JP3830639B2 - Method for producing high density granular detergent - Google Patents

Description

【０００８】
（式中、Ｒは炭素数７〜１９の飽和または不飽和炭化水素基を表し、ＥＯはオキシエチレン基を表し、ｎはオキシエチレン基の平均付加モル数であり、０．５≦ｎ≦３である。）
及びｃ）無機性成分の三成分を含有する水性混合物の噴霧乾燥によって調製される乾燥粉粒体を、１）圧密成形後破砕造粒するか又は２）転動造粒し、高嵩密度粒状洗剤を製造する過程において、該成形又は造粒工程中、乾燥粉粒体を、前記ｂ）成分の融点を５℃以上上回る温度域に保持することを特徴とする高密度粒状洗剤の製造方法を提供するものである。
【０００９】
【発明の実施の形態】
以下に本発明に用いられるａ）〜ｃ）成分について説明する。
＜ａ）非石けん性アニオン性界面活性剤＞
本発明に用いられる非石けん性アニオン性界面活性剤としては、炭素数１０〜１８の直鎖又は分岐鎖の１級または２級アルコールの硫酸エステル塩、炭素数８〜２０のアルコールのエトキシレート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が好ましい。本発明では特に、アルキル鎖の炭素数が１２〜１４の直鎖アルキルベンゼンスルホン酸塩および／または炭素数１２〜１８の１級アルコールの硫酸エステル塩が好ましく、対イオンとしては、アルカリ金属類が好ましい（Ｎａが最も好ましい）。これらの非石けん性アニオン性界面活性剤は本発明の製造方法によって得られた高嵩密度粒状洗剤粒子中に１０〜３０重量％配合される。
【００１０】
＜ｂ）ポリオキシエチレン高級脂肪酸モノエタノールアミド＞
本発明に使用されるポリオキシエチレン高級脂肪酸モノエタノールアミドは、下式（Ｉ）
【００１１】
【化３】

【００１２】
で表され、Ｒ部分および／またはｎが異なる種々の構造をもつ化合物の混合物である。
この混合物は、例えば下式(III)
【００１３】
【化４】

【００１４】
〔式中のＲは、式（Ｉ）と同意〕
に示す高級脂肪酸モノエタノールアミドに、アルカリ触媒下エチレンオキサイドを付加することによって合成できる。高級脂肪酸モノエタノールアミドは、脂肪酸や脂肪酸の短鎖アルキルエステル（好ましくはメチルエステル）とモノエタノールアミンのアミド化反応生成物として、常法により合成可能である。エチレンオキサイド付加反応生成物の付加モル数は低付加（あるいは未付加）分子から高付加分子まで分布しており、その平均〔式（Ｉ）中のｎに相当〕として扱うことが一般的である。洗浄性能が最も高く、且つ好ましい粉末物性を与えるために、一般式（Ｉ）中の平均付加モル数ｎは、０．５〜３であり、より好ましくは０．５〜１．８である。平均付加モル数ｎが０．５以下の場合、充分な洗浄効果が得られず、３を越えると粒子強度を高める効果が充分でない。Ｒ鎖部分は、洗浄性能および粒子強度の点から、Ｃ₁₁Ｈ₂₃が最も好ましいが、全てがＣ₁₁Ｈ₂₃である必要はなく、好ましくは混合物中、Ｒ部分がＣ₁₁Ｈ₂₃である化合物が５０重量％以上である。また、ｂ）成分のポリオキシエチレン高級脂肪酸モノエタノールアミド混合物は、本発明の製造方法によって得られた高嵩密度粒状洗剤粒子中に３重量％以上、好ましくは５重量％以上含有されることが好ましく、ｂ）成分の量が少なすぎると粒子強度を高める効果が充分でない。また、噴霧乾燥工程での製造のしやすさから、１５重量％を越えない範囲で配合することが望ましい。
【００１５】
＜ｃ）無機性成分＞
本発明に用いられる無機性成分ｃ）としては、芒硝等の増量剤や無機性アルカリ剤、結晶性アルミノケイ酸塩等の無機性硬度成分捕捉剤、亜硫酸塩等の酵素安定化剤のほか、従来公知の物質を配合することが出来る。アルカリ剤として具体的には、ＪＩＳ１号、２号、３号等の非晶質のアルカリ金属珪酸塩、並びにデンス灰や軽灰と総称される炭酸ナトリウム等のアルカリ金属炭酸塩が挙げられる。これら、無機性のアルカリ剤は、比較的硬く、流動性に優れた洗剤を製造する際、それらの物性を補完するのに適している。特に、水性スラリーを噴霧乾燥する製造法において非晶質珪酸ナトリウムを該スラリーへ配合すれば、洗剤粒子の物性を向上させる効果が大きい。本発明には、本発明によって得られた高嵩密度粒状洗剤粒子中に１〜１０重量％の非晶質珪酸ナトリウムを配合することが好ましい。これら以外のアルカリ剤としては、セスキ炭酸ナトリウム、炭酸水素ナトリウムなどが挙げられ、またトリポリリン酸塩等のリン酸塩もアルカリ剤としての作用を有する。アルカリ剤は総量で５〜50重量％、好ましくは15〜35重量％配合される。
【００１６】
また、本発明では、無機性成分ｃ）として、結晶性アルミノ珪酸塩を用いるのが好ましい。本発明に用いられる結晶性アルミノ珪酸塩は、一般にゼオライトといわれているものであり、下記式
a(M₂O)・Al₂O₃・b(SiO₂)・w(H₂O) （IV）
〔式中、M はアルカリ金属原子、a, b, w は各成分のモル比を表し、一般的には0.7 ≦a ≦1.5 、0.8 ≦b ＜６、w は任意の正数である。〕
で表されるものであり、中でも次の一般式（Ｖ）
Na₂O・Al₂O₃ ・n'(SiO₂)・w'(H₂O) （Ｖ）
〔ここで、n'は1.8 〜3.0 、w'は１〜６の数を表す。〕
で表されるものが好ましい。結晶性アルミノ珪酸塩（ゼオライト）としては、Ａ型、Ｘ型、Ｐ型ゼオライトに代表される平均一次粒径０．１〜１０μｍの合成ゼオライトが好適に使用される。ゼオライトは、水性スラリー中はもちろん、粉末及び／又はゼオライトスラリーを乾燥して得られるゼオライト凝集乾燥粒子として配合してもよい。
【００１７】
本発明において、結晶性アルミノ珪酸塩は、高密度粒状洗剤粒子中に５〜４０重量％、好ましくは１５〜３５重量％配合される。
【００１８】
また、本発明において無機性成分ｃ）は総量として、高嵩密度粒状洗剤粒子中に４０〜８０重量％、好ましくは４０〜６０重量％配合される。
【００１９】
＜各成分の重量比＞
本発明においてａ）非石けん性アニオン性界面活性剤、ｂ）ポリオキシエチレン高級脂肪酸モノエタノールアミド界面活性剤混合物及びｃ）無機性成分は、最終的に得られた高密度粒状洗剤中に、ｂ）／ａ）＝０．０５〜１、特に０．１〜０．７、〔ａ）＋ｂ）〕／ｃ）＝０．２〜１の重量比となるように用いるのが、製造適性及び耐ケーキング性と粒子の強度の面で好ましい。
【００２０】
＜任意成分＞
本発明においては、上記ａ）〜ｃ）成分に加えてその他の界面活性剤や高密度洗剤に配合される公知の成分を配合することができる。
【００２１】
（１）その他の界面活性剤
その他の界面活性剤としては、ポリオキシアルキレンアルキルエーテル型、ポリオキシアルキレンアルキルフェニルエーテル型、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高級脂肪酸低級アルキルエステル、Ｎ−メチルグルコース高級脂肪酸アミド、アルキル（オリゴ）グルコシド等のノニオン界面活性剤、ベタイン型等の両性界面活性剤、４級アンモニウム塩型等のカチオン界面活性剤等、洗剤粒子の強度を損なわない範囲であれば、目的に応じて公知の界面活性剤を配合することができる。
【００２２】
（２）その他の配合成分
本発明においては、エチレンジアミン四酢酸（ＥＤＴＡ）及びクエン酸塩等の有機金属イオン封鎖剤、ポリアクリル酸、アクリル酸とマレイン酸のコポリマーおよびカルボキシメチルセルロース等のカルボン酸系ポリマー、ポリエチレングリコール（ＰＥＧ）、ポリビニルピロリドン（ＰＶＰ）及びポリビニルアルコール（ＰＶＡ）等の分散剤もしくは色移り防止剤、過炭酸ナトリウム等の漂白剤、特開平６−３１６７００号公報記載及びテトラアセチルエチレンジアミン（ＴＡＥＤ）等の漂白活性化剤、プロテアーゼ，セルラーゼ、アミラーゼ及びリパーゼ等の酵素、ホウ素化合物及び亜硫酸ナトリウム等の酵素安定剤、ビフェニル型、スチルベン型の蛍光染料、シリコーン／シリカ系等の消泡剤、酸化防止剤、青味付剤並びに香料等の従来から公知の成分を公知の配合量で配合することができる。また消泡剤として脂肪酸塩を配合してもよい。上記成分として具体的には特開平８−２１８０９３号公報に記載されているものを使用することができる。
【００２３】
＜製造方法＞
上記の通り、本発明は、少なくとも、ａ）非石けん性アニオン性界面活性剤、ｂ）下式（Ｉ）で表されるポリオキシエチレン高級脂肪酸モノエタノールアミド界面活性剤の混合物
【００２４】
【化５】

【００２５】
（式中、Ｒは炭素数７〜１９の飽和または不飽和炭化水素基を表し、ＥＯはオキシエチレン基を表し、ｎはオキシエチレン基の平均付加モル数であり、０．５≦ｎ≦３、好ましくは０．５≦ｎ≦１．８である。）
及びｃ）無機性成分の三成分を含有する水性混合物の噴霧乾燥によって調製される乾燥粉粒体を、１）圧密成形後破砕造粒するか又は２）転動造粒し、高嵩密度粒状洗剤を製造する過程において、該成形又は造粒工程中、乾燥粉粒体を、前記ｂ）成分の融点を５℃以上上回る温度域に保持することを特徴とする高密度粒状洗剤の製造方法に関するものである。
【００２６】
衣料用洗剤のように一般家庭で常用される消費財は、市場への大量供給が必要であり、効率よく大量に生産する手段として、噴霧乾燥工法は欠かせないものとなっている。一般的に、噴霧乾燥された粉粒体は、多量の水分を含む有機／無機原料の液滴を高温熱風中で短時間に乾燥するため、非常にポーラスになり、高い嵩密度が得られない（通常は０．３ｇ／ｃｍ³ 前後）。このようにポーラスな粉粒体の嵩密度を高めるための工業的加工法として、ローラーや押し出し機を用い、圧力を加えて押し固める方法（圧密化）と、容器内で高速撹拌することで、粒子を破砕しながら、雪だるま様に粒子を凝集させる方法（転動造粒）とが挙げられる。いずれの方法においても、嵩密度を高める上で、乾燥直後の状態からの粒子の変形や、複数粒子との凝集を回避することは原理的に不可能である。
【００２７】
これに対して、本発明の製造方法の最も強調すべき特徴として、噴霧乾燥によって得られた粉粒体をさらに、１）圧密成形後破砕造粒するか又は２）転動造粒することにより加工し、高嵩密度、高流動性、適当な粒度を具備する造粒物とする過程において、目的物の１個粒子内に、均一且つ発達したポリオキシエチレン高級脂肪酸モノエタノールアミド界面活性剤混合物の固化ネットワークを成長させ、粒子強度を高めることが挙げられる。
【００２８】
ポリオキシエチレン高級脂肪酸モノエタノールアミド界面活性剤混合物ｂ）の固化ネットワークを利用して粒子を硬くするには、該ｂ）成分の量は洗剤粒子に対し３重量％以上（好ましくは５重量％以上）の配合量において効果が大きい。また、前述の粒子変形、複数粒子の凝集が完了したのち、均一に分布している該ｂ）成分の融解物が固化することで粒子強度向上効果が最大限得られるため、粒子変形および／または複数粒子の凝集が起こる工程（即ち成形および／または造粒工程）を該ｂ）成分が液化した状態で行う必要がある。乾燥粉粒体中の該ｂ）成分がムラなく液化状態をなすには、少なくとも、該ｂ）成分の融点を５℃以上上回る温度で乾燥粉粒体を取り扱う必要がある。乾燥粉粒体を温度コントロールすることでポリオキシエチレン高級脂肪酸モノエタノールアミドをムラなく液化状態ならしめるには、高温である方が効率的であるが、融点を３０℃以上超える領域になると、もはやそれ以上の効果向上はないため、単にエネルギーの損失を生むだけであり、無意味である。また、工程中の乾燥粉粒体の温度が明瞭でないときは、一部を取り出し、温度計を用いて実測する必要があるが、乾燥粉粒体の温度を確認してから同一手順（操作条件、環境条件）で製造機械の運転を続けるのであれば、頻繁にモニターしなくてもよい。理想的には、予備混合機内および／または成形機内および／または転動造粒機内に温度センサーを設け、これに付帯する温度コントロール手段（ジャケット等）に自動制御をかけることが望ましい。
【００２９】
圧密成形の方法を更に具体的に述べると、乾燥粉粒体および他の添加成分を予備的に一時混合したものを、軸圧を有するローラーを通過させることによって圧縮されたシート状に成形する方法又は例えば、前押し出し式２軸押し出し成形機のような押し出し成形機にて１０ｍｍ程度の棒状に成形する方法が挙げられる。予備混合時には、他の粉末成分や、洗剤粒子物性を損なわない範囲であれば、液状成分もスプレー等の方法で加えることが可能である。それぞれの工程時には、乾燥粉粒体の温度を、使用するポリオキシエチレン高級脂肪酸モノエタノールアミド界面活性剤混合物の融点を５℃以上上回る温度域に保持するよう、前者の場合は、予備混合時の混合機および／またはローラーの温度をコントロールする必要がある。後者の場合も同様で、予備混合時の混合機および／または押し出し成形機の温度をコントロールする必要がある。上記のようにして得られた、成形物は、破砕造粒工程を経て適度な粒度に、具体的には平均粒径を２００〜１０００μｍの粒子に更に加工する必要がある。本破砕造粒工程中は、温度コントロールを必要としないが、破砕器への過負荷を避けるため、高温は好ましくない。
【００３０】
また、転動造粒の方法を具体的に述べると、例えば、ハイスピードミキサー（深江工業（株）製）のようなアジテータおよびチョッパを有する竪型ミキサーや、レディゲミキサー（松坂技研（株）製）のようなブレードおよびチョッパを有する横型ミキサー内に乾燥粉粒体および他の添加成分を仕込み、撹拌を続けることで、破砕を行いながら凝集を進行させ、適当な粒度（具体的には２００〜１０００μｍの粒度）および向上した嵩密度を兼備する粒体に造粒する方法が考えられる。添加成分としては粉末成分の他、洗剤粒子物性を損なわない範囲であれば、液状成分をスプレー等の方法で添加することも可能である。それぞれの造粒工程時には、乾燥粉粒体の温度が含有されるポリオキシエチレン高級脂肪酸モノエタノールアミド界面活性剤混合物の融点を５℃以上上回る温度域に保持されるよう、ミキサーのジャケット等の温度をコントロールする必要がある。転動造粒工程を経て得られた造粒物は、過大粒子を篩い分けて粉砕し、篩い通過粒子とミックスすることで目的とする洗剤粒子が得られる。いずれの工程においても、乾燥粉粒体を圧密成形または転動造粒した以降、結晶性アルミノケイ酸塩のような微粒子を洗剤粒子の表面被覆剤として付着させる以外、実質的に粒子の凝集を起こさないことが好ましい。
【００３１】
本発明で得られた高嵩密度粒状洗剤は、非石けん性アニオン性界面活性剤ａ）、特定のポリオキシエチレン高級脂肪酸モノエタノールアミド界面活性剤混合物ｂ）及び無機性成分ｃ）を含有する高嵩密度粒子であるが、通常洗剤に添加される成分、具体的には別途造粒した酵素粒子や漂白剤粒子、消泡剤粒子などを本発明の高嵩密度粒状洗剤に別途ドライブレンドしてもよい。また、アルカリ剤として及び金属イオン封鎖剤として優れた化合物である特開昭60−227895号及び特開平７−89712 号記載の結晶性珪酸塩を配合する場合は、別粒子としてドライブレンドするか又は圧密工程ないし造粒工程で添加することが好ましい。
【００３２】
なお、蛍光染料を配合する場合は水性スラリーに添加するが、熱による分解を懸念する場合は、高嵩密度化の工程で添加してもよい。勿論その場合は、蛍光染料が洗剤粒子内で局所的に凝集しないように注意すべきである。香料成分はその揮発性のために、高温による処理工程での添加は好ましくないことは言うまでもなく、従って、高温での処理である噴霧乾燥工程を通る水性スラリー中への配合は好ましくない。通常は高嵩密度化工程ないし造粒終了後で添加するが、その際は揮発による匂いの変化に十分注意すべきである。そのためには、香料の添加を製造工程のなるべく最後の方ないし工程終了後に行うことが好ましい。
【００３３】
＜洗剤粒度および嵩密度＞
本発明の製造方法によって得られる高嵩密度粒状洗剤の平均粒径は、好ましい粉末物性を得るために２００〜１０００μｍ、特に２００〜６００μｍであることが望ましい。また、本発明の高嵩密度粒状洗剤の嵩密度は、０．５〜１．２ｇ／ｃｍ³ 、好ましくは０．６〜１．０ｇ／ｃｍ³ 程度である。
【００３４】
【実施例】
以下実施例にて本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００３５】
＜調製例１＞
純度８５％のラウリン酸メチル（花王（株）製、商品名エキセパールＭＬ−８５）とモノエタノールアミンの混合物（モル比１：１．０３）を８０℃に加温し、触媒としてナトリウムメチラートを添加した。更に９５℃、３０ｍｍＨｇの条件下、副生するメタノールを留去しながら、６時間反応を続け、アミド化物を得た。これを精製することなく次の反応に供した。オートクレーブにアミド化物および、触媒のナトリウムメチラートをアミド化物に対して０．０２モル等量を仕込み、続いて、０．７５モル等量のエチレンオキサイドを１００℃、０．３５ＭＰａを越えないよう注意しながら導入し、エチレンオキサイドが反応し終わるまで、約２時間熟成した。８０℃、１００ｍｍＨｇで窒素ガスをバブリングしながら極微量の未反応エチレンオキサイドを除去し、目的とするポリオキシエチレン脂肪酸モノエタノールアミドＡＤＥＯ１〔式（Ｉ）においてＲ＝Ｃ₁₁Ｈ₂₃アルキル基、ｎ＝０．７５の化合物〕を得た。
同様に、エチレンオキサイドの導入量を変えることによって、ＡＤＥＯ２、３、７を合成した。
【００３６】
＜調製例２＞
ラウリン酸／ミリスチン酸混合の脂肪酸（ラウリン酸／ミリスチン酸＝７５／２５（重量比））を９０℃に加熱し、モノエタノールアミン１．１モル等量を加え、１６０℃、５０ｍｍＨｇの条件下で、副生する水を留去しながら、反応を６時間続け、アミド化物を得た。調製例１と同様の条件下、エトキシレート化し、ポリオキシエチレン脂肪酸モノエタノールアミドＡＤＥＯ４及びＡＤＥＯ５を合成した。同様に、ヤシ油由来の脂肪酸の低沸点分除去品〔花王（株）製、商品名ルナックＬ−55、ガスクロマトグラフィーによる組成：カプリン酸／ラウリン酸／ミリスチン酸／ステアリン酸／その他＝１／５７／２２／１０／３／７（重量比）〕を用い、ポリオキシエチレン脂肪酸モノエタノールアミドＡＤＥＯ６を合成した。
【００３７】
＜ポリオキシエチレン高級脂肪酸モノエタノールアミドの融点測定法＞
下記条件のＤＳＣ法によりポリオキシエチレン高級脂肪酸モノエタノールアミドの融点を決定した。
・測定装置：示差走査熱量計 ＤＳＣ１２０〔セイコー電子工業（株）製〕
熱分析システム ＳＳＣ５２００Ｈ〔同上〕
・測定条件：走査温度範囲０〜１００℃、昇温速度０．５℃／ｍｉｎ
・試料：試料５〜１０ｍｇをＡＧ１５型サンプルパン（セイコー電子工業（株）製）に入れ測定用試料とし、同型パンをリファレンスとして使用した。
・数値の読みとり：グラフ〔横軸；温度（℃）、縦軸；熱量差（μＷ）〕から、最大吸熱ピークの頂点の温度を読みとらせ、融点とした。
表１に、上記調製例で得た種々のポリオキシエチレン高級脂肪酸モノエタノールアミドの組成及び融点の測定結果を示す。
【００３８】
【表１】

【００３９】
＜実施例１〜８及び比較例１〜２＞
表２〜５の組成により、下記の方法で高密度洗剤組成物を調製した。表２〜５において、組成Ｉは最終組成物における比率であり、組成IIは組成Ｉのうち噴霧乾燥粉粒体として配合した分の比率であり、組成III は組成Ｉのうちミキサー添加成分又は成形機添加成分として配合した分の比率であり、組成IVは組成Ｉのうち整粒被覆剤として又は破砕助剤として配合した分の比率であり、組成Ｖは組成Ｉのうちアフターブレンド成分として配合した分の比率である。
【００４０】
〔Ａ〕噴霧乾燥物の調製方法
表２〜５記載の各組成中IIの組成（揮発分を除外）を明記された比率で含有する水スラリー（水分４５％）を調製し、噴霧乾燥して、表２〜５記載の各IIの組成の乾燥粉粒体を得た。表中の揮発分は、噴霧乾燥して得られた粉粒体１０ｇをシャーレに入れ、１１０℃／３０分の条件で測定した重量減少分であり、大部分が水であると考えられるが、特に分析は行わず、そのまま後続工程に供した。
【００４１】
〔Ｂ−１〕高嵩密度粒状洗剤の調製方法１（実施例１、２、７）
乾燥粉粒体８３重量部（表中II）および、ゼオライト１０重量部（表中III ）を７０℃（実施例２は６５℃、実施例７は６５℃）のジャケット水を循環したリボンミキサー内に入れ、予備混合した。予備混合終了時点で、実施例１の混合粉体の温度は５５℃（実施例２は５０℃、実施例７は５２℃）を示していた。得られた混合粉体温度が変化しないよう、速やかに前押し出し式２軸押し出し成形機（ペレッターダブル；不二パウダル（株）製）に入れ、粉体温度がそれぞれ前述の値を維持するよう、成形機温度をコントロールしながら、押し出し成形して連続した棒状の成型物を得た。放冷後棒状成型物を適度な長さに調整後、成形物９３重量部にゼオライト４重量部を加えて（表中IV）、フラッシュミル（不二パウダル（株）製）にて粉砕造粒と表面被覆を行った。目開き１．５ｍｍの篩で粗大粒子を回収し、これを再粉砕後、１回目の粉砕後の篩通過分とあわせて目的の洗剤粒子とした。Ｖ型ブレンダーにて、洗剤粒子９７重量部、ゼオライト１重量部、酵素粒子２重量部をブレンドして（表中Ｖ）最終形態の洗剤組成物が得られた（表中Ｉ）。
【００４２】
〔Ｂ−２〕高嵩密度粒状洗剤の調製方法２（実施例３〜５、比較例１）
乾燥粉粒体８３重量部（表中II）とゼオライト１０重量部（表中III ）を６０℃（実施例４は６５℃、実施例５は６０℃、比較例１は室温）の温水をジャケット部に循環させたハイスピードミキサー（深江工業（株）製）に入れ、撹拌した。撹拌開始後、５分の段階でミキサーを止め、内部の洗剤粒子を取り出して温度測定したところ、４０℃（実施例４は４５℃、実施例５は４０℃、比較例１は２０℃）であった。さらに、１０分間以上撹拌を続けて転動造粒を行い、適度な粒度にした後、ゼオライト５重量部を加えて（表中IV）、約１分間撹拌して、粒子表面をゼオライトで被覆した。得られた造粒物は、もはや温度管理することなく、次の篩工程に供した。目開き１．５ｍｍの篩で過大粒子を篩い分けて粉砕し、篩通過分とあわせて、目的とする洗剤粒子とした。洗剤粒子９８重量部に対して酵素造粒物が２重量部の割合で、Ｖ型ブレンダーにてブレンドして（表中Ｖ）最終形態の洗剤組成物が得られた（表中Ｉ）。
【００４３】
〔Ｂ−３〕高嵩密度粒子洗剤の調製方法３（実施例６、比較例２）
表記載組成の乾燥粉粒体８３重量部（表中II）とゼオライト１０重量部（表中III ）を７５℃（比較例３は室温）の温水をジャケット部に循環させたレディゲミキサー（松坂技研（株）製）に入れ、撹拌した。撹拌開始後、５分の段階でミキサーを止め、内部の洗剤粒子を取り出して温度測定したところ、６０℃（比較例３は２０℃）であった。さらに、１０分間以上撹拌を続けて転動造粒を行い、適度な粒度にした後、ゼオライト５重量部を加えて（表中IV）、１分間撹拌して、粒子表面をゼオライトで被覆した。得られた造粒物は、もはや温度管理することなく、次の篩工程に供した。目開き１．５ｍｍの篩で過大粒子を篩い分けて粉砕し、篩通過分とあわせて、目的とする洗剤粒子とした。洗剤粒子９８重量部に対して酵素造粒物が２重量部の割合で、Ｖ型ブレンダーにてブレンドして（表中Ｖ）最終形態の洗剤組成物が得られた（表中Ｉ）。
【００４４】
〔Ｂ−４〕高嵩密度粒子洗剤の調製方法４（実施例８）
表記載組成の乾燥粉粒体７９重量部（表中II）と、ゼオライト９重量部、結晶性シリケート４重量部（表中III ）を７０℃の温水をジャケット部に循環させたハイスピードミキサー（深江工業（株）製）に入れ、撹拌しながら５０℃に加温したＡＥ１重量部（表中III ）をスプレーすることで徐々に添加した。スプレー終了後、５分撹拌を行った時点でミキサーを止め、内部の洗剤粒子を取り出して温度測定したところ、５６℃であった。更に１０分間撹拌を続けて転動造粒を行い、適度な粒度にした後、適度な粒度にした後、ゼオライト５重量部を加えて（表中IV）、約１分間撹拌して、粒子表面をゼオライトで被覆した。得られた造粒物は、もはや温度管理することなく、次の篩工程に供した。目開き１．５ｍｍの篩で過大粒子を篩い分けて粉砕し、篩通過分とあわせて、目的とする洗剤粒子とした。洗剤粒子９８重量部に対して酵素造粒物が２重量部の割合で、Ｖ型ブレンダーにてブレンドして（表中Ｖ）最終形態の洗剤組成物が得られた（表中Ｉ）。
【００４５】
〔Ｃ〕粒状洗剤粒子強度の測定
上記実施例１〜７及び比較例１〜２で得られた高密度粒状洗剤組成物について、下記の方法で粒子強度を測定した。洗剤粒子が硬い場合は、圧力を加えても塑性変形を招かず、その結果、固まりにならないか、固まっても弱い力で崩壊させることができる。洗剤粒子の強度を表す指標として、圧力を与えたときの固まり易さ、固まった洗剤粒子塊の崩れ易さを『圧密破壊荷重』として測定した。以下に測定方法を示すが、『圧密破壊荷重』が『測定不能』のものは、一定圧力条件下で洗剤塊を生じなかったためであり、最も好ましい洗剤粒子と言える。測定可能な場合は、数字は小さい方がより好ましい。
【００４６】
＜圧密破壊荷重測定法＞
▲１▼使用機器
・タッピング機：タッピング式密充填カサ密度測定器ＴＶＰ−１型（筒井理化学器械（株）製）
・破壊荷重測定器：FUDO RHEOMETER RT-3020D-CW型（（株）レオテック製）
▲２▼測定条件：室温（洗剤粒子温度は２０℃）
▲３▼測定方法：
外直径５０ｍｍ、内直径３０ｍｍの金属製円筒を、大きさが合致するカップ状容器に入れ、円筒部内に洗剤粒子３０ｇを、表面が滑らかになるように入れた。次いで金属製のシリンダー（３８０ｇ）を錘として洗剤粒子の上に静かに載せて、上記タッピング機にて、３０回タッピング（落下距離２５ｍｍ）した。カップからシリンダーを取り出し、シリンダー内部に残る、圧縮を受けた洗剤粒子（洗剤粒子塊）を上部からシリンダーで慎重に押し出し、洗剤粒子塊を板の上に（円状部を底面として）静かに置いた。洗剤塊を板に載せたまま上記レオメーターのサンプル昇降台に移動し、２ｃｍ／ｍｉｎの速度で破壊時の最大荷重を測定した。このとき、洗剤粒子を固まりとして取り出せなかったものは、『測定不能』として示した。
【００４７】
【表２】

【００４８】
【表３】

【００４９】
【表４】

【００５０】
【表５】

【００５１】
（注）
・ＬＡＳ：アルキルベンゼンスルホン酸ソーダ〔日石洗剤（株）製、アルキルベンベンゼンスルホン酸「アルケンＬ（アルキル鎖の炭素数１０〜１４）」を４８％ＮａＯＨで中和したもの〕
・ＡＳ：三菱化学（株）製ドバノール２５サルフェート（Ｃ₁₂〜Ｃ₁₅硫酸）のナトリウム塩
・ＳＦＥ：パーム油由来、アルファスルホ脂肪酸メチルエステルソーダ
・脂肪酸塩：パルミチン酸ナトリウム
・ＡＥ：ノニデッドＲ−７（Ｃ₁₂〜Ｃ₁₅アルコールにエチレンオキサイドを平均７．２モル付加したもの、三菱化学（株）製）〕
・ゼオライト：Ａ型ゼオライト、平均粒径３μｍ
・結晶性シリケート：ＳＫＳ−６、δーＮａ₂Ｓｉ₂Ｏ₅ 、結晶性層状珪酸ナトリウム，平均粒子径２０μｍ、ヘキストトクヤマ社製
・シリケート：非晶質珪酸ナトリウム、ＪＩＳ１号珪酸ナトリウム
・炭酸ソーダ：デンス粒灰
・ＰＡＳ：ポリアクリル酸ソーダ、平均分子量１２０００
・ＡＡ−ＭＡ：ソカランＣＰ５、アクリル酸−マレイン酸共重合体、平均分子量７００００
・蛍光染料：チノパールＣＢＳ（チバガイギー社製）と、ホワイテックスＳＡ（住友化学社製）を重量比で同量配合したもの
・酵素：サビナーゼ１２．０Ｔ ｔｙｐｅＷ（プロテアーゼ）、リポラーゼ１００Ｔ（リパーゼ）、ターマミル６０Ｔ（アミラーゼ）（以上の酵素、ノボノルディスク製）及びＫＡＣ５００（アルカリセルラーゼ、花王株式会社製）を重量比率で２：１：１：１の割合で混合したもの[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a high bulk density granular detergent. More specifically, the present invention relates to a production method in which a high-density granular detergent for clothing having improved particle strength and excellent resistance to caking is obtained by blending polyoxyethylene higher fatty acid monoethanolamide.
[0002]
[Prior art]
Detergent for clothing is a surfactant that solubilizes soil and dissolves / disperses it from the fibers in the washing liquid, a sequestering agent for removing calcium and magnesium from the washing liquid, which reduces the ability of the surfactant, It consists of an alkaline agent that promotes the degradation and solubilization of dirt, and other cleaning builders. The basic concept of the ingredients to be blended in the laundry detergent has not changed much so far, but the specific ingredients have been reviewed from the consideration of the environment. One example is the dephosphorization of the detergent. In the past, phosphorus detergents such as sodium tripolyphosphate were blended in clothing detergents as sequestering agents. However, there is concern about these phosphorus compounds as one of the causes of eutrophication of lakes and swamps, and crystalline sodium aluminosilicates with a specific structure (synthesized in this industry as sequestering agents to replace phosphorus compounds). (Referred to as zeolite) has come into use. On the other hand, various shapes such as liquids, slurries, pastes, granules (powder), tablets or rods have been proposed for the shape of the detergent, and many technologies have been filed and published for each. . Among these shapes, the increase in bulk density of powder detergents in the latter half of the 1980s was that compactness greatly contributed to transportation, carrying and storage, so compact detergents are now dominant. . As described above, even when the powder detergent is made compact, the composition of the basic components does not change greatly, and it is an extender that has been incorporated in a large amount in a conventional low bulk density detergent, such as mirabilite with a low cleaning effect. Inorganic salts were only reduced. In addition to an increase in the compression due to gravity on the bottom of the storage container due to an increase in the bulk density of the product, the detergent particles have become plastic due to an increase in the ratio of organic substances such as surfactants that are the main cleaning components. As a result, the problem of caking powder detergent during long-term storage was caused.
[0003]
In addition, the surfactants used in laundry detergents are compatible with various types of stains, and in order to obtain a synergistic effect with multiple surfactants, they are usually used in combination with several types of surfactants. In general, an anionic surfactant and a nonionic surfactant are often used in combination. As the nonionic surfactant, polyoxyethylene alkyl ether represented by the following formula (II) is generally used.
R-O- (C ₂ H _Four O) _m -H (II)
[In Formula (II), R represents a long-chain alkyl group, and m represents the average number of moles of ethylene oxide added. ]
This type of nonionic surfactant has a melting point that increases in accordance with the average number of moles of ethylene oxide added (that is, average molecular weight). Among these, those having a detergency suitable for detergent use for clothing are liquid at room temperature, and the active agent may ooze out during long-term storage of the detergent. The formulation was delicate.
[0004]
[Problems to be solved by the invention]
From the background as described above, an object of the present invention is to establish a manufacturing technique of a high bulk density powder detergent that has sufficient particle strength and does not cause problems such as caking.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a high bulk density granular detergent containing a polyoxyethylene higher fatty acid monoethanolamide having an anionic surfactant as a main surfactant component and a specific structure. In the manufacturing process, compaction or rolling granulation is performed under specific temperature conditions, so that the particle strength is sufficient (the plasticity of the particles can be reduced), and the bulkiness is excellent in fluidity and caking resistance. It has been found that a density granular cleaning composition can be obtained, and the present invention has been completed.
[0006]
That is, the present invention comprises at least a mixture of a non-soap anionic surfactant and b) a polyoxyethylene higher fatty acid monoethanolamide surfactant represented by the following formula (I):
[0007]
[Chemical 2]

[0008]
(In the formula, R represents a saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, EO represents an oxyethylene group, n is the average number of moles added of the oxyethylene group, and 0.5 ≦ n ≦ 3. .)
And c) a dry granule prepared by spray drying of an aqueous mixture containing the three components of the inorganic component, 1) crushing granulation after compaction molding or 2) rolling granulation and high bulk density granulation In the process of producing a detergent, a method for producing a high-density granular detergent, characterized in that, during the molding or granulating step, the dry powder is maintained in a temperature range that exceeds the melting point of the component b) by 5 ° C or more. It is to provide.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The components a) to c) used in the present invention are described below.
<A) Non-soap anionic surfactant>
Examples of the non-soap anionic surfactant used in the present invention include a sulfate ester salt of a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms, and an ethoxylate product of an alcohol having 8 to 20 carbon atoms. Of these, sulfuric acid ester salts, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts, and α-sulfo fatty acid alkyl ester salts are preferred. In the present invention, in particular, a linear alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl chain and / or a sulfate ester salt of a primary alcohol having 12 to 18 carbon atoms is preferable, and alkali metals are preferable as the counter ion. (Na is most preferred). These non-soap anionic surfactants are blended in an amount of 10 to 30% by weight in the high bulk density granular detergent particles obtained by the production method of the present invention.
[0010]
<B) Polyoxyethylene higher fatty acid monoethanolamide>
The polyoxyethylene higher fatty acid monoethanolamide used in the present invention has the following formula (I)
[0011]
[Chemical 3]

[0012]
And a mixture of compounds having various structures in which the R moiety and / or n are different.
This mixture is, for example, the following formula (III)
[0013]
[Formula 4]

[0014]
[R in the formula agrees with the formula (I)]
It can be synthesized by adding ethylene oxide to the higher fatty acid monoethanolamide shown in FIG. Higher fatty acid monoethanolamide can be synthesized by a conventional method as an amidation reaction product of fatty acid or a short-chain alkyl ester (preferably methyl ester) of fatty acid and monoethanolamine. The number of moles of addition of the ethylene oxide addition reaction product is distributed from a low addition (or non-addition) molecule to a high addition molecule, and is generally handled as an average [corresponding to n in formula (I)]. . In order to provide the highest washing performance and to give preferable powder physical properties, the average added mole number n in the general formula (I) is 0.5 to 3, more preferably 0.5 to 1.8. When the average added mole number n is 0.5 or less, a sufficient cleaning effect cannot be obtained, and when it exceeds 3, the effect of increasing the particle strength is not sufficient. The R chain portion is C in terms of washing performance and particle strength. ₁₁ H _{twenty three} Is most preferred, but all are C ₁₁ H _{twenty three} Preferably, in the mixture, the R moiety is C ₁₁ H _{twenty three} Is 50% by weight or more. In addition, the polyoxyethylene higher fatty acid monoethanolamide mixture as component b) is contained in the high bulk density granular detergent particles obtained by the production method of the present invention in an amount of 3% by weight or more, preferably 5% by weight or more. Preferably, if the amount of component b) is too small, the effect of increasing the particle strength is not sufficient. Moreover, it is desirable to mix | blend in the range which does not exceed 15 weight% from the ease of manufacture in a spray-drying process.
[0015]
<C) Inorganic component>
Examples of the inorganic component c) used in the present invention include bulking agents such as mirabilite, inorganic alkaline agents, inorganic hardness component scavengers such as crystalline aluminosilicates, enzyme stabilizers such as sulfites, and the like. Known substances can be blended. Specific examples of the alkali agent include amorphous alkali metal silicates such as JIS Nos. 1, 2, and 3 and alkali metal carbonates such as sodium carbonate collectively called dense ash and light ash. These inorganic alkaline agents are suitable for complementing their physical properties when producing detergents that are relatively hard and excellent in fluidity. In particular, if amorphous sodium silicate is added to the slurry in the production method of spray drying an aqueous slurry, the effect of improving the physical properties of the detergent particles is great. In this invention, it is preferable to mix | blend 1-10 weight% amorphous sodium silicate in the high bulk density granular detergent particle | grains obtained by this invention. Examples of the alkali agent other than these include sodium sesquicarbonate and sodium hydrogen carbonate, and phosphates such as tripolyphosphate also have an action as an alkali agent. The total amount of the alkaline agent is 5 to 50% by weight, preferably 15 to 35% by weight.
[0016]
Also, in the present invention, it is preferable to use crystalline aluminosilicate as the inorganic component c). The crystalline aluminosilicate used in the present invention is generally referred to as zeolite and has the following formula:
a (M ₂ O) ・ Al ₂ O _Three ・ B (SiO ₂ ) ・ W (H ₂ O) (IV)
[Wherein, M represents an alkali metal atom, a, b, and w represent molar ratios of the respective components, generally 0.7 ≦ a ≦ 1.5, 0.8 ≦ b <6, and w is an arbitrary positive number. ]
In particular, the following general formula (V)
Na ₂ O ・ Al ₂ O _Three ・ N '(SiO ₂ ) ・ W '(H ₂ O) (V)
[Wherein n ′ represents a number of 1.8 to 3.0 and w ′ represents a number of 1 to 6. ]
The thing represented by these is preferable. As the crystalline aluminosilicate (zeolite), synthetic zeolite having an average primary particle size of 0.1 to 10 μm represented by A-type, X-type, and P-type zeolite is preferably used. Zeolite may be blended as agglomerated dry particles of zeolite obtained by drying the powder and / or zeolite slurry as well as in the aqueous slurry.
[0017]
In the present invention, the crystalline aluminosilicate is blended in the high density granular detergent particles in an amount of 5 to 40% by weight, preferably 15 to 35% by weight.
[0018]
In the present invention, the inorganic component c) is added in a total amount of 40 to 80% by weight, preferably 40 to 60% by weight, in the high bulk density granular detergent particles.
[0019]
<Weight ratio of each component>
In the present invention, a) a non-soap anionic surfactant, b) a polyoxyethylene higher fatty acid monoethanolamide surfactant mixture and c) an inorganic component are added to the final high-density granular detergent, b ) / A) = 0.05 to 1, particularly 0.1 to 0.7, and [a) + b)] / c) = 0.2 to 1 so that the weight ratio is suitable for production and resistance. It is preferable in terms of caking property and particle strength.
[0020]
<Optional component>
In this invention, in addition to said component a) -c), the well-known component mix | blended with other surfactant or a high-density detergent can be mix | blended.
[0021]
(1) Other surfactants
Other surfactants include polyoxyalkylene alkyl ether type, polyoxyalkylene alkyl phenyl ether type, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene higher fatty acid lower alkyl ester, N-methyl glucose higher fatty acid amide, alkyl (oligo ) Nonionic surfactants such as glucoside, amphoteric surfactants such as betaine type, and cationic surfactants such as quaternary ammonium salt type, as long as they do not impair the strength of the detergent particles. An active agent can be blended.
[0022]
(2) Other ingredients
In the present invention, sequestering agents such as ethylenediaminetetraacetic acid (EDTA) and citrate, polyacrylic acid, copolymers of acrylic acid and maleic acid, and carboxylic acid-based polymers such as carboxymethylcellulose, polyethylene glycol (PEG), Dispersants or color transfer inhibitors such as polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA), bleaching agents such as sodium percarbonate, bleaching activators such as JP-A-6-316700 and tetraacetylethylenediamine (TAED) , Enzymes such as protease, cellulase, amylase and lipase, enzyme stabilizers such as boron compounds and sodium sulfite, biphenyl-type and stilbene-type fluorescent dyes, antifoaming agents such as silicone / silica, antioxidants and bluing agents As well as fragrances Known ingredients can be formulated by a known amount from. Moreover, you may mix | blend a fatty acid salt as an antifoamer. Specific examples of the above components include those described in JP-A-8-218093.
[0023]
<Manufacturing method>
As described above, the present invention provides a mixture of at least a) a non-soap anionic surfactant and b) a polyoxyethylene higher fatty acid monoethanolamide surfactant represented by the following formula (I):
[0024]
[Chemical formula 5]

[0025]
(In the formula, R represents a saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, EO represents an oxyethylene group, n is the average number of moles added of the oxyethylene group, and 0.5 ≦ n ≦ 3. Preferably, 0.5 ≦ n ≦ 1.8.
And c) a dry granule prepared by spray drying of an aqueous mixture containing the three components of the inorganic component, 1) crushing granulation after compaction molding or 2) rolling granulation and high bulk density granulation In the process of producing a detergent, during the molding or granulating step, the dry powder is maintained in a temperature range that exceeds the melting point of the component b) by 5 ° C. or more. Is.
[0026]
Consumer goods that are regularly used in general households, such as laundry detergents, need to be supplied to the market in large quantities, and the spray-drying method is indispensable as a means to produce large quantities efficiently. In general, spray-dried powder particles are extremely porous and do not have high bulk density because droplets of organic / inorganic raw materials containing a large amount of water are dried in high-temperature hot air in a short time. (Normally 0.3 g / cm ^Three Before and after). As an industrial processing method for increasing the bulk density of the porous granular material in this way, using a roller or an extruder, a method of pressing and solidifying by applying pressure (consolidation), and by stirring at high speed in the container, A method (rolling granulation) in which the particles are aggregated like a snowman while crushing the particles. In any of the methods, in order to increase the bulk density, it is theoretically impossible to avoid deformation of particles from the state immediately after drying and aggregation with a plurality of particles.
[0027]
On the other hand, the most emphasized feature of the production method of the present invention is that the powder obtained by spray drying is further subjected to 1) crush granulation after compaction molding or 2) rolling granulation. Uniform and developed polyoxyethylene higher fatty acid monoethanolamide surfactant mixture in one particle of the target product in the process of granulation with high bulk density, high fluidity and appropriate particle size It is possible to increase the particle strength by growing a solidified network of
[0028]
In order to harden the particles using the solidification network of polyoxyethylene higher fatty acid monoethanolamide surfactant mixture b), the amount of component b) is 3% by weight or more (preferably 5% by weight or more) based on the detergent particles. ) In the blending amount. In addition, after the above-described particle deformation and aggregation of a plurality of particles are completed, the melt of the component b) that is uniformly distributed solidifies so that the effect of improving the particle strength can be maximized, so that the particle deformation and / or It is necessary to carry out a process in which agglomeration of a plurality of particles occurs (that is, a molding and / or granulation process) in a state where the component b) is liquefied. In order for the b) component in the dry granule to be in a liquefied state without unevenness, it is necessary to handle the dry granule at a temperature at least 5 ° C. higher than the melting point of the b) component. In order to make the polyoxyethylene higher fatty acid monoethanolamide uniformly liquefied by controlling the temperature of the dried granule, it is more efficient at high temperature, but when the melting point exceeds 30 ° C, it is no longer necessary. Since there is no further improvement in the effect, it simply causes a loss of energy and is meaningless. In addition, when the temperature of the dry granular material in the process is not clear, it is necessary to take out a part and actually measure it using a thermometer, but after confirming the temperature of the dry granular material, the same procedure (operating conditions) If the operation of the manufacturing machine is continued under environmental conditions), it is not necessary to monitor frequently. Ideally, it is desirable to provide a temperature sensor in the premixer and / or in the molding machine and / or in the rolling granulator, and to automatically control the temperature control means (jacket or the like) attached thereto.
[0029]
More specifically, the compacting method will be described. A method of preliminarily temporarily mixing dry powder and other additive components into a compressed sheet by passing a roller having axial pressure. Alternatively, for example, there is a method of forming into a rod shape of about 10 mm with an extrusion molding machine such as a pre-extrusion type biaxial extrusion molding machine. At the time of preliminary mixing, liquid components can be added by a method such as spraying as long as other powder components and the properties of the detergent particles are not impaired. At each step, the temperature of the dry granule is maintained in a temperature range exceeding 5 ° C. above the melting point of the polyoxyethylene higher fatty acid monoethanolamide surfactant mixture to be used. It is necessary to control the temperature of the mixer and / or roller. The same applies to the latter case, and it is necessary to control the temperature of the mixer and / or the extruder during premixing. The molded product obtained as described above needs to be further processed into particles having an appropriate particle size through a crushing granulation step, specifically, particles having an average particle size of 200 to 1000 μm. During this crushing and granulating process, temperature control is not required, but high temperature is not preferable in order to avoid overloading the crusher.
[0030]
The rolling granulation method is specifically described. For example, a vertical mixer having an agitator and a chopper such as a high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), and a Redige mixer (Matsuzaka Giken Co., Ltd.). In a horizontal mixer having a blade and a chopper as in the above, a dry powder granule and other additive components are charged, and by continuing stirring, agglomeration is advanced while crushing, and an appropriate particle size (specifically, 200 A method of granulating a granule having a particle size of ˜1000 μm) and an improved bulk density is conceivable. As an additive component, in addition to the powder component, the liquid component can be added by a method such as spraying as long as the physical properties of the detergent particles are not impaired. During each granulation process, the temperature of the jacket of the mixer, etc., is maintained so that the temperature of the dry granular material is maintained in a temperature range that is 5 ° C. or more higher than the melting point of the polyoxyethylene higher fatty acid monoethanolamide surfactant mixture. Need to control. The granulated product obtained through the rolling granulation step is obtained by sieving excessive particles and pulverizing them and mixing them with sieve passing particles to obtain the desired detergent particles. In any process, after the dry granulate is compacted or tumbled granulated, the particles are substantially agglomerated except that fine particles such as crystalline aluminosilicate are adhered as a surface coating agent for the detergent particles. Preferably not.
[0031]
The high bulk density granular detergent obtained in the present invention is a high soap containing a non-soap anionic surfactant a), a specific polyoxyethylene higher fatty acid monoethanolamide surfactant mixture b) and an inorganic component c). It is a bulk density particle, but the components usually added to the detergent, specifically, separately granulated enzyme particles, bleach particles, antifoam particles, etc. are separately dry blended into the high bulk density granular detergent of the present invention. Also good. When blending the crystalline silicate described in JP-A-60-227895 and JP-A-7-89712, which is an excellent compound as an alkali agent and a sequestering agent, dry blending as separate particles or It is preferable to add in the consolidation step or granulation step.
[0032]
In addition, when mix | blending fluorescent dye, it adds to an aqueous | water-based slurry, but when there is a concern about decomposition | disassembly by a heat | fever, you may add at the process of high bulk density. Of course, in that case, care should be taken that the fluorescent dye does not aggregate locally within the detergent particles. It goes without saying that perfume ingredients are unfavorable for high temperature processing due to their volatility, and therefore are not preferred for incorporation into an aqueous slurry through a spray drying process which is a high temperature processing. Usually, it is added after the bulk density increasing step or after the granulation is finished, but in that case, it should be noted that the odor changes due to volatilization. For that purpose, it is preferable to add the fragrance as much as possible in the last part of the production process or after the completion of the process.
[0033]
<Detergent particle size and bulk density>
The average particle size of the high bulk density granular detergent obtained by the production method of the present invention is preferably 200 to 1000 μm, particularly 200 to 600 μm in order to obtain preferable powder physical properties. Moreover, the bulk density of the high bulk density granular detergent of the present invention is 0.5 to 1.2 g / cm. ^Three , Preferably 0.6 to 1.0 g / cm ^Three Degree.
[0034]
【Example】
EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
[0035]
<Preparation Example 1>
A mixture of 85% pure methyl laurate (trade name Exepal ML-85, manufactured by Kao Corporation) and monoethanolamine (molar ratio 1: 1.03) was heated to 80 ° C., and sodium methylate was added as a catalyst. Added. Furthermore, the reaction was continued for 6 hours while distilling off by-produced methanol under the conditions of 95 ° C. and 30 mmHg to obtain an amidated product. This was subjected to the next reaction without purification. The autoclave is charged with 0.02 molar equivalent of amidated product and sodium methylate of catalyst relative to the amidated product, and then care is taken not to exceed 0.75 molar equivalent of ethylene oxide at 100 ° C. and 0.35 MPa. Then, the mixture was aged for about 2 hours until ethylene oxide was completely reacted. A trace amount of unreacted ethylene oxide was removed while bubbling nitrogen gas at 80 ° C. and 100 mmHg, and the target polyoxyethylene fatty acid monoethanolamide ADEO1 [R = C in the formula (I)] ₁₁ H _{twenty three} Compound of alkyl group, n = 0.75] was obtained.
Similarly, ADEO 2, 3, and 7 were synthesized by changing the amount of ethylene oxide introduced.
[0036]
<Preparation Example 2>
Lauric acid / myristic acid mixed fatty acid (lauric acid / myristic acid = 75/25 (weight ratio)) was heated to 90 ° C., 1.1 mol equivalent of monoethanolamine was added, and the conditions were 160 ° C. and 50 mmHg. While the by-produced water was distilled off, the reaction was continued for 6 hours to obtain an amidated product. Under the same conditions as in Preparation Example 1, ethoxylation was performed to synthesize polyoxyethylene fatty acid monoethanolamides ADEO4 and ADEO5. Similarly, a product obtained by removing a low-boiling point fatty acid derived from coconut oil [manufactured by Kao Corporation, trade name LUNAC L-55, composition by gas chromatography: capric acid / lauric acid / myristic acid / stearic acid / others = 1 / 57/22/10/3/7 (weight ratio)] to synthesize polyoxyethylene fatty acid monoethanolamide ADEO6.
[0037]
<Measuring method of melting point of polyoxyethylene higher fatty acid monoethanolamide>
The melting point of polyoxyethylene higher fatty acid monoethanolamide was determined by DSC method under the following conditions.
・ Measuring device: Differential scanning calorimeter DSC120 [manufactured by Seiko Electronics Co., Ltd.]
Thermal analysis system SSC5200H [Same as above]
Measurement conditions: scanning temperature range 0 to 100 ° C., heating rate 0.5 ° C./min
Sample: A sample of 5 to 10 mg was placed in an AG15 type sample pan (manufactured by Seiko Denshi Kogyo Co., Ltd.) as a measurement sample, and the same type pan was used as a reference.
Reading of numerical values: From the graph [horizontal axis: temperature (° C.), vertical axis: calorific value difference (μW)], the temperature at the apex of the maximum endothermic peak was read and taken as the melting point.
Table 1 shows the measurement results of the compositions and melting points of various polyoxyethylene higher fatty acid monoethanolamides obtained in the above preparation examples.
[0038]
[Table 1]

[0039]
<Examples 1-8 and Comparative Examples 1-2>
According to the compositions shown in Tables 2 to 5, high-density detergent compositions were prepared by the following method. In Tables 2 to 5, composition I is a ratio in the final composition, composition II is a ratio of composition I blended as a spray-dried powder, and composition III is a component added to mixer or molded from composition I The ratio of the amount blended as a machine addition component, the composition IV is the proportion blended as a sizing coating agent or as a crushing aid in the composition I, and the composition V was blended as an after blend component in the composition I The ratio of minutes.
[0040]
[A] Preparation method of spray-dried product
A water slurry (45% moisture) containing the composition of II in each composition shown in Tables 2 to 5 (excluding volatile matter) in a specified ratio was prepared, spray-dried, and each II shown in Tables 2 to 5 A dry granular material having a composition of The volatile content in the table is a weight loss measured under conditions of 110 ° C./30 minutes by putting 10 g of a granular material obtained by spray drying into a petri dish, and it is considered that most is water. No particular analysis was performed and the product was directly subjected to the subsequent process.
[0041]
[B-1] Preparation method 1 of high bulk density granular detergent 1 (Examples 1, 2, and 7)
In a ribbon mixer in which 83 parts by weight (II in the table) of dry powder and 10 parts by weight (III in the table) of zeolite were circulated through jacket water at 70 ° C (65 ° C in Example 2 and 65 ° C in Example 7). And premixed. At the end of preliminary mixing, the temperature of the mixed powder of Example 1 was 55 ° C. (Example 2 was 50 ° C. and Example 7 was 52 ° C.). In order not to change the temperature of the obtained mixed powder, it is immediately put into a pre-extrusion type twin screw extruder (Pelleter Double; manufactured by Fuji Powder Co., Ltd.) so that the powder temperature maintains the above-mentioned value. While controlling the molding machine temperature, extrusion molding was performed to obtain a continuous rod-shaped molded product. After standing to cool, the rod-shaped molded product was adjusted to an appropriate length, 4 parts by weight of zeolite was added to 93 parts by weight of the molded product (IV in the table), and pulverized and granulated with a flash mill (Fuji Powder Co., Ltd.). And surface coating. Coarse particles were collected with a sieve having a mesh size of 1.5 mm, and after re-pulverization, the particles were passed through the sieve after the first pulverization to obtain target detergent particles. In a V-type blender, 97 parts by weight of detergent particles, 1 part by weight of zeolite, and 2 parts by weight of enzyme particles were blended (V in the table) to obtain a final form of the detergent composition (I in the table).
[0042]
[B-2] Preparation method 2 of high bulk density granular detergent (Examples 3 to 5, Comparative Example 1)
Jacketed with 83 parts by weight (II in the table) of dry granules and 10 parts by weight (III in the table) of hot water at 60 ° C. (65 ° C. in Example 4, 60 ° C. in Example 5 and room temperature in Comparative Example 1). The mixture was placed in a high speed mixer (manufactured by Fukae Kogyo Co., Ltd.) circulated in the section and stirred. The mixer was stopped at the stage of 5 minutes after the start of stirring, and the internal detergent particles were taken out and the temperature was measured. At 40 ° C (Example 4 was 45 ° C, Example 5 was 40 ° C, and Comparative Example 1 was 20 ° C). there were. Further, stirring was continued for 10 minutes or more to perform rolling granulation to obtain an appropriate particle size. Then, 5 parts by weight of zeolite was added (IV in the table) and stirred for about 1 minute to coat the particle surface with zeolite. . The obtained granulated product was subjected to the next sieving step without any temperature control. Oversized particles were sieved and pulverized with a sieve having a mesh opening of 1.5 mm, and combined with the sieve passage to obtain target detergent particles. The enzyme granulated product was blended in a V-type blender at a ratio of 2 parts by weight with respect to 98 parts by weight of the detergent particles (V in the table) to obtain a final form of the detergent composition (I in the table).
[0043]
[B-3] Preparation method 3 of high bulk density particle detergent (Example 6, Comparative Example 2)
A Readyge mixer (Matsuzaka) in which 83 parts by weight (II in the table) and 10 parts by weight of zeolite (III in the table) of the composition described in the table were circulated through the jacket part with warm water of 75 ° C. (comparative example 3 was room temperature). And stirred. The mixer was stopped at the stage of 5 minutes after the start of stirring, and the internal detergent particles were taken out and the temperature was measured. As a result, the temperature was 60 ° C. (Comparative Example 3 was 20 ° C.). Further, the mixture was stirred for 10 minutes or more to perform rolling granulation to obtain an appropriate particle size, and then 5 parts by weight of zeolite (IV in the table) was added and stirred for 1 minute to coat the particle surface with zeolite. The obtained granulated product was subjected to the next sieving step without any temperature control. Oversized particles were sieved and pulverized with a sieve having a mesh opening of 1.5 mm, and combined with the sieve passage to obtain target detergent particles. The enzyme granulated product was blended in a V-type blender at a ratio of 2 parts by weight with respect to 98 parts by weight of the detergent particles (V in the table) to obtain a final form of the detergent composition (I in the table).
[0044]
[B-4] Preparation method 4 of high bulk density particle detergent (Example 8)
A high-speed mixer in which 79 parts by weight (II in the table) of dry granule having the composition described in the table, 9 parts by weight of zeolite, and 4 parts by weight of crystalline silicate (III in the table) were circulated through the jacket part with 70 ° C hot water ( Fukae Kogyo Co., Ltd.) and gradually added by spraying 1 part by weight of AE (III in the table) heated to 50 ° C. while stirring. When the stirring was performed for 5 minutes after the end of spraying, the mixer was stopped, the detergent particles inside were taken out, and the temperature was measured. Continue stirring for 10 minutes to perform tumbling granulation to obtain an appropriate particle size, then to an appropriate particle size, add 5 parts by weight of zeolite (IV in the table), and stir for about 1 minute. Was coated with zeolite. The obtained granulated product was subjected to the next sieving step without any temperature control. Oversized particles were sieved and pulverized with a sieve having a mesh opening of 1.5 mm, and combined with the sieve passage to obtain target detergent particles. The enzyme granulated product was blended in a V-type blender at a ratio of 2 parts by weight with respect to 98 parts by weight of the detergent particles (V in the table) to obtain a final form of the detergent composition (I in the table).
[0045]
[C] Measurement of granular detergent particle strength
About the high-density granular detergent composition obtained in the said Examples 1-7 and Comparative Examples 1-2, particle | grain intensity | strength was measured with the following method. When the detergent particles are hard, plastic deformation is not caused even when pressure is applied, and as a result, the detergent particles do not clump or can be broken down with a weak force even when solidified. As an index representing the strength of the detergent particles, the ease of solidification when pressure was applied and the ease of collapse of the solid detergent particle mass were measured as “consolidation fracture load”. The measurement method will be described below, and those having a “consolidation fracture load” of “not measurable” are because the detergent lump was not formed under a constant pressure condition and can be said to be the most preferable detergent particles. If it is measurable, the smaller the number, the better.
[0046]
<Consolidated fracture load measurement method>
(1) Equipment used
・ Tapping machine: Tapping type close-packed bulk density meter TVP-1 (manufactured by Tsutsui Rika Instruments Co., Ltd.)
・ Fracture load measuring device: FUDO RHEOMETER RT-3020D-CW type (manufactured by Leotech Co., Ltd.)
(2) Measurement conditions: room temperature (detergent particle temperature is 20 ° C.)
(3) Measuring method:
A metal cylinder having an outer diameter of 50 mm and an inner diameter of 30 mm was placed in a cup-shaped container having a matching size, and 30 g of detergent particles were placed in the cylindrical portion so that the surface was smooth. Next, a metal cylinder (380 g) was gently placed on the detergent particles as a weight, and tapped 30 times (falling distance 25 mm) with the above tapping machine. Remove the cylinder from the cup, carefully press the compressed detergent particles (detergent particle lump) remaining inside the cylinder from the top with the cylinder, and gently place the detergent particle lump on the plate (with the circular part at the bottom) It was. The detergent lump was placed on the plate and moved to the sample lifting platform of the rheometer, and the maximum load at break was measured at a speed of 2 cm / min. At this time, the detergent particles that could not be taken out as a lump were indicated as “not measurable”.
[0047]
[Table 2]

[0048]
[Table 3]

[0049]
[Table 4]

[0050]
[Table 5]

[0051]
(note)
LAS: alkylbenzene sulfonic acid soda [manufactured by Nisseki Detergent Co., Ltd., alkyl benzene sulfonic acid "alkene L (alkyl 10 to 14 carbon atoms) neutralized with 48% NaOH]]
AS: Mitsubishi Chemical Co., Ltd. Dovanol 25 sulfate (C ₁₂ ~ C ₁₅ Sodium salt of sulfuric acid)
・ SFE: Palm oil derived, alpha sulfo fatty acid methyl ester soda
・ Fatty acid salt: Sodium palmitate
・ AE: Noned R-7 (C ₁₂ ~ C ₁₅ Alcohol with an average of 7.2 moles of ethylene oxide added, manufactured by Mitsubishi Chemical Corporation)
・ Zeolite: A-type zeolite, average particle size 3μm
・ Crystalline silicate: SKS-6, δ-Na ₂ Si ₂ O _Five , Crystalline layered sodium silicate, average particle size 20 μm, manufactured by Hoechst Tokuyama
・ Silicate: Amorphous sodium silicate, JIS No. 1 sodium silicate
・ Soda carbonate: dense grain ash
PAS: sodium polyacrylate, average molecular weight 12000
AA-MA: Socaran CP5, acrylic acid-maleic acid copolymer, average molecular weight 70000
・ Fluorescent dye: Cinopal CBS (Ciba Geigy) and Whitetex SA (Sumitomo Chemical Co., Ltd.) blended in the same amount by weight
Enzyme: Sabinase 12.0T typeW (protease), lipolase 100T (lipase), Termamyl 60T (amylase) (the above enzyme, manufactured by Novo Nordisk) and KAC500 (alkaline cellulase, manufactured by Kao Corporation) in a weight ratio of 2: Mixed at a ratio of 1: 1: 1

Claims (5)

a) 10-30% by weight of a non-soap anionic surfactant,
b) a mixture of polyoxyethylene higher fatty acid monoethanolamide surfactant represented by the following formula (I): 5 wt% or more and 15 wt% or less, and

(In the formula, R represents a saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, EO represents an oxyethylene group, n represents the average number of added moles of the oxyethylene group, and 0.5 ≦ n ≦ 3. .)
c) Inorganic component
A method for producing a high-density granular detergent containing
At least, a) non-soap anionic surfactant, b) a mixture of polyoxyethylene higher fatty acid monoethanolamide surfactant represented by the formula (I), the three components of 及 beauty c) inorganic component In the process of 1) crushing granulation after compaction molding or 2) rolling granulation to produce a high bulk density granular detergent, A method for producing a high-density granular detergent, characterized in that, during the granulation step, the dry powder is maintained in a temperature range that exceeds the melting point of the component b) by 5 ° C or more. The weight ratio of components a), b) and c) in the high-density granular detergent is b) / a) = 0.05 to 1, [a) + b)] / c) = 0.2 to 1. The manufacturing method of description. The method according to claim 1 or 2, wherein the component c) contains amorphous sodium silicate. The compacting is performed by A) sheet-like molding using a roller or B) rod-like molding using an extrusion molding machine, and thereafter crushing and granulating the molded product to a particle size having an average particle size of 200 to 1000 µm. The manufacturing method of any one of 1-3. The production method according to any one of claims 1 to 3, wherein the rolling granulation is performed with C) vertical high-speed mixer or D) horizontal mixer, and the average particle size is granulated to a particle size of 200 to 1000 µm.