JP4379675B2 - Cation-modified polysaccharide and composition containing the substance - Google Patents

Description

（式中Ｒ₁、Ｒ₂は各々炭素数１〜３個のアルキル基、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の時、（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。）
【００１１】
ここで、本明細書で用いられる「熱ゲル化多糖類」とは、約６０℃の加熱温度でゲル化する高分子多糖類を意味する。本発明で用いられる熱ゲル化多糖類は、例えばβ−１，３−グルカン、β−１，３−キシラン、熱凝固性デンプンであり、これらの中で好ましくはβ−1，３−グルカン、β−1，３−キシランであり、さらにより好ましくは容易に入手可能である商品名「カードラン」(武田薬品工業株式会社)である。このカードランはβ−1，３−グルカンの一種であり、微生物Agrobacterium biovar 1によってブドウ糖から生成され、その構成糖はＤ−グルコースのみであり、そのグルコシド結合の９９％以上がβ−1，３結合である。カードラン以外のβ−1，３グルカンとしては、例えばシゾフィラン、スクレログルカン、スクレロタン、レンチナン、パラミロン、カロース、ラミナラン等をマイルドスミス分解（polym.J.13(12)1135-1143(1981)参照）などの方法で処理することで、カードランと同様の性質を持つ多糖類が得られる。これらのβ−1，３−グルカンは水に不溶であるが、水中に分散させた後、加熱することにより分子間水素結合により三重螺旋構造をとり、弾力性のあるゲルを形成することが知られている。
【００１２】
本発明のカチオン変性多糖類は熱ゲル化性多糖類をカチオン変性することにより、その水分散性を向上させ、シャンプー、リンス、ボディ用洗浄剤等の化粧料組成物への配合を容易にしている。さらに、水分散性の向上による均一な膜形成及び、カチオン性にすることによる吸着性向上によって、より強力なセット効果が得られる。また均一な膜形成は、シャンプー、ボディ用洗浄剤等の泡質を改善する。
【００１３】
本発明によるカチオン変性は、熱ゲル化性多糖類に第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、熱ゲル化性多糖類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のカチオン変性多糖類を製造することができる。
【００１４】
本発明で熱ゲル化性多糖類中に導入する上記化学式(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、エチル及びプロピルが挙げられ、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、デシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル、ドコシル等が挙げられる。Ｒ₄Ｏの具体例としては、エトキシ、プロポキシ及びブトキシが挙げられる。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。
【００１５】
本発明のカチオン変性多糖類は化粧料組成物の配合成分として優れたものである。例えば、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とセット効果の両方を与え、また、皮膚化粧料組成物、例えばボディ用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しない。
従って、本発明はまた、前記本発明のカチオン変性多糖類を配合したこれらの化粧料組成物にも関する。
【００１６】
本発明のカチオン変性多糖類の４級窒素含有基由来のカチオン電荷量は、０．５〜３．５meq/gであるが、より好ましくは１．５〜２．０meq/gである。カチオン電荷量が０．５meq/g未満では、カチオン変性多糖類の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、カチオン電荷量が３．５meq/gを越えると、そのようなカチオン変性多糖類を配合した毛髪処理用組成物を使用しても、熱による乾燥時に毛髪にセット効果を与えられないばかりか、使用時にべたつき感、ぬるつき感を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い。
【００１７】
なお、カチオン変性多糖類の４級窒素含有基由来のカチオン電荷量とは、カチオン変性多糖類１ｇ当たりに含まれる化学式（１）で示された４級窒素含有基の当量数である。通常は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熱ゲル化性多糖類中には、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のカチオン変性多糖類中の窒素分から、本発明で用いる熱ゲル化性多糖類由来の窒素分を引いた値が、４級窒素含有基由来の窒素分となる。カードランを例に取り具体的に説明すると、化学式（１）で示された４級窒素含有基のＲ₁、Ｒ₂、Ｒ₃はメチル、Ｘ^-は塩素イオン、ｎは、n=0の４級窒素含有基でカードラン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、１．６０％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カードラン中には、通常窒素分を０．４０％前後含有している。
【数１】

【００１８】
また本発明のカチオン変性多糖類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、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ごわつき感、ぬるつき感が生じ、使用感が悪くなる傾向がある。
【００１９】
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多糖類の毛髪に対する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、カチオン変性多糖類の示す毛髪に対するセット効果の付与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。
【００２０】
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。
【００２１】
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。
【００２２】
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。
【００２３】
上述のように、本発明のカチオン変性多糖類を公知の処方により処方系内に所要量配合することで、本発明の毛髪処理用組成物や皮膚化粧料組成物が得られるが、毛髪処理用組成物や皮膚化粧料組成物中の他の成分は特に限定されず、毛髪処理用組成物や皮膚化粧料組成物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。
【００２４】
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）化メチルタウリン塩、アシル（炭素数８〜２４）化タウリン塩、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。
【００２５】
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。
【００２６】
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）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。
【００２７】
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。
【００２８】
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。
【００２９】
さらに、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）、アクリルアミドメチルプロパンスルホン酸誘導体（ポリアクリルアミドメチルプロパンスルホン酸及びその塩、アクリルアミドメチルプロパンスルホン酸とアクリルアミド、ジメチルアクリルアミド、ビニルピロリドン等との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、会合性アニオンポリマー（疎水変性アクリレート・メタクリル酸共重合体及びその塩、疎水変性メタクリレート・メタクリル酸共重合体及びその塩、疎水変性アクリレート・メタクリル酸・アクリルアミド共重合体及びその塩等）、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。
【００３０】
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）、会合性ノニオンポリマー（疎水変性ポリエーテルウレタン、疎水変性セルロース誘導体等）、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。
【００３１】
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の有機酸及び／または無機酸と、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、ヌルつきを生じ、使用感が悪くなる。また、本発明品のセット効果も十分に発揮されなくなる。
【００３２】
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、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、ジプロピレングリコール、ソルビトール、マルチトール、１，３−ブチレングリコール、ヒアルロン酸Na等）、エステル類（ミリスチン酸イソプロピル、２−エチルヘキサン酸セチル等）、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等）、高級アルコール、高級脂肪酸（ラウリン酸、ステアリン酸、イソステアリン酸等）、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）、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、香料、起泡増進剤等が挙げられる。
【００３３】
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、ヘアジェル、ヘアクリーム、ヘアワックス、ヘアローション、ヘアフォーム、ヘアミスト、ヘアリキッド等が挙げられ、いずれも、本発明のカチオン変性多糖類のコンディショニング効果とセット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、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。
その他、毛髪と同様に本発明のケラチンに対するコンディショニング効果、セット効果を利用して、まつげ用化粧料（マスカラ）等への応用も可能である。
【００３４】
【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。
【００３５】
［カチオン変性多糖類の製造］
実施例１
カードラン １６２ｇ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１２．０ｇを添加した。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１００ｇを加え、加温し５０℃で３時間反応させた。反応終了後３５％塩酸１５．０ｇを６０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８００ｍｌ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多糖類のカチオン電荷量は０．９５meq／ｇであった。この結果を表１に示した（表１中、試料番号１）
【００３６】
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多糖類を合成した。この結果を表１中に示した（表１中、試料番号２、３）。
【００３７】
実施例２
カードラン １６２ｇを、５０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５７．５ｇを添加した。次に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１８６ｇを加え、加温し５０℃で３時間反応させた。反応終了後３５％塩酸１５．０ｇ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８００ｍｌ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多糖類のカチオン電荷量は０．６５meq／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)。
【００３８】
実施例３
β‐１，３‐キシラン １３１ｇ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１２．０ｇを添加した。次に８０質量％GTA水溶液１００ｇを加え、加温し５０℃で３時間反応させた。反応終了後３５％塩酸１５．０ｇを６０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８００ｍｌ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多糖類のカチオン電荷量は０．８９meq／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）
【００３９】
実施例４
加圧密閉容器内でカードラン １６２ｇ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１２．０ｇ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２４０ｇ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１５０ｇを加え、５０℃で３時間反応させる。反応終了後３５％塩酸１５．０ｇを６０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８００ｍｌ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多糖類のカチオン電荷量は１．０５meq／ｇであった。この結果を表１に示した（表１中、試料番号６）
【００４０】
実施例５
シゾフィランからマイルドスミス分解により側鎖を間引いたβ−1，３−グルカンを用い、実施例１の方法に準じてカチオン変性多糖類を合成した。この結果を表１中に示した。（表１中、試料番号７）
【００４１】
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多糖類を合成した。この結果を表１中に示した（表１中、試料番号８、９）。
【００４２】
【表１】

【００４３】
［カチオン変性多糖類を配合した各化粧料の製造とその評価］
実施例６ セット効果（その１）
カチオン変性した熱ゲル化性多糖類の毛髪に対するセット効果を以下の方法で確認した。測定方法は、日本化粧品技術者会誌、第３３巻、第２号、１１９〜１２７（１９９９）に記載されている方法を準用した。具体的には
１．０ｇの毛髪ストランド（全長１６０ｍｍ）に、０．４０ｇの試験溶液（０．５％水溶液）を塗布し、櫛で整えた後、カーラー（内径２０ｍｍ）に巻いた。８０℃の恒温槽内で３０分間乾燥させた後、恒温恒湿（２０℃、５８％ＲＨ）雰囲気中に１時間放置した。その後カールした毛髪ストランドのみを取り出し、レオメーター（不動工業製）にて圧縮し、その際にかかる押しつぶし時の応力を測定した。同試験を２回繰り返し、２回の平均値を本試験の測定値とし、結果を表２に示した。表２の数値は、数値が大きいほどセット力が大きいことを示す。
【００４４】
【表２】

【００４５】
表２の結果から、本発明のカチオン変性した熱ゲル化性多糖類は、未変性の熱ゲル化性多糖類であるカードランに比べてセット力が増加していることが証明された。これは、カチオン変性により熱ゲル化性多糖類の水分散性が向上して、毛髪表面に均一に塗布されるので、均一な膜形成が得られた結果である。よって、本発明品を塗布型の毛髪処理用化粧料に配合した場合、未変性の熱ゲル化性多糖類を含むものよりもセット効果が期待できる。
【００４６】
実施例７ セット効果（その２）
カチオン変性した熱ゲル化性多糖類の毛髪に対するセット効果を洗い流し製品で確認した。
（ヘアシャンプーの調製）
７−ａ
実施例１、２及び４で得たカチオン変性多糖類を用いて表３中の(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８０℃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、２、４及び６に対応するカチオン変性多糖類から調製したものを順に本発明品の処方Ｓ１〜Ｓ４とした。
【００４７】
７−ｂ
実施例１で得た試料番号２のカチオン変性多糖類を用い、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中の(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８０℃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。
【００４８】
７−ｃ
実施例１で得た試料番号２のカチオン変性多糖類を用い、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中の(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８０℃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、本発明品の処方Ｓ６とした。
【００４９】
７−ｄ
実施例１で得た試料番号２のカチオン変性多糖類を用い、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８０℃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。
【００５０】
７−ｅ（比較品の調製）
本発明で用いるカチオン変性多糖類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９のカチオン変性多糖類を用いて表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８０℃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、比較品Ｃ１とした。
【００５１】
７−ｆ（比較品の調製）
本発明で用いるカチオン変性多糖類のシャンプーにおける効果を比較するため、上記７−ｅで使用した試料番号９の代わりに同じ配合割合の未変性熱ゲル化性多糖類（カードラン）を使用する他は表３の比較品(Ｅ)に示した組成のシャンプーを同様に調製しこれを比較品Ｃ２とした。
【００５２】
【表３】

【００５３】
（評価）
上記７−ａ〜７−ｆで調製した各々の本発明品の処方Ｓ１〜Ｓ６のシャンプーと比較品Ｃ１およびＣ２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８０℃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４】

【００５４】
表４の結果から、熱ゲル化性多糖類をカチオン変性した試料番号１、２、４、６のカチオン変性多糖類を含む本発明品のシャンプーはブランクと比較すると曲げ剛性（Ｂ値）、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９のカチオン変性多糖類を含む比較品Ｃ１にもみられた。一方、塗布型の化粧料ではセット効果を示す未変性の熱ゲル化性多糖類はブランクと同じ結果となった。これは未変性の熱ゲル化性多糖類は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、該熱ゲル化性多糖類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、熱ゲル化性多糖類を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、シャンプーのような洗い流し製品に於いてもセット効果が得られる。その結果、曲げ剛性、ヒステリシス値の向上、さらに、手による感触面では毛髪へコシを与える等の効果が得られた。よって、本発明のカチオン変性多糖類はシャンプー、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ことが判った。
【００５５】
また、本発明のカチオン変性多糖類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曲げ剛性（Ｂ値）、ヒステリシス幅（２ＨＢ）に差は無く、併用によってもその効果は失われないことが確認された。
【００５６】
実施例８ 泡立ち試験
本発明のカチオン変性した熱ゲル化性多糖類（表１の試料番号１および２）を表５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、他の水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）、および未変性熱ゲル化性多糖類としてカードランを含む化粧料組成物をそれぞれ表５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５の処方の各化粧料組成物を、それぞれ実施例７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３％水溶液４００ｍｌ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６に示した。
【００５７】
【表５】

【表６】

【００５８】
表６の結果から、本発明のカチオン変性した熱ゲル化性多糖類は未変性の熱ゲル化性多糖類に比べて水分散性が向上し、泡立ちが優れることが証明された。また、本発明品は他のカチオン変性ポリマー（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、セット効果で見られた結果と同様、膜特性においても、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かめられた。よって、本発明品はシャンプー、ボディ洗浄料、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、泡立ちの改善が期待できる。
【００５９】
以下、カチオン変性した熱ゲル化性多糖類により得られるセット効果、泡立ちの改善及びコンディショニング効果を、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。
【００６０】
ヘアシャンプー
（調製）
実施例９
９−ａ
実施例１、２、３、４及び５で得た本発明の試料番号１〜７のカチオン変性多糖類を用いて表７中の(Ａ)に示した組成のシャンプーを調製した。表７中の（A）の成分(14)を８０℃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１〜７に対応するカチオン変性多糖類を配合した表７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１〜７を順に本発明品の処方１〜７とした。
【００６１】
９−ｂ
実施例１で得た試料番号２のカチオン変性多糖類を用い、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７中の(Ｂ)に示した組成のシャンプーを調製した。表７中の（B）の成分(14)を８０℃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８とした。
【００６２】
９−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７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９とした。
【００６３】
９−ｄ
実施例１で得た試料番号２のカチオン変性多糖類を用い、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７中の(Ｄ)に示した組成のシャンプーを調製した。表７中の（Ｄ）の成分(14)を８０℃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１０とした。
【００６４】
９−ｅ
実施例１で得た試料番号２のカチオン変性多糖類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７の(E)に示した組成のシャンプーを調製した。表７中の（E）の成分(14)を８０℃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１１とした。
【００６５】
９−ｆ（比較品の調製）
本発明によるカチオン変性多糖類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多糖類、すなわち表１中の試料番号８及び９を用いて表７の比較品(G)に示した組成のシャンプーを調製した。表７中の比較品(G)の成分(14)を８０℃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。
【００６６】
９−ｇ（比較品の調製）
さらに効果を比較する為、上記９−ｅにおけるカチオン変性多糖類の代わりに、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７の比較品（G）に示した組成のシャンプーを９−ｆと同様に調製し比較品３とした。
【００６７】
【表７】

【００６８】
（評価）
実施例１０
実施例９−ａないし９−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１〜１１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２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、自然乾燥後の使用感を、標準品（Ｆ）を基準にして、
・洗髪使用時におけるコンディショニング効果の有無（櫛通り感、髪の手触り、及びすすぎ後のきしみ感など）、
・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、髪の手触りなど）、毛髪のコシの強さ
について比較し、下記表８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９に示した。尚、上記標準品（Ｆ）は表７の標準品（Ｆ）中の成分(14)を８０℃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。
【００６９】
【表８】

【００７０】
比較例１
９−ｆ及び９−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１０と同様に性能評価を実施し、その結果を表９中に示した。
【００７１】
【表９】

【００７２】
表９の結果から、カチオン変性多糖類のカチオン電荷量が０．５〜３．５meq/gにある本発明のカチオン変性多糖類は、シャンプーに用いた場合コンディショニング効果が優れるとともに、シャンプー等の洗い流し製品においても、セット効果によるコシの強さが確認された。
【００７３】
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、コンディショニング効果については使用時及び使用後で同等以上であるが、使用後において従来のコンディショニング剤には無い熱ゲル化性多糖類のもつセット効果による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、本発明のカチオン変性多糖類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。
【００７４】
実施例１１
洗い流し製品に於けるセット効果を更に検証するため、９−ａで得た本発明品の処方１〜４と、９−ｂで得た本発明品の処方８、ならびに９−ｃで得た本発明品の処方１０よりなるシャンプーで毛髪を洗浄後、恒温恒湿（２０℃、４０％ＲＨ）雰囲気中に２４時間放置し、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）にて性能評価した。その結果を純曲げ試験結果として表１０に示した。
【００７５】
比較例２
９−ｆで得た比較品１及び２ならびに９−ｇで得た比較品３について、実施例１１と同様の性能評価を行い、その結果を表１０中に示した。
【００７６】
【表１０】

【００７７】
表１０の結果から、従来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、本発明のカチオン変性多糖類を含むシャンプーでは、曲げ剛性、ヒステリシス値の向上が見られた。従って、シャンプー等の洗い流し製品においても、毛髪に対して、熱ゲル化性多糖類をカチオン変性した本発明品のセット効果によるコシの強さを付与できることが、確認された。さらに、処方８および９の結果から明らかなよう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との併用によっても、その効果は失われないことが確認された。
【００７８】
（配合例１〜５）
以下に、シャンプーへの本発明の好適な配合例を示す。
【表１１】

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。
【００７９】
【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。
【００８０】
【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。
【００８１】
【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。
【００８２】
【表１５】

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。
【００８３】
ヘアリンス
（調製）
実施例１２
１２−ａ
実施例１、２で得られた試料番号１〜４のカチオン変性多糖類を用いて下記表１６の（Ａ）に示した、アミドアミン化合物の有機酸塩（ステアリン酸ジメチルアミノプロピルアミド・クエン酸塩）と高級アルコール（セタノール）を含む組成のリンスを調製した。表１６中の（A）の成分(4)〜(9)を80℃に加熱し、攪拌して均一にした溶液に、予め成分(11)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(10)を加えて均一に混合した。こうして表１６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のカチオン変性多糖類を含むリンスを順に本発明品の処方１２〜１５とした。
【００８４】
１２−ｂ
実施例１で得た試料番号２のカチオン変性多糖類を用い、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１６の(Ｂ)に示した組成のリンスを調製した。表１６の(B)の成分(4)〜(9)を80℃に加熱し、攪拌して均一にした溶液に、予め成分(11)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(10)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１６とした。
【００８５】
１２−ｃ
さらに同様に試料番号２のカチオン性多糖類と、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１６の（C）に示した組成のリンスを調製し、本発明品の処方１７とした。
【００８６】
１２−ｄ（比較品の調製）
本発明のカチオン変性多糖類の、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多糖類、すなわち表１中の試料番号８及び９を用いて表１６の比較品(E)に示した組成のリンスを調製した。表１６中の比較品（E）の成分(4)〜(9)を80℃に加熱し、攪拌して均一にした溶液に、予め成分(11)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(10)を加えて均一に混合し、試料番号８を含むリンスを比較品４、試料番号９を含むリンスを比較品５とした。
【００８７】
１２−ｅ（比較品の調製）
さらに本発明のカチオン変性多糖類の効果を比較する為、前記試料番号８及び９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)製）について表１６の比較品（E）に示した組成のリンスを１２−ｄと同様に調製し、得られたリンスを比較品６とした。
【００８８】
【表１６】

【００８９】
（評価）
実施例１３
１２−ａないし１２−ｃで調製した各々のリンス、すなわち本発明品の処方１２〜１７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１０の標準品（D）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（８０℃）による乾燥後の使用感を、標準品（D）を基準にして、
・乾いた髪のコンディション効果の有無（櫛通り感、髪の手触りなど）、
・毛髪のコシの強さ
について比較し、それを下記表１７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１８に示した。尚、上記標準品（D）は表１６の標準品（D）中の成分(4)〜(9)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(11)を攪拌しながら加えた後、冷却しながら成分(10)を加えて均一に混合し調製した。
【００９０】
比較例３
１２−ｄ及び１２−ｅで調製した各々のリンス、すなわち比較品４〜６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１８中に示した。
【００９１】
【表１７】

【００９２】
【表１８】

【００９３】
表１８の結果から、カチオン電荷量が０．５〜３．５meq/gにある本発明のカチオン変性多糖類を含み、さらにアミドアミン化合物の有機酸塩（ステアリン酸ジメチルアミノプロピルアミド・クエン酸塩）と高級アルコール（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、セット効果によるコシの強さが得られる事が確認された。
【００９４】
本発明のカチオン変性多糖類の性能は、コンディショニング効果においては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、使用時及び使用後は同等以上であり、さらに使用後には熱ゲル化性多糖類の有するセット効果によるコシの強さが得られた。また、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、カチオン変性多糖類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。
【００９５】
（配合例６〜８）
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組成物への、本発明の好適な配合例を示す。
【表１９】

表１９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、グリセリン、色素を加え７０℃に保ち（水相）、他の成分を混合し、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。
【００９６】
【表２０】

表２０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、Ｌ−グルタミン酸、グリセリン、フェノキシエタノール、法定色素を加え７０℃に保ち（水相）、他の成分を混合し、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。
【００９７】
【表２１】

表２１の精製水に、本発明品、Ｎ−（３−アルキル（１２，１４）オキシ−２−ヒドロキシプロピル）−Ｌ−アルギニン塩酸塩、ステアリン酸ジメチルアミノプロピルアミド、クエン酸、グリセリン、フェノキシエタノール、安息香酸ナトリウム、を加え７０℃に保ち（水相）、他の成分を混合し、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。
【００９８】
ヘアジェル
（調製）
実施例１４
１４−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のカチオン変性多糖類を用いて表２２の（Ａ）に示した組成のヘアジェルを調製した。表２２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２２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のカチオン変性多糖類を含むヘアジェルをそれぞれ本発明品の処方１８、１９及び２０とした。
【００９９】
１４−ｂ
実施例１で得た試料番号２のカチオン変性多糖類を用い、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２２の(B)に示した組成のヘアジェルを調製した。表２２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２２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２１とした。
【０１００】
１４−ｃ
実施例１で得た試料番号２のカチオン変性多糖類を用い、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２２の(Ｃ)に示した組成のヘアジェルを調製した。表２２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２２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２２とした
【０１０１】
１４−ｄ（比較品の調製）
本発明で用いるカチオン変性多糖類のヘアジェルにおける効果を比較するため、例１で得たカチオン変性多糖類、すなわち表１中の試料番号８及び９を用いて表２２の比較品(Ｅ)に示した組成のヘアジェルを調製した。表２２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、試料番号８のカチオン変性多糖類を含むヘアジェルを比較品７、試料番号９のカチオン変性多糖類を含むヘアジェルを比較品８とした。
【０１０２】
１４−ｅ（比較品の調製）
さらに効果を比較するため、１４−ｄで使用したカチオン変性多糖類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２２の比較品（Ｅ）に示した組成のヘアジェルを調製し、それを比較品９とした。
【０１０３】
【表２２】

【０１０４】
（評価）
実施例１５
上記１４−ａ〜１４−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１８、１９、２０、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、成分にカチオン性水溶性高分子や、両性水溶性高分子等を含まない表２２の標準品（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２３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２５に示した。尚、標準品は表２２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。
【０１０５】
比較例４
上記１４−ｄおよび１４−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１５と同様に性能評価を実施し、その結果を表２５中に示した。
【０１０６】
【表２３】

【０１０７】
実施例１６
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、実施例１４−ａ〜１４−ｃで調製したヘアジェル、すなわち本発明品の処方１８、１９、２０、２１及び２２を塗布し、ロッド（外径２ｃｍ）に巻き、その状態でドライヤー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２４の評価基準に従って評価し、その結果を表２５中に示した。
【０１０８】
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。
【０１０９】
【表２４】

【０１１０】
比較例５
１４−ｄおよび１４−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１６と同様に性能評価を実施し、その結果を表２５中に示した。
【０１１１】
【表２５】

【０１１２】
表２５の結果から、本発明のカチオン変性多糖類は熱による乾燥時に、毛髪に対してセット効果を付与できるとともに、さらに水分散性の向上により使用時に塗布しやすく、また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０．５〜３．５meq/gの範囲外にある、試料番号８及び９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、本発明のカチオン変性多糖類と、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、本発明のカチオン変性多糖類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。
【０１１３】
（配合例９〜１３）
以下に、ヘアジェル及びヘアジェル以外のセット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２６】

本発明品とグリセリン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。
【０１１４】
【表２７】

【０１１５】
【表２８】

【０１１６】
【表２９】

【０１１７】
【表３０】

【０１１８】
ボディ用洗浄剤
（調製）
実施例１７
１７−ａ
実施例１、２で得られた試料番号２及び４のカチオン変性多糖類を用いて表３１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３１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３１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２及び４のカチオン変性多糖類を含むものを各々本発明品の処方２３及び２４とした。
【０１１９】
１７−ｂ（比較品の調製）
本発明で用いるカチオン変性多糖類の、ボディ用洗浄剤におけるその効果を比較するため、未変性の熱ゲル化性多糖類であるカードランについて表３１の(Ｃ)に示した組成のボディ用洗浄剤を調製した。表３１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３１の（Ｃ）に示した組成のボディ用洗浄剤を調製し、比較品１０とした。
【０１２０】
１７−ｃ（比較品の調製）
同様に、本発明で用いるカチオン変性多糖類の、ボディ用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：東邦化学工業社製）について表３１の(Ｃ)に示した組成のボディ用洗浄剤を調製した。表３１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３１の（Ｃ）に示した組成のボディ用洗浄剤を調製し、それを比較品１１とした。
【０１２１】
【表３１】

【０１２２】
（評価）
実施例１８
実施例１７−ａで得た本発明品の処方２３及び２４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３１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ボディ用洗浄剤とを使用し、
・ 使用時の泡の量及び質、
・ すすぎ易さ、すすぎ後のつっぱり感及びぬめり感、
・ 乾いた後のつっぱり感、滑らかさ感、しっとり感
について、標準品（Ｂ）の使い心地について比較し、それを下記表３２及び表３３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３４に示した。なお、標準品は表３１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、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、表３１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。
【０１２３】
【表３２】

【０１２４】
【表３３】

【０１２５】
比較例６
１７−ｂ及び１７−ｃで得た比較品１０および１１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３４中に示した。
【０１２６】
【表３４】

【０１２７】
表３４の結果から、本発明のカチオン変性多糖類を含む処方は比較品に比べて、ボディ用洗浄剤の泡立ち、泡質及び使用感が改善される事が確認された。
【０１２８】
また、未変性の熱ゲル化性多糖類と比較すると、本発明のカチオン変性多糖類を用いる場合、水分散性が向上することにより、均一な処方組成物が得られる為に、使用時には皮膚に対し均一に塗布されることで感触の改善が認められた。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と比較すると、熱ゲル化性多糖類の持つセット効果に見られる柔軟な膜特性と、カチオン変性する事によって得られる水分散性の向上による均一な膜形成により、泡の膜質が改善され、泡立ち、泡質が改善される事が確認できた。また、本発明のカチオン変性多糖類の有するコンディショニング効果により、ぬめり感が少なく、すすぎ易く、滑らかな感触が得られることが確認できた。
【０１２９】
（配合例１４）
以下に、本発明のコンディショニング効果と泡の改善を利用した、ボディ用洗浄剤の配合例を示す。
【表３５】

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。
【０１３０】
（配合例１５−１６）
以下に、本発明のカチオン変性多糖類のケラチンに対するコンディショニング効果とセット効果を利用する、他の適用例としてマスカラの配合例を示す。
【表３６】

【０１３１】
【表３７】

【０１３２】
【発明の効果】
本発明のカチオン変性多糖類は、シャンプー・リンスなど毛髪処理用組成物に配合した場合、使用時には毛髪に対し、従来のカチオン変性ヒドロキシエチルセルロースと同等のコンディショニング効果を与えつつ、乾燥後にはコシを与え、尚且つ熱による乾燥後、毛髪に対しセット効果を与えることができる。さらに、本発明のカチオン変性多糖類を、ボディ用洗浄剤などの皮膚化粧料組成物に配合した場合、泡の改善とコンディショニング効果による、豊かな泡立ちと、しっとり感、滑らかさ感などの使用感の改善を与える。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できる。[0001]
BACKGROUND OF THE INVENTION
The present invention is a cosmetic composition, particularly a hair treatment composition, a cation-modified polysaccharide that improves foaming and provides a conditioning effect and a set effect when blended with a cosmetic composition, particularly a hair treatment composition. Relates to the composition.
[0002]
[Prior art]
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, a water-soluble polymer obtained by introducing a quaternary nitrogen-containing group into a polysaccharide such as a cellulose derivative, guar gum or starch, a dialkyl diallylammonium salt polymer, or the like is used. For example, Patent Document 1 discloses that a cation-modified cellulose derivative into which a quaternary nitrogen-containing group is introduced is used for shampoos and hair cosmetics. Furthermore, Patent Document 2 uses cation-modified starch introduced with quaternary nitrogen-containing groups, and Patent Document 3 uses cation-modified guar gum introduced with quaternary nitrogen-containing groups in hair care products such as shampoos and rinses. It is shown to do. Patent Document 4 uses a cation-modified cellulose derivative that has good adhesion to hair and also functions as a set component, and further has a high molecular weight dimethylsiloxane that can give smoothness and gloss, and a specific that can give moist feeling. A hair cosmetic containing a sugar alcohol or the like is shown. Furthermore, Patent Document 5 is characterized by containing a polyglycerin-modified silicone compound that exhibits a setting effect when blended in a hair conditioner such as mousse while exerting a conditioning effect when blended in a shampoo, rinse, or conditioner. Hair cosmetics to be shown.
[0003]
Further, in the case of a hair treatment composition exhibiting a set effect, a polymer having a set effect is blended, and a hair styling agent using a thermogelling polymer substance as one of them is a non-patent document. 1 and Patent Document 6. However, in the above use examples, there is no description of an example in which a cation-modified polysaccharide as in the present invention is used in a hair treatment composition and gives both an excellent conditioning effect and a setting effect when dried by heat.
[0004]
On the other hand, in Patent Document 7, a cationized derivative obtained by cationizing curdlan with guar gum, locust bean gum, agar, alginic acid or the like as one of polysaccharides is a liquid detergent composition in a spray container as a dispersant. Patent Document 8 shows that the cationized derivative is used as a thickener in cleaning detergent-impregnated sheets. Patent Document 9 discloses the use of these as a dispersant in a solid particle dispersion cleaning composition. However, there is no description in the above use examples that the cation-modified polysaccharide of the present invention is used in a hair treatment composition and that it provides an excellent conditioning effect and a setting effect when dried by heat.
[0005]
On the other hand, in the case of a skin cosmetic composition, soaps and anionic surfactants are generally used, but when washing, the oily and fat components of the skin are removed more than necessary, and the skin feels tight. There is also a problem. From the effect of eliminating such inconvenience and imparting a moist feeling, a skin cosmetic composition such as a body cleaning agent is blended with a conditioning agent such as a cationic polymer and a humectant such as glycerin.
[0006]
Furthermore, Patent Document 10 discloses that a shampoo composition containing a copolymer of a dialkyl diallylammonium salt and a cellulose derivative having a quaternary nitrogen-containing group introduced provides a smooth foam feel during shampooing, It has been shown to give the hair a smooth and smooth finger passage. In addition, since a smooth foam quality can be obtained by blending these cationic polymers, they are also blended into skin cosmetic compositions such as body detergents.
[0007]
[Patent Document 1]
Japanese Examined Patent Publication No. 47-20635 (Page 5)
[Patent Document 2]
Japanese Patent Publication No. 60-42761 (page 1-9)
[Patent Document 3]
Japanese Patent Publication No. 7-17491 (page 1-4)
[Patent Document 4]
JP-A-5-112437 (page 1-3)
[Patent Document 5]
JP-A-10-316540 (page 2-3)
[Patent Document 6]
JP 2001-342117 A (page 2-4)
[Patent Document 7]
JP 10-121099 (pages 4-5 and 9)
[Patent Document 8]
JP-A-10-287900 (pages 3 and 6)
[Patent Document 9]
JP-A-10-88196 (2nd and 5th pages)
[Patent Document 10]
Japanese Patent Laid-Open No. 1-128914 (page 1-3)
[Non-Patent Document 1]
Proceedings of the 47th SCCJ Research Discussion Meeting November 21, 2000 (pages 28-30)
[0008]
[Problems to be solved by the invention]
The conventional cationic polymer blended in the hair treatment composition does not show the setting effect even if the conditioning effect is sufficient, and also shows the conditioning effect and the setting effect depending on the application as in Patent Document 5. Even though it is nonionic, it can not be expected to adsorb much on the hair surface that is anionic compared with conventional cationic polymers such as cellulose derivatives with quaternary nitrogen-containing groups. There is a case. Furthermore, in the case of a thermogelling polymer substance that exhibits a good setting effect, the conditioning effect may not be expected because it is nonionic. In addition, a conditioning agent such as a cationic polymer and a humectant such as glycerin blended in the skin cosmetic composition may cause stickiness or sliminess depending on the blending amount in the formulation. On the other hand, these cationic polymers can obtain a smooth foam quality, but depending on the formulation, there is a problem that sufficient foaming cannot be obtained and the feeling during use cannot be fully satisfied. It was.
[0009]
[Means for Solving the Problems]
In such a situation, the present inventors have a conditioning effect of a conventional cationic polymer, give the hair a set effect, further eliminate the feeling of tension on the skin, and improve the feeling of stickiness, stickiness, foaming, and foam. The compounds to be studied were intensively studied. As a result, the cation-modified polysaccharide in which a specific amount of a quaternary nitrogen-containing group is introduced into the thermogelable polysaccharide and the cationic charge amount is adjusted to a specific range has excellent characteristics as a conditioning agent in a cosmetic composition. In particular, in the hair treatment composition, it was found that a setting effect can be imparted to the hair when dried by heat, and furthermore, the foam feel can be improved by forming a uniform film by improving water dispersibility, and the present invention has been completed. It came to do.
[0010]
Therefore, the present invention is suitable for use in various hair treatment compositions, skin cosmetic compositions, and other cosmetic compositions such as make-up agents. A cation-modified polysaccharide substituted with a quaternary nitrogen-containing group represented by the chemical formula (1), wherein the cation charge amount derived from the quaternary nitrogen-containing group is 0.5 to 3.5 meq / g. It relates to cationically modified polysaccharides.
[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. )
[0011]
Here, the “thermal gelling polysaccharide” used in the present specification means a high molecular polysaccharide that gels at a heating temperature of about 60 ° C. The heat-gelling polysaccharide used in the present invention is, for example, β-1,3-glucan, β-1,3-xylan, thermocoagulable starch, and among these, β-1,3-glucan is preferable. It is β-1,3-xylan, and even more preferably, it is a trade name “Cardlan” (Takeda Pharmaceutical Co., Ltd.) that is easily available. This curdlan is a kind of β-1,3-glucan and is a microorganismAgrobacterium biovar 1Is produced from glucose, and its constituent sugar is only D-glucose, and 99% or more of its glucoside bonds are β-1,3 bonds. As β-1,3 glucans other than curdlan, for example, schizophyllan, scleroglucan, sclerotane, lentinan, paramylon, callose, laminaran, etc. are treated with mild Smith decomposition (see polym.J.13 (12) 1135-1143 (1981)). ), A polysaccharide having the same properties as curdlan can be obtained. These β-1,3-glucans are insoluble in water, but are dispersed in water and then heated to form a triple helical structure by intermolecular hydrogen bonding to form an elastic gel. It has been.
[0012]
The cation-modified polysaccharide of the present invention improves the water dispersibility by cation-modifying the heat-gelling polysaccharide and facilitates its incorporation into cosmetic compositions such as shampoos, rinses and body cleaning agents. Yes. Further, a more powerful setting effect can be obtained by forming a uniform film by improving water dispersibility and improving adsorption by making it cationic. Uniform film formation also improves the foam quality of shampoos, body cleaners and the like.
[0013]
The cation modification according to the present invention can be produced by reacting a thermogelling polysaccharide with a glycidyl trialkylammonium salt having a quaternary nitrogen-containing group or a 3-halogeno-2-hydroxypropyltrialkylammonium salt. it can. 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 thermogelling polysaccharide, the glycidyl trialkylammonium salt or the 3-halogeno-2-hydroxypropyltrialkylammonium salt The cation-modified polysaccharide of the present invention can be produced by reacting with the quaternary nitrogen-containing group.
[0014]
In the quaternary nitrogen-containing group represented by the chemical formula (1) introduced into the thermogelling polysaccharide in the present invention, R₁And R₂Specific examples of such include methyl, ethyl and propyl, and R as an alkyl group having 1 to 24 carbon atoms._ThreeAs a specific example of R₁And R₂Other than the same, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl and the like can be mentioned. R_FourSpecific examples of O include ethoxy, propoxy and butoxy. 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.
[0015]
The cation-modified polysaccharide of the present invention is excellent as a blending component of a cosmetic composition. For example, when formulated into a hair treatment composition, it provides both conditioning and set effects. When formulated into a skin cosmetic composition, such as a body cleanser, the skin oil and fat components are more than necessary. Do not remove.
Therefore, the present invention also relates to these cosmetic compositions containing the cation-modified polysaccharide of the present invention.
[0016]
The cation charge amount derived from the quaternary nitrogen-containing group of the cation-modified polysaccharide of the present invention is 0.5 to 3.5 meq / g, more preferably 1.5 to 2.0 meq / g. If the amount of cationic charge is less than 0.5 meq / g, the amount of cationically modified polysaccharide adsorbed on the hair or skin becomes insufficient, and in fact, hair treatment compositions such as shampoos, rinses, body cleaning agents, and skin cosmetic compositions. Even if it is blended in, no effect is recognized. In addition, when the cationic charge exceeds 3.5 meq / g, not only the hair treatment composition containing such a cation-modified polysaccharide can give a set effect to the hair when dried by heat. It is unfavorable because it causes stickiness and sliminess during use and deteriorates the feeling of use, and the finished feeling after use also causes a feeling of stickiness and stickiness.
[0017]
The cation charge amount derived from the quaternary nitrogen-containing group of the cation-modified polysaccharide is the equivalent number of quaternary nitrogen-containing groups represented by the chemical formula (1) contained in 1 g of the cation-modified polysaccharide. Usually, the nitrogen content derived from a 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, but the thermal gelation used in the present invention Since the nitrogen content is contained in the functional polysaccharide, the value obtained by subtracting the nitrogen content derived from the thermogelling polysaccharide used in the present invention from the nitrogen content in the cation-modified polysaccharide of the present invention determined by the Kjeldahl method is The nitrogen content is derived from a quaternary nitrogen-containing group. Taking a curdlan as an example, the quaternary nitrogen-containing group R represented by the chemical formula (1) will be described in detail.₁, R₂, R_ThreeIs methyl, X^-Is a chloride ion, and n is 1.60% of the nitrogen content of the product of the present invention obtained by cation modification of curdlan with a quaternary nitrogen-containing group of n = 0, as measured by Kjeldahl method. In this case, the cation charge amount of this substance is obtained by the following formula. The curdlan used in the present invention usually contains about 0.40% nitrogen.
[Expression 1]

[0018]
Further, the blending amount of the cation-modified polysaccharide of the present invention 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, and less than 0.05% by mass. However, the conditioning effect and the setting effect tend not to be sufficiently exhibited. If the amount exceeds 5% by mass, a feeling of stickiness and a feeling of slimness are generated during use, and the feeling of use tends to deteriorate.
[0019]
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. In the range where the setting effect on the hair is not impaired, the total composition is 100% by mass, and preferably 5% by mass or less. The set effect on the hair shown is not sufficiently exhibited. Furthermore, in the skin cosmetic composition, a feeling of sliminess is generated and the feeling of use becomes worse.
[0020]
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.
[0021]
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), dimethyl diallylammonium chloride derivatives (dimethyl diallylammonium chloride). Acrylamide copolymers, polydimethylmethylenepiperidinium chloride, etc.), vinylpyrrolidone derivatives (vinylpyrrolidone / dimethylaminoethylmethacrylic acid copolymer salt, vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer, vinylpyrrolidone / chloride) Methyl vinyl imidazolium copolymer, etc.), methacrylic acid derivatives (methacryloylethyldimethylbetaine / methacryloylethyltrimethylammonium chloride) -Time 2-hydroxyethyl methacrylate copolymer, methacryloyl ethyl dimethyl betaine chloride methacryloyloxyethyl trimethyl ammonium methacrylate methoxy polyethylene glycol copolymer, etc.) and the like.
[0022]
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.).
[0023]
As described above, the required amount of the cation-modified polysaccharide of the present invention is blended in the formulation system by a known formulation to obtain the hair treatment composition or skin cosmetic composition of the present invention. Other components in the composition and skin cosmetic composition are not particularly limited, and components generally used in hair treatment compositions and skin cosmetic compositions can be blended as optional components. Other components that can be blended are exemplified below.
[0024]
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) methyl taurate, acyl (carbon number 24-24) taurine salt, - sulfofatty acid ester salts, ether carboxylates, polyoxyalkylene fatty acid monoethanolamide sulfates, long chain (8 to 24 carbon atoms) carboxylic acid salts, and the like.
[0025]
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.
[0026]
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) amide. Propylhydroxysulfobetaine, alkyl (carbon number 8-24) hydroxysulfobetaine, 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.
[0027]
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.
[0028]
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.
[0029]
Furthermore, examples of anionic polymers include acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid / acrylamide / ethyl acrylate copolymers and salts thereof), methacrylic acid derivatives (polymethacrylic acid and salts thereof, Methacrylic acid / acrylamide / diacetone acrylamide / acrylic acid alkyl ester / methacrylic acid alkyl ester copolymer and salts thereof), acrylamide methyl propane sulfonic acid derivatives (polyacrylamide methyl propane sulfonic acid and salts thereof, acrylamide methyl propane sulfonic acid and the like) Copolymers with acrylamide, dimethylacrylamide, vinyl pyrrolidone, etc. and their salts), crotonic acid derivatives (vinyl acetate / crotonic acid copolymer, etc.), maleic acid derivatives (maleic anhydride / diisobutylene copolymer) , Isobutylene / maleic acid copolymer, etc.), polyglutamic acid and its salt, hyaluronic acid and its salt, associative anionic polymer (hydrophobic modified acrylate / methacrylic acid copolymer and its salt, hydrophobic modified methacrylate / methacrylic acid copolymer) And a salt thereof, a hydrophobically modified acrylate / methacrylic acid / acrylamide copolymer and a salt thereof), carboxymethyl cellulose, carboxyvinyl polymer, and the like.
[0030]
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.), associative nonionic polymers (hydrophobic modified polyether urethane, hydrophobic modified cellulose derivatives, etc.), polysaccharides and Examples thereof include guar gum, locust bean gum, dextran, and the like.
[0031]
In still another embodiment, the hair treatment composition and the skin cosmetic composition of the present invention have a conditioning effect by adding an organic acid and / or inorganic acid of an amidoamine compound and a higher fatty acid and / or a higher alcohol. Can be improved. The blending amount 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 causes a null, resulting in poor usability. Further, the effect of setting the product of the present invention is not sufficiently exhibited.
[0032]
Other components blended in the hair treatment composition and skin cosmetic composition of the present invention include cationic surfactants, solubilizers (ethanol, ethylene glycol, propylene glycol, etc.), waxes (carnauba wax, candelilla). Waxes, etc.), hydrocarbon oils (liquid paraffin, squalane, etc.), humectants (glycerin, trehalose, dipropylene glycol, sorbitol, maltitol, 1,3-butylene glycol, sodium hyaluronate, etc.), esters (isopropyl myristate) Cetyl 2-ethylhexanoate, etc.), antioxidants (tocopherol, BHT, etc.), silicones (methylpolysiloxane, methylphenylpolysiloxane etc.) and silicone derivatives (polyether-modified silicone, amino-modified silicone etc.), higher alcohols, High-grade fat Acids (lauric acid, stearic acid, isostearic acid, etc.), ultraviolet absorbers (benzophenone derivatives, paraaminobenzoic acid derivatives, methoxycinnamic acid derivatives, etc.), thickeners, sequestering agents (edetates, etc.), pH adjusters, Examples include bactericides, preservatives, hair restorers, vitamins, anti-inflammatory agents, pigments, fragrances, and foam enhancers.
[0033]
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 shampoos, rinses, conditioners, hair gels, hair creams, hair waxes, hair lotions, hair foams, hair mists, hair liquids, etc., both of which are the conditioning and setting effects of the cation-modified polysaccharide of the present invention. Is used. In addition, it can be used in body cleaning agents and lotions because of the effect of improving the feeling of use, and can also be blended into acidic hair dyes, oxidative hair dyes, permanent agents, and the like.
In addition, it can be applied to cosmetics for eyelashes (mascara) and the like using the conditioning effect and setting effect on the keratin of the present invention as in the case of hair.
[0034]
【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%.
[0035]
[Production of cation-modified polysaccharide]
Example 1
162 g of curdlan was dispersed in 900 ml of a 70% by volume isopropanol aqueous solution, and 12.0 g of a 48% by mass sodium hydroxide aqueous solution was added. Next, 100 g of an 80% by mass glycidyltrimethylammonium chloride (hereinafter also referred to as GTA) aqueous solution was added, heated and reacted at 50 ° C. for 3 hours. After completion of the reaction, 15.0 g of 35% hydrochloric acid was diluted with 1500 ml of 60 volume% isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 800 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 charge of the cation-modified polysaccharide thus obtained was 0.95 meq / g. The results are shown in Table 1 (Sample No. 1 in Table 1).
[0036]
Similarly, cation-modified polysaccharides with different cation charges were synthesized by changing the amount of GTA added. The results are shown in Table 1 (Sample numbers 2 and 3 in Table 1).
[0037]
Example 2
162 g of curdlan was dispersed in 900 ml of 50% by volume isopropanol aqueous solution, and 57.5 g of 48% by mass sodium hydroxide aqueous solution was added. Next, 186 g of 3-halogeno-2-hydroxypropyldimethylmonolauryl ammonium chloride was added, and the mixture was heated and reacted at 50 ° C. for 3 hours. After completion of the reaction, 15.0 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 800 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 polysaccharide thus obtained had a cation charge of 0.65 meq / g. The results are shown in Table 1 (Sample No. 4 in Table 1).
[0038]
Example 3
131 g of β-1,3-xylan was dispersed in 900 ml of a 70 volume% isopropanol aqueous solution, and 12.0 g of a 48 mass% sodium hydroxide aqueous solution was added. Next, 100 g of an 80% by mass GTA aqueous solution was added, heated, and reacted at 50 ° C. for 3 hours. After completion of the reaction, 15.0 g of 35% hydrochloric acid was diluted with 1500 ml of 60 volume% isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 800 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 polysaccharide thus obtained had a cation charge of 0.89 meq / g. The results are shown in Table 1 (Sample No. 5 in Table 1).
[0039]
Example 4
In a pressurized sealed container, 162 g of curdlan was dispersed in 900 ml of a 70% by volume isopropanol aqueous solution, and 12.0 g of a 48% by mass sodium hydroxide aqueous solution was added. Next, 66 g of ethylene oxide and 240 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, 150 g of an 80 mass% GTA aqueous solution is added and reacted at 50 ° C. for 3 hours. After completion of the reaction, 15.0 g of 35% hydrochloric acid was diluted with 1500 ml of 60 volume% isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 800 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 polysaccharide thus obtained had a cation charge of 1.05 meq / g. The results are shown in Table 1 (Sample No. 6 in Table 1).
[0040]
Example 5
A cation-modified polysaccharide was synthesized according to the method of Example 1 by using β-1,3-glucan whose side chain was thinned out from Schizophyllan by mild Smith decomposition. The results are shown in Table 1. (Sample number 7 in Table 1)
[0041]
Example 1
According to the method of Example 1, cation-modified polysaccharides having different charge amounts were synthesized by changing the amount of GTA to be added. The results are shown in Table 1 (Sample numbers 8 and 9 in Table 1).
[0042]
[Table 1]

[0043]
[Manufacture and evaluation of cosmetics containing cation-modified polysaccharides]
Example 6 Set effect (1)
The setting effect on the hair of the cation-modified thermogelling polysaccharide was confirmed by the following method. The measuring method applied mutatis mutandis to the method described in Japan Cosmetics Engineers Journal, Vol. 33, No. 2, 119-127 (1999). In particular
After applying 0.40 g of a test solution (0.5% aqueous solution) to 1.0 g of a hair strand (160 mm in total length) and arranging with a comb, it was wound around a curler (inner diameter 20 mm). After drying in an 80 ° C. constant temperature bath for 30 minutes, it was left in a constant temperature and humidity (20 ° C., 58% RH) atmosphere for 1 hour. Thereafter, only the curled hair strand was taken out and compressed with a rheometer (manufactured by Fudo Kogyo Co., Ltd.), and the crushing stress at that time was measured. The same test was repeated twice, and the average value of the two times was taken as the measurement value of this test, and the results are shown in Table 2. The numerical values in Table 2 indicate that the set force increases as the numerical value increases.
[0044]
[Table 2]

[0045]
From the results in Table 2, it was proved that the cation-modified thermogelling polysaccharide of the present invention has an increased set power compared to curdlan, which is an unmodified thermogelling polysaccharide. This is a result of uniform film formation because the water-dispersibility of the thermogelling polysaccharide is improved by cation modification and is uniformly applied to the hair surface. Therefore, when the product of the present invention is blended in a coating-type hair treatment cosmetic, a set effect can be expected more than that containing an unmodified thermogelling polysaccharide.
[0046]
Example 7 Set effect (2)
The setting effect on the hair of the cation-modified thermogelling polysaccharide was washed out and confirmed with the product.
(Preparation of hair shampoo)
7-a
A shampoo having the composition shown in (A) of Table 3 was prepared using the cation-modified polysaccharide obtained in Examples 1, 2, and 4. Ingredient (12) (A) in Table 3 was heated to 80 ° C. and component (1) was slowly added and dissolved while stirring. After confirming dissolution, heating was stopped and ingredients (5) to (7) were replaced. 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 those prepared from the cation-modified polysaccharides corresponding to Sample Nos. 1, 2, 4 and 6 in Table 1 were formulated in this order. To S4.
[0047]
7-b
Using the cation-modified polysaccharide of Sample No. 2 obtained in Example 1, and 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 (B) of Table 3 was prepared, including HC-100 (manufactured by Toho Chemical Co., Ltd.). Ingredient (B) (12) in Table 3 was heated to 80 ° C., components (1) and (3) were slowly added and dissolved while stirring, and after dissolution was confirmed, heating was stopped and ingredients (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.
[0048]
7-c
Using the cation-modified polysaccharide of sample number 2 obtained in Example 1, N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) 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 is heated to 80 ° C., and components (1) and (4) are slowly added and dissolved while stirring. (7) was added and stirred to make it uniform, and then components (8) to (11) were added and mixed uniformly at 30 to 40 ° C. to obtain Prescription S6 of the product of the present invention.
[0049]
7-d
A shampoo having the composition shown in (D) of Table 3 was prepared using the cation-modified polysaccharide of sample number 2 obtained in Example 1 and further containing both a cationic water-soluble polymer and an amphoteric water-soluble high molecule. . In Table 3, the component (D) (12) is heated to 80 ° C., and the components (1), (3), and (4) are slowly added and dissolved while stirring. 5) to (7) were added and stirred to make uniform, then components (8) to (11) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was designated as the formulation S7 of the present invention.
[0050]
7-e (Preparation of comparative product)
In order to compare the effect of the cation-modified polysaccharide used in the present invention on the shampoo, the composition shown in the comparative product (E) of Table 3 using the cation-modified polysaccharide of Sample No. 9 in Table 1 obtained in Example 1 was used. A shampoo was prepared. The component (12) of the comparative product (E) in Table 3 was heated to 80 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming dissolution, heat was stopped and ingredients (5) to (7) were added and stirred to make uniform, then ingredients (8) to (11) were added and mixed uniformly at 30 to 40 ° C. did.
[0051]
7-f (Preparation of comparative product)
In order to compare the effect of the cation-modified polysaccharide used in the present invention on the shampoo, in addition to the sample number 9 used in the above 7-e, an unmodified thermogelling polysaccharide (curdlan) having the same blending ratio is used. Prepared a shampoo having the composition shown in Comparative Product (E) in Table 3 in the same manner as Comparative Product C2.
[0052]
[Table 3]

[0053]
(Evaluation)
The shampoos of the formulations S1 to S6 of the products of the present invention prepared in 7-a to 7-f and the shampoos of comparative products C1 and C2, and the shampoo having the composition shown in the blank (F) of Table 3 as a blank, Each 1.0 g 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 80 degreeC, and adding and stirring a component (5)-(7) and making it uniform, a blank is cooled at 30-40 degreeC. Components (8) to (11) were added and mixed uniformly.
[Table 4]

[0054]
From the results shown in Table 4, the shampoo of the present invention containing the cation-modified polysaccharides of Sample Nos. 1, 2, 4 and 6 obtained by cation-modifying the thermogelling polysaccharide has bending stiffness (B value) and hysteresis compared to the blank. Both widths (2HB) are improved. Similar results were also found in comparative product C1 containing the cation-modified polysaccharide of sample number 9 having a cation charge value higher than the range of the present invention. On the other hand, in the application-type cosmetics, the unmodified heat-gelling polysaccharide showing a setting effect has the same result as the blank. This is because when unmodified heat-gelling polysaccharides are used in washing-off products, the ability to adsorb hair based on ionic properties cannot be obtained, and the effect of the heat-gelling polysaccharides on hair is low. It is thought that it was shown that was not obtained. On the other hand, since the product of the present invention obtained by cationically modifying a thermogelling polysaccharide has an adsorption ability based on ionicity to hair, a setting effect can be obtained even in a washing product such as a shampoo. As a result, there were obtained effects such as improvement in bending rigidity and hysteresis value, and also the firmness to the hair in terms of the hand-feeling surface. Therefore, it was found that the cation-modified polysaccharide of the present invention exerts its effect sufficiently even when it is blended in a shampoo, rinse or the like.
[0055]
In addition, the cation-modified polysaccharide of the present invention, 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 (Kachinal HC-100; manufactured by Toho Chemical Co., Ltd.), N -In combination with water-soluble polymers with conditioning effects such as -methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer SM; manufactured by Mitsubishi Chemical Corporation) There was no difference in flexural rigidity (B value) and hysteresis width (2HB), and it was confirmed that the effect was not lost even when used together.
[0056]
Example 8 Foaming test
The foaming of a cosmetic composition in which the cation-modified thermogelling polysaccharide of the present invention (sample numbers 1 and 2 in Table 1) was blended with the composition shown in (A) of Table 5 was measured. For comparison, cation-modified hydroxyethyl cellulose having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by weight (Kachinal HC-100; manufactured by Toho Chemical Co., Ltd.) as another aqueous polymer, and A cosmetic composition containing curdlan as an unmodified thermogelling polysaccharide was blended in the composition shown in Table 5 (B), and foaming was measured in the same manner.
For the measurement, each cosmetic composition having the formulation shown in Table 5 was prepared by a method according to the procedure shown in Example 7, and 400 ml of a 3% 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 6.
[0057]
[Table 5]

[Table 6]

[0058]
From the results of Table 6, it was proved that the cation-modified thermogelling polysaccharide of the present invention has improved water dispersibility and excellent foaming as compared to the unmodified thermogelling polysaccharide. In addition, when compared with other cation-modified polymers (Catinal HC-100: cation-modified hydroxyethyl cellulose), the product of the present invention has a strong foam film in the film characteristics as well as the result seen in the set effect. It was confirmed that it was excellent in foaming and quick foaming. Therefore, improvement of foaming can be expected when the product of the present invention is blended in a cosmetic composition having foaming such as shampoo, body cleansing agent, face wash.
[0059]
Hereinafter, the setting effect, the improvement of foaming and the conditioning effect obtained by the cation-modified thermogelling polysaccharide were further confirmed by sensory evaluation and instrumental measurement in each of the cosmetic compositions having different dosage forms.
[0060]
Hair shampoo
(Preparation)
Example 9
9-a
Using the cation-modified polysaccharides of Sample Nos. 1 to 7 of the present invention obtained in Examples 1, 2, 3, 4 and 5, shampoos having the composition shown in (A) of Table 7 were prepared. In Table 7, component (14) (A) is heated to 80 ° C. and component (1) is slowly added and dissolved while stirring. After confirming dissolution, heating is stopped and (5) to (10) are added. The mixture was stirred to make it uniform, and then components (11) to (13) were added at 30 to 40 ° C. and mixed uniformly. In this way, shampoos having the compositions shown in Table 7 (A) in which the cation-modified polysaccharides corresponding to the sample numbers 1 to 7 in Table 1 were blended were prepared, and the sample numbers 1 to 7 in Table 1 were sequentially used in the present invention. It was set as prescription 1-7 of goods.
[0061]
9-b
Using the cation-modified polysaccharide of Sample No. 2 obtained in Example 1, and a 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 7 was prepared, including Kachinal HC-100 (manufactured by Toho Chemical Co., Ltd.). Ingredient (14) of (B) in Table 7 was heated to 80 ° C., and components (1) and (3) were slowly added and dissolved while stirring. After confirming dissolution, heating was stopped and ingredients (5) to (7) (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 designated as Formulation 8 of the product of the present invention.
[0062]
9-c
A shampoo having the composition shown in Table 7 (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 Formulation 9 for the product of the present invention.
[0063]
9-d
Using the cation-modified polysaccharide of Sample No. 2 obtained in Example 1, and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) as the amphoteric water-soluble polymer A shampoo having the composition shown in (D) of Table 7 was prepared, including SM (manufactured by Mitsubishi Chemical Corporation). (D) component (14) in Table 7 was heated to 80 ° C. and components (1) and (4) were slowly added and dissolved with stirring. After dissolution was confirmed, heating was stopped and components (5) to ( 10) was added and stirred to make it 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 10 of the product of the present invention.
[0064]
9-e
Using the cation-modified polysaccharide of sample number 2 obtained in Example 1, a shampoo having the composition shown in (E) of Table 7 containing a cationic water-soluble polymer and an amphoteric water-soluble polymer was prepared. In Table 7, component (14) (E) is heated to 80 ° C. and components (1), (3) and (4) are slowly added and dissolved with stirring. 5) to (10) were added and stirred to be uniform, then components (11) to (13) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was used as the formulation 11 of the product of the present invention.
[0065]
9-f (Preparation of comparative product)
In order to compare the effect of the cation-modified polysaccharide according to the present invention on the shampoo, the cation-modified polysaccharide obtained in Example 1, ie, sample Nos. 8 and 9 in Table 1, was used as a comparative product (G) shown in Table 7. A shampoo of the same composition was prepared. The component (14) of the comparative product (G) in Table 7 was heated to 80 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming dissolution, heat was stopped, ingredients (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.
[0066]
9-g (preparation of comparative product)
In order to further compare the effect, in place of the cation-modified polysaccharide in 9-e, 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 (Catinal HC-100; Toho) A shampoo having the composition shown in Comparative Product (G) in Table 7 was prepared in the same manner as 9-f, and used as Comparative Product 3.
[0067]
[Table 7]

[0068]
(Evaluation)
Example 10
Each shampoo prepared in Examples 9-a to 9-e, that is, formulations 1 to 11 of the present invention, was subjected to performance evaluation of the following items by 10 testers.
The performance evaluation method uses a shampoo having the composition shown in the standard product (F) of Table 2 that does not contain a cationic polymer or the like as a component, and a shampoo to be evaluated, and a feeling of use at the time of shampooing, natural drying Based on the standard product (F),
・ Presence or absence of conditioning effect when using shampoo (comb feeling, feel of hair, squeak after rinsing, etc.)
・ Presence or absence of conditioning effect after use (dry hair) (comb feeling, feel of hair, etc.), strength of hair stiffness
Were compared and digitized by the method shown in Table 8 below, and the evaluation values of 10 testers for each item were totaled. The evaluation results are shown in Table 9. In addition, after heating the component (14) in the standard product (F) in Table 7 to 80 ° C., adding the components (5) to (10), stirring and homogenizing the above standard product (F), cooling The components (11) to (13) were added at 30 to 40 ° C. and mixed uniformly.
[0069]
[Table 8]

[0070]
Comparative Example 1
Each shampoo prepared in 9-f and 9-g and Comparative products 1 to 3 were subjected to performance evaluation in the same manner as in Example 10, and the results are shown in Table 9.
[0071]
[Table 9]

[0072]
From the results shown in Table 9, the cation-modified polysaccharide of the present invention having a cation charge amount of 0.5 to 3.5 meq / g of the cation-modified polysaccharide has excellent conditioning effects when used in shampoos, and is used to wash out shampoos and the like. Also in the product, the strength of the stiffness due to the set effect was confirmed.
[0073]
In addition, the performance of the shampoo containing the product of the present invention is the same as that of Comparative Product 3 containing only cation-modified hydroxyethyl cellulose (Catinal HC-100), which is conventionally used as a conditioning agent, at the time of use and after use. Although it is above, the strength of the firmness by the set effect which the thermogelling polysaccharide which is not in the conventional conditioning agent has after use was obtained. In addition, by using a cationic water-soluble polymer (Catinal HC-100, Merquat 550) and / or an amphoteric water-soluble polymer (Yukaformer SM) in combination, the performance of the cation-modified polysaccharide of the present invention can be improved. It was confirmed that the conditioning effect was improved without loss.
[0074]
Example 11
In order to further verify the set effect in the rinse-off product, the prescriptions 1 to 4 of the present invention product obtained in 9-a, the prescription 8 of the present invention product obtained in 9-b, and the book obtained in 9-c After washing the hair with a shampoo comprising the formulation 10 of the invention, it is left in a constant temperature and humidity (20 ° C., 40% RH) atmosphere for 24 hours to determine the firmness of the hair by a pure bending tester (manufactured by Kato Tech Co., Ltd.). , KES-FB2-S) for performance evaluation. The results are shown in Table 10 as pure bending test results.
[0075]
Comparative Example 2
The comparative products 1 and 2 obtained in 9-f and the comparative product 3 obtained in 9-g were subjected to the same performance evaluation as in Example 11, and the results are shown in Table 10.
[0076]
[Table 10]

[0077]
From the results shown in Table 10, the shampoo containing the cation-modified polysaccharide of the present invention has a higher bending stiffness and hysteresis value than the comparative product 3 containing only the cation-modified hydroxyethyl cellulose (Catinal HC-100) used as a conventional conditioning agent. An improvement was seen. Therefore, it was confirmed that even in a wash-out product such as a shampoo, it is possible to impart firmness to the hair by the set effect of the product of the present invention in which the thermogelling polysaccharide is cation-modified. Furthermore, as is clear from the results of Formulas 8 and 9, it was confirmed that the effect was not lost even in combination with other cationic water-soluble polymers and / or amphoteric water-soluble polymers.
[0078]
(Formulation examples 1-5)
Below, the suitable compounding example of this invention to a shampoo is shown.
[Table 11]

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
[0079]
[Table 12]

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
[0080]
[Table 13]

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
[0081]
[Table 14]

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
[0082]
[Table 15]

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
[0083]
Hair rinse
(Preparation)
Example 12
12-a
Using the cation-modified polysaccharides of Sample Nos. 1 to 4 obtained in Examples 1 and 2, the organic acid salt of amide amine compound (stearic acid dimethylaminopropylamide citrate) shown in (A) of Table 16 below ) And a higher alcohol (cetanol). The components (4) to (9) of (A) in Table 16 were heated to 80 ° C. and stirred to make a uniform solution, and the component (1) was previously added to the component (11) with stirring and dissolved. A solution heated to 80 ° C. was added with stirring, and then component (10) was added while cooling and mixed uniformly. Thus, the rinses having the compositions shown in Table 16 (A) were prepared, and the rinses containing the cation-modified polysaccharides of Sample Nos. 1 to 4 in Table 1 were used as the prescriptions 12 to 15 of the present invention.
[0084]
12-b
Using the cation-modified polysaccharide of Sample No. 2 obtained in Example 1, and 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 16 containing HC-100; Toho Chemical Industry Co., Ltd.) was prepared. Ingredients (4) to (9) in Table 16 (B) were heated to 80 ° C. and stirred to add a uniform solution to ingredients (11) with ingredients (1) and (3) added in advance. The dissolved solution heated to 80 ° C. was added with stirring, and then component (10) was added and mixed uniformly while cooling. The resulting rinse was designated as formulation 16 of the product of the present invention.
[0085]
12-c
Similarly, the cationic polysaccharide of sample number 2 and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer SM; Mitsubishi Chemical Corporation) as an amphoteric water-soluble polymer A rinse having the composition shown in (C) of Table 16 was prepared and used as the formulation 17 of the present invention.
[0086]
12-d (Preparation of comparative product)
In order to compare the effect of the cation-modified polysaccharide of the present invention on rinsing, the cation-modified polysaccharide obtained in Example 1, that is, sample Nos. 8 and 9 in Table 1, was used as a comparative product (E) in Table 16. A rinse of the indicated composition was prepared. Ingredients (4) to (9) of comparative product (E) in Table 16 were heated to 80 ° C. and stirred to make a uniform solution. A solution heated to 80 ° C. was added with stirring, and then component (10) was added while cooling and mixed uniformly. The rinse containing sample number 8 was rinsed containing comparative product 4 and sample number 9 Was designated as comparative product 5.
[0087]
12-e (Preparation of comparative product)
Further, in order to compare the effects of the cation-modified polysaccharide of the present invention, instead of the sample numbers 8 and 9, 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 Industry Co., Ltd.), a rinse having the composition shown in Comparative Product (E) in Table 16 was prepared in the same manner as 12-d, and the resulting rinse was designated as Comparative Product 6.
[0088]
[Table 16]

[0089]
(Evaluation)
Example 13
For each of the rinses prepared in 12-a to 12-c, that is, the formulations 12 to 17 of the present invention, performance evaluation of the following items was performed by 10 testers.
The performance evaluation method uses a rinse of the composition shown in the standard product (D) in Table 10 that does not contain a cationic polymer as a component, and a rinse to be evaluated for each, and after drying with a dryer (80 ° C.) The feeling of use is based on the standard product (D).
・ The presence or absence of dry hair condition effects (comb feeling, hair feel, etc.)
・ Strength of hair
Were compared with each other, digitized by the method shown in Table 17 below, and the values of the 10 testers who performed the evaluation were totaled. The evaluation results are shown in Table 18. The standard product (D) was prepared by heating the components (4) to (9) in the standard product (D) in Table 16 to 80 ° C. and stirring to make a uniform solution. 11) was added with stirring, and then component (10) was added while cooling to prepare a uniform mixture.
[0090]
Comparative Example 3
For each of the rinses prepared in 12-d and 12-e, ie, comparative products 4 to 6, performance evaluation was performed in the same manner as in Example 13, and the results are shown in Table 18.
[0091]
[Table 17]

[0092]
[Table 18]

[0093]
From the results of Table 18, the cation-modified polysaccharide of the present invention having a cation charge amount of 0.5 to 3.5 meq / g, and an organic acid salt of amide amine compound (dimethylaminopropylamide citrate stearate) In addition, it was confirmed that a rinse containing higher alcohol (cetanol) has excellent conditioning effects on the hair of the composition, and that the firmness of the set effect can be obtained.
[0094]
The performance of the cation-modified polysaccharide of the present invention is equal to or better than that of cation-modified hydroxyethyl cellulose (Kachinal HC-100) in the conditioning effect. The strength of the stiffness due to the set effect of was obtained. In addition, 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 polysaccharide.
[0095]
(Formulation examples 6-8)
Below, the suitable compounding example of this invention to the hair treatment composition which requires conditioning effects, such as a rinse and a conditioner, is shown.
[Table 19]

The product of the present invention, stearyltrimethylammonium chloride, glycerin and a dye are added to purified water in Table 19 and kept at 70 ° C. (aqueous phase), and 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.
[0096]
[Table 20]

To the purified water of Table 20, the product of the present invention, hydroxypropyltrimonium chloride, dimethylaminopropylamide stearate, L-glutamic acid, glycerin, phenoxyethanol, and legal dye are added and kept at 70 ° C. (aqueous phase), and other ingredients are added. Mix, heat dissolve and keep at 70 ° C. (oil phase). The aqueous phase and the oil phase were added and emulsified with a homomixer, and then cooled with stirring.
[0097]
[Table 21]

In purified water of Table 21, the product of the present invention, N- (3-alkyl (12,14) oxy-2-hydroxypropyl) -L-arginine hydrochloride, stearic acid dimethylaminopropylamide, citric acid, glycerin, phenoxyethanol, Sodium benzoate is added and kept at 70 ° C. (aqueous phase), and other ingredients 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.
[0098]
Hair gel
(Preparation)
Example 14
14-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 polysaccharides of Sample Nos. 1, 2 and 3 obtained in Example 1, hair gels having the compositions shown in Table 22 (A) were prepared. Add component (1) and components (5) to (9) in Table 22 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 22 were prepared, and hair gels containing the cation-modified polysaccharides of Sample Nos. 1, 2 and 3 in Table 1 were respectively formulated with the formulations 18, 19 and 20 of the present invention. did.
[0099]
14-b
Using the cation-modified polysaccharide of Sample No. 2 obtained in Example 1, and 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 HC-100 (manufactured by Toho Chemical Industry Co., Ltd.) was prepared, and a hair gel having the composition shown in Table 22 (B) was prepared. Ingredients (1), (3) and (5) to (9) shown in (B) of Table 22 are added to the stirring ingredient (11), and after uniform dissolution, the ingredient (10) is added. Mix until clear. In this way, a hair gel having the composition shown in Table 22 (B) was prepared and used as the formulation 21 of the present invention.
[0100]
14-c
Using the cation-modified polysaccharide of sample number 2 obtained in Example 1, N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) as an amphoteric water-soluble polymer A hair gel having the composition shown in (C) of Table 22 was prepared, including SM (manufactured by Mitsubishi Chemical Corporation). Ingredients (1), (4) and (5) to (9) shown in Table 22 (C) are added to the stirring ingredient (11). Mix until. Thus, a hair gel having the composition shown in (C) of Table 22 was prepared and used as the formulation 22 of the present invention.
[0101]
14-d (Preparation of comparative product)
In order to compare the effect of the cation-modified polysaccharide used in the present invention on the hair gel, the cation-modified polysaccharide obtained in Example 1, that is, the sample numbers 8 and 9 in Table 1, is used as a comparative product (E) in Table 22. A hair gel having the composition described above was prepared. Add components (2) and (5) to (9) in Table 22 to the stirring component (11), dissolve uniformly, add component (10) and mix until clear, sample no. 8 The hair gel containing the cation-modified polysaccharide of Comparative Example 7 was used as Comparative Product 7, and the hair gel containing the cation-modified polysaccharide of Sample No. 9 was used as Comparative Product 8.
[0102]
14-e (Preparation of comparative product)
In order to further compare the effect, 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 (Kachinal HC-100; Toho) instead of the cation-modified polysaccharide used in 14-d The hair gel of the composition shown to the comparative product (E) of Table 22 including Chemical Industry Co., Ltd. was prepared, and it was set as the comparative product 9.
[0103]
[Table 22]

[0104]
(Evaluation)
Example 15
For each of the hair gels prepared in the above 14-a to 14-c, that is, the formulations 18, 19, 20, 21 and 22 of the present invention, performance evaluation of the following items was performed by 10 testers.
The performance evaluation method is based on the standard product (D) in Table 22 that does not contain a cationic water-soluble polymer or an amphoteric water-soluble polymer as a component.
・ Easy to apply,
・ Feel after use
Were compared, numerically expressed by the method shown in Table 23 below, and the values of 10 testers who performed evaluation were totaled. The results are shown in Table 25. For standard products, add the components (5) to (9) in Table 22 (D) to the stirring component (11), dissolve uniformly, add the component (10) and mix until clear. Prepared.
[0105]
Comparative Example 4
For each of the hair gels prepared in 14-d and 14-e and Comparative products 7, 8 and 9, performance evaluation was performed in the same manner as in Example 15, and the results are shown in Table 25.
[0106]
[Table 23]

[0107]
Example 16
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 was wetted with water, and the hair gel prepared in Examples 14-a to 14-c, that is, the formulations 18, 19, 20, 21 and 22 of the present invention, were applied. It was wound around an outer diameter of 2 cm) and dried with a drier in that state to be curled. After drying, the curled hair bundle was removed from the rod. The hair bundle is hung in a constant temperature and humidity (20 ° C., 40% RH) atmosphere for 30 minutes, the curl elongation is observed, and the set holding force is evaluated according to the evaluation criteria in Table 24 below based on the degree of curl elongation. The results are shown in Table 25.
[0108]
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 drier in the same manner as described above except that no hair gel was 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.
[0109]
[Table 24]

[0110]
Comparative Example 5
The hair gel prepared in 14-d and 14-e, ie, comparative products 7, 8 and 9, were subjected to performance evaluation in the same manner as in Example 16, and the results are shown in Table 25.
[0111]
[Table 25]

[0112]
From the results shown in Table 25, the cation-modified polysaccharide of the present invention can impart a set effect to the hair when dried by heat, and can be easily applied at the time of use due to improved water dispersibility. It was confirmed that the feel was good due to the conditioning effect. On the other hand, sample numbers 8 and 9 whose cation charge amount is outside the range of 0.5 to 3.5 meq / g defined in the present invention are evaluated as in the present invention in terms of ease of application and feel after use. Was not obtained. Further, by using the cation-modified polysaccharide of the present invention in combination with other cationic water-soluble polymers and / or amphoteric water-soluble polymers, the conditioning effect can be obtained without impairing the performance of the cation-modified polysaccharide of the present invention. Has been confirmed to improve.
[0113]
(Formulation examples 9 to 13)
Below, the suitable compounding example of this invention to the coating type hair treatment composition of hair mist, hair mousse, etc. which require set effects other than hair gel and hair gel is shown.
[Table 26]

A part of purified water was added to the product of the present invention and glycerin and dissolved by heating at 70 ° C. The other ingredients were dissolved in the remaining purified water and added with stirring.
[0114]
[Table 27]

[0115]
[Table 28]

[0116]
[Table 29]

[0117]
[Table 30]

[0118]
Body cleaner
(Preparation)
Example 17
17-a
Using the cation-modified polysaccharides of Sample Nos. 2 and 4 obtained in Examples 1 and 2, body cleaning agents (body soaps) having the compositions shown in Table 31 (A) were prepared. The component (11) of (A) in Table 31 is heated to 60 ° C., and the component (1) is 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 31 were prepared, and those containing the cation-modified polysaccharides of Sample Nos. 2 and 4 in Table 1 were used as the formulations 23 and 24 of the present invention, respectively. .
[0119]
17-b (Preparation of comparative product)
In order to compare the effect of the cation-modified polysaccharide used in the present invention in a body cleaning agent, the body cleaning of the composition shown in Table 31 (C) with respect to curdlan, which is an unmodified thermogelling polysaccharide An agent was prepared. The component (11) of (C) in Table 31 was heated to 60 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming the dissolution, the 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. In this way, a body cleaning agent having the composition shown in Table 31 (C) was prepared as Comparative Product 10.
[0120]
17-c (Preparation of comparative product)
Similarly, in order to compare the effects of the cation-modified polysaccharide used in the present invention on a 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 Industry Co., Ltd.) body cleaners having the compositions shown in Table 31 (C) were prepared. The component (11) of (C) in Table 31 was heated to 60 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming the dissolution, the 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. In this way, a body cleaning agent having the composition shown in Table 31 (C) was prepared and used as Comparative Product 11.
[0121]
[Table 31]

[0122]
(Evaluation)
Example 18
The performance evaluation of the following items was carried out by 10 testers for each of the body cleansing agents 23 and 24 of the product of the present invention obtained in Example 17-a.
The performance evaluation method uses a body cleaning agent having a composition shown in a standard product (B) in Table 31 that does not contain a high molecular compound such as a cationic polymer as a component, and a body cleaning agent to be evaluated.
・ Quantity and quality of foam during use,
・ Ease of rinsing, feeling of squeezing and slimming after rinsing,
・ Tightness, smoothness and moistness after drying
The standard products (B) were compared in terms of comfort, converted into numerical values by the methods shown in Tables 32 and 33 below, and the values of the 10 testers who performed the evaluation were totaled. The evaluation results are shown in Table 34. In addition, after heating the component (11) of the standard product (B) in Table 31 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. Add components (8) to (10) at -40 ° C. while stirring in the same manner and mix evenly to prepare a body cleaner having the composition shown in (B) of Table 31. did.
[0123]
[Table 32]

[0124]
[Table 33]

[0125]
Comparative Example 6
The performance evaluation similar to Example 18 was performed about the body washing | cleaning agent of the comparative products 10 and 11 obtained by 17-b and 17-c. These results are shown in Table 34.
[0126]
[Table 34]

[0127]
From the results in Table 34, it was confirmed that the formulation containing the cation-modified polysaccharide of the present invention improved the foaming, foam quality and feeling of use of the body cleaning agent as compared with the comparative product.
[0128]
In addition, when using the cation-modified polysaccharide of the present invention as compared with the unmodified thermogelling polysaccharide, the water dispersibility is improved, so that a uniform formulation composition can be obtained. On the other hand, the improvement of the touch was recognized by applying uniformly. Furthermore, compared with the conventional cation-modified hydroxyethyl cellulose as a conditioning agent, the flexible membrane characteristics seen in the setting effect of the thermogelling polysaccharide and the uniform water dispersibility obtained by cation modification It was confirmed that the film formation improved the foam film quality, and the foaming and foam quality were improved. In addition, it was confirmed that the conditioning effect of the cation-modified polysaccharide of the present invention has little sliminess, is easy to rinse, and has a smooth feel.
[0129]
(Formulation example 14)
The following is a blending example of a body cleaning agent utilizing the conditioning effect and foam improvement of the present invention.
[Table 35]

A liquid body cleaning agent (body soap) is manufactured based on a conventional method.
[0130]
(Formulation example 15-16)
Below, the mascara compounding example is shown as another application example utilizing the conditioning effect and setting effect of the cation-modified polysaccharide of the present invention on keratin.
[Table 36]

[0131]
[Table 37]

[0132]
【The invention's effect】
The cation-modified polysaccharide of the present invention, when formulated in a hair treatment composition such as shampoo and rinse, gives the hair a conditioning effect after drying while giving the hair a conditioning effect equivalent to that of conventional cation-modified hydroxyethyl cellulose. In addition, after drying by heat, a setting effect can be given to the hair. Furthermore, when the cation-modified polysaccharide of the present invention is blended in a skin cosmetic composition such as a body cleaning agent, the foam is improved, and the feeling of use such as moistness and smoothness due to the conditioning effect is obtained. Give improvement. Therefore, it is possible to provide a cosmetic composition that is more comfortable to use than conventional products.

Claims (14)

A cation-modified polysaccharide in which a part of hydroxyl groups contained in β-1,3-glucan or β-1,3-xylan is substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1) A hair treatment composition , wherein the cationic charge amount derived from the quaternary nitrogen-containing group is 0.5 to 3.5 meq / g .

(Wherein R ₁ and R ₂ are each an alkyl group having 1 to ₃ carbon atoms, R ₃ is an alkyl group having 1 to 24 carbon atoms, X ⁻ represents an anion, and n is n = 0 or n. = 1-30, and when n = 1-30, (R ₄ O) _n is a polymer residue of alkylene oxide having 2 to 4 carbon atoms, and is a polyalkylene glycol chain comprising a single alkylene oxide And / or a polyalkylene glycol chain composed of two or more types of alkylene oxides.) beta-1,3-glucan is produced from glucose by a microorganism Agrobacterium biovar 1, the hair treatment composition of claim 1, wherein the curdlan. Ca thione modified polysaccharides, glycidyl trialkyl ammonium salts or 3-halogeno-2-hydroxypropyl trialkylammonium salt using those which are cation-modified according to claim 1 or 2 hair treatment composition according. Ca thione modified polysaccharide, on a part of the hydroxyl groups contained in the beta-1,3-glucan or beta-1,3-xylan, after adding an alkylene oxide having 2 to 4 carbon atoms, Gurishijirutori as cationizing agent The composition for hair treatment according to any one of claims 1 to 3, wherein the composition is cationically modified using an alkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt . Ca content of thione modified polysaccharide on the total composition as 100 mass%, the hair treatment composition according to any one of claims 1 to 4, 0.05 to 5.0 wt%. Still other cationic water-soluble polymer and / or amphoteric water-soluble polymer, the total composition as 100 mass%, either one of claims 1 to 5, characterized in that it contains more than 5 wt% The composition for hair treatment as described in 2. above . Furthermore , the composition for hair treatment as described in any one of Claims 1-6 containing the organic acid and / or inorganic acid of an amidoamine compound, and a higher fatty acid and / or a higher alcohol. A cationically modified polysaccharide in which a part of hydroxyl groups contained in β-1,3-glucan or β-1,3-xylan is substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1) A skin cleansing composition having a cationic charge amount derived from the quaternary nitrogen-containing group of 0.5 to 3.5 meq / g.

(Where R ₁ , R ₂ Are each an alkyl group having 1 to 3 carbon atoms, R _Three Represents 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 _Four O) _n Is 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. ) The skin cleansing composition according to claim 8, wherein β-1,3-glucan is a curdlan produced from glucose by the microorganism Agrobacterium biovar 1. The skin cleansing composition according to claim 8 or 9, wherein the cation-modified polysaccharide is cation-modified using a glycidyl trialkyl ammonium salt or a 3-halogeno-2-hydroxypropyl trialkyl ammonium salt. The cation-modified polysaccharide is prepared by adding a glycidyl trialkyl as a cationizing agent after adding an alkylene oxide having 2 to 4 carbon atoms to a part of hydroxyl groups contained in β-1,3-glucan or β-1,3-xylan. The skin cleansing composition according to any one of claims 8 to 10, wherein the composition is cationically modified using an ammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt. The skin cleansing composition according to any one of claims 8 to 11, wherein the content of the cation-modified polysaccharide is 0.05 to 5.0% by mass, based on 100% by mass of the entire composition. Furthermore, other cationic water-soluble polymers and / or amphoteric water-soluble polymers are contained in an amount of 5% by mass or less based on 100% by mass of the entire composition. A skin cleansing composition as described in 1. above. The skin cleansing composition according to any one of claims 8 to 13, further comprising an organic acid and / or an inorganic acid of an amidoamine compound and a higher fatty acid and / or a higher alcohol.