JP4799798B2 - Bleaching detergent composition and method for producing the same - Google Patents

Description

（式中、Ｒ¹ は炭素数７〜１３のアルキル基またアルケニル基であり、Ｒ² は炭素数７〜１３のアルキル基またはアルケニル基、Ｍは塩形成カチオン又は水素である。）
【００３５】
本発明で用いる漂白活性化剤は、上記一般式（Ｉ）又は（II）で表され、式中、アルキル基及びアルケニル基としては、直鎖及び分枝状のいずれもが使用できるが、直鎖状のものが好ましい。Ｒ¹としては炭素数９〜１３のアルキル基が好ましく、炭素数９〜１１のアルキル基がさらに好ましい。Ｒ²としては炭素数７〜１１のアルキル基が好ましく、炭素数７〜９のアルキル基がさらに好ましい。又、Ｍとしては、水素、又はナトリウム、カリウムなどのアルカリ金属、アンモニウム、アルカノールアミンなどのアミン類といった漂白活性化剤に水溶性を与えるものが好ましい。このうちアルカリ金属が好ましい。式中、ＳＯ₃Ｍ基やＣＯＯＭ基は、オルト、メタ又はパラ位をとることができるが、パラ位が好ましい。
【００３６】
本発明における漂白活性化剤としては、下記式（III）または（IV）で表されるものも好ましいものとして挙げられる。
【化２】

（式中、Ｒ¹はエステル基、アミド基又はエーテル基で分断されていても良い炭素数１〜６、好ましくは１〜４、特に好ましくは１〜３のアルキル基であり、Ｒ⁶はエステル基、アミド基又はエーテル基で分断されていても良く、ヒドロキシ基で置換されていても良い炭素数１〜８、好ましくは２〜６のアルキレン基である。Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁷、Ｒ⁸はそれぞれ独立に炭素数１〜３のアルキル基又はヒドロキシアルキル基、好ましくはメチル基、エチル基又はヒドロキシエチル基である。Ｘ-は陰イオンであり、好ましくはハロゲンイオン、硫酸イオン、脂肪酸イオン又は炭素数１〜３のアルキル硫酸イオンである。）
【００３７】
本発明の漂白活性化剤は造粒物として配合される。造粒物中の漂白活性化剤の含有量は、好ましくは１〜９５質量％、より好ましくは１０〜９０質量％、特に好ましくは３０〜８５質量％である。これらはポリエチレングリコール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される。ポリエチレングリコールとしては好ましくは質量平均分子量２０００〜２００００、より好ましくは４０００〜１００００、特に好ましくは４０００〜８０００のものが良好である。また、脂肪酸としては好ましくは炭素数８〜２０、より好ましくは１０〜１８、特に好ましくは１２〜１８であり、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。このようなバインダー物質は造粒物中に０．５〜３０質量％、好ましくは１〜２５質量％、より好ましくは５〜２０質量％使用する。
【００３８】
また、該造粒物には漂白活性化剤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、オレフィンスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫酸エステル塩またはポリオキシエチレンアルキルエーテル硫酸エステル塩あるいはこれらの混合物を好ましくは０〜５０質量％、より好ましくは３〜４０質量％、特に好ましくは５〜３０質量％配合することが好ましい。
ポリオキシアルキレンアルキルエーテルとしては、アルキル基の炭素数は１０〜１５が好ましく、好ましくはエチレンオキシド（以下ＥＯと略す）及び／又はプロピレンオキシド（以下ＰＯと略す）の付加体である。平均付加モル数はＥＯ、ＰＯ、あるいはＥＯとＰＯの混合の何れの場合も、合計で好ましくは４〜３０、より好ましくは５〜１５であり、ＥＯ／ＰＯのモル比は、好ましくは５／０〜１／５、より好ましくは５／０〜１／２である。
【００３９】
オレフィンスルホン酸塩としてはアルキル基の炭素数が１４〜１８であるα−オレフィンスルホン酸のナトリウム又はカリウム塩が好ましい。
アルキルベンゼンスルホン酸塩としてはアルキル基の炭素数が１０〜１４である直鎖アルキルベンゼンスルホン酸のナトリウム又はカリウム塩が好ましい。
また、アルキル硫酸エステル塩としては、アルキル基の炭素数が１０〜１８であり、しかもナトリウム塩などのアルカリ金属塩が好ましく、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好ましい。
また、ポリオキシエチレンアルキルエーテル硫酸エステル塩としては、炭素数１０〜１８のアルキル基を有するポリオキシエチレンアルキルエーテル硫酸エステル塩が好ましく、またナトリウム塩が良好である。
ここでオキシエチレン基の平均重合度（以下、平均重合度をＰＯＥで示す）は１〜１０、好ましくは１〜５が良好であり、特にポリオキシエチレンラウリルエーテル硫酸エステルナトリウム（ＰＯＥ＝２〜５）、ポリオキシエチレンミリスチルエーテル硫酸エステルナトリウム（ＰＯＥ＝２〜５）が良好である。
【００４０】
漂白活性化剤造粒物は上記組成物を任意の方法で混合し造粒することによって得られる。また、バインダー物質は予め融解して添加することで好ましい結果を得ることができる。バインダー物質は４０〜１００℃、好ましくは５０〜１００℃、より好ましくは５０〜９０℃で融解させて添加する。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、好ましくは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。
【００４１】
また、本発明では漂白活性化剤の安定性を向上させる目的で所望により造粒物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、フマル酸、クエン酸、グリコール酸、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好ましくは造粒物中０．５〜２０質量％、より好ましくは１〜１５質量％、最も好ましくは１〜１０質量％が好適である。
漂白活性化剤造粒物には、上記以外の成分として、着色剤、香料等の他の成分を添加することもできる。
漂白活性化剤の配合量は、通常、組成物全体に対して０．１〜２０％、より好ましくは０．２〜１０％、更に好ましくは０．５〜５％が好適である。
漂白活性化剤粒子における漂白活性化剤の配合量は安定性等の点から、５０〜８０質量％、好ましくは６０〜７５質量％とされる。
【００４２】
また、本発明の漂白洗浄剤組成物には、洗剤成分として周知の成分を適宜含有させることができる。以下に例を挙げる。
・界面活性剤
上記ノニオン界面活性剤、アニオン界面活性剤の他に両性界面活性剤などを用いることができる。
好ましい両性界面活性剤としては、例えば、イミダゾリン系や、アミドベタイン系などの両性界面活性剤を挙げることができる。特に好ましい両性界面活性剤としては、例えば、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタインや、ラウリン酸アミドプロピルベタインなどが挙げられる。
【００４３】
・洗剤ビルダー
洗剤ビルダーとしては、通常洗剤に使用されるアルカリビルダーやキレートビルダーが好ましく使用される。
アルカリビルダーとしては、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、炭酸ナトリウムカリウムなどのアルカリ金属炭酸塩や、ケイ酸ナトリウム、ケイ酸カリウム、層状ケイ酸ナトリウムなどのアルカリ金属ケイ酸塩などが挙げられる。
キレートビルダーとしては、アルミノ珪酸塩、トリポリリン酸塩、ピロリン酸塩、クエン酸塩、コハク酸塩、ポリアクリル酸塩、アクリル酸−マレイン酸共重合体、イミノカルボン酸／塩、ＥＤＴＡなどが挙げられる。
洗剤ビルダーは、漂白洗浄剤組成物中に、通常１０〜９０質量％、好ましくは、２０〜８０質量％、特に好ましくは、３０〜７０質量％配合される。
【００４４】
・吸油性担体
吸油性担体は、主にノニオン界面活性剤などの液体成分を吸収、担持させるために用いられる。
好ましい吸油性担体としては、例えば珪酸塩化合物として、無定形含水非晶質珪酸、球状多孔質含水非晶質珪酸、無定形無水非晶質珪酸、花弁状含水非晶質珪酸カルシウム、針状含水非晶質珪酸カルシウム、非晶質アルミノ珪酸塩、珪酸マグネシウムなどが挙げられる。
また、炭酸塩化合物として、炭酸マグネシウム、炭酸カルシウム、超微粒子スピネルなどが挙げられる。
吸油性担体は、漂白洗浄剤組成物中に配合する場合には、０．１〜２５質量％、好ましくは、０．５〜２０質量％、さらに好ましくは１〜１５質量％配合される。
【００４５】
・粘土鉱物
粘土鉱物としては、特に、スメクタイト群に属し、その結晶構造がジオクタヘドラル型３層構造またはトリオクタヘドラル型３層構造をとるものが好ましい。
また、吸油量が８０ｍｌ／１００ｇ未満、好ましくは３０〜７０ｍｌ／１００ｇであり、嵩密度が０．１ｇ／ｍｌ以上、好ましくは０．２〜１．５ｇ／ｍｌであると望ましい。
具体例には、例えば、ジオクタヘドラル型３層構造をとる粘土鉱物として、モンモリロナイト、ノントロナイト、バイデライト、パイロフィライトなどが挙げられる。
また、トリオクタヘドラル型３層構造をとる粘土鉱物として、サポナイト、ヘクトライト、スチーブンサイト、タルクなどが挙げられる。
粘土鉱物は、漂白洗浄剤組成物中に配合する場合には、通常０．１〜３０質量％、好ましくは０．５〜２０質量％、さらに好ましくは１〜１０質量％配合される。
【００４６】
・蛍光増白剤
蛍光増白剤としては、ビス（トリアゾニルアミノ）スチルベンジスルホン酸誘導体、ビス（スルホスチリル）ビフェニル塩〔チノパールＣＢＳ−Ｘ〕などを挙げることができる。
・酵素
酵素としては、リパーゼ、プロテアーゼ、セルラーゼ、アミラーゼなどを挙げることができる。
・帯電防止剤
帯電防止剤としては、ジアルキル型４級アンモニウム塩などのカチオン界面活性剤などを挙げることができる。
・表面改質剤
表面改質剤としては、微粉炭酸カルシウム、微粉ゼオライト、ポリエチレングリコールなどを挙げることができる。
・再汚染防止剤
再汚染防止剤としては、カルボキシメチルセルロースなどのセルロース誘導体などを挙げることができる。
・粒子強度保持剤
粒子強度保持剤としては、硫酸ナトリウム、硫酸カリウム、塩酸ナトリウムなどを挙げることができる。
・還元剤
還元剤としては、亜硫酸ナトリウム、亜硫酸カリウムなどを挙げることができる。
・消泡剤
・各種香料類
・各種色素類
・各種柔軟性付与剤
【００４７】
これらの洗剤成分は、固体洗浄剤、漂白剤粒子、および／または漂白活性化剤粒子に含有させて用いることもできるし、粉体混合してもよく、噴霧などの方法によって配合することもできる。なお、酵素および柔軟性付与剤は、通常、粒子形態として使用される。
また、漂白洗浄剤組成物中の界面活性剤（全界面活性剤の合計）と上記炭酸塩化合物（上記金属炭酸塩を含む）との質量比（界面活性剤／炭酸塩化合物）が、１／８〜３／１の範囲内であることが好ましく、より好ましくは１／３〜２／１、さらに好ましくは１／２〜２／１である。界面活性剤／炭酸塩化合物の値が、上記範囲より小さいと低温溶解性の点で好ましくなく、上記範囲を超えると界面活性剤が過剰となり経済上好ましくない。
【００４８】
また、本発明の固化性の判定方法は、下記式（１）を用いて漂白洗浄剤組成物の固化性を判定する方法である。すなわち、ノニオン界面活性剤とアニオン界面活性剤を含有する固体洗浄剤と、漂白剤粒子を必須成分として含有する漂白洗浄剤組成物において下記式（１）を満足する場合に固化性が良好である、すなわち保存中に固化し難いと判定することができる。
σ／Ｐａｖ＜０．５ …式（１）
式中、Ｐａｖは、固体洗浄剤の割断面を複数の微細エリアに分割したときの、該微細エリア毎の界面活性剤の濃度または相対濃度Ｐの平均値を示し、σはＰの標準偏差を示す。
【００４９】
【実施例】
以下、本発明を実施例を示して詳しく説明する。
まず、実施例で用いた使用原料、評価法は以下の通りである。特に断りがない限り％は質量％である。
【００５０】
＜使用原料＞
使用原料を以下に示す。
・ＬＡＳ−Ｋ：直鎖アルキル(炭素数１０〜１４)ベンゼンスルホン酸カリウム（ライオン（株）製ライポンＬＨ−２００（純分９６％）を４８％水酸化カリウム水溶液で中和したもの）
・ＬＡＳ−Ｎａ：直鎖アルキル(炭素数１０〜１４)ベンゼンスルホン酸ナトリウム（ライオン（株）製ライポンＬＨ−２００（純分９６％）を４８％水酸化ナトリウム水溶液で中和したもの）
・ＡＯＳ−Ｋ：炭素数１４〜１８のアルキル基をもつα−オレフィンスルホン酸カリウム（ライオン（株）製 純分７０％の水性スラリー）
・α−ＳＦ−Ｎａ：炭素数１２〜１８のアルキル基をもつα−スルホ脂肪酸メチルエステルのナトリウム塩（ライオン（株）製、純分７０％、固形分７２〜７３％）
・ＡＳ−Ｎａ：炭素数１０〜１８のアルキル基を持つアルキル硫酸ナトリウム塩（三洋化成工業(株)製 サンデットＬＮＭ）
・石鹸：炭素数１２〜１８のアルキル基をもつ脂肪酸ナトリウム（ライオン（株）製、Ｃ１２：０．９％、Ｃ１８：８０．２％、不飽和脂肪酸 ８０．２％、分子量２８９、純分６７〜６８％、タイター４７．０℃ ）
・ノニオンＡ（Ｃ１３・ＥＯ１２）：ダイアドール１３（三菱化学）の酸化エチレン１２モル付加体（ライオン化学（株）製、純分８４％）
・ノニオンＢ（Ｃ１３・ＥＯ２５）：ダイアドール１３（三菱化学）の酸化エチレン２５モル付加体（ライオン化学（株）製、純分８４％）
・ノニオンＣ（Ｃ１３・ＥＯ１５）：ダイアドール１３（三菱化学）の酸化エチレン１５モル付加体（ライオン化学（株）製、純分９０％）
【００５１】
・ゼオライト：Ａ型ゼオライト （水澤化学（株）製 シルトンＢ）
・高分子ビルダー（ＭＡ／ＡＡ）：アクリル酸／マレイン酸共重合体のナトリウム塩（ＢＡＳＦ社製、ソカランＣＰ７）
・炭酸カリウム：旭硝子（株）製、炭酸カリウム（粉末）
・珪酸ナトリウム：ＪＩＳ １号珪酸ナトリウム（大阪珪酸曹達社製）
・炭酸ナトリウム：重質炭酸ナトリウム、旭硝子（株）製、ソーダ灰
・塩化ナトリウム：千葉塩業社製、並塩
・蛍光増白剤Ａ：チノパールＣＢＳ−Ｘ（チバ・スペシャルティ・ケミカルズ）・蛍光増白剤Ｂ：チノパールＡＭＳ−ＧＸ（チバ・スペシャルティ・ケミカルズ）
・酵素：蛋白分解酵素、ノボザイムズ社製、エバラーゼ８Ｔ
・香料：特開２００２−１４６３９９号公報［表１１］〜［表１８］に示す香料組成物Ａ
・色素：群青（大日精化工業社製、Ｕｌｔｒａｍａｒｉｎｅ Ｂｌｕｅ）
・ＰＣ剤：三菱ガス化学社製、ＳＰＣ−Ｄ
・漂白活性化剤Ａ：漂白活性化剤として４−ドデカノイルオキシベンゼンスルホン酸ナトリウム７０質量部、ＰＥＧ〔ポリエチレングリコール＃６０００Ｍ（ライオン（株）製）〕２０質量部、炭素数１４のα−オレフィンスルホン酸ナトリウム粉末品（リポランＰＪ−４００（ライオン（株）製））５質量部の割合で合計５０００ｇになるようにホソカワミクロン社製エクストルード・オーミックスEM-6型に投入し、混練押し出しすることにより径が０．８ｍｍφのヌードル状の押し出し品を得た。この押し出し品（６０℃）を、ホソカワミクロン社製フィッツミルＤＫＡ−３型に導入し、また助剤としてＡ型ゼオライト粉末５質量部を同様に供給し、粉砕して平均粒径約７００μｍの漂白活性化剤造粒物を得た。
・漂白活性化剤Ｂ：漂白活性化剤として４−ノナノイルオキシベンゼンスルホン酸ナトリウムを用いた他は、漂白活性化剤Ａと同様にして漂白活性化剤造粒物を調製した。
・漂白活性化剤Ｃ：漂白活性化剤として４−デカノイルオキシ安息香酸を用いた他は、漂白活性化剤Ａと同様にして漂白活性化剤造粒物を調製した。
【００５２】
＜界面活性剤の均一混合性の評価＞
固体洗浄剤（下記の例では粒子状）を分割し、その割断面を顕微鏡用のスライドガラスにエポキシ系接着剤を用いて貼りつけて測定用試料とした。
そして、PerkinElmer社AutoIMAGE FT-IRマイクロスコープ（顕微ＦＴ−ＩＲ）を用いて、試料切片表面（割断面）のアルコールエトキシレート（ノニオン界面活性剤）の濃度分布の測定を行った。
測定は２０μｍ×２０μｍの微細エリアに分割し、約３ｍｍ×３ｍｍの測定範囲についてスキャンを２０回繰り返し、積算した結果を１３００〜１０００ｃｍ^−１の波長範囲の赤外スペクトルとした。
微細エリアの数は３００とした。得られた赤外スペクトルの、スルホン酸基由来の１２００ｃｍ^-1付近のピークＡと、ノニオン界面活性剤のエーテル結合に由来する１１２０ｃｍ^-1付近のピークＢとから、ピークの高さの比（吸光度の比）を求め、これを相対濃度Ｐとした。
ピークＡに対するピークＢの高さの比からノニオン界面活性剤の相対濃度を、各微細エリア毎に求めて、Ｐａｖとσの値を算出し、σ／Ｐａｖを求めた。
【００５３】
＜固化性の評価方法＞
密閉された容器内に漂白洗浄剤組成物を入れ、これを温度３５℃、相対湿度８５％の条件下で４０日保管した後に取り出し、温度２０℃、相対湿度６０％で６時間放置後に、容器中の漂白洗浄剤組成物を静かに目開き５ｍｍの篩上に移し、篩を穏やかに左右に１０回揺動した後、篩上の残分と篩の通過分の質量とを求め、下記の数式から固化率を算出した。
【００５４】
【数１】

【００５５】
固化率の値から、固化性を下記の４段階で評価した。
◎：０〜５％
○：５〜２０％
△：２０〜５０％
×：５０％以上
【００５６】
（例１〜３および５，６）
下記表１に示した洗剤組成からノニオン界面活性剤、ゼオライトの一部、酵素、色素、香料、ＰＣ剤、漂白活性化剤粒子を除いた各成分を用いて固形分５８％の洗剤スラリーを調製し、水道水にて適当な粘度に調整した。このスラリーを、向流式噴霧乾燥塔を用い、熱風温度２８０℃で水分７％となるように乾燥して噴霧乾燥品を得た。
ついで、この乾燥品、ノニオン界面活性剤および水を、表１に記載の所定温度に保持された連続ニーダに導入し、表１に記載の所定の滞留時間を経た捏和物を得、ニーダの排出口に設置した多孔板を用い捏和物を５ｍｍφ×１０ｍｍの円筒状ペレットとした。このペレットをスピードミルに導入し破砕された粒子に、５質量％のゼオライトを混合し、これに酵素、色素、香料、ＰＣ剤、漂白活性化剤粒子を添加して、下記表１に示した組成を有し、平均粒径４５０〜５５０μｍ、嵩密度０．８ｇ／ｍＬの漂白洗浄剤組成物を得た（例３，５，６）。
【００５７】
また、例１、２においては、より均一に混練するために、ペレットをスピードミルにて破砕して得られた粒子を、再び連続ニーダに導入して、捏和、ペレット化、および破砕からなる成形操作を繰り返して粒子状の漂白洗浄剤組成物を得た。
なお、表１において、例３においてはこの成形操作を１回のみ行ったので、ニーダ通過回数の項目に１回、例１においては３回行ったので３回、例２においては２回行ったので２回と記載した。
【００５８】
（例４）
下記表に示した洗剤組成からα-スルホ脂肪酸メチルエステル、ノニオン界面活性剤、ゼオライトの一部、酵素、色素、香料、ＰＣ剤、漂白活性化剤粒子を除いた各成分を用いて固形分６０％の洗剤スラリーを調製し、水道水にて適当な粘度に調整した。このスラリーを、向流式噴霧乾燥塔を用い、熱風温度２８０℃で水分５％となるように乾燥して噴霧乾燥品を得た。
一方、原料の脂肪酸エステルをスルホン化し、中和して得られたα-スルホ脂肪酸メチルエステルナトリウムの水性スラリー（水分濃度２５質量％）に、ノニオン界面活性剤の一部（α-スルホ脂肪酸メチルエステルナトリウムに対して２５質量％）を添加し、水分を１１質量％になるまで薄膜式乾燥機で減圧濃縮して、α-スルホ脂肪酸メチルエステルナトリウムとノニオン界面活性剤の混合濃縮物を得た。
上述の乾燥品と、この濃縮物、残りのノニオン界面活性剤および水を、表１に示した温度に保持された連続ニーダに導入し、表１に示した滞留時間を経た捏和物を得た。この捏和物は、ニーダの排出口に設置した多孔板を用い、５ｍｍφ×１０ｍｍの円筒状ペレットとした。
ついで、このペレットをスピードミルに導入し、破砕するとともに、この破砕された粒子に３質量％のゼオライトを混合し、さらにこれに酵素、色素、香料、ＰＣ剤、漂白活性化剤粒子を添加して、以下の表１に示した組成を有し、かつ嵩密度０．８ｇ／ｍＬの漂白洗浄剤組成物を得た。
【００５９】
例１〜６について、最終的に得られた粒子状の漂白洗浄剤組成物を１０個採取し、これを割断し、それぞれについて顕微ＦＴ−ＩＲ測定を行い、測定値からσ／Ｐａｖを求めた。
また、各例について固化性を評価し、結果を表１に示した。
【００６０】
【表１】

【００６１】
表１から明らかな様に、σ／Ｐａｖが０．５未満の場合には固化性が良好であった。一方この条件を満たさない例５，６においては固化性が著しく低下した。
【００６２】
【発明の効果】
以上説明したように本発明は、ノニオン界面活性剤およびアニオン界面活性剤を含有する固体洗浄剤と、漂白剤粒子を含有する漂白洗浄剤組成物およびその製造方法において、前記式（１）を満足することにより、漂白洗浄剤組成物の固化性を著しく向上させることができる。
また、前記式（１）を用いて漂白洗浄剤組成物の固化性を判定することができる。これにより、実際の固化性の実験を行わずに固化性を評価することができる。
【図面の簡単な説明】
【図１】 顕微ＦＴ−ＩＲにて得られるチャートの一例を示した図である。
【図２】 顕微ＦＴ−ＩＲを用いて測定した値を基に微細エリアのσ／Ｐａｖを求め、これをプロットしたグラフの一例である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a bleaching detergent composition containing a bleaching agent, a nonionic surfactant, and an anionic surfactant, and a method for producing the same, and in particular, can improve the solidification properties of the bleaching detergent composition.
[0002]
[Prior art]
Conventionally, various solid detergent compositions such as particles have been put on the market for clothing. Among these detergent compositions, there are also bleach detergent compositions containing a bleach (see Patent Documents 1, 2, and 3).
[0003]
[Patent Document 1]
Japanese Patent Laid-Open No. 02-173199
[Patent Document 2]
Japanese Patent Laid-Open No. 04-031498
[Patent Document 3]
Japanese Patent Application Laid-Open No. 08-157877
[0004]
[Problems to be solved by the invention]
However, the conventional bleaching detergent composition has a problem that it easily absorbs moisture and easily solidifies during storage.
Such a phenomenon is more serious in a cleaning composition containing a bleaching agent than in a cleaning composition not containing a bleaching agent.
[0005]
This invention is made in view of the said situation, and makes it a subject to provide the technique which can improve a solidification property in a bleaching detergent composition.
[0006]
[Means for Solving the Problems]
The present inventors have discovered that the solidification property of the bleaching detergent composition varies depending on the production conditions and the like even if the same material is used, and intensively studied based on this.
As a result, in the bleaching detergent composition, the solidification of the bleaching detergent composition is controlled by controlling the concentration distribution of the surfactant in the solid part containing the surfactant, for example, the detergent particles within a certain range. The present invention has been completed by finding that the characteristics can be remarkably improved.
[0007]
  That is, the present invention provides a polyoxyalkylene alkyl ether obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms orAn average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms was added to an aliphatic alcohol having 6 to 22 carbon atoms.A nonionic surfactant that is a polyoxyalkylene alkenyl ether;At least one selected from linear alkylbenzene sulfonates, α-olefin sulfonates, α-sulfo fatty acid methyl ester saltsAn anionic surfactant and sodium salt of acrylic acid / maleic acid copolymer: 4 to 6% by mass;Consists of sodium carbonate and potassium carbonateA carbonate compound, a surfactant andSaidThe mass ratio with the carbonate compound is surfactant / carbonate compound = 1/2 to 2/1, and at leastSaidA bleaching detergent composition comprising a solid detergent obtained by kneading and extruding after preparing a slurry containing a part of an anionic surfactant, spray-drying the slurry in advance, and bleaching particles. ,
  Surfactant for each fine area when the split surface of the solid detergent is divided into a plurality of fine areasPhase ofWhen the counter concentration is P, the bleaching composition satisfies the following formula (1) obtained by the following relative concentration measurement method.
              σ / Pav≦ 0.3... Formula (1)
  In the formula, Pav represents the average value of P, and σ represents the standard deviation of P.
  <Relative concentration measurement method>
  The solid cleaning agent is divided, and the cut section is attached to a microscope slide glass with an epoxy adhesive to obtain a measurement sample.
  Then, using a microscope, the concentration distribution of alcohol ethoxylate (nonionic surfactant) on the surface of the sample section (fracture surface) is measured.
  The measurement was divided into 20 μm × 20 μm fine areas, the scan was repeated 20 times for a measurement range of about 3 mm × 3 mm, and the integrated result was 1300 to 1000 cm^-1The infrared spectrum in the wavelength range of
  The number of fine areas is 300. 1200 cm derived from the sulfonic acid group of the obtained infrared spectrum^-11120 cm derived from nearby peak A and ether bond of nonionic surfactant^-1A peak height ratio (absorbance ratio) is obtained from the nearby peak B, and this is defined as a relative concentration P.
  From the ratio of the height of peak B to peak A, the relative concentration of the nonionic surfactant is obtained for each fine area, the values of Pav and σ are calculated, and σ / Pav is obtained.
The bleaching detergent composition of the present invention comprises:in frontTo satisfy the formula (1),A slurry containing at least a part of the anionic surfactant is prepared, the slurry is spray-dried in advance, and then a solid detergent is obtained by a kneading / extrusion method.Can be obtained.
In addition, the method for suppressing solidification of the bleaching detergent composition of the present invention,Polyoxyalkylene alkyl ether obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms or an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms Is a polyoxyalkylene alkenyl ether having an average of 5 to 20 moles added theretoNonionic surfactantAnd at least one selected from linear alkylbenzene sulfonates, α-olefin sulfonates, α-sulfo fatty acid methyl ester saltsAnionic surfactantAnd a sodium salt of acrylic acid / maleic acid copolymer: 4 to 6% by mass, and a carbonate compound composed of sodium carbonate and potassium carbonate, and the mass ratio of the surfactant to the carbonate compound is as follows: Surfactant / carbonate compound = 1/2 to 2/1, and a slurry containing at least a part of the anionic surfactant is prepared. The slurry is spray-dried in advance, and then obtained by a kneading and extrusion method. BeFor a solid detergent and a bleach detergent composition containing bleach particles,When the relative concentration of the surfactant for each fine area when the split surface of the solid detergent is divided into a plurality of fine areas,When the following formula (1) obtained by the relative concentration measurement method is satisfied, it is determined that the solidification property is good, that is, it is difficult to solidify.
              σ / Pav≦ 0.3... Formula (1)
  Where Pav isSaidThe average value of P is shown, and σ shows the standard deviation of P.
<Relative concentration measurement method>
The solid cleaning agent is divided, and the cut section is attached to a microscope slide glass with an epoxy adhesive to obtain a measurement sample.
Then, using a microscope, the concentration distribution of alcohol ethoxylate (nonionic surfactant) on the surface of the sample section (fracture surface) is measured.
The measurement was divided into 20 μm × 20 μm fine areas, the scan was repeated 20 times for a measurement range of about 3 mm × 3 mm, and the integrated result was 1300 to 1000 cm ^-1 The infrared spectrum in the wavelength range of
The number of fine areas is 300. 1200 cm derived from the sulfonic acid group of the obtained infrared spectrum ^-1 1120 cm derived from nearby peak A and ether bond of nonionic surfactant ^-1 A peak height ratio (absorbance ratio) is obtained from the nearby peak B, and this is defined as a relative concentration P.
From the ratio of the height of peak B to peak A, the relative concentration of the nonionic surfactant is obtained for each fine area, the values of Pav and σ are calculated, and σ / Pav is obtained.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The bleach detergent composition of the present invention is a solid detergent containing a nonionic surfactant and an anionic surfactant and a bleach detergent composition containing bleach particles, and the solid detergent is divided (cut). And if it can measure the density | concentration distribution of a containing component about the crack surface, it will not specifically limit.
Although the form of the bleaching detergent composition of the present invention is not particularly limited, it is preferably in the form of particles comprising a mixture of detergent particles as a solid detergent, bleaching particles, and, if necessary, bleaching activator particles.
[0009]
First, a method for evaluating whether or not the expression (1) is satisfied will be described.
First, the solid detergent that constitutes the bleaching detergent composition is divided, the fractured surface is exposed, and a part of the fractured surface is set as the measurement range.
Examples of the dividing method include cleaving with a microtome and cutting with a cutter or knife. The division position is not particularly limited, but the vicinity of the center of the particle is preferable because the measurement range and the number of fine areas are ensured.
[0010]
The measurement range is divided into a plurality of fine areas of a certain size, and the concentration or relative concentration of the surfactant is determined for each of these fine areas. The concentration or relative concentration of this surfactant may be the total concentration or total relative concentration of the nonionic surfactant and the anionic surfactant, or the concentration or relative concentration of the nonionic surfactant, or the anionic surfactant Or a relative concentration.
[0011]
The size of the fine area is 5 × 5 μm to 100 × 100 μm, preferably 5 × 5 μm to 25 × 25 μm. Usually, for the convenience of measurement, the shape of the fine area is a quadrangle. If it is smaller than this range, it becomes difficult to measure, and if it is larger than this range, the concentration distribution is too coarse to make accurate evaluation difficult.
The number of fine areas in the measurement range is 50 or more, preferably 100 or more, and substantially 50000 or less. If it is less than 50, there may be too few measurement points and accurate evaluation may not be performed.
For example, when the solid detergent is in the form of particles having an average particle size of about 100 to 500 μm, the number of fine areas is preferably about 100 to 500, and the measurement range is preferably about 50 × 50 μm to 500 × 500 μm.
[0012]
In addition, in order to evaluate the uniformity of the surfactant concentration distribution in the solid detergent, in one bleach detergent composition product, take a split section of a plurality of solid detergent, for each solid detergent, It is preferable to measure the concentration or relative concentration. That is, it is preferable to perform measurement on a plurality of detergent particles. In this case, the number of detergent particles is preferably about 5 to 30, more preferably about 10 to 20. If the number is too small, accurate evaluation may not be possible. If there are too many, the results will not be significantly affected, but they are time consuming and inefficient.
[0013]
In addition, in terms of evaluating the mixing uniformity of the surfactant, the surfactant in the cut section is in the state of a kneaded product, pellet, or crushed particles in the process of producing a particulate solid detergent. The concentration or relative concentration of the surfactant may be measured and may be considered as the surfactant concentration or relative concentration in the solid detergent.
[0014]
The total concentration or relative concentration of the surfactant for each fine area thus measured, or the concentration or relative concentration of the nonionic surfactant, or the concentration or relative concentration of the anionic surfactant is defined as P, respectively. And the average value Pav of these P and the standard deviation (sigma) of these P are calculated using several P calculated | required about several fine area.
As a result, if the value of σ / Pav is less than 0.5, good solidification is obtained, and if it is 0.3 or less, further excellent solidification is obtained. Since the value of σ / Pav is preferably as small as possible, the lower limit value is not particularly limited in the present invention, but is substantially 0.01 or more.
[0015]
The reason for the improvement in solidification by satisfying the above formula (1) is not clear, but is presumed as follows, for example.
That is, the smaller the value of σ / Pav, the smaller the variation in P for each fine area. This means that the concentration distribution in the solid detergent of all the surfactants selected for obtaining P, or the nonionic surfactant or the anionic surfactant is high.
And a nonionic surfactant gels and aggregates when it contacts water, forms a lump, and is easy to solidify. Regarding the relationship between the concentration of the nonionic surfactant and gelation, gelation tends to occur in a certain concentration range, and gelation tends to hardly occur in a lower concentration range and a higher concentration range. Therefore, if the concentration of the nonionic surfactant in the bleach detergent composition (solid detergent) is the same, the higher the uniformity of the nonionic surfactant concentration distribution, the more the bleach detergent composition comes into contact with moisture. In addition, since the nonionic surfactant comes into contact with water in a lower concentration state, it can be estimated that this can suppress solidification due to gelation of the nonionic surfactant.
[0016]
On the other hand, anionic surfactants are easily crystallized during production, and tend to aggregate and solidify when contacted with water in a state where the concentration of the crystallized anionic surfactant is high. Therefore, if the concentration of the anionic surfactant in the bleach detergent composition (solid detergent) is the same, the higher the uniformity of the anionic surfactant concentration distribution, the more the bleach detergent composition comes into contact with moisture. In addition, since the anionic surfactant comes into contact with water at a lower concentration, it can be presumed that this can suppress solidification due to aggregation of the anionic surfactant.
These nonionic surfactants or anionic surfactants can be mixed with other surfactants to suppress aggregation and solidification due to gelation of the nonionic surfactant and crystallization of the anionic surfactant.
[0017]
Here, generally, the solid detergent containing a nonionic surfactant and an anionic surfactant is obtained by mixing a nonionic surfactant, an anionic surfactant, and other materials into a solid form.
Therefore, if the entire surface of the solid detergent or one of the nonionic surfactant and the anionic surfactant is evenly distributed in the broken section of the solid detergent, it can be evaluated that the mixing has been sufficiently performed. It is presumed that the concentration of the other materials constituting the solid cleaning agent is uniform.
Moreover, since the dispersion | variation in a density | concentration tends to arise so that the compounding quantity in a solid cleaning agent is small, if the uniformity of the density distribution is good, it can be estimated that the density uniformity of other materials is also good.
Therefore, if the concentration distribution of all the surfactants and nonionic surfactants and anionic surfactants, preferably those having a small blending amount, is obtained and satisfies the above formula (1), the nonionic surfactants and the anionic interfaces are obtained. It can be considered that both of the active agents and the sum of their concentrations satisfy the formula (1), whereby the solidification property of the bleaching detergent composition can be determined.
[0018]
Here, in the bleaching detergent composition of the present invention, the mass ratio of the anionic surfactant / nonionic surfactant is 1/2 to 20/1, preferably 1/2 to 10/1, and more preferably 1 / 1 to 10/1, more preferably 2/1 to 6/1.
This is because outside this range, the low-temperature solubility may deteriorate or problems may occur in production.
In general, in a bleaching detergent composition containing a nonionic surfactant and an anionic surfactant, the content of the nonionic surfactant is often smaller, so the concentration or relative concentration of the nonionic surfactant is defined as the P. It can be used suitably.
[0019]
Further, regarding the ratio of the concentration of the surfactant (nonionic surfactant and / or anionic surfactant) in the solid detergent and other components, that is, the relative concentration of the surfactant, The closer the relative concentration of the surfactant is to a certain level, the more the materials constituting the solid cleaning agent are mixed, and the higher the uniformity of the surfactant concentration distribution in the solid cleaning agent. Therefore, whether or not the solidification property is good can be determined using the total relative concentration of the nonionic surfactant and the anionic surfactant, the relative concentration of the nonionic surfactant, or the relative concentration of the anionic surfactant. . Moreover, the relative concentration shown by the ratio of the density | concentration of a nonionic surfactant and the density | concentration of an anionic surfactant can be used similarly. These relative concentrations can be determined using the quantity corresponding to the concentration and the abundance ratio of the functional group.
For example, as a specific example of the abundance ratio of functional groups, when microscopic FT-IR is used, the anionic surfactant SO₃Basic stretching vibration (νSO₃The ratio of the absorption peak area of the stretching vibration (νC-OC) of the ether bond (C—O—C) of the nonionic surfactant to the absorption peak area of the nonionic surfactant, or the ratio of the height of the absorption peak, the anionic surfactant The relative concentration of the nonionic surfactant relative to can be determined.
[0020]
Specifically, a part of the cut surface of the solid cleaning agent is set as a measurement range, and this is divided into fine areas having a constant size, and one fine area is analyzed by microscopic FT-IR, as shown in FIG. A graph of the relationship between wavelength and absorbance (infrared spectrum) is obtained. In this graph, a plurality of absorbance peaks corresponding to organic compounds such as anionic surfactants and nonionic surfactants are generated.
Here, the peak A is a peak derived from the sulfonic acid group of the anionic surfactant. Peak B is a peak derived from the ether bond of the nonionic surfactant. The higher the peak height, the higher the density, and the smaller the peak height, the lower the density.
[0021]
Therefore, when the ratio of the height of peak B to the height of peak A is determined, the relative concentration of the nonionic surfactant based on the concentration of the anionic surfactant having a sulfonic acid group can be determined. This value is P in this example.
Then, this operation is performed for each fine area, the values of Pav and σ are calculated using P obtained for each fine area, and evaluated by substituting into the equation (1).
Thus, it contains as a nonionic surfactant on the basis of the density | concentration of some components (component which has a sulfonic acid group in this example) (a) of the some components contained as an anionic surfactant Relative concentrations of some or all of the components being treated (b) can be determined. In this case, the mass ratio a / b of the component (a) of the anionic surfactant used as a reference and the component (b) of the nonionic surfactant for obtaining the relative concentration based on the component is 1/2 to 10/1. Furthermore, it is preferable to select the components (a) and (b) to be measured, that is, the peak to be measured, so that the ratio is 1/1 to 10/1.
[0022]
FIG. 2 shows an example of the measurement result.
The horizontal axis represents the ratio of the height of peak B to the height of peak A.
The vertical axis indicates the ratio (existence ratio) of the number of fine areas from which the value of P is obtained for each value of P, where the number of fine areas to be measured is 1.
In graph E, it can be seen that there are an extremely large number of fine areas where P is around 0.2, and the variation in the concentration of the nonionic surfactant is small. On the other hand, in the graph F, the value of P varies for each minute area, and it can be seen that the variation in the concentration of the nonionic surfactant is large.
Note that σ / Pav of the bleaching detergent composition of graph E is 0.15, and σ / Pav of graph F is 0.55.
[0023]
The bleaching detergent composition of the present invention can be produced, for example, by the following method.
For example, an anionic surfactant, a nonionic surfactant, and other materials are put into a production apparatus used for kneading / extrusion method, stirring granulation method, rolling granulation method, etc. A bleaching detergent is prepared by mixing the bleaching agent particles produced separately and, if necessary, the bleaching activator particles, etc., by carrying out processing such as crushing as necessary. A composition can be produced.
[0024]
And the range which a bleaching detergent composition satisfy | fills said (1) Formula can be achieved by mixing as uniformly as possible in the process of mixing the material which comprises a solid cleaning agent.
For example, when producing a particulate solid detergent, it is preferable to mix (preliminarily mix) a part or all of the anionic surfactant and part or all of the nonionic surfactant before introducing the apparatus. In the premixing, the anionic surfactant uses an aqueous slurry having a water concentration of about 20 to 30% by mass, and a nonionic surfactant is added thereto, preferably heated to a temperature of 60 to 70 ° C., and after sufficient mixing, Concentrate under reduced pressure to a moisture of 5 to 17% by mass with a thin film dryer or the like. And this is thrown into the said apparatus with another material, is compression-molded according to a conventional method, is made into a solid substance, and processes, such as crushing, are performed as needed, and a particulate solid cleaning agent is obtained.
By preliminarily mixing part or all of the nonionic surfactant and the anionic surfactant in this way, it is estimated that the uniformity of the material after mixing is remarkably improved.
[0025]
Moreover, after obtaining a bleaching detergent composition of a predetermined shape by an apparatus used for the kneading / extrusion method, the stirring granulation method, the rolling granulation method, etc., this is again put into the apparatus and molded. By repeating the operation, the uniformity of the material can be improved.
Further, the materials can be mixed more uniformly by changing the temperature conditions of compression molding and the apparatus used. Since these conditions are greatly affected by the composition of the solid detergent and the like, there is no particular limitation. For example, in the kneading / extrusion method, the temperature at which kneading is performed is about 5 ° C. higher than before, preferably Exemplifies a method in which the residence time is increased or the shape of the blade (paddle pattern) is made a pattern with a higher degree of mixing in an apparatus for performing kneading such as a kneader or the like under a temperature condition of 60 to 70 ° C. be able to.
[0026]
The bleach detergent composition of the present invention contains bleach particles and a solid detergent containing a nonionic surfactant and an anionic surfactant as essential components, and preferably contains bleach activator particles and the like. Hereinafter, these components will be described with specific examples.
[0027]
・ Bleach particles
The composition of the bleaching particle is not particularly limited as long as it contains a bleaching agent. In general, in order to prevent the bleaching particle surface from being decomposed by contact with detergent fabric (moisture) or the like. Various types of coatings have been proposed.
As the bleaching agent, one or both of sodium percarbonate and sodium perborate are usually used, and sodium percarbonate is preferred from the viewpoint of solubility.
Specifically, for example, bleach particles described in Japanese Patent No. 2918991 can be mentioned. The bleaching agent particles are granulated by spraying and drying a boric acid aqueous solution and an alkali metal silicate aqueous solution separately onto sodium percarbonate particles kept in a fluid state.
[0028]
The average particle diameter of the bleaching particles is not particularly limited, but is, for example, 100 to 2000 μm, preferably 200 to 1500 μm, and particularly preferably 250 to 1000 μm from the viewpoint of the stability and usability of the bleaching agent.
The blending amount of the bleaching agent in the bleaching particles is 50 to 95% by mass, preferably 70 to 90% by mass from the viewpoint of stability and the like.
The blending amount of the bleaching agent particles in the bleaching detergent composition is 1 to 40% by mass, preferably 2 to 20% by mass from the viewpoint of the bleaching effect.
[0029]
・ Nonionic surfactant
Examples of preferred nonionic surfactants include the following.
(I) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or argenyl) ether are preferable. As the aliphatic alcohol used here, a primary alcohol or a secondary alcohol is used. The alkyl group may have a branched chain. As a preferable aliphatic alcohol, a primary alcohol is used.
(Ii) Polyoxyethyl alkyl (or alkenyl) phenyl ether.
(Iii) A fatty acid alkyl ester alkoxylate represented by the following formula, for example, having an alkylene oxide added between the ester bonds of a long-chain fatty acid alkyl ester.
[0030]
R¹CO (OA) nOR²
(R¹CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents an addition unit of alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide. n shows the average addition mole number of alkylene oxide, and is generally 3-30, Preferably it is the number of 5-20. R²Represents a lower alkyl group which may have a substituent having 1 to 3 carbon atoms. )
(Iv) Polyoxyethylene sorbitan fatty acid ester.
(V) Polyoxyethylene sorbite fatty acid ester.
(Vi) Polyoxyethylene fatty acid ester.
(Vii) Polyoxyethylene hydrogenated castor oil.
(Viii) Glycerin fatty acid ester.
Among the above nonionic surfactants, ethylene oxide is present in polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether having a melting point of 40 ° C. or less and 9 to 16 HLB, and fatty acid methyl ester. Particularly suitable are fatty acid methyl ester ethoxylates added, fatty acid methyl ester ethoxypropoxylates obtained by adding ethylene oxide and propylene oxide to fatty acid methyl esters, and the like. These nonionic surfactants may be used as a mixture.
[0031]
・ Anionic surfactant
Preferred anionic surfactants include, for example, linear or branched alkylbenzene sulfonates having an alkyl group having 8 to 16 carbon atoms, alkyl sulfate (AS) salts or alkenyl sulfates having 10 to 20 carbon atoms, carbon numbers 10-20 α-olefin sulfonic acid (AOS) salt, C10-20 alkane sulfonate, C10-20 linear or branched alkyl or alkenyl group, average 0.5 Alkyl ether sulfuric acid (AES) salt or alkenyl ether added at a ratio of ˜8 mol of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 Sulfate, linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms Alkyl ether carboxylate added in an average ratio of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 Or an alkenyl ether carboxylate, an alkyl polyhydric alcohol ether sulfate such as an alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms, a higher fatty acid salt having 10 to 20 carbon atoms, and a saturation having 8 to 20 carbon atoms is unsaturated α -Sulfo fatty acid (α-SF) salts or anionic surfactants such as methyl, ethyl or propyl esters thereof, or mixtures thereof can be used.
Particularly preferred anionic surfactants include, for example, alkali metal salts of linear alkylbenzene sulfonic acid (LAS) (for example, sodium or potassium salt), alkali metal salts of AOS, α-SF, AES (for example, sodium or Potassium salts), alkali metal salts of higher fatty acids (for example, sodium or potassium salts), and the like.
[0032]
The content of the anionic surfactant in the solid detergent is 10 to 40% by mass, preferably 15 to 35% by mass, from the balance between detergency and other ingredients.
Moreover, 2-20 mass%, preferably 5-15 mass% of nonionic surfactant is mix | blended from the point of a detergency in a solid detergent.
[0033]
・ Bleaching activator particles
The bleaching detergent composition of the present invention is preferably blended with bleach activator particles, which can further improve the bleaching effect of the bleach particles.
As bleach activators, organic peracid precursors, metal ions, metal complex catalysts, etc. are known, and hydrogen peroxide (sodium percarbonate, etc.) blended as a bleaching agent is essential as an oxygen supply source. It is.
Since the bleach activator is unstable with respect to the alkali component, it is blended in the form of bleach activator particles granulated using, for example, a binder component such as polyethylene glycol.
As a bleaching activator in this invention, what is represented by the following general formula (I) or (II) is mentioned as a preferable thing.
[0034]
[Chemical 1]

(Wherein R¹ Is an alkyl or alkenyl group having 7 to 13 carbon atoms, and R² Is an alkyl group or alkenyl group having 7 to 13 carbon atoms, and M is a salt-forming cation or hydrogen. )
[0035]
The bleach activator used in the present invention is represented by the above general formula (I) or (II). In the formula, as the alkyl group and the alkenyl group, both linear and branched can be used. A chain is preferable. R¹Is preferably an alkyl group having 9 to 13 carbon atoms, and more preferably an alkyl group having 9 to 11 carbon atoms. R²Is preferably an alkyl group having 7 to 11 carbon atoms, and more preferably an alkyl group having 7 to 9 carbon atoms. M is preferably hydrogen or an alkali metal such as sodium or potassium, or an amine such as ammonium or alkanolamine that imparts water solubility to a bleach activator. Of these, alkali metals are preferred. Where SO_ThreeThe M group and the COOM group can be in the ortho, meta or para position, but the para position is preferred.
[0036]
As a bleaching activator in the present invention, those represented by the following formula (III) or (IV) are also preferred.
[Chemical 2]

(Wherein R¹Is an alkyl group having 1 to 6, preferably 1 to 4, particularly preferably 1 to 3, carbon atoms which may be interrupted by an ester group, an amide group or an ether group, and R⁶Is an alkylene group having 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms which may be divided by an ester group, an amide group or an ether group, and may be substituted by a hydroxy group. R², R^Three, R^Four, R^Five, R⁷, R⁸Are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably a methyl group, an ethyl group or a hydroxyethyl group. X <-> is an anion, preferably a halogen ion, a sulfate ion, a fatty acid ion or an alkyl sulfate ion having 1 to 3 carbon atoms. )
[0037]
The bleach activator of the present invention is formulated as a granulated product. The content of the bleach activator in the granulated product is preferably 1 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 30 to 85% by mass. These are formulated using a binder material selected from polyethylene glycol and fatty acids. The polyethylene glycol preferably has a mass average molecular weight of 2,000 to 20,000, more preferably 4,000 to 10,000, and particularly preferably 4,000 to 8,000. The fatty acid preferably has 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, and particularly preferably 12 to 18 carbon atoms, and these may be in the form of sodium or potassium soap. Such a binder substance is used in the granulated product in an amount of 0.5 to 30% by mass, preferably 1 to 25% by mass, more preferably 5 to 20% by mass.
[0038]
In addition, the granulated product may contain polyoxyalkylene alkyl ether, olefin sulfonate, alkyl benzene sulfonate, alkyl sulfate ester or polyoxyethylene alkyl to improve the solubility of the bleach activator in the washing bath. The ether sulfate ester salt or a mixture thereof is preferably added in an amount of 0 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 30% by mass.
As polyoxyalkylene alkyl ether, the alkyl group preferably has 10 to 15 carbon atoms, and is preferably an adduct of ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO). The average number of added moles in any case of EO, PO, or a mixture of EO and PO is preferably 4 to 30, more preferably 5 to 15, and the molar ratio of EO / PO is preferably 5 / 0 to 1/5, more preferably 5/0 to 1/2.
[0039]
The olefin sulfonate is preferably a sodium or potassium salt of an α-olefin sulfonic acid having an alkyl group with 14 to 18 carbon atoms.
The alkylbenzene sulfonate is preferably a sodium or potassium salt of a linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms in the alkyl group.
Further, as the alkyl sulfate ester salt, the alkyl group has 10 to 18 carbon atoms, and an alkali metal salt such as sodium salt is preferable, and sodium lauryl sulfate ester or myristyl sulfate ester sodium is particularly preferable.
Moreover, as a polyoxyethylene alkyl ether sulfate ester salt, the polyoxyethylene alkyl ether sulfate ester salt which has a C10-C18 alkyl group is preferable, and a sodium salt is favorable.
Here, the average degree of polymerization of the oxyethylene group (hereinafter, the average degree of polymerization is represented by POE) is 1 to 10, preferably 1 to 5, and particularly sodium polyoxyethylene lauryl ether sulfate (POE = 2 to 5). ), Sodium polyoxyethylene myristyl ether sulfate (POE = 2 to 5) is good.
[0040]
The bleaching activator granulated product can be obtained by mixing and granulating the above composition by any method. In addition, a preferable result can be obtained by adding the binder substance after being melted in advance. The binder material is added after being melted at 40 to 100 ° C, preferably 50 to 100 ° C, more preferably 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, preferably 500 to 3000 μm. As another granulation method, a tablet shape by a briquetting machine can be cited as a preferable granulation method.
[0041]
Moreover, in this invention, you may mix | blend an acidic substance in a granulated material as needed for the purpose of improving the stability of a bleaching activator. 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 blending amount of such an acidic substance is preferably 0.5 to 20% by mass in the granulated product, more preferably 1 to 15% by mass, and most preferably 1 to 10% by mass.
Other components such as a colorant and a fragrance can be added to the bleaching activator granulated product as components other than those described above.
The blending amount of the bleach activator is usually 0.1 to 20%, more preferably 0.2 to 10%, still more preferably 0.5 to 5% with respect to the entire composition.
The blending amount of the bleach activator in the bleach activator particles is 50 to 80% by mass, preferably 60 to 75% by mass from the viewpoint of stability and the like.
[0042]
Further, the bleaching detergent composition of the present invention can appropriately contain a known component as a detergent component. Examples are given below.
・ Surfactant
In addition to the nonionic surfactant and the anionic surfactant, amphoteric surfactants and the like can be used.
Preferred amphoteric surfactants include, for example, amphoteric surfactants such as imidazoline series and amide betaine series. Particularly preferred amphoteric surfactants include, for example, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine.
[0043]
・ Detergent Builder
As the detergent builder, an alkali builder or chelate builder usually used for detergents is preferably used.
Examples of the alkali builder include alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and sodium potassium carbonate, and alkali metal silicates such as sodium silicate, potassium silicate, and layered sodium silicate. Is mentioned.
Examples of chelate builders include aluminosilicate, tripolyphosphate, pyrophosphate, citrate, succinate, polyacrylate, acrylic acid-maleic acid copolymer, iminocarboxylic acid / salt, EDTA, and the like. .
The detergent builder is usually blended in the bleaching detergent composition in an amount of 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass.
[0044]
・ Oil absorbent carrier
The oil-absorbing carrier is mainly used to absorb and carry a liquid component such as a nonionic surfactant.
Preferable oil-absorbing carriers include, for example, amorphous hydrated amorphous silicic acid, spherical porous hydrated amorphous silicic acid, amorphous anhydrous amorphous silicic acid, petal hydrated amorphous calcium silicate, acicular hydrated water as silicate compounds, for example. Examples thereof include amorphous calcium silicate, amorphous aluminosilicate, magnesium silicate, and the like.
Examples of the carbonate compound include magnesium carbonate, calcium carbonate, and ultrafine spinel.
When blended in the bleaching detergent composition, the oil-absorbing carrier is blended in an amount of 0.1 to 25 mass%, preferably 0.5 to 20 mass%, more preferably 1 to 15 mass%.
[0045]
・ Clay minerals
As the clay mineral, those belonging to the smectite group and having a crystal structure of a dioctahedral trilayer or a trioctahedral trilayer are particularly preferable.
The oil absorption is less than 80 ml / 100 g, preferably 30 to 70 ml / 100 g, and the bulk density is 0.1 g / ml or more, preferably 0.2 to 1.5 g / ml.
Specific examples include, for example, montmorillonite, nontronite, beidellite, pyrophyllite and the like as clay minerals having a dioctahedral type three-layer structure.
Examples of the clay mineral having a trioctahedral three-layer structure include saponite, hectorite, stevensite, and talc.
When blended in the bleaching detergent composition, the clay mineral is usually blended in an amount of 0.1 to 30% by mass, preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass.
[0046]
・ Fluorescent brightener
Examples of the optical brightener include bis (triazonylamino) stilbene disulfonic acid derivative, bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X] and the like.
·enzyme
Examples of the enzyme include lipase, protease, cellulase, and amylase.
・ Antistatic agent
Examples of the antistatic agent include cationic surfactants such as dialkyl quaternary ammonium salts.
・ Surface modifier
Examples of the surface modifier include finely powdered calcium carbonate, finely powdered zeolite, and polyethylene glycol.
・ Recontamination inhibitor
Examples of the recontamination inhibitor include cellulose derivatives such as carboxymethylcellulose.
・ Particle strength retention agent
Examples of the particle strength retaining agent include sodium sulfate, potassium sulfate, sodium hydrochloride and the like.
・ Reducing agent
Examples of the reducing agent include sodium sulfite and potassium sulfite.
・ Defoamer
・ Various fragrances
・ Various pigments
・ Various softening agents
[0047]
These detergent components can be used by being contained in solid detergent, bleach particles and / or bleach activator particles, or may be mixed with powder or blended by a method such as spraying. . In addition, an enzyme and a softness | flexibility imparting agent are normally used as a particle form.
Further, the mass ratio (surfactant / carbonate compound) of the surfactant (total of all surfactants) and the carbonate compound (including the metal carbonate) in the bleaching detergent composition is 1 / It is preferably within the range of 8 to 3/1, more preferably 1/3 to 2/1, and still more preferably 1/2 to 2/1. If the value of the surfactant / carbonate compound is smaller than the above range, it is not preferable in terms of low-temperature solubility, and if it exceeds the above range, the surfactant becomes excessive, which is not economically preferable.
[0048]
Moreover, the determination method of the solidification property of this invention is a method of determining the solidification property of a bleaching detergent composition using following formula (1). That is, solidification is good when the following formula (1) is satisfied in a solid detergent containing a nonionic surfactant and an anionic surfactant and a bleach detergent composition containing bleach particles as essential components. That is, it can be determined that it is difficult to solidify during storage.
σ / Pav <0.5 Formula (1)
In the formula, Pav represents the average value of the surfactant concentration or relative concentration P for each fine area when the split surface of the solid detergent is divided into a plurality of fine areas, and σ represents the standard deviation of P Show.
[0049]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples.
First, the raw materials used and the evaluation methods used in the examples are as follows. Unless otherwise indicated, “%” means “% by mass”.
[0050]
<Raw materials>
The raw materials used are shown below.
LAS-K: linear alkyl (carbon number 10 to 14) potassium benzenesulfonate (Lypon LH-200 (96% pure) manufactured by Lion Co., Ltd. neutralized with 48% aqueous potassium hydroxide)
LAS-Na: linear alkyl (carbon number 10-14) sodium benzenesulfonate (Lypon LH-200 (96% pure) manufactured by Lion Co., Ltd. neutralized with 48% aqueous sodium hydroxide)
AOS-K: α-olefin potassium sulfonate having an alkyl group having 14 to 18 carbon atoms (pure water 70% pure slurry manufactured by Lion Corporation)
Α-SF-Na: sodium salt of α-sulfo fatty acid methyl ester having an alkyl group having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content 70%, solid content 72 to 73%)
AS-Na: alkyl sulfate sodium salt having an alkyl group having 10 to 18 carbon atoms (Sandet LNM, manufactured by Sanyo Chemical Industries, Ltd.)
Soap: Fatty acid sodium having an alkyl group having 12 to 18 carbon atoms (manufactured by Lion Corporation, C12: 0.9%, C18: 80.2%, unsaturated fatty acid 80.2%, molecular weight 289, pure content 67 ~ 68%, titer 47.0 ° C)
Nonionic A (C13 / EO12): Diador 13 (Mitsubishi Chemical) ethylene oxide 12 mol adduct (manufactured by Lion Chemical Co., Ltd., 84% pure)
-Nonion B (C13 / EO25): 25 mol of ethylene oxide adduct of Diador 13 (Mitsubishi Chemical) (manufactured by Lion Chemical Co., Ltd., 84% pure)
Nonionic C (C13 / EO15): Diadol 13 (Mitsubishi Chemical) ethylene oxide 15 mol adduct (manufactured by Lion Chemical Co., Ltd., 90% pure)
[0051]
・ Zeolite: A-type zeolite (Shilton B manufactured by Mizusawa Chemical Co., Ltd.)
-High molecular builder (MA / AA): sodium salt of acrylic acid / maleic acid copolymer (manufactured by BASF, Socharan CP7)
-Potassium carbonate: Asahi Glass Co., Ltd., potassium carbonate (powder)
・ Sodium silicate: JIS No. 1 sodium silicate (manufactured by Osaka Silicate Soda Co., Ltd.)
・ Sodium carbonate: Heavy sodium carbonate, manufactured by Asahi Glass Co., soda ash
・ Sodium chloride: manufactured by Chiba Salt Industry Co., Ltd.
・ Fluorescent brightener A: Chinopearl CBS-X (Ciba Specialty Chemicals) ・ Fluorescent brightener B: Chinopearl AMS-GX (Ciba Specialty Chemicals)
Enzyme: Proteolytic enzyme, Novozymes, Evalase 8T
Fragrance: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18]
-Dye: Ultramarine (Daiichi Seika Kogyo Co., Ltd., Ultramarine Blue)
PC agent: Mitsubishi Gas Chemical Company, SPC-D
Bleach activator A: As a bleach activator, sodium 4-dodecanoyloxybenzenesulfonate 70 parts by mass, PEG [polyethylene glycol # 6000M (manufactured by Lion Corporation)] 20 parts by mass, α-olefin having 14 carbon atoms Sodium sulfonate powder product (Lipolane PJ-400 (manufactured by Lion Corporation)) is put into Hosokawa Micron's Extrude Ohmic EM-6 so that the total amount is 5000 g at a rate of 5 parts by mass, and kneaded and extruded. Thus, a noodle-like extruded product having a diameter of 0.8 mmφ was obtained. This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 manufactured by Hosokawa Micron Co., Ltd., and 5 parts by mass of A-type zeolite powder was supplied in the same manner as an auxiliary, and pulverized to give bleaching activity having an average particle size of about 700 μm An agent granulated product was obtained.
Bleach activator B: A bleach activator granulated product was prepared in the same manner as Bleach activator A except that sodium 4-nonanoyloxybenzenesulfonate was used as the bleach activator.
Bleach activator C: A bleach activator granulated product was prepared in the same manner as Bleach activator A except that 4-decanoyloxybenzoic acid was used as the bleach activator.
[0052]
<Evaluation of uniform mixing property of surfactant>
A solid cleaning agent (particulate in the following example) was divided, and the cut surface was attached to a microscope slide glass using an epoxy adhesive to obtain a measurement sample.
Then, using a PerkinElmer AutoIMAGE FT-IR microscope (microscopic FT-IR), the concentration distribution of alcohol ethoxylate (nonionic surfactant) on the surface of the sample section (split cross section) was measured.
The measurement was divided into 20 μm × 20 μm fine areas, the scan was repeated 20 times for a measurement range of about 3 mm × 3 mm, and the integrated result was 1300 to 1000 cm^-1The infrared spectrum in the wavelength range of
The number of fine areas was 300. 1200 cm derived from the sulfonic acid group of the obtained infrared spectrum^-11120 cm derived from nearby peak A and ether bond of nonionic surfactant^-1The peak height ratio (absorbance ratio) was determined from the nearby peak B, and this was used as the relative concentration P.
From the ratio of the height of peak B to peak A, the relative concentration of the nonionic surfactant was determined for each fine area, the values of Pav and σ were calculated, and σ / Pav was determined.
[0053]
<Evaluation method of solidification>
The bleaching detergent composition is placed in a sealed container, which is taken out after storage for 40 days under conditions of a temperature of 35 ° C. and a relative humidity of 85%, and left for 6 hours at a temperature of 20 ° C. and a relative humidity of 60%. Gently transfer the bleaching detergent composition inside onto a sieve with a mesh opening of 5 mm, gently shake the sieve left and right 10 times, and then determine the residue on the sieve and the mass passed through the sieve. The solidification rate was calculated from the formula.
[0054]
[Expression 1]

[0055]
From the value of the solidification rate, the solidification property was evaluated in the following four stages.
A: 0 to 5%
○: 5 to 20%
Δ: 20 to 50%
×: 50% or more
[0056]
(Examples 1-3 and 5,6)
A detergent slurry having a solid content of 58% was prepared using each component excluding nonionic surfactant, part of zeolite, enzyme, dye, fragrance, PC agent and bleach activator particles from the detergent composition shown in Table 1 below. And adjusted to an appropriate viscosity with tap water. This slurry was dried using a counter-current spray drying tower at a hot air temperature of 280 ° C. to a moisture content of 7% to obtain a spray-dried product.
Next, the dried product, the nonionic surfactant and water were introduced into a continuous kneader maintained at a predetermined temperature shown in Table 1 to obtain a kneaded product having passed through a predetermined residence time shown in Table 1. The kneaded product was made into a cylindrical pellet of 5 mmφ × 10 mm using a perforated plate installed at the discharge port. The pellets were introduced into a speed mill and crushed particles were mixed with 5% by mass of zeolite. Enzyme, dye, fragrance, PC agent, and bleach activator particles were added to the particles. A bleaching detergent composition having a composition, an average particle size of 450 to 550 μm, and a bulk density of 0.8 g / mL was obtained (Examples 3, 5 and 6).
[0057]
In Examples 1 and 2, in order to knead more uniformly, particles obtained by crushing pellets with a speed mill are again introduced into a continuous kneader, and kneading, pelletizing, and crushing are performed. The molding operation was repeated to obtain a particulate bleaching detergent composition.
In Table 1, since this molding operation was performed only once in Example 3, it was performed once for the item of the number of passes through the kneader, 3 times in Example 1, and therefore 3 times in Example 2, and twice in Example 2. So it was described twice.
[0058]
(Example 4)
Solid content 60 using each component excluding α-sulfo fatty acid methyl ester, nonionic surfactant, part of zeolite, enzyme, dye, fragrance, PC agent, bleach activator particles from the detergent composition shown in the following table % Detergent slurry was prepared and adjusted to an appropriate viscosity with tap water. This slurry was dried using a counter-current spray drying tower so that the water content was 5% at a hot air temperature of 280 ° C. to obtain a spray-dried product.
On the other hand, a part of nonionic surfactant (α-sulfo fatty acid methyl ester) was added to an aqueous slurry of sodium α-sulfo fatty acid methyl ester (water concentration 25% by mass) obtained by sulfonating and neutralizing the fatty acid ester of the raw material. 25% by mass with respect to sodium) and concentrated under reduced pressure with a thin film dryer until the water content became 11% by mass to obtain a mixed concentrate of sodium α-sulfo fatty acid methyl ester and a nonionic surfactant.
The above-mentioned dried product, this concentrate, the remaining nonionic surfactant and water are introduced into a continuous kneader maintained at the temperature shown in Table 1, and a kneaded product having undergone the residence time shown in Table 1 is obtained. It was. This kneaded product was made into a cylindrical pellet of 5 mmφ × 10 mm using a perforated plate installed at the outlet of the kneader.
Next, the pellet is introduced into a speed mill and crushed, and 3% by mass of zeolite is mixed with the crushed particles, and further, enzyme, dye, fragrance, PC agent, and bleach activator particles are added thereto. Thus, a bleaching detergent composition having the composition shown in Table 1 below and having a bulk density of 0.8 g / mL was obtained.
[0059]
For Examples 1 to 6, 10 particulate bleaching detergent compositions finally obtained were collected, cleaved, and subjected to microscopic FT-IR measurement for each to determine σ / Pav from the measured values. .
Moreover, solidification property was evaluated about each case and the result was shown in Table 1.
[0060]
[Table 1]

[0061]
As is apparent from Table 1, the solidification was good when σ / Pav was less than 0.5. On the other hand, in Examples 5 and 6, which did not satisfy this condition, the solidification property was remarkably lowered.
[0062]
【The invention's effect】
As described above, the present invention satisfies the above formula (1) in a solid detergent containing a nonionic surfactant and an anionic surfactant, a bleach detergent composition containing bleach particles, and a method for producing the same. By doing so, the solidification property of the bleaching detergent composition can be remarkably improved.
Moreover, the solidification property of a bleaching detergent composition can be determined using said Formula (1). Thereby, solidification property can be evaluated without conducting an actual solidification experiment.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a chart obtained by microscopic FT-IR.
FIG. 2 is an example of a graph in which σ / Pav of a fine area is obtained based on a value measured using microscopic FT-IR and plotted.

Claims (4)

Polyoxyalkylene alkyl ether obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms or an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms A nonionic surfactant which is a polyoxyalkylene alkenyl ether having an average of 5 to 20 moles added, and at least one selected from linear alkylbenzene sulfonates, α-olefin sulfonates and α-sulfo fatty acid methyl ester salts and anionic surfactants, sodium salts of acrylic acid / maleic acid copolymer: 4-6 mass%, and containing a carbonate compound consisting of sodium carbonate and potassium carbonate, and surfactant and the carbonate compound mass ratio is a surfactant / carbonate compound = 1 / 2-2 / 1, at least the a A bleaching detergent composition comprising a solid detergent obtained by kneading and extruding after preparing a slurry containing a part of a nonionic surfactant, spray-drying the slurry in advance, and bleaching particles. ,
The split cross section of the solid detergent when the divided plurality of fine area, when the relative concentration of the surfactant for each the fine area is P, the following expression obtained by the relative densitometry of the following (1 The bleaching detergent composition characterized by satisfying
σ / Pav ≦ 0.3 (1)
In the formula, Pav represents the average value of P, and σ represents the standard deviation of P.
<Relative concentration measurement method>
The solid cleaning agent is divided, and the cut section is attached to a microscope slide glass with an epoxy adhesive to obtain a measurement sample.
Then, using a microscope, the concentration distribution of alcohol ethoxylate (nonionic surfactant) on the surface of the sample section (fracture surface) is measured.
The measurement is divided into fine areas of 20 μm × 20 μm, scanning is repeated 20 times for a measurement range of about 3 mm × 3 mm, and the result of integration is an infrared spectrum in the wavelength range of 1300 to 1000 cm ⁻¹ .
The number of fine areas is 300. From the obtained infrared spectrum, a peak height ratio (absorbance) from a peak A near 1200 cm ⁻¹ derived from a sulfonic acid group and a peak B near 1120 cm ⁻¹ derived from an ether bond of a nonionic surfactant. The ratio is determined as a relative concentration P.
From the ratio of the height of peak B to peak A, the relative concentration of the nonionic surfactant is obtained for each fine area, the values of Pav and σ are calculated, and σ / Pav is obtained. The bleaching detergent composition according to claim 1, further comprising bleach activator particles. A method for producing the bleaching detergent composition according to claim 1, comprising:
So as to satisfy pre above formula (1) is to prepare a slurry containing at least a portion of the anionic surfactant, after previous spray drying the slurry to obtain a solid detergent by kneading, extrusion A method for producing a bleaching detergent composition. Polyoxyalkylene alkyl ether obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms or an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms A nonionic surfactant which is a polyoxyalkylene alkenyl ether having an average of 5 to 20 moles added, and at least one selected from linear alkylbenzene sulfonates, α-olefin sulfonates and α-sulfo fatty acid methyl ester salts An anionic surfactant , an acrylic acid / maleic acid copolymer sodium salt: 4 to 6% by mass, and a carbonate compound composed of sodium carbonate and potassium carbonate, and the surfactant and the carbonate compound The mass ratio is surfactant / carbonate compound = 1/2 to 2/1. A slurry containing a part of a nonionic surfactant is prepared, and the slurry is spray-dried in advance, and then the solid detergent obtained by a kneading / extrusion method and the bleach detergent composition containing bleach particles are described above. When the relative concentration of the surfactant for each fine area when the split surface of the solid detergent is divided into a plurality of fine areas is P, the following formula (1) obtained by the following relative concentration measurement method is A solidification inhibiting method for a bleaching detergent composition, wherein the solidification property is determined to be good when satisfied.
σ / Pav ≦ 0.3 (1)
Wherein, Pav represents a mean value of the P, sigma represents a standard deviation of P.
<Relative concentration measurement method>
The solid cleaning agent is divided, and the cut section is attached to a microscope slide glass with an epoxy adhesive to obtain a measurement sample.
Then, using a microscope, the concentration distribution of alcohol ethoxylate (nonionic surfactant) on the surface of the sample section (fracture surface) is measured.
The measurement is divided into fine areas of 20 μm × 20 μm, scanning is repeated 20 times for a measurement range of about 3 mm × 3 mm, and the result of integration is an infrared spectrum in the wavelength range of 1300 to 1000 cm ⁻¹ .
The number of fine areas is 300. From the obtained infrared spectrum , a peak height ratio (absorbance) from a peak A near 1200 cm ⁻¹ derived from a sulfonic acid group and a peak B near 1120 cm ⁻¹ derived from an ether bond of a nonionic surfactant. The ratio is determined as a relative concentration P.
From the ratio of the height of peak B to peak A, the relative concentration of the nonionic surfactant is obtained for each fine area, the values of Pav and σ are calculated, and σ / Pav is obtained.

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