外用として使用する香粧品全般、更に台所用洗浄剤等の食器用、家具用の洗浄剤、殺菌剤などの各種用途に使用することができ、特に毛髪用組成物又は皮膚外用組成物として有用である。また、本発明の組成物は、更に、泡立ちや泡感触を良好なものとすることも可能であるので、毛髪用組成物又は皮膚外用組成物の中でも特に毛髪用洗浄剤組成物、皮膚用洗浄剤組成物のような身体用洗浄剤組成物においてその効果を顕著に発揮するものである。
【００４４】
【実施例】
以下、本発明の実施例及び比較例を示し、本発明をより具体的に説明するが、本発明は下記実施例により限定されるものではない。なお、以下に示す％はいずれも質量百分率である。
【００４５】
［実施例１〜６、比較例１〜３］
表１に示すａ）成分（ポリオキシエチレンアルキルエーテル硫酸ナトリウム）を用いて、表２に示す組成に従って常法に準じて毛髪用洗浄剤及び皮膚用洗浄剤を調製し、各組成物の泡性能と殺菌効果を有する化合物（殺菌性化合物）の毛髪又は皮膚への残留性、マイルド性、保存安定性、組成物の粘性を下記評価方法に従って評価した。結果を表２に併記する。
【００４６】
なお、以下に表１のアルキルエトキシサルフェートの調製方法を述べる。
＜分布の狭いアルキルエトキシサルフェート：サンプルＡ−１＞
本発明の実施例で使用した分布の狭いラウリルエトキシサルフェートの調製は、以下の方法で実施した。
【００４７】
４リットル容のオートクレーブ中にラウリルアルコール４００ｇ及びＡｌ／Ｍｇ／Ｍｎ（アルミニウム／マグネシウム／マンガン）で構成される複合金属酸化物ルイス酸焼結固体触媒０．４ｇを仕込み、オートクレーブ内を窒素置換し、撹拌しながら昇温した。次いで、温度を１８０℃、圧力を０．３ｍＰａに維持しながらエチレンオキサイド５４ｇを導入し、反応物を得た。次に、このようにして得たアルコールエトキシレート２７４ｇを撹拌装置付の５００ｍｌ容フラスコにとり、窒素置換後、液体無水硫酸（サルファン）８１ｇを反応温度を４０℃に保ちながらゆっくりと滴下した。滴下終了後、１時間撹拌を続け、目的とするアルキルエトキシサルフェート（ラウリルエトキシサルフェート）を得た。得られたアルキルエトキシサルフェートの性状及びオキシエチレン鎖長の分布は表１に示した通りであった。なお、サンプルＡ−２の調製も同様の方法により行った。
【００４８】
＜分布の広いアルキルエトキシサルフェート：サンプルＡＥＳ−１＞
また、比較例で使用した通常の分布の広いラウリルエトキシサルフェートの調製は、以下の方法で実施した。
【００４９】
４リットル容のオートクレーブ中にラウリルアルコール４００ｇ及び水酸化カリウム触媒０．８ｇを仕込み、オートクレーブ内を窒素置換し、撹拌しながら昇温した。次いで、温度１８０℃、圧力を０．３ｍＰａに維持しながらエチレンオキサイド５４ｇを導入し、反応物を得た。次に、このようにして得たアルコールエトキシレート２７４ｇを撹拌装置付の５００ｍｌ容のフラスコにとり、窒素置換後、液体無水硫酸（サルファン）８１ｇを反応温度を４０℃に保ちながらゆっくりと滴下した。滴下終了後、１時間撹拌を続けて目的とするアルキルエトキシサルフェート（ラウリルエトキシサルフェート）を得た。得られたアルキルエトキシサルフェートの性状及びオキシエチレン鎖長の分布は表１に示した通りであった。なお、サンプルＡＥＳ−２の調製も同様の方法により行った。
【００５０】
（１）泡性能の評価方法
熟練した専門家による官能評価により、泡立ち、泡の感触などを総合的に評価し、下記判定基準に従って判定した。
判定基準
○；泡性能が良好である。
×；泡性能が良くない。
【００５１】
（２）毛髪又は皮膚への殺菌効果を有する化合物（殺菌性化合物）の滞留性の評価方法
それぞれ処方した組成物について、毛髪又は皮膚に使用した後、毛髪又は皮膚に吸着した殺菌成分をそれぞれの殺菌成分をよく溶解する溶媒にてそれぞれ抽出し、液体クロマトグラフィーにより、それぞれの殺菌成分の定量法に従って定量して毛髪又は皮膚への残留量を求め、後述する標準組成の使用時と比較して、残留量の多いものを滞留性良好（○）とし、残留量が同じか少なくものを滞留性不良（×）とした。
【００５２】
ここで用いた標準組成は、エチレンオキシド付加モル数の分布の広い表１のＡＥＳ−１であるポリオキシエチレン（３モル）ラウリルエーテル硫酸ナトリウム塩を１０％、殺菌成分として、市販のピロクトンオラミン（Ｃｌａｒｉａｎｔ社製；オクトピロックス）０．１％、残部精製水、合計１００％というものである。
【００５３】
（３）マイルド性の評価方法
敏感肌パネル１０名が組成物を使用したときの刺激感を上述の標準組成と比較評価し、下記評価基準に従って判定した。
判定基準
〇；刺激感が標準組成と比較して、小さい。
△；刺激感が標準組成と比較して同等である。
×；刺激感が標準組成と比較して、大きい。
【００５４】
（４）保存安定性の評価方法
４０℃、１ケ月の高温条件での保存及び−５℃、１ケ月の低温条件での保存の結果、目視観察によって、調製直後のものと比べてほとんど変化が認められないものについて保存安定性を○とし、著しい変色や、析出、分離などが認められたものについて保存安定性を×とした。
【００５５】
（５）組成物の粘性の評価方法
組成物の粘度をブルックフィールドＢＬ型粘度計で２５℃において測定し、下記判定基準に従って、粘性を評価した。
判定基準
○；粘性が適度（１０ｍＰａ・ｓ以上）である。
×；粘性が低い（１０ｍＰａ・ｓ未満）。
【００５６】
【表１】

【００５７】
【表２】

【００５８】
表２の結果からも明らかなように、本発明の組成物は、いずれも優れた泡性能、毛髪又は皮膚への滞留性、マイルド性、保存安定性を有し、使用時の粘性が良好である。
【００５９】
なお、表２においてＢ−１〜Ｂ−６で示した殺菌効果を有する化合物は、以下の通りである。
【００６０】
【化２】

【００６１】
【化３】

【００６２】
Ｂ−３ サリチル酸
Ｂ−４ トリクロサン
Ｂ−５ 塩化ベンザルコニウム
Ｂ−６ イソチアゾリン液（「ケーソンＣＧ」：ローム＆ハース社製）
なお、これらの化合物は、表２及び以下の実施例に共通である。
【００６３】
［実施例７］
組成
Ａ−１ １５．０
ラウリン酸アミドプロピルベタイン ２．０
アルキルジメチルアミンオキシド ２．０
ヤシ油脂肪酸ジエタノールアミド ３．０
ＰＯＥジオレイン酸メチルグルコシド ０．８
ラウリルピロリドン ３．０
Ｂ−１ ０．５
コレウス抽出物 ０．２
ＰＯＥ硬化ヒマシ油（ＨＬＢ９） １．５
ＰＯＥ（１５モル）アルキルエーテル ０．５
硫酸ナトリウム ２．０
安息香酸ナトリウム １．０
ジステアリン酸エチレングリコール ２．０
グリセリン脂肪酸エステル ０．２
グリシン ０．５
１，３−ブチレングリコール １．０
ジブチルヒドロキシトルエン ０．００５
オキシベンゾン ０．５
Ｂ−６ ０．０３
黄色２０３号 ０．００１
橙色２０５号 ０．００２
香料 ０．７
クエン酸 ０．５
精製水 残部
合計 １００ ％
【００６４】
上記組成のシャンプー組成物を常法に準じて調製した。このシャンプー組成物は、２５℃における粘度が１０ｍＰａ・ｓ以上であり、泡立ち、泡感触に優れ、マイルドであり、毛髪へのＢ−１、Ｂ−６化合物の滞留性に優れており、保存安定性も良好で、使用時の粘性も低すぎることなく適度であった。
【００６５】

【００６６】
上記組成に従ってシャンプー組成物を常法に準じて調製した。このシャンプー組成物は、２５℃における粘度が１０ｍＰａ・ｓ以上であり、優れた泡性能、マイルド性、Ｂ−３化合物の頭皮への滞留性を有しており、保存安定性に優れ、適度な粘性を有していた。
【００６７】
［実施例９］
組成
Ａ−１ ７．０
ミリスチン酸カリウム １５．０
パルミチン酸 ８．０
ステアリン酸 ８．０
Ｂ−１ ０．５
Ｂ−３ ０．２
オレイルアルコール １．０
グリセリン １０．０
ポリエチレングリコール ５．０
ヤシ油脂肪酸モノエタノールアミド ０．１
プロピレングリコール １．０
植物性スクワラン ０．５
エデト酸４ナトリウム４水塩 ０．２
ＰＯＥ硬化ヒマシ油（ＨＬＢ９） １．５
グリセリン脂肪酸エステル ０．２
ベンクレー ０．８
イソプレングリコール １．０
青色４０３号 ０．００１
香料 ０．２
精製水 残部
合計 １００ ％
【００６８】
上記組成に従って、常法に準じて洗顔剤組成物を調製した。この洗顔剤組成物は、２５℃における粘度が１０ｍＰａ・ｓ以上であり、泡性能が良好で、Ｂ−１及びＢ−３化合物の皮膚への滞留性に優れ、マイルドでかつ保存安定性が良好であり、適度な粘性を有し、使い勝手が良好であった。
【００７１】
［実施例１１］
組成
Ａ−２ ５．０
アシルメチル−β−アラニントリエタノールアミン １０．０
アシルグルタミン酸トリエタノールアミン ５．０
エーテルカルボン酸ナトリウム １．０
アルキルアミノプロピオン酸 ０．０５
ラウリルジメチルアミンオキシド ０．８
塩化ステアリルトリメチルアンモニウム １．０
パーム核油脂肪酸ジエタノールアミド ２．０
ＰＯＥ硬化ヒマシ油（ＨＬＢ９） ３．０
プロピレングリコール ０．２
エタノール ３．０
グリチルリチン酸ジカリウム ０．３
Ｂ−１ １．５
流動パラフィン ０．２
グリセリン脂肪酸エステル ０．８
安息香酸ナトリウム ０．７
加水分解タンパク ０．５
硫酸マグネシウム １．５
カチオン化セルロース ０．２
塩化アルキルジメチルアンモニウム／アクリル酸共重合体 ０．４
ジブチルヒドロキシトルエン ０．２
香料 ０．３
クエン酸 ０．１
エデト酸 １．０
精製水 残部
合計 １００ ％
【００７２】
上記組成に従ってシャンプー組成物を常法に準じて調製した。このシャンプー組成物は、２５℃における粘度が１０ｍＰａ・ｓ以上であり、泡立ち、泡感触に優れ、マイルドであり、毛髪へのＢ−１化合物の滞留性に優れており、保存安定性も良好で、使用時の粘性も低すぎることなく適度であった。
【００７３】
［実施例１２］
組成
Ａ−２ ７．０
ミリスチン酸カリウム １５．０
ラウロイルメチル−β−アラニンカリウム塩 ２．０
ラウロイルグルタミン酸モノカリウム塩 ２．０
ラウリルジメチルアミンオキシド １．０
Ｂ−１ ０．５
Ｂ−４ ０．２
オレイルアルコール １．０
ポリエチレングリコール ５．０
ヤシ油脂肪酸ジエタノールアミド ３．０
プロピレングリコール ６．０
ヒドロキシプロピルメチルセルロース^*1 ０．５
植物性スクワラン ０．５
エデト酸４ナトリウム４水塩 ０．２
ＰＯＥ硬化ヒマシ油（ＨＬＢ９） １．５
ベンクレー ０．８
水酸化カリウム 微量
青色４０３号 ０．００１
香料 ０．２
精製水 残部
合計 １００ ％
＊１ 信越化学工業（株） メトロース ６５ＳＨ−１５００
【００７４】
上記組成に従って、皮膚洗浄剤組成物を常法に準じて調製した。この皮膚洗浄剤組成物は、２５℃における粘度が１０ｍＰａ・ｓ以上であり、泡性能が良好で、Ｂ−１及びＢ−４化合物の皮膚への滞留性に優れ、マイルドでかつ保存安定性が良好であり、適度な粘性を有し、使い勝手が良好であった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a bactericidal compound-containing composition with improved retention of the bactericidal compound, and more specifically, the bactericidal compound not only has excellent retention on hair, skin, etc., but also has excellent usability. In addition, it is mild and has good storage stability, and can be suitably used as a composition for hair, a composition for external use on the skin, etc., and it is also possible to obtain good foaming and foam feel. The present invention relates to a bactericidal compound-containing composition that is also suitable as a body cleaner composition such as a skin cleaner or a skin cleaner.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, the composition which mix | blended the compound which has the bactericidal effect used for hair or skin has been devised to maximize the effect of the compound having the bactericidal effect. For example, in detergent compositions such as shampoos and body soaps, a formulation that enhances the retention of bactericidal components (bactericidal compounds) on the hair and skin when washed away has a film-forming property on the hair and skin after rinsing. Compounding a molecular compound or the like in the composition has been performed.
[0003]
In addition, in order to prevent acne, even in facial cleansers intended to clean the skin, measures such as suppressing the blending amount of the cleaning base that reduces the persistence of the bactericidal compound on the skin to the minimum required amount have been made. However, such a device has been a factor that reduces the degree of freedom in performance other than the bactericidal effect in formulating a prescription.
[0004]
Particularly in the case of hair cleansing agents such as shampoos, examples of a suitable cleaning base include polyoxyethylene alkyl ether sulfate (AES), which is an anionic active agent. Since the distribution of the number of moles of ethylene added is wide, in order to express the specific performance originally exhibited in AES having a specific number of moles added, AES itself or a combination additive is used in excess of the required amount. It had the disadvantage that it had to be done.
[0005]
That is, AES, which has been conventionally used industrially for cleaning agents and the like, has a wide distribution in the oxyethylene chain length of the hydrophilic portion. Therefore, for example, when AES having 3 moles of added ethylene oxide is selected, those having 1 to 6 moles of added ethylene oxide suitable in terms of detergency and foam performance are contained in an amount of about 63% by mass. The content of the alkyl sulfate with 0 mole addition of ethylene oxide having high detergency and mildness and low film formation with a polymer compound is increased to about 13% by mass. Is a compound having a bactericidal effect in the formulation because the film-forming property is insufficient compared to the blending amount of AES, or the cleaning power is too strong and the blended components such as the bactericidal compound are easily washed away. Inferior to the hair and skin, the mildness was insufficient.
[0006]
On the other hand, when AES with 5 moles of ethylene oxide added is selected in consideration of the retention of mildness and bactericidal compounds in hair and skin, and usability, foam performance is good, mildness, and storage stability. The alkyl ethoxy sulfate having 1 to 6 moles of addition of ethylene oxide, which is preferable in terms of the above, actually contains only about 45%, and most of the remainder has a viscosity that is easy to use for cleaning purposes and compositions. It has a structure that hardly contributes to providing it, and it was not economically preferable to increase the amount of AES to satisfy these requirements.
[0007]
The present invention was made in view of the above circumstances, not only can improve the retention of bactericidal compounds in hair, skin, etc., but is easy to use when applied to hair, skin, etc. In addition, it is mild and has good storage stability, and can be suitably used as a composition for hair or a composition for external use on the skin. Furthermore, foaming and foam feel can be improved, and particularly for hair washing. An object of the present invention is to provide a bactericidal compound-containing composition suitable as a body cleaner composition such as a skin cleaner and a skin cleaner.
[0008]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventors have come to focus on a specific alkyl ethoxy sulfate and / or a salt thereof having a narrow distribution width of ethylene oxide addition mole number represented by the following general formula (1). As a result of further intensive studies, as shown in the examples described later, the specific alkyl ethoxy sulfate and / or salt thereof is used in combination with a bactericidal compound having a bactericidal effect, and the viscosity of the composition is adjusted to a predetermined range. In addition to improving the retention of the bactericidal compound in the hair, skin, etc., the composition is excellent in usability when applied to hair, skin, etc., and is mild and has good storage stability. It was found that a product can be obtained, and further, good foaming and foam performance can be obtained.
[0009]
R¹O- (CH₂CH₂O)_n-SO_ThreeM (1)
(However, in the above formula, R¹Is a C6-C24 linear or branched alkyl group or alkenyl group, n is the average number of moles of ethylene oxide group added, is in the range of 1-6, and M is a hydrogen atom , Alkali metal, alkaline earth metal, alkanolamine or ammonium. )
[0010]
That is, particularly in recent years, the development of AES overcoming the drawback of the wide distribution of the number of added moles of polyoxyethylene and its application have been studied, as disclosed in JP-A-4-72395. A method of using AES having such a narrow distribution has been proposed. As described above, in order to achieve the above-mentioned object, the present inventor came to pay attention to this narrow distribution of alkyl ethoxy sulfate, and as a result of intensive studies on this alkyl ethoxy sulfate, the range of 1 to 6 moles of added ethylene oxide was obtained. In the case of 5 mol addition product of ethylene oxide, almost 80% of the addition product of 5 mol of ethylene oxide is contained, and in the case of addition product of 3 mol of ethylene oxide, about 90% of the addition product of 3 mol addition. As described above, in the case of an ethylene oxide 2-mole addition product, nearly 90% of the 2-mole addition product is contained, while the content of the alkyl sulfate having an ethylene oxide addition mole number of 0 is the same even in the case of the ethylene oxide 2-mole addition product. Since it is a little over 10%, it is advantageous in terms of mildness and storage stability. Not only that, it was found that it is very suitable as a main base for freely adjusting the performance of the composition, and this specific alkyl ethoxy sulfate is used in combination with a bactericidal compound, and the viscosity of the composition is within a predetermined range. Thus, the inventors have found that the above object can be achieved, and have made the present invention.
[0011]
Accordingly, the present invention includes: a) the mass% represented by the following general formula (1), including those having a different number of moles of ethylene oxide addition, wherein the number of moles of addition of ethylene oxide being 0 does not show the maximum value, and the maximum The alkyl ethoxy sulfate and / or its salt whose mass% of the ethylene oxide adduct showing the value is 15 to 35, and whose total amount with the ethylene oxide adduct having the added mole number before and after this is 55 to 75 mass%, and b) A bactericidal compound-containing composition comprising a bactericidal compound and having a viscosity at 25 ° C. of 10 mPa · s or more is provided.
[0012]
R¹O- (CH₂CH₂O)_n-SO_ThreeM (1)
(However, in the above formula, R¹Is a C6-C24 linear or branched alkyl group or alkenyl group, n is the average number of moles of ethylene oxide group added, is in the range of 1-6, and M is a hydrogen atom , Alkali metal, alkaline earth metal, alkanolamine or ammonium. )
[0013]
  Here, the component b) is one or more selected from 1-hydroxy-2-pyridone compounds, salicylic acid and salts thereof, triclosan, benzalkonium chloride and methylchloroisothiazoline / methylisothiazoline fungicides. It is a bactericidal compound. The bactericidal compound-containing composition is a hair composition or a skin external composition.
[0014]
Hereinafter, the present invention will be described in more detail. As described above, the bactericidal compound-containing composition of the present invention contains a) an alkyl ethoxy sulfate represented by the general formula (1) and / or a salt thereof, and b) a bactericidal compound. Viscosity at 10 mPa · s or higher.
[0015]
Here, the alkyl ethoxy sulfate and its salt which are the component a) of the present invention are represented by the general formula R¹O- (CH₂CH₂O)_n-SO_ThreeM is represented by (1), where R¹Is a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms, preferably 10 to 18 carbon atoms. When the number of carbon atoms is less than 6, sufficient foam performance cannot be obtained. On the other hand, when the number of carbon atoms exceeds 24, the solubility of the activator itself is reduced, so that precipitation is likely to occur during storage.
[0016]
Specific examples of preferred alkyl groups or alkenyl groups include hexyl group, octyl group, decyl group, dodecyl group, myristyl group, palmityl group, stearyl group, oleyl group, aralkyl group, and behenyl group. The alkyl ethoxy sulfate of the present invention is not limited to these.
[0017]
In the case of the present invention, these alkyl groups or alkenyl groups may be one kind alone, or may be a mixture of two or more kinds, and these are linear alkyl groups that can be obtained from natural raw materials. Or a branched alkyl group, or an alkenyl group corresponding to these, or a synthesized one. For example, commercially available synthetic alcohols such as Dovanox, Dovanol, Diador and Neodol, and natural alcohols such as coconut oil higher alcohol can be used very suitably as raw materials.
[0018]
Moreover, in the said General formula (1), n shows the average addition mole number of an ethylene oxide group, It is the range of 1-6, More preferably, it is 1.5-4, More preferably, it is the range of 2-3. When n is less than 1, the content of the alkyl sulfate having 0 ethylene oxide addition moles is too large, the detergency is too strong, for example, a membrane made of a complex formed by the action with a cationic polymer compound, etc. Since the formability is hindered, the retention of the bactericidal compound on the hair, skin, etc. is lowered, and the mildness and storage stability cannot be satisfied. On the other hand, when n is larger than 6, not only the problem that the foam performance cannot be satisfied, but also the effect of increasing the viscosity of the composition is small, and the viscosity of the composition of the present invention is small. In order to adjust the amount to the above-mentioned predetermined range, there is a limitation in formulation design such as the necessity to add or increase the component having a thickening effect separately from the component a).
[0019]
Furthermore, M in the alkyl ethoxy sulfate represented by the general formula (1) or a salt thereof is a counter ion, an alkali metal such as a hydrogen atom, sodium or potassium, an alkaline earth metal, monoethanolamine, diethanolamine or triethanol. A cationic group derived from an alkanolamine such as amine or isopropanolamine or ammonium.
[0020]
The alkyl ethoxy sulfate as component a) of the present invention includes those having different ethylene oxide addition mole numbers, that is, alkyl ethoxy sulfate having a distribution of ethylene oxide addition mole numbers, and has the characteristics described in detail below. The distribution of the number of added moles is narrow.
[0021]
First, in the above distribution, the mass% occupied by the ethylene oxide addition mole number of 0 does not show the maximum value. That is, it is characterized by not containing most alkyl sulfates having disadvantages in mildness and storage stability.
[0022]
  In addition, the ratio of the ethylene oxide adduct having the maximum value in the above distribution to the total alkyl ethoxy sulfate is 20 to 30% by mass, and the ethylene oxide adduct and the number of moles added before and after that, for example, the ethylene oxide adduct If the ethylene oxide addition mole number is P, the total amount of the ethylene oxide adduct having an addition mole number of P ± 1 is 60 to 70% by mass of a narrowly distributed alkyl ethoxy sulfate and a salt thereof. .
[0023]
In other words, the alkyl ethoxy sulfate according to the present invention has been integrated into one having a structure suitable as a main base of a composition containing a bactericidal compound, particularly as a main base of a composition for hair and an external composition for skin. In other words, it is a purified alkyl ethoxy sulfate.
[0024]
The alkyl ethoxy sulfate or salt thereof as the component a) of the present invention is not particularly limited by other elements as long as it satisfies the above characteristics. For example, the production method is not particularly limited. It may be produced using a specific Lewis acid solid catalyst as shown in Kaihei 1-164437, etc., or may be produced in the presence of an acidic liquid catalyst such as sulfuric acid, and is generally industrially used. In the presence of an alkali catalyst such as sodium hydroxide, a product having a wide distribution may be first synthesized and purified by distillation or the like.
[0025]
The blending amount of the component a) in the composition of the present invention is not particularly limited. However, when one kind is used alone, or two or more kinds are used in appropriate combination, usually the whole composition is used. The content is preferably 5 to 25% (mass%, the same applies hereinafter), particularly 6 to 20%. When the blending amount is less than 5%, foaming tends to be insufficient as the main base of the composition, the foam feel becomes watery, and sufficient satisfaction may not be obtained during use. In addition, if the blending amount exceeds 25%, the retention of the bactericidal compound may be significantly hindered, or the mildness of the composition may be reduced, and the storage stability of the composition at low temperatures may be maintained. There may not be.
[0026]
The component b), which is the second essential component of the present invention, is usually used in cosmetic compositions and the like, and any compound can be used as long as it provides a bactericidal effect on hair, skin and the like. Can do.
[0027]
Examples of such compounds include 1-hydroxy-2-pyridone compounds, salicylic acid and salts thereof, pyrithione zincs, trichlorocarbanilide, triclosan, benzalkonium chloride, alkyldiaminoethylglycine hydrochloride, methylchloroisothiazoline and methyl Examples include isothiazoline fungicides and sulfur, and these can be used alone or in combination of two or more. The methylchloroisothiazoline / methylisothiazoline fungicide is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one. In the present invention, among these, a 1-hydroxy-2-pyridone compound represented by the following general formula (2) is particularly preferably used.
[0028]
[Chemical 1]

[0029]
(However, in the above formula, R²Are alkyl groups having 1 to 17 carbon atoms, alkenyl groups having 2 to 17 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, and bicycloalkyl having 7 to 9 carbon atoms. A cycloalkyl-alkyl group wherein the cycloalkyl group has 5 to 8 carbon atoms and the alkyl group has 1 to 4 carbon atoms (provided that the cycloalkyl group has a part of its hydrogen atoms Optionally substituted by an alkyl group having 1 to 4 carbon atoms), an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkyl group of 1 to 4 An aralkyl group having 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkenyl group having 2 to 4 carbon atoms, an aryl alkenyl group having 6 to 14 carbon atoms An aryloxyalkyl group or an arylmercaptoalkyl group, a benzhydryl group, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a phenylsulfonylalkyl group, a furyl group, or An alkenyl group represents a furylalkenyl group having 2 to 4 carbon atoms. However, in the above aryl group, a part of the hydrogen atoms is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, or a halogen atom. It may be. R^ThreeIs a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a halogen atom, a phenyl group or a benzyl group. To express. X represents an organic base, an alkali metal ion, an ammonium ion, or a divalent to tetravalent cation. )
[0030]
Specific examples of the compound represented by the general formula (2) include the following compounds and salts thereof.
[0031]
1-hydroxy-2-pyridone, 1-hydroxy-4-methyl-2-pyridone, 1-hydroxy-6-methyl-2-pyridone, 1-hydroxy-4,6-dimethyl-2-pyridone, 1-hydroxy- 4-methyl-6-heptyl-2-pyridone, 1-hydroxy-4-methyl-6- (1-ethylpentyl) -2-pyridone, 1-hydroxy-4-methyl-6- (2,4,4- Trimethylpentyl) -2-pyridone, 1-hydroxy-4-methyl-6-undecyl-2-pyridone, 1-hydroxy-4-methyl-6-propenyl-2-pyridone, 1-hydroxy-4-methyl-6 Octenyl-2-pyridone, 1-hydroxy-4-methyl-6- (2,2-dibutyl-vinyl) -2-pyridone, 1-hydroxy-4-methyl-6- (cyclohexe Ridene-methyl) -2-pyridone, 1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone, 1-hydroxy-4-methyl-6- (methyl-cyclohexyl) -2-pyridone, 1-hydroxy-4 -Methyl-6- (2-bicyclo [2,2,1] heptyl) -2-pyridone, 1-hydroxy-4-methyl-6- [2- (dimethylcyclohexyl) -propyl] -2-pyridone, 1- Hydroxy-4-methyl-6- (4-methyl-phenyl) -2-pyridone, 1-hydroxy-4-methyl-6- (3-methyl-phenyl) -2-pyridone, 1-hydroxy-4-methyl- 6- (4-tert-butyl-phenyl) -2-pyridone, 1-hydroxy-4-methyl-6- (3-methyl-4-chloro-phenyl) -2-pyridone, 1-hydroxy 4-methyl-6- (3,5-dichloro-phenyl) -2-pyridone, 1-hydroxy-4-methyl-6- (3-bromo-4-chloro-phenyl) -2-pyridone, 1-hydroxy- 4-methyl-6- (4-methoxystyryl) -2-pyridone, 1-hydroxy-4-methyl-6- [1- (4-nitrophenoxy) -butyl] -2-pyridone, 1-hydroxy-4- Methyl-6- (4-cyanophenoxymethyl) -2-pyridone, 1-hydroxy-4-methyl-6- (phenylsulfonylmethyl) -2-pyridone, 1-hydroxy-4-methyl-6- [1- ( 4-chlorophenylsulfonyl) -butyl] -2-pyridone, 1-hydroxy-4-methyl-6-benzyl-2-pyridone, 1-hydroxy-4-methyl-6- (2,4-dimethylben Dil) -2-pyridone, 1-hydroxy-4-methyl-6- (tert-butyl-benzyl) -2-pyridone, 1-hydroxy-4-methyl-6- (2-chloro-benzyl) -2-pyridone 1-hydroxy-4-methyl-6- (4-chlorobenzyl) -2-pyridone, 1-hydroxy-4-methyl-6- (2,5-dichloro-benzyl) -2-pyridone, 1-hydroxy- 4-methyl-6- (4-bromo-benzyl) -2-pyridone, 1-hydroxy-4-methyl-6- (phenoxymethyl) -2-pyridone, 1-hydroxy-4-methyl-6- (3- Methylphenoxy-methyl) -2-pyridone, 1-hydroxy-4-methyl-6- (4-secondary phenphenoxy-methyl) -2-pyridone, 1-hydroxy-4-methyl-6- (2,4,4) 5-to Chlorophenoxy-methyl) -2-pyridone, 1-hydroxy-4-methyl-6- (4-bromophenoxy-methyl) -2-pyridone, 1-hydroxy-4-methyl-6- (4-chlorophenylmercapto- Methyl) -2-pyridone, 1-hydroxy-4-methyl-6- (4-methylphenylmercapto-methyl) -2-pyridone, 1-hydroxy-4-methyl-6- (2-naphthyl) -2-pyridone 1-hydroxy-4-methyl-6-benzhydryl-2-pyridone, 1-hydroxy-4-methyl-6-furyl-2-pyridone, 1-hydroxy-4-methyl-6- (furylvinyl) -2- Pyridone, 1-hydroxy-4-methyl-6-styryl-2-pyridone, 1-hydroxy-4-methyl-6- (phenylbutadienyl) -2-pyridone Down, 1-hydroxy-4-phenyl-6-methyl-2-pyridone, mention may be made of 1-hydroxy-4,6-diphenyl-2-pyridone and the like.
[0032]
The said compound is used as a salt, for example, can be used conveniently as a salt with an organic amine. Specifically, for example, ethanolamine, diethanolamine, N-ethylethanolamine, N-methyl-diethanolamine, triethanolamine, diethylamino-ethanol, 2-amino-2-methyl-n-propanol, dimethylaminopropanol, 2-amino 2-methyl-propanediol, tri-isopropanolamine, ethylenediamine, hexamethylenediamine, morpholine, piperidine, cyclohexylamine, tributylamine, dodecylamine, N, N-dimethyl-dodecylamine, stearylamine, oleylamine, benzylamine, di Benzylamine, N-ethylbenzylamine, dimethylstearylamine, N-methyl-morpholine, N-methylpiperazine, 4-methylcyclohexylamine, N- Dorokishiechiru - morpholine, and the like.
[0033]
The 1-hydroxy-2-pyridone compound used in the present invention may be a salt with an inorganic ion, for example, alkali metal salts such as sodium salt and potassium salt, ammonium salt and magnesium salt, calcium salt and the like. Alkaline earth metal salts can be used. Furthermore, salts with divalent to tetravalent cations such as zinc salts, aluminum salts and zirconium salts can also be used.
[0034]
The blending amount of the component b) in the composition of the present invention is not particularly limited, but when one of these compounds is used alone or in combination of two or more, it is usually 0 of the entire composition. 0.01 to 3%, particularly 0.05 to 2% is preferable. If the amount of the bactericidal compound is too small, a sufficient bactericidal effect may not be obtained. On the other hand, if the amount is too large, for example, the bactericidal compound is not sufficiently dissolved, and the storage stability such as precipitation during storage at a low temperature. In some cases, the blended amount may not be effectively utilized due to adsorption to the container during storage.
[0035]
Furthermore, the composition of the present invention needs to have a viscosity of 10 mPa · s or more at 25 ° C., preferably 10 to 10000 mPa · s, more preferably 15 to 8000 mPa · s. If the viscosity is too low, it will spill out when used in use, or if it is used as a shampoo, for example, it may cause problems such as running down the scalp and getting into the eyes, which is not convenient and unfavorable for safety. There are things to do.
[0036]
In order to bring the viscosity of the composition of the present invention into the above range, the viscosity of the composition can be obtained by blending the above-mentioned a) alkyl ethoxy sulfate. Accordingly, known thickeners can be used in combination, and the type of such thickeners is not particularly limited. For example, nonionics such as fatty acid alkanolamides, alkyl ethers and esters, sugar-based ones These activators, polymer compounds, betaines, and the like can be preferably used.
[0037]
Further, when the composition of the present invention is used as, for example, a hair composition such as a hair cleanser or a skin external composition such as a skin cleanser, an anionic surfactant or amphoteric agent usually contained in these cleanser One or more surfactants selected from surfactants and semipolar surfactants can be contained within a range that does not interfere with the effects of the present invention, thereby further foaming, foam feel, and washing A composition which is excellent in strength, rinsing and finishing feeling, and is mild and has good storage stability can be obtained.
[0038]
Specifically, as the anionic surfactant, for example, conventional polyoxyethylene alkyl ether sulfates and alkyl sulfates having a wide distribution of ethylene oxide addition mole number can be used. It is necessary to make it a combined amount that does not eliminate the characteristics of the component a), which has a narrow distribution of the number of moles of ethylene oxide added, which is a characteristic of the above composition, and it is necessary to determine the balance with other ingredients. In addition, α-olefin sulfonate, acylmethyl taurate, amide ether sulfate, ether carboxylate, alkane sulfonate, amino acid anion activator, and the like can be used. Alternatively, two or more kinds can be used in appropriate combination, but are not particularly limited thereto. In addition, when using these anionic surfactant together, it is preferable that these total compounding quantities shall be about 0 to 40% with respect to the whole composition.
[0039]
Further, the type of amphoteric surfactant is not particularly limited. For example, one or more amphoteric surfactants such as betaine type, imidazoline type, and aminocarboxylic acid type can be used. Specific examples include alkylbetaines, alkylamidopropylbetaines, sulfobetaines, imidazolinium betaines, aminocarboxylic acids, aminopropionic acids, and salts thereof. The content of the amphoteric surfactant is usually preferably 0 to 15%, particularly preferably 0 to 6% of the entire composition.
[0040]
Further, the kind of the semipolar surfactant is not particularly limited, but for example, an amine oxide type nonionic surfactant can be mentioned as a representative one. Specific examples include lauryl dimethylamine oxide and polyoxyethylene lauryl dimethylamine oxide. These amine oxides can be used alone or in combination of two or more in the composition. The blending amount is 0 to 15% of the whole composition, preferably 0 to 6%.
[0041]
When the composition of the present invention is used as a hair composition or a composition for external use on the skin, a film-forming polymer compound can be used in combination for the purpose of enhancing the retention of the bactericidal compound in the hair and skin. . Examples of such a polymer compound include cationic polymer compounds such as cationized cellulose and cationized guar gum, amphoteric polymers such as betainized dialkylaminoalkyl (meth) acrylate or dialkylaminoalkyl (meth) acrylamide, and polybetaines. Amphoteric polymer compounds such as acrylic anionic polymer compounds, nonionic polymer compounds such as hydroxyethyl cellulose, etc., and these may be used singly or in appropriate combination of two or more. Can do.
[0042]
As long as the composition of the present invention does not impede the effects of the present invention, depending on the type and use mode, the composition of the present invention is optionally used as an optional component, in addition to the above components, for example, a regular composition for hair or an external composition for skin. Components such as cationic surfactants and hydrophobic nonionic surfactants can also be added. Solid or liquid oils, higher alcohols, ester oils, polyhydric alcohols, preservatives, hydrotropes, inorganics Salt, thickener, fragrance, animal and plant extracts, anti-dandruff agent, medicinal agent, emulsion agent, pearlizing agent, UV absorber, UV scattering agent, tonic agent, pH adjuster, pigment, antioxidant, lower Alcohols, vitamins, volatile oils, hydrophobic solvents, diluting solvents, and the like can be contained, but these are not particularly limited and may be formulated according to the purpose.
[0043]
【The invention's effect】
The bactericidal compound-containing composition of the present invention is not only excellent in the retention of the bactericidal compound on the hair, skin, etc., but also has excellent usability and is mild and has good storage stability. It can be used for cosmetics in general, and for various uses such as kitchen cleaners and other tableware, furniture cleaners, disinfectants, etc., especially as a hair composition or skin external composition Useful. In addition, since the composition of the present invention can further improve foaming and foam feel, among hair compositions or skin external compositions, hair cleaning compositions, skin cleansings in particular. The effect is remarkably exhibited in a body cleaning composition such as a cleaning composition.
[0044]
【Example】
EXAMPLES Hereinafter, although the Example and comparative example of this invention are shown and this invention is demonstrated more concretely, this invention is not limited by the following Example. In addition, all the% shown below are mass percentages.
[0045]
[Examples 1-6, Comparative Examples 1-3]
Using the a) component (polyoxyethylene alkyl ether sodium sulfate) shown in Table 1 and preparing a hair cleanser and skin cleanser according to a conventional method according to the composition shown in Table 2, foam performance of each composition In addition, the persistence to hair or skin of a compound having a bactericidal effect (bactericidal compound), mildness, storage stability, and viscosity of the composition were evaluated according to the following evaluation methods. The results are also shown in Table 2.
[0046]
In addition, the preparation method of the alkyl ethoxy sulfate of Table 1 is described below.
<Narrowly distributed alkyl ethoxy sulfate: Sample A-1>
The narrow distribution lauryl ethoxy sulfate used in the examples of the present invention was prepared by the following method.
[0047]
Into a 4-liter autoclave was charged 400 g of lauryl alcohol and 0.4 g of a composite metal oxide Lewis acid sintered solid catalyst composed of Al / Mg / Mn (aluminum / magnesium / manganese), and the inside of the autoclave was purged with nitrogen. The temperature was raised with stirring. Next, 54 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 mPa, to obtain a reaction product. Next, 274 g of the alcohol ethoxylate thus obtained was placed in a 500 ml flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the target alkyl ethoxy sulfate (lauryl ethoxy sulfate). The properties of the resulting alkyl ethoxy sulfate and the distribution of the oxyethylene chain length were as shown in Table 1. Sample A-2 was prepared in the same manner.
[0048]
<Wide distribution of alkyl ethoxy sulfate: Sample AES-1>
Moreover, the preparation of the lauryl ethoxy sulfate with a wide distribution normally used in the comparative example was carried out by the following method.
[0049]
Into a 4 liter autoclave, 400 g of lauryl alcohol and 0.8 g of potassium hydroxide catalyst were charged, the inside of the autoclave was purged with nitrogen, and the temperature was increased while stirring. Next, 54 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 mPa, to obtain a reaction product. Next, 274 g of the alcohol ethoxylate thus obtained was placed in a 500 ml flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropping, stirring was continued for 1 hour to obtain the target alkyl ethoxy sulfate (lauryl ethoxy sulfate). The properties of the resulting alkyl ethoxy sulfate and the distribution of the oxyethylene chain length were as shown in Table 1. Sample AES-2 was prepared in the same manner.
[0050]
(1) Evaluation method of foam performance
Based on sensory evaluation by a skilled expert, foaming, foam feel, etc. were comprehensively evaluated and judged according to the following criteria.
Judgment criteria
Good: Foam performance is good.
X: Foam performance is not good.
[0051]
(2) Method for evaluating retention of compound (bactericidal compound) having bactericidal effect on hair or skin
About each prescribed composition, after using for hair or skin, each bactericidal component adsorbed on hair or skin is extracted with a solvent that dissolves each bactericidal component well, and the amount of each bactericidal component is determined by liquid chromatography. Determine the amount of residue on hair or skin by quantifying according to the method. Compared to the use of the standard composition described later, the retention amount is better (○), and the remaining amount is the same or less. It was set as a defect (x).
[0052]
The standard composition used here is 10% polyoxyethylene (3 mol) lauryl ether sulfate sodium salt, which is AES-1 in Table 1 with a wide distribution of the number of moles of ethylene oxide added. (Clariant; Octopirox) 0.1%, remaining purified water, 100% in total.
[0053]
(3) Mildness evaluation method
The irritation feeling when 10 sensitive skin panels used the composition was compared with the above-mentioned standard composition and evaluated according to the following evaluation criteria.
Judgment criteria
◯: The feeling of irritation is small compared to the standard composition.
Δ: The feeling of irritation is equivalent to that of the standard composition.
X: The feeling of irritation is larger than that of the standard composition.
[0054]
(4) Storage stability evaluation method
As a result of storage at 40 ° C for 1 month under high temperature conditions and storage at -5 ° C for 1 month under low temperature conditions, the storage stability of those that are hardly observed by comparison with those immediately after preparation is visually observed. The storage stability was evaluated as x for those in which significant discoloration, precipitation, separation, or the like was observed.
[0055]
(5) Evaluation method of viscosity of composition
The viscosity of the composition was measured with a Brookfield BL viscometer at 25 ° C., and the viscosity was evaluated according to the following criteria.
Judgment criteria
○: The viscosity is moderate (10 mPa · s or more).
X: Viscosity is low (less than 10 mPa · s).
[0056]
[Table 1]

[0057]
[Table 2]

[0058]
As is apparent from the results in Table 2, the compositions of the present invention all have excellent foam performance, retention on hair or skin, mildness, storage stability, and good viscosity during use. is there.
[0059]
In addition, the compound which has the bactericidal effect shown by B-1 to B-6 in Table 2 is as follows.
[0060]
[Chemical 2]

[0061]
[Chemical 3]

[0062]
B-3 Salicylic acid
B-4 Triclosan
B-5 Benzalkonium chloride
B-6 isothiazoline solution ("Caisson CG" manufactured by Rohm & Haas)
These compounds are common to Table 2 and the following examples.
[0063]
[Example 7]
composition
A-1 15.0
Amidopropyl betaine laurate 2.0
Alkyldimethylamine oxide 2.0
Palm oil fatty acid diethanolamide 3.0
POE dioleic acid methyl glucoside 0.8
Laurylpyrrolidone 3.0
B-1 0.5
Coleus extract 0.2
POE hydrogenated castor oil (HLB9) 1.5
POE (15 mol) alkyl ether 0.5
Sodium sulfate 2.0
Sodium benzoate 1.0
Ethylene glycol distearate 2.0
Glycerin fatty acid ester 0.2
Glycine 0.5
1,3-butylene glycol 1.0
Dibutylhydroxytoluene 0.005
Oxybenzone 0.5
B-6 0.03
Yellow No. 203 0.001
Orange 205 No. 0.002
Fragrance 0.7
Citric acid 0.5
Purified water balance
Total 100%
[0064]
A shampoo composition having the above composition was prepared according to a conventional method. This shampoo composition has a viscosity at 25 ° C. of 10 mPa · s or more, excellent foaming, foam feel, mildness, excellent retention of B-1 and B-6 compounds in hair, and stable storage. The viscosity at the time of use was moderate without being too low.
[0065]

[0066]
A shampoo composition was prepared according to a conventional method according to the above composition. This shampoo composition has a viscosity at 25 ° C. of 10 mPa · s or more, excellent foam performance, mildness, and B-3 compound retention on the scalp, excellent storage stability, It had a viscosity.
[0067]
[Example 9]
composition
A-1 7.0
Potassium myristate 15.0
Palmitic acid 8.0
Stearic acid 8.0
B-1 0.5
B-3 0.2
Oleyl alcohol 1.0
Glycerin 10.0
Polyethylene glycol 5.0
Palm oil fatty acid monoethanolamide 0.1
Propylene glycol 1.0
Plant-based squalane 0.5
Edetic acid tetrasodium tetrahydrate 0.2
POE hydrogenated castor oil (HLB9) 1.5
Glycerin fatty acid ester 0.2
Benclay 0.8
Isoprene glycol 1.0
Blue No. 403 0.001
Fragrance 0.2
Purified water balance
Total 100%
[0068]
According to the above composition, a face cleansing composition was prepared according to a conventional method. This facial cleanser composition has a viscosity at 25 ° C. of 10 mPa · s or more, good foam performance, excellent retention of B-1 and B-3 compounds in the skin, mild and good storage stability. It had moderate viscosity and was easy to use.
[0071]
[Example 11]
composition
A-2 5.0
Acylmethyl-β-alanine triethanolamine 10.0
Acyl glutamic acid triethanolamine 5.0
Sodium ether carboxylate 1.0
Alkylaminopropionic acid 0.05
Lauryldimethylamine oxide 0.8
Stearyltrimethylammonium chloride 1.0
Palm kernel fatty acid diethanolamide 2.0
POE hydrogenated castor oil (HLB9) 3.0
Propylene glycol 0.2
Ethanol 3.0
Dipotassium glycyrrhizinate 0.3
B-1 1.5
Liquid paraffin 0.2
Glycerin fatty acid ester 0.8
Sodium benzoate 0.7
Hydrolyzed protein 0.5
Magnesium sulfate 1.5
Cationized cellulose 0.2
Alkyldimethylammonium chloride / acrylic acid copolymer 0.4
Dibutylhydroxytoluene 0.2
Fragrance 0.3
Citric acid 0.1
Edetic acid 1.0
Purified water balance
Total 100%
[0072]
A shampoo composition was prepared according to a conventional method according to the above composition. This shampoo composition has a viscosity at 25 ° C. of 10 mPa · s or more, is excellent in foaming and foam feel, is mild, has excellent retention of the B-1 compound in hair, and has good storage stability. Also, the viscosity at the time of use was moderate without being too low.
[0073]
[Example 12]
composition
A-2 7.0
Potassium myristate 15.0
Lauroylmethyl-β-alanine potassium salt 2.0
Lauroyl glutamic acid monopotassium salt 2.0
Lauryldimethylamine oxide 1.0
B-1 0.5
B-4 0.2
Oleyl alcohol 1.0
Polyethylene glycol 5.0
Palm oil fatty acid diethanolamide 3.0
Propylene glycol 6.0
Hydroxypropyl methylcellulose^{* 1}                        0.5
Plant-based squalane 0.5
Edetic acid tetrasodium tetrahydrate 0.2
POE hydrogenated castor oil (HLB9) 1.5
Benclay 0.8
Potassium hydroxide
Blue No. 403 0.001
Fragrance 0.2
Purified water balance
Total 100%
* 1 Shin-Etsu Chemical Co., Ltd. Metroose 65SH-1500
[0074]
According to the above composition, a skin cleanser composition was prepared according to a conventional method. This skin cleanser composition has a viscosity at 25 ° C. of 10 mPa · s or more, good foam performance, excellent retention of B-1 and B-4 compounds on the skin, mild and storage stability. It was good, had an appropriate viscosity, and was easy to use.

Claims (1)

a) An ethylene oxide adduct represented by the following general formula (1), including those having a different number of moles of ethylene oxide addition, wherein the mass% occupied by those having a number of moles of ethylene oxide addition of 0 does not show the maximum value, and shows the maximum value The alkyl ethoxy sulfate and / or salt thereof in which the total amount of the ethylene oxide adduct having the added mole number before and after this is 20 to 30% by mass, and b) 1-hydroxy- Contains one or more fungicidal compounds selected from 2-pyridone compounds, salicylic acid and salts thereof, triclosan, benzalkonium chloride and methylchloroisothiazoline / methylisothiazoline fungicides, and has a viscosity at 25 ° C. A bactericidal compound-containing composition for hair or external skin, characterized by being 10 mPa · s or more.
R ¹ O— (CH ₂ CH ₂ O) _n —SO ₃ M (1)
(However, in the above formula, R ¹ is a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms, n is represents an average addition mole number of ethylene oxide groups, 1-6 And M is a hydrogen atom, an alkali metal, an alkaline earth metal, an alkanolamine or ammonium.)