JP2004196852A - Bleaching detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bleaching detergent composition with enhanced bleaching detergency. <P>SOLUTION: The bleaching detergent composition contains (a) a peroxide generating hydrogen peroxide in an aqueous solution, (b) a peracid precursor reacting with hydrogen peroxide to generate an organic peracid, (c) a nonionic surfactant, and (d) a polyalkylene glycol. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１２】
〔式中、Ｒ_１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、炭素数４〜１８のアルケニル基、炭素数４〜１８のアシル基、又は下記一般式（II）で表される基を示し、
【００１３】
【化５】

【００１４】
（式中、
Ｒ_２は、水素原子、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルケニル基又はアシル基を示し；
Ｒ_３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；
Ｒ_４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）
Ｌは、下記一般式（III）、（IV）、（Ｖ）、又は（VI）で表される基を示す。
【００１５】
【化６】

【００１６】
（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、Ｒ_５及びＲ_６は、炭素数１〜８の直鎖又は分岐鎖のアルキレン基を示す）〕
【００１７】
【発明の実施の形態】
＜（ａ）成分＞
本発明の組成物は、（ａ）成分として、水溶液中で過酸化水素を放出する化合物から選ばれる１種以上の化合物を含有する。
【００１８】
（ａ）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。これらの中でも、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。
【００１９】
（ａ）成分は、貯蔵安定性の点で無機化合物や有機化合物等で被覆されていることが好ましい。無機化合物としては、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。
【００２０】
被覆に用いる無機化合物や有機化合物の量は、（ａ）成分を含む粒子として用いる場合、粒子中において５〜２０質量％であることが、安定性、溶解性の点で好ましい。なお、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。これらの安定化剤等の中でも、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、それらの含有量は、それぞれ、前記粒子中０．１〜５質量％が好ましい。
【００２１】
（ａ）成分として、無機や有機化合物等で被覆したものを用いる場合、例えば特開昭５９−１９６３９９号公報の実施例等に記載の方法を適用して製造できる。
【００２２】
本発明の組成物中における（ａ）成分の含有量は、洗浄性能の点で、０．１〜２０質量％が好ましく、０．５〜１０質量％がより好ましく、１〜８質量％が更に好ましく、２〜７質量％が特に好ましい。
【００２３】
＜（ｂ）成分＞
本発明の組成物は、（ｂ）成分として、過酸化水素と反応して有機過酸を生成する一般式（Ｉ）で表される過酸前駆体を含有する。
【００２４】
一般式（Ｉ）中のＲ_１は、洗浄性能の点で、直鎖又は分岐鎖の炭素数４〜１８、好ましくは炭素数７〜１８、より好ましくは炭素数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）である。
【００２５】
一般式（Ｉ）中の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、アンモニウム塩、アルカノールアミン塩等が挙げられ、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。
【００２６】
本発明の組成物では、（ｂ）成分は、安定性を高めるために（ｂ）成分を含む粒子形態にすることが好ましい。（ｂ）成分を含む粒子中の（ｂ）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。
【００２７】
（ｂ）成分を含む粒子には、（ｂ）成分の洗濯浴中での溶解性を改善するため、ポリオキシアルキレンアルキルエーテル、アルキル硫酸塩及びポリオキシアルキレンアルキルエーテル硫酸塩から選ばれる少なくとも１種の界面活性剤を、好ましくは５０質量％以下、より好ましくは１〜４５質量％、更に好ましくは２〜４０質量％配合することができる。
【００２８】
ポリオキシアルキレンアルキルエーテルとしては、エチレンオキシドとプロピレンオキシドがブロック状に付加したものが好ましく、エチレンオキシド平均付加モル数は３〜２０、特に４〜１５が好ましく、プロピレンオキシド平均付加モル数は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。
【００２９】
アルキル硫酸塩としては、炭素数１０〜１８で、ナトリウム塩が好ましく、特にラウリル硫酸ナトリウム又はミリスチル硫酸ナトリウムが好ましい。
【００３０】
ポリオキシアルキレンアルキルエーテル硫酸塩としては、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好ましい。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が好ましく、特にポリオキシエチレン（ＥＯｐ＝２〜５）ラウリルエーテル硫酸ナトリウム、ポリオキシエチレン（ＥＯｐ＝２〜５）ミリスチルエーテル硫酸ナトリウムが好ましい。
【００３１】
（ｂ）成分を含む粒子には、製剤化を容易にするための成分として、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を配合しても良い。
【００３２】
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。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又はカリウム石鹸の状態であってもよい。バインダーは、（ｂ）成分を含む粒子中に、好ましくは０．５〜３０質量％、より好ましくは１〜２０質量％、更に好ましくは５〜２０質量％使用する。
【００３３】
本発明の組成物には、（ｂ）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、更に酸性物質を配合してもよい。
【００３４】
酸性物質としては有機カルボン酸類が好ましく、特にコハク酸、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、（ｂ）成分を含む粒子中に、好ましくは２０質量％以下、より好ましくは１〜１５質量％、更に好ましくは１〜１０質量％である。
【００３５】
（ｂ）成分を含む粒子は、上記成分を所望の方法で混合した後、通常の造粒機により造粒して得ることができるが、特に（ｂ）成分と溶解性改善のための界面活性剤の一部又は全部を先に混合し、その後バインダー等を添加する方法が好ましい。バインダーは、予め４０〜１００℃、更に５０〜１００℃、特に５０〜９０℃で融解させて添加することが好ましい。
【００３６】
造粒法は押出造粒法が好ましく、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。その他、ブリケット機により錠剤形状にすることも好ましい造粒法として適用できる。
【００３７】
本発明の組成物中における（ｂ）成分の含有量は、、洗浄性能の点で、０．０５〜５質量％が好ましく、０．１〜３質量％がより好ましく、０．３〜２質量％が更に好ましく、０．５〜１．５質量％が特に好ましい。
【００３８】
＜（ｃ）成分＞
本発明の組成物は、（ｃ）成分として非イオン界面活性剤を含有する。（ｃ）成分の非イオン界面活性剤としては、ポリオキシアルキレンアルキル（炭素数８〜２０）エーテル、アルキルポリグリコシド、ポリオキシアルキレンアルキル（炭素数８〜２０）フェニルエーテル、ポリオキシアルキレンソルビタン脂肪酸（炭素数８〜２２）エステル、ポリオキシアルキレングリコール脂肪酸（炭素数８〜２２）エステル、ポリオキシエチレンポリオキシプロピレンブロックポリマーが挙げられる。特に、洗浄性能の点で、（ｃ）成分としては、炭素数１０〜１８のアルコールにエチレンオキシドやプロピレンオキシド等のアルキレンオキシドを平均で４〜２０モル付加したポリオキシアルキレンアルキルエーテルが好ましい。（ｃ）成分は、洗浄性能の点で、ＨＬＢ値（グリフィン法で算出）が１０.５〜１５.０、更に１１.０〜１４.５のものが好ましい。
【００３９】
本発明の組成物において、ＪＩＳ Ｋ３３６２：１９９８記載の界面活性剤相当分中の（ｃ）成分は１０質量％以上が好ましく、３０質量％以上がより好ましく、５０質量％以上が更に好ましい。また、非イオン界面活性剤と共に陰イオン界面活性剤を用いることが、多種な汚れに対する洗浄性能の点で好ましく、非イオン界面活性剤と陰イオン界面活性剤との質量比は１／９〜９／１がより好ましく、３／７〜９／１が更に好ましく、５／５〜９／１が特に好ましい。
【００４０】
本発明の組成物中の（ｃ）成分は、洗浄性能の点で、１〜３０質量％が好ましく、３〜２５質量％がより好ましく、５〜２０質量％が更に好ましく、８〜１８質量％が特に好ましい。
【００４１】
＜（ｄ）成分＞
本発明の組成物は、（ｄ）成分としてポリアルキレングリコールを含有する。（ｄ）成分は、（ｂ）成分からのジアシル体の生成を抑制し、過酸発生量を増加させることで、漂白洗浄力を増強させる作用をするものである。
【００４２】
この増強作用は、（ａ）、（ｂ）及び（ｃ）成分を含有する漂白洗浄剤を用いた水系洗浄において、（ｄ）成分を存在させることにより、非イオン界面活性剤のミセル中に（ｂ）成分の過酸前駆体が取り込まれることによる過酸生成阻害が抑制されることによるものと思われる。
【００４３】
（ｄ）成分としては、ポリエチレングリコール、ポリプロピレングリコール等が挙げられ、ジアシル体の生成を抑制する点でポリエチレングリコールが好ましい。
【００４４】
（ｄ）成分は、ジアシル体の生成を抑制する点で、重量平均分子量は５００〜１５，０００が好ましく、１，０００〜１０，０００がより好ましく、２，０００〜９，０００が更に好ましい。
【００４５】
本発明の組成物中における（ｄ）成分は、ジアシル体の生成を抑制する点で、４．５〜３０質量％が好ましく、５〜２５質量％がより好ましく、７〜２０質量％が更に好ましく、１０〜２０質量％が特に好ましい。
【００４６】
＜その他成分＞
（ｃ）成分以外の界面活性剤としては、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。
【００４７】
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、α−スルホ脂肪酸塩若しくはそのエステル塩、又は脂肪酸塩が挙げられる。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。
【００４８】
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。
【００４９】
上記した界面活性剤の内、洗浄性能、溶解性の点で、ＪＩＳ Ｋ３３６２：１９９８記載の界面活性剤相当分は１０〜６０質量％が好ましく、１５〜４５質量％がより好ましく、１８〜４０質量％が更に好ましく、２０〜３５質量％が特に好ましい。
【００５０】
本発明の組成物は、ビルダー、その他の漂白活性化剤、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（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。
【００５１】
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、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、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３つの作用中、少なくとも１つの作用をするものである。ビルダーとしては、水溶性無機化合物、水不溶性無機化合物、有機化合物等が挙げられる。
【００５２】
水溶性無機化合物としては、リン酸塩（トリポリリン酸塩、ピロリン酸塩、メタリン酸塩、リン酸三ナトリウム等）、ケイ酸塩、炭酸塩、硫酸塩等が挙げられる。これらの中でも３つの作用の全てをする点でリン酸塩が好ましい。
【００５３】
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。これらの中でも粒子径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。
【００５４】
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（アクリル酸重合体及び共重合体、多価カルボン酸重合体及び共重合体、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。これらの中でも有機カルボン酸（塩）ポリマーが好ましい。
【００５５】
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。
【００５６】
本発明の組成物において、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。特に、ビルダーとしては、前記水溶性無機化合物を含有することが好ましく、水溶性無機化合物及び有機化合物を併用することがより好ましく、水溶性無機化合物、有機化合物及び水不溶性無機化合物を併用することが更に好ましい。
【００５７】
本発明の組成物においては、洗浄性能の点で、ビルダーの合計含有量は、組成物中２０〜８０質量％が好ましく、３０〜７０質量％がより好ましく、３５〜６０質量％が更に好ましい。また、水溶性無機化合物ビルダーは、組成物中１０〜５０質量％が好ましく、１５〜４５質量％がより好ましく、２０〜４０質量％が更に好ましい。水不溶性無機化合物ビルダーは、組成物中５〜５０質量％が好ましく、１０〜４５質量％がより好ましく、１５〜４０質量％が更に好ましい。有機化合物ビルダーは、組成物中０．１〜２０質量％が好ましく、０．３〜１５質量％がより好ましく、０．５〜１０質量％が更に好ましい。
【００５８】
本発明の組成物では、洗浄性能の点で、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。多価金属陽イオンの捕捉作用のあるビルダーの組成物中の含有量は、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。なお、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。
【００５９】
（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ＮＨ_４Ｃｌ−ＮＨ_４ＯＨ（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。Ｃａ^２＋濃度の測定にはオリオン(株)製のイオンメーター９２０ＡとＣａ^２＋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Ｃａ^２＋濃度を、Ｃａ^２＋イオン電極を用いて測定する。キレート剤はＣａ^２＋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。
【００６０】
【数１】

【００６１】
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（３）、（４）記載の化合物等を含有することができる。
【００６２】
【化７】

【００６３】
〔式中、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１３、Ｒ^１４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、Ｒ^１２は炭素数２〜１０のアルキレン基であり、Ｘ⁻は陰イオンを示す。〕
＜漂白洗浄剤組成物＞
本発明の組成物は、洗浄性能、損傷性の点で、ＪＩＳ Ｋ3362：1998記載の２０℃で測定する０．１質量％のｐＨが８〜１２であることが好ましく、９〜１１．５であることがより好ましく、９．５〜１１であることが更に好ましく、１０〜１１であることが特に好ましい。ｐＨは、ｐＨ調整剤により調整することが好ましく、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸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等を用いることができる。
【００６４】
本発明の組成物は、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が1600ｇ/L以下であることが好ましく、1300ｇ/L以下であることがより好ましく、1000ｇ/L以下であることが更に好ましい。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以上であることがより好ましく、700ｇ/L以上であることが更に好ましい。
【００６５】
本発明の組成物は、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平均粒径が、１５０〜１０００μｍであることが好ましく、より好ましくは１５０〜８００μｍ、更に好ましくは１８０〜６００μｍである。
【００６６】
本発明の組成物は、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又は水不溶性の容器に収納することができる。
【００６７】
本発明の組成物は、流動性及び非ケーキング性の点で、粒子形態にした上で、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。
【００６８】
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。これらの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。
【００６９】
【実施例】
実施例１
固形分48質量％のスラリーを、熱風温度250℃で噴霧乾燥し、粉末洗浄剤組成物ベースで、ポリアクリル酸ナトリウム（平均分子量10000）4質量％、炭酸ナトリウム16質量％、硫酸ナトリウム15質量％、蛍光染料0.1質量％、ゼオライト16質量％、水0.5質量％のベース顆粒を得た。
【００７０】
次に、レディゲミキサー（松阪技研（株）製、容量20L、ジャケット付き）にベース顆粒を投入し、主軸（150rpm）の攪拌下、非イオン界面活性剤9質量％、直鎖アルキル（炭素数10〜13）ベンゼンスルホン酸ナトリウム10質量％、石鹸2質量％、ＰＥＧ４．５質量％、水2質量％の混合液を、３分間で投入し、その後５分間攪拌を行った。
【００７１】
更に、このミキサーに結晶性シリケート8質量％、ゼオライト10質量％を投入し、表面被覆を行った。2000μｍの篩を通過させた後、リボンミキサーに移し、過炭酸ナトリウム、過酸前駆体、酵素、香料を加え、混合して、粉末の漂白洗浄剤組成物を得た。
【００７２】
実施例２〜８、比較例１〜５
実施例１と同様の方法にて、表１に示す粉末の漂白洗浄剤組成物を得た。
【００７３】
＜ペルオキソ酸生成率の測定＞
表1に示す粉末の各組成物を０．０６７質量％、２０℃、１リットルとなるように添加し、５分攪拌した後、０．１質量％カタラーゼ溶液１０ｍｌを加え、１分間攪拌する。この溶液に１０質量％ヨウ化カリウム溶液１０ｍｌと２０質量％硫酸溶液２０ｍｌを添加し、０．０１Ｎチオ硫酸ナトリウム溶液で滴定を行い、下式によってペルオキソ酸生成率を算出した。
【００７４】
【数２】

【００７５】
ここで算出されたペルオキソ酸生成率が高い程、高い漂白性能を得るのに好ましい。
【００７６】
＜漂白効果＞
表1に示す粉末の各組成物を０．０６７質量％、２０℃、１リットルとなるように添加し、下記の通り調製したカレー汚染布（親油性汚れ）５枚を投入し、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。
【００７７】
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
＜カレー汚染布の調製＞
ハウス食品製レトルトカレー（カレーマルシェ）の固形分をメッシュで除去した後、得られた液を煮沸するまで加熱した。この液に木綿金布＃２００３を浸し、約１５分間煮沸した。そのまま火よりおろし、約２時間程度放置後、布を取りだし、余分に付着しているカレー液をへらで除去し自然乾燥させた。その後プレスし、１０ｃｍ×１０ｃｍの試験片として実験に供した。
【００７８】
【表１】

【００７９】
・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）
・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。）
・ＡＥ：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
・ＰＥＧ：ポリエチレングリコール（平均分子量８５００）
・ＰＰＧ：ポリプロピレングリコール（平均分子量３０００）
・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）を３：１の重量比で混合
・結晶性シリケート：粉末ＳＫＳ−６（ヘキストトクヤマ（株）製）
・ポリアクリル酸Ｎａ：ポリアクリル酸ナトリウム（平均分子量１００００）
・蛍光剤：チノパールＣＢＳ−Ｘ（チバガイギー社製）
【００８０】
【発明の効果】
本発明の組成物は、（ａ）〜（ｃ）成分の併用系に、（ｄ）成分のポリアルキレングリコールを配合することにより、過酸の生成量が増加して、ジアシル体の生成が抑制されるため、漂白洗浄力が増強されている。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a bleaching detergent composition particularly suitable for textile products, and to a means for improving a water-based cleaning method.
[0002]
[Prior art]
Detergent compositions are strongly directed to higher densities and lower usage in consideration of consumer convenience and environmental considerations. In addition, consumer demand for “easy washing” and “washing clothes carefully” and responding to the environment, energy, and economy have led to the trend toward water saving, low-temperature washing, and shortening of washing time. is there.
[0003]
With changes in the living environment, the stains that adhere to clothing and the like in daily life are also diversifying, and washing with ordinary detergents alone will prevent blood stains, food stains, so-called stain stains such as plant stains, and lipophilic stains. Detergency is not enough. Further, in particular, collar 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 for stains and the like, it is common to add bleaching components to detergents. Bleaching components are roughly classified into oxygen-based and chlorine-based. Examples of the chlorine type include hypochlorous acid and dichlorocyanuric acid. These have problems in stability, smell, and the like, are not suitable for blending detergents, and have to be nervous when used for colored or patterned clothing because of their strong bleaching power. Oxygen bleaches have a slight decrease in bleaching power at room temperature compared to chlorine bleaches, but do not lose color when applied to colored or patterned clothing, do not damage the fabric, and yellow. It is widely used as a cleaning agent because of its lack. Further, in order to improve the bleaching performance, an organic peracid precursor or the like is used in combination.
[0005]
Nonionic surfactants used as detergent bases have good hard water resistance, outstanding washing power for oily stains such as sebum stains, and very good biodegradability. Therefore, the technical development of detergents containing nonionic surfactants has been actively conducted.
[0006]
However, in a bleaching system in which a detergent containing a nonionic surfactant and an organic peracid precursor are used in combination, the amount of peracid generated decreases because the organic peracid precursor forms a diacyl compound, and the bleaching power decreases. There is a problem. For this reason, studies have been made to improve the bleaching detergency of a detergent containing a nonionic surfactant and an organic peracid precursor. For example, improvement of the bleaching power by containing a sequestering agent (for example, Patent Document 1, 2, 3) are known, but they do not solve the phenomenon that the bleaching power decreases due to the decrease in the amount of peracid generated from the organic precursor.
[0007]
[Patent Document 1]
JP-A-9-3497 [Patent Document 2]
JP-A-10-316996 [Patent Document 3]
JP-A-11-35978
[Problems to be solved by the invention]
An object of the present invention is to provide a bleaching detergent composition exhibiting excellent cleaning performance against yellowish stains such as sebum stains and underwear, and to provide means for improving an aqueous washing method.
[0009]
[Means for Solving the Problems]
The present inventors have proposed a diacyl produced from a peracid precursor in the presence of a polyalkylene glycol in a system in which a peracid precursor that reacts with hydrogen peroxide to generate an organic peracid and a nonionic surfactant are used in combination. The present inventors have found that the bleaching detergency can be enhanced by suppressing the amount of body produced and, as a result, increasing the amount of peracid generated, thereby completing the present invention.
[0010]
That is, the present invention provides, as a means for solving the problem, the following general formula (I) in which (a) a peroxide that generates hydrogen peroxide in an aqueous solution, and (b) an organic peroxide is formed by reacting with hydrogen peroxide. It is intended to provide a bleaching detergent composition containing a peracid precursor represented by the formula (c), a nonionic surfactant, and (d) a polyalkylene glycol as a diacyl compound formation inhibitor.
[0011]
Embedded image

[0012]
[Wherein, R ₁ is a linear or branched alkyl group having 4 to 18 carbon atoms, an aryl group, an alkenyl group having 4 to 18 carbon atoms, an acyl group having 4 to 18 carbon atoms, or a compound represented by the following general formula (II) ) Represents a group represented by
[0013]
Embedded image

[0014]
(Where
R ₂ represents a hydrogen atom, a linear or branched alkyl group, alkenyl group or acyl group having 1 to 18 carbon atoms;
R ₃ represents a linear or branched alkylene group having 1 to 8 carbon atoms;
p represents 0 or 1;
R ₄ 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;
A represents a linear or branched alkylene group having 1 to 4 carbon atoms;
q is an average number of added moles of alkylene oxide, and represents a number of 0 to 100, and q A's may be the same or different)
L represents a group represented by the following formula (III), (IV), (V) or (VI).
[0015]
Embedded image

[0016]
(Wherein, M represents a hydrogen atom or a cation forming a water-soluble salt, and R ₅ and R ₆ represent a linear or branched alkylene group having 1 to 8 carbon atoms)]
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
<(A) component>
The composition of the present invention contains, as the component (a), one or more compounds selected from compounds that release hydrogen peroxide in an aqueous solution.
[0018]
The component (a) includes carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct, tripolyphosphate / hydrogen peroxide adduct, pyrophosphate / hydrogen peroxide adduct, urea / hydrogen peroxide And adducts. Among these, carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct are preferable, and sodium carbonate / hydrogen peroxide adduct and sodium borate / hydrogen peroxide adduct are more preferable.
[0019]
The component (a) is preferably coated with an inorganic compound, an organic compound, or the like from the viewpoint of storage stability. Examples of the inorganic compound include sodium carbonate, sodium sulfate, magnesium sulfate, magnesium silicate, magnesium chloride, magnesium oxide, and sodium silicate. Examples of the organic compound include polyethylene glycol, polyvinylpyrrolidone, and hydroxypropyl cellulose.
[0020]
When used as particles containing the component (a), the amount of the inorganic compound or organic compound used for coating is preferably 5 to 20% by mass in the particles in terms of stability and solubility. In addition, conventionally known stabilizers, dissolution promoters, chelating agents and the like may be contained in the particles. Among these stabilizers and the like, chlorides, urea, anionic surfactants and nonionic surfactants are preferable from the viewpoint of solubility, and their contents are respectively 0.1 to 5 in the particles. % By mass is preferred.
[0021]
When a component coated with an inorganic or organic compound or the like is used as the component (a), it can be produced, for example, by applying the method described in Examples of JP-A-59-196399.
[0022]
The content of the component (a) in the composition of the present invention is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, further preferably from 1 to 8% by mass in terms of cleaning performance. It is particularly preferably 2 to 7% by mass.
[0023]
<(B) component>
The composition of the present invention contains, as a component (b), a peracid precursor represented by the general formula (I) which reacts with hydrogen peroxide to generate an organic peracid.
[0024]
R ₁ in the general formula (I) is a linear or branched alkyl group or alkenyl having 4 to 18, preferably 7 to 18 carbon atoms, more preferably 10 to 13 carbon atoms in terms of washing performance. Group (more preferably an alkyl group).
[0025]
L in the general formula (I) is preferably a group represented by the general formula (III) or (IV) (particularly, a group represented by (III)). M includes an alkali metal ion, an alkaline earth metal ion, an ammonium salt, an alkanolamine salt, and the like. Among them, a sodium ion and a potassium ion are preferable, and a sodium ion is particularly preferable.
[0026]
In the composition of the present invention, the component (b) is preferably in the form of particles containing the component (b) in order to enhance stability. The amount of the component (b) in the particles containing the component (b) is preferably 1 to 80% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass.
[0027]
In order to improve the solubility of the component (b) in a washing bath, the particles containing the component (b) include at least one selected from polyoxyalkylene alkyl ethers, alkyl sulfates and polyoxyalkylene alkyl ether sulfates. Of the surfactant can be blended preferably in an amount of 50% by mass or less, more preferably 1 to 45% by mass, and still more preferably 2 to 40% by mass.
[0028]
As the polyoxyalkylene alkyl ether, those in which ethylene oxide and propylene oxide are added in a block shape are preferable, the average number of moles of ethylene oxide added is preferably 3 to 20, particularly 4 to 15, and the average number of moles of propylene oxide added is 1 to 10, Particularly, 2 to 7 are preferable. The alkyl group preferably has 10 to 18 carbon atoms, particularly preferably 12 to 16 carbon atoms.
[0029]
As the alkyl sulfate, a sodium salt having 10 to 18 carbon atoms is preferable, and sodium lauryl sulfate or sodium myristyl sulfate is particularly preferable.
[0030]
As the polyoxyalkylene alkyl ether sulfate, a polyoxyethylene alkyl ether sulfate having 10 to 18 carbon atoms in the alkyl group is preferable, and a sodium salt is preferable. Here, the average degree of polymerization of polyoxyethylene groups (hereinafter referred to as EOp) is preferably from 1 to 10, particularly preferably from 1 to 5, particularly preferably polyoxyethylene (EOp = 2 to 5) sodium lauryl ether sulfate, polyoxyethylene (EOp = 2 to 5). 5) Sodium myristyl ether sulfate is preferred.
[0031]
The particles containing the component (b) may be blended with a binder selected from polyoxyethylene and a fatty acid as a component for facilitating formulation.
[0032]
As polyoxyethylene, those having an average molecular weight of 2,000 to 20,000, more preferably 4,000 to 10,000, and particularly preferably 4,000 to 8,000, are preferable. Fatty acids are preferably those having 8 to 20, more preferably 10 to 18, and especially 12 to 18 carbon atoms, and these may be in the form of sodium or potassium soap. The binder is used in the particles containing the component (b) in an amount of preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 5 to 20% by mass.
[0033]
If desired, the composition of the present invention may further contain an acidic substance for the purpose of improving the stability of the particles containing the component (b).
[0034]
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 20% by mass or less, more preferably 1 to 15% by mass, and still more preferably 1 to 10% by mass in the particles containing the component (b).
[0035]
The particles containing the component (b) can be obtained by mixing the above components by a desired method and then granulating the mixture with a usual granulator. Particularly, the component (b) and the surface activity for improving the solubility can be obtained. A method in which part or all of the agent is mixed first, and then a binder or the like is added is preferable. It is preferable that the binder is added after being melted in advance at 40 to 100 ° C, more preferably 50 to 100 ° C, particularly 50 to 90 ° C.
[0036]
The granulation method is preferably an extrusion granulation method, and is preferably a granulated product having an average particle diameter of 500 μm to 5000 μm, particularly 500 to 3000 μm. In addition, tableting by a briquetting machine can be applied as a preferable granulation method.
[0037]
The content of the component (b) in the composition of the present invention is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, and 0.3 to 2% by mass in terms of cleaning performance. % Is more preferable, and 0.5 to 1.5% by mass is particularly preferable.
[0038]
<(C) component>
The composition of the present invention contains a nonionic surfactant as the component (c). As the nonionic surfactant of the component (c), polyoxyalkylene alkyl (C 8-20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (C 8-20) phenyl ether, polyoxyalkylene sorbitan fatty acid ( C8 to C22 esters, polyoxyalkylene glycol fatty acid (C22 to C22) esters, and polyoxyethylene polyoxypropylene block polymers. In particular, from the viewpoint of cleaning performance, the component (c) is preferably a polyoxyalkylene alkyl ether in which an alkylene oxide such as ethylene oxide or propylene oxide is added in an amount of 4 to 20 mol on average to an alcohol having 10 to 18 carbon atoms. The component (c) preferably has an HLB value (calculated by the Griffin method) of from 10.5 to 15.0, more preferably from 11.0 to 14.5, from the viewpoint of cleaning performance.
[0039]
In the composition of the present invention, the content of the component (c) in the equivalent of the surfactant described in JIS K3362: 1998 is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. In addition, it is preferable to use an anionic surfactant together with a nonionic surfactant in terms of cleaning performance against various kinds of dirt, and the mass ratio of the nonionic surfactant to the anionic surfactant is 1/9 to 9/9. / 1 is more preferable, 3/7 to 9/1 is further preferable, and 5/5 to 9/1 is particularly preferable.
[0040]
The component (c) in the composition of the present invention is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, still more preferably 5 to 20% by mass, and 8 to 18% by mass in terms of cleaning performance. Is particularly preferred.
[0041]
<(D) component>
The composition of the present invention contains a polyalkylene glycol as the component (d). The component (d) functions to suppress the generation of a diacyl compound from the component (b) and increase the amount of peracid generated, thereby enhancing the bleaching detergency.
[0042]
This enhancing effect is achieved by the presence of the component (d) in aqueous washing using a bleaching detergent containing the components (a), (b) and (c), whereby the micelles of the nonionic surfactant ( It is considered that the inhibition of peracid production due to the incorporation of the peracid precursor of component b) is suppressed.
[0043]
Examples of the component (d) include polyethylene glycol, polypropylene glycol, and the like, and polyethylene glycol is preferred in terms of suppressing the formation of a diacyl compound.
[0044]
The component (d) has a weight average molecular weight of preferably from 500 to 15,000, more preferably from 1,000 to 10,000, and still more preferably from 2,000 to 9,000, from the viewpoint of suppressing the formation of a diacyl compound.
[0045]
The component (d) in the composition of the present invention is preferably from 4.5 to 30% by mass, more preferably from 5 to 25% by mass, and still more preferably from 7 to 20% by mass, from the viewpoint of suppressing the formation of a diacyl compound. , 10 to 20% by mass is particularly preferred.
[0046]
<Other components>
Examples of the surfactant other than the component (c) include an anionic surfactant, an amphoteric surfactant, and a cationic surfactant.
[0047]
Examples of anionic surfactants include higher alcohol sulfates, higher alcohol ethoxylated sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts and esters thereof. Salts or fatty acid salts. In particular, a linear alkylbenzene sulfonate having an alkyl chain having 10 to 18 (preferably 12 to 14) carbon atoms and an α-sulfofatty acid alkyl ester salt having 10 to 20 carbon atoms are preferable. Examples of the counter ion include alkali metals, alkaline earth metals, ammonium, and alkanolamines. From the viewpoint of adjusting the dissolution rate, it is also preferable to use potassium ions in combination. The potassium ion in all the counter ions is preferably 5% by mass or more, more preferably 20% by mass or more, and particularly preferably 40% by mass or more.
[0048]
Examples of the cationic surfactant include an alkyltrimethylammonium salt and the like, and examples of the amphoteric surfactant include a carbobetaine-type and a sulfobetaine-type amphoteric surfactant.
[0049]
Among the above-mentioned surfactants, in terms of cleaning performance and solubility, the amount corresponding to the surfactant described in JIS K3362: 1998 is preferably 10 to 60% by mass, more preferably 15 to 45% by mass, and 18 to 40% by mass. % Is more preferable, and 20 to 35% by mass is particularly preferable.
[0050]
The composition of the present invention comprises a builder, another bleaching activator, a re-staining inhibitor (such as carboxymethylcellulose), a softener (such as a dialkyl-type quaternary ammonium salt, or a clay mineral), and a reducing agent (such as a sulfite). And additives such as a fluorescent whitening agent (biphenyl type, aminostilbene type, etc.), a foam control agent (silicone, etc.), a fragrance, and an enzyme (protease, pectinase, amylase, lipase, etc.).
[0051]
In the present invention, the builder itself has no detergency itself, or is not so remarkable, but when added to the composition, remarkably improves the detergency, and a polyvalent metal cation-trapping action, At least one of the three functions of the soil dispersing action and the alkaline buffering action is performed. Examples of the builder include a water-soluble inorganic compound, a water-insoluble inorganic compound, and an organic compound.
[0052]
Examples of the water-soluble inorganic compound include phosphates (tripolyphosphate, pyrophosphate, metaphosphate, trisodium phosphate, etc.), silicates, carbonates, sulfates and the like. Of these, phosphates are preferred in that they perform all three functions.
[0053]
Examples of the water-insoluble inorganic compound include aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, amorphous aluminosilicate and the like), crystalline silicate and the like. Among these, A-type zeolite having a particle diameter of 3 μm or less (more preferably 1 μm or less) is preferable.
[0054]
Examples of the organic compound include carboxylate (aminocarboxylate, hydroxyaminocarboxylate, hydroxycarboxylate, cyclocarboxylate, maleic acid derivative, oxalate, etc.) and organic carboxylic acid (salt) polymer (acrylic acid) Polymers and copolymers, polyvalent carboxylic acid polymers and copolymers, glyoxylic acid polymers, polysaccharides and salts thereof). Among these, an organic carboxylic acid (salt) polymer is preferable.
[0055]
In the builder salt, the counter ion is preferably an alkali metal salt or an amine, particularly preferably sodium and / or potassium, monoethanolamine or diethanolamine.
[0056]
In the composition of the present invention, the builders can be used alone or in combination of two or more. In particular, the builder preferably contains the water-soluble inorganic compound, more preferably uses a water-soluble inorganic compound and an organic compound in combination, and uses a water-soluble inorganic compound, an organic compound and a water-insoluble inorganic compound in combination. More preferred.
[0057]
In the composition of the present invention, the total content of the builder in the composition is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass, and still more preferably from 35 to 60% by mass, from the viewpoint of cleaning performance. Further, the content of the water-soluble inorganic compound builder in the composition is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass. The content of the water-insoluble inorganic compound builder in the composition is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 40% by mass. The organic compound builder in the composition is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and still more preferably 0.5 to 10% by mass.
[0058]
The composition of the present invention preferably contains a builder having a polyvalent metal cation-trapping action, particularly from the viewpoint of cleaning performance. As a builder having a polyvalent metal cation-trapping action, 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). The content of the builder capable of capturing polyvalent metal cations in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass. In the present invention, the calcium stability constant is determined by the following method.
[0059]
(Method of measuring calcium stability constant)
A 0.1 mol / liter NH ₄ Cl—NH ₄ OH (pH 10) solution is prepared as a buffer. All sample solutions are prepared using this buffer. For the measurement of the Ca ²⁺ concentration, an ion meter 920A manufactured by Orion Co., Ltd. and a Ca ²⁺ ion electrode are used. First, the relationship between the calcium chloride concentration and the potential of the electrode is determined, and a calibration curve is created. 5.36 × ¹⁰ -2 mol / l solution of calcium chloride, a 5.36 × ¹⁰ -4 mol / l solution of a chelating agent sample are prepared. 1 ml of calcium chloride solution is added to 100 ml of the chelating agent sample solution, and the mixture is stirred for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. The calcium stability constant (Ca stability constant) is determined from the following equation, assuming that the chelating agent forms a chelate complex with Ca ²⁺ at 1: 1.
[0060]
(Equation 1)

[0061]
Other bleach activators include glucose pentaacetate, triacetin, N, N, N ', N'-tetraacetylethylenediamine, tetraacetylglycolyluril, and compounds described in the following general formulas (3) and (4). Can be contained.
[0062]
Embedded image

[0063]
[Wherein, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹³ , and R ¹⁴ are each independently an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group, and R ¹² is 2 to 10 alkylene groups, and X ⁻ represents an anion. ]
<Bleaching detergent composition>
The composition of the present invention preferably has a pH of 0.1 to 12% by mass, as measured at 20 ° C. described in JIS K3362: 1998, of 8 to 12, and 9 to 11.5 in terms of cleaning performance and damageability. More preferably, it is more preferably from 9.5 to 11, and particularly preferably from 10 to 11. The pH is preferably adjusted with a pH adjuster, such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal silicates such as sodium silicate and potassium silicate. Salts and the like can be used.
[0064]
From the viewpoint of solubility, the composition of the present invention preferably has an apparent density of 1600 g / L or less, more preferably 1300 g / L or less, as measured by the method defined by JIS K 3362: 1998, More preferably, it is 1000 g / L or less. Further, in terms of convenience and reduction of waste (eg, boxes and the like), the apparent density is preferably 300 g / L or more, more preferably 600 g / L or more, and further preferably 700 g / L or more. preferable.
[0065]
In terms of solubility, the composition of the present invention has a mean particle size of 150 to 1000 μm obtained by vibrating for 5 minutes using a standard sieve of JIS Z 8801, and then calculating from the mass fraction according to the sieve size. It is preferably 150 to 800 μm, more preferably 180 to 600 μm.
[0066]
For convenience, the composition of the present invention may be further compressed into a tablet form, or a single use amount may be stored in a water-soluble or water-insoluble container.
[0067]
The composition of the present invention is preferably formed into particles and then subjected to surface modification with a surface coating agent in terms of fluidity and non-caking properties. 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.
[0068]
Examples of the surface coating agent include silicate compounds such as aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate compounds, metal soaps, powdered surfactants, and the like. Water-soluble polymers such as fine powder, carboxymethyl cellulose, 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.
[0069]
【Example】
Example 1
A slurry having a solid content of 48% by mass is spray-dried at a hot air temperature of 250 ° C., and based on a powder detergent composition, 4% by mass of sodium polyacrylate (average molecular weight 10,000), 16% by mass of sodium carbonate, 15% by mass of sodium sulfate Thus, base granules of 0.1% by mass of fluorescent dye, 16% by mass of zeolite and 0.5% by mass of water were obtained.
[0070]
Next, the base granules were charged into a Redige mixer (manufactured by Matsusaka Giken Co., Ltd., capacity 20 L, with jacket), and 9 mass% of a nonionic surfactant, linear alkyl (carbon number) under stirring of the main shaft (150 rpm). 10-13) A mixture of 10% by mass of sodium benzenesulfonate, 2% by mass of soap, 4.5% by mass of PEG, and 2% by mass of water was charged in 3 minutes, and then stirred for 5 minutes.
[0071]
Further, 8% by mass of crystalline silicate and 10% by mass of zeolite were added to the mixer to coat the surface. After passing through a 2000 μm sieve, the mixture was transferred to a ribbon mixer, and sodium percarbonate, a peracid precursor, an enzyme, and a flavor were added and mixed to obtain a powdery bleaching detergent composition.
[0072]
Examples 2 to 8, Comparative Examples 1 to 5
In the same manner as in Example 1, powder bleaching detergent compositions shown in Table 1 were obtained.
[0073]
<Measurement of peroxoic acid production rate>
Each composition of the powder shown in Table 1 was added at 0.067% by mass at 20 ° C. and 1 liter, and the mixture was stirred for 5 minutes. Then, 10 ml of a 0.1% by mass catalase solution was added, and the mixture was stirred for 1 minute. To this solution, 10 ml of a 10% by mass potassium iodide solution and 20 ml of a 20% by mass sulfuric acid solution were added, and titration was performed with a 0.01N sodium thiosulfate solution, and the peroxoic acid production rate was calculated by the following equation.
[0074]
(Equation 2)

[0075]
The higher the peroxoacid production rate calculated here is, the more preferable it is to obtain high bleaching performance.
[0076]
<Bleaching effect>
Each composition of the powder shown in Table 1 was added at 0.067% by mass at 20 ° C. and 1 liter, and 5 pieces of curry-stained cloth (lipophilic stain) prepared as described below were charged. (80 rpm × 10 minutes). Then, it was rinsed with tap water, dried, and the bleaching ratio was calculated by the following equation. The reflectance was measured using Nippon Denshoku Industries Co., Ltd. ND-300A using a 460 nm filter.
[0077]
Bleaching washing rate (%) = [(reflectance after washing−reflectance before washing) / (reflectivity of original cloth−reflectance before washing)] × 100
<Preparation of curry-contaminated cloth>
After the solid content of the house food retort curry (curry Marche) was removed with a mesh, the obtained liquid was heated to boiling. Cotton gold cloth # 2003 was dipped in this solution and boiled for about 15 minutes. The mixture was removed from the heat and left for about 2 hours, and then the cloth was taken out. The excess curry liquid was removed with a spatula and air-dried. Then, it pressed and used for the experiment as a 10 cm x 10 cm test piece.
[0078]
[Table 1]

[0079]
-Na percarbonate: sodium carbonate hydrogen peroxide adduct, sodium percarbonate; bleach particles described in paragraph 0019 of JP-A-2000-256699)
LOBS: sodium lauroyloxybenzenesulfonate granules (bleach particles described in paragraph 0018 of JP-A-2000-256699)
DOBA: sodium decanoyloxybenzoate (manufactured in the same manner as LOBS)
AE: polyoxyethylene alkyl ether having an alkyl group having 12 to 14 carbon atoms and an EO average addition mole number of 7 PEG: polyethylene glycol (average molecular weight 8500)
・ PPG: polypropylene glycol (average molecular weight 3000)
Enzyme: Cellulase K (described in JP-A-63-264699) and cannase 24TK (manufactured by Novo) are mixed at a weight ratio of 3: 1. Crystalline silicate: powder SKS-6 (manufactured by Hoechst Tokuyama Co., Ltd.)
-Sodium polyacrylate: sodium polyacrylate (average molecular weight 10,000)
・ Fluorescent agent: Tinopearl CBS-X (manufactured by Ciba Geigy)
[0080]
【The invention's effect】
The composition of the present invention, by adding the polyalkylene glycol of the component (d) to the combined system of the components (a) to (c), increases the production amount of peracid and suppresses the production of the diacyl compound. Therefore, the bleaching detergency is enhanced.

Claims (3)

(A) a peroxide that generates hydrogen peroxide in an aqueous solution, (b) a peracid precursor represented by the following general formula (I) that reacts with hydrogen peroxide to generate an organic peracid, (c) A bleaching detergent composition containing a nonionic surfactant and (d) a polyalkylene glycol as a diacyl compound formation inhibitor.

[Wherein, R ₁ is a linear or branched alkyl group having 4 to 18 carbon atoms, an aryl group, an alkenyl group having 4 to 18 carbon atoms, an acyl group having 4 to 18 carbon atoms, or a compound represented by the following general formula (II) ) Represents a group represented by

(Where
R ₂ represents a hydrogen atom, a linear or branched alkyl group, alkenyl group or acyl group having 1 to 18 carbon atoms;
R ₃ represents a linear or branched alkylene group having 1 to 8 carbon atoms;
p represents 0 or 1;
R ₄ 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;
A represents a linear or branched alkylene group having 1 to 4 carbon atoms;
q is an average number of added moles of alkylene oxide, and represents a number of 0 to 100, and q A's may be the same or different)
L represents a group represented by the following formula (III), (IV), (V) or (VI).

(Wherein, M represents a hydrogen atom or a cation forming a water-soluble salt, and R ₅ and R ₆ represent a linear or branched alkylene group having 1 to 8 carbon atoms)] (A) a peroxide that generates hydrogen peroxide in an aqueous solution; (b) a peracid precursor represented by the general formula (I) that reacts with hydrogen peroxide to generate an organic peracid; Contains an ionic surfactant (10% by mass or more of the surfactant equivalent to 100% by mass based on the measurement method described in JIS K3362: 1998), and (d) 4.5 to 30% by mass of a polyalkylene glycol. The bleaching detergent composition according to claim 1, wherein A method of using a component (d) as a diacyl compound formation inhibitor in aqueous washing using a bleaching detergent containing the components (a), (b) and (c) according to claim 1 or 2.