JP4198530B2 - Liquid detergent composition - Google Patents

Description

【００２９】
〔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。
【００３０】
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。
【００３１】
＜その他の成分＞
本発明では、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、（ｅ）成分という〕を配合することが好ましい。（ｅ）成分のマグネシウムは、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存在していてもよく、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。
【００３２】
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、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。
【００３３】
本発明では、洗浄力を強化する目的から、（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好ましく、特に（ｃ）成分以外の両性界面活性剤、及び非イオン界面活性剤から選ばれる化合物が好適である。
【００３４】
両性界面活性剤としては、下記一般式（３）の化合物〔以下、（ｆ−１）成分という〕が好ましい。
【００３５】
【化２】

【００３６】
〔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 ⁻、−ＯＳＯ_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、ｄ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は−ＳＯ_３ ⁻、又は−ＣＯＯ⁻が好ましく、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。
【００３７】
非イオン界面活性剤〔以下、（ｆ−２）成分という〕としては、下記一般式（４）の化合物が好適である。
【００３８】
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は、以下の化合物を挙げることができる。
【００３９】
Ｒ^４ａ−Ｏ−(Ｃ_２Ｈ_４Ｏ)_g−Ｈ （４−ａ）
〔式中、Ｒ^{４ a}は前記の意味を示す。ｇは２〜１００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。〕
【００４０】
【化３】

【００４１】
〔式中、Ｒ^４ａは前記の意味を示す。ｊ及びｋの合計は３〜１５０の数である。〕
本発明では、貯蔵安定性を向上させる目的でハイドロトロープ剤〔以下、（ｇ）成分という〕を含有させることが好ましい。
【００４２】
ハイドロトロープ剤としては、トルエンスルホン酸、キシレンスルホン酸、クメンスルホン酸及びこれらのナトリウム、カリウム又はマグネシウム塩が良好であり、特にｐ−トルエンスルホン酸又はその塩が良好である。
【００４３】
本発明では、貯蔵安定性の改善を目的に、及び粘度調節剤として溶剤〔以下、（ｈ）成分という〕を含有させることができる。溶剤としては、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。
【００４４】
本発明では、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、（ｉ）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。
【００４５】
ポリアルキレングリコールとしては、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。
【００４６】
＜液体洗浄剤組成物＞
本発明の組成物における各成分の含有量は、以下のとおりである。
【００４７】
（ａ）成分は、０．１〜１０質量％、好ましくは０．３〜７質量％、より好ましくは０．５〜５質量％含有する。
【００４８】
（ｂ）成分は、５〜５０質量％、好ましくは１０〜４５質量％、より好ましくは１０〜４０質量％含有することが、洗浄効果の点から好ましい。
【００４９】
（ｃ）成分は、１〜１５質量％、好ましくは１〜１０質量％、より好ましくは２〜１０質量％含有する。
【００５０】
（ｂ）及び（ｃ）成分は、（ｂ）成分／（ｃ）成分の含有量の質量比が、２０／１〜１／１、更に１０／１〜１／１、特に５／１〜１／１の範囲であることが、洗浄力及び泡立ち性の点から好適である。
【００５１】
（ａ）、（ｂ）及び（ｃ）成分は、〔（ｂ）成分＋（ｃ）成分〕／（ａ）成分の質量比が、好ましくは２００／１〜１／１、より好ましくは１００／１〜１．５／１、最も好ましくは２０／１〜２／１の範囲である。（ａ）、（ｂ）及び（ｃ）成分の質量比が前記範囲を満たさない場合、食器洗浄時のぬるつきを抑制することができず、泡立ち性が抑制される傾向にあるため好ましくない。
【００５２】
本発明の（ｅ）成分は、（ｂ）成分との相互作用により高い洗浄効果を得ることができ、さらに（ａ）成分と併用することでぬるつきをより低減化することができるため、含有させることが好ましい。（ｅ）成分は、マグネシウムとして０．０１〜２質量％、更に０．０５〜１質量％、特に０．１〜１質量％含有することが好ましい。
【００５３】
（ｂ）及び（ｅ）成分は、（ｂ）成分／（ｅ）成分（マグネシウムとして）のモル比が３００／１〜１／１、更に１００／１〜１／１、特に５０／１〜２／１であることが好ましい。
【００５４】
本発明の（ｆ）成分は、洗浄効果の増強、及び貯蔵安定性を改善する目的から含有させることが好ましく、特に一般式（３）の化合物は泡立ち性を改善することができるので好ましい。しかしながら、多量配合は食器洗浄時のぬるつきを助長し、（ａ）成分の効果を減じる傾向にある。このため、組成物中の（ｆ）成分の含有量は、０．１〜２０質量％、更に０．５〜１５質量％、特に１．０〜１５質量％が好適である。
【００５５】
なお、本発明の効果が顕著に得られる要件として、〔（ａ）成分＋（ｂ）成分＋（ｃ）成分〕／〔（ａ）成分＋（ｂ）成分＋（ｃ）成分＋（ｆ）成分〕の質量比は０．５以上が好ましく、０．６以上がより好ましく、０．７以上が更に好ましく、洗浄力向上の観点からも前記質量比を満たすことが望ましい。
【００５６】
本発明の（ｇ）成分は、貯蔵安定性の点から含有させることが好ましく、組成物中に０．１〜１０質量％、更に０．５〜１０質量％、特に１〜６質量％が好適である。
【００５７】
本発明の（ｈ）成分及び（ｉ）成分は、貯蔵安定性の向上の点で含有させることが好ましく、また粘度調節剤としても有効である。（ｈ）成分は、組成物中に１〜２０質量％、更に３〜２０質量％、特に５〜１５質量％、（ｉ）成分は、組成物中に０．０５〜１０質量％、更に０．０５〜５質量％、特に０．１〜３質量％が好適である。
【００５８】
本発明の組成物は、上記成分を（ｄ）成分である水に溶解又は分散させた液状の形態であり、水の含有量は貯蔵安定性の点から、好ましくは２０〜６０質量％、より好ましくは３０〜６０質量％、更に好ましくは４０〜６０質量％、特に好ましくは４５〜５５質量％である。
【００５９】
本発明の組成物は、２０℃におけるｐＨが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、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、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、単独もしくは組み合わせ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。
【００６０】
本発明の組成物は、使い勝手の点から、２０℃における粘度が、好ましくは１０〜１０００ｍＰａ・ｓ、より好ましくは３０〜７００ｍＰａ・ｓ、特に好ましくは５０〜５００ｍＰａ・ｓである。このような粘度範囲は、例えば上記（ｇ）成分、（ｈ）成分、（ｉ）成分などを用いて調整する。
【００６１】
本発明でいう粘度は、次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.３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、回転を始めてから６０秒後の粘度を本発明でいう粘度とする。
【００６２】
その他の成分としては、粘度特性に影響のない限り、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る。例えば、香料成分、除菌成分、防腐剤、濁り剤、着色剤が挙げられる。
【００６３】
本発明の組成物は、食器、各種調理器具の洗浄等の台所用、台所回りの洗浄などの硬質表面用（特に台所用）として好適である。
【００６４】
本発明の組成物は、組成物をスポンジなどの可撓性材料（好ましくは水を含む）に染み込ませ、直接食器や調理用器具に接触させて（擦って）洗浄する方法に適用できる。この洗浄方法を実施することにより、洗浄時において食器等の硬質表面のぬるつきを抑制し、濯ぎ時においてぬるつきを速やかに洗い流すことができる。この効果は（ａ）成分を含有することによる特有の効果であり、（ａ）成分の類似化合物を用いても同様の効果を得ることはできない。
【００６５】
【発明の効果】
本発明の液体洗浄剤組成物によれば、泡立ち及び洗浄性が良く、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。
【００６６】
【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。
【００６７】
＜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になるまで絞った。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いた。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回圧縮した。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）を測定した。
【００６８】
＜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。
【００６９】
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を染み込ませた。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した。
【００７０】
次に、擦り洗いしたモデル汚染食器を水道水で濯ぎ、濯いでいる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した。
【００７１】
［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：×
［濯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１ｇ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。
【００７２】
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を染み込ませた。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、洗浄できた皿の枚数（食器に付着した色が消えることにより確認）を求めた。
【００７３】
【表１】

【００７４】
本発明品と比較品１との対比から明らかなとおり、（ａ）成分を含有することにより、比較品１と同等以上の泡立ち性及び洗浄力が得られており、洗浄時のぬるつきも少なく、濯ぎ時には速やかにぬるつきが除かれている。
【００７５】
更に本発明品と比較品２〜４との対比から明らかなとおり、（ａ）成分である一般式（１）の化合物と類似構造の化合物を用いた場合でも、本願発明と同等の効果を得ることはできない。
【００７６】
次に、表２に本発明の液体洗浄剤組成物を台所用（食器や調理器具等の硬質表面用）として適用する場合の配合例を示す。
【００７７】
【表２】

【００７８】
（注）表中の記号は以下のものを表す。
・２ＥＨ−ＡＯ２：２−エチルヘキシルアルコールにエチレンオキシドを平均２モル付加させた化合物（２−エチルヘキシルアルコールの含有量１質量％以下）
・２ＥＨ−ＡＯ４：２−エチルヘキシルアルコールにエチレンオキシドを平均４モル付加させた化合物（２−エチルヘキシルアルコールの含有量１質量％以下）
・２ＥＨ−ＡＯ５：２−エチルヘキシルアルコールにエチレンオキシドを平均５モル付加させた化合物（２−エチルヘキシルアルコールの含有量１質量％以下）
・２ＥＨ−ＡＯ６：２−エチルヘキシルアルコールにエチレンオキシドを平均６モル付加させた化合物（２−エチルヘキシルアルコールの含有量１質量％以下）
・Ｃ６−ＡＯ４：ｎ−ヘキシルアルコールにエチレンオキシドを平均４モル付加させた化合物
・Ｃ８−ＡＯ４：ｎ−オクチルアルコールにエチレンオキシドを平均４モル付加させた化合物
・ＥＳ−Ｉ：ポリオキシエチレンアルキルエーテル硫酸エステルナトリウム〔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エステル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エステル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エステルアンモニウム（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エステルアンモニウム（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：Ｎ−ラウリン酸アミドプロピル−Ｎ，Ｎ−ジメチルアミンオキシド・ノニオン−Ｉ：炭素数１２、１３混合アルキル２級アルコールに、ＥＯを平均７モル付加させたもの（ソフタノール７０Ｈ、日本触媒株式会社製）
・スルホベタイン：Ｎ−ラウリル−Ｎ，Ｎ−ジメチル−Ｎ−（２−ヒドロキシ−１−スルホプロピル）アンモニウムスルホベタイン
・ｐ−ＴＳ：ｐ−トルエンスルホン酸ナトリウム
・ＰＧ：プロピレングリコール
・防腐剤：プロキセルＢＤＮ（アビシア株式会社製）
・ｐＨ：１Ｎ−硫酸水溶液又は１Ｎ−水酸化ナトリウムのｐＨ調整剤を用いて調整した。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid cleaning composition, a liquid cleaning composition suitable for cleaning hard surfaces such as tableware and cooking utensils, and hard surfaces around kitchens, and a cleaning method using the same.
[0002]
[Prior art]
Many dishwashing detergents use an anionic surfactant as a surfactant as a surfactant from the viewpoint of detergency, and in order to further improve the detergency against oil stains, an amine oxide surfactant Is often used as a foaming agent. This is because amine oxide has a cationic property in the middle and acidic regions, so it forms an ionic complex with the anion of the anionic surfactant, thereby improving the emulsifying power to oil, resulting in washing It seems that power improves.
[0003]
On the other hand, in recent years, from the viewpoint of reducing environmental impact, concentrated liquid cleaners in which the concentration of the surfactant is increased and the amount of resin in the container is reduced are favored and used. Despite this tendency to concentrate, the use of dishwashing detergents has become more common than before, in which the detergent is applied directly to the sponge and washed. In addition, a high concentration surfactant is easily brought into contact with the hard surface of a cooking utensil such as a cutting board.
[0004]
The contact between the high concentration surfactant and the hard surface facilitates removal of oil stains adhering to the hard surface, while excess surfactant causes the problem of sliminess. Luster is something that is felt between the finger, palm, etc. and the surface to be cleaned during cleaning or rinsing, and the feeling that the cleaning agent is present on the smooth surface to be cleaned as an oil film, Its feel cannot be easily removed not only during washing 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.
[0005]
The sliminess becomes more prominent when an amine oxide type surfactant is used. The cause is that the amidoxide-type surfactant itself exhibits a property that it is easy to become slippery as compared with other surfactants, but it is presumed that the formation of the complex also has an influence. Reducing the amount of amine oxide surfactant improves the wetness during washing and rinsing, but the foaming properties are impaired, so both the foaming properties and the improvement in wetness during washing and rinsing are satisfied. There is a need for liquid detergents.
[0006]
The polyoxyalkylene type nonionic surfactant is a surfactant that is widely used in liquid detergents as in the case of the above-described anionic surfactants and amine oxide type surfactants. Are known.
[0007]
Patent Document 1 discloses a kitchen cleaner containing a specific anionic surfactant, an amine oxide type surfactant, and a nonionic surfactant, wherein the alkyl group of the nonionic surfactant is isooctyl. Examples thereof are branched alkyl groups such as isononyl and isodecyl. Patent Document 2 discloses an aqueous disinfecting liquid formulation suitable for dishwashing, which contains a nonionic surfactant having an alkyl group having a specific chain length. Patent Document 3 exemplifies a dishwashing detergent containing a nonionic surfactant obtained by adding an alkylene oxide to a C 2-30 branched alcohol. Patent Document 4 discloses a nonionic surfactant obtained by adding 4 to 9 mol of ethylene oxide to a medium chain alcohol such as octanol or decanol.
[0008]
However, in these patent documents, there is a suggestion that an excellent effect that a limited number of specific compounds suppress the wetness of an object to be cleaned at the time of washing and quickly remove the wetness of the object to be cleaned at the time of rinsing. This effect is not anticipated by those skilled in the art. Moreover, these patent documents do not solve the problem of satisfying both the foaming property of the dishwashing detergent and the improvement of the wetness during washing and rinsing.
[0009]
Patent Document 5 discloses a cleaning agent containing a compound corresponding to the component (a), which is a constituent element of the present invention, and discloses that a cleaning agent effective for cleaning hard surfaces such as plastics can be obtained. ing. However, there is no disclosure regarding the problem of sliminess when a high concentration anionic surfactant and an amine oxide type surfactant are used in combination.
[0010]
[Patent Document 1]
Japanese Patent Laid-Open No. 2002-226887
[Patent Document 2]
Japanese Patent Application Laid-Open No. 7-188697
[Patent Document 3]
JP-A-6-116587
[Patent Document 4]
JP-T 8-502540
[Patent Document 5]
JP2003-13092A
[0011]
[Problems to be solved by the invention]
An object of the present invention is to provide a liquid detergent composition that satisfies both foaming properties and improvement of wetness when washing and rinsing hard surfaces such as tableware, and a washing method using the same.
[0012]
[Means for Solving the Problems]
The present invention provides, as means for solving the problems, (a) 0.1 to 10% by mass of a compound of the following general formula (1) and (b) an anionic surfactant having a hydrocarbon group having 10 to 18 carbon atoms. 5 to 50% by mass, (c) 1 to 15% by mass of an amine oxide type surfactant having a hydrocarbon group having 10 to 18 carbon atoms, and (d) a liquid detergent composition containing water, and a cleaning method I will provide a.
[0013]
R^1a− (OR^1b)_a-OH (1)
[In the formula, R^1aIs a 2-ethylhexyl group and R^1bRepresents an alkylene group having 2 to 4 carbon atoms, and a represents a number having an average value of 2 to 5. ]
[0014]
DETAILED DESCRIPTION OF THE INVENTION
<(A) component>
The component (a) of the present invention is a compound represented by the general formula (1). Where R^1aIs a 2-ethylhexyl group and R^1bIs 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 an average value of 2 to 5.
[0015]
The compound of the general formula (1) is obtained by reacting 2-ethylhexanol and alkylene oxide, preferably propylene oxide and / or ethylene oxide, particularly ethylene oxide so that the molar ratio of alcohol / alkylene oxide is 1/2 to 1/5. It is a mixture of the compounds of which a is about 0-10 (2-5 on average) which may contain unreacted 2-ethylhexanol.
[0016]
The component (a) may contain an unreacted alcohol (2-ethylhexanol) generated at the time of synthesis together with the compound of the general formula (1). However, the smaller the content, the better the effect of the present invention. preferable.
[0017]
When the component (a) is a mixture of the compound of the general formula (1) and the unreacted alcohol, the content of the unreacted alcohol (2-ethylhexanol) in the component (a) is preferably 5% by mass or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less, and the thing whose average value of a containing unreacted alcohol is 2-5 is suitable.
[0018]
In addition, the component (a) is obtained by synthesizing the compound of the general formula (1) by the above method, and further performing an operation such as distillation to obtain an unreacted alcohol (a = 0 compound) and / or a> 5 compound. The removed one may be used.
[0019]
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.
[0020]
<(B) component>
The component (b) of the present invention is an anionic surfactant having a hydrocarbon group having 10 to 18 carbon atoms, and preferred examples thereof include alkylbenzene sulfonic acid having an alkyl group having 10 to 15 carbon atoms or a salt thereof, C10-16 monoalkyl sulfate ester salt, polyoxyalkylene alkyl ether having an alkyl group having 10-16 carbon atoms and having an average of 1.0-4.0 moles of oxyalkylene groups having 2 or 3 carbon atoms added Examples thereof include a sulfate ester salt, an α-olefin sulfonate having 8 to 16 carbon atoms, and an α-sulfo fatty acid (8 to 16 carbon atoms) lower alkyl (1 to 3 carbon atoms) ester salt. Examples of the salt include sodium salt, potassium salt, magnesium salt, and alkanolamine salt, and sodium salt, potassium salt, and magnesium salt are particularly preferable from the viewpoint of viscosity.
[0021]
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.
[0022]
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.
[0023]
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.
[0024]
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.
[0025]
When using a polyoxyalkylene alkyl ether sulfate ester salt containing a branched alkyl group as described above, the content of the polyoxyalkylene branched alkyl ether sulfate ester salt in the total polyoxyalkylene alkyl ether sulfate ester salt is: 5-80 mass%, Furthermore, it is preferable in order to achieve the outstanding cleaning effect that it is 10-70 mass%.
[0026]
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. .
[0027]
<(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.
[0028]
[Chemical 1]

[0029]
[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.
[0030]
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.
[0031]
<Other ingredients>
In the present invention, magnesium [hereinafter referred to as component (e)] is preferably blended for the purpose of improving the emulsifying power of the anionic surfactant and enhancing the cleaning effect. The component (e) magnesium is present in the system as a salt or a free ion, may be present as a counter ion of the component (b), and can be blended as a water-soluble magnesium compound.
[0032]
As a water-soluble magnesium compound, the chemical handbook basic edition II (3rd revised edition), page 166, table 8.42 and page 190, the magnesium compound described in table 8.47 has a solubility in water at 20 ° C. of 1 g / 100 g or more. A compound of 10 g / 100 g or more is preferable. Of these, magnesium sulfate, magnesium chloride, magnesium carbonate, magnesium nitrate, and magnesium acetate are most preferred.
[0033]
In the present invention, for the purpose of enhancing the detergency, it is preferable to contain a surfactant other than the component (b) and the component (c) [hereinafter referred to as the component (f)]. A compound selected from a surfactant and a nonionic surfactant is preferred.
[0034]
As the amphoteric surfactant, a compound of the following general formula (3) [hereinafter referred to as component (f-1)] is preferable.
[0035]
[Chemical 2]

[0036]
[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 ⁻, -OSO₃ ⁻, -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 d is preferably 0 or 1. R^3c, R^3dIs preferably a methyl group or a hydroxyethyl group. D is -SO₃ ⁻Or -COO⁻Is preferred, and D is -SO.₃ ⁻In the case of R^3eIs -CH₂CH (OH) CH₂-Is preferred, D is -COO⁻In the case of R^3eIs preferably a methylene group.
[0037]
As the nonionic surfactant [hereinafter referred to as component (f-2)], a compound of the following general formula (4) is suitable.
[0038]
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 shows the number of 2-100. 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.
[0039]
R^4a-O- (C₂H₄O)_g-H (4-a)
[In the formula, R^{4 a}Indicates the above meaning. g is a number from 2 to 100. ]
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, and ethylene oxide and propylene oxide may be random or block adducts. ]
[0040]
[Chemical 3]

[0041]
[In the formula, R^4aIndicates the above meaning. The sum of j and k is a number from 3 to 150. ]
In the present invention, it is preferable to contain a hydrotrope agent (hereinafter referred to as component (g)) for the purpose of improving storage stability.
[0042]
As the hydrotrope, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid and their sodium, potassium or magnesium salts are preferable, and p-toluenesulfonic acid or a salt thereof is particularly preferable.
[0043]
In the present invention, for the purpose of improving storage stability, a solvent (hereinafter referred to as component (h)) can be contained as a viscosity modifier. As the solvent, 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.
[0044]
In the present invention, a polymer for preventing gelation, for example, a gelation preventing polymer described in JP-A-11-513067 (hereinafter referred to as component (i)), particularly polyalkylene glycol is blended. Is preferable from the viewpoint of viscosity control and storage stability.
[0045]
Examples of the polyalkylene glycol include polypropylene glycol and polyethylene glycol having a weight average molecular weight of 200 to 3000 determined by gel permeation chromatography using polyethylene glycol as a standard.
[0046]
<Liquid cleaning composition>
The content of each component in the composition of the present invention is as follows.
[0047]
(A) A component contains 0.1-10 mass%, Preferably it is 0.3-7 mass%, More preferably, it contains 0.5-5 mass%.
[0048]
Component (b) is preferably contained in an amount of 5 to 50% by mass, preferably 10 to 45% by mass, more preferably 10 to 40% by mass, from the viewpoint of the cleaning effect.
[0049]
(C) A component contains 1-15 mass%, Preferably it is 1-10 mass%, More preferably, 2-10 mass% is contained.
[0050]
The components (b) and (c) have a mass ratio of (b) component / (c) component content of 20/1 to 1/1, more preferably 10/1 to 1/1, particularly 5/1 to 1. A range of / 1 is preferable from the viewpoint of detergency and foamability.
[0051]
The components (a), (b) and (c) have a mass ratio of [(b) component + (c) component] / (a) component, preferably 200/1 to 1/1, more preferably 100 / It is in the range of 1 to 1.5 / 1, most preferably 20/1 to 2/1. When the mass ratio of the components (a), (b), and (c) does not satisfy the above range, it is not preferable because it is not possible to suppress sliminess during dishwashing and the foaming property tends to be suppressed.
[0052]
The component (e) of the present invention can obtain a high cleaning effect due to the interaction with the component (b), and can further reduce sliminess when used in combination with the component (a). It is preferable to make it. The component (e) is preferably contained as magnesium in an amount of 0.01 to 2% by mass, more preferably 0.05 to 1% by mass, and particularly preferably 0.1 to 1% by mass.
[0053]
The (b) and (e) components have a molar ratio of (b) component / (e) component (as magnesium) of 300/1 to 1/1, further 100/1 to 1/1, especially 50/1 to 2. / 1 is preferable.
[0054]
The component (f) of the present invention is preferably contained for the purpose of enhancing the cleaning effect and improving the storage stability. In particular, the compound of the general formula (3) is preferable because it can improve foaming properties. However, a large amount of blending tends to promote luster when washing dishes, and tends to reduce the effect of component (a). For this reason, the content of the component (f) in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 15% by mass.
[0055]
In addition, as a requirement that the effect of the present invention is remarkably obtained, [(a) component + (b) component + (c) component] / [(a) component + (b) component + (c) component + (f) The mass ratio of the component] is preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, and it is desirable that the mass ratio is satisfied from the viewpoint of improving detergency.
[0056]
The component (g) of the present invention is preferably contained from the viewpoint of storage stability, and is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 6% by mass in the composition. It is.
[0057]
The component (h) and component (i) of the present invention are preferably contained from the viewpoint of improving storage stability, and are also effective as a viscosity modifier. (H) Component is 1-20 mass% in a composition, Furthermore, 3-20 mass%, Especially 5-15 mass%, (i) A component is 0.05-10 mass% in a composition, Furthermore, 0 0.05 to 5 mass%, particularly 0.1 to 3 mass% is preferable.
[0058]
The composition of the present invention is in a liquid form in which the above components are dissolved or dispersed in water as component (d), and the water content is preferably 20 to 60% by mass from the viewpoint of storage stability. Preferably it is 30-60 mass%, More preferably, it is 40-60 mass%, Most preferably, it is 45-55 mass%.
[0059]
The composition of the present invention preferably has a pH of 6 to 8, preferably 6.5 to 7.5 at 20 ° C. from the viewpoint of storage stability and safety to the skin. pH adjusters include inorganic acids such as hydrochloric acid and sulfuric acid, acid agents such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid and maleic acid, sodium hydroxide, potassium hydroxide and ammonia. Or an alkali salt such as sodium carbonate or potassium carbonate, such as amine salts such as monoethanolamine, diethanolamine, and triethanolamine, alone or in combination, particularly an acid selected from hydrochloric acid, sulfuric acid, and citric acid It is preferable to use an alkali agent selected from sodium hydroxide and potassium hydroxide.
[0060]
From the viewpoint of ease of use, the composition of the present invention has a viscosity at 20 ° C. of preferably 10 to 1000 mPa · s, more preferably 30 to 700 mPa · s, and particularly preferably 50 to 500 mPa · s. Such a viscosity range is adjusted using, for example, the component (g), the component (h), the component (i), and the like.
[0061]
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. 3. The sample is filled in a tall beaker and adjusted to 20 ° C. in a constant temperature bath at 20 ° C. 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 60 seconds after the start of rotation is defined as the viscosity in the present invention.
[0062]
As other components, as long as the viscosity characteristics are not affected, components that are usually blended in liquid detergents can be blended. For example, a fragrance | flavor component, disinfection component, antiseptic | preservative, a clouding agent, and a coloring agent are mentioned.
[0063]
The composition of the present invention is suitable for kitchens such as washing dishes and various cooking utensils, and hard surfaces (particularly for kitchens) such as washing around kitchens.
[0064]
The composition of the present invention can be applied to a method in which a composition is impregnated with a flexible material such as sponge (preferably containing water) and directly contacted (rubbed) with tableware or cooking utensils. By carrying out this cleaning method, it is possible to suppress the stickiness of hard surfaces such as tableware during cleaning and to quickly wash away the stickiness during rinsing. This effect is a peculiar effect by containing (a) component, and the same effect cannot be acquired even if it uses the similar compound of (a) component.
[0065]
【The invention's effect】
According to the liquid detergent composition of the present invention, foaming and detergency are good, and there is little sliminess of hard surfaces such as dishes and cooking utensils during washing, and lusteriness is quickly removed during rinsing.
[0066]
【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.
[0067]
<Measurement of foamability>
A commercially available new sponge (flexible absorber, Kikuron) was washed with tap water and squeezed until the tap water content was 15 g. 30 g of a 1% by weight aqueous solution of the composition of Table 1 was soaked in a sponge and placed on a ceramic dish. Using a plastic plate the same size as the sponge, the sponge on the dish was compressed twice by hand. The foam from the sponge was collected in a measuring cylinder, and the volume (ml) of the foam was measured.
[0068]
<Feel evaluation>
A model-oiled 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.
[0069]
A commercially available new sponge (flexible absorber, Kikuron) was rinsed with tap water and squeezed until the content of tap water became 15 g, and then impregnated with 1 g of the composition shown in Table 1 and 30 g of tap water. The sponge was squeezed 2 to 3 times on the model-contaminated tableware and foamed, and then 5 pieces of the model-contaminated tableware were scrubbed, and the wetness during the washing was subjected to sensory evaluation based on the following criteria.
[0070]
Next, the rubbed model-contaminated tableware was rinsed with tap water, and the ease of removal of the moisture during the rinsing (relative evaluation of the time required until the moisture disappeared) was sensorially evaluated according to the following criteria.
[0071]
[Standard for sliminess during cleaning]
Not so slim: ○
Slightly slim: △
Very slimy: ×
[Standard for ease of luster removal during rinsing]
You can get wet quickly: ○
It takes a little time to get slimy: △
It takes time to get slimy: ×
<Detergency test>
A model-contaminated tableware was obtained by uniformly spreading 1 g of a model oil stain in which 0.1% by weight of a pigment (stan red) was uniformly mixed with a salad oil on a polypropylene plate.
[0072]
A commercially available new sponge (flexible absorber, Kikuron) was rinsed with tap water and squeezed until the content of tap water became 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 were washed (confirmed by the disappearance of the color attached to the tableware) was determined.
[0073]
[Table 1]

[0074]
As is clear from the comparison between the product of the present invention and the comparative product 1, by containing the component (a), the foaming property and the cleaning power equal to or higher than those of the comparative product 1 are obtained, and there is little stickiness during cleaning. In the case of rinsing, the sliminess is quickly removed.
[0075]
Further, as is clear from the comparison between the product of the present invention and the comparative products 2 to 4, even when the compound of the general formula (1) as the component (a) and a compound having a similar structure are used, the same effect as the present invention is obtained. It is not possible.
[0076]
Next, Table 2 shows formulation examples in the case of applying the liquid detergent composition of the present invention for kitchen use (for hard surfaces such as tableware and cooking utensils).
[0077]
[Table 2]

[0078]
(Note) The symbols in the table represent the following.
2EH-AO2: Compound obtained by adding an average of 2 moles of ethylene oxide to 2-ethylhexyl alcohol (content of 2-ethylhexyl alcohol is 1% by mass or less)
2EH-AO4: Compound obtained by adding an average of 4 moles of ethylene oxide to 2-ethylhexyl alcohol (content of 2-ethylhexyl alcohol is 1% by mass or less)
2EH-AO5: Compound obtained by adding an average of 5 moles of ethylene oxide to 2-ethylhexyl alcohol (content of 2-ethylhexyl alcohol is 1% by mass or less)
2EH-AO6: a compound obtained by adding an average of 6 moles of ethylene oxide to 2-ethylhexyl alcohol (content of 2-ethylhexyl alcohol is 1% by mass or less)
C6-AO4: a compound obtained by adding an average of 4 moles of ethylene oxide to n-hexyl alcohol
C8-AO4: Compound obtained by adding an average of 4 moles of ethylene oxide to n-octyl alcohol
ES-I: Sodium polyoxyethylene alkyl ether sulfate ester [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 polyoxyethylene branched chain alkyl ether sulfate sodium in the total polyoxyethylene alkyl ether sulfate sodium 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: N-lauric acid amidopropyl-N, N-dimethylamine oxide Nonion-I: 12 and 13 mixed alkyl secondary alcohol with an average of 7 mol of EO (Softanol 70H, Japan) (Made by Catalyst Co., Ltd.)
Sulfobetaine: N-lauryl-N, N-dimethyl-N- (2-hydroxy-1-sulfopropyl) ammonium sulfobetaine
・ P-TS: Sodium p-toluenesulfonate
・ PG: Propylene glycol
-Preservative: Proxel BDN (Avisia Co., Ltd.)
-PH: It adjusted using the pH adjuster of 1N-sulfuric acid aqueous solution or 1N-sodium hydroxide.

Claims (3)

(A) 0.1 to 10% by mass of a compound of the following general formula (1), (b) 5 to 50% by mass of an anionic surfactant having a hydrocarbon group having 10 to 18 carbon atoms, (c) carbon A liquid detergent composition containing 1 to 15% by mass of an amine oxide type surfactant having a hydrocarbon group of several 10 to 18 and (d) water.
R ^1a- (OR ^1b ) _a -OH (1)
[Wherein, R ^1a represents a 2-ethylhexyl group, R ^1b represents an alkylene group having 2 to 4 carbon atoms, and a represents an average value of 2 to 5. ] The liquid detergent composition according to claim 1, wherein the mass ratio of (b) / (c) is 20/1 to 1/1. A method for cleaning a hard surface using a flexible material impregnated with the liquid detergent composition according to claim 1 or 2 without dilution.