JP4596689B2 - Cleaning composition - Google Patents

Description

また、２級アルコールとは、下記一般式（７）で表される。
【化１１】

【００４１】
したがって、Ｒ⁵は、上記の一般式（５）〜（７）において水酸基を除いた基である。上記の一般式（５）〜（７）においてＲ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁰およびＲ¹¹は炭化水素基である。
【００４２】
上記の一般式（６）において、Ｒ⁹は炭化水素基である。
【００４３】
また、Ｒ⁵は、炭素原子数２４以上の炭化水素であり、そのうちアルキル基であることが好ましく、さらにその合計の炭素原子数２４が好ましく、デシルテトラデシルアルコールから誘導された炭化水素基が特に好ましい。
本発明は、炭素原子数２４以上というＲ⁵のアルキル鎖長の基づく予期せぬ効果を発見したことに基づく。
すなわち、疎水変性ポリエーテルウレタンが会合性増粘剤として作用する場合、Ｒ⁵の炭素原子数を２４以上にすることにより、疎水性会合力が高まり、アニオン性界面活性剤及び／又は両性界面活性剤配合の洗浄剤組成物の粘度を、効率的に増すことが出来る。
【００４４】
また、付加させるアルキレンオキサイド、スチレンオキサイド等は、単独重合、２種以上のランダム重合あるいはブロック重合であって良い。付加の方法は通常の方法であって良い。重合度ｎは０〜１０００であり、好ましくは１〜２００、更に好ましくは１０〜５０が良い。また、Ｒ⁴に占めるエチレン基の割合が、好ましくは全Ｒ⁴の５０〜１００重量％、さらに好ましくは、６５〜１００重量％であると、本発明の目的に好ましい会合性増粘剤が得られる。
【００４５】
上記の一般式（１）で表される化合物を製造する方法としては、通常のポリエーテルとイソシアネートとの反応と同様にして例えば８０〜９０℃で１〜３時間加熱し、反応せしめて得ることができる。
【００４６】
また、Ｒ¹−[(Ｏ−Ｒ²)_k−ＯＨ]_mで表されるポリエーテルポリオール（ａ）と、Ｒ³−(ＮＣＯ)_h+1で表されるポリイソシアネート（ｂ）と、ＨＯ−(Ｒ⁴−Ｏ)_n−Ｒ⁵で表されるポリエーテルモノアルコール（ｃ）とを反応させる場合には、一般式（１）の構造の化合物以外のものも副生することがある。例えば、ジイソシアネートを用いた場合、主生成物としては一般式（１）で表されるｃ−ｂ−ａ−ｂ−ｃ型の化合物が生成するが、その他、ｃ−ｂ−ｃ型、ｃ−ｂ−(ａ−ｂ)_x−ａ−ｂ−ｃ型等の化合物が副生することがある。この場合、特に一般式（１）型の化合物を分離することなく、一般式（１）型の化合物を含む混合物の状態で本発明に使用することができる。
【００４７】
本発明にかかる洗浄剤組成物には、上記疎水変性ポリエーテルウレタンを０．１〜１０重量％配合することが好適である。配合量が０．１重量％より少ない場合には添加効果が認められないことがあり、１０重量％より多い場合には、粘度が高くなりすぎて、製造時の取り扱いに不都合を生じるようになり、作業効率が低下したり、実使用時に容器からの取り出しに不都合を生じたり、髪や肌へ塗布時の伸びが悪くなる場合がある。
【００４８】
（Ｂ）アニオン性界面活性剤及び／又は両性界面活性剤。
次に（Ｂ）成分の界面活性剤について詳述する。
「アニオン性界面活性剤」
本発明において用いるアニオン性界面活性剤は特に限定されないが、好ましくは上記一般式（２）（３）（４）で表わされるアニオン性界面活性剤が挙げられる。例えば、（２）ではヤシ脂肪酸Ｎ−メチルタウリン塩ラウリルメチルタウリン塩、ミリスチルメチルタウリン塩、ヤシ脂肪酸タウリンナトリウム塩、ヤシ油脂肪酸イセチオネート等が、（３）ではラウロイルグルタミン酸モノ塩、ラウロイルグルタミン酸ジ塩、ミリストイルグルタミン酸モノ塩、ミリストイルグルタミン酸ジ塩、ヤシ油脂肪酸アシルグルタミン酸モノ塩、ヤシ油脂肪酸アシルグルタミン酸ジ塩、ヤシ油脂肪酸アシルグリシン塩が、（４）ではラウリン酸塩、ミリスチン酸塩、ヤシ脂肪酸塩などの高級脂肪酸塩等が挙げられる。
【００４９】
また、これら一般式（２）（３）（４）のＭ１、Ｍ２、Ｍ３、Ｍ４としてはナトリウム、カリウム、アンモニウム、トリエタノールアミン、Ｎ−メチルタウリンナトリウム等が挙げられる。これらのアニオン界面活性剤は任意の一種又は二種以上を使用できる。
【００５０】
「両性界面活性剤」
本発明に用いる両性界面活性剤としては特に限定されないが、ベタイン型両性活性剤としてはラウリルジメチルアミノ酢酸ベタイン、ミリスチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルベタイン等が、イミダゾリン型両性界面活性剤としては２−ココイル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン、２−ラウリル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン等が挙げられる。これらの両性界面活性剤は任意の一種又は二種以上を使用できる。
【００５１】
上述のアニオン性界面活性剤と両性界面活性剤とを併用する場合において、その重量比は１０：０〜２：８であることが望ましい。両性界面活性剤が上記比率よりも多くなると、起泡性・泡持続性に劣るものとなり、洗浄剤組成物としては好ましくない。
【００５２】
また、界面活性剤の配合量としては洗浄剤組成物全量中５〜４０重量％であることが好ましい。すなわち、５重量％未満の配合量では、起泡性に劣り、充分な洗浄効果が得られない。また、４０重量％より多い配合量では、界面活性剤の溶解性が不十分で飽和濃度以上の析出が見られる場合があったり、洗浄効果の濃度依存性が見られなくなり、実質的にこれ以上の配合は無意味になる。
【００５３】
「粘性」
本発明の毛髪処理剤組成物の粘度は、２５℃、１s^-1で測定して１〜１０Ｐａ・ｓであるか、又は、２５℃、１００s^-1で測定して０．１〜１Ｐａ・ｓであることが好ましい。両者を満たすことが好ましい。
２５℃、１s^-1の測定条件（低ずり速度）では上記の高粘度の範囲が好ましい。上記範囲以外の粘度では、容器からの取り出しが困難になり、塗りのばし時の伸びが悪くなるなど、使用に不都合を生じるようになることがある。
２５℃、１００s^-1の測定条件（高ずり速度）では上記の低粘度の範囲が好ましい。
上記範囲以外の粘度では、使用場面で毛髪処理剤組成物を手に取った場合、垂れ落ち等を生じるとともに、組成物が希薄な印象を与え、いわゆるリッチな感触を与えることが困難になる。
上記の粘度は、一般式（１）の特定の疎水変性ポリエーテルウレタンにより、容易に達成できる。
粘度の測定法としては、市販のコーンプレート型又は二重円筒型粘度計、例えばＣａｒｒｉ−Ｍｅｄ社製ＣＳＬ−１００等を用いて測定することができる。
【００５４】
「その他の添加物」
本発明の洗浄剤組成物は上記必須成分の他に、本発明の効果を損なわない範囲において、通常、洗浄料に配合される他の成分、例えば、プロピレングリコール、ソルビトール、グリセリン等の保湿剤、カチオン性界面活性剤、シリコーン誘導体、高級アルコール等のコンディショニング剤、薬効剤、保湿剤、キレート剤、ｐＨ調整剤、抗炎症剤、防腐剤、紫外線吸収剤、酸化防止剤、色素、香料等を添加し、目的の剤形および用途に応じて常法により各種洗浄料が製造される。
なお、本発明の組成物において、カチオン化デンプンを配合すると以下の予期せぬ効果を発揮することを発見した。
▲１▼すすぎ時の毛髪のなめらか感が優れている。
▲２▼毛髪のべたつき感がない。
カチオン化デンプンは市販品（例えば、Sensomer CI-50:Nalco）を使用し、組成物全量に対して通常０．０１〜２重量％、好ましくは０．２〜１．５重量％配合される。
【００５５】
【実施例】
以下、実施例により本発明を更に詳しく説明する。なお、本発明は実施例に限定されるものではない。また、配合量は特に指定がない限り重量％で示す。
【００５６】
実施例に先だって、疎水変性ポリエーテルウレタンの製造例について示す。
＜製造例Ａ＞
温度計、窒素導入管及び攪拌機を付した容器１０００ｍＬの４つ口フラスコにポリエチレングリコール（ＰＥＧ）（分子量約１１０００）（Ｒ¹−[(Ｏ−Ｒ²)_k−ＯＨ]_mに相当）を５５０部、下記一般式
【化１２】

の分岐アルコールのエチレンオキサイド(ＥＯ)２０モル付加物（ＨＯ−(Ｒ⁴−Ｏ)_n−Ｒ⁵に相当）を１９８部仕込み、次いで、８０℃に冷却しヘキサメチレンジイソシアネート（ＨＭＤＩ）（Ｒ³−(ＮＣＯ)_h+1に相当）２９．６部を加え、窒素気流下８０〜１００℃に２時間反応させ、イソシアネートが０％であることを確認し、常温で淡黄色固体の反応生成物を得た。
【００５７】
製造例Ａと同様にして、種々の疎水変性ポリエーテルウレタンを調製することができる。例えば、「表１」に示される製造例Ａ〜Ｇによる疎水変性ポリエーテルウレタンは、本発明に好適に用いることができる。
【００５８】
【表１】
製造例A〜G

【００５９】
上記製造例の他、市販の疎水変性ポリエーテルウレタンも使用できる。
【００６０】
下記実施例、比較例を常法により調製した。これらの各試料を用いて、以下に示す評価法に従って洗浄料の「温度安定性（粘度）」、「粘弾性（製品粘性の官能評価）」、「泡立ち」、「泡の持続性」、「洗浄時のさっぱり感」の評価を行った。
【００６１】
温度安定性（粘度）
調製したサンプルを５０ｍｌ透明ガラス管に充填し、５０℃、３７℃、２５℃、０℃の各恒温槽に保存し、６ヵ月経時した後のサンプル状態（粘度）を観察した。粘度測定は、コーンプレート又は二重円筒型粘度計を用い、２５℃、１ｓ^-1及び１００ｓ^-1おける見かけの粘度を求めた。評価は以下のとおりに行った。
「評価」
◎：当初粘度（25℃）と比較し各温度サンプル粘度が１０％以下の変化
○：当初粘度（25℃）と比較し各温度サンプル粘度が２０％以下の変化
△：当初粘度（25℃）と比較し各温度サンプル粘度が２０％より大きく変化
【００６２】
粘弾性（製品粘性の官能評価）
各サンプルとも５０ｍｌ透明ガラス管から手に取りだした際、手からの液垂れの有無、伸ばしやすさを２０名のパネルにて評価した。
評価は以下の基準に従いおこなった。
「評価」
◎：２０名中１５名以上が洗浄時の塗布性（手からの液垂れがない・塗布時にのびが良い）に優れていると判定
○：２０名中１１〜１４名が洗浄時の塗布性（手からの液垂れがない・塗布時にのびが良い）に優れると判定
△：２０名中１０名以下が洗浄時の塗布性（手からの液垂れがない・塗布時にのびが良い）に優れると判定
【００６３】
泡立ち
調製したサンプルを用いて２５００ｍｌ容器の攪拌機付き円筒形シリンダーに４０℃の人工硬水（７０ｐｐｍ炭酸カルシウム）を４００ｍｌ入れ、被検試料４ｇを添加後、４５００ｒｐｍで１分間攪拌した直後の泡容量を測定した。
「評価」
◎：泡立ち良好（泡容量１２００ｍｌ以上）
○：泡立ち普通（泡容量８００ｍｌ以上）
△：泡立ち不良（泡容量８００ｍｌ未満）
【００６４】
泡の持続性
上記の泡立ち測定後５分後の泡容量を測定し、攪拌直後の泡立ちに対する比率を求めた。
比率は（5分後の泡容量／直後の泡容量）で計算した。
「評価」
◎：泡持続性良好（比率０．８以上）
○：泡持続性普通（比率０．６以上０．８未満）
△：泡持続性不良（比率０．６未満）
【００６５】
さっぱり感（洗い流し時及びタオルドライ後の官能評価）
各サンプル３ｇをとり、洗顔したとき、洗い流し時及びタオルドライ後のさっぱり感を２０名のパネルにて評価した。評価は以下の基準に従いおこなった。
「評価」
◎：２０名中１５名以上が洗い流し時及びタオルドライ後にさっぱりすると判定
○：２０名中１１〜１４名が洗い流し時及びタオルドライ後にさっぱりすると判定
△：２０名中１０名以下が洗い流し時及びタオルドライ後にさっぱりすると判定
【００６６】
【表２】

【００６７】
上記検討から、本発明の洗浄剤組成物は、優れた温度安定性、粘性、起泡性、泡持続性を有することが分かる。一方、疎水変性ポリエーテルウレタンを配合しない場合、特に温度安定性と粘性の官能評価に劣ることが分かる。
【００６８】
【表３】

【００６９】
上記検討から、本発明の洗浄剤組成物が優れた性質を示すことが分かる。一方、アニオン性界面活性剤と両性界面活性剤の重量比が２：８より大きい場合、特に粘性の官能評価と起泡性に劣ることが分かる。
【００７０】
【表４】

【００７１】
上記検討から、本発明の洗浄剤組成物では、疎水変性ポリエーテルウレタンの配合量は０．１〜１０重量％で至適となることが分かる。
【００７２】
【表５】

【００７３】
上記検討から、本発明による洗浄剤組成物では、界面活性剤の配合量が５〜４０重量％で至適となることが分かる。
【００７４】
【表６】

【００７５】
上記検討から、本発明の洗浄剤組成物では、疎水変性ポリエーテルウレタンの配合が、他の高分子増粘剤に比較し顕著に優れていることが分かる。
また、上記実施例から、粘弾性（粘性の官能評価）で高い評価結果を得るためには、粘度が２５℃、１s^-1で１〜１０Ｐａ・ｓ、２５℃、１００s^-1で０．１〜１Ｐａ・ｓであることが好ましいことが分かる。
【００７６】
以下にその他の実施例を挙げる。いずれも優れた粘性を有し、起泡性及び泡持続性に優れ、洗い流し後にもさっぱりしてぬめり感のない洗浄剤組成物である。
【００７７】
実施例１９ ボディー洗浄料
ヤシ脂肪酸カリウム ２０
ミリスチルジメチルアミノ酢酸ベタイン ３
本発明の製造例Ａ〜Ｇに記載の疎水変性ポリエーテルウレタン ２
グリセリン ５
タウリン ２．０
クエン酸 ０．５
ドデカン−１，２−ジオール酢酸エーテルナトリウム ３
ヒドロキシプロピルメチルセルロース ０．３
香料 適量
精製水 残部（全量１００）
上記成分を70℃に加熱して溶解し３０℃に冷却して製造した。
【００７８】
実施例２０ ジェル状洗浄料
ヤシ脂肪酸トリエタノールアミン １０
ミリスチルジメチルアミノ酢酸ベタイン １０
本発明の製造例Ａ〜Ｇに記載の疎水変性ポリエーテルウレタン １
グリセリン ５
クエン酸 ０．５
ドデカン−１，２−ジオール酢酸エーテルナトリウム ５
香料 適量
精製水 残部（全量１００）
上記成分を70℃に加熱して溶解し３０℃に冷却して製造した。
【００７９】
実施例２１ シャンプー
ヤシ脂肪酸アシルメチルタウリンナトリウム １０
ヤシ脂肪酸アミドプロピルベタイン ５
グリセリン １
クエン酸 １
タウリン １．５
メチルタウリン ０．５
本発明の製造例Ａ〜Ｇに記載の疎水変性ポリエーテルウレタン ０．５
カチオン化セルロース ０．５
香料 適量
精製水 残部（全量１００）
上記成分を80℃に加熱して溶解し３０℃に冷却して製造した。
【００８０】
実施例２２ リンス
Ｎ−ステアロイル−Ｎ−メチルタウリンナトリウム ２．０
ステアリルアルコール ８．５
グリセリン ５．０
クエン酸 ０．０３
本発明の製造例Ａ〜Ｇに記載の疎水変性ポリエーテルウレタン ０．５
ＫＡＴＨＯＮ ＣＧ（防腐剤、ロームアンドハース社） 適量
香料 適量
精製水 残部（全量１００）
【００８１】
実施例２３ 洗顔フォーム
ヤシ脂肪酸カリウム ２５
ヤシ脂肪酸Ｎ−メチルタウリンナトリウム ５
ポリエチレングリコール４００ １０
グリセリン ２０
ステアリン酸 ３
ドデカン―１，２―ジオール酢酸エーテルナトリウム ３
タウリン ２
本発明の製造例Ａ〜Ｇに記載の疎水変性ポリエーテルウレタン ０．５
香料 適量
精製水 残部（全量１００）
上記成分を80℃に加熱して溶解し３０℃に冷却して製造した。
【００８２】
実施例２４ ボディシャンプー
ヤシ脂肪酸カリウム ５
ヤシ脂肪酸アミドプロピルベタイン ２
プロピレングリコール １０
ドデカン−１，２−ジオール酢酸エーテルナトリウム １０
Ｎ−ヤシ脂肪酸−Ｎ−メチルタウリンナトリウム ５
タウリン １
本発明の製造例Ａ〜Ｇに記載の疎水変性ポリエーテルウレタン ０．５
香料 適量
精製水 残部（全量１００）
上記成分を80℃に加熱して溶解し３０℃に冷却して製造した。
【００８３】
下記試験を行って、本発明の予期せぬ効果を確認した。
「一般式（１）のＲ⁵の影響」
一般式（１）の会合性増粘剤において、末端疎水基の鎖長を長くすることで、疎水性会合力が高まり、より効率的に系を増粘出来ることを、確かめた。
粘度測定は、コーンプレート又は二重円筒型粘度計を用い、２５℃、１ｓ^-1及び１００s^-1における見かけの粘度を求めた。
【表７】

*1：製造例Ａと同様にしてＲ⁵の炭素数の異なる会合性増粘剤（疎水変性ポリエーテルウレタン）を調製した。
炭素原子数２４の化合物は、製造例Ａの疎水変性ポリエーテルウレタンである。
炭素原子数１８の化合物は、製造例Ａの一般式「化１２」に相当する化合物にステアリルアルコールのＥＯ２０モル付加物を使用して製造した。
炭素原子数１６の化合物は、製造例Ａの一般式「化１２」に相当する化合物にセチルアルコールのＥＯ２０モル付加物を使用して製造した。
炭素原子数１２の化合物は、製造例Ａの一般式「化１２」に相当する化合物にラウリルアルコールのＥＯ２０モル付加物を使用して製造した。
*2：シャンプー処方
ヤシ脂肪酸メチルタウリンナトリウム 10重量％
ヤシ脂肪酸アミドプロピルベタイン 6重量％
表に記載の会合性増粘剤 0.5重量％
カチオン化デンプン 0.5重量％
イオン交換水 残部
上記検討から、Ｒ⁵の炭素原子数が２４の疎水変性ポリエーテルウレタンを使用した場合、単純水溶液のみならず、本発明の洗浄剤組成物において、増粘効果が高くなることが分かる。
【００８４】
「カチオン化デンプンの影響」
下記の処方のシャンプーを調製し、これを使用したあとのすすぎのなめらか感、べたつき感を評価した。
下記の処方のシャンプーを用いて試験を行った。
ヤシ脂肪酸メチルタウリンナトリウム 10重量％
ヤシ脂肪酸アミドプロピルベタイン 6重量％
製造例Ａの化合物 0.5重量％
カチオン化デンプンまたはカチオン化セルロース 下記記載の量
イオン交換水 残部
評価方法
絶対評価による評点を、７段階（−３、−２、−１、０、＋１、＋２、＋３）で行なった。
−３と＋３の評価を下記に従って行った。
なめらか感；（大変なめらかでない：−３ → 大変なめらか：＋３）
べたつき感；（大変べたつく：−３ → 大変べたつかない：＋３）
パネル８名の平均値を求め、下記に従い判定した。
×：−１．５未満
△：−１．５ 〜 ＋０．５未満
○：＋０．５ 〜 ＋１．５未満
◎：＋１．５以上
【表８】

上記の結果から、カチオン化デンプンを配合したシャンプーで洗髪した場合、すすぎ時になめらかで、べたつき感のない良好な使用感が得られることが分かる。
【００８５】
本発明のその他の実施例を追加する。下記の実施例において、疎水変性ポリエーテルウレタンは、全て市販品(アデカノールＧＴ−７００：旭電化工業株式会社)である。
【００８６】

常温で精製水にカチオン化セルロースを水和させたあと８０℃に加熱し、その他の原料を投入し攪拌混合した後冷却し、シャンプーを調製する。
【００８７】

精製水に原料を順次投入し８０℃で攪拌混合した後冷却し、シャンプーを調製する。
【００８８】

精製水に原料を順次投入し８０℃で攪拌混合した後冷却し、シャンプーを調製する。
【００８９】

精製水に原料を順次投入し８０℃で攪拌混合した後冷却し、シャンプーを調製する。
【００９０】

精製水２０部に原料を順次投入し８０℃で攪拌混合した後冷却した後、常温の精製水残部を投入し、熱交換器にて冷却してヘアマニキュアコンディショナー(洗浄剤リンス)を調製する。
【００９１】

常温で精製水にカチオン化セルロースを水和させたあと８０℃に加熱し、その他の原料を投入し攪拌混合した後冷却し、シャンプーを調整する。
【００９２】

精製水に原料を順次投入し８０℃で攪拌混合した後冷却し、シャンプーを調整する。
【００９３】

精製水に原料を順次投入し８０℃で攪拌混合した後冷却し、シャンプーを調整する。
【００９４】

精製水に原料を順次投入し８０℃で攪拌混合した後冷却し、シャンプーを調整する。
【００９５】
【発明の効果】
本発明によれば、優れた粘性を有し、起泡性及び泡持続性に優れ、洗い流し後にもさっぱりしてぬめり感のない洗浄剤組成物を提供することが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cleaning composition. More specifically, the present invention relates to a detergent composition having excellent viscosity, excellent foaming properties and foam persistence, and refreshing after washing and without a slimy feeling.
[0002]
[Prior art]
In detergents, there are many products in the market that have been adjusted to a viscosity that is convenient for handling by adding an appropriate thickener to the surfactant solution, such as shampoos for hair, body shampoos, and facial cleansers. .
[0003]
These products usually contain several to several tens of weight percent of surfactants, mainly anionic surfactants, for the purpose of removing sufficient foam and dirt. In order to increase the viscosity of the surfactant solution, the combination of amphoteric surfactants, cationic surfactants, lipophilic nonionic surfactants, and salts such as sodium chloride is usually used to promote micelle growth and increase the system. I am trying to stick.
[0004]
[Problems to be solved by the invention]
However, certain anionic surfactants such as N-acylmethyl taurine salts, N-acyl taurine salts, N-acyl isethionates, fatty acid soaps, amino acid surfactants, etc. It is difficult to cause micelle growth, and as a result, it is difficult to impart a sufficiently satisfactory viscosity to the product.
[0005]
If the desired viscosity cannot be obtained, it not only causes inconveniences such as spillage and dripping during use, but also the comfort when using products that are very important to consumers in recent years, for example, richness with moderate viscosity It is difficult to satisfy sensory properties such as feeling and easiness to stretch, and it is extremely difficult to receive high evaluation in the market.
[0006]
On the other hand, when a thickener commonly used in cosmetics or the like, for example, a so-called polymer thickener such as carboxyvinyl polymer or xanthan gum is blended with these cleaning agents, various disadvantages occur. For example, when these polymer thickeners are blended, foaming (foaming property), which is most important for cleaning agents, is inhibited, and the foamed foam is also fragile, leaving problems in foam sustainability. It becomes like this. In addition, after the polymer thickener has been washed away, properties unfavorable in terms of use, such as wetness peculiar to the polymer, appear. Further, in a surfactant solution with a high concentration, the surfactant acts as a kind of salt and lowers the solubility of the polymer due to the salting out effect. In such a case, not only does the effect of the polymer thickener not be exhibited, but the thickener precipitates with time, resulting in unacceptable issues as a product.
[0007]
As a result of intensive studies in view of the above-mentioned problems, the present inventors have assembled in a water-soluble medium, thereby increasing the viscosity of the water-soluble medium, and a hydrophobic modified polyether urethane and an anionic interface The present inventors have found that a composition containing an activator or an amphoteric surfactant solves the above problems and exhibits excellent performance as a cleaning agent, and has completed the present invention.
[0008]
An object of the present invention is to provide a cleaning composition that has excellent viscosity, is excellent in foaming properties and foam persistence, and is refreshed after washing and has no sliminess.
[0009]
[Means for Solving the Problems]
That is, this invention provides the cleaning composition characterized by containing the following component (A) and (B).
(A) Hydrophobically modified polyether urethane represented by the following general formula (1)
[Chemical formula 5]
General formula (1)
R¹− {(O−R²)_k−OCONH−R^Three[-NHCOO- (R^Four-O)_n−R^Five]_h}_m      (1)
[In the formula, R¹, R²And R^FourRepresents a hydrocarbon group which may be the same or different from each other, and R^ThreeRepresents a hydrocarbon group which may have a urethane bond, R^FiveRepresents a linear, branched or secondary hydrocarbon group (24 or more carbon atoms, preferably 24 carbon atoms), m is a number of 2 or more, h is a number of 1 or more, k And n is independently a number in the range of 0 to 1000]
(B) Anionic surfactant and / or amphoteric surfactant
[0010]
The present invention also relates to a hydrophobically modified polyether urethane of the general formula (1):
R²And / or R^FourIs an alkylene group having 2 to 4 carbon atoms which may be the same as or different from each other, or a phenylethylene group.
[0011]
Furthermore, the present invention relates to a hydrophobically modified polyether urethane of the general formula (1)^ThreeIs R^Three-(NCO)_{h + 1}The above-mentioned detergent composition is provided which is a residue of a polyisocyanate represented by the formula:
[0012]
The present invention also provides the R^Three-(NCO)_{h + 1}Wherein the polyisocyanate residue is a polyisocyanate residue obtained by reacting a divalent to octavalent polyol with a divalent to tetravalent polyisocyanate. Is to provide.
[0013]
Furthermore, the present invention relates to a hydrophobically modified polyether urethane of the general formula (1)¹Is R¹-(OH)_mThe above-mentioned detergent composition is provided which is a residue of a polyol represented by the formula:
[0014]
The present invention also relates to a hydrophobically modified polyether urethane of the general formula (1):
R^FiveIs a hydrocarbon group derived from decyltetradecyl alcohol. The above-mentioned cleaning composition is provided.
[0015]
Further, in the present invention, the hydrophobically modified polyether urethane of the general formula (1) is
R¹-[(O-R²)_k-OH]_mAnd one or more polyether polyols represented by^Three-(NCO)_{h + 1}And one or more polyisocyanates represented by HO- (R^Four-O)_n-R^FiveThe above-mentioned cleaning composition, which is a reaction product of one or two or more polyether monoalcohols represented by the formula:
[0016]
The present invention also provides the above-mentioned cleaning composition, wherein the anionic surfactant is any one of the following general formulas (2), (3), and (4).
[Chemical 6]
General formula (2)
R1CO-a- (CH₂NSO_ThreeM1 (2)
(In the formula, R1CO- represents a saturated or unsaturated fatty acid residue having an average carbon number of 10 to 22, and a represents -O-, -NH-, -N (CH_Three)-Represents any structure of a linking group containing an electron-donating atom, M1 represents hydrogen, an alkali metal, an alkaline earth metal, ammonium or an organic amine, and n represents an integer of 1 to 3. To express)
[Chemical 7]
General formula (3)
R2CONH-C (b) H-COO M2 (3)
(In the formula, R2CO- represents a saturated or unsaturated fatty acid residue having an average carbon number of 10 to 22, b is a hydrogen atom, -CH_{Three ,}Or-(CH₂) Represents n-COOM3, M2 and M3 represent hydrogen, alkali metals, alkaline earth metals, ammonium or organic amines, and n represents an integer of 1 to 3)
[Chemical 8]
General formula (4)
R3COO-M4
(Wherein R3COO- represents a saturated or unsaturated fatty acid residue having an average carbon number of 10 to 22, M4 represents hydrogen, alkali metals, alkaline earth metals, ammonium or organic amines, and n represents Represents an integer of 1 to 3)
[0017]
Further, the present invention is characterized in that the anionic surfactant is one or more selected from the group consisting of N-acylmethyl taurine salts, N-acyl taurine salts or N-acyl isethionates. The above-mentioned cleaning composition is provided.
[0018]
The present invention also provides the above-mentioned cleaning composition, wherein the amphoteric surfactant is a betaine acetate type or imidazoline type amphoteric surfactant.
[0019]
Furthermore, the present invention provides the above-mentioned cleaning composition, wherein the weight ratio of the anionic surfactant to the amphoteric surfactant is 10: 0 to 2: 8.
[0020]
In the present invention, the amount of the hydrophobic modified polyether urethane of the general formula (1) is 0.1 to 10% by weight based on the total amount of the cleaning composition. Is to provide.
[0021]
Furthermore, the present invention provides the above-mentioned cleaning composition, wherein the amount of the anionic surfactant or amphoteric surfactant is 5 to 40% by weight based on the total amount of the cleaning composition. Is.
[0022]
In the present invention, the viscosity of the cleaning composition is 25 ° C., 1 s.^-1Measured at 1-10 Pa · s and / or 25 ° C., 100 s^-1The above-mentioned cleaning composition is characterized in that it is 0.1 to 1 Pa · s as measured by.
[0023]
Furthermore, the present invention provides the above-mentioned cleaning composition further comprising cationized starch.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the configuration of the present invention will be described in detail.
[0025]
(A) Hydrophobically modified polyether urethane of general formula (1)
The cleaning composition of the present invention contains a specific hydrophobically modified polyether urethane. The hydrophobically modified polyether urethane used in the present invention functions as an associative thickener and can increase the viscosity of a water-soluble medium. See the official gazette).
[0026]
The hydrophobically modified polyether urethane represented by the general formula (1) is, for example, R¹-[(O-R²)_k-OH]_mOne or more polyether polyols represented by the formula:^Three-(NCO)_{h + 1}And one or more polyisocyanates represented by HO- (R^Four-O)_n-R^FiveIt can obtain by making 1 type, or 2 or more types of polymonoalcohol represented by these react. In this case, R in the general formula (1)¹~ R^FiveR to use¹-[(O-R²)_k-OH]_m, R^Three-(NCO)_{h + 1}, HO- (R^Four-O)_n-R^FiveDetermined by. The charging ratio of the three members is not particularly limited, but the ratio of the hydroxyl group derived from polyether polyol and polyether monoalcohol to the isocyanate group derived from polyisocyanate is NCO / OH = 0.8: 1 to 1.4: 1. Is preferred.
[0027]
R preferably used for obtaining a hydrophobically modified polyether urethane of the general formula (1)¹-[(O-R²)_k-OH]_mThe polyether polyol compound represented by the formula can be obtained by addition polymerization of m-valent polyol with alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, or the like.
[0028]
  Here, the m-valent polyol is preferably a divalent to octavalent polyol, for example, a dihydric alcohol such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol; glycerin, trioxyisobutane, 1, 2,3-butanetriol, 1,2,3-pentatriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2, 3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol , Pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylol Trihydric alcohols such as tan and trimethylolpropane; pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, Tetrahydric alcohols such as 1,3,4,5-hexanetetrol; pentahydric alcohols such as adnit, arabit and xylit;Sorbit,Examples thereof include hexavalent alcohols such as mannit and exit; octavalent alcohols such as sucrose.
[0029]
In addition, depending on the alkylene oxide or styrene oxide to be added, R²In particular, alkylene oxide or styrene oxide having 2 to 4 carbon atoms is preferable in order to easily obtain and exhibit excellent effects.
[0030]
Alkylene oxide, styrene oxide and the like to be added may be homopolymerization, two or more kinds of random polymerization, or block polymerization. The adding method may be a normal method. The degree of polymerization k is 0 to 1000, preferably 1 to 500, and more preferably 10 to 50. R²The proportion of ethylene groups in the²When the content is 50 to 100% by weight, a good associative thickener for this purpose can be obtained.
[0031]
R¹-[(O-R²)_k-OH]_mThe molecular weight is preferably from 500 to 100,000, particularly preferably from 1,000 to 50,000.
[0032]
R preferably used for obtaining a hydrophobically modified polyether urethane of the general formula (1)^Three-(NCO)_{h + 1}The polyisocyanate represented by is not particularly limited as long as it has two or more isocyanate groups in the molecule. For example, aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, diisocyanate of phenylmethane, triisocyanate, tetraisocyanate and the like can be mentioned.
[0033]
Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene Range isocyanate, Examples include tetramethylxylylene diisocyanate.
Examples of the aromatic diisocyanate include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, and 1,4- Naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate and the like can be mentioned.
[0034]
Examples of the alicyclic diisocyanate include hydrogenated xylylene diisocyanate and isophorone diisocyanate.
[0035]
Examples of biphenyl diisocyanate include biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate, and the like.
[0036]
Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ′. , 5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis (4-isothiontphenyl) methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane 3,3′-diisocyanate, 4,4′-diethoxydiphenylmethane-3,3′-diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenylmethane-4,4′-diisocyanate, 3,3′- Dichlorodiphenyldimethylmethane-4,4'-diisocyanate, benzophenone -3,3'-diisocyanate and the like.
[0037]
Examples of the triisocyanate include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalene triisocyanate, and biphenyl. -2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, triphenylmethane-4,4 ', 4' ' -Triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenyl) thiophosphate, etc. Is mentioned.
[0038]
Moreover, you may use with the dimer and trimer (isocyanurate coupling | bonding) of these polyisocyanate compounds, and you may make it react with an amine and use it as a biuret. Further, polyisocyanates having urethane bonds obtained by reacting these polyisocyanate compounds with polyols can also be used. As a polyol, the thing of 2-8 valence is preferable, and the above-mentioned polyol is preferable. R^Three-(NCO)_{h + 1}When using a polyisocyanate having 3 or more valences, a polyisocyanate having this urethane bond is preferred.
[0039]
HO— (R) preferably used for obtaining the hydrophobic modified polyether urethane of the general formula (1)^Four-O)_n-R^FiveThe polyether monoalcohol represented by the formula is not particularly limited as long as it is a polyether of a linear, branched or secondary monohydric alcohol.
[0040]
Such a compound can be obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, or the like to linear, branched or secondary monohydric alcohol.
Here, the linear alcohol is represented by the following general formula (5).
[Chemical 9]
R⁶-OH (5)
The branched chain alcohol is represented by the following general formula (6).
Embedded image

The secondary alcohol is represented by the following general formula (7).
Embedded image

[0041]
Therefore, R^FiveIs a group excluding the hydroxyl group in the above general formulas (5) to (7). In the general formulas (5) to (7), R⁶, R⁷, R⁸, R^TenAnd R¹¹Is a hydrocarbon group.
[0042]
In the above general formula (6), R⁹Is a hydrocarbon group.
[0043]
R^FiveIs a hydrocarbon having 24 or more carbon atoms, preferably an alkyl group, more preferably a total of 24 carbon atoms, particularly preferably a hydrocarbon group derived from decyltetradecyl alcohol.
The present invention provides an R having 24 or more carbon atoms.^FiveBased on the discovery of an unexpected effect based on the alkyl chain length.
That is, when the hydrophobic modified polyether urethane acts as an associative thickener, R^FiveBy setting the number of carbon atoms to 24 or more, the hydrophobic associative power is increased, and the viscosity of the detergent composition containing the anionic surfactant and / or the amphoteric surfactant can be efficiently increased.
[0044]
Moreover, the alkylene oxide, styrene oxide, etc. to be added may be homopolymerization, two or more kinds of random polymerization, or block polymerization. The adding method may be a normal method. The degree of polymerization n is 0 to 1000, preferably 1 to 200, more preferably 10 to 50. R^FourThe proportion of ethylene groups in the^FourWhen it is 50 to 100% by weight, more preferably 65 to 100% by weight, an associative thickener preferable for the purpose of the present invention can be obtained.
[0045]
As a method for producing the compound represented by the above general formula (1), it can be obtained by heating and reacting at 80 to 90 ° C. for 1 to 3 hours, for example, in the same manner as in the reaction of an ordinary polyether and isocyanate. Can do.
[0046]
R¹-[(O-R²)_k-OH]_mA polyether polyol (a) represented by^Three-(NCO)_{h + 1}Polyisocyanate (b) represented by HO- (R^Four-O)_n-R^FiveIn the case of reacting with the polyether monoalcohol (c) represented by formula (1), compounds other than the compound having the structure of the general formula (1) may be by-produced. For example, when diisocyanate is used, the main product is a c-b-a-b-c type compound represented by the general formula (1). b- (ab)_xA compound such as -abc type may be by-produced. In this case, the compound of the general formula (1) type can be used in the present invention in the form of a mixture containing the compound of the general formula (1) type without separation.
[0047]
The detergent composition according to the present invention preferably contains 0.1 to 10% by weight of the hydrophobic modified polyether urethane. When the blending amount is less than 0.1% by weight, the effect of addition may not be observed. When the blending amount is more than 10% by weight, the viscosity becomes too high, resulting in inconvenience in handling during production. In some cases, work efficiency may be reduced, inconvenience in taking out from the container during actual use, or elongation at the time of application to hair or skin may be deteriorated.
[0048]
(B) Anionic surfactant and / or amphoteric surfactant.
Next, the surfactant (B) will be described in detail.
"Anionic surfactant"
Although the anionic surfactant used in the present invention is not particularly limited, anionic surfactants represented by the above general formulas (2), (3) and (4) are preferable. For example, in (2) coconut fatty acid N-methyltaurine salt laurylmethyltaurine salt, myristylmethyltaurine salt, coconut fatty acid taurine sodium salt, coconut oil fatty acid isethionate, etc. Myristoyl glutamic acid mono salt, myristoyl glutamic acid di salt, coconut oil fatty acid acyl glutamic acid mono salt, coconut oil fatty acid acyl glutamic acid di salt, coconut oil fatty acid acyl glycine salt, (4) laurate, myristic acid salt, coconut fatty acid salt, etc. And higher fatty acid salts.
[0049]
Examples of M1, M2, M3, and M4 in the general formulas (2), (3), and (4) include sodium, potassium, ammonium, triethanolamine, and sodium N-methyltaurine. Any one kind or two or more kinds of these anionic surfactants can be used.
[0050]
"Amphoteric surfactant"
The amphoteric surfactant used in the present invention is not particularly limited, but betaine-type amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, myristylaminoacetic acid betaine, coconut oil fatty acid amide propylbetaine, and the like as imidazoline-type amphoteric surfactants. Examples include 2-cocoyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, 2-lauryl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, and the like. These amphoteric surfactants can be used alone or in combination of two or more.
[0051]
In the case where the above-mentioned anionic surfactant and amphoteric surfactant are used in combination, the weight ratio is preferably 10: 0 to 2: 8. If the amphoteric surfactant is larger than the above ratio, the foaming property and the foam persistence are inferior, which is not preferable as a cleaning composition.
[0052]
Moreover, it is preferable that the compounding quantity of surfactant is 5 to 40 weight% in the washing | cleaning agent composition whole quantity. That is, when the blending amount is less than 5% by weight, the foaming property is inferior and a sufficient cleaning effect cannot be obtained. In addition, when the blending amount is more than 40% by weight, the solubility of the surfactant is insufficient and precipitation exceeding the saturation concentration may be observed, or the concentration dependency of the cleaning effect is not observed, and substantially more than this. The blending becomes meaningless.
[0053]
"viscosity"
The viscosity of the hair treatment composition of the present invention is 25 ° C., 1 s.^-11 to 10 Pa · s measured at 25 ° C., 100 s^-1It is preferable that it is 0.1-1 Pa.s as measured by. It is preferable to satisfy both.
25 ° C, 1s^-1In the above measurement conditions (low shear rate), the above high viscosity range is preferable. If the viscosity is outside the above range, it may be difficult to take out from the container, resulting in inconvenience in use, such as poor elongation during coating.
25 ° C, 100s^-1In the measurement conditions (high shear rate), the above low viscosity range is preferable.
When the hair treatment composition is picked up at the scene of use, when the viscosity is outside the above range, dripping or the like occurs, and the composition gives a thin impression, making it difficult to give a so-called rich feel.
The above viscosity can be easily achieved by the specific hydrophobically modified polyether urethane of the general formula (1).
The viscosity can be measured using a commercially available cone plate type or double cylinder type viscometer, for example, CSL-100 manufactured by Carri-Med.
[0054]
"Other additives"
In addition to the essential components described above, the cleaning composition of the present invention is not limited to the effects of the present invention, and other components that are usually blended in the cleaning material, for example, humectants such as propylene glycol, sorbitol, glycerin, Addition of conditioning agents such as cationic surfactants, silicone derivatives, higher alcohols, medicinal agents, moisturizers, chelating agents, pH adjusters, anti-inflammatory agents, preservatives, UV absorbers, antioxidants, pigments, fragrances, etc. However, various cleaning materials are produced by a conventional method according to the intended dosage form and application.
In addition, in the composition of this invention, when the cationized starch was mix | blended, it discovered that the following unexpected effects were exhibited.
(1) The smoothness of the hair during rinsing is excellent.
(2) There is no stickiness of hair.
The cationized starch is a commercially available product (for example, Sensomer CI-50: Nalco), and is usually added in an amount of 0.01 to 2% by weight, preferably 0.2 to 1.5% by weight, based on the total amount of the composition.
[0055]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to an Example. In addition, unless otherwise specified, the blending amount is indicated by weight%.
[0056]
Prior to the examples, production examples of hydrophobically modified polyether urethane will be described.
<Production Example A>
Polyethylene glycol (PEG) (molecular weight about 11000) in a 1000 mL four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer (R¹-[(O-R²)_k-OH]_m550 parts, the following general formula
Embedded image

A 20 mol adduct of branched-chain alcohol ethylene oxide (EO) (HO- (R^Four-O)_n-R^Five198 parts), then cooled to 80 ° C. and hexamethylene diisocyanate (HMDI) (R^Three-(NCO)_{h + 1}29.6 parts) was added and reacted at 80 to 100 ° C. for 2 hours under a nitrogen stream. It was confirmed that the isocyanate was 0%, and a light yellow solid reaction product was obtained at room temperature.
[0057]
In the same manner as in Production Example A, various hydrophobically modified polyether urethanes can be prepared. For example, hydrophobically modified polyether urethanes according to Production Examples A to G shown in “Table 1” can be suitably used in the present invention.
[0058]
[Table 1]
Production examples A to G

[0059]
In addition to the above production examples, commercially available hydrophobically modified polyether urethanes can also be used.
[0060]
The following examples and comparative examples were prepared by conventional methods. Using each of these samples, “temperature stability (viscosity)”, “viscoelasticity (sensory evaluation of product viscosity)”, “foaming”, “foam persistence”, “ Evaluation of “freshness at the time of washing” was performed.
[0061]
Temperature stability (viscosity)
The prepared sample was filled into a 50 ml transparent glass tube, stored in each thermostat at 50 ° C., 37 ° C., 25 ° C., and 0 ° C., and the sample state (viscosity) after aging for 6 months was observed. Viscosity is measured using a cone plate or double cylinder viscometer at 25 ° C for 1 s.^-1And 100s^-1The apparent viscosity was determined. Evaluation was performed as follows.
"Evaluation"
A: Change in sample viscosity at each temperature is 10% or less compared to the initial viscosity (25 ° C)
○: Change in sample viscosity at each temperature is 20% or less compared to the initial viscosity (25 ° C)
Δ: Viscosity of each temperature sample changed more than 20% compared to the initial viscosity (25 ° C)
[0062]
Viscoelasticity (sensory evaluation of product viscosity)
When each sample was taken out from a 50 ml transparent glass tube, the presence or absence of liquid dripping from the hand and the ease of extension were evaluated using a panel of 20 people.
Evaluation was performed according to the following criteria.
"Evaluation"
◎: 15 or more out of 20 people are judged to be excellent in applicability at the time of washing (no dripping from the hand and good spreading at the time of application)
○: It is determined that 11 to 14 out of 20 people are excellent in application property at the time of washing (no dripping from the hand and good spreading at the time of application).
Δ: 10 or less out of 20 people are judged to have excellent application properties during washing (no dripping from the hand, good spreading during application)
[0063]
Bubbling
Using the prepared sample, 400 ml of artificial hard water (70 ppm calcium carbonate) at 40 ° C. was placed in a cylindrical cylinder with a stirrer in a 2500 ml container, and after adding 4 g of the test sample, the foam volume immediately after stirring at 4500 rpm for 1 minute was measured. .
"Evaluation"
A: Good foaming (foam volume of 1200 ml or more)
○: Normal foaming (bubble capacity 800ml or more)
Δ: Poor foaming (foam volume less than 800 ml)
[0064]
Bubble persistence
The foam volume 5 minutes after the above foaming measurement was measured, and the ratio to the foaming immediately after stirring was determined.
The ratio was calculated by (foam volume after 5 minutes / foam volume immediately after).
"Evaluation"
A: Good foam persistence (ratio 0.8 or more)
○: Normal foam persistence (ratio of 0.6 to less than 0.8)
Δ: Poor bubble persistence (ratio less than 0.6)
[0065]
Refreshing feeling (sensory evaluation after washing and after towel drying)
A sample of 3 g was taken, and when the face was washed, the refreshing feeling after washing and after towel drying was evaluated by a panel of 20 people. Evaluation was performed according to the following criteria.
"Evaluation"
◎: More than 15 out of 20 people decide to refresh after washing and towel drying
○: It is determined that 11 to 14 out of 20 people are refreshed after washing and towel drying.
△: It is determined that 10 or less of 20 people will refresh after washing and towel drying.
[0066]
[Table 2]

[0067]
From the above study, it can be seen that the cleaning composition of the present invention has excellent temperature stability, viscosity, foamability, and foam persistence. On the other hand, it can be seen that when the hydrophobically modified polyether urethane is not blended, the sensory evaluation of temperature stability and viscosity is particularly poor.
[0068]
[Table 3]

[0069]
From the above examination, it can be seen that the cleaning composition of the present invention exhibits excellent properties. On the other hand, when the weight ratio of the anionic surfactant to the amphoteric surfactant is larger than 2: 8, it is found that the viscosity sensory evaluation and the foaming property are particularly poor.
[0070]
[Table 4]

[0071]
From the above examination, it can be seen that, in the cleaning composition of the present invention, the blending amount of the hydrophobic modified polyether urethane is optimal at 0.1 to 10% by weight.
[0072]
[Table 5]

[0073]
From the above examination, it can be seen that the detergent composition according to the present invention is optimal when the blending amount of the surfactant is 5 to 40% by weight.
[0074]
[Table 6]

[0075]
From the above study, it can be seen that in the cleaning composition of the present invention, the blend of hydrophobically modified polyether urethane is remarkably superior to other polymer thickeners.
Moreover, in order to obtain a high evaluation result by viscoelasticity (viscous sensory evaluation) from the said Example, a viscosity is 25 degreeC, 1s.^-11 to 10 Pa · s, 25 ° C., 100 s^-1It can be seen that 0.1 to 1 Pa · s is preferable.
[0076]
Other examples are given below. All of them are detergent compositions that have excellent viscosity, are excellent in foaming properties and foam persistence, and are refreshed after washing and have no sliminess.
[0077]
Example 19 Body Wash
Palm fatty acid potassium 20
Myristyldimethylaminoacetic acid betaine 3
Hydrophobic modified polyetherurethane described in Production Examples A to G of the present invention 2
Glycerin 5
Taurine 2.0
Citric acid 0.5
Sodium dodecane-1,2-diol acetate 3
Hydroxypropyl methylcellulose 0.3
Perfume
Purified water balance (total 100)
The above components were prepared by heating to 70 ° C to dissolve and cooling to 30 ° C.
[0078]
Example 20 Gel-like cleaning material
Palm fatty acid triethanolamine 10
Myristyldimethylaminoacetic acid betaine 10
Hydrophobic modified polyetherurethane described in Production Examples A to G of the present invention 1
Glycerin 5
Citric acid 0.5
Sodium dodecane-1,2-diol acetate ether 5
Perfume
Purified water balance (total 100)
The above components were prepared by heating to 70 ° C to dissolve and cooling to 30 ° C.
[0079]
Example 21 Shampoo
Palm Fatty Acid Acylmethyl Taurine Sodium 10
Palm Fatty Acid Amidopropyl Betaine 5
Glycerin 1
Citric acid 1
Taurine 1.5
Methyl taurine 0.5
Hydrophobically modified polyether urethane as described in Production Examples A to G of the present invention 0.5
Cationized cellulose 0.5
Perfume
Purified water balance (total 100)
The above components were prepared by heating to 80 ° C to dissolve and cooling to 30 ° C.
[0080]
Example 22 Rinse
N-stearoyl-N-methyltaurine sodium 2.0
Stearyl alcohol 8.5
Glycerin 5.0
Citric acid 0.03
Hydrophobically modified polyether urethane as described in Production Examples A to G of the present invention 0.5
KATHON CG (preservative, Rohm and Haas)
Perfume
Purified water balance (total 100)
[0081]
Example 23 Face Washing Foam
Palm fatty acid potassium 25
Coconut fatty acid sodium N-methyltaurine 5
Polyethylene glycol 400 10
Glycerin 20
Stearic acid 3
Dodecane-1,2-diol sodium acetate ether 3
Taurine 2
Hydrophobically modified polyether urethane as described in Production Examples A to G of the present invention 0.5
Perfume
Purified water balance (total 100)
The above components were prepared by heating to 80 ° C to dissolve and cooling to 30 ° C.
[0082]
Example 24 Body Shampoo
Palm fatty acid potassium 5
Palm Fatty Acid Amidopropyl Betaine 2
Propylene glycol 10
Sodium dodecane-1,2-diol acetate ether 10
N-coconut fatty acid-N-methyl taurine sodium 5
Taurine 1
Hydrophobically modified polyether urethane as described in Production Examples A to G of the present invention 0.5
Perfume
Purified water balance (total 100)
The above components were prepared by heating to 80 ° C to dissolve and cooling to 30 ° C.
[0083]
The following tests were conducted to confirm the unexpected effects of the present invention.
“R in general formula (1)^FiveImpact of"
In the associative thickener represented by the general formula (1), it was confirmed that by increasing the chain length of the terminal hydrophobic group, the hydrophobic associative power is increased and the system can be thickened more efficiently.
Viscosity is measured using a cone plate or double cylinder viscometer at 25 ° C for 1 s.^-1And 100s^-1The apparent viscosity at was determined.
[Table 7]

* 1: R as in Production Example A^FiveThe associative thickeners (hydrophobic modified polyether urethane) having different carbon numbers were prepared.
The compound having 24 carbon atoms is the hydrophobically modified polyether urethane of Production Example A.
The compound having 18 carbon atoms was produced by using EO 20 mol adduct of stearyl alcohol with the compound corresponding to the general formula “Chemical Formula 12” of Production Example A.
The compound having 16 carbon atoms was produced by using an EO 20 molar adduct of cetyl alcohol to the compound corresponding to the general formula “Chemical Formula 12” of Production Example A.
The compound having 12 carbon atoms was produced by using an EO 20 molar adduct of lauryl alcohol to the compound corresponding to the general formula “Chemical Formula 12” of Production Example A.
* 2: Shampoo prescription
Palm fatty acid methyl taurine sodium 10% by weight
Palm fatty acid amidopropyl betaine 6% by weight
Associative thickener listed in the table 0.5% by weight
Cationized starch 0.5% by weight
Ion exchange water balance
From the above examination, R^FiveWhen the hydrophobic modified polyether urethane having 24 carbon atoms is used, it can be seen that the thickening effect is enhanced not only in the simple aqueous solution but also in the cleaning composition of the present invention.
[0084]
"Effects of cationized starch"
A shampoo having the following formulation was prepared, and the smoothness and stickiness after rinsing were evaluated.
The test was conducted using a shampoo having the following formulation.
Palm fatty acid methyl taurine sodium 10% by weight
Palm fatty acid amidopropyl betaine 6% by weight
Compound of Production Example A 0.5% by weight
Cationized starch or cationized cellulose
Ion exchange water balance
Evaluation methods
The score by absolute evaluation was performed in 7 steps (-3, -2, -1, 0, +1, +2, +3).
-3 and +3 were evaluated according to the following.
Smooth feeling; (not very smooth: -3 → very smooth: +3)
Stickiness; (very sticky: -3 → not very sticky: +3)
The average value of 8 panelists was calculated and judged according to the following.
×: less than −1.5
Δ: -1.5 to less than +0.5
○: +0.5 to less than +1.5
A: +1.5 or more
[Table 8]

From the above results, it can be seen that when the hair is washed with a shampoo containing cationized starch, a good feeling of use is obtained which is smooth during rinsing and has no stickiness.
[0085]
Other embodiments of the present invention are added. In the following examples, the hydrophobically modified polyether urethanes are all commercially available products (Adecanol GT-700: Asahi Denka Kogyo Co., Ltd.).
[0086]

The cationized cellulose is hydrated in purified water at room temperature and then heated to 80 ° C., and other raw materials are added, stirred and mixed, and then cooled to prepare a shampoo.
[0087]

Raw materials are sequentially added to purified water, stirred and mixed at 80 ° C., and then cooled to prepare a shampoo.
[0088]

Raw materials are sequentially added to purified water, stirred and mixed at 80 ° C., and then cooled to prepare a shampoo.
[0089]

Raw materials are sequentially added to purified water, stirred and mixed at 80 ° C., and then cooled to prepare a shampoo.
[0090]

Raw materials are sequentially added to 20 parts of purified water, stirred and mixed at 80 ° C., and then cooled, and then the remaining purified water at room temperature is added and cooled in a heat exchanger to prepare a hair manicure conditioner (cleaner rinse).
[0091]

After cationized cellulose is hydrated in purified water at room temperature, the mixture is heated to 80 ° C., other raw materials are added, stirred and mixed, and then cooled to adjust the shampoo.
[0092]

Raw materials are sequentially added to purified water, stirred and mixed at 80 ° C., cooled, and shampoo is adjusted.
[0093]

Raw materials are sequentially added to purified water, stirred and mixed at 80 ° C., cooled, and shampoo is adjusted.
[0094]

Raw materials are sequentially added to purified water, stirred and mixed at 80 ° C., cooled, and shampoo is adjusted.
[0095]
【The invention's effect】
According to the present invention, it is possible to provide a cleaning composition that has excellent viscosity, is excellent in foaming property and foam persistence, and is refreshed after washing and has no slimy feeling.

Claims (15)

A cleaning composition comprising the following components (A) and (B):
(A) Hydrophobically modified polyether urethane represented by the following general formula (1)
General formula (1)
R ¹ -{(O-R ² ) _k -OCONH-R ³ [-NHCOO- (R ⁴ -O) _n -R ⁵ ] _h } _m (1)
[Wherein R ¹ , R ² and R ⁴ represent a hydrocarbon group which may be the same or different from each other, R ³ represents a hydrocarbon group which may have a urethane bond, R ⁵ represents a straight chain, Represents a branched or secondary hydrocarbon group (24 or more carbon atoms), m is a number of 2 or more, h is a number of 1 or more, and k and n are independently a number in the range of 0 to 1000. Is)
(B) Anionic surfactant and / or amphoteric surfactant In the hydrophobically modified polyether urethane of the general formula (1),
The cleaning composition according to claim 1, wherein R ² and / or R ⁴ is an alkylene group having 2 to 4 carbon atoms which may be the same or different from each other, or a phenylethylene group. In the hydrophobically modified polyether urethane of the general formula (1),
The cleaning composition according to claim 1 or 2, wherein R ³ is a residue of a polyisocyanate represented by R ^3- (NCO) _{h + 1} . The polyisocyanate residue represented by R ^3- (NCO) _{h + 1} is a polyisocyanate residue obtained by reacting a 2 to 8 valent polyol with a 2 to 4 valent polyisocyanate. The cleaning composition according to claim 3. In the hydrophobically modified polyether urethane of the general formula (1),
The cleaning composition according to claim 1, 2, 3 or 4, wherein R ¹ is a residue of a polyol represented by R ^1- (OH) _m . In the hydrophobically modified polyether urethane of the general formula (1),
The cleaning composition according to claim 1, 2, 3, 4 or 5, wherein the R ⁵ is a hydrocarbon group derived from decyltetradecyl alcohol. The hydrophobically modified polyether urethane of the general formula (1)
^One or more polyether polyols represented by R ¹ -[(O—R ² ) _k —OH] _m and one or more types represented by R ³ — (NCO) _{h + 1} Wherein the polyisocyanate is a reaction product of one or more polyether monoalcohols represented by HO— (R ⁴ —O) _n —R ⁵ . The cleaning composition according to 4, 5, or 6. The anionic surfactant is any one of the following general formulas (2), (3) or (4), and the cleaning agent according to claim 1, 2, 3, 4, 5, 6 or 7 Composition.
[Chemical 2]
General formula (2)
_{R1CO-a- (CH 2) nSO} 3 M1 (2)
(Wherein, R1CO- represents a fatty acid residue of a saturated or unsaturated average carbon atoms 10 to 22, a is -O -, - NH -, - N (CH 3) - of the electron donating atom And any one of the linking groups to be included, M1 represents hydrogen, alkali metals, alkaline earth metals, ammonium or organic amines, and n represents an integer of 1 to 3)
[Chemical Formula 3]
General formula (3)
R2CONH-C (b) H-COO M2 (3)
(Wherein, R2CO- denotes a saturated or unsaturated fatty acid residue having an average carbon number 10 to 22, b represents a hydrogen atom, -CH _3, or, - (CH ₂₎ represents an n-COOM3, M2, M3 represents hydrogen, alkali metals, alkaline earth metals, ammonium or organic amines, and n represents an integer of 1 to 3)
[Formula 4]
General formula (4)
R3COO-M4 (4)
(Wherein R3COO- represents a saturated or unsaturated fatty acid residue having an average carbon number of 10 to 22, M4 represents hydrogen, alkali metals, alkaline earth metals, ammonium or organic amines, and n represents Represents an integer of 1 to 3)   The anionic surfactant is one or more selected from the group consisting of N-acylmethyl taurine salt, N-acyl taurine salt or N-acyl isethionate. The cleaning composition according to 3, 4, 5, 6, 7 or 8.   The detergent composition according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the amphoteric surfactant is a betaine acetate type or imidazoline type amphoteric surfactant.   11. The weight ratio of an anionic surfactant to an amphoteric surfactant is 10: 0 to 2: 8, wherein the weight ratio is 10: 2 to 8:10. Cleaning composition.   The amount of the hydrophobically modified polyether urethane of the general formula (1) is 0.1 to 10% by weight with respect to the total amount of the cleaning composition, The cleaning composition according to 6, 7, 8, 9, 10 or 11.   The amount of the anionic surfactant or amphoteric surfactant is 5 to 40% by weight with respect to the total amount of the detergent composition, characterized in that it is 1, 2, 3, 4, 5, 6, 7 , 8, 9, 10, 11 or 12. The viscosity of the cleaning composition is ¹ to 10 Pa · s measured at 25 ° C. and 1 s ⁻¹ and / or 0.1 to ¹ Pa · s measured at 25 ° C. and 100 s ^−1. The cleaning composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13.   The detergent composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, further comprising cationized starch.