JP2004210927A

JP2004210927A - Surfactant composition

Info

Publication number: JP2004210927A
Application number: JP2002381246A
Authority: JP
Inventors: Katsuhiko Kasai; 克彦笠井
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2002-12-27
Filing date: 2002-12-27
Publication date: 2004-07-29

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition containing crystalline layered sodium silicate of a specific structure which exhibits improved preservation stability and suffers from no deterioration in deterging performances after a long-term preservation. <P>SOLUTION: The detergent composition comprises a detergent particle and, existing on the surface thereof, (a) crystalline layered sodium silicate represented by formula (I): NaMO-x(SiO<SB>2</SB>)-y(H<SB>2</SB>O) (M is sodium and/or hydrogen; x is 1.5-2.6; and y is 0-20) having a particle size of 1-100 μm and/or formula (II): z(NaMO)-w(SiO<SB>2</SB>)-v(Me<SB>m</SB>O<SB>n</SB>)-u(H<SB>2</SB>O) (M is sodium or hydrogen; Me is calcium and/or magnesium; w/z is 1.5-2.6; v/z is 0.001-1.0; n/m is 0.5-2.0; and u is 0-20), and (b) a deliquescent potassium and/or lithium salt having a particle size of 1-50 μm. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【０００１】
【発明の属する技術分野】
本発明は、特定構造の結晶性層状珪酸ナトリウムを含有する洗浄剤組成物及び、特定構造の結晶性層状珪酸ナトリウムの安定化剤の使用に関する。
【０００２】
【従来の技術】
アルカリ金属珪酸塩は、カチオン交換能を有するイオン交換体であり、古くから洗浄剤用のビルダー等に利用されている。その特徴はアルミノケイ酸塩系の洗浄剤用ビルダーであるゼオライトと異なり、水に対して溶解性を持つことである。このため洗浄後のすすぎ性が良好で、衣類への残留性が低い等といった利点がある。またアルカリ緩衝能を有している点もゼオライトにはない機能である。このようなことから、近年Ｃａイオン交換能にすぐれたケイ酸塩の開発が活発になっている。
【０００３】
例えば、特定構造の結晶性アルカリ金属珪酸塩（例えば、特許文献１、２、３参照。）は、優れたアルカリ能を有するばかりでなく、ゼオライトに匹敵しうるカチオン交換容量をも有するマルチビルダーであるとして、高嵩密度化や低使用量化等の消費者の指向とあいまって、商品化されている。これら結晶性アルカリ金属珪酸塩の性能を十分に発揮させる方法として、その平均粒径が０．１〜１０μｍ程度に調整されたものを用いることが好ましいことが知られている（例えば、非特許文献１参照。）。
【０００４】
しかしながら、特に特定構造の結晶性層状珪酸ナトリウムは、洗浄剤組成物に配合された場合、吸湿性や吸炭酸ガス性が高いため、比表面積が高まる微粒化された状態においては、固化しやすく、またカチオン交換能が低下する等、保存安定性に大いに課題があった。
【０００５】
この課題に対しては、例えばローラーコンパクター処理を施すことにより顆粒化し、該顆粒を洗剤粒子群にアフターブレンドして用いる方法が知られている（例えば、特許文献４参照。）。また、結晶性アルカリ金属珪酸塩とアルミノ珪酸塩が特定比率で混合された共粒質物をローラーコンパクター処理を施すことにより、平均粒径が５００μｍ程度の顆粒を得る記載がある（例えば、特許文献５参照。）。
【０００６】
しかし、これらの顆粒を洗浄剤組成物に配合（ブレンド）した場合には、製品として容器充填された後の輸送時の振動等に起因する分級等により製品中で結晶性アルカリ金属珪酸塩が不均一化してしまう危険性があり、それを回避するために、洗浄剤組成物の粒径や流動性等の粉末物性を制御する等の工夫を施さねばなければならないという制限が加わる。また、別途調製した洗浄剤組成物に対して、単純にアフターブレンドしている点から、これらの顆粒成分は、洗浄剤組成物を構成する粉体化助剤（例えば吸油基剤や表面改質剤）としての役割を全く見込むことが出来ないため、総組成量が増大し、洗浄剤使用量のコンパクト化を行う上で不利である等の問題点を抱えていた。
【０００７】
【特許文献１】
特開昭６０―２２７８９５号公報
【特許文献２】
特開平５―２７９０１３号公報
【特許文献３】
特開平７―０８９７１２号公報
【特許文献４】
特開平３―１６４４２２号公報
【特許文献５】
特開平６―４１５８５号公報
【非特許文献１】
第２８回洗浄に関するシンポジウム講演要旨集１６７頁
（日本油化学協会、１９９６年）
【０００８】
【発明が解決しようとする課題】
本発明の課題は、保存安定性が改善され、長期保存後においても洗浄性能が劣化しない、特定構造の結晶性層状珪酸ナトリウムを含有する洗浄剤組成物を提供することにある。
【０００９】
【課題を解決するための手段】
即ち、本発明の要旨は、
〔１〕（ａ）粒子径１〜１００μｍの下記式（Ｉ）及び／又は（ＩＩ）で表される結晶性層状珪酸ナトリウム、及び（ｂ）粒子径１〜５０μｍの潮解性のカリウム及び／又はリチウム塩が洗浄剤粒子表面に存在してなる洗浄剤組成物、
ＮａＭＯ・ｘ（ＳｉＯ_２）・ｙ（Ｈ_２Ｏ）（Ｉ）
（式中、Ｍはナトリウム及び／又は水素を表し、ｘは１．５〜２．６の数を表し、ｙは０〜２０の数を表す。）
ｚ（ＮａＭＯ）・ｗ（ＳｉＯ_２）・ｖ（ＭｅｍＯｎ）・ｕ（Ｈ_２Ｏ）（ＩＩ）
（式中、Ｍはナトリウム又は水素を表し、Ｍｅはカルシウム及び／又はマグネシウムを表し、ｗ／ｚは１．５〜２．６の数であり、ｖ／ｚは０．００１〜１．０の数であり、ｎ／ｍは０．５〜２．０の数であり、ｕは０〜２０の数を表す。）
〔２〕洗浄剤粒子表面に、（ａ）粒子径１〜１００μｍの前記式（Ｉ）及び／又は（ＩＩ）で表される結晶性層状珪酸ナトリウム、及び（ｂ）粒子径１〜５０μｍの潮解性のカリウム及び／又はリチウム塩を添加して得られる洗浄剤組成物、並びに
〔３〕（ｂ）粒子径１〜５０μｍの潮解性のカリウム及び／又はリチウム塩の、（ａ）粒子径１〜１００μｍの前記式（Ｉ）及び／又は（ＩＩ）で表される結晶性層状珪酸ナトリウムの安定化剤としての使用
に関するものである。
【００１０】
【発明の実施の形態】
＜（ａ）成分＞
本発明の洗浄剤組成物においては、（ａ）洗浄剤粒子表面に粒子径１〜１００μｍの下記式（Ｉ）及び／又は（ＩＩ）で表される結晶性層状珪酸ナトリウムが存在する。
ＮａＭＯ・ｘ（ＳｉＯ_２）・ｙ（Ｈ_２Ｏ）（Ｉ）
（式中、Ｍはナトリウム及び／又は水素を表し、ｘは１．５〜２．６（好ましくは１．７〜２．２）の数を表し、ｙは０〜２０（好ましくは実質的に０）の数を表す。）
ｚ（ＮａＭＯ）・ｗ（ＳｉＯ_２）・ｖ（ＭｅｍＯｎ）・ｕ（Ｈ_２Ｏ）（ＩＩ）
（式中、Ｍはナトリウム又は水素を表し、Ｍｅはカルシウム及び／又はマグネシウムを表し、ｗ／ｚは１．５〜２．６（好ましくは１．７〜２．２）の数であり、ｖ／ｚは０．００１〜１．０（好ましくは０．００５〜０．６）の数であり、ｎ／ｍは０．５〜２．０（好ましくは実質的に１．０）の数であり、ｕは０〜２０（好ましくは実質的に０）の数を表す。）
【００１１】
洗浄性能、安定性の点で、前記（ａ）成分の粒子径は、１〜５０μｍが好ましく、１〜３０μｍがより好ましく、５〜２０μｍが更に好ましい。
【００１２】
洗浄性能、安定性の点で、式（Ｉ）及び／又は（ＩＩ）で表される結晶性層状珪酸ナトリウム中の（ａ）成分は、５０質量％以上が好ましく、７０質量％以上がより好ましく、９０質量％以上が更に好ましい。
【００１３】
洗浄性能、安定性の点で、洗浄剤粒子表面上の（ａ）成分の量は、１〜３０質量％が好ましく、３〜２０質量％がより好ましく、５〜１５質量％が更に好ましい。
【００１４】
＜（ｂ）成分＞
本発明の洗浄剤組成物においては、洗浄剤粒子表面に粒子径１〜５０μｍの潮解性のカリウム及び／又はリチウム塩が存在する。
【００１５】
本発明においては、かかる（ｂ）成分と前記（ａ）成分とを併用して、これらの成分が洗浄剤粒子表面に存在することに一つの大きな特徴があり、かかる特徴を有することで、本発明の洗剤組成物は、保存安定性が改善され、長期保存後においても洗浄性能が劣化しないという優れた効果が発現される。
【００１６】
前記のような効果が発現するメカニズムは明確ではないが、（ａ）成分が劣化を起こす保存条件下、潮解によってもたらされる（ｂ）成分のカリウムイオン及びリチウムイオンの少なくとも一部が、（ａ）成分のカチオン成分と置換することによって、（ａ）成分の安定化が発現すると考えられる。従って、本発明は、（ａ）成分の安定化剤としての（ｂ）成分の使用に関する。
【００１７】
洗浄性能、安定性の点で、（ｂ）成分の粒子径は、３〜３０μｍが好ましく、５〜２０μｍがより好ましい。
【００１８】
（ｂ）成分としては、塩化リチウム、炭酸カリウム、水酸化カリウム、ピロリン酸カリウム、リン酸三カリウム、臭化カリウム等が挙げられる。洗浄性能の点で潮解性のカリウム塩が好ましく、中でも炭酸カリウム、ピロリン酸カリウム、リン酸三カリウムがより好ましく、炭酸カリウムが更に好ましい。
【００１９】
洗浄性能、安定性の点で、潮解性のカリウム及び／又はリチウム塩中の（ｂ）成分は、５０質量％以上が好ましく、７０質量％以上がより好ましく、９０質量％以上が更に好ましい。
【００２０】
洗浄性能、安定性の点で、洗浄剤粒子表面上の（ｂ）成分の量は、０．１〜２０質量％が好ましく、０．５〜１０質量％がより好ましく、１〜５質量％が更に好ましい。特に、洗浄剤粒子表面上の（ａ）成分と（ｂ）成分の質量比は、３０／７０〜９９／１が好ましく、５０／５０〜９５／５がより好ましく、７０／３０〜９０／１０が更に好ましい。
【００２１】
＜（ｃ）成分＞
本発明の洗浄剤組成物においては、安定性の点で、（ｃ）洗浄剤粒子表面に粒子径０．１〜５０μｍの水不溶性無機化合物が存在することが好ましい。
【００２２】
洗浄性能、安定性の点で、（ｃ）成分の粒子径は、０．３〜３０μｍが好ましく、０．５〜１５μｍがより好ましい。
【００２３】
水不溶性無機化合物としては、結晶性もしくは非晶質のアルミノ珪酸塩や、二酸化珪素、珪酸カルシウム、水和珪酸化合物、パーライト、クレイ、タルク、ベントナイト、等が挙げられる。中でも、結晶性もしくは非晶質のアルミノ珪酸塩や、二酸化珪素、水和珪酸化合物が好適であり、特に金属イオン封鎖能及び界面活性剤の担持能の点で結晶性アルミノ珪酸塩が好ましい。
【００２４】
安定性の点で、洗浄剤粒子表面に存在する水不溶性無機化合物中の（ｃ）成分の量は、５０質量％以上が好ましく、７０質量％以上がより好ましく、９０質量％以上が更に好ましい。
【００２５】
安定性の点で、洗浄剤粒子表面上の（ｃ）成分は１〜３０質量％が好ましく、２〜２５質量％がより好ましく、５〜２０質量％が更に好ましい。特に、洗浄剤粒子表面上の（ａ）成分と（ｃ）成分の質量比は１０／９０〜９０／１０が好ましく、２０／８０〜８０／２０がより好ましく、３０／７０〜７０／３０が更に好ましい。
【００２６】
＜表面改質剤＞
本発明の洗浄剤組成物は、（ｃ）成分のみならず、（ｃ）成分以外の表面改質剤を用いることができる。例えば、金属石鹸、粉末の界面活性剤等の微粉体、カルボキシメチルセルロース、ポリエチレングリコール、ポリアクリル酸ソーダ、アクリル酸とマレイン酸のコポリマー又はその塩等のポリカルボン酸塩等の水溶性ポリマー；脂肪酸が挙げられる。
【００２７】
表面改質剤は（ｃ）成分を含めて洗浄剤組成物中１〜３０質量％が好ましく、２〜２５質量％がより好ましく、５〜２５質量％が更に好ましい。
【００２８】
＜洗浄剤粒子＞
本発明に用いられる洗浄剤粒子としては、酵素含有粒子、漂白剤含有粒子、漂白活性化剤含有粒子、香料含有粒子、ビルダー粒子、柔軟剤粒子、界面活性剤粒子、洗剤ベース粒子等の通常公知の方法で製造される洗浄剤に配合され得る粒子が挙げられる。洗浄剤粒子の代表例としては、結晶性アルミノ珪酸塩、無機塩等を含有するスラリーを噴霧乾燥して得られるベース顆粒群にポリオキシエチレンアルキルエーテル、アルキルベンゼンスルホン酸ナトリウム等を含有する液状の界面活性剤を担持させて得られる粒子が挙げられる。
【００２９】
また、アルカリ緩衝能を付与する観点から、洗浄剤粒子は、炭酸ナトリウムを含有することが好ましい。該炭酸ナトリウム含有量としては、洗浄剤粒子中において、５〜５０質量％が好ましく、１０〜３０質量％がより好ましい。
【００３０】
洗浄剤粒子に用いられる、界面活性剤、ビルダー、アルカリ剤、水溶性ポリマー、再汚染防止剤、柔軟化剤、蛍光増白剤、泡コントロール剤、酵素、酵素安定化剤、着色剤、香料等としては、洗剤の分野で公知のものであればよい。これらの化合物としては、例えば、特許庁公報周知・慣用技術集（衣料用粉末洗剤）平成１０年３月２６日発行に記載のものが挙げられる。
【００３１】
＜洗浄剤組成物＞
本発明の洗浄剤組成物は、前記洗浄剤粒子表面に（ａ）成分及び（ｂ）成分、必要であれば（ｃ）成分を、好ましくは他の表面改質剤とともに添加することで得られる。この添加方法としては、通常公知の表面改質工程において行われる方法であれば、特に限定はない。例えば、（ａ）成分、（ｂ）成分及び（ｃ）成分を予め混合したものを洗浄剤粒子に添加する方法、（ａ）成分、（ｂ）成分及び（ｃ）成分を別々に添加する方法等が挙げられる。
【００３２】
前記のようにして得られる本発明の洗浄剤組成物は、洗浄剤粒子の表面に、（ａ）成分及び（ｂ）成分、要すれば（ｃ）成分やその他の表面改質剤が存在する粒子を含有する。洗浄性能、安定性の点で、該粒子を洗浄剤組成物中５０質量％以上含有することが好ましく、６０質量％以上がより好ましく、７０質量％以上が更に好ましい。
【００３３】
本発明の洗浄剤組成物は、前記洗浄剤粒子の他、酵素含有粒子、漂白剤含有粒子、漂白活性化剤含有粒子、香料含有粒子、ビルダー粒子、柔軟剤粒子、界面活性剤粒子等を添加することができる。
【００３４】
＜平衡相対湿度＞
本発明の洗浄剤組成物の４０℃における平衡相対湿度は、保存安定性の点で１５〜３５％が好ましく、１８〜３２％がより好ましく、２０〜３０％が更に好ましい。平衡相対湿度の測定は、２．４リットル容の防湿容器に本発明の洗浄剤組成物６００ｇと高分子膜湿度センサ（好適にはティアンドディ社製、ＴｈｅｒｍｏＲｅｃｏｒｄｅｒおんどとりＲＨＴＲ−７２ＳとＴＲ−３１１０温湿度センサの組み合わせ）を入れ密閉する。これを４０℃に維持し、２４時間保存する。３０分ごとに湿度測定値を読み取り、変化がなくなった値を平衡相対湿度とする。
【００３５】
本発明の洗浄剤組成物は、以下の物性を有するものが好ましい。
＜嵩密度＞
本発明の洗浄剤組成物は、利便性や廃棄物低減の点で、ＪＩＳＫ３３６２により規定された方法で測定する嵩密度は６００ｇ／Ｌ以上が好ましく、７００ｇ／Ｌ以上がより好ましく、８００ｇ／Ｌ以上が更に好ましい。また、溶解性の点で、嵩密度は１６００ｇ／Ｌ以下が好ましく、１３００ｇ／Ｌ以下がより好ましく、１０００ｇ／Ｌ以下が更に好ましい。
【００３６】
＜平均粒径＞
洗浄力、溶解性の点で、ＪＩＳＺ８８０１の標準篩を用いて５分間振動させた後、篩目のサイズによる質量分率から求める平均粒径は１５０〜７００μｍが好ましく、より好ましくは１５０〜６００μｍ、更に好ましくは１８０〜５００μｍである。
【００３７】
＜水分＞
保存安定性の点で、洗浄剤組成物の水分は５質量％以下が好ましく、０．１〜５質量％がより好ましく、０．５〜３質量％が更に好ましく、０．５〜２．５質量％が特に好ましい。
【００３８】
＜ｐＨ＞
本発明の洗浄剤組成物としては、０．０５質量％の水溶液にした場合、洗浄性能、損傷性の点で、ＪＩＳＫ３３６２：１９９８記載の２０℃で測定するｐＨが８〜１２が好ましく、９〜１１．５がより好ましく、９．５〜１１が更に好ましく、１０〜１１が特に好ましい。
【００３９】
【実施例】
〔洗剤粒子の調製〕
（ベース顆粒群Ａの調製）
下記の手順にてベース顆粒群Ａを作製した。
水４５８ｋｇを攪拌翼を有した１ｍ^３の混合槽に加え、水温が５０℃に達した後に、硫酸ナトリウム８０ｋｇ、亜硫酸ナトリウム５ｋｇ、炭酸ナトリウム１３０ｋｇ、蛍光染料２ｋｇ、４０重量％のポリアクリル酸ナトリウム水溶液６５ｋｇ、結晶性アルミノ珪酸塩２２０ｋｇを順次添加した後、３０分攪拌して均質なスラリーを得た。
このスラリーを６０℃に保持し、噴霧乾燥塔の塔頂付近に設置した圧力噴霧ノズルから噴霧圧力２．５ＭＰａで噴霧を行った。噴霧乾燥塔に供給する高温ガスは塔下部より温度が２１０℃で供給され、塔頂より１０５℃で排出された。得られたベース顆粒群Ａの組成及び物性を表１に示す。なお、使用した原料を以下に示す。
【００４０】
〔使用した原料〕結晶性アルミノ珪酸塩（トヨビルダー、東ソー（株）製）、炭酸ナトリウム（デンス灰：セントラル硝子（株）製）、硫酸ナトリウム（無水中性芒硝：四国化成（株）製）、亜硫酸ナトリウム（亜硫酸ソーダ：三井東圧（株）製）、ポリアクリル酸ナトリウム水溶液（分子量１万、花王（株）製）、蛍光染料（チノパールＣＢＳ−Ｘ：チバスペシャリティケミカルス社製）
【００４１】
【表１】

【００４２】
（界面活性剤Ａの調製）
下記の手順にて界面活性剤Ａを作製した。
ポリオキシエチレンアルキルエーテル１０００ｇと６０重量％のポリエチレングリコール水溶液１６７ｇを攪拌翼を有した３Ｌの混合槽に加え、温度が６０℃に達した後に、ジャケットに１０℃の水を流して冷却しながら、アルキルベンゼンスルホン酸１２１７ｇと４８重量％の水酸化ナトリウム水溶液３３０ｇを同時に２０分間で添加した。混合液の温度は９０℃であった。該混合液にパルミチン酸４６ｇを添加した。得られた界面活性剤Ａの組成及び物性を表２に示す。なお、使用した原料を以下に示す。
【００４３】
〔使用した原料〕ポリオキシエチレンレンアルキルエーテル（エマルゲン１０８ＫＭ（エチレンオキサイド平均付加モル数：８．５、アルキル鎖の炭素数：１２〜１４、融点：１８℃）：花王（株）製）、ポリエチレングリコール（ＸＧ−１３００（平均分子量：１３０００）：花王（株）製）、アルキルベンゼンスルホン酸（ネオペレックスＦＳ：花王（株）製）、パルミチン酸（ルナックＰ−９５：花王（株）製）
【００４４】
【表２】

【００４５】
実施例１、２（洗浄剤粒子群の調製）
前記ベース顆粒群Ａに、前記界面活性剤Ａを添加して担持させた後、以下に示すようにａ）結晶性層状アルカリ金属珪酸塩、ｂ）塩化リチウムおよびｃ）不溶性無機粉末で表面被覆を行い、本発明の洗浄剤粒子群１を得た。
先ず、レディゲミキサー（松坂技研（株）製、容量２０Ｌ、ジャケット付）に上記ベース顆粒群Ａ、５５重量部を投入し、主軸：６０ｒ／ｍｉｍ、チョッパー：停止の攪拌条件にて攪拌を開始した。なお、ジャケットには８０℃の温水を流した。そこに、８０℃に保温した界面活性剤Ａ、２５重量部を噴霧ノズル（スプレーイングシステムスジャパン製、ＴＰ８００１５−ＳＳ）を用いて噴霧圧力０．２８ＭＰａで噴霧した。噴霧時間は２分間で、その後４分間攪拌を行い洗剤生地粒子群Ａを得た。続いて、ジャケットへの温水の供給を続けながら、このミキサー内にａ）結晶性層状アルカリ金属珪酸塩、ｂ）塩化リチウムおよびｃ）不溶性無機粉末（結晶性アルミノ珪酸塩；トヨビルダー：平均粒径３μｍ）を予め別途レディゲミキサーで十分に混合した表面改質剤（質量比ａ：ｂ：ｃ＝９：２：９）２０重量部を投入し、主軸：１２０ｒ／ｍｉｍ、チョッパー：３６００ｒ／ｍｉｎの攪拌条件にて１分間攪拌を行った後、洗浄剤粒子群１を排出した。ここで、塩化リチウムは、シグマアルドリッチ社製試薬ＳＡＪ一級を振動ミルにて平均粒径５μｍに粉砕したものを用いた。また、結晶性層状アルカリ金属珪酸塩はトクヤマシルテック社製、商品名：プリフィード（粉末）を、ローラーミル（石川島播磨重工業（株）製）にて平均粒径９μｍに粉砕したものを用いた。その組成式は、Ｎａ_２Ｏ・２．０ＳｉＯ_２であった。
【００４６】
実施例２
ｂ）成分として炭酸カリウム（シグマアルドリッチ社製試薬「ＳＡＪ」（一級）をアトマイザー（不二パウダル（株）製）にて平均粒径５μｍに粉砕したもの）を用いた以外は実施例１と同様の方法で洗浄剤粒子群２を得た。
【００４７】
比較例１
表面改質剤としてａ）結晶性層状アルカリ金属珪酸塩およびｃ）不溶性無機粉末（トヨビルダー：平均粒径３μｍ）、を予め別途レディゲミキサーで十分に混合した（質量比、ｂ：ｃ＝１：１）２０質量部を用いた以外は、実施例１と同様の方法で洗浄剤粒子群３を得た。
【００４８】
比較例２
表面改質剤として、ａ）炭酸カリウム（シグマアルドリッチ社製試薬ＳＡＪ一級）をアトマイザー（不二パウダル（株）製）にて平均粒径５μｍに粉砕したもの、およびｃ）不溶性無機粉末（トヨビルダー：平均粒径３μｍ）とを予め別途レディゲミキサーで十分に混合した（質量比、ａ：ｂ＝１：９）２０質量部を用いた以外は、実施例１と同様の方法で、洗剤粒子群４を得た。
【００４９】
得られた洗浄剤粒子群１〜４の物性を以下の方法に従って測定した。得られた結果を表３に示す。なお、嵩密度、平衡相対湿度は、前記の方法に従って測定した。
【００５０】
（ケーキング性）：ＪＩＳＰ３８０１に規定される２種型ろ紙（例えば、東洋濾紙（株）製「定性Ｎｏ２濾紙」）を用いた縦×横×高さ＝１０ｃｍ×６ｃｍ×４ｃｍの上面が開口した容器を作った。この箱に試料（洗浄剤粒子群）１００ｇを入れ、その上にアクリル樹脂板と鉛板（又は鉄板）の合計重量１５ｇ＋２５０ｇをのせた。これを温度４０℃の恒温、湿度を１サイクル８０％１２時間、５０％２４時間の条件で５サイクル後にケーキング状態について判定を行った。判定は、以下のようにして通過率を求めることによって行った。通過率が高いほど、ケーキング性が低く、洗浄剤組成物として好ましい物性である。
（通過率）：試験後の試料を篩（ＪＩＳＺ８８０１規定の目開き４７６０μｍ）上に静かにあけ、通過した粉末の重量を計り、試験後の試料に対する通過率を求める。
【００５１】
（Ｃａイオン交換能）：試料０．０４ｇを精秤し、塩化カルシウム溶液（濃度はＣａＣＯ_３として１００ｐｐｍ）１００ｍＬ中に加え、２０℃で１０分間攪拌した。その後、得られた液体を０．２μｍのフィルターでろ過し、ろ液１０ｍＬ中に含まれるＣａ量（ＣａＣＯ_３換算量）をＥＤＴＡ滴定により定量した。その値よりＣａイオン交換能を求めた。
評価基準 ○：保存後の減少が１０％未満。
△：保存後の減少が１０〜３０％未満。
×：保存後の減少が３０％以上。
【００５２】
（洗浄力試験）：
（人工汚染布の調製）
下記組成の人工汚染液を布に付着して人工汚染布を調製した。人工汚染液の布への付着は、グラビアロールコーターを用いて人工汚染液を布に印刷することで行った。人工汚染液を布に付着させ人工汚染布を作製する工程は、グラビアロールのセル容量５８ｃｍ^３／ｃｍ^２、塗布速度１．０ｍ／ｍｉｎ、乾燥温度１００℃、乾燥時間１分で行った。布は木綿金巾２００３布（谷頭商店製）を使用した。人工汚染液の組成は、ラウリン酸０．４重量％、ミリスチン酸３．１重量％、ペンタデカン酸２．３重量％、パルミチン酸６．２重量％、ヘプタデカン酸０．４重量％、ステアリン酸１．６重量％、オレイン酸７．８重量％、トリオレイン１３．１重量％、パルミチン酸ｎ−ヘキサデシル２．２重量％、スクアレン６．５重量％、卵白レシチン液晶物１．９重量％、鹿沼赤土８．１重量％、カーボンブラック０．０１重量％及びバランス量の水である。
【００５３】
（洗浄条件及び評価方法）
評価用洗剤水溶液１リットルに、上記で作成した１０ｃｍ×１０ｃｍの人工汚染布を５枚入れ、ターゴトメーターにて１００ｒｐｍで洗浄した。洗浄条件は、洗浄時間：１０分、洗浄剤濃度：０．０６７重量％、水の硬度：４°ＤＨ、水温：２０℃、すすぎ：水道水にて５分間であった。洗浄力は汚染前の原布及び洗浄前後の汚染布の５５０ｎｍにおける反射率を自記色彩計（島津製作所製）にて測定し、次式によって洗浄率（％）を求め、５枚の測定平均値を洗浄力として示した。本試験において洗浄率が６０％以上を「○」、６０％未満を「×」で示す。
【００５４】
【数１】

【００５５】
【表３】

【００５６】
表３の結果より、実施例１、２で得られた洗浄剤粒子群１、２は、比較例１、２で得られた洗浄剤粒子群３、４に比べ、耐ケーキング性及び安定性に優れたものであることがわかる。
【００５７】
【発明の効果】
本発明により、保存安定性に優れ、長期保存後においても洗浄性能が劣化しない洗浄剤組成物が得られるという効果が奏される。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a detergent composition containing a crystalline sodium silicate having a specific structure, and a use of a stabilizer for the crystalline sodium lamellar silicate having a specific structure.
[0002]
[Prior art]
Alkali metal silicate is an ion exchanger having a cation exchange ability, and has been used for a long time as a builder for a detergent. Its characteristic is that it is soluble in water, unlike zeolite, which is a builder for aluminosilicate detergents. For this reason, there are advantages such as good rinsing properties after washing and low residual properties on clothes. Another feature that zeolite does not have is that it has an alkaline buffering capacity. For these reasons, the development of silicates having excellent Ca ion exchange capacity has recently been active.
[0003]
For example, a crystalline alkali metal silicate having a specific structure (see, for example, Patent Documents 1, 2, and 3) is a multibuilder having not only excellent alkalinity but also a cation exchange capacity comparable to zeolite. As a matter of fact, it has been commercialized in conjunction with consumer orientation such as higher bulk density and lower usage. It is known that, as a method for sufficiently exhibiting the performance of these crystalline alkali metal silicates, it is preferable to use a crystalline alkali metal silicate whose average particle diameter is adjusted to about 0.1 to 10 μm (for example, Non-Patent Documents). 1).
[0004]
However, in particular, crystalline layered sodium silicate having a specific structure, when blended in a detergent composition, has a high hygroscopicity or carbon dioxide absorption property, and in a atomized state in which the specific surface area increases, it is easy to solidify. In addition, there was a great problem in storage stability such as a decrease in cation exchange ability.
[0005]
To solve this problem, there is known a method of granulating by, for example, performing a roller compactor treatment, and using the granules after-blended with detergent particles (see, for example, Patent Document 4). Further, there is a description that a granule having an average particle size of about 500 μm is obtained by subjecting a cogranulate in which a crystalline alkali metal silicate and an aluminosilicate are mixed at a specific ratio to a roller compactor treatment (for example, Patent Document 5). reference.).
[0006]
However, when these granules are blended (blended) with the detergent composition, the crystalline alkali metal silicate is not contained in the product due to classification caused by vibrations or the like during transportation after the product is filled in a container. There is a risk of uniformity, and in order to avoid this, there is a restriction that the powder composition such as the particle size and fluidity of the detergent composition must be controlled to take measures. In addition, these granules are used as powdering aids (for example, an oil-absorbing base or a surface-modifying agent) constituting the detergent composition, since they are simply after-blended with a separately prepared detergent composition. Since no role as the agent can be expected, the total amount of the composition increases, which is disadvantageous in reducing the amount of the detergent used.
[0007]
[Patent Document 1]
JP-A-60-227895 [Patent Document 2]
Japanese Patent Application Laid-Open No. Hei 5-27913 [Patent Document 3]
JP-A-7-089712 [Patent Document 4]
Japanese Patent Application Laid-Open No. Hei 3-164422 [Patent Document 5]
JP-A-6-41585 [Non-Patent Document 1]
28th Annual Symposium on Cleaning, 167 pages (Japan Oil Chemical Association, 1996)
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a detergent composition containing crystalline layered sodium silicate having a specific structure, which has improved storage stability and does not deteriorate in cleaning performance even after long-term storage.
[0009]
[Means for Solving the Problems]
That is, the gist of the present invention is:
[1] (a) a crystalline layered sodium silicate represented by the following formula (I) and / or (II) having a particle diameter of 1 to 100 μm, and (b) deliquescent potassium and / or a particle diameter of 1 to 50 μm. A detergent composition in which a lithium salt is present on the surface of the detergent particles,
_{NaMO · x (SiO 2) ·} y (H 2 O) (I)
(In the formula, M represents sodium and / or hydrogen, x represents a number of 1.5 to 2.6, and y represents a number of 0 to 20.)
_{z (NaMO) · w (SiO} 2) · v (MemOn) · u (H 2 O) (II)
(Wherein, M represents sodium or hydrogen, Me represents calcium and / or magnesium, w / z is a number from 1.5 to 2.6, and v / z is from 0.001 to 1.0. Is a number, n / m is a number from 0.5 to 2.0, and u represents a number from 0 to 20.)
[2] On the surface of the detergent particles, (a) crystalline layered sodium silicate represented by the formula (I) and / or (II) having a particle diameter of 1 to 100 μm, and (b) deliquescent of a particle diameter of 1 to 50 μm (3) (b) a deliquescent potassium and / or lithium salt having a particle diameter of 1 to 50 μm, and (a) a detergent composition obtained by adding a neutral potassium and / or lithium salt. The present invention relates to the use of 100 μm of the crystalline layered sodium silicate represented by the formula (I) and / or (II) as a stabilizer.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
<(A) component>
In the cleaning composition of the present invention, (a) crystalline layered sodium silicate represented by the following formula (I) and / or (II) having a particle diameter of 1 to 100 μm is present on the surface of the cleaning particles.
_{NaMO · x (SiO 2) ·} y (H 2 O) (I)
(Wherein M represents sodium and / or hydrogen, x represents a number from 1.5 to 2.6 (preferably 1.7 to 2.2), and y represents 0 to 20 (preferably substantially 0).)
_{z (NaMO) · w (SiO} 2) · v (MemOn) · u (H 2 O) (II)
(Wherein M represents sodium or hydrogen, Me represents calcium and / or magnesium, w / z is a number from 1.5 to 2.6 (preferably 1.7 to 2.2), and v / Z is a number of 0.001 to 1.0 (preferably 0.005 to 0.6), and n / m is a number of 0.5 to 2.0 (preferably substantially 1.0). And u represents a number from 0 to 20 (preferably substantially 0).
[0011]
In terms of washing performance and stability, the particle diameter of the component (a) is preferably from 1 to 50 μm, more preferably from 1 to 30 μm, even more preferably from 5 to 20 μm.
[0012]
In terms of washing performance and stability, the component (a) in the crystalline layered sodium silicate represented by the formula (I) and / or (II) is preferably at least 50% by mass, more preferably at least 70% by mass. , 90% by mass or more is more preferable.
[0013]
In terms of cleaning performance and stability, the amount of the component (a) on the surface of the detergent particles is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 5 to 15% by mass.
[0014]
<(B) component>
In the detergent composition of the present invention, a deliquescent potassium and / or lithium salt having a particle size of 1 to 50 μm is present on the surface of the detergent particles.
[0015]
In the present invention, there is one major feature that the component (b) and the component (a) are used in combination, and these components are present on the surface of the detergent particles. The detergent composition of the present invention has an excellent effect that storage stability is improved and cleaning performance is not deteriorated even after long-term storage.
[0016]
The mechanism by which the above-described effects are exhibited is not clear, but at least a part of the potassium ions and lithium ions of the component (b) caused by deliquescence under the storage conditions under which the component (a) deteriorates, It is considered that the component (a) is stabilized by substituting the component with the cationic component. Accordingly, the present invention relates to the use of component (b) as a stabilizer for component (a).
[0017]
In terms of washing performance and stability, the particle diameter of the component (b) is preferably from 3 to 30 μm, more preferably from 5 to 20 μm.
[0018]
Examples of the component (b) include lithium chloride, potassium carbonate, potassium hydroxide, potassium pyrophosphate, tripotassium phosphate, potassium bromide and the like. A deliquescent potassium salt is preferable in terms of washing performance, and among them, potassium carbonate, potassium pyrophosphate, and tripotassium phosphate are more preferable, and potassium carbonate is still more preferable.
[0019]
In terms of washing performance and stability, the component (b) in the deliquescent potassium and / or lithium salt is preferably at least 50% by mass, more preferably at least 70% by mass, and even more preferably at least 90% by mass.
[0020]
In terms of washing performance and stability, the amount of the component (b) on the surface of the detergent particles is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and 1 to 5% by mass. More preferred. In particular, the mass ratio of component (a) to component (b) on the surface of the detergent particles is preferably 30/70 to 99/1, more preferably 50/50 to 95/5, and 70/30 to 90/10. Is more preferred.
[0021]
<(C) component>
In the detergent composition of the present invention, from the viewpoint of stability, it is preferable that a water-insoluble inorganic compound having a particle diameter of 0.1 to 50 μm exists on the surface of the (c) detergent particles.
[0022]
In terms of washing performance and stability, the particle diameter of the component (c) is preferably from 0.3 to 30 μm, more preferably from 0.5 to 15 μm.
[0023]
Examples of the water-insoluble inorganic compound include crystalline or amorphous aluminosilicates, silicon dioxide, calcium silicate, hydrated silicate compounds, pearlite, clay, talc, bentonite, and the like. Among them, crystalline or amorphous aluminosilicates, silicon dioxide, and hydrated silicate compounds are preferred, and crystalline aluminosilicates are particularly preferred in terms of sequestering ability and supporting ability of a surfactant.
[0024]
In terms of stability, the amount of the component (c) in the water-insoluble inorganic compound present on the surface of the detergent particles is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.
[0025]
From the viewpoint of stability, the component (c) on the surface of the detergent particles is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and still more preferably 5 to 20% by mass. In particular, the mass ratio of component (a) to component (c) on the surface of the detergent particles is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, and preferably 30/70 to 70/30. More preferred.
[0026]
<Surface modifier>
In the cleaning composition of the present invention, not only the component (c) but also a surface modifier other than the component (c) can be used. For example, water-soluble polymers such as metal soaps, fine powders such as powdered surfactants, carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, copolymers of acrylic acid and maleic acid or polycarboxylates such as salts thereof; No.
[0027]
The surface modifier contains preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and still more preferably 5 to 25% by mass in the detergent composition including the component (c).
[0028]
<Cleaner particles>
As the detergent particles used in the present invention, generally known enzyme-containing particles, bleach-containing particles, bleach activator-containing particles, fragrance-containing particles, builder particles, softener particles, surfactant particles, detergent base particles and the like. Particles which can be blended in the cleaning agent produced by the method of (1). Typical examples of the detergent particles include a liquid interface containing polyoxyethylene alkyl ether, sodium alkylbenzene sulfonate, etc. in a base granule obtained by spray-drying a slurry containing a crystalline aluminosilicate, an inorganic salt, or the like. Examples include particles obtained by supporting an activator.
[0029]
Further, from the viewpoint of imparting an alkaline buffering ability, the detergent particles preferably contain sodium carbonate. The content of sodium carbonate in the detergent particles is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass.
[0030]
Surfactants, builders, alkaline agents, water-soluble polymers, anti-redeposition agents, softening agents, fluorescent whitening agents, foam control agents, enzymes, enzyme stabilizers, coloring agents, fragrances, etc. used for detergent particles As long as it is known in the field of detergents. These compounds include, for example, those described in the JPO Gazette Well-known / Common Techniques Collection (Powder Detergent for Clothing) published on March 26, 1998.
[0031]
<Cleaning composition>
The cleaning composition of the present invention is obtained by adding the components (a) and (b), and if necessary, the component (c) to the surface of the cleaning particles, preferably together with another surface modifier. . The addition method is not particularly limited as long as it is a method usually performed in a known surface modification step. For example, a method in which components (a), (b) and (c) are premixed and added to the detergent particles, and a method in which components (a), (b) and (c) are separately added. And the like.
[0032]
In the cleaning composition of the present invention obtained as described above, the components (a) and (b), if necessary, the component (c) and other surface modifiers are present on the surface of the cleaning particles. Contains particles. In terms of cleaning performance and stability, the particles preferably contain 50% by mass or more of the particles in the detergent composition, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
[0033]
The detergent composition of the present invention contains, in addition to the detergent particles, enzyme-containing particles, bleach-containing particles, bleach activator-containing particles, fragrance-containing particles, builder particles, softener particles, surfactant particles, and the like. can do.
[0034]
<Equilibrium relative humidity>
The equilibrium relative humidity at 40 ° C. of the cleaning composition of the present invention is preferably from 15 to 35%, more preferably from 18 to 32%, even more preferably from 20 to 30%, from the viewpoint of storage stability. The measurement of the equilibrium relative humidity was carried out in a 2.4-liter moisture-proof container by using 600 g of the cleaning composition of the present invention and a polymer film humidity sensor (preferably Thermo Recorder Ondori RH TR-72S and TR, manufactured by T & D Corporation). -3110 temperature / humidity sensor) and hermetically sealed. It is kept at 40 ° C. and stored for 24 hours. The measured humidity value is read every 30 minutes, and the value at which there is no change is defined as the equilibrium relative humidity.
[0035]
The cleaning composition of the present invention preferably has the following physical properties.
<Bulk density>
In the detergent composition of the present invention, the bulk density measured by the method specified by JIS K 3362 is preferably 600 g / L or more, more preferably 700 g / L or more, and 800 g / L in terms of convenience and waste reduction. L or more is more preferable. From the viewpoint of solubility, the bulk density is preferably 1600 g / L or less, more preferably 1300 g / L or less, and even more preferably 1000 g / L or less.
[0036]
<Average particle size>
In terms of detergency and solubility, the average particle size determined from the mass fraction according to the size of the sieve is preferably 150 to 700 μm, more preferably 150 to 700 μm after shaking for 5 minutes using a standard sieve of JIS Z 8801. It is 600 μm, more preferably 180 to 500 μm.
[0037]
<Moisture>
From the viewpoint of storage stability, the water content of the detergent composition is preferably 5% by mass or less, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 3% by mass, and preferably 0.5 to 2.5% by mass. % By weight is particularly preferred.
[0038]
<PH>
When the cleaning composition of the present invention is made into an aqueous solution of 0.05% by mass, the pH measured at 20 ° C. described in JIS K3362: 1998 is preferably 8 to 12, from the viewpoint of cleaning performance and damageability, and 9 To 11.5 is more preferable, 9.5 to 11 is further preferable, and 10 to 11 is particularly preferable.
[0039]
【Example】
(Preparation of detergent particles)
(Preparation of Base Granule Group A)
A base granule group A was prepared according to the following procedure.
458 kg of water was added to a 1 m ³ mixing tank having stirring blades, and after the water temperature reached 50 ° C., 80 kg of sodium sulfate, 5 kg of sodium sulfite, 130 kg of sodium carbonate, 2 kg of fluorescent dye, and a 40% by weight aqueous solution of sodium polyacrylate of 40% by weight. After 65 kg and 220 kg of crystalline aluminosilicate were sequentially added, the mixture was stirred for 30 minutes to obtain a homogeneous slurry.
This slurry was maintained at 60 ° C. and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the spray drying tower. The high-temperature gas supplied to the spray drying tower was supplied at a temperature of 210 ° C. from the lower part of the tower, and was discharged at 105 ° C. from the top of the tower. Table 1 shows the composition and physical properties of the obtained base granule group A. The raw materials used are shown below.
[0040]
[Raw materials] Crystalline aluminosilicate (Toyo Builder, manufactured by Tosoh Corporation), sodium carbonate (dense ash: manufactured by Central Glass Co., Ltd.), sodium sulfate (anhydrous neutral sodium sulfate: manufactured by Shikoku Chemicals Co., Ltd.) , Sodium sulfite (sodium sulfite: manufactured by Mitsui Toatsu Co., Ltd.), aqueous solution of sodium polyacrylate (molecular weight 10,000, manufactured by Kao Corporation), fluorescent dye (Tinopearl CBS-X: manufactured by Ciba Specialty Chemicals)
[0041]
[Table 1]

[0042]
(Preparation of surfactant A)
Surfactant A was prepared according to the following procedure.
1000 g of polyoxyethylene alkyl ether and 167 g of a 60% by weight aqueous solution of polyethylene glycol were added to a 3 L mixing tank having stirring blades. After the temperature reached 60 ° C., 10 ° C. water was flowed through the jacket while cooling, while cooling. 1217 g of alkylbenzenesulfonic acid and 330 g of a 48% by weight aqueous sodium hydroxide solution were added simultaneously over 20 minutes. The temperature of the mixture was 90 ° C. 46 g of palmitic acid was added to the mixture. Table 2 shows the composition and physical properties of the obtained surfactant A. The raw materials used are shown below.
[0043]
[Raw materials] Polyoxyethylene len alkyl ether (Emulgen 108KM (average number of moles of ethylene oxide added: 8.5, carbon number of alkyl chain: 12 to 14, melting point: 18 ° C): manufactured by Kao Corporation), polyethylene Glycol (XG-1300 (average molecular weight: 13000): manufactured by Kao Corporation), alkylbenzenesulfonic acid (Neoperex FS: manufactured by Kao Corporation), palmitic acid (Lunac P-95: manufactured by Kao Corporation)
[0044]
[Table 2]

[0045]
Examples 1 and 2 (Preparation of detergent particle group)
After the surfactant A is added to and supported on the base granule group A, the surface is coated with a) a crystalline layered alkali metal silicate, b) lithium chloride and c) an insoluble inorganic powder as shown below. As a result, detergent particle group 1 of the present invention was obtained.
First, 55 parts by weight of the above-mentioned base granule group A is put into a Lodige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity: 20 L, with jacket), and stirring is started under stirring conditions of main shaft: 60 r / mim, chopper: stop. did. Note that hot water of 80 ° C. was flowed through the jacket. 25 parts by weight of Surfactant A kept at 80 ° C. was sprayed thereto at a spray pressure of 0.28 MPa using a spray nozzle (TP80015-SS, manufactured by Spraying Systems Japan). The spraying time was 2 minutes, followed by stirring for 4 minutes to obtain detergent dough particle group A. Subsequently, a) a crystalline layered alkali metal silicate, b) lithium chloride and c) an insoluble inorganic powder (crystalline aluminosilicate; Toyobuilder: average particle size) while continuing to supply hot water to the jacket. 3 μm) and 20 parts by weight of a surface modifier (mass ratio a: b: c = 9: 2: 9), which was sufficiently mixed in advance with a Loedige mixer, were charged, and the main shaft was 120 r / mim and the chopper was 3600 r / min. After stirring for 1 minute under the above stirring conditions, the detergent particle group 1 was discharged. Here, the lithium chloride used was a reagent SAJ first grade manufactured by Sigma-Aldrich Co., Ltd. which was pulverized to an average particle size of 5 μm with a vibration mill. The crystalline layered alkali metal silicate was prepared by pulverizing Prefeed (powder) (trade name, manufactured by Tokuyama Siltec Co., Ltd.) with a roller mill (produced by Ishikawajima-Harima Heavy Industries, Ltd.) to an average particle size of 9 μm. . Its composition formula was Na ₂ O · 2.0 SiO ₂ .
[0046]
Example 2
b) Same as in Example 1 except that potassium carbonate (reagent "SAJ" (first grade) manufactured by Sigma-Aldrich Co., Ltd., first grade) was pulverized to an average particle size of 5 μm with an atomizer (manufactured by Fuji Paudal Co., Ltd.) as a component. Thus, detergent particle group 2 was obtained.
[0047]
Comparative Example 1
As a surface modifier, a) a crystalline layered alkali metal silicate and c) an insoluble inorganic powder (Toyobuilder: average particle size: 3 μm) were separately and thoroughly mixed in advance with a Loedige mixer (mass ratio, b: c = 1). 1) Detergent particle group 3 was obtained in the same manner as in Example 1 except that 20 parts by mass was used.
[0048]
Comparative Example 2
As a surface modifier, a) potassium carbonate (reagent SAJ first grade manufactured by Sigma-Aldrich Co.) was pulverized to an average particle size of 5 μm with an atomizer (manufactured by Fuji Paudal Co., Ltd.), and c) insoluble inorganic powder (Toyobuilder) : Average particle size of 3 μm) and detergent particles in the same manner as in Example 1 except that 20 parts by mass of the mixture (mass ratio, a: b = 1: 9) were separately sufficiently mixed with a Loedige mixer in advance. Group 4 was obtained.
[0049]
The physical properties of the obtained detergent particle groups 1 to 4 were measured according to the following methods. Table 3 shows the obtained results. In addition, the bulk density and the equilibrium relative humidity were measured according to the methods described above.
[0050]
(Caking property): A container having a vertical x horizontal x height = 10 cm x 6 cm x 4 cm upper surface opened using two types of filter paper specified in JISP3801 (for example, "Qualitative No2 filter paper" manufactured by Toyo Roshi Kaisha Co., Ltd.). made. 100 g of a sample (cleaning agent particle group) was put in this box, and a total weight of 15 g + 250 g of an acrylic resin plate and a lead plate (or iron plate) was placed thereon. After 5 cycles of this at a constant temperature of 40 ° C. and a humidity of 80% for 12 hours and 50% for 24 hours in one cycle, the caking state was judged. The judgment was made by obtaining the pass rate as follows. The higher the pass ratio, the lower the caking property, which is a preferable physical property as a detergent composition.
(Passage): The sample after the test is gently opened on a sieve (mesh size of 4760 μm specified in JISZ8801), the weight of the passed powder is weighed, and the passivity to the sample after the test is determined.
[0051]
(Ca ion exchange capacity): A 0.04 g sample was precisely weighed, added to 100 mL of a calcium chloride solution (concentration: 100 ppm as CaCO ₃ ), and stirred at 20 ° C. for 10 minutes. Thereafter, the obtained liquid was filtered through a 0.2 μm filter, and the amount of Ca (equivalent to CaCO ₃ ) contained in 10 mL of the filtrate was quantified by EDTA titration. The Ca ion exchange capacity was determined from the value.
Evaluation criteria ：: Decrease after storage is less than 10%.
Δ: Decrease after storage is less than 10 to 30%.
X: The decrease after storage is 30% or more.
[0052]
(Detergency test):
(Preparation of artificially stained cloth)
An artificially contaminated cloth having the following composition was attached to the cloth to prepare an artificially contaminated cloth. The artificial contaminant was attached to the cloth by printing the artificial contaminant on the cloth using a gravure roll coater. The step of preparing the artificially contaminated cloth by adhering the artificially contaminated liquid to the cloth was performed with a gravure roll cell capacity of 58 cm ³ / cm ² , a coating speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 minute. The cloth used was a cotton cloth 2003 (manufactured by Tanito Shoten). The composition of the artificial contaminated liquid was 0.4% by weight of lauric acid, 3.1% by weight of myristic acid, 2.3% by weight of pentadecanoic acid, 6.2% by weight of palmitic acid, 0.4% by weight of heptadecanoic acid, and 1% of stearic acid. 2.6% by weight, 7.8% by weight of oleic acid, 13.1% by weight of triolein, 2.2% by weight of n-hexadecyl palmitate, 6.5% by weight of squalene, 1.9% by weight of egg white lecithin liquid crystal, Kanuma 8.1% by weight of red clay, 0.01% by weight of carbon black and the balance amount of water.
[0053]
(Cleaning conditions and evaluation method)
Five 1 cm × 10 cm artificially-stained cloths prepared as described above were placed in 1 liter of the aqueous detergent solution for evaluation, and washed at 100 rpm with a tergotometer. The washing conditions were as follows: washing time: 10 minutes, detergent concentration: 0.067% by weight, water hardness: 4 ° DH, water temperature: 20 ° C., rinsing: tap water for 5 minutes. The detergency was determined by measuring the reflectance at 550 nm of the original cloth before and after the cleaning and the contaminated cloth before and after the cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation). Was shown as detergency. In this test, a cleaning rate of 60% or more is indicated by "O", and a cleaning rate of less than 60% is indicated by "X".
[0054]
(Equation 1)

[0055]
[Table 3]

[0056]
From the results in Table 3, the detergent particle groups 1 and 2 obtained in Examples 1 and 2 have better caking resistance and stability than the detergent particle groups 3 and 4 obtained in Comparative Examples 1 and 2. It turns out that it is excellent.
[0057]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the effect that the cleaning composition which is excellent in storage stability and does not deteriorate the cleaning performance even after long-term storage is obtained is produced.

Claims

(A) a crystalline layered sodium silicate represented by the following formula (I) and / or (II) having a particle diameter of 1 to 100 μm, and (b) a deliquescent potassium and / or lithium salt having a particle diameter of 1 to 50 μm. A detergent composition present on the surface of detergent particles.
_{NaMO · x (SiO 2) ·} y (H 2 O) (I)
(In the formula, M represents sodium and / or hydrogen, x represents a number of 1.5 to 2.6, and y represents a number of 0 to 20.)
_{z (NaMO) · w (SiO} 2) · v (MemOn) · u (H 2 O) (II)
(Wherein, M represents sodium or hydrogen, Me represents calcium and / or magnesium, w / z is a number from 1.5 to 2.6, and v / z is from 0.001 to 1.0. Is a number, n / m is a number from 0.5 to 2.0, and u represents a number from 0 to 20.)

The cleaning composition according to claim 1, wherein (c) a water-insoluble inorganic compound having a particle diameter of 0.1 to 50 µm is present on the surface of the cleaning particles.

3. The detergent composition according to claim 1, wherein the detergent particles contain sodium carbonate.

The cleaning composition according to any one of claims 1 to 3, wherein the equilibrium relative humidity is 15 to 35% (40 ° C).

On the surface of the detergent particles, (a) crystalline layered sodium silicate represented by the following formula (I) and / or (II) having a particle diameter of 1 to 100 μm, and (b) deliquescent potassium having a particle diameter of 1 to 50 μm And / or a cleaning composition obtained by adding a lithium salt.
_{NaMO · x (SiO 2) ·} y (H 2 O) (I)
(In the formula, M represents sodium and / or hydrogen, x represents a number of 1.5 to 2.6, and y represents a number of 0 to 20.)
_{z (NaMO) · w (SiO} 2) · v (MemOn) · u (H 2 O) (II)
(Wherein, M represents sodium or hydrogen, Me represents calcium and / or magnesium, w / z is a number from 1.5 to 2.6, and v / z is from 0.001 to 1.0. Is a number, n / m is a number from 0.5 to 2.0, and u represents a number from 0 to 20.)

(B) a deliquescent potassium and / or lithium salt having a particle diameter of 1 to 50 μm, and (a) a crystalline layered sodium silicate represented by the following formula (I) and / or (II) having a particle diameter of 1 to 100 μm: Use as stabilizer.
_{NaMO · x (SiO 2) ·} y (H 2 O) (I)
(In the formula, M represents sodium and / or hydrogen, x represents a number of 1.5 to 2.6, and y represents a number of 0 to 20.)
_{z (NaMO) · w (SiO} 2) · v (MemOn) · u (H 2 O) (II)
(Wherein, M represents sodium or hydrogen, Me represents calcium and / or magnesium, w / z is a number from 1.5 to 2.6, and v / z is from 0.001 to 1.0. Is a number, n / m is a number from 0.5 to 2.0, and u represents a number from 0 to 20.)