JP4303789B2 - Delivery system - Google Patents

Abstract

Glassy particles containing agents useful for laundry and cleaning products (preferably perfumes, bleaching agents, soil release polymers), and laundry and cleaning products containing these glassy particles. The particles comprise a glass derived from one or more at least partially water-soluble hydroxylic compounds, such as hydrogenated starch hydrolysates, sucrose, glucose, and starch hydrolysates. The glassy particle also has a hygroscopicity value of less than about 80 %.

Description

更にもう１つのクラスの好ましいブリーチアクチベーターには、アシルラクタムアクチベーター、特に下記式のアシルカプロラクタムおよびアシルバレロラクタムがある：

上記式中Ｒ^６はＨ、あるいは１〜約１２の炭素原子を有するアルキル、アリール、アルコキシアリールまたはアルカリール基である。高度に好ましいラクタムアクチベーターには、ベンゾイルカプロラクタム、オクタノイルカプロラクタム、３，５，５-トリメチルヘキサノイルカプロラクタム、ノナノイルカプロラクタム、デカノイルカプロラクタム、ウンデセノイルカプロラクタム、ベンゾイルバレロラクタム、オクタノイルバレロラクタム、デカノイルバレロラクタム、ウンデセノイルバレロラクタム、ノナノイルバレロラクタム、３，５，５‐トリメチルヘキサノイルバレロラクタムおよびそれらの混合物がある。過ホウ酸ナトリウム中に吸着されたベンゾイルカプロラクタムを含むアシルカプロラクタムについて開示する、参考のため本明細書に組み込まれる１９８５年１０月８日付で発行されたSandersonの米国特許第４，５４５，７８４号明細書も参照。
酸素漂白剤以外の漂白剤も当業界で知られており、本発明で利用できる。特に興味ある非酸素漂白剤の１タイプには、スルホン化亜鉛および／またはアルミニウムフタロシアニンのような光活性化漂白剤がある。１９７７年７月５日付で発行されたHolcombeらの米国特許第４，０３３，７１８号明細書参照。用いられるならば、洗剤組成物はこのようなブリーチ、特にスルホン化亜鉛フタロシアニンを典型的には約０．０２５〜約１．２５重量％で含有する。
所望であれば、漂白化合物はマンガン化合物により触媒できる。このような化合物は当業界で周知であり、例えば米国特許第５，２４６，６２１号、米国特許第５，２４４，５９４号、米国特許第５，１９４，４１６号、米国特許第５，１１４，６０６号明細書と、欧州特許出願公開第５４９，２７１号Ａ１、第５４９，２７２号Ａ１、第５４４，４４０号Ａ２および第５４４，４９０号Ａ１明細書に開示されたマンガンベース触媒を含む。これら触媒の好ましい例には、
Ｍｎ^IV _２（ｕ-Ｏ）_３（１，４，７-トリメチル-１，４，７-トリアザシクロノナン）_２（ＰＦ_６）_２、Ｍｎ^III _２（ｕ-Ｏ）_１（ｕ-ＯＡｃ）_２（１，４，７-トリメチル-１，４，７-トリアザシクロノナン）_２（ＣｌＯ_４）_２、Ｍｎ^IV _４（ｕ-Ｏ）_６（１，４，７-トリアザシクロノナン）_４（ＣｌＯ_４）_４、Ｍｎ^IIIＭｎ^IV _４（ｕ-Ｏ）_１（ｕ-ＯＡｃ）_２（１，４，７-トリメチル-１，４，７-トリアザシクロノナン）_２（ＣｌＯ_４）_３、Ｍｎ^IV（１，４，７-トリメチル-１，４，７-トリアザシクロノナン）（ＯＣＨ_３）_３（ＰＦ_６）およびそれらの混合物がある。他の金属ベースブリーチ触媒には、米国特許第４，４３０，２４３号および米国特許第５，１１４，６１１号明細書に開示されたものがある。漂白を高める上でマンガンと様々な錯体リガンドとの併用も下記米国特許明細書で報告されている：第４，７２８，４５５号；第５，２８４，９４４号；第５，２４６，６１２号；第５，２５６，７７９号；第５，２８０，１１７号；第５，２７４，１４７号；第５，１５３，１６１号；第５，２２７，０８４号
実施上、限定ではないが、本発明の組成物およびプロセスは水性洗浄液中で少くとも０．１ｐｐｍ程度の活性ブリーチ触媒種を供給するように調整でき、好ましくは洗濯液中で約０．１〜約７００ｐｐｍ、更に好ましくは約１〜約５００ｐｐｍの触媒種を供給する。
自動皿洗い適用向けの本発明組成物および方法では、下記式を有するコバルト（III）ブリーチ触媒を利用してもよい：
〔Ｃｏ（ＮＨ_３）_ｎ（Ｍ）_ｍ（Ｂ）_ｂ〕Ｔ_ｙ
上記式中コバルトは＋３酸化状態である；ｎは４または５（好ましくは５）である；Ｍは１つの部位でコバルトに配位結合された１以上のリガンドである；ｍは０、１または２（好ましくは１）である；Ｂは２つの部位でコバルトに配位結合されたリガンドである；ｂは０または１（好ましくは０）であり、ｂ＝０のときｍ＋ｎ＝６で、ｂ＝１のときｍ＝０およびｎ＝４である；Ｔはｙの数で存在する１以上の適切に選択された対アニオンであり、ｙは電荷均衡塩を得るための整数である（好ましくはｙは１〜３、最も好ましくはＴが−１荷電アニオンであるときに２である）；上記触媒は０．２３Ｍ^−１ｓ^−１以下（２５℃）の塩基加水分解速度定数を有している。
好ましいＴはクロリド、ヨージド、Ｉ_３ ⁻、ホルメート、ニトレート、ニトライト、サルフェート、サルファイト、シトレート、アセテート、カーボネート、ブロミド、ＰＦ_６ ⁻、ＢＦ_４ ⁻、Ｂ（Ｐｈ）_４ ⁻、ホスフェート、ホスファイト、シリケート、トシレート、メタンスルホネートおよびそれらの組合せからなる群より選択される。場合により、２以上のアニオン基がＴ、例えばＨＰＯ_４ ^２−、ＨＣＯ_３ ⁻、Ｈ_２ＰＯ_４ ⁻などに存在するならば、Ｔはプロトン化させることができる。更に、Ｔはアニオン性界面活性剤（例えば、直鎖アルキルベンゼンスルホネート（ＬＡＳ）、アルキルサルフェート（ＡＳ）、アルキルエトキシスルホネート（ＡＥＳ）等）および／またはアニオン性ポリマー（例えば、ポリアクリレート、ポリメタクリレート等）のような非伝統的無機アニオンからなる群より選択される。
Ｍ部分には、例えばＦ⁻、ＳＯ_４ ^２−、ＮＣＳ⁻、ＳＣＮ⁻、Ｓ_２Ｏ_３ ^２−、ＮＨ_３、ＰＯ_４ ^３−およびカルボキシレート（好ましくはモノカルボキシレートであるが、コバルトへの結合が部分当たり１つだけのカルボキシレートであるかぎり、２以上のカルボキシレートがその部分に存在していてもよく、その場合にはＭ部分で他のカルボキシレートがプロトン化されているか、または塩形になっている）があるが、それらに限定されない。場合により、２以上のアニオン基がＭ（例えば、ＨＰＯ_４ ^２−、ＨＣＯ_３ ⁻、Ｈ_２ＰＯ_４ ⁻、ＨＯＣ（Ｏ）ＣＨ_２Ｃ（Ｏ）Ｏ-など）に存在するならば、Ｍはプロトン化させることができる。好ましいＭ部分は下記式を有する置換および非置換Ｃ_１-Ｃ_３０カルボン酸である：
ＲＣ（Ｏ）Ｏ-
上記式中Ｒは好ましくは水素とＣ_１-Ｃ_３０（好ましくはＣ_１-Ｃ_１８）非置換および置換アルキル、Ｃ_６-Ｃ_３０（好ましくはＣ_６-Ｃ_１８）非置換および置換アリール、Ｃ_３-Ｃ_３０（好ましくはＣ_５-Ｃ_１８）非置換および置換ヘテロアリールからなる群より選択され、置換基は-ＮＲ′_３、-ＮＲ′_４ ^＋、-Ｃ（Ｏ）ＯＲ′、-ＯＲ′、-Ｃ（Ｏ）ＮＲ′_２からなる群より選択され、Ｒ′は水素およびＣ_１-Ｃ_６部分からなる群より選択される。したがって、このような置換Ｒには部分-（ＣＨ_２）_ｎＯＨおよび-（ＣＨ_２）_ｎＮＲ′_４ ^＋があり、ｎは１〜約１６、好ましくは約２〜約１０、最も好ましくは約２〜約５の整数である。
最も好ましいＭは、Ｒが水素、メチル、エチル、プロピル、直鎖または分岐Ｃ_４-Ｃ_１２アルキルおよびベンジルからなる群より選択される、上記式を有したカルボン酸である。最も好ましいＭはメチルである。好ましいカルボン酸Ｍ部分には、ギ酸、安息香酸、オクタン酸、ノナン酸、デカン酸、ドデカン酸、マロン酸、マレイン酸、コハク酸、アジピン酸、フタル酸、２-エチルヘキサン酸、ナフテン酸、オレイン酸、パルミチン酸、トリフレート、タートレート、ステアリン酸、酪酸、クエン酸、アクリル酸、アスパラギン酸、フマル酸、ラウリン酸、リノール酸、乳酸、リンゴ酸と、特に酢酸がある。
Ｂ部分にはカーボネート、ジおよびそれ以上のカルボキシレート（例えば、オキサレート、マロネート、マレート、サクシネート、マレエート）、ピコリン酸と、α-およびβ-アミノ酸（例えば、グリシン、アラニン、β-アラニン、フェニルアラニン）がある。
本発明で有用なコバルトブリーチ触媒は公知であり、M.L.Tobe,”Base Hydrolysis of Transition-Metal Complexes”,Adv.Inorg.Bioinorg.Mech.,（1983）,2,pages 1-94で、例えばそれらの塩基加水分解速度と一緒に記載されている。例えば、１７頁の表１は、オキサレート（ｋ_ＯＨ＝２．５×１０^−４Ｍ^−１ｓ^−１（２５℃））、ＮＣＳ⁻（ｋ_ＯＨ＝５．０×１０^−４Ｍ^−１ｓ^−１（２５℃））、ホルメート（ｋ_ＯＨ＝５．８×１０^−４Ｍ^−１ｓ^−１（２５℃））およびアセテート（ｋ_ＯＨ＝９．６×１０^−４Ｍ^−１ｓ^−１（２５℃））と錯体形成されたコバルトペンタアミン触媒の塩基加水分解速度を示している（そこではｋ_ＯＨとして表示されている）。本発明で有用な好ましいコバルト触媒は、式〔Ｃｏ（ＮＨ_３）_５ＯＡｃ〕Ｔ_ｙ（ＯＡｃはアセテート部分を表す）、特にコバルトペンタアミンアセテートクロリド〔Ｃｏ（ＮＨ_３）_５ＯＡｃ〕Ｃｌ_２（以下“ＰＡＣ”）と、〔Ｃｏ（ＮＨ_３）_５ＯＡｃ〕（ＯＡｃ）_２、
〔Ｃｏ（ＮＨ_３）_５ＯＡｃ〕（ＰＦ_６）_２、
〔Ｃｏ（ＮＨ_３）_５ＯＡｃ〕（ＳＯ_４）および
〔Ｃｏ（ＮＨ_３）_５ＯＡｃ〕（ＢＦ_４）_２を有している。
これらのコバルト触媒は、例えば前記Tobe論文とそこで引用された文献、１９８９年３月７日付で発行されたDiakunらの米国特許第４，８１０，４１０号、J.Chem.Ed.（1989）,66（12）,1043-45；The Synthesis and Characterization of Inorganic Compounds,W.L.Jolly（Prentice-Hall;1970）,pp.461-3；Inorg.Chem.,18,1497-1502（1979）；Inorg.Chem.,21,2881-2885（1982）；Inorg.Chem.,18,2023-2025（1979）；Inorg.Synthesis,173-176（1960）；およびJournal of Physical Chemistry,56,22-25（1952）に開示されたような公知の操作で容易に製造される。
これらのコバルト触媒は、所望であれば製品の美観上カラーインパクトを減少させるために補助物質で共加工処理しても、または組成物は触媒“スペクル”（speckle）を含有するように製造してもよい。
実務面として、制限のためではなく、本発明の自動皿洗い組成物および方法は水性洗浄媒体で少くとも１部／１０百万程度の活性コバルト触媒種を供するように調整でき、好ましくは約０．１〜約５０ｐｐｍ、更に好ましくは約１〜約２５ｐｐｍ、最も好ましくは約２〜約１０ｐｐｍのコバルト触媒種を洗浄液に供する。洗浄液でこのようなレベルを得るために、典型的な本組成物は組成物の約０．０４〜約１重量％、更に好ましくは約０．０８〜約０．３６％で含有する。
ビルダー-洗剤ビルダーは、ミネラル硬度のコントロールを助ける上で、本組成物中に場合により含有させることができる。無機および有機ビルダーが使用できる。ビルダーは粒状汚れの除去を助けるために布帛洗濯組成物中で典型的に用いられる。
ビルダーのレベルは組成物の最終用途およびその望ましい物理的形態に応じて広く変わる。存在するとき、組成物は典型的には少くとも約１％のビルダーを含んでいる。液体処方物は、典型的には約５〜約５０重量％、更に典型的には約５〜約３０％の洗浄ビルダーを含む。顆粒処方物は、典型的には約１０〜約８０重量％、更に典型的には約１５〜約５０％の洗剤ビルダーを含む。しかしながら、それ以下または以上のレベルのビルダーが排除される意味ではない。
無機またはＰ含有洗剤ビルダーには、ポリホスフェート（トリポリホスフェート、ピロホスフェートおよびガラス質ポリマーメタホスフェートで例示される）、ホスホネート、フィチン酸、シリケート、カーボネート（ビカーボネートおよびセスキカーボネートを含む、）サルフェートおよびアルミノシリケートのアルカリ金属、アンモニウムおよびアルカノールアンモニウム塩があるが、それらに限定されない。しかしながら、無リン酸ビルダーは一部の地方で必要とされる。重要なことは、本組成物がシトレートのようないわゆる“弱い”（ホスフェートと比較して）ビルダーの存在下、あるいはゼオライトまたは積層シリケートビルダーで生じるいわゆる“アンダービルト”状況下であっても意外によく機能することである。
シリケートビルダーの例は、アルカリ金属シリケート、特に１．６：１〜３．２：１範囲のＳｉＯ_２：Ｎａ_２Ｏ比を有するものと、１９８７年５月１２日付で発行されたH.P.Rieckの米国特許第４，６６４，８３９号明細書に記載された積層ナトリウムシリケートのような積層シリケートである。ＮａＳＫＳ-６はHoechstにより販売される結晶積層シリケートの商標名である（一般的に本明細書では“ＳＫＳ-６”と略記される）。ゼオライトビルダーと異なり、ＮａＳＫＳ-６シリケートビルダーはアルミニウムを含んでいない。ＮａＳＫＳ-６はδ-Ｎａ_２ＳｉＯ_５形態の積層シリケートを有している。それはドイツＤＥ-Ａ-３，４１７，６４９およびＤＥ-Ａ-３，７４２，０４３に記載されたような方法により製造できる。ＳＫＳ-６が本発明で使用上高度に好ましい積層シリケートであるが、他のこのような積層シリケート、例えば一般式ＮａＭＳｉ_ｘＯ_2x+1・ｙＨ_２Ｏ（Ｍはナトリウムまたは水素であり、ｘは１．９〜４、好ましくは２の数であり、ｙは０〜２０、好ましくは０の数である）を有したものも本発明で使用できる。Hoechstによる様々な他の積層シリケートには、α、βおよびγ形としてＮａＳＫＳ-５、ＮａＳＫＳ-７およびＮａＳＫＳ-１１がある。上記のように、δ-Ｎａ_２ＳｉＯ_５（ＮａＳｋＳ-６形）が本発明で使用上最も好ましい。顆粒処方でクリスプニング（crispening）剤として、酸素ブリーチ用の安定剤として、および起泡コントロール系の成分として働ける、例えばマグネシウムシリケートのような他のシリケートも有用である。
カーボネートビルダーの例は、１９７３年１１月１５日付で公開されたドイツ特許出願第２，３２１，００１号明細書に開示されるようなアルカリ土類およびアルカリ金属カーボネートである。
アルミノシリケートビルダーが本発明で有用である。アルミノシリケートビルダーはほとんどの現行市販重質顆粒洗剤組成物で非常に重要であり、液体洗剤処方で重要なビルダー成分でもある。アルミノシリケートビルダーには下記実験式を有するものがある：
Ｍ_ｚ〔（ｚＡｌＯ_２）_ｙ〕・ｘＨ_２Ｏ
上記式中ｚおよびｙは少くとも６の整数であり、ｚ対ｙのモル比は１．０〜約０．５の範囲であり、ｘは約１５〜約２６４の整数である。
有用なアルミノシリケートイオン交換物質が市販されている。これらのアルミノシリケートは構造上結晶でも非晶質でもよく、天然アルミノシリケートでもまたは合成してもよい。アルミノシリケートイオン交換物質の製造方法は、１９７６年１０月１２日付で発行されたKrummelらの米国特許第３，９８５，６６９号明細書に開示されている。本発明で有用な好ましい合成結晶アルミノシリケートイオン交換物質はゼオライトＡ、ゼオライトＰ（Ｂ）、ゼオライトＭＡＰおよびゼオライトＸという名称で市販されている。特に好ましい態様において、結晶アルミノシリケートイオン交換物質は下記式を有している：
Ｎａ₁₂〔（ＡｌＯ_２）₁₂（ＳｉＯ_２）₁₂〕・ｘＨ_２Ｏ
上記式中ｘは約２０〜約３０、特に約２７である。この物質はゼオライトＡとして知られる。脱水ゼオライト（ｘ＝０〜１０）も本発明で使用できる。好ましくは、アルミノシリケートは直径約０．１〜１０ミクロンの粒度を有する。
本発明の目的に適した有機洗剤ビルダーには様々なポリカルボキシレート化合物があるが、それらに限定されない。本明細書で用いられる“ポリカルボキシレート”とは、多数のカルボキシレート基、好ましくは少くとも３つのカルボキシレートを有した化合物に関する。ポリカルボキシレートビルダーは通常酸形で組成物に加えられるが、中和塩の形で加えてもよい。塩形で利用される場合には、ナトリウム、カリウムおよびリチウムのようなアルカリ金属、またはアルカノールアンモニウム塩が好ましい。
ポリカルボキシレートビルダーの中には、様々なカテゴリーの有用な物質が含まれる。ポリカルボキシレートビルダーの１つの重要なカテゴリーには、１９６４年４月７日付で発行されたBergの米国特許第３，１２８，２８７号および１９７２年１月１８日付で発行されたLambertiらの米国特許第３，６３５，８３０号明細書に開示されているような、オキシジサクシネートを含めたエーテルポリカルボキシレートを含む。１９８７年５月５日付でBushらに発行された米国特許第４，６６３，０７１号の“ＴＭＳ／ＴＤＳ”ビルダーも参照。適切なエーテルポリカルボキシレートには、米国特許第３，９２３，６７９号、第３，８３５，１６３号、第４，１５８，６３５号、第４，１２０，８７４号および第４，１０２，９０３号明細書に記載されたような環式化合物、特に脂環式化合物も含む。
他の有用な洗浄性ビルダーには、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また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と、エチレンジアミン四酢酸およびニトリロ三酢酸のようなポリ酢酸の様々なアルカリ金属、アンモニウムおよび置換アンモニウム塩と、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およびそれらの可溶性塩のようなポリカルボキシレートがある。
シトレートビルダー、例えばクエン酸およびその可溶性塩（特にナトリウム塩）は、再生源からのそれらの利用性とそれらの生分解性のために、重質液体洗剤処方で特に重要なポリカルボキシレートビルダーである。シトレートは、特にゼオライトおよび／または積層シリケートビルダーと組合せて、顆粒組成物でも使用できる。オキシジサクシネートもこのような組成物および組合せで特に有用である。
本発明の洗剤組成物では、１９８６年１月２８日付で発行されたBushの米国特許第４，５６６，９８４号明細書で開示された３，３-ジカルボキシ-４-オキサ-１，６-ヘキサンジオエート類と関連化合物も適している。有用なコハク酸ビルダーには、Ｃ_５-Ｃ₂₀アルキルおよびアルケニルコハク酸とその塩がある。このタイプの特に好ましい化合物はドデセニルコハク酸である。サクシネートビルダーの具体例には、ラウリルサクシネート、ミリスチルサクシネート、パルミチルサクシネート、２-ドデセニルサクシネート（好ましい）、２-ペンタデセニルサクシネート等がある。ラウリルサクシネートがこのグループの好ましいビルダーであり、１９８６年１１月５日付で公開された欧州特許出願第８６２００６９０．５／０，２００，２６３号明細書に記載されている。
他の適切なポリカルボキシレートは、１９７９年３月１３日付で発行されたCrutchfieldらの米国特許第４，１４４，２２６号および１９６７年３月７日付で発行されたDiehlの米国特許第３，３０８，０６７号明細書に開示されている。Diehlの米国特許第３，７２３，３２２号明細書も参照。
脂肪酸、例えばＣ₁₂-Ｃ₁₈モノカルボン酸も単独で、あるいは追加ビルダー活性を与えるために前記ビルダー、特にシトレートおよび／またはサクシネートビルダーと組合せて、組成物中に配合できる。脂肪酸のこのような使用は起泡性の減少を通常起こすため、これは業者により考慮されるべきである。
リンベースビルダーが使用できる状況下、特に手で洗濯する操作に用いられる固形製品の処方では、周知のナトリウムポリホスフェート、ナトリウムピロホスフェートおよびナトリウムオルトホスフェートのような様々なアルカリ金属ホスフェートが使用できる。エタン-１-ヒドロキシ-１，１-ジホスホネートおよび他の公知ホスホネートのようなホスホネートビルダー（例えば、米国特許第３，１５９，５８１号、第３，２１３，０３０号、第３，４２２，０２１号、第３，４００，１４８号および第３，４２２，１３７号明細書参照）も使用できる。
ポリマー汚れ放出剤-公知のポリマー汚れ放出剤、以下“ＳＲＡ”は、場合により本洗剤組成物に用いることができる。利用されるならば、ＳＲＡは通常組成物の０．０１〜約１０．０重量％、典型的には０．１〜約５％、好ましくは０．２〜約３．０％である。
好ましいＳＲＡは、典型的には、ポリエステルおよびナイロンのような疎水性繊維の表面を親水化させる親水性セグメントと、疎水性繊維上に付着し、洗浄およびすすぎサイクルの終了までそれに付着したままであり、こうして親水性セグメントのためのアンカーとして働く疎水性セグメントとを有している。これにより、ＳＲＡ処理後に生じる汚れを、その後の洗浄操作でより容易にクリーニングすることができる。
ＳＲＡには、様々な荷電、例えばアニオンまたはカチオン種（１９９０年９月１１日付で発行されたGosselinkらの米国特許第４，９５６，４４７号明細書参照）と無荷電モノマー単位があり、それらの構造には直鎖、分岐または星形さえもある。それらは、分子量をコントロールするか、あるいは物理的または界面活性性質を変える上で特に有効なキャップ部分も含んでいてよい。構造および荷電分布は、異なる繊維またはテクスタイルタイプへの適用と、様々な洗剤または洗剤添加製品向けに調整される。
好ましいＳＲＡには、しばしばチタン（IV）アルコキシドのような金属触媒による少くとも１回のエステル交換／オリゴマー化からなるプロセスにより典型的に作られるオリゴマーテレフタレートエステルがある。このようなエステルは、もちろん密接に架橋した全体構造を形成することなく、１、２、３、４またはそれ以上の位置でエステル構造中に取り込める追加モノマーを用いて作ってもよい。
適切なＳＲＡには、例えば１９９０年１１月６日付J.J.ScheibelおよびE.P.Gosselinkの米国特許第４，９６８，４５１号明細書に記載されているような、テレフタロイルおよびオキシアルキレンオキシ反復単位のオリゴマーエステル主鎖とその主鎖に共有結合されたアリル誘導スルホン化末端部分から構成される、実質的に直鎖のエステルオリゴマーのスルホン化産物がある。このようなエステルオリゴマーは：（ａ）アリルアルコールをエトキシル化し、（ｂ）（ａ）の産物とジメチルテレフタレート（“ＤＭＴ”）および１，２-プロピレングリコール（“ＰＧ”）を２段階エステル交換／オリゴマー化操作で反応させ、（ｃ）（ｂ）の産物をメタ重亜硫酸ナトリウムと水中で反応させることにより製造できる。他のＳＲＡには、１９８７年１２月８日付Gosselinkらの米国特許第４，７１１，７３０号のノニオン性末端キャップ化１，２-プロピレン／ポリオキシエチレンテレフタレートポリエステル、例えばポリ（エチレングリコール）メチルエーテル、ＤＭＴ、ＰＧおよびポリ（エチレングリコール）（“ＰＥＧ”）のエステル交換／オリゴマー化による作られるものがある。ＳＲＡの他の例には、エチレングリコール（“ＥＧ”）、ＰＧ、ＤＭＴおよび３，６-ジオキサ-８-ヒドロキシオクタンスルホン酸ナトリウムからのオリゴマーのような、１９８８年１月２６日付Gosselinkの米国特許第４，７２１，５８０号の部分および完全アニオン性末端キャップ化オリゴマーエステル；例えばＤＭＴ、メチル（Ｍｅ）キャップ化ＰＥＧおよびＥＧおよび／またはＰＧ、またはＤＭＴ、ＥＧおよび／またはＰＧ、Ｍｅキャップ化ＰＥＧおよびジメチル-５-スルホイソフタル酸ナトリウムの組合せから作られる、１９８７年１０月２７日付Gosselinkの米国特許第４，７０２，８５７号のノニオン性末端キャップ化ブロックポリエステルオリゴマー化合物；１９８９年１０月３１日付Maldonado,Gosselinkらの米国特許第４，８７７，８９６号のアニオン性、特にスルホアロイルの末端キャップ化テレフタレートエステルがあり、後者は洗濯および布帛コンディショニング製品の双方で有用なＳＲＡの典型であり、例はｍ-スルホ安息香酸一ナトリウム塩、ＰＧおよびＤＭＴから作られるエステル組成物であり、場合により、但し好ましくは添加ＰＥＧ、例えばＰＥＧ３４００を更に含んでいる。
ＳＲＡには、エチレンテレフタレートまたはプロピレンテレフタレートとポリエチレンオキシドまたはポリプロピレンオキシドテレフタレートとの単純コポリマーブロック（１９７６年５月２５日付Haysの米国特許第３，９５９，２３０号および１９７５年７月８日付Basadurの米国特許第３，８９３，９２９号明細書参照）；DowからMETHOCELとして市販されるヒドロキシエーテルセルロース系ポリマーのようなセルロース系誘導体；Ｃ_１-Ｃ_４アルキルセルロースおよびＣ_４ヒドロキシアルキルセルロース（１９７６年１２月２８日付Nicolらの米国特許第４，０００，０９３号明細書参照）；アンヒドログルコース単位当たり約１．６〜約２．３の平均置換（メチル）度と、２０℃で２％水溶液として測定したときに約８０〜約１２０センチポイズの溶液粘度を有するメチルセルロースエーテルもある。このような物質は、信越化学工業ＫＫにより製造されるメチルセルロースエーテルの商品名である、METOLOSE ＳＭ１００およびMETOLOSE ＳＭ２００として市販されている。
ポリ（ビニルエステル）疎水性セグメントで特徴付けられる適切なＳＲＡには、ポリアルキレンオキシド主鎖にグラフト化された、ポリ（ビニルエステル）、例えばＣ_１-Ｃ_６ビニルエステル、好ましくはポリ（ビニルアセテート）のグラフトコポリマーがある。１９８７年４月２２日付で公開されたKudらの欧州特許出願第０，２１９，０４８号明細書参照。市販例には、ＢＡＳＦ,Germanyから市販されるSOKALAN ＨＰ-２２のようなSOKALAN ＳＲＡがある。他のＳＲＡは、エチレンテレフタレート１０〜１５重量％と、平均分子量３００〜５０００のポリオキシエチレングリコールから誘導されるポリオキシエチレンテレフタレート８０〜９０重量％を含有した反復単位からなるポリエステルである。市販例にはDupontのZELCON ５１２６およびＩＣＩのMILEASE Ｔがある。
もう１つの好ましいＳＲＡは実験式（ＣＡＰ）_２（ＥＧ／ＰＧ）_５（Ｔ）_５（ＳＩＰ）_１を有するオリゴマーであり、テレフタロイル（Ｔ）、スルホイソフタロイル（ＳＩＰ）、オキシエチレンオキシおよびオキシ-１，２-プロピレン（ＥＧ／ＰＧ）単位を有して、好ましくは末端キャップ（ＣＡＰ）、好ましくは修飾されたイセチオネートで終わり、オリゴマー中において、１つのスルホイソフタロイル単位、５つのテレフタロイル単位、規定された比率、好ましくは約０．５：１〜約１０：１でオキシエチレンオキシおよびオキシ-１，２-プロピレンオキシ単位と、２-（２-ヒドロキシエトキシ）エタンスルホン酸ナトリウムから誘導される２つの末端キャップ単位からなる。上記ＳＲＡは、好ましくは、オリゴマーの０．５〜２０重量％の結晶性減少安定剤、例えば直鎖ドデシルベンゼンスルホン酸ナトリウムのようなアニオン性界面活性剤、あるいはキシレン-、クメン-およびトルエン-スルホネートまたはそれらの混合物から選択されるメンバーを更に含み、これらの安定剤または調整剤は合成容器中に導入されるが、すべて１９９５年５月１６日付で発行されたGosselink,Pan,Kellett & Hallの米国特許第５，４１５，８０７号明細書に開示されている。上記ＳＲＡ用に適したモノマーには、２-（２-ヒドロキシエトキシ）エタンスルホン酸ナトリウム、ＤＭＴ、ジメチル-５-スルホイソフタル酸ナトリウム、ＥＧおよびＰＧがある。
好ましいＳＲＡの更にもう１つのグループは、（１）（ａ）ジヒドロキシスルホネート、ポリヒドロキシスルホネート、少くとも三官能性であって、エステル結合が形成されると分岐オリゴマー主鎖になる単位、およびそれらの組合せからなる群より選択される少くとも１つの単位；（ｂ）テレフタロイル部分である少くとも１つの単位；および（ｃ）１，２-オキシアルキレンオキシ部分である少くとも１つの非スルホン化単位を含んだ主鎖と；（２）アルコキシル化、好ましくはエトキシル化イセチオネート、アルコキシル化プロパンスルホネート、アルコキシル化プロパンジスルホネート、アルコキシル化フェノールスルホネート、スルホアロイル誘導体のようなノニオン性キャップ化単位、アニオン性キャップ化単位、およびそれらの混合物から選択される１以上のキャップ化単位を含んでなるオリゴマーエステルである。下記実験式のエステルが好ましい：
〔（ＣＡＰ）_ｘ（ＥＧ／ＰＧ）_ｙ′（ＤＥＧ）_ｙ″（ＰＥＧ）_ｙ″′
（Ｔ）_ｚ（ＳＩＰ）_ｚ′（ＳＥＧ）_ｑ（Ｂ）_ｍ〕
上記式中ＣＡＰ、ＥＧ／ＰＧ、ＰＥＧ、ＴおよびＳＩＰは前記のとおりであり、（ＤＥＧ）はジ（オキシエチレン）オキシ単位を表し、（ＳＥＧ）はグリセリンおよび関連部分単位のスルホエチルエーテルから誘導される単位を表し、（Ｂ）は、少くとも三官能性であって、エステル結合が形成されると分岐オリゴマー主鎖になる、分岐単位を表し、ｘは約１〜約１２であり、ｙ′は約０．５〜約２５であり、ｙ″は０〜約１２であり、ｙ″′は０〜約１０であり、ｙ′＋ｙ″＋ｙ″′は合計で約０．５〜約２５であり、ｚは約１．５〜約２５であり、ｚ′は０〜約１２であり、ｚ＋ｚ′は合計で約１．５〜約２５であり、ｑは約０．０５〜約１２であり、ｍは約０．０１〜約１０であり、ｘ、ｙ′、ｙ″、ｙ″′、ｚ、ｚ′、ｑおよびｍは上記エステルのモル当たり対応単位の平均モル数を表し、上記エステルは約５００〜約５０００範囲の分子量を有している。
上記エステルの好ましいＳＥＧおよびＣＡＰモノマーは、２-（２，３-ジヒドロキシプロポキシ）エタンスルホン酸ナトリウム（“ＳＥＧ”）、２-〔２-（２-ヒドロキシエトキシ）エトキシ〕エタンスルホン酸ナトリウム（“ＳＥ３”）、そのホモログおよびそれらの混合物と、アリルアルコールをエトキシル化およびスルホン化した産物がある。このクラスで好ましいＳＲＡエステルには、適切なＴｉ（IV）触媒を用いて２-〔２-（２-ヒドロキシエトキシ）エトキシ〕エタンスルホン酸ナトリウムおよび／または２-〔２-〔２-（２-ヒドロキシエトキシ）エトキシ〕エトキシ〕エタンスルホン酸ナトリウム、ＤＭＴ、２-（２，３-ジヒドロキシプロポキシ）エタンスルホン酸ナトリウム、ＥＧおよびＰＧをエステル交換およびオリゴマー化した産物があり、（ＣＡＰ）_２（Ｔ）_５（ＥＧ／ＰＧ）_1.4（ＳＥＧ）_2.5（Ｂ）_0.13として表示でき、ここでＣＡＰは（Ｎａ＋Ｏ_３Ｓ〔ＣＨ_２ＣＨ_２Ｏ〕_3.5）-であり、Ｂはグリセリンからの単位であり、ＥＧ／ＰＧモル比は完全加水分解後に慣用的ガスクロマトグラフィーにより測定すると約１．７：１である。
ＳＲＡの追加クラスには、（Ｉ）ポリマーエステル構造を連結させるためにジイソシアネートカップリング剤を用いたノニオン性テレフタレート（Viollandらの米国特許第４，２０１，８２４号およびLagasseらの米国特許第４，２４０，９１８号明細書参照）；および（II）末端ヒドロキシル基をトリメリテートエステルに変換するために公知のＳＲＡに無水トリメリット酸を加えることにより作られる、カルボキシレート末端基を有したＳＲＡがある。触媒の適正な選択で、無水トリメリット酸は、無水物結合の開裂によるよりもむしろ無水トリメリット酸の単離カルボン酸のエステルから、ポリマーの末端に結合を形成させる。ノニオン性またはアニオン性いずれのＳＲＡも、それらがエステル化させてもよいヒドロキシル末端基を有しているかぎり、出発物質として用いてよい。Tungらの米国特許第４，５２５，５２４号明細書参照。他のクラスには、（III）ウレタン結合体のアニオン性テレフタレートベースＳＲＡ（Viollandらの米国特許第４，２０１，８２４号明細書参照）；（IV）ノニオン性およびカチオン性双方のポリマーを含めた、ビニルピロリドンおよび／またはジメチルアミノエチルメタクリレートのようなモノマーとのポリ（ビニルカプロラクタム）および関連コポリマー（Ruppertらの米国特許第４，５７９，６８１号明細書参照）；（Ｖ）アクリル系モノマーをスルホン化ポリエステル上にグラフト化させて作られた、ＢＡＳＦのSOKALANタイプ以外の、グラフトコポリマーがある。これらのＳＲＡは公知のセルロースエーテルと類似した汚れ放出および再付着防止活性を確かに有している（Rhone-Poulenc Chemieの１９８８年ＥＰ２７９，１３４Ａ参照）。更に他のクラスには、（VI）カゼインのようなタンパク質上へのアクリル酸および酢酸ビニルのようなビニルモノマーのグラフト（ＢＡＳＦ（１９９１）のＥＰ４５７，２０５Ａ参照）；および（VII）特にポリアミド布帛を処理するために、アジピン酸、カプロラクタムおよびポリエチレングリコールを縮合することで作られるポリエステル-ポリアミドＳＲＡ（Bevanら、１９７４年Unilever N.V.のＤＥ２，３３５，０４４参照）がある。他の有用なＳＲＡは、米国特許第４，２４０，９１８号、第４，７８７，９８９号および第４，５２５，５２４号明細書に記載されている。
キレート化剤-本洗剤組成物は、１種以上の鉄および／またはマンガンキレート化剤も場合により含有していてよい。このようなキレート化剤は、すべて以下に記載されているようなアミノカルボキシレート、アミノホスホネート、多官能性置換芳香族キレート化剤およびそれらの混合物からなる群より選択できる。理論に拘束されず、これら物質の効果は可溶性キレートの形成により洗浄液から鉄およびマンガンイオンを除去しうるそれらの例外的能力に一部起因していると考えられる。
任意のキレート化剤として有用なアミノカルボキシレートには、エチレンジアミンテトラアセテート、Ｎ-ヒドロキシエチルエチレンジアミントリアセテート、ニトリロトリアセテート、エチレンジアミンテトラプロピオネート、トリエチレンテトラアミンヘキサアセテート、ジエチレントリアミンペンタアセテート、エタノールジグリシン、それらのアルカリ金属、アンモニウム、置換アンモニウム塩およびそれらの混合物がある。
アミノホスホネートも、少くとも低レベルの全リンが洗剤組成物で許容されるときに本発明の組成物でキレート化剤として使用に適しており、DEQUESTのようなエチレンジアミンテトラキス（メチレンホスホネート）を含む。好ましくは、これらのアミノホスホネートは炭素原子約７以上のアルキルまたはアルケニル基を含まない。
多官能性置換芳香族キレート化剤も本組成物で有用である。１９７４年５月２１日付で発行されたConnorらの米国特許第３，８１２，０４４号明細書参照。このタイプの好ましい化合物は、酸形の場合、１，２-ジヒドロキシ-３，５-ジスルホベンゼンのようなジヒドロキシジスルホベンゼンである。
本発明で使用上好ましい生分解性キレーターは、１９８７年１１月３日付HartmanおよびPerkinsの米国特許第４，７０４，２３３号明細書に記載されたようなエチレンジアミンジサクシネート（“ＥＤＤＳ”）、特に〔Ｓ，Ｓ〕異性体である。
利用されるならば、これらのキレート化剤は通常本洗剤組成物の約０．１〜約１０重量％である。更に好ましくは、利用されるならば、キレート化剤はこのような組成物の約０．１〜約３．０重量％である。
土汚れ除去／再付着防止剤-本発明の組成物は、土汚れ除去および再付着防止性を有する水溶性エトキシル化アミンも場合により含有することができる。これらの化合物を含有した顆粒洗剤組成物は、典型的には約０．０１〜約１０．０重量％の水溶性エトキシル化アミンを含有し、液体洗剤組成物は典型的には約０．０１〜約５％を含有する。
最も好ましい汚れ放出および再付着防止剤はエトキシル化テトラエチレンペンタミンである。例示エトキシル化アミンは、１９８６年７月１日付で発行されたVanderMeerの米国特許第４，５９７，８９８号明細書で更に記載されている。好ましい土汚れ除去-再付着防止剤のもう１つのグループは、１９８４年６月２７日付で公開されたOhおよびGosselinkの欧州特許出願第１１１，９６５号明細書に開示されたカチオン性化合物である。使用できる他の土汚れ除去／再付着防止剤には、１９８４年６月２７日付で公開されたGosselinkの欧州特許出願第１１１，９８４号明細書に開示されたエトキシル化アミンポリマー、１９８４年７月４日付で公開されたGosselinkの欧州特許出願第１１２，５９２号明細書に開示された双極性ポリマー、１９８５年１０月２２日付で発行されたConnorの米国特許第４，５４８，７４４号明細書に開示されたアミンオキシドがある。当業界で知られる他の土汚れ除去および／または再付着防止剤も本組成物で利用できる。もう１つのタイプの好ましい再付着防止剤には、カルボキシメチルセルロース（ＣＭＣ）物質がある。これらの物質は当業界で周知である。
ポリマー分散剤-ポリマー分散剤は、特にゼオライトおよび／または積層シリケートビルダーの存在下において、本組成物中約０．１〜約７重量％のレベルで有利に利用することができる。適切なポリマー分散剤にはポリマーポリカルボキシレートおよびポリエチレングリコールがあるが、当業界で知られるその他のものも使用できる。理論に制限されるつもりはないが、ポリマー分散剤は、結晶成長阻害、粒状汚れ放出解膠および再付着防止により、他のビルダー（低分子量ポリカルボキシレートを含む）と併用されたときに、全体的洗剤ビルダー性能を高めると考えられる。
ポリマーポリカルボキシレート物質は、適切な不飽和モノマーを好ましくはそれらの酸形で重合または共重合させることにより製造できる。重合して適切なポリマーポリカルボキシレートを形成しうる不飽和モノマー酸には、アクリル酸、マレイン酸（または無水マレイン酸）、フマル酸、イタコン酸、アコニチン酸、メサコン酸、シトラコン酸およびメチレンマロン酸がある。ビニルメチルエーテル、スチレン、エチレン等のようなカルボキシレート基を含まないモノマーセグメントの本ポリマーポリカルボキシレート中における存在は、このようなセグメントが約４０重量％以上を占めないならば適切である。
特に適切なポリマーポリカルボキシレートはアクリル酸から誘導できる。本発明で有用なこのようなアクリル酸ベースポリマーは、重合アクリル酸の水溶性塩である。酸形をしたこのようなポリマーの平均分子量は、好ましくは約２０００〜１０，０００、更に好ましくは約４０００〜７０００、最も好ましくは約４０００〜５０００の範囲内である。このようなアクリル酸ポリマーの水溶性塩には、例えばアルカリ金属、アンモニウムおよび置換アンモニウム塩がある。このタイプの可溶性ポリマーは公知物質である。洗剤組成物中におけるこのタイプのポリアクリレートの使用は、例えば１９６７年３月７日付で発行されたDiehlの米国特許第３，３０８，０６７号明細書に開示されている。
アクリル酸／マレイン酸ベースコポリマーも、分散／再付着防止剤の好ましい成分として用いてよい。このような物質には、アクリル酸およびマレイン酸のコポリマーの水溶性塩がある。酸形をしたこのようなコポリマーの平均分子量は、好ましくは約２０００〜１００，０００、更に好ましくは約５０００〜７５，０００、最も好ましくは約７０００〜６５，０００の範囲内である。このようなコポリマーにおけるアクリレート対マレエートセグメントの比率は、通常約３０：１〜約１：１、更に好ましくは約１０：１〜２：１の範囲内である。このようなアクリル酸／マレイン酸コポリマーの水溶性塩には、例えばアルカリ金属、アンモニウムおよび置換アンモニウム塩がある。このタイプの可溶性アクリレート／マレエートコポリマーは、１９８２年１２月１５日付で公開された欧州特許出願第６６９１５号明細書に記載された公知物質であり、１９８６年９月３日付で公開されたＥＰ第１９３，３６０号明細書でもヒドロキシプロピルアクリレートを含むこのようなポリマーについて記載している。更に他の有用な分散剤には、マレイン酸／アクリル酸／ビニルアルコールターポリマーがある。このような物質も、例えばアクリル酸／マレイン酸／ビニルアルコールの４５／４５／１０ターポリマーを含めて、ＥＰ１９３，３６０に開示されている。
含有させうるもう１つのポリマー物質はポリエチレングリコール（ＰＥＧ）である。ＰＥＧは分散剤性能を示して、しかも土汚れ除去・再付着防止剤として作用することができる。これら目的のために典型的な分子量範囲は、約５００〜約１００，０００、好ましくは約１０００〜約５０，０００、更に好ましくは約１５００〜約１０，０００の範囲内である。
ポリアスパルテートおよびポリグルタメート分散剤も、特にゼオライトビルダーと組合せて用いることができる。ポリアスパルテートのような分散剤は、好ましくは約１０，０００の分子量（平均）を有する。
増白剤-当業界で知られるいかなる蛍光増白剤、あるいは他の増白またはホワイトニング剤も、典型的には約０．０１〜約１．２重量％のレベルで本洗剤組成物中に配合できる。本発明で有用な市販蛍光増白剤は、必ずしも限定されないが、スチルベン、ピラゾリン、クマリン、カルボン酸、メチンシアニン類、ジベンゾチオフェン-５，５-ジオキシド、アゾール類、５および６員環式ヘテロ環と他の様々な物質の誘導体を含めたサブグループに分類できる。このような増白剤の例は”The Production and Application of Fluorescent Brightening Agents”,M.Zahradnik,John Wiley & Sons発行,New York(1982)に開示されている。
本組成物で有用な蛍光増白剤の具体例は、１９８８年１２月１３日付で発行されたWixonの米国特許第４，７９０，８５６号明細書に開示されたものである。これらの増白剤には、Veronaから増白剤のPHORWHITEシリーズがある。この参考文献に開示された他の増白剤には、Ciba-Geigy市販のTinopal ＵＮＰＡ、Tinopal ＣＢＳおよびTinopal ５ＢＭ；Artic White ＣＣおよびArtic White ＣＷＤ；２-（４-スチリルフェニル）-２Ｈ-ナフトール〔１，２-ｄ〕トリアゾール類；４，４′-ビス（１，２，３-トリアゾール-２-イル）スチルベン類；４，４′-ビス（スチリル）ビスフェニル類；アミノクマリン類がある。これら増白剤の具体例には、４-メチル-７-ジエチルアミノクマリン、１，２-ビス（ベンゾイミダゾール-２-イル）エチレン、１，３-ジフェニルピラゾリン類、２，５-ビス（ベンゾオキサゾール-２-イル）チオフェン、２-スチリルナフト〔１，２-ｄ〕オキサゾールおよび２-（スチルベン-４-イル）-２Ｈ-ナフト〔１，２-ｄ〕トリアゾールがある。１９７２年２月２９日付で発行されたHamiltonの米国特許第３，６４６，０１５号明細書も参照。
起泡抑制剤-泡の形成を減少または抑制する化合物も本発明の組成物中に配合することができる。起泡抑制は、米国特許第４，４８９，４５５号および第４，４８９，５７４号明細書に記載されたようないわゆる“高濃度クリーニングプロセス”と、フロントローディング（front loading）ヨーロッパスタイル洗濯機で特に重要である。
様々な物質が起泡抑制剤として使用でき、起泡抑制剤は当業者に周知である。例えば、Kirk Othmer Encyclopedia of Chemical Technology,Third Edition,Volume 7,pages 430-447(John Wiley & Sons,Inc.,1979）参照。特に興味ある起泡抑制剤の１カテゴリーには、モノカルボン脂肪酸およびその可溶性塩がある。１９６０年９月２７日付で発行されたWayne St.Johnの米国特許第２，９５４，３４７号明細書参照。起泡抑制剤として用いられるモノカルボン脂肪酸およびその塩は、典型的には炭素原子１０〜約２４、好ましくは炭素原子１２〜１８のヒドロカルビル鎖を有する。適切な塩にはナトリウム、カリウムおよびリチウム塩のようなアルカリ金属塩と、アンモニウムおよびアルカノールアンモニウム塩がある。
本洗剤組成物は非界面活性起泡抑制剤も含有していてよい。これらには、例えばパラフィンのような高分子量炭化水素、脂肪酸エステル（例えば、脂肪酸トリグリセリド）、一価アルコールの脂肪酸エステル、脂肪族Ｃ₁₈-Ｃ₄₀ケトン（例えば、ステアロン）等がある。他の起泡抑制剤には、塩化シアヌルと１〜２４の炭素原子を有する２または３モルの一級または二級アミンとの生成物として形成されるトリ〜ヘキサアルキルメラミンまたはジ〜テトラアルキルジアミンクロルトリアジンのようなＮ-アルキル化アミノトリアジン、プロピレンオキシドと、モノステアリルアルコールホスフェートエステルおよびモノステアリルジアルカリ金属（例えば、Ｋ、ＮａおよびＬｉ）ホスフェートおよびホスフェートエステルのようなモノステアリルホスフェートがある。パラフィンおよびハロパラフィンのような炭化水素は液体形で利用できる。液体炭化水素は室温および大気圧下で液体であり、約−４０〜約５０℃範囲の流動点と、約１１０℃以上の最小沸点（大気圧）を有する。好ましくは約１００℃以下の融点を有するロウ状炭化水素を利用することも知られている。炭化水素は洗剤組成物向けの起泡抑制剤の好ましいカテゴリーである。炭化水素起泡抑制剤は、例えば１９８１年５月５日付で発行されたGandolfoらの米国特許第４，２６５，７７９号明細書に記載されている。その炭化水素には、約１２〜約７０の炭素原子を有した脂肪族、脂環式、芳香族およびヘテロ環式飽和または不飽和炭化水素がある。この起泡抑制剤の説明で用いられている“パラフィン”という用語は、真のパラフィンと環式炭化水素の混合物を含めた意味である。
非界面活性起泡抑制剤のもう１つの好ましいカテゴリーには、シリコーン起泡抑制剤がある。このカテゴリーには、ポリジメチルシロキサンのようなポリオルガノシロキサン油、ポリオルガノシロキサン油または樹脂の分散物またはエマルジョンと、ポリオルガノシロキサンがシリカ上に化学吸着または溶融されたポリオルガノシロキサンとシリカ粒子との組合せの使用を含む。シリコーン起泡抑制剤は当業界で周知であり、例えば１９８１年５月５日付で発行されたGandolfoらの米国特許第４，２６５，７７９号および１９９０年２月７日付で公開されたStarch,M.S.の欧州特許出願第８９３０７８５１．９号明細書に開示されている。
他のシリコーン起泡抑制剤は米国特許第３，４５５，８３９号明細書に開示されており、そこでは少量のポリジメチルシロキサン流体を配合することにより水溶液を消泡させるための組成物および方法に関する。
シリコーンおよびシラン化シリカの混合物は、例えばドイツ特許出願ＤＯＳ第２，１２４，５２６号明細書に記載されている。顆粒洗剤組成物におけるシリコーン消泡剤および起泡抑制剤は、Bartolottaらの米国特許第３，９３３，６７２号および１９８７年３月２４日付で発行されたBaginskiらの米国特許第４，６５２，３９２号明細書に開示されている。
本発明で有用な例示シリコーンベース起泡抑制剤は：
（ｉ）２５℃で約２０〜約１５００ｃｓの粘度を有するポリジメチルシロキサン流体
（ii）約０．６：１〜約１．２：１の（ＣＨ_３）_３ＳｉＯ_1/2単位対ＳｉＯ_２単位の比率でＳｉＯ_２単位の（ＣＨ_３）_３ＳｉＯ_1/2単位から構成されるシロキサン樹脂約５〜約５０重量部／（ｉ）１００部、および
（iii）固体シリカゲル約１〜約２０重量部／（ｉ）１００部
から本質的になる起泡抑制量の起泡抑制剤である。
本発明で用いられる好ましいシリコーン起泡抑制剤において、連続相用の溶媒はあるポリエチレングリコール、ポリエチレン-ポリプロピレングリコールコポリマーまたはそれらの混合物（好ましい）、あるいはポリプロピレングリコールから構成される。主要なシリコーン起泡抑制剤は分岐／架橋されており、好ましくは直鎖でない。
この点を更に説明するため、起泡を抑制する典型的な液体洗濯洗剤組成物は約０．００１〜約１、好ましくは約０．０１〜約０．７、最も好ましくは約０．０５〜約０．５重量％の上記シリコーン起泡抑制剤を場合により含み、これは（１）（ａ）ポリオルガノシロキサン、（ｂ）樹脂シロキサンまたはシリコーン樹脂生成シリコーン化合物、（ｃ）微細フィラー物質、および（ｄ）混合物成分（ａ）、（ｂ）および（ｃ）の反応を促進してシラノレートを形成するための触媒の混合物である、主要消泡剤の非水性エマルジョン；（２）少くとも１種のノニオン性シリコーン界面活性剤；および（３）室温で約２重量％以上の水中溶解度を有するポリエチレングリコールまたはポリエチレン-ポリプロピレングリコールのコポリマーを含んでなるが、ポリプロピレングリコールは含まない。同様の量が顆粒組成物、ゲル等で使用できる。１９９０年１２月１８日付で発行されたStarchの米国特許第４，９７８，４７１号、１９９１年１月８日付で発行されたStarchの第４，９８３，３１６号、１９９４年２月２２日付で発行されたHuberらの第５，２８８，４３１号、Aizawaらの米国特許第４，６３９，４８９号および第４，７４９，７４０号明細書、第１欄４６行目〜第４欄３５行目も参照。
本シリコーン起泡抑制剤には、好ましくはポリエチレングリコールおよびポリエチレングリコール／ポリプロピレングリコールのコポリマーを含み、すべて約１０００以下、好ましくは約１００〜８００の平均分子量を有している。本発明のポリエチレングリコールおよびポリエチレン／ポリプロピレンコポリマーは室温で約２重量％以上、好ましくは約５重量％以上の水中溶解度を有する。
本発明で好ましい溶媒は約１０００以下、更に好ましくは約１００〜８００、最も好ましくは２００〜４００の平均分子量を有するポリエチレングリコールと、ポリエチレングリコール／ポリプロピレングリコール、好ましくはＰＰＧ２００／ＰＥＧ３００のコポリマーである。約１：１〜１：１０、最も好ましくは１：３〜１：６のポリエチレングリコール：ポリエチレン-ポリプロピレングリコールのコポリマーの重量比が好ましい。
本発明で用いられる好ましいシリコーン起泡抑制剤は、特に分子量４０００のポリプロピレングリコールを含有しない。それらは、PLURONIC Ｌ１０１のように、エチレンオキシドおよびプロピレンオキシドのブロックコポリマーも含有していないことが好ましい。
本発明で有用な他の起泡抑制剤には、二級アルコール（例えば、２-アルキルアルカノール）、およびこのようなアルコールとシリコーン油、例えば米国特許第４，７９８，６７９号、第４，０７５，１１８号およびＥＰ第１５０，８７２号明細書に開示されたシリコーンとの混合物がある。二級アルコールにはＣ_１-Ｃ₁₆鎖を有したＣ_６-Ｃ₁₆アルキルアルコールがある。好ましいアルコールは２-ブチルオクタノールであり、これはCondeaから商標名ISOFOL １２として入手できる。二級アルコールの混合物はEnichemから商標名ISALCHEM １２３として入手できる。混合起泡抑制剤は、典型的には１：５〜５：１の重量比でアルコール＋シリコーンの混合物からなる。
自動洗濯機で用いられるいかなる洗剤組成物においても、泡は洗濯機からあふれるほど生じるべきではない。起泡抑制剤は利用されるならば起泡抑制量で存在することが好ましい。“起泡抑制量”とは、組成物の業者が自動洗濯機で使用上低起泡性の洗濯洗剤となるように起泡を十分に抑制するこの起泡抑制剤の量を選択しうることを意味する。
本組成物は通常０〜約５％の起泡抑制剤を含む。起泡抑制剤として利用されるとき、モノカルボン脂肪酸およびその塩は典型的には洗剤組成物の約５重量％以内の量で存在する。好ましくは約０．５〜約３％の脂肪モノカルボキシレート起泡抑制剤が利用される。シリコーン起泡抑制剤は典型的には洗剤組成物の約２．０重量％以内の量で利用されるが、それ以上の量で用いてもよい。この上限は、主にコストを最小に抑えられるかという関心と、起泡を有効に抑制する上でより低い量での有効性からみて、性質上実際的である。好ましくは約０．０１〜約１％、更に好ましくは約０．２５〜約０．５％のシリコーン起泡抑制剤が用いられる。本発明で用いられるこれらの重量％値には、ポリオルガノシロキサンと組合せて利用されるあらゆるシリカと、利用されるあらゆる補助物質を含めている。リン酸モノステアリル起泡抑制剤は組成物の約０．１〜約２重量％の範囲内の量で通常利用される。炭化水素起泡抑制剤は典型的には約０．０１〜約５．０％の範囲内の量で利用されるが、それより高いレベルでも使用できる。アルコール起泡抑制剤は典型的には最終組成物の０．２〜３重量％で用いられる。
布帛柔軟剤-様々なスルー・ザ・ウォッシュ布帛柔軟剤、特に１９７７年１２月１３日付で発行されたStormおよびNirschlの米国特許第４，０６２，６４７号の微細スメクタイトクレーと、当業界で知られる他の柔軟剤クレーは、布帛クリーニングと共に布帛柔軟剤効果を発揮させるために、典型的には本組成物中約０．５〜約１０重量％のレベルで場合により用いることができる。クレー柔軟剤は、例えば１９８３年３月１日付で発行されたCrispらの米国特許第４，３７５，４１６号および１９８１年９月２２日付で発行されたHarrisらの米国特許第４，２９１，０７１号明細書に開示されたようなアミンおよびカチオン性柔軟剤と併用できる。
染料移動阻止剤-本発明の組成物は、クリーニングプロセス中にある布帛から他への染料の移動を阻止するために有効な１種以上の物質を含有することもできる。通常、このような染料移動阻止剤には、ポリビニルピロリドンポリマー、ポリアミンＮ-オキシドポリマー、Ｎ-ビニルピロリドンおよびＮ-ビニルイミダゾールのコポリマー、マンガンフタロシアニン、ペルオキシダーゼおよびそれらの混合物がある。用いられるならば、これらの剤は典型的には組成物の約０．０１〜約１０重量％、好ましくは約０．０１〜約５％、更に好ましくは約０．０５〜約２％である。
更に具体的には、本発明で使用上好ましいポリアミンＮ-オキシドポリマーは下記構造式：Ｒ-Ａ_ｘ-Ｐを有した単位を含んでいる；式中Ｐは重合性単位であって、それにはＮ-Ｏ基が結合できるか、またはＮ-Ｏ基は重合性単位の一部を形成できるか、またはＮ-Ｏ基は双方の単位に結合できる；Ａは次の構造：-ＮＣ（Ｏ）-、-Ｃ（Ｏ）Ｏ-、-Ｓ-、-Ｏ-、-Ｎ＝のうち１つである；ｘは０または１である；Ｒは脂肪族、エトキシル化脂肪族、芳香族、ヘテロ環式または脂環式基あるいはそれらの組合せであって、それにはＮ-Ｏ基の窒素が結合できるか、またはＮ-Ｏ基はこれらの基の一部である。好ましいポリアミンＮ-オキシドは、Ｒがピリジン、ピロール、イミダゾール、ピロリジン、ピペリジンおよびそれらの誘導体のようなヘテロ環式基である場合である。
Ｎ-Ｏ基は下記一般構造で表すことができる：

上記式中Ｒ_１、Ｒ_２、Ｒ_３は脂肪族基、芳香族、ヘテロ環式または脂環式基、あるいはそれらの組合せであり、ｘ、ｙおよびｚは０または１であり、Ｎ-Ｏ基の窒素は結合するかまたは上記基のいずれかの一部を形成することができる。ポリアミンＮ-オキシドのアミンオキシド単位はｐＫａ＜１０、好ましくはｐＫａ＜７、更に好ましくはｐＫａ＜６を有する。
いかなるポリマー主鎖も、形成されるアミンオキシドポリマーが水溶性であって染料移動阻止性を有しているかぎり、使用できる。適切なポリマー主鎖の例は、ポリビニル、ポリアルキレン、ポリエステル、ポリエーテル、ポリアミド、ポリイミド、ポリアクリレートおよびそれらの混合物である。これらのポリマーには、１つのモノマータイプがアミンＮ-オキシドで、他のモノマータイプがＮ-オキシドである、ランダムまたはブロックコポリマーがある。アミンＮ-オキシドポリマーは、典型的には１０：１〜１：１，０００，０００のアミン対アミンＮ-オキシドの比率を有している。しかしながら、ポリアミンオキシドポリマー中に存在するアミンオキシド基の数は、適切な共重合によるかまたは適切なＮ-酸化度で変えることができる。ポリアミンオキシドはほぼいずれの重合度でも得られる。典型的には、平均分子量は５００〜１，０００，０００、更に好ましくは１０００〜５００，０００、最も好ましくは５０００〜１００，０００の範囲内である。この好ましいクラスの物質は“ＰＶＮＯ”と称される。
本洗剤組成物で有用な最も好ましいポリアミンＮ-オキシドは、約５０，０００の平均分子量と約１：４のアミン対アミンＮ-オキシド比を有したポリ（４-ビニルピリジン-Ｎ-オキシド）である。
Ｎ-ビニルピロリドンおよびＮ-ビニルイミダゾールポリマーのコポリマー（“ＰＶＰＶＩ”のクラスと称される）も本発明で使用上好ましい。好ましくは、ＰＶＰＶＩは５０００〜１，０００，０００、更に好ましくは５０００〜２００，０００、最も好ましくは１０，０００〜２０，０００の平均分子量範囲を有している（平均分子量範囲はBarth,et al.,Chemical Analysis,Vol.113,”Modern Methods of Polymer Characterization”で記載されたような光散乱法により決められ、その開示は参考のため本明細書に組み込まれる）。ＰＶＰＶＩコポリマーは、典型的には１：１〜０．２：１、更に好ましくは０．８：１〜０．３：１、最も好ましくは０．６：１〜０．４：１のＮ-ビニルイミダゾール対Ｎ-ビリルピロリドンのモル比を有している。これらのコポリマーは直鎖または分岐鎖である。
本発明の組成物では約５０００〜約４００，０００、好ましくは約５０００〜約２００，０００、更に好ましくは約５０００〜約５０，０００の平均分子量を有したポリビニルピロリドン（“ＰＶＰ”）も用いることができる。ＰＶＰは洗剤分野の業者に公知である；参考のため本明細書に組み込まれる、例えばＥＰ-Ａ-２６２，８９７およびＥＰ-Ａ-２５６，６９６明細書参照。ＰＶＰを含有した組成物は、約５００〜約１００，０００、好ましくは約１０００〜約１０，０００の平均分子量を有したポリエチレングリコール（“ＰＥＧ”）も含有することができる。好ましくは、洗浄液中にデリバリーされるＰＥＧ対ＰＶＰの比率は、ｐｐｍベースで、約２：１〜約５０：１、更に好ましくは約３：１〜約１０：１である。
本洗剤組成物は、染料移動阻止作用も示すあるタイプの親水性蛍光増白剤約０．００５〜５重量％を場合により含有することができる。用いられるならば、本組成物は好ましくは約０．０１〜１重量％のこのような蛍光増白剤を含む。
本発明で有用な親水性蛍光増白剤は下記構造式を有した化合物である：

上記式中Ｒ_１はアニリノ、Ｎ-２-ビス-ヒドロキシエチルおよびＮＨ-２-ヒドロキシエチルから選択される；Ｒ_２はＮ-２-ビス-ヒドロキシエチル、Ｎ-２-ヒドロキシエチル-Ｎ-メチルアミノ、モルフィリノ、クロロおよびアミノから選択される；Ｍはナトリウムまたはカリウムのような塩形成カチオンである。
上記式中Ｒ_１がアニリノ、Ｒ_２がＮ-２-ビス-ヒドロキシエチル、およびＭがナトリウムのようなカチオンであるとき、増白剤は４，４′-ビス〔〔４-アニリノ-６-（Ｎ-２-ビス-ヒドロキシエチル）-ｓ-トリアジン-２-イル〕アミノ〕-２，２′-スチルベンジスルホン酸および二ナトリウム塩である。この具体的な増白剤種はCiba-Gaigy Corporationから商品名Tinopal-UNPA-GXで市販されている。Tinopal-UNPA-GXが本洗剤組成物で有用な好ましい親水性蛍光増白剤である。
上記式中Ｒ_１がアニリノ、Ｒ_２がＮ-２-ヒドロキシエチル-Ｎ-２-メチルアミノ、およびＭがナトリウムのようなカチオンであるとき、増白剤は４，４′-ビス〔〔４-アニリノ-６-（Ｎ-２-ヒドロキシエチル-Ｎ-メチルアミノ）-ｓ-トリアジン-２-イル〕アミノ〕-２，２′-スチルベンジスルホン酸二ナトリウム塩である。この具体的な増白剤種はCiba-Gaigy Corporationから商品名Tinopal 5BM-GXで市販されている。
上記式中Ｒ_１がアニリノ、Ｒ_２がモルフィリノ、およびＭがナトリウムのようなカチオンであるとき、増白剤は４，４′-ビス〔（４-アニリノ-６-モルフィリノ-ｓ-トリアジン-２-イル）アミノ〕-２，２′-スチルベンジスルホン酸、ナトリウム塩である。この具体的な増白剤種はCiba-Geigy Corporationから商品名Tinopal AMS-GXで市販されている。
本発明で使用上選択される特定の蛍光増白剤種は、前記の選択されたポリマー染料移動阻止剤と併用されたときに、特に有効な染料移動阻止性能効果を発揮する。このような選択されたポリマー物質（例えば、ＰＶＮＯおよび／またはＰＶＰＶＩ）とこのような選択された蛍光増白剤（例えばTinopal-UNPA-GX、Tinopal 5BM-GXおよび／またはTinopal AMS-GX）との組合せは、これら２種の洗剤組成物成分が単独で用いられたときよりも、洗浄水溶液中で有意に優れた染料移動阻止性を発揮する。理論に拘束されず、このような増白剤は洗浄液中で布帛に高い親和性を有し、したがってこれらの布帛に比較的早く付着することから、このように働くと考えられる。増白剤が洗浄液中で布帛に付着する程度は、“イグゾースション係数”（exhaustion coefficient）と呼ばれるパラメーターにより規定できる。イグゾースション係数とは、一般的にａ）布帛に付着した増白剤物質対ｂ）洗浄液中の初期増白剤濃度の比率のことである。比較的高いイグゾースション係数の増白剤が、本発明の関係で染料移動を阻止するために最も適している。
もちろん、他の慣用的な蛍光増白剤タイプの化合物が、真の染料移動阻止効果よりもむしろ慣用的な布帛“輝き”効果を出すために、本組成物で場合により使用できることは明らかであろう。このような用法は洗剤処方上慣用的でかつ周知である。
ｐＨおよび緩衝バリエーション
本発明で多くの自動皿洗い洗剤組成物は緩衝化されていて、即ちそれらは酸性汚れの存在下でｐＨ低下に比較的抵抗する。しかしながら、他の組成物は例外的に低い緩衝能力を有しているか、または実質的に緩衝化されていない。勧められる使用レベルにｐＨをコントロールまたは変えるための技術には、更に一般的に、緩衝剤だけでなく、追加アルカリ、酸、ｐＨジャンプ系、二重区画容器などの使用もあり、当業者に周知である。
本発明で好ましいＡＤＤ組成物は、水溶性アルカリ無機塩と水溶性有機または無機ビルダーから選択されるｐＨ調整成分を含んでいる。ｐＨ調整成分は、ＡＤＤが１０００〜５０００ｐｐｍの濃度で水中に溶解されたときに、ｐＨが約８以上、好ましくは約９．５〜約１１の範囲内であるように選択される。本発明の好ましい非リン酸ｐＨ調整成分は：
（ｉ）炭酸またはセスキ炭酸ナトリウム
（ii）ケイ酸ナトリウム、好ましくは約１：１〜約２：１のＳｉＯ_２：Ｎａ_２Ｏ比を有する水和ケイ酸ナトリウム、並びにそれと限定量のメタケイ酸ナトリウムとの混合物
（iii）クエン酸ナトリウム
（iv）クエン酸
（ｖ）重炭酸ナトリウム
（vi）ホウ酸ナトリウム、好ましくはホウ砂
（vii）水酸化ナトリウム、および
（viii）（ｉ）〜（vii）の混合物
からなる群より選択される。
好ましい態様では低レベルのシリケート（即ち、約３〜約１０％のＳｉＯ_２）を含有している。
高度に好ましいｐＨ調整成分系の例には、顆粒クエン酸ナトリウムと無水炭酸ナトリウムとの二元混合物、顆粒クエン酸ナトリウム三水和物、クエン酸一水和物と無水炭酸ナトリウムの三成分混合物がある。
本ＡＤＤ組成物中におけるｐＨ調整成分の量は、好ましくは組成物の約１〜約５０重量％である。好ましい態様では、ｐＨ調整成分は約５〜約４０重量％、好ましくは約１０〜約３０％の量でＡＤＤ組成物中に存在している。
初期洗浄液で約９．５〜約１１のｐＨを有する本組成物の場合、特に好ましいＡＤＤ態様ではＡＤＤの約５〜約４０重量％、好ましくは約１０〜約３０％、最も好ましくは約１５〜約２０％のクエン酸ナトリウムと、約５〜約３０％、好ましくは約７〜約２５％、最も好ましくは約８〜約２０％の炭酸ナトリウムを含んでいる。
必須ｐＨ調整系は、様々な水溶性のアルカリ金属、アンモニウムまたは置換アンモニウムボレート、ヒドロキシスルホネート、ポリアセテートおよびポリカルボキシレートを含めた、当業界で知られる非リン酸洗浄性ビルダーから選択される他の任意洗浄性ビルダー塩で（即ち、硬水中で改善された金属イオン封鎖のために）補充することができる。このような物質のアルカリ金属、特にナトリウム塩が好ましい。別な水溶性非リン有機ビルダーもそれらの金属イオン封鎖性のために用いてよい。ポリアセテートおよびポリカルボキシレートビルダーの例は、エチレンジアミン四酢酸のナトリウム、カリウム、リチウム、アンモニウムおよび置換アンモニウム塩；ニトリロ三酢酸、タートレートモノコハク酸、タートレートジコハク酸、オキシジコハク酸、カルボキシメトキシコハク酸、メリット酸とナトリウムベンゼンポリカルボキシレート塩である。
（ａ）水溶性シリケート
本自動皿洗い洗剤組成物は水溶性シリケートを更に含んでいてもよい。本発明の水溶性シリケートは、ＡＤＤ組成物のしみ付き／皮膜化特徴に悪影響を与えない程度に可溶性である、あらゆるシリケートである。
シリケートの例は、ナトリウムメタシリケートと、更に一般的にはアルカリ金属シリケート、特に１．６：１〜３．２：１範囲のＳｉＯ_２：Ｎａ_２Ｏ比を有するものと、１９８７年５月１２日付で発行されたH.P.Rieckの米国特許第４，６６４，８３９号明細書に記載された積層ナトリウムシリケートのような積層シリケートである。ＮａＳＫＳ-６^▲Ｒ▼はHoechstにより販売される結晶積層シリケートである（一般的に本明細書では“ＳＫＳ-６”と略記される）。ゼオライトビルダーと異なり、本発明で有用なＮａＳＫＳ-６および他の水溶性シリケートはアルミニウムを含んでいない。ＮａＳＫＳ-６はδ-Ｎａ_２ＳｉＯ_５形態の積層シリケートであり、ドイツＤＥ-Ａ-３，４１７，６４９およびＤＥ-Ａ-３，７４２，０４３に記載されたような方法により製造できる。ＳＫＳ-６が本発明で使用上好ましい積層シリケートであるが、他のこのような積層シリケート、例えば一般式ＮａＭＳｉ_ｘＯ_2x+1・ｙＨ_２Ｏ（Ｍはナトリウムまたは水素であり、ｘは１．９〜４、好ましくは２の数であり、ｙは０〜２０、好ましくは０の数である）を有したものも使用できる。Hoechstによる様々な他の積層シリケートには、α、βおよびγ形としてＮａＳＫＳ-５、ＮａＳＫＳ-７およびＮａＳＫＳ-１１がある。顆粒処方でクリスプニング剤として、酸素ブリーチ用の安定剤として、および起泡コントロール系の成分として働ける、例えばマグネシウムシリケートのような他のシリケートも有用である。
自動皿洗い（ＡＤＤ）適用で特に有用なシリケートには、ＰＱ Corp.からBRITESIL^▲Ｒ▼Ｈ２０および同一市販元のBRITESIL^▲Ｒ▼Ｈ２４のような顆粒水和２-レシオシリケートがあるが、ＡＤＤ組成物が液体形態を有するときには、液体グレートの様々なシリケートが使用できる。安全な限界内で、ナトリウムメタシリケートまたは水酸化ナトリウムは、単独で、または他のシリケートと組合せて、洗浄ｐＨを望ましいレベルに上げるためにＡＤＤ関係で用いられる。
物質ケア剤-本ＡＤＤ組成物は、腐食阻止剤および／または曇り防止助剤として有効な１種以上の物質ケア剤を含有していてもよい。このような物質は、特に電気メッキされたニッケル銀およびスターリング銀の使用が家庭平食器でなお比較的に一般的であるある欧州諸国、またはアルミニウム保護に関心があって、組成物が低シリケートであるときに、機械皿洗い組成物の好ましい成分である。通常、このような物質ケア剤には、メタシリケート、シリケート、ビスマス塩、マンガン塩、パラフィン、チアゾール類、ピラゾール類、チオール類、メルカプタン類、アルミニウム脂肪酸塩およびそれらの混合物がある。
存在するとき、このような保護物質は、好ましくは低レベルで、例えばＡＤＤ組成物の約０．０１〜約５％で配合される。適切な腐食阻止剤には、パラフィン油、典型的には約２０〜約５０範囲の炭素原子数を有する主に分岐した脂肪族炭化水素があり、好ましいパラフィン油は約３２：６８の環式対非環式炭化水素比を有する主に分岐したＣ_25-45種から選択される。それらの特徴を満たすパラフィン油は、商品名WINOG ７０でWintershall,Salzbergen,Germanyから販売されている。加えて、低レベルのビスマスニトレート（即ち、Ｂｉ（ＮＯ_３）_３）の添加も好ましい。
他の腐食阻止剤化合物には、ベンゾトリアゾールと相当化合物；チオナフトールおよびチオアントラノールを含めたメルカプタン類またはチオール類；トリステアリン酸アルミニウムのような微細アルミニウム脂肪酸塩がある。業者は、ガラス食器でしみ付きもしくは皮膜を生じるか、または組成物の漂白作用を損う傾向を避けるために、このような物質が通常正しくかつ限定量で用いられることをわかっている。この理由から、特にカルシウムと沈降する、かなり強いブリーチ反応性で一般的な脂肪カルボン酸である、メルカプタン曇り防止剤は、好ましくは避けられる。
他の成分-他の活性成分、キャリア、ヒドロトロープ、加工助剤、染料または顔料、液体処方用の溶媒、固形組成物用の固形フィラー等を含めた、洗剤組成物で有用な様々な他の成分が、本組成物中に含有させることができる。高起泡性が望まれるならば、Ｃ₁₀-Ｃ₁₆アルカノールアミドのような起泡増進剤も、典型的には１〜１０％レベルで組成物中に配合できる。Ｃ₁₀-Ｃ₁₄モノエタノールおよびジエタノールアミドがこのような起泡増進剤の典型的クラスについて例示する。このような起泡増進剤と高起泡性補助界面活性剤、例えば前記のアミンオキシド、ベタインおよびスルタインとの併用も有利である。所望であれば、ＭｇＣｌ_２、ＭｇＳＯ_４等のような可溶性マグネシウム塩が、追加の起泡性を出して、油脂除去性能を高めるために、典型的には０．１〜２％のレベルで添加できる。
本組成物で用いられる様々な洗浄成分は、場合により、上記成分を多孔質疎水性基材に吸収させてから、その基材を疎水性コーティングでコートすることにより、更に安定化させることができる。好ましくは、洗浄成分は多孔質基材中に吸収される前に界面活性剤と混合される。使用時に、洗浄成分は基材から水性洗浄液中に放出され、そこでそれは意図された洗浄機能を発揮する。
この技術を更に詳細に説明すると、多孔質疎水性シリカ（商標名SIPERNAT Ｄ１０、DeGussa）はＣ_13-15エトキシル化アルコール（ＥＯ７）ノニオン性界面活性剤３〜５％を含有したタンパク質分解酵素溶液と混合される。典型的には、酵素／界面活性剤溶液はシリカの重量×２．５である。得られた粉末はシリコーン油中で撹拌しながら分散される（５００〜１２，５００範囲の様々なシリコーン油粘度が使用できる）。得られたシリコーン油分散液は乳化されるか、または最終洗剤マトリックスに加えられる。このようにして、前記酵素、ブリーチ、ブリーチアクチベーター、ブリーチ触媒、フォトアクチベーター、染料、蛍光剤、布帛コンディショナーおよび加水分解性界面活性剤のような成分が、液体洗濯洗剤組成物を含めた洗剤で使用のために“保護”することができる。
液体洗剤組成物は、キャリアとして水および他の溶媒を含有することができる。メタノール、エタノール、プロパノールおよびイソプロパノールで例示される低分子量一級または二級アルコールが適切である。一価アルコールが界面活性剤を溶解させる上で好ましいが、２〜約６の炭素原子と２〜約６のヒドロキシ基を有するようなポリオール（例えば、１，３-プロパンジオール、エチレングリコール、グリセリンおよび１，２-プロパンジオール）も使用できる。組成物は５〜９０％、典型的には１０〜５０％のこのようなキャリアを含有することができる。
本洗剤組成物は、水クリーニング操作で使用中に、洗浄水が約６．５〜約１１、好ましくは約７．５〜１０．５のｐＨを有するように処方されることが好ましい。液体皿洗い製品処方物は、好ましくは約６．８〜約９．０のｐＨを有する。洗濯製品は、典型的にはｐＨ９〜１１である。勧められる使用レベルでｐＨをコントロールするための技術には、緩衝剤、アルカリ、酸などの使用があり、当業者に周知である。
高密度顆粒洗剤組成物
ガラス状粒子デリバリーシステムは、低密度（５５０ｇ／ｌ未満）、および顆粒の密度が少くとも５５０ｇ／ｌである高密度顆粒洗剤組成物の双方で用いることができる。このような高密度洗剤組成物は、典型的には約３０〜約９０％の洗浄性界面活性剤を含んでいる。
低密度組成物は標準スプレー乾燥プロセスにより製造できる。様々な手段および装置が高密度顆粒洗剤組成物を製造するために利用しうる。その分野の現行商慣行では、約５００ｇ／ｌ未満の密度を有する顆粒洗濯洗剤を製造するために、スプレー乾燥タワーを用いる。したがって、スプレー乾燥が全体プロセスの一部として用いられるならば、得られるスプレー乾燥洗剤粒子は後で記載される手段および装置を用いて更に高密化されねばならない。代わりに、業者は、市販されているミキシング、高密化および造粒装置を用いることにより、スプレー乾燥を省略することができる。以下は本発明で使用に適したこのような装置の非限定的な記載である。
高速ミキサー／高密化装置が本プロセスで使用できる。例えば、商標名“Lodige CB30”リサイクラーで販売される装置は、中央回転シャフトとそれに設置されたミキシング／切断刃を有する固定円筒形ミキシングドラムからなる。他のこのような装置には、商標名“Shugi Granulator”および商標名“Drais K-TTP 80”で販売される装置がある。商標名“Lodige KM600 Mixer”で販売されるような装置が、更なる高密化のために使用できる。
操作の一方式において、組成物は２つのミキサーおよび高密化装置を連続して操作することにより製造および高密化される。このため、望ましい組成物成分はミックスして、０．１〜１．０分間の滞留時間を用いてLodigeミキサーに通され、その後１〜５分間の滞留時間を用いて第二Lodigeミキサーに通される。
もう１つの方式において、望ましい処方成分を含んだ水性スラリーは粒状界面活性剤の流体層中にスプレーされる。得られた粒子は、上記のように、Lodige装置に通すことで更に高密化させることができる。ガラス状粒子はLodige装置で洗剤組成物とミックスされる。
本粒子の最終密度は様々な簡単な技術により測定でき、典型的には既知容量の容器中に顆粒洗剤を入れて、洗剤の重量を測定し、密度をｇ／ｌで報告する。
低または高密度顆粒洗剤“ベース”組成物が作られると、本発明のガラス状粒子デリバリーシステムはいずれか適切なドライミキシング操作でそれに加えられる。
布帛を洗浄して、それに香料を付着させる方法では、少くとも約１００ｐｐｍの前記慣用的洗浄成分と少くとも約１ｐｐｍの上記香料デリバリーシステムを含有した水性洗液と上記布帛を接触させる。好ましくは、上記水性液は約５００〜約２０，０００ｐｐｍの慣用的洗浄成分と、約１０〜約２００ｐｐｍの香料デリバリーシステムを含有している。
ガラス状粒子デリバリーシステムはすべての環境下で働くが、貯蔵、乾燥またはアイロンかけ中に香料臭効果を布帛に供する上で特に有用である。その方法では、香料入りゼオライト粒子が布帛に捕捉されるように、少くとも約１００ｐｐｍの慣用的洗浄成分と少くとも約１ｐｐｍの香料デリバリー組成物を含有した水性液と布帛を接触させ、湿度少くとも２０％の環境条件下でライン乾燥布帛を貯蔵して、布帛を慣用的な自動乾燥機で乾燥させるか、または慣用的なアイロンかけ手段（好ましくはスチームまたは事前に濡らす）により低熱（約５０℃以下）でライン乾燥または機械乾燥された布帛に熱を適用する。
下記非制限例では本発明のパラメーターとそこで用いられる組成物について説明している。すべてのパーセンテージ、部および比率は、他で指摘されないかぎり重量による。
例Ｉ
１．香料担持ゼオライトの製造
活性化ゼオライトＮａ-Ｘ（残留水分＜５％）１０ｇを単純ミキサーまたはコーヒーグラインダータイプのミキシング装置に入れる。これに香料１．５ｇを滴下式に加える。混合物を約１０分間撹拌して、１５％w/w担持のＰＬＺ（香料担持ゼオライト）を得る。
２．低水分水素付加デンプン加水分解産物（Ｔｇ＝１２０℃）の製造
Roquette AmericaのPOLYSORB RA-1000（固形分７５％）のような水素付加デンプン加水分解産物１００ｇを、５％未満で水を含有する低水分シロップを得るために十分な水が除去されるまで、連続撹拌下で加熱する。大気圧下で、このような低水分レベルから、１５０〜１６０℃範囲の粘稠シロップの沸点になる。
３．ＰＬＺと低水分シロップとの組合せ
ＰＬＺを加温低水分シロップに加える。典型的には、２０〜４０重量％レベルのＰＬＺを加える。効率的なミキシングのためには（高トルクミキサーまたは押出機の使用のような）高エネルギーのインプットが好ましい。
４．ガラス粒子形成／サイズ減少
低水分シロップ中のＰＬＺ分散物を環境温度まで冷却させる。系の温度がシロップのガラス転移温度より下がると、粉砕して様々な粒度にしうるガラス系が得られる。代わりに、そのゴム状または溶融状態の系を小球またはペレットにして、望ましいサイズおよび形状の粒子を形成することができる。
５．ステップ（４）の粒状ガラスと洗剤ベースとの組合せ
２．２２％ガラス状粒子を洗剤処方物に加えて、０．６７％ＰＬＺおよび０．１％香料をデリバリーさせてもよい。
例II
例Ｉと同様であるが、但し水素付加デンプン加水分解産物の代わりにスクロース／マルトデキストリン８０：２０混合物（Ｄ．Ｅ．＝１０）を用いた実施例。このような系は、スクロースまたは他の低ＭＷオリゴ糖およびＤ．Ｅ．１５未満、好ましくは＜１０の多糖またはデンプンの混合物を少くとも１０％w/wのレベルで含んでいてもよい。典型的なスクロース／マルトデキストリン溶融物は、２％水を含有した８０％スクロースおよび２０％ＬｏＤｅｘ５（ex American Maize）からできていた。次いで溶融物をＺＳＫ３０ Werner & Pfleidererツインスクリュー押出機に供して、ＰＬＺを押出機の第七ゾーンに２０％w/w／レベルで加える。押出物を９０℃に冷却し、５００〜１０００μｍ粒子に切断およびサイズ分けする。 Field of Invention
The present invention relates to glassy particles containing agents useful for laundry and cleaning products, and laundry and cleaning products containing these glassy particles. The particles comprise a glass derived from one or more at least partially water soluble hydroxyl compounds such as sucrose, glucose and maltodextrin. Glassy particles also have a moisture absorption value of less than about 80%. Agents useful in laundry and cleaning products delivered from these particles include, for example, fragrances, bleaches, soil release polymers and mixtures thereof.
Background of the Invention
Laundry and cleaning products continue to evolve not only for good cleaning, but also for effects such as color and fabric care and aesthetics. Although new agents capable of producing such results can be developed, often in-product stability or through the wash release is a problem in their use. A variety of carrier systems and coating technologies have been developed to address these needs. For the most part, such systems are not widely useful.
For example, research continues on methods and compositions for the effective and efficient delivery of perfumes from laundry baths to fabric surfaces. As can be seen from the literature as mentioned later, various methods of perfume delivery have been developed. U.S. Pat. No. 4,096,072 issued June 20, 1978 to Brock et al. Describes a method for delivering fabric conditioning agents, including perfumes, with fatty quaternary ammonium salts during washing and drying cycles. Disclosure. Schnoring et al., US Pat. No. 4,402,856, issued September 6, 1983, discloses a microencapsulation technique consisting of a shell material formulation that allows a fragrance to diffuse from a capsule only at a certain temperature. is doing. Young's US Pat. No. 4,152,272, issued May 1, 1979, contains perfume in waxy particles to protect the perfume during storage and laundry processes with dry compositions. Is disclosed. The perfume diffuses without fail from the wax onto the fabric with a dryer. No. 5,066,419 issued Nov. 19, 1991 to Walley et al. By dispersing with a water-insoluble, non-polymeric carrier material and coating with a water-insoluble brittle coating material. Disclosed is a perfume encapsulated in a protective shell. U.S. Pat. No. 5,094,761 issued March 10, 1992 to Trinh et al. Discloses a clay-protected perfume / cyclodextrin that imparts a perfume effect to at least partially wetted fabrics. A composite is disclosed.
Another method for the delivery of fragrances during a wash cycle is Whyte US Pat. No. 4,209,417 issued June 24, 1980, Whyte issued July 13, 1982. As described in U.S. Pat. No. 4,339,356 and Gould et al. U.S. Pat. No. 3,576,760 issued Apr. 27, 1971, a perfume is combined with an emulsifier and a water-soluble polymer. Mix, form the mixture into particles and add them to the laundry composition.
The perfume can also be adsorbed on a porous carrier material, such as a polymeric material, as described in Bares et al., British Patent Publication No. 2,066,839, published July 15, 1981. it can. The perfume could also be adsorbed on clay or zeolitic material and then mixed into the granular detergent composition. Typically, the preferred zeolite was Type A or 4A zeolite with a nominal pore size of about 4 Angstrom units. In zeolite A or 4A, the perfume is adsorbed on the surface of the zeolite pores, but in comparison it is now believed that the perfume is actually not well absorbed in the zeolite pores. Perfume adsorption on zeolite or polymer carriers will probably be improved somewhat by the addition of neat fragrance mixed with the detergent composition, but the industry believes that the long shelf life of laundry compositions without loss of fragrance characteristics. We are still investigating improvements regarding the intensity or amount of fragrance delivered to the fabric and the duration of the fragrance odor on the treated fabric surface.
Combinations of perfume and usually larger pore size zeolites X and Y are also disclosed in the art. In German Offenlegungsschrift 248,508, published Aug. 12, 1987, a perfume dispenser (eg, air freshener) containing a faujasite type zeolite (eg, zeolites X and Y) carrying a perfume. About. It is said that the critical molecular diameter of a perfume molecule is 2 to 8 angstroms. Moreover, East German Patent Publication No. 137,599, published September 12, 1979, discloses a composition intended for use in powder detergents to effect temperature controlled release of perfumes. Zeolite A, X and Y are disclosed for use in these compositions. These initial disclosures include European Application Publication No. 535,942, which was subsequently published on April 7, 1993, Publication 536,942 published on April 14, 1993 by Unilever PLC, and Garner- Repeated in US Pat. No. 5,336,665, issued Aug. 9, 1994 to Gray et al.
An efficient perfume delivery composition is disclosed in WO 94/28107 published December 8, 1994 by The Procter & Gamble Company. These compositions comprise a zeolite having a pore size of at least 6 angstroms (eg, zeolite X or Y), a perfume releasably incorporated into the pores of the zeolite, and at least one having four or more hydroxyl moieties. A water-soluble fragrance that is substantially insoluble, comprising 0 to about 80% by weight of a solid polyol, and about 20 to about 100% by weight of a fluid diol or polyol in which the fragrance is substantially insoluble and the solid polyol is substantially soluble. Comprising a matrix coated on a scented zeolite containing a functional (wash-removable) composition.
Both U.S. Pat. No. 5,258,132 issued Nov. 2, 1993 and U.S. Pat. No. 5,230,822 issued Jul. 27, 1993 to Kamel et al. The wax has a melting point of about 40 to about 50 ° C and a solids content of 100 to about 35% at 40 ° C and 0 to about 15% at 50 ° C. . This coating is said to extend the period during which the encapsulated particles remain active in an aqueous environment. US Pat. No. 5,141,664 issued Aug. 25, 1992 to Corring et al. Describes a cleaning composition comprising a transparent gel having opaque particles of active agent uniformly dispersed and suspended in the gel. Related to things. The active substance is surrounded by a protective substance such as an encapsulating layer.
U.S. Pat. No. 2,809,895, issued to Swisher on Oct. 15, 1957, relates to a solid essential oil-containing composition suitable for use as an ingredient in various foods, pharmaceuticals, fragrances, soaps and cosmetics. This is said to form a finely dispersed essential oil-corn syrup emulsion that, when solidified and further processed, gives a particulate oxidation protected essential oil product. The process is described as emulsifying the essential oil with antioxidants and dispersants added in a solid corn syrup solution to form a granular solid emulsion.
Despite these efforts, there continues to be a need for a granular delivery system that can incorporate various laundry agents in laundry and cleaning compositions, particularly granular detergent compositions and granulated automatic dishwashing detergent compositions. Such particles that are stable under high heat and humidity storage conditions are particularly desirable. Such compositions that protect the water sensitive agent from harmful levels of water are also preferred for use.
Background art
Ramachhandran et al., U.S. Pat. No. 4,539,135, issued September 3, 1985, discloses a granular laundry compound containing a perfume-carrying clay or zeolitic material. Tai, U.S. Pat. No. 4,713,193, issued Dec. 15, 1987, discloses a free-flowing granular detergent additive containing a liquid or oily supplement with a zeolitic material. Nishishiro's Japanese Patent No. 4 (1992) -218583, published August 10, 1992, discloses a controlled release material containing perfume + zeolite. Corey et al., US Pat. No. 4,304,675, issued Dec. 8, 1981, discloses a method and composition containing zeolite to deodorize articles. East German Patent Publication No. 248,508 published on August 12, 1987; East German Patent Publication No. 137,599 published on September 12, 1979; European application published on April 7, 1993 Publication 535,942 and publication 536,942 published on April 14, 1993 by Unilever PLC; US Pat. No. 5,336,665 issued August 9, 1994 to Garner-Gray et al. WO 94/28107 published on December 8, 1994; both issued to Kamel et al., US Pat. No. 5,258,132 issued November 2, 1993 and issued July 27, 1993 US Pat. No. 5,230,822 issued to Gorring et al. On August 25, 1992, US Pat. No. 5,141,664 issued to Swiss, October 15, 1957 Issued US Pat. No. 2,809,895 by the biasing
Summary of the Invention
The present invention is:
(A) Fragrance, bleach, bleach promoter, bleach activator, bleach catalyst, chelant, antiscalant, threshold inhibitor, dye transfer inhibitor, photo bleach, enzyme, catalytic antibody, whitening agent, fabric Agents useful in laundry or cleaning compositions (preferably selected from direct dyes, antifungal agents, antibacterial agents, anthelmintic agents, soil release polymers, fabric softeners, color fasteners, pH jump systems and mixtures thereof (preferably Glassy particles comprising these agents useful at low levels in detergent compositions; and
(B) At least one non-soap detergent active
Comprising
An anhydrous unplasticized glass transition wherein the glassy particles comprise a glass derived from one or more at least partially water-soluble hydroxyl compounds, at least one of the hydroxyl compounds being above about 0 ° C Having a temperature Tg;
It further relates to a laundry or cleaning composition wherein the glassy particles have a moisture absorption value of less than about 80%.
The present invention is:
(A) Fragrance, bleach, bleach promoter, bleach activator, bleach catalyst, killer, antiscalant, threshold inhibitor, dye transfer inhibitor, photo bleach, enzyme, catalyst antibody, whitening agent, fabric direct dye, antifungal agent Agents useful in laundry or cleaning compositions selected from antibacterial agents, anthelmintic agents, soil release polymers, fabric softeners, color fixatives, pH jump systems and mixtures thereof (preferably perfume agents in zeolite carriers, Bleach, soil release polymer, photo bleach, enzyme are preferred); and
(B) Glass derived from one or more at least partially water-soluble hydroxyl compounds
Comprising
At least one of the hydroxyl compounds has an anhydrous unplasticized glass transition temperature Tg of about 0 ° C. or higher,
The glassy particles have a moisture absorption value of less than about 80%;
Furthermore, when the agent is a fragrance agent, the glassy particles further comprise at least one fragrance carrier material (preferably zeolite X or Y),
It also relates to glassy particles useful in laundry and cleaning compositions.
All percentages, ratios and proportions are on a weight basis unless otherwise indicated. All references cited are incorporated herein by reference in their entirety.
Detailed Description of the Invention
The present invention relates to a glassy particle delivery system comprising agents useful in laundry or cleaning compositions. The glass is derived from one or more at least partially water-soluble hydroxyl compounds, wherein at least one of the hydroxyl compounds has an anhydrous unplasticized glass transition temperature Tg of about 0 ° C. or higher. . Further, the glassy particles have a moisture absorption value of less than about 80%. These delivery systems are particularly useful in granular detergent compositions, particularly for delivering laundry and cleaning agents useful at low levels in the composition.
The at least partially water-soluble hydroxyl compounds useful in the present invention are preferably selected from the following classes of materials:
1. i) simple sugars (or monosaccharides), ii) oligosaccharides (defined as carbohydrate chains consisting of 2 to 35 monosaccharide molecules), iii) polysaccharides (defined as carbohydrate chains consisting of at least 35 monosaccharide molecules) Iv), iv) starch including modified starches and hydrolysates, and carbohydrates that are any of hydrogenated products of v) i), ii), iii) and iv) or mixtures thereof.
Both straight and branched carbohydrate chains are used. In addition, chemically modified starches and poly / oligosaccharides may be used. Typical modifications include the addition of hydrophobic moieties in the form of alkyls, aryls, etc., identical to those found in surfactants in order to confer some surface activity on these compounds. Preferred carbohydrate materials are hydrogenated products, particularly hydrogenated starch hydrolysates. Most preferred are hydrogenated starch hydrolysates derived from carbohydrates having a dextrose equivalent (DE) of less than 45 and typically made by hydrogenation of starch hydrolysates of less than DE45. Suitable examples of hydrogenated starch hydrolysates include those marketed under the trade names POLYSORB and LYCASINE from Roquette America of Keokuk, Iowa and HYSTAR from Lonza of Fairlawn, NJ.
As used herein, the terms “dextrose equivalent” and abbreviated “DE” relate to the total amount of reducing sugar expressed as dextrose present, calculated as a percentage of total dry matter. The amount is measured on a scale of 0-100, where 100 is the amount present in pure sugar. A common technique for determining dextrose equivalent is the alkaline copper capacity method. Both dextrose equivalents and methods for measuring dextrose equivalents are well known in the art, particularly in the food and syrup industry.
2. All natural or synthetic gums such as alginate esters, carrageenan, agar, pectic acid and natural gums such as gum arabic, tragacanth and karaya gum.
3. Chitin and chitosan.
4). Cellulose and cellulose derivatives. Examples include i) cellulose acetate and cellulose acetate phthalate (CAP), ii) hydroxypropyl methylcellulose (HPMC), iii) carboxymethylcellulose (CMC), iv) all enteric / aqueous coatings and mixtures thereof.
5). Silicates, phosphates and borates.
6). Polyvinyl alcohol (PVA).
7. Polyethylene glycol (PEG).
Substances belonging to these classes that are at least partially not water-soluble and have a glass transition temperature Tg below the lower limit of about 0 ° C. are such that the resulting glassy particles have a required moisture absorption value of less than about 80%. In addition, it is useful in the present invention only when mixed in such amounts with hydroxyl compounds useful in the present invention having the required high Tg.
The glass transition temperature, usually abbreviated as “Tg”, is a well-known and easily investigated property for glassy materials. This transition is expressed as corresponding to liquefaction by heating in the Tg region from a glassy state to a liquid state substance. It is not a phase transition such as melting, vaporization or sublimation (William P. Brennan, “What is a Tg? A review of the scanning calorimetry of the glass transition”, Thermal Analysis Application Study # 7, Perkin-Elmer Corporation, March) (See 1973). Tg can be easily measured by using a differential scanning calorimeter.
For purposes of the present invention, the Tg of the hydroxyl compound is obtained for an anhydrous compound that does not contain any plasticizer (which affects the measured Tg value of the hydroxyl compound). Glass transition temperatures are also described in detail in P. Peyser, “Glass Transition Temperatures of Polymers”, Polymer Handbook, Third edition, J. Brandrup and EHImmergut (Wiley-Interscience; 1989), pp. VI / 209-VI / 277. Has been.
At least one of the hydroxyl compounds useful in the glassy particles of the present invention is at least 0 ° C., and in the case of particles having no moisture barrier coating, at least about 20 ° C., preferably at least about 40 ° C., more preferably Must have an anhydrous unplasticized Tg of at least 60 ° C, most preferably at least about 100 ° C. It is also preferred that these compounds can be processed at low temperatures, preferably in the range of about 50 to about 200 ° C, more preferably in the range of about 60 to about 180 ° C. Such hydroxyl compounds include sucrose, glucose, lactose, starch hydrolysates such as corn syrup and maltodextrin, and hydrogenated starch hydrolysates.
As used herein, “moisture absorption value” means the level of moisture uptake by glassy particles as measured by the increased weight percent of the particles in the following test method. The hygroscopic value required for the glassy particles of the present invention is 2 g of particles (about 500 micron size particles; moisture-proof coating) in an open container Petri dish under 90 ° F. (about 32 ° C.) and 80% relative humidity for 4 weeks. Is not included). The increased weight percent of particles at the end of this time is the particle moisture absorption value as used in the present invention. Preferred particles have a moisture absorption value of less than about 50%, more preferably less than about 10%.
The glassy particles of the present invention are typically about 10 to about 99.99%, preferably about 20 to about 90%, more preferably about 20 to about 75% at least partially water soluble hydroxyl compounds. Is included. The glassy particles of the present invention are also typically useful in laundry or cleaning compositions of about 0.01 to about 90%, preferably about 10 to about 80%, more preferably about 25 to about 80%. Contains.
The method of making the glassy particles of the present invention is deduced from the candy manufacturing industry. Such methods include those described, for example, in Swiss U.S. Pat. No. 2,809,895 issued Oct. 15, 1957.
Useful agents for laundry or cleaning compositions:
Agents useful in the laundry or cleaning composition according to the present invention include perfume, bleach, bleach promoter, bleach activator, bleach catalyst, killer, antiscalant, threshold inhibitor, dye transfer inhibitor, photo bleach, enzyme, catalytic antibody, Selected from the group consisting of brighteners, fabric direct dyes, antifungal agents, antibacterial agents, anthelmintic agents, soil release polymers, fabric softeners, color-fastening agents, pH jump systems and mixtures thereof. As will be apparent to the present invention, these agents useful in laundry or cleaning compositions incorporated into the glassy particles of the present invention are useful for formulating the remainder of laundry and cleaning compositions containing glassy particles. It may be the same as or different from the agent used. For example, the glassy particles may contain a fragrance agent, and the agent (same or different) may be blended into the final composition together with the fragrance-containing glassy particles. These agents are selected as desired depending on the type of composition being formulated, such as a granular laundry detergent composition, a granulated automatic dishwashing composition or a hard surface cleaner.
Various types of agents useful in laundry and cleaning compositions are described below. Compositions containing glassy particles may contain one or more other detergent additives, or other aids to assist or improve cleaning performance, treat the substrate being cleaned, or modify the aesthetics of the detergent composition. Substances (eg, fragrances, colorants, dyes, etc.) can optionally be included.
Fragrance
As used herein, the term “perfume” is used to indicate a fragrance that is subsequently released into a water bath and / or onto a fabric in contact therewith. Most perfumes are liquid at ambient temperature. Various chemicals are known for fragrances, including substances such as aldehydes, ketones and esters. More generally, natural plant and animal oils and exudates consisting of complex mixtures of various chemical components are known for use as perfumes. The perfumes in the present invention are selected so that their composition is relatively simple or consists of a highly sophisticated complex mixture of natural and synthetic chemical components, all exhibiting the desired aroma. Typical fragrances are made from a wood / soil base containing exotic materials such as sandalwood, musk and patchouli oil. The perfume may be made of a light floral fragrance, such as rose extract, violet extract and lilac. Perfumes may be formulated to have a desirable fruity flavor, such as lime, lemon and orange. Any chemically compatible material that emits a pleasant or desirable aroma can be used in the scented compositions of the present invention.
Perfumes also include pro-fragrances such as acetal pro-fragrances, ketal pro-fragrances, ester pro-fragrances (eg digeranyl succinate), hydrolyzable inorganic-organic pro-fragrances and mixtures thereof. These fragrances either release perfume materials as a result of simple hydrolysis, are pH change-inducing fragrances (eg, pH reduction), or are enzyme-releasing fragrances.
Preferred perfume agents useful in the present invention are defined as follows.
For the purposes of the composition of the present invention exposed to the aqueous medium of the laundry washing process, several characteristic parameters of the perfume molecules specify and define their longest and widest width measurements, cross-sectional area, molecular volume, molecular surface area Is important above. These values can be obtained individually using the CHEMX program of molecules (Chemical Design, Ltd.) with the lowest energy conformation investigated with standard geometry optimized in CHEMX, and using standard atomic van der Waals radii. Of perfume molecules. The parameter definitions are as follows:
“Longest”: Maximum distance between atoms in molecules (angstroms) increased by their van der Waals radii
“Widest”: the projection of molecules on a plane perpendicular to the “longest” axis of the molecule, the maximum distance between atoms in the angstroms, increased by their van der Waals radius
“Cross-sectional area”: the area occupied by the projection of molecules on the plane perpendicular to the longest axis (in square angstroms)
“Molecular volume”: the volume occupied by a molecule in its lowest energy configuration (in cubic angstroms)
“Molecular surface area”: Arbitrary units defined as square angstroms (for calibration purposes, molecular methyl β-naphthyl ketone, benzyl salicylate and camphor gum have a surface area of 128 ± 3, 163.5 ± 3 and 122.5 ± 3 units. Each)
The shape of the molecule is also important for uptake. For example, a symmetric perfect spherical molecule that is small enough to be included in a zeolite groove does not have the preferred orientation and is taken from any approach direction. However, in the case of molecules having a length exceeding the pore size, there is a preferred “approach direction” for inclusion. The calculation of the molecular volume / surface area ratio is used in the present invention to represent the “shape index” for a molecule. As the value increases, the molecule becomes spherical.
For the purposes of the present invention, fragrances are classified by their ability to be incorporated into the zeolite pores and thus their utility as ingredients for delivery from the zeolite carrier into an aqueous environment. Plotting these agents in volume / surface area ratio vs. cross-sectional area planes can successfully classify agents into groups based on their incorporation into the zeolite. In particular, in the case of zeolite X and Y carriers according to the present invention, if the agent belongs under the line defined by the following formula (referred to herein as the “uptake line”), they are incorporated:
y = −0.01068x + 1.497
In the above, x is a cross-sectional area and y is a volume / surface area ratio. Agents that belong under the uptake line are referred to herein as “delivery agents”; agents that belong over that line are referred to herein as “non-delivery agents”.
Due to containment during washing, the delivery agents remain on the zeolite carrier as a function of their affinity for the carrier compared to the competitive delivery agent. Affinity is affected by molecular size, hydrophobicity, functionality, volatility, etc., and is brought about by interactions between delivery agents within the zeolite carrier. These interactions can provide improved containment during cleaning for the incorporated delivery agent mixture. In particular, in the present invention, the use of a delivery agent having at least one dimension that closely matches the zeolite carrier pore size delays the loss of other delivery agents in an aqueous cleaning environment. A delivery agent that functions in this manner is referred to herein as a “blocker agent” and is under the “uptake line” (as described above) and is defined by the following formula (herein referred to as “blocker line”: As defined in the present invention by volume / surface area ratio vs. cross-sectional area plane as delivery agent molecules belonging to the line):
y = −0.01325x + 1.46
In the above, x is a cross-sectional area and y is a volume / surface area ratio.
For the compositions of the present invention that utilize zeolites X and Y as carriers, all delivery agents under the “uptake line” can be delivered and released from the compositions of the present invention, with preferred materials belonging under the “blocker line”. Also preferred are mixtures of blockers and other delivery agents. The laundry perfume mixture useful for the laundry particles of the present invention preferably comprises about 5 to about 100% (preferably about 25 to about 100%; more preferably about 50 to about 100%) of the delivery agent of the laundry mixture. Preferably about 0.1 to about 100% (preferably about 0.1 to about 50%) of a blocker.
Obviously, in the case of the compositions according to the invention in which the perfume is delivered by the composition, sensory perception is necessary for the effect perceived by the consumer. In the case of the fragrance composition of the present invention, the most preferred fragrance agent useful is no more than 10 parts / billion ("ppb") fragrance under carefully controlled GC conditions, as described in detail later. Recognition threshold (measured as detection threshold ("ODT")). An agent of ODT 10 ppb to 1 part / million (“ppm”) is less preferred. It is preferable to avoid agents with an ODT of 1 ppm or more. The laundry perfume mixture useful for the laundry particles of the present invention preferably comprises from about 0 to about 80% delivery agent at ODT 10 ppb to 1 ppm and from about 20 to about 100% (preferably from about 30 to about 100%) delivery agent at ODT 10 ppb or less. And more preferably from about 50 to about 100%).
Also preferred are perfumes that are subjected to a washing process and released into the air around the dry fabric (eg, the space around the fabric during storage). This requires the perfume to move out of the zeolite pores before being released into the air around the fabric. Accordingly, preferred perfumes are further specified based on their volatility. Boiling point is used in the present invention as a measure of volatility, and preferred materials have boiling points below 300 ° C. The laundry perfume mixture useful for the laundry particles of the present invention preferably comprises at least about 50% (preferably at least about 60%, more preferably at least about 70%) of a delivery agent having a boiling point of less than 300 ° C.
In addition, preferred laundry particles in the present invention comprise a composition wherein at least about 80%, more preferably at least about 90% of the delivery agent has a “ClogP value” greater than about 1.0. . The ClogP value is obtained as follows.
Calculation of ClogP:
These perfume ingredients are characterized by their octanol / water partition coefficient P. The octanol / water partition coefficient of a perfume ingredient is the ratio of its equilibrium concentration between octanol and water. Because the partition coefficients of most perfume ingredients are large, they are shown more conveniently in the form of their log base 10, log P.
A number of perfume ingredients log P have been reported; for example, the Pomona 92 database available from Daylight Chemical Information Systems, Inc. (Daylight CIS) contains many along with citations of the original literature.
However, it is most convenient to calculate the log P value with the “CLOGP” program available from Daylight CIS. The program also lists experimental logP values when they are available in the Pomona 92 database. “Calculated log P” (Clog P) is determined by Hansch & Leo's fragment approach (cf., A. Loe in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JBTaylor & CARamsden, Eds., p.295, Pergamon Press, 1990). The fragment approach is based on the chemical structure of each perfume ingredient and considers the number and type of atoms, atomic bonds and chemical bonds. The ClogP value, the most reliable and widely used estimate for this physicochemical property, can be used in place of the experimental logP value in the selection of perfume ingredients.
Determination of aroma detection threshold:
The gas chromatograph is characterized to examine the hydrocarbon response using the exact volume of material injected by syringe, the exact split ratio, and hydrocarbon standards of known concentration and chain length distribution. The air flow rate is accurately measured assuming a human inhalation time of 0.2 minutes and the sampled volume is calculated. Since the exact concentration is known at any point in the detector, the mass per inhaled volume and thus the concentration of the substance is known. In order to determine if the substance has a threshold of 10 ppb or less, the solution is delivered to the odor mouth at a back-calculated concentration. Panelists smell the GC effluent and specify the retention time when they notice the smell. The average for all panelists determines the recognition threshold.
The required amount of analyte is injected into the column to reach a 10 ppb concentration with a detector. Typical gas chromatographic parameters for examining the aroma detection threshold are listed below.
GC: FID detector 5890 series II
7673 Autosampler
Column: J & W Scientific DB-1
30 meters long ID 0.25mm Film thickness 1 micron
Method:
Split injection: 17/1 split ratio
Autosampler: 1.13 μl / injection
Column flow: 1.10 ml / min
Air flow: 345ml / min
Inlet temperature 245 ° C
Detector temperature 285 ° C
Temperature information
Initial temperature: 50 ° C
Speed: 5 ℃ / min
Final temperature: 280 ° C
Final time: 6 min
Leading assumptions:
0.02min / 1 odor smell
GC air is increasing sample dilution
Perfume fixing agent
Optionally, the fragrance can be combined with a fragrance fixing agent. The perfume fixing materials used in the present invention are characterized by several criteria that make them particularly suitable for the practice of the present invention. Dispersible, toxicologically acceptable, skin-irritating, inert to fragrances, degradable and / or available from regenerative sources and relatively odorless additives are used. Perfume fixatives are believed to delay the evaporation of the more volatile components of the perfume.
Examples of suitable fixing agents include members selected from the group consisting of diethyl phthalate, musk and mixtures thereof. If used, the perfume fixing agent is about 10 to about 50% by weight of the perfume, preferably about 20 to about 40%.
Perfume carrier substance
As used herein, “perfume carrier material” means a material that can support a perfume agent (eg, by absorption on a surface or adsorption into a pore) for incorporation into glassy particles. Such materials include amorphous silicate, crystalline layerless silicate, laminated silicate, calcium carbonate, calcium carbonate / sodium double salt, sodium carbonate, clay, zeolite, sodalite, alkali metal phosphate, porous zeolite, There is a porous solid selected from the group consisting of chitin microbeads, carboxyalkyl cellulose, carboxyalkyl starch, cyclodextrin, porous starch and mixtures thereof.
Preferred perfume carrier materials are zeolite X, zeolite Y and mixtures thereof. The term “zeolite” as used herein relates to a crystalline aluminosilicate material. The structural formula of zeolite is based on the smallest unit of structure represented by the following, the crystal unit cell:
M_{m / n}[(AlO₂)_m(SiO₂)_y] XH₂O
Where n is the valence of the cation M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y / m is 1-100. . Most preferably, y / m is 1-5. The cation M is a group IA and group IIA element such as sodium, potassium, magnesium and calcium.
Zeolites useful in the present invention include faujasite type zeolites, including type X zeolites or type Y zeolites, both having a nominal pore size in the range of about 8 angstrom units, typically in the range of about 7.4 to about 10 angstrom units. It is.
Aluminosilicate zeolitic materials useful in the practice of this invention are commercially available. Methods for producing X and Y type zeolites are well known and can be seen from standard texts. Preferred synthetic crystalline aluminosilicate materials useful in the present invention are commercially available with a Type X or Type Y designation.
For purposes of illustration and not limitation, in a preferred embodiment, the crystalline aluminosilicate material is type X and is:
(I) Na₈₆[(AlO₂)₈₆(SiO₂)₁₀₆] XH₂O
(II) K₈₆[(AlO₂)₈₆(SiO₂)₁₀₆] XH₂O
(III) Ca₄₀Na₆[(AlO₂)₈₆(SiO₂)₁₀₆] XH₂O
(IV) Sr₂₁Ba₂₂[(AlO₂)₈₆(SiO₂)₁₀₆] XH₂O
And mixtures thereof, wherein x is from about 0 to about 276. The zeolites of formulas (I) and (II) have a nominal pore size or opening of 8.4 angstrom units. The zeolites of formula (III) and (IV) have a nominal pore size or opening of 8.0 angstrom units.
In another preferred embodiment, the crystalline aluminosilicate material is type Y and is:
(V) Na₅₆[(AlO₂)₅₆(SiO₂)₁₃₆] XH₂O
(VI) K₅₆[(AlO₂)₅₆(SiO₂)₁₃₆] XH₂O
And mixtures thereof, wherein x is from about 0 to about 276. The zeolites of formulas (V) and (VI) have a nominal pore size or opening of 8.0 Angstrom units.
The zeolite used in the present invention takes the form of particles having an average particle size of about 0.5 to about 120 microns, preferably about 0.5 to about 30 microns, as measured by standard particle size analysis techniques.
If it is the size of the zeolite particles, they can be captured by the fabric they come into contact with. Once settled on the fabric surface (the coating matrices are washed off during the laundry process), the zeolites can begin to release their incorporated laundry, especially when subjected to heat or moisture conditions.
Incorporation of perfume into zeolite-The type X or type Y zeolite used in the present invention preferably contains less than about 10% desorbable water, more preferably less than about 8% desorbed water, most preferably less than about 5% desorbed water. ing. Such materials are obtained by first heating / dehydrating, optionally by heating to about 150-350 ° C. for at least 12 hours under reduced pressure (about 0.001 to about 20 Torr). After activation, the agent is slowly and thoroughly mixed with the activated zeolite and, optionally, heated to about 60 ° C. within about 2 hours to promote absorption equilibrium within the zeolite particles. The perfume / zeolite mixture is then cooled to room temperature and takes the form of a free-flowing powder.
The amount of detergent incorporated into the zeolite carrier is less than about 20% by weight of the supported particles, typically less than about 18.5%, given the pore volume of the zeolite. However, it will be appreciated that the particles of the present invention may exceed this level of laundry by weight of the particles, but that no extra level of laundry will be incorporated into the zeolite, even if only delivery agents are used. Should be recognized. Accordingly, the particles of the present invention may contain more than 20% by weight of a laundry agent. Since no extra laundry (as well as any non-delivery agent present) is incorporated into the zeolite pores, it appears that these materials are immediately released to the cleaning liquid upon contact with the aqueous cleaning medium.
In addition to its ability to contain / protect perfume with zeolite particles, glassy particles agglomerate a large number of perfume zeolite particles into agglomerates having an overall particle size in the range of 200-1000 microns, preferably 400-600 microns. Works as well. This reduces dustiness. In addition, it reduces the tendency of smaller individual scented zeolites to move to the bottom of a container that is typically filled with granular detergents having a particle size in the 200-1000 micron range.
Detergent surfactant-The detersive surfactant contained in the fully formulated detergent composition obtained according to the invention is preferably at least 1% by weight of the detergent composition, depending on the specific surfactant used and the desired effect. Is from about 1 to about 99.8%. In highly preferred embodiments, the detersive surfactant is about 5 to about 80% by weight of the composition.
Detersive surfactants can be nonionic, anionic, amphoteric, bipolar or cationic. Mixtures of these surfactants may also be used. Preferred detergent compositions comprise an anionic detersive surfactant or a mixture of an anionic surfactant and other surfactants, especially nonionic surfactants.
Non-limiting examples of surfactants useful in the present invention include conventional C₁₁-C₁₈Alkylbenzene sulfonates and primary, secondary and random alkyl sulfates, C_Ten-C₁₈Alkyl alkoxy sulfate, C_Ten-C₁₈Alkyl polyglycosides and their corresponding sulfated polyglycosides, C₁₂-C₁₈α-sulfonated fatty acid ester, C₁₂-C₁₈Alkyl and alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C₁₂-C₁₈Betaine and sulfobetaine ("Sultain"), C_Ten-C₁₈There are amine oxides. Other conventional and useful surfactants are listed in the standard text.
One class of nonionic surfactants particularly useful in the detergent compositions of the present invention is an average hydrophilic-lipophilic balance (HLB) in the range of 5-17, preferably 6-14, more preferably 7-12. It is a condensate of ethylene oxide and a hydrophobic moiety that gives a surfactant having Hydrophobic (lipophilic) moieties are aliphatic or aromatic in nature. The length of the polyoxyethylene group condensed with any particular hydrophobic group can be easily adjusted to obtain a water-soluble compound with the desired balance between hydrophilic and hydrophobic elements.
Particularly preferred nonionic surfactants of this type are C having 3 to 8 moles of ethylene oxide per mole of alcohol.₉-C₁₅Primary alcohol ethoxylates, especially C with 6-8 moles of ethylene oxide per mole of alcohol₁₄-C₁₅Primary alcohol, C with 3-5 moles of ethylene oxide per mole of alcohol₁₂-C₁₅Primary alcohols and mixtures thereof.
Another suitable class of nonionic surfactants consists of polyhydroxy fatty acid amides of the formula:
(I) R²C (O) N (R¹Z
In the above formula: R¹H, C₁-C₈Hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, preferably C₁-C₄Alkyl, more preferably C₁Or C₂Alkyl, most preferably C₁Alkyl (ie, methyl); R²Is C₅-C₃₂Hydrocarbyl moiety, preferably linear C₇-C₁₉Alkyl or alkenyl, more preferably linear C₉-C₁₇Alkyl or alkenyl, most preferably linear C₁₁-C₁₉Alkyl or alkenyl, or a mixture thereof; Z is a linear hydrocarbyl chain and at least two (in the case of glyceraldehyde) or at least three hydroxyls (in the case of other reducing sugars) linearly bonded to the chain ) Or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose, and glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup and the above-mentioned individual sugars can also be used. These corn syrups produce a mix of sugar components for Z. It should be understood that it is not meant to exclude other suitable ingredients. Z is preferably —CH₂-(CHOH)_n-CH₂OH, -CH (CH₂OH)-(CHOH)_n-1-CH₂OH, -CH₂-(CHOH)₂(CHOR ') (CHOH) -CH₂OH (n is an integer from 1 to 5 and R 'is H or a cyclic mono- or polysaccharide) and their alkoxylated derivatives. Glycytyl where n is 4, especially —CH₂-(CHOH)₄-CH₂OH is most preferred.
In formula (I), R¹Is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxyethyl or N-2-hydroxypropyl. R for maximum foaming¹Is preferably methyl or hydroxyalkyl. If lower foamability is desired, R¹Is preferably C₂-C₈Alkyl, especially n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl and 2-ethylhexyl.
R²-CO-N <is, for example, cocamide, stearamide, oleamide, lauramide, myristamide, caprylamide, palmitoamide, tallow amide and the like.
Soap (ie, fatty acid salts) may also be used as part of the detersive surfactant in the present invention if desired.
Low foaming nonionic surfactants are useful in automatic dishwashing to aid in cleaning, in particular to help remove food soil foam with proteins, and to suppress smudge / film formation, preferably about It is contained in the detergent composition at a level of 0.1 to about 20%. In general, bleach-stable surfactants are preferred. The ADD (automatic dishwashing detergent) composition of the present invention preferably comprises a low foaming nonionic surfactant (LFNI). LFNI can be present in an amount of 0 to about 10% by weight, preferably about 0.25 to about 4%. LFNI is most typically used in ADD because of the improved water sheeting action they impart to ADD products (especially from glass). They also include non-silicone, non-phosphate polymeric materials that are further described below, which are known to remove food fouling foams encountered in automatic dishwashing.
Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO) / PO) Blends with reverse block polymers. It is well known that PO / EO / PO polymer type surfactants have antifoaming or defoaming action, particularly with respect to normal food soil ingredients such as eggs.
The present invention includes preferred embodiments in which LFNI is present and this component is solid at about 95 ° F. (35 ° C.), more preferably solid at about 77 ° F. (25 ° C.). For ease of manufacture, the preferred LFNI is from about 77 ° F (25 ° C) to about 140 ° F (60 ° C), more preferably from about 80 ° F (26.6 ° C) to 110 ° F (43.3 ° C). Has a melting point of
In a preferred embodiment, LFNI is derived from the reaction of a monohydroxy alcohol or alkylphenol having from about 8 to about 20 carbon atoms with about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkylphenol on an average basis. It is a surfactant.
Particularly preferred LFNI is about 16 to about 20 carbons condensed with about 6 to about 15 moles, preferably about 7 to about 12 moles, and most preferably about 7 to about 9 moles of ethylene oxide per mole of alcohol. Straight chain fatty alcohol having atoms (C₁₆-C₂₀Alcohol), preferably C₁₈Derived from alcohol. Preferably, the ethoxylated nonionic surfactant thus derived has a narrow ethoxylate distribution compared to the average.
LFNI can optionally contain propylene oxide in an amount up to about 15% by weight. Other preferred LFNI surfactants are prepared by the process described in Builloty US Pat. No. 4,223,163, issued September 16, 1980, which is incorporated herein by reference. be able to.
A highly preferred ADD in which LFNI is present uses an ethoxylated monohydroxy alcohol or alkylphenol and further comprises a polyoxyethylene, polyoxypropylene block polymer compound, wherein the LFNI ethoxylated monohydroxy alcohol or alkylphenol fraction is a fraction of all LFNI. About 20 to about 100%, preferably about 30 to about 70%.
Suitable block polyoxyethylene-polyoxypropylene polymer compounds that meet the above requirements include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compounds. C_12-18Polymer compounds made from continuous ethoxylation and propoxylation of initiator compounds having a single reactive hydrogen atom, such as aliphatic alcohols, usually do not exhibit satisfactory foam suppression with the present ADD. PLURONIC by BASF-Wyandotte Corp., Wyandotte, Michigan^{▲ R ▼}And TETRONIC^{▲ R ▼}Certain block polymer surfactant compounds labeled as are suitable for the ADD compositions of the present invention.
A particularly preferred LFNI starts with about 75% by weight of the blend, polyoxyethylene and polyoxypropylene reverse block copolymer having 17 moles of ethylene oxide and 44 moles of propylene oxide, and about 25% by weight of the blend, trimethylolpropane. A polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend consisting of a block copolymer of polyoxyethylene and polyoxypropylene having 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane from about 40 to Contains about 70%.
LFNI having a relatively low cloud point and high hydrophilic-lipophilic balance (HLB) is suitable for use as LFNI in ADD compositions. The cloud point of a 1% solution in water is typically about 32 ° C. or less, preferably lower, for example 0 ° C., for optimal control of foamability over the full range of water temperatures.
LFNI that may be used is C having a degree of ethoxylation of about 8 commercially available as SLF 18 from Olin Corp.₁₈There are alcohol polyethoxylates and biodegradable LFNI having the melting point properties described above.
enzyme-Enzymes are used in this detergent for a variety of purposes, including removal of protein-based, carbohydrate-based or triglyceride-based soils from surfaces such as textiles or dishes, such as prevention of free dye transfer in laundry and fabric repair. It can be contained in the composition. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof of any suitable origin, such as plant, animal, bacterial, fungal and yeast sources. The preferred choice is influenced by factors such as pH activity and / or optimum stability, thermal stability and stability against active detergents, builders and the like. In this respect, bacterial or fungal enzymes such as bacterial amylases and proteases and fungal cellulases are preferred.
As used herein, “detersive enzyme” refers to an enzyme that has a cleaning, stain removal or other beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include but are not limited to proteases, cellulases, lipases and peroxidases. Highly preferred for automatic dishwashing is amylase and / or including both current commercial types and improved types that are more bleach-compatible with continuous improvement but have a degree of residual bleach inactivation sensitivity. Or a protease.
The enzyme is usually formulated in the detergent or detergent additive composition at a level sufficient to provide a “cleaning effective amount”. The term “cleaning effective amount” relates to an amount that can produce a cleaning, stain removal, soil removal, whitening, deodorizing or freshness improving effect on substrates such as fabrics, tableware and the like. In practice, typical amounts of current products are within about 5 mg by weight per gram of detergent composition, more typically 0.01 to 3 mg of active enzyme. In other words, the composition typically comprises 0.001 to 5% by weight, preferably 0.01 to 1%, of a commercial enzyme product. Protease enzymes are usually present in such products at a level sufficient to provide 0.005-0.1 Anson units (AU) of activity per gram of composition. In some detergents, such as automatic dishwashing, it is desirable to increase the active enzyme content of the product in order to minimize the total amount of non-catalytically active material, thereby improving stain / filming or other end results . Higher activity levels are desirable for highly concentrated detergent formulations.
A suitable example of a protease is subtilisin obtained from a specific strain of B. subtilis and B. licheniformis. One suitable protease is obtained from a strain of Bacillus that has maximum activity in the pH range of 8-12 and is from Denmark Novo Industries A / S, hereinafter “Novo” to ESPERASE^{▲ R ▼}Developed and sold as. Products of this and similar enzymes are described in Novo GB 1,243,784. Other suitable proteases include Novo's ALCALASE^{▲ R ▼}And SAVINASE^{▲ R ▼}, MAXATASE of International Bio-Synthetics, Inc. of the Netherlands^{▲ R ▼}Protease A, disclosed in EP130,756A on January 9, 1985, EP303,761A on April 28, 1987, and Protease B, disclosed in EP130,75.6A on January 9,1985. See also the high pH protease from Bacillus sp. NCIMB 40338 described in Novo WO 9318140A. Enzymatic detergents including proteases, one or more other enzymes and a reversible protease inhibitor are described in Novo WO 9203529A. Another preferred protease is that of WO 9510591A from Procter & Gamble. If desired, proteases with reduced adsorptivity and increased hydrolyzability are commercially available as described in Procter & Gamble, WO 9507791. A recombinant trypsin-like protease for detergents suitable for the present invention is described in Novo WO 9255583.
More particularly, a particularly preferred protease referred to as “protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, both filed on Oct. 13, 1994, A. Baeck et al. USSN 08 / 322,676, "Protease-containing cleaning composition" and C. Ghosh et al., USSN 08 / 322,677, "Protease enzyme-containing bleaching composition". Thus, according to the numbering of Bacillus amyloliquefaciens subtilisin, preferably +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210 , +216, +217, +218, +22 In place of multiple amino acid residues at the position of the carbonyl hydrolase corresponding to position +76 in combination with one or more amino acid residue positions corresponding to those selected from the group consisting of 2, +260, +265 and / or +274 Derived from a precursor carbonyl hydrolase by using different amino acids.
Although not limited, amylases that are particularly suitable for automatic dishwashing purposes include α-amylases described in, for example, Novo GB 1,296,839; RAPIDASE^{▲ R ▼}, International Bio-Synthetics, Inc. and TERMAMYL^{▲ R ▼}There is Novo. Novo FUNGAMYL^{▲ R ▼}Is particularly useful. Enzymatic engineering is known for improved stability, such as oxidative stability. See, for example, J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. In one preferred embodiment of the composition, TERMAMYL marketed in 1993.^{▲ R ▼}Amylases having improved stability, especially improved oxidative stability, with detergents such as the automatic dishwashing type, as measured against the reference can be used. These preferred amylases are oxidatively stable to hydrogen peroxide / tetraacetylethylenediamine, for example in a pH 9-10 buffer, as measured against the above reference amylase; heat stable at normal washing temperatures such as about 60 ° C. Share the characteristics of being a “stability-enhanced” amylase, characterized by minimal improvement by an improvement that can be measured by one or more of alkaline stability at a pH of about 8 to about 11, for example. Stability can be measured using any industry disclosed technical test. See, for example, the literature disclosed in WO 9402597. Stability-enhancing amylases are obtained from Novo or Genencor International. One class of highly preferred amylases in the present invention is a site from one or more Bacillus amylases, particularly Bacillus α-amylases, regardless of whether one, two or many amylase strains are direct precursors. It has the common feature of being induced using specific mutagenesis. Amylases with increased oxidative stability relative to the reference amylase are preferred for use in oxygen bleached detergent compositions, especially as distinguished from bleaching, more preferably chlorine bleaching. Such preferred amylases include: (A) TERMAMYL in which substitution of the methionine residue located at position 197 of B. licheniformis α-amylase was performed using alanine or threonine, preferably threonine.^{▲ R ▼}A homologous positional variant of the amylase according to WO 9402597, Nov. 3, 1994, Nov. 3, 1994, or a similar parent amylase such as B. amyloliquefaciens, B. subtilis or B. stearothermophilus, as further shown in the variant known as (B) Stability-enhanced amylase as described by Genencor International in a paper entitled “Oxidatively Resistant alpha-Amylases” published by C. Matchinson in the 207th American Chemical Society National Meeting, March 13-17,1994. is there. It describes that bleach in automatic dishwashing detergents inactivates α-amylase, but an improved oxidative stable amylase was made by Genencor from B. licheniformis NCIB8061. Methionine (Met) has been identified as the most amenable residue. Met is substituted once at positions 8, 15, 197, 256, 304, 366 and 438 to make specific mutants, but of particular importance are M197L and M197T, with the M197T variant being the most stable expression variant It is. Stability is CASCADE^{▲ R ▼}And SUNLIGHT^{▲ R ▼}Measured in (C) Particularly preferred amylases in the present invention include amylase variants having additional modifications on the direct parent as described in WO 9510603A, and DURAMYL^{▲ R ▼}It is commercially available from Assignee Novo. Other particularly preferred oxidative stability-enhancing amylases are those described in Genencor International, WO 9418314 and Novo, WO 9402597. Any other oxidative stability-enhancing amylase may be used, such as derived by site-directed mutagenesis from, for example, known chimeric, hybrid or simple mutant parent forms of amylase. Other preferred enzyme modifications can also be made. See Novo, WO 9509909A.
Cellulases that can be used in the present invention include both bacterial and fungal types and preferably have an optimum pH of 5 to 9.5. US Pat. No. 4,435,307 to Barbesgoard et al., Mar. 6, 1984, describes a suitable fungal cellulase from Humicola insolens or Humicola strain DSM1800 or cellulase 212-producing fungi belonging to the genus Aeromonas and the marine mollusc dolabella Auricula. Cellulase extracted from Solander's hepatopancreas is disclosed. Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME^{▲ R ▼}(Novo) is particularly useful. See Novo, WO 9117243.
Suitable lipase enzymes for detergents include those produced by microorganisms of the genus Pseudomonas such as Pseudomonas stutzeri ATCC 19.154 disclosed in GB 1,372,034. See also the lipase of Japanese Patent Application No. 53/20487 published on Feb. 24, 1978. This lipase is commercially available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name lipase P “Amano” or “amano-P”. Other suitable commercially available lipases include Amano-CES, lipase ex Chromobacter viscosum, such as Chromobacter viscosum var.lipolyticum NRRLB 3673 from Toho Brewery of Takata, Japan; USBiochemical Corp. of USA and Disoynth Co. of the Netherlands Chromobacter viscosum lipase; lipase ex Pseudomonas gladioli. LIPOLASE commercially available from Novo, derived from Humicola lanuginosa^{▲ R ▼}Enzymes (see also EP341,947) are preferred lipases for use in the present invention. Lipase and amylase variants stabilized against the peroxidase enzyme are described in Novo WO 9414951. See also WO 9205249 and RD94359044.
A cutinase enzyme suitable for use in the present invention is described in Genencor, WO 8809367A.
Peroxidase enzymes are used to “solution bleach” or to prevent migration of dyes or pigments that have fallen from the substrate during washing to other substrates present in the washing solution, such as peroxycarbonate, perborate, peroxygen. Used in combination with hydrogen oxide or the like. Known peroxidases include horseradish peroxidase, ligninase and haloperoxidases such as chloro or bromoperoxidase. Peroxidase-containing detergent compositions are disclosed in WO 89099813A dated 19 October 1989 and WO 8909813A from Novo.
Various enzyme substances and their means of incorporation into synthetic detergent compositions are also described in Genencor International, WO 9307263A and WO 9307260A, and McCarty et al. S. 3,553,139. Enzymes are further disclosed in U.S. Pat. No. 4,101,457 issued July 18, 1978 to Place et al. And U.S. Pat. No. 4,507,219 issued March 26, 1985 to Hughes. Enzymatic substances useful in liquid detergent formulations and their incorporation in such formulations are disclosed in US Pat. No. 4,261,868 issued Apr. 14, 1981 to Hora et al. Enzymes useful in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and illustrated in U.S. Pat. No. 3,600,319, August 17, 1971 to Gedge et al., Venegas, EP 199,405 and EP 200,586, Oct. 29, 1986. Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. A useful Bacillus sp. AC13 that produces proteases, xylanases and cellulases is described in Novo WO 9401532A.
Enzyme stabilization system-Although not limited, the enzyme-containing liquid composition provides about 0.001 to about 10% by weight of enzyme stabilization, preferably about 0.005 to about 8%, most preferably about 0.01 to about 6%. A system may be included. The enzyme stabilization system may be any stabilization system that is compatible with the washing enzyme. Such systems are either natively supplied by other prescription actives or added separately, for example by the formulator or manufacturer of the detergent enzyme. Such stabilization systems consist of, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof, and deal with different stabilization problems depending on the type and physical form of the detergent composition. Is considered to be.
One stabilization approach is the use of a water soluble calcium and / or magnesium ion source in the final composition, which supplies such ions to the enzyme. Calcium ions are usually slightly more effective than magnesium ions and are preferred in the present invention if only one type of cation is used. Typical detergent compositions, particularly liquids, are formulated with about 1 to about 30, preferably about 2 to about 20, more preferably about 8 to about 12 millimoles of calcium ions per liter of final detergent composition. Variations are possible depending on factors including enzyme diversity, type and level. Preferably, water-soluble calcium or magnesium salts including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate are used, more generally calcium sulfate or examples Magnesium salts corresponding to the formed calcium salts are used. Higher levels of calcium and / or magnesium are of course also useful, for example, in promoting the oil cut action of certain types of surfactants.
Another stabilization approach is through the use of borate species. See Severson U.S. Pat. No. 4,537,706. The borate stabilizer, when used, is at a level within 10% or more of the composition, but more typically at a level within about 3% by weight boric acid or other borate compounds such as borax or ortho Borate is suitable for liquid detergents. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid, etc. can also be used in place of boric acid, and the total boron level can be reduced in detergent compositions by using such substituted boron derivatives. It is.
Certain cleaning compositions, for example, automatic dishwashing composition stabilization systems, further comprise 0 to about 10% by weight, preferably about 0.01 to about 6%, of chlorine bleach scavengers, which can be used in many water supplies. Existing chlorine bleach species are added to prevent attack and inactivation of the enzyme, especially under alkaline conditions. The chlorine level in the water is typically as low as about 0.5 to about 1.75 ppm, but the available chlorine is relatively high in the total volume of water that comes into contact with the enzyme, for example during dish or fabric washing; Enzyme stability against chlorine during use is sometimes a problem. The use of additional stabilizers for chlorine is the most common because perborate or percarbonate with the ability to react with chlorine bleach is present in some of the compositions in amounts from sources other than the stabilizing system. Although not essential, improved results are obtained from their use. Suitable chlorine scavenger anions are widely known and readily available and, if used, include salts containing ammonium cations with sulfites, bisulfites, thiosulfites, thiosulfates, iodides, and the like. Antioxidants such as carbamates, ascorbates and the like, organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts, monoethanolamine (MEA) and mixtures thereof may be used as well. Similarly, special enzyme inhibition systems can be formulated so that different enzymes have maximum compatibility. Other conventional scavengers such as bisulfate, nitrate, chloride, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate and phosphates, condensed phosphates, acetates , Benzoates, citrates, formates, lactates, malates, tartrates, salicylic acids and the like and mixtures thereof can also be used if desired. In general, since the chlorine scavenger function can be exerted by a component (for example, a hydrogen peroxide source) separately listed under a well-recognized function, a compound that exhibits that function to a desired level is an enzyme-containing embodiment of the present invention. There is no absolute need to add another chlorine scavenger unless it is present; even then, the scavenger is added only for best results. In addition, if employed, the chemist's normal skill will be exercised in avoiding the use of enzyme scavengers or stabilizers that, if used, are highly incompatible with other reaction components when formulated. With respect to the use of ammonium salts, such salts can be simply mixed with detergent compositions, but are prone to adsorb water and / or liberate ammonia during storage. Thus, if present, such materials should be protected with particles as described in Baginski et al. US Pat. No. 4,652,392.
Bleaching compounds-bleach and bleach activators-The detergent composition may optionally contain a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. When present, the bleaching agent is particularly for fabric laundry, typically at a level of from about 1 to about 30%, more typically from about 5 to about 20% of the detergent composition. If present, the amount of bleach activator is typically from about 0.1 to about 60%, more typically from about 0.5 to about 40, of the bleaching composition containing the bleach + bleach activator. %.
The bleach used in the present invention may be any bleach useful in detergent compositions for textile cleaning, hard surface cleaning or other cleaning purposes now known or becoming known. These include enzyme bleach and other bleaching agents. Perborate bleaches such as sodium perborate (eg mono- or tetrahydrate) can be used in the present invention.
Another category of bleach that can be used without limitation is percarboxylic acid bleach and its salts. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxide decanedioic acid. Such bleaches are described in Hartman, U.S. Pat. No. 4,483,781, issued Nov. 20, 1984, and Burns et al., U.S. Pat. No. 740,446, filed Jun. 3, 1985. Banks et al., European Patent Application 0,133,354, published February 20, 1985, and Chung et al., US Pat. No. 4,412,934, issued Nov. 1, 1983. It is disclosed. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in Burns et al. US Pat. No. 4,634,551 issued Jan. 6, 1987. .
Peroxygen bleach can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and the corresponding “percarbonate” bleach, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (for example, OXONE, DuPont) can also be used.
Preferred carbonate bleaches consist of dry particles having an average particle size in the range of about 500 to about 1000 μm, wherein no more than about 10% by weight of the particles are less than about 200 μm and no more than about 10% by weight of the particles are greater than about 1250 μm. Optionally, the percarbonate can be coated with a silicate, borate or water soluble surfactant. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaches, perborates, percarbonates and the like are preferably mixed with the bleach activator to produce the peroxyacid corresponding to the bleach activator in-situ in the aqueous solution (ie during the cleaning process). Various non-limiting examples of activators are disclosed in US Pat. No. 4,915,854 and US Pat. No. 4,412,934 issued April 10, 1990 to Mao et al. Nonanoyloxybenzene sulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. Pat. No. 4,634,551 for other exemplary bleaches and activators useful in the present invention.
Highly preferred amide bleach activators are compounds of the formula:
R¹N (R⁵) C (O) R²C (O) L or
R¹C (O) N (R⁵) R²C (O) L
R in the above formula¹Is an alkyl group having from about 6 to about 12 carbon atoms and R²Is an alkylene having from 1 to about 6 carbon atoms and R⁵Is H, or alkyl, aryl or alkaryl having from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is a group that is released from a bleach activator as a result of a nucleophilic attack on the bleach activator by a perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formula include (6-octaneamidocaproyl) oxybenzene, as described in US Pat. No. 4,634,551, incorporated herein by reference. There are sulfonates, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamidocaproyl) oxybenzene sulfonate and mixtures thereof.
Another class of bleach activators is a benzoxazine disclosed in Hodge et al., US Pat. No. 4,966,723 issued Oct. 30, 1990, which is incorporated herein by reference. It consists of a type activator. Highly preferred activators of the benzoxazine type are:

Yet another class of preferred bleach activators include acyl lactam activators, particularly acyl caprolactams and acyl valerolactams of the formula:

R in the above formula⁶Is H or an alkyl, aryl, alkoxyaryl or alkaryl group having from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, deca There are noyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. Sanderson, U.S. Pat. No. 4,545,784, issued Oct. 8, 1985, which is incorporated herein by reference, discloses acylcaprolactam including benzoylcaprolactam adsorbed in sodium perborate. See also book.
Bleaching agents other than oxygen bleaching agents are known in the art and can be used in the present invention. One type of non-oxygen bleach of particular interest is a photoactivated bleach such as sulfonated zinc and / or aluminum phthalocyanine. See Holcombe et al., U.S. Pat. No. 4,033,718, issued July 5, 1977. If used, detergent compositions typically contain from about 0.025 to about 1.25% by weight of such bleaches, particularly sulfonated zinc phthalocyanines.
If desired, the bleaching compound can be catalyzed by a manganese compound. Such compounds are well known in the art, such as US Pat. No. 5,246,621, US Pat. No. 5,244,594, US Pat. No. 5,194,416, US Pat. And the manganese-based catalysts disclosed in EP 549,271 A1, 549,272 A1, 544,440 A2 and 544,490 A1. Preferred examples of these catalysts include
Mn^IV ₂(U-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂, Mn^III ₂(U-O)₁(U-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂, Mn^IV ₄(U-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^IIIMn^IV ₄(U-O)₁(U-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃, Mn^IV(1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH₃)₃(PF₆) And their mixtures. Other metal-based bleach catalysts include those disclosed in US Pat. No. 4,430,243 and US Pat. No. 5,114,611. Combinations of manganese and various complex ligands to enhance bleaching have also been reported in the following US patent specifications: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084
In practice, but not as a limitation, the compositions and processes of the present invention can be adjusted to provide at least about 0.1 ppm active bleach catalyst species in an aqueous wash liquor, preferably about 0.1 to 0.1 in a wash liquor. About 700 ppm, more preferably about 1 to about 500 ppm of catalyst species is provided.
The present compositions and methods for automated dishwashing applications may utilize a cobalt (III) bleach catalyst having the formula:
[Co (NH₃)_n(M)_m(B)_b] T_y
Where cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to cobalt at one site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to cobalt at two sites; b is 0 or 1 (preferably 0), and when b = 0, m + n = 6 and b M = 0 and n = 4 when = 1; T is one or more appropriately selected counter anions present in the number of y and y is an integer to obtain a charge balancing salt (preferably y is 1 to 3, most preferably 2 when T is a -1 charged anion); the catalyst is 0.23M^-1s^-1It has the following base hydrolysis rate constant (25 ° C.).
Preferred T is chloride, iodide, I₃ ⁻, Formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF₆ ⁻, BF₄ ⁻, B (Ph)₄ ⁻, Phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, two or more anionic groups are T, such as HPO₄ ^2-, HCO₃ ⁻, H₂PO₄ ⁻Etc. can be protonated if present. Further, T represents an anionic surfactant (eg, linear alkylbenzene sulfonate (LAS), alkyl sulfate (AS), alkyl ethoxy sulfonate (AES), etc.) and / or anionic polymer (eg, polyacrylate, polymethacrylate, etc.) Are selected from the group consisting of non-traditional inorganic anions.
For example, F part is F⁻, SO₄ ^2-, NCS⁻, SCN⁻, S₂O₃ ^2-, NH₃, PO₄ ^3-And carboxylates (preferably monocarboxylates, but as long as the bond to cobalt is only one carboxylate per moiety, more than one carboxylate may be present in that moiety, in which case Other carboxylates are protonated or in salt form at the M moiety), but are not limited thereto. In some cases, two or more anionic groups are M (eg, HPO₄ ^2-, HCO₃ ⁻, H₂PO₄ ⁻, HOC (O) CH₂M can be protonated if present in C (O) O- and the like. Preferred M moieties are substituted and unsubstituted C having the formula₁-C₃₀Carboxylic acid is:
RC (O) O-
In the above formula, R is preferably hydrogen and C₁-C₃₀(Preferably C₁-C₁₈) Unsubstituted and substituted alkyl, C₆-C₃₀(Preferably C₆-C₁₈) Unsubstituted and substituted aryl, C₃-C₃₀(Preferably C₅-C₁₈) Selected from the group consisting of unsubstituted and substituted heteroaryl, wherein the substituent is —NR ′₃, -NR '₄ ⁺, -C (O) OR ', -OR', -C (O) NR '₂R ′ is selected from the group consisting of hydrogen and C₁-C₆Selected from the group consisting of parts. Thus, such a substitution R has the moiety — (CH₂)_nOH and-(CH₂)_nNR '₄ ⁺N is an integer from 1 to about 16, preferably from about 2 to about 10, and most preferably from about 2 to about 5.
Most preferred M is that R is hydrogen, methyl, ethyl, propyl, linear or branched C₄-C₁₂A carboxylic acid having the above formula, selected from the group consisting of alkyl and benzyl. Most preferred M is methyl. Preferred carboxylic acid M moieties include formic acid, benzoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, malonic acid, maleic acid, succinic acid, adipic acid, phthalic acid, 2-ethylhexanoic acid, naphthenic acid, olein Acids, palmitic acid, triflate, tartrate, stearic acid, butyric acid, citric acid, acrylic acid, aspartic acid, fumaric acid, lauric acid, linoleic acid, lactic acid, malic acid and in particular acetic acid.
The B moiety includes carbonates, di and higher carboxylates (eg, oxalate, malonate, malate, succinate, maleate), picolinic acid, and α- and β-amino acids (eg, glycine, alanine, β-alanine, phenylalanine). There is.
Cobalt bleach catalysts useful in the present invention are known and are described in MLTobe, “Base Hydrolysis of Transition-Metal Complexes”, Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94, for example Listed with base hydrolysis rate. For example, Table 1 on page 17 shows oxalate (k_OH= 2.5 × 10^-4M^-1s^-1(25 ° C)), NCS⁻(K_OH= 5.0 × 10^-4M^-1s^-1(25 ° C)), formate (k_OH= 5.8 × 10^-4M^-1s^-1(25 ° C.)) and acetate (k_OH= 9.6 × 10^-4M^-1s^-1(25 ° C)) shows the base hydrolysis rate of the cobalt pentaamine catalyst complexed with_OHDisplayed as). Preferred cobalt catalysts useful in the present invention are those of the formula [Co (NH₃)₅OAc] T_y(OAc represents the acetate moiety), especially cobalt pentaamine acetate chloride [Co (NH₃)₅OAc] Cl₂(Hereinafter “PAC”) and [Co (NH₃)₅OAc] (OAc)₂,
[Co (NH₃)₅OAc] (PF₆)₂,
[Co (NH₃)₅OAc] (SO₄)and
[Co (NH₃)₅OAc] (BF₄)₂have.
These cobalt catalysts are described, for example, in the Tobe article and references cited therein, Diakun et al., U.S. Pat. No. 4,810,410, issued Mar. 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, WLJolly (Prentice-Hall; 1970), pp.461-3; Inorg.Chem., 18,1497-1502 (1979); Inorg.Chem ., 21,2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952). It is easily manufactured by a known operation as disclosed in the above.
These cobalt catalysts can be co-processed with auxiliary materials to reduce the aesthetic color impact of the product if desired, or the composition can be prepared to contain a catalyst “speckle”. Also good.
In practice, but not for limitation, the automatic dishwashing compositions and methods of the present invention can be adjusted to provide at least about 1 part / 10 million active cobalt catalyst species in an aqueous cleaning medium, preferably about 0. 1 to about 50 ppm, more preferably about 1 to about 25 ppm, and most preferably about 2 to about 10 ppm of cobalt catalyst species is provided to the cleaning liquid. In order to achieve such levels in the cleaning solution, a typical present composition contains from about 0.04 to about 1% by weight of the composition, more preferably from about 0.08 to about 0.36%.
builder-Detergent builders can optionally be included in the composition to help control mineral hardness. Inorganic and organic builders can be used. Builders are typically used in fabric laundry compositions to help remove particulate soil.
Builder levels vary widely depending on the end use of the composition and its desired physical form. When present, the composition typically contains at least about 1% builder. Liquid formulations typically comprise about 5 to about 50% by weight, more typically about 5 to about 30%, of a cleaning builder. Granule formulations typically comprise from about 10 to about 80% by weight, more typically from about 15 to about 50% detergent builder. However, lower or higher levels of builders are not meant to be excluded.
Inorganic or P-containing detergent builders include polyphosphates (exemplified by tripolyphosphates, pyrophosphates and glassy polymer metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminos There are, but are not limited to, alkali metal, ammonium and alkanol ammonium salts of silicates. However, phosphate-free builders are required in some regions. Importantly, the composition is surprising even in the presence of so-called “weak” builders (compared to phosphates) such as citrate, or even in the so-called “underbuild” situations that occur with zeolites or laminated silicate builders. It works well.
Examples of silicate builders are alkali metal silicates, especially SiO in the range 1.6: 1 to 3.2: 1.₂: Na₂Those having an O ratio are laminated silicates such as the laminated sodium silicate described in US Pat. No. 4,664,839 of H.P.Rieck, issued May 12, 1987. NaSKS-6 is a trade name for crystal laminated silicate sold by Hoechst (generally abbreviated herein as “SKS-6”). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 is δ-Na₂SiO₅It has a laminated silicate in the form. It can be produced by methods as described in Germany DE-A-3,417,649 and DE-A-3,742,043. While SKS-6 is a highly preferred laminated silicate for use in the present invention, other such laminated silicates such as the general formula NaMSi_xO_{2x + 1}・ YH₂Those having O (M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2 and y is a number from 0 to 20, preferably 0) can also be used in the present invention. . Various other laminated silicates by Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as α, β and γ forms. As above, δ-Na₂SiO₅(NaSkS-6 form) is most preferred for use in the present invention. Other silicates, such as magnesium silicate, that work as crispening agents in granule formulations, as stabilizers for oxygen bleaching, and as a component of the foam control system are also useful.
Examples of carbonate builders are alkaline earth and alkali metal carbonates as disclosed in German Patent Application 2,321,001 published November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are very important in most current commercial heavy granular detergent compositions and are also important builder ingredients in liquid detergent formulations. Some aluminosilicate builders have the following empirical formula:
M_z[(ZAlO₂)_y] XH₂O
Wherein z and y are integers of at least 6, the molar ratio of z to y ranges from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure, and may be natural aluminosilicate or synthesized. A method for producing an aluminosilicate ion exchange material is disclosed in U.S. Pat. No. 3,985,669 issued to Krummel et al. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are commercially available under the names zeolite A, zeolite P (B), zeolite MAP and zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Na₁₂[(AlO₂)₁₂(SiO₂)₁₂] XH₂O
In the above formula, x is about 20 to about 30, especially about 27. This material is known as zeolite A. Dehydrated zeolite (x = 0-10) can also be used in the present invention. Preferably, the aluminosilicate has a particle size of about 0.1 to 10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, various polycarboxylate compounds. As used herein, “polycarboxylate” refers to a compound having a number of carboxylate groups, preferably at least three carboxylates. The polycarboxylate builder is usually added to the composition in the acid form, but may be added in the form of a neutralized salt. When utilized in salt form, alkali metals such as sodium, potassium and lithium, or alkanol ammonium salts are preferred.
Among the polycarboxylate builders are various categories of useful substances. One important category of polycarboxylate builders includes Berg's US Pat. No. 3,128,287 issued April 7, 1964 and Lamberti et al. US Patent issued January 18, 1972. Ether polycarboxylates including oxydisuccinates as disclosed in US Pat. No. 3,635,830. See also the “TMS / TDS” builder in US Pat. No. 4,663,071, issued May 5, 1987 to Bush et al. Suitable ether polycarboxylates include U.S. Pat. Nos. 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903. Also included are cyclic compounds, particularly alicyclic compounds, as described in the specification.
Other useful detergency builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxy Methyloxysuccinic acid and various alkali metal, ammonium and substituted ammonium salts of polyacetic acid such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, merit acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5 There are polycarboxylates such as tricarboxylic acids, carboxymethyloxysuccinic acid and their soluble salts.
Citrate builders such as citric acid and its soluble salts (especially sodium salts) are polycarboxylate builders of particular importance in heavy liquid detergent formulations because of their availability from regenerative sources and their biodegradability. is there. Citrate can also be used in granule compositions, especially in combination with zeolites and / or laminated silicate builders. Oxydisuccinate is also particularly useful in such compositions and combinations.
The detergent composition of the present invention contains 3,3-dicarboxy-4-oxa-1,6-dissociated in US Pat. No. 4,566,984 issued on January 28, 1986 to Bush. Hexanedioates and related compounds are also suitable. Useful succinic acid builders include C₅-C₂₀There are alkyl and alkenyl succinic acids and their salts. A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinate is a preferred builder of this group and is described in European Patent Application No. 86200690.5 / 0,200,263, published November 5, 1986.
Other suitable polycarboxylates are Crutchfield et al., U.S. Pat. No. 4,144,226, issued March 13, 1979, and Diehl, U.S. Pat. No. 3,308, issued March 7, 1967. No. 067. See also Diehl U.S. Pat. No. 3,723,322.
Fatty acids such as C₁₂-C₁₈Monocarboxylic acids can also be incorporated into the composition alone or in combination with the builder, particularly citrate and / or succinate builder, to provide additional builder activity. Since such use of fatty acids usually causes a reduction in foamability, this should be considered by the vendor.
Various alkali metal phosphates such as the well known sodium polyphosphate, sodium pyrophosphate and sodium orthophosphate can be used in situations where phosphorus-based builders can be used, particularly in solid product formulations used in hand washing operations. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (eg, US Pat. Nos. 3,159,581, 3,213,030, 3,422,021) 3,400,148 and 3,422,137) can also be used.
Polymer soil release agent-Known polymer soil release agents, hereinafter "SRA" can optionally be used in the detergent composition. If utilized, the SRA is usually 0.01 to about 10.0% by weight of the composition, typically 0.1 to about 5%, preferably 0.2 to about 3.0%.
Preferred SRAs typically adhere to the hydrophilic segments that hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and remain attached to the hydrophobic fibers until the end of the wash and rinse cycle. And thus have a hydrophobic segment that acts as an anchor for the hydrophilic segment. Thereby, the stain | pollution | contamination which arises after SRA process can be cleaned more easily by subsequent washing operation.
SRA has a variety of charged, for example, anionic or cationic species (see Gosselink et al. US Pat. No. 4,956,447 issued September 11, 1990) and uncharged monomeric units, The structure can be linear, branched or even star-shaped. They may also contain capping moieties that are particularly effective in controlling molecular weight or altering physical or surfactant properties. The structure and charge distribution are tailored for different fiber or textile types and for various detergents or detergent additive products.
Preferred SRAs are oligomeric terephthalate esters that are typically made by a process consisting of at least one transesterification / oligomerization with a metal catalyst, often a titanium (IV) alkoxide. Such esters may of course be made with additional monomers that can be incorporated into the ester structure at 1, 2, 3, 4 or more positions without forming a tightly cross-linked overall structure.
Suitable SRAs include, for example, oligomeric ester backbones of terephthaloyl and oxyalkyleneoxy repeating units as described in JJ Scheibel and EP Gosselink US Pat. No. 4,968,451 dated 6 November 1990. And sulfonated products of substantially linear ester oligomers composed of allyl-derived sulfonated end moieties covalently bonded to the backbone. Such ester oligomers are: (a) ethoxylation of allyl alcohol, (b) two-stage transesterification of the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) / It can be produced by reacting with an oligomerization operation and reacting the products of (c) and (b) with sodium metabisulfite in water. Other SRAs include nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters such as poly (ethylene glycol) methyl ether of US Pat. No. 4,711,730 issued Dec. 8, 1987 to Gosselink et al. Some are made by transesterification / oligomerization of DMT, PG and poly (ethylene glycol) ("PEG"). Other examples of SRA include Gosselink's US patent dated January 26, 1988, such as ethylene glycol ("EG"), PG, DMT and oligomers from sodium 3,6-dioxa-8-hydroxyoctanesulfonate. No. 4,721,580 and fully anionic end-capped oligomeric esters; such as DMT, methyl (Me) -capped PEG and EG and / or PG, or DMT, EG and / or PG, Me-capped PEG and Nonionic end-capped block polyester oligomer compound of Gosselink, U.S. Pat. No. 4,702,857, Oct. 27, 1987, made from the combination of sodium dimethyl-5-sulfoisophthalate; Maldonado, Oct. 31, 1989; US Pat. No. 4,877,896 to Gosselink et al. Anionic, particularly sulfoaroyl end-capped terephthalate esters, the latter being typical of SRA useful in both laundry and fabric conditioning products, examples made from monosodium m-sulfobenzoate, PG and DMT An ester composition, optionally but preferably further comprising added PEG, eg PEG 3400.
SRA includes simple copolymer blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate (Hays US Pat. No. 3,959,230 dated May 25, 1976 and Basadur US patent dated July 8, 1975). No. 3,893,929); cellulosic derivatives such as hydroxy ether cellulosic polymers commercially available as METHOCEL from Dow; C₁-C₄Alkylcellulose and C₄Hydroxyalkyl cellulose (see Nicol et al., US Pat. No. 4,000,093, Dec. 28, 1976); an average degree of substitution (methyl) of about 1.6 to about 2.3 per anhydroglucose unit; Some methyl cellulose ethers have a solution viscosity of about 80 to about 120 centipoise when measured as a 2% aqueous solution at 20 ° C. Such materials are commercially available as METALOSE SM100 and METALOSE SM200, which are trade names of methyl cellulose ethers manufactured by Shin-Etsu Chemical KK.
Suitable SRAs characterized by poly (vinyl ester) hydrophobic segments include poly (vinyl esters), such as C, grafted to the polyalkylene oxide backbone.₁-C₆There are graft copolymers of vinyl esters, preferably poly (vinyl acetate). See European Patent Application No. 0,219,048, issued April 22, 1987 to Kud et al. Commercial examples include SOKALAN SRA such as SOKALAN HP-22 available from BASF, Germany. The other SRA is a polyester composed of repeating units containing 10 to 15% by weight of ethylene terephthalate and 80 to 90% by weight of polyoxyethylene terephthalate derived from polyoxyethylene glycol having an average molecular weight of 300 to 5000. Commercial examples include Dupont's ZELCON 5126 and ICI's MILEASE T.
Another preferred SRA is the empirical formula (CAP)₂(EG / PG)₅(T)₅(SIP)₁Having terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG) units, preferably end caps (CAP), preferably Ends with a modified isethionate and, in the oligomer, oxyethyleneoxy and oxy-oxy in one sulfoisophthaloyl unit, five terephthaloyl units, in a defined ratio, preferably about 0.5: 1 to about 10: 1. It consists of 1,2-propyleneoxy units and two end cap units derived from sodium 2- (2-hydroxyethoxy) ethanesulfonate. The SRA is preferably 0.5 to 20% by weight of oligomeric crystallinity reducing stabilizer, for example anionic surfactants such as linear sodium dodecylbenzenesulfonate, or xylene-, cumene- and toluene-sulfonates. Or a member selected from a mixture thereof, these stabilizers or modifiers being introduced into the synthesis vessel, all of which were issued on May 16, 1995 in the United States of Gosselink, Pan, Kellett & Hall This is disclosed in Japanese Patent No. 5,415,807. Suitable monomers for the SRA include sodium 2- (2-hydroxyethoxy) ethanesulfonate, DMT, sodium dimethyl-5-sulfoisophthalate, EG and PG.
Yet another group of preferred SRAs is (1) (a) dihydroxy sulfonates, polyhydroxy sulfonates, units that are at least trifunctional and become branched oligomer backbones when ester bonds are formed, and their At least one unit selected from the group consisting of combinations; (b) at least one unit that is a terephthaloyl moiety; and (c) at least one unsulfonated unit that is a 1,2-oxyalkyleneoxy moiety. (2) alkoxylated, preferably ethoxylated isethionate, alkoxylated propane sulfonate, alkoxylated propane disulfonate, alkoxylated phenol sulfonate, nonionic capping units such as sulfoaroyl derivatives, anionic capping units And those An oligomeric ester comprising one or more capped units selected from a mixture. Esters of the following empirical formula are preferred:
[(CAP)_x(EG / PG)_{y '}(DEG)_{y ″}(PEG)_{y ″ ′}
(T)_z(SIP)_{z '}(SEG)_q(B)_m]
In the above formula, CAP, EG / PG, PEG, T and SIP are as described above, (DEG) represents a di (oxyethylene) oxy unit, and (SEG) is derived from glycerin and sulfoethyl ether of a related partial unit. (B) represents a branched unit that is at least trifunctional and becomes a branched oligomer backbone when an ester bond is formed, x is from about 1 to about 12, y 'Is from about 0.5 to about 25, y "is from 0 to about 12, y"' is from 0 to about 10, and y '+ y "+ y"' is about 0.5 to about 25 in total. Z is from about 1.5 to about 25, z 'is from 0 to about 12, z + z' is about 1.5 to about 25 in total, and q is from about 0.05 to about 12. M is from about 0.01 to about 10, and x, y ′, y ″, y ″ ′, z, z ′, q and m are Represents the average number of moles per mole corresponding unit of serial ester, said ester has a molecular weight of from about 500 to about 5000 range.
Preferred SEG and CAP monomers of the ester are sodium 2- (2,3-dihydroxypropoxy) ethane sulfonate ("SEG"), sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethane sulfonate ("SE3 "), Its homologues and mixtures thereof, and the products of ethoxylation and sulfonation of allyl alcohol. Preferred SRA esters in this class include sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate and / or 2- [2- [2- (2- (2-)] with an appropriate Ti (IV) catalyst. Hydroxyethoxy) ethoxy] ethoxy] sodium ethanesulfonate, DMT, 2- (2,3-dihydroxypropoxy) ethane sulfonate sodium, EG and PG are transesterified and oligomerized products (CAP)₂(T)₅(EG / PG)_1.4(SEG)_2.5(B)_0.13Where CAP is (Na + O₃S [CH₂CH₂O]_3.5)-, B is a unit from glycerin, and the EG / PG molar ratio is about 1.7: 1 as measured by conventional gas chromatography after complete hydrolysis.
Additional classes of SRA include (I) nonionic terephthalates using diisocyanate coupling agents to link polymer ester structures (US Pat. No. 4,201,824 to Violland et al. And US Pat. 240,918); and (II) SRA with carboxylate end groups, made by adding trimellitic anhydride to known SRAs to convert terminal hydroxyl groups to trimellitate esters. is there. With the proper choice of catalyst, trimellitic anhydride forms a bond at the end of the polymer from the ester of the isolated carboxylic acid of trimellitic anhydride rather than by cleavage of the anhydride bond. Either nonionic or anionic SRAs may be used as starting materials as long as they have hydroxyl end groups that may be esterified. See U.S. Pat. No. 4,525,524 to Tung et al. Other classes included (III) urethane-linked anionic terephthalate-based SRA (see US Pat. No. 4,201,824 to Violland et al.); (IV) both nonionic and cationic polymers. Poly (vinyl caprolactam) and related copolymers with monomers such as vinylpyrrolidone and / or dimethylaminoethyl methacrylate (see Ruppert et al US Pat. No. 4,579,681); (V) acrylic monomers to sulfone There are graft copolymers other than BASF's SOKALAN type made by grafting onto a modified polyester. These SRAs certainly have a soil release and anti-redeposition activity similar to known cellulose ethers (see Rhone-Poulenc Chemie 1988 EP279, 134A). Yet another class includes (VI) grafting of vinyl monomers such as acrylic acid and vinyl acetate onto proteins such as casein (see EP457, 205A of BASF (1991)); and (VII) especially polyamide fabrics. For processing, there is a polyester-polyamide SRA made by condensing adipic acid, caprolactam and polyethylene glycol (see DE 2,335,044 of Unilever NV, 1974). Other useful SRAs are described in US Pat. Nos. 4,240,918, 4,787,989 and 4,525,524.
Chelating agent-The detergent composition may optionally also contain one or more iron and / or manganese chelators. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, multifunctional substituted aromatic chelating agents and mixtures thereof, all as described below. Without being bound by theory, it is believed that the effects of these materials are due in part to their exceptional ability to remove iron and manganese ions from the wash liquor through the formation of soluble chelates.
Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, ethanoldiglycine, etc. Alkali metal, ammonium, substituted ammonium salts, and mixtures thereof.
Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are tolerated in the detergent composition and include ethylenediaminetetrakis (methylenephosphonates) such as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups of about 7 or more carbon atoms.
Multifunctional substituted aromatic chelating agents are also useful in the present compositions. See Connor et al., US Pat. No. 3,812,044, issued May 21, 1974. A preferred compound of this type is dihydroxydisulfobenzene such as 1,2-dihydroxy-3,5-disulfobenzene in the acid form.
Preferred biodegradable chelators for use in the present invention include ethylenediamine disuccinate ("EDDS") as described in US Pat. No. 4,704,233 to Hartman and Perkins dated November 3, 1987, particularly [S, S] isomer.
If utilized, these chelating agents are usually about 0.1 to about 10% by weight of the detergent composition. More preferably, if utilized, the chelating agent is about 0.1 to about 3.0% by weight of such composition.
Soil removal / anti-redeposition agent-The composition according to the invention can optionally also contain water-soluble ethoxylated amines having soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01 to about 10.0% by weight of a water soluble ethoxylated amine, and liquid detergent compositions typically contain about 0.01. Contains ~ 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in US Pat. No. 4,597,898 to VanderMeer, issued July 1, 1986. Another group of preferred soil removal-antiredeposition agents are the cationic compounds disclosed in Oh and Gosselink, European Patent Application No. 111,965, published June 27, 1984. Other soil removal / anti-redeposition agents that can be used include ethoxylated amine polymers disclosed in Gosselink European Patent Application No. 111,984, published June 27, 1984, July 1984. Bipolar polymer disclosed in Gosselink European Patent Application No. 112,592, published on date 4, Connor, U.S. Pat. No. 4,548,744 issued Oct. 22, 1985 There are disclosed amine oxides. Other soil removal and / or anti-redeposition agents known in the art can also be utilized in the present compositions. Another type of preferred anti-redeposition agent is carboxymethylcellulose (CMC) material. These materials are well known in the art.
Polymer dispersant-The polymeric dispersant may be advantageously utilized at a level of about 0.1 to about 7 wt% in the composition, particularly in the presence of zeolite and / or laminated silicate builder. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, but others known in the art can also be used. While not intending to be bound by theory, the polymer dispersants can be used when combined with other builders (including low molecular weight polycarboxylates) due to crystal growth inhibition, particulate soil release peptization and anti-redeposition. It is thought to improve the performance of detergent builder.
Polymeric polycarboxylate materials can be made by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid There is. The presence in the polymer polycarboxylate of monomer segments free of carboxylate groups such as vinyl methyl ether, styrene, ethylene, etc. in the present polymer polycarboxylate is appropriate if such segments do not account for more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably in the range of about 2000 to 10,000, more preferably about 4000 to 7000, and most preferably about 4000 to 5000. Such water-soluble salts of acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts. This type of soluble polymer is a known substance. The use of this type of polyacrylate in detergent compositions is disclosed, for example, in US Pat. No. 3,308,067 issued to Diehl, issued March 7, 1967.
Acrylic acid / maleic acid based copolymers may also be used as a preferred component of the dispersion / redeposition inhibitor. Such materials include water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form is preferably in the range of about 2000 to 100,000, more preferably about 5000 to 75,000, and most preferably about 7000 to 65,000. The ratio of acrylate to maleate segment in such copolymers is usually in the range of about 30: 1 to about 1: 1, more preferably about 10: 1 to 2: 1. Such water-soluble salts of acrylic acid / maleic acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. This type of soluble acrylate / maleate copolymer is a known material described in European Patent Application No. 66915 published on Dec. 15, 1982, EP No. published on Sep. 3, 1986. 193,360 also describes such polymers containing hydroxypropyl acrylate. Yet another useful dispersant is a maleic acid / acrylic acid / vinyl alcohol terpolymer. Such materials are also disclosed in EP 193,360, including for example 45/45/10 terpolymers of acrylic acid / maleic acid / vinyl alcohol.
Another polymeric material that can be included is polyethylene glycol (PEG). PEG exhibits dispersant performance and can act as a soil removal / re-deposition inhibitor. Typical molecular weight ranges for these purposes are in the range of about 500 to about 100,000, preferably about 1000 to about 50,000, more preferably about 1500 to about 10,000.
Polyaspartate and polyglutamate dispersants can also be used, particularly in combination with zeolite builders. Dispersants such as polyaspartate preferably have a molecular weight (average) of about 10,000.
BrightenerAny optical brightener known in the art, or other whitening or whitening agent, can be incorporated into the detergent composition, typically at a level of about 0.01 to about 1.2% by weight. Commercially available optical brighteners useful in the present invention include, but are not necessarily limited to, stilbenes, pyrazolines, coumarins, carboxylic acids, methicyanines, dibenzothiophene-5,5-dioxides, azoles, 5- and 6-membered heterocyclic heterocycles It can be divided into subgroups including derivatives of various other substances. Examples of such brighteners are disclosed in “The Production and Application of Fluorescent Brightening Agents”, published by M. Zahradnik, John Wiley & Sons, New York (1982).
Specific examples of optical brighteners useful in the present composition are those disclosed in Wixon, U.S. Pat. No. 4,790,856, issued Dec. 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include Ciba-Geigy commercially available Tinopal UNPA, Tinopal CBS and Tinopal 5BM; Artic White CC and Artic White CWD; 2- (4-styrylphenyl) -2H-naphthol [ 1,2-d] triazoles; 4,4′-bis (1,2,3-triazol-2-yl) stilbenes; 4,4′-bis (styryl) bisphenyls; aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin, 1,2-bis (benzimidazol-2-yl) ethylene, 1,3-diphenylpyrazolines, 2,5-bis (benzo There are oxazol-2-yl) thiophene, 2-styrylnaphtho [1,2-d] oxazole and 2- (stilben-4-yl) -2H-naphtho [1,2-d] triazole. See also Hamilton U.S. Pat. No. 3,646,015, issued February 29,1972.
Antifoaming agent-Compounds that reduce or inhibit foam formation can also be incorporated into the compositions of the present invention. Foam suppression is a so-called “high concentration cleaning process” as described in US Pat. Nos. 4,489,455 and 4,489,574, and in front loading European style washing machines. Of particular importance.
A variety of materials can be used as foam inhibitors, and foam inhibitors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of foam inhibitors of particular interest is monocarboxylic fatty acids and their soluble salts. See Wayne St. John, U.S. Pat. No. 2,954,347, issued September 27, 1960. Monocarboxylic fatty acids and salts thereof used as suds suppressors typically have a hydrocarbyl chain of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts and ammonium and alkanol ammonium salts.
The detergent composition may also contain a non-surfactant foam inhibitor. These include high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C₁₈-C₄₀There are ketones (eg stearons) and the like. Other antifoaming agents include tri-hexaalkylmelamine or di-tetraalkyldiamine chloride formed as a product of cyanuric chloride and 2 or 3 moles of primary or secondary amines having 1 to 24 carbon atoms. There are N-alkylated aminotriazines such as triazines, propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate esters and monostearyl dialkali metal (eg K, Na and Li) phosphates and phosphate esters. Hydrocarbons such as paraffin and haloparaffin are available in liquid form. Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, and have a pour point in the range of about -40 to about 50 ° C and a minimum boiling point (atmospheric pressure) of about 110 ° C or higher. It is also known to utilize waxy hydrocarbons preferably having a melting point of about 100 ° C. or less. Hydrocarbons are a preferred category of foam control agents for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Pat. No. 4,265,779 issued to Gandolfo et al., Issued May 5, 1981. The hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term “paraffin” used in the description of the foam control agent is meant to include a mixture of true paraffin and cyclic hydrocarbons.
Another preferred category of non-surfactant foam inhibitors is silicone foam inhibitors. This category includes polyorganosiloxane oils such as polydimethylsiloxane, polyorganosiloxane oil or resin dispersions or emulsions, and polyorganosiloxanes and silica particles in which the polyorganosiloxane is chemisorbed or melted onto silica. Including the use of combinations. Silicone suds suppressors are well known in the art, for example, Gandolfo et al., U.S. Pat. No. 4,265,779 issued May 5, 1981 and Starch, MS, published Feb. 7, 1990. European Patent Application No. 89307851.9.
Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by incorporating small amounts of polydimethylsiloxane fluid. .
Mixtures of silicone and silanized silica are described, for example, in German patent application DOS 2,124,526. Silicone antifoams and antifoaming agents in granular detergent compositions are described in Bartolotta et al. US Pat. No. 3,933,672 and Baginski et al. US Pat. No. 4,652,392 issued on Mar. 24, 1987. It is disclosed in the specification.
Exemplary silicone-based antifoaming agents useful in the present invention are:
(I) a polydimethylsiloxane fluid having a viscosity of about 20 to about 1500 cs at 25 ° C.
(Ii) about 0.6: 1 to about 1.2: 1 (CH₃)₃SiO_1/2Unit vs. SiO₂SiO in unit ratio₂Unit (CH₃)₃SiO_1/2About 5 to about 50 parts by weight of siloxane resin composed of units / 100 parts of (i), and
(Iii) about 1 to about 20 parts by weight of solid silica gel / (i) 100 parts
Is a foam suppression agent consisting essentially of a foam suppression amount.
In the preferred silicone suds suppressor used in the present invention, the solvent for the continuous phase is composed of certain polyethylene glycols, polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched / crosslinked and is preferably not linear.
To further illustrate this point, typical liquid laundry detergent compositions that suppress foaming are about 0.001 to about 1, preferably about 0.01 to about 0.7, most preferably about 0.05 to Optionally containing about 0.5% by weight of said silicone foam inhibitor, comprising (1) (a) a polyorganosiloxane, (b) a resin siloxane or a silicone resin-forming silicone compound, (c) a fine filler material, and (D) a non-aqueous emulsion of a main antifoam, which is a mixture of catalysts for promoting the reaction of mixture components (a), (b) and (c) to form silanolates; (2) at least one A nonionic silicone surfactant; and (3) a polyethylene glycol or polyethylene-polypropylene glycol copolymer having a solubility in water of about 2% by weight or more at room temperature. However, polypropylene glycol is not included. Similar amounts can be used in granule compositions, gels and the like. Starch US Patent No. 4,978,471 issued December 18, 1990, Starch No. 4,983,316 issued January 8, 1991, issued February 22, 1994 Huber et al., 5,288,431, Aizawa et al., U.S. Pat. Nos. 4,639,489 and 4,749,740, column 1, line 46 to column 4, line 35. reference.
The silicone antifoaming agents preferably include polyethylene glycol and polyethylene glycol / polypropylene glycol copolymers, all having an average molecular weight of about 1000 or less, preferably about 100-800. The polyethylene glycols and polyethylene / polypropylene copolymers of the present invention have a water solubility at room temperature of about 2% or more, preferably about 5% or more.
A preferred solvent in the present invention is a copolymer of polyethylene glycol having an average molecular weight of about 1000 or less, more preferably about 100 to 800, most preferably 200 to 400, and polyethylene glycol / polypropylene glycol, preferably PPG200 / PEG300. A weight ratio of polyethylene glycol: polyethylene-polypropylene glycol copolymer of about 1: 1 to 1:10, most preferably 1: 3 to 1: 6 is preferred.
The preferred silicone foam inhibitor used in the present invention does not contain polypropylene glycol having a molecular weight of 4000. They preferably do not contain block copolymers of ethylene oxide and propylene oxide as PLURONIC L101.
Other foam control agents useful in the present invention include secondary alcohols (eg, 2-alkylalkanols), and such alcohols and silicone oils, such as US Pat. Nos. 4,798,679, 4,075. 118 and EP 150,872 are mixtures with silicones. C for secondary alcohol₁-C₁₆C with chain₆-C₁₆There are alkyl alcohols. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. A mixture of secondary alcohols is available from Enichem under the trade name ISALCHEM 123. The mixed foam inhibitor typically consists of a mixture of alcohol + silicone in a weight ratio of 1: 5 to 5: 1.
In any detergent composition used in an automatic washing machine, foam should not occur so much that it overflows from the washing machine. If used, the antifoaming agent is preferably present in an antifoaming amount. “Foam suppression amount” means that the composition supplier can select the amount of the foam suppressor that sufficiently suppresses foaming so that it becomes a low-foaming laundry detergent in an automatic washing machine. Means.
The composition usually contains 0 to about 5% foam inhibitor. When utilized as a foam inhibitor, monocarboxylic fatty acids and salts thereof are typically present in an amount within about 5% by weight of the detergent composition. Preferably about 0.5 to about 3% of a fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to about 2.0% by weight of the detergent composition, but may be used in higher amounts. This upper limit is practical in nature, primarily in view of the interest in minimizing costs and the effectiveness of lower amounts in effectively suppressing foaming. Preferably from about 0.01 to about 1%, more preferably from about 0.25 to about 0.5% silicone foam inhibitor is used. These weight percent values used in the present invention include any silica utilized in combination with the polyorganosiloxane and any auxiliary material utilized. Monostearyl phosphate suds suppressors are typically utilized in an amount within the range of about 0.1 to about 2% by weight of the composition. The hydrocarbon suds suppressor is typically utilized in an amount in the range of about 0.01 to about 5.0%, although higher levels can be used. Alcohol suds suppressors are typically used at 0.2 to 3% by weight of the final composition.
Fabric softener-Various through-the-wash fabric softeners, especially the fine smectite clays of Storm and Nirschl US Pat. No. 4,062,647 issued December 13, 1977, and other softeners known in the art The agent clay can be optionally used, typically at a level of from about 0.5 to about 10% by weight in the composition to provide a fabric softener effect with fabric cleaning. Clay softeners are described in, for example, Crisp et al., US Pat. No. 4,375,416, issued March 1, 1983, and Harris et al., US Pat. No. 4,291,071, issued September 22, 1981. Can be used in combination with amines and cationic softeners as disclosed in the specification.
Dye transfer inhibitorThe composition of the present invention may also contain one or more substances effective to prevent migration of dye from one fabric to another during the cleaning process. Typically, such dye transfer inhibitors include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase and mixtures thereof. If used, these agents are typically about 0.01 to about 10% by weight of the composition, preferably about 0.01 to about 5%, more preferably about 0.05 to about 2%. .
More specifically, the polyamine N-oxide polymer preferred for use in the present invention is represented by the following structural formula: R—A_xIncluding units having —P, wherein P is a polymerizable unit, to which an N—O group can be attached, or an N—O group can form part of the polymerizable unit; Or an N—O group can be attached to both units; A is one of the following structures: —NC (O) —, —C (O) O—, —S—, —O—, —N═ X is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group, or a combination thereof, to which a nitrogen of the N—O group can be attached. Or the N—O group is part of these groups. Preferred polyamine N-oxides are those where R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N—O group can be represented by the following general structure:

R in the above formula₁, R₂, R₃Is an aliphatic group, aromatic, heterocyclic or alicyclic group, or a combination thereof, x, y and z are 0 or 1, and the nitrogen of the N—O group is bonded or A part of either can be formed. The amine oxide unit of the polyamine N-oxide has a pKa <10, preferably pKa <7, more preferably pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. Amine N-oxide polymers typically have a ratio of amine to amine N-oxide of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or with an appropriate degree of N-oxidation. Polyamine oxide can be obtained at almost any degree of polymerization. Typically, the average molecular weight is in the range of 500 to 1,000,000, more preferably 1000 to 500,000, most preferably 5000 to 100,000. This preferred class of materials is referred to as “PVNO”.
The most preferred polyamine N-oxide useful in the present detergent composition is poly (4-vinylpyridine-N-oxide) having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4. is there.
Also preferred for use in the present invention are copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as the “PVPVI” class). Preferably, the PVPVI has an average molecular weight range of 5000 to 1,000,000, more preferably 5000 to 200,000, most preferably 10,000 to 20,000 (the average molecular weight range is Barth, et al ., Chemical Analysis, Vol. 113, “Modern Methods of Polymer Characterization”, as determined by light scattering methods, the disclosure of which is incorporated herein by reference). PVPVI copolymers typically have an N- of 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1. It has a molar ratio of vinylimidazole to N-bilylpyrrolidone. These copolymers are linear or branched.
The composition of the present invention also uses polyvinylpyrrolidone ("PVP") having an average molecular weight of about 5000 to about 400,000, preferably about 5000 to about 200,000, more preferably about 5000 to about 50,000. Can do. PVP is known to those skilled in the detergent art; see for example EP-A-262,897 and EP-A-256,696, which are incorporated herein by reference. A composition containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of about 500 to about 100,000, preferably about 1000 to about 10,000. Preferably, the ratio of PEG to PVP delivered in the wash solution is from about 2: 1 to about 50: 1, more preferably from about 3: 1 to about 10: 1, on a ppm basis.
The detergent composition can optionally contain from about 0.005 to 5% by weight of a type of hydrophilic fluorescent whitening agent that also exhibits dye migration inhibition. If used, the composition preferably comprises about 0.01 to 1% by weight of such optical brightener.
The hydrophilic optical brightener useful in the present invention is a compound having the following structural formula:

R in the above formula₁Is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂Is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; M is a salt-forming cation such as sodium or potassium.
R in the above formula₁Anilino, R₂When N is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4′-bis [[4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl] amino] -2,2'-stilbene disulfonic acid and disodium salt. This specific brightener species is commercially available from Ciba-Gaigy Corporation under the trade name Tinopal-UNPA-GX. Tinopal-UNPA-GX is a preferred hydrophilic optical brightener useful in the present detergent compositions.
R in the above formula₁Anilino, R₂When N is 2-N-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis [[4-anilino-6- (N-2- Hydroxyethyl-N-methylamino) -s-triazin-2-yl] amino] -2,2'-stilbene disulfonic acid disodium salt. This specific brightener species is commercially available from Ciba-Gaigy Corporation under the trade name Tinopal 5BM-GX.
R in the above formula₁Anilino, R₂Is a morpholino and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] -2,2 ' -Stilbene disulfonic acid, sodium salt. This specific brightener species is commercially available from Ciba-Geigy Corporation under the trade name Tinopal AMS-GX.
Certain fluorescent brightener species selected for use in the present invention exhibit particularly effective dye migration inhibition performance when used in combination with the selected polymeric dye migration inhibitors. Such selected polymeric materials (eg PVNO and / or PVPVI) and such selected optical brighteners (eg Tinopal-UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) The combination exhibits significantly better dye transfer inhibition in the aqueous cleaning solution than when these two detergent composition components are used alone. Without being bound by theory, it is believed that such brighteners work this way because they have a high affinity for fabrics in the wash liquor and thus adhere relatively quickly to these fabrics. The degree to which the whitening agent adheres to the fabric in the cleaning liquid can be defined by a parameter called “exhaustion coefficient”. The exhaustion coefficient is generally the ratio of a) the brightener substance adhering to the fabric to b) the initial brightener concentration in the cleaning solution. A brightener with a relatively high exhaustion coefficient is most suitable for preventing dye migration in the context of the present invention.
Of course, it is clear that other conventional optical brightener-type compounds can optionally be used in the present compositions to produce a conventional fabric “shine” effect rather than a true dye transfer inhibiting effect. Let's go. Such usage is conventional and well known in detergent formulations.
pH and buffer variations
Many automatic dishwashing detergent compositions in the present invention are buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions have exceptionally low buffering capacity or are not substantially buffered. Techniques for controlling or changing the pH to the recommended use level more generally include the use of additional alkalis, acids, pH jump systems, double compartment vessels, etc., as well as buffers, well known to those skilled in the art. It is.
A preferred ADD composition in the present invention includes a pH adjusting component selected from a water-soluble alkali inorganic salt and a water-soluble organic or inorganic builder. The pH adjusting component is selected such that the pH is in the range of about 8 or higher, preferably about 9.5 to about 11, when ADD is dissolved in water at a concentration of 1000 to 5000 ppm. Preferred non-phosphate pH adjusting components of the present invention are:
(I) Sodium carbonate or sesquicarbonate
(Ii) sodium silicate, preferably about 1: 1 to about 2: 1 SiO₂: Na₂Hydrated sodium silicate having an O ratio and mixtures thereof with limited amounts of sodium metasilicate
(Iii) Sodium citrate
(Iv) Citric acid
(V) Sodium bicarbonate
(Vi) Sodium borate, preferably borax
(Vii) sodium hydroxide, and
(Viii) A mixture of (i) to (vii)
Selected from the group consisting of
In a preferred embodiment, low levels of silicate (ie, about 3 to about 10% SiO₂).
Examples of highly preferred pH-adjusting component systems include binary mixtures of granular sodium citrate and anhydrous sodium carbonate, granular sodium citrate trihydrate, ternary mixture of citric acid monohydrate and anhydrous sodium carbonate. is there.
The amount of pH adjusting component in the ADD composition is preferably from about 1 to about 50% by weight of the composition. In a preferred embodiment, the pH adjusting component is present in the ADD composition in an amount of about 5 to about 40% by weight, preferably about 10 to about 30%.
For the present compositions having a pH of from about 9.5 to about 11 in the initial wash solution, in a particularly preferred ADD embodiment, from about 5 to about 40% by weight of ADD, preferably from about 10 to about 30%, most preferably from about 15 to About 20% sodium citrate and about 5 to about 30%, preferably about 7 to about 25%, most preferably about 8 to about 20% sodium carbonate.
The essential pH adjustment system is selected from other non-phosphate detergency builders known in the art, including various water soluble alkali metals, ammonium or substituted ammonium borates, hydroxy sulfonates, polyacetates and polycarboxylates. It can be replenished with an optional detergency builder salt (ie for improved sequestration in hard water). Alkali metals, especially sodium salts of such substances are preferred. Other water-soluble non-phosphorus organic builders may also be used for their sequestering properties. Examples of polyacetates and polycarboxylate builders are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid; nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethoxysuccinic acid , Merit acid and sodium benzene polycarboxylate salt.
(A)Water-soluble silicate
The automatic dishwashing detergent composition may further comprise a water-soluble silicate. The water-soluble silicate of the present invention is any silicate that is soluble to the extent that it does not adversely affect the stain / filming characteristics of the ADD composition.
Examples of silicates are sodium metasilicates and more generally alkali metal silicates, especially SiO in the range 1.6: 1 to 3.2: 1.₂: Na₂Those having an O ratio are laminated silicates such as the laminated sodium silicate described in US Pat. No. 4,664,839 of H.P.Rieck, issued May 12, 1987. NaSKS-6^{▲ R ▼}Is a crystal stacked silicate sold by Hoechst (generally abbreviated herein as “SKS-6”). Unlike zeolite builders, NaSKS-6 and other water-soluble silicates useful in the present invention do not contain aluminum. NaSKS-6 is δ-Na₂SiO₅In the form of laminated silicates, which can be produced by methods as described in DE-A-3,417,649 and DE-A-3,742,043. While SKS-6 is the preferred laminated silicate for use in the present invention, other such laminated silicates such as the general formula NaMSi_xO_{2x + 1}・ YH₂Those having O (M is sodium or hydrogen, x is a number of 1.9 to 4, preferably 2, and y is a number of 0 to 20, preferably 0) can be used. Various other laminated silicates by Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as α, β and γ forms. Other silicates, such as magnesium silicate, that work as crispening agents in granule formulations, as stabilizers for oxygen bleaching, and as components of the foam control system are also useful.
A particularly useful silicate for automated dishwashing (ADD) applications is PITE Corp.'s BRITESIL^{▲ R ▼}H20 and BRITESIL of the same commercial source^{▲ R ▼}While there are granulated hydrated 2-ratio silicates such as H24, when the ADD composition has a liquid form, various silicates of liquid great can be used. Within safe limits, sodium metasilicate or sodium hydroxide is used in an ADD relationship to raise the wash pH to the desired level, either alone or in combination with other silicates.
Substance care agentThe ADD composition may contain one or more substance care agents effective as corrosion inhibitors and / or anti-fogging aids. Such materials are particularly interesting in European countries where the use of electroplated nickel silver and sterling silver is still relatively common in household flatware, or aluminum protection, and the composition is low silicate. At certain times, it is a preferred component of a machine dishwashing composition. Such substance care agents typically include metasilicates, silicates, bismuth salts, manganese salts, paraffins, thiazoles, pyrazoles, thiols, mercaptans, aluminum fatty acid salts and mixtures thereof.
When present, such protective substances are preferably formulated at low levels, for example, from about 0.01 to about 5% of the ADD composition. Suitable corrosion inhibitors include paraffin oil, typically branched aliphatic hydrocarbons having a number of carbon atoms in the range of about 20 to about 50, with preferred paraffin oils having a cyclic pair of about 32:68. Mainly branched C with acyclic hydrocarbon ratio_25-45Selected from species. Paraffin oil that meets these characteristics is sold under the trade name WINOG 70 from Wintershall, Salzbergen, Germany. In addition, low levels of bismuth nitrate (ie Bi (NO₃)₃) Is also preferred.
Other corrosion inhibitor compounds include benzotriazole and corresponding compounds; mercaptans or thiols including thionaphthol and thioanthranol; fine aluminum fatty acid salts such as aluminum tristearate. Those skilled in the art have found that such materials are usually used correctly and in limited amounts to avoid the tendency to stain or film glassware or impair the bleaching action of the composition. For this reason, mercaptan anti-fogging agents, which are common fatty carboxylic acids with a fairly strong bleach reactivity, precipitating with calcium in particular, are preferably avoided.
Other ingredients-Various other ingredients useful in detergent compositions, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for solid compositions, etc. It can be contained in the present composition. If high foaming is desired, C_Ten-C₁₆Foam enhancers such as alkanolamides can also be incorporated into the composition, typically at the 1-10% level. C_Ten-C₁₄Monoethanol and diethanolamide exemplify a typical class of such foam enhancers. The combined use of such foam enhancers with high foam co-surfactants such as the amine oxides, betaines and sultaines mentioned above is also advantageous. MgCl if desired₂, MgSO₄Soluble magnesium salts such as can be added typically at levels of 0.1 to 2% to provide additional foaming properties and enhance fat removal performance.
Various cleaning ingredients used in the composition can optionally be further stabilized by absorbing the above ingredients into a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. . Preferably, the cleaning component is mixed with a surfactant before being absorbed into the porous substrate. In use, the cleaning component is released from the substrate into an aqueous cleaning liquid where it performs its intended cleaning function.
To describe this technique in more detail, porous hydrophobic silica (trade name SIPERNAT D10, DeGussa) is C_13-15Mixed with a proteolytic enzyme solution containing 3-5% ethoxylated alcohol (EO7) nonionic surfactant. Typically, the enzyme / surfactant solution is silica weight x 2.5. The resulting powder is dispersed in silicone oil with stirring (various silicone oil viscosities ranging from 500 to 12,500 can be used). The resulting silicone oil dispersion is emulsified or added to the final detergent matrix. In this way, components such as the enzyme, bleach, bleach activator, bleach catalyst, photoactivator, dye, fluorescent agent, fabric conditioner and hydrolyzable surfactant are included in the detergent including the liquid laundry detergent composition. Can be “protected” for use.
Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for dissolving the surfactant, but polyols having 2 to about 6 carbon atoms and 2 to about 6 hydroxy groups (eg, 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol) can also be used. The composition can contain 5 to 90%, typically 10 to 50% of such a carrier.
The detergent composition is preferably formulated so that the wash water has a pH of about 6.5 to about 11, preferably about 7.5 to 10.5, during use in a water cleaning operation. The liquid dishwashing product formulation preferably has a pH of about 6.8 to about 9.0. Laundry products typically have a pH of 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., which are well known to those skilled in the art.
High density granular detergent composition
The glassy particle delivery system can be used in both low density (less than 550 g / l) and high density granular detergent compositions where the density of the granules is at least 550 g / l. Such high density detergent compositions typically contain from about 30 to about 90% detersive surfactant.
Low density compositions can be made by standard spray drying processes. A variety of means and equipment may be utilized to produce the high density granular detergent composition. Current commercial practice in the field uses spray drying towers to produce granular laundry detergents having a density of less than about 500 g / l. Thus, if spray drying is used as part of the overall process, the resulting spray dried detergent particles must be further densified using the means and equipment described below. Alternatively, the trader can omit spray drying by using commercially available mixing, densification and granulation equipment. The following is a non-limiting description of such a device suitable for use with the present invention.
A high speed mixer / densifier can be used in the process. For example, an apparatus sold under the trade name “Lodige CB30” recycler consists of a fixed cylindrical mixing drum with a central rotating shaft and a mixing / cutting blade installed on it. Other such devices include those sold under the trade name “Shugi Granulator” and the trade name “Drais K-TTP 80”. A device such as that sold under the trade name “Lodige KM600 Mixer” can be used for further densification.
In one mode of operation, the composition is made and densified by operating two mixers and a densification device in succession. For this reason, the desired composition components are mixed and passed through a Lodige mixer using a residence time of 0.1 to 1.0 minutes and then passed through a second Lodige mixer using a residence time of 1 to 5 minutes. The
In another system, an aqueous slurry containing the desired formulation ingredients is sprayed into a fluid layer of particulate surfactant. The obtained particles can be further densified by passing through a Lodige apparatus as described above. The glassy particles are mixed with the detergent composition in a Lodige device.
The final density of the particles can be measured by various simple techniques, typically placing the granular detergent in a container of known volume, measuring the weight of the detergent and reporting the density in g / l.
Once the low or high density granular detergent “base” composition is made, the glassy particle delivery system of the present invention is added to it by any suitable dry mixing operation.
In a method of washing a fabric and attaching a perfume thereto, the fabric is contacted with an aqueous wash containing at least about 100 ppm of the conventional cleaning ingredients and at least about 1 ppm of the perfume delivery system. Preferably, the aqueous liquid contains from about 500 to about 20,000 ppm of conventional cleaning ingredients and from about 10 to about 200 ppm of perfume delivery system.
Although the glassy particle delivery system works in all environments, it is particularly useful for providing the fabric with a perfume odor effect during storage, drying or ironing. In that method, the fabric is contacted with an aqueous liquid containing at least about 100 ppm of a conventional cleaning ingredient and at least about 1 ppm of a fragrance delivery composition so that the scented zeolite particles are trapped in the fabric and the humidity is at least Store the line-dried fabric under 20% environmental conditions and allow the fabric to dry in a conventional automatic dryer or low heat (about 50 ° C.) by conventional ironing means (preferably steam or pre-wet). Heat is applied to the line dried or machine dried fabric in
The following non-limiting examples illustrate the parameters of the present invention and the compositions used therein. All percentages, parts and ratios are by weight unless otherwise indicated.
Example I
1.Production of perfume-carrying zeolite
10 g of activated zeolite Na-X (residual moisture <5%) is placed in a simple mixer or coffee grinder type mixing device. To this, 1.5 g of fragrance is added dropwise. The mixture is stirred for about 10 minutes to obtain 15% w / w-supported PLZ (perfume-supported zeolite).
2.Production of low moisture hydrogenated starch hydrolyzate (Tg = 120 ° C)
100 g of hydrogenated starch hydrolyzate such as Roquette America's POLYSORB RA-1000 (75% solids) continuously until enough water is removed to obtain a low moisture syrup containing less than 5% water Heat with stirring. Under atmospheric pressure, this low moisture level leads to the boiling point of a viscous syrup in the range of 150-160 ° C.
3.Combination of PLZ and low moisture syrup
Add PLZ to warm low moisture syrup. Typically, 20 to 40 weight percent levels of PLZ are added. A high energy input (such as using a high torque mixer or extruder) is preferred for efficient mixing.
4).Glass particle formation / size reduction
Allow PLZ dispersion in low moisture syrup to cool to ambient temperature. When the temperature of the system falls below the glass transition temperature of the syrup, a glass system is obtained that can be ground to various particle sizes. Alternatively, the rubbery or molten system can be made into spheres or pellets to form particles of the desired size and shape.
5).Combination of granular glass and detergent base from step (4)
2.22% glassy particles may be added to the detergent formulation to deliver 0.67% PLZ and 0.1% perfume.
Example II
Example as in Example I but using a sucrose / maltodextrin 80:20 mixture (DE = 10) instead of hydrogenated starch hydrolysate. Such systems include sucrose or other low MW oligosaccharides and D.I. E. It may contain a mixture of polysaccharides or starches of less than 15, preferably <10, at a level of at least 10% w / w. A typical sucrose / maltodextrin melt was made of 80% sucrose containing 2% water and 20% LoDex5 (ex American Maize). The melt is then subjected to a ZSK30 Werner & Pfleiderer twin screw extruder and PLZ is added to the seventh zone of the extruder at 20% w / w / level. The extrudate is cooled to 90 ° C. and cut and sized into 500-1000 μm particles.

Claims (5)

(A) 0.1-10% by weight of the composition of glassy particles; provided that the glassy particles comprise zeolite particles incorporating perfume, the zeolite particles being coated on the particles with a water-soluble starch hydrolyzate. And the water-soluble starch hydrolyzate has an anhydrous unplasticized glass transition temperature Tg of 50-200 ° C .; and the glassy particles have a moisture absorption value of less than 80%; and ( b) A laundry or cleaning composition comprising 5 to 80% by weight of the composition of a detersive surfactant. The composition is a heavy granular laundry detergent comprising 0.1 to 10% glassy particles of the composition,
The glassy particles have an average particle size of 1 to 500 microns and contain perfume adsorbed on the zeolite and trapped in the starch hydrolyzate glass, the glass having a Tg in the range of 50-200 ° C. And
The composition of the glassy particles, when expressed as% of the component as% of the total glassy particles, is as follows:
(A) 2-40% of the above fragrance,
(B) ^{2 to} 95% of the zeolite; provided that the zeolite has a surface area of 50 m ² / g or more,
(C) 12-96% of the above carbohydrates having a melting point in the range of 30-300 ° C., and (d) 0.05-35% of water or plasticizer.
The composition of claim 1. The composition of claim 1 wherein the glassy particles have an average particle size in the range of 1 to 500 microns. The composition according to any one of claims 1 to 3, wherein the starch hydrolyzate is a hydrogenated starch hydrolysate. The composition according to any one of claims 1 to 4, further comprising a perfume fixing agent.