JP4163058B2 - Bleach-containing detergent composition - Google Patents

Description

【００１６】
〔式中、Ｒは、炭素原子数１０〜２２、好ましくは１２〜１８、特に好ましくは１４〜１８の直鎖又は分岐鎖のアルキル基若しくはアルケニル基である。Ｒ’は、炭素原子数１〜５、好ましくは１〜４の直鎖又は分岐鎖のアルキル基であり、例えば、メチル基、エチル基、プロピル基、イソプロピル基などが挙げられる。Ｍは、アルカリ金属又はアンモニウムであり、アルカリ金属の具体例としては、例えば、リチウム、ナトリウム、カリウムなどが挙げられる。〕
【００１７】
（ｂ）成分は、通常、公知の製法によって得られる。例えば、油脂に低級アルコールを反応させて得られた脂肪酸エステルを無水硫酸等でスルホン化し、最後に苛性アルカリ等で中和することによって製造することができる。前記原料油脂としては、例えば、ヤシ油、パーム核油、豚油、牛脂、米ヌカ油、パーム油、魚油などが挙げられる。
【００１８】
本発明の組成物は、（ｂ）成分を０．５〜２０質量％含有する。有機過酸生成量向上の点で、組成物中１〜１８質量％含有することが好ましく、２〜１５質量％がより好ましく、３〜１３質量％が更に好ましい。
【００１９】
（ｂ）成分を含有することにより、非イオン界面活性剤の影響により有機過酸前駆体から有機過酸の発生量が減少し、洗浄力が低下するという問題を回避することができる。すなわち、本発明では、（ｂ）成分を使用することにより、有機過酸の生成量を増加させることができる。
【００２０】
＜（ｃ）成分＞
水中で過酸化水素を発生する過酸化物である（ｃ）成分としては、炭酸塩・過酸化水素付加物、硼酸塩・過酸化水素付加物、トリポリリン酸塩・過酸化水素付加物、ピロリン酸塩・過酸化水素付加物、尿素・過酸化水素付加物等が挙げられる。この中でも、炭酸塩・過酸化水素付加物、硼酸塩・過酸化水素付加物が好ましく、炭酸ナトリウム・過酸化水素付加物、硼酸ナトリウム・過酸化水素付加物がより好ましい。
【００２１】
本発明の組成物は、（ｃ）成分を０．１〜９質量％含有する。洗浄性能の点で、組成物中０．５〜８質量％含有することが好ましく、１〜７質量％がより好ましく、２〜６質量％が更に好ましい。
【００２２】
また、（ｃ）成分は、無機化合物や有機化合物で被覆されることが貯蔵安定性の点で好ましい。無機化合物としては、ホウ酸、ホウ酸塩、炭酸ナトリウム、硫酸ナトリウム、硫酸マグネシウム、珪酸マグネシウム、塩化マグネシウム、酸化マグネシウム、珪酸ナトリウム等が挙げられ、有機化合物としては、ポリエチレングリコール、ポリビニルピロリドン、ヒドロキシプロピルセルロース等が挙げられる。中でも、ホウ酸又はホウ酸塩を用いて被覆することが好ましい。ホウ酸としては、オルトホウ酸、メタホウ酸、四ホウ酸等が挙げられ、その塩としては、ナトリウム、カリウム等のアルカリ金属塩が挙げられる。
【００２３】
（ｃ）成分を含む被覆粒子は、例えば特開昭５９−１９６３９９号公報記載の方法により製造できる。被覆量は、（ｃ）成分が（ｃ）成分を含む粒子として用いられる場合、該粒子中０．５〜２０質量％が安定性、溶解性の点で好ましく、１〜１０質量％がより好ましい。また、従来より知られている安定化剤、溶解促進剤、キレート剤等を前記粒子に含有させても良い。中でも塩化物、尿素、陰イオン界面活性剤、非イオン界面活性剤が溶解性の点で好ましく、それらの比率は、それぞれ、前記粒子中０．１〜５質量％が好ましい。なお、非イオン界面活性剤は、（ａ）成分としても使用できるので、その量は（ａ）成分の量に算入される。また、このような被覆粒子のうち、特にホウ酸又はホウ酸塩で被覆された（ｃ）成分を含有する粒子は、後述の第二の粒子として使用できる。
【００２４】
＜（ｄ）成分＞
水中で過酸化水素と反応し有機過酸を発生する化合物である（ｄ）成分としては、酸素系漂白剤含有洗剤に一般的に用いられる、グルコースペンタアセテート、トリアセチン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラアセチルエチレンジアミン、テトラアセチルグリコリルウリル等の漂白活性化剤を使用することができるが、効果の点で、下記一般式（Ｉ）で表される過酸前駆体が好ましい。
【００２５】
【化２】

【００２６】
〔式中、Ｒ¹は、直鎖又は分岐鎖の炭素数４〜１８のアルキル基、アリール基、アルケニル基、アシル基、又は下記一般式（II）で表される基を示し、
【００２７】
【化３】

【００２８】
（式中、Ｒ²は、水素原子、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルケニル基、アシル基を示し、Ｒ³は、炭素数１〜８の直鎖又は分岐鎖のアルキレン基を示し、ｐは、０又は１を示し、Ｒ⁴は、炭素数１〜８の直鎖もしくは分岐鎖のアルキレン基又は炭素数１〜５の直鎖もしくは分岐鎖のアルキル基で置換されていてもよいフェニレン基を示し、Ａは、炭素数１〜４の直鎖又は分岐鎖のアルキレン基を示し、ｑは、アルキレンオキシドの平均付加モル数で、０〜１００の数を示し、ｑ個のＡは同一でも異なっていてもよい）
【００２９】
Ｌは、下記一般式（III）、（IV）、（Ｖ）、又は（VI）で表される基を示す。
【００３０】
【化４】

【００３１】
（式中、Ｍは、水素原子又は水溶性塩を形成する陽イオンを示し、Ｒ⁵及びＲ⁶は、それぞれ炭素数１〜８の直鎖又は分岐鎖のアルキレン基を示す。）〕
【００３２】
洗浄性能の点で、Ｒ¹は、直鎖又は分岐鎖の炭素数４〜１８（より好ましくは炭素数７〜１８、更に好ましくは１０〜１３）のアルキル基又はアルケニル基（より好ましくはアルキル基）が好ましい。また、Ｌは、一般式（III）又は（IV）で表される基（特に（III）で表される基）が好ましい。また、Ｍは、アルカリ金属イオン、アルカリ土類金属イオン、アンモニウムイオン、アルカノールアンモニウムイオン等が挙げられ、中でもナトリウムイオン、カリウムイオンが好ましく、特にナトリウムイオンが好ましい。
【００３３】
本発明の組成物は、（ｄ）成分を０．１〜９質量％含有する。洗浄性能の点で、組成物中０．１〜７質量％含有することが好ましく、０．２〜５質量％がより好ましく、０．２〜４質量％が更に好ましく、０．３〜３質量％が特に好ましい。
【００３４】
（ｄ）成分を組成物中に配合するとき、安定性の点で（ｄ）成分を含む粒子として配合することが好ましい。（ｄ）成分を含む粒子中の（ｄ）成分の量は、好ましくは１〜８０質量％、より好ましくは２０〜８０質量％、特に好ましくは３０〜７５質量％である。また、（ｄ）成分を含む粒子には（ｄ）成分の洗濯浴中での溶解性を改善するためにポリオキシアルキレンアルキルエーテル、アルキル硫酸エステル塩及びポリオキシアルキレンアルキルエーテル硫酸エステル塩から選ばれる少なくとも１種の界面活性剤を（ｄ）成分を含む粒子中に０〜５０質量％、更に１〜４５質量％、特に２〜４０質量％配合するのが好ましい。ポリオキシアルキレンアルキルエーテルとしては、ＥＯとＰＯがブロック状に付加したものが好ましく、ＥＯ平均付加モル数は３〜２０、特に４〜１５が好ましく、ＰＯ平均付加モル数は１〜１０、特に２〜７が好ましい。アルキル基の炭素数は１０〜１８、特に１２〜１６が好ましい。アルキル硫酸エステル塩としては、炭素数１０〜１８で、ナトリウム塩が好ましく、特にラウリル硫酸エステルナトリウム又はミリスチル硫酸エステルナトリウムが特に好ましい。また、ポリオキシアルキレンアルキルエーテル硫酸エステル塩としては、アルキル基の炭素数が１０〜１８のポリオキシエチレンアルキルエーテル硫酸塩が好ましく、またナトリウム塩が良好である。ここでポリオキシエチレン基の平均重合度（以下ＥＯｐ）は１〜１０、特に１〜５が良好であり、特にポリオキシエチレン（ＥＯｐ＝２〜５）ラウリルエーテル硫酸エステルナトリウム、ポリオキシエチレン（ＥＯｐ＝２〜５）ミリスチルエーテル硫酸エステルナトリウムが良好である。なお、かかる界面活性剤のうち、ポリオキシアルキレンアルキルエーテルは、（ａ）成分としても使用できるので、その量は（ａ）成分の量に算入される。（ｄ）成分を含む粒子は、上記成分を、ポリオキシエチレン及び脂肪酸から選ばれるバインダー物質を用いて製剤化して得られる。ポリオキシエチレンとしては平均分子量２０００〜２００００、更に４０００〜１００００、特に４０００〜８０００のものが良好である。また、脂肪酸としては炭素数８〜２０、更に１０〜１８、特に１２〜１８のものが好ましく、これらはナトリウムあるいはカリウム石鹸の状態であってもよい。バインダー物質は（ｄ）成分を含む粒子中に０．５〜３０質量％、更に１〜２０質量％、特に５〜２０質量％使用するのが好ましい。（ｄ）成分を含む粒子は上記組成物を上記比率で配合することが、安定性の点で好ましい。また、本発明では（ｄ）成分を含む粒子の安定性を向上させる目的で所望により（ｄ）成分を含む粒子中に酸性物質を配合してもよい。酸性物質としては有機カルボン酸類が好ましく、特にこはく酸、マレイン酸、フマール酸、クエン酸、グリコール酸及びｐ−ヒドロキシ安息香酸から選ばれる少なくとも１種が好ましい。このような酸性物質の配合量は、（ｄ）成分を含む粒子中に０〜２０質量％、更に１〜１５質量％、特に１〜１０質量％が好適である。（ｄ）成分を含む粒子は、上記成分を任意の方法で混合して得ることができるが、特に（ｄ）成分と前記界面活性剤の一部もしくはすべてを先に混合し、その後バインダー物質等を添加する方法が好ましい。また、バインダー物質は予め融解して添加することが好ましい。バインダー物質は４０〜１００℃、更に５０〜１００℃、特に５０〜９０℃で融解させて添加するのが好ましい。これらは均一になるまで攪拌混合された後、通常の造粒機により製剤化される。好ましい造粒法として押し出し造粒を挙げることができ、平均粒径が５００μｍ〜５０００μｍ、特に５００〜３０００μｍの造粒物にすることが好ましい。また、その他の造粒法としてはブリケット機による錠剤形状にすることも好ましい造粒法として挙げることができる。上記のような（ｄ）成分を含む押し出し造粒物は、後述の第三の粒子として使用できる。
【００３５】
＜（ｅ）成分＞
（ｅ）成分としては、例えば炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム等のアルカリ金属炭酸塩、珪酸ナトリウム、珪酸カリウム等のアルカリ金属珪酸塩、オルトリン酸塩、メタリン酸塩、ピロリン酸塩、ヘキサメタリン酸塩等のポリリン酸塩、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン類、リン酸水素二ナトリウム、リン酸三ナトリウム、ホウ酸塩等が挙げられる。
【００３６】
（ｅ）成分は洗浄性能の点で、（ｅ）成分の０．０２５質量％濃度の水溶液もしくは分散液の最大ｐＨが１０以上（２０℃）であり、且つ該水溶液もしくは分散液１リットルをｐＨ９（２０℃）にするために０．１Ｎの塩酸水溶液を１０ｍｌ以上必要とする化合物であることが好ましい。このような化合物としては、炭酸ナトリウム、炭酸カリウム、珪酸ナトリウム、リン酸三ナトリウム、モノエタノールアミン等が挙げられる。中でも炭酸ナトリウム、炭酸カリウム、珪酸ナトリウムがより好ましく、特に炭酸ナトリウムが好ましい。
【００３７】
本発明の組成物は、（ｅ）成分を１５〜４０質量％含有する。洗浄性能の点で、組成物中１７〜３８質量％含有することが好ましく、２０〜３５質量％がより好ましい。
【００３８】
＜水分＞
本発明の組成物は、ＪＩＳ Ｋ３３６２：１９９８記載の加熱減量法による水分が０．１〜５質量％である。保存安定性、生産性の点で、０．５〜４．８質量％が好ましく、１〜４．５質量％がより好ましい。
【００３９】
＜その他＞
本発明に用いることができる（ａ）成分、（ｂ）成分以外の界面活性剤としては、（ｂ）成分以外の陰イオン界面活性剤、両性界面活性剤、陽イオン界面活性剤等が挙げられる。
【００４０】
陰イオン界面活性剤としては、高級アルコールの硫酸エステル塩、高級アルコールのエトキシル化物の硫酸エステル塩、アルキルベンゼンスルホン酸塩、パラフィンスルホン酸塩、α−オレフィンスルホン酸塩が挙げられる。特に、アルキル鎖の炭素数が１０〜１８（好ましくは１２〜１４）の直鎖アルキルベンゼンスルホン酸塩、炭素数が１０〜２０のα−スルホ脂肪酸アルキルエステル塩が好ましい。また、対イオンとしては、アルカリ金属、アルカリ土類金属、アンモニウム、アルカノールアミン等が挙げられる。溶解速度調整の観点から、カリウムイオンを併用することも好ましい。全対イオン中カリウムイオンは５質量％以上が好ましく、２０質量％以上がより好ましく、４０質量％以上が特に好ましい。
【００４１】
なお、石鹸を配合することもできるが、その量は陰イオン界面活性剤には算入しない。石鹸としては、炭素数１２〜２０の脂肪酸のナトリウム塩、カリウム塩が挙げられる。石鹸の比率は組成物中１〜１０質量％であることが好ましい。
【００４２】
本発明の組成物は（ｂ）成分を含む陰イオン界面活性剤（石鹸を除く）を１〜２５質量％含有する。洗浄性能、溶解性の点で５〜２２質量％が好ましく、８〜２０質量％がより好ましい。
【００４３】
また、本発明の組成物は、（ａ）成分と、（ｂ）成分を含む陰イオン界面活性剤（石鹸を除く）とを、総量で１５〜４０質量％含有する。洗浄性能、溶解性の点で、１５〜３５質量％が好ましく、１５〜３０質量％がより好ましく、１５〜２５質量％が更に好ましい。
【００４４】
陽イオン界面活性剤として、アルキルトリメチルアンモニウム塩等が、両性界面活性剤として、カルボベタイン型、スルホベタイン型両性活性剤等が挙げられる。
【００４５】
本発明の組成物は、その他のビルダー、その他漂白活性化剤、再汚染防止剤（カルボキシメチルセルロース等）、柔軟化剤（ジアルキル型第四級アンモニウム塩、粘土鉱物等）、還元剤（亜硫酸塩等）、蛍光増白剤（ビフェニル型、アミノスチルベン型等）、泡コントロール剤（石鹸、シリコーン等）、香料、酵素（プロテアーゼ、ペクチナーゼ、アミラーゼ、リパーゼ等）等の添加剤を含有させることができる。
【００４６】
本発明においてビルダーとは、そのもの自身では洗浄力がないか、またはあってもそれ程著しくないが、洗浄剤組成物に配合されると著しく洗浄性能を向上させるものである。作用として、多価金属陽イオンの捕捉作用、汚れ分散作用及びアルカリ緩衝作用の少なくとも１つの作用を有するものである。
【００４７】
ビルダーとなり得る水不溶性無機化合物としては、アルミノケイ酸塩（Ａ型ゼオライト、Ｐ型ゼオライト、Ｘ型ゼオライト、非晶質アルミノケイ酸塩等）、結晶性ケイ酸塩等が挙げられる。中でも粒子径３μｍ以下（より好ましくは１μｍ以下）のＡ型ゼオライトが好ましい。
【００４８】
ビルダーとなり得る有機化合物としては、カルボン酸塩（アミノカルボン酸塩、ヒドロキシアミノカルボン酸塩、ヒドロキシカルボン酸塩、シクロカルボン酸塩、マレイン酸誘導体、シュウ酸塩等）、有機カルボン酸（塩）ポリマー（アクリル酸重合体および共重合体、多価カルボン酸重合体および共重合体、グリオキシル酸重合体、多糖類及びこれらの塩等）等が挙げられる。中でも有機カルボン酸（塩）ポリマーが好ましい。
【００４９】
前記ビルダーの塩において、対イオンとしては、アルカリ金属塩、アミン類が好ましく、特にナトリウム及び／又はカリウム、モノエタノールアミン、ジエタノールアミンが好ましい。
【００５０】
本発明において、これらのビルダーは、単独で又は２種以上を併用することができる。
【００５１】
本発明において、特に多価金属陽イオンの捕捉作用のあるビルダーを含有させることが洗浄性能の点で好ましい。多価金属陽イオンの捕捉作用のあるビルダーとして、カルシウム安定度定数が４〜１５（好ましくは５〜１４、より好ましくは６〜１３）である化合物を含有することが好ましい。洗浄剤組成物中０．１〜２０質量％が好ましく、０．５〜１５質量％がより好ましく、１〜１０質量％が更に好ましい。尚、本発明において、カルシウム安定度定数は次の方法で求められるものをいう。
【００５２】
（カルシウム安定度定数の測定方法）
緩衝液として０．１ｍｏｌ／リットルのＮＨ₄Ｃｌ−ＮＨ₄ＯＨ（ｐＨ１０）溶液を調製する。この緩衝液を用いて全ての試料溶液を調製する。Ｃａ²⁺濃度の測定にはオリオン（株）製のイオンメーター９２０ＡとＣａ²⁺イオン電極を用いる。先ず、塩化カルシウム濃度と電極の電位の関係を求め、検量線を作成する。塩化カルシウムの５．３６×１０^-2ｍｏｌ／リットル溶液、キレート剤試料の５．３６×１０^-4ｍｏｌ／リットル溶液を調製する。キレート剤試料溶液１００ｍｌに塩化カルシウム溶液を１ｍｌ加え、５分間撹拌する。残存しているＣａ²⁺濃度をＣａ²⁺イオン電極を用いて測定する。キレート剤はＣａ²⁺と１：１でキレート錯体を形成すると仮定して下記の式からカルシウム安定度定数（Ｃａ安定度定数）を求める。
【００５３】
【数１】

【００５４】
その他の漂白活性化剤として、グルコースペンタアセテート、トリアセチン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラアセチルエチレンジアミン、テトラアセチルグリコリルウリル、及び下記一般式（１）、（２）記載の化合物等を含有することができる。
【００５５】
【化５】

【００５６】
〔式中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²¹、Ｒ²²、Ｒ²⁴、Ｒ²⁵は、それぞれ独立して炭素数１〜５のアルキル基又はヒドロキシアルキル基であり、Ｒ²³は炭素数２〜１０のアルキレン基であり、Ｘ^-はアルカリ金属イオン等の陰イオンを示す。〕
【００５７】
＜漂白剤含有洗浄剤組成物＞
本発明の漂白剤含有洗浄剤組成物は、（ａ）成分と（ｂ）成分の質量比が、（ａ）：（ｂ）＝７：１〜１：５、更に６：１〜１：３、特に４：１〜２．５：１であることが好ましい。過酸生成が十分であるという観点から（ａ）：（ｂ）は７：１以下が好ましく、耐硬水性、油性汚れ洗浄性に優れるという観点から１：５以上が好ましい。
【００５８】
また、本発明の漂白剤含有洗浄剤組成物は、（ｂ）成分と（ｄ）成分の質量比が、（ｂ）：（ｄ）＝３０：１〜１：１．５、更に２０：１〜１：１、更に１０：１〜３：１であることが好ましい。過酸生成が十分であるという観点から（ｂ）：（ｄ）は３０：１以下が好ましく、経済性の観点から１：１．５以上が好ましい。
【００５９】
本発明の漂白剤含有洗浄剤組成物は洗浄性能、損傷性の点で、ＪＩＳ Ｋ ３３６２：１９９８記載の20℃で測定する0.1質量％水溶液のｐＨが8〜12が好ましく、9〜11.5がより好ましく、9.5〜11が更に好ましく、10〜11が特に好ましい。
（ｃ）成分や水酸化ナトリウム、水酸化カリウム等のｐＨ調整剤によりこのような範囲になるように調製することが好ましい。
【００６０】
本発明の漂白剤含有洗浄剤組成物は溶解性の点で、ＪＩＳ Ｋ ３３６２：１９９８により規定された方法で測定する見掛け密度は1600ｇ/L以下が好ましく、1300ｇ/L以下がより好ましく、1000ｇ/L以下が更に好ましい。また、利便性や廃棄物（例えば箱等）低減の点で、見掛け密度は300ｇ/L以上であることが好ましく、600ｇ/L以上がより好ましく、700ｇ/L以上が更に好ましい。
【００６１】
本発明の漂白剤含有洗浄剤組成物は溶解性の点で、ＪＩＳ Ｚ ８８０１の標準篩を用いて５分間振動させた後、篩目のサイズによる質量分率から求める粒状洗浄剤組成物の平均粒径は150〜1000μｍが好ましく、より好ましくは150〜800μｍ、更に好ましくは180〜600μｍである。
【００６２】
本発明の漂白剤含有洗浄剤組成物は、利便性の点で、更に圧縮して錠剤形態にしても良いし、１回の使用量を水溶性或いは水不溶性の容器に収納することができる。
【００６３】
本発明の漂白剤含有洗浄剤組成物は、保存安定性、流動性及び非ケーキング性の点で、表面被覆剤により表面改質を行うことが好ましい。表面被覆剤は洗浄剤粒子中1〜30質量％が好ましく、2〜15質量％がより好ましく、5〜10質量％が更に好ましい。表面被覆剤としては、例えば、アルミノケイ酸塩、ケイ酸カルシウム、二酸化ケイ素、ベントナイト、タルク、クレイ、非晶質シリカ誘導体、結晶性シリケート化合物等のシリケート化合物、金属石鹸、粉末の界面活性剤等の微粉体、カルボキシメチルセルロース、ポリエチレングリコール、ポリアクリル酸ソーダ、アクリル酸とマレイン酸のコポリマー又はその塩等のポリカルボン酸塩等の水溶性ポリマー；脂肪酸が挙げられる。中でも水不溶性無機物が好ましく、特に結晶性アルミノケイ酸塩、非晶質アルミノケイ酸塩、結晶性シリケート化合物が好ましい。
【００６４】
本発明の漂白剤含有洗浄剤組成物において、保存安定性の点で、（ａ）〜（ｄ）成分は、（ａ）成分、（ｂ）成分、（ｅ）成分を含有する第一の粒子と、（ｃ）成分を含有する第二の粒子と、（ｄ）成分を含有する第三の粒子として存在することが好ましい。
【００６５】
特に、本発明の漂白剤含有洗浄剤組成物は、（ａ）成分、（ｂ）成分、（ｅ）成分を含有し、粉末被覆剤で被覆された第一の粒子と、（ｃ）成分を含有し、ホウ酸またはホウ酸塩で被覆された第二の粒子と、（ｄ）成分を含有する押し出し造粒物からなる第三の粒子を含有することが好ましい。ここで、第一の粒子の粉末被覆剤は、上記の表面被覆剤が使用でき、第一の粒子中の該粉末被覆剤の量は
〜 質量％が好ましい。
【００６６】
【実施例】
実施例１〜８、比較例１〜４
表１に示す成分のうち、（ａ）成分、（ｃ）成分、（ｄ）成分、結晶性シリケート、ゼオライトの一部、酵素、及び香料を除いた各成分を用いて、固形分４０質量％の水性スラリーを調製し、これを乾燥塔を用いてスプレー乾燥し、水分量３質量％の乾燥生地を得た。これを（ａ）成分、結晶性シリケート、ゼオライトの一部、香料、及び水分調整用の水と共に攪拌造粒し、ゼオライトの一部で表面被覆し、平均粒径４８０μｍ、見掛け密度８２０ｇ／Ｌの粒子を得た。これに、（ｃ）成分、（ｄ）成分、及び酵素を混合して、平均粒径４８０μｍ、見掛け密度８２０ｇ／Ｌの漂白剤含有洗浄剤組成物を得た。なお、表１中の水分は、ＪＩＳ Ｋ３３６２：１９９８記載の加熱減量法によるものである。
【００６７】
得られた漂白剤含有洗浄剤組成物を４０℃で３０日間保存し、評価用サンプルとした。
【００６８】
＜漂白効果＞
評価用サンプルの０．０６７質量％水溶液１リットル（２０℃）を用いて、下記の通り調製した汚染布５枚を、ターゴトメーターにて普通洗浄した（８０ｒｐｍ×１０分）。その後、水道水ですすぎ、乾燥させて、次式により漂白洗浄率を算出した。反射率は日本電色工業（株）製ＮＤ−３００Ａで４６０ｎｍフィルターを使用して測定した。
漂白洗浄率（％）＝［（洗浄後の反射率−洗浄前の反射率）／（原布の反射率−洗浄前の反射率）］×１００
【００６９】
＜汚染布の調製＞
カゴメ社製トマトソース（カゴメトマトソース）の固形分をメッシュで除去した後、得られた液を刷毛で木綿金布＃２００３に塗布した。余分に付着しているトマトソースをへらで除去し自然乾燥させ、１０ｃｍ×１０ｃｍの試験片として実験に供した。
【００７０】
【表１】

【００７１】
・ＡＥ１：アルキル基の炭素数が12〜14でＥＯ平均付加モル数が７であるポリオキシエチレンアルキルエーテル
・ＡＥ２：アルキル基の炭素数が12〜14でＥＯ平均付加モル数が１５、ＰＯ平均付加モル数が３であるポリオキシエチレン・ポリオキシプロピレンアルキルエーテル
・ＡＥ３：アルキル基の炭素数が12〜14でＥＯ平均付加モル数が１３であるポリオキシエチレンアルキルエーテル
・α−ＳＦ：アルキル基の炭素数が１２〜１４のα−スルホ脂肪酸メチルエステルナトリウム
・過炭酸Ｎａ：炭酸ナトリウム過酸化水素付加物，過炭酸ナトリウム；特開２０００−２５６６９９号公報の段落００１９に記載の漂白剤粒子）
・過ホウ酸Ｎａ：ホウ酸ナトリウム過酸化水素付加物（過炭酸Ｎａと同様にして製造した。）
・ＬＯＢＳ：ラウロイルオキシベンゼンスルホン酸ナトリウム造粒物（特開２０００−２５６６９９号公報の段落００１８記載の漂白剤粒子）
・ＤＯＢＡ：デカノイルオキシ安息香酸ナトリウム（ＬＯＢＳと同様にして製造した。）
・結晶性シリケート：プリフィード（トクヤマシルテック（株）製）
・ＬＡＳ−Ｎａ：アルキル基の炭素数１２〜１４の直鎖アルキルベンゼンスルホン酸ナトリウム
・ＡＯＳ−Ｎａ：アルキル基の炭素数１４〜１８のα−オレフィンスルホン酸ナトリウム
・ＰＥＧ：ポリエチレングリコール（平均分子量８５００）
・ＡＡ／ＭＡコポリマー：アクリル酸マレイン酸コポリマー、ソカランＣＰ−５（ＢＡＳＦ製）
・ＣＭＣ：カルボキシメチルセルロース
・石鹸：アルキル基の炭素数１４〜１８の脂肪酸ナトリウム
・酵素：セルラーゼＫ（特開昭６３−２６４６９９号公報記載）、カンナーゼ２４ＴＫ（ノボ社製）、サビナーゼ６．０Ｔ（ノボ社製）を３：１：２の質量比で使用
・蛍光染料：チノパールＣＢＳ−ＸとチノパールＡＭＳ−ＧＸ（チバガイギー社製）を１：１質量比で使用
【発明の効果】
本発明によれば、非イオン界面活性剤と有機過酸前駆体を併用した漂白系においても、食べ物汚れ等のシミ汚れや皮脂汚れ及び下着等の黄ばみ汚れに対して優れた洗浄性能を示す漂白洗浄剤組成物が得られる。これは、本発明では、特に（ｂ）成分のα−スルホ脂肪酸エステル塩を配合することにより、非イオン界面活性剤と有機過酸前駆体の併用系における有機過酸発生量が増加され、漂白洗浄力も増強されるためと考えられる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a bleach detergent composition, particularly a bleach-containing detergent composition suitable for textile products.
[0002]
[Prior art]
Detergent compositions are strongly directed toward higher density and lower usage due to consumer convenience and consideration for the environment. In addition, there is a trend toward saving water, low temperature washing, and shortening of washing time in response to consumer needs such as "I want to finish washing easily" and "I want to wash clothes carefully", and respond to the environment, energy and economy. .
[0003]
Various stains adhere to clothes, etc. in daily life. Among such changes in the laundry environment, so-called stain stains such as blood stains, food stains, plant pigment stains, and lipophilicity can be achieved only by washing with ordinary detergents. The cleaning power against dirt is not sufficient. In particular, wrinkles and cuff stains cannot be completely removed by ordinary washing, and such residual sebum causes yellowing of clothing during storage.
[0004]
Since bleaching agents are very effective against these stains and the like, attempts have been made to add bleaching ingredients to detergents. The bleaching component is roughly divided into oxygen and chlorine. Examples of the chlorine-based ones include hypochlorous acid and dichlorocyanuric acid. These have problems in stability, odor, etc., and are not suitable for detergent formulation, and because of their strong bleaching power, they have to be nervous about clothing colors and patterns.
[0005]
Oxygen bleach has a slightly lower bleaching power at room temperature than chlorine bleach, but it does not lose color even when applied to colored or patterned clothing, and the fabric may not be damaged and yellowing may occur. It is widely used as a cleaning agent because it does not exist. In addition, in order to improve the bleaching performance, an organic peracid precursor or the like is used in combination.
[0006]
On the other hand, nonionic surfactants have characteristics such as good hard water resistance, outstanding detergency of oily dirt such as sebum dirt, and very good biodegradability. Therefore, the technical development of detergents containing nonionic surfactants has been actively conducted. However, in a bleaching system that uses a combination of a detergent containing a nonionic surfactant and an organic peracid precursor, the organic peracid precursor has a high affinity with the nonionic surfactant and is not contained in the micelle of the nonionic surfactant. Since it is strongly incorporated and difficult to get out of the micelle, there is a problem that the generation amount of peracid is reduced and the bleaching power is greatly reduced. A detergent containing a nonionic surfactant and an organic peracid precursor Considerations have been made to improve bleach detergency. For example, the improvement of the bleaching power by containing a sequestering agent (see, for example, Patent Documents 1, 2, and 3) is known.
[0007]
[Patent Document 1]
JP-A-9-3497
[Patent Document 2]
JP-A-10-316996
[Patent Document 3]
Japanese Patent Laid-Open No. 11-35978
[0008]
[Problems to be solved by the invention]
However, according to the above Patent Documents 1 to 3, the bleaching detergency is still not sufficient. This is presumably because the phenomenon that the bleaching power is lowered due to the decrease in the amount of peracid generated from the organic peracid precursor has not been sufficiently solved.
[0009]
An object of the present invention is to provide a bleaching detergent composition exhibiting excellent cleaning performance against stain stains such as food stains, sebum stains, and yellowing stains such as underwear. More specifically, an object of the present invention is to provide a bleaching detergent composition having an increased amount of organic peracid generated and enhanced bleaching detergency.
[0010]
[Means for Solving the Problems]
The present invention relates to (a) a nonionic surfactant (hereinafter referred to as component (a)) 1 to 25% by mass, (b) an α-sulfo fatty acid ester salt (hereinafter referred to as component (b)) 0.5 to 20 Mass%, (c) peroxide that generates hydrogen peroxide in water (hereinafter referred to as component (c)) 0.1-9 mass%, (d) reacts with hydrogen peroxide to produce an organic peracid It contains 0.1 to 9% by mass of a peracid precursor (hereinafter referred to as component (d)), 15 to 40% by mass of (e) an alkali agent (hereinafter referred to as component (e)), and includes component (b). The total amount of the anionic surfactant (excluding soap) is 1 to 25% by mass, the total amount of the anionic surfactant (excluding soap) containing the component (a) and the component (b) is 15 to 40% by mass, The present invention relates to a bleach-containing detergent composition having a moisture content of 0.1 to 5% by mass according to the heat loss method described in JIS K3362: 1998. That.
[0011]
The present invention also includes a nonionic surfactant, a peroxide that generates hydrogen peroxide in water, a peracid precursor that reacts with hydrogen peroxide to produce an organic peracid, and a bleaching agent containing an alkali agent. The present invention relates to a method for increasing the amount of organic peracid produced in water of a cleaning composition by adding an α-sulfo fatty acid ester salt to the composition. In this case, the composition after addition of the α-sulfo fatty acid ester salt is preferably the composition of the present invention.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
<(A) component>
As the component (a) which is a nonionic surfactant, polyoxyalkylene alkyl (carbon number 8 to 20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (carbon number 8 to 20) phenyl ether, polyoxyalkylene sorbitan fatty acid (C8-C22) ester, polyoxyalkylene glycol fatty acid (C8-C22) ester, polyoxyethylene polyoxypropylene block polymer are mentioned. In particular, in terms of cleaning performance, the component (a) includes, on average, an alkylene oxide such as ethylene oxide (hereinafter referred to as EO) or propylene oxide (hereinafter referred to as PO) to an alcohol having 10 to 18 carbon atoms. A polyoxyalkylene alkyl ether having 4 to 20 moles added (preferably 4 to 14 moles added, more preferably 4 to 12 moles added) is preferred. The component (a) preferably has an HLB value (calculated by the Griffin method) of 10.5 to 15.0, more preferably 11.0 to 14.5 in terms of cleaning performance.
[0013]
The composition of this invention contains 1-25 mass% of (a) component. 2-20 mass% is preferable at the point of washing | cleaning performance, 3-15 mass% is more preferable, and 5-12 mass% is still more preferable.
[0014]
<(B) component>
As the α-sulfo fatty acid ester salt of the component (b), those represented by the following general formula are used.
[0015]
[Chemical 1]

[0016]
[Wherein, R represents a linear or branched alkyl or alkenyl group having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and particularly preferably 14 to 18 carbon atoms. R ′ is a linear or branched alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. M is an alkali metal or ammonium, and specific examples of the alkali metal include lithium, sodium, potassium, and the like. ]
[0017]
The component (b) is usually obtained by a known production method. For example, it can be produced by sulfonating a fatty acid ester obtained by reacting oil and fat with a lower alcohol with sulfuric anhydride and finally neutralizing with caustic alkali or the like. Examples of the raw oil and fat include coconut oil, palm kernel oil, pig oil, beef tallow, rice bran oil, palm oil, and fish oil.
[0018]
The composition of this invention contains (b) component 0.5-20 mass%. It is preferable to contain 1-18 mass% in a composition at the point of an organic peracid production amount improvement, 2-15 mass% is more preferable, and 3-13 mass% is still more preferable.
[0019]
By containing the component (b), it is possible to avoid the problem that the amount of organic peracid generated from the organic peracid precursor is reduced due to the influence of the nonionic surfactant and the detergency is reduced. That is, in this invention, the production amount of organic peracid can be increased by using the component (b).
[0020]
<(C) component>
Component (c), which is a peroxide that generates hydrogen peroxide in water, includes carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct, tripolyphosphate / hydrogen peroxide adduct, pyrophosphoric acid Examples include salts / hydrogen peroxide adducts, urea / hydrogen peroxide adducts, and the like. Among these, carbonate / hydrogen peroxide adduct and borate / hydrogen peroxide adduct are preferable, and sodium carbonate / hydrogen peroxide adduct and sodium borate / hydrogen peroxide adduct are more preferable.
[0021]
The composition of the present invention contains 0.1 to 9% by mass of component (c). In terms of cleaning performance, the composition preferably contains 0.5 to 8% by mass, more preferably 1 to 7% by mass, and still more preferably 2 to 6% by mass.
[0022]
The component (c) is preferably coated with an inorganic compound or an organic compound from the viewpoint of storage stability. Examples of inorganic compounds include boric acid, borate, sodium carbonate, sodium sulfate, magnesium sulfate, magnesium silicate, magnesium chloride, magnesium oxide, and sodium silicate. Organic compounds include polyethylene glycol, polyvinyl pyrrolidone, and hydroxypropyl. A cellulose etc. are mentioned. Among these, it is preferable to coat with boric acid or borate. Examples of boric acid include orthoboric acid, metaboric acid, and tetraboric acid, and examples of the salt include alkali metal salts such as sodium and potassium.
[0023]
The coated particles containing the component (c) can be produced, for example, by the method described in JP-A-59-196399. When the component (c) is used as a particle containing the component (c), the coating amount is preferably 0.5 to 20% by mass in the particle in terms of stability and solubility, and more preferably 1 to 10% by mass. . In addition, conventionally known stabilizers, dissolution accelerators, chelating agents, and the like may be included in the particles. Among these, chloride, urea, anionic surfactant, and nonionic surfactant are preferable from the viewpoint of solubility, and the ratio thereof is preferably 0.1 to 5% by mass in the particles. In addition, since a nonionic surfactant can be used also as (a) component, the quantity is included in the quantity of (a) component. Of such coated particles, particles containing the component (c) coated with boric acid or borate can be used as second particles described later.
[0024]
<(D) component>
As the component (d), which is a compound that reacts with hydrogen peroxide in water to generate an organic peracid, glucose pentaacetate, triacetin, N, N, N ′, Bleach activators such as N′-tetraacetylethylenediamine and tetraacetylglycolyluril can be used, but peracid precursors represented by the following general formula (I) are preferable in terms of effects.
[0025]
[Chemical 2]

[0026]
[In the formula, R ¹ Represents a linear or branched alkyl group having 4 to 18 carbon atoms, an aryl group, an alkenyl group, an acyl group, or a group represented by the following general formula (II);
[0027]
[Chemical 3]

[0028]
(Wherein R ² Represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an alkenyl group, an acyl group, and R ^Three Represents a linear or branched alkylene group having 1 to 8 carbon atoms, p represents 0 or 1, and R represents ^Four Represents a phenylene group which may be substituted with a linear or branched alkylene group having 1 to 8 carbon atoms or a linear or branched alkyl group having 1 to 5 carbon atoms, and A represents a carbon number having 1 to 5 carbon atoms. 4 is a linear or branched alkylene group, q is the average number of moles of alkylene oxide added and represents a number of 0 to 100, and q A's may be the same or different.
[0029]
L represents a group represented by the following general formula (III), (IV), (V), or (VI).
[0030]
[Formula 4]

[0031]
(In the formula, M represents a hydrogen atom or a cation that forms a water-soluble salt, and R ^Five And R ⁶ Each represents a linear or branched alkylene group having 1 to 8 carbon atoms. )]
[0032]
In terms of cleaning performance, R ¹ Is preferably a linear or branched alkyl group or alkenyl group (more preferably an alkyl group) having 4 to 18 carbon atoms (more preferably 7 to 18 carbon atoms, still more preferably 10 to 13 carbon atoms). L is preferably a group represented by the general formula (III) or (IV) (particularly a group represented by (III)). Examples of M include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions. Among them, sodium ions and potassium ions are preferable, and sodium ions are particularly preferable.
[0033]
The composition of this invention contains 0.1-9 mass% of (d) component. In terms of cleaning performance, the composition preferably contains 0.1 to 7% by mass, more preferably 0.2 to 5% by mass, further preferably 0.2 to 4% by mass, and 0.3 to 3% by mass. % Is particularly preferred.
[0034]
(D) When mix | blending a component in a composition, it is preferable to mix | blend as a particle | grain containing (d) component from a stability point. The amount of the component (d) in the particles containing the component (d) is preferably 1 to 80% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass. The particles containing the component (d) are selected from polyoxyalkylene alkyl ether, alkyl sulfate ester salt and polyoxyalkylene alkyl ether sulfate salt to improve the solubility of the component (d) in the washing bath. It is preferable that 0 to 50% by mass, further 1 to 45% by mass, particularly 2 to 40% by mass of at least one surfactant is contained in the particles containing the component (d). As the polyoxyalkylene alkyl ether, those in which EO and PO are added in a block form are preferable, the EO average addition mole number is preferably 3 to 20, particularly 4 to 15, and the PO average addition mole number is 1 to 10, especially 2. ~ 7 is preferred. The number of carbon atoms of the alkyl group is preferably 10-18, particularly 12-16. The alkyl sulfate ester salt has 10 to 18 carbon atoms and is preferably a sodium salt, particularly preferably sodium lauryl sulfate or sodium myristyl sulfate. Moreover, as a polyoxyalkylene alkyl ether sulfate salt, the polyoxyethylene alkyl ether sulfate whose carbon number of an alkyl group is 10-18 is preferable, and a sodium salt is favorable. Here, the average degree of polymerization (hereinafter referred to as EOp) of the polyoxyethylene group is preferably 1 to 10, particularly 1 to 5, particularly polyoxyethylene (EOp = 2 to 5) sodium lauryl ether sulfate, polyoxyethylene (EOp). = 2 to 5) Sodium myristyl ether sulfate is good. Of these surfactants, polyoxyalkylene alkyl ethers can also be used as the component (a), so the amount is included in the amount of the component (a). (D) The particle | grains containing a component are obtained by formulating the said component using the binder substance chosen from polyoxyethylene and a fatty acid. As the polyoxyethylene, those having an average molecular weight of 2000 to 20000, 4000 to 10000, particularly 4000 to 8000 are preferable. Moreover, as a fatty acid, C8-C20, Furthermore, a thing of 10-18, especially 12-18 are preferable, and these may be in the state of sodium or potassium soap. It is preferable to use the binder substance in the particles containing the component (d) in an amount of 0.5 to 30% by mass, further 1 to 20% by mass, and particularly 5 to 20% by mass. It is preferable from the viewpoint of stability that the particles containing the component (d) are blended with the above composition at the above ratio. Moreover, in this invention, you may mix | blend an acidic substance with the particle | grains containing (d) component as needed for the purpose of improving the stability of the particle | grains containing (d) component. As the acidic substance, organic carboxylic acids are preferable, and at least one selected from succinic acid, maleic acid, fumaric acid, citric acid, glycolic acid and p-hydroxybenzoic acid is particularly preferable. The compounding amount of such an acidic substance is preferably 0 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass in the particles containing the component (d). The particles containing the component (d) can be obtained by mixing the above components by any method. In particular, the component (d) and a part or all of the surfactant are mixed first, and then the binder substance or the like. The method of adding is preferable. The binder substance is preferably added after being melted in advance. The binder material is preferably added after being melted at 40 to 100 ° C., further 50 to 100 ° C., particularly 50 to 90 ° C. These are stirred and mixed until uniform, and then formulated with a normal granulator. Extrusion granulation can be mentioned as a preferable granulation method, and it is preferable to make a granulated product having an average particle diameter of 500 μm to 5000 μm, particularly 500 to 3000 μm. As another granulation method, a tablet shape by a briquetting machine can be cited as a preferable granulation method. The extruded granulated product containing the component (d) as described above can be used as third particles described later.
[0035]
<(E) component>
Examples of the component (e) include alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate, alkali metal silicates such as sodium silicate and potassium silicate, orthophosphate, metaphosphate, pyrophosphate Examples thereof include salts, polyphosphates such as hexametaphosphate, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, disodium hydrogen phosphate, trisodium phosphate, and borate.
[0036]
The component (e) has a cleaning performance, and the maximum pH of the 0.025 mass% aqueous solution or dispersion of the component (e) is 10 or more (20 ° C.), and 1 liter of the aqueous solution or dispersion is pH 9 It is preferable that the compound requires 10 ml or more of a 0.1N hydrochloric acid aqueous solution in order to achieve (20 ° C.). Examples of such compounds include sodium carbonate, potassium carbonate, sodium silicate, trisodium phosphate, monoethanolamine and the like. Of these, sodium carbonate, potassium carbonate, and sodium silicate are more preferable, and sodium carbonate is particularly preferable.
[0037]
The composition of the present invention contains 15 to 40% by mass of component (e). In terms of cleaning performance, the composition preferably contains 17 to 38% by mass, more preferably 20 to 35% by mass.
[0038]
<Moisture>
The composition of the present invention has a water content of 0.1 to 5% by mass according to the heat loss method described in JIS K3362: 1998. In terms of storage stability and productivity, 0.5 to 4.8% by mass is preferable, and 1 to 4.5% by mass is more preferable.
[0039]
<Others>
Examples of surfactants other than component (a) and component (b) that can be used in the present invention include anionic surfactants, amphoteric surfactants, and cationic surfactants other than component (b). .
[0040]
Examples of the anionic surfactants include higher alcohol sulfates, higher alcohol ethoxylate sulfates, alkylbenzene sulfonates, paraffin sulfonates, and α-olefin sulfonates. In particular, linear alkylbenzene sulfonates having 10 to 18 (preferably 12 to 14) carbon atoms in the alkyl chain and α-sulfo fatty acid alkyl ester salts having 10 to 20 carbon atoms are preferred. Examples of the counter ion include alkali metals, alkaline earth metals, ammonium, and alkanolamine. From the viewpoint of adjusting the dissolution rate, it is also preferable to use potassium ions in combination. The potassium ion in all counter ions is preferably 5% by mass or more, more preferably 20% by mass or more, and particularly preferably 40% by mass or more.
[0041]
In addition, although soap can also be mix | blended, the quantity is not included in an anionic surfactant. Examples of the soap include sodium salts and potassium salts of fatty acids having 12 to 20 carbon atoms. It is preferable that the ratio of soap is 1-10 mass% in a composition.
[0042]
The composition of the present invention contains 1 to 25% by mass of an anionic surfactant (excluding soap) containing the component (b). 5-22 mass% is preferable at the point of washing | cleaning performance and solubility, and 8-20 mass% is more preferable.
[0043]
Moreover, the composition of this invention contains 15-40 mass% in total of (a) component and the anionic surfactant (except soap) containing (b) component. 15-35 mass% is preferable at a washing | cleaning performance and a soluble point, 15-30 mass% is more preferable, 15-25 mass% is still more preferable.
[0044]
Examples of the cationic surfactant include alkyltrimethylammonium salts, and examples of the amphoteric surfactant include carbobetaine type and sulfobetaine type amphoteric surfactants.
[0045]
The composition of the present invention includes other builders, other bleach activators, anti-staining agents (carboxymethyl cellulose, etc.), softeners (dialkyl quaternary ammonium salts, clay minerals, etc.), reducing agents (sulfites, etc.) ), Optical brighteners (biphenyl type, aminostilbene type, etc.), foam control agents (soap, silicone, etc.), fragrances, enzymes (proteases, pectinases, amylases, lipases, etc.) and the like.
[0046]
In the present invention, the builder itself has no detergency or is not so remarkably present, but when it is incorporated into a detergent composition, it significantly improves the detergency. As an action, it has at least one action of capturing a polyvalent metal cation, a dirt dispersing action and an alkali buffering action.
[0047]
Examples of the water-insoluble inorganic compound that can be a builder include aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, amorphous aluminosilicate, etc.), crystalline silicate, and the like. Among these, A-type zeolite having a particle size of 3 μm or less (more preferably 1 μm or less) is preferable.
[0048]
Examples of organic compounds that can be builders include carboxylates (aminocarboxylates, hydroxyaminocarboxylates, hydroxycarboxylates, cyclocarboxylates, maleic acid derivatives, oxalates, etc.), organic carboxylic acid (salt) polymers (Acrylic acid polymers and copolymers, polyvalent carboxylic acid polymers and copolymers, glyoxylic acid polymers, polysaccharides and their salts, etc.). Of these, organic carboxylic acid (salt) polymers are preferred.
[0049]
In the builder salt, the counter ion is preferably an alkali metal salt or an amine, and particularly preferably sodium and / or potassium, monoethanolamine, or diethanolamine.
[0050]
In the present invention, these builders can be used alone or in combination of two or more.
[0051]
In the present invention, it is particularly preferable from the viewpoint of cleaning performance to contain a builder capable of capturing a polyvalent metal cation. It is preferable to contain a compound having a calcium stability constant of 4 to 15 (preferably 5 to 14, more preferably 6 to 13) as a builder capable of capturing a polyvalent metal cation. 0.1-20 mass% is preferable in a cleaning composition, 0.5-15 mass% is more preferable, and 1-10 mass% is still more preferable. In the present invention, the calcium stability constant is determined by the following method.
[0052]
(Measurement method of calcium stability constant)
0.1 mol / liter NH as buffer _Four Cl-NH _Four An OH (pH 10) solution is prepared. All sample solutions are prepared using this buffer. Ca ²⁺ To measure the concentration, ion meter 920A manufactured by Orion Co., Ltd. and Ca ²⁺ An ion electrode is used. First, a relationship between the calcium chloride concentration and the electrode potential is obtained, and a calibration curve is created. Calcium chloride 5.36 × 10 ^-2 Mol / liter solution, chelating agent sample 5.36 × 10 ^-Four Prepare a mol / liter solution. Add 1 ml of calcium chloride solution to 100 ml of chelating agent sample solution and stir for 5 minutes. Remaining Ca ²⁺ Concentration is Ca ²⁺ Measurement is performed using an ion electrode. Chelating agent is Ca ²⁺ Assuming that a chelate complex is formed 1: 1, the calcium stability constant (Ca stability constant) is obtained from the following formula.
[0053]
[Expression 1]

[0054]
Other bleach activators include glucose pentaacetate, triacetin, N, N, N ′, N′-tetraacetylethylenediamine, tetraacetylglycolyluril, and compounds described in the following general formulas (1) and (2). Can be contained.
[0055]
[Chemical formula 5]

[0056]
[In the formula, R ¹¹ , R ¹² , R ¹³ , R ^{twenty one} , R ^{twenty two} , R ^{twenty four} , R ^{twenty five} Are each independently an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group, and R ^{twenty three} Is an alkylene group having 2 to 10 carbon atoms, and X ^- Represents an anion such as an alkali metal ion. ]
[0057]
<Bleaching agent-containing cleaning composition>
In the bleach-containing cleaning composition of the present invention, the mass ratio of the component (a) to the component (b) is (a) :( b) = 7: 1 to 1: 5, and further 6: 1 to 1: 3. In particular, the ratio is preferably 4: 1 to 2.5: 1. (A) :( b) is preferably 7: 1 or less from the viewpoint of sufficient peracid generation, and preferably 1: 5 or more from the viewpoint of excellent hard water resistance and oily soil cleaning properties.
[0058]
In the bleach-containing cleaning composition of the present invention, the mass ratio of the component (b) to the component (d) is (b) :( d) = 30: 1 to 1: 1.5, and further 20: 1. ˜1: 1, more preferably 10: 1 to 3: 1. From the viewpoint of sufficient peracid generation, (b) :( d) is preferably 30: 1 or less, and preferably 1: 1.5 or more from the viewpoint of economy.
[0059]
The bleaching agent-containing cleaning composition of the present invention has a pH of 0.1% by weight aqueous solution measured at 20 ° C. described in JIS K 3362: 1998 is preferably 8 to 12, more preferably 9 to 11.5 in terms of cleaning performance and damage. Preferably, 9.5 to 11 are more preferable, and 10 to 11 are particularly preferable.
(C) It is preferable to prepare so that it may become such a range with pH adjusters, such as a component and sodium hydroxide, potassium hydroxide.
[0060]
In terms of solubility, the bleach-containing detergent composition of the present invention preferably has an apparent density of 1600 g / L or less, more preferably 1300 g / L or less, more preferably 1000 g / L, as measured by the method defined by JIS K 3362: 1998. L or less is more preferable. In terms of convenience and reduction of waste (such as boxes), the apparent density is preferably 300 g / L or more, more preferably 600 g / L or more, and even more preferably 700 g / L or more.
[0061]
The bleach-containing detergent composition of the present invention is an average of the granular detergent composition obtained from the mass fraction according to the size of the mesh after vibrating for 5 minutes using a standard sieve of JIS Z 8801 in terms of solubility. The particle size is preferably 150 to 1000 μm, more preferably 150 to 800 μm, and still more preferably 180 to 600 μm.
[0062]
The bleach-containing detergent composition of the present invention may be further compressed into a tablet form for convenience, and a single use amount can be stored in a water-soluble or water-insoluble container.
[0063]
The bleach-containing detergent composition of the present invention is preferably subjected to surface modification with a surface coating agent in terms of storage stability, fluidity and non-caking property. The surface coating agent is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, and still more preferably 5 to 10% by mass in the detergent particles. Examples of the surface coating agent include aluminosilicates, calcium silicates, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate compounds such as silicate compounds, metal soaps, powder surfactants, etc. Water-soluble polymers such as fine powders, carboxymethylcellulose, polyethylene glycol, sodium polyacrylate, polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof; and fatty acids. Of these, water-insoluble inorganic substances are preferred, and crystalline aluminosilicates, amorphous aluminosilicates, and crystalline silicate compounds are particularly preferred.
[0064]
In the bleach-containing cleaning composition of the present invention, the components (a) to (d) are the first particles containing the component (a), the component (b), and the component (e) in terms of storage stability. And (c) a second particle containing the component and (d) a third particle containing the component.
[0065]
In particular, the bleach-containing detergent composition of the present invention comprises (a) component, (b) component, (e) component, the first particles coated with a powder coating agent, and (c) component. It is preferable to contain the 2nd particle | grains which contain and coat | covered with boric acid or a borate, and the 3rd particle | grains which consist of an extrusion granulated material containing (d) component. Here, the powder coating agent of the first particles can use the above surface coating agent, and the amount of the powder coating agent in the first particles is
~ Mass% is preferred.
[0066]
【Example】
Examples 1-8, Comparative Examples 1-4
Among the components shown in Table 1, (a) component, (c) component, (d) component, crystalline silicate, part of zeolite, each component excluding enzyme and fragrance, solid content 40% by mass An aqueous slurry was prepared and spray-dried using a drying tower to obtain a dry dough having a moisture content of 3% by mass. This was agitated and granulated together with component (a), crystalline silicate, part of zeolite, fragrance, and water for adjusting water, and surface-coated with part of zeolite, with an average particle size of 480 μm and an apparent density of 820 g / L. Particles were obtained. This was mixed with the component (c), the component (d), and the enzyme to obtain a bleach-containing cleaning composition having an average particle size of 480 μm and an apparent density of 820 g / L. In addition, the water | moisture content of Table 1 is based on the heat loss method of JISK3362: 1998 description.
[0067]
The obtained bleach-containing cleaning composition was stored at 40 ° C. for 30 days to obtain a sample for evaluation.
[0068]
<Bleaching effect>
Using 1 liter (20 ° C.) of a 0.067% by weight aqueous solution of the sample for evaluation, 5 sheets of contaminated cloth prepared as follows were washed with a targotometer (80 rpm × 10 minutes). Thereafter, it was rinsed with tap water and dried, and the bleaching washing rate was calculated by the following formula. The reflectance was measured with ND-300A manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.
Bleach washing rate (%) = [(reflectance after washing−reflectivity before washing) / (reflectance of base fabric−reflectivity before washing)] × 100
[0069]
<Preparation of contaminated cloth>
After removing the solid content of Kagome Tomato Sauce (Kagome Tomato Sauce) with a mesh, the obtained liquid was applied to cotton gold cloth # 2003 with a brush. The excessively attached tomato sauce was removed with a spatula and allowed to dry naturally, and the specimen was used as a 10 cm × 10 cm test piece.
[0070]
[Table 1]

[0071]
AE1: polyoxyethylene alkyl ether having an alkyl group with 12 to 14 carbon atoms and an EO average addition mole number of 7
AE2: polyoxyethylene polyoxypropylene alkyl ether having 12 to 14 carbon atoms in the alkyl group, 15 EO average addition mole number, and 3 PO average addition mole number
AE3: polyoxyethylene alkyl ether having an alkyl group with 12 to 14 carbon atoms and an EO average addition mole number of 13
Α-SF: sodium α-sulfo fatty acid methyl ester having 12 to 14 carbon atoms in the alkyl group
Na percarbonate: sodium carbonate hydrogen peroxide adduct, sodium percarbonate; bleaching agent particles described in paragraph 0019 of JP-A No. 2000-256699)
Na perborate: sodium borate hydrogen peroxide adduct (produced in the same manner as Na percarbonate)
LOBS: sodium lauroyloxybenzenesulfonate granulated product (bleaching agent particles described in paragraph 0018 of JP 2000-256699 A)
DOBA: sodium decanoyloxybenzoate (produced in the same manner as LOBS)
・ Crystalline silicate: Pre-feed (manufactured by Tokuyama Siltech Co., Ltd.)
LAS-Na: linear alkylbenzene sulfonate sodium having 12 to 14 carbon atoms in the alkyl group
AOS-Na: sodium α-olefin sulfonate having 14 to 18 carbon atoms in the alkyl group
PEG: polyethylene glycol (average molecular weight 8500)
AA / MA copolymer: maleic acid acrylate copolymer, Socaran CP-5 (manufactured by BASF)
・ CMC: Carboxymethylcellulose
・ Soap: Fatty acid sodium with alkyl group of 14-18 carbon atoms
Enzyme: Cellulase K (described in JP-A 63-264699), cannase 24TK (manufactured by Novo), sabinase 6.0T (manufactured by Novo) in a mass ratio of 3: 1: 2
・ Fluorescent dyes: Chinopearl CBS-X and Chinopearl AMS-GX (Ciba Geigy) are used at a mass ratio of 1: 1.
【The invention's effect】
According to the present invention, even in a bleaching system using a combination of a nonionic surfactant and an organic peracid precursor, bleaching that exhibits excellent cleaning performance against stain stains such as food stains, sebum stains, and yellowing stains such as underwear A cleaning composition is obtained. In the present invention, the amount of organic peracid generated in the combined system of the nonionic surfactant and the organic peracid precursor is increased by blending the α-sulfo fatty acid ester salt of component (b). This is probably because the cleaning power is also enhanced.

Claims (3)

(A) 1 to 25% by mass of polyoxyalkylene alkyl ether obtained by adding 4 to 20 mol of alkylene oxide on average in an alcohol having 10 to 18 carbon atoms , (b) 0.5 to 20% by mass of α-sulfo fatty acid ester salt, (C) 0.1 to 9% by mass of a peroxide that generates hydrogen peroxide in water, (d) 0.1 to 9% by mass of a peracid precursor that reacts with hydrogen peroxide to generate an organic peracid, (E) An anionic interface containing 20 to 35 % by mass of an alkaline agent and 1 to 25% by mass in total of anionic surfactant (excluding soap) containing (b), and (a) and (b) The total amount of the active agent (excluding soap) is 15 to 40% by mass, and the mass ratio of (a) and (b) is (a) :( b) = 7: 1 to 1: 5, JIS K3362: 1998 A bleach-containing detergent composition having a water content of 0.1 to 5% by mass according to the heat loss method.   (A) nonionic surfactant, (b) α-sulfo fatty acid ester salt, (e) first particles containing an alkali agent and coated with a powder coating agent, and (c) hydrogen peroxide in water Extruded structure containing second particles containing generated peroxide and coated with boric acid or borate, and (d) a peracid precursor that reacts with hydrogen peroxide to produce an organic peracid. The bleach-containing detergent composition according to claim 1, comprising third particles made of granules. The bleach-containing detergent composition according to claim 1 or 2 , wherein the mass ratio of (b) to (d) is (b) :( d) = 30: 1 to 1: 1.5.