JP4230304B2 - Liquid detergent composition - Google Patents

Description

【００４３】
〔式中、Ｒ^２ａは炭素数８〜１８のアルキル基又はアルケニル基であり、Ｒ^２ｂは炭素数１〜６のアルキレン基であり、Ａは−ＣＯＯ−、−ＣＯＮＨ−、−ＯＣＯ−、−ＮＨＣＯ−から選ばれる基である。ｃは０又は１の数であり、Ｒ^２ｃ、Ｒ^２ｄは、それぞれ炭素数１〜３のアルキル基又はヒドロキシアルキル基である。〕
一般式（２）の化合物において、Ｒ^２ａは、好ましくは炭素数１０〜１６、より好ましくは１０〜１４のアルキル基又はアルケニル基であり、特に好ましくはラウリル基（又はラウリン酸残基）及び／又はミリスチル基（又はミリスチン酸残基）である。Ａは、好ましくは−ＣＯＯ−又は−ＣＯＮＨ−であり、最も好ましくは−ＣＯＮＨ−である。Ｒ^２ｂの炭素数は、好ましくは２又は３であり、Ｒ^２ｃ、Ｒ^２ｄは、好ましくはメチル基である。
【００４４】
一般式（２）の化合物は、式中のＲ^２ａが単独のアルキル（又はアルケニル）鎖長のものでも、異なるアルキル（又はアルケニル）鎖長を有するものの混合物でもよい。後者の場合には、ヤシ油、パーム核油から選ばれる植物油から誘導される混合アルキル（又はアルケニル）鎖長を有するものが好適である。具体的には式中のＲ^２ａがラウリル基（又はラウリン酸残基）とミリスチル基（又はミリスチン酸残基）のものの混合物であり、ラウリル基（又はラウリン酸残基）／ミリスチル基（又はミリスチン酸残基）のモル比が９５／５〜２０／８０、好ましくは９０／１０〜３０／７０の混合物であることが、洗浄効果及び泡立ち性の点から好ましい。
【００４５】
＜（ｄ）成分＞
本発明の（ｄ）成分は、（ａ）成分以外の水溶性有機溶媒であり、好ましくは炭素数１〜５の１価アルコール、及び炭素数４〜１２の多価アルコールから選ばれる化合物である。具体的には、エタノール、イソプロピルアルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリン、イソプレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルから選ばれる水溶性有機溶媒が好ましい。
【００４６】
＜（ｅ）成分＞
本発明の（ｅ）成分は、ハイドロトロープ剤であり、好ましい化合物としては、炭素数１〜３のアルキル基が１〜３個置換していてもよいベンゼンスルホン酸もしくはその塩を挙げることができる。（ｅ）成分としては、クメンスルホン酸、ｍ−キシレンスルホン酸、ｐ−トルエンスルホン酸から選ばれる１種以上が好ましく、特にｐ−トルエンスルホン酸が、粘度調整の目的から好ましい。塩としてはナトリウム塩、カリウム塩又はマグネシウム塩が好適である。
【００４７】
＜その他成分＞
本発明では、（ｂ）成分及び（ｃ）成分以外の界面活性剤（以下（ｆ）成分という）を含有させることができる。具体的には（ｃ）成分以外の両性界面活性剤、非イオン界面活性剤、及び陽イオン界面活性剤を挙げることができる。
【００４８】
両性界面活性剤（以下（ｆ−１）成分という）は、液体洗浄剤の起泡力を高め、（ｃ）成分を補助する目的から含有させることが好ましく、具体的には炭素数９〜１８の炭化水素基を１つと、炭素数１〜３のアルキル基又はヒドロキシアルキル基を２つ有する、スルホベタイン型界面活性剤とカルボベタイン型界面活性剤を挙げることができる。より具体的には、下記一般式（３）の化合物が好ましい。
【００４９】
【化２】

【００５０】
〔式中、Ｒ^３ａは炭素数９〜２３のアルキル基又はアルケニル基であり、Ｒ^３ｂは炭素数１〜６のアルキレン基である。Ｂは−ＣＯＯ−、−ＣＯＮＨ−、−ＯＣＯ−、−ＮＨＣＯ−、−Ｏ−から選ばれる基であり、ｂは０又は１の数である。Ｒ^３ｃ、Ｒ^３ｄは、それぞれ炭素数１〜３のアルキル基又はヒドロキシアルキル基であり、Ｒ^３ｅはヒドロキシ基で置換していてもよい炭素数１〜５のアルキレン基である。Ｄは−ＳＯ_３ ⁻、−ＣＯＯ⁻から選ばれる基である。〕
一般式（３）において、Ｒ^３ａは、好ましくは炭素数９〜１５、特に９〜１３のアルキル基であり、Ｒ^３ｂは、好ましくは炭素数２又は３のアルキレン基である。Ｂは−ＣＯＮＨ−が好ましく、ｂは０又は１が好適である。Ｒ^３ｃ、Ｒ^３ｄはメチル基、又はヒドロキシエチル基が好ましい。Ｄが−ＳＯ_３ ⁻の場合にはＲ^３ｅは−ＣＨ_２ＣＨ(ＯＨ)ＣＨ_２−が好ましく、Ｄが−ＣＯＯ⁻の場合にはＲ^３ｅはメチレン基が好ましい。
【００５１】
非イオン界面活性剤〔以下、（ｆ−２）成分という〕は、液体洗浄剤の洗浄力を向上させる目的、及び液体洗浄剤の貯蔵安定性を改善する目的から重要な界面活性剤の１つであり、好ましい具体的例としては、下記一般式（４）の化合物を挙げることができる。
【００５２】
Ｒ^４ａ−Ｅ−[(Ｒ^４ｂＯ)_ｅ−Ｈ]_ｆ （４）
〔式中、Ｒ^４ａは、炭素数７〜１８のアルキル基又はアルケニル基であり、Ｒ^４ｂは炭素数２又は３のアルキレン基である。ｅは２〜１００、好ましくは４〜８０、より好ましくは５〜５０の数を示す。Ｅは−Ｏ−、−ＣＯＮ−又は−Ｎ−であり、Ｅが−Ｏ−の場合はｆは１であり、Ｅが−ＣＯＮ−又は−Ｎ−の場合はｆは２である。〕
一般式（４）の化合物の具体例として、以下の化合物を挙げることができる。
【００５３】
Ｒ^４ａ−Ｏ−(Ｃ_２Ｈ_４Ｏ)_g−Ｈ （４−ａ）
〔式中、Ｒ^４ａは前記の意味を示す。ｇは２〜１００、好ましくは４〜８０、より好ましくは５〜５０の数である。〕
Ｒ^４ａ−Ｏ−(Ｃ_２Ｈ_４Ｏ)_h(Ｃ_３Ｈ_６Ｏ)_i−Ｈ （４−ｂ）
〔式中、Ｒ^４ａは前記の意味を示す。ｈ及びｉはそれぞれ独立に２〜７０、好ましくは２〜５０、より好ましくは３〜３０の数であり、エチレンオキシドとプロピレンオキシドはランダム又はブロック付加体であってもよい。〕
【００５４】
【化３】

【００５５】
〔式中、Ｒ^４ａは前記の意味を示す。ｊ及びｋの合計は３〜１５０、好ましくは４〜１００、より好ましくは６〜５０の数である。〕
陽イオン界面活性剤（以下（ｆ−３）成分という）は、被洗浄対象物に好ましい感触を付与したり、液体洗浄剤に抗菌効果を付与する目的から使用することができるが、（ｂ）成分とイオンコンプレックスを形成し、洗浄効果を減じる点、及び被洗浄対象物のぬるつきを助長する点などの問題があるため、使用する場合には注意を要する。
【００５６】
具体的に使用することができる陽イオン界面活性剤としては、エステル基、アミド基、エーテル基で分断されていてもよい炭素数８〜１８の炭化水素基が１つ又は２つと、残りが炭素数１〜３のアルキル基，炭素数１〜３のヒドロキシアルキル基又はベンジル基である４級アンモニウム塩、又は３級アミン、もしくは３級アミンの酸塩を挙げることができる。塩としては、ハロゲン塩、硫酸塩、脂肪酸塩が好適である。
【００５７】
本発明では、（ｂ）成分の陰イオン界面活性剤の乳化力を向上させ、洗浄効果を強化する目的から、マグネシウム〔以下、（ｇ）成分という〕を配合することが好ましく、マグネシウムは塩又は遊離したイオンとして系中に存在するものであり、（ｂ）成分の対イオンとして配合してもよく、また水溶性のマグネシウム化合物として配合することができる。水溶性マグネシウム化合物としては、化学便覧基礎編II（改定３版）１６６頁、表８．４２、及び１９０頁、表８．４７に記載のマグネシウム化合物において２０℃における水への溶解度が１ｇ／１００ｇ以上、好ましくは１０ｇ／１００ｇ以上の化合物が好適である。これらの中でも本発明では、硫酸マグネシウム、塩化マグネシウム、炭酸マグネシウム、硝酸マグネシウム、酢酸マグネシウムが最も好適である。
【００５８】
本発明の組成物には、ゲル化防止のための重合体、例えば特表平１１−５１３０６７号公報に記載されているゲル化防止重合体〔以下、（ｈ）成分という〕、とりわけポリアルキレングリコールを配合することが粘度調節及び貯蔵安定性の点から好ましい。
【００５９】
ポリアルキレングリコールの具体例としては、ポリエチングリコールを標準としたときのゲルパーミエーションクロマトグラフィーによって求められた重量平均分子量が２００〜３０００のポリプロピレングリコール、及びポリエチレングリコールが挙げられる。
【００６０】
本発明では、好ましい香りを液体洗浄剤組成物に付与する目的から香料〔以下、（ｉ）成分という〕を含有させることが好ましい。また、本発明において（ｂ）成分として分岐鎖を有する陰イオン界面活性剤を用いる場合には香料成分の安定配合を考慮して、ＬｏｇＰowが１．８〜７、好ましくは１．８〜５、特に２．０〜４．５の範囲にある香料成分を用いることが好ましい。これらＬｏｇＰowの規定を満たす香料成分を全香料中、３０質量％以上、より好ましくは５０質量％以上を占めることが望ましい。ここでＬｏｇＰowとは、有機物質（この場合は香料成分）の水と１−オクタノールに対する親和性を示す係数であり、香料成分の分野では香料成分の性質を示す上で、よく利用されているものである。ＬｏｇＰowは１−オクタノール／水分配係数で、ｆ値法（疎水性フラグメント定数法）により計算で求められた値をいう。具体的には、化合物の化学構造を、その構成要素に分解し、各フラグメントの有する疎水性フラグメント定数（ｆ値）を積算して求められる（CLOGP3 Reference Manual Daylight Software 4.34, Albert Leo, David Weininger,Version 1, March 1994）。
【００６１】
このようなＬｏｇＰowを満足する香料成分としては、以下の化合物を挙げることができる（かっこ内の数値はＬｏｇＰowの値を示す）。
【００６２】
アセチルイソイオゲノール（３．０）、アリルヘプタノエート（３．４）、カンフェン（４．２）、シトラール（３．１）、シトロネラール（３．３）、シトロネロール（３．３）、シトロネリルアセテート（４．２）、シクラメンアルデヒド（３．５）、リモネン（４．４）、ゲラニオール（２．８）、ゲラリルアセテート（３．７）、ゲラニルニトリル（３．９）、ヘキシルシンナミックアルデヒド（４．９）、α−ヨノン（３．７）、β―ヨノン（３．８）、１−メントール（３．２）、α−ピネン（４．２）、β−ピネン（４．２）、ターピネオール（２．６）、ターピノレン（４．４）、リナロール（２．５）、フェノキシエタノール（１．８）。
【００６３】
これらの中でも特に組成物の外観を改善する目的で、リモネン、リナロール、ゲラニルニトリル、ターピノレン、シトラール、ゲラニオール、フェノキシエタノールが好ましい。また、リモネンは液体洗浄剤中に安定に香料成分を配合するために重要な香料成分であり、特に全香料中に３０質量％以上、好ましくは５０質量％以上、より好ましくは７０質量％以上含まれることが好ましい。
【００６４】
また、上記以外にもイソアミルアセテート、シトロネリルニトリル、メチルベンゾエート、オイゲノール、ベンジルアルコール、ｃｉｓ−３−ヘキセノール、ジエチルマロネート、フェニルエチルアルコール、メチルヘプテノン、リナロールオキサイド、ジハイドロインデニル−２，４−ジオキシラン、クマリン、ヘキシルホルメート、ベンジルアセテート、アニスアルコール、ｌ−カルボン、メントン、ターピノレン、チモール、カンファー、ボルネオール、ターピニルアセテート等の香料成分を用いることができる。
【００６５】
本発明では（ｉ）成分として天然植物精油を用いることもできる。具体的にはハッカ油、アーモンド油、カラムス油、ペパーミント油、スペアミント油、シンナモン油、バジル油、セージ油、オールスパイス油、クローブ油、タイム油、ローズマリー油、レモングラス油、レモン油、ユズ油、ライム油、グレープフルーツ油、マンダリン油、アジョワン油、ベルガモット油、ローレル油、スターアニス油、マジョラム油、メース油、ボアドローズ油、キャラウエイ油、パルマローサ油、レモンベルベナ油、レモンバーム油、ラベンダー油、ローズ油、オレンジ油、カシア油、カッシー油、ガーリック油、キャロットシード油、カヤブテ油、シソ油、シナモン油、樟脳油、セダーウッド油、バチュリ油、ヒノキ油、ヒバ油、米油、ベニーロイヤル油、リセアキュベバ油、ユーカリ油、ティーツリー油、イランイラン油、ベチバー油、カナンガ油、シトロネラ油、ナツメグ油、ペッパー油、サンダルウッド油、ジンジャー油、アニス油、メース油、フェンネル油等を挙げることができる。
【００６６】
本発明ではこれら植物精油の中でもハッカ油、スペアミント油、バジル油、セージ油、ローズマリー油、レモングラス油、キャラウエイ油、キャロットシード油、ジンジャー油、ライム油から選ばれるものが液体洗浄剤に安定に配合することができるため好適である。
【００６７】
本発明では本発明の効果を損なわない限り、通常液体洗浄剤に配合されている成分を配合することができ、例えば、香料成分、除菌成分、防腐剤、濁り剤、着色剤を挙げることができる。
【００６８】
＜液体洗浄剤組成物＞
本発明は上記（ａ）成分〜（ｅ）成分、及び所望により（ｆ）成分、（ｇ）成分、（ｈ）成分、（ｉ）成分を含有する、２０℃における粘度が２００〜８００ｍＰａ・ｓの液体洗浄剤組成物である。
【００６９】
また、高い洗浄力と洗浄力の持続性を付与する目的から、組成物を水で希釈した場合の粘度が希釈濃度１００質量％未満、４０質量％以上の範囲で１０００ｍＰａ・ｓを越えず、希釈濃度４０質量％の粘度が希釈濃度１００質量％（未希釈を意味する）の粘度以上であり、且つ希釈濃度１００質量％の粘度の３倍を越えない粘度特性を有する組成物が好ましい。
【００７０】
本発明者らは、先願発明（特開２００２−２１２６００号公報）に希釈濃度１０〜６０質量％の範囲内に粘度の最大値が存在する液体洗浄剤が優れた洗浄力と洗浄力の持続性を実現できることを開示しているが、本発明の組成物は（ａ）成分を含有することにより、希釈濃度４０質量％まで未希釈のものの粘度以下に維持でき（希釈濃度４０質量％以上で未希釈のものの粘度以上になる。）、しかも高い洗浄効果を付与できる点で、先願発明にはない成分を含むことによる優れた効果を有するものである。
【００７１】
本発明でいう粘度は、以下のようにして測定する。まずＴＯＫＩＭＥＣ.ＩＮＣ製Ｂ型粘度計モデルＢＭに、ローター番号Ｎｏ.２のローターを備え付けたものを準備する。試料をトールビーカーに充填し２０℃の恒温槽内にて２０℃に調製する。恒温に調製された試料を粘度計にセットする。ローターの回転数を３０ｒ／ｍに設定し、回転を始めてから６０秒後の粘度を本発明の粘度とする。
【００７２】
また、本発明において希釈濃度とは、液体洗浄剤組成物を水で希釈する場合の液体洗浄剤組成物の濃度を指す。例えば希釈濃度４０質量％とは、液体洗浄剤４０重量部と水６０重量部を混合した場合の状態を指す。
【００７３】
（ａ）成分は、組成物中に０．１〜１０質量％、好ましくは０．３〜８質量％、特に好ましくは０．５〜５質量％含有され、このような範囲で優れた洗浄力と洗浄力の持続性を維持しながら、洗浄初期の泡立ちを改善し、しかも洗浄時又は濯ぎ時のぬるつきを軽減できる効果を得ることができる。
【００７４】
（ｂ）成分は、組成物中に１５〜５０質量％、好ましくは１５〜４０質量％、特に好ましくは２０〜３５質量％含有され、（ｃ）成分は、組成物中に１〜１５質量％、好ましくは１．５〜１２質量％、特に好ましくは２．０〜１０質量％含有される。
【００７５】
また、上記粘度挙動を呈し、洗浄力及び洗浄力の持続性を付与する目的から、（ｂ）成分／（ｃ）成分の含有量の質量比は、好ましくは２／１〜１０／１、より好ましくは２／１〜９／１、特に好ましくは２．５／１〜８／１である。
【００７６】
（ｄ）成分及び（ｅ）成分は、上記粘度挙動を呈し、洗浄力及び洗浄力の持続性を達成する目的から重要な成分である。
【００７７】
（ｄ）成分は、組成物中に０．１〜２０質量％、好ましくは０．５〜１８質量％、特に好ましくは１．０〜１５質量％含有され、（ｅ）成分は、組成物中に０．１〜１５質量％、好ましくは０．１〜１０質量％、特に好ましくは０．５〜８質量％であり、（ｄ）成分及び（ｅ）成分は合計で０．５〜２５質量％、好ましくは１．０〜２０質量％、特に好ましくは２．０〜１８質量％含有される。
【００７８】
また、（ｄ）成分／（ｅ）成分の含有量の質量比は、好ましくは１／１〜１５／１、より好ましくは１／１〜１０／１、特に好ましくは１．５／１〜８／１にすることが、上記粘度挙動を達成し、高い洗浄力と持続性を得るために好ましい。
【００７９】
（ｆ）成分は任意であるが、洗浄力、安定性、起泡性などに効果を有するため含有させることが好ましい。（ｆ−１）成分は、起泡性の点から、組成物中に好ましくは０．１〜１５質量％、より好ましくは０．３〜１０質量％、特に好ましくは０．５〜８質量％含有され、（ｆ−２）成分は、洗浄力の点及び安定性の点から、組成物中に好ましくは０．１〜１５質量％、より好ましくは０．３〜１０質量％、特に好ましくは０．５〜８質量％含有される。なお、（ｆ−３）成分は、洗浄効果を低下させたり、被洗浄対象物のぬるつきを助長する傾向にあるため、組成物中に、好ましくは５質量％以下、より好ましくは３質量％以下、特に好ましくは１質量％以下にとどめる。
【００８０】
（ｇ）成分は、（ｂ）成分と併用することで油への乳化力を向上させ、洗浄力を高めることができるため含有させることが好ましく、マグネシウムとして組成物中に、好ましくは０．０１〜２質量％、より好ましくは０．０５〜１質量％、特に好ましくは０．１〜１質量％が好適である。
【００８１】
（ｈ）成分は、ゲル化防止機能を有する反面、上記粘度特性に影響する成分でもあるため、含有させる場合には注意が必要であり、組成物中に、好ましくは１０質量％以下、より好ましくは５質量％以下、特に好ましくは３質量％以下にとどめる。
【００８２】
（ｉ）成分は、組成物に好ましい香りを付与する目的から含有させることが好ましく、組成物中に好ましくは０．０１〜２質量％、より好ましくは０．０５〜１．５質量％、特に好ましくは０．１〜１．０質量％含有させる。
【００８３】
本発明の組成物は、上記成分及び水を配合した水溶液の形態であり、水の含有量は、粘度の点から、好ましくは２０〜６０質量％、更に好ましくは３０〜６０質量％、より好ましくは３５〜６０質量％、特に好ましくは３５〜５０質量％である。
【００８４】
組成物の２０℃におけるｐＨを６〜８、好ましくは６．５〜７．５にすることが、貯蔵安定性や皮膚への安全性の点から好ましい。ｐＨ調整剤としては塩酸や硫酸など無機酸や、クエン酸、コハク酸、リンゴ酸、フマル酸、酒石酸、マロン酸、マレイン酸などの有機酸などの酸剤や、水酸化ナトリウムや水酸化カリウム、アンモニアやその誘導体、モノエタノールアミンやジエタノールアミン、トリエタノールアミンなどのアミン塩など、炭酸ナトリウム、炭酸カリウムなどのアルカリ剤を、単独もしくは複合して用いることが好ましく、特に塩酸、硫酸、クエン酸から選ばれる酸と水酸化ナトリウムや水酸化カリウムから選ばれるアルカリ剤を用いることが好ましい。いずれの化合物も、粘度特性に対し大きな影響のない範囲で配合される。
【００８５】
＜可撓性吸収体及び洗浄方法＞
本発明の液体洗浄剤組成物は、上記液体洗浄剤組成物と水とを含浸させた可撓性吸収体を用いて硬質表面を洗浄する洗浄方法に適用できる。
【００８６】
上記したような粘度特性を示す液体洗浄剤組成物は、可撓性吸収体に直接含浸させ、少量の水とともに、好ましくは硬質表面を被洗浄物とした場合に、被洗浄面を擦ることによって洗浄する洗浄方法に最適な液体洗浄剤組成物であり、とりわけ食器、調理器具に対する洗浄に関して優れた洗浄力と洗浄持続性を示す。
【００８７】
ここで含浸とは、液体洗浄剤組成物が可撓性吸収体に染込むことを意味する。可撓性吸収体としては、ポリ塩化ビニル、ポリ塩化ビニリデン、ナイロン、ポリプロピレン、ポリエステル、セルロース、ポリアクリルアミド、ポリウレタンを原材料としたスポンジやたわしが好ましく、特にポリウレタン、セルロースを原材料としたものがよい。
【００８８】
また、１回の洗浄工程に０．１〜２ｇの液体洗浄剤組成物を可撓性吸収体に含浸させることが好ましい。本発明の粘度特性を有する液体洗浄剤組成物を用いる場合、可撓性吸収体に対して水を含浸させる操作と液体洗浄剤組成物を含浸させる操作の順序は、何れが先であっても優れた洗浄持続性を得ることができ、継ぎ足し洗いにおいても同様である。
【００８９】
【発明の効果】
本発明の液体洗浄剤組成物によれば、泡立ち性及び洗浄性が良く、洗浄時には食器や調理器具等の硬質表面のぬるつきが少なく、濯ぎ時にはぬるつきが速やかに除かれる。
【００９０】
【実施例】
表１に示す成分を用いて液体洗浄剤組成物を調製した。これら組成物の泡立ち性、感触、洗浄力を下記の方法で評価した。結果を表１に示す。
【００９１】
＜泡立ち性の測定＞
市販の新品スポンジ（可撓性吸収体、キクロン）を水道水でもみ洗いし、水道水の含有量が１５ｇになるまで絞る。表１の組成物の１質量％水溶液３０ｇをスポンジに染み込ませ陶器皿上に置く。スポンジと同じ大きさのプラスチックプレートを用いて皿上のスポンジを手で２回圧縮する。スポンジから出た泡をメスシリンダーに回収し泡の体積（ml）を測定する。
【００９２】
＜感触評価＞
サラダ油に０．１質量％の色素（スダンレッド）を均一に混ぜ込んだモデル油汚れ１ｇを陶器皿に均一に塗り広げたものをモデル汚染食器とした。
【００９３】
市販の新品スポンジ（可撓性吸収体、キクロン）を水道水でもみ洗いし、水道水の含有量が１５ｇになるまで絞った後、表１の組成物１ｇと水道水３０ｇを染み込ませる。モデル汚染食器上で上記スポンジを２〜３回手でもみ泡立たせた後、モデル汚染食器５枚を擦り洗いし、洗っている最中のぬるつきを下記基準で官能評価を行った。
【００９４】
次に、擦り洗いしたモデル汚染食器を水道水ですすぎ、すすぎ最中のぬるつきのとれやすさ（ぬるつきがなくなるまでに要した時間の相対評価）を下記基準で官能評価を行った。
【００９５】
［洗浄時のぬるつきの基準］
あまりぬるつかない：○
ややぬるつく：△
非常にぬるつく：×
［すすぎ時のぬるつきのとれやすさの基準］
すぐにぬるつきがとれる：○
ぬるつきがとれるまでにやや時間がかかる：△
ぬるつきがとれるまでに時間がかかる：×
＜洗浄力試験＞
サラダ油／牛脂（試薬）＝９／１（質量比）混合油に、０．１質量％の色素（スタンレッド）を均一に混ぜ込んだモデル油汚れ０．５ｇをポリプロピレン製の皿に均一に塗り広げたものをモデル汚染食器とした。
【００９６】
市販の新品スポンジ（可撓性吸収体、キクロン）を水道水でもみ洗いし、水道水の含有量が１５ｇになるまで絞った後、表１の組成物１ｇと水道水３０ｇを染み込ませる。モデル汚染食器上で上記スポンジを２〜３回手でもみ泡立たせた後、モデル汚染食器を擦り洗いし、洗浄（食器に付着した色が消えることにより確認）できた皿の枚数を求めた。
【００９７】
＜粘度の測定＞
（液体洗浄剤組成物の粘度測定方法）
ＴＯＫＩＭＥＣ ＩＮＣ．製Ｂ型粘度計モデルＢＭにローター番号Ｎｏ．３のローターを備えた付けたものを準備する。表１の液体洗浄剤組成物を粘度測定用ビーカーに充填し２０℃の恒温槽にて２０℃に調製する。恒温に調製された試料を粘度計にセットする。ローターの回転数を３０ｒ／ｍに設定し、回転をはじめてから６０秒後の粘度を液体洗浄剤組成物の粘度とする。
【００９８】
（希釈された液体洗浄剤組成物の粘度測定方法）
表１の組成物をイオン交換水又は蒸留水を用いて1０質量％、２０質量％、３０質量％、４０質量％５０質量％、６０質量％、７０質量％、８０質量％、９０質量％となるように希釈し、均一に攪拌する。希釈組成物を粘度測定用ビーカーに移し２０℃の恒温槽にて２０℃に調整する。恒温に調整された試料を粘度計にセットする。ローターの回転数を３０ｒ／ｍに設定し、回転をはじめてから６０秒後の粘度を測定する。
【００９９】
測定した粘度が希釈濃度９０質量％〜４０質量％以上の範囲で１０００ｍＰａ・ｓを越えず、希釈濃度４０質量％の粘度が未希釈の粘度以上、かつ未希釈の粘度の３倍を越えない粘度特性を有するものを合格、そうでないものを不合格とした。
【０１００】
【表１】

【０１０１】
（注）かっこ内の数字は、マグネシウムとしての組成物中の濃度（質量％）
【０１０２】
【表２】

【０１０３】
（注１）かっこ内の数字は、マグネシウムとしての組成物中の濃度（質量％）
（注２）配合例１〜８の組成物は、ｐＨ（２０℃）が６．６〜７．０の範囲であり、粘度（２０℃）は、２００〜８００ｍＰａ・ｓの範囲である。
（注３）表中の記号は以下のものを表す。
・２ＥＨ-ＧＥ：２−エチルヘキシルモノグリセリルエーテル（多量体含量０．５質量％以下）
・２ＥＨ-ＡＧ：２−エチルヘキシルグリコシド（グルコース平均縮合度１．３）
・isoＮ−ＡＧ：イソノニルグリコシド（グルコース平均縮合度１．３）
・isoD−ＡＧ：イソデシルグリコシド（グルコース平均縮合度１．３）
・Ｃ６−ＧＥ：ｎ−ヘキシルモノグリセリルエーテル
・Ｃ８-ＧＥ：ｎ−オクチルモノグリセリルエーテル
・Ｃ１０−ＧＥ：ｎ−デシルモノグリセリルエーテル
・Ｃ８−ＡＧ：ｎ−オクチルグリコシド（グルコース平均縮合度１．３）
・Ｃ１０−ＡＧ：ｎ−デシルグリコシド（グルコース平均縮合度１．３）
・ＥＳ−Ｉ：ポリオキシエチレンアルキルエーテル硫酸ナトリウム〔原料アルコールは、１−デセン及び１−ドデセン５０／５０（質量比）を原料にヒドロホルミル化して得られたアルコールである。このアルコールにＥＯを平均２モル付加させた後、三酸化イオウにより硫酸化し、水酸化ナトリウムで中和した。全ポリオキシエチレンアルキルエーテル硫酸ナトリウム中の全ポリオキシエチレン分岐鎖アルキルエーテル硫酸ナトリウムの割合は４２質量％％であった。〕
・ＥＳ−II：ポリオキシエチレンココナッツアルキルエーテル硫酸アンモニウム（ＥＯ平均付加モル数２モル）
・ＥＳ−III：ポリオキシエチレンラウリルエーテル硫酸アンモニウム（ＥＯ平均付加モル数４モル）
・ＡＯ−I：Ｎ−ラウリル−Ｎ，Ｎ−ジメチルアミンオキシド
・ＡＯ−II：ラウリン酸アミドプロピルアミンオキサイド
・ｐ−ＴＳ：ｐ−トルエンスルホン酸ナトリウム
・スルホベタイン：ラウリルジメチルヒドロキシスルホベタイン
・ノニオン−Ｉ：Ｃ12、Ｃ13混合アルキル２級アルコールに、ＥＯを平均１２モル付加させたもの（ソフタノール１２０、日本触媒株式会社製）
・ノニオン−II：アルキル基の組成が炭素数１２／炭素数１４＝６０／４０（モル比）混合アルキルで、グルコシド平均縮合度１．５のアルキルグルコシド
・防腐剤：プロキセルＢＤＮ（アビシア株式会社社製）
・ｐＨ：１Ｎ−硫酸水溶液又は１Ｎ−水酸化ナトリウムを用いて調整した。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid detergent composition. In particular, the present invention relates to a liquid cleaning composition suitable for a method of cleaning by directly impregnating a flexible absorbent such as a sponge or towel and rubbing the surface of an object to be cleaned with water.
[0002]
[Prior art]
Liquid detergents such as dishwashing detergents require high detergency and durability of the detergency, and increase the viscosity of the liquid detergent as an achievement means to increase the holding power to the flexible absorbent, Techniques for improving the durability of the cleaning power are known.
[0003]
Patent Document 1, Patent Document 2, and Patent Document 3 disclose liquid cleaning agents adjusted to a specific viscosity. Further, the present inventors have found a liquid detergent having a specific viscosity behavior when diluted in water as a liquid detergent satisfying high detergency and durability, and disclosed in Patent Document 4, Patent Document 5, and the like. ing. These are inventions related to the technology for controlling the release of liquid detergent by increasing the viscosity of the liquid detergent by being diluted with water and being held by the flexible absorber. Sustainability.
[0004]
However, when the cleaning agent with increased viscosity is impregnated into a flexible absorbent such as a sponge for cleaning, since the release of the liquid cleaning agent is suppressed at the initial stage of cleaning, compared with a normal liquid cleaning agent, There is a tendency that foaming at the initial stage of washing is also suppressed. In liquid detergents such as dishwashing detergents, preferred foamability is regarded as important, and therefore it is desired to further improve the initial foamability in the above technique.
[0005]
Another problem of these cleaning agents is that the object to be cleaned becomes wet during cleaning or rinsing, and such a phenomenon is a problem that is often caused in normal liquid cleaning agents. Since the liquid detergent with improved viscosity as described above is a concentrated liquid detergent with improved surfactant concentration, the contact between the high concentration surfactant and the hard surface adheres to the hard surface. While making it easier to remove oil stains, excess surfactant causes the problem of sliminess. Luster is felt between a finger, palm, etc. and the surface of the object to be cleaned during washing or rinsing, and the feeling is that the cleaning agent is present on the surface of the object to be cleaned as an oil film. The touch is not easy to remove during rinsing but also during rinsing. Basically, it can be resolved by rinsing thoroughly (making the rinsing time longer than the usual rinsing time). In addition to disbelief in rinsing water, the rinsing water is wasted due to an increase in rinsing time.
[0006]
The sliminess becomes more prominent when an amine oxide type surfactant is used. Amine oxide surfactants form a complex with anionic surfactants commonly used in liquid detergents, thereby improving the emulsifying power of oil and, as a result, improving the cleaning power. It is thought to be a cause of sliminess during rinsing. Reducing the amount of the amine oxide type surfactant improves the wetness during washing and rinsing, but the foaming properties are impaired, especially when the flexible absorbent is impregnated and washed. Sexuality is impaired. Accordingly, there is a need for a liquid cleaning agent that improves foaming properties at the initial stage of cleaning and improves luster during cleaning and rinsing.
[0007]
  Alkyl glyceryl etherWhen, Anionic surfactants and amine oxide surfactants described aboveTheCombined liquid detergents are known.
[0008]
Patent Document 6 discloses a technique of a dishwashing detergent containing an anionic surfactant, an amine oxide type surfactant, and an alkyl glyceryl ether. Patent Document 7 describes the combined use with an amine oxide surfactant, and the technique of this document is also to improve the cleaning effect. Patent Document 8 discloses a technique of a cleaning agent using a branched alkyl glyceryl ether, and suggests that the cleaning agent can be used for kitchen applications.
[0009]
Also known are liquid detergents in which alkyl glycosides and anionic surfactants are combined.
[0010]
Patent Document 9 describes that an alkyl glycoside having 6 to 22 carbon atoms has an effect on the stability of an aqueous solution of an anionic surfactant and can be applied to a dishwashing detergent. Patent Document 10 describes that an alkyl glycoside having 4 to 22 carbon atoms has foaming power and cleanliness. Patent Document 11 describes that an alkyl glycoside having 8 to 12 carbon atoms is used as a rinsing agent in dishwashing. Patent Document 12 discloses a cleaning agent suitable for dishwashing that does not cause roughening and the like, containing an alkyl glycoside having 8 to 18 carbon atoms, an anionic surfactant, and an amine oxide type surfactant. Patent Document 13 discloses a detergent composition suitable for dishwashing or the like using a combination of an alkyl glycoside having 8 to 18 carbon atoms and an amine oxide type surfactant. Patent Document 14 describes that an alkyl glycoside having an alkyl group having 2 to 6 carbon atoms is effective in reducing the viscosity and improving the stability of the detergent composition.
[0011]
These alkyl glyceryl ethers and alkyl glycosides are also known to improve foaming properties, but when applied to the above thickened liquid detergent technology, foaming properties can be improved, but not at a satisfactory level. In addition, it has no effect on the improvement of luster during washing or rinsing. That is, it cannot be recalled from the above-mentioned prior art that a specific compound has an excellent effect of improving the initial foamability and improving the wetness during washing or rinsing.
[0012]
[Patent Document 1]
JP 2002-256299 A
[Patent Document 2]
JP 2002-256300 A
[Patent Document 3]
No. 2002-235100
[Patent Document 4]
JP 2002-212600 A
[Patent Document 5]
JP 2002-194388 A
[Patent Document 6]
JP 2001-19993 A
[Patent Document 7]
JP 2001-49291 A
[Patent Document 8]
JP 11-310792 A
[Patent Document 9]
JP-T 8-502540
[Patent Document 10]
Japanese National Patent Publication No. 8-502310
[Patent Document 11]
JP-T-8-501817
[Patent Document 12]
JP-A-5-148494
[Patent Document 13]
JP 2000-26889 A
[Patent Document 14]
US Pat. No. 4,488,981
[0013]
[Problems to be solved by the invention]
The problem of the present invention is that it has a high detergency and durability of the detergency, and can give a preferable foaming property at the initial stage of washing, and further, it can reduce the wetness of the object to be washed during washing and / or rinsing. It is an object of the present invention to provide a liquid detergent composition suitable for a method of washing by directly impregnating a flexible absorbent and rubbing the surface of an object to be washed with water.
[0014]
[Means for Solving the Problems]
As a means for solving the problem, the present invention provides a compound selected from (a) 2-ethylhexyl monoglyceryl ether, a compound represented by the following general formula (1-1) and a compound represented by the following general formula (1-2): 10% by weight, (b) 15-50% by weight of anionic surfactant, (c) 1-15% by weight of amine oxide type surfactant, (d) 0% water-soluble organic solvent other than component (a) Provided is a liquid detergent composition containing 0.1 to 20% by mass, (e) 0.1 to 15% by mass of a hydrotrope and water, and having a viscosity at 20 ° C. of 200 to 800 mPa · s.
[0015]
R^1-1a− (OR^1-1b)_aG_b        (1-1)
[In the formula, R^1-1aIs a group selected from 2-ethylhexyl group, isononyl group, and isodecyl group;^1-1bRepresents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar, a represents a number having an average value of 0 to 6, and b represents a number having an average value of 1 to 5. ]
R^1-2a− (OR^1-2b)_{a '}-OH (1-2)
[In the formula, R^1-2aIs a 2-ethylhexyl group and R^1-2bRepresents an alkylene group having 2 to 4 carbon atoms, and a 'represents a number having an average value of 2 to 5. ]
[0016]
DETAILED DESCRIPTION OF THE INVENTION
<(A) component>
The component (a) of the present invention comprises (a-1) 2-ethylhexyl monoglyceryl ether, (a-2) a compound of the general formula (1-1), and (a-3) a compound of the general formula (1-2). It is a compound chosen from.
[0017]
The component (a) maintains the detergency of the liquid detergent with improved viscosity and the durability of the detergency, and remarkably improves the initial foaming when it is impregnated and washed with a flexible absorbent such as a sponge. Moreover, it has an excellent effect that cannot be obtained with other compounds having a similar structure, such as reducing the wetness of the object to be cleaned during washing and rinsing.
[0018]
2-Ethylhexyl monoglyceryl ether of (a-1) is BF-epoxy compound such as 2-ethylhexanol and epihalohydrin or glycidol.₃In general, the reaction is carried out using an acid catalyst such as an aluminum catalyst or an aluminum catalyst, and is a mixture containing a plurality of products as described in JP-A-2001-49291.
[0019]
Specifically, as 2-ethylhexyl monoglyceryl ether, a compound in which 2-ethylhexanol is added to the 1-position of the epoxy compound (3- (2-ethylhexyloxy) -1,2-propanediol or the 2-position of the epoxy compound) Added compound (2- (2-ethylhexyloxy) -1,3-propanediol, and the following. Further, as a by-product, a multi-addition compound in which an epoxy compound is further added to these compounds can be given.
[0020]
In the present invention, 2-ethylhexyl monoglyceryl ether having a polyaddition compound content of 30% by mass or less, preferably 10% by mass or less, particularly preferably 1% by mass or less based on 2-ethylhexyl monoglyceryl ether is used. Is preferred.
[0021]
In the compound of the general formula (1-1) of (a-2), R is^1-1aIs a group selected from a 2-ethylhexyl group, an isononyl group, and an isodecyl group, with a 2-ethylhexyl group being particularly preferred. R^1-1bIs an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, particularly an ethylene group, G is a residue derived from a reducing sugar, a is an average value of 0 to 6, preferably 0 to 3, particularly preferably Is 0, and b represents an average value of 1 to 5, preferably 1 to 3, particularly preferably 1 to 2.
[0022]
G is a residue derived from a reducing sugar, and the reducing sugar as a raw material may be either aldose or ketose, and may be triose, tetrose, pentose, or hexose having 3 to 6 carbon atoms. Examples of aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, galose, aldose, idose, talose, and xylose. Examples of ketose include fructose.
[0023]
Among these, aldopentose or aldohexose having 5 or 6 carbon atoms is particularly preferable, and glucose is most preferable. As the reducing sugar of G, the above monosaccharide is preferable, but an oligosaccharide obtained by condensing 2 to 5, preferably 2 or 3 of these monosaccharides may be used. Further, a mixture of monosaccharide and oligosaccharide may be used. In this case, the average degree of condensation is 1 to 5, preferably 1 to 3, particularly preferably 1 to 2, and 1 to 1.5 is most preferable. preferable.
[0024]
In the compound of general formula (1-1), a compound in which a is 0 can be easily synthesized by acetalization reaction or ketalization reaction using 2-ethylhexanol, isononanol, isodecanol and the above reducing sugar using an acid catalyst. Can do. A compound in which a is not 0 is obtained by adding an alkylene oxide to 2-ethylhexanol, isononanol, or isodecanol.^1-1a− (OR^1-1b)_a—OH and reducing sugar can be easily synthesized by an acetalization reaction or a ketalization reaction using an acid catalyst. When the acetalization reaction is applied, a hemiacetal structure or a normal acetal structure may be used.
[0025]
In addition, 2-ethylhexanol can be obtained by hydrogenating n-butyraldehyde after aldol condensation. Isononanol is obtained by hydroformylating diisobutylene by the oxo method and then hydrogenating, and its representative structure is 3,5,5-trimethylhexanol. Isodecanol is obtained by hydroformylating nonene by the oxo method and then hydrogenating, and is a mixture of many isomers having methyl branches at each position of the alkyl chain. -1-Nonanol.
[0026]
In the compound of the general formula (1-2) of (a-3), R is^1-2aIs a 2-ethylhexyl group and R^1-2bIs an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, particularly preferably an ethylene group, and a 'represents a number having an average value of 2 to 5.
[0027]
The compound of the general formula (1-2) is used so that the molar ratio of 2-ethylhexanol and alkylene oxide, preferably propylene oxide and / or ethylene oxide, particularly ethylene oxide, alcohol / alkylene oxide is 1/2 to 1/5. It is a mixture of compounds obtained by reacting and containing unreacted 2-ethylhexanol and having a ′ of about 0 to 10 (average 2 to 5).
[0028]
The component (a-3) may contain an unreacted alcohol (2-ethylhexanol) generated during the synthesis together with the compound of the general formula (1-2), but the effect of the present invention is smaller in content. It is preferable in obtaining.
[0029]
When the component (a) is a mixture of the compound of the general formula (1-2) and the unreacted alcohol, the content of the unreacted alcohol (2-ethylhexanol) in the component (a) is preferably 5% by mass. Hereinafter, it is more preferably 3% by mass or less, further preferably 1% by mass or less, and an average value of a containing unreacted alcohol is 2 to 5.
[0030]
In addition, the component (a) is obtained by synthesizing the compound of the general formula (1-2) by the above method, and further performing an operation such as distillation to obtain an unreacted alcohol (a = 0 compound) and / or a> 5. You may use what removed the compound.
[0031]
The average value of a 'is H¹Using -NMR, it can be easily determined by the integral value of the α-position proton of the 2-ethylhexyl group and the proton of the oxyethylene group.
[0032]
In the present invention, as component (a), 2-ethylhexyl monoglyceryl ether, R in the general formula (1-1)^1-1aWherein R is a 2-ethylhexyl group, and R in the general formula (1-2)^1-2aIs a 2-ethylhexyl group and R^1-2bIs an ethylene group, and 2-ethylhexyl monoglyceryl ether is most preferred.
[0033]
<(B) component>
(B) component of this invention is an anionic surfactant, and the anionic surfactant which has a C10-C18 hydrocarbon group is suitable.
[0034]
Preferred examples include alkylbenzene sulfonic acid having an alkyl group having 10 to 15 carbon atoms or a salt thereof, a monoalkyl sulfate ester salt having 10 to 16 carbon atoms, an alkyl group having 10 to 16 carbon atoms, and 2 or A polyoxyalkylene alkyl ether sulfate ester salt having an average of 1.0 to 4.0 moles of 3 oxyalkylene groups added, an α-olefin sulfonate having 8 to 16 carbon atoms, an α-sulfo fatty acid (8 to 16 carbon atoms) A lower alkyl (C1-C3) ester salt can be mentioned. Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt and alkanolamine salt, and sodium salt, potassium salt, calcium salt and magnesium salt are particularly preferable from the viewpoint of viscosity.
[0035]
In the present invention, an alkyl group having 10 to 14 carbon atoms in particular and an oxyalkylene group having 2 or 3 carbon atoms, preferably an oxyethylene group, is on average 1.0 to 3.0 mol, particularly preferably 1.5 to Use of 3.0 mol added polyoxyalkylene alkyl ether sulfate ester salt, preferably sodium salt, potassium salt, calcium salt, or magnesium salt improves the cleaning effect and contains a high concentration of anionic surfactant This is preferable because the storage stability of the composition at low or high temperatures can be improved.
[0036]
When a polyoxyalkylene alkyl ether sulfate salt is used as the component (b), a polyoxyalkylene alkyl ether having a branched primary alkyl group produced from an alcohol obtained by hydroformylating a linear 1-alkene as a raw material Sulfuric acid ester salts are preferred. Here, hydroformylation is a method for obtaining an alcohol by adding carbon monoxide to a linear 1-alkene using a carbonyl complex such as iron, cobalt or nickel as a catalyst. Alcohols containing groups can be obtained.
[0037]
The polyoxyalkylene alkyl ether sulfate ester salt is obtained by further adding an alkylene oxide, preferably propylene oxide (hereinafter referred to as PO) or ethylene oxide (hereinafter referred to as EO) to the alcohol obtained by hydroformylation. Preferably, EO can be added, further sulfonated with sulfur trioxide or chlorosulfonic acid, and neutralized with an alkali agent.
[0038]
The average added mole number of EO and / or PO is preferably 1.0 to 3.0, more preferably 1.5 to 3.0, and particularly preferably 1.5 to 2.5. From the point of view, it is preferable. As an alkaline agent used for neutralization, sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, and magnesium carbonate are preferable, and sodium hydroxide, potassium hydroxide, and magnesium hydroxide are more preferable.
[0039]
When using a polyoxyalkylene alkyl ether sulfate salt containing a branched alkyl group as described above, the content of the polyoxyalkylene branched alkyl ether sulfate salt in the total polyoxyalkylene alkyl ether sulfate salt is: 5 to 80% by mass, and further 10 to 70% by mass is preferable for achieving an excellent cleaning effect.
[0040]
In particular, when the polyoxyalkylene alkyl ether sulfate salt is blended in the composition in an amount exceeding 10% by mass (for example, when blended at a concentration of 15 to 40% by mass), in the polyoxyalkylene alkyl ether sulfate salt The content of the polyoxyalkylene branched alkyl ether sulfate ester salt preferably satisfies the above content range. The polyoxyalkylene alkyl ether sulfate salt itself has a characteristic that it is less sticky than other surfactants, but it increases with the increase in concentration as it increases with the use of amine oxide surfactants. Since it tends to remain on the surface to be cleaned due to viscosity or gelation, there is concern about an increase in the feeling of sliminess, but satisfying the content range of the branched chain described above is preferable because the feeling of sliminess is reduced. .
[0041]
<(C) component>
Component (c) of the present invention is an amine oxide surfactant having a hydrocarbon group having 10 to 18 carbon atoms, and a compound of the following general formula (2) is preferred.
[0042]
[Chemical 1]

[0043]
[In the formula, R^2aIs an alkyl or alkenyl group having 8 to 18 carbon atoms, and R^2bIs an alkylene group having 1 to 6 carbon atoms, and A is a group selected from —COO—, —CONH—, —OCO—, and —NHCO—. c is a number of 0 or 1, and R^2c, R^2dAre each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. ]
In the compound of the general formula (2), R^2aIs preferably an alkyl or alkenyl group having 10 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, and particularly preferably a lauryl group (or lauric acid residue) and / or a myristyl group (or myristic acid residue). is there. A is preferably —COO— or —CONH—, and most preferably —CONH—. R^2bIs preferably 2 or 3, and R^2c, R^2dIs preferably a methyl group.
[0044]
The compound of general formula (2) is represented by R in the formula^2aMay be a single alkyl (or alkenyl) chain length or a mixture of different alkyl (or alkenyl) chain lengths. In the latter case, those having a mixed alkyl (or alkenyl) chain length derived from a vegetable oil selected from coconut oil and palm kernel oil are preferred. Specifically, R in the formula^2aIs a mixture of lauryl group (or lauric acid residue) and myristyl group (or myristic acid residue), and the molar ratio of lauryl group (or lauric acid residue) / myristyl group (or myristic acid residue) is 95 A mixture of / 5 to 20/80, preferably 90/10 to 30/70 is preferable from the viewpoint of cleaning effect and foaming property.
[0045]
<(D) component>
(D) component of this invention is a water-soluble organic solvent other than (a) component, Preferably it is a compound chosen from C1-C5 monohydric alcohol and C4-C12 polyhydric alcohol. . Specifically, a water-soluble organic solvent selected from ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether is preferable.
[0046]
<(E) component>
(E) component of this invention is a hydrotrope agent, As a preferable compound, the benzenesulfonic acid which the C1-C3 alkyl group may substitute 1-3 can mention the salt. . The component (e) is preferably at least one selected from cumene sulfonic acid, m-xylene sulfonic acid, and p-toluenesulfonic acid, and p-toluenesulfonic acid is particularly preferable for the purpose of adjusting the viscosity. The salt is preferably a sodium salt, potassium salt or magnesium salt.
[0047]
<Other ingredients>
In the present invention, a surfactant other than the component (b) and the component (c) (hereinafter referred to as the component (f)) can be contained. Specific examples include amphoteric surfactants other than the component (c), nonionic surfactants, and cationic surfactants.
[0048]
The amphoteric surfactant (hereinafter referred to as component (f-1)) is preferably contained for the purpose of enhancing the foaming power of the liquid detergent and assisting component (c), specifically 9 to 18 carbon atoms. And a sulfobetaine-type surfactant and a carbobetaine-type surfactant having one hydrocarbon group and two alkyl groups having 1 to 3 carbon atoms or two hydroxyalkyl groups. More specifically, the compound of the following general formula (3) is preferable.
[0049]
[Chemical formula 2]

[0050]
[In the formula, R^3aIs an alkyl or alkenyl group having 9 to 23 carbon atoms, and R^3bIs an alkylene group having 1 to 6 carbon atoms. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and b is a number of 0 or 1. R^3c, R^3dAre each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R^3eIs an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. D is -SO₃ ⁻, -COO⁻Is a group selected from ]
In the general formula (3), R^3aIs preferably an alkyl group having 9 to 15 carbon atoms, particularly 9 to 13 carbon atoms, and R^3bIs preferably an alkylene group having 2 or 3 carbon atoms. B is preferably -CONH-, and b is preferably 0 or 1. R^3c, R^3dIs preferably a methyl group or a hydroxyethyl group. D is -SO₃ ⁻In the case of R^3eIs -CH₂CH (OH) CH₂-Is preferred, D is -COO⁻In the case of R^3eIs preferably a methylene group.
[0051]
Nonionic surfactant (hereinafter referred to as “component (f-2)”) is one of the important surfactants for the purpose of improving the detergency of the liquid detergent and the storage stability of the liquid detergent. As a preferred specific example, a compound of the following general formula (4) can be mentioned.
[0052]
R^4a-E-[(R^4bO)_e-H]_f      (4)
[In the formula, R^4aIs an alkyl or alkenyl group having 7 to 18 carbon atoms, and R^4bIs an alkylene group having 2 or 3 carbon atoms. e represents a number of 2 to 100, preferably 4 to 80, more preferably 5 to 50. E is —O—, —CON—, or —N—. When E is —O—, f is 1, and when E is —CON— or —N—, f is 2. ]
Specific examples of the compound of the general formula (4) include the following compounds.
[0053]
R^4a-O- (C₂H₄O)_g-H (4-a)
[In the formula, R^4aIndicates the above meaning. g is a number of 2 to 100, preferably 4 to 80, more preferably 5 to 50. ]
R^4a-O- (C₂H₄O)_h(C₃H₆O)_i-H (4-b)
[In the formula, R^4aIndicates the above meaning. h and i are each independently a number of 2 to 70, preferably 2 to 50, more preferably 3 to 30, and ethylene oxide and propylene oxide may be random or block adducts. ]
[0054]
[Chemical 3]

[0055]
[In the formula, R^4aIndicates the above meaning. The sum of j and k is a number of 3 to 150, preferably 4 to 100, more preferably 6 to 50. ]
A cationic surfactant (hereinafter referred to as the component (f-3)) can be used for the purpose of imparting a preferable feel to the object to be cleaned or imparting an antibacterial effect to the liquid detergent. There are problems such as forming an ion complex with the component, reducing the cleaning effect, and promoting the wetness of the object to be cleaned.
[0056]
Specific examples of the cationic surfactant that can be used include one or two hydrocarbon groups having 8 to 18 carbon atoms that may be separated by an ester group, an amide group, or an ether group, and the remainder being carbon. A quaternary ammonium salt that is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group, a tertiary amine, or an acid salt of a tertiary amine can be given. As the salt, a halogen salt, a sulfate, or a fatty acid salt is preferable.
[0057]
In the present invention, for the purpose of improving the emulsifying power of the anionic surfactant of component (b) and enhancing the cleaning effect, it is preferable to blend magnesium [hereinafter referred to as component (g)], It is present in the system as free ions, and may be blended as a counter ion for component (b) or may be blended as a water-soluble magnesium compound. As a water-soluble magnesium compound, the solubility in water at 20 ° C. in the magnesium compounds described in Chemical Handbook II (Revised 3rd Edition), page 166, Table 8.42, page 190, and Table 8.47 is 1 g / 100 g. Above, preferably a compound of 10 g / 100 g or more is suitable. Of these, magnesium sulfate, magnesium chloride, magnesium carbonate, magnesium nitrate, and magnesium acetate are most preferred in the present invention.
[0058]
The composition of the present invention includes a polymer for preventing gelation, for example, a polymer for preventing gelation described in JP-A-11-513067 (hereinafter referred to as component (h)), particularly polyalkylene glycol. It is preferable from the viewpoint of viscosity control and storage stability.
[0059]
Specific examples of the polyalkylene glycol include polypropylene glycol having a weight average molecular weight of 200 to 3000 and polyethylene glycol determined by gel permeation chromatography using polyethylene glycol as a standard.
[0060]
In the present invention, it is preferable to contain a fragrance [hereinafter referred to as component (i)] for the purpose of imparting a preferable scent to the liquid detergent composition. In the present invention, when an anionic surfactant having a branched chain is used as the component (b), LogPow is 1.8 to 7, preferably 1.8 to 5, in consideration of stable blending of the fragrance component. In particular, it is preferable to use a fragrance component in the range of 2.0 to 4.5. It is desirable that the fragrance components satisfying the regulations of LogPow occupy 30% by mass or more, more preferably 50% by mass or more in the total fragrance. Here, LogPow is a coefficient indicating the affinity of an organic substance (in this case, a fragrance component) to water and 1-octanol, and is often used in the field of fragrance components to show the properties of the fragrance components. It is. LogPow is a 1-octanol / water partition coefficient, which is a value obtained by calculation using the f-value method (hydrophobic fragment constant method). Specifically, the chemical structure of a compound is decomposed into its constituent components, and the hydrophobic fragment constant (f value) of each fragment is integrated (CLOGP3 Reference Manual Daylight Software 4.34, Albert Leo, David Weininger, Version 1, March 1994).
[0061]
Examples of the fragrance component satisfying such LogPow include the following compounds (the values in parentheses indicate the value of LogPow).
[0062]
Acetylisoiogenol (3.0), allyl heptanoate (3.4), camphene (4.2), citral (3.1), citronellal (3.3), citronellol (3.3), citro Neryl acetate (4.2), cyclamenaldehyde (3.5), limonene (4.4), geraniol (2.8), geralyl acetate (3.7), geranyl nitrile (3.9), hexylcinnamic Aldehyde (4.9), α-ionone (3.7), β-ionone (3.8), 1-menthol (3.2), α-pinene (4.2), β-pinene (4.2) ), Terpineol (2.6), terpinolene (4.4), linalool (2.5), phenoxyethanol (1.8).
[0063]
Of these, limonene, linalool, geranyl nitrile, terpinolene, citral, geraniol, and phenoxyethanol are particularly preferred for the purpose of improving the appearance of the composition. Limonene is an important fragrance component for stably blending a fragrance component in a liquid detergent, and particularly 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more in the total fragrance. It is preferable that
[0064]
In addition to the above, isoamyl acetate, citronellyl nitrile, methyl benzoate, eugenol, benzyl alcohol, cis-3-hexenol, diethyl malonate, phenyl ethyl alcohol, methyl heptenone, linalool oxide, dihydroindenyl-2,4-dioxirane Perfume ingredients such as coumarin, hexyl formate, benzyl acetate, anis alcohol, l-carvone, menthone, terpinolene, thymol, camphor, borneol and terpinyl acetate can be used.
[0065]
In the present invention, natural plant essential oil can also be used as component (i). Specifically, mint oil, almond oil, columnus oil, peppermint oil, spearmint oil, cinnamon oil, basil oil, sage oil, allspice oil, clove oil, thyme oil, rosemary oil, lemongrass oil, lemon oil, yuzu Oil, lime oil, grapefruit oil, mandarin oil, ajowan oil, bergamot oil, laurel oil, star anise oil, marjoram oil, mace oil, boad rose oil, caraway oil, palmarosa oil, lemon berbena oil, lemon balm oil, lavender oil, rose Oil, orange oil, cassia oil, cassy oil, garlic oil, carrot seed oil, cypress oil, perilla oil, cinnamon oil, camphor oil, cedarwood oil, baturi oil, cypress oil, hiba oil, rice oil, Benny Royal oil, Lycea Cubeba Oil, eucalyptus oil, tea tree oil, ylang yi Down oil, vetiver oil, cananga oil, citronella oil, nutmeg oil, pepper oil, sandalwood oil, ginger oil, anise oil, mace oil, mention may be made of fennel oil, and the like.
[0066]
In the present invention, among these plant essential oils, those selected from mint oil, spearmint oil, basil oil, sage oil, rosemary oil, lemongrass oil, caraway oil, carrot seed oil, ginger oil, lime oil are liquid detergents. It is suitable because it can be blended stably.
[0067]
In the present invention, as long as the effects of the present invention are not impaired, components that are usually blended in liquid detergents can be blended, and examples thereof include fragrance components, disinfecting components, preservatives, turbidity agents, and coloring agents. it can.
[0068]
<Liquid cleaning composition>
The present invention comprises the above components (a) to (e), and optionally (f) component, (g) component, (h) component, (i) component, and a viscosity at 20 ° C. of 200 to 800 mPa · s. This is a liquid detergent composition.
[0069]
In addition, for the purpose of imparting high detergency and durability of detergency, the viscosity when the composition is diluted with water does not exceed 1000 mPa · s in the range where the dilution concentration is less than 100% by mass and 40% by mass or more. A composition having a viscosity characteristic that the viscosity at a concentration of 40% by mass is equal to or higher than the viscosity at a diluted concentration of 100% by mass (meaning undiluted) and does not exceed 3 times the viscosity at a diluted concentration of 100% by mass.
[0070]
The inventors of the present invention (Japanese Patent Laid-Open No. 2002-212600) have excellent cleaning power and detergency with a liquid detergent having a maximum viscosity within a range of 10 to 60% by weight. Although the composition of the present invention contains the component (a), it can be maintained below the viscosity of the undiluted product up to a diluted concentration of 40% by mass (at a diluted concentration of 40% by mass or more). The viscosity is higher than that of undiluted ones.) In addition, it has an excellent effect due to the inclusion of a component not present in the invention of the prior application in that a high cleaning effect can be imparted.
[0071]
The viscosity as used in the present invention is measured as follows. First, a B-type viscometer model BM manufactured by TOKIMEC. INC is provided with a rotor of rotor number No. 2. The sample is filled into a tall beaker and prepared at 20 ° C. in a constant temperature bath at 20 ° C. A sample prepared at a constant temperature is set in a viscometer. The rotational speed of the rotor is set to 30 r / m, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the present invention.
[0072]
In the present invention, the dilution concentration refers to the concentration of the liquid detergent composition when the liquid detergent composition is diluted with water. For example, the dilution concentration of 40% by mass refers to a state where 40 parts by weight of the liquid detergent and 60 parts by weight of water are mixed.
[0073]
The component (a) is contained in the composition in an amount of 0.1 to 10% by mass, preferably 0.3 to 8% by mass, and particularly preferably 0.5 to 5% by mass. In addition, while maintaining the durability of the cleaning power, it is possible to improve the foaming at the initial stage of cleaning and to obtain an effect of reducing the sliminess during cleaning or rinsing.
[0074]
The component (b) is contained in the composition in an amount of 15 to 50% by mass, preferably 15 to 40% by mass, particularly preferably 20 to 35% by mass, and the component (c) is 1 to 15% by mass in the composition. , Preferably it is 1.5-12 mass%, Most preferably, it contains 2.0-10 mass%.
[0075]
Further, for the purpose of exhibiting the above-mentioned viscosity behavior and imparting detergency and durability of the detergency, the mass ratio of the content of the component (b) / (c) is preferably 2/1 to 10/1. The ratio is preferably 2/1 to 9/1, particularly preferably 2.5 / 1 to 8/1.
[0076]
The component (d) and the component (e) are important components for the purpose of exhibiting the above viscosity behavior and achieving detergency and durability of the detergency.
[0077]
The component (d) is contained in the composition in an amount of 0.1 to 20% by mass, preferably 0.5 to 18% by mass, particularly preferably 1.0 to 15% by mass, and the component (e) is contained in the composition. 0.1 to 15% by mass, preferably 0.1 to 10% by mass, particularly preferably 0.5 to 8% by mass, and the total amount of component (d) and component (e) is 0.5 to 25% by mass. %, Preferably 1.0 to 20% by mass, particularly preferably 2.0 to 18% by mass.
[0078]
The mass ratio of the content of the component (d) / component (e) is preferably 1/1 to 15/1, more preferably 1/1 to 10/1, and particularly preferably 1.5 / 1 to 8. / 1 is preferable in order to achieve the above-mentioned viscosity behavior and to obtain high detergency and durability.
[0079]
The component (f) is optional, but is preferably contained because it has an effect on detergency, stability, foaming properties, and the like. The component (f-1) is preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, and particularly preferably 0.5 to 8% by mass in the composition from the viewpoint of foamability. The component (f-2) is preferably contained in the composition in an amount of from 0.1 to 15% by mass, more preferably from 0.3 to 10% by mass, particularly preferably from the viewpoint of detergency and stability. 0.5-8 mass% is contained. In addition, since the component (f-3) tends to reduce the cleaning effect or promote the sliminess of the object to be cleaned, it is preferably 5% by mass or less, more preferably 3% by mass in the composition. Hereinafter, it is particularly preferably limited to 1% by mass or less.
[0080]
The component (g) is preferably contained because the emulsifying power to oil can be improved and the detergency can be increased by using together with the component (b), and magnesium is preferably contained in the composition as 0.01. ˜2% by mass, more preferably 0.05 to 1% by mass, particularly preferably 0.1 to 1% by mass.
[0081]
The component (h) has a function of preventing gelation, but is also a component that affects the above-mentioned viscosity characteristics. Therefore, care must be taken when it is contained, and preferably 10% by mass or less, more preferably in the composition. Is 5% by mass or less, particularly preferably 3% by mass or less.
[0082]
The component (i) is preferably contained for the purpose of imparting a preferable scent to the composition, and is preferably 0.01 to 2% by mass, more preferably 0.05 to 1.5% by mass, particularly in the composition. Preferably 0.1 to 1.0 mass% is contained.
[0083]
The composition of the present invention is in the form of an aqueous solution in which the above components and water are blended, and the content of water is preferably 20 to 60% by mass, more preferably 30 to 60% by mass, more preferably from the viewpoint of viscosity. Is 35 to 60% by mass, particularly preferably 35 to 50% by mass.
[0084]
The pH of the composition at 20 ° C. is preferably 6 to 8, preferably 6.5 to 7.5 from the viewpoint of storage stability and safety to the skin. As pH adjusters, acid agents such as inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, sodium hydroxide and potassium hydroxide, It is preferable to use alkali agents such as sodium carbonate and potassium carbonate alone or in combination, such as ammonia and derivatives thereof, amine salts such as monoethanolamine, diethanolamine, and triethanolamine, and particularly selected from hydrochloric acid, sulfuric acid, and citric acid. It is preferable to use an acid selected from the group consisting of an acid selected from sodium hydroxide and potassium hydroxide. Any compound is blended within a range that does not have a great influence on the viscosity characteristics.
[0085]
<Flexible absorber and cleaning method>
The liquid cleaning composition of the present invention can be applied to a cleaning method for cleaning a hard surface using a flexible absorbent impregnated with the liquid cleaning composition and water.
[0086]
A liquid detergent composition having the above-described viscosity characteristics is obtained by directly impregnating a flexible absorbent and rubbing the surface to be cleaned with a small amount of water, preferably a hard surface as an object to be cleaned. It is a liquid detergent composition that is most suitable for the washing method to be washed, and exhibits excellent detergency and washing persistence particularly with respect to washing of dishes and cooking utensils.
[0087]
Here, impregnation means that the liquid cleaning composition is infiltrated into the flexible absorbent. The flexible absorbent is preferably a sponge or a scourer made of polyvinyl chloride, polyvinylidene chloride, nylon, polypropylene, polyester, cellulose, polyacrylamide, or polyurethane, and particularly preferably made of polyurethane or cellulose.
[0088]
Moreover, it is preferable to impregnate a flexible absorber with 0.1-2 g of liquid detergent composition in one washing | cleaning process. When the liquid detergent composition having the viscosity characteristics of the present invention is used, the order of the operation of impregnating the flexible absorbent with water and the operation of impregnating the liquid detergent composition is the first. Excellent cleaning durability can be obtained, and the same is true for extra washing.
[0089]
【The invention's effect】
According to the liquid detergent composition of the present invention, the foaming property and detergency are good, the slim surface of hard surfaces such as tableware and cooking utensils is small during cleaning, and the slime is quickly removed during rinsing.
[0090]
【Example】
A liquid detergent composition was prepared using the components shown in Table 1. The foaming property, feel, and detergency of these compositions were evaluated by the following methods. The results are shown in Table 1.
[0091]
<Measurement of foamability>
A commercially available new sponge (flexible absorber, Kikuron) is rinsed with tap water and squeezed until the tap water content is 15 g. 30 g of a 1% by weight aqueous solution of the composition of Table 1 is soaked in a sponge and placed on a ceramic dish. Using a plastic plate the same size as the sponge, compress the sponge on the dish twice by hand. Collect the foam from the sponge in a measuring cylinder and measure the volume (ml) of the foam.
[0092]
<Feel evaluation>
A model soiled dish was prepared by uniformly spreading 1 g of a model oil stain in which 0.1% by weight of a pigment (Sudan Red) was uniformly mixed with salad oil on a ceramic dish.
[0093]
A commercially available new sponge (flexible absorber, Kikuron) is rinsed with tap water and squeezed until the content of tap water is 15 g, and then impregnated with 1 g of the composition shown in Table 1 and 30 g of tap water. After the sponge was foamed by hand on the model-contaminated tableware 2 to 3 times, 5 model-contaminated tableware were scrubbed, and the wetness during the washing was subjected to sensory evaluation based on the following criteria.
[0094]
Next, the washed model contaminated dishes were rinsed with tap water, and the sensory evaluation was performed based on the following criteria for the ease of removal of moisture during rinsing (relative evaluation of the time required until the moisture disappeared).
[0095]
[Standard for sliminess during cleaning]
Not so slim: ○
Slightly slim: △
Very slimy: ×
[Standard for ease of slipping during rinsing]
You can get wet quickly: ○
It takes a little time to get slimy: △
It takes time to get slimy: ×
<Detergency test>
Apply evenly 0.5 g of model oil stain, which is a mixture of salad oil / beef tallow (reagent) = 9/1 (mass ratio) and 0.1% by weight of pigment (stan red), evenly to a polypropylene dish. The spread was used as a model contaminated tableware.
[0096]
A commercially available new sponge (flexible absorber, Kikuron) is rinsed with tap water and squeezed until the content of tap water is 15 g, and then impregnated with 1 g of the composition shown in Table 1 and 30 g of tap water. After the sponge was bubbled with the hand 2-3 times on the model-contaminated tableware, the model-contaminated tableware was rubbed and the number of dishes that could be washed (confirmed by the disappearance of the color attached to the tableware) was determined.
[0097]
<Measurement of viscosity>
(Method for measuring viscosity of liquid detergent composition)
TOKIMEC INC. The rotor type no. Prepare the one with 3 rotors. The liquid detergent composition shown in Table 1 is filled in a beaker for viscosity measurement and prepared at 20 ° C. in a constant temperature bath at 20 ° C. A sample prepared at a constant temperature is set in a viscometer. The rotation speed of the rotor is set to 30 r / m, and the viscosity after 60 seconds from the start of rotation is defined as the viscosity of the liquid detergent composition.
[0098]
(Method for measuring viscosity of diluted liquid detergent composition)
10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% by weight of the composition of Table 1 using ion-exchanged water or distilled water Dilute and stir uniformly. The diluted composition is transferred to a viscosity measuring beaker and adjusted to 20 ° C. in a 20 ° C. constant temperature bath. A sample adjusted to a constant temperature is set in a viscometer. The rotation speed of the rotor is set to 30 r / m, and the viscosity is measured 60 seconds after the rotation starts.
[0099]
The measured viscosity does not exceed 1000 mPa · s in the range of 90% by mass to 40% by mass or more, and the viscosity of 40% by mass of the diluted concentration is not less than the undiluted viscosity and does not exceed 3 times the undiluted viscosity. Those having the characteristics were passed, and those not having the characteristics were rejected.
[0100]
[Table 1]

[0101]
(Note) The numbers in parentheses are the concentration in the composition as magnesium (mass%)
[0102]
[Table 2]

[0103]
(Note 1) The number in parentheses is the concentration in the composition as magnesium (mass%)
(Note 2) The compositions of Formulation Examples 1 to 8 have a pH (20 ° C) in the range of 6.6 to 7.0, and a viscosity (20 ° C) in the range of 200 to 800 mPa · s.
(Note 3) Symbols in the table represent the following.
2EH-GE: 2-ethylhexyl monoglyceryl ether (multimer content 0.5% by mass or less)
2EH-AG: 2-ethylhexyl glycoside (glucose average condensation degree 1.3)
IsoN-AG: isononyl glycoside (glucose average condensation degree 1.3)
IsoD-AG: Isodecyl glycoside (glucose average condensation degree 1.3)
C6-GE: n-hexyl monoglyceryl ether
C8-GE: n-octyl monoglyceryl ether
C10-GE: n-decyl monoglyceryl ether
C8-AG: n-octyl glycoside (glucose average condensation degree 1.3)
C10-AG: n-decyl glycoside (glucose average condensation degree 1.3)
ES-I: Sodium polyoxyethylene alkyl ether sulfate [The raw material alcohol is an alcohol obtained by hydroformylation using 1-decene and 1-dodecene 50/50 (mass ratio) as raw materials. After adding an average of 2 moles of EO to this alcohol, it was sulfated with sulfur trioxide and neutralized with sodium hydroxide. The ratio of the total sodium polyoxyethylene alkyl ether sodium sulfate in the total sodium polyoxyethylene alkyl ether sulfate was 42% by mass. ]
ES-II: ammonium polyoxyethylene coconut alkyl ether sulfate (EO average addition mole number 2 mol)
ES-III: ammonium polyoxyethylene lauryl ether sulfate (EO average addition mole number 4 mol)
AO-I: N-lauryl-N, N-dimethylamine oxide
AO-II: lauric acid amidopropylamine oxide
・ P-TS: Sodium p-toluenesulfonate
・ Sulfobetaine: Lauryldimethylhydroxysulfobetaine
Nonion-I: C12, C13 mixed alkyl secondary alcohol with 12 moles of EO added on average (Softanol 120, manufactured by Nippon Shokubai Co., Ltd.)
Nonion-II: alkyl glucoside having an alkyl group composition of 12/14 carbon atoms = 60/40 (molar ratio) mixed alkyl and an average degree of condensation of glucoside of 1.5
-Preservative: Proxel BDN (Avisia Co., Ltd.)
-PH: adjusted using 1N-sulfuric acid aqueous solution or 1N-sodium hydroxide.

Claims (1)

(A) Compound 0.1 to 10 wt% of the lower following general formula (1-1),
(B) 20 to 35 % by mass of a polyoxyalkylene alkyl ether sulfate ester salt having an alkyl group having 10 to 16 carbon atoms ,
(C) 2.0 to 10 % by mass of an amine oxide type surfactant,
(D) 1.0 to 7.5 % by mass of a water-soluble organic solvent other than the component (a),
(E) A liquid detergent composition containing 0.5 to 2.5 % by mass of a hydrotrope agent and water and having a viscosity at 20 ° C. of 200 to 800 mPa · s ,
When the liquid detergent composition is diluted with water, the viscosity does not exceed 1000 mPa · s when the dilution concentration is less than 100% by weight and is 40% by weight or more, and the viscosity at the dilution concentration of 40% by weight is the dilution concentration of 100% by weight ( A liquid detergent composition having a viscosity characteristic equal to or higher than that of undiluted and not exceeding 3 times the viscosity of a diluted concentration of 100% by mass.
R ^1-1a- (OR ^1-1b ) _a G _b (1-1)
[Wherein R ^1-1a is a group selected from a 2-ethylhexyl group, an isononyl group, and an isodecyl group, R ^1-1b is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar, a shows the number of average values 0-6, b shows the number of average values 1-5. ]