JP2004510033A - Coated granular N-alkylammonium acetonitrile salts and their use as bleach activators - Google Patents

Abstract

The present invention relates to a compound of the general formula (I) R ² R ³ NR ¹ -CR ⁴ R ⁵ -CN ⁺ Y ^{− wherein} R ¹ may be interrupted by a non-adjacent oxygen atom, or optionally have a hydroxyl group at the _C 1 _{-C 24} - alkyl _group, C 4 _{-C 24} - represents an alkaryl group, or the formula ^-CR 4 ^R 5 -CN groups - _cycloalkyl, C 7 _{-C 24} , R ² and R ³ each independently represent, independently of ^one another, those represented by R ¹ or, together with the nitrogen atom to which they are attached, at least one carbon atom and from the group of oxygen, sulfur and nitrogen Represents a saturated 4- to 9-membered ring having at least one other heteroatom, wherein R ⁴ and R ⁵ are each independently of the other optionally hydrogen or a non-adjacent oxygen atom, Or additionally hydro Represents a C ₁ -C ₂₄ -alkyl group which may have a xyl group, a C ₄ -C ₂₄ -cycloalkyl group or a C ₇ -C ₂₄ -alkaryl group, and Y represents the corresponding stoichiometric Coated N-alkylammonium acetonitrile salt coated with a material selected from the group consisting of organic, inorganic, hydrophilic and hydrophobic substances About.

Description

【００４５】
［式中、Ｒ^１はＣ_８〜Ｃ_２０−炭化水素基、有利にはアルキルを表し、かつＲはＣ_１〜Ｃ_６−炭化水素基、有利にはアルキルを表す］の化合物である。Ｍはアルキルエーテルスルホネートと水溶性の塩を形成するカチオンを表す。適切なカチオンはナトリウム、カリウム、リチウムまたはアンモニウムカチオン、たとえばモノエタノールアミン、ジエタノールアミンおよびトリエタノールアミンである。有利にはＲ^１はＣ_１０〜Ｃ_１６−アルキルを表し、かつＲはメチル、エチルもしくはイソプロピルを表す。多くの場合、式中でＲ^１がＣ_１０〜Ｃ_１６−アルキルを表すメチルエステルスルホネートが有利である。
【００４６】
アルキルスルフェートは式ＲＯＳＯ_３Ｍの水溶性の塩もしくは酸であり、その際、ＲはＣ_１０〜Ｃ_２４−炭化水素基、有利にはＣ_１０〜Ｃ_２０−アルキル成分を有するアルキル−もしくはヒドロキシアルキル基、特に有利にはＣ_１２〜Ｃ_１８−アルキル−もしくはヒドロキシアルキル基である。Ｍは水素または適切なカチオン、たとえばアルカリ金属カチオン、有利にはナトリウム、カリウム、リチウムまたはアンモニウム−もしくは置換されたアンモニウムカチオン、有利にはメチル−、ジメチル−およびトリメチルアンモニウムカチオンまたは第四アンモニウムカチオン、たとえばテトラメチルアンモニウム−およびジメチルピペリジニウムカチオンおよびアルキルアミン、たとえばエチルアミン、ジエチルアミン、トリエチルアミンおよびこれらの混合物から誘導される第四アンモニウムカチオンである。Ｃ_１２〜Ｃ_１６を有するアルキル鎖は低い洗浄温度（たとえば約５０℃未満）およびＣ_６〜Ｃ_１８を有するアルキル鎖は高い洗浄温度（たとえば約５０℃以上）のために有利である。
【００４７】
アルキルエーテルスルフェートは、式ＲＯ（Ａ）_ｍＳＯ_３Ｍの水溶性の塩もしくは酸であり、その際、Ｒは非置換のＣ_１０〜Ｃ_２４−アルキル基もしくはヒドロキシアルキル基、有利にはＣ_１２〜Ｃ_２０−アルキル基もしくはヒドロキシアルキル基、特に有利にはＣ_１２〜Ｃ_１８−アルキル基もしくはヒドロキシアルキル基を表す。Ａはエトキシ単位またはプロポキシ単位であり、ｍは０より大きい数であり、有利には約０．５〜約６であり、特に有利には約０．５〜約３であり、かつＭは水素原子またはカチオン、たとえばナトリウム、カリウム、リチウム、カルシウム、マグネシウム、アンモニウムまたは置換されたアンモニウムカチオンである。置換されたアンモニウムカチオンの例はメチル−、ジメチル−、トリメチルアンモニウム−および第四アンモニウムカチオン、たとえばテトラメチルアンモニウムおよびジメチルピペリジニウムカチオンならびにアルキルアミン、たとえばエチルアミン、ジエチルアミン、トリエチルアミンもしくはこれらの混合物から誘導されるカチオンである。例としてＣ_１２〜Ｃ_１８−脂肪アルコールエーテルスルフェートが挙げられ、その際、エチレンオキシド単位の含有率は脂肪アルコールエーテルスルフェート１モルあたり、１、２、２．５、３もしくは４モルであり、かつその際、Ｍはナトリウムまたはカリウムである。
【００４８】
第二アルカンスルホネート中でアルキル基は飽和もしくは不飽和であってもよく、分枝鎖状もしくは直鎖状および場合によりヒドロキシル基により置換されていてもよい。スルホ基は炭素鎖の任意の位置にあってよく、その際、鎖の始まりおよび鎖の終わりにある第一メチル基はスルホネート基を有していない。有利な第二アルカンスルホネートは約９〜２５の炭素原子を有する、有利には約１０〜約２０の炭素原子および特に有利には約１３〜１７の炭素原子を有する直鎖状のアルキル鎖を有している。カチオンはたとえばナトリウム、カリウム、アンモニウム、モノ−、ジ−もしくはトリエタノールアンモニウム、カルシウムまたはマグネシウムおよびこれらの混合物である。ナトリウムがカチオンとして有利である。
【００４９】
その他の適切なアニオン性界面活性剤はアルケニル−もしくはアルキルベンゼンスルホネートである。アルケニル−もしくはアルキル基は分枝鎖状もしくは直鎖状であってよく、かつ場合によりヒドロキシル基により置換されていてもよい。有利なアルキルベンゼンスルホネートは約９〜２５の炭素原子を有する、有利には約１０〜約１３の炭素原子を有する直鎖状のアルキル鎖を有しており、カチオンはナトリウム、カリウム、アンモニウム、モノ−、ジ−もしくはトリエタノールアンモニウム、カルシウムまたはマグネシウムまたはこれらの混合物である。緩和な界面活性剤系に関してマグネシウムがカチオンとして有利であり、これに対して標準的な洗浄の適用のためにはナトリウムが有利である。同じことがアルケニルベンゼンスルホネートにも該当する。
【００５０】
アニオン界面活性剤の概念はオレフィンスルホネートも含み、これはＣ_１２〜Ｃ_２４−、有利にはＣ_１４〜Ｃ_１６−α−オレフィンを三酸化硫黄によりスルホン化し、かつ引き続き中和することにより得られる。製造方法により限定されて、これらのオレフィンスルホネートは比較的少ない量のヒドロキシアルカンスルホネートおよびアルカンジスルホネートを含有していてもよい。α−オレフィンスルホネートの特殊な混合はＵＳ３，３３２，８８０に記載されている。
【００５１】
その他の有利なアニオン性界面活性剤はカルボキシレート、たとえば脂肪酸セッケンおよびこれに匹敵する界面活性剤である。セッケンは飽和もしくは不飽和であってもよく、かつ種々の置換基、たとえばヒドロキシル基またはα−スルホネート基を有していてもよい。直鎖状の飽和もしくは不飽和炭化水素基が約６〜約３０、有利には約１０〜約１８の炭素原子を有する疎水性の割合として有利である。
【００５２】
アニオン性界面活性剤としてさらに次のものが考えられる：アシルアミノカルボン酸の塩；脂肪酸塩化物とサルコシン酸ナトリウムとをアルカリ性媒体中で反応させることにより生じるアシルサルコシネート；脂肪酸塩化物とオリゴペプチドとを反応させることにより得られる脂肪酸−タンパク質−縮合生成物；アルキルスルホアミドカルボン酸の塩；アルキル−およびアルキルアリールエーテルカルボン酸の塩；Ｃ_８〜Ｃ_２４−オレフィンスルホネート；アルカリ土類金属クエン酸塩の熱分解生成物をスルホン化することにより製造されるスルホン化されたポリカルボン酸、たとえばＧＢ−１．０８２．１７９に記載されているもの；アルキルグリセリンスルフェート；オレイルグリセリンスルフェート；アルキルフェノールエーテルスルフェート；第一パラフィンスルフェート；アルキルホスフェート；アルキルエーテルホスフェート；イセチオネート、たとえばアシルイセチオネート、Ｎ−アシルタウリド；アルキルスクシネート；スルホスクシネート；スルホスクシネートのモノエステル（特に飽和および不飽和のＣ_１２〜Ｃ_１８−モノエステル）およびスルホスクシネートのジエステル（特に飽和および不飽和のＣ_１２〜Ｃ_１８−ジエステル）；アシルサルコシネート；アルキル多糖類のスルフェート、たとえばアルキルポリグリコシドのスルフェート、分枝鎖状の第一アルキルスルフェートおよびアルキルポリエトキシカルボキシレート、たとえば式ＲＯ（ＣＨ_２ＣＨ_２）_ｋＣＨ_２ＣＯＯ⁻Ｍ^＋（式中、ＲはＣ_８〜Ｃ_２２−アルキルであり、ｋは０〜１０の数であり、かつＭはカチオンである）のもの；樹脂酸または水素化した樹脂酸、たとえばロジンまたは水素化したロジンまたはトール油樹脂およびトール油樹脂酸。その他の例は”Ｓｕｒｆａｃｅ Ａｃｔｉｖｅ Ａｇｅｎｔｓ ａｎｄ Ｄｅｔｅｒｇｅｎｔｓ”（第ＩおよびＩＩ巻、Ｓｃｈｗａｒｔｚ、ＰｅｒｒｙおよびＢｅｒｃｈ）に記載されている。
【００５３】
非イオン性界面活性剤としてたとえば次の化合物が考えられる：
−　アルキルフェノールのポリエチレン−、ポリプロピレン−およびポリブチレンオキシド縮合物。
【００５４】
これらの化合物は、直鎖状もしくは分枝鎖状であってよいＣ_６〜Ｃ_２０−アルキル基を有するアルキルフェノールとアルケンオキシドとの縮合生成物を含む。アルキルフェノール１モルあたり約５〜２５モルのアルケンオキシドを有する化合物が有利である。
【００５５】
−　脂肪族アルコールと約１〜約２５モルのエチレンオキシドとの縮合生成物。
【００５６】
脂肪族アルコールのアルキル鎖は直鎖状もしくは分枝鎖状、第一もしくは第二であってよく、かつ一般に約８〜２２個の炭素原子を有する。特に有利であるのはＣ_１０〜Ｃ_２０−アルコールとアルコール１モルあたり約２〜約１８モルのエチレンオキシドとの縮合生成物である。アルキル鎖は飽和であっても不飽和であってもよい。アルコールエトキシレートはエチレンオキシドの狭い同族体分布（”Ｎａｒｒｏｗ Ｒａｎｇｅ Ｅｔｈｏｘｙｌａｔｅｓ”）もしくは広い分布（”Ｂｒｏａｄ Ｒａｎｇｅ Ｅｔｈｏｘｙｌａｔｅｓ”）を有していてよい。
【００５７】
この種の市販の非イオン性界面活性剤の例はたとえばＢＡＳＦ社の商品名Ｌｕｔｅｎｓｏｌ　^（Ｒ）である。
【００５８】
−　プロピレンオキシドとプロピレングリコールとの縮合により形成される疎水性ベースのエチレンオキシドの縮合生成物。
【００５９】
これらの化合物の疎水性部分は有利には約１５００〜約１８００の分子量を有する。この疎水性部分におけるエチレンオキシドの付加は水溶性の改善をもたらす。生成物は縮合生成物の全質量の約５０％のポリオキシエチレン含有率まで液状であり、これは約４０モルのエチレンオキシドとの縮合に相応する。これらの生成物クラスの市販の例はたとえばＢＡＳＦ社の商品名Ｐｌｕｒｏｎｉｃ　^（Ｒ）である。
【００６０】
−　エチレンオキシドと、プロピレンオキシドおよびエチレンジアミンの反応生成物との縮合生成物。
【００６１】
これらの化合物の疎水性単位は、エチレンジアミンと過剰のプロピレンオキシドとの反応生成物からなり、かつ一般に約２５００〜３０００の分子量を有する。これらの疎水性単位において、エチレンオキシドはポリオキシエチレンの約４０〜約８０質量％の含有率まで、および約５０００〜１１０００の分子量まで付加される。これらの化合物の市販の例はたとえばＢＡＳＦ社の商品名Ｔｅｔｒｏｎｉｃ　^（Ｒ）である。
【００６２】
−　半極性の非イオン性界面活性剤。
【００６３】
この非イオン性化合物のカテゴリーは水溶性のアミンオキシド、水溶性のホスフィンオキシドおよび水溶性のスルホキシドを含み、それぞれ約１０〜約１８個の炭素原子のアルキル基を有する。半極性の非イオン性界面活性剤は式
【００６４】
【化２】

【００６５】
のアミンオキシドでもある。
【００６６】
Ｒはこの場合、約８〜２２個の炭素原子の鎖長を有するアルキル基、ヒドロキシアルキル基もしくはアルキルフェノール基である。Ｒ^２は約２〜３個の炭素原子を有するアルキレン基もしくはヒドロキシアルキレン基またはこれらの混合物であり、それぞれの基Ｒ^１は約１〜約３の炭素原子を有するアルキル基もしくはヒドロキシアルキル基であるか、または約１〜約３のエチレンオキシド単位を有するポリエチレンオキシド基であり、かつｘは０〜約１０の数を表す。Ｒ^１基は相互に酸素原子もしくは窒素原子を介して結合していてもよく、従って環を形成してもよい。この種のアミンオキシドは特にＣ_１０〜Ｃ_１８−アルキルジメチルアミンオキシドおよびＣ_８〜Ｃ_１２−アルコキシエチル−ジヒドロキシエチルアミンオキシドである。
【００６７】
−　脂肪酸アミド。
【００６８】
脂肪酸アミドは式
【００６９】
【化３】

【００７０】
［式中、Ｒは約７〜約２１、有利には約９〜約１７個の炭素原子を有するアルキル基であり、かつＲ^１は相互に無関係に水素、Ｃ_１〜Ｃ_４−アルキル、Ｃ_１〜Ｃ_４−ヒドロキシアルキルまたは（Ｃ_２Ｈ_４Ｏ）_ｘＨを表し、その際、ｘは約１〜約３まで変化する］を有する。Ｃ_８〜Ｃ_２０−アミド、−モノエタノールアミド、−ジエタノールアミドおよび−イソプロパノールアミドが有利である。
【００７１】
その他の適切な非イオン性界面活性剤はアルキル−およびアルケニルオリゴグリコシドならびにそれぞれ脂肪アルキル基中に８〜２０個、有利には１２〜１８個の炭素原子を有する脂肪酸ポリグリコールエステルまたは脂肪アミンポリグリコールエステル、アルコキシル化トリグリカミド、混合エーテルもしくは混合ホルマール、アルキルオリゴグリコシド、アルケニルオリゴグリコシド、脂肪酸−Ｎ−アルキルグルカミド、ホスフィンオキシド、ジアルキルスルホキシドおよびタンパク質加水分解物である。
【００７２】
両性もしくは両性イオン性界面活性剤のための典型的な例は、アルキルベタイン、アルキルアミドベタイン、アミノプロピオネート、アミノグリシネートもしくは式
【００７３】
【化４】

【００７４】
［式中、Ｒ^１はＣ_８〜Ｃ_２２−アルキル−もしくは−アルケニルを表し、Ｒ^２は水素もしくはＣＨ_２ＣＯ_２Ｍ、Ｒ^３はＣＨ_２ＣＨ_２ＯＨまたはＣＨ_２ＣＨ_２ＯＣＨ_２ＣＨ_２ＣＯ_２Ｍを表し、Ｒ^４は水素、ＣＨ_２ＣＨ_２ＯＨもしくはＣＨ_２ＣＨ_２ＣＯＯＭを表し、ＺはＣＯ_２ＭもしくはＣＨ_２ＣＯ_２Ｍを表し、ｎは２もしく３、有利には２を表し、Ｍは水素またはカチオン、たとえばアルカリ金属カチオン、アルカリ土類金属カチオン、アンモニウムカチオンもしくはアルカノールアンモニウムカチオンを表す］の両性イミダゾリニウム化合物である。
【００７５】
この式の有利な両性界面活性剤はモノカルボキシレートおよびジカルボキシレートである。このための例はココアンフォカルボキシプロピオネート（ｃｏｃｏａｍｐｈｏｃａｒｂｏｘｙｐｒｏｐｉｏｎａｔｅ）、ココアミドカルボキシプロピオン酸（ｃｏｃｏａｍｉｄｏｃａｒｂｏｘｙｐｒｏｐｉｏｎｉｃ ａｃｉｄ）、ココアンフォカルボキシグリシネート（ｃｏｃｏａｍｐｈｏｃａｒｂｏｘｙｇｌｙｃｉｎａｔｅ）（ココアンフォジアセテート（ｃｏｃｏａｍｐｈｏｄｉａｃｅｔａｔｅ）ともよばれる）およびココアンフォアセテートである。
【００７６】
別の有利な両親媒性界面活性剤は約８〜約２２個の炭素原子を有するアルキル基を有し、直鎖状もしくは分枝鎖状であってよいアルキルジメチルベタインおよびアルキルジポリエトキシベタインであり、有利には８〜１８個の炭素原子および特に有利には１２〜１８個の炭素原子を有する。
【００７７】
適切なカチオン性界面活性剤の例は、Ｒ^１Ｎ（ＣＨ_３）_３ ^＋Ｘ⁻、Ｒ^１Ｒ^２Ｎ（ＣＨ_３）_２ ^＋Ｘ⁻、Ｒ^１Ｒ^２Ｒ^３Ｎ（ＣＨ_３）^＋Ｘ⁻またはＲ^１Ｒ^２Ｒ^３Ｒ^４Ｎ^＋Ｘ⁻のタイプの置換もしくは非置換の直鎖状もしくは分枝鎖状の第四アンモニウム塩である。基Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は相互に無関係に有利に８〜２４のＣ原子、特に有利には１０〜１８のＣ原子の鎖長を有する非置換のアルキル基、１〜４のＣ原子を有するヒドロキシアルキル基、フェニル、Ｃ_２〜Ｃ_１８−アルケニル、Ｃ_７〜Ｃ_２４−アラルキル、（Ｃ_２Ｈ_４Ｏ）_ｘＨであり、その際、ｘは１〜３の整数を表し、１つもしくは複数のエステル基を有するアルキル基または環式の第四アンモニウム塩であってもよい。Ｘは当業者に公知の適切なアニオンである。
【００７８】
本発明中に含まれていてもよい、その他の洗剤および洗浄剤含有物質は、水の硬度を低減するための無機および／または有機のビルダーであってもよい。
【００７９】
これらのビルダーは約５％〜約８０％の質量割合で洗剤および洗浄剤組成物中に含有されていてもよい。無機ビルダーはたとえばポリホスフェートのアルカリ金属塩、アンモニウム塩およびアルカノールアンモニウム塩、たとえばトリポリリン酸塩、ピロリン酸塩およびガラス状のポリマーのメタリン酸塩、ホスホン酸塩、ケイ酸塩、重炭酸塩およびセスキ炭酸塩を含む炭酸塩、硫酸塩およびアルミノケイ酸塩を含む。
【００８０】
ケイ酸塩ビルダーのための例は、アルカリ金属ケイ酸塩、特にＳｉＯ_２：Ｎａ_２Ｏの比が１．６：１〜３．２：１であるアルカリ金属ケイ酸塩ならびに層状ケイ酸塩、たとえばＵＳ４，６６４，８３９に記載されているナトリウムの層状ケイ酸塩、これは商品名ＳＫＳ−６　^（Ｒ）でＣｌａｒｉａｎｔ社から市販されている。ＳＫＳ−６　^（Ｒ）は特に有利な層状ケイ酸塩ビルダーである。
【００８１】
アルミノケイ酸塩ビルダーは本発明にとって特に有利である。これは特に式Ｎａ_ｚ［（ＡｌＯ_２）_ｚ（ＳｉＯ_２）_ｙ］・_ｘＨ_２Ｏを有するゼオライトであり、その際、ｚおよびｙは少なくとも６の整数を表し、ｚ対ｙの比は約１．０〜０．５であり、かつｘは１５〜２６４の整数である。
【００８２】
アルミノケイ酸塩をベースにした適切なイオン交換体は市販されている。これらのアルミノケイ酸塩は結晶質もしくは不定形の構造であってもよく、かつ天然に由来するか、または合成によって製造されていてもよい。アルミノケイ酸塩ベースのイオン交換体の製造方法はたとえばＵＳ３，９８５，６６９およびＵＳ４，６０５，５０９に記載されている。合成の結晶質アルミノケイ酸塩をベースとする有利なイオン交換体は商品名ゼオライトＡ、ゼオライトＰ（Ｂ）（ＥＰ−Ａ−０３８４０７０に開示されているものを含む）およびゼオライトＸで入手することができる。０．１〜１０μｍの粒径を有するアルミノケイ酸塩は有利である。
【００８３】
適切な有機ビルダーはポリカルボキシル化合物、たとえばエーテルポリカルボキシレートおよびオキシジスクシネートを含み、これらはたとえばＵＳ−３，１２８，２８７およびＵＳ−３，６３５，８３０に記載されている。同様にＵＳ−４，６６３，０７１から公知のＴＭＳ／ＴＤＳ−ビルダーもまた適切である。
【００８４】
その他の適切なビルダーはエーテルヒドロキシポリカルボキシレート、無水マレイン酸とエチレンもしくはビニルメチルエーテルとのコポリマー、１，３，５−トリヒドロキシベンゼン−２，４，６−トリスルホン酸およびカルボキシメチルオキシコハク酸、ポリ酢酸、たとえばエチレンジアミン四酢酸およびニトリロ三酢酸ならびにポリカルボン酸、たとえばメリット酸、コハク酸、オキシジコハク酸、ポリマレイン酸、ベンゼン−１，３，５−トリカルボン酸、カルボキシメチルオキシコハク酸のアルカリ塩、アンモニウム塩および置換されたアンモニウム塩ならびにこれらの可溶性の塩を含む。
【００８５】
クエン酸塩、たとえばクエン酸およびその可溶性の塩、特にナトリウム塩をベースとするビルダーは有利なポリカルボン酸ビルダーであり、これは造粒された調製物として、特にゼオライトおよび／または層状ケイ酸塩と共に使用することができる。
【００８６】
その他の適切なビルダーは３，３−ジカルボキシ−４−オキサ−１，６−ヘキサンジオエートおよびＵＳ−４，５６６，９８４に開示されている関連する化合物である。
【００８７】
リンベースのビルダーを使用することができ、かつ特にセッケンが手洗い用に調整されているべき場合、種々のアルカリ金属ホスフェート、たとえばトリポリリン酸ナトリウム、ピロリン酸ナトリウムおよびオルトリン酸ナトリウムを使用することができる。同様にホスホン酸塩ビルダー、たとえばエタン−１−ヒドロキシ−１，１−ジホスホネートおよびその他の公知のホスホネート、たとえばＵＳ３，１５９，５８１、ＵＳ−３，２１３，０３０、ＵＳ３，４２２，０２１、ＵＳ−３，４００，１４８およびＵＳ−３，４２２，１３７に開示されているものを使用することができる。
【００８８】
一般に本発明により被覆される式（Ｉ）の塩と共に使用される洗浄剤含有物質は洗浄剤のために一般的な成分、たとえば表面活性物質およびビルダーから選択される。場合により洗浄剤含有物質は１種もしくは数種の洗浄助剤またはその他の材料を含有していてもよく、これは洗浄効果を高め、洗浄すべき物品の処理もしくは手入れのために使用されるか、または洗浄剤組成物の使用特性を変える。洗浄剤組成物中の適切な洗浄助剤はたとえばＵＳ３，９３６，５３７に挙げられている物質である。本発明の洗浄剤組成物中で使用することができる洗浄助剤はたとえば酵素、特にプロテアーゼ、リパーゼおよびセルラーゼ、増泡剤、制泡剤、変色防止剤および／または腐食防止剤、懸濁剤、着色剤、増量剤、蛍光増白剤、殺菌剤、アルカリ、ヒドロトロープ化合物、酸化防止剤、酵素安定化剤、香料、溶剤、可溶化剤、再汚染防止剤、分散剤、色移り防止剤、たとえばポリアミン−Ｎ−オキシド、たとえばポリ−（４−ビニルピリジン−Ｎ−オキシド）、ポリビニルピロリドン、ポリ−Ｎ−ビニル−Ｎ−メチルアセトアミドおよびＮ−ビニルイミダゾールおよびＮ−ビニルピロリドンのコポリマー、加工助剤、柔軟剤および耐電防止剤である。
【００８９】
本発明により被覆した粒状のＮ−アルキルアンモニウムアセトニトリルとの組み合わせにおいて使用されるような典型的な漂白剤は上記のものである。
【００９０】
洗剤組成物は本発明により被覆される粒状のＮ−アルキルアンモニウムアセトニトリル以外に、１種もしくは数種の通例の酵素、たとえばプロテアーゼ、アミラーゼ、リパーゼおよびセルラーゼを含有していてもよい。特に有利な酵素はセルラーゼである。この場合に使用されるセルラーゼは微生物もしくは真菌類から得られるものであってもよく、かつ５〜９．５の最適なｐＨ値を有しているべきである。適切なセルラーゼはＵＳ−４，４３５，３０７に開示されている。これはフミコラ・インソレンス（Ｈｕｍｉｃｏｌａ ｉｎｓｏｌｅｎｓ） の菌株、特にフミコラＤＳＭ１８００の菌株、またはその他の、アエロモナス（Ａｅｒｏｍｏｎａｓ）属に属するその他のセルラーゼ−２１２−産生真菌から製造されるセルラーゼ、ならびに特定の海洋軟体類の肝膵臓から抽出されたセルラーゼである。適切なセルラーゼは同様にＧＢ−Ａ−２，０７５，０２８、ＧＢ−Ａ−２，０８５，２７５およびＤＥ−ＯＳ−２，２４７，８３２に開示されている。
【００９１】
有利なセルラーゼはＷＯ−９１／１７２４３に記載されている。本発明による洗浄剤組成物は洗浄剤組成物１グラムあたり、酵素を約５０ｍｇまで、有利には約０．０１ｍｇ〜約１０ｍｇの量で含有している。洗剤組成物の質量に対して酵素の割合は少なくとも０．００１質量％、有利には約０．００１質量％〜約５質量％、特に約０．００１質量％〜約１質量％、とりわけ約０．０１質量％〜約１質量％である。
【００９２】
食器洗い機用洗剤の組成
ビルダー：水溶性および水不溶性のビルダーを使用することができ、その主な課題はカルシウムとマグネシウムを結合することである。全調製物に対して１０〜９０質量％添加することができる通常のビルダーを以下に記載する。
【００９３】
ホスフェート、たとえばアルカリ金属ホスフェートおよびポリマーのアルカリ金属ホスフェート、これらはそのアルカリ性、中性もしくは酸性のナトリウム塩もしくはカリウム塩の形で存在していてもよい。このための例はリン酸三ナトリウム、二リン酸四ナトリウム、リン酸二水素二ナトリウム、トリポリリン酸五ナトリウム、いわゆるヘキサメタリン酸ナトリウム、オリゴマー化度５〜１０００、特に５〜５０を有するオリゴマーのリン酸三ナトリウム、ならびに相応するカリウム塩もしくはヘキサメタリン酸ナトリウムと相応するカリウム塩とからなる混合物もしくはナトリウム塩とカリウム塩とからなる混合物。これらのリン酸塩は有利には全調製物に対して、および無水の活性物質として計算して２５質量％〜６５質量％の範囲で使用する。
【００９４】
低分子量のカルボン酸およびその塩、たとえばアルカリ金属クエン酸塩（たとえば無水のクエン酸三ナトリウムまたはクエン酸三ナトリウム二水和物）、アルカリ金属コハク酸塩、アルカリ金属マロン酸塩、脂肪酸スルホン酸塩、オキシジスクシネート、アルキル−もしくはアルケニルジスクシネート、グルコン酸、オキサジアセテート、カルボキシメチルオキシスクシネート、酒石酸モノスクシネート、酒石酸ジスクシネート、酒石酸モノアセテート、酒石酸ジアセテート、α−ヒドロキシプロピオン酸、酸化されたデンプン、酸化された多糖類；ホモポリマーおよびコポリマーのポリカルボン酸およびこれらの塩、たとえばポリアクリル酸、ポリメタクリル酸、マレイン酸／アクリル酸のコポリマー、マレイン酸／アクリル酸／ビニル酢酸のコポリマー；モノエチレン性不飽和モノカルボン酸および／またはジカルボン酸の、単糖類、オリゴ糖類、多糖類もしくはポリアスパラギン酸上のグラフトポリマー；アミンポリカルボキシレートおよびポリアスパラギン酸；炭酸塩、たとえば炭酸ナトリウムおよび重炭酸ナトリウム。
【００９５】
錯化剤およびホスホン酸塩およびこれらの塩、たとえばニトリロ三酢酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、ヒドロキシエチルエチレンジアミン三酢酸、メチルグリシン二酢酸、２−ホスホノ−１，２，４−ブタントリカルボン酸、アミノトリ−（メチレンホスホン酸）、１−ヒドロキシエチレン（１，１−ジホスホン酸）、エチレンジアミン−テトラメチレンホスホン酸、ヘキサメチレンジアミン−テトラメチレン−ホスホン酸およびジエチレントリアミン−ペンタメチレン−ホスホン酸。
【００９６】
ケイ酸塩、たとえば二ケイ酸ナトリウムおよびメタケイ酸ナトリウム。水不溶性のビルダーにはゼオライトおよび結晶質の層状ケイ酸塩も数えられ、その際、後者は特に一般式ＮａＭＳｉ_ｘＯ_２ｘ＋１＊ｙＨ_２Ｏに相応し、その際、Ｍはナトリウムもしくは水素を表し、ｘは１．９〜２２の数、有利には１．９〜４の数であり、かつｙは０〜３３の数を表す。このために公知の例は特にα−Ｎａ_２Ｓｉ_２Ｏ_５、β−Ｎａ_２Ｓｉ_２Ｏ_５、δ−Ｎａ_２Ｓｉ_２Ｏ_５である。同様に前記のビルダー物質の混合物も挙げられる。有利にはクエン酸三ナトリウムおよび／またはトリポリリン酸五ナトリウムムおよび／または炭酸ナトリウムおよび／または重炭酸ナトリウムおよび／またはグルコン酸塩および／または二ケイ酸塩および／またはメタケイ酸塩のクラスからのケイ酸塩ビルダーを使用する。
【００９７】
アルカリキャリア：その他の成分としてアルカリキャリアが存在していてもよい。アルカリキャリアとしてアルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩、アルカリ金属セスキ炭酸塩、アルカリ金属ケイ酸塩、アルカリ金属メタケイ酸塩および前記の物質の混合物が該当し、その際、有利にはアルカリ金属炭酸塩、特に炭酸ナトリウム、炭酸水素ナトリウムまたはセスキ炭酸ナトリウムを使用することができる。ビルダーとアルカリキャリアとからなる有利な組み合わせはトリポリリン酸塩と炭酸ナトリウムもしくはトリポリリン酸塩、炭酸ナトリウムおよび二ケイ酸ナトリウムからなる混合物である。
【００９８】
界面活性剤：有利には弱い、もしくは低起泡性の非イオン性界面活性剤を０．１〜２０質量％（有利には０．１〜１０質量％、０．２５〜４質量％）の割合で使用する。これはたとえば脂肪アルコールエトキシレートの群からの界面活性剤、たとえば商品名Ｐｌｕｒａｆａｃ　^（Ｒ）（ＢＡＳＦ社）またはＤｅｈｙｐｏｎ　^（Ｒ）（Ｃｏｇｎｉｓ）で市販されている界面活性剤である。さらにエチレンオキシドおよびプロピレンオキシドから構成されているジ−およびマルチブロックコポリマーを使用することができ、これらはたとえばＰｌｕｒｏｎｉｃ　^（Ｒ）（ＢＡＳＦ社）またはＴｅｔｒｏｎｉｃ　^（Ｒ）（ＢＡＳＦ）の商品名で市販されている。さらにソルビタンエステルとエチレンオキシドおよび／またはプロピレンオキシドとの反応生成物を使用することができる。同様にアミンオキシドまたはアルキルグリコシドが適切である。適切な非イオン性界面活性剤の概要はたとえばＥＰ−Ａ０８５１０２３およびＤＥ−Ａ１９８１９１８７に記載されている。
【００９９】
調製物はさらにアニオン性もしくは両性イオン性の界面活性剤を含有していてもよく、有利にはこれらと非イオン性界面活性剤との混合物である。適切なアニオン性および両性イオン性界面活性剤は同様に文献ＥＰ−Ａ０８５１０２３およびＤＥ−Ａ１９８１９１８７に挙げられている。
【０１００】
本発明により使用される式（Ｉ）の塩と組み合わせて使用することができる典型的な漂白剤は上記のものである。
【０１０１】
腐食防止剤：特にトリアゾール、ベンゾトリアゾール、ビスベンゾトリアゾール、アミノトリアゾール、アルキルアミノトリアゾールおよび遷移金属の塩もしくは錯体の群からの銀保護剤を使用することができる。特に有利に使用すべきものはベンゾトリアゾールおよび／またはアルキルアミノトリアゾールである。さらに洗浄剤調製物中にしばしば、銀表面の腐食を明らかに低減することができる活性塩素含有の薬剤が見られる。塩素不含の洗浄剤は有利には酸素および窒素を含有する有機レドックス活性化合物、たとえば二価および三価のフェノール、たとえばヒドロキノン、ピロカテキン、ヒドロキシヒドロキノン、没食子酸、フロログルシン、ピロガロールもしくはこれらの化合物クラスの誘導体を使用する。塩および錯体状の無機化合物、たとえば金属Ｍｎ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、ＣｏおよびＣｅの塩がしばしば使用される。この場合、マンガン塩およびコバルト塩およびこれらの錯体、特に有利にはコバルト（アムミン）錯体、コバルト（アセテート）錯体、コバルト（カルボニル）錯体、コバルトおよびマンガンの塩化物および硫酸マンガンの群から選択されている遷移金属塩が有利である。同様に洗浄物における腐食を低減するための亜鉛化合物またはビスマス化合物を使用することができる。
【０１０２】
酵素：洗浄剤の効果を向上する、もしくは緩和な条件下で同質の洗浄効果を保証するために、全調製物に対して酵素を０〜５質量％、洗浄剤に添加することができる。もっとも頻繁に使用される酵素にはリパーゼ、アミラーゼ、セルラーゼおよびプロテアーゼが属する。さらにエステラーゼ、ペクチナーゼ、ラクターゼおよびペルオキシダーゼを使用することができる。有利なプロテアーゼはたとえばＢｉｏｚｙｍ社のＢＬＡＰ ^（Ｒ） １４０、Ｓｏｌｖａｙ Ｅｎｚｙｍｅｓ社のＯｐｔｉｍａｓｅ ^（Ｒ） Ｍ−４４０およびＯｐｔｉｃｌｅａｎ ^（Ｒ） Ｍ−２５０；Ｇｉｓｔ Ｂｒｏｃａｄｅｓ社のＭａｘａｃａｌ ^（Ｒ） ＣＸおよびＭａｘａｐｅｍ ^（Ｒ）またはＥｓｐｅｒａｓｅ ^（Ｒ）あるいはＮｏｖｏ社のＳａｖｉｎａｓｅ ^（Ｒ）またはＧｅｎｅｎｃｏｒ社のＰｕｒａｆｅｃｔ ＯｘＰである。特に好適なセルラーゼおよびリパーゼはＮｏｖｏ Ｎｏｒｄｉｓｋ社のＣｅｌｌｕｚｙｍ ^（Ｒ） ０．７ＴおよびＬｉｐｏｌａｓｅ ^（Ｒ） ３０Ｔである。アミラーゼとして特にＮｏｖｏ社のＤｕｒａｍｙｌ ^（Ｒ）およびＴｅｒｍａｍｙｌ ^（Ｒ） ６０ ＴおよびＴｅｒｍａｍｙｌ ^（Ｒ） ９０Ｔ、Ｓｏｌｖａｙ Ｅｎｚｙｍｅｓ社のＡｍｙｌａｓｅ−ＬＴ ^（Ｒ）、Ｇｉｓｔ Ｂｒｏｃａｄｅｓ 社のＭａｘａｍｙｌ ^（Ｒ） Ｐ５０００またはＧｅｎｅｎｃｏｒ社のＰｕｒａｆｅｃｔ ^（Ｒ） ＯｘＡｍが使用される。その他の酵素を使用することもできる。
【０１０３】
その他の添加剤：パラフィン油およびシリコーン油を任意で消泡剤としておよびプラスチックおよび金属の表面の保護のために使用することができる。消泡剤は一般に０．００１〜５％の割合で供給する。
【０１０４】
本発明により被覆される粒状のＮ−アルキルアンモニウムアセトニトリルは洗浄剤調製物中で、ならびに家事の分野のために、ならびに商業分野で使用することができる。商業用洗浄剤の種類は多くの場合、三リン酸五ナトリウム、および／またはクエン酸ナトリウム、および／または錯化剤、たとえばニトリロ三酢酸をベースとするビルダー系を含有している。しばしば家庭用洗浄剤と比較してアルカリキャリアとして水酸化ナトリウムとリムもしくは水酸化カリウムを用いて加工される。
【０１０５】
本発明により被覆すべき粒状のＮ−アルキルアンモニウムアセトニトリルは液状、ゲル状、粉末状、顆粒状であっても、また錠剤形の食器用洗浄剤としても使用することができる。本発明により被覆される粒状のＮ−アルキルアンモニウムアセトニトリルを場合によりその他の調製物成分と共に特にコンパートメント、たとえばマイクロカプセル、ゲルカプセルに加工することも可能である。さらに特殊なコンパートメント中の本発明によるコポリマーを、食器洗い機用洗浄剤の錠剤の中にで組み込むこともでき、これは場合によりその他の錠剤形コンパートメントとは異なった溶解挙動を示してもよい。これは特定の錠剤層であってもよいし、錠剤中に組み込まれているか、錠剤に結合しているか、もしくは錠剤により包囲されている特定の成形体であってもよい。
【０１０６】
次いで本発明を次の実施例において詳細に説明する。その際、略号は当業者に公知のものを表す。
【０１０７】
実施例
例１
粒状のＮ−メチルモルホリニウムアセトニトリル硫酸水素塩（ＭＭＡ）の製造
８０リットルのガラス容器中にＮ−メチルモルホリニウムアセトニトリル−メチルスルフェートの６５質量％の水溶液６０リットルを装入した。該溶液を１１０℃に加熱し、かつ圧力６００ミリバールで３時間にわたって蒸発濃縮させた。Ｎ−メチルモルホリニウムアセトニトリル−硫酸水素塩約８０質量％（残分は実質的に無機塩および水からなる）の含有率を有する溶融物を引き続き１６０リットルのＬｏｅｄｉｇｅミキサー中で市販のケイ酸１６ｋｇ上に施与し、かつ該混合物を硬化させた。その後、硬化した混合物を３５０〜１６００マイクロメートルの粒径に分級する。１６００マイクロメートルよりも大きな物質を粉砕し、かつ引き続きふたたび分級した。こうしてＮ−メチルモルホリニウム−アセトニトリル−硫酸水素塩約６０質量％を含有する粒状の顆粒が得られた。
【０１０８】
例２
粒状のトリメチルアンモニウムアセトニトリル硫酸水素塩（ＴＭＡＱ）の製造
８０リットルのガラス容器中にトリメチルアンモニウムアセトニトリル−メチルスルフェートの４８質量％の水溶液６０リットルを装入した。該溶液を１１０℃に加熱し、かつ圧力５００ミリバールで４時間にわたって蒸発濃縮させた。トリメチルアンモニウムアセトニトリル硫酸水素塩約８０質量％（残分は実質的に無機塩および水からなる）を含有する溶融物を引き続き１６０リットルのＬｏｅｄｉｇｅミキサー中で市販のケイ酸１６ｋｇ上に施与し、かつ該混合物を硬化させた。その後、硬化した混合物を３５０〜１６００マイクロメートルの粒径に分級する。１６００マイクロメートルよりも大きな物質を粉砕し、かつ引き続きふたたび分級した。こうしてＮ−メチルモルホリニウム−アセトニトリル−硫酸水素塩約６０質量％を含有する粒状の顆粒が得られた。
【０１０９】
例３
ポリエチレングリコールＭｗ６０００による粒状のＮ−メチルモルホリニウムアセトニトリル硫酸水素塩の被覆（負荷率１５％）
実験室用の噴霧流動床中に粒状のＮ−メチルモルホリニウム−アセトニトリル硫酸水素塩２ｋｇを装入し、かつ室温の空気を用いて流動させた。加熱した受け器中に固体のポリエチレングリコールＭｗ６０００を３００ｇ添加し、かつ温度８０℃で溶融した。該溶融液を加熱したノズルにより３０分間にわたり流動床に噴霧し、かつこうして流動するメチルモルホリニウムアセトニトリル硫酸水素塩の粒子を被覆した。
【０１１０】
例４
酢酸エチルおよびメタクリル酸からなるコポリマー（質量比１：１、Ｍｗ２５００００）の水性分散液による粒状のトリメチルアンモニウムアセトニトリル硫酸水素塩の被覆（負荷率１０％）
実験室用噴霧流動床中にトリメチルアンモニウムアセトニトリル硫酸水素塩２ｋｇを装入し、かつ６５℃の空気で流動させた。攪拌される受け器中にエチルアクリレートおよびメタクリル酸からなるコポリマーの水性分散液（固体含有率２０質量％）を装入した。流動床が温度５０℃に達した後で、分散液を２．５時間にわたって噴霧した。噴霧後、被覆した粒子を４０℃の空気温度で３０分にわたって後乾燥させた。
【０１１１】
例５
ステアリン酸による粒状のトリメチルアンモニウムアセトニトリル硫酸水素塩の被覆（負荷率１０％）
実験室用噴霧流動床中にトリメチルアンモニウムアセトニトリル硫酸水素塩２ｋｇを装入し、かつ室温の空気で流動させた。加熱した受け器中に固体のステアリン酸２００ｇを装入し、かつ撹拌下に温度８５℃で溶融した。該溶融物を加熱したノズルにより４５分の時間にわたって流動床に噴霧した。
【０１１２】
例６〜１６の被覆は例３〜５と同様に行った：
【０１１３】
【表１】

【０１１４】
例１７
スポッティング挙動の試験
方法
寸法１０ｃｍ×１０ｃｍの６つの着色した織布（木綿上のリアクティブレッド（ｒｅａｋｔｉｖｅ ｒｅｄ）２１）を寸法３０ｃｍ×５０ｃｍの浅いプラスチック容器に置き、かつ寸法２５ｃｍ×４５ｃｍの金属ネット（孔径５ｍｍ）で覆った。該容器に織布が完全に覆われるよう、水道水（温度２１℃、硬度３．５ミリモル／ｌ）２５０ｍｌを添加した。それぞれの織布上に洗剤調製物５ｇを均一に施与した。２１℃で湿った洗剤を１０分間、織布上に作用させた。その後、織布を水道水で洗浄し、かつ乾燥させた。
【０１１５】
スポッティング損傷の評価を目視により次の尺度で実施した：
【０１１６】
【表２】

【０１１７】
試験調製物
スポッティング挙動の試験のために使用した洗剤調製物は次の組成を有していた：
【０１１８】
【表３】

【０１１９】
【表４】

【０１２０】
例１８
アルカリ性洗浄剤調製物の安定性
方法
以下に記載する洗浄剤調製物１０ｇを調温室中２５℃および相対空気湿度７０％で３週間開放して貯蔵した。その後、ＨＰＬＣにより加水分解されていない漂白活性化剤の分析的な測定を行った。ここから被覆材料の割合を考慮して活性化剤の当初の含有率に対する、変化していない漂白活性化剤の百分率を算出した。
【０１２１】
【表５】

【０１２２】
【表６】

【０１２３】
例１９（比較例）
漂白挙動
ラウンダー−オ−メーター（Ｌａｕｎｄｅｒ−ｏ−Ｍｅｔｅｒ）中で標準的な洗浄試験として実施した。試験織布は赤ワインでシミ形成の処理したＥＭＰＡタイプの織布、もしくはシミの形成のために紅茶で処理したＥＭＰＡ１６７タイプの織布（それぞれＥＭＰＡ　Ｔｅｓｔｇｅｗｅｂｅ社製、Ｓｔ．Ｇａｌｌｅｎ、スイス）であった。試験の終了後、反射率（［％］で記載）をツァイス社のＥｌｒｅｐｈｏタイプの測定装置で測定した。
【０１２４】
洗剤は次の組成を有していた：
Ｎａ−Ｃ_１２〜Ｃ_１４−アルキルベンゼンスルホネート　　　　　　　０．８％、
Ｎａ−Ｃ_１２〜Ｃ_１４−アルキルスルフェート　　　　　　　　　　１２．０％、
非イオン性界面活性剤（Ｃ_１３〜_１５−オキソアルコール−７ＥＯ）　４．７％、
セッケン　　　　　　　　　　　　　　　　　　　　　　　　　　０．４％、
ゼオライトＡ　　　　　　　　　　　　　　　　　　　　　　　１５．０％、
層状ケイ酸塩　　　　　　　　　　　　　　　　　　　　　　　１４．０％、
ケイ酸マグネシウム　　　　　　　　　　　　　　　　　　　　　０．８％、
炭酸水素Ｎａ　　　　　　　　　　　　　　　　　　　　　　　　９．０％、
クエン酸Ｎａ　　　　　　　　　　　　　　　　　　　　　　　　５．０％、
ポリカルボン酸Ｎａ（Ｓｏｋａｌａｎ　^（Ｒ）　ＣＰ５、ＢＡＳＦ社）　　　　５．０％、
ＣＭＣ　　　　　　　　　　　　　　　　　　　　　　　　　　　０．６％、
ホスホン酸塩　　　　　　　　　　　　　　　　　　　　　　　　０．８％、
ＮａＳＯ_４　　　　　　　　　　　　　　　　　　　　　　　　　３．２％、
過炭酸Ｎａ　　　　　　　　　　　　　　　　　　　　　　　　１８．０％、
活性化剤（任意）　　　　　　　　　　　　　　　　　　　　　　５．０％、
漂白増強剤（任意）　　　　　　　　　　　　　　　　　　　　　１．０％、
残分水。
【０１２５】
結果は次の表に記載されている：
【０１２６】
【表７】

【０１２７】
ＭＭＡ＝Ｎ−メチルモルホリンアセトニトリル−硫酸水素塩顆粒、
被覆＝ステアリン酸、
ＨＭＩ＝ヘキサメチレンイミン。
【０１２８】
例２０（比較例）
例１７と同様に実施し、織布はダイレクトブラック（Ｄｉｒｅｃｔ Ｂｌａｃｋ）１２２で着色したＥＭＰＡ　１３２であった。色の損失はツァイス社のＥｌｒｅｐｈｏタイプの測定装置で測定し、色の損失を次のように算出した［％］：
（１−試験後の色の濃さ／試験前の色の濃さ）×１００
スポッティング効果：評価は例１７と同様に行った。
【０１２９】
結果は次の表に記載されている。
【０１３０】
【表８】

【０１３１】
ＭＭＡ＝Ｎ−メチルモルホリンアセトニトリル−硫酸水素塩顆粒、
被覆＝ステアリン酸、
ＨＭＩ＝ヘキサメチレンイミン。[0001]
The present invention relates to a compound of the formula, which is present in granular form and is coated.
R²R³NR¹-CR⁴R⁵-CN⁺Y⁻(I)
[Wherein, R¹~ R⁶And Y represent those described in the detailed description]. The salts of the formula (I) are based on their coatings suitable for use as bleach activators in detergents and dishwashing detergents.
[0002]
Bleach activators have long been used in modern detergents and cleaners. In this case, the bleach activator sufficiently activates the compound normally used as a bleach, initiating the decomposition of this compound completely and / or at already low temperatures, and thus achieving the desired bleaching action Used for
[0003]
The bleaching action on different substrates is known, and thus there are a number of compound classes or compounds that are used as bleaching agents in different detergents and cleaners and in general in the fields of hygiene, personal care and industry. They are generally organic and inorganic peroxo compounds, often peroxo acids and perborates and percarbonates, which are used in free or salt form, preferably in the form of alkali salts. This peroxide often does not decompose to the desired degree under the conditions selected; for example, the temperature selected in the washing step is not sufficient for the decomposition of the bleach. Therefore, in practice, it has been found that the use of these compounds in known applications requires the addition of so-called bleach activators, which decompose the compounds used as bleach and thus bleach Initiate action.
[0004]
In practice, bleach activators often have a layer surrounding the activator, which allows the activator to be easily supplied and handled, and often to provide better cleaning results. . Furthermore, hydrolysis is generally initiated easily in customary detergent and cleaning preparations on the basis of cleaning actives having an alkaline pH value, whereas the coated form of the activator is Less tendency.
[0005]
Known classes of bleach activators have the general formula
R²R³NR¹-CR⁴R⁵-CN⁺Y⁻(I)
[Wherein, R¹Is a C 5 optionally substituted by a non-adjacent oxygen atom or optionally having a hydroxyl group.₁~ C₂₄-Alkyl group, C₄~ C₂₄-Cycloalkyl group, C₇~ C₂₄-Alkaryl group or formula -CR⁴R⁵Represents a group of -CN,
R²And R³Is R independently of each other¹Or together represent a saturated 4- to 9-membered ring having at least one carbon atom and at least one other heteroatom from the group of oxygen, sulfur and nitrogen;
R⁴And R⁵Is independently a hydrogen, a carbon atom which may be interrupted by a non-adjacent oxygen atom or which additionally has a hydroxyl group₁~ C₂₄-Alkyl group, C₄~ C₂₄-Cycloalkyl group or C₇~ C₂₄Represents an alkaryl group, and
Y represents a suitable anion.] Is an N-alkylammonium acetonitrile salt.
[0006]
Bleaching activators of this group are described in patent application publications EP-A-303 520 (Kao Corporation, earliest priority date: August 14, 1987), WO 96/40661 (Clorox Company, priority date: June 7, 1995) and EP -A790244 (Hoechst AG, priority date February 15, 1996) and DE-A19740669 (Clariant GmbH, filing date September 17, 1997). This last mentioned application also describes the coating of the compound with a suitable substance.
[0007]
The nitriles disclosed in the applications cited in the preceding paragraph do have good bleach activating properties, but have certain disadvantages. For example, a commonly used counter ion Cl⁻Or CH₃OSO₃ ⁻When used, it is not granular, but generally occurs in a form that is difficult to process and difficult to feed, and likewise the production of this salt is cumbersome, time-consuming and has high energy costs. Thus, it is not without doubt that there has been no attempt to convert the salt into an easily applicable form.
[0008]
An unpublished German application with the application number 199 399.55.4 (filing date March 29, 1999) from BASF describes a process for preparing this nitrile salt in granular particulate form. For this purpose, the respective nitrile, which is present as a salt of methyl sulphate, is evaporated to a melt at 80 to 250 ° C. and a pressure of 10 mbar to 2 bar and subsequently solidified. During or after the evaporation, customary carrier materials and / or auxiliaries are added and the nitrile thus obtained, present as sulfate or hydrogen sulfate, is converted into the crystalline state.
[0009]
The process disclosed in the above-mentioned German patent application having the application number 19911395.4 and the formula (I) thus obtained, wherein Y = HOSO₃ ⁻Or SO₄ ^{2 −}Is an essential component of the present invention and is incorporated herein by reference.
[0010]
The salts thus obtained are in principle suitable for use as bleach activators in applications containing detergents and cleaning agents and other bleaching agents, but there is room for improvement in handling. As with any chemical substance, the handling personnel should avoid unnecessarily taking up the substance. This is not guaranteed, especially when granules that are not abrasion resistant are present.
[0011]
Formula (I) wherein R¹~ R⁶Represents the above, and Y represents SO₄ ^{2 −}Ion or HSO₃ ⁻It is an object of the present invention to prepare substances of the type that are ions) in such a way that they allow the handling of substances without danger and at the same time guarantee easy handling.
[0012]
This problem is solved by the general formula (I)
R²R³NR¹-CR⁴R⁵-CN⁺Y⁻(I)
[Where,
R¹Is a C 5 optionally substituted by a non-adjacent oxygen atom or optionally having a hydroxyl group.₁~ C₂₄-Alkyl group, C₄~ C₂₄-Cycloalkyl group, C₇~ C₂₄-Alkaryl group or formula -CR⁴R⁵Represents a group of -CN,
R²And R³Is R independently of each other¹Or together with the nitrogen atom to which they are attached, a saturated 4-membered member having at least one carbon atom and at least one other heteroatom from the group of oxygen, sulfur and nitrogen. Represents a 9-membered ring,
R⁴And R⁵Is independently a hydrogen, a carbon atom which may be interrupted by a non-adjacent oxygen atom or which additionally has a hydroxyl group₁~ C₂₄-Alkyl group, C₄~ C₂₄-Cycloalkyl group or C₇~ C₂₄Represents an alkaryl group, and
Y represents a corresponding stoichiometric amount of sulfate anion or hydrogen sulfate anion] in the granular coated N-alkyl ammonium acetonitrile salt, wherein the salt of formula (I) is an organic, inorganic, hydrophilic The problem is solved by being coated with a material selected from the group consisting of hydrophobic and hydrophobic substances.
[0013]
The N-alkylammonium acetonitrile salts of the formula (I) coated according to the invention are coated by evaporation in a manner known per se and the salts are prepared by the method disclosed in the application with the application number 199 399.55.4. It can be prepared by converting into a granular form corresponding to the granules obtained. Inorganic or organic, hydrophilic and hydrophobic substances are used as coating materials.
[0014]
Examples for organic hydrophilic coating materials include fatty alcohols (including mixtures with aluminum stearate), ethoxylated fatty alcohols and oxo alcohols, such as C with 1-150 moles of ethylene oxide.₈~ C₃₁Fatty alcohol polyalkoxylates, fatty acids such as lauric acid, myristic acid, stearic acid and their Na, K, Ca and ammonium salts, fatty acid esters, waxes such as paraffin wax, montan ester wax, montanic acid wax, Polyethylene wax, oxidized polyethylene wax, ethylene / acrylic acid copolymer wax, ethylene / vinyl acetate copolymer wax, polyalkyl vinyl ether wax, dispersion of suitable polymers such as alkyl acrylates, styrene, alkyl acrylate / (meth) Acrylic acid copolymer, maleic acid / olefin copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / ethylene / methacrylate copolymer Including.
[0015]
Examples for organic hydrophilic coating materials include polyethylene glycols having a molecular weight of 1000 to 50,000 and block and random copolymers of ethylene glycol and propylene glycol.
[0016]
Examples for suitable inorganic coating materials are magnesium sulfate, sodium hexaphosphate, dihydrogen phosphate, pyrophosphate, phosphonic acid, sodium metaborate, sodium metasilicate, water glass, sodium polyphosphate, sodium sulfate, carbonate Includes sodium, sodium silicate, sodium bicarbonate, sodium borate, magnesium sulfate and boric acid.
[0017]
All of the above coating materials can be used alone or as a mixture with one or more other coating materials from the same or other groups.
[0018]
Suitable coating materials must have a melting point of a value above 30 ° C., preferably above 40 ° C., especially above 45 ° C.
[0019]
Advantageously, polyethylene glycol having a molecular weight of 1500 or more, long-chain fatty acids, fatty alcohol-ethoxylates (for example Lutensol® from BASF)^(R)Type) and block copolymers of ethylene oxide and propylene oxide (eg Pluronic® from BASF)^(R)Type) is used as the jacket material.
[0020]
In particular, polyethylene glycol having a molecular weight of about 6000, Lutensol® from BASF^(R)AT-type fatty alcohol-ethoxylate (C₁₆~ C₁₈-Fatty alcohol-ethoxylate), Pluronic^(R)An ethylene oxide / propylene oxide block copolymer of the type {PE} 6800 (ethylene oxide content approx. 80%, molecular weight approx. 8000) and stearic acid are used as jacket material.
[0021]
Preferred substances of formula (I) are R²And R³Together with the nitrogen atom to which they are attached form a 6-membered ring optionally having another N or oxygen atom, and R¹~ R³Are the same or different and C₁~ C₄-An alkyl group. Materials which are often preferred according to the invention are N-methyl-morpholinium acetonitrile-sulfate or hydrogensulfate and trimethylammonium acetonitrile-sulfate and hydrogensulfate.
[0022]
Application of the coating can be effected from a melt or a solution or dispersion, in which the solvent or emulsifier is removed by evaporation. It is also possible to apply as fine powder, for example by electrostatic techniques. In that case, the coating material can be applied to granular N-alkylammonium acetonitrile in a stirring, mixing and granulating apparatus. The coating of the jacket material in a fluidized bed is advantageous, so that the particles can be classified at the same time. If the jacket material is to be a sticky product under certain conditions, the coated particulate N-alkylammonium acetonitrile is additionally treated with a further particulate material ("dusting"). ) Is meaningful. All dusting agents are conceivable as dusting agents, in which case other detergent components such as builder substances can also be used. Preference is given to using zeolites, silicates, polycarboxylates, carbonates, citrates and starches as additional dusting agents.
[0023]
The amount of coating material used for the bleach activator used according to the invention is a value of 2 to 30% by weight, based on the base granules containing the bleach activator. Preferred amounts of coating material are in each case values of 5 to 20% by weight, in particular 5 to 15% by weight, based on the base granulate.
[0024]
Furthermore, to achieve optimum coating, the temperature in the coating process can be consciously maintained over a relatively long time in the range of the melting point to achieve improved coating.
[0025]
The average particle size of the granular N-alkylammonium acetonitrile coated according to the invention is in the range from 100 μm to 3000 μm, preferably from 300 μm to 2000 μm, particularly preferably from 500 μm to 1200 μm.
[0026]
The particulate N-alkyl ammonium acetonitrile to be coated can be coated or used in combination with other bleach activators. This means that, for example, under perhydrolysis conditions, aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acids are converted. The resulting compound. This is often the case with bleach activators having one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, such as anhydrides, esters, imides and acylated It is a substance from the imidazole or oxime class. Examples for this are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acyl imides, especially N-nonanoyl succinimides (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and lauroyloxybenzenesulfonate (LOBS), pentaacetylglucose (PAG), 1,5-diacetyl -2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).
[0027]
In combination with the particulate N-alkylammonium acetonitrile coated according to the invention, furthermore carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2 , 5-dihydrofuran and the enol esters known from German Patent Applications DE 19616693 and DE 19616767 and acetylated sorbitol and mannitol or their mixtures (SORMAN) as described in European Patent Application EP 0 525 239, acylated sugar derivatives, in particular pentaacetylglucose ( PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated Bleaching activators from the group consisting of Lucamine and gluconolactone, and / or N-acylated lactams, such as N-benzoylcaprolactam and carbonylbiscaprolactam, can be used, which are described in WO 94/27970, WO 94/27. 28102, WO 94/28103, WO 95/00626, WO 95/14759, WO 95/17498 and WO 96/36686, and furthermore bis (2-propylimino) carbonates can be used, for example DE-A 195 180 39, 19541012, 19699953. And 19704149.
[0028]
Furthermore, in combination with the particulate N-alkylammonium acetonitriles coated according to the invention, hydrophilic substituted acylacetals known from German Patent Application DE 196 16 770 and acyl acylates described in German Patent Application DE 196 16 770 and WO 95/14075. Lactam is appropriate.
[0029]
In addition to or instead of the customary bleach activators mentioned above, the sulfonimines and / or bleaching-enhancement transition metal salts or transition metal complexes known from EP-A 0 449 982 and EP-A 0 453 003 are used as so-called bleach catalysts. It can be combined with the particulate N-alkyl ammonium acetonitrile coated according to the invention. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from DE 195 29 905 and their N-analogous compounds known from DE 196 20 267, the manganese known from DE 195 360 82 , Iron, cobalt, ruthenium or molybdenum-carbonyl complexes, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tridentate ligands described in German Patent Application DE 19605688, German Patent Application DE 19620411 Ammine complexes of cobalt, iron, copper and ruthenium, complexes of manganese, copper and cobalt as described in DE 44 16 438, EP-A 272030, manganese complexes known from European Patent Application EP-A 069 550, manganese, iron, cobalt and copper complexes known from European Patent Application EP-A 0 392 592 and / or European Patent Application EP-A 0 443 651 or European Patent Application EP- The manganese complexes described in A0458397, EP-A0458398, EP-A0549271, EP-A0549272, EP-A0544490 and EP-A0544519 belong to this group.
[0030]
Bleach-enhancing transition metal complexes, in particular those having a central atom Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably manganese, in combination with the particulate N-alkylammonium acetonitrile described according to the invention And salts and complexes of cobalt, particularly preferably cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt and manganese and manganese sulfate. These bleach-enhancing transition metal complexes are present in customary amounts, preferably in amounts of up to 5% by weight, in each case based on the total detergent preparation, in particular from 0.0025% to 1% by weight, and particularly preferably It can be used in an amount of 0.01% to 0.25% by weight.
[0031]
Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), furthermore glucose pentaacetate (GPA), xylosetetraacetate (TAX), sodium- 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxylbenzenesulfonate (STHOBS), tetraacetylglycoluril (TAGU), tetraacetylcyanic acid (TACA), di-N-acetyldimethylglyoxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), acylated phenolsulfonate, nonanoylbenzenesulfonate (NOBS), isononanoylbenzenes Honeto (iso NOBS), lauroyl benzenesulfonate (LOBS), using a carbonyl bis-caprolactam and bis (2-propylimino) carbonate.
[0032]
The particulate N-alkyl ammonium acetonitrile coated according to the present invention can generally be used in combination with the bleaches described below. Alkali metal perborates and their hydrates and alkali metal percarbonates, advantageously sodium perborate in the form of monohydrate or tetrahydrate, or sodium percarbonate and its hydration Use things. Also persulphates and hydrogen peroxide and typical oxygen bleaching agents such as organic peracids such as perbenzoic acid, peroxy-α-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimide peroxycaproic acid, nonylimide Peroxysuccinic acid, nonyl imido peroxy adipic acid, 1,12-diperoxide decane diacid, 1,9-diperoxy azelaic acid, diperoxoisophthalic acid and 2-decyl diperoxybutane-1,4-diacid can be used It is. Further suitable are cationic peroxy acids, such as those described in patent applications US 5,422,028, US 5,294,362 and US 5,292,447, and sulfonyl peroxy acids as described, for example, in patent application US 5039447. It is. In addition, the addition of small amounts of bleach stabilizers, such as phosphonates, borates, metaborates, metasilicates and magnesium salts, may be significant.
[0033]
The peroxyacid-containing bleach is used in such an amount that the available oxygen occurs in an amount of about 0.1% to about 10%, preferably about 0.5% to about 5%, especially about 1% to 4%. I do. The percentages are based on the total weight of the detergent composition.
[0034]
The proportion of peroxide-containing bleach in the cleaning composition according to the invention is from about 0.1% to about 95% by weight and preferably from about 1% to about 60% by weight. When the bleach composition is a fully prepared detergent composition, the proportion of peroxide containing bleach is advantageously from about 1% to about 20% by weight.
[0035]
The N-alkylammonium acetonitrile coated according to the invention can be used in combination with so-called bleaching power enhancers. This is a substance that further enhances the effects of known bleaching agents. Particularly suitable as bleach activators are the diamines described in DE-A 19 61 1992. This is a secondary amine group NHR¹And a compound of low molecular weight, oligomer or high molecular weight. In particular, this corresponds to the general formula R¹NH-[(CR³R⁴)_m-NH]_n-R²A secondary amine of the formula (II), wherein n is an integer from 0 to 20 and m is an integer from 2 to 4,³And R⁴Is independent of C₁~ C₃₀A hydrocarbyl group, preferably C₁~ C_FifteenA hydrocarbyl group and the group R¹And R²Is independent of C₁~ C₃₀A hydrocarbyl group, preferably C₁~ C_Fifteen-Is a hydrocarbyl group or optionally forms a ring together. The bleach activator disclosed in DE-A 196111992 is an essential component of the present invention and is incorporated herein by reference.
[0036]
The N-alkylammonium acetonitrile salts coated according to the invention are used in particular with the bleaching power enhancers disclosed in the above-mentioned application. In this case, particularly good results are obtained with regard to the action of the bleach activator / bleaching power enhancer combination. In this context, of course, mention is made of the particularly outstanding bleaching effects which are achieved in particular, and are thus desired in principle. This bleaching effect can lead to undesired curing when an uncoated N-alkylammonium acetonitrile salt of the general formula (I) described in DE 199 13 996 is combined with a bleach activator. found. In that case, what is called pinhole spotting (Pinhole-Spotting) is mentioned. This is understood to be punctate damage in the colored textile fabric, which results from the undesired, accelerated partial hydrolysis of the salt (I), with the result that the bleach activator / bleach This results in local overconcentrations in the force enhancer and damage due to too strong local bleaching in the affected areas. The coating according to the invention avoids such pinhole spotting.
[0037]
Granular N-alkylammonium acetonitriles coated according to the invention can be used as detergents, detergents, dishwashing detergents, stain-removal salts, disinfectants, toothpastes, fiber bleaches such as cellulose bleaches, wood bleaches or It can be used as a bleach activator for application in cotton fiber bleaches as well as in hair bleaches. Preferred fields of use are detergents and dishwashing detergents.
[0038]
The bleach activators are preferably 10% by weight, in particular from 0.1% to 8% by weight, in particular from 0.5% to 8% by weight, based on the total preparation, in the preparations respectively intended for these applications. It is used in an amount of 8% by weight and especially 0.8-5% by weight. The main fields of application are household and industrial textile detergents and household and industrial dishwashing preparations. Preparations in which the granular N-alkylammonium acetonitriles coated according to the invention can be used are described below, for example, with regard to the field of application of textile detergents and dishwashing detergents.
[0039]
By means of the coating according to the invention, the substances of the formula (I) can be handled easily and without risk and virtually no dust formation is observed. The substance is protected, for example, from undesired initiation of hydrolysis which easily occurs in detergent preparations.
[0040]
Household textile detergent composition
The detergent preparations in which the granular N-alkylammonium acetonitrile coated according to the invention can be used are powdered, granular, pasty, gel or liquid, or solid detergent tablets. . The preparation should be adapted in its composition to the type of textile to be washed, depending on its intended application. The preparations contain conventional detergent-containing substances, which correspond to the prior art. Representative examples of such detergent and detergent containing materials are described below.
[0041]
The total concentration of surfactant in the finished detergent preparation may be from 1 to 99% by weight, preferably from 5 to 80% by weight. The surfactant used may be anionic, nonionic, amphoteric or cationic. Mixtures of the abovementioned surfactants can also be used. Preferred detergent formulations contain anionic and / or nonionic surfactants and mixtures of these with other surfactants.
[0042]
Sulfates, sulfonates, carboxylates, phosphates and mixtures thereof are conceivable as anionic surfactants. Suitable cations are alkali metals, such as sodium or potassium or alkaline earth metals, such as calcium or magnesium, and ammonium, substituted ammonium compounds, in which case the mono-, di- or triethanolammonium cation and these Of mixtures. Among the anionic surfactants, alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, secondary alkane sulfonates and soaps are advantageous. These are described below.
[0043]
Alkyl ether sulfonates are especially C₁₈~ C₂₀-Straight-chain esters of carboxylic acids (fatty acids), which are₃And is described, for example, in "The Journal of the American Oil Chemistry Society", 52 (1975), pp. 323-329. Suitable starting materials are natural fats, such as tallow, coconut oil and palm oil, or also fats of synthetic origin. Preferred alkyl ether sulfonates have the formula
[0044]
Embedded image

[0045]
[Wherein, R¹Is C₈~ C₂₀-Represents a hydrocarbon radical, preferably alkyl, and R is C₁~ C₆-Represents a hydrocarbon radical, preferably alkyl]. M represents a cation that forms a water-soluble salt with the alkyl ether sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Advantageously R¹Is C₁₀~ C₁₆-Represents alkyl and R represents methyl, ethyl or isopropyl. In many cases, R¹Is C₁₀~ C₁₆-Methyl ester sulfonates representing alkyl are preferred.
[0046]
The alkyl sulfate has the formula ROSO₃A water-soluble salt or acid of M, wherein R is C₁₀~ C₂₄A hydrocarbon radical, preferably C₁₀~ C₂₀Alkyl- or hydroxyalkyl groups having an alkyl component, particularly preferably C₁₂~ C₁₈-Alkyl- or hydroxyalkyl groups. M is hydrogen or a suitable cation, such as an alkali metal cation, preferably a sodium, potassium, lithium or ammonium- or substituted ammonium cation, preferably a methyl-, dimethyl- and trimethylammonium cation or a quaternary ammonium cation, for example Tetramethylammonium- and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. C₁₂~ C₁₆Alkyl chains with low washing temperatures (eg, less than about 50 ° C.) and C₆~ C₁₈Alkyl chains with are advantageous for high wash temperatures (eg, above about 50 ° C.).
[0047]
Alkyl ether sulfates have the formula RO (A)_mSO₃A water-soluble salt or acid of M wherein R is unsubstituted C₁₀~ C₂₄-Alkyl or hydroxyalkyl, preferably C₁₂~ C₂₀-Alkyl or hydroxyalkyl groups, particularly preferably C₁₂~ C₁₈-Represents an alkyl group or a hydroxyalkyl group. A is an ethoxy or propoxy unit, m is a number greater than 0, preferably from about 0.5 to about 6, particularly preferably from about 0.5 to about 3, and M is hydrogen An atom or cation, such as a sodium, potassium, lithium, calcium, magnesium, ammonium or substituted ammonium cation. Examples of substituted ammonium cations are derived from methyl-, dimethyl-, trimethylammonium- and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Cation. C as an example₁₂~ C₁₈Fatty alcohol ether sulfates, the content of ethylene oxide units being 1, 2, 2.5, 3 or 4 mol per mol of fatty alcohol ether sulfate, wherein M is sodium Or potassium.
[0048]
In the second alkane sulfonate the alkyl group may be saturated or unsaturated, branched or linear and optionally substituted by hydroxyl groups. The sulfo group may be at any position on the carbon chain, with the primary methyl group at the beginning and end of the chain having no sulfonate group. Preferred secondary alkane sulfonates have a straight-chain alkyl chain having about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms and particularly preferably about 13 to 17 carbon atoms. are doing. Cations are, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Sodium is preferred as cation.
[0049]
Other suitable anionic surfactants are alkenyl- or alkylbenzenesulfonates. Alkenyl- or alkyl groups can be branched or straight-chain and can be optionally substituted by hydroxyl groups. Preferred alkylbenzene sulfonates have a linear alkyl chain having about 9 to 25 carbon atoms, preferably about 10 to about 13 carbon atoms, and the cations are sodium, potassium, ammonium, mono- , Di- or triethanolammonium, calcium or magnesium or mixtures thereof. Magnesium is preferred as a cation for mild surfactant systems, whereas sodium is preferred for standard cleaning applications. The same applies to alkenylbenzenesulfonates.
[0050]
The concept of anionic surfactants also includes olefin sulfonates, which are₁₂~ C₂₄-, Preferably C₁₄~ C₁₆Obtained by sulfonating the α-olefin with sulfur trioxide and subsequently neutralizing it. Depending on the method of preparation, these olefin sulfonates may contain relatively small amounts of hydroxyalkanesulfonates and alkanedisulfonates. A special mixture of α-olefin sulfonates is described in US Pat. No. 3,332,880.
[0051]
Other advantageous anionic surfactants are carboxylate, such as fatty acid soaps and comparable surfactants. The soap may be saturated or unsaturated and may have various substituents, for example, a hydroxyl group or an α-sulfonate group. Preference is given to a proportion of hydrophobicity in which the straight-chain saturated or unsaturated hydrocarbon radical has about 6 to about 30, preferably about 10 to about 18, carbon atoms.
[0052]
Further possible anionic surfactants are: salts of acylaminocarboxylic acids; acylsarcosinates produced by reacting fatty acid chlorides with sodium sarcosine in an alkaline medium; fatty acid chlorides and oligopeptides With a fatty acid-protein-condensation product obtained by reacting the following: a salt of an alkylsulfamidocarboxylic acid; a salt of an alkyl- and alkylarylethercarboxylic acid;₈~ C₂₄Olefin sulfonates; sulfonated polycarboxylic acids prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, such as those described in GB-1.082.179; alkylglycerin Sulphate; oleyl glycerin sulphate; alkyl phenol ether sulphate; primary paraffin sulphate; alkyl phosphate; alkyl ether phosphate; Monoesters of succinates, especially saturated and unsaturated C₁₂~ C₁₈-Monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C₁₂~ C₁₈Acyl sarcosineates; sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxycarboxylates, such as the formula RO (CH₂CH₂)_kCH₂COO⁻M⁺(Where R is C₈~ C₂₂-Alkyl, k is a number from 0 to 10 and M is a cation); resin acids or hydrogenated resin acids, such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids . Other examples are described in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch).
[0053]
As non-ionic surfactants, for example, the following compounds are conceivable:
-Polyethylene-, polypropylene- and polybutylene oxide condensates of alkylphenols.
[0054]
These compounds have C or C, which may be linear or branched.₆~ C₂₀-Condensation products of alkylphenols having alkyl groups and alkene oxides. Compounds having about 5 to 25 moles of alkene oxide per mole of alkylphenol are preferred.
[0055]
-Condensation products of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide.
[0056]
The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally has about 8 to 22 carbon atoms. Particularly advantageous is C₁₀~ C₂₀-Condensation products of alcohols with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. The alkyl chain may be saturated or unsaturated. Alcohol ethoxylates may have a narrow homolog distribution of ethylene oxide ("Narrow Row Ethoxylates") or a broad distribution ("Broad Range Ethoxylates").
[0057]
Examples of commercially available nonionic surfactants of this kind are, for example, the Lutensol® trade name of BASF.^(R)It is.
[0058]
-Condensation products of ethylene oxide on a hydrophobic basis formed by the condensation of propylene oxide with propylene glycol.
[0059]
The hydrophobic portion of these compounds advantageously has a molecular weight of about 1500 to about 1800. Addition of ethylene oxide at this hydrophobic moiety results in improved water solubility. The product is liquid up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation with about 40 mol of ethylene oxide. Commercial examples of these product classes are, for example, the product name Pluronic® from BASF.^(R)It is.
[0060]
-A condensation product of ethylene oxide with the reaction product of propylene oxide and ethylene diamine.
[0061]
The hydrophobic unit of these compounds consists of the reaction product of ethylene diamine with excess propylene oxide and generally has a molecular weight of about 2500-3000. In these hydrophobic units, ethylene oxide is added to a content of about 40 to about 80% by weight of polyoxyethylene and to a molecular weight of about 5000 to 11000. Commercial examples of these compounds include, for example, the trade name Tetronic® from BASF.^(R)It is.
[0062]
-Semipolar nonionic surfactants.
[0063]
This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides, and water-soluble sulfoxides, each having an alkyl group of from about 10 to about 18 carbon atoms. Semipolar nonionic surfactants have the formula
[0064]
Embedded image

[0065]
Is also an amine oxide.
[0066]
R is in this case an alkyl, hydroxyalkyl or alkylphenol group having a chain length of about 8 to 22 carbon atoms. R²Is an alkylene or hydroxyalkylene group having about 2 to 3 carbon atoms or a mixture thereof;¹Is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms, or a polyethylene oxide group having about 1 to about 3 ethylene oxide units, and x represents a number from 0 to about 10. R¹The groups may be linked to each other via an oxygen or nitrogen atom and may thus form a ring. This type of amine oxide is especially₁₀~ C₁₈-Alkyldimethylamine oxide and C₈~ C₁₂-Alkoxyethyl-dihydroxyethylamine oxide.
[0067]
-Fatty acid amides.
[0068]
Fatty acid amide has the formula
[0069]
Embedded image

[0070]
Wherein R is an alkyl group having from about 7 to about 21, preferably from about 9 to about 17, carbon atoms;¹Is independently of each other hydrogen, C₁~ C₄-Alkyl, C₁~ C₄-Hydroxyalkyl or (C₂H₄O)_xH, wherein x varies from about 1 to about 3]. C₈~ C₂₀Preference is given to -amide, -monoethanolamide, -diethanolamide and -isopropanolamide.
[0071]
Other suitable nonionic surfactants are alkyl- and alkenyl oligoglycosides and fatty acid polyglycol esters or fatty amine polyglycols each having 8 to 20, preferably 12 to 18, carbon atoms in the fatty alkyl group. Esters, alkoxylated triglycamides, mixed ethers or mixed formals, alkyl oligoglycosides, alkenyl oligoglycosides, fatty acid-N-alkyl glucamides, phosphine oxides, dialkyl sulfoxides and protein hydrolysates.
[0072]
Typical examples for amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates or formulas
[0073]
Embedded image

[0074]
[Wherein, R¹Is C₈~ C₂₂-Alkyl- or -alkenyl;²Is hydrogen or CH₂CO₂M, R³Is CH₂CH₂OH or CH₂CH₂OCH₂CH₂CO₂M, R⁴Is hydrogen, CH₂CH₂OH or CH₂CH₂COOM, where Z is CO₂M or CH₂CO₂M, n represents 2 or 3, advantageously 2, and M represents hydrogen or a cation, for example an alkali metal cation, an alkaline earth metal cation, an ammonium cation or an alkanolammonium cation] It is.
[0075]
Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples for this are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also cocoamphocarboxyphycocyanchocophytococoa cocoa) and cocoamphocarboxyglycoate cocoa cocoa cocoa cocoa cocoa cocoa cocoa cocoa cocoa cocoa cocoa cocoa cocoa cocoa carboxypropionate cocoampho carboxypropionate (cocoamphocarboxypropionate), cocoamido carboxypropionic acid (cocoamphocarboxypropionate) Fore acetate.
[0076]
Another preferred amphiphilic surfactant has an alkyl group having from about 8 to about 22 carbon atoms and may be linear or branched alkyl dimethyl betaine and alkyl dipolyethoxy betaine. And preferably has 8 to 18 carbon atoms and particularly preferably 12 to 18 carbon atoms.
[0077]
Examples of suitable cationic surfactants include R¹N (CH₃)₃ ⁺X⁻, R¹R²N (CH₃)₂ ⁺X⁻, R¹R²R³N (CH₃)⁺X⁻Or R¹R²R³R⁴N⁺X⁻And substituted or unsubstituted linear or branched quaternary ammonium salts. Group R¹, R², R³And R⁴Are independently of each other preferably unsubstituted alkyl groups having a chain length of from 8 to 24 C atoms, particularly preferably from 10 to 18 C atoms, hydroxyalkyl groups having from 1 to 4 C atoms, phenyl, C₂~ C₁₈-Alkenyl, C₇~ C₂₄-Aralkyl, (C₂H₄O)_xH, wherein x represents an integer of 1 to 3, and may be an alkyl group having one or more ester groups or a cyclic quaternary ammonium salt. X is a suitable anion known to those skilled in the art.
[0078]
Other detergent and detergent-containing substances that may be included in the present invention may be inorganic and / or organic builders to reduce water hardness.
[0079]
These builders may be included in detergent and cleaning compositions in a weight percentage of from about 5% to about 80%. Inorganic builders are, for example, alkali metal, ammonium and alkanolammonium salts of polyphosphates, such as tripolyphosphates, pyrophosphates and metaphosphates, phosphonates, silicates, bicarbonates and sesquicarbonates of glassy polymers. Includes carbonates, sulfates and aluminosilicates, including salts.
[0080]
Examples for silicate builders are alkali metal silicates, especially SiO 2₂: Na₂Alkali metal silicates having a ratio of O of 1.6: 1 to 3.2: 1 as well as layered silicates, such as the layered silicates of sodium described in US Pat. SKS-6^(R)Is commercially available from Clariant. SKS-6^(R)Are particularly advantageous layered silicate builders.
[0081]
Aluminosilicate builders are particularly advantageous for the present invention. This is especially true for the formula Na_z[(AlO₂)_z(SiO₂)_y]_xH₂Zeolite having O, wherein z and y represent an integer of at least 6, the ratio of z to y is about 1.0 to 0.5, and x is an integer of 15 to 264.
[0082]
Suitable ion exchangers based on aluminosilicates are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be derived from nature or produced synthetically. Processes for preparing aluminosilicate-based ion exchangers are described, for example, in US 3,985,669 and US 4,605,509. Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the trade names Zeolite A, Zeolite P (B) (including those disclosed in EP-A-0384070) and Zeolite X. it can. Aluminosilicates having a particle size of from 0.1 to 10 μm are advantageous.
[0083]
Suitable organic builders include polycarboxyl compounds, such as ether polycarboxylates and oxydisuccinates, which are described, for example, in US-3,128,287 and US-3,635,830. Also suitable are the TMS / TDS-builders known from U.S. Pat. No. 4,663,071.
[0084]
Other suitable builders are ether hydroxy polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid , Polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid and polycarboxylic acids such as melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, alkali salts of carboxymethyloxysuccinic acid, Includes ammonium salts and substituted ammonium salts and their soluble salts.
[0085]
Citrates, such as builders based on citric acid and its soluble salts, in particular the sodium salt, are advantageous polycarboxylic acid builders, which are used as granulated preparations, in particular as zeolites and / or sheet silicates Can be used with
[0086]
Other suitable builders are 3,3-dicarboxy-4-oxa-1,6-hexanedioate and related compounds disclosed in US Pat. No. 4,566,984.
[0087]
Various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used, if phosphorus-based builders can be used, and especially if the soap is to be adjusted for hand washing. Similarly, phosphonate builders, such as ethane-1-hydroxy-1,1-diphosphonate, and other known phosphonates, such as US Pat. No. 3,159,581, US-3,213,030, US 3,422,021, US- 3,400,148 and U.S. Pat. No. 3,422,137 can be used.
[0088]
In general, the detergent-containing substances used with the salts of the formula (I) coated according to the invention are chosen from the ingredients customary for detergents, such as surfactants and builders. Optionally, the detergent-containing substance may contain one or several cleaning aids or other materials, which enhance the cleaning effect and are used to treat or care for the articles to be cleaned. Or alter the use characteristics of the cleaning composition. Suitable cleaning aids in the cleaning compositions are, for example, the substances listed in US Pat. No. 3,936,537. The cleaning aids which can be used in the cleaning compositions according to the invention are, for example, enzymes, in particular proteases, lipases and cellulases, foaming agents, antifoaming agents, discoloration inhibitors and / or corrosion inhibitors, suspending agents, Coloring agents, extenders, fluorescent brighteners, bactericides, alkalis, hydrotropic compounds, antioxidants, enzyme stabilizers, fragrances, solvents, solubilizers, re-staining inhibitors, dispersants, color transfer inhibitors, For example polyamine-N-oxides, such as poly- (4-vinylpyridine-N-oxide), polyvinylpyrrolidone, poly-N-vinyl-N-methylacetamide and copolymers of N-vinylimidazole and N-vinylpyrrolidone, processing aids , Softeners and antistatic agents.
[0089]
Typical bleaches as used in combination with the particulate N-alkyl ammonium acetonitrile coated according to the present invention are described above.
[0090]
The detergent composition may contain, besides the granular N-alkylammonium acetonitrile coated according to the invention, one or several customary enzymes, such as proteases, amylases, lipases and cellulases. A particularly advantageous enzyme is cellulase. The cellulase used in this case may be obtained from microorganisms or fungi and should have an optimal pH value of 5 to 9.5. Suitable cellulases are disclosed in US Pat. No. 4,435,307. This includes cellulase produced from strains of Humicola insolens, especially Humicola DSM1800, or other cellulase-212-producing fungi belonging to the genus Aeromonas, as well as certain marine mollusks. Cellulase extracted from the hepatopancreas. Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,085,275 and DE-OS-2,247,832.
[0091]
Advantageous cellulases are described in WO-91 / 17243. The cleaning composition according to the present invention contains up to about 50 mg, preferably from about 0.01 mg to about 10 mg, of enzyme per gram of cleaning composition. The proportion of enzyme relative to the weight of the detergent composition is at least 0.001% by weight, preferably from about 0.001% to about 5% by weight, especially from about 0.001% to about 1% by weight, especially about 0% by weight. 0.01% to about 1% by weight.
[0092]
Composition of dishwasher detergent
builderA: Water-soluble and water-insoluble builders can be used, the main task of which is to bind calcium and magnesium. The usual builders which can be added in an amount of 10 to 90% by mass based on the whole preparation are described below.
[0093]
Phosphates such as alkali metal phosphates and polymeric alkali metal phosphates, which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples for this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium tripolyphosphate, so-called sodium hexametaphosphate, phosphoric acid of oligomers having an oligomerization degree of 5 to 1000, in particular 5 to 50 Trisodium, as well as a mixture of the corresponding potassium salt or sodium hexametaphosphate and the corresponding potassium salt or a mixture of the sodium and potassium salts. These phosphates are preferably used in the entire preparation and in the range from 25% to 65% by weight, calculated as anhydrous active substance.
[0094]
Low molecular weight carboxylic acids and salts thereof, such as alkali metal citrates (eg anhydrous trisodium citrate or trisodium citrate dihydrate), alkali metal succinates, alkali metal malonates, fatty acid sulfonates Oxydisuccinate, alkyl- or alkenyldisuccinate, gluconic acid, oxadiacetate, carboxymethyloxysuccinate, tartaric acid monosuccinate, tartaric acid disuccinate, tartaric acid monoacetate, tartaric acid diacetate, α-hydroxypropionic acid, oxidized Starch, oxidized polysaccharides; homopolymeric and copolymeric polycarboxylic acids and their salts, such as polyacrylic acid, polymethacrylic acid, maleic / acrylic acid copolymers, maleic / acrylic / vinyl vinegar Graft copolymers of monoethylenically unsaturated mono- and / or dicarboxylic acids on monosaccharides, oligosaccharides, polysaccharides or polyaspartic acid; amine polycarboxylates and polyaspartic acids; carbonates, for example sodium carbonate And sodium bicarbonate.
[0095]
Complexing agents and phosphonates and salts thereof, such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycine diacetate, 2-phosphono-1,2,4-butanetricarboxylic acid, Aminotri- (methylenephosphonic acid), 1-hydroxyethylene (1,1-diphosphonic acid), ethylenediamine-tetramethylenephosphonic acid, hexamethylenediamine-tetramethylene-phosphonic acid and diethylenetriamine-pentamethylene-phosphonic acid.
[0096]
Silicates, such as sodium disilicate and sodium metasilicate. Zeolites and crystalline layered silicates are also counted among the water-insoluble builders, the latter having, in particular, the general formula NaMSi_xO_{2x + 1}* YH₂Corresponds to O, wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4 and y is a number from 0 to 33. Known examples for this purpose are, in particular, α-Na₂Si₂O₅, Β-Na₂Si₂O₅, Δ-Na₂Si₂O₅It is. Similarly, mixtures of the aforementioned builder substances are also mentioned. Preference is given to silicon from the trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconate and / or disilicate and / or metasilicate classes. Use a salt builder.
[0097]
Alkaline carrier: An alkali carrier may be present as another component. As the alkali carrier, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal bicarbonate, an alkali metal sesquicarbonate, an alkali metal silicate, an alkali metal metasilicate and a mixture of the above substances, Preference is given to using alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate. An advantageous combination of builder and alkali carrier is a mixture of tripolyphosphate and sodium carbonate or tripolyphosphate, sodium carbonate and sodium disilicate.
[0098]
Surfactant: Preferably a weak or low foaming nonionic surfactant in a proportion of 0.1 to 20% by weight (preferably 0.1 to 10% by weight, 0.25 to 4% by weight) I do. This is, for example, a surfactant from the group of the fatty alcohol ethoxylates, for example the brand name Plurafac®^(R)(BASF) or Dehypon @^(R)(Cognis). In addition, di- and multi-block copolymers composed of ethylene oxide and propylene oxide can be used, these being, for example, Pluronic®^(R)(BASF) or Tetronic^(R)It is commercially available under the trade name (BASF). Furthermore, reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used. Similarly, amine oxides or alkyl glycosides are suitable. A summary of suitable non-ionic surfactants is described, for example, in EP-A 0 85 023 and DE-A 198 19 187.
[0099]
The preparations may also contain anionic or zwitterionic surfactants, advantageously mixtures of these with non-ionic surfactants. Suitable anionic and zwitterionic surfactants are likewise mentioned in the documents EP-A0851023 and DE-A19819187.
[0100]
Typical bleaches which can be used in combination with the salts of the formula (I) used according to the invention are those mentioned above.
[0101]
Corrosion inhibitor: In particular, silver protecting agents from the group of the salts or complexes of the triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metals can be used. Particularly advantageous are benzotriazoles and / or alkylaminotriazoles. In addition, active chlorine-containing agents which can clearly reduce the corrosion of silver surfaces are often found in detergent formulations. The chlorine-free cleaning agents are preferably organic redox-active compounds containing oxygen and nitrogen, such as divalent and trivalent phenols, such as hydroquinone, pyrocatechin, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or a class of these compounds. Is used. Salts and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. In this case, manganese salts and cobalt salts and their complexes, particularly preferably selected from the group of cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt and manganese and manganese sulfate Some transition metal salts are advantageous. Similarly, zinc or bismuth compounds can be used to reduce corrosion in the wash.
[0102]
enzyme: 0 to 5% by weight of enzyme, based on the total preparation, can be added to the detergent in order to improve the effect of the detergent or to guarantee a homogeneous washing effect under mild conditions. The most frequently used enzymes include lipases, amylases, cellulases and proteases. Further, esterases, pectinases, lactases and peroxidases can be used. Advantageous proteases are, for example, BLAP from Biozym^(R) 140, Optimaase from Solvay Enzymes^(R) M-440 and Opticlean^(R) M-250; Maxacal from Gist Brocades^(R) CX and Maxapem^(R)Or Esperase^(R)Or Novo's Savinase^(R)Or Purafect OxP from Genencor. Particularly preferred cellulases and lipases are Celluzym from Novo Nordisk.^(R) 0.7T and Lipolase^(R) 30T. As amylase, in particular, Duramyl from Novo^(R)And Termamyl^(R) 60 T and Termamyl^(R) 90T, Amylase-LT from Solvay Enzymes^(R), Maxamyl from Gist Brocades^(R) P5000 or Purafect from Genencor^(R) OxAm is used. Other enzymes can be used.
[0103]
Other additives: Paraffin oils and silicone oils can optionally be used as defoamers and for protection of plastic and metal surfaces. The defoamer is generally supplied at a rate of 0.001 to 5%.
[0104]
The granular N-alkylammonium acetonitriles coated according to the invention can be used in detergent preparations, as well as for the domestic sector, as well as in the commercial sector. Commercial cleaning agents often contain pentasodium triphosphate and / or sodium citrate, and / or builder systems based on complexing agents such as nitrilotriacetic acid. Often processed using sodium hydroxide and rim or potassium hydroxide as alkaline carriers compared to household cleaners.
[0105]
The granular N-alkylammonium acetonitrile to be coated according to the invention can be used in liquid, gel, powder, granule or tablet form as a dishwashing liquid. It is also possible to process the particulate N-alkylammonium acetonitrile coated according to the invention, optionally together with other preparation components, in particular into compartments, for example microcapsules, gel capsules. In addition, the copolymers according to the invention in special compartments can be incorporated into the dishwasher detergent tablets, which may optionally exhibit a dissolution behavior different from the other tablet-shaped compartments. This may be a specific tablet layer, or a specific compact incorporated in, bound to, or surrounded by the tablet.
[0106]
Next, the present invention will be described in detail in the following examples. In this case, abbreviations represent those known to those skilled in the art.
[0107]
Example
Example 1
Production of granular N-methylmorpholinium acetonitrile bisulfate (MMA)
An 80 liter glass vessel was charged with 60 liter of a 65% by weight aqueous solution of N-methylmorpholinium acetonitrile-methyl sulfate. The solution was heated to 110 ° C. and evaporated at a pressure of 600 mbar for 3 hours. The melt having a content of about 80% by weight of N-methylmorpholinium acetonitrile-bisulfate (substantially consisting essentially of inorganic salts and water) is subsequently mixed in a 160 liter Lodige mixer with 16 kg of commercially available silica. And the mixture was cured. Thereafter, the cured mixture is classified to a particle size of 350-1600 micrometers. Materials larger than 1600 micrometers were ground and subsequently reclassified. Thus, granular granules containing about 60% by mass of N-methylmorpholinium-acetonitrile-hydrogensulfate were obtained.
[0108]
Example 2
Production of granular trimethylammonium acetonitrile hydrogen sulfate (TMAQ)
An 80-liter glass vessel was charged with 60 liters of a 48% by weight aqueous solution of trimethylammonium acetonitrile-methyl sulfate. The solution was heated to 110 ° C. and evaporated at a pressure of 500 mbar for 4 hours. The melt containing about 80% by weight of trimethylammonium acetonitrile bisulfate (the balance consists essentially of inorganic salts and water) is subsequently applied to 16 kg of commercial silica in a 160 liter Lodige mixer, and The mixture was cured. Thereafter, the cured mixture is classified to a particle size of 350-1600 micrometers. Materials larger than 1600 micrometers were ground and subsequently reclassified. Thus, granular granules containing about 60% by mass of N-methylmorpholinium-acetonitrile-hydrogensulfate were obtained.
[0109]
Example 3
Coating of granular N-methylmorpholinium acetonitrile bisulfate with polyethylene glycol Mw6000 (15% load factor)
2 kg of granular N-methylmorpholinium-acetonitrile hydrogensulfate were charged into a laboratory spray fluidized bed and fluidized with air at room temperature. 300 g of solid polyethylene glycol Mw6000 was added to the heated receiver and melted at a temperature of 80 ° C. The melt was sprayed onto the fluidized bed for 30 minutes by means of a heated nozzle, and the particles of methyl morpholinium acetonitrile bisulfate thus flowing were coated.
[0110]
Example 4
Coating of granular trimethylammonium acetonitrile bisulfate with an aqueous dispersion of a copolymer consisting of ethyl acetate and methacrylic acid (weight ratio 1: 1, Mw 250,000) (load factor 10%)
A laboratory spray fluidized bed was charged with 2 kg of trimethylammonium acetonitrile bisulfate and fluidized with air at 65 ° C. An aqueous dispersion of a copolymer of ethyl acrylate and methacrylic acid (solids content 20% by weight) was charged into a stirred receiver. After the fluidized bed reached a temperature of 50 ° C., the dispersion was sprayed for 2.5 hours. After spraying, the coated particles were post-dried at an air temperature of 40 ° C. for 30 minutes.
[0111]
Example 5
Coating granular trimethylammonium acetonitrile bisulfate with stearic acid (10% load factor)
A laboratory spray fluidized bed was charged with 2 kg of trimethylammonium acetonitrile bisulfate and fluidized with room temperature air. 200 g of solid stearic acid were charged into a heated receiver and melted at a temperature of 85 ° C. with stirring. The melt was sprayed onto the fluidized bed via a heated nozzle over a period of 45 minutes.
[0112]
The coating of Examples 6 to 16 was carried out analogously to Examples 3 to 5:
[0113]
[Table 1]

[0114]
Example 17
Testing spotting behavior
Method
Six colored woven fabrics (reactive red 21 on cotton) measuring 10 cm × 10 cm are placed in a shallow plastic container measuring 30 cm × 50 cm and covered with a metal net measuring 25 cm × 45 cm (pore diameter 5 mm). Was. 250 ml of tap water (temperature: 21 ° C., hardness: 3.5 mmol / l) was added so that the woven fabric was completely covered by the container. 5 g of the detergent preparation were evenly applied on each woven fabric. The detergent moistened at 21 ° C. was applied on the woven fabric for 10 minutes. Thereafter, the woven fabric was washed with tap water and dried.
[0115]
Evaluation of spotting damage was performed visually on the following scale:
[0116]
[Table 2]

[0117]
Test preparation
The detergent preparation used for testing the spotting behavior had the following composition:
[0118]
[Table 3]

[0119]
[Table 4]

[0120]
Example 18
Stability of alkaline detergent preparations
Method
10 g of the detergent preparations described below were stored open for 3 weeks at 25 ° C. and 70% relative air humidity in a temperature-controlled room. Thereafter, an analytical determination of the unhydrolyzed bleach activator was made by HPLC. From this, the percentage of unchanged bleach activator relative to the initial content of activator was calculated, taking into account the proportion of coating material.
[0121]
[Table 5]

[0122]
[Table 6]

[0123]
Example 19 (comparative example)
Bleaching behavior
Performed as a standard wash test in a Rounder-o-Meter. The test woven fabric was an EMPA type woven fabric stained with red wine, or an EMPA167 type woven fabric (each EMPA @ Testgewebe, St. Gallen, Switzerland) treated with black tea for stain formation. After the end of the test, the reflectance (expressed in [%]) was measured with a Zeiss Elrepho type measuring device.
[0124]
The detergent had the following composition:
Na-C₁₂~ C₁₄-Alkylbenzene sulfonate 0.8%,
Na-C₁₂~ C₁₄-Alkyl sulfate @ 12.0%,
Nonionic surfactant (C_Thirteen~_Fifteen-Oxo alcohol-7EO) 4.7%,
Soap 0.4%,
Zeolite A 15.0%,
Layered silicate 14.0%,
Magnesium silicate 0.8%,
Na hydrogen carbonate 9.0%,
Na citrate@5.0%,
Sodium polycarboxylate (Sokalan)^(R)CP5, BASF) 5.0%,
CMC 0.6%,
Phosphonate 0.8%,
NaSO₄3.2%,
Na percarbonate@18.0%,
Activator (optional) $ 5.0%,
Bleach enhancer (optional) @ 1.0%
Residual water.
[0125]
The results are listed in the following table:
[0126]
[Table 7]

[0127]
MMA = N-methylmorpholine acetonitrile-hydrogensulfate granules,
Coating = stearic acid,
HMI = hexamethyleneimine.
[0128]
Example 20 (comparative example)
The operation was performed in the same manner as in Example 17, and the woven fabric was EMPA # 132 colored with Direct Black 122. The color loss was measured with a Zeiss Elrepho type measuring device and the color loss was calculated as follows [%]:
(1-color intensity after test / color intensity before test) × 100
Spotting effect: Evaluation was performed in the same manner as in Example 17.
[0129]
The results are listed in the following table.
[0130]
[Table 8]

[0131]
MMA = N-methylmorpholine acetonitrile-hydrogensulfate granules,
Coating = stearic acid,
HMI = hexamethyleneimine.

Claims (12)

General formula (I)
^{R 2 R 3 NR 1 -CR 4} R 5 -CN + Y - (I)
[Where,
R ¹ is a C ₁ -C ₂₄ -alkyl group, which may be interrupted by a non-adjacent oxygen atom or may additionally have a hydroxyl group, a C ₄ -C ₂₄ -cycloalkyl group, It represents an alkaryl group, or the formula ^-CR 4 ^R 5 -CN radical, - C ₇ ~C ₂₄
R ² and R ³ each independently of ^one another have the meaning of R ¹ or, together with the nitrogen atom to which they are attached, have at least one carbon atom and another member from the group of oxygen, sulfur and nitrogen. Represents a saturated 4- to 9-membered ring having at least one hetero atom,
R ⁴ and R ⁵ are each independently of the other C ₁ -C ₂₄ -alkyl which may be interrupted by hydrogen, a non-adjacent oxygen atom or may additionally have a hydroxyl group; Represents a C ₄ -C ₂₄ -cycloalkyl group or a C ₇ -C ₂₄ -alkaryl group, and Y represents a corresponding stoichiometric amount of a sulfate anion or a hydrogen sulfate anion]. The coated N-alkylammonium acetonitrile salt of formula (I) is coated with a material selected from the group consisting of organic, inorganic, hydrophilic and hydrophobic substances. Coating material, fatty alcohols, fatty alcohol / stearic acid ammonium mixture, ethoxylated fatty alcohols, particularly C ₈ -C 31 having 1-150 moles of ethylene oxide _- fatty alcohol polyalkoxylates, ethoxylated oxo alcohols, fatty acids, especially lauric Acids, myristic acid, stearic acid and the Na, K, Ca and ammonium salts of these acids, fatty acid esters, waxes, in particular paraffin wax, montan ester wax, montanic acid wax, polyethylene wax, polyethylene oxide wax, ethylene / Acrylic acid copolymer waxes, ethylene / vinyl acetate copolymer waxes, polyalkyl vinyl ether waxes, dispersions of suitable polymers, especially polyalkyl acrylates, polystyrene 2. The granular coated coating of claim 1, wherein the coating is selected from the group consisting of ren, alkyl acrylate / (meth) acrylic acid copolymer, maleic acid / olefin copolymer, vinyl chloride / ethylene copolymer and vinyl chloride / ethylene / methacrylate copolymer. N-alkyl ammonium acetonitrile salt. The inorganic coating material is magnesium sulfate, sodium hexaphosphate, dihydrogen phosphate, pyrophosphate, phosphonic acid, sodium metaborate, sodium metasilicate, water glass, sodium polyphosphate, sodium sulfate, sodium carbonate, sodium silicate, The granular coated N-alkyl ammonium acetonitrile salt of claim 1, wherein the salt is selected from the group consisting of sodium bicarbonate, sodium borate, magnesium sulfate and boric acid. The granular coated coating according to claim 1, wherein the organic hydrophilic coating material is selected from the group consisting of polyethylene glycol having a molecular weight of 1000 to 50,000 and block copolymers and random copolymers of ethylene glycol and propylene glycol. N-alkyl ammonium acetonitrile salt. The coating material is a group consisting of polyethylene glycol having a molecular weight of 1500 or more, long-chain fatty acids, fatty alcohol ethoxylates and block copolymers of ethylene oxide and propylene oxide, in particular polyethylene glycol having a molecular weight of about 6000, C ₁₆ -C 5. The fatty alcohol-ethoxylate of ₁₈ -fatty alcohol, selected from the group consisting of ethylene oxide / propylene oxide block copolymers having an ethylene oxide content of about 80% and a molecular weight of about 8000 and stearic acid. A granular coated N-alkylammonium acetonitrile salt according to any one of the preceding claims. R ² and R ³ together with the nitrogen atom to which they are attached form a 6-membered ring, which may optionally have another nitrogen or oxygen atom, or R ¹ -R ³ are the same or different and are C ₁ -C ₄ -alkyl groups, especially N-methylmorpholinium acetonitrile-sulfate or -bisulfate or trimethyl-ammonium acetonitrile-sulfate or -bisulfate 6. A granular coated N-alkylammonium acetonitrile salt according to any one of claims 1 to 5, representing a salt. Other bleach activators, preferably multi-acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), glucose pentaacetate (GPA), xylosetetraacetate (TAX), sodium-4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzene (STHOBS), tetraacetylglycoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglycol Oxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), acylated phenolsulfonate, nonanoylbenzenesulfonate (NOBS), isononanoylbenzene 7. The granular coated product according to claim 1, which is used in combination with rufonate (isoNOBS), lauroylbenzenesulphonate (LOBS), carbonylbiscaprolactam and / or bis (2-propylimino) carbonate. N-alkyl ammonium acetonitrile salt. Bleaching power enhancers, preferably a low molecular weight having a secondary amine group -NHR ^1, a compound of oligomeric or polymeric, in particular the general formula _{^{R 1 NH - [(CR 3}} R 4) m -NH] N-R 2 ( II)
Wherein N is an integer from 0 to 20 and m is an integer from 2 to 4, and the radicals R ³ and R ⁴ independently of _one another are C ₁ -C ₃₀ -hydrocarbyl radicals, advantageously A C ₁ -C ₁₅ -hydrocarbyl radical, and the radicals R ¹ and R ² , independently of _one another, are a C ₁ -C ₃₀ -hydrocarbyl radical, preferably a C ₁ -C ₁₅ -hydrocarbyl radical; Together with a bleaching power enhancer from the group consisting of the secondary amines of the invention to form a cyclic group. -Alkyl ammonium acetonitrile salts. Alkali metal perborates and their hydrates, alkali metal percarbonates, especially sodium perborate, sodium percarbonate and their hydrates, in the form of monohydrate or tetrahydrate, persulfates Hydrogen peroxide, oxygen-based bleaching agents, preferably organic peracids, especially perbenzoic acid, peroxy-α-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, nonylimideperoxysuccinic acid, nonylimide Peroxyadipic acid, 1,12-diperoxidedecandioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid, and 2-decyldiperoxybutane-1,4-diacid, cationic peroxyacids and sulfonyl 9. The method according to claim 1, wherein the bleaching agent is selected from the group consisting of peroxy acids. Coated N- alkylammonium acetonitrile salts granular described (1). The appropriate coating material is applied from the melt, solution or dispersion by removal of the solvent or dispersant by evaporation and concentrating, or in the form of a fine powder, preferably by applying the jacket material in a fluidized bed. A process for producing a granular coated N-alkylammonium acetonitrile salt according to any one of claims 1 to 9. A bleach activator comprising at least one granular coated N-alkylammonium acetonitrile salt according to any one of claims 1 to 9. A detergent, a detergent, a dishwashing detergent, a stain remover, a bactericide, a dentifrice, a fiber containing at least one granular coated N-alkylammonium acetonitrile salt according to any one of claims 1 to 9. Bleaching agents, especially cellulose bleaches, wood bleaches or cotton fiber bleaches, or hair bleaches, especially detergents or dishwashing agents.