JP2004210819A - Bleach detergent composition and its manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bleach detergent composition with high aroma stability. <P>SOLUTION: The bleach detergent composition contains a bleach-containing particle (A) and a detergent-containing particle (B). The detergent-containing particle (B) satisfies (1)-(3) below. (1) It contains a crystalline anionic surfactant and a crystalline inorganic compound. (2) Its main surfactant is the anionic surfactant. (3) The percent area of the anisotropic substance in the split cross section of the detergent-containing particle (B) as determined by polarized light microscopy is ≤ 12%. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００５２】
（式中、Ｒ^１は炭素数７〜１３のアルキル基またアルケニル基であり、Ｒ^２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。）
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。Ｒ^１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。Ｒ^２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、ＳＯ_３Ｍ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。
【００５３】
また、漂白活性化剤としては、以下の[化２]に示す一般式（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。
【００５４】
【化２】

【００５５】
（式中、Ｒ^１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、Ｒ^６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。Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^７、Ｒ^８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。）。
【００５６】
本発明の漂白活性化剤は造粒物（漂白活性化剤含有粒子）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、通常、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等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。
【００５７】
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。
【００５８】
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の混合の何れも場合も、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。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。
【００５９】
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。
【００６０】
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。
本発明では上記組成物を任意の方法で混合し造粒することができる。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。
【００６１】
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質量％、より好ましくは０．２〜１０質量％、更に好ましくは０．５〜５質量％が好適である。
【００６２】
その他、漂白洗浄剤組成物に配合可能なものとしては、例えば以下の成分など挙げられる。
・各種柔軟性付与剤
・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。
【００６３】
本発明の漂白洗浄剤組成物は、例えば漂白剤含有粒子（Ａ）、洗剤粒子（Ｂ）、及び必要に応じて漂白活性化剤含有粒子、酵素、柔軟性付与剤等（通常、これらはいずれも粒子形態として配合される）を粉体混合して得られる。
漂白洗浄剤組成物の嵩密度は、ほぼ洗剤粒子（Ｂ）と同様の範囲とされる。
なお、香料、ノニオン界面活性剤等は、必要に応じて、漂白剤含有粒子（Ａ）、洗剤粒子（Ｂ）等の混合時に漂白洗浄剤組成物全体に噴霧して配合することもできる。
また、洗剤粒子（Ｂ）に配合可能なものとして例示した成分を、適宜必要に応じて粉体混合等することもできる。
【００６４】
［第２の実施形態例］
第２の実施形態例の漂白洗浄剤組成物は、漂白剤含有粒子（Ｃ）と、洗剤粒子（Ｄ）とを含有する漂白洗浄剤組成物において、
前記洗剤粒子（Ｄ）が、以下の（４）〜（６）を満足することを特徴とする。（４）結晶性アニオン界面活性剤と結晶性無機化合物を含有し、
（５）１０質量％を超えるノニオン界面活性剤（Ｅ）を含有し、
（６）当該洗剤粒子（Ｄ）の割断面の偏光顕微鏡映像から求めた、該割断面中の異方性物質の面積比率が３０〜５０％である。
【００６５】
洗剤粒子（Ｄ）において、かかる数値限定により、香気安定性が得られる理由は定かではないが、第１の実施形態例と同様であると推測される。
【００６６】
・漂白剤含有粒子（Ｃ）
漂白剤含有粒子（Ｃ）にいては、前記第１の実施形態例と同様である。
【００６７】
・洗剤粒子（Ｄ）
第２の実施形態例の洗剤粒子（Ｄ）は、結晶性無機化合物を含む無機化合物の多孔質体に、アニオン界面活性剤を主とする界面活性剤を担持させた構造のものに適用すると好ましい。
なお、洗剤粒子（Ｄ）に配合される無機化合物には、上述の結晶性無機化合物と、ゼオライトなどの異方性を示さないものがあり、洗剤ビルダーなどとして、通常、必ず洗剤粒子（Ｄ）に配合されているものである。
このタイプの洗剤粒子（Ｄ）は、異方性物質の面積比率の範囲が、第１の実施形態例の洗剤粒子（Ｂ）よりも大きくても、香気安定性が良好であり、溶解性も良好である。
【００６８】
その理由は、定かではないが、以下のふたつが考えられる。
すなわち、このタイプの洗浄剤組成物は、結晶性無機化合物を含む無機化合物の骨格を備えているため、偏光顕微鏡映像においては、多数の細かい点状の結晶性無機化合物が、洗浄剤組成物の割断面全体に略均一に分布する。そのため、偏光顕微鏡映像において、異方性を示す部分が全体に分布して、見かけ上、異方性物質の面積比率が大きな値になる、と推測される。
洗剤粒子（Ｄ）の真密度（嵩密度に対して使用するもので、例えばひとつの粒子の密度）は０．９〜１．３ｇ／ｍｌ、好ましくは１〜１．２ｇ／ｍｌとされる。
【００６９】
第２の実施形態例において、漂白洗浄剤組成物中の洗剤粒子（Ｄ）の配合量は、洗浄力の確保等の点から５５〜９５質量％、好ましくは７５〜９０質量％とされる。
第２の実施形態例において、洗剤粒子（Ｄ）中のアニオン界面活性剤の含有量は、洗浄力と、他の配合成分とのバランスから、１０〜３０質量％、好ましくは１５〜２５質量％とされる。このうち結晶性アニオン界面活性剤は、通常、全アニオン界面活性剤中の２０質量％以上、好ましくは３０〜７０質量％配合される。
【００７０】
また、多孔質体を形成するための無機化合物は、洗剤粒子（Ｄ）中、３０〜７０質量％、好ましくは４５〜６５質量％とされる。下限値未満では洗剤粒子（Ｄ）の骨格を形成するのに充分ではなく、 上限値をこえると他の配合成分の配合量が低下するためである。
なお、結晶性無機化合物の含有量は、洗剤粒子（Ｄ）中、１０〜５０質量％、好ましくは３０〜４０質量％とされる。
そして、結晶性アニオン界面活性剤と結晶性無機化合物との合計は洗剤粒子（Ｄ）中、２０〜６０質量％、好ましくは２０〜５５質量％とされる。この範囲外では異方性物質の面積比率を所定の範囲とすることが困難となるおそれがある。また、洗浄力の低下などの問題もある。
【００７１】
また、第２の実施形態例の洗剤粒子（Ｄ）は、ノニオン界面活性剤（Ｅ）を１０質量％越えて含有する。好ましくは１１〜４０質量％、さらに好ましくは１１〜２０質量％である。
充分な量のノニオン界面活性剤を配合すると、ノニオン界面活性剤とともに前記多孔質体に担持させる結晶性アニオン界面活性剤の結晶化を防ぐことができ、異方性物質の面積比率を所定の範囲に調製することが容易になる。また、溶解性を向上させることもできる。また、洗浄剤成分が均一に分布することにより、香気安定性も向上する。なお、添加量がこの範囲よりも少ないと充分な効果を得ることができない。
【００７２】
ノニオン界面活性剤を多く含むことが香気安定性に寄与する理由は定かではないが、以下の様に推測される。
すなわち、上述の様に、洗剤粒子（Ｄ）の製造において、粒子の表面に香料を噴霧すると、香料は親油性であるためノニオン界面活性剤に引きつけられる。そして、ノニオン界面活性剤が多く含まれ、かつ本発明の異方性物質の面積比率を指針として、組成が均一になっていると、香料も、洗剤粒子（Ｄ）中に均一に分布し、香気安定性が得られる。
これに対して、香料が均一に分布していない場合は、保存中等に、洗剤粒子（Ｄ）の表面に吸着している香料が、香料の濃度の低い他の粒子の表面と接触すると、香料は接触している部分と同じ濃度になろうとして移動する。この様に香料が漂白洗浄剤組成物中を移動することにより、香料が漂白剤等の、香料の分解を促進する物質と接触する機会が増加し、香気安定性が損なわれると考えられる。
【００７３】
ノニオン界面活性剤は、衣料用に用いられる公知のものを特に制限なく用いることができる。
好ましいノニオン界面活性剤としては、例えば以下のものを挙げることができる。
（i）炭素数６〜２２、好ましくは８〜１８の脂肪族アルコールに炭素数２〜４のアルキレンオキシドを平均３〜３０モル、好ましくは５〜２０モル付加したポリオキシアルキレンアルキル（またはアルケニル）エーテル。この中でも、ポリオキシエチレンアルキル（またはアルケニル）エーテル、ポリオキシエチレンポリオキシプロピレンアルキル（またはアルゲニル）エーテルが好適である。ここで使用される脂肪族アルコールとしては、第１級アルコールや、第２級アルコールが使用される。また、そのアルキル基は、分岐鎖を有していてもよい。好ましい脂肪族アルコールとしては、第１級アルコールが使用される。
（ii）ポリオキシエチルアルキル（またはアルケニル）フェニルエーテル。
（iii）長鎖脂肪酸アルキルエステルのエステル結合間にアルキレンオキシドが付加した、例えば以下の式で示される脂肪酸アルキルエステルアルコキシレート。
【００７４】
Ｒ^１ＣＯ（ＯＡ）_ｎＯＲ^２
（Ｒ^１ＣＯは、炭素数６〜２２、好ましくは８〜１８の脂肪酸残基を表わす。ＯＡは、エチレンオキシド、プロピレンオキシドなどの炭素数２〜４、好ましくは２〜３のアルキレンオキシドの付加単位を表わす。ｎは、アルキレンオキシドの平均付加モル数を示し、一般に３〜３０、好ましくは５〜２０の数である。Ｒ^２は、炭素数１〜３の置換基を有してもよい低級アルキル基を表す。）
（iv）ポリオキシエチレンソルビタン脂肪酸エステル。
（v）ポリオキシエチレンソルビット脂肪酸エステル。
（vi）ポリオキシエチレン脂肪酸エステル。
（vii）ポリオキシエチレン硬化ヒマシ油。
（viii）グリセリン脂肪酸エステル。
上記のノニオン界面活性剤の中でも、融点が４０℃以下でＨＬＢが９〜１６のポリオキシエチレンアルキル（またはアルケニル）エーテル、ポリオキシエチレンポリオキシプロピレンアルキル（またはアルケニル）エーテル、脂肪酸メチルエステルにエチレンオキシドが付加した脂肪酸メチルエステルエトキシレート、脂肪酸メチルエステルにエチレンオキシドとプロピレンオキシドが付加した脂肪酸メチルエステルエトキシプロポキシレートなどが特に好適に用いられる。また、これらのノニオン界面活性剤は混合物として使用してもよい。
【００７５】
また、第２の実施形態例においては、洗剤粒子（Ｄ）の割断面の偏光顕微鏡映像から求めた、この割断面中の異方性物質の面積比率は３０〜５０％、好ましくは３４〜３８％とされる。この範囲外では、香気安定性が低下するおそれがある。
【００７６】
洗剤粒子（Ｄ）は、以下の様にして製造することができる。
まず、無機化合物の多孔質体は、例えば噴霧乾燥法；撹拌造粒、転動造粒法、流動層造粒法；などの方法によって以下の様にして製造することができる。
・噴霧乾燥法
無機化合物と水溶性高分子を含有する水性スラリーを噴霧乾燥し、多孔質の無機粒子を得る。なお、このとき、界面活性剤の一部を添加することもできる。
・撹拌造粒、転動造粒法、流動層造粒法
無機化合物の微粒子（平均粒径２００μm以下、好ましくは１５０μm以下）を、水溶性高分子を含有する水溶液などのバインダーを用いて造粒する。
水溶性高分子としては、例えば、アクリル酸／マレイン酸共重合体のナトリウム塩、ポリアクリル酸ナトリウム、ポリアセタールカルボキシレート、ＣＭＣ（カルボキシメチルセルロースのナトリウム塩）、ヒドロキシプロピルセルロース、マレイン酸共重合体のナトリウム塩、ヒロドキシエチルセルロース、ポリビニルピロリドン、ポリビニルアルコールなどを用いることができる。また、無機化合物／水溶性高分子の質量比率は５〜４０程度とされる。
【００７７】
これらの方法で得られる無機化合物の多孔質体は粒子状である。また、多孔質体の平均粒径は２００〜４００μｍ程度であり、また、多孔質体の嵩密度は０．６〜０．８５ｇ／ｍｌとされる。この範囲であると香気安定性が向上し、かつ、好ましくは溶解性が向上し、好ましい。
【００７８】
そして、この様にして得られた無機化合物の多孔質体に、アニオン界面活性剤とノニオン界面活性剤を含む界面活性剤を担持させる。
例えば、撹拌造粒機、転動造粒機、流動層造粒機などを用いて、無機化合物の多孔質体に、好ましくはノニオン界面活性剤とアニオン界面活性剤の水性スラリー（界面活性剤濃度６０〜９０質量％程度）との混合物を一度に、あるいは徐々に添加し、混合しながら行うことが出来る。
【００７９】
第２の実施形態例においても、洗剤粒子（Ｄ）の異方性物質の面積比率は、以下の様に、製造条件を設定あるいは制御することによって、コントロールすることができる。
設定または制御する製造条件は、第１の実施形態例で説明した方法のうち、配合方法；造粒の温度、時間、水分量などの操作条件；配合組成；などである。
なお、この例においては、無機化合物は多孔質体を形成しており、結晶性アニオン界面活性剤の結晶化をコントロールすることが、異方性物質の面積比率による香気安定性向上のために特に有効である。ノニオン界面活性剤は結晶性アニオン界面活性剤の結晶化を抑制する作用があり、アニオン界面活性剤とノニオン界面活性剤とを予め混合すると、結晶性アニオン界面活性剤の結晶化を抑制することができるため、異方性物質の面積比率のコントロールは比較的容易である。
よって、上述の異方性物質の面積比率の値が３０〜５０％になる様に製造条件を設定または、制御することにより、洗剤粒子（Ｄ）を得ることができる。
【００８０】
第２の実施形態例において、洗剤粒子（Ｄ）に配合可能な成分、平均粒径、嵩密度等の例は、第１の実施形態例の洗剤粒子（Ｂ）と同様である。
また、漂白剤含有粒子（Ｃ）と洗剤粒子（Ｄ）とを混合して漂白洗浄剤組成物を得る方法や、漂白洗浄剤組成物に、漂白活性化剤を混合すると好ましい点、他の配合成分が配合可能な点等は第１の実施形態例と同様である。
【００８１】
また、本発明の漂白洗浄剤組成物の製造方法においては、上述の第１乃至第２の実施形態例の様な、結晶性アニオン界面活性剤、結晶性無機化合物を含有し、アニオン界面活性剤を主界面活性剤とする洗剤粒子（Ｂ）または（Ｄ）を製造する場合に、この洗浄剤組成物の割断面の偏光顕微鏡映像から求めた、割断面中の異方性物質の面積比率が、溶解性良好な所定範囲となる様に製造条件を制御または設定して得られる洗剤粒子（Ｂ）、または（Ｄ）を用いることにより、香気安定性の良好、かつ好ましくは溶解性の良好な漂白洗浄剤組成物を得ることができる。
【００８２】
【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。また、特に断りがない限り％は質量％である。
【００８３】
＜使用原料＞
使用原料を以下に示す。
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％）
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）
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℃ ）
ＡＥ・ＥＯ８：ダイアドール１３（三菱化学）の酸化エチレン８モル付加体（ライオン化学（株）製、純分９９％）
ＡＥ・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％）
炭酸ナトリウム：旭硝子（株）製、ソーダ灰
炭酸カリウム：旭硝子（株）製、炭酸カリウム（粉末）
亜硫酸ナトリウム：神州化学（株）製、無水亜硫酸ナトリウム
硫酸ナトリウム：日本化学（株）製、中性無水芒硝Ｋ
ＳＫＳ−６：結晶性層状ケイ酸ナトリウム （ヘキスト社製、製品名ＳＫＳ−６）
ゼオライト：Ａ型ゼオライト （水澤化学（株）製、製品名 シルトンＢ）
ＭＡ剤：アクリル酸／マレイン酸共重合体のナトリウム塩（ＢＡＳＦ社製、製品名 ソカランＣＰ７）
ＰＡＡ−Ｎａ：ポリアクリル酸ナトリウム（ＢＡＳＦ社製、製品名 ソカランＰＡ３０）
蛍光増白剤Ａ（表中には、蛍光剤Ａと記載）：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（表中には、蛍光剤Ｂと記載）：チノパールＡＭＳ−ＧＸ（チバ・スペシャルティ・ケミカルズ）
酵素Ａ：エバラーゼ８Ｔ（製品名、ノボザイムズ社製）
酵素Ｂ：サビナーゼ１２Ｔ（製品名、ノボザイムズ社製）
酵素Ｃ：リポラーゼ ウルトラ５０Ｔ（製品名、ノボザイムズ社製）
香料Ａ：特願２０００−３４６６２６[表１１〜１８]に示す香料組成物Ａ
香料Ｃ：特願２０００−３４６６２６[表１１〜１８]に示す香料組成物Ｃ
色素：群青（大日精化工業社製、Ｕｌｔｒａｍａｒｉｎｅ Ｂｌｕｅ）
ＰＣ剤：漂白剤含有粒子（製品名 ＳＰＣ−Ｄ、三菱ガス化学株式会社製）
・ＯＢＳ−１２：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。
・ＮＯＢＳ：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、ＯＢＳ−１２と同様にして漂白活性化剤造粒物を調製した。
・ＯＢＣ−１０：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、ＯＢＳ−１２と同様にして漂白活性化剤造粒物を調製した。
塩化ナトリウム：並塩（千葉塩業株式会社製）
【００８４】
これらの原料のうち、
結晶性アニオン界面活性剤はα−ＳＦ−Ｎａ、ＡＯＳ−Ｋ、ＡＳ−Ｎａ、石鹸である。
結晶性無機化合物は、炭酸ナトリウム、炭酸カリウム、亜硫酸ナトリウムである。
【００８５】
＜偏光顕微鏡映像からの異方性物質の面積比率＞
粒子状の洗浄剤組成物を分割し、その割断面を顕微鏡用のスライドガラスとカバーグラスにはさみ、測定用試料とした。そして、上述の様にして偏光顕微鏡にて映像を撮影し、画像処理により、異方性物質の面積比率を求めた。
【００８６】
＜香気安定性の評価方法＞
ワックスサンドした板紙（紙秤量 ４５０ｇ／ｍ^２、ワックス ３２g／ｍ^２からなる低吸湿性の紙製洗剤容器（縦１１ｃｍ×横１５ｃｍ×高さ９ｃｍ）に、漂白洗浄剤組成物６００ｇを入れ、密閉した状態で、２５℃、湿度６０％ＲＨと、３５℃、湿度８５％の条件で、それぞれ８時間、１６時間行う恒温試験室に交互に入れ、４０日間静置した。
その後２０℃、湿度６０％に１日静置後、容器上面を開封し、漂白洗浄剤組成物の香気の強さを基準洗剤（香料０．０５質量％で製造直後のもの）と比較し、容器上面から５ｃｍの距離より、以下の基準で評価した。
５点：基準洗剤より香りが強い。
４点：基準洗剤よりやや香りが強い。
３点：基準洗剤と同等の香りである。
２点：基準洗剤よりやや香りが弱い。
１点：基準洗剤より香りが弱い。
以上の評価はパネラー１０人で行い、その平均値を求めた。
【００８７】
＜製造方法Ａ：第１の実施形態例に係る実施例１〜４、比較例１＞
表１に示す組成の内、漂白剤含有粒子、漂白活性化剤含有粒子、ゼオライトの一部、ＡＥ、酵素、色素、香料を除く成分を含有する固形分６３％の水性スラリー（調製温度８０℃、撹拌時間１７分）を噴霧乾燥し、水分５．５質量％の噴霧乾燥粒子を調製した。
この噴霧乾燥粒子とともに、ＡＥ（水分１０質量％）と少量の水道水（東京都江戸川区）を連続ニーダー（栗本鉄工所製、ＫＲＣ−Ｓ４型）に投入し、温度６０℃で連続的に混練し、ペレッター（不二パウダル製、ダイス孔径１０ｍｍφ）で押出して固形洗剤を形成した。
次いで、フィッツミル（ホソカワミクロン（株）製、ＤＫＡＳＯ−６型）を３段直列に配置し、得られた固形洗剤と粉砕助剤としてのゼオライトを（４．３質量％対固形洗剤）１５℃の冷風とともに導入し、平均粒子径が４５０〜５５０μｍとなるよう破砕造粒した。
最後に、転動ドラム内でゼオライト（２．０質量％対粉砕粒子）を加え得られた洗剤粒子を被覆し、漂白剤含有粒子、漂白活性化剤含有粒子、酵素、色素、香料（噴霧）を加えて高嵩密度の粒状の漂白洗浄剤組成物を得た。
このようにして得られた漂白洗浄剤組成物は、嵩密度０．８〜０．９ｇ／ｍＬ、真密度１．１〜１．３ｇ／ｍｌの範囲のものであった。
【００８８】
得られた洗剤粒子（Ｂ）について異方性物質の面積比率を求めた。そして、香気安定性の試験を行い、結果を表１に併せて示した。
【００８９】
【表１】

【００９０】
＜製造方法Ｂ：第２の実施形態例に係る実施例５〜６、比較例１＞
表２に示す無機化合物（炭酸Ｎａ、炭酸Ｋ、硫酸Ｎａ、ＮａＣｌ、ゼオライトの一部、ＳＫＳ−６）と高分子（ＭＡ剤）、ＰＡＡ−Ｎａ、及びアニオン界面活性剤の一部を含有する固形分６０％の水性スラリーを噴霧乾燥して、水分５質量％の噴霧乾燥粒子を調製した。この噴霧乾燥粒子をレディーゲミキサーで、漂白剤含有粒子、漂白活性化剤含有粒子、酵素、香料を除く残りの成分と共に撹拌造粒した。造粒時、予め、アニオン界面活性剤と非イオン界面活性剤とを溶融混合して、レディーゲミキサーに投入し、洗剤粒子を得た。
次いで、ゼオライト（２％）、漂白剤含有粒子、漂白活性化剤含有粒子、酵素造粒物と香料を混合し、平均粒径４００〜４５０μm、嵩密度０．８〜０．９ｇ／ｍｌ、真密度１．０〜１．２ｇ／ｍｌの範囲の粒状の漂白洗浄剤組成物を得た。
この漂白洗浄剤組成物について実施例１〜４と同様に評価し、結果を表２のあわせて示した。
【００９１】
【表２】

【００９２】
＜製造方法Ｃ：第１の実施形態例に係る実施例７〜９、比較例２＞
表３に記載の製造条件以外は、上述の製造方法Ａと同様にして漂白洗浄剤組成物を製造した。
得られた洗浄剤組成物について香気安定性の試験を行い、結果を表３に併せて示した。
【００９３】
【表３】

【００９４】
表３に示した結果より、スラリー配合及び捏和の温度条件が低かった比較例においては、異方性物質の面積比率が高くなり、香気安定性が低下した。一方、第１の実施形態例の構成を満足する実施例においては、香気安定性が良好であった。
【００９５】
（実施例１０）
表３、実施例７の組成のうち、漂白剤含有粒子、漂白活性化剤含有粒子、酵素、香料、ノニオン界面活性剤、色素、及び一部のゼオライトをのぞく成分を水道水に、８０℃に加熱しながら溶解、分散させ、２０分攪拌し、スラリー（固形分濃度６３質量％）を調製した。このスラリーを向流式噴霧乾燥塔を用い、熱風２６０℃で乾燥して噴霧乾燥粒子（平均粒径４００μｍ、嵩密度２７０ｇ／Ｌ、安息角４０℃）を得た。ついで、ノニオン界面活性剤、水分調整用の水道水とともに、連続ニーダー（栗本鐵工所製、ＫＲＣ−Ｓ４型）に投入した。このときの噴霧乾燥粒子の温度は５０℃であった。
ニーダーの温度６０℃、処理速度１８０ｋｇ／ｈｒで連続的に混練し、ペレッター（不二パウダル製、ダイス孔径１０ｍｍ）で固形洗剤を形成した。この固形洗剤を１５℃の冷風（風速１６ｍ／ｓ、気／固比 ２．０ｍ^３／ｋｇ）とともに３段直列に配置したフィッツミル（ホソカワミクロン（株）製、ＤＫＡＳＯ−６型）（１段目：スクリーン径６ｍｍφ、回転数１８８０ｒｐｍ、２段目：スクリーン孔径４ｍｍφ、回転数２３５０ｒｐｍ、３段目：スクリーン孔径２ｍｍφ、回転数３７６０ｒｐｍ）へと導入した。粉砕助剤はゼオライトを４．３質量％（対固形洗剤）導入し、処理速度１８８ｋｇ／ｈｒで平均粒子径が５００〜５５０μｍになるよう粉砕した。
スクリーンを通過した粒子を、転動ドラム（直径０．６ｍｍ、長さ０．４８ｍ、厚さ１ｍｍ×１２０ｍｍ×長さ４８０ｍｍの邪魔板４枚付き、回転数２０ｒｐｍ）内で、残りのゼオライト（２．０質量％対粉砕粒子）で洗剤粒子を被覆してから、漂白剤含有粒子、漂白活性化剤含有粒子、酵素、色素、香料、等を加えて高嵩密度の漂白洗浄剤組成物を製造した。
この条件で継続して製造を行い、定期的（２時間ごと）に洗剤粒子の異方性物質の面積比率を測定した。
製造条件にはときどき振れが生じ、特に捏和前の噴霧乾燥粒子の温度が５０±１０℃で推移したが、洗剤粒子の異方性物質の面積比率は１０．０〜１１．０％で安定していた。
１０時間連続稼働後、１４時間製造機器を停止した。再稼働する際に、スラリー配合温度が下がり（６５℃）、捏和前の噴霧乾燥粒子の温度も低くなり（３５℃）、異方性物質の比率が１１．５％と増加する傾向にあったので、洗剤粒子の異方性物質の面積比率が１０．０〜１１．０％に保たれる様に、スラリー配合温度を７５±５℃に維持した。
この様にして得られた漂白洗浄剤組成物は、平均粒径５００〜５５０μｍ、嵩密度８４０〜８６０ｇ／Ｌ、真密度１．２〜１．３ｇ／ｍｌ、水分７〜８質量％であった。また、異方性物質の面積比率は１０％であった。
香気安定性について評価したところ、４．２であった。
【００９６】
表１〜３に示した結果、及び実施例１０の結果より、本発明に係る実施例では香気安定性が良好であることが確認できた。
【００９７】
【発明の効果】
以上説明した様に、本発明においては、香気安定性の良好な漂白洗浄剤組成物を提供することができる。
【図面の簡単な説明】
【図１】偏光顕微鏡映像を画像処理した図の一例である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a bleaching detergent composition and a method for producing the same.
[0002]
[Prior art]
Conventionally, various solid detergent compositions such as particles have been marketed for clothing. Among these detergent compositions, there are also bleach detergent compositions containing bleach-containing particles (see Patent Documents 1 to 3).
[0003]
[Patent Document 1]
JP-A-02-173199
[Patent Document 2]
JP-A-04-031498 (Japanese Patent No. 2918991)
[Patent Document 3]
JP 08-157877 A
[0004]
[Problems to be solved by the invention]
However, the conventional bleaching detergent composition has a problem that even when a fragrance is blended, the fragrance component is deteriorated during storage, for example, and the fragrance is not stable.
Such a phenomenon is more serious in bleaching detergent compositions containing a bleaching agent than in detergent compositions not containing a bleaching agent.
[0005]
The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a technique capable of stabilizing aroma in a bleaching detergent composition.
[0006]
[Means for Solving the Problems]
The present inventors have found that the stability of the aroma of the bleaching detergent composition differs depending on the production conditions and the like even when the materials used are the same, and have studied diligently based on this.
As a result, the bleaching detergent composition mainly contains detergent particles containing a surfactant and bleaching agent-containing particles containing a bleaching agent. It has been found that the area ratio of the anisotropic substance in the medium can be determined.
In a detergent composition containing a crystalline anionic surfactant and a crystalline inorganic compound, and having an anionic surfactant as a main surfactant, the area ratio is defined within a predetermined range to perform bleaching and washing. It has been found that the stability of the aroma of the agent composition can be remarkably improved, and the present invention has been completed.
That is, the first invention provides a bleaching detergent composition containing bleaching agent-containing particles (A) and detergent particles (B).
The bleaching detergent composition, wherein the detergent particles (B) satisfy the following (1) to (3).
(1) containing a crystalline anionic surfactant and a crystalline inorganic compound,
(2) an anionic surfactant as a main surfactant;
(3) The area ratio of the anisotropic substance in the cross section of the detergent particle (B) is 12% or less, which is obtained from a polarizing microscope image of the cross section.
The second invention provides a bleaching detergent composition containing bleach-containing particles (C) and detergent particles (D).
The bleaching detergent composition, wherein the detergent particles (D) satisfy the following (4) to (6).
(4) containing a crystalline anionic surfactant and a crystalline inorganic compound,
(5) containing a nonionic surfactant (E) exceeding 10% by mass;
(6) The area ratio of the anisotropic substance in the cross section of the detergent particle (D) is 30 to 50%, which is obtained from a polarizing microscope image of the cross section.
A third invention is the bleaching detergent composition according to the first or second invention, further comprising a bleach activator.
A fourth invention is a method for producing the bleach detergent composition according to any one of the first to third inventions,
The production conditions are controlled or set such that the area ratio of the anisotropic substance in the fractured surface obtained from the polarizing microscope image of the fractured surface of the cleaning particles (B) or the detergent particles (D) falls within a predetermined range. A method for producing a bleaching detergent composition, comprising using the detergent particles (B) or the detergent particles (D) produced by the above method.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[Form of bleaching detergent composition]
The invention applies to bleach detergent compositions containing solid detergent particles. The solid detergent particles are not particularly limited as long as they can divide (cut) the particles and obtain a polarizing microscope image of the fractured surface.
Specifically, the form of the bleaching detergent composition is preferably particulate. Depending on the case, various forms such as a sheet form, a tablet form, a briquette form and the like are also possible.
[0008]
[Method for measuring area ratio of anisotropic substance in cross section of detergent particles]
The anisotropic substance is a substance in which a crystalline inorganic compound and a crystalline anionic surfactant are mainly contained in detergent particles in the form of crystals or liquid crystals.
In addition, even if it is a crystalline inorganic compound or a crystalline anionic surfactant, the state of crystallization contained in the final product differs depending on the manufacturing conditions of the detergent particles and the like, and is not always an anisotropic substance.
[0009]
In the method of measuring the area ratio, first, solid detergent particles are divided, and the cut surface is exposed. It is to be noted that only one particle is divided and photographed at one time. Examples of the dividing method include cutting using a microtome and cutting using a cutter or a canner. In any case, it is desirable to prepare the sample as thin as possible. The division position is not particularly limited, but is preferably near the center of the sphere in order to secure the measurement range.
Then, a color image of each of these fractured sections is taken with a polarizing microscope. The polarizing microscope used in this example is Olympus BH-2 (product name).
Although the magnification is not particularly limited, in this example, it is 5 (eyepiece) × 20 (objective), that is, 100 ×. Normally, it is preferably about 20 to 200 times in view of the accuracy and the like when obtaining the area ratio of the anisotropic substance.
Then, for example, a photograph in which the anisotropic substance is dispersed in the matrix is obtained. In this example, the matrix appears purple and the anisotropic material appears as a yellow component and a blue component.
Thereafter, predetermined image processing is performed. In this example, image processing is performed using free software: ImageTool from the University of Texas Health Science Center in San Antonio (downloadable on the Internet).
[0010]
First, a predetermined processing range is cut out from the polarization microscope image. The width of the processing range is set to 20% or more and substantially 70% or less with respect to the entire fractured surface. If it is less than the lower limit, it is too small to perform an accurate evaluation.
Although depending on the form of the detergent particles, for example, in the case of particles having an average particle diameter of about 400 to 700 μm, the processing range is about 50 × 50 μm to 250 × 250 μm in the size before expansion.
Then, this polarized microscope image is decomposed into the three primary colors of light (red, green, and blue). Then, when the green component is converted to black and the other colors are converted to white, a two-tone color diagram as shown in FIG. 1 is obtained. Then, the total area of the black portions distributed is calculated and defined as the area of the anisotropic substance in the present invention. The green component is used as a reference for the anisotropic substance because the yellow and blue portions of the anisotropic substance have almost the same intensity when decomposed into the three primary color components, and the image is processed by a computer. This is because when converting to a two-tone color, more accurate conversion can be performed.
Then, the ratio of the area of the anisotropic substance to the area of the processing range is the area ratio of the anisotropic substance in the fractured surface of the detergent particle, which is obtained from a polarizing microscope image of the fractured surface.
[0011]
The present inventors have found that the area ratio of the anisotropic substance obtained in this manner contains detergent particles containing a crystalline anionic surfactant and a crystalline inorganic compound, and having an anionic surfactant as a main surfactant. It has been found that it is greatly related to the aroma stability of the bleaching detergent composition containing the aroma, and that by defining the value of the area ratio, the aroma stability can be remarkably improved.
[0012]
In the present invention, the crystalline anionic surfactant has a diffraction peak in X-ray diffraction, and is not particularly limited as long as it forms a crystal.
Examples of the crystalline anionic surfactant include the following.
An alkyl sulfate (AS) salt or alkenyl sulfate having 10 to 20 carbon atoms,
An α-olefin sulfonic acid (AOS) salt having 10 to 20 carbon atoms,
A higher fatty acid salt having 10 to 20 carbon atoms,
C8-C20 saturated unsaturated [alpha] -sulfofatty acid ([alpha] -SF) salt or its methyl, ethyl or propyl ester.
[0013]
Examples of other preferable non-crystalline anionic surfactants include the following.
A linear or branched alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms,
An alkanesulfonic acid salt having 10 to 20 carbon atoms,
Having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and having an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9 Alkyl ether sulfate (AES) or alkenyl ether sulfate added at a ratio of 9.9 to 9.9 / 0.1,
Having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and having an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9 An alkyl ether carboxylate or alkenyl ether carboxylate added at a ratio of 9.9 to 9.9 / 0.1,
An alkyl polyhydric alcohol ether sulfate such as an alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms,
These anionic surfactants can be used alone or as a mixture.
[0014]
Particularly preferred anionic surfactants include, for example, alkali metal salts of linear alkylbenzene sulfonic acid (LAS) (eg, sodium or potassium salt) and alkali metal salts of AOS, α-SF, AES, AS (eg, Sodium or potassium salts) and alkali metal salts of higher fatty acids (eg, sodium or potassium salts).
[0015]
The crystalline inorganic compound shows a diffraction peak in X-ray diffraction and an anisotropy in a polarizing microscope image among inorganic compounds generally mixed in detergent particles for clothing. This type of crystalline inorganic compound is almost always incorporated into the detergent particles, for example, as a detergent builder, a particle strength retainer, an oil-absorbing carrier, and the like.
Examples thereof include alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and sodium potassium carbonate; sulfates such as sodium sulfite, sodium sulfate, and potassium sulfate; sodium hydrochloride.
[0016]
Further, “using an anionic surfactant as a main surfactant” means that among the surfactants, an anionic surfactant is most contained.
For example, when all of the surfactants are anionic surfactants or when anionic surfactants and nonionic surfactants are contained, the mass ratio (anionic surfactant / nonionic surfactant) is 1 It is a value exceeding, preferably 2 or more, more preferably 4 or more.
As the amount of the anionic surfactant increases, the amount of the anionic surfactant tends to be increased, so that the relationship between the area ratio of the anisotropic substance and the aroma stability tends to be easily defined.
[0017]
The area ratio of the anisotropic substance does not always correspond to the sum of the crystalline inorganic compound and the crystalline anionic surfactant in the composition.
One reason for this is that not all crystalline inorganic compounds and crystalline anionic surfactants form crystals and are ultimately not contained in detergent particles as anisotropic substances. It is presumed that there is.
[0018]
Hereinafter, the bleaching detergent composition of the present invention will be described with reference to a first embodiment and a second embodiment.
[0019]
[First Embodiment]
The bleaching detergent composition of the first embodiment is a bleaching detergent composition containing bleaching agent-containing particles (A) and detergent particles (B).
The detergent particles (B) satisfy the following (1) to (3). (1) containing a crystalline anionic surfactant and a crystalline inorganic compound,
(2) an anionic surfactant as a main surfactant;
(3) The area ratio of the anisotropic substance in the cross section of the detergent particle (B) is 12% or less, which is obtained from a polarizing microscope image of the cross section.
[0020]
・ Bleaching agent-containing particles (A)
The composition of the bleach-containing particles (A) is not particularly limited as long as the bleach-containing particles are contained. In order to prevent this, treatment such as coating has been performed, and various types 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.
[0021]
Specifically, there may be mentioned, for example, the bleach-containing particles described in Japanese Patent No. 2918991. The bleach-containing particles are obtained by separately spraying an aqueous solution of boric acid and an aqueous solution of an alkali metal silicate onto particles of sodium percarbonate that is kept in a fluid state, and drying and granulating the particles.
[0022]
The average particle size of the bleach-containing particles (A) 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 bleach. It is said.
The amount of the bleaching agent in the bleaching agent-containing particles (A) is from 50 to 95% by mass, preferably from 70 to 90% by mass, from the viewpoint of stability and the like.
The blending amount of the bleach-containing particles (A) in the bleaching detergent composition is 1 to 40% by mass, preferably 2 to 20% by mass from the viewpoint of the bleaching effect.
[0023]
・ Detergent particles (B)
The detergent particles (B) used in the first embodiment are applied to those in which the composition of the main body (inside) of the detergent particles (B) is substantially uniform except for those applied to the surface thereof. It is preferable. The more uniform, the better.
Here, what is applied to the surface is, for example, fine particles blended as a surface modifier, a polymer coating layer provided for suppressing fine powder, and the like.
The term "substantially uniform mixing" means that the respective components are randomly mixed in a particle unit or a molecular unit at the time of molding the detergent particles (B) or the like, so that a uniform state is obtained.
Accordingly, the detergent particles (B) used in the first embodiment were molded after the crystalline anionic surfactant and the crystalline inorganic compound were uniformly mixed or at the same time. It is preferable to apply one.
The true density (used for the bulk density, for example, the density of one particle) of the detergent particles (B) is 0.9 to 1.4 g / ml, preferably 1 to 1.3 g / ml.
[0024]
In the first embodiment, the detergent particles (B) are blended in the bleaching detergent composition in an amount of 55 to 95% by mass, preferably 75 to 90% by mass in view of the washing effect.
The content of the anionic surfactant in the detergent particles (B) is from 10 to 40% by mass, and preferably from 25 to 35% by mass, based on the balance between detergency and other components. Among them, the crystalline anionic surfactant is generally blended in an amount of 20% by mass or more, preferably 30 to 100% by mass of the total anionic surfactant.
The bleaching detergent composition contains the anionic surfactant in an amount of 5 to 40% by mass, preferably 10 to 30% by mass, from the viewpoint of detergency.
[0025]
In addition, the content of the crystalline inorganic compound in the detergent particles (B) is 5 to 50% by mass, and preferably 30 to 40% by mass. If the amount is less than the lower limit, the amount of the detergent builder or the like added becomes small, so that the detergency may decrease. If the upper limit is exceeded, it may be difficult to reduce the area ratio of the anisotropic substance to 12% or less.
The total of the crystalline anionic surfactant and the crystalline inorganic compound is 15 to 60% by mass, preferably 20 to 55% by mass in the detergent particles (B). If the amount is less than the lower limit, there is a problem such as a decrease in detergency. If the amount exceeds the upper limit, it may be difficult to reduce the area ratio of the anisotropic substance to 12% or less.
[0026]
The detergent particles (B) preferably contain zeolite in the detergent particles (B) in an amount of 24% by mass or more, preferably 24 to 50% by mass, more preferably 24 to 40% by mass. If the zeolite content is less than 24% by mass, the solubility, particularly the low-temperature melting property, tends to decrease. In some cases, the area ratio of the anisotropic substance tends to increase.
[0027]
Further, in the present embodiment, the area ratio of the anisotropic substance in the fractured surface of the detergent particle (B) determined from a polarizing microscope image is 12% or less, preferably 10% or less. . Since the fragrance stability is improved as the area ratio is smaller, there is no significance in defining the lower limit, but it is practically 0.1% or more, for example.
By setting the area ratio to 12% or less, an effect of improving solubility can be obtained.
By using the detergent particles (B) having the area ratio of 12% or less, the aroma stability of the bleaching detergent composition is remarkably improved.
The reason why such numerical limitation contributes to the aroma stability is not clear, but is presumed as follows.
That is, in the production of the detergent particles (B), when a fragrance is sprayed on the surface of the particles, the fragrance is attracted to components close to oil, such as a nonionic surfactant, because it is lipophilic. At that time, when the composition of the detergent particles (B) is uniform, using the area ratio of the anisotropic substance of the present invention as a guideline, the fragrance is also uniformly distributed in the detergent particles (B), and the fragrance stability is improved. Is obtained.
On the other hand, when the fragrance is not uniformly distributed, the fragrance adsorbed on the surface of the detergent particles (B) comes into contact with the surface of other particles having a low fragrance concentration during storage or the like. The perfume moves to reach the same concentration as the parts in contact. As described above, it is considered that the perfume moves in the bleaching detergent composition, thereby increasing the chance that the perfume comes into contact with a substance that promotes decomposition of the perfume such as a bleaching agent, and impairs the perfume stability.
[0028]
The detergent particles (B) are produced by various granulation methods such as a kneading and crushing granulation method; a stirring granulation method, a tumbling granulation method; a fluidized bed granulation method; can do.
In particular, as described above, the detergent particles (B) used in the first embodiment are applied to those in which the composition of the main body (inside) except for those applied to the surface is almost uniformly mixed. It is preferable. This is because the effect of the aroma stability is particularly easily exhibited by setting the area ratio of the anisotropic substance to 12% or less.
[0029]
Specifically, for example, at least the surfactant is made into a liquid (molten state, solution state, etc.) or slurry form, and the operation of mixing with other compounding components is performed during or before the step of adjusting the particle size. The detergent particles (B) obtained by the production method performed in the step are preferred.
A typical example of such a method is a kneading crushing granulation method. This means that, when a dough containing a surfactant is formed by kneading, the surfactant such as an anionic surfactant is usually in the form of a solution or a slurry, preferably while the surfactant is melted by heating during mixing. It is a method of mixing.
The anionic surfactant is generally a compound obtained by neutralizing an acid component (acid type precursor) with an alkali component. Therefore, as described later, there is a granulation method in which the acid-type precursor is granulated while being mixed with other components to be mixed with the detergent particles (B) while neutralizing the precursor with an alkali component. This is, for example, mixing an alkali component and other compounding components, dripping a liquid acid-type precursor while stirring, neutralizing the acid precursor with an alkali component, and mixing with other compounding components. This is a kind of rolling granulation method in which the particles are formed almost simultaneously. Also in this case, when the acid-type precursor is in a liquid state, it is mixed with other components, so that the uniformity of the material tends to be higher than, for example, a method of aggregating and granulating a material of solid particles. Is preferred.
[0030]
The operation for each manufacturing method will be described below.
・ Kneading crushing granulation method
Using at least one selected from the following a) to c) as a starting material, together with other components that can be generally blended into the detergent particles (B), preferably by heating with a kneader, while uniformly mixing. Then, the mixture is formed into a dough-like mass, and is subjected to one or both operations of extrusion molding and crushing and granulation to be formed into particles. In addition, when heating with a kneader, a part or all of the anionic surfactant becomes a molten state, and is uniformly mixed with other components.
[0031]
(Starting material)
a) A spray-dried product containing an anionic surfactant and an inorganic compound.
Specifically, for example, the following are mentioned.
-Among the blended components, components that are unstable to heat (for example, nonionic surfactants, enzymes, bleaching agents, bleaching activators, fragrances, and the like) and components that are required in later steps (for example, grinding aids, surfaces) Spray-dried product containing components excluding modifiers).
A spray-dried product mainly composed of an anionic surfactant and containing a small amount of an inorganic compound added for facilitating spray-drying.
A spray-dried product containing some anionic surfactants and some inorganic compounds among the components.
b) concentrated aqueous slurry of anionic surfactant.
For example, it is an aqueous slurry having a solid content of about 60 to 80% by mass obtained by neutralizing an acid-type precursor of an anionic surfactant with an aqueous alkali solution (NaOH, KOH, or the like).
Here, the acid-type precursor refers to a precursor before neutralizing an anionic surfactant with an alkali.
c) An acid precursor of an anionic surfactant.
In this case, LAS-H (linear alkylbenzene sulfonic acid) having excellent stability can be suitably used.
[0032]
At this time, in the kneader, it is preferable to appropriately adjust the water content by adding water or removing water by drying, etc., from the viewpoint of handling and crystallization. It is preferable to attach fine particles such as aluminosilicate, silica, and carbonate to the surface of the particles from the viewpoint of improving fluidity.
After being formed into particles, components such as perfume are further sprayed to obtain detergent particles (B).
[0033]
・ Agitated granulation method, rolling granulation method
Using one or more selected from the above a) to c) as starting materials, together with other compounding components, in a stirring granulator or a tumbling granulator, a liquid component (liquid nonionic surfactant, low molecular weight polyethylene glycol) , An aqueous solution of an anionic surfactant or a polymer) as a binder to granulate the powder component to produce detergent particles (B).
When the above component c) is used as a starting material, excess granular alkali components (carbonate, hydrogencarbonate, etc.) are fluidized in a granulator, and the acid type precursor of the anionic surfactant is gradually dissolved. It is preferable to neutralize the acid type precursor by adding it while maintaining the particle state.
[0034]
・ Fluidized bed granulation
Using the same liquid component as described above as a binder, the powder component is fluidized in an air stream, and the addition and drying of the binder are alternately repeated, thereby granulating the powder component, and forming a particulate detergent. Produce particles (B).
[0035]
・ Spray drying method
This is a method for producing high-bulk-density particulate detergent particles (B) mainly by a spray drying method. For example, known methods described in JP-A-8-501118, JP-A-9-502214, and JP-T10-512007 can be used.
In the apparatus used for granulation, when the amount of water is appropriately adjusted by addition of water or removal of water by drying, etc., it is preferable from the viewpoint of handling and crystallization adjustment. The fact that it is preferable from the viewpoint of improving the fluidity, and that the detergent particles (B) can be obtained by mixing components such as fragrances as necessary after molding into particles, is also kneaded and crushed in other methods. It is the same as the grain method.
[0036]
Further, the area ratio of the anisotropic substance can be controlled by setting or controlling the manufacturing conditions as described below.
The production conditions include, for example, the following conditions for preparing a spray-dried product; a method for blending materials; operating conditions such as the temperature, time, and water content of kneading and granulation; and a composition.
Therefore, by setting or controlling these conditions so that the area ratio of the above-mentioned anisotropic substance is 12% or less, a bleaching detergent composition having good odor stability and preferably good meltability can be obtained. Thus, solid detergent particles (B) that can constitute a product can be obtained.
[0037]
・ Preparation conditions for spray-dried products
The above-mentioned spray-dried product is obtained by preparing an aqueous slurry containing an anionic surfactant and a crystalline inorganic compound, and spray-drying this with other components. However, when the preparation temperature is increased (for example, about 60 to 70 ° C. depending on the composition and the like) and the mixing time is increased, the area ratio of the anisotropic substance can be reduced.
[0038]
・ Blending method
When a compounding ingredient that inhibits crystallization or a compounding ingredient that does not crystallize and a crystalline anionic surfactant are previously uniformly mixed and mixed, crystallization of the crystalline anionic surfactant that occurs during production can be suppressed. . Therefore, the area ratio of the anisotropic substance can be changed by changing the ratio of the crystalline anionic surfactant to be mixed in advance with the component that inhibits crystallization or the component that does not crystallize. Examples of the components that inhibit crystallization and the components that do not crystallize include a noonin surfactant, polyethylene glycol, and a non-crystalline anionic surfactant.
[0039]
・ Manufacturing conditions such as temperature, time, and water content of kneading and granulation
When the temperature is increased, the time is extended, and the water content is increased, the area ratio of the anisotropic substance tends to decrease. Further, when the granulated product of the detergent particles (B) is rapidly cooled, the area ratio of the anisotropic substance tends to decrease.
[0040]
・ Compound composition
The area ratio of the anisotropic substance can be reduced by increasing the amount of the above-mentioned compounding component that inhibits crystallization or the compounding component that does not crystallize.
[0041]
In the detergent particles (B), components used in known detergents can be blended with the above-mentioned essential components without any particular limitation.
These components can be blended when the raw material is formed into a solid state, or can be blended by a method such as spraying.
Hereinafter, components that can be blended will be exemplified. The anionic surfactant has already been exemplified and will not be described. The crystalline inorganic compound overlaps with the above-mentioned examples, but preferred examples are again shown below for each purpose of addition.
[0042]
(1) Fragrance
The bleaching detergent composition is blended with a fragrance so as to be almost indispensable. Usually, a fragrance having bleaching resistance is used. Various kinds of such fragrances are on the market.
Preferred examples include those described in JP-A-09-310097.
The fragrance is added, for example, in an amount of 0.01 to 0.7 part by mass, preferably 0.1 to 0.5 part by mass, per 100 parts by mass of the detergent particles (B).
In the bleaching detergent composition of the present invention, the fragrance generated from the fragrance is stably maintained for a long time, and the effect of the fragrance can be sufficiently exhibited.
[0043]
(2) surfactant
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
As the nonionic surfactant, the same nonionic surfactant as that used in the second embodiment described later can be used.
Preferred amphoteric surfactants include, for example, imidazoline-based and amidobetaine-based amphoteric surfactants. Particularly preferred amphoteric surfactants include, for example, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric amide propyl betaine.
[0044]
(3) Detergent builder
As a detergent builder, an alkali builder and a polyvalent metal cation supplement builder which are usually used in detergents are 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. No.
Polyvalent metal cation supplement builders include aluminosilicate, tripolyphosphate, pyrophosphate, citrate, succinate, polyacrylate, acrylic acid-maleic acid copolymer, iminocarboxylic acid / salt, EDTA and the like.
The detergent builder is generally added to the detergent particles (B) in an amount of 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass.
[0045]
(4) Oil-absorbing carrier
The oil-absorbing carrier is mainly used for absorbing and supporting a liquid component such as a nonionic surfactant.
Preferred oil-absorbing carriers include, for example, silicate compounds such as amorphous hydrous amorphous silicic acid, spherical porous hydrous amorphous silicic acid, amorphous anhydrous amorphous silicic acid, petal-like hydrous amorphous calcium silicate, and acicular hydrous amorphous silica. Examples include amorphous calcium silicate, amorphous aluminosilicate, and magnesium silicate.
Examples of the carbonate compound include magnesium carbonate, calcium carbonate, and ultrafine spinel.
The oil-absorbing carrier is incorporated in the detergent particles (B) in an amount of 0.1 to 25% by mass, preferably 0.5 to 20% by mass, and more preferably 1 to 15% by mass.
[0046]
(5) Clay mineral
As the clay mineral, those belonging to the smectite group and having a dioctahedral three-layer structure or a trioctahedral three-layer structure are preferable. It is desirable that 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.
[0047]
Specific examples include, for example, montmorillonite, nontronite, beidellite, and pyrophyllite as clay minerals having a dioctahedral three-layer structure.
Examples of the clay mineral having a trioctahedral three-layer structure include saponite, hectorite, stevensite, and talc.
The clay mineral is generally added to the detergent particles (B) 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.
[0048]
(6) Fluorescent agent
Examples of the fluorescent agent include a bis (triazonylamino) stilbene disulfonic acid derivative, a bis (sulfostyryl) biphenyl salt [Tinopearl CBS], and the like.
(7) Antistatic agent
Examples of the antistatic agent include cationic surfactants such as dialkyl-type quaternary ammonium salts.
(8) Surface modifier
Examples of the surface modifier include fine calcium carbonate, fine zeolite, and polyethylene glycol.
(9) Recontamination inhibitor
Examples of the anti-redeposition agent include cellulose derivatives such as carboxymethyl cellulose.
(10) Particle strength retaining agent
Examples of the particle strength retaining agent include sodium sulfate, potassium sulfate, and sodium hydrochloride.
(11) Reducing agent
Examples of the reducing agent include sodium sulfite and potassium sulfite.
(12) Various dyes
[0049]
The bulk density of the detergent particles (B) is, for example, 0.6 to 1.0 g / l, preferably 0.75 to 0.90 g / l. If it is less than the lower limit, it is unsuitable as a compact detergent, and if it exceeds the upper limit, the solubility tends to decrease.
The average particle size is from 250 to 1000 μm, preferably from 300 to 800 μm, from the viewpoint of solubility and usability.
[0050]
・ Bleaching activator
By adding a bleach activator to the bleaching detergent composition of the present invention, the bleaching effect of the bleach-containing particles (A) can be further improved, which is preferable. As the bleach activator, organic peracid precursors, metal ions, metal complex catalysts, etc. are known, and hydrogen peroxide (sodium percarbonate, etc.) blended as a bleach is essential as an oxygen supply source. It is.
Since the bleaching activator is unstable with respect to the alkali component, it is blended in a state of being granulated using a binder component such as polyethylene glycol.
Preferred examples of the bleach activator that can be used in the present invention include those represented by the following general formula (I) or (II).
[0051]
Embedded image

[0052]
(Where R¹Is an alkyl or alkenyl group having 7 to 13 carbon atoms;²Is an alkyl or alkenyl group having 7 to 13 carbon atoms, and M is a salt-forming cation or hydrogen. )
In the formula, as the alkyl group and the alkenyl group, any of a linear group and a branched group can be used, but a linear group 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. As M, it is preferable to give water to a bleaching activator such as hydrogen or an alkali metal such as sodium or potassium, or an amine such as ammonium or alkanolamine. Of these, alkali metals are preferred. Where SO₃The M group or COOM group can be in the ortho, meta or para position, with the para position being preferred.
[0053]
Preferred examples of the bleaching activator include those represented by the following general formula (III) or (IV).
[0054]
Embedded image

[0055]
(Where R¹Is an alkyl group having 1 to 6, preferably 1 to 4, particularly preferably 1 to 3, carbon atoms which may be separated by an ester group, an amide group or an ether group;⁶Is an alkylene group having 1 to 8, preferably 2 to 6 carbon atoms which may be separated by an ester group, an amide group or an ether group and may be substituted by a hydroxy group. R², R³, R⁴, R⁵, R⁷, R⁸Is each independently an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, 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. ).
[0056]
The bleach activator of the present invention is blended as granules (bleach activator-containing particles). 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 usually 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, particularly preferably 12 to 18 carbon atoms, and these may be in the form of sodium or potassium soap.
Such a binder material is used in the granulated material in an amount of 0.5 to 30% by mass, preferably 1 to 25% by mass, more preferably 5 to 20% by mass.
[0057]
Further, in order to improve the solubility of the bleaching activator in the washing bath, the granulated material may be a polyoxyalkylene alkyl ether, an olefin sulfonate, an alkylbenzene sulfonate, an alkyl sulfate or a polyoxyethylene. Alkyl ether sulfate or a mixture thereof is preferably incorporated in an amount of 0 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 30% by mass.
[0058]
The polyoxyalkylene alkyl ether preferably has an alkyl group having 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). In any case of EO, PO, or a mixture of EO and PO, the average addition mole number is preferably 4 to 30, more preferably 5 to 15 in total, and the EO / PO molar ratio is preferably 5 / 0/5, more preferably 5/0 to 1/2. As the olefin sulfonate, a sodium or potassium salt of an α-olefin sulfonic acid having an alkyl group having 14 to 18 carbon atoms is preferable.
[0059]
As the alkylbenzenesulfonic acid salt, a sodium or potassium salt of a linear alkylbenzenesulfonic acid having an alkyl group having 10 to 14 carbon atoms is preferable. Further, as the alkyl sulfate salt, an alkyl group having 10 to 18 carbon atoms, and an alkali metal salt such as a sodium salt is preferable, and sodium lauryl sulfate or sodium myristyl sulfate is particularly preferable. As the polyoxyethylene alkyl ether sulfate, a polyoxyethylene alkyl ether sulfate having an alkyl group having 10 to 18 carbon atoms is preferable, and a sodium salt is preferable.
[0060]
Here, the average degree of polymerization of oxyethylene groups (hereinafter, the average degree of polymerization is indicated by POE) is preferably 1 to 10, preferably 1 to 5, and particularly sodium polyoxyethylene lauryl ether sulfate (POE = 2 to 5). ) And sodium polyoxyethylene myristyl ether sulfate (POE = 2-5) are good.
In the present invention, the above composition can be mixed and granulated by any method. In addition, a preferable result can be obtained by adding the binder substance by melting it in advance. The binder material is added by melting 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 by a usual granulator. Extrusion granulation can be mentioned as a preferable granulation method, and it is preferable to form granules having an average particle diameter of 500 μm to 5000 μm, preferably 500 to 3000 μm. Further, as another preferable granulation method, forming into a tablet shape by a briquetting machine can be cited as a preferable granulation method.
[0061]
Further, in the present invention, an acidic substance may be incorporated into the granulated material, if desired, for the purpose of improving the stability of the 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 compounding amount of such an acidic substance is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and most preferably 1 to 10% by mass in the granulated product.
The bleaching activator granules can also contain other components such as coloring agents and fragrances as components other than the above.
The blending amount of the bleaching activator is usually 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, and still more preferably 0.5 to 5% by mass based on the whole composition. .
[0062]
In addition, the following components can be included in the bleaching detergent composition.
・ Various flexibility-imparting agents
·enzyme
Examples of the enzyme include lipase, protease, cellulase, amylase and the like.
[0063]
The bleaching detergent composition of the present invention includes, for example, bleach-containing particles (A), detergent particles (B), and, if necessary, bleach activator-containing particles, enzymes, and a softening agent. Are also mixed in the form of particles).
The bulk density of the bleaching detergent composition is substantially in the same range as the detergent particles (B).
In addition, a fragrance | flavor, a nonionic surfactant, etc. can also be sprayed and mix | blended with the whole bleaching detergent composition at the time of mixing a bleaching agent containing particle (A), a detergent particle (B), etc. as needed.
In addition, the components exemplified as those that can be blended with the detergent particles (B) can be mixed with powder as needed.
[0064]
[Second Embodiment]
The bleaching detergent composition of the second embodiment is a bleaching detergent composition containing bleach-containing particles (C) and detergent particles (D),
The detergent particles (D) satisfy the following (4) to (6). (4) containing a crystalline anionic surfactant and a crystalline inorganic compound,
(5) containing a nonionic surfactant (E) exceeding 10% by mass;
(6) The area ratio of the anisotropic substance in the cross section of the detergent particle (D) is 30 to 50%, which is obtained from a polarizing microscope image of the cross section.
[0065]
In the detergent particles (D), the reason why the fragrance stability is obtained by such numerical limitation is not clear, but is presumed to be the same as in the first embodiment.
[0066]
・ Bleaching agent-containing particles (C)
The bleaching agent-containing particles (C) are the same as in the first embodiment.
[0067]
・ Detergent particles (D)
The detergent particles (D) of the second embodiment are preferably applied to those having a structure in which a surfactant mainly composed of an anionic surfactant is supported on a porous body of an inorganic compound containing a crystalline inorganic compound. .
Inorganic compounds to be added to the detergent particles (D) include the above-mentioned crystalline inorganic compounds and those which do not show anisotropy such as zeolite. It has been blended in.
The detergent particles (D) of this type have good aroma stability and good solubility even if the range of the area ratio of the anisotropic substance is larger than that of the detergent particles (B) of the first embodiment. Good.
[0068]
The reason is not clear, but the following two are considered.
That is, since this type of cleaning composition has a skeleton of an inorganic compound including a crystalline inorganic compound, in a polarizing microscope image, a large number of fine point-like crystalline inorganic compounds are used in the cleaning composition. It is distributed almost uniformly over the entire fractured surface. Therefore, it is presumed that in the polarizing microscope image, anisotropic parts are distributed throughout, and the area ratio of the anisotropic substance becomes apparently a large value.
The true density (used for the bulk density, for example, the density of one particle) of the detergent particles (D) is 0.9 to 1.3 g / ml, preferably 1 to 1.2 g / ml.
[0069]
In the second embodiment, the amount of the detergent particles (D) in the bleaching detergent composition is 55 to 95% by mass, and preferably 75 to 90% by mass from the viewpoint of securing detergency.
In the second embodiment, the content of the anionic surfactant in the detergent particles (D) is from 10 to 30% by mass, and preferably from 15 to 25% by mass, based on the balance between detergency and other components. It is said. Of these, the crystalline anionic surfactant is usually blended in an amount of 20% by mass or more, preferably 30 to 70% by mass of the total anionic surfactant.
[0070]
Further, the amount of the inorganic compound for forming the porous body is 30 to 70% by mass, preferably 45 to 65% by mass in the detergent particles (D). If the amount is less than the lower limit, it is not sufficient to form the skeleton of the detergent particles (D). If the amount exceeds the upper limit, the amount of other components is reduced.
In addition, content of a crystalline inorganic compound is 10-50 mass% in detergent particle (D), Preferably it is 30-40 mass%.
And the total of the crystalline anionic surfactant and the crystalline inorganic compound is 20 to 60% by mass, preferably 20 to 55% by mass in the detergent particles (D). Outside this range, it may be difficult to set the area ratio of the anisotropic substance to a predetermined range. In addition, there is a problem such as a decrease in detergency.
[0071]
Further, the detergent particles (D) of the second embodiment contain more than 10% by mass of the nonionic surfactant (E). Preferably it is 11-40 mass%, More preferably, it is 11-20 mass%.
When a sufficient amount of the nonionic surfactant is blended, crystallization of the crystalline anionic surfactant to be supported on the porous body together with the nonionic surfactant can be prevented, and the area ratio of the anisotropic substance can be controlled within a predetermined range. Can be easily prepared. In addition, solubility can be improved. In addition, the uniform distribution of the detergent component improves the aroma stability. If the amount is less than this range, a sufficient effect cannot be obtained.
[0072]
The reason why the large amount of the nonionic surfactant contributes to the aroma stability is not clear, but is presumed as follows.
That is, as described above, in the production of the detergent particles (D), when a fragrance is sprayed on the surface of the particles, the fragrance is attracted to the nonionic surfactant because it is lipophilic. When the composition contains a large amount of nonionic surfactant and the composition is uniform based on the area ratio of the anisotropic substance of the present invention, the fragrance is also uniformly distributed in the detergent particles (D). Aroma stability is obtained.
On the other hand, when the fragrance is not uniformly distributed, the fragrance adsorbed on the surface of the detergent particles (D) comes into contact with the surface of other particles having a low fragrance concentration during storage or the like. Move to reach the same concentration as the contacting part. It is considered that the movement of the fragrance in the bleaching detergent composition as described above increases the chance that the fragrance comes into contact with a substance that promotes the decomposition of the fragrance such as a bleaching agent, thereby impairing the fragrance stability.
[0073]
As the nonionic surfactant, a known nonionic surfactant used for clothing can be used without particular limitation.
Preferred nonionic surfactants include, for example, the following.
(I) polyoxyalkylene alkyl (or alkenyl) obtained by adding 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, preferably 3 to 30 mol, preferably 5 to 20 mol. ether. Among them, 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. Further, the alkyl group may have a branched chain. As preferred aliphatic alcohols, primary alcohols are used.
(Ii) polyoxyethyl alkyl (or alkenyl) phenyl ether.
(Iii) A fatty acid alkyl ester alkoxylate represented by the following formula, in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
[0074]
R¹CO (OA)_nOR²
(R¹CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents an additional unit of an alkylene oxide having 2 to 4, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide. n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R²Represents a lower alkyl group which may have a substituent having 1 to 3 carbon atoms. )
(Iv) Polyoxyethylene sorbitan fatty acid esters.
(V) Polyoxyethylene sorbite fatty acid ester.
(Vi) Polyoxyethylene fatty acid esters.
(Vii) Polyoxyethylene hydrogenated castor oil.
(Viii) glycerin fatty acid esters.
Among the above-mentioned nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ether having a melting point of 40 ° C. or less and HLB of 9 to 16; polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether; Particularly preferred 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.
[0075]
In the second embodiment, the area ratio of the anisotropic substance in the fractured surface of the detergent particle (D) is 30 to 50%, preferably 34 to 38, which is obtained from a polarizing microscope image of the fractured surface. %. Outside this range, the aroma stability may be reduced.
[0076]
The detergent particles (D) can be produced as follows.
First, a porous body of an inorganic compound can be produced as follows by a method such as a spray drying method; a stirring granulation method, a tumbling granulation method, or a fluidized bed granulation method.
・ Spray drying method
An aqueous slurry containing an inorganic compound and a water-soluble polymer is spray-dried to obtain porous inorganic particles. At this time, a part of the surfactant may be added.
・ Agitation granulation, tumbling granulation, fluidized bed granulation
Fine particles (average particle diameter of 200 μm or less, preferably 150 μm or less) of an inorganic compound are granulated using a binder such as an aqueous solution containing a water-soluble polymer.
Examples of the water-soluble polymer include sodium salt of acrylic acid / maleic acid copolymer, sodium polyacrylate, polyacetal carboxylate, CMC (sodium salt of carboxymethyl cellulose), hydroxypropyl cellulose, and sodium of maleic acid copolymer. Salt, hydroxyethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol and the like can be used. The mass ratio of the inorganic compound / water-soluble polymer is about 5 to 40.
[0077]
The porous body of the inorganic compound obtained by these methods is in the form of particles. The average particle size of the porous body is about 200 to 400 μm, and the bulk density of the porous body is 0.6 to 0.85 g / ml. Within this range, the aroma stability is improved, and the solubility is preferably improved, which is preferable.
[0078]
Then, a surfactant containing an anionic surfactant and a nonionic surfactant is supported on the porous body of the inorganic compound thus obtained.
For example, using a stirring granulator, a tumbling granulator, a fluidized bed granulator, or the like, an aqueous slurry of a nonionic surfactant and an anionic surfactant (surfactant concentration (Approximately 60 to 90% by mass) at once, or gradually adding and mixing.
[0079]
Also in the second embodiment, the area ratio of the anisotropic substance of the detergent particles (D) can be controlled by setting or controlling the manufacturing conditions as described below.
The manufacturing conditions to be set or controlled are, among the methods described in the first embodiment, the blending method; operating conditions such as granulation temperature, time, and water content; and the blending composition.
In this example, the inorganic compound forms a porous body, and controlling the crystallization of the crystalline anionic surfactant is particularly effective for improving the fragrance stability by the area ratio of the anisotropic substance. It is valid. The nonionic surfactant has an action of suppressing crystallization of the crystalline anionic surfactant, and when the anionic surfactant and the nonionic surfactant are mixed in advance, the crystallization of the crystalline anionic surfactant can be suppressed. Therefore, it is relatively easy to control the area ratio of the anisotropic substance.
Therefore, the detergent particles (D) can be obtained by setting or controlling the production conditions so that the value of the area ratio of the anisotropic substance is 30 to 50%.
[0080]
In the second embodiment, examples of components, average particle size, bulk density, and the like that can be blended in the detergent particles (D) are the same as the detergent particles (B) in the first embodiment.
Further, a method of obtaining a bleaching detergent composition by mixing the bleaching agent-containing particles (C) and the detergent particles (D), and a point that it is preferable to mix a bleaching activator with the bleaching detergent composition, The points at which components can be blended are the same as in the first embodiment.
[0081]
Further, in the method for producing the bleaching detergent composition of the present invention, the composition contains a crystalline anionic surfactant and a crystalline inorganic compound as described in the first and second embodiments, and comprises an anionic surfactant. When the detergent particles (B) or (D) having (A) as a main surfactant are produced, the area ratio of the anisotropic substance in the fractured surface obtained from a polarizing microscope image of the fractured surface of the detergent composition is determined. By using the detergent particles (B) or (D) obtained by controlling or setting the production conditions so that the solubility is within a predetermined range, the odor stability is good, and preferably the solubility is good. A bleaching detergent composition can be obtained.
[0082]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples.
First, the raw materials used and evaluation methods used in the examples are as follows. Further, unless otherwise specified,% is% by mass.
[0083]
<Raw materials>
The raw materials used are shown below.
α-SF-Na: sodium salt of α-sulfofatty 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%)
LAS-K: potassium linear alkyl (10 to 14 carbon atoms) benzenesulfonate (Lypon LH-200 manufactured by Lion Corporation (96% pure) neutralized with a 48% aqueous potassium hydroxide solution)
LAS-Na: straight-chain alkyl (C10-14) sodium benzenesulfonate (Lypon LH-200 (96% pure) neutralized with a 48% aqueous sodium hydroxide solution)
AOS-K: potassium α-olefin sulfonate having an alkyl group having 14 to 18 carbon atoms (aqueous slurry with a pure content of 70%, manufactured by Lion Corporation)
AS-Na: sodium alkyl sulfate having an alkyl group having 10 to 18 carbon atoms (Sandet LNM manufactured by Sanyo Chemical Industries, Ltd.)
Soap: Sodium fatty acid having an alkyl group having 12-18 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)
AE · EO8: 8 moles of ethylene oxide adduct of Diadol 13 (Mitsubishi Chemical) (Lion Chemical Co., Ltd., 99% pure)
AE / EO15: 15 mol ethylene oxide adduct of Diadol 13 (Mitsubishi Chemical) (manufactured by Lion Chemical Co., Ltd., 90% pure)
Sodium carbonate: Soda ash manufactured by Asahi Glass Co., Ltd.
Potassium carbonate: made by Asahi Glass Co., Ltd., potassium carbonate (powder)
Sodium sulfite: Anhydrous sodium sulfite manufactured by Shinshu Chemical Co., Ltd.
Sodium sulfate: manufactured by Nippon Chemical Co., Ltd., neutral anhydrous sodium sulfate K
SKS-6: crystalline layered sodium silicate (product name: SKS-6, manufactured by Hoechst)
Zeolite: A-type zeolite (product name: Shilton B, manufactured by Mizusawa Chemical Co., Ltd.)
MA agent: sodium salt of acrylic acid / maleic acid copolymer (manufactured by BASF, product name Sokaran CP7)
PAA-Na: sodium polyacrylate (manufactured by BASF, product name Sokaran PA30)
Fluorescent whitening agent A (in the table, described as fluorescent agent A): Tinopearl CBS-X (Ciba Specialty Chemicals)
Fluorescent whitening agent B (in the table, described as fluorescent agent B): Tinopearl AMS-GX (Ciba Specialty Chemicals)
Enzyme A: Everase 8T (product name, manufactured by Novozymes)
Enzyme B: Savinase 12T (product name, manufactured by Novozymes)
Enzyme C: Lipolase Ultra 50T (product name, manufactured by Novozymes)
Fragrance A: Fragrance composition A shown in Japanese Patent Application No. 2000-346626 [Tables 11 to 18].
Perfume C: Perfume composition C shown in Japanese Patent Application No. 2000-346626 [Tables 11 to 18].
Dye: Ultramarine (Ultramarine Blue)
PC agent: Bleaching agent-containing particles (product name SPC-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
OBS-12: 70 parts by mass of sodium 4-dodecanoyloxybenzenesulfonate as a bleach activator, 20 parts by mass of PEG [polyethylene glycol # 6000M (manufactured by Lion Corporation)], α-olefin sulfonic acid having 14 carbon atoms A sodium powder product (Lipolane PJ-400 (manufactured by Lion Corporation)) is charged into Extruded Omics EM-6 type manufactured by Hosokawa Micron Co., Ltd. at a ratio of 5 parts by mass to a total of 5,000 g, and is kneaded and extruded to obtain a diameter. Obtained a noodle-shaped extruded product having a diameter of 0.8 mmφ. The extruded product (60 ° C.) was introduced into Fitzmill DKA-3 manufactured by Hosokawa Micron Corporation, and 5 parts by mass of zeolite A powder was supplied as an auxiliary in the same manner and pulverized to obtain a bleaching activity having an average particle size of about 700 μm. An agent granulated product was obtained.
NOBS: A bleach activator granule was prepared in the same manner as OBS-12 except that sodium 4-nonanoyloxybenzenesulfonate was used as the bleach activator.
OBC-10: A bleach activator granule was prepared in the same manner as OBS-12, except that 4-decanoyloxybenzoic acid was used as the bleach activator.
Sodium chloride: normal salt (manufactured by Chiba Salt Industry Co., Ltd.)
[0084]
Of these ingredients,
Crystalline anionic surfactants are α-SF-Na, AOS-K, AS-Na, and soap.
Crystalline inorganic compounds are sodium carbonate, potassium carbonate and sodium sulfite.
[0085]
<Area ratio of anisotropic substance from polarizing microscope image>
The particulate detergent composition was divided, and the fractured surface was sandwiched between a microscope slide glass and a cover glass to obtain a measurement sample. Then, an image was taken with a polarizing microscope as described above, and the area ratio of the anisotropic substance was determined by image processing.
[0086]
<Evaluation method of aroma stability>
Paperboard with wax sand (paper weighing 450g / m², Wax 32g / m²600 g of the bleaching detergent composition is placed in a low-hygroscopic paper detergent container (length 11 cm × width 15 cm × height 9 cm) consisting of: 25 ° C., humidity 60% RH, 35 ° C., humidity Under a condition of 85%, they were alternately placed in a constant temperature test chamber for 8 hours and 16 hours, respectively, and allowed to stand for 40 days.
After that, the container was left standing at 20 ° C. and a humidity of 60% for 1 day, and then the upper surface of the container was opened. From the distance of 5 cm from the upper surface of the container, evaluation was made according to the following criteria.
5 points: Stronger fragrance than standard detergent.
4 points: Slightly stronger than standard detergent.
3 points: Smell equivalent to standard detergent.
2 points: Slightly weaker than standard detergent.
1 point: The fragrance is weaker than the standard detergent.
The above evaluation was performed by 10 panelists, and the average value was obtained.
[0087]
<Manufacturing method A: Examples 1 to 4 according to the first embodiment, Comparative example 1>
Among the compositions shown in Table 1, a 63% solids aqueous slurry (preparation temperature: 80 ° C.) containing components excluding bleaching agent-containing particles, bleaching activator-containing particles, a part of zeolite, AE, enzymes, dyes, and fragrances , Stirring time 17 minutes) to prepare spray-dried particles having a water content of 5.5% by mass.
Along with the spray-dried particles, AE (water content: 10% by mass) and a small amount of tap water (Edogawa-ku, Tokyo) are charged into a continuous kneader (KRC-S4, manufactured by Kurimoto Tekkosho) and continuously kneaded at a temperature of 60 ° C. Then, the mixture was extruded with a pelletizer (made by Fuji Paudal Co., Ltd., die hole diameter: 10 mmφ) to form a solid detergent.
Next, Fitzmill (manufactured by Hosokawa Micron Corporation, DKASO-6 type) was arranged in three stages in series, and the obtained solid detergent and zeolite as a grinding aid (4.3% by mass to solid detergent) at 15 ° C. It was introduced together with cold air, and crushed and granulated so that the average particle diameter became 450 to 550 μm.
Finally, zeolite (2.0% by mass vs. crushed particles) is added in a tumbling drum to coat the obtained detergent particles, and the bleach-containing particles, the bleach activator-containing particles, enzymes, pigments, and fragrance (spray) Was added to obtain a granular bleaching detergent composition having a high bulk density.
The bleaching detergent composition thus obtained had a bulk density of 0.8 to 0.9 g / mL and a true density of 1.1 to 1.3 g / mL.
[0088]
With respect to the obtained detergent particles (B), the area ratio of the anisotropic substance was determined. Then, an aroma stability test was performed, and the results are shown in Table 1.
[0089]
[Table 1]

[0090]
<Manufacturing method B: Examples 5 to 6 according to the second embodiment, Comparative example 1>
Contains inorganic compounds (Na carbonate, K carbonate, Na sulfate, NaCl, part of zeolite, SKS-6), polymer (MA agent), PAA-Na, and part of anionic surfactant shown in Table 2. The aqueous slurry having a solid content of 60% was spray-dried to prepare spray-dried particles having a water content of 5% by mass. The spray-dried particles were stirred and granulated with a Ladyge mixer together with the bleaching agent-containing particles, the bleaching activator-containing particles, the enzyme, and the remaining components excluding the fragrance. At the time of granulation, an anionic surfactant and a nonionic surfactant were melt-mixed in advance, and then charged into a Ladyge mixer to obtain detergent particles.
Next, zeolite (2%), bleach-containing particles, bleach-activator-containing particles, enzyme granules and perfume were mixed, and the average particle size was 400 to 450 μm, the bulk density was 0.8 to 0.9 g / ml, and the A granular bleaching detergent composition having a density in the range of 1.0 to 1.2 g / ml was obtained.
This bleaching detergent composition was evaluated in the same manner as in Examples 1 to 4, and the results are shown in Table 2.
[0091]
[Table 2]

[0092]
<Manufacturing method C: Examples 7 to 9 according to the first embodiment, Comparative example 2>
A bleaching detergent composition was produced in the same manner as in Production Method A described above except for the production conditions described in Table 3.
An aroma stability test was performed on the obtained detergent composition, and the results are shown in Table 3.
[0093]
[Table 3]

[0094]
From the results shown in Table 3, in the comparative example in which the temperature conditions of the slurry mixing and kneading were low, the area ratio of the anisotropic substance was increased, and the aroma stability was reduced. On the other hand, in the examples satisfying the configuration of the first embodiment, the aroma stability was good.
[0095]
(Example 10)
Of the compositions of Table 3 and Example 7, bleaching agent-containing particles, bleaching activator-containing particles, enzymes, fragrances, nonionic surfactants, pigments, and components excluding some zeolites were added to tap water at 80 ° C. The mixture was dissolved and dispersed with heating, and stirred for 20 minutes to prepare a slurry (solid content concentration: 63% by mass). The slurry was dried using hot air at 260 ° C. using a countercurrent spray drying tower to obtain spray-dried particles (average particle size: 400 μm, bulk density: 270 g / L, angle of repose: 40 ° C.). Then, it was put into a continuous kneader (KRC-S4, manufactured by Kurimoto Iron Works) together with a nonionic surfactant and tap water for adjusting water content. At this time, the temperature of the spray-dried particles was 50 ° C.
The mixture was continuously kneaded at a kneader temperature of 60 ° C. and a processing speed of 180 kg / hr, and a solid detergent was formed with a pelletizer (made by Fuji Paudal, die hole diameter: 10 mm). This solid detergent is cooled at a temperature of 15 ° C. (wind speed 16 m / s, air / solid ratio 2.0 m).³/ Kg) and a Fitzmill (DKASO-6 type, manufactured by Hosokawa Micron Corporation) arranged in three stages in series (first stage: screen diameter 6 mmφ, rotation speed 1880 rpm, second stage: screen hole diameter 4 mmφ, rotation speed 2350 rpm, 3 Stage: Introduced to a screen hole diameter of 2 mmφ and a rotation speed of 3760 rpm. As a grinding aid, zeolite was introduced in an amount of 4.3% by mass (based on a solid detergent), and pulverization was performed at a processing speed of 188 kg / hr so that the average particle diameter became 500 to 550 μm.
The particles passing through the screen are transferred to the remaining zeolite (2) in a rolling drum (0.6 mm in diameter, 0.48 m in length, with 4 baffles of 1 mm × 120 mm × 480 mm in length, rotation speed 20 rpm). 0.0% by mass to ground particles) and then adding bleaching agent-containing particles, bleaching activator-containing particles, enzymes, pigments, fragrances, etc. to produce a bleaching detergent composition with a high bulk density. did.
The production was continued under these conditions, and the area ratio of the anisotropic substance of the detergent particles was measured periodically (every 2 hours).
The manufacturing conditions sometimes fluctuated, and especially the temperature of the spray-dried particles before kneading changed at 50 ± 10 ° C., but the area ratio of the anisotropic substance of the detergent particles was stable at 10.0 to 11.0%. Was.
After the continuous operation for 10 hours, the production equipment was stopped for 14 hours. Upon restarting, the temperature of the slurry mixture decreases (65 ° C.), the temperature of the spray-dried particles before kneading also decreases (35 ° C.), and the ratio of the anisotropic substance tends to increase to 11.5%. Therefore, the slurry mixing temperature was maintained at 75 ± 5 ° C. so that the area ratio of the anisotropic substance of the detergent particles was maintained at 10.0 to 11.0%.
The bleaching detergent composition thus obtained had an average particle size of 500 to 550 μm, a bulk density of 840 to 860 g / L, a true density of 1.2 to 1.3 g / ml, and a water content of 7 to 8% by mass. . The area ratio of the anisotropic substance was 10%.
It was 4.2 when evaluated about fragrance stability.
[0096]
From the results shown in Tables 1 to 3 and the result of Example 10, it was confirmed that the Example according to the present invention had good aroma stability.
[0097]
【The invention's effect】
As described above, the present invention can provide a bleaching detergent composition having good aroma stability.
[Brief description of the drawings]
FIG. 1 is an example of a diagram obtained by performing image processing on a polarizing microscope image.

Claims (4)

In a bleaching detergent composition containing bleach-containing particles (A) and detergent particles (B),
A bleaching detergent composition, wherein the detergent particles (B) satisfy the following (1) to (3).
(1) containing a crystalline anionic surfactant and a crystalline inorganic compound,
(2) an anionic surfactant as a main surfactant;
(3) The area ratio of the anisotropic substance in the cross section of the detergent particle (B) is 12% or less, which is obtained from a polarizing microscope image of the cross section. In a bleaching detergent composition containing bleach-containing particles (C) and detergent particles (D),
A bleaching detergent composition, wherein the detergent particles (D) satisfy the following (4) to (6).
(4) containing a crystalline anionic surfactant and a crystalline inorganic compound,
(5) containing a nonionic surfactant (E) exceeding 10% by mass;
(6) The area ratio of the anisotropic substance in the cross section of the detergent particle (D) is 30 to 50%, which is obtained from a polarizing microscope image of the cross section. The bleaching detergent composition according to claim 1, further comprising a bleaching activator. A method for producing a bleaching detergent composition according to any one of claims 1 to 3,
The production conditions are controlled or set so that the area ratio of the anisotropic substance in the fractured surface obtained from the polarizing microscope image of the fractured surface of the cleaning particles (B) or the detergent particles (D) falls within a predetermined range. A method for producing a bleaching detergent composition, comprising using the detergent particles (B) or the detergent particles (D) produced by the above method.

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