JP3720632B2 - Base granule group - Google Patents

Description

【００３９】
によって水溶性成分の溶解率が算出される。但し、算出される上記溶解率が１００％を超える場合は、溶解率は１００％とする。
【００４０】
スラリーの乾燥方法としては、流動槽乾燥、凍結乾燥、噴霧乾燥法等が挙げられ、これらの中ではスラリーを球状に瞬間乾燥する噴霧乾燥が特に好ましい。これは、粒子形状が実質的に球状となるだけでなく、粒度分布のばらつきが抑えられるため、溶解性、流動性、耐ケーキング性が向上した洗剤粒子群を得ることができる。スラリーの微粒化装置としては圧力噴霧ノズル、２流体噴霧ノズル、回転円盤式のいずれの形態でも構わないが、ベース顆粒群の平均粒径が１５０〜５００μｍ、好ましくは１８０〜３００μｍであることから、圧力噴霧ノズルが特に好ましい。噴霧乾燥塔としては向流塔、並流塔の何れの形態でも構わないが、熱効率や、ベース顆粒群の粒子強度が向上することから向流塔がより好ましい。また、噴霧乾燥塔に供給される高温ガスの温度は、生産性、製造し易さの点で好ましくは１５０〜３００℃、より好ましくは１７０〜２５０℃である。また、乾燥塔より排出されるガスの温度は、乾燥塔の熱効率の点で好ましくは７０〜１３０℃、より好ましくは８０〜１２０℃である。
【００４１】
４．ベース顆粒群の物性
本発明のベース顆粒群は、低温領域での皮脂汚れに効果のある融点が４０℃以下の非イオン性界面活性剤を多量担持できる。このようなベース顆粒群の吸油能は、非イオン性界面活性剤滴下法で、０．４０g/g 以上であり、好ましくは、０．５０g/g 以上、さらに好ましくは、０．６０g/g 以上である。なお、非イオン性界面活性剤滴下法による吸油能の測定は、以下のように行う。即ち、内部に攪拌翼を備えた内径約５cm×約１５cmの円筒型混合槽に３０℃に維持されたベース顆粒群１００ｇを入れ、３５０rpm で攪拌しながら、液温３０℃で維持された非イオン性界面活性剤（アルキル基炭素数12/14(以下、C12/C14 という) ＝6/4 、平均エチレンオキサイド付加数（以下、EOという) ＝7.7 、融点；25℃）を約１０ｇ/ 分の速度で投入し、攪拌動力が最も高くなった時の非イオン性界面活性剤の投入量を吸油能とする。
【００４２】
また、ベース顆粒群の嵩密度は、コンパクト洗剤を製造する観点から、４００〜１０００g/L であり、４５０〜８００g/L が好ましく、５００〜７００g/L がより好ましく、５００〜６５０g/L がさらに好ましい。なお、嵩密度は、JIS K 3362により規定された方法で測定する。
【００４３】
次に、ベース顆粒群の平均粒径としては、１５０〜５００μｍが好ましく、１８０〜３００μｍがより好ましい。なお、測定方法としては、ＪＩＳ Ｚ ８８０１に規定の篩を用いて求める。例えば、目開きが２０００μｍ、１４００μｍ、１０００μｍ、７１０μｍ、５００μｍ、３５５μｍ、２５０μｍ、１８０μｍ、１２５μｍである９段の篩と受け皿を用い、ロータップマシーン（ＨＥＩＫＯ ＳＥＩＳＡＫＵＳＨＯ製、タッピング：１５６回／分、ローリング：２９０回／分）に取り付け、１００ｇの試料を１０分間振動して篩い分けを行った後、受け皿、１２５μｍ、１８０μｍ、２５０μｍ、３５５μｍ、５００μｍ、７１０μｍ、１０００μｍ、１４００μｍ、２０００μｍの順番に受け皿及び各篩上に重量頻度を積算していくと、積算の重量頻度が５０％以上となる最初の篩の目開きをａμｍとし、またａμｍよりも一段大きい篩の目開きをｂμｍとした時、受け皿からａμｍの篩までの重量頻度の積算をｃ％、またａμｍの篩上の重量頻度をｄ％とした場合、
式：平均粒径＝１０ ^A ：

にしたがって求めることができる。
なお、用いる篩は測定粉体の粒度分布を正確に見積もることが出来るように適宜調整する。
【００４４】
また、ベース顆粒群の水不溶物発生率は、洗濯機中での洗剤粒子の溶け残りを低減できる観点から、好ましくは３重量％以下、より好ましくは１．５重量％以下、さらに好ましくは０．８重量％以下である。なお、ベース顆粒の水不溶物発生率は、以下のようにして測定できる。即ち、ベース顆粒群１００部を８０℃に温度調節した後、レディゲミキサー（松坂技研（株）製）に投入し、レディゲミキサーの主軸回転数５０rpm で混合しながら、８０℃に温度調節した非イオン性界面活性剤（C12/C14 ＝6/4 、EO＝6.0 、融点；15℃）２０部を２分間で滴下投入する。滴下後さらに１０分間撹拌した後、ゼオライト（「トヨビルダー」；東ソー（株）製）２５部を添加し、主軸回転数１５０rpm 、チョッパー回転数５０００rpm で１分間撹拌混合する。得られた粉体を７１０μｍの篩で粗粒を除き、試験洗剤粒子群とする。得られた試験洗剤粒子群１００ｇをJIS P 3801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の上面が開口した箱に充填し、４０℃、８０％ＲＨの恒温室に１２時間保存する。保存後のサンプル全量を濾紙箱から取り出して混合した後、回転式縮分機を用いて縮分された試験洗剤粒子群を得る。次いで、硝子製１Ｌビーカーに水道水１Ｌ（水温２０℃）を入れ、回転数１２００rpm 、長さ３５mm×直径８mmの撹拌子にてあらかじめ撹拌を行い回転数を安定させた後、前記縮分された試験洗剤粒子群０．６６７ｇを投入し、１０分間試験洗剤粒子群の溶解を行う。１０分後直ちに試験洗剤懸濁液をあらかじめ精秤した２００メッシュの金属篩で濾し取り、試験洗剤残留物を金属篩と共に１０５℃／３０分後の乾燥を行い、更にデシケーター中で３０分間放冷し、精秤を行う。試験前後の金属篩の重量差及び供試した試験洗剤粒子群重量から残留率を計算しベース顆粒群の水不溶物発生率（％）とする。
【００４５】
かかる方法で得られる本発明のベース顆粒群は、嵩密度や吸油能が高く、かつ未溶解残留物が極めて少ないので、高嵩密度洗剤組成物の原料として好適に利用することができる。
【００４６】
５．ベース顆粒群への界面活性剤の担持
本発明の洗剤粒子群は溶解性の観点より単核性洗剤粒子を含有することが好ましい。「単核性洗剤粒子」とは、ベース顆粒に界面活性剤が担持された洗剤粒子であって、１個の洗剤粒子の中に１個のベース顆粒を核として有する洗剤粒子をいう。なお、単核性を表現する因子として、以下の式で定義される粒子成長度を用いることができ、その値は、好ましくは１．５以下、より好ましくは１．３以下である。
【００４７】
粒子成長度＝（最終の洗剤粒子群の平均粒径）／（ベース顆粒群の平均粒径）
【００４８】
ここで、最終の洗剤粒子群とは、ベース顆粒群に界面活性剤を担持させた後の洗剤粒子群、又は該粒子群に表面改質処理を施した洗剤粒子群のいずれかをいう。
また、単核性粒子は、下記（α）法、（β）法、（γ）法のうち少なくとも一つの方法により確認できる。
（α）法：洗剤粒子群の平均粒径付近から任意にサンプリングした洗剤粒子を切断し、洗剤粒子内におけるベース顆粒の有無及びその個数を走査型電子顕微鏡（ＳＥＭ）で観察することによって洗剤粒子の単核性を確認する方法。本発明の洗剤粒子群に含有される洗剤粒子は、ベース顆粒を核としてなる単核性の洗剤粒子であることがわかる。
（β）法：洗剤粒子内のベース顆粒中の水溶性ポリマーを溶解しない有機溶媒（例えば、ベース顆粒中に、水溶性ポリマーとしてポリアクリル酸塩、界面活性剤として陰イオン性界面活性剤（ＬＡＳ）や非イオン性界面活性剤が存在する場合、エタノールを好適に用いることができる）により、洗剤粒子中の有機溶媒可溶分を抽出し、その後の有機溶媒不溶分をＳＥＭ観察によって観察する方法。即ち、１個の洗剤粒子を上記有機溶媒で処理して得た有機溶媒不溶分に１個のベース顆粒が存在する場合、単核性の洗剤粒子であることがわかる。
（γ）法：樹脂で包理した洗剤粒子の切断面の２次元の元素分布をＥＤＳやＥＰＭＡによって検出することによって洗剤粒子の単核性を確認する方法。
【００４９】
５−ａ）界面活性剤の担持
ベース顆粒群に担持させる界面活性剤の量は、洗浄力を発揮させる点から、ベース顆粒群１００重量部に対して１０〜１００重量部が好ましく、２０〜８０重量部がより好ましく、３０〜７０重量部がさらに好ましく、３５〜６５重量部が特に好ましい。また、ベース顆粒に担持させる界面活性剤中に融点４０℃以下の非イオン性界面活性剤を２０重量％以上、好ましくは３０重量％以上配合したとき、皮脂汚れへの洗浄性能が向上する。ここで、非イオン性界面活性剤は単独で用いることもできるが、各種汚れへの洗浄力、衣類への溶け残りから、陰イオン性界面活性剤と混合して用いるのが良い。陰イオン界面活性剤の配合量は、好ましくは界面活性剤の２０重量％以上、より好ましくは３０重量％以上、さらに好ましくは４０重量％以上である。また、両性界面活性剤や陽イオン性界面活性剤を目的に合わせ併用することもできる。ここでいう界面活性剤の担持量には、スラリー調製時に界面活性剤が配合される場合、その界面活性剤の配合量を含まないものである。
【００５０】
また、前記非イオン性界面活性剤の融点は、好ましくは４０℃以下、さらに好ましくは３０℃以下、特に好ましく２５℃以下、その中でも好ましくは２２℃以下のものであり、例えば、ポリオキシアルキレンアルキル（フェニル）エーテル、アルキルポリグリコキシド、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシアルキレングリコール脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリオキシアルキレンアルキロール（脂肪酸）アミドが好ましいものとして例示される。陰イオン性界面活性剤としては、炭素数１０〜１８のアルコールの硫酸エステル塩、炭素数８〜２０のアルコールのアルコキシル化物の硫酸エステル塩、アルキルベンゼンスルホン酸塩、パラフィンスルホン酸塩、α−オレフィンスルホン酸塩、α−スルホ脂肪酸塩、α−スルホ脂肪酸アルキルエステル塩又は脂肪酸塩が好ましい。本発明では特に、アルキル鎖の炭素数が１０〜１４の、より好ましくは１２〜１４の直鎖アルキルベンゼンスルホン酸塩が好ましく、対イオンとしては、アルカリ金属類やアミン類が好ましく、特にナトリウムイオン及び／又はカリウムイオン、モノエタノールアミン、ジエタノールアミンが好ましい。
【００５１】
ベース顆粒群への界面活性剤の担持方法は、例えば、回分式や連続式の混合機を用いることができる。また、回分式で行う場合は、混合機への仕込み方法は、(1) 混合機に先ずベース顆粒群を仕込んだ後、界面活性剤を添加する、(2) 混合機にベース顆粒群と界面活性剤とを少量ずつ仕込む、(3) ベース顆粒群の一部を混合機に仕込んだ後、残りのベース顆粒群と界面活性剤とを少量ずつ仕込む、等の方法をとることができる。なお、(1) 〜(3) の方法は、混合機を運転させながら行うことが好ましい。これらの方法の中で、特に上記(1) が好ましい。また、界面活性剤は液体状態で添加することが好ましく、さらに液体状態の界面活性剤を噴霧して供給することが好ましい。かかる添加方法によれば、ベース顆粒の単核性を維持しつつ、洗剤粒子群を製造することができるため、好ましい。
【００５２】
界面活性剤の中で、実用上の温度範囲内において、例えば、５０〜９０℃において昇温しても固体あるいはペースト状で存在するものについては、これらを予め粘性の低い、例えば、非イオン性界面活性剤、非イオン性界面活性剤水溶液、あるいは水中に分散又は溶解させた界面活性剤の混合液又は水溶液として調製し、該混合液又は水溶液の形態でベース顆粒群に添加することができる。この方法により、固体あるいはペースト状で存在する界面活性剤をも容易にベース顆粒群に添加することができ、さらに単核性洗剤粒子を含有する洗剤粒子群の製造に有利である。粘性の低い界面活性剤又は水と固体あるいはペースト状の界面活性剤との混合比率は、得られる混合液又は水溶液が噴霧可能である粘度範囲であれば好ましい。
【００５３】
上記混合液の製法は、例えば、粘性の低い界面活性剤又は水に固体あるいはペースト状の界面活性剤を投入して混合する方法や、粘性の低い界面活性剤中又は水中で界面活性剤の酸前駆体をアルカリ剤（例えば苛性ソーダ水溶液や苛性カリ水溶液）で中和することにより界面活性剤混合液を調製してもよい。
【００５４】
また、この工程において、界面活性剤の添加前、その添加と同時、その添加途中、又はその添加後に陰イオン性界面活性剤の酸前駆体を添加することも可能である。陰イオン性界面活性剤の酸前駆体を添加することで、界面活性剤の高配合化、ベース顆粒群の吸油能制御及び洗剤粒子群の非イオン性界面活性剤のシミ出し抑制、流動性等の物性、品質の向上が可能となる。
【００５５】
陰イオン性界面活性剤の酸前駆体としては、例えば、アルキルベンゼンスルホン酸、アルキル又はアルケニルエーテル硫酸、アルキル又はアルケニル硫酸、α−オレフィンスルホン酸、α−スルホン化脂肪酸、アルキル又はアルケニルエーテルカルボン酸、脂肪酸等が挙げられる。特に脂肪酸を界面活性剤の添加後に添加することが洗剤粒子群の流動性向上の観点より好ましい。
【００５６】
陰イオン性界面活性剤の酸前駆体の使用量は、洗剤粒子群中の粒子の単核性が維持され、良好な高速溶解性を呈する観点から、ベース顆粒群１００重量部に対して０．５〜３０重量部が好ましく、１〜２０重量部がより好ましく、１〜１０重量部がさらに好ましく、１〜５重量部が特に好ましい。なお、該酸前駆体の使用先は、本発明にかける界面活性剤には算出しない。また、陰イオン性界面活性剤の酸前駆体の添加方法としては、常温で液体のものは噴霧して供給することが好ましく、常温で固体のものは粉末として添加してもよく、溶融させた後噴霧して供給してもよい。ただし、粉末で添加する場合は、粉末が溶融する温度まで混合機中の洗剤粒子群の温度を昇温するのが好ましい。
【００５７】
界面活性剤の担持工程で好ましく用いられる装置としては、ヘンシェルミキサー（三井三池化工機（株）製）、ハイスピードミキサー（深江工業（株）製）、バーチカルグラニュレーター（パウレック（株）製）、レディゲミキサー（松坂技研（株）製）、プロシェアミキサー（太平洋機工（株）製）、ナウターミキサー（ホソカワミクロン（株）製）等がある。
【００５８】
好ましい混合機としては、単核性洗剤粒子を多く含有する洗剤粒子群を製造する観点からベース顆粒に強い剪断力がかかりにくい（ベース顆粒を崩壊させにくい）装置であり、界面活性剤の分散効率の観点から混合効率のよい装置が好ましい。上記の混合機の中で特に好ましくは、横型の混合槽で円筒の中心に攪拌軸を有し、この軸に攪拌羽根を取り付けて粉末の混合を行う形式のミキサー（横型混合機）でレディゲミキサー、プロシェアミキサー等がある。
【００５９】
また、ここで、非イオン性界面活性剤が使用される場合、この界面活性剤の融点を上昇させる作用を有する、融点４５〜１００℃、分子量１０００〜３００００の水溶性非イオン性有機化合物（以下、融点上昇剤という）又はこの水溶液を、界面活性剤の添加前、界面活性剤の添加と同時、界面活性剤の添加途中、又は界面活性剤添加後、あるいは界面活性剤に予め混合して添加することが好ましい。融点上昇剤を添加することで、洗剤粒子群のケーキング性、洗剤粒子群中の界面活性剤のシミ出し性を抑制することができる。本発明で用いることのできる融点上昇剤としては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシエチレンアルキルエーテル、プルロニック型非イオン性界面活性剤等が挙げられる。
融点上昇剤の使用量は、ベース顆粒群１００重量部に対して０．５〜８重量部が好ましく、０．５〜５重量部がより好ましく、１〜３重量部が最も好ましい。この範囲が、洗剤粒子群に含有される洗剤粒子の粒子間の凝集の抑制、高速溶解性、及びシミ出し性やケーキング性の抑制の点から好ましい。融点上昇剤の添加方法として、予め界面活性剤と任意の方法で混合して添加すること、又は界面活性剤の添加後に融点上昇剤を添加することが洗剤粒子群のシミ出し性やケーキング性の抑制に有利である。
【００６０】
本工程における混合機内の温度は、JIS K 2269に規定の方法によって測定される界面活性剤の流動点以上に昇温して混合を行えば、より好ましい。ここで、昇温させる温度としては、界面活性剤の担持を促進させるために添加する界面活性剤の流動点より高ければよいが、実用的な範囲を挙げると流動点を越えて流動点より５０℃高い温度までが好ましく、流動点より１０℃〜３０℃高い温度がより好ましい。また、この工程で陰イオン性界面活性剤の酸前駆体を添加する場合は、当該陰イオン性界面活性剤の酸前駆体が反応できる温度に昇温して混合を行えばより好ましい。
【００６１】
好適な洗剤粒子群を得るための回分式の混合時間、及び連続式の混合における平均滞留時間は、１〜２０分間が好ましく、２〜１０分間が更に好ましい。
【００６２】
また、界面活性剤の水溶液や水溶性非イオン性有機化合物水溶液を使用した場合には余剰の水分を混合中及び／又は混合後に乾燥する工程を有してもよく、界面活性剤の添加前、その添加と同時、その添加途中、又はその添加後に粉末の界面活性剤及び／又は粉末ルダーを添加することも可能である。粉末ビルダーを添加することで、洗剤粒子群の粒子径を制御することができ、また洗浄力の向上を図ることができる。特に陰イオン性界面活性剤の酸前駆体を添加する場合は該酸前駆体を添加する前にアルカリ性を呈する粉末ビルダーを添加することが中和反応を促進する観点から有効である。なお、ここで言う「粉末ビルダー」とは、界面活性剤以外の粉末の洗浄力強化剤を意味し、具体的には、ゼオライト、クエン酸塩等の金属イオン封鎖能を示す基剤や、炭酸ナトリウム、炭酸カリウム等のアルカリ能を示す基剤、結晶性珪酸塩等の金属イオン封鎖能・アルカリ能いずれも有する基剤、その他硫酸ナトリウム等のイオン強度を高める基剤等を指す。
【００６３】
ここで、結晶性珪酸塩として、特開平5-279013号公報第３欄第17行〜第６欄第24行（特に、５００〜１０００℃で焼成して結晶化させたものが好ましい）、特開平7-89712 号公報第２欄第45行〜第９欄第34行、特開昭60-227895 号公報第２頁右下欄第18行〜第４頁右上欄第３行（特に第２表の珪酸塩が好ましい）に記載の結晶性珪酸塩を粉末ビルダーとして用いることができる。ここで、アルカリ金属珪酸塩のＳｉＯ₂ ／Ｍ₂ Ｏ（モル比；但しＭはアルカリ金属原子を表す）は、０．５〜３．２が好ましく、１．５〜２．６がより好ましい。
【００６４】
粉末ビルダーの使用量としては、洗剤粒子群に含有される洗剤粒子の単核性を維持し、良好な高速溶解性を得られ、また、粒子径の制御も好適である点から、ベース顆粒群１００重量部に対して０．５〜１２重量部が好ましく、１〜６重量部がさらに好ましい。
【００６５】
また、本発明の洗剤粒子群は多核性洗剤粒子を含有することができる。多核性洗剤粒子は、前述の単核性洗剤粒子を構成するベース顆粒を凝集させたものでも、水溶性塩類、例えば炭酸ナトリウム等を核として凝集させたものでもよい。また、界面活性剤の量を増やすことにより、多核性洗剤粒子を容易に形成することができる。なお、重曹や過炭酸塩等の発泡剤を添加して、ベース顆粒間の溶解促進を助長させても良い。
【００６６】
５−ｂ）表面改質工程
本発明においては、前述の方法により界面活性剤を担持させた洗剤粒子群の粒子表面を改質するために、添加時の形態として以下の（１）微粉体、（２）液状物のような種々の表面被覆剤を添加する表面改質工程を一工程あるいは二工程重複して行ってもよい。
本発明の洗剤粒子群の粒子表面を被覆すると、洗剤粒子群の流動性と非ケーキング性が向上する傾向があるため、表面改質工程は好ましい。表面改質工程で使用される装置は特に限定されず、公知の混合機を用いることができるが、上述５−ａ) で例示した混合機が好ましい。以下に表面被覆剤についてそれぞれ説明する。
【００６７】
（１）微粉体
微粉体の一次粒子の平均粒径は、洗剤粒子群の粒子表面の被覆率が向上し、洗剤粒子群の流動性と耐ケーキング性の向上の観点から、１０μｍ以下が好ましく、０．１〜１０μｍがより好ましい。この平均粒径は、光散乱を利用した方法、例えばパーティクルアナライザー（堀場製作所（株）製）、又は顕微鏡観察による測定等で測定される。また、微粉体は、高いイオン交換能や高いアルカリ能を有していることが洗浄面から好ましい。
【００６８】
微粉体としては、アルミノ珪酸塩が好ましく、結晶性、非晶質の何れでも構わない。アルミノ珪酸塩以外では、硫酸ナトリウム、珪酸カルシウム、二酸化珪素、ベントナイト、タルク、クレイ、非晶質シリカ誘導体、結晶性シリケート化合物等のシリケート化合物、一次粒子の平均粒径が０．１〜１０μｍの金属石鹸、粉末の界面活性剤（例えばアルキル硫酸塩等）、水溶性有機塩等も好ましい。結晶性シリケート化合物を用いる場合、吸湿や吸炭酸ガスによる結晶性シリケートの凝集等による劣化を防ぐ目的から、結晶性シリケート化合物以外の微粉体と混合して用いることが好ましい。非晶質アルミノ珪酸塩としては、本発明に用られる孔径が制御された非晶質アルミノ珪酸塩が好ましい。
【００６９】
微粉体の使用量としては、流動性が向上し、消費者に良好な使用感を与える観点から、洗剤粒子群１００重量部に対して０．５〜４０重量部が好ましく、１〜３０重量部がより好ましく、２〜２０重量部が特に好ましい。
【００７０】
（２）液状物
液状物としては、水溶性ポリマーや脂肪酸等の、水溶液や溶融物が挙げられる。
（２−１）水溶性ポリマー
水溶性ポリマーとしては、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が挙げられる。水溶性ポリマーの使用量としては、洗剤粒子群１００重量部に対して０．５〜１０重量部が好ましく、１〜８重量部がより好ましく、２〜６重量部が特に好ましい。当該水溶性ポリマーの使用量はこの範囲において、洗剤粒子群に含有される洗剤粒子の単核性を維持し、良好な高速溶解性を得られつつ、良好な流動性、耐ケーキング性を示す粉体を得ることができる。
（２−２）脂肪酸
脂肪酸としては、例えば、炭素数１０〜２２の脂肪酸等が挙げられる。脂肪酸の使用量としては、単核性洗剤粒子を含有する洗剤粒子群１００重量部に対して０．５〜５重量部が好ましく、０．５〜３重量部が特に好ましい。常温で固体のものの場合は、流動性を示す温度まで加温した後に、噴霧して供給することが好ましい。
【００７１】
本発明の洗剤粒子群の平均粒径は、溶解性、粉の感触及び保存安定性の点から１５０〜７５０μｍが好ましく、２００〜４５０μｍがより好ましく、２２０〜３５０μｍが特に好ましい。また、輸送や収納性の観点や溶解性の観点から、その嵩密度は５００〜１２００ｇ／Ｌが好ましく、６００〜９００ｇ／Ｌがより好ましく、６５０〜８００ｇ／Ｌが特に好ましい。
【００７２】
本発明のベース顆粒群は、高嵩密度洗剤組成物の原料として好適に用いることができる。例えば、洗剤組成物を製造する際に、噴霧乾燥等で得られたベース顆粒群を必要に応じて界面活性剤を添加しながら、圧密化・造粒処理を行ってもよく、特に本願で示した単核性の洗剤を得る造粒方法に限定されるものではない。また、これら洗剤粒子群を５０重量％以上、好ましくは６０重量％以上、さらに好ましくは７０重量％以上、特に好ましくは８０重量％以上含有し、さらに該洗剤粒子群内に別途添加された洗剤成分（例えばビルダー顆粒、酵素、蛍光染料、香料、漂白剤、漂白活性剤など）をアフターブレンドした洗剤組成物も本発明の権利範囲とする。
【００７３】
かかる方法で得られた本発明の洗剤組成物は、その嵩密度が好ましくは５００〜１２００g/L 、より好ましくは６００〜９００g/L のように高いものであるので、輸送ないし持ち運び並びに収納性に優れたコンパクト洗剤になりうる。
【００７４】
【実施例】
合成例 1〜 5〔孔径が制御された非晶質アルミノ珪酸塩の合成〕
５０℃、５０％アルミン酸ナトリウム水溶液１７．６２ｋｇに、５０℃、４０％珪酸ナトリウム水溶液１９．７２ｋｇと１％塩化カルシウム水溶液４５．１８ｋｇの混合溶液を▲１▼６０分、▲２▼３０分、▲３▼２０分、▲４▼５分、▲５▼２分（それぞれ合成例 1〜 5とする）で滴下終了するようポンプを調節した。その後、反応温度５０℃で１０分、熟成温度８０℃で１０分経過した後、６０℃に冷却して孔径が制御された非晶質アルミノ珪酸塩を得た。次に、このスラリー溶液に濃硫酸５．０ｋｇ滴下することで、ｐＨ１０．５程度まで中和し、２０％濃度スラリー溶液を得た。なお、スラリー溶液の一部を水洗洗浄後得られた孔径が制御された非晶質アルミノ珪酸塩の組成式は、▲１▼０．９２Ｎａ₂ Ｏ・０．０１１ＣａＯ・Ａｌ₂ Ｏ₃ ・２．１３ＳｉＯ₂ 、▲２▼０．９４Ｎａ₂ Ｏ・０．０１ＣａＯ・Ａｌ₂ Ｏ₃ ・２．１４ＳｉＯ₂ 、▲３▼０．９３Ｎａ₂ Ｏ・０．０１２ＣａＯ・Ａｌ₂ Ｏ₃ ・２．１３ＳｉＯ₂ 、▲４▼０．９２Ｎａ₂ Ｏ・０．０１１ＣａＯ・Ａｌ₂ Ｏ₃ ・２．１４ＳｉＯ₂ 、▲５▼０．９３Ｎａ₂ Ｏ・０．０１ＣａＯ・Ａｌ₂ Ｏ₃ ・２．１４ＳｉＯ₂ であった。また、その物性を表１に示す。
【００７５】
【表１】

【００７６】
表１の結果より、得られた非晶質アルミノ珪酸塩を「LA-700」（堀場製作所（株）製）にて粒径測定すると滴下速度を速めることによってメジアン径が大きくなった。これより、滴下速度が速いほど吸油能が高くなっていた。
【００７７】
ベース顆粒群の製造例１
水１３６．０ｋｇを攪拌翼を有した１ｍ³ の混合槽に加え、水温が５５℃に達した後、１５分間攪拌した後に、炭酸ナトリウム６５．０ｋｇ、硫酸ナトリウム５６．５ｋｇ、亜硫酸ナトリウム２．５ｋｇ、蛍光染料２．５ｋｇを添加した。次に、４０重量％のポリアクリル酸ナトリウム水溶液３７．５ｋｇを添加し、前記合成例 1〜 5で得られた孔径が制御された非晶質アルミノ珪酸塩（ 5は除く）の２０％濃度スラリー溶液１２５．０ｋｇ、ゼオライト７５．０ｋｇを添加し、３０分間攪拌して均質なスラリーを得た。このスラリーの最終温度は５８℃、スラリー中の水分は４９重量％であった。次いで、このスラリーをポンプで噴霧乾燥塔に供給し、塔頂付近に設置した圧力噴霧ノズルから噴霧圧力２５kg/cm²で噴霧を行い、ベース顆粒群ａ〜ｅ（合成例 1〜 5にそれぞれ対応）を得た。なお、噴霧乾燥塔に供給する高温ガスは塔下部より温度が２２５℃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〜ｅはいずれも赤外線水分計での水分量４重量％であった。ベース顆粒群ａ〜ｅの物性を表２に示す。
【００７８】
【表２】

【００７９】
表２の結果より、使用した非晶質アルミノ珪酸塩の吸油能が大きいほど（表１を参照）、ベース顆粒群の吸油能が向上することがわかる。
【００８０】
ベース顆粒群の評価
ベース顆粒群ａ〜ｅの水不溶物発生率及び衣類残留性を表２に示す。なお、水不溶物発生率は、前記のようにして測定した。また、衣類残留性は、以下のようにして評価した。
【００８１】
＜衣類残留性試験＞
松下電器（株）製全自動洗濯機「NA-F50A1」に黒色布（「綿ブロード40」、染色試剤（株）谷頭商店社製、４０cm×４０cm）５枚に加え、浴比の調整布として木綿肌着（グンゼ社製；ＮＯ. ＹＧ６６１４）を洗濯機に投入し、布量が総量６００ｇとなるようにする。つづいて前記水不溶物発生率測定に供した洗剤組成物２７ｇを投入し、洗濯機の水位を低（４０Ｌ）に手動設定し、標準コースで洗濯を開始する。水温は５℃で行った。洗濯終了後、黒色布を２５℃、４０％ＲＨの室内に１２時間吊るし干しした後、衣類に付着した水不溶物（５０〜３００μｍ程度）を黒色布１面当たりにつき、目視で、以下の評価基準に基づいて評価した。
【００８２】
評価基準
凝視しても水不溶物が残留していないものを「０」、
凝視して、水不溶物がわずかに残留しているものを「０．２５」、
一見して、水不溶物の点在する部分の割合が１割程度以上のものを「０．５」、
一見して、水不溶物の点在する部分の割合が５分５分以上のものを「１．０」
一見して、水不溶物の点在する部分の割合が９割以上のものを「２．０」
【００８３】
黒色布５枚、両面の計１０面の評価を行い、１面平均のスコアを衣類残留性指数とした。なお、衣類残留性指数が０．２０以下のものを合格品とする。
表２の結果より、使用した非晶質アルミノ珪酸塩の0.015 〜0.5 μm における容積(mL/g)が、少ないほど、ベース顆粒群の水不溶物発生率が低減することがわかる。また、実際の衣類残留性指数も同様であった。
【００８４】
ベース顆粒群の製造例２
組成式Ｎａ₂ Ｏ・Ａｌ₂ Ｏ₃ ・１２．２ＳｉＯ₂ の非晶質アルミノ珪酸塩（「チキソレックス２５」；コフランケミカル( 株) ）配合のベース顆粒合成法を以下に示す。なお、チキソレックス２５の物性値を表３に示す。
【００８５】
【表３】

【００８６】
水２３６．０ｋｇを攪拌翼を有した１ｍ³ の混合槽に加え、水温が５５℃に達した後、１５分間攪拌した後に、炭酸ナトリウム６５．０ｋｇ、硫酸ナトリウム５６．５ｋｇ、亜硫酸ナトリウム２．５ｋｇ、蛍光染料２．５ｋｇを添加した。次に、４０重量％のポリアクリル酸ナトリウム水溶液３７．５ｋｇを添加し、チキソレックス２５．０ｋｇ、ゼオライト７５．０ｋｇを添加し、３０分間攪拌して均質なスラリーを得た。このスラリーの最終温度は５８℃であった。また、このスラリー中の水分は４９重量％である。このスラリーをポンプで噴霧乾燥塔に供給し、塔頂付近に設置した圧力噴霧ノズルから噴霧圧力２５kg/cm²で噴霧を行い、ベース顆粒群を得た。噴霧乾燥塔に供給する高温ガスは塔下部より温度が２２５℃で供給され、塔頂より１０５℃で排出された。このベース顆粒群（平均粒径２４５μｍ、嵩密度５５０g/L 、吸油能０．６１g/g)の水不溶物発生率は１１．５％、衣類残留性指数は１．５０であった。
【００８７】
〔洗剤粒子群の製造〕
ベース顆粒群ｂ及びｅを用いて界面活性剤組成物を担持させ洗剤粒子群（Ａ）及び洗剤粒子群（Ａ）’を、ベース顆粒群ｂを用いて界面活性剤組成物を担持させ洗剤粒子群（Ｂ）及び（Ｃ）を得た。各洗剤粒子群の造粒は以下のようにした。
【００８８】
〔洗剤粒子群（Ａ）及び（Ａ）’の造粒〕
非イオン性界面活性剤（C12/C14=6/4, EO=7.7)、「エマルゲン107KM 」；花王（株）製）２３重量部を５０℃になるように加熱した。レディゲミキサー（松坂技研（株）製、容量２０Ｌ、ジャケット付）に前期ベース顆粒群ｂ又はｅ１００重量部を投入し、主軸（１５０ｒｐｍ）の攪拌を開始した。なお、ジャケットには６０℃の温水を１０Ｌ／分で流し、そこに上記非イオン性界面活性剤を２分間で投入し、その後４分間攪拌を行なった。更にこの洗剤粒子群の表面をあらかじめ平均粒径１０μｍに粉砕した結晶性珪酸塩（「ＳＫＳ−６」；クラリアントトクヤマ（株）製）５重量部及び結晶性アルミノ珪酸塩（４Ａ型ゼオライト、「トヨビルダー」；東ソー（株）製）１０重量部で表面被覆し、洗剤粒子群（Ａ）または（Ａ）’を得た。
【００８９】
〔洗剤粒子群（Ｂ）の造粒〕
非イオン性界面活性剤（C12/C14=6/4, EO=7.7)、「エマルゲン１０７ＫＭ」；花王（株）製）２０重量部と陰イオン性界面活性剤（アルキルベンゼンスルホン酸ナトリウム３０重量部に相当する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）並びに中和剤として水酸化ナトリウム水溶液とポリエチレングリコール（「Ｋ−ＰＥＧ６０００」；花王（株）製）２重量部を８０℃になるように加熱混合し、混合液を作製した。上記レディゲミキサーに前期ベース顆粒群ｂ１００重量部を投入し、主軸（１５０ｒｐｍ）の攪拌を開始した。なお、ジャケットには８０℃の温水を１０Ｌ／分で流し、そこに上記界面活性剤組成物を３分間で投入し、その後７分間攪拌を行った。更にこの洗剤粒子群の表面をあらかじめ平均粒径１０μｍに粉砕した結晶性珪酸塩（「ＳＫＳ−６」；クラリアントトクヤマ（株）製）１０重量部及び結晶性アルミノ珪酸塩（４Ａ型ゼオライト、「トヨビルダー」；東ソー（株）製）１０重量部で表面被覆し、洗剤粒子群（Ｂ）を得た。
【００９０】
（洗剤粒子群（Ｃ）の造粒）
ポリオキシエチレンポリオキシプロピレンポリオキシエチレンアルキルエーテル（C12, EO=3, PO=2, EO = 3 ブロックタイプ) ２３重量部を用い、洗剤粒子群（Ｂ）と同様の方法にて洗剤粒子群（Ｃ) を得た。
【００９１】
ここでの洗剤粒子群の水不溶物発生率は、以下の測定方法による。洗剤粒子群１００ｇをJIS P 3801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の上面が開口した箱に充填し、４０℃、８０％ＲＨの恒温室に１２時間保存する。保存後のサンプル全量を濾紙箱から取り出し混合した後、回転式縮分機にて縮分を行う。水不量の測定は水温２０℃で行う。まず硝子製１Ｌビーカーに水道水１Ｌを入れ、回転数１２００rpm 、長さ３５mm×直径８mmの撹拌子にてあらかじめ撹拌を行い回転数を安定させる。回転数が安定した後、上記縮分洗剤粒子群０．６６７ｇを投入し、１０分間洗剤粒子群の溶解を行う。１０分後直ちに洗剤懸濁液をあらかじめ精秤した２００メッシュの金属篩で濾し取り、洗剤残留物を金属篩と共に１０５℃／３０分後の乾燥を行い、更にデシケーター中で３０分間放冷し、精秤を行う。試験前後の金属篩の重量差及び供試した洗剤粒子群重量から残留率を計算し洗剤粒子群水不溶物発生率（％）とする。
【００９２】
以上、得られた洗剤粒子群（Ａ）〜（Ｃ）の物性を表４に示す。
【００９３】
【表４】

【００９４】
表４の結果より、本発明のベース顆粒群ｂを含有した洗剤粒子群（Ａ）〜（Ｃ）はいずれも、水不溶物発生率と衣類残留性指数の高いベース顆粒群ｅを含有した洗剤粒子群（Ａ’）に比べ、洗剤粒子群水不溶物発生率が格段に低いことがわかる。
また、非イオン性界面活性剤に陰イオン性界面活性剤を共存させると洗剤粒子の水不溶物発生率がさらに低減し、衣類残も低減できることがわかる。なお、洗剤粒子群（Ａ）と（Ｂ）は、良好な溶解性を保持し、流動性が良好であった。特に、洗剤粒子群（Ｂ）は、ポリエチレングリコールを配合したことで、洗剤粒子群の耐ケーキング性が更に向上し、非イオン性界面活性剤のシミ出しが更に抑制された。
【００９５】
【発明の効果】
本発明のベース顆粒群は、高吸油能で、かつ衣類に洗剤の未溶解残留物の極めて少ない高嵩密度のものであり、該ベース顆粒群に界面活性剤を担持させることにより高嵩密度の洗剤粒子群を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a high-bulk-density surfactant-supporting base granule group containing an amorphous aluminosilicate having a specific structure, and a high-bulk-density detergent particle group in which a surfactant is supported on the base granule.
[0002]
[Prior art]
The increase in bulk density of powder detergents in the latter half of the 1980's was that compactness greatly contributed to transportation, carrying and storage, so compact detergents are now dominant. Numerous studies have been made on a method for producing this high bulk density detergent. For example, a method of supporting a surfactant on a group of base granules obtained by spray drying has been devised. This method is advantageous in that a large amount of a nonionic surfactant that is liquid at room temperature, which has excellent detergency such as sebum dirt, can be blended.
[0003]
However, if the base granule group has a low oil absorption capacity, if a sufficient amount of surfactant is absorbed to satisfy the cleaning performance, the surfactant may ooze out. Use of a large amount of a modifier is not preferable from the viewpoint of cost. Therefore, in order to utilize the above method, it is necessary that the oil absorption capacity of the base granule group is at a very high level.
[0004]
As a powder detergent with improved oil absorption capacity of the base granule group, JP-A-9-20900 discloses a detergent builder powder obtained by spray-drying a detergent builder slurry containing amorphous zeolite and amorphous silica. There is a description of a package-type detergent soaked with an agent solution. However, when such a powder detergent is used, there is a problem that the undissolved residue of the detergent remains on clothes after completion of washing.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a base granule group having a high oil absorption capacity and extremely little undissolved residue of detergent in clothes, and a high bulk density detergent particle group in which a surfactant is supported on the base granule group. It is in.
[0006]
[Means for Solving the Problems]
  That is, the gist of the present invention is as follows.
[1] A base granule group containing a water-insoluble inorganic substance, a water-soluble polymer, and a water-soluble salt, and further containing 0 to 10% by weight of a surfactant, having a bulk density of 400 to 1000 g / L, Insoluble inorganic matterButAmorphous aluminosilicate with a pore diameter of 0.015 to 0.5 μm measured with a mercury porosimeter of 0 to 1.0 mL / g and a pore diameter of 0.5 to 2 μm with a volume of 0.30 mL / g or more.And the content of the amorphous aluminosilicate is 1 to 20% by weight in the base granule groupA surfactant-supporting base granule group (hereinafter referred to as a base granule group), and
[2] 10 to 100 parts by weight of a surfactant composition containing 20% by weight or more of a nonionic surfactant having a melting point of 40 ° C. or less with respect to 100 parts by weight of the base granule group described in [1]. It relates to a high bulk density detergent particle group.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
1. Definition of base granules, detergent particles and detergent composition
In the present invention, the “base granule” contains 0 to 10% by weight of a surfactant and is mainly composed of a water-insoluble inorganic substance (A), a water-soluble polymer (B), and a water-soluble salt (C). In this case, the particles used to carry the surfactant are referred to, and the “base granule group” means an aggregate thereof. The “detergent particle” is a particle containing a surfactant, a builder, and the like, and in particular, in the present invention, refers to a particle obtained by supporting a surfactant on a base granule. Means the aggregate. In addition, the “detergent composition” includes a detergent particle group and a detergent component (for example, builder granule, fluorescent dye, enzyme, fragrance, antifoam, bleach, It means a composition containing a bleach activator and the like.
[0008]
2. Composition of base granule
(A) Water-insoluble inorganic substance
At least a part of the water-insoluble inorganic substance used in the present invention has a pore diameter of 0.015 to 0.5 μm measured with a mercury porosimeter and a volume of 0 to 1.0 mL / g and a pore diameter of 0.5 to 2 μm is 0.00. An amorphous aluminosilicate (hereinafter also referred to as an amorphous aluminosilicate having a controlled pore size) of 30 mL / g or more.
[0009]
The volume of pores of 0.015 to 0.5 μm of amorphous aluminosilicate with controlled pore diameter measured by mercury porosimeter is related to the formation of undissolved residue of detergent remaining in clothing, The smaller the amount, the better, preferably 0 to 0.70 mL / g, more preferably 0 to 0.60 mL / g, still more preferably 0 to 0.50 mL / g, and most preferably 0 to 0.45 mL / g. is there. Moreover, the volume of the pore diameter of the amorphous aluminosilicate having a controlled pore diameter of 0.5 to 2 μm has an effect of increasing the amount of the surfactant loaded, and the larger the volume, the better. 40 mL / g or more, more preferably 0.55 mL / g or more, still more preferably 0.60 mL / g or more.
[0010]
In addition, the measurement of the volume of the pore diameter 0.015-0.5 micrometer and the pore diameter 0.5-2 micrometer of an amorphous aluminosilicate with a mercury porosimeter uses Shimadzu Corporation Corp. "SHIMADZU pore sizer 9320", Perform as follows based on the instruction manual. That is, 100 mg of amorphous aluminosilicate was put in a cell having a cell volume of 5.2 mL and a stem volume of 0.392 mL, and the mercury to be injected was put into a low pressure part (0 to 14.2 psia) and a high pressure part (14.2 to 20000 psia). Measured at 20 ° C. In addition, there is a possibility that the powder particles are crushed during the measurement, but here, a value including these is shown.
[0011]
In addition, the higher the oil absorption capacity of the amorphous aluminosilicate having a controlled pore size, the higher the amount of the surfactant that is supported. For example, the oil absorption capacity value measured by the JIS K 5101 method is preferably 100 mL / 100 g or more, more preferably 120 mL / 100 g or more, more preferably 150 mL / 100 g or more, and particularly preferably 170 mL / 100 g or more.
[0012]
The composition of the amorphous aluminosilicate having a controlled pore size is preferably represented by the following formula (1).
xM₂O ・ yMeO ・ Al₂O_Three・ ZSiO₂      (1)
(In the formula, M represents an alkali metal atom, Me represents a divalent metal atom, x is 0.2 to 2.0, y is 0 to 0.1, and z is 0.5 to 5.0).
[0013]
In the formula (1), M is preferably Na or K, and Na is more preferable from the viewpoint of cost or the like. Me is preferably Mg, Ca and Fe, and more preferably Ca. Me is an optional component in the amorphous aluminosilicate whose pore size is controlled, but it is blended because it has an effect of improving oil absorption and reducing elution of aluminum and silicon in the amorphous aluminosilicate. It is preferable that M and Me may be used alone or in combination of two or more. x is preferably 0.5 to 1.5, more preferably 0.85 to 1. y is preferably 0.001 to 0.08, more preferably 0.005 to 0.05.
[0014]
z is related to the structure and chemical stability of the amorphous aluminosilicate with controlled pore size. If the value is too small, it will be difficult to increase the oil absorption capacity of the amorphous aluminosilicate. If the value is too large, Si—O—Si bonds that are susceptible to hydrolysis increase in the molecules of the amorphous aluminosilicate, and free silicic acid and / or polymers thereof are likely to be formed. Free silicic acid and / or its polymers can produce undissolved residues of detergent remaining on clothing, with a mechanism different from that derived from 0.015 to 0.5 μm pore size, especially base granules When 10% by weight or more of an alkali agent is blended therein, z is preferably 1.5 to 4.0 because undissolved residues derived from free silicic acid and / or polymers thereof tend to be generated. More preferably, it is 2.0-3.5. The “alkali agent” means a component having a pH of 10.1 or higher when 0.1 g of this component is dispersed in 1 L of distilled water at 25 ° C., specifically sodium carbonate, Examples thereof include potassium carbonate, JIS No. 1 sodium silicate, and JIS No. 2 sodium silicate. The composition of the amorphous aluminosilicate with controlled pore size can be determined by a known elemental analysis method, for example, by a fluorescent X-ray method or high frequency inductively coupled plasma emission spectroscopy (ICP). Can do.
[0015]
In addition, the chemical stability of the amorphous aluminosilicate with controlled pore size with respect to the alkaline agent in the base granule is determined by the amount of free silicic acid and / or its polymer eluted from the amorphous aluminosilicate under alkaline conditions. It can be evaluated by measuring. Free silicic acid and / or its polymer is conveniently SiO 2₂The amount of elution was 0.20% by weight or less, preferably 0.15% by weight or less, more preferably 0.10% by weight or less, based on the controlled controlled aluminosilicate whose elution amount was tested. When it is, the generation | occurrence | production rate of the undissolved residue of a detergent can be reduced. In particular, it is effective when the blending amount of the alkaline agent is 10% by weight or more in the base granule.
[0016]
In addition, the measurement of the elution amount of free silicic acid and / or its polymer under alkaline conditions is performed as follows. That is, in a 100 mL container (for example, made of high-density polyethylene, Teflon, etc.) resistant to alkalinity, 5.0 g of amorphous aluminosilicate with controlled pore size and 50 mL of 20.0% sodium carbonate are placed, Shake and stir at 20 ° C. for 16 hours, and then filter the powder suspension through a 0.2 μm filter. Weigh 5.0 mL of the filtrate into a 100 mL volumetric flask, add 5 mL of 6N HCl aqueous solution, and make a total amount of 100 mL with ion-exchanged water.₂In terms of amount, the amount of free silicic acid and / or their polymers eluted is obtained.
[0017]
Next, a method for synthesizing amorphous aluminosilicate with controlled pore diameter will be described. The amorphous aluminosilicate with controlled pore size can be obtained, for example, by mixing and reacting synthetic raw materials at an appropriate temperature, stirring strength, dropping method, dropping speed, concentration and ratio.
[0018]
Examples of the synthetic raw material include an alkali metal aluminate aqueous solution, an alkali metal silicate aqueous solution, and a divalent metal salt aqueous solution. As the alkali metal aluminate salt solution and the alkali metal silicate aqueous solution, a commercially available product or an aluminum source such as aluminum hydroxide or a silica source such as silicic acid subjected to alkali treatment together with the alkali metal salt aqueous solution may be used. . As the divalent metal salt aqueous solution, a water-soluble divalent metal salt such as a chloride such as calcium chloride or magnesium chloride, or a sulfate is preferably used. Further, when the divalent metal atom is Ca or Mg, hard water may be used.
[0019]
The concentration of the raw material used will be described. The concentration of the aqueous alkali metal aluminate salt solution and the aqueous alkali metal silicate salt solution is not particularly limited, but is preferably 15 to 60% by weight from the viewpoints of operability and productivity due to increased adhesiveness of the aqueous solution. The concentration of the divalent metal salt aqueous solution is preferably 0 to 5% by weight. As a blending ratio, it is preferable that the alkali metal aluminate aqueous solution is 5 to 50% by weight, the alkali metal silicate aqueous solution is 1 to 40% by weight, and the divalent metal salt aqueous solution is 0 to 3% by weight in the raw material mixture. . Here, the concentration ratio of the alkali metal silicate aqueous solution to the alkali metal aluminate aqueous solution is preferably 0.8 or less from the viewpoint of controlling the pore diameter.
The synthesis temperature is preferably 10 to 80 ° C, more preferably 20 to 60 ° C, and particularly preferably 25 to 55 ° C.
As the stirring strength, it is preferable not only to increase the reaction rate but also to control the pore size so that the reaction liquid is uniformly stirred so as to disperse uniformly.
As a dropping method, it is preferable to drop the alkali metal silicate aqueous solution having the above concentration into the alkali metal aluminate aqueous solution having the above concentration, and it is preferable to perform the dropping speed as slowly as possible for controlling the pore diameter.
[0020]
In addition, by introducing a ripening step after the reaction step, elution of silicon and aluminum from the amorphous aluminosilicate with improved oil absorption ability and controlled pore size can be suppressed. The aging temperature is preferably 50 to 100 ° C. from the viewpoint of oil absorption capacity and elution amount.
[0021]
The amorphous aluminosilicate with controlled pore size synthesized by the above method is separated from the mother liquor by an operation such as filtration, and then repeatedly washed with filtration, or neutralized with an acid such as sulfuric acid or carbon dioxide, and surplus. Al in the reaction solution by removing alkali components, etc.₂O_Three, SiO₂It is preferable to reduce unreacted substances such as This is because when a base granule is produced using a slurry containing an unreacted substance, a shell of the unreacted substance is formed on the surface, and the oil absorption capacity of the base granule is reduced. The median diameter of the amorphous aluminosilicate having a controlled pore diameter thus obtained is preferably 1 to 30 μm.
[0022]
The blending amount of the amorphous aluminosilicate whose pore size is controlled is preferably 1 to 20% by weight, more preferably 1 to 10% by weight, and further preferably 2 to 8% by weight in the base granule group.
[0023]
Examples of other water-insoluble inorganic substances include crystalline aluminosilicates, amorphous aluminosilicates other than those mentioned above, silicon dioxide, hydrated silicate compounds, clay compounds such as perlite, bentonite, and the like. Crystalline aluminosilicates are preferred because they do not promote the generation of undissolved residues. A suitable crystalline aluminosilicate is A-type zeolite (for example, trade name: “Toyo Builder”; manufactured by Tosoh Corporation), which is also preferable in terms of sequestering ability and economy. Here, the value of the oil absorption capacity of the A-type zeolite according to the JIS K 5101 method is preferably 40 to 50 mL / 100 g. In addition, P type (for example, trade names “Doucil A24”, “ZSE064”, etc .; all manufactured by Crosfield; oil absorption capacity 60 to 150 mL / 100 g), X type (for example, trade name “WessalithXD”; manufactured by Degussa; oil absorption capacity) 80 to 100 mL / 100 g) and hybrid zeolite described in WO9842622 are also suitable as a crystalline aluminosilicate. Here, the average particle diameter of the primary particles of these water-insoluble inorganic substances is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm.
[0024]
The water-insoluble inorganic substance other than the amorphous aluminosilicate whose pore size is controlled is appropriately blended in consideration of cleaning performance and quality, and the blending amount thereof is preferably 5 to 60% by weight in the base granule group. More preferably, it is 15 to 50% by weight, particularly preferably 20 to 40% by weight.
[0025]
(B) Water-soluble polymer
The water-soluble polymer used in the present invention is not particularly limited as long as it has an effect of improving the washing performance and / or improving the particle strength of the base granule, but is not limited to carboxylic acid polymer, carboxymethyl cellulose, soluble Starch, saccharides and the like can be mentioned, among which carboxylic acid polymers are preferred. Among the carboxylic acid polymers, acrylic acid-maleic acid copolymer salts and polyacrylates are particularly excellent. The counter ions of these salts are preferably sodium ions, potassium ions and ammonium ions. The carboxylic acid-based polymer preferably has a molecular weight of 1000 to 100,000, more preferably 2000 to 80000, and particularly preferably 5000 to 50000.
[0026]
In addition to carboxylic acid polymers, polymers such as polyglyoxylate, cellulose derivatives such as carboxymethyl cellulose, and aminocarboxylic acid polymers such as polyaspartate can also be used.
[0027]
The compounding amount of these water-soluble polymers not only has the effect of increasing the particle strength of the base granules, but also improves the dispersibility in the slurry of amorphous aluminosilicate with controlled pore size, and aggregated particles 2 to 20% by weight, more preferably 4 to 12% by weight, and most preferably 5 to 9% by weight of the base granule group.
[0028]
(C) Water-soluble salts
Examples of water-soluble salts include carbonates, bicarbonates, sulfates, sulfites, hydrogen sulfates, alkali metal salts such as phosphates, ammonium salts, and water-soluble inorganic salts such as amine salts and citrates. And low molecular weight water-soluble organic acid salts such as fumarate. Of these, carbonates, sulfates, sulfites and phosphates are preferred. For example, sodium carbonate is preferable as an alkaline agent that exhibits a suitable pH buffer region in the washing liquid. In addition, water-soluble salts having a high degree of dissociation such as sodium sulfate, potassium sulfate, sodium sulfite, etc. increase the ionic strength of the washing liquid, and act suitably for sebum soil washing and the like. In addition, sulfite is important because it reduces hypochlorite ions contained in tap water and prevents oxidative degradation of detergent components such as enzymes and perfumes by hypochlorite ions. Also preferred is sodium tripolyphosphate.
[0029]
In addition, examples of low molecular weight water-soluble organic salts include carboxylates such as citrate and fumarate.^{2 +}A base having a large and / or large cation exchange capacity is preferred. Specifically, methyliminodiacetate, iminodisuccinate, ethylenediamine disuccinate, taurine diacetate, hydroxyethyliminodiacetate, β-alanine diacetate, hydroxyiminodisuccinate, methylglycine diacetate, glutamic acid Examples thereof include diacetate, asparagine diacetate, and serine diacetate.
[0030]
In addition, mixing an anion different from carbonates such as sulfate and sulfite and a cation different from sodium such as ammonium in the base granule is effective in terms of non-paste formation between detergent particles in water. There is.
[0031]
The blending amount of the water-soluble salts is preferably from 5 to 75% by weight, more preferably from 10 to 70% by weight, more preferably from 20 to 70% by weight of the base granule group, since the particle strength is sufficient and the solubility of the detergent composition is also preferable. 60% by weight is most preferred.
[0032]
In the base granule group of the present invention, a surfactant may or may not be contained. If a slurry containing a large amount of a surfactant is spray-dried, for example, the base granule may become a film, which may reduce the oil absorption capacity. If a surfactant is present in the base granule, the oil is absorbed. There is an advantage that the amount of the surfactant can be reduced, and addition of the surfactant into the slurry also has an effect of improving the drying efficiency at the time of spray drying. Therefore, the blending amount is 0 to 10% by weight of the base granule group, preferably 0 to 5% by weight, and more preferably 0 to 3% by weight.
[0033]
The surfactant content of the base granule group of the present invention is 0 to 10% by weight. Here, when a slurry containing a surfactant is spray-dried to produce a base granule, a coating tends to be formed on the surface of the resulting base granule. As a result, the oil absorption capacity of the base granule group is reduced. May be reduced. Therefore, from this viewpoint, it is preferable that the content of the surfactant in the base granule group is smaller, and it is preferable that the surfactant is not present.
On the other hand, the addition of a surfactant to the slurry also has the advantage that the drying efficiency during spray drying is improved. Therefore, from this viewpoint, it is preferable to add a surfactant to the base granule group. From the above, the content of the surfactant in the base granule group is 0 to 10% by weight, more preferably 0 to 5% by weight, and particularly preferably 0 to 3% by weight.
[0034]
Examples of the surfactant herein include, for example, a surfactant supported on the base granule group.
[0035]
In the base granule group of the present invention, auxiliary components such as builder granules, fluorescent dyes, pigments, and dyes suitable for the detergent composition can be appropriately blended, and the moisture content of the base granule group is 1 by the infrared moisture method. About 10 to 10% by weight is preferable, more preferably 1.5 to 8% by weight, more preferably 2 to 6% by weight, and most preferably 2 to 5% by weight.
[0036]
The moisture content of the base granule group is measured by the infrared moisture method. That is, 3 g of a sample is weighed to 0.01 g on a sample dish having a known mass, and the sample is heated and dried for 3 minutes by an infrared moisture meter (manufactured by Kett Scientific Laboratory (infrared lamp 185W)). After drying, weigh the sample pan and dry sample to 0.01 g. The difference between the container before and after drying obtained by the above operation and the sample is divided by the amount of the sample taken and multiplied by 100 to calculate the moisture content in the sample.
[0037]
3. Manufacturing method of base granules
The base granule group of the present invention can be prepared, for example, by preparing a slurry containing a water-insoluble inorganic substance and dissolving 60% by weight or more of a water-soluble polymer and a water-soluble salt, and drying the slurry. The amorphous aluminosilicate having a controlled pore diameter may be blended as a slurry of the reaction product described in the above-mentioned section “(A) Water-insoluble inorganic substance”. What was filtered and washed may be blended. Further, it can be confirmed by the following method that 60% by weight or more of the water-soluble polymer and the water-soluble salt are dissolved in the slurry. That is, the slurry is filtered under reduced pressure, and the water concentration (P%) in the filtrate is measured. The slurry moisture is (Q%), and the concentration of the water-soluble component in the slurry is (R%). Formula (2):
[0038]
[Expression 1]

[0039]
Is used to calculate the dissolution rate of the water-soluble component. However, when the calculated dissolution rate exceeds 100%, the dissolution rate is set to 100%.
[0040]
Examples of the drying method of the slurry include fluidized tank drying, freeze drying, spray drying, and the like. Among these, spray drying is particularly preferable in which the slurry is instantaneously dried in a spherical shape. This not only makes the particle shape substantially spherical, but also suppresses variations in the particle size distribution, so that a detergent particle group with improved solubility, fluidity and caking resistance can be obtained. The slurry atomization device may be any form of a pressure spray nozzle, a two-fluid spray nozzle, and a rotating disk type, but the average particle size of the base granule group is 150 to 500 μm, preferably 180 to 300 μm. A pressure spray nozzle is particularly preferred. The spray drying tower may be in the form of either a countercurrent tower or a cocurrent tower, but a countercurrent tower is more preferred because of improved thermal efficiency and particle strength of the base granule group. Moreover, the temperature of the hot gas supplied to the spray drying tower is preferably 150 to 300 ° C, more preferably 170 to 250 ° C in terms of productivity and ease of manufacture. The temperature of the gas discharged from the drying tower is preferably 70 to 130 ° C, more preferably 80 to 120 ° C, from the viewpoint of the thermal efficiency of the drying tower.
[0041]
4). Physical properties of base granules
The base granule group of the present invention can carry a large amount of a nonionic surfactant having a melting point of 40 ° C. or less which is effective for sebum stains in a low temperature region. The oil absorption capacity of such base granules is 0.40 g / g or more, preferably 0.50 g / g or more, more preferably 0.60 g / g or more by the nonionic surfactant dropping method. It is. In addition, the measurement of the oil absorption ability by the nonionic surfactant dropping method is performed as follows. That is, 100 g of the base granule group maintained at 30 ° C. was placed in a cylindrical mixing vessel having an inner diameter of about 5 cm × about 15 cm with a stirring blade inside, and the liquid temperature was maintained at 30 ° C. while stirring at 350 rpm. Surfactant (alkyl group carbon number 12/14 (hereinafter referred to as C12 / C14) = 6/4, average ethylene oxide addition number (hereinafter referred to as EO) = 7.7, melting point: 25 ° C.) about 10 g / min The amount of the nonionic surfactant added when the stirring power becomes the highest is determined as the oil absorption capacity.
[0042]
The bulk density of the base granule group is 400 to 1000 g / L, preferably 450 to 800 g / L, more preferably 500 to 700 g / L, and further 500 to 650 g / L from the viewpoint of producing a compact detergent. preferable. The bulk density is measured by the method specified by JIS K 3362.
[0043]
Next, as an average particle diameter of a base granule group, 150-500 micrometers is preferable and 180-300 micrometers is more preferable. In addition, as a measuring method, it calculates | requires using the screen prescribed | regulated to JISZ8801. For example, using a 9-stage sieve and saucer with openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm, and 125 μm, a low-tapping machine (made by HEIKO SEISAKUSHO, tapping: 156 times / minute, rolling: 290 times / minute), 100 g of the sample was shaken for 10 minutes and sieved, and then the saucer and each sieve in the order of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 μm When the weight frequency is accumulated on the top, the opening of the first sieve where the accumulated weight frequency is 50% or more is aμm, and the opening of the sieve that is one step larger than aμm is bμm. Of the weight frequency up to the sieve of c% on the sieve of aμm If the weight frequency was d%,
Formula: Average particle size = 10 ^A :

Can be determined according to
The sieve to be used is appropriately adjusted so that the particle size distribution of the measured powder can be accurately estimated.
[0044]
Further, the water insoluble matter generation rate of the base granule group is preferably 3% by weight or less, more preferably 1.5% by weight or less, and still more preferably 0, from the viewpoint of reducing the remaining undissolved detergent particles in the washing machine. .8% by weight or less. In addition, the water insoluble matter generation rate of a base granule can be measured as follows. That is, 100 parts of the base granule group was temperature-adjusted to 80 ° C., then charged into a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd.), and the temperature was adjusted to 80 ° C. while mixing at a spindle rotation speed of 50 rpm. 20 parts of a nonionic surfactant (C12 / C14 = 6/4, EO = 6.0, melting point; 15 ° C.) are added dropwise over 2 minutes. After the dropwise addition, the mixture is further stirred for 10 minutes, and then 25 parts of zeolite (“Toyo Builder”; manufactured by Tosoh Corporation) is added, followed by stirring and mixing for 1 minute at a spindle rotation speed of 150 rpm and a chopper rotation speed of 5000 rpm. Coarse particles are removed from the obtained powder with a 710 μm sieve to obtain a test detergent particle group. Vertical x horizontal x height = 10 cm x 6 cm x 4 cm using 100 g of the obtained test detergent particle group using two types of filter paper defined by JIS P 3801 (for example, "Qualitative No. 2 filter paper" manufactured by Toyo Roshi Kaisha, Ltd.). Is filled in a box with an open top and stored in a constant temperature room at 40 ° C. and 80% RH for 12 hours. After the whole sample after storage is taken out from the filter paper box and mixed, a test detergent particle group reduced by using a rotary type reducer is obtained. Next, 1 L of tap water (water temperature 20 ° C.) was put into a 1 L beaker made of glass, and after stirring with a stirring bar having a rotation speed of 1200 rpm, a length of 35 mm and a diameter of 8 mm in advance, the rotation speed was stabilized, and then the above-mentioned contraction was performed. Add 0.667 g of the test detergent particle group and dissolve the test detergent particle group for 10 minutes. Immediately after 10 minutes, the test detergent suspension was filtered with a 200-mesh metal sieve that had been weighed in advance, and the test detergent residue was dried together with the metal sieve at 105 ° C./30 minutes, and then allowed to cool in a desiccator for 30 minutes. And weigh accurately. The residual rate is calculated from the weight difference of the metal sieve before and after the test and the weight of the tested detergent particle group, and the water insoluble matter generation rate (%) of the base granule group is obtained.
[0045]
Since the base granule group of the present invention obtained by such a method has a high bulk density and oil absorption capacity and has very little undissolved residue, it can be suitably used as a raw material for a high bulk density detergent composition.
[0046]
5. Surfactant loading on base granules
The detergent particle group of the present invention preferably contains mononuclear detergent particles from the viewpoint of solubility. “Mononuclear detergent particles” are detergent particles in which a surfactant is supported on base granules, and each detergent particle has one base granule as a core in one detergent particle. As a factor expressing mononuclearity, the degree of grain growth defined by the following formula can be used, and the value is preferably 1.5 or less, more preferably 1.3 or less.
[0047]
Particle growth degree = (average particle size of final detergent particles) / (average particle size of base granules)
[0048]
Here, the final detergent particle group refers to either a detergent particle group after a surfactant is supported on the base granule group, or a detergent particle group obtained by subjecting the particle group to surface modification treatment.
Mononuclear particles can be confirmed by at least one of the following (α) method, (β) method, and (γ) method.
(Α) method: detergent particles arbitrarily cut from the vicinity of the average particle diameter of the detergent particles, and the presence and number of base granules in the detergent particles are observed with a scanning electron microscope (SEM) to thereby obtain detergent particles. To confirm the mononuclear nature of It can be seen that the detergent particles contained in the detergent particle group of the present invention are mononuclear detergent particles having a base granule as a core.
Method (β): An organic solvent that does not dissolve the water-soluble polymer in the base granule in the detergent particles (for example, polyacrylate as the water-soluble polymer and an anionic surfactant (LAS as the surfactant) in the base granule). ) Or a nonionic surfactant, ethanol can be preferably used), and the organic solvent-soluble component in the detergent particles is extracted, and the subsequent organic solvent-insoluble component is observed by SEM observation. . That is, when one base granule exists in the organic solvent insoluble matter obtained by treating one detergent particle with the organic solvent, it is understood that the detergent particle is mononuclear.
(Γ) Method: A method for confirming the mononuclearity of the detergent particles by detecting the two-dimensional element distribution on the cut surface of the detergent particles embedded with the resin by EDS or EPMA.
[0049]
5-a) Loading of surfactant
The amount of the surfactant to be supported on the base granule group is preferably 10 to 100 parts by weight, more preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight based on 100 parts by weight of the base granule group, from the viewpoint of exerting detergency. Part by weight is more preferable, and 35 to 65 parts by weight is particularly preferable. Further, when a nonionic surfactant having a melting point of 40 ° C. or lower is blended in the surfactant to be supported on the base granule in an amount of 20% by weight or more, preferably 30% by weight or more, the cleaning performance against sebum soil is improved. Here, the nonionic surfactant can be used alone, but it is preferably mixed with an anionic surfactant because of its detergency to various stains and undissolved residue in clothing. The amount of the anionic surfactant is preferably 20% by weight or more of the surfactant, more preferably 30% by weight or more, and further preferably 40% by weight or more. Further, amphoteric surfactants and cationic surfactants can be used in combination for the purpose. When the surfactant is blended at the time of slurry preparation, the loading amount of the surfactant here does not include the blending amount of the surfactant.
[0050]
The melting point of the nonionic surfactant is preferably 40 ° C. or less, more preferably 30 ° C. or less, particularly preferably 25 ° C. or less, and preferably 22 ° C. or less. For example, polyoxyalkylene alkyl Preferred examples include (phenyl) ether, alkyl polyglycoxide, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, and polyoxyalkylene alkylol (fatty acid) amide. Examples of the anionic surfactant include a sulfate ester salt of an alcohol having 10 to 18 carbon atoms, a sulfate ester salt of an alkoxylate of an alcohol having 8 to 20 carbon atoms, an alkylbenzene sulfonate, a paraffin sulfonate, and an α-olefin sulfone. Acid salts, α-sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts or fatty acid salts are preferred. In the present invention, a linear alkylbenzene sulfonate having an alkyl chain with 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms is preferred, and alkali ions and amines are preferred as the counter ion, particularly sodium ions and Preference is given to potassium ions, monoethanolamine and diethanolamine.
[0051]
As a method for supporting the surfactant on the base granule group, for example, a batch type or continuous type mixer can be used. In addition, when the batch method is used, the mixing method is as follows: (1) First, the base granule group is charged into the mixer and then a surfactant is added; (2) The base granule group and the interface are mixed into the mixer. The activator can be charged in small amounts, (3) after a part of the base granule group is charged into the mixer, the remaining base granule group and the surfactant are charged in small amounts. The methods (1) to (3) are preferably performed while the mixer is operated. Among these methods, the above (1) is particularly preferable. The surfactant is preferably added in a liquid state, and it is preferable to spray and supply a surfactant in the liquid state. This addition method is preferable because the detergent particles can be produced while maintaining the mononuclearity of the base granules.
[0052]
Among the surfactants, those that exist in a solid or paste form within a practical temperature range, for example, at a temperature of 50 to 90 ° C., are previously low in viscosity, for example, nonionic It can be prepared as a surfactant, a nonionic surfactant aqueous solution, or a mixed solution or aqueous solution of a surfactant dispersed or dissolved in water, and added to the base granules in the form of the mixed solution or aqueous solution. By this method, a surfactant present in a solid or paste form can be easily added to the base granule group, which is advantageous for the production of a detergent particle group containing mononuclear detergent particles. The mixing ratio of the low-viscosity surfactant or water and the solid or pasty surfactant is preferably within a viscosity range in which the resulting mixed solution or aqueous solution can be sprayed.
[0053]
Examples of the method for producing the above mixed liquid include a method in which a surfactant having a low viscosity or a surfactant in the form of a solid or paste is added to water and mixing, or a surfactant acid in a low viscosity surfactant or in water. A surfactant mixed solution may be prepared by neutralizing the precursor with an alkali agent (for example, an aqueous caustic soda solution or an aqueous caustic potash solution).
[0054]
In this step, it is also possible to add an acid precursor of an anionic surfactant before, simultaneously with, during or after the addition of the surfactant. Addition of acid precursor of anionic surfactant, high surfactant content, oil absorption control of base granule group, anti-bleaching of nonionic surfactant of detergent particle group, fluidity, etc. The physical properties and quality of the product can be improved.
[0055]
Examples of the acid precursor of the anionic surfactant include alkylbenzene sulfonic acid, alkyl or alkenyl ether sulfuric acid, alkyl or alkenyl sulfuric acid, α-olefin sulfonic acid, α-sulfonated fatty acid, alkyl or alkenyl ether carboxylic acid, fatty acid. Etc. In particular, it is preferable to add the fatty acid after the addition of the surfactant from the viewpoint of improving the fluidity of the detergent particles.
[0056]
The amount of the acid precursor of the anionic surfactant used is 0.1% relative to 100 parts by weight of the base granule group from the viewpoint of maintaining the mononuclearity of the particles in the detergent particle group and exhibiting good high-speed solubility. 5-30 weight part is preferable, 1-20 weight part is more preferable, 1-10 weight part is further more preferable, and 1-5 weight part is especially preferable. The usage destination of the acid precursor is not calculated for the surfactant according to the present invention. In addition, as a method for adding the acid precursor of the anionic surfactant, it is preferable to spray and supply a liquid at room temperature, and a solid at room temperature may be added as a powder or melted. You may supply after spraying. However, when adding with a powder, it is preferable to raise the temperature of the detergent particle group in a mixer to the temperature which a powder fuse | melts.
[0057]
As an apparatus preferably used in the surfactant loading step, Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), vertical granulator (manufactured by Paulek Co., Ltd.), There are Redige Mixer (manufactured by Matsuzaka Giken Co., Ltd.), Proshare Mixer (manufactured by Taiheiyo Kiko Co., Ltd.), Nauter Mixer (manufactured by Hosokawa Micron Co., Ltd.), and the like.
[0058]
As a preferred mixer, from the viewpoint of producing a detergent particle group containing a large amount of mononuclear detergent particles, an apparatus in which a strong shearing force is not easily applied to the base granule (the base granule is difficult to disintegrate), and the surfactant dispersion efficiency is obtained. In view of the above, an apparatus with good mixing efficiency is preferable. Among the mixers described above, it is particularly preferable that a horizontal mixing tank has a stirring shaft at the center of a cylinder, and a mixer (horizontal mixer) of a type in which a stirring blade is attached to this shaft to mix powder is ready. There are mixers and professional share mixers.
[0059]
In addition, here, when a nonionic surfactant is used, a water-soluble nonionic organic compound having a melting point of 45 to 100 ° C. and a molecular weight of 1000 to 30000 (hereinafter referred to as “the surfactant”) has an effect of increasing the melting point of the surfactant. , Or a melting point raising agent) or this aqueous solution is added before adding the surfactant, at the same time as adding the surfactant, in the middle of adding the surfactant, after adding the surfactant, or by mixing with the surfactant in advance. It is preferable to do. By adding the melting point increasing agent, it is possible to suppress the caking property of the detergent particle group and the bleed-out property of the surfactant in the detergent particle group. Examples of the melting point raising agent that can be used in the present invention include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and pluronic-type nonionic surfactant.
The amount of the melting point raising agent used is preferably 0.5 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, and most preferably 1 to 3 parts by weight with respect to 100 parts by weight of the base granule group. This range is preferable from the viewpoint of suppression of aggregation between detergent particles contained in the detergent particle group, high-speed solubility, and suppression of spotting and caking properties. As a method for adding the melting point increasing agent, mixing with a surfactant in advance by an arbitrary method, or adding a melting point increasing agent after the addition of the surfactant is effective for the detergent particles to cause stains and caking properties. It is advantageous for suppression.
[0060]
It is more preferable that the temperature in the mixer in this step is mixed by raising the temperature above the pour point of the surfactant measured by the method defined in JIS K 2269. Here, the temperature for raising the temperature may be higher than the pour point of the surfactant to be added to promote the loading of the surfactant. A temperature up to a higher temperature is preferable, and a temperature higher by 10 to 30 ° C. than the pour point is more preferable. Moreover, when adding the acid precursor of an anionic surfactant at this process, it is more preferable if it heats up to the temperature which can react the acid precursor of the said anionic surfactant, and it mixes.
[0061]
The batch mixing time for obtaining a suitable detergent particle group and the average residence time in continuous mixing are preferably 1 to 20 minutes, more preferably 2 to 10 minutes.
[0062]
In addition, when an aqueous solution of a surfactant or an aqueous solution of a water-soluble nonionic organic compound is used, it may have a step of drying excess water during and / or after mixing, before adding the surfactant, It is also possible to add a powdery surfactant and / or a powder rudder simultaneously with the addition, during the addition, or after the addition. By adding a powder builder, the particle diameter of the detergent particle group can be controlled, and the cleaning power can be improved. In particular, when an acid precursor of an anionic surfactant is added, it is effective from the viewpoint of accelerating the neutralization reaction to add an alkaline powder builder before adding the acid precursor. The term “powder builder” as used herein means a detergency enhancing agent for powders other than surfactants, and specifically, a base that exhibits sequestering ability such as zeolite and citrate, and carbonic acid. It refers to a base having an alkaline ability such as sodium and potassium carbonate, a base having both a sequestering ability and an alkaline ability such as crystalline silicate, and other bases which increase ionic strength such as sodium sulfate.
[0063]
Here, as the crystalline silicate, JP-A-5-279913, column 3, line 17 to column 6, line 24 (particularly, those which are fired and crystallized at 500 to 1000 ° C. are preferred), Kohei 7-89712, column 2, line 45 to column 9, line 34, JP-A-60-227895, page 2, lower right column, line 18 to page 4, upper right column, line 3 (especially second line) The crystalline silicates described in Table 1 are preferred as powder builders. Where alkali metal silicate SiO₂/ M₂O (molar ratio; M represents an alkali metal atom) is preferably 0.5 to 3.2, more preferably 1.5 to 2.6.
[0064]
The amount of powder builder used is the base granule group because the mononuclearity of the detergent particles contained in the detergent particle group is maintained, good high-speed solubility can be obtained, and control of the particle diameter is also suitable. 0.5 to 12 parts by weight is preferable with respect to 100 parts by weight, and 1 to 6 parts by weight is more preferable.
[0065]
Moreover, the detergent particle group of this invention can contain a polynuclear detergent particle. The polynuclear detergent particles may be agglomerated base granules constituting the mononuclear detergent particles described above, or may be agglomerated using water-soluble salts such as sodium carbonate as a nucleus. Moreover, the polynuclear detergent particle can be easily formed by increasing the amount of the surfactant. A foaming agent such as baking soda or percarbonate may be added to promote dissolution between base granules.
[0066]
5-b) Surface modification step
In the present invention, in order to modify the particle surface of the detergent particle group carrying the surfactant by the above-described method, the following (1) fine powder, (2) liquid, etc. The surface modification step for adding various surface coating agents may be performed in one step or two steps.
Since the flowability and non-caking property of the detergent particle group tends to be improved when the particle surface of the detergent particle group of the present invention is coated, the surface modification step is preferable. The apparatus used in the surface modification step is not particularly limited, and a known mixer can be used, but the mixer exemplified in the above 5-a) is preferable. Each surface coating agent will be described below.
[0067]
(1) Fine powder
The average particle size of the primary particles of the fine powder is preferably 10 μm or less, preferably 0.1 to 10 μm from the viewpoint of improving the coverage of the particle surface of the detergent particle group and improving the fluidity and caking resistance of the detergent particle group. Is more preferable. The average particle diameter is measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba, Ltd.), or measurement by microscopic observation. Moreover, it is preferable from a cleaning surface that the fine powder has a high ion exchange ability and a high alkali ability.
[0068]
The fine powder is preferably an aluminosilicate, which may be crystalline or amorphous. Other than aluminosilicates, silicate compounds such as sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate compounds, metals with an average primary particle size of 0.1 to 10 μm Soaps, powder surfactants (eg alkyl sulfates), water-soluble organic salts and the like are also preferred. When a crystalline silicate compound is used, it is preferably used by mixing with a fine powder other than the crystalline silicate compound for the purpose of preventing deterioration due to moisture absorption or aggregation of the crystalline silicate due to carbon dioxide gas. As the amorphous aluminosilicate, an amorphous aluminosilicate having a controlled pore size used in the present invention is preferable.
[0069]
The amount of the fine powder used is preferably 0.5 to 40 parts by weight, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the detergent particle group, from the viewpoint of improving fluidity and giving a good feeling to the consumer. Is more preferable, and 2 to 20 parts by weight is particularly preferable.
[0070]
(2) Liquid material
Examples of the liquid material include aqueous solutions and melts such as water-soluble polymers and fatty acids.
(2-1) Water-soluble polymer
Examples of the water-soluble polymer include carboxymethyl cellulose, polyethylene glycol, polyacrylic acid soda, a polycarboxylic acid salt such as a copolymer of acrylic acid and maleic acid or a salt thereof, and the like. As a usage-amount of a water-soluble polymer, 0.5-10 weight part is preferable with respect to 100 weight part of detergent particle groups, 1-8 weight part is more preferable, and 2-6 weight part is especially preferable. Within this range, the amount of the water-soluble polymer used is a powder that maintains the mononuclear nature of the detergent particles contained in the detergent particle group, provides good high-speed solubility, and exhibits good fluidity and caking resistance. You can get a body.
(2-2) Fatty acid
Examples of the fatty acid include fatty acids having 10 to 22 carbon atoms. As the usage-amount of a fatty acid, 0.5-5 weight part is preferable with respect to 100 weight part of detergent particle groups containing mononuclear detergent particle | grains, and 0.5-3 weight part is especially preferable. In the case of a solid at room temperature, it is preferable to spray and supply after heating to a temperature showing fluidity.
[0071]
The average particle size of the detergent particle group of the present invention is preferably 150 to 750 μm, more preferably 200 to 450 μm, and particularly preferably 220 to 350 μm from the viewpoints of solubility, powder feel and storage stability. Further, from the viewpoints of transportation and storage properties and solubility, the bulk density is preferably 500 to 1200 g / L, more preferably 600 to 900 g / L, and particularly preferably 650 to 800 g / L.
[0072]
The base granule group of the present invention can be suitably used as a raw material for a high bulk density detergent composition. For example, when producing a detergent composition, the base granule group obtained by spray drying or the like may be subjected to compaction / granulation treatment while adding a surfactant as necessary, and particularly shown in the present application. It is not limited to the granulation method for obtaining a mononuclear detergent. Further, a detergent component containing 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more of these detergent particle groups, and further added separately in the detergent particle group Detergent compositions in which after blending (for example, builder granules, enzymes, fluorescent dyes, fragrances, bleaching agents, bleach activators, etc.) are also within the scope of the present invention.
[0073]
The detergent composition of the present invention obtained by such a method has a bulk density of preferably 500 to 1200 g / L, more preferably 600 to 900 g / L, so that it can be transported, carried and stored. It can be an excellent compact detergent.
[0074]
【Example】
Synthesis Examples 1 to 5 (Synthesis of amorphous aluminosilicate with controlled pore size)
50 ° C, 50% sodium aluminate aqueous solution 17.62 kg, 50 ° C, 40% sodium silicate aqueous solution 19.72 kg and 1% calcium chloride aqueous solution 45.18 kg mixed solution (1) 60 minutes, (2) 30 minutes, (3) The pump was adjusted so that the dripping was completed in 20 minutes, (4), 5 minutes, and (5) 2 minutes (respectively, Synthesis Examples 1 to 5). Then, after 10 minutes at a reaction temperature of 50 ° C. and 10 minutes at an aging temperature of 80 ° C., the mixture was cooled to 60 ° C. to obtain an amorphous aluminosilicate having a controlled pore size. Next, 5.0 kg of concentrated sulfuric acid was added dropwise to this slurry solution to neutralize it to about pH 10.5 to obtain a 20% concentration slurry solution. The composition formula of the amorphous aluminosilicate having a controlled pore size obtained after washing and washing a part of the slurry solution is as follows: (1) 0.92Na₂O · 0.011CaO · Al₂O_Three2.13SiO₂, (2) 0.94Na₂O ・ 0.01CaO ・ Al₂O_Three2.14SiO₂, (3) 0.93Na₂O.0.012CaO.Al₂O_Three2.13SiO₂, (4) 0.92Na₂O · 0.011CaO · Al₂O_Three2.14SiO₂, (5) 0.93Na₂O ・ 0.01CaO ・ Al₂O_Three2.14SiO₂Met. The physical properties are shown in Table 1.
[0075]
[Table 1]

[0076]
From the results shown in Table 1, when the particle size of the obtained amorphous aluminosilicate was measured using “LA-700” (manufactured by Horiba, Ltd.), the median diameter was increased by increasing the dropping speed. Accordingly, the higher the dropping speed, the higher the oil absorption capacity.
[0077]
Production example 1 of base granule group
136.0kg of water 1m with stirring blades^ThreeAfter the water temperature reached 55 ° C. and stirred for 15 minutes, 65.0 kg of sodium carbonate, 56.5 kg of sodium sulfate, 2.5 kg of sodium sulfite, and 2.5 kg of fluorescent dye were added. Next, 37.5 kg of 40% by weight sodium polyacrylate aqueous solution was added, and a 20% concentration slurry of amorphous aluminosilicate (excluding 5) with controlled pore size obtained in Synthesis Examples 1-5. 125.0 kg of the solution and 75.0 kg of zeolite were added and stirred for 30 minutes to obtain a homogeneous slurry. The final temperature of this slurry was 58 ° C., and the water content in the slurry was 49% by weight. Next, this slurry is supplied to the spray drying tower by a pump, and the spray pressure is 25 kg / cm from a pressure spray nozzle installed near the top of the tower.²Was sprayed to obtain base granule groups a to e (corresponding to synthesis examples 1 to 5, respectively). The hot gas supplied to the spray-drying tower was supplied at a temperature of 225 ° C. from the bottom of the tower and discharged at 105 ° C. from the top of the tower. All of the obtained base granule groups a to e had a moisture content of 4% by weight in the infrared moisture meter. Table 2 shows the physical properties of the base granule groups a to e.
[0078]
[Table 2]

[0079]
From the results in Table 2, it can be seen that the greater the oil absorption capacity of the amorphous aluminosilicate used (see Table 1), the better the oil absorption capacity of the base granule group.
[0080]
Evaluation of base granule group
Table 2 shows the water insoluble matter generation rate and clothing residue of the base granule groups a to e. The water insoluble matter generation rate was measured as described above. Moreover, clothing residue was evaluated as follows.
[0081]
<Clothing residue test>
Matsushita Electric Co., Ltd. fully automatic washing machine "NA-F50A1" and 5 sheets of black cloth (Cotton Broad 40, dyeing agent Tanigami Shoten Co., Ltd., 40cm x 40cm) Cotton underwear (manufactured by Gunze Co., Ltd .; NO. YG6614) is put into the washing machine so that the total amount of cloth is 600 g. Subsequently, 27 g of the detergent composition used for the water insoluble matter generation rate measurement is charged, the water level of the washing machine is manually set to low (40 L), and washing is started on the standard course. The water temperature was 5 ° C. After washing, the black cloth was hung in a room at 25 ° C. and 40% RH for 12 hours and dried, and then the water insoluble matter (about 50 to 300 μm) attached to the clothing was visually observed per surface of the black cloth as follows. Evaluation was based on criteria.
[0082]
Evaluation criteria
“0” means that no water insoluble matter remains even when staring.
When staring, “0.25” indicates that water insoluble matter remains slightly.
At first glance, the ratio of the portion where the water insoluble matter is scattered is about 0.5% or more.
At first glance, the ratio of the portion where the water-insoluble matter is scattered is 5 minutes 5 minutes or more “1.0”
At first glance, "2.0" when the proportion of water-insoluble matter is 90% or more
[0083]
A total of 10 black cloths and 10 double-sided sheets were evaluated, and the average score on one side was defined as the clothing residue index. In addition, an article having a clothing residue index of 0.20 or less is regarded as an acceptable product.
From the results of Table 2, it can be seen that the smaller the volume (mL / g) of the used amorphous aluminosilicate at 0.015-0.5 μm, the lower the water insoluble matter generation rate of the base granule group. The actual clothes persistence index was also the same.
[0084]
Production example 2 of base granule group
Composition formula Na₂O ・ Al₂O_Three・ 12.2SiO₂A method for synthesizing a base granule containing an amorphous aluminosilicate (“Tixorex 25”; Cofran Chemical Co., Ltd.) is shown below. Table 3 shows physical property values of thixorex 25.
[0085]
[Table 3]

[0086]
16.0m with stirring blades 236.0kg of water^ThreeAfter the water temperature reached 55 ° C. and stirred for 15 minutes, 65.0 kg of sodium carbonate, 56.5 kg of sodium sulfate, 2.5 kg of sodium sulfite, and 2.5 kg of fluorescent dye were added. Next, 37.5 kg of 40 wt% sodium polyacrylate aqueous solution was added, 25.0 kg of thixolex and 75.0 kg of zeolite were added, and stirred for 30 minutes to obtain a homogeneous slurry. The final temperature of this slurry was 58 ° C. Moreover, the water | moisture content in this slurry is 49 weight%. This slurry is supplied to the spray drying tower by a pump, and the spray pressure is 25 kg / cm from a pressure spray nozzle installed near the top of the tower.²Spraying was performed to obtain a base granule group. The hot gas supplied to the spray-drying tower was supplied at a temperature of 225 ° C. from the bottom of the tower and discharged at 105 ° C. from the top of the tower. This base granule group (average particle size 245 μm, bulk density 550 g / L, oil absorption capacity 0.61 g / g) had a water insoluble matter generation rate of 11.5% and a clothing residue index of 1.50.
[0087]
[Production of detergent particles]
Detergent particles carrying detergent composition (A) and detergent particle group (A) 'using base granule groups b and e, and detergent particles carrying surfactant composition using base granule group b Groups (B) and (C) were obtained. Granulation of each detergent particle group was as follows.
[0088]
[Granulation of detergent particles (A) and (A) ']
23 parts by weight of a nonionic surfactant (C12 / C14 = 6/4, EO = 7.7), “Emulgen 107KM” (manufactured by Kao Corporation) was heated to 50 ° C. Ladyge mixer (pineSlopeThe base granule group b or e100 parts by weight of the previous term was put into Giken Co., Ltd. (volume: 20 L, with jacket), and stirring of the main shaft (150 rpm) was started. In addition, 60 degreeC warm water was poured at 10 L / min to the jacket, the said nonionic surfactant was thrown into it in 2 minutes, and it stirred for 4 minutes after that. Furthermore, 5 parts by weight of a crystalline silicate (“SKS-6”; manufactured by Clariant Tokuyama Co., Ltd.) and a crystalline aluminosilicate (4A type zeolite, The surface was coated with 10 parts by weight of “builder” (manufactured by Tosoh Corporation) to obtain a detergent particle group (A) or (A) ′.
[0089]
[Granulation of detergent particles (B)]
20 parts by weight of nonionic surfactant (C12 / C14 = 6/4, EO = 7.7), “Emulgen 107KM” manufactured by Kao Corporation and anionic surfactant (sodium alkylbenzenesulfonate 30 parts by weight) Corresponding alkylbenzene sulfonic acid (“Neoperex FS”; manufactured by Kao Corporation) and 2 parts by weight of sodium hydroxide aqueous solution and polyethylene glycol (“K-PEG6000”; manufactured by Kao Corporation) as a neutralizing agent at 80 ° C. The mixture was prepared by heating and mixing so that 100 parts by weight of the base granule group b was added to the above-mentioned Redige mixer, and the stirring of the main shaft (150 rpm) was started. The surfactant composition was poured into the mixture for 3 minutes, followed by stirring for 7 minutes. 10 parts by weight of crystalline silicate (“SKS-6”; manufactured by Clariant Tokuyama Co., Ltd.) and 10 parts by weight of crystalline aluminosilicate (type 4A zeolite, “Toyo Builder”; manufactured by Tosoh Corporation) The surface was coated with and a detergent particle group (B) was obtained.
[0090]
(Granulation of detergent particles (C))
Polyoxyethylene polyoxypropylene polyoxyethylene alkyl ether (C12, EO = 3, PO = 2, EO = 3 block type) Using 23 parts by weight, the detergent particles ( C) was obtained.
[0091]
The water insoluble matter generation rate of the detergent particle group here is based on the following measurement method. The top surface of vertical x horizontal x height = 10 cm x 6 cm x 4 cm using two types of filter paper as defined in JIS P 3801 (for example, "Qualitative No. 2 filter paper" manufactured by Toyo Roshi Kaisha, Ltd.) And stored in a temperature-controlled room at 40 ° C. and 80% RH for 12 hours. The whole sample after storage is taken out from the filter paper box and mixed, and then reduced by a rotary type reducer. The amount of water is measured at a water temperature of 20 ° C. First, 1 L of tap water is put into a 1 L beaker made of glass, and the rotation speed is stabilized by stirring in advance with a stirring bar having a rotation speed of 1200 rpm and a length of 35 mm × diameter of 8 mm. After the rotational speed is stabilized, 0.667 g of the above-mentioned reduced detergent particle group is added and the detergent particle group is dissolved for 10 minutes. Immediately after 10 minutes, the detergent suspension was filtered with a 200-mesh metal sieve that had been precisely weighed in advance, the detergent residue was dried together with the metal sieve at 105 ° C./30 minutes, and allowed to cool in a desiccator for 30 minutes. Weigh accurately. The residual rate is calculated from the difference in the weight of the metal sieve before and after the test and the weight of the tested detergent particle group, and is defined as the detergent particle group water insoluble matter generation rate (%).
[0092]
Table 4 shows the physical properties of the obtained detergent particle groups (A) to (C).
[0093]
[Table 4]

[0094]
From the results of Table 4, the detergent particle groups (A) to (C) containing the base granule group b of the present invention are all detergents containing the base granule group e having a high water-insoluble matter generation rate and a clothing persistence index. It can be seen that the detergent particle group water insoluble matter generation rate is remarkably lower than that of the particle group (A ′).
It can also be seen that when an anionic surfactant is allowed to coexist with a nonionic surfactant, the water insoluble matter generation rate of the detergent particles is further reduced, and the clothes residue can be reduced. In addition, detergent particle group (A) and (B) maintained favorable solubility, and fluidity | liquidity was favorable. In particular, the detergent particle group (B) was further blended with polyethylene glycol to further improve the caking resistance of the detergent particle group, and to further prevent the nonionic surfactant from being stained.
[0095]
【The invention's effect】
The base granule group of the present invention has a high oil absorption capacity and a high bulk density with very little undissolved residue of detergent in the garment. A high bulk density can be obtained by loading a surfactant on the base granule group. A detergent particle group can be obtained.

Claims (5)

A group of base granules containing a water-insoluble inorganic substance, a water-soluble polymer and a water-soluble salt, and further containing 0 to 10% by weight of a surfactant, the bulk density is 400 to 1000 g / L, and the water-insoluble inorganic substance is Including an amorphous aluminosilicate having a pore size of 0.015 to 0.5 μm measured with a mercury porosimeter of 0 to 1.0 mL / g and a pore size of 0.5 to 2 μm of 0.30 mL / g or more. And the base granule group for surfactant support whose content of this amorphous aluminosilicate is 1 to 20 weight% in a base granule group. The base granule group according to claim 1, wherein the composition of the amorphous aluminosilicate is represented by the following formula (1):
xM ₂ O.yMeO.Al ₂ O ₃ .zSiO ₂ (1)
(In the formula, M represents an alkali metal atom, Me represents a divalent metal atom, x is 0.2 to 2.0, y is 0 to 0.1, and z is 0.5 to 5.0). The base granule group according to claim 2, wherein x is 0.2 to 1.5 and y is 0.001 to 0.1 in formula (1). The base granule group according to any one of claims 1 to 3 , wherein the oil absorption capacity of the base granule group is 0.40 g / g or more. Claims 1-4 or surfactant compositions having a melting point to for supporting a surfactant base particles 100 parts by weight containing 40 ° C. The following non-ionic surfactant 20% by weight or more according 10-100 A high bulk density detergent particle group supported by parts by weight.