JP4711069B2 - Cation-modified alginic acid derivative and cosmetic composition containing the substance - Google Patents

Description

（式中Ｒ₁、Ｒ₂は各々炭素数１〜３のアルキル基、Ｒ₃は炭素数１〜２４のアルキル基を示し、Ｘ^-は陰イオンを示す。ｎは、ｎ＝０又はｎ＝１〜３０を示し、ｎ＝１〜３０のとき、（Ｒ₄Ｏ）_nは炭素数２〜４のアルキレンオキサイドの重合体残基であって、単一のアルキレンオキサイドからなるポリアルキレングリコール鎖及び／又は２種類以上のアルキレンオキサイドからなるポリアルキレングリコール鎖を示す。）
本発明の第二の態様は、前記ウロン酸ユニットが１，４グリコシド結合で結合した重合体であるアルギン酸誘導体が、海藻中の褐藻類（学名Ｐｈａｅｏｐｈｙｃｅａｅ）に含まれるＬ−グルロン酸とＤ−マンヌロン酸の２種類のウロン酸から構成される天然多糖類の誘導体である第一の態様記載の化粧料組成物に関する。
本発明の第三の態様は、前記カチオン変性アルギン酸誘導体のカチオン変性が、グリシジルトリアルキルアンモニウム塩または、３−ハロゲノ−２−ヒドロキシプロピルトリアルキルアンモニウム塩を用いてなされたものである第一又は第二の態様記載の化粧料組成物に関する。
本発明の第四の態様は、前記カチオン変性アルギン酸誘導体のカチオン変性が、アルギン酸誘導体に含まれる水酸基の一部に、炭素数２〜４のアルキレンオキサイドを付加し、続いてカチオン化剤としてグリシジルトリアルキルアンモニウム塩または、３−ハロゲノ−２−ヒドロキシプロピルトリアルキルアンモニウム塩を用いてなされたものである第一又は第二の態様記載の化粧料組成物に関する。
本発明の第五の態様は、前記カチオン変性アルギン酸誘導体がナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩等のアルギン酸塩である第一ないし第四の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第六の態様は、前記カチオン変性アルギン酸誘導体の含有量が組成物全体を１００質量％として、０．０５〜５質量％である第一ないし第五の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第七の態様は、さらに、他のカチオン性水溶性高分子及び／又は両性水溶性高分子を、組成物全体を１００質量％として、５質量％以下含有することを特徴とする第一ないし第六の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第八の態様は、さらに、アミドアミン化合物と有機酸及び／又は無機酸等の中和剤とさらに、高級脂肪酸及び／又は高級アルコールを含むことを特徴とする第一ないし第七の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第九の態様は、さらに、シリコーン及び／又はシリコーン誘導体を含むことを特徴とする第一ないし第八の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第十の態様は、前記化粧料組成物が毛髪処理用組成物であることを特徴とする第一ないし第九の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
【発明を実施するための最良の形態】
本発明で用いられるアルギン酸誘導体は、コンブやワカメなどの褐藻類（学名Ｐｈａｅｏｐｈｙｃｅａｅ）の細胞壁にカルシウム塩等として含まれ、Ｌ−グルロン酸とＤ−マンヌロン酸の２種類のウロン酸から構成される直鎖状多糖で、Ｌ−グルロン酸同士の結合からなるブロックと、Ｄ−マンヌロン酸同士の結合からなるブロックと、Ｌ−グルロン酸とＤ−マンヌロン酸の結合からなるブロックの３種類のブロックが共存するポリウロン酸である。また、ウロン酸ユニットが有するカルボキシル基はイオン交換性をもち、そのため海藻中では海水中に含まれる様々な金属イオンと塩を形成し、水に不溶性のゼリー状態になっているが、抽出・精製する工程で、純アルギン酸及び、目的に応じた各種の塩或いはエステルへと変換される。さらに目的に応じ、酵素などの生物学的処理及び、酸、アルカリによる加水分解等の化学的処理により解重合し、低分子化されることもある。よって、本明細書で用いられる「アルギン酸誘導体」とは、純アルギン酸及び純アルギン酸から得られる各種のアルギン酸塩、アルギン酸エステル、さらに低分子化されたこれらの誘導体の意味である。これらのアルギン酸誘導体は、商品名「ダックアルギンＮＳＰＨ」、「ダックアルギンＮＳＰＬ」「ダックアルギンＮＳＰＬＬ」「ダックアッシド」（（株）紀文フードケミファ社製）として、また「キミロイド」（君津化学工業（株）社製）として、さらに、褐藻類コンブ目に属する海藻でラミナリアディギタータより得られる「ＰＨＹＣＯ ＡＮＴＩ−ＰＯＬＬＵ」、「ＰＨＹＣＯ ＡＮＴＩ−ＩＮＦＬＡ」（コディフ社製）として容易に入手可能である。
本発明で用いられるカチオン変性アルギン酸誘導体は、アルギン酸誘導体をカチオン変性することによる吸着性向上によって、コンディショニング効果が得られる。また、造膜性を有することにより塗布型の化粧料組成物へ配合したした場合、強力なセット効果が得られ、シャンプー、リンス等の洗い流しの化粧料組成物へ配合した場合、毛髪に弾力性が付与され、毛髪にコシやハリを付与する。さらにシャンプー、ボディ用洗浄剤等へ配合した場合、造膜性を有することで均一な膜が形成され、使用時の泡立ち、泡質等の泡の感触改善をする。
本発明によるカチオン変性は、Ｌ−グルロン酸とＤ−マンヌロン酸の２種類のウロン酸から構成されるアルギン酸誘導体に、第４級窒素含有基を有するグリシジルトリアルキルアンモニウム塩または、３−ハロゲノ−２−ヒドロキシプロピルトリアルキルアンモニウム塩を反応させることによって製造することができる。この場合、反応は適当な溶媒、好適には含水アルコール中において、アルカリの存在下で実施される。このような第４級窒素含有基の導入は、従来公知の方法に従って行うことができるが、必ずしもこれらに限定されるものではない。例えば、アルギン酸誘導体に含まれる水酸基の一部に、炭素数２〜４のアルキレンオキサイドを付加した後、上記グリシジルトリアルキルアンモニウム塩または、３−ハロゲノ−２−ヒドロキシプロピルトリアルキルアンモニウム塩の第４級窒素含有基と反応させることによって本発明に用いられるカチオン変性アルギン誘導体を製造することができる。さらに、アルギン酸誘導体として低分子化した、アルギン酸及びアルギン酸塩を用いる他に、アルギン酸誘導体を酸又はアルカリにより加水分解し低分子化した後に、第４級窒素含有基と反応させることでも本発明品は製造することができる。またさらに、アルギン酸誘導体に第４級窒素含有基の導入した後、酸又はアルカリにより加水分解することでも製造することができる。また、反応時に溶媒中でのアルギン酸誘導体の凝集を防ぐため、無機塩、好適には塩化ナトリウムを添加することもできる。さらに、アルギン酸誘導体の凝集を防ぎ、分散性を良くし反応率を上げるため、反応溶媒中にアルカリ及び無機塩を添加後溶解又は分散させ、その後該アルギン酸誘導体を添加し、溶解又は分散させた後、上記の第４級窒素含有基を導入することでも製造することができる。
本発明でアルギン酸誘導体中に導入する前記化学式（１）で示された第４級窒素含有基において、Ｒ₁及びＲ₂の具体例としては、メチル基、エチル基及びプロピル基が挙げられ、炭素数１〜２４のアルキル基としてのＲ₃の具体例としては上記Ｒ₁及びＲ₂と同じものの他、オクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、ドコシル基等が挙げられる。Ｒ₄Ｏの具体例としては、エトキシ基、プロポキシ基及びブトキシ基が挙げられる。また、陰イオンＸ^-の具体例としては、塩素イオン、臭素イオン及び沃素イオンなどのハロゲンイオンの他、メチル硫酸イオン、エチル硫酸イオン、酢酸イオン等を挙げることができる。
本発明に用いられるカチオン変性アルギン酸誘導体は、造膜性と毛髪及び皮膚への吸着能を有することから化粧料組成物の配合成分として優れたものであり、例えば、化粧料組成物に配合した場合、造膜性により泡立ち、泡質等の泡感触を改善し、さらに毛髪処理用組成物に配合した場合、コンディショニング効果、弾力性の付与及びセット効果を与え、また皮膚化粧料組成物、例えばボディ洗浄剤に配合した場合には、皮膚の油脂成分を必要以上に除去せず、さらに感触の改善をもたらす。すなわち本発明は、前記本発明に用いられるカチオン変性アルギン酸誘導体を配合したこれらの化粧料組成物に関する。
本発明に用いられるカチオン変性アルギン酸誘導体の、第４級窒素含有基由来のカチオン電荷量は０．１〜３．０ｍｅｑ／ｇであるが、より好ましくは０．５〜２．５ｍｅｑ／ｇである。カチオン電荷量が０．１ｍｅｑ／ｇ未満では毛髪や皮膚に対する吸着量が不十分となり、実際シャンプー、リンス、ボディ用洗浄剤等の毛髪処理用組成物や皮膚化粧料組成物に配合しても効果は認められない。また、電荷量が３．０ｍｅｑ／ｇを越えると、そのようなカチオン変性アルギン酸誘導体を配合した毛髪処理用組成物及び皮膚化粧料組成物を使用しても、使用時に泡立ちの悪化及び、べたつき感、ぬるつき感が生じ使用感を悪化させ、使用後の仕上がり感も、ごわつき感、べたつき感を生じるなど好ましくなく、さらには弾力性の付与及びセット効果も得られない。
なお、カチオン変性アルギン酸誘導体の第４級窒素含有基由来のカチオン電荷量とは、カチオン変性アルギン酸誘導体１ｇ当たりに含まれる化学式（１）で示された第４級窒素含有基の当量数である。通常は第４級窒素含有基由来の窒素分をケルダール法（旧化粧品原料基準、一般試験方法、窒素定量法、第２法）により求め、測定値から算出できるが、本発明で用いられるＬ−グルロン酸とＤ−マンヌロン酸の２種類のウロン酸から構成されるアルギン酸誘導体中には、窒素分が含まれるため、ケルダール法により求めた本発明に用いられるカチオン変性アルギン酸誘導体の窒素分から、本発明で用いるＬ−グルロン酸とＤ−マンヌロン酸の２種類のウロン酸から構成されるアルギン酸誘導体由来の窒素分を引いた値が、第４級窒素含有基由来の窒素分となる。具体的に説明すると、化学式（１）で示された第４級窒素含有基のＲ₁、Ｒ₂、Ｒ₃はメチル基、Ｘ^-は塩素イオン、ｎは、ｎ＝０の第４級窒素含有基でアルギン酸ナトリウムをカチオン変性することで得られた本発明品の窒素分は、ケルダール法により測定した結果、１．００％であった場合、この物質のカチオン電荷量は以下の式にて求められる。本発明で用いられるアルギン酸ナトリウム中には、通常窒素分を０．０２％前後含有している。
カチオン電荷量（ｍｅｑ／ｇ）＝第４級窒素含有基由来の窒素分（％）×１０００
窒素の原子量（１４．０）×１００
＝（１．００−０．０２）／１．４０
＝０．７０
本発明に用いられるカチオン変性アルギン酸誘導体の毛髪処理用組成物や皮膚化粧料組成物に対する配合量は、組成物全体を１００質量％として、０．０５〜５質量％が好ましく、０．０５質量％未満ではコンディショニング効果、弾力性の付与及びセット効果が十分に発揮されない傾向にあり、５質量％を越えると使用時にぬるつき感、べたつき感が生じると共に、柔軟性が悪化し、ごわつき感が見られ使用感等が悪くなる傾向がある。
また、本発明の毛髪処理用組成物にはコンディショニング効果の向上の為、さらに種々のカチオン性水溶性高分子、両性水溶性高分子を併用することができるが、その配合量はカチオン変性アルギン酸誘導体の造膜性及びセット効果を損なわない範囲であり、組成物全体を１００質量％として、５質量％以下が好ましく、これを超えると使用時にごわつき感が生じ使用感が悪くなると共に、カチオン変性アルギン酸誘導体の示す造膜性及びセット効果が十分に発揮されなくなる。さらに、皮膚化粧料組成物に於いては、ぬるつき感が生じ、使用感が悪くなる。
配合されるカチオン性水溶性高分子、両性水溶性高分子としては、下記のようなものが挙げられるが、必ずしもこれらに限定されるものではない。
カチオン性水溶性高分子の例としては、第４級窒素変性ポリサッカライド（カチオン変性ヒドロキシエチルセルロース、カチオン変性グアーガム、カチオン変性ローカストビーンガム、カチオン変性デンプン、カチオン変性タラガム、カチオン変性タマリンドガム等）、塩化ジメチルジアリルアンモニウム誘導体（塩化ジメチルジアリルアンモニウム・アクリルアミド共重合体、ポリ塩化ジメチルメチレンピペリジニウム等）、ビニルピロリドン誘導体（ビニルピロリドン・ジメチルアミノエチルメタクリル酸共重合体塩、ビニルピロリドン・メタクリルアミドプロピルトリメチルアンモニウムクロライド共重合体、ビニルピロリドン・塩化メチルビニルイミダゾリウム共重合体等）、メタクリル酸誘導体（メタクリロイルエチルジメチルベタイン・塩化メタクリロイルエチルトリメチルアンモニウム・メタクリル酸２−ヒドロキシエチル共重合体、メタクリロイルエチルジメチルベタイン・塩化メタクリロイルエチルトリメチルアンモニウム・メタクリル酸メトキシポリエチレングリコール共重合体等）等が挙げられる。
両性水溶性高分子の例としては、両性化デンプン、塩化ジメチルジアリルアンモニウム誘導体（アクリルアミド・アクリル酸・塩化ジメチルジアリルアンモニウム共重合体、アクリル酸・塩化ジメチルジアリルアンモニウム共重合体等）、メタクリル酸誘導体（ポリメタクリロイルエチルジメチルベタイン、Ｎ−メタクリロイルオキシエチルＮ，Ｎ−ジメチルアンモニウム−α−メチルカルボキシベタイン・メタクリル酸アルキル共重合体等）等が挙げられる。
上述のように、本発明に用いられるカチオン変性アルギン酸誘導体を公知の処方により処方系内に所要量配合することで本発明の化粧料が得られるが、化粧料中の他の成分は特に限定されず、化粧料に一般に用いられる成分を任意成分として配合することが可能である。配合可能な他の成分を下記に例示する。
アニオン界面活性剤としては、アルキル（炭素数８〜２４）硫酸塩、アルキル（炭素数８〜２４）エーテル硫酸塩、アルキル（炭素数８〜２４）ベンゼンスルホン酸塩、アルキル（炭素数８〜２４）リン酸塩、ポリオキシアルキレンアルキル（炭素数８〜２４）エーテルリン酸塩、アルキル（炭素数８〜２４）スルホコハク酸塩、ポリオキシアルキレンアルキル（炭素数８〜２４）エーテルスルホコハク酸塩、アシル（炭素数８〜２４）化アラニン塩、アシル（炭素数８〜２４）化Ｎ−メチル−β−アラニン塩、アシル（炭素数８〜２４）化グルタミン酸塩、アシル（炭素数８〜２４）化イセチオン酸塩、アシル（炭素数８〜２４）化サルコシン酸塩、アシル（炭素数８〜２４）化タウリン塩、アシル（炭素数８〜２４）化メチルタウリン塩、α−スルホ脂肪酸エステル塩、エーテルカルボン酸塩、ポリオキシアルキレン脂肪酸モノエタノールアミド硫酸塩、長鎖（炭素数８〜２４）カルボン酸塩等が挙げられる。
ノニオン界面活性剤としては、アルカノールアミド、グリセリン脂肪酸エステル、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレングリコールエーテル、ポリオキシアルキレンソルビタン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシアルキレンソルビット脂肪酸エステル、ソルビット脂肪酸エステル、ポリオキシアルキレングリセリン脂肪酸エステル、ポリオキシアルキレン脂肪酸エステル、ポリオキシアルキレンアルキルフェニルエーテル、テトラポリオキシアルキレンエチレンジアミン縮合物類、ショ糖脂肪酸エステル、ポリオキシアルキレン脂肪酸アミド、ポリオキシアルキレングリコール脂肪酸エステル、ポリオキシアルキレンヒマシ油誘導体、ポリオキシアルキレン硬化ヒマシ油誘導体、アルキルポリグリコシド、ポリグリセリン脂肪酸エステル等が挙げられる。
両性界面活性剤としては、アルキル（炭素数８〜２４）アミドプロピルベタイン、アルキル（炭素数８〜２４）カルボキシベタイン、アルキル（炭素数８〜２４）スルホベタイン、アルキル（炭素数８〜２４）ヒドロキシスルホベタイン、アルキル（炭素数８〜２４）アミドプロピルヒドロキシスルホベタイン、アルキル（炭素数８〜２４）ヒドロキシホスホベタイン、アルキル（炭素数８〜２４）アミノカルボン酸塩、アルキル（炭素数８〜２４）イミダゾリニウムベタイン、アルキル（炭素数８〜２４）アミンオキシド、３級窒素及び４級窒素を含むアルキル（炭素数８〜２４）リン酸エステル等が挙げられる。
油分としては、オリーブ油、ホホバ油、流動パラフィン、脂肪酸アルキルエステル等が挙げられる。また、パール化剤としては、脂肪酸エチレングリコール等、懸濁剤としてはポリスチレン乳化物等が挙げられる。
また本発明の毛髪処理用組成物や皮膚化粧料組成物に配合されるカチオン性、両性水溶性高分子以外にも、粘度調整及びスタイリング時の使用性をある程度改善するなどの目的によりアニオン性、ノニオン性高分子を、本発明の効果を損なわない範囲でさらに配合することができ、例えば下記のようなものが挙げられる。
アニオン性高分子の例としては、アクリル酸誘導体（ポリアクリル酸及びその塩、アクリル酸・アクリルアミド・アクリル酸エチル共重合体及びその塩等）、メタクリル酸誘導体（ポリメタクリル酸及びその塩、メタクリル酸・アクリルアミド・ジアセトンアクリルアミド・アクリル酸アルキルエステル・メタクリル酸アルキルエステル共重合体及びその塩等）、クロトン酸誘導体（酢酸ビニル・クロトン酸共重合体等）、マレイン酸誘導体（無水マレイン酸・ジイソブチレン共重合体、イソブチレン・マレイン酸共重合体等）、ポリグルタミン酸及びその塩、ヒアルロン酸及びその塩、カルボキシメチルセルロース、カルボキシビニルポリマー等が挙げられる。
ノニオン性高分子の例としては、アクリル酸誘導体（アクリル酸ヒドロキシエチル・アクリル酸メトキシエチル共重合体、ポリアクリル酸アミド等）、ビニルピロリドン誘導体（ポリビニルピロリドン、ビニルピロリドン・酢酸ビニル共重合体等）、ポリオキシアルキレングリコール誘導体（ポリエチレングリコール、ポリプロピレングリコール等）、セルロース誘導体（メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース等）、ポリサッカライド及びその誘導体（グアーガム、ローカストビーンガム、デキストラン等）等が挙げられる。
さらに別の態様において、本発明の毛髪処理用組成物及び皮膚化粧料組成物に、アミドアミン化合物と有機酸及び／または無機酸等の中和剤とさらに、高級脂肪酸及び／または高級アルコールを添加することで、コンディショニング効果を向上することができる。その配合量はアミドアミン化合物として組成物全体を１００質量％として、５質量％以下が好ましく、これを越えると、使用後の感触が重くなったり、ぬるつきを生じ、使用感が悪くなる。
本発明の毛髪処理用組成物及び皮膚化粧料組成物に配合されるその他の成分としては、カチオン界面活性剤（アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルピリジウム塩、アルキルジメチルベンジルアンモニウム塩、塩化ベンゼトニウム、塩化ベンザルコニウム等）、可溶化剤（エタノール、エチレングリコール、プロピレングリコール等）、ワックス類（カルナバロウ、キャンデリラロウ等）、炭化水素油（流動パラフィン、スクワラン等）、保湿剤（グリセリン、トレハロース、ソルビトール、マルチトール、ジプロピレングリコール、１，３−ブチレングリコール、ヒアルロン酸Ｎａ等）、エステル類（ラウリン酸ヘキシル、ミリスチン酸イソプロピル、ミリスチン酸オクチルドデシル、ミリスチン酸ミリスチル、ミリスチン酸−２−ヘキシルデシル、トリミリスチン酸グリセリン、パルミチン酸イソプロピル、パルミチン酸−２−ヘプチルウンデシル、パルミチン酸−２−ヘキシルデシル、ステアリン酸ブチル、ステアリン酸イソセチル、１２−ヒドロキシステアリン酸コレステリル、セトステアリルアルコール、オクタン酸セチル、ジメチルオクタン酸ヘキシルデシル、イソステアリン酸イソセチル、トリイソステアリン酸トリメチロールプロパン、オレイン酸デシル、オレイン酸オイル、乳酸セチル、乳酸ミリスチル、酢酸エチル、酢酸ブチル酢酸アミル、酢酸ラノリン、２−エチルヘキサン酸セチル、２−エチルヘキシルパルミテート、ジ−２−エチルヘキシル酸エチレングリコール、トリ−２−エチルヘキシル酸トリメチロールプロパン、トリ−２−エチルヘキシル酸グリセリン、テトラ−２−エチルヘキシル酸ペンタエリスリトール、セチル−２−エチルヘキサノエート、アジピン酸ジイソブチル、アジピン酸−２−ヘプチルウンデシル、アジピン酸−２−ヘキシルデシル、ジペンタエリスリトール脂肪酸エステル、ジカプリン酸ネオペンチルグリコール、リンゴ酸ジイソステアリル、ジ−２−ヘプチルウンデカン酸グリセリン、トリ−２−ヘプチルウンデカン酸グリセライド、ヒマシ油脂肪酸メチルエステル、アセトグリセライド、Ｎ−ラウロイル−Ｌ−グルタミン酸−２−オクチルドデシルエステル、セバシン酸ジ−２−エチルヘキシル、セバシン酸ジイソプロピル、コハク酸−２−エチルヘキシル、クエン酸トリエチル、エチルラウレート、ミンク油脂肪酸エチル等）、酸化防止剤（トコフェロール、ＢＨＴ等）、シリコーン（メチルポリシロキサン、メチルフェニルポリシロキサン、高重合度メチルポリシロキサン、環状ポリシロキサン等）及びシリコーン誘導体（ポリエーテル変性シリコーン、アミノ変性シリコーン、（メタ）アクリル−シリコーン系グラフト共重合物等）、高級アルコール、高級脂肪酸（ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、ベヘニン酸、オレイン酸、ウンデシレン酸、トール油脂肪酸、ヤシ油脂肪酸、パーム脂肪酸、パーム核脂肪酸、リノール酸、リノレイン酸、エイコサペンタエン酸、ドコサヘキサエン酸等）、アミノ酸類（アルギニン、グルタミン酸等）、紫外線吸収剤（ベンゾフェノン誘導体、パラアミノ安息香酸誘導体、メトキシ桂皮酸誘導体等）、紫外線散乱剤（酸化亜鉛、酸化ジルコニウム、酸化チタン等の無機化合物）、増粘剤、金属封鎖剤（エデト酸塩等）、ｐＨ調整剤、殺菌剤、防腐剤、育毛剤、ビタミン類、抗炎症剤、色素、顔料（二酸化チタン等の無機白色顔料、酸化鉄（ベンガラ）、チタン酸鉄等の無機赤色系顔料、チタン酸コバルト等の無機緑色系顔料、酸化鉄処理雲母チタン、カーボンブラック処理雲母チタン等）、香料、起泡増進剤等が挙げられる。
上述の本発明にかかる化粧料組成物の剤型は限定されず任意の剤型を取ることができ、さらに上記（必須）成分の他に本発明の効果を損なわない範囲で、その剤型によって通常当該化粧料組成物に配合される各種成分を加え常法により製造することができるが、中でも毛髪処理用組成物として好ましく使用できる。剤型としては、シャンプー、リンス、コンディショナー、ヘアワックス、ヘアローション、ヘアミスト等が挙げられ、いずれも、本発明に用いられるカチオン変性アルギン酸誘導体の造膜性による泡立ち、泡質等の泡の感触改善とセット効果、弾力性の付与及び、コンディショニング効果を利用したものである。また、使用感触向上効果から、ボディ用洗浄剤、洗顔料、ローションへの利用も可能であり、酸性染毛料、酸化染毛料、パーマ剤等へ配合することも可能である。
【実施例】
以下に本発明を実施例に基づいてさらに詳細に説明するが、本発明はこれらに限定されるものではない。特に指定のない限り、配合量は質量％で示す。
［カチオン変性アルギン酸誘導体の製造］
【実施例１】
４８質量％の水酸化ナトリウム水溶液５．９ｇ及び塩化ナトリウム１．０ｇを、５０容量％のイソプロパノール水溶液６００ｍｌに添加した後、アルギン酸ナトリウム９９．５ｇを徐々に添加し分散させた。次に８０質量％グリシジルトリメチルアンモニウムクロライド（以下ＧＴＡとも記す）水溶液６０．８ｇを加え、加温し５０℃で３時間反応させた。反応終了後３５％塩酸７．０ｇを７０容量％のイソプロパノール水溶液８００ｍｌで希釈し、中和に使用した。室温で１時間中和後、メタノール５００ｍｌに反応液を注ぎ、反応生成物を沈殿させ、濾別した。得られた沈殿物をメタノール水溶液にて洗浄した後、反応生成物を減圧下で乾燥した。このようにして得られたカチオン変性アルギン酸誘導体のカチオン電荷量は０．６６ｍｅｑ／ｇであった。この結果を表１に示した（表１中、試料番号１）。
同様に添加するＧＴＡの量を変えることでカチオン電荷量の異なるカチオン変性アルギン酸誘導体を合成した。この結果を表１中に示した（表１中、試料番号２、３）。
【実施例２】
アルギン酸（ダックアッシド；（株）紀文フードケミファ社製）１７６ｇを、６０容量％のイソプロパノール水溶液１１００ｍｌに分散させ、塩化ナトリウム６．０ｇ及び４８質量％の水酸化ナトリウム水溶液１３６．８ｇを添加した。添加後加温し、７０℃で３時間加水分解を行った。加水分解後５０℃迄冷却する。冷却後、３−ハロゲノ−２−ヒドロキシプロピルジメチルモノラウリルアンモニウムクロライド５１４．５ｇを加え、５０℃で３時間反応させた。反応終了後３５％塩酸１４．０ｇを７０容量％のイソプロパノール水溶液１７００ｍｌで希釈し、中和に使用した。室温で１時間中和後、メタノール１２００ｍｌに反応液を注ぎ、反応生成物を沈殿させ、濾別した。得られた沈殿物をメタノール水溶液にて洗浄した後、反応生成物を減圧下で乾燥した。このようにして得られたカチオン変性アルギン酸誘導体のカチオン電荷量は０．７１ｍｅｑ／ｇであった。この結果を表１中に示した（表１中、試料番号４）。
【実施例３】
加圧密閉容器内でアルギン酸ナトリウム（ダックアルギンＮＳＰＨ；（株）紀文フードケミファ社製）１９９ｇを、７０容量％のイソプロパノール水溶液９００ｍｌに分散させ、４８質量％の水酸化ナトリウム水溶液１１．８ｇを添加した。次にエチレンオキサイド６６ｇ、プロピレンオキサイド２３４ｇを加え、加温し７０℃で３時間、加圧密閉下で反応させた。反応終了後解圧し、５０℃まで冷却する。冷却後、８０質量％ＧＴＡ水溶液２４２．４ｇを加え、５０℃で３時間反応させる。反応終了後３５％塩酸１４．０ｇを７０容量％のイソプロパノール水溶液１５００ｍｌで希釈し、中和に使用した。室温で１時間中和後、メタノール１０００ｍｌに反応液を注ぎ、反応生成物を沈殿させ、濾別した。得られた沈殿物をメタノール水溶液にて洗浄した後、反応生成物を減圧下で乾燥した。このようにして得られたカチオン変性アルギン酸誘導体のカチオン電荷量は０．６０ｍｅｑ／ｇであった。この結果を表１中に示した（表１中、試料番号５）。
例１
実施例１の方法に準じ、添加するＧＴＡの量を変えることで電荷量の異なるカチオン変性アルギン酸誘導体を合成した。この結果を表１中に示した（表１中、試料番号６、７）。
【表１】

［カチオン変性アルギン酸誘導体の評価］
実施例４ 造膜性
カチオン変性したアルギン酸誘導体（表１の試料番号１、２、４及び５）の造膜性を以下の方法で確認した。２０ｍｌの試験液（０．２％水溶液）を角形のステンレス製の容器（縦×横×深さ＝１３５ｍｍ×１７０ｍｍ×３０ｍｍ）に流し、真空乾燥機にて発泡に注意しながら乾燥（７５℃）を行う。乾燥後、恒温恒湿（２０℃、４０％ＲＨ）雰囲気中に２４時間放置した後、ステンレス容器から乾燥物を取り出し、乾燥物の状態を目視にて観察した。比較のため、他のカチオン性ポリマーとしてエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）及び窒素含有率１．９質量％のカチオン変性グアーガム（カチナールＣＧ−１００；東邦化学工業（株）社製）、さらには未変性のアルギン酸誘導体（アルギン酸ナトリウム、商品名：ダックアルギンＮＳＰＨ、（株）紀文フードケミファ社製）、各々について同様の造膜性試験を実施した。結果を表２に示す。
【表２】

表２の結果から、アルギン酸誘導体をカチオン変性した本発明品のカチオン変性アルギン酸誘導体は、従来のコンディショニング剤に使用されているカチオン性ポリマーと比較し、造膜性に優れていることが確認された。
［カチオン変性アルギン酸誘導体を配合した各化粧料の製造とその評価］
実施例５ 毛髪に対する弾力性付与（その１）
カチオン変性したアルギン酸誘導体の毛髪に対する弾力性付与効果を洗い流し製品（ヘアシャンプー）で確認した。
（ヘアシャンプーの調製）
５−ａ
実施例１、２及び３で得た表１中の試料番号１、３、４及び５のカチオン変性アルギン酸誘導体を用いて表３の（Ａ）に示した組成のシャンプーを調製した。表３中の（Ａ）の成分（１２）を６０℃に加熱し、成分（１）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合した。こうして表３の（Ａ）に示した組成のシャンプーを各々調製し、表１中の試料番号１、３、４及び５に対応するカチオン変性アルギン酸誘導体から調製したシャンプーを順に、本発明品の処方Ｓ１〜Ｓ４とした。
５−ｂ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらにカチオン性水溶性高分子としてエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を含む、表３の（Ｂ）に示した組成のシャンプーを調製した。表３中の（Ｂ）の成分（１２）を６０℃に加熱し、成分（１）及び（３）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合し、得られたシャンプーを本発明品の処方Ｓ５とした。
５−ｃ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらに両性水溶性高分子としてＮ−メタクリロイルオキシエチルＮ，Ｎ−ジメチルアンモニウム−α−メチルカルボキシベタイン・メタクリル酸アルキル共重合体（Ｙｕｋａｆｏｒｍｅｒ ＳＭ；三菱化学株式会社製）を含む、表３の（Ｃ）に示した組成のシャンプーを調製した。表３中の（Ｃ）の成分（１２）を６０℃に加熱し、成分（１）及び（４）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合し、得られたシャンプーを本発明品の処方Ｓ６とした。
５−ｄ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらにカチオン性水溶性高分子と両性水溶性高子の両方を含む、表３の（Ｄ）に示した組成のシャンプーを調製した。表３中の（Ｄ）の成分（１２）を６０℃に加熱し成分（１）及び（３）、（４）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合し、得られたシャンプーを本発明品の処方Ｓ７とした。
【表３】

５−ｅ（比較品の調製）
本発明で用いるカチオン変性アルギン酸誘導体のシャンプーにおける効果を比較するため、例１で得た表１中の試料番号６、７のカチオン変性アルギン酸誘導体を用いて表３の比較品（Ｅ）に示した組成のシャンプーを調製した。表３中の比較品（Ｅ）の成分（１２）を６０℃に加熱し成分（２）を攪拌しながらゆっくり加え溶解させた。溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合し、得られたシャンプーをそれぞれ比較品Ｃ１及びＣ２とした。
５−ｆ（比較品の調製）
本発明で用いるカチオン変性アルギン酸誘導体のシャンプーにおける効果を比較するため、上記５−ｅで使用した試料番号６の代わりに、同じ配合割合の未変性アルギン酸誘導体（アルギン酸ナトリウム、商品名：ダックアルギンＮＳＰＨ、（株）紀文フードケミファ社製）を用い、表３の比較品（Ｅ）に示した組成のシャンプーを５−ｅと同様に調製し、これを比較品Ｃ３とした。
（評価）
先述の５−ａ〜５−ｆで調製した各々の本発明品の処方Ｓ１〜Ｓ７のシャンプーと比較品Ｃ１、Ｃ２及びＣ３のシャンプー、さらにブランクとして表３のブランク（Ｆ）に示す組成からなるシャンプーを、それぞれ１．０ｇ用いて１５ｇの毛髪ストランド（全長１８０ｍｍ）を洗髪した。その後流水中ですすぎ、恒温恒湿（２０℃、４０％ＲＨ）雰囲気中に２４時間放置し、自然乾燥を行った。その後毛髪のコシの強さを純曲げ試験機（カトーテック株式会社製、ＫＥＳ−ＦＢ２−Ｓ）にて測定した。その結果を表４に示した。尚、ブランクは表３のブランク（Ｆ）中の成分（１２）を６０℃に加熱した後、成分（５）〜（７）を加え攪拌して均一とした後、冷却し３０〜４０℃で成分（８）〜（１１）を加え均一に混合して調製した。
先述の５−ａ〜５−ｆで調製した、各々の本発明品の処方Ｓ１〜Ｓ７のシャンプーと比較品Ｃ１、Ｃ２及びＣ３のシャンプー、さらにブランクとして表３のブランク（Ｆ）に示す組成からなるシャンプーについて、１０名のテスターにより洗髪した後、ドライヤーにて乾燥した後の毛髪の弾力性（毛髪のコシ）を確認した。仕上がりの髪にコシがあると感じたテスターの人数により次の基準で評価し、その結果を表４中に示した。
・髪にコシが有ると感じたテスターが８名以上・・・◎
・髪にコシが有ると感じたテスターが６〜７名・・・○
・髪にコシが有ると感じたテスターが４〜５名・・・△
・髪にコシが有ると感じたテスターが４名未満・・・×
【表４】

表４の結果から、アルギン酸誘導体をカチオン変性した試料番号１、３、４及び５のカチオン変性アルギン酸誘導体を含む本発明品のシャンプーＳ１〜Ｓ４はブランクと比較すると曲げ剛性（Ｂ値）及びヒステリシス幅（２ＨＢ）が共に向上している。同様の結果はカチオン電荷量値が本発明の範囲よりも高い試料番号７のカチオン変性アルギン酸誘導体を含む比較品Ｃ２にもみられるが、曲げ剛性が大きくなりすぎ、ごわつき感を示唆する結果となった。一方、カチオン電荷量値が本発明の範囲よりも低い、試料番号６のカチオン変性アルギン酸誘導体を含む比較品Ｃ１及び、未変性のアルギン酸誘導体を含む比較品Ｃ３は、ブランクと同じ結果となった。これは未変性のアルギン酸誘導体及びカチオン電荷量値が本発明の範囲よりも低いカチオン変性アルギン酸誘導体を洗い流し製品に用いた場合、毛髪に対しイオン性に基づく吸着能が得られず、該アルギン酸誘導体の毛髪への吸着が少ないので、その効果が得られなかったことを示したものと考えられる。これに対し、アルギン酸誘導体を特定の範囲でカチオン変性した本発明品は、毛髪へのイオン性に基づく吸着能を有するので、シャンプー、リンスのような洗い流し製品に於いて弾力性が付与され、毛髪のコシの強さが改善された。よって、本発明に用いられるカチオン変性アルギン酸誘導体はシャンプー、リンス等の洗い流し製品に配合した場合においても、その効果を十分発揮すると共に、ヘアスプレー、ヘアジェル等の塗布型の毛髪処理用組成物に配合した場合においても造膜性を有することによる弾力性の付与から、セット効果が期待できることが判った。
また、本発明に用いられるカチオン変性アルギン酸誘導体とエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）、Ｎ−メタクリロイルオキシエチルＮ，Ｎ−ジメチルアンモニウム−α−メチルカルボキシベタイン・メタクリル酸アルキル共重合体（Ｙｕｋａｆｏｒｍｅｒ ＳＭ；三菱化学株式会社製）等のコンディショニング効果を持つ水溶性高分子と併用した系に於いてもその効果は失われないことが確認された。
実施例６ 毛髪に対する弾力性付与（その２）
（評価）
実施例５で調製した各々の本発明品の処方Ｓ１〜Ｓ７のシャンプーと、比較品Ｃ１、Ｃ２及びＣ３のシャンプーを用い、本発明に用いられるカチオン変性アルギン酸誘導体の損傷した毛髪に対する弾力性付与効果を洗い流し製品で確認した。実施例５で使用したものと同様の毛髪ストランドを、６％Ｈ₂Ｏ₂と３％アンモニア水の２対１混合液（ｗ／ｗ）のブリーチ剤に、浴比１対１００（毛髪ストランド重量対ブリーチ剤溶液重量）、４０℃の条件下で６０分間浸漬した。温水で洗浄後、ドライヤーで乾燥した。このブリーチ処理により得られた損傷の著しい毛髪ストランドを、先述の５−ａ〜５−ｄで調製した本発明品の処方Ｓ１〜Ｓ７、５−ｅ及び５−ｆで調製した比較品Ｃ１〜Ｃ３、さらにブランクとして表３のブランク（Ｆ）に示す組成からなるシャンプーを、それぞれ１．０ｇ用いて１５ｇの毛髪ストランド（全長１８０ｍｍ）を洗髪した。その後流水中ですすぎ、恒温恒湿（２０℃、４０％ＲＨ）雰囲気中に２４時間放置し、自然乾燥を行った。その後毛髪のコシの強さを純曲げ試験機（カトーテック株式会社製、ＫＥＳ−ＦＢ２−Ｓ）にて測定した。その結果を表５に示した。尚、ブランクは実施例５同様に、表３のブランク（Ｆ）中の成分（１２）を６０℃に加熱した後、成分（５）〜（７）を加え攪拌して均一とした後、冷却し３０〜４０℃で成分（８）〜（１１）を加え均一に混合して調製した。
【表５】

表５の結果から損傷毛髪で評価した場合、本発明品を含むシャンプーＳ１〜Ｓ４をブランクと比較すると、曲げ剛性（Ｂ値）とヒステリシス幅（２ＨＢ）がともに向上している。同様の結果は、カチオン電荷量値が本発明の範囲よりも高い試料番号７のカチオン変性アルギン酸誘導体を含む比較品Ｃ２にもみられるが、曲げ剛性が大きくなりすぎ、ごわつき感を示唆する結果となった。一方、カチオン電荷量値が本発明の範囲よりも低い試料番号６のカチオン変性アルギン酸誘導体を含む比較品Ｃ１では、曲げ剛性とヒステリシス幅が僅かに向上しているが、優位差を確認できる程度の向上は得られず、未変性のアルギン酸誘導体を含む比較品Ｃ３では、ブランクと同じ結果となった。更に、実施例５のブリーチ未処理の健常毛髪で評価した場合よりも、曲げ剛性、ヒステリシス幅ともにブランクとの差が大きくなっていることから、本発明品の損傷毛髪での有用性が確認された。
実施例７ 泡立ち試験
本発明に用いられるカチオン変性したアルギン酸誘導体（表１の試料番号１、２、４及び５）を表６の（Ａ）に示す組成で配合した化粧料組成物の泡立ちについて測定した。比較のため、他のカチオン性ポリマーとしてエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）及び、未変性アルギン酸誘導体としてアルギン酸ナトリウム（ダックアルギンＮＳＰＨ；（株）紀文フードケミファ社製）を含む化粧料組成物をそれぞれ表６の（Ｂ）に示す組成で配合し、同様に泡立ちを測定した。
測定方法は、表６の処方の各化粧料組成物を、それぞれ実施例５に示した手順に準じた方法にて調製し、この調製した化粧料組成物の５％水溶液１５０ｍｌを市販のジューサーミキサーに入れ撹拌し泡立てる。撹拌時間と泡の量を測定し、その結果を表７に示した。
【表６】

【表７】

表７の結果から、本発明に用いられるカチオン変性したアルギン酸誘導体は、他のカチオン性ポリマー（カチナールＨＣ−１００：カチオン変性ヒドロキシエチルセルロース）と比較した場合、毛髪への弾力性の付与で見られた結果と同様、造膜性が優れる為、泡の膜が強固で、直後の泡立ち、速泡性に優れていることが確認された。よって、本発明品はシャンプー、ボディ用洗浄剤、洗顔料等の泡立ちを有する化粧料組成物に配合した場合、泡立ち、泡質などの泡の感触改善が期待できる。
以下、カチオン変性したアルギン酸誘導体により得られる造膜性、セット効果、弾力性の付与、コンディショニング効果及び泡立ち、泡質等の泡の感触改善を剤型の異なる化粧料組成物それぞれにおいて、官能評価及び機器測定によりさらに確認した。
ヘアシャンプー
（調製）
【実施例８】
８−ａ
実施例１、２及び３で得た本発明の試料番号１〜５のカチオン変性アルギン酸誘導体を用いて表８の（Ａ）に示した組成のシャンプーを調製した。表８中の（Ａ）の成分（１４）を６５℃に加熱し成分（１）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め（５）〜（１０）を加えて攪拌して均一とし、さらに３０〜４０℃で成分（１１）〜（１３）を加え均一に混合した。こうして表１中の試料番号１〜５に対応するカチオン変性アルギン酸誘導体を配合した表８の（Ａ）に示した組成のシャンプーを各々調製し、表１中の試料番号１〜５を含むシャンプーを順に本発明品の処方１〜５とした。
８−ｂ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらにカチオン性水溶性高分子Ａとしてエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を含む、表８の（Ｂ）に示した組成のシャンプーを調製した。表８中の（Ｂ）の成分（１４）を６５℃に加熱し、成分（１）及び（３）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（１０）を加えて攪拌して均一とし、さらに３０〜４０℃で成分（１１）〜（１３）を加え均一に混合し、得られたシャンプーを本発明品の処方６とした。
８−ｃ
上記カチオン性水溶性高分子Ａの代わりにカチオン性水溶性高分子Ｂとして塩化ジアリルジメチルアンモニウム・アクリルアミド共重合体（Ｍｅｒｑｕａｔ ５５０；ＮＡＬＣＯ社製）を含む表８の（Ｃ）に示した組成のシャンプーを同様に調製し、これを本発明品の処方７とした。
８−ｄ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらに両性水溶性高分子としてＮ−メタクリロイルオキシエチルＮ，Ｎ−ジメチルアンモニウム−α−メチルカルボキシベタイン・メタクリル酸アルキル共重合体（Ｙｕｋａｆｏｒｍｅｒ ＳＭ；三菱化学株式会社製）を含む、表８の（Ｄ）に示した組成のシャンプーを調製した。表８中の（Ｄ）の成分（１４）を６５℃に加熱し成分（１）及び（４）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（１０）を加えて攪拌して均一とし、さらに３０〜４０℃で成分（１１）〜（１３）を加え均一に混合し、得られたシャンプーを本発明品の処方８とした。
８−ｅ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用いてカチオン性水溶性高分子、両性水溶性高子を含む、表８の（Ｅ）に示した組成のシャンプーを調製した。表８中の（Ｅ）の成分（１４）を６５℃に加熱し成分（１）及び（３）、（４）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（１０）を加えて攪拌して均一とし、３０〜４０℃で成分（１１）〜（１３）を加え均一に混合し、得られたシャンプーを本発明品の処方９とした。
８−ｆ（比較品の調製）
本発明によるカチオン変性アルギン酸誘導体のシャンプーにおけるその効果を比較するため、例１で得たカチオン変性アルギン酸誘導体、すなわち表１中の試料番号６及び７を用いて表８の比較品（Ｇ）に示した組成のシャンプーを調製した。表８中の比較品（Ｇ）の成分（１４）を６５℃に加熱し成分（２）を攪拌しながらゆっくり加え溶解させた。溶解を確認した後、加熱を止め成分（５）〜（１０）を加えて攪拌して均一とし、３０〜４０℃で成分（１１）〜（１３）を加え均一に混合し、得られたシャンプーをそれぞれ比較品１及び２とした。
【表８】

８−ｇ（比較品の調製）
さらに他のカチオン性ポリマーと効果を比較する為、上記８−ｆにおける例１で得たカチオン変性アルギン酸誘導体の代わりに、エチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を用い、表８の比較品（Ｇ）に示した組成のシャンプーを８−ｆと同様に調製し、これを比較品３とした。
（評価）
【実施例９】
先述の８−ａ〜８−ｅで調製した各々のシャンプー、すなわち本発明品の処方１〜９について１０名のテスターにより次に示した項目の性能評価を実施した。性能評価方法は、成分にカチオン性ポリマー等を含まない表８の標準品（Ｆ）に示される組成のシャンプーと、それぞれ評価するべき対象のシャンプーとを使用し、洗髪時の使用感、ドライヤーによる乾燥後の使用感を、標準品（Ｆ）を基準にして、
・洗髪時の泡立ち
・使用時コンディショニング効果の有無（指通り及び髪の手触り）、
・使用後（乾いた髪）のコンディショニング効果の有無（櫛通り感、髪の手触り）及び毛髪のコシの強さ、
について比較し、下記表９及び１０に示す方法にて数値化し、それぞれの項目について１０名のテスターの評価の値を合計した。この評価結果を表１１に示した。尚、上記標準品（Ｆ）は表８の標準品（Ｆ）中の成分（１４）を６５℃に加熱した後、成分（５）〜（１０）を加え攪拌して均一とした後、冷却し３０〜４０℃で成分（１１）〜（１３）を加え均一に混合して調製した。
【表９】

【表１０】

比較例１
先述の８−ｆ及び８−ｇで調製した各々のシャンプー、比較品１〜３について、実施例９と同様に性能評価を実施し、その結果を表１１中に示した。
【表１１】

表１１の結果から、カチオン変性アルギン酸誘導体のカチオン電荷量が０．１〜３．０ｍｅｑ／ｇにある本発明に用いられるカチオン変性アルギン酸誘導体は、シャンプーに用いた場合、洗髪時の泡立と、使用時の指通り、手触りなどのコンディショニング効果に優れ、使用後ではしっとり感、櫛通りなどのコンディショニング効果と、造膜性による弾力性の付与から、毛髪のコシの強さが得られることが確認された。
また、本発明品を含むシャンプーの性能は、従来よりコンディショニング剤として用いられるカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００）のみを含む比較品３と比較すると、泡立ちに優れ、使用時のコンディショニング効果は同等以上であり、使用後においては、従来のコンディショニング剤には無い、本発明に用いられるカチオン変性アルギン酸誘導体のもつ造膜性による弾力性の付与から、毛髪のコシの強さが得られた。また、配合成分に、カチオン性水溶性高分子（カチナールＨＣ−１００、Ｍｅｒｑｕａｔ ５５０）及び／又は両性水溶性高分子（Ｙｕｋａｆｏｒｍｅｒ ＳＭ）を併用することにより、本発明に用いられるカチオン変性アルギン酸誘導体のもつ性能を損なうこと無く、コンディショニング効果が向上することが確認された。
（配合例１〜３）
以下に、シャンプーへの本発明の好適な配合例を示す。
【表１２】

精製水を７０℃に加熱し、他成分を加え均一に溶解した後、冷却した。
【表１３】

精製水を７０℃に加熱し、他成分を加え均一に溶解した後、冷却した。
【表１４】

精製水を７０℃に加熱し、他成分を加え均一に溶解した後、冷却した。
ヘアリンス
（調製）
【実施例１０】
１０−ａ
実施例１及び２で得られた試料番号１〜４のカチオン変性アルギン酸誘導体を用いて下記表１５の（Ａ）に示した、アミドアミン化合物と中和剤としてクエン酸を用い中和した、ベヘン酸ジメチルアミノプロピルアミド・クエン酸塩とさらには、高級アルコール（セタノール）を含む組成のリンスを調製した。表１５中の（Ａ）の成分（５）〜（１０）を８０℃に加熱し、攪拌して均一にした溶液に、予め成分（１２）に成分（１）を攪拌しながら加え溶解させた溶液を８０℃に加熱したものを攪拌しながら加えた後、冷却しながら成分（１１）を加えて均一に混合した。こうして表１５の（Ａ）に示した組成のリンスを各々調製し、表１中の試料番号１〜４のカチオン変性アルギン酸誘導体を含むリンスを順に、本発明品の処方１０〜１３とした。
１０−ｂ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらにカチオン性水溶性高分子としてエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を含む、表１５の（Ｂ）に示した組成のリンスを調製した。表１５中の（Ｂ）の成分（５）〜（１０）を８０℃に加熱し、攪拌して均一にした溶液に、予め成分（１２）に成分（１）、（３）を攪拌しながら加え溶解させた溶液を８０℃に加熱したものを攪拌しながら加えた後、冷却しながら成分（１１）を加えて均一に混合し、得られたリンスを本発明品の処方１４とした。
１０−ｃ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらに両性水溶性
高分子としてＮ−メタクリロイルオキシエチルＮ，Ｎ−ジメチルアンモニウム−α−メチルカルボキシベタイン・メタクリル酸アルキル共重合体（Ｙｕｋａｆｏｒｍｅｒ ＳＭ；三菱化学株式会社製）を含む、表１５の（Ｃ）に示した組成のリンスを調製した。表１５中の（Ｃ）の成分（５）〜（１０）を８０℃に加熱し、攪拌して均一にした溶液に、予め成分（１２）に成分（１）、（４）を攪拌しながら加え溶解させた溶液を８０℃に加熱したものを攪拌しながら加えた後、冷却しながら成分（１１）を加えて均一に混合し、得られたリンスを本発明品の処方１５とした。
【表１５】

１０−ｄ（比較品の調製）
本発明によるカチオン変性アルギン酸誘導体のリンスにおけるその効果を比較するため、例１で得たカチオン変性アルギン酸誘導体、すなわち表１中の試料番号６及び７を用いて表１５の比較品（Ｄ）に示した組成のリンスを調製した。表１５中の比較品（Ｄ）の成分（５）〜（１０）を８０℃に加熱し、攪拌して均一にした溶液に、予め成分（１２）に成分（２）を攪拌しながら加え溶解させた溶液を８０℃に加熱したものを攪拌しながら加えた後、冷却しながら成分（１１）を加えて均一に混合し、表１中の試料番号６及び７を含むリンスをそれぞれ比較品４及び５とした。
１０−ｅ（比較品の調製）
さらに他のカチオン性水溶性高分子と効果を比較する為、上記１０−ｄにおける例１で得たカチオン変性アルギン酸誘導体の代わりに、エチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を用い、表１５の比較品（Ｄ）に示した組成のリンスを１０−ｄと同様に調製し、これを比較品６とした。
（評価）
【実施例１１】
先述の１０−ａ〜１０−ｃで調製した各々のリンス、すなわち本発明品の処方１０〜１５について、１０名のテスターにより次に示した項目の性能評価を実施した。
性能評価方法は、成分にカチオン性ポリマーを含まない表１５の標準品（Ｅ）に示される組成のリンスと、それぞれ評価するべき対象のリンスとを使用し、ドライヤーによる乾燥後の使用感を、標準品（Ｅ）を基準にして、
・乾いた髪のコンディション効果の有無（櫛通り、きしみ感など）、
・毛髪のコシの強さ、
について比較し、それを下記表１６の方法にて数値化し、評価を実施した１０名のテスターの値を合計した。この評価結果を表１７に示した。尚、上記標準品（Ｅ）は表１５の標準品（Ｅ）中の成分（５）〜（１０）を８０℃に加熱し、攪拌して均一にした溶液に、８０℃に加熱した成分（１２）を攪拌しながら加えた後、冷却しながら成分（１１）を加えて均一に混合し調製した。
比較例２
先述の１０−ｄ及び１０−ｅで調製した各々のリンス、すなわち比較品４、５及び６について、実施例１１と同様に性能評価を実施し、その結果を表１７中に示した。
【表１６】

【表１７】

表１７の結果から、カチオン電荷量が０．１〜３．０ｍｅｑ／ｇにある本発明に用いられるカチオン変性アルギン酸誘導体を含み、さらにアミドアミン化合物、中和剤及び高級アルコール（セタノール）を含むリンスでは、組成物の毛髪へのコンディショニング効果が優れるとともに、弾力性の付与による毛髪のコシの強さが得られることが確認された。
またアミドアミン化合物、中和剤及び高級アルコールを含むリンスにおける本発明品の性能を、他のカチオン性ポリマーと比較すると、コンディショニング効果は使用時及び使用後で同等以上であり、かつ使用後には弾力性の付与によるによる毛髪のコシの強さが得られた。またさらに、カチオン性水溶性高分子及び／又は両性水溶性高分子を併用することにより、カチオン変性アルギン酸誘導体のもつ性能を損なうこと無く、コンディショニング効果が向上することが確認された。
（配合例４〜６）
以下に、リンス、コンディショナー等のコンディショニング効果を必要とする毛髪処理用組成物への、本発明の好適な配合例を示す。
【表１８】

表１８の精製水に、本発明品、塩化ステアリルトリメチルアンモニウム、１，３−ブチレングリコール、アルキル（Ｃ１２、１４）オキシヒドロキシプロピルアルギニン塩酸塩、ヒドロキシプロピルトリモニウム加水分解ケラチン、色素を加え７５℃に保つ（水相）。残りの他の成分を混合、加熱溶解し、７５℃に保つ（油相）。水相と油相を加えた後、イソプロパノールを加えホモミキサーで乳化後、撹拌しながら冷却した。
【表１９】

表１９の精製水に、本発明品、塩化ヒドロキシプロピルトリモニウムデンプン、ステアリン酸ジメチルアミノプロピルアミド、加水分解コムギ、Ｌ−グルタミン酸、グリセリン、フェノキシエタノール、色素を加え８０℃に保つ（水相）。残りの他の成分を混合、加熱溶解し、８０℃に保つ（油相）。水相と油相を加えホモミキサーで乳化後、撹拌しながら冷却した。
【表２０】

表２０の精製水に、本発明品、ステアリン酸ジメチルアミノプロピルアミド、５０％乳酸、グリセリン、フェノキシエタノール、安息香酸ナトリウム、加水分解シルクを加え７０℃に保つ（水相）。残りの他の成分を混合、加熱溶解し、７０℃に保つ（油相）。水相と油相を加えホモミキサーで乳化後、撹拌しながら冷却した。
ヘアジェル
（調製）
【実施例１２】
１２−ａ
塗布型の毛髪化粧料に於ける本発明品の効果を以下の方法で確認した。実施例１で得た試料番号１、２及び３のカチオン変性アルギン酸誘導体を用いて表２１の（Ａ）に示した組成のヘアジェルを調製した。表２１中の（Ａ）の成分（１）及び成分（５）〜（９）を攪拌している成分（１１）に加え、均一溶解した後、成分（１０）を加えて透明になるまで混合した。こうして表２１の（Ａ）に示した組成のヘアジェルを各々調製し、表１中の試料番号１、２及び３のカチオン変性アルギン酸誘導体を含むヘアジェルをそれぞれ本発明品の処方１６、１７及び１８とした。
１２−ｂ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらにカチオン性水溶性高分子としてエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を含む、表２１の（Ｂ）に示した組成のヘアジェルを調製した。表２１中の（Ｂ）に示した成分（１）、（３）及び（５）〜（９）を攪拌している成分（１１）に加え、均一溶解した後、成分（１０）を加えて透明になるまで混合した。こうして表２１の（Ｂ）に示した組成のヘアジェルを調製し本発明品の処方１９とした。
１２−ｃ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらに両性水溶性高分子としてＮ−メタクリロイルオキシエチルＮ，Ｎ−ジメチルアンモニウム−α−メチルカルボキシベタイン・メタクリル酸アルキル共重合体（Ｙｕｋａｆｏｒｍｅｒ ＳＭ；三菱化学株式会社製）を含む、表２１の（Ｃ）に示した組成のヘアジェルを調製した。表２１中の（Ｃ）に示した成分（１）、（４）及び（５）〜（９）を攪拌している成分（１１）に加え、均一溶解した後（１０）を加えて透明になるまで混合した。こうして表２１の（Ｃ）に示した組成のヘアジェルを調製し本発明品の処方２０とした
１２−ｄ（比較品の調製）
本発明によるカチオン変性アルギン酸誘導体のヘアジェルにおけるその効果を比較するため、例１で得たカチオン変性アルギン酸誘導体、すなわち表１中の試料番号６及び７を用いて表２１の比較品（Ｅ）に示した組成のヘアジェルを調製した。表２１中の成分（２）及び（５）〜（９）を攪拌している成分（１１）に加え、均一溶解した後、成分（１０）を加えて透明になるまで混合した。こうして表２１の（Ｅ）に示した組成のヘアジェルを各々調製し、表１中の試料番号６及び７を含むヘアジェルをそれぞれ比較品７及び８とした。
１２−ｅ（比較品の調製）
さらに他のカチオン性ポリマーと効果を比較するため、上記１２−ｄで使用した例１で得たカチオン変性アルギン酸誘導体の代わりにエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を含む、表２１の比較品（Ｅ）に示した組成のヘアジェルを１２−ｄと同様に調製し、これを比較品９とした。
【表２１】

（評価）
【実施例１３】
先述の１２−ａ〜１２−ｃで調製した各々のヘアジェル、すなわち本発明品の処方１６、１７、１８、１９及び２０について、１０名のテスターにより次に示した項目の性能評価を実施した。
性能評価方法は、成分にカチオン性水溶性高分子や、両性水溶性高分子等を含まない表２１の標準品（Ｄ）に示される組成のヘアジェルと、それぞれ評価するべき対象のヘアジェルとを使用し使用感を、標準品（Ｄ）を基準にして、
・塗布のしやすさ、
・使用後の感触
について比較し、下記表２２に示す方法にて数値化し、評価を実施した１０名のテスターの値を合計した。この結果を表２４に示した。尚、標準品は表２１の（Ｄ）の成分（５）〜（９）を攪拌している成分（１１）に加え、均一溶解した後、成分（１０）を加えて透明になるまで混合し調製した。
比較例３
先述の１２−ｄ及び１２−ｅで調製した各々のヘアジェル、比較品７、８及び９について、実施例１３と同様に性能評価を実施し、その結果を表２４中に示した。
【表２２】

【実施例１４】
セット保持力については次の方法にて評価を実施した。長さ１８ｃｍ、重さ１５ｇの毛束を水で濡らし、先述の１２−ａ〜１２−ｃで調製したヘアジェル、すなわち本発明品の処方１６、１７、１８、１９及び２０を塗布し、ロッド（外径２ｃｍ）に巻き、その状態でドライヤー（８０℃）により乾燥させカールをつけた。乾燥した後、カールのついた毛束をロッドから外した。この毛束を恒温恒湿（２０℃、４０％ＲＨ）雰囲気中に３０分間つるしカールの伸びを観察し、カールの伸びの程度を基準に、セット保持力を下記表２３の評価基準に従って評価し、その結果を表２４中に示した。
尚、評価の尺度は以下の通りである。ヘアジェルを塗布しない以外は、前述と同様にロッドに巻き、ドライヤー（８０℃）で乾燥させた毛束の、ロッドを外した直後の長さを保持力１００％とした。また、ロッドを外し恒温恒湿（２０℃、４０％ＲＨ）雰囲気中に２４時間放置し、その状態での毛束の長さを保持力０％とした。
【表２３】

比較例４
先述の１２−ｄ及び１２−ｅで調製したヘアジェル、すなわち比較品７、８及び９について実施例１４と同様に性能評価を実施し、その結果を表２４中に示した。
【表２４】

表２４の結果から、塗布型の毛髪処理用組成物においても本発明に用いられるカチオン変性アルギン酸誘導体は造膜性を有することから、乾燥時に毛髪に対してセット効果を付与できるとともに、カチオン変性することで得られるコンディショニング効果により感触も良好であることが確認された。一方、カチオン電荷量が本発明に規定する０．１〜３．０ｍｅｑ／ｇの範囲外にある、試料番号６及び７では、塗布のしやすさや、使用後の感触において本発明のような評価は得られなかった。
また、従来のコンディショニング剤としてのカチオン性ポリマー（カチオン変性ヒドロキシエチルセルロース、カチナールＨＣ−１００）と比較すると、セット保持力に差が認められ、本発明品の有する造膜性によりセット効果が得られることが確認された。さらに、本発明に用いられるカチオン変性アルギン酸誘導体と、他のカチオン性水溶性高分子及び／又は両性水溶性高分子を併用することにより、本発明に用いられるカチオン変性アルギン酸誘導体のもつ性能を損なうこと無く、コンディショニング効果が向上することが確認された。
（配合例７〜１０）
以下に、ヘアジェル及びヘアジェル以外のセット効果及びコンディショニング効果を必要とするヘアミスト、ヘアムース等の塗布型の毛髪処理組成物への本発明の好適な配合例を示す。
【表２５】

本発明品とポリビニルピロリドン、グリセリン、ポリエチレングリコール、パラオキシ安息香酸メチルに一部の精製水を加え７０℃で加熱溶解した。他の成分を残部の精製水に溶解し、撹拌しながら添加した。
【表２６】

【表２７】

【表２８】

ヘアカラー
（調製）
【実施例１５】
１５−ａ
実施例１及び２で得られた試料番号１及び４のカチオン変性アルギン酸誘導体を用いて下記表２９の（Ａ）に示した、二剤式酸化染毛剤を調製し、表１中の試料番号１及び４のカチオン変性アルギン酸誘導体を含む二剤式酸化染毛剤を本発明品の処方２１及び２２とした。使用時には、この二剤式酸化染毛剤の第一剤と第二剤とを重量比１対１で混合し、毛髪に塗布した。
１５−ｂ（比較品の調製）
本発明によるカチオン変性アルギン酸誘導体のヘアカラーにおけるその効果を他のカチオン性ポリマーと効果を比較するため、上記１５−ａで使用した本発明に用いられるカチオン変性アルギン酸誘導体の代わりにエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を用いて上記表２９の比較品（Ｃ）に示した、二剤式酸化染毛剤を調製した。こうしてカチオン変性ヒドロキシエチルセルロースを含む二剤式酸化染毛剤を比較品１０とした。使用時には、この二剤式酸化染毛剤の第一剤と第二剤とを重量比１対１で混合し、毛髪に塗布した。
【表２９】

（評価）
【実施例１６】
先述の１５−ａで調製した各々の二剤式酸化染毛剤、すなわち本発明品の処方２１及び２２について、１０名のテスターにより次に示した項目の性能評価を実施した。性能評価方法は、成分にカチオン性ポリマーを含まない表２９の標準品（Ｂ）に示される組成の二剤式酸化染毛剤と、それぞれ評価するべき対象の酸化染毛剤とを使用し、第一剤と第二剤の等量混合液を毛髪に塗布し、室温下で３０分間放置した後、４０℃の流水で３分間すすぎ、ドライヤーで乾燥した。この時のすすぎ時のすべり性と、ドライヤーで乾燥後の感触を、標準品（Ｂ）を基準にして、
・すすぎ時のすべり性
・乾燥後の感触（しっとり感、弾力性（毛髪のコシ））
について比較し、それを下記表３０の方法にて数値化し、評価を実施した１０名のテスターの値を合計した。この評価結果を表３１に示した。尚、上記標準品（Ｂ）は１５−ａに準じて調製し、第一剤と第二剤とを重量比１対１で混合して毛髪に塗布した。
比較例５
先述の１５−ｂで調製した比較品１０のニ剤式酸化染毛剤について、実施例１６と同様に性能評価を実施し、その結果を表３１中に示した。
【表３０】

【表３１】

表３１の結果より、本発明に用いられるカチオン変性アルギン酸誘導体を染毛剤に配合した場合、損傷毛髪に対するコンディショニング効果により、すすぎ時におけるすべり性が向上し、良好な指通り感が得られ、乾燥後の仕上がり感もしっとり感が得られ改善された。さらに本発明品の有する損傷毛髪に対する弾力性の付与から毛髪のコシの改善が認められた。よって、染毛剤等の組成物として優れていることが確認された。
さらに、他のカチオン性ポリマーを含む比較品１０と比べて、本発明品の処方２１及び２２はともに、乾燥後の感触が向上してわり、損傷毛髪においても、本発明に用いられるカチオン変性アルギン酸誘導体が優れていることが確認された。
（配合例１１、１２）
以下に本発明に用いられるカチオン変性アルギン酸誘導体の損傷毛髪に対するコンディショニング効果及び弾力性付与効果を利用した、好適な配合例を示す。
【表３２】

【表３３】

ボディ用洗浄剤
（調製）
【実施例１７】
１７−ａ
実施例１及び２で得られた試料番号１、２及び４のカチオン変性アルギン酸誘導体を用いて表３４の（Ａ）に示した組成のボディ用洗浄剤（ボディソープ）を調製した。表３４中の（Ａ）の成分（１１）を６０℃に加熱し、成分（１）を攪拌しながら加え溶解させ、溶解を確認した後、５０〜６０℃で成分（３）〜（７）を撹拌しながら加えて均一とし、更に３０〜４０℃で成分（８）〜（１０）を同様に撹拌しながら加え、均一に混合した。こうして表３４の（Ａ）に示した組成のボディ用洗浄剤を各々調製し、表１中の試料番号１、２及び４のカチオン変性アルギン酸誘導体を含むボディ用洗浄剤を順に、本発明品の処方２３、２４及び２５とした。
【表３４】

１７−ｂ（比較品の調製）
本発明で用いるカチオン変性アルギン酸誘導体の、ボディ用洗浄剤におけるその効果を比較するため、未変性のアルギン酸誘導体であるアルギン酸ナトリウム（ダックアルギンＮＳＰＨ；（株）紀文フードケミファ社製）について表３４の（Ｃ）に示した組成のボディ用洗浄剤を調製した。表３４中の（Ｃ）の成分（１１）を６０℃に加熱し、成分（２）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、５０〜６０℃で成分（３）〜（７）を撹拌しながら加えて均一とし、更に３０〜４０℃で成分（８）〜（１０）を同様に撹拌しながら加え、均一に混合した。こうして表３４の（Ｃ）に示した組成のボディ用洗浄剤を調製し、これを比較品１１とした。
１７−ｃ（比較品の調製）
同様に、本発明で用いるカチオン変性アルギン酸誘導体の、ボディ洗浄剤における効果を比較するため、エチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００：東邦化学工業（株）社製）について表３４の（Ｃ）に示した組成のボディ用洗浄剤を調製した。表３４中の（Ｃ）の成分（１１）を６０℃に加熱し、成分（２）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、５０〜６０℃で成分（３）〜（７）を撹拌しながら加えて均一とし、更に３０〜４０℃で成分（８）〜（１０）を同様に撹拌しながら加え、均一に混合した。こうして表３４の（Ｃ）に示した組成のボディ用洗浄剤を調製し、これを比較品１２とした。
（評価）
【実施例１８】
先述の１７−ａで得た本発明品の処方２３、２４及び２５各々のボディ用洗浄剤について、１０名のテスターにより次に示した項目の性能評価を実施した。
性能評価方法は、成分にカチオン性ポリマー等の高分子化合物を含まない表３４の標準品（Ｂ）に示される組成のボディ用洗浄剤と、それぞれ評価するべき対象のボディ用洗浄剤とを使用し、
・使用時の泡の量及び泡質、
・使用時の使用感（すすぎ易さ、すすぎ後のつっぱり感及びぬめり感）、
・使用後（乾いた後）の使用感（つっぱり感、滑らかさ感、しっとり感）、
について、標準品（Ｂ）の使い心地と比較し、それを下記表３５及び３６の方法にて数値化し、評価を実施した１０名のテスターの値を合計した。この評価結果を表３７に示した。なお、標準品は表３４の標準品（Ｂ）の成分（１１）を６０℃に加熱した後、５０〜６０℃で成分（３）〜（７）を撹拌しながら加えて均一とし、さらに３０〜４０℃で成分（
８）〜（１０）を同様に撹拌しながら加え、均一に混合し、表３４の（Ｂ）に示した組成のボディ用洗浄剤を調製し、本評価の標準品とした。
比較例６
先述の１７−ｂ及び１７−ｃで得た比較品１１及び１２のボディ用洗浄剤について、実施例１８と同様の性能評価を行った。これらの結果を表３７中に示した。
【表３５】

【表３６】

表３７の結果から、本発明に用いられるカチオン変性アルギン酸誘導体は、ボディ用洗浄剤に用いた場合、ボディ用洗浄剤の泡立ち、泡質及び使用感が改善されるとともに、使用後には、つっぱり感を解消し、しっとり感を与えることが確認された。
また、未変性のアルギン酸誘導体（アルギン酸ナトリウム）を含む比較品１１と比較すると、カチオン変性したことにより、皮膚への吸着が増し、使用時及び使用後の感触が改善されることが確認された。さらに、従来のコンディション剤としてのカチオン変性ヒドロキシエチルセルロース（比較品１２）と比較すると、造膜性の差から泡立ち、泡質が改善されると共にべたつき感、かさつき感、つっぱり感を解消し、しっとり感を得ることが確認された。
【表３７】

（配合例１３〜１７）
以下に、本発明に用いられるカチオン変性アルギン酸誘導体の造膜性を有することによる泡質の感触改善及び、コンディショニング効果による感触改善を利用した、ボディ用洗浄剤、洗顔料等の皮膚化粧料組成物の配合例を示す。
【表３８】

常法に基づき、液体状ボディ用洗浄剤（ボディソープ）を製造する。
【表３９】

常法に基づき、液体状ボディ用洗浄剤（ボディソープ）を製造する。
【表４０】

常法に基づき、洗顔料を製造する。
【表４１】

表４１の精製水に、本発明品、グリセリン、ソルビトール、アルギニン、香料を加え溶解し７０℃に保つ（水相）。真空乳化釜にヤシ油脂肪酸グルタミン酸カリウム２５％液、ヤシ油脂肪酸タウリンナトリウム３０％液、モノオレイン酸グリセリル、セテアレス−６０ミリスチルグリコール、エデト酸２ナトリウム、フェノキシエタノールを順次添加混合し、７０℃まで加熱し溶解する。溶解確認後、ヤシ油脂肪酸アミドプロピルベタイン３０％液、７０℃に保持した水相、ジステアリン酸エチレングリコールを順次添加し、均一に溶解する。溶解後、３５℃まで冷却し、精製水、１０％クエン酸水溶液で水分、ｐＨを調整する。
【表４２】

常法に基づき、洗顔料を製造する。
（配合例１８〜２１）
以下に、本発明に用いられるカチオン変性アルギン酸誘導体の皮膚化粧料組成物に対する感触改善を利用する他の適用例としてアフターシェーブローション等の配合例を示す。
【表４３】

【表４４】

表４４の精製水に本発明品を溶解した後、グリセリン、スクワラン及び１，３−ブタンジオールを添加して水相部とした。次に、エチルアルコールにポリオキシエチレン（６０）硬化ヒマシ油、ポリオキシエチレン（８）セチルエーテル、オクチルドデカノール、ビタミンアセテート、メチルパラベン及び香料を添加して調整したアルコール相部を水相部に添加し混合した。この混合物に、タルク、黄酸化鉄、赤酸化鉄、黒酸化鉄を添加して分散処理し、メーキャップローションを製造する。
【表４５】

常法に基づき、ファンデーションを製造する。
【表４６】

常法に基づき、入浴剤を製造する。
本発明に用いられるカチオン変性アルギン酸誘導体は、毛髪処理用組成物や皮膚化粧料組成物等の化粧料組成物に配合した場合、造膜性が良好なことから均一な膜が形成され、泡立ち、泡質などの泡の感触改善が得られる。また、シャンプー・リンスなど洗い流しの毛髪処理用組成物に配合した場合、使用時、使用後には毛髪に対し、従来のコンディショニング剤として用いられるカチオン性ポリマーと同等以上のコンディショニング効果を与えつつ、乾燥後には造膜性を有することで得られる弾力性の付与により、毛髪のコシの強さが得られ、ヘアジェル等の塗布型の毛髪処理用組成物に配合した場合には、従来のコンディショニング剤として用いられるカチオン性ポリマーと同等以上のコンディショニング効果と、造膜性を有することで得られるセット効果を与える。さらに、本発明に用いられるカチオン変性アルギン酸誘導体をボディ用洗浄剤等の皮膚化粧料組成物に配合した場合、べたつき感、つっぱり感を解消し、しっとり感を与える。従って、従来品よりもより使い心地の優れた化粧料組成物を提供することが出来る。【Technical field】
  When the present invention is blended in a cosmetic composition, it improves foam feel such as foaming and foam quality, and has a good conditioning effect with good adsorptivity to hair and skin. Relates to a cation-modified alginic acid derivative that provides a good finish without stickiness, and a cosmetic composition, in particular a hair treatment composition, containing the same.
[Background]
  The hair treatment composition for the purpose of washing contains a conditioning agent for damaging hair entangled during washing and rinsing and for improving touch after washing. For this reason, it is essential that the conditioning agent be adsorbed on the hair, and a cationic polymer having an adsorption action based on ionicity is mainly used as the substance that gives the conditioning effect. As the cationic polymer, water-soluble polymers obtained by introducing quaternary nitrogen-containing groups into polysaccharides such as cellulose derivatives, guar gum and starch, dialkyl diallyl ammonium salt polymers, and the like are used. For example, Patent Document 1 discloses that a cation-modified cellulose derivative having a quaternary nitrogen-containing group introduced therein is used for shampoos and hair cosmetics. Furthermore, Patent Document 2 discloses cation-modified starch introduced with a quaternary nitrogen-containing group, Patent Document 3 and Patent Document 4 include cation-modified guar gum introduced with a quaternary nitrogen-containing group, shampoo, rinse, etc. It has been shown for use in hair care products. Further, Patent Document 5 uses a cation-modified cellulose derivative that has good adhesion to hair and also functions as a set component, and can provide a moist feeling with high molecular weight dimethylsiloxane that can impart smoothness and glossiness. Hair cosmetics containing specific sugar alcohols and the like are shown.
  On the other hand, in the composition for hair treatment which shows a set effect, when it mix | blends with shampoo, rinse, and a conditioner in patent document 6, when it mix | blends in hairdressing agents, such as a mousse, while showing a conditioning effect, polyglycerin which shows a set effect Patent Document 7 discloses a hair styling agent using a thermogelling polymer substance having a setting effect, which is a hair cosmetic characterized by containing a modified silicone compound. However, in the above-mentioned use examples, the cation-modified alginic acid derivative as in the present invention is used in the hair treatment composition to improve the feel of foam such as foaming foam quality, excellent conditioning effect and set effect after drying. There is no description.
  On the other hand, in the case of a skin cosmetic composition, soaps and anionic surfactants are generally used, but during washing, oily and fat components of the skin are removed more than necessary, and the skin feels tight. There is also a problem that occurs. From the effect of eliminating such inconvenience and giving a moist feeling, skin cosmetic compositions such as body cleaning agents are also blended with conditioning agents such as cationic polymers, and humectants such as glycerin. Document 8 shows that cation-modified polygalactomannan obtained by cation modification of guar gum and locust bean gum having a similar structure is used in hair care products such as shampoos and rinses and body cleaning agents (body soaps).
  Further, in Patent Document 9, a shampoo composition containing a copolymer of a dialkyl diallylammonium salt and a cellulose derivative having a quaternary nitrogen-containing group is introduced, which gives a smooth and smooth feel to the fingers when shampooing. In addition, it has been shown to give a smooth and smooth finger passage to the hair when rinsed, and to give a good gloss to the hair when finished. Also, by blending these cationic polymers, it is possible to obtain a creamy foam quality, to eliminate the feeling of tension on the skin, and to give a moist feeling to skin cosmetic compositions such as body cleaning agents. Is also blended.
  On the other hand, Patent Document 10 discloses a detergent composition having an excellent feeling of use by blending an alginate and an alkyl glucoside fatty acid ester having a specific structure with a higher fatty acid as a cleaning main component. Is a lipid-lowering agent characterized by containing a polyelectrolyte complex of polyuronic acid such as alginic acid and pectinic acid and a cationized dextran derivative as an active ingredient. Patent Document 12 discloses a polysaccharide and L-arginine. An external skin preparation excellent in moisture retention and flexibility is shown, and alginic acid is included as a polysaccharide together with acidic heteropolysaccharide, xanthan gum, cationized cellulose and the like. However, there is no description in the above use examples that a cation-modified alginic acid derivative in which a quaternary nitrogen-containing group is introduced into the alginic acid derivative of the present invention gives an excellent effect as a conditioning agent.
  Furthermore, Patent Document 13 discloses a water-soluble cationic polysaccharide substituted with a hydrophob (hydrophobic) for body care products and shampoo applications, and as the polysaccharide, cellulose, starch, hydroxyethyl cellulose, carrageenan, chitosan, natural gum Alternatively, alginates (alginic acid) are included together with biologically derived polysaccharides, but a cation-modified alginic acid derivative having a quaternary nitrogen-containing group introduced into the alginic acid derivative of the present invention has an excellent effect as a conditioning agent, There is no description that it gives a feeling of foam improvement such as foaming and foam quality and a set effect by having film-forming properties, and gives a feeling improvement when blended into a skin cosmetic composition.
  Furthermore, Patent Document 14 discloses a cationized derivative obtained by cationizing alginic acid together with guar gum, locust bean gum, agar, curdlan and the like as one of polysaccharides in a liquid detergent composition in a spray container as a dispersant. Patent Document 15 shows that the cationized derivative is used as a thickener in cleaning detergent-impregnated sheets. Patent Document 16 discloses the use of these as a dispersant in a solid particle dispersion cleaning composition. However, the present invention also applies to the above use examples.Used forCation-modified alginic acid derivatives are used in hair treatment compositions and skin cosmetic compositions, and have excellent conditioning effects and film-forming properties to improve foam feel such as foaming and foam quality and set effects after drying. There is no description to give.
  On the other hand, a natural polysaccharide contained as a calcium salt or the like in the cell wall of brown algae such as kombu and seaweed in seaweed, and a polymer in which uronic acid units of L-guluronic acid and D-mannuronic acid are linked by 1,4 glycoside bonds As for the alginic acid derivative, a polymer of guluronic acid and mannuronic acid is disclosed in Non-Patent Document 1 as a thickener or gelling agent in the food or feed industry, and from a fixing agent or heat or fire in the biochemical field. It is used as a protective material, and in Non-Patent Document 2, it is used in the field of foods, cosmetics and medical materials because of its property of forming a gel in the presence of a cation, and further, seaweed belonging to brown algae, Laminaria diguitarta Argye obtained by depolymerizing a polysaccharide consisting of L-guluronic acid and D-mannuronic acid obtained from (Laminaria digita) with an enzyme The acid-based oligosaccharides and their chelate compounds have skin protective effects, sedative effects, anti-inflammatory effects, and immunoprotective effects, and are useful as cosmetic raw materials. In Non-Patent Document 3, sodium alginate is an anion. In addition to being well compatible with non-ions, blending with shampoo creates a thin film on the hair to give it a finish, and it is also used in shave creams to improve water retention and foam stability. It has properties such as emulsifying stability and colloidal dispersibility, and has been shown to be used in applications such as a viscosity imparting agent, a dispersing agent, an emulsifying stabilizer, and a film forming agent. In Non-Patent Document 4, since the spherical polymer of calcium alginate has water absorption, it has been improved in functionality by blending it into seasonal products such as deolant powder and summer foundation. It has been shown that However, in any of the above-mentioned documents, the quaternary nitrogen-containing group is introduced into the alginic acid derivative of the present invention. There is no description that gives the improvement of the feeling of foam and the setting effect, and further improves the feeling when blended into the skin cosmetic composition.
[Patent Document 1]
Japanese Examined Patent Publication No. 47-20635 (No. 5page)
[Patent Document 2]
Japanese Patent Publication No. 60-42761 (page 1-9)
[Patent Document 3]
JP-A-55-164300 (1-2)page)
[Patent Document 4]
JP-A-4-364111 (No. 1-6page)
[Patent Document 5]
JP-A-5-112437 (No. 1-3)page)
[Patent Document 6]
JP-A-10-316540 (No. 2-3)page)
[Patent Document 7]
JP 2001-342117 A (2-4page)
[Patent Document 8]
JP-A-7-238186 (No. 2-3)page, 5-6page)
[Patent Document 9]
Japanese Patent Laid-Open No. 1-128914 (1-3page)
[Patent Document 10]
Japanese Patent Laid-Open No. 10-310798 (No. 1-6page)
[Patent Document 11]
JP-A-61-64701 (No. 2-42)page)
[Patent Document 12]
JP 7-33635 A (1-2)page)
[Patent Document 13]
JP-A-61-1181801 (No. 1-34)page)
[Patent Document 14]
JP-A-10-121099 (No. 2-4page)
[Patent Document 15]
JP-A-10-287900 (No. 3page, 6thpage)
[Patent Document 16]
JP-A-10-88196 (secondpage, 5thpage)
[Non-Patent Document 1]
FRAGANCE JOURNAL, April 1994 (71-73page)
[Non-Patent Document 2]
FRAGRANCE JOURNAL, May 2002 (74-83)page)
[Non-Patent Document 3]
FRAGRANANCE JOURNAL, April 1999 issue (82-83)page)
[Non-Patent Document 4]
FRAGRANCE JOURNAL, April 1999 (65-67page)
  The cation-modified cellulose derivative forms a complex salt with an anionic surfactant when blended with a hair treatment composition and adsorbs it to the hair. While it exhibits an excellent conditioning effect upon rinsing, it exhibits a feeling of stiffness after drying and a poor feel. There is a problem. In addition, the cation-modified guar gum has a problem that the amount of adsorption is small and the conditioning effect at the time of rinsing is weak although the feeling of stiffness after drying is small. Furthermore, even if the conditioning effect is sufficient, it does not show the setting effect, and even if it shows the conditioning effect and the setting effect depending on the application as in Patent Document 6, it is anionic because it is nonionic. Compared to conventional cationic polymers such as cellulose derivatives having a quaternary nitrogen-containing group introduced on the hair surface, much adsorption cannot be expected and the effect may not be fully satisfactory. In addition, when a conditioning agent such as a cationic polymer or a moisturizing agent such as glycerin is blended in the skin cosmetic composition, stickiness or sliminess may occur depending on the blending amount in the formulation. There is a problem that we cannot be satisfied. Furthermore, although these cationic polymers can obtain a smooth foam quality, there is a problem that, depending on the formulation, sufficient foaming cannot be obtained, and the feeling during use cannot be sufficiently satisfied. .
DISCLOSURE OF THE INVENTION
  In such a situation, the present inventors can improve the conditioning effect at the time of rinsing when blended with the hair treatment composition of conventional cationic polymers and the finishing feeling after drying, and can impart a set effect to the hair. Furthermore, intensive studies on compounds that eliminate the feeling of firmness and bulkiness when added to skin cosmetic compositions, improve the feeling of stickiness and sliminess, and improve the feel of foam such as foaming and foam quality. did. As a result, L-guluronic acid and D-mannuronic acid uronic acid units are composed of 1,4 glycosidic bonds, which are natural polysaccharides contained as calcium salts in the cell walls of brown algae (scientific name: Phaeophyceae) such as kombu and seaweed in seaweed. A cation-modified alginic acid derivative in which a specific amount of a quaternary nitrogen-containing group is introduced into a combined polymer alginate derivative and the cationic charge amount is adjusted to a specific range has excellent properties as a conditioning agent in a cosmetic composition. In particular, in the composition for treating hair, it has been found that since the film-forming property is good, it is possible to impart a set effect to the hair at the time of drying, and further, the foam feel can be improved by forming a uniform film. It came.
  Accordingly, the first aspect of the present invention is a cosmetic composition such as shampoo, rinse, set agent, hair styling composition, various hair treatment compositions such as hair color, skin cosmetic composition, and other makeup agents.Intended forCation-modified polysaccharide in which a part of the hydroxyl group contained in the alginic acid derivative which is a polymer in which uronic acid units are bonded by 1,4 glycosidic bonds is substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1) A cosmetic composition comprising a cation-modified alginic acid derivative having a cation charge amount derived from the quaternary nitrogen-containing group of 0.1 to 3.0 meq / g.InRelated.
[Chemical formula 2]

(Where R₁, R₂Are each an alkyl group having 1 to 3 carbon atoms, R_ThreeRepresents an alkyl group having 1 to 24 carbon atoms, and X^-Indicates an anion. n represents n = 0 or n = 1-30, and when n = 1-30, (R_FourO)_nIs a polymer residue of an alkylene oxide having 2 to 4 carbon atoms, and represents a polyalkylene glycol chain composed of a single alkylene oxide and / or a polyalkylene glycol chain composed of two or more types of alkylene oxide. )
  First of the present inventiontwoIn the embodiment, the alginic acid derivative, which is a polymer in which the uronic acid units are linked by 1,4 glycosidic bonds, includes two kinds of L-guluronic acid and D-mannuronic acid contained in brown algae (scientific name: Phaeophyceae) in seaweed. A natural polysaccharide derivative composed of uronic acid.oneIt relates to the cosmetic composition described in the embodiment.
  First of the present inventionthreeIn the embodiment of the present invention, the cation modification of the cation-modified alginic acid derivative is performed using a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt.oneOr the secondtwoIt relates to the cosmetic composition described in the embodiment.
  First of the present inventionFourIn the embodiment, the cation modification of the cation-modified alginic acid derivative is performed by adding an alkylene oxide having 2 to 4 carbon atoms to a part of the hydroxyl group contained in the alginic acid derivative, followed by a glycidyl trialkylammonium salt as a cationizing agent, or No. 1 made using 3-halogeno-2-hydroxypropyltrialkylammonium saltoneOr the secondtwoIt relates to the cosmetic composition described in the embodiment.
  First of the present inventionFiveIn the embodiment, the cation-modified alginic acid derivative is an alginate such as sodium salt, potassium salt, calcium salt, magnesium salt, etc.oneOr the secondFourThe cosmetic composition according to any one of the embodiments.
  First of the present inventionSixIn the embodiment, the content of the cation-modified alginic acid derivative is 0.05 to 5% by mass based on 100% by mass of the entire composition.oneOr the secondFiveThe cosmetic composition according to any one of the embodiments.
  First of the present inventionSevenThe embodiment of the present invention further comprises 5% by mass or less of another cationic water-soluble polymer and / or an amphoteric water-soluble polymer based on 100% by mass of the entire composition.oneOr the secondSixThe cosmetic composition according to any one of the embodiments.
  First of the present inventionEightThe embodiment of the invention further comprises an amidoamine compound, a neutralizing agent such as an organic acid and / or an inorganic acid, and a higher fatty acid and / or a higher alcohol.oneOr the secondSevenThe cosmetic composition according to any one of the embodiments.
  First of the present inventionNineThe embodiment of the present invention further comprises silicone and / or a silicone derivative.oneOr the secondEightThe cosmetic composition according to any one of the embodiments.
  First of the present inventionTenThe aspect of the present invention is characterized in that the cosmetic composition is a hair treatment composition.oneOr the secondNineThe cosmetic composition according to any one of the embodiments.
BEST MODE FOR CARRYING OUT THE INVENTION
  The alginic acid derivative used in the present invention is contained as a calcium salt or the like in the cell wall of brown algae (scientific name: Phaeophyceae) such as kombu and wakame, and is composed of two types of uronic acids, L-guluronic acid and D-mannuronic acid. Three types of block polysaccharides: a block composed of a bond between L-guluronic acids, a block composed of a bond between D-mannuronic acids, and a block composed of a bond between L-guluronic acid and D-mannuronic acid Polyuronic acid. In addition, the carboxyl group of the uronic acid unit has ion exchange properties, so it forms salts with various metal ions contained in seawater in seaweed and is in a water-insoluble jelly state. In this step, it is converted into pure alginic acid and various salts or esters according to the purpose. Further, depending on the purpose, the polymer may be depolymerized and reduced in molecular weight by a biological treatment such as an enzyme and a chemical treatment such as hydrolysis with acid or alkali. Therefore, the “alginate derivative” used in the present specification means pure alginic acid, various alginates obtained from pure alginic acid, alginic acid esters, and these derivatives having a reduced molecular weight. These alginic acid derivatives are trade names “Duck Algin NSPH”, “Duck Algin NSPL”, “Duck Algin NSPLL”, “Duck Assid” (manufactured by Kibun Food Chemifa Co., Ltd.), and “Kimiroid” (Kimitsu Chemical Co., Ltd.). Furthermore, it is easily available as “PHYCO ANTI-POLLU” and “PHYCO ANTI-INFLA” (manufactured by Kodif), which are seaweeds belonging to the order of brown algae and obtained from Laminaria diguita.
  The present inventionUsed inThe cation-modified alginic acid derivative can obtain a conditioning effect by improving the adsorptivity by cationically modifying the alginic acid derivative. In addition, when it is formulated into a coating-type cosmetic composition due to its film-forming properties, a strong setting effect is obtained, and when it is formulated into a wash-out cosmetic composition such as shampoo and rinse, it is elastic to the hair. Is added, and it gives firmness and firmness to the hair. Furthermore, when blended into shampoos, body cleaners, etc., it has a film-forming property to form a uniform film, improving foam feel such as foaming and foam quality during use.
  The cation modification according to the present invention is carried out by adding a glycidyl trialkylammonium salt having a quaternary nitrogen-containing group to an alginic acid derivative composed of two types of uronic acids, L-guluronic acid and D-mannuronic acid, or 3-halogeno-2. -It can be produced by reacting a hydroxypropyltrialkylammonium salt. In this case, the reaction is carried out in a suitable solvent, preferably a hydrous alcohol, in the presence of alkali. The introduction of such a quaternary nitrogen-containing group can be performed according to a conventionally known method, but is not necessarily limited thereto. For example, after adding an alkylene oxide having 2 to 4 carbon atoms to a part of the hydroxyl group contained in the alginic acid derivative, the quaternary glycidyl trialkylammonium salt or the 3-halogeno-2-hydroxypropyltrialkylammonium salt is added. The present invention by reacting with a nitrogen-containing groupUsed forCationic modified algin derivatives can be produced. Furthermore, in addition to using alginic acid and alginates that have been reduced in molecular weight as alginic acid derivatives, the product of the present invention can also be reacted with a quaternary nitrogen-containing group after hydrolyzing the alginic acid derivative with an acid or alkali to lower the molecular weight. Can be manufactured. Furthermore, it can also be produced by introducing a quaternary nitrogen-containing group into the alginic acid derivative and then hydrolyzing with an acid or alkali. Also, an inorganic salt, preferably sodium chloride, can be added to prevent aggregation of the alginic acid derivative in the solvent during the reaction. Furthermore, in order to prevent aggregation of the alginic acid derivative, improve dispersibility and increase the reaction rate, after adding or dissolving the alkali and inorganic salt in the reaction solvent, and then adding the alginic acid derivative and dissolving or dispersing It can also be produced by introducing the quaternary nitrogen-containing group.
  In the quaternary nitrogen-containing group represented by the chemical formula (1) introduced into the alginic acid derivative in the present invention, R₁And R₂Specific examples thereof include a methyl group, an ethyl group, and a propyl group, and R as an alkyl group having 1 to 24 carbon atoms._ThreeAs a specific example of R₁And R₂In addition, the octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosyl group and the like can be mentioned. R_FourSpecific examples of O include an ethoxy group, a propoxy group, and a butoxy group. Anion X^-Specific examples thereof include halogen ions such as chlorine ions, bromine ions and iodine ions, as well as methyl sulfate ions, ethyl sulfate ions and acetate ions.
  The present inventionUsed forThe cation-modified alginic acid derivative is excellent as a blending component of a cosmetic composition because it has film-forming properties and adsorbability to hair and skin. For example, when it is blended in a cosmetic composition, Improves foam feel such as foaming and foam quality, and when added to a hair treatment composition, provides a conditioning effect, elasticity imparting and setting effect, and is added to a skin cosmetic composition such as a body cleanser. In some cases, the oil component of the skin is not removed more than necessary, and the touch is further improved.IeThe present inventionIsThe present inventionUsed forThese cosmetic compositions containing a cationically modified alginic acid derivativeInRelated.
  The present inventionUsed forThe cationic charge amount derived from the quaternary nitrogen-containing group of the cation-modified alginic acid derivative is 0.1 to 3.0 meq / g, more preferably 0.5 to 2.5 meq / g. When the amount of cationic charge is less than 0.1 meq / g, the amount of adsorption to hair and skin becomes insufficient, and even if it is actually blended with a hair treatment composition such as a shampoo, rinse, body cleaning agent or skin cosmetic composition, it is effective. It is not allowed. Further, when the charge amount exceeds 3.0 meq / g, even if a hair treatment composition and a skin cosmetic composition containing such a cation-modified alginic acid derivative are used, deterioration of foaming and stickiness are felt at the time of use. Further, a feeling of stickiness is generated, the feeling of use is deteriorated, and a feeling of finish after use is also undesirable, such as a feeling of stickiness and stickiness, and further, imparting elasticity and setting effect cannot be obtained.
  The cation charge amount derived from the quaternary nitrogen-containing group of the cation-modified alginic acid derivative is the number of equivalents of the quaternary nitrogen-containing group represented by the chemical formula (1) contained in 1 g of the cation-modified alginic acid derivative. Usually, the nitrogen content derived from the quaternary nitrogen-containing group can be calculated by the Kjeldahl method (former cosmetic raw material standard, general test method, nitrogen determination method, second method) and calculated from the measured value. Since the alginic acid derivative composed of two types of uronic acids, guluronic acid and D-mannuronic acid, contains nitrogen, the present invention determined by the Kjeldahl methodUsed forThe value obtained by subtracting the nitrogen content derived from the alginic acid derivative composed of two types of uronic acids of L-guluronic acid and D-mannuronic acid used in the present invention from the nitrogen content of the cation-modified alginic acid derivative is derived from the quaternary nitrogen-containing group. Of nitrogen. Specifically, R of the quaternary nitrogen-containing group represented by the chemical formula (1)₁, R₂, R_ThreeIs a methyl group, X^-Is a chloride ion, and n is 1.00% of the nitrogen content of the product of the present invention obtained by cation modification of sodium alginate with a quaternary nitrogen-containing group of n = 0, as a result of measurement by the Kjeldahl method. In this case, the cation charge amount of this substance can be obtained by the following formula. The sodium alginate used in the present invention usually contains about 0.02% nitrogen.
  Cationic charge (meq / g) =Nitrogen content from quaternary nitrogen-containing groups (%) x 1000
                                      Atomic weight of nitrogen (14.0) × 100
                              = (1.00-0.02) /1.40
                              = 0.70
  The present inventionUsed forThe blending amount of the cation-modified alginic acid derivative with respect to the hair treatment composition or the skin cosmetic composition is preferably 0.05 to 5% by mass, based on 100% by mass of the whole composition. Providing elasticity and setting effect tend not to be fully exhibited, and if it exceeds 5% by mass, a feeling of stickiness and stickiness will occur at the time of use, and the flexibility will deteriorate and the feeling of stickiness will be seen and the feeling of use will be poor. Tend to be.
  The hair treatment composition of the present invention may further contain various cationic water-soluble polymers and amphoteric water-soluble polymers in order to improve the conditioning effect. The film-forming property and the setting effect are not impaired, and the total composition is 100% by mass, and is preferably 5% by mass or less. The film forming property and the setting effect exhibited by the derivative are not sufficiently exhibited. Furthermore, in the skin cosmetic composition, a feeling of sliminess is generated and the feeling of use becomes worse.
  Examples of the cationic water-soluble polymer and the amphoteric water-soluble polymer to be blended include the following, but are not necessarily limited thereto.
  Examples of cationic water-soluble polymers include quaternary nitrogen-modified polysaccharides (cation-modified hydroxyethyl cellulose, cation-modified guar gum, cation-modified locust bean gum, cation-modified starch, cation-modified tara gum, cation-modified tamarind gum, etc.), chloride Dimethyldiallylammonium derivatives (dimethyldiallylammonium chloride / acrylamide copolymer, polydimethylmethylenepiperidinium chloride, etc.), vinylpyrrolidone derivatives (vinylpyrrolidone / dimethylaminoethylmethacrylic acid copolymer salt, vinylpyrrolidone / methacrylamidopropyltrimethylammonium salt) Chloride copolymer, vinylpyrrolidone / methylvinylimidazolium chloride copolymer, etc.), methacrylic acid derivatives (methacryloylethyldimethylbenzene) IN chloride methacryloyloxyethyl trimethyl ammonium-2-hydroxyethyl methacrylate copolymer, methacryloyl ethyl dimethyl betaine chloride methacryloyloxyethyl trimethyl ammonium methacrylate methoxy polyethylene glycol copolymer, etc.) and the like.
  Examples of amphoteric water-soluble polymers include amphoteric starch, dimethyldiallylammonium chloride derivatives (acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer, etc.), methacrylic acid derivatives ( Polymethacryloylethyldimethylbetaine, N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer, etc.).
  As mentioned above, the present inventionUsed forThe cosmetic composition of the present invention can be obtained by blending a required amount of a cation-modified alginic acid derivative in a formulation system according to a known formulation, but the other ingredients in the cosmetic composition are not particularly limited, and ingredients generally used in cosmetics are not limited. It is possible to mix | blend as an arbitrary component. Other ingredients that can be blended are exemplified below.
  Examples of the anionic surfactant include alkyl (carbon number 8-24) sulfate, alkyl (carbon number 8-24) ether sulfate, alkyl (carbon number 8-24) benzenesulfonate, alkyl (carbon number 8-24). ) Phosphate, polyoxyalkylene alkyl (C8-24) ether phosphate, alkyl (C8-24) sulfosuccinate, polyoxyalkylene alkyl (C8-24) ether sulfosuccinate, acyl (C8-C24) alanine salt, acyl (C8-C24) N-methyl-β-alanine salt, acyl (C8-C24) glutamate, acyl (C8-24) Isethionate, acyl (carbon number 8-24) sarcosine salt, acyl (carbon number 8-24) taurine salt, acyl (carbon number 8-24) methyl taurate α- sulfofatty acid ester salts, ether carboxylates, polyoxyalkylene fatty acid monoethanolamide sulfates, long chain (8 to 24 carbon atoms) carboxylic acid salts, and the like.
  Nonionic surfactants include alkanolamide, glycerin fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene glycol ether, polyoxyalkylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbite fatty acid ester, sorbite fatty acid ester, polyoxy Alkylene glycerin fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl phenyl ether, tetrapolyoxyalkylene ethylene diamine condensate, sucrose fatty acid ester, polyoxyalkylene fatty acid amide, polyoxyalkylene glycol fatty acid ester, polyoxyalkylene castor oil Derivatives, polyoxyalkylene hydrogenated castor oil derivatives, alkyl poly Glycosidic, polyglycerol fatty acid esters, and the like.
  Examples of amphoteric surfactants include alkyl (carbon number 8-24) amidopropyl betaine, alkyl (carbon number 8-24) carboxybetaine, alkyl (carbon number 8-24) sulfobetaine, alkyl (carbon number 8-24) hydroxy. Sulfobetaine, alkyl (carbon number 8-24) amidopropylhydroxysulfobetaine, alkyl (carbon number 8-24) hydroxyphosphobetaine, alkyl (carbon number 8-24) aminocarboxylate, alkyl (carbon number 8-24) Examples include imidazolinium betaine, alkyl (carbon number 8 to 24) amine oxide, alkyl (carbon number 8 to 24) phosphate ester containing tertiary nitrogen and quaternary nitrogen.
  Examples of the oil include olive oil, jojoba oil, liquid paraffin, and fatty acid alkyl ester. Examples of the pearlizing agent include fatty acid ethylene glycol, and examples of the suspending agent include polystyrene emulsion.
  In addition to the cationic and amphoteric water-soluble polymers blended in the hair treatment composition and skin cosmetic composition of the present invention, anionic properties for purposes such as improving viscosity and styling usability to some extent, The nonionic polymer can be further blended within a range not impairing the effects of the present invention, and examples thereof include the following.
  Examples of anionic polymers include acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid / acrylamide / ethyl acrylate copolymers and salts thereof), and methacrylic acid derivatives (polymethacrylic acid and salts thereof, methacrylic acid).・ Acrylamide, diacetone acrylamide, acrylic acid alkyl ester, methacrylic acid alkyl ester copolymers and salts thereof, crotonic acid derivatives (vinyl acetate, crotonic acid copolymers, etc.), maleic acid derivatives (maleic anhydride, diisobutylene, etc.) Copolymer, isobutylene / maleic acid copolymer, etc.), polyglutamic acid and its salt, hyaluronic acid and its salt, carboxymethylcellulose, carboxyvinyl polymer and the like.
  Examples of nonionic polymers include acrylic acid derivatives (hydroxyethyl acrylate / methoxyethyl acrylate copolymer, polyacrylic acid amide, etc.), vinyl pyrrolidone derivatives (polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, etc.) , Polyoxyalkylene glycol derivatives (polyethylene glycol, polypropylene glycol, etc.), cellulose derivatives (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polysaccharides and derivatives thereof (guar gum, locust bean gum, dextran, etc.) and the like.
  In yet another embodiment, an amidoamine compound, a neutralizing agent such as an organic acid and / or an inorganic acid, and a higher fatty acid and / or a higher alcohol are added to the hair treatment composition and skin cosmetic composition of the present invention. Thus, the conditioning effect can be improved. The blending amount thereof is preferably 5% by mass or less based on 100% by mass of the entire composition as an amidoamine compound, and if it exceeds this, the feeling after use becomes heavy or it becomes slippery and the usability is deteriorated.
  Other components to be blended in the hair treatment composition and skin cosmetic composition of the present invention include cationic surfactants (alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylpyridium salt, alkyldimethylbenzylammonium salt, Benzethonium chloride, benzalkonium chloride, etc.), solubilizers (ethanol, ethylene glycol, propylene glycol, etc.), waxes (carnauba wax, candelilla wax, etc.), hydrocarbon oils (liquid paraffin, squalane, etc.), humectants (glycerin) , Trehalose, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, sodium hyaluronate, etc.), esters (hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristate) Myristyl acid, myristate-2-hexyldecyl, glyceryl trimyristate, isopropyl palmitate, 2-heptylundecyl palmitate, 2-hexyldecyl palmitate, butyl stearate, isocetyl stearate, 12-hydroxystearic acid Cholesteryl, cetostearyl alcohol, cetyl octanoate, hexyldecyl dimethyloctanoate, isocetyl isostearate, trimethylolpropane triisostearate, decyl oleate, oleic oil, cetyl lactate, myristyl lactate, ethyl acetate, amyl acetate butyl acetate, acetic acid Lanolin, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, ethylene glycol di-2-ethylhexylate, trimethylo tri-2-ethylhexylate Propane, glyceryl tri-2-ethylhexylate, pentaerythritol tetra-2-ethylhexylate, cetyl-2-ethylhexanoate, diisobutyl adipate, 2-heptylundecyl adipate, 2-hexyldecyl adipate, di Pentaerythritol fatty acid ester, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, acetoglyceride, N-lauroyl-L- Glutamic acid-2-octyldodecyl ester, di-2-ethylhexyl sebacate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, ethyl laurate, mink oil fatty acid ester Chill, etc.), antioxidants (tocopherol, BHT, etc.), silicones (methylpolysiloxane, methylphenylpolysiloxane, highly polymerized methylpolysiloxane, cyclic polysiloxane, etc.) and silicone derivatives (polyether-modified silicone, amino-modified silicone, (Meth) acrylic-silicone graft copolymers), higher alcohols, higher fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, coconut oil Fatty acids, palm fatty acids, palm kernel fatty acids, linoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, etc.), amino acids (arginine, glutamic acid, etc.), UV absorbers (benzophenone derivatives, paraaminobenzoic acid derivatives, Toxiccinnamic acid derivatives), UV scattering agents (inorganic compounds such as zinc oxide, zirconium oxide, titanium oxide), thickeners, metal sequestering agents (edetates, etc.), pH adjusters, bactericides, preservatives, hair growth Agents, vitamins, anti-inflammatory agents, dyes, pigments (inorganic white pigments such as titanium dioxide, iron oxide (bengala), inorganic red pigments such as iron titanate, inorganic green pigments such as cobalt titanate, iron oxide treatment) Mica titanium, carbon black-treated mica titanium, etc.), fragrances, foam enhancers and the like.
  The dosage form of the cosmetic composition according to the present invention described above is not limited and can be any dosage form. Further, in addition to the above (essential) component, the dosage form may be used as long as the effects of the present invention are not impaired. Usually, various components blended in the cosmetic composition can be added and produced by conventional methods, but among them, it can be preferably used as a hair treatment composition. Examples of the dosage form include shampoo, rinse, conditioner, hair wax, hair lotion, hair mist, etc.Used forFoaming due to the film-forming property of the cation-modified alginic acid derivative, improvement in the feel of foam such as foam quality, setting effect, imparting elasticity, and conditioning effect are utilized. In addition, it can be used in body cleaning agents, facial cleansers, lotions, and can be blended into acidic hair dyes, oxidative hair dyes, permanent agents, etc. due to the effect of improving the feeling of use.
【Example】
  The present invention will be described below in more detail based on examples, but the present invention is not limited thereto. Unless otherwise specified, the amount is expressed in mass%.
[Production of cation-modified alginic acid derivative]
[Example 1]
  After adding 5.9 g of 48 mass% sodium hydroxide aqueous solution and 1.0 g of sodium chloride to 600 ml of 50 volume% isopropanol aqueous solution, 99.5 g of sodium alginate was gradually added and dispersed. Next, 60.8 g of an 80% by mass glycidyltrimethylammonium chloride (hereinafter also referred to as GTA) aqueous solution was added, and the mixture was heated and reacted at 50 ° C. for 3 hours. After completion of the reaction, 7.0 g of 35% hydrochloric acid was diluted with 800 ml of a 70% by volume isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 500 ml of methanol to precipitate the reaction product, which was filtered off. The obtained precipitate was washed with an aqueous methanol solution, and then the reaction product was dried under reduced pressure. The cationic charge amount of the cation-modified alginic acid derivative thus obtained was 0.66 meq / g. The results are shown in Table 1 (Sample No. 1 in Table 1).
  Similarly, cation-modified alginic acid derivatives having different cation charge amounts were synthesized by changing the amount of GTA to be added. The results are shown in Table 1 (Sample numbers 2 and 3 in Table 1).
[Example 2]
  176 g of alginic acid (duck acid; manufactured by Kibun Food Chemifa Co., Ltd.) was dispersed in 1100 ml of 60% by volume isopropanol aqueous solution, and 6.0 g sodium chloride and 136.8 g 48% by weight sodium hydroxide aqueous solution were added. After the addition, the mixture was heated and hydrolyzed at 70 ° C. for 3 hours. Cool to 50 ° C after hydrolysis. After cooling, 514.5 g of 3-halogeno-2-hydroxypropyldimethylmonolauryl ammonium chloride was added and reacted at 50 ° C. for 3 hours. After completion of the reaction, 14.0 g of 35% hydrochloric acid was diluted with 1700 ml of 70% by volume isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 1200 ml of methanol to precipitate the reaction product, which was filtered off. The obtained precipitate was washed with an aqueous methanol solution, and then the reaction product was dried under reduced pressure. The cation-modified alginic acid derivative thus obtained had a cation charge of 0.71 meq / g. The results are shown in Table 1 (Sample No. 4 in Table 1).
[Example 3]
  199 g of sodium alginate (Duck Algin NSPH; manufactured by Kibun Food Chemifa Co., Ltd.) was dispersed in 900 ml of 70% by volume isopropanol aqueous solution in a pressurized airtight container, and 11.8 g of 48% by mass sodium hydroxide aqueous solution was added. . Next, 66 g of ethylene oxide and 234 g of propylene oxide were added, and the mixture was heated and reacted at 70 ° C. for 3 hours under pressure and hermetic sealing. After completion of the reaction, the pressure is released and cooled to 50 ° C. After cooling, 242.4 g of 80% by mass GTA aqueous solution is added and reacted at 50 ° C. for 3 hours. After completion of the reaction, 14.0 g of 35% hydrochloric acid was diluted with 1500 ml of a 70% by volume isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 1000 ml of methanol to precipitate the reaction product, which was filtered off. The obtained precipitate was washed with an aqueous methanol solution, and then the reaction product was dried under reduced pressure. The cation-modified alginic acid derivative thus obtained had a cation charge of 0.60 meq / g. The results are shown in Table 1 (Sample No. 5 in Table 1).
Example 1
  According to the method of Example 1, cation-modified alginic acid derivatives having different charge amounts were synthesized by changing the amount of GTA to be added. The results are shown in Table 1 (Sample numbers 6 and 7 in Table 1).
[Table 1]

[Evaluation of cation-modified alginic acid derivatives]
Example 4 Film-forming property
  The film forming property of the cation-modified alginic acid derivative (sample numbers 1, 2, 4 and 5 in Table 1) was confirmed by the following method. Pour 20 ml of the test solution (0.2% aqueous solution) into a rectangular stainless steel container (length x width x depth = 135 mm x 170 mm x 30 mm), and dry (75 ° C) while paying attention to foaming in a vacuum dryer. I do. After drying, the substrate was left in a constant temperature and humidity (20 ° C., 40% RH) atmosphere for 24 hours, and then the dried product was taken out from the stainless steel container and the state of the dried product was visually observed. For comparison, as other cationic polymers, cation-modified hydroxyethyl cellulose having an average addition mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass (Kachinal HC-100; manufactured by Toho Chemical Co., Ltd.) and nitrogen Cation-modified guar gum (Catinal CG-100; manufactured by Toho Chemical Industry Co., Ltd.) having a content of 1.9% by mass, and an unmodified alginic acid derivative (sodium alginate, trade name: Duck Algin NSPH, Kibun Food Co., Ltd.) Chemifa Co., Ltd.) and the same film-forming property test were carried out for each. The results are shown in Table 2.
[Table 2]

  From the results in Table 2, it was confirmed that the cation-modified alginic acid derivative of the present invention obtained by cation-modifying an alginic acid derivative is superior in film-forming properties as compared with the cationic polymer used in the conventional conditioning agent. .
[Production and Evaluation of Cosmetics Containing Cation-Modified Alginic Acid Derivatives]
Example 5 Giving elasticity to hair (part 1)
  The effect of imparting elasticity to the hair of the cation-modified alginic acid derivative was confirmed by washing with a product (hair shampoo).
(Preparation of hair shampoo)
5-a
  Using the cation-modified alginic acid derivatives of Sample Nos. 1, 3, 4, and 5 in Table 1 obtained in Examples 1, 2, and 3, shampoos having the compositions shown in Table 3 (A) were prepared. Ingredient (12) (A) in Table 3 was heated to 60 ° C., and component (1) was slowly added and dissolved while stirring. After dissolution was confirmed, heating was stopped and ingredients (5) to (7) were added. In addition, the mixture was stirred to make it uniform, and components (8) to (11) were added and mixed uniformly at 30 to 40 ° C. Thus, shampoos having the compositions shown in (A) of Table 3 were prepared, and the shampoos prepared from the cation-modified alginic acid derivatives corresponding to Sample Nos. 1, 3, 4, and 5 in Table 1 were sequentially prepared. S1 to S4.
5-b
  Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further, as a cationic water-soluble polymer, cation-modified hydroxyethyl cellulose (Catinal) having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass A shampoo having the composition shown in Table 3 (B) was prepared, including HC-100 (manufactured by Toho Chemical Co., Ltd.). The component (12) of (B) in Table 3 was heated to 60 ° C., and the components (1) and (3) were slowly added and dissolved while stirring. After confirming the dissolution, the heating was stopped and the components (5) to (5) to (7) was added and stirred to make it uniform, then components (8) to (11) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was designated as prescription S5 of the product of the present invention.
5-c
  The cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1 was used, and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) was used as an amphoteric water-soluble polymer. A shampoo having the composition shown in (C) of Table 3 was prepared, including SM; manufactured by Mitsubishi Chemical Corporation. Ingredient (12) of (C) in Table 3 was heated to 60 ° C. and components (1) and (4) were slowly added and dissolved while stirring. After confirming dissolution, heating was stopped and ingredients (5) to (5) to (7) was added and stirred to be uniform, then components (8) to (11) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was designated as formulation S6 of the present invention.
5-d
  Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further containing both a cationic water-soluble polymer and an amphoteric water-soluble high molecule, a shampoo having the composition shown in (D) of Table 3 was prepared. . The component (12) of (D) in Table 3 was heated to 60 ° C. and components (1), (3) and (4) were slowly added and dissolved while stirring. After confirming dissolution, heating was stopped and the component ( 5) to (7) were added and stirred to be uniform, and components (8) to (11) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was designated as S7 of the present invention.
[Table 3]

5-e (Preparation of comparative product)
  In order to compare the effect of the cation-modified alginic acid derivative used in the present invention on the shampoo, the cation-modified alginic acid derivatives of Sample Nos. 6 and 7 in Table 1 obtained in Example 1 were used and shown in the comparative product (E) of Table 3. A shampoo of composition was prepared. The component (12) of the comparative product (E) in Table 3 was heated to 60 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming dissolution, heating was stopped, components (5) to (7) were added and stirred to make uniform, components (8) to (11) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo Were designated as comparative products C1 and C2, respectively.
5-f (Preparation of comparative product)
  In order to compare the effect of the cation-modified alginic acid derivative used in the present invention on the shampoo, an unmodified alginic acid derivative (sodium alginate, trade name: Duck Algin NSPH, A shampoo having the composition shown in Comparative Product (E) in Table 3 was prepared in the same manner as 5-e, and this was designated as Comparative Product C3.
(Evaluation)
  The shampoos of the formulations S1 to S7 of the products of the present invention prepared in the above-mentioned 5-a to 5-f and the shampoos of comparative products C1, C2 and C3, and further, the composition shown in the blank (F) of Table 3 as a blank Each 1.0 g of shampoo was used to wash 15 g of hair strands (total length: 180 mm). Thereafter, it was rinsed with running water, left in a constant temperature and humidity (20 ° C., 40% RH) atmosphere for 24 hours, and then naturally dried. Thereafter, the firmness of the hair was measured with a pure bending tester (KES-FB2-S, manufactured by Kato Tech Co., Ltd.). The results are shown in Table 4. In addition, after heating the component (12) in the blank (F) of Table 3 to 60 degreeC, adding a component (5)-(7), stirring a blank, and cooling, it is 30-40 degreeC after cooling. Components (8) to (11) were added and mixed uniformly.
  From the composition shown in the blank (F) of Table 3 as shampoos of the formulations S1 to S7 and comparative products C1, C2 and C3 of the present invention products prepared in the above-mentioned 5-a to 5-f. About the shampoo which becomes, after wash | cleaning hair by 10 testers, the elasticity (hair stiffness) of the hair after drying with a dryer was confirmed. The number of testers who felt that the finished hair was stiff was evaluated according to the following criteria, and the results are shown in Table 4.
  ・ There are more than 8 testers who feel that the hair is stiff ... ◎
  ・ 6-7 testers who felt that their hair was stiff ... ○
  ・ 4 to 5 testers who feel that their hair is stiff ... △
  ・ There are less than 4 testers who feel that hair is stiff ... ×
[Table 4]

  From the results of Table 4, the shampoos S1 to S4 of the present invention containing the cation-modified alginic acid derivatives of Sample Nos. 1, 3, 4 and 5 in which the alginic acid derivative was cation-modified are compared with the blank in terms of bending rigidity (B value) and hysteresis width. Both (2HB) are improved. Similar results are also seen in comparative product C2 containing the cation-modified alginic acid derivative of Sample No. 7 whose cation charge value is higher than the range of the present invention, but the bending rigidity was too large, suggesting a sense of stiffness. . On the other hand, Comparative Product C1 containing a cation-modified alginic acid derivative of Sample No. 6 and Comparative Product C3 containing an unmodified alginic acid derivative, which had a cation charge value lower than the range of the present invention, had the same results as the blank. This is because when an unmodified alginic acid derivative and a cation-modified alginic acid derivative having a cation charge value lower than the range of the present invention are washed out and used as a product, the adsorptive capacity based on ionicity cannot be obtained with respect to the hair. It is considered that the effect was not obtained because of less adsorption to the hair. On the other hand, the product of the present invention in which the alginic acid derivative is cation-modified within a specific range has an adsorption ability based on the ionicity to the hair, so that elasticity is imparted in a washing product such as shampoo and rinse. The strength of the body has been improved. Thus, the present inventionUsed forThe cation-modified alginic acid derivative exerts its effect sufficiently even when it is blended in a shampoo, rinse, or other washing product, and also when it is blended in an application-type hair treatment composition such as a hair spray or hair gel. It was found that a set effect can be expected from the provision of elasticity due to having the.
  In addition, the present inventionUsed forCation-modified alginic acid derivative and ethylene oxide average addition mole number 1.8, cation-modified hydroxyethyl cellulose (Catinal HC-100; manufactured by Toho Chemical Co., Ltd.) having a nitrogen content of 1.8% by mass, N-methacryloyloxyethyl N , N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer SM; manufactured by Mitsubishi Chemical Co., Ltd.), etc. It was confirmed that it was not broken.
Example 6 Giving elasticity to hair (part 2)
(Evaluation)
  Using the shampoos of the formulations S1 to S7 of each product of the present invention prepared in Example 5 and the shampoos of comparative products C1, C2 and C3, the present inventionUsed forThe effect of imparting elasticity to the damaged hair of the cation-modified alginic acid derivative was washed away and confirmed with the product. A hair strand similar to that used in Example 5 was prepared with 6% H₂O₂And a 2: 1 mixture (w / w) of 3% aqueous ammonia (w / w) was immersed in a bath ratio of 1 to 100 (hair strand weight to bleach solution weight) at 40 ° C for 60 minutes. After washing with warm water, it was dried with a dryer. Comparatively damaged products C1 to C3 prepared according to the formulations S1 to S7, 5-e and 5-f of the products of the present invention prepared according to the aforementioned 5-a to 5-d, were obtained by the bleaching treatment. Furthermore, 1.0 g of a shampoo having the composition shown in the blank (F) of Table 3 was used as a blank to wash 15 g of hair strands (total length: 180 mm). Thereafter, it was rinsed with running water, left in a constant temperature and humidity (20 ° C., 40% RH) atmosphere for 24 hours, and then naturally dried. Thereafter, the firmness of the hair was measured with a pure bending tester (KES-FB2-S, manufactured by Kato Tech Co., Ltd.). The results are shown in Table 5. In addition, after heating the component (12) in the blank (F) of Table 3 to 60 degreeC similarly to Example 5, adding a component (5)-(7) and stirring and making it uniform, cooling The ingredients (8) to (11) were added at 30 to 40 ° C. and mixed uniformly.
[Table 5]

  When evaluated with damaged hair from the results in Table 5, when the shampoos S1 to S4 including the product of the present invention are compared with the blank, both the bending rigidity (B value) and the hysteresis width (2HB) are improved. Similar results can be seen in Comparative Product C2 containing the cation-modified alginic acid derivative of Sample No. 7 whose cation charge value is higher than the range of the present invention, but the bending rigidity becomes too large, suggesting a sense of stiffness. It was. On the other hand, in the comparative product C1 containing the cation-modified alginic acid derivative of Sample No. 6 whose cation charge amount value is lower than the range of the present invention, the bending rigidity and the hysteresis width are slightly improved. No improvement was obtained, and Comparative Product C3 containing the unmodified alginic acid derivative gave the same result as the blank. Furthermore, since the difference between the bending rigidity and the hysteresis width from the blank is larger than that in the case of the unbleached untreated healthy hair of Example 5, the usefulness of the product of the present invention on the damaged hair was confirmed. It was.
Example 7 Foaming test
  The present inventionUsed forFoaming of a cosmetic composition in which cation-modified alginic acid derivatives (sample numbers 1, 2, 4 and 5 in Table 1) were blended with the composition shown in Table 6 (A) was measured. For comparison, as other cationic polymer, an average addition mole number of ethylene oxide of 1.8, a cation-modified hydroxyethyl cellulose having a nitrogen content of 1.8% by mass (Kachinal HC-100; manufactured by Toho Chemical Co., Ltd.), and A cosmetic composition containing sodium alginate (Duck Algin NSPH; manufactured by Kibun Food Chemifa Co., Ltd.) as an unmodified alginate derivative was blended in the composition shown in Table 6 (B), and foaming was measured in the same manner.
  For the measurement, each cosmetic composition having the formulation shown in Table 6 was prepared according to the procedure shown in Example 5, and 150 ml of a 5% aqueous solution of the prepared cosmetic composition was commercially available as a juicer mixer. Stir and whisk. The stirring time and the amount of foam were measured, and the results are shown in Table 7.
[Table 6]

[Table 7]

  From the results in Table 7, the present inventionUsed forThe cation-modified alginic acid derivative has excellent film-forming properties as well as the results seen in imparting elasticity to the hair when compared with other cationic polymers (Catinal HC-100: cation-modified hydroxyethyl cellulose). It was confirmed that the foam film was strong, and the foaming immediately after the foaming was excellent. Therefore, when the product of the present invention is blended in a foamed cosmetic composition such as a shampoo, a body cleaner, or a facial cleanser, improvement in foam feel such as foaming and foam quality can be expected.
Hereinafter, in each cosmetic composition having a different dosage form, the sensory evaluation and the film forming property obtained by the cation-modified alginic acid derivative, setting effect, imparting elasticity, conditioning effect and improvement of foaming feeling such as foaming, foam quality, etc. Further confirmation by instrument measurements.
Hair shampoo
(Preparation)
[Example 8]
8-a
  Using the cation-modified alginic acid derivatives of Sample Nos. 1 to 5 of the present invention obtained in Examples 1, 2, and 3, shampoos having the compositions shown in Table 8 (A) were prepared. The component (14) of (A) in Table 8 was heated to 65 ° C. and the component (1) was slowly added and dissolved while stirring. After confirming the dissolution, the heating was stopped and (5) to (10) were added. The mixture was stirred to make it uniform, and components (11) to (13) were further added at 30 to 40 ° C. and mixed uniformly. In this way, each shampoo having the composition shown in Table 8 (A) in which the cation-modified alginic acid derivative corresponding to the sample numbers 1 to 5 in Table 1 was blended was prepared, and the shampoo containing the sample numbers 1 to 5 in Table 1 was prepared. It was set as prescription 1-5 of this invention product in order.
8-b
  Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further, as the cationic water-soluble polymer A, a cation-modified hydroxyethyl cellulose having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass ( A shampoo having the composition shown in (B) of Table 8 was prepared, including Kachinal HC-100 (manufactured by Toho Chemical Co., Ltd.). The component (14) of (B) in Table 8 is heated to 65 ° C., components (1) and (3) are slowly added and dissolved while stirring, and after confirming dissolution, the heating is stopped and components (5) to (5) (10) was added and stirred to make it uniform, and then components (11) to (13) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was used as Formulation 6 for the product of the present invention.
8-c
  A shampoo having the composition shown in Table 8 (C) containing diallyldimethylammonium chloride / acrylamide copolymer (Merquat 550; manufactured by NALCO) as the cationic water-soluble polymer B instead of the cationic water-soluble polymer A Was prepared in the same manner, and this was designated as the formulation 7 of the present invention.
8-d
  The cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1 was used, and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) was used as an amphoteric water-soluble polymer. A shampoo having the composition shown in (D) of Table 8 was prepared, including SM; manufactured by Mitsubishi Chemical Corporation. The component (14) of (D) in Table 8 was heated to 65 ° C., and the components (1) and (4) were slowly added and dissolved while stirring. After confirming the dissolution, the heating was stopped and the components (5) to (5)-( 10) was added and stirred to make it uniform, and then components (11) to (13) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was used as the formulation 8 of the present invention product.
8-e
  Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, a shampoo having a composition shown in (E) of Table 8 containing a cationic water-soluble polymer and an amphoteric water-soluble polymer was prepared. The component (14) of (E) in Table 8 was heated to 65 ° C. and components (1), (3) and (4) were slowly added and dissolved while stirring. After confirming dissolution, the heating was stopped and the component ( 5) to (10) were added and stirred to be uniform, and components (11) to (13) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was used as the formulation 9 of the product of the present invention.
8-f (Preparation of comparative product)
  In order to compare the effect of the cation-modified alginic acid derivative according to the present invention on the shampoo, the cation-modified alginic acid derivative obtained in Example 1, ie, sample Nos. 6 and 7 in Table 1, was used as a comparative product (G) shown in Table 8. A shampoo of the same composition was prepared. The component (14) of the comparative product (G) in Table 8 was heated to 65 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming dissolution, heating was stopped, components (5) to (10) were added and stirred to make uniform, components (11) to (13) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo Were comparative products 1 and 2, respectively.
[Table 8]

8-g (preparation of comparative product)
  Furthermore, in order to compare the effect with other cationic polymers, instead of the cation-modified alginic acid derivative obtained in Example 1 in 8-f, an ethylene oxide average added mole number of 1.8 and a nitrogen content of 1.8% by mass were obtained. Using cation-modified hydroxyethyl cellulose (Kachinal HC-100; manufactured by Toho Chemical Industry Co., Ltd.), a shampoo having the composition shown in Comparative Product (G) in Table 8 was prepared in the same manner as 8-f, and this was compared product. It was set to 3.
(Evaluation)
[Example 9]
  The performance evaluation of the following items was performed by 10 testers for each shampoo prepared in the above-mentioned 8-a to 8-e, that is, the formulations 1 to 9 of the present invention. The performance evaluation method uses a shampoo having the composition shown in the standard product (F) in Table 8 that does not contain a cationic polymer or the like as a component, and a shampoo to be evaluated, and the feeling of use at the time of shampooing, depending on the dryer The feeling of use after drying is based on the standard product (F).
  ・ Bubbling when washing hair
  ・ Presence or absence of conditioning effect during use (hand touch and hair feel)
  ・ Presence or absence of conditioning effect after use (dry hair) (comb feeling, feel of hair) and strength of hair
Were compared and digitized by the methods shown in Tables 9 and 10 below, and the evaluation values of 10 testers for each item were summed. The evaluation results are shown in Table 11. The standard product (F) was heated after the component (14) in the standard product (F) in Table 8 was heated to 65 ° C., and the components (5) to (10) were added and stirred until uniform. The components (11) to (13) were added at 30 to 40 ° C. and mixed uniformly.
[Table 9]

[Table 10]

Comparative Example 1
  For each shampoo and comparative products 1 to 3 prepared in 8-f and 8-g described above, performance evaluation was carried out in the same manner as in Example 9, and the results are shown in Table 11.
[Table 11]

  From the results shown in Table 11, the cation-modified alginic acid derivative has a cation charge amount of 0.1 to 3.0 meq / g.Used forCation-modified alginic acid derivatives, when used in shampoos, have excellent foaming effects during shampooing, conditioning effects such as fingering and touching during use, conditioning effects such as moist feeling and combing, and film-forming properties after use. It was confirmed that the firmness of the hair can be obtained from the imparting of elasticity by.
  Moreover, the performance of the shampoo containing the product of the present invention is superior to that of Comparative Product 3 containing only cation-modified hydroxyethyl cellulose (Catinal HC-100), which is conventionally used as a conditioning agent, and has the same conditioning effect when used. The present invention is not present in conventional conditioning agents after use.Used forThe firmness of the hair was obtained from the elasticity imparted by the film-forming property of the cation-modified alginic acid derivative. Further, by using a cationic water-soluble polymer (Kachinal HC-100, Merquat 550) and / or an amphoteric water-soluble polymer (Yukaformer SM) in combination,Used forIt was confirmed that the conditioning effect was improved without impairing the performance of the cation-modified alginic acid derivative.
(Formulation Examples 1 to 3)
  Below, the suitable compounding example of this invention to a shampoo is shown.
[Table 12]

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
[Table 13]

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
[Table 14]

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
Hair rinse
(Preparation)
[Example 10]
10-a
  Behenic acid neutralized with citric acid as the neutralizing agent and the amidoamine compound shown in Table 15 (A) below using the cation-modified alginic acid derivatives of Sample Nos. 1-4 obtained in Examples 1 and 2 A rinse having a composition containing dimethylaminopropylamide citrate and further a higher alcohol (cetanol) was prepared. The components (5) to (10) of (A) in Table 15 were heated to 80 ° C. and stirred, and the component (1) was previously added to the component (12) with stirring and dissolved. A solution heated to 80 ° C. was added with stirring, and then component (11) was added while cooling and mixed uniformly. Thus, the rinses having the compositions shown in Table 15 (A) were prepared, and the rinses containing the cation-modified alginic acid derivatives of Sample Nos. 1 to 4 in Table 1 were used as the formulations 10 to 13 in this order.
10-b
  Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further, as a cationic water-soluble polymer, cation-modified hydroxyethyl cellulose (Catinal) having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass The rinse of the composition shown to (B) of Table 15 containing HC-100; Toho Chemical Industry Co., Ltd.) was prepared. While stirring the components (1) and (3) in the component (12) in advance, the components (5) to (10) of (B) in Table 15 were heated to 80 ° C. and stirred to make a uniform solution. The solution dissolved and heated to 80 ° C. was added with stirring, and then component (11) was added and mixed uniformly while cooling, and the resulting rinse was designated as formulation 14 of the product of the present invention.
10-c
  Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further amphoteric water solubility
A composition shown in (C) of Table 15 containing N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer SM; manufactured by Mitsubishi Chemical Corporation) as a polymer. A rinse was prepared. While stirring the components (1) and (4) in the component (12) in advance, the components (5) to (10) of (C) in Table 15 were heated to 80 ° C. and stirred to make a uniform solution. The solution dissolved and heated to 80 ° C. was added with stirring, and then component (11) was added and mixed uniformly while cooling, and the resulting rinse was designated as formulation 15 of the product of the present invention.
[Table 15]

10-d (Preparation of comparative product)
  In order to compare the effect of the cation-modified alginic acid derivative according to the present invention on rinsing, the cation-modified alginic acid derivative obtained in Example 1, ie, sample Nos. 6 and 7 in Table 1, was used as a comparative product (D) shown in Table 15. A rinse of the same composition was prepared. Ingredients (5) to (10) of comparative product (D) in Table 15 were heated to 80 ° C. and stirred to make a uniform solution. The solution heated to 80 ° C. was added with stirring, and then the component (11) was added while cooling and mixed uniformly. The rinses containing the sample numbers 6 and 7 in Table 1 were compared with the comparative product 4 respectively. And 5.
10-e (Preparation of comparative product)
  Furthermore, in order to compare the effect with other cationic water-soluble polymers, instead of the cation-modified alginic acid derivative obtained in Example 1 in 10-d above, ethylene oxide average added mole number 1.8, nitrogen content 1.8 Using 10% by mass of cation-modified hydroxyethyl cellulose (Kachinal HC-100; manufactured by Toho Chemical Industry Co., Ltd.), a rinse having the composition shown in Comparative Product (D) in Table 15 was prepared in the same manner as 10-d. Was designated as comparative product 6.
(Evaluation)
Example 11
  For each of the rinses prepared in the above-mentioned 10-a to 10-c, that is, the formulations 10 to 15 of the product of the present invention, the performance evaluation of the following items was performed by 10 testers.
  The performance evaluation method uses the rinse of the composition shown in the standard product (E) of Table 15 that does not contain a cationic polymer as a component, and the rinse of the object to be evaluated, and the feeling of use after drying with a dryer. Based on the standard product (E),
  -The presence or absence of dry hair condition effect (comb street, squeak, etc.)
  ・ The strength of the hair
Were compared with each other, digitized by the method of Table 16 below, and the values of 10 testers who performed the evaluation were totaled. The evaluation results are shown in Table 17. The standard product (E) was prepared by heating the components (5) to (10) in the standard product (E) in Table 15 to 80 ° C. and stirring them to make a uniform solution. 12) was added with stirring, and then component (11) was added while cooling to prepare a uniform mixture.
Comparative Example 2
  For each of the rinses prepared in 10-d and 10-e described above, that is, comparative products 4, 5 and 6, performance evaluation was performed in the same manner as in Example 11, and the results are shown in Table 17.
[Table 16]

[Table 17]

  From the results in Table 17, the present invention has a cationic charge amount of 0.1 to 3.0 meq / g.Used forA rinse containing a cation-modified alginic acid derivative and further containing an amidoamine compound, a neutralizing agent, and a higher alcohol (cetanol) provides an excellent hair conditioning effect as well as a firmness of the hair by imparting elasticity. It was confirmed that
  In addition, the performance of the product of the present invention in a rinse containing an amidoamine compound, a neutralizing agent and a higher alcohol is compared with other cationic polymers, and the conditioning effect is equal to or higher than that after use and after use. The firmness of the hair due to the application of was obtained. Furthermore, it was confirmed that the conditioning effect was improved by using a cationic water-soluble polymer and / or an amphoteric water-soluble polymer in combination without impairing the performance of the cation-modified alginic acid derivative.
(Formulation examples 4 to 6)
  Below, the suitable example of a mixing | blending of this invention to the composition for hair treatment which requires conditioning effects, such as a rinse and a conditioner, is shown.
[Table 18]

  To the purified water shown in Table 18, the product of the present invention, stearyltrimethylammonium chloride, 1,3-butylene glycol, alkyl (C12,14) oxyhydroxypropylarginine hydrochloride, hydroxypropyltrimonium hydrolyzed keratin, and dye are added to 75 ° C. Keep (water phase). The remaining other components are mixed, dissolved by heating and kept at 75 ° C. (oil phase). After adding an aqueous phase and an oil phase, isopropanol was added and emulsified with a homomixer, followed by cooling with stirring.
[Table 19]

  To the purified water of Table 19, the product of the present invention, hydroxypropyltrimonium chloride, dimethylaminopropylamide stearate, hydrolyzed wheat, L-glutamic acid, glycerin, phenoxyethanol, and pigment are added and kept at 80 ° C. (aqueous phase). The remaining other components are mixed, dissolved by heating and kept at 80 ° C. (oil phase). The aqueous phase and the oil phase were added and emulsified with a homomixer, and then cooled with stirring.
[Table 20]

  To the purified water shown in Table 20, the product of the present invention, dimethylaminopropylamide stearate, 50% lactic acid, glycerin, phenoxyethanol, sodium benzoate and hydrolyzed silk are added and kept at 70 ° C. (aqueous phase). The remaining other components are mixed, dissolved by heating and kept at 70 ° C. (oil phase). The aqueous phase and the oil phase were added and emulsified with a homomixer, and then cooled with stirring.
Hair gel
(Preparation)
Example 12
12-a
  The effect of the product of the present invention in the application-type hair cosmetic was confirmed by the following method. Using the cation-modified alginic acid derivatives of Sample Nos. 1, 2 and 3 obtained in Example 1, hair gels having the composition shown in Table 21 (A) were prepared. Add component (1) and components (5) to (9) in Table 21 to the stirring component (11), dissolve uniformly, then add component (10) and mix until clear did. Thus, hair gels having the composition shown in (A) of Table 21 were prepared, and hair gels containing the cation-modified alginic acid derivatives of Sample Nos. 1, 2 and 3 in Table 1 were respectively formulated with the formulations 16, 17 and 18 of the present invention. did.
12-b
  Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further, as a cationic water-soluble polymer, cation-modified hydroxyethyl cellulose (Catinal) having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass The hair gel of the composition shown to (B) of Table 21 was prepared including HC-100; Add the components (1), (3) and (5) to (9) shown in (B) of Table 21 to the stirring component (11) and uniformly dissolve, then add the component (10) Mix until clear. Thus, a hair gel having the composition shown in (B) of Table 21 was prepared and used as the formulation 19 of the present invention.
12-c
  The cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1 was used, and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) was used as an amphoteric water-soluble polymer. A hair gel having the composition shown in Table 21 (C) was prepared, including SM (manufactured by Mitsubishi Chemical Corporation). Add components (1), (4) and (5) to (9) shown in (C) of Table 21 to the stirring component (11), and after uniformly dissolving, add (10) to make it transparent Mix until. Thus, a hair gel having the composition shown in (C) of Table 21 was prepared and used as the formulation 20 of the present invention.
12-d (Preparation of comparative product)
  In order to compare the effect of the cation-modified alginic acid derivative according to the present invention on the hair gel, the cation-modified alginic acid derivative obtained in Example 1, ie, sample Nos. 6 and 7 in Table 1, was used as a comparative product (E) in Table 21. A hair gel having the composition described above was prepared. The components (2) and (5) to (9) in Table 21 were added to the stirring component (11), and after uniform dissolution, the component (10) was added and mixed until transparent. In this way, hair gels having the compositions shown in Table 21 (E) were prepared, and hair gels containing sample numbers 6 and 7 in Table 1 were designated as comparative products 7 and 8, respectively.
12-e (Preparation of comparative product)
  In order to compare the effect with other cationic polymers, the average number of moles of ethylene oxide added was 1.8 instead of the cation-modified alginic acid derivative obtained in Example 1 used in 12-d above, and the nitrogen content was 1.8% by mass. The hair gel of the composition shown in the comparative product (E) of Table 21 containing the cation-modified hydroxyethyl cellulose (Katinal HC-100; manufactured by Toho Chemical Industry Co., Ltd.) was prepared in the same manner as 12-d, and the comparison was made. Product 9.
[Table 21]

(Evaluation)
Example 13
  For each of the hair gels prepared in the above-mentioned 12-a to 12-c, that is, the formulations 16, 17, 18, 19 and 20 of the present invention, performance evaluation of the following items was performed by 10 testers.
  The performance evaluation method uses a hair gel having a composition shown in the standard product (D) of Table 21 that does not contain cationic water-soluble polymer or amphoteric water-soluble polymer as a component, and a hair gel to be evaluated. The feeling of use is based on the standard product (D).
  ・ Easy to apply,
  ・ Feel after use
The values of 10 testers who were evaluated and evaluated by the method shown in Table 22 below were totaled. The results are shown in Table 24. In addition, in the standard product, the components (5) to (9) in Table 21 (D) are added to the stirring component (11), and after uniform dissolution, the component (10) is added and mixed until clear. Prepared.
Comparative Example 3
  For each of the hair gels prepared in 12-d and 12-e described above and comparative products 7, 8 and 9, performance evaluation was performed in the same manner as in Example 13, and the results are shown in Table 24.
[Table 22]

Example 14
  The set holding force was evaluated by the following method. A hair bundle having a length of 18 cm and a weight of 15 g is wetted with water, and the hair gel prepared in the above-mentioned 12-a to 12-c, that is, the formulations 16, 17, 18, 19, and 20 of the present invention are applied, and the rod ( It was wound around an outer diameter of 2 cm), and in that state, it was dried with a dryer (80 ° C.) and curled. After drying, the curled hair bundle was removed from the rod. The hair bundle was suspended in a constant temperature and humidity (20 ° C., 40% RH) atmosphere for 30 minutes, and the curl elongation was observed. Based on the degree of curl elongation, the set holding force was evaluated according to the evaluation criteria shown in Table 23 below. The results are shown in Table 24.
  The evaluation scale is as follows. The length immediately after removing the rod of the hair bundle wound around the rod and dried with a dryer (80 ° C.) in the same manner as described above except that the hair gel was not applied was defined as a holding power of 100%. Further, the rod was removed and left in an atmosphere of constant temperature and humidity (20 ° C., 40% RH) for 24 hours, and the length of the hair bundle in this state was set to 0% holding force.
[Table 23]

Comparative Example 4
  The hair gel prepared in the above 12-d and 12-e, that is, comparative products 7, 8 and 9, were subjected to performance evaluation in the same manner as in Example 14, and the results are shown in Table 24.
[Table 24]

  From the results shown in Table 24, the present invention also applies to a coating-type hair treatment composition.Used forSince the cation-modified alginic acid derivative has a film-forming property, it was confirmed that it can impart a set effect to the hair during drying and also has a good feel due to the conditioning effect obtained by cation-modification. On the other hand, in sample numbers 6 and 7, in which the cation charge amount is outside the range of 0.1 to 3.0 meq / g specified in the present invention, the evaluation as in the present invention in terms of ease of application and feel after use. Was not obtained.
  In addition, when compared with a cationic polymer (cation-modified hydroxyethyl cellulose, kachinal HC-100) as a conventional conditioning agent, there is a difference in the set holding power, and the setting effect is obtained by the film-forming property of the product of the present invention. Was confirmed. Furthermore, the present inventionUsed forBy using a cationically modified alginic acid derivative in combination with another cationic water-soluble polymer and / or an amphoteric water-soluble polymer, the present inventionUsed forIt was confirmed that the conditioning effect was improved without impairing the performance of the cation-modified alginic acid derivative.
(Formulation examples 7 to 10)
  Below, the suitable compounding example of this invention to application type hair treatment compositions, such as hair mist and hair mousse which require the setting effect and conditioning effect other than a hair gel and a hair gel, is shown.
[Table 25]

  A part of purified water was added to the product of the present invention and polyvinylpyrrolidone, glycerin, polyethylene glycol, and methyl paraoxybenzoate, and the mixture was heated and dissolved at 70 ° C. The other ingredients were dissolved in the remaining purified water and added with stirring.
[Table 26]

[Table 27]

[Table 28]

Hair color
(Preparation)
Example 15
15-a
  Using the cation-modified alginic acid derivatives of Sample Nos. 1 and 4 obtained in Examples 1 and 2, two-part oxidative hair dyes shown in (A) of Table 29 below were prepared. Two-component oxidative hair dyes containing 1 and 4 cation-modified alginic acid derivatives were designated as formulations 21 and 22 of the present invention. At the time of use, the first agent and the second agent of this two-component oxidative hair dye were mixed at a weight ratio of 1: 1 and applied to the hair.
15-b (Preparation of comparative product)
  In order to compare the effect of the cation-modified alginic acid derivative according to the present invention on the hair color with other cationic polymers, the present invention used in 15-a above.Used forIn place of the cation-modified alginic acid derivative, cation-modified hydroxyethyl cellulose (Catinal HC-100; manufactured by Toho Chemical Industry Co., Ltd.) having an average addition mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass is used. A two-component oxidative hair dye as shown in 29 comparative products (C) was prepared. In this way, a two-part oxidative hair dye containing cation-modified hydroxyethyl cellulose was used as Comparative Product 10. At the time of use, the first agent and the second agent of this two-component oxidative hair dye were mixed at a weight ratio of 1: 1 and applied to the hair.
[Table 29]

(Evaluation)
Example 16
  With respect to each of the two-part oxidative hair dyes prepared in the above 15-a, that is, the formulations 21 and 22 of the present invention, the performance evaluation of the following items was performed by 10 testers. The performance evaluation method uses a two-component oxidative hair dye having a composition shown in a standard product (B) in Table 29 that does not contain a cationic polymer as a component, and an oxidative hair dye to be evaluated, An equal volume mixture of the first and second agents was applied to the hair, allowed to stand at room temperature for 30 minutes, rinsed with running water at 40 ° C. for 3 minutes, and dried with a drier. The sliding property at the time of rinsing and the feeling after drying with a dryer, based on the standard product (B),
  ・ Slipperiness during rinsing
  -Feel after drying (moist feeling, elasticity (hair stiffness))
Were compared with each other, digitized by the method shown in Table 30 below, and the values of 10 testers who performed the evaluation were totaled. The evaluation results are shown in Table 31. The standard product (B) was prepared according to 15-a, and the first agent and the second agent were mixed at a weight ratio of 1: 1 and applied to the hair.
Comparative Example 5
  Performance evaluation was carried out in the same manner as in Example 16 for the two-component oxidative hair dye of Comparative Product 10 prepared in 15-b above, and the results are shown in Table 31.
[Table 30]

[Table 31]

  From the results in Table 31, the present inventionUsed forWhen a cation-modified alginic acid derivative is added to the hair dye, the conditioning effect on damaged hair improves slipperiness during rinsing, gives a good feeling of fingering, and gives a moist feeling after drying. It was done. Furthermore, the improvement of the stiffness of hair was recognized from the elasticity imparted to the damaged hair of the product of the present invention. Therefore, it was confirmed that it is excellent as a composition such as a hair dye.
  Furthermore, compared with the comparative product 10 containing other cationic polymers, both the formulations 21 and 22 of the product of the present invention have improved feeling after drying, and the present invention is also applied to damaged hair.Used forIt was confirmed that the cation-modified alginic acid derivative is excellent.
(Formulation examples 11 and 12)
  In the following, the present inventionUsed forA preferred formulation example using the conditioning effect and elasticity imparting effect on damaged hair of the cation-modified alginic acid derivative is shown.
[Table 32]

[Table 33]

Body cleaner
(Preparation)
[Example 17]
17-a
  Using the cation-modified alginic acid derivatives of Sample Nos. 1, 2 and 4 obtained in Examples 1 and 2, body detergents (body soaps) having the compositions shown in Table 34 (A) were prepared. The component (11) of (A) in Table 34 was heated to 60 ° C., and the component (1) was added and dissolved while stirring. After confirming the dissolution, the components (3) to (7) at 50 to 60 ° C. Was added with stirring to make it uniform, and components (8) to (10) were similarly added at 30 to 40 ° C. with stirring and mixed uniformly. Thus, body cleaners having the compositions shown in (A) of Table 34 were prepared, and the body cleaners containing the cation-modified alginic acid derivatives of Sample Nos. 1, 2 and 4 in Table 1 were sequentially prepared. Formulations 23, 24 and 25 were used.
[Table 34]

17-b (Preparation of comparative product)
  In order to compare the effect of the cation-modified alginic acid derivative used in the present invention on a body cleaning agent, sodium alginate (Duck Algin NSPH; manufactured by Kibun Food Chemifa Co., Ltd.), which is an unmodified alginic acid derivative, is shown in Table 34. A body cleaning agent having the composition shown in C) was prepared. The component (11) of (C) in Table 34 was heated to 60 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming the dissolution, components (3) to (7 ) Was added with stirring to make it uniform, and components (8) to (10) were similarly added at 30 to 40 ° C. with stirring and mixed uniformly. Thus, a body cleaner having the composition shown in (C) of Table 34 was prepared, and this was designated as Comparative Product 11.
17-c (Preparation of comparative product)
  Similarly, in order to compare the effect of the cation-modified alginic acid derivative used in the present invention on the body cleaning agent, cation-modified hydroxyethyl cellulose (Catinal HC-) having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass. 100: manufactured by Toho Chemical Co., Ltd.), a body cleaning agent having the composition shown in Table 34 (C) was prepared. The component (11) of (C) in Table 34 was heated to 60 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming the dissolution, components (3) to (7 ) Was added with stirring to make it uniform, and components (8) to (10) were similarly added at 30 to 40 ° C. with stirring and mixed uniformly. Thus, a body cleaner having the composition shown in (C) of Table 34 was prepared, and this was designated as Comparative Product 12.
(Evaluation)
Example 18
  The performance evaluation of the following items was carried out by 10 testers for each of the body cleansing agents 23, 24 and 25 of the product of the present invention obtained in the aforementioned 17-a.
  The performance evaluation method uses a body cleaning agent having a composition shown in the standard product (B) of Table 34 that does not contain a high molecular compound such as a cationic polymer as a component, and a body cleaning agent to be evaluated. And
  ・ The amount and quality of foam during use
  ・ Usage feeling during use (ease of rinsing, feeling of squeezing and slimming after rinsing),
  ・ Usage after use (after drying) (tiffness, smoothness, moistness),
In comparison with the comfort of the standard product (B), it was quantified by the methods shown in Tables 35 and 36 below, and the values of the 10 testers who performed the evaluation were totaled. The evaluation results are shown in Table 37. In addition, after heating the component (11) of the standard product (B) in Table 34 to 60 ° C., the standard product was added to the components (3) to (7) with stirring at 50 to 60 ° C. to make it uniform, and further 30 Ingredients at ~ 40 ° C (
8) to (10) were similarly added with stirring and mixed uniformly to prepare a body cleaning agent having the composition shown in (B) of Table 34 as a standard product for this evaluation.
Comparative Example 6
  The performance evaluation similar to Example 18 was performed about the cleaning agent for bodies of the comparative products 11 and 12 obtained by 17-b and 17-c mentioned above. These results are shown in Table 37.
[Table 35]

[Table 36]

  From the results in Table 37, the present inventionUsed forCation-modified alginic acid derivative improves body foaming, foam quality and feel when used in body cleaning agents, and eliminates the feeling of stickiness and gives a moist feeling after use. It was done.
Moreover, compared with the comparative product 11 containing an unmodified alginic acid derivative (sodium alginate), it was confirmed that adsorption to the skin increased due to cation modification, and the feeling during and after use was improved. Furthermore, compared with the conventional cation-modified hydroxyethyl cellulose (Comparative product 12) as a conditioning agent, foaming and foam quality are improved due to the difference in film-forming properties, and the stickiness, bulkiness, and feeling of stickiness are eliminated, and it is moist. It was confirmed that a feeling was obtained.
[Table 37]

(Formulation examples 13-17)
  In the following, the present inventionUsed forAn example of blending a skin cosmetic composition such as a body cleanser or a facial cleanser using the improvement in the feel of foam due to the film-forming property of the cation-modified alginic acid derivative and the improvement in the feel due to the conditioning effect is shown.
[Table 38]

A liquid body cleaning agent (body soap) is manufactured based on a conventional method.
[Table 39]

A liquid body cleaning agent (body soap) is manufactured based on a conventional method.
[Table 40]

A face wash is manufactured based on a conventional method.
[Table 41]

  The product of the present invention, glycerin, sorbitol, arginine, and fragrance are added to the purified water of Table 41 and dissolved and maintained at 70 ° C. (aqueous phase). In a vacuum emulsification pot, add coconut oil fatty acid potassium glutamate 25% solution, coconut oil fatty acid sodium taurine solution 30%, glyceryl monooleate, ceteares-60 myristyl glycol, disodium edetate, phenoxyethanol, and heat to 70 ° C. Dissolve. After dissolution is confirmed, a 30% solution of coconut oil fatty acid amidopropyl betaine, an aqueous phase maintained at 70 ° C., and ethylene glycol distearate are sequentially added and dissolved uniformly. After dissolution, the solution is cooled to 35 ° C., and water and pH are adjusted with purified water and a 10% aqueous citric acid solution.
[Table 42]

A face wash is manufactured based on a conventional method.
(Formulation examples 18-21)
  In the following, the present inventionUsed forAn example of blending after shave lotion and the like will be shown as another application example of utilizing the improvement in feel of the cation-modified alginic acid derivative with respect to the skin cosmetic composition.
[Table 43]

[Table 44]

  The product of the present invention was dissolved in purified water shown in Table 44, and glycerin, squalane and 1,3-butanediol were added to form an aqueous phase part. Next, the alcohol phase part prepared by adding polyoxyethylene (60) hydrogenated castor oil, polyoxyethylene (8) cetyl ether, octyldodecanol, vitamin acetate, methyl paraben and fragrance to ethyl alcohol is added to the aqueous phase part. And mixed. To this mixture, talc, yellow iron oxide, red iron oxide, and black iron oxide are added and dispersed to produce a makeup lotion.
[Table 45]

A foundation is manufactured based on a conventional method.
[Table 46]

A bath preparation is produced based on a conventional method.
  The present inventionUsed forWhen the cation-modified alginic acid derivative is blended in a cosmetic composition such as a hair treatment composition or a skin cosmetic composition, a uniform film is formed because of good film-forming properties, and foams such as foaming and foam quality are formed. Improved feel. In addition, when blended into a rinse-off hair treatment composition such as shampoo and rinse, after use, after drying, while giving a conditioning effect equivalent to or better than the cationic polymer used as a conventional conditioning agent to the hair after use Gives the elasticity of hair obtained by having a film-forming property, and gives the firmness of the hair. When blended in an application-type hair treatment composition such as a hair gel, it is used as a conventional conditioning agent. A conditioning effect equal to or better than that of the cationic polymer to be obtained and a set effect obtained by having a film-forming property. Furthermore, the present inventionUsed forWhen a cation-modified alginic acid derivative is blended in a skin cosmetic composition such as a body cleanser, it eliminates stickiness and firmness and gives a moist feeling. Therefore, it is possible to provide a cosmetic composition that is more comfortable to use than conventional products.

Claims (10)

Cation-modified polysaccharide in which a part of the hydroxyl group contained in the alginic acid derivative which is a polymer in which uronic acid units are bonded by 1,4 glycosidic bonds is substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1) A cosmetic composition containing a cation-modified alginic acid derivative having a cation charge amount derived from the quaternary nitrogen-containing group of 0.1 to 3.0 meq / g.

(In the formula, R ₁ and R ₂ each represent an alkyl group having 1 to ₃ carbon atoms, R ₃ represents an alkyl group having 1 to 24 carbon atoms, and X ⁻ represents an anion. N is n = 0 or n = 1 to 30 and when n = 1 to 30, (R ₄ O) _n is a polymer residue of alkylene oxide having 2 to 4 carbon atoms, and a polyalkylene glycol chain composed of a single alkylene oxide and (Or a polyalkylene glycol chain composed of two or more alkylene oxides) The alginic acid derivative, which is a polymer in which the uronic acid units are linked by 1,4 glycosidic bonds, is composed of two types of uronic acids, L-guluronic acid and D-mannuronic acid, contained in brown algae (scientific name: Phaeophyceae) in seaweeds. the cosmetic composition of claim 1 wherein the natural polysaccharide derivatives. The cosmetic composition according to claim 1 or 2, wherein the cation modification of the cation-modified alginic acid derivative is performed using a glycidyl trialkyl ammonium salt or a 3-halogeno-2-hydroxypropyl trialkyl ammonium salt. The cation modification of the cation-modified alginic acid derivative is carried out by adding an alkylene oxide having 2 to 4 carbon atoms to a part of the hydroxyl group contained in the alginic acid derivative, followed by glycidyl trialkylammonium salt or 3-halogeno- The cosmetic composition according to claim 1 or 2 , wherein the cosmetic composition is made using a 2-hydroxypropyltrialkylammonium salt. The cosmetic composition according to any one of claims 1 to 4 , wherein the cation-modified alginic acid derivative is an alginate such as a sodium salt, a potassium salt, a calcium salt, or a magnesium salt. The cosmetic composition according to any one of claims 1 to 5 , wherein the content of the cation-modified alginic acid derivative is 0.05 to 5% by mass, based on 100% by mass of the entire composition. Further, other cationic water-soluble polymer and / or amphoteric water-soluble polymer, the total composition as 100 mass%, either one of claims 1 to 6, characterized in that it contains more than 5 wt% 1 The cosmetic composition according to Item. The cosmetic composition according to any one of claims 1 to 7 , further comprising an amidoamine compound, a neutralizing agent such as an organic acid and / or an inorganic acid, and a higher fatty acid and / or a higher alcohol. object. The cosmetic composition according to any one of claims 1 to 8 , further comprising silicone and / or a silicone derivative. The cosmetic composition according to any one of claims 1 to 9 , wherein the cosmetic composition is a hair treatment composition.